JP2011231017A - Process for producing optically active epoxy compound and optically active sulfoxide compound, ligand and complex for use in the process, and process for producing the complex - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a process for producing an optically active epoxy compound and an optically active sulfoxide compound; a ligand and a complex for use in the process; and a process for producing the complex.SOLUTION: Disclosed are: an optically active titanium-salen complex, an optically active titanium-salalen complex and an optically active titanium-salen complex having structures represented by formulae (21a), (21b), (22) and others; a process for producing an optically active epoxy compound or an optically active sulfoxide compound through the asymmetric oxidation reaction of an olefin compound or a sulfide compound using any one of the complexes as a catalyst; a ligand and a complex for use in the process; and a process for producing any one of the complexes.

Description

  The present invention relates to a method for producing an optically active epoxy compound and an optically active sulfoxide compound, a ligand used in the method, a complex, and a method for producing the complex.

  It has been reported that the asymmetric epoxidation reaction of various olefin compounds proceeds with high enantioselectivity using an optically active titanium salalene complex and hydrogen peroxide as an oxidizing agent. However, since the optically active titanium complex used in this technique has a plurality of optically active sites, a plurality of optically active compounds are required for the synthesis of the ligand, and there are multiple steps such as functional group protection and deprotection. Since synthesis is required, it took time and cost to synthesize and procure the titanium salalene complex. Furthermore, since the intramolecular Meerwein-Pondorf-Verley reduction reaction is used to synthesize the titanium salalene complex, there is a problem that the application is insufficient (see Patent Document 1 and Non-Patent Document 1). The amount of catalyst in Non-Patent Document 1 can be reduced by 0.02 mol% to 1 mol% at best, but by reducing the amount of catalyst, the reaction time can be extended or the addition control of the oxidant becomes necessary. A complicated aspect of the manufacturing operation such as tsunami occurred.

  In 2007, it was reported that the di-μ-oxotitanium salalene complex reacts with high yield and high selectivity even with respect to aliphatic olefins which are difficult to control reaction and selectivity (non-patent). Reference 4). Since the titanium salalene complex used in Non-Patent Document 4 is also the same complex as Non-Patent Document 1, it has the same problem as described above. Patent Document 3 relates to a method for producing an optically active titanium salalene complex used in Non-Patent Document 1 and Non-Patent Document 4.

  Furthermore, in 2007, Berkessel et al. Reported an optically active titanium salalene complex using a stepwise synthesis of a salalene ligand. Although the molecular weight was simplified to about 1000, the reduction of the catalyst amount was insufficient, and the reaction selectivity was inferior to the examples of Patent Document 1 and Non-Patent Document 1 (Non-Patent Document 5). reference). The report of optically active titanium salalene complex by Berkessel et al. In 2008 relates to the reaction mechanism (see Non-Patent Document 7).

  It has been reported that the reaction proceeds with high enantioselectivity in an asymmetric epoxidation reaction of various olefin compounds using an optically active titanium-saran complex with hydrogen peroxide as an oxidizing agent (Patent Document 1 and Non-patent document 2). The molecular weight of the optically active titanium-saran complex used in this technology has been simplified to about 1000, and the cost and time required for synthesis and procurement can be reduced as compared with the optically active titanium salalene complex. However, when this titanium-saran complex is used, there are problems that the enantioselectivity and chemical yield of the optically active epoxy compound are lowered, and the amount of catalyst used is 5 mol% and cannot be reduced.

  Next, in the optically active titanium-saran complex, it has been reported that the catalytic performance has been successfully improved by examining substituents of the optically active saran ligand (Non-patent Document 3). However, when this titanium-saran complex is used, there is a problem that a part of the produced epoxy compound becomes a by-product under the reaction conditions and the chemical yield is lowered, and purification of the by-product takes time and cost. In this respect, a problem remains (see Non-Patent Document 3). Therefore, in the optically active titanium-saran complex, by adding a buffer to control the pH in the reaction solution, it is possible to prevent a part of the epoxy compound that is the target compound from becoming a by-product under the reaction conditions. Moreover, it has been reported that the amount of catalyst has also been reduced from 1 mol% to 2 mol% (see Non-Patent Document 6). The main solvent used in the reactions in these reports was dichloromethane.

  In 2007, it was reported that an optically active titanium salalene complex and an optically active titanium-saran complex, which are optically active titanium complexes, react with high yield and selectivity with respect to olefin compounds and chromene compounds having heteroatoms. . The amount of catalyst at that time was 1 mol% to 10 mol% (see Patent Document 2).

  It has been reported that the asymmetric oxidation reaction of various sulfide compounds proceeds with high enantioselectivity using optically active titanium-salen complex as an oxidizing agent with hydrogen peroxide solution or urea / hydrogen peroxide adduct ( Patent Document 4 and Non-Patent Document 9). To give high enantioselectivity, it was necessary to use a urea / hydrogen peroxide adduct in a methanol solution.

  It has been reported that the asymmetric oxidation reaction of various sulfide compounds proceeds with high enantioselectivity using an optically active titanium-saran complex as an oxidizing agent (Non-patent Document 8).

  Regarding optically active titanium complexes, it is desired to reduce the amount of catalyst while ensuring reproducibility to withstand actual production, avoid the extension of the reaction time due to the reduction of the amount of catalyst, and expand the application range of the solvent used in the reaction. .

  (Optically active titanium salalene catalyst, optically active titanium salane catalyst)

WO2006 / 087874A1 WO2007 / 105658A1 JP2007-284438A

Angew. Chem. Int. Ed. (2005), 44, 4935-4939. Angew. Chem. Int. Ed. (2006), 45, 3478-3480. Synlett (2006), 20, 3545-3547. Angew. Chem. Int. Ed. (2007), 46, 4559-4561. Adv. Synth. Catal. (2007), 349, 2385-2391. Synlett (2007), 25, 2445-2447. Adv. Synth. Catal. (2008), 350, 1287-1294. Eur. J. et al. Org. Chem. (2008), 3369-3376.

  (Optically active titanium salen catalyst)

JP2002-308845A

Tetrahedron Letters (2001), 42, 3873-3876.

  An object of the present invention is to solve the problems of the prior art and to provide a method for producing an optically active epoxy compound, a ligand used in the method, a complex, and a method for producing the complex.

As a result of intensive studies on the production methods of optically active epoxy compounds and optically active sulfoxide compounds, and the ligands, complexes and methods of producing the complexes used in the methods, the present inventors have obtained optically active titanium salen complexes and optically active titanium salalene complexes. In addition, the skeleton necessary for the high catalytic activity of optically active titanium-saran complex and the useful substituents and the positions of these substituents are identified, and high enantioselectivity and high chemical yield are maintained as in the case of conventional optically active titanium complexes. While reducing the amount of catalyst while ensuring reproducibility to withstand actual production, avoiding extending the reaction time by reducing the amount of catalyst, optically active titanium salen complex, optically active titanium salalene complex and optical activity that can apply toluene as a reaction solvent Titanium-saran complexes are found, and these complexes are optical with high enantioselectivity and high chemical yield. It found to be able to produce sexual epoxy compound and an optically active sulfoxide compound, and completed the present invention.
That is, the present invention

[1]
Formula (1a), Formula (1a ′), Formula (1b), Formula (1b ′), Formula (2), Formula (2 ′), Formula (3a), Formula (3a ′), Formula (3b), Formula (3b ′), formula (4) and formula (4 ′)

(Formula (1a), Formula (1a ′), Formula (1b), Formula (1b ′), Formula (2), Formula (2 ′), Formula (3a), Formula (3a ′), Formula (3b), R ¹ in formula (3b ′), formula (4), and formula (4 ′) represents partial structural formula (AA) and partial structural formula (AB).

(X in the partial structural formula (AA) and the partial structural formula (AB) is an oxygen atom or a sulfur atom, and Y in the partial structural formula (AA) and the partial structural formula (AB) is a single bond or a methylene group. (The methylene group is unsubstituted or substituted with a fluorine atom.), An ethylene group (the ethylene group is unsubstituted or substituted with a fluorine atom), -SO _2- , a carbonyl group, —CH (C _1-4 alkyl group) — (the alkyl group in —CH (C _1-4 alkyl group) — is unsubstituted or substituted with a halogen atom. Or the aryl group in —CH (C _6-14 aryl group) — (the —CH (C _6-14 aryl group) — is unsubstituted or substituted with a halogen atom. Z in the partial structural formula (AA) and the partial structural formula (AB) is C _3-12 alkyl group (said alkyl group is substituted or unsubstituted, or a halogen _{atom.), C 3-8} cycloalkyl _{group, C 6-22} aryl group (the aryl group is unsubstituted Substituted or halogen atom, C _1-4 alkyl group (the alkyl group is unsubstituted or substituted with a halogen atom or C _6-16 aryl group), C _6-16. An aryl group (the aryl group is unsubstituted or substituted with a halogen atom), or optionally substituted with a C _1-4 alkoxy group) or a C _2-9 heteroaryl group ( The heteroaryl group is unsubstituted or substituted with a halogen atom.), And R ² in the partial structural formula (AA) and the partial structural formula (AB) is a hydrogen atom, a halogen atom, C _1-4 alkyl Group (the alkyl group is substituted or unsubstituted, or a halogen atom.), Or C _1-4 alkoxy group, the partial structural formula (AA) and a partial structural formulas (AB) R ⁴ each independently represents a hydrogen atom, a halogen atom, a C _1-4 alkyl group (the alkyl group is unsubstituted or substituted with a halogen atom), a C _1-4 alkoxy group, a nitro group; Group or a cyano group).
Formula (1a), Formula (1a ′), Formula (1b), Formula (1b ′), Formula (2), Formula (2 ′), Formula (3a), Formula (3a ′), Formula (3b), Formula (3b ') ^{R 2} of formula (4) and formula (4') in a hydrogen atom, a halogen _{atom, C 1-4} alkyl group (said alkyl group is unsubstituted or substituted with a halogen atom Or a C _1-4 alkoxy group,
Formula (1a), Formula (1a ′), Formula (1b), Formula (1b ′), Formula (2), Formula (2 ′), Formula (3a), Formula (3a ′), Formula (3b), Formula R ³ in (3b ′), formula (4), and formula (4 ′) is a C _6-18 aryl group or, when two R ³ together form a ring, C _3-5 Valent group,
Formula (1a), Formula (1a ′), Formula (1b), Formula (1b ′), Formula (2), Formula (2 ′), Formula (3a), Formula (3a ′), Formula (3b), Formula (3b ') or ^{R 4} of the formula (4) and formula (4') during each independently represent a hydrogen atom, a halogen _{atom, C 1-4} alkyl group (said alkyl group is unsubstituted, Or a C _1-4 alkoxy group, a nitro group, or a cyano group. The optically active titanium complex obtained by reacting the optically active ligand represented by any of the above and a titanium compound (the optically active titanium complex is an optically active titanium salen complex, an optically active titanium salalene complex, or an optically active titanium salen). Is used as a catalyst, and the following formula (5), formula (6), formula (7), formula (8), formula (9) and formula (10) are used.

(In formula (5) and formula (6), R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, cyano group, nitro group, amino group (the amino group is a protecting group) Unprotected or protected.), C _1-4 alkylamino group (the alkylamino group is unprotected or protected by a protecting group), halogen atom, C _{1 -4} alkyl group (the alkyl group is unsubstituted or substituted with a halogen atom), C _1-4 alkoxy group, carboxyl group, formyl group, C _1-4 alkylcarbonyl group (the alkyl The carbonyl group is unsubstituted or substituted with a halogen atom.), A C _6-12 arylcarbonyl group (the arylcarbonyl group is unsubstituted or substituted with a halogen atom). ), Cal Moil _{group, C 1-4} alkylsulfinyl _{group, C 6-7} arylsulfinyl _{group, C 1-4} alkylsulfonyl _{group, C 6-12} arylsulfonyl group, a sulfamoyl group, a mono _{C 1-3} alkylaminosulfonyl group, or a di A C _1-3 alkylaminosulfonyl group,
R ⁹ in formula (5), formula (6), formula (9) and formula (10) is a hydrogen atom, a C _1-4 alkyl group (the alkyl group is unsubstituted or a halogen atom) Or a C _1-4 alkoxy group, and R ¹⁰ in formula (5), formula (6), formula (9) and formula (10) is a hydrogen atom, C _1-22 alkyl. Group, C _1-4 alkoxy group, C _6-10 aryl group (the aryl group is unsubstituted or substituted by a halogen atom, a C _1-4 alkyl group, or a C _1-4 alkoxy group) .) However, R ⁹ and R ¹⁰ in Formula (5), Formula (6), Formula (9), and Formula (10) are combined with each other, and the following Formula (11), Formula (12), and Formula (13) And formula (14)

(R ¹² in formula (11), formula (12), formula (13) and formula (14) is each independently a hydrogen atom or a C _1-4 alkyl group). Divalent groups may be formed. R ¹¹ in Formula (6) is a C _1-4 alkyl group (the alkyl group is unsubstituted or substituted with a halogen atom).
R ^a and R ^{b in} formula (7) and formula (8) are each independently a hydrogen atom, a C _1-22 alkyl group (the alkyl group is unsubstituted or a halogen atom, C _{1 -4} alkyl group, C _6-10 aryl group (the aryl group is unsubstituted or substituted with a halogen atom, a C _1-4 alkyl group, or a C _1-4 alkoxy group), benzoyl. An oxy group, a benzyloxy group, or a pivaloyloxy group), a C _3-8 cycloalkyl group (the cycloalkyl group is unsubstituted or a halogen atom, a C _1-4 alkyl group, benzoyloxy group, benzyloxy group, or is substituted with pivaloyloxy group.), C _1-4 alkoxy groups, C _6-22 aryl group (the aryl group is unsubstituted, and Halogen _{atom, C 1-4} alkyl group (said alkyl group is substituted by unsubstituted or substituted with halogen atom, or a _{C 6-16} aryl _{group.), C 6-16} aryl group (the aryl group Is unsubstituted or substituted with a halogen atom), or optionally substituted with a C _1-4 alkoxy group.
The ring partial structure A in the formula (9) and the formula (10) is a 5-membered ring, 6-membered ring or 7-membered ring condensed with a benzene ring. Or h substituents R ¹³ (wherein R ¹³ is a halogen atom, a hydroxyl group, a C _1-6 alkyl group (the alkyl group is unsubstituted or a halogen atom, a hydroxyl group, A cyano group, an amino group, a nitro group, a C _1-4 alkoxy group (the alkoxy group is unsubstituted or substituted with a halogen atom), a C _1-4 alkylcarbonyloxy group (the alkylcarbonyl The oxy group is unsubstituted or substituted with a halogen atom.), A C _1-4 alkylcarbonylamino group (the alkylcarbonylamino group is unsubstituted or substituted with a halogen atom) there.), or _{C 1-} Alkoxycarbonyl group (the alkoxy group is unsubstituted or substituted by substituted by halogen atom.) Are replaced by.), C _1-6 alkoxy group (said alkoxy group is unsubstituted Or a halogen atom, a hydroxyl group, a cyano group, an amino group, a nitro group, a C _1-4 alkoxy group (the alkoxy group is unsubstituted or substituted with a halogen atom), C _1-4. An alkylcarbonyloxy group (the alkylcarbonyloxy group is unsubstituted or substituted with a halogen atom), a C _1-4 alkylcarbonylamino group (whether the alkylcarbonylamino group is unsubstituted) or substituted with a halogen atom.), or C _1-4 alkoxycarbonyl group (the alkoxy group is unsubstituted, or Substituted with a halogen atom))), nitro group, cyano group, formyl group, formamide group, carbamoyl group, sulfo group, sulfoamino group, sulfamoyl group, sulfonyl group, amino group, carboxyl group, C _1-6 alkylamino group (the alkylamino group is unsubstituted or substituted with a halogen atom), diC _1-6 alkylamino group (the dialkylamino group is unsubstituted) Or a C _1-6 alkylcarbonylamino group (the alkylcarbonylamino group is unsubstituted or substituted with a halogen atom), C _1-6. An alkylsulfonamido group (the alkylsulfonamido group is unsubstituted or substituted with a halogen atom). ), A C _6-14 arylsulfonamido group (the arylsulfonamido group is unsubstituted or substituted with a halogen atom), a C _1-6 alkylaminocarbonyl group (the alkylaminocarbonyl group is , Unsubstituted or substituted with a halogen atom), a di-C _1-6 alkylaminocarbonyl group (the dialkylaminocarbonyl group is unsubstituted or substituted with a halogen atom). ), C _1-6 alkylcarbonyl group (the alkylcarbonyl group is unsubstituted or substituted with a halogen atom), C _1-6 alkoxycarbonyl group (the alkoxycarbonyl group is unsubstituted) substituted with some or halogen atom.), C _1-4 alkylsulfonyl group (the alkylsulfonyl group is unsubstituted der Or substituted with halogen atoms.), C _6-14 arylsulfonyl group (the aryl sulfonyl group is substituted or unsubstituted, or a halogen atom.), Or C _6-14 aryl A carbonyl group (the arylcarbonyl group is unsubstituted or substituted with a halogen atom), h is an integer of 1 to 6, and when h is 2 to 6, R ¹³ is It can be the same or different. ) And can contain 1 to 3 oxygen atoms, nitrogen atoms or sulfur atoms as ring constituents, alone or in combination, and the number of unsaturated bonds in the ring is One, two or three carbon atoms including a ring unsaturated bond may be carbonyl or thiocarbonyl. ). The following formula (15), formula (16), formula (17), formula (18), formula (19), wherein the unsaturated compound represented by any one of And equation (20)

(In formula (15), formula (16), formula (17), formula (18), formula (19) and formula (20), R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ^a , R ^b and the ring partial structure A are the same as described above).

[2]
R ¹ is partial structural formula (AA) (X in partial structural formula (AA) is an oxygen atom, Y in partial structural formula (AA) is a methylene group (the methylene group is unsubstituted) Or Z in the partial structural formula (AA) is a C _6-22 aryl group (the aryl group is unsubstituted or a halogen atom, C _{1 -4} alkyl group (the alkyl group is unsubstituted or substituted with a halogen atom or a C _6-16 aryl group), a C _6-16 aryl group (the aryl group is unsubstituted Or optionally substituted with a C _1-4 alkoxy group) or a C _2-9 heteroaryl group (wherein the heteroaryl group is unsubstituted) Or substituted with a halogen atom. , ^{R 2} in the partial structural formula (AA) is a hydrogen atom, or a methoxy group, ^{R 4} in the partial structural formula (AA) is a hydrogen atom, or a methoxy group.), ^{R 2} is , R ³ is a tetramethylene group, which is a divalent group, and R ⁴ is a hydrogen atom. Formula (1a), Formula (1a ′), Formula (1b) according to [1] ), An optically active titanium complex obtained by reacting an optically active ligand represented by any one of formula (1b ′), formula (2) and formula (2 ′) with a titanium compound (the optically active titanium complex) Is an optically active titanium salen complex, an optically active titanium salalene complex, or an optically active titanium salen complex) as a catalyst. 18), an optically active epoxy compound represented by any one of formula (19) and formula (20) Manufacturing method.

[3]
R ¹ is a partial structural formula (AB) (X in the partial structural formula (AB) is an oxygen atom, Y in the partial structural formula (AB) is a methylene group (the methylene group is unsubstituted) Or Z in the partial structural formula (AB) is a C _6-22 aryl group (the aryl group is unsubstituted or a halogen atom, C _{1 -4} alkyl group (the alkyl group is unsubstituted or substituted with a halogen atom or a C _6-16 aryl group), a C _6-16 aryl group (the aryl group is unsubstituted Or optionally substituted with a C _1-4 alkoxy group) or a C _2-9 heteroaryl group (wherein the heteroaryl group is unsubstituted) Or substituted with a halogen atom. And R ² in the partial structural formula (AB) is a hydrogen atom, R ⁴ in the partial structural formula (AB) is a hydrogen atom), R ² is a hydrogen atom, and R ³ Is a tetramethylene group that is a divalent group, and R ⁴ is a hydrogen atom. The formula (3a), formula (3a ′), formula (3b), formula (3b ′), An optically active titanium complex obtained by reacting an optically active ligand represented by any one of formula (4) and formula (4 ′) with a titanium compound (the optically active titanium complex is an optically active titanium salen complex, optical Active titanium salalene complex or optically active titanium-saran complex) is used as a catalyst. The formula (15), formula (16), formula (17), formula (18), formula (19) and The manufacturing method of the optically active epoxy compound represented by either of Formula (20).

[4]
Following formula (5) and formula (6)

(R ⁵ , R ⁶ , R ⁷ and R ⁸ in the formula (5) and the formula (6) are each independently a hydrogen atom, a cyano group, a nitro group, a mesylamino group, a dimethylylamino group, or a trifluoromethylsulfonyl group. Amino group, ditrifluoromethylsulfonylamino group, tosylamino group, benzylamino group, acetylamino group, propionylamino group, benzoylamino group, methoxycarbonylamino group, ethoxycarbonylamino group, n-propoxycarbonylamino group, i-propoxycarbonyl Amino group, t-butoxycarbonylamino group benzylmethylamino group, benzylethylamino group, benzyl-n-propylamino group, benzyl-n-butylamino group, acetylmethylamino group, acetylethylamino group, acetyl-n-propyl Amino group, benzo Rumethylamino group, benzoylethylamino group, benzoyl-n-propylamino group, benzoyl-n-butylamino group, t-butoxycarbonylmethylamino group, t-butoxycarbonylethylamino group, t-butoxycarbonyl-n-propylamino group T-butoxycarbonyl-n-butylamino group, fluorine atom, chlorine atom, bromine atom, iodine atom, methyl group, trifluoromethyl group, monochloromethyl group, ethyl group, pentafluoroethyl group, n-propyl group, i -Propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, s-butoxy group, t-butoxy group, methylcarbonyl group, trifluoromethylcarbonyl Group, monochloromethylcarbonyl group, ethylcarbonyl group, pentafluoroethylcarbonyl group, n-propylcarbonyl group, i-propylcarbonyl group, n-butylcarbonyl group, i-butylcarbonyl group, s-butylcarbonyl group, t-butyl Carbonyl group, phenylcarbonyl group, o-toluoyl group, m-toluoyl group, p-toluoyl group, o-biphenylylcarbonyl group, m-biphenylylcarbonyl group, p-biphenylylcarbonyl group, 1-naphthylcarbonyl group, 2 -Naphtylcarbonyl group, methylsulfonyl group, ethylsulfonyl group, n-propylsulfonyl group, i-propylsulfonyl group, n-butylsulfonyl group, i-butylsulfonyl group, s-butylsulfonyl group, t-butylsulfonyl group, methyl Aminosulfonyl group , Ethylaminosulfonyl group, n-propylaminosulfonyl group, i-propylaminosulfonyl group, dimethylaminosulfonyl group, diethylaminosulfonyl group, di-n-propylaminosulfonyl group, or di-i-propylaminosulfonyl group. R ⁹ in the formulas (5) and (6) is a hydrogen atom, a methyl group, a trifluoromethyl group, a monochloromethyl group, an ethyl group, a pentafluoroethyl group, an n-propyl group, an i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, s-butoxy group , or a t- butoxy group, the formula (5) and ^{R 10} in the formula (6) is a hydrogen atom, a methyl group, an ethyl group, n- Propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, 2- Ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, isotridecyl group, myristyl group, palmityl group, stearyl group, icosyl group, docosyl group, phenyl group, o-fluorophenyl group, m-fluoro Phenyl group, p-fluorophenyl group, o-chlorophenyl group, m-chlorophenyl group, p-chlorophenyl group, o-bromophenyl group, m-bromophenyl group, p-bromophenyl group, o-tolyl group, m-tolyl Group, p-tolyl group, o-ethylphenyl group, m-ethylphenyl group, p-ethylphenyl group, o- (t-butyl) L) phenyl group, m- (t-butyl) phenyl group, p- (t-butyl) phenyl group, 3,5-dimethylphenyl group, o-methoxyphenyl group, m-methoxyphenyl group, or p-methoxy It may be a phenyl group, or R ⁹ and R ^{10 in the} formulas (5) and (6) may be combined with each other to form a divalent group. The compound of the formula (5) is a divalent group of the formula (11), formula (12), formula (13) or formula (14).

(Equation (11), equation (12), ^{R 12} in the formula (13) and (14) is a methyl group.) Is a compound which can be described by combinations of one selected from the formula (11) Regarding the substitution position, the R ⁹ side is an oxygen atom, and the R ⁹ side is a carbon atom. The compound of the formula (6) is a compound that can be described in one combination selected from the formula (12) and the formula (13), and R ¹¹ in the formula (6) is a methyl group. ), Wherein the unsaturated compound represented by any one of the following formulas (15) and (16)

(In formula (15) and formula (16), R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are the same as described above). ] To [3] The method for producing an optically active epoxy compound according to any one of [3].

[5]
Following formula (7) and formula (8)

(In the formulas (7) and (8), ^Ra represents a methyl group, a benzoyloxymethyl group, a benzyloxymethyl group, a phenylmethyl group, an ethyl group, a 2-benzoyloxyethyl group, and a 2-benzyloxyethyl group. Phenylethyl group, n-propyl group, 3-benzoyloxy-n-propyl group, 3-benzyloxy-n-propyl group, n-butyl group, 4-benzoyloxy-n-butyl group, 4-benzyloxy- n-butyl group, t-butyl group, n-pentyl group, 5-benzoyloxy-n-pentyl group, 5-benzyloxy-n-pentyl group, n-hexyl group, 6-benzoyloxy-n-hexyl Group, 6-benzyloxy-n-hexyl group, n-heptyl group, 7-benzoyloxy-n-heptyl group, 7-benzyloxy-n-heptyl group, octyl Group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group, c-propyl group, c-butyl group, c-pentyl group, 3-benzoyl-c-pentyl group, 3-benzyloxy -C-pentyl group, c-hexyl group, 3-benzoyl-c-hexyl group, 3-benzyloxy-c-hexyl group, 4-benzoyl-c-hexyl group, 4-benzyloxy-c-hexyl group, phenyl Group, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2-bromophenyl group, 3-bromophenyl group, 4-bromo Phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2-ethylphenyl group, 3-ethylphenyl group, -Ethylphenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2-naphthyl group, 6-bromo-2-naphthyl group, 6-methoxy-2-naphthyl group, 2-biphenylyl group , 3-biphenylyl group, or 4-biphenylyl group, and R ^{b in} formula (7) and formula (8) is a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, t -Butyl group, c-propyl group, c-butyl group, c-pentyl group, c-hexyl group)), and asymmetric epoxidation with an oxidizing agent. The following formula (17) and formula (18)

(In formula (17) and formula (18), R ^a and R ^b are the same as described above.) The optical activity according to any one of [1] to [3] Production method of epoxy compound.

[6]
Following formula (9) and formula (10)

(The ring partial structure A in the formula (9) and the formula (10) has the formula (a), formula (b), formula (c), formula (d), formula (e), formula (f), formula (G), Formula (h), Formula (i), Formula (j), Formula (k), Formula (l), Formula (m), Formula (n), Formula (o), Formula (p), Formula (Q), formula (r), formula (s), formula (t), formula (u), formula (v), formula (w), formula (x), formula (y), formula (z), formula (Aa), formula (ab), formula (ac), formula (ad), formula (ae), formula (af), formula (ag), and formula (ah)

(Formula (a), Formula (b), Formula (e), Formula (f), Formula (g), Formula (h), Formula (i), Formula (j), Formula (k), Formula (l ), Formula (m), formula (n), formula (p), formula (q), formula (v), formula (w), formula (x), formula (ab), formula (ae), formula (af) And R ¹⁴ and R ^{15 in} formula (ag) are each independently a hydrogen atom, a C _1-6 alkyl group (the alkyl group is unsubstituted or a halogen atom, C _1-6 alkoxy) A group (the alkoxy group is unsubstituted or substituted with a halogen atom), an amino group, a hydroxyl group, a C _6-14 aryl group (the aryl group is unsubstituted or q Substituted with R ²⁰ (wherein R ²⁰ represents the same meaning as R ¹³ , q represents an integer of 1 to 3, and when q is 2 or 3, R ²⁰ may be the same or different). The C _2-9 heteroaryl group (the heteroaryl group is unsubstituted or q substituents R ²⁰ (the R ²⁰ represents the same meaning as R ¹³ , q is 1 Represents an integer of ˜3, and when q is 2 or 3, R ²⁰ may be the same or different.)), C _1-6 alkylaminocarbonyl group, diC _1-6 alkyl An aminocarbonyl group, a C _1-6 alkylcarbonyloxy group (the alkylcarbonyloxy group is unsubstituted or substituted with a halogen atom), a C _1-6 alkylcarbonyl group (the alkylcarbonyl group is is substituted or unsubstituted, or a halogen atom.), C _1-6 alkylcarbonylamino group, C _3-8 cycloalkyl group (said cycloalkyl group is unsubstituted Luke, or substituted with a halogen atom.), C _1-6 alkoxycarbonyl group (the alkoxy group is substituted or unsubstituted, or a halogen atom.), C _1-4 alkyl A sulfonyl group (the alkylsulfonyl group is unsubstituted or substituted with a halogen atom), a carboxyl group, a C _6-14 arylcarbonyl group (the arylcarbonyl group is unsubstituted, or Substituted with a halogen atom) or a C _2-9 heteroarylcarbonyl group), a C _6-14 aryl group (the aryl group is unsubstituted or q substituents) R ²⁰ (wherein R ²⁰ represents the same meaning as R ¹³ , q represents an integer of 1 to 3, and when q is 2 or 3, R ²⁰ may be the same or different. ). ), C _2-9 heteroaryl group (the heteroaryl group is unsubstituted or q substituents R ²⁰ (the R ²⁰ represents the same meaning as R ¹³ , q is an integer of 1 to 3) And when q is 2 or 3, R ²⁰ may be the same or different.)), A C _1-6 alkylaminocarbonyl group, a diC _1-6 alkylaminocarbonyl group, C _1-6 alkylcarbonyl group, C _3-8 cycloalkylcarbonyl group, C _1-6 alkoxycarbonyl group, C _1-4 alkylsulfonyl group (the alkylsulfonyl group is unsubstituted or substituted with a halogen atom) C _6-14 arylsulfonyl group (the arylsulfonyl group is unsubstituted or q substituents R ²⁰ (wherein R ²⁰ has the same meaning as R ¹³ , q is 1 ~ 3 Represents an integer, and when q is 2 or 3, R ²⁰ is substituted with or.) To be the same or different.), C _2-9 heteroarylsulfonyl group (the hetero arylsulfonyl group, an unsubstituted Or q substituents R ²⁰ (wherein R ²⁰ represents the same meaning as R ¹³ , q represents an integer of 1 to 3, and when q is 2 or 3, R ²⁰ is the same or different. Substituted), a carboxyl group, a C _6-14 arylcarbonyl group (the arylcarbonyl group is unsubstituted or q substituents R ²⁰ (the R ²⁰ is R) represents the same meaning as ^13, q represents an integer of 1 to 3, when q is 2 or ^{3, R 20} is substituted with or.) to be the same or different. or _{C 2-9} heteroaryl A carbonyl group (the heteroarylcarbonyl group is Or is unsubstituted, or q substituents, ^{R 20} (wherein ^{R 20} has the same meaning as ^{R 13,} q represents an integer of 1 to 3, when q is 2 or ^3, also ^{R 20} is the same And may be different from each other.), And the above formula (a), formula (b), formula (c), formula (d), formula (f), formula (g), formula ( h), formula (j), formula (k), formula (m), formula (n), formula (o), formula (p), formula (q), formula (r), formula (s), formula ( t), formula (u), formula (v), formula (w), formula (y), formula (z), formula (aa), formula (ab), formula (ac), formula (ad), formula ( ae) and R ¹⁶ , R ¹⁷ , R ¹⁸ and R ^{19 in} formula (af) are each independently a hydrogen atom, a halogen atom or a C _1-6 alkyl group (the alkyl group is unsubstituted or or halogen _{atom, C 1-6} alkoxy group (該A Kokishi group is substituted or unsubstituted, or a halogen atom. ), An amino group, a hydroxyl group, a C _6-14 aryl group (the aryl group is unsubstituted or has r substituents R ²¹ (the R ²¹ has the same meaning as R ¹³ , r is q and Substituted with a C _2-9 heteroaryl group (the heteroaryl group is unsubstituted or r substituents R ²¹ (the R ²¹ is R ¹³ and The same meaning, and r is the same meaning as q.)), A C _1-6 alkylaminocarbonyl group, a di C _1-6 alkylaminocarbonyl group, a C _1-6 alkylcarbonyloxy group. (The alkylcarbonyloxy group is unsubstituted or substituted with a halogen atom.), A C _1-6 alkylcarbonyl group (the alkylcarbonyl group is unsubstituted or substituted with a halogen atom. Has been.) C _1-6 alkylcarbonylamino _{group, C 3-8} cycloalkyl group (the cycloalkyl group is substituted or unsubstituted, or a halogen _{atom.), C 1-6} alkoxycarbonyl group ( The alkoxycarbonyl group is unsubstituted or substituted with a halogen atom.), A C _1-4 alkylsulfonyl group (the alkylsulfonyl group is unsubstituted or substituted with a halogen atom) ), A carboxyl group, a C _6-14 arylcarbonyl group (the arylcarbonyl group is unsubstituted or substituted with a halogen atom) or a C _2-9 heteroarylcarbonyl group. Yes. ), A C _3-8 cycloalkyl group (the cycloalkyl group is unsubstituted or substituted with a halogen atom, a C _1-6 alkoxy group (the alkoxy group is unsubstituted or substituted with a halogen atom) Substituted with an amino group or a hydroxyl group), a C _1-6 alkoxy group (the alkoxy group is unsubstituted, or a halogen atom, a C _1-6 alkoxy group (the alkoxy group is , Unsubstituted or substituted with a halogen atom), a carboxyl group, an amino group, a hydroxyl group, a C _6-14 aryl group (the aryl group is unsubstituted or r substituents) Substituted with R ²¹ (wherein R ²¹ represents the same meaning as R ¹³ and r represents the same meaning as q)) or a C _2-9 heteroaryl group (the heteroaryl group is unsubstituted) Is or r substituents, ^{R 21} (wherein ^{R 21} has the same meaning as ^{R 13,} r represents. the same meaning as q) is substituted with.) which is substituted _{with.), C 1-6} thio An alkoxy group (the thioalkoxy group is unsubstituted or a halogen atom, a C _1-6 alkoxy group (the alkoxy group is unsubstituted or substituted with a halogen atom), a carboxyl group; , A hydroxyl group, a C _6-14 aryl group (the aryl group is unsubstituted or r substituents R ²¹ (the R ²¹ represents the same meaning as R ^13, and r represents the same meaning as q). ), Or a C _2-9 heteroaryl group (the heteroaryl group is unsubstituted or r substituents R ²¹ (wherein R ²¹ has the same meaning as R ^13). And r represents the same meaning as q). ), A hydroxyl group, a C _6-14 aryl group (the aryl group is unsubstituted or r substituents R ²¹ (wherein R ²¹ represents the same meaning as R ¹³⁾ , r represents the same meaning as q.)), a C _2-9 heteroaryl group (the heteroaryl group is unsubstituted or r substituents R ²¹ (the R ²¹ Represents the same meaning as R ^13, and r represents the same meaning as q).), C _1-6 alkylcarbonyloxy group, nitro group, cyano group, formyl group, formamide group, amino group , A sulfo group, a C _1-6 alkylamino group, a di C _1-6 alkylamino group, a C _6-14 arylamino group (the arylamino group is unsubstituted or r substituents R ²¹ ( the ^{R 21} are as defined ^{R 13,} r is equal and q Meaning represents a. ). ), C _2-9 heteroarylamino group (the heteroarylamino group is unsubstituted or r substituents R ²¹ (the R ²¹ represents the same meaning as R ¹³ , r is the same as q) Represents a meaning.)), C _1-6 alkylcarbonylamino group, C _1-6 alkylsulfonamido group, carbamoyl group, C _1-6 alkylaminocarbonyl group, di-C _1-6 alkylamino A carbonyl group, a C _1-6 alkylcarbonyl group, a C _6-14 arylcarbonyl group (the arylcarbonyl group is unsubstituted or r substituents R ²¹ (the R ²¹ has the same meaning as R ¹³⁾ ; And r represents the same meaning as q.)), A C _2-9 heteroarylcarbonyl group (the heteroarylcarbonyl group is unsubstituted or r substituents) Substituted with R ²¹ (wherein R ²¹ has the same meaning as R ¹³ and r has the same meaning as q)), C _1-6 alkoxycarbonyl group, sulfamoyl group, C _1-4 alkylsulfonyl. A group (the alkylsulfonyl group is unsubstituted or substituted with a halogen atom), a C _6-14 arylsulfonyl group (the arylsulfonyl group is unsubstituted or substituted with r substituents); Substituted with a group R ²¹ (wherein R ²¹ has the same meaning as R ¹³ and r has the same meaning as q)), a C _2-9 heteroarylsulfonyl group (the heteroarylsulfonyl group is It is unsubstituted or substituted with r substituents R ²¹ (wherein R ²¹ has the same meaning as R ¹³ and r has the same meaning as q)), a carboxyl group, or C _2-9 non Aromatic heterocyclyl group (non-aromatic heterocyclyl group is unsubstituted, or halogen atom, C _1-6 alkyl group (said alkyl group is unsubstituted, or halogen atom, C _1-6 An alkoxy group (the alkoxy group is unsubstituted or substituted with a halogen atom), an amino group, a carboxyl group, or a hydroxyl group), a C _1-6 alkoxy group (the alkoxy group Is unsubstituted or substituted with a halogen atom.), A C _6-14 aryl group (the aryl group is unsubstituted or r substituents R ²¹ (the R ²¹ is R ¹³ represents the same meaning as R ^13, and r represents the same meaning as q.)), A C _2-9 heteroaryl group (the heteroaryl group is unsubstituted or r substituents ^{R 21} (wherein ²¹ has the same meaning as ^{R 13,} r represents the same meaning as q. ). ), Hydroxyl group, nitro group, cyano group, formyl group, formamide group, amino group, C _1-6 alkylamino group, diC _1-6 alkylamino group, C _1-6 alkylcarbonylamino group, C _1-6 alkyl Sulfonamide group, carbamoyl group, C _1-6 alkylaminocarbonyl group, diC _1-6 alkylaminocarbonyl group, C _1-6 alkylcarbonyl group, C _1-6 alkoxycarbonyl group, sulfamoyl group, C _1-4 alkyl Substituted with a sulfonyl group, a carboxyl group, or a C _6-14 arylcarbonyl group. In the formula (c), formula (d), formula (p), formula (q), formula (v), formula (w), formula (ab), formula (ac) and formula (ad) Q in the formula means O (oxygen atom), S (sulfur atom), SO (sulfyl group) or SO ₂ (sulfonyl group). And R ⁹ and R ¹⁰ in formula (9) and formula (10) are combined together to form the following formula (11):

(R ¹² in the formula (11) which is a divalent group is a methyl group, and the substitution position of the formula (11) is located on the oxygen atom on the R ⁹ side and on the carbon atom on the R ¹⁰ side.) It is a bivalent group represented by these. ), Wherein the unsaturated compound represented by any one of the following formulas (19) and (20)

(The ring partial structures A, R ⁹ and R ¹⁰ in the formula (19) and the formula (20) are the same as described above.) Any one of [1] to [3] A method for producing the optically active epoxy compound according to 1.

[7]
The ring partial structure A in formula (9) or formula (10) is represented by formula (a), formula (b), formula (i), formula (k), formula (o), formula (p), formula (s ), Formula (v), formula (y), formula (ae), formula (ag) and formula (ah)

(Formula (a), Formula (b), Formula (i), Formula (k), Formula (o), Formula (p), Formula (s), Formula (v), Formula (y), Formula (ae ), Formula (ag) or formula (ah), formula (a), formula (b), formula (i), formula (k), formula (p), formula (v), formula (ae) and formula R ¹⁴ and R ^{15 in} (ag) are a hydrogen atom and a methyl group, and the formula (a), formula (b), formula (k), formula (o), formula (p), formula (s), formula (V), R ¹⁶ , R ¹⁷ and R ¹⁸ in formula (y) and formula (ae) are each independently a hydrogen atom, a halogen atom, or a C _1-6 alkyl group (the alkyl group is a halogen atom) , C _1-6 alkoxy group (the alkoxy group may be optionally substituted with a halogen atom), amino group, hydroxyl group, C _1-6 alkylaminocarbonyl group, di-C _1-6 alkylaminocarbonyl. Group, C _1-6 alkylcarbonyloxy group (the alkylcarbonyloxy group may be optionally substituted with a halogen atom), C _1-6 alkylcarbonyl group (the alkylcarbonyloxy group is a halogen atom) Optionally substituted with a C _1-6 alkylcarbonylamino group, a C _3-8 cycloalkylcarbonyl group, or a C _1-6 alkoxycarbonyl group. , Q is O (oxygen atom).) An unsaturated compound represented by any one of the following formulas (19) and (20) (formula (19)): And the ring partial structure A, R ⁹ and R ¹⁰ in the formula (20) are the same as defined above.) The optical activity according to any one of [1] to [3] Production of epoxy compounds Method.

[8]
The method for producing an optically active epoxy compound according to any one of [1] to [7], wherein the oxidizing agent is a hydrogen peroxide solution.

[9]
Formula (21a), Formula (21a ′), Formula (21b), Formula (21b ′), Formula (22), Formula (22 ′), Formula (23a), Formula (23a ′), Formula (23b), Formula (23b ′), formula (24) and formula (24 ′)

(Formula (21a), Formula (21a ′), Formula (21b), Formula (21b ′), Formula (22), Formula (22 ′), Formula (23a), Formula (23a ′), Formula (23b), R ¹ in formula (23b ′), formula (24), and formula (24 ′) represents partial structural formula (AA) and partial structural formula (AB).

(X in the partial structural formula (AA) and the partial structural formula (AB) is an oxygen atom or a sulfur atom, and Y in the partial structural formula (AA) and the partial structural formula (AB) is a single bond or a methylene group. (The methylene group is unsubstituted or substituted with a fluorine atom.), An ethylene group (the ethylene group is unsubstituted or substituted with a fluorine atom), -SO _2- , a carbonyl group, —CH (C _1-4 alkyl group) — (the alkyl group in —CH (C _1-4 alkyl group) — is unsubstituted or substituted with a halogen atom. Or the aryl group in —CH (C _6-14 aryl group) — (the —CH (C _6-14 aryl group) — is unsubstituted or substituted with a halogen atom. Z in the partial structural formula (AA) and the partial structural formula (AB) is C _3-12 alkyl group (said alkyl group is substituted or unsubstituted, or a halogen _{atom.), C 3-8} cycloalkyl _{group, C 6-22} aryl group (the aryl group is unsubstituted Substituted or halogen atom, C _1-4 alkyl group (the alkyl group is unsubstituted or substituted with a halogen atom or C _6-16 aryl group), C _6-16. An aryl group (the aryl group is unsubstituted or substituted with a halogen atom), or optionally substituted with a C _1-4 alkoxy group) or a C _2-9 heteroaryl group ( The heteroaryl group is unsubstituted or substituted with a halogen atom.), And R ² in the partial structural formula (AA) and the partial structural formula (AB) is a hydrogen atom, a halogen atom, C _1-4 alkyl Group (the alkyl group is substituted or unsubstituted, or a halogen atom.), Or C _1-4 alkoxy group, the partial structural formula (AA) and a partial structural formulas (AB) R ⁴ each independently represents a hydrogen atom, a halogen atom, a C _1-4 alkyl group (the alkyl group is unsubstituted or substituted with a halogen atom), a C _1-4 alkoxy group, a nitro group; Group or a cyano group).
Formula (21a), Formula (21a ′), Formula (21b), Formula (21b ′), Formula (22), Formula (22 ′), Formula (23a), Formula (23a ′), Formula (23b), Formula R ² in (23b ′), formula (24), and formula (24 ′) is a hydrogen atom, a halogen atom, or a C _1-4 alkyl group (the alkyl group is unsubstituted or substituted with a halogen atom) Or a C _1-4 alkoxy group,
Formula (21a), Formula (21a ′), Formula (21b), Formula (21b ′), Formula (22), Formula (22 ′), Formula (23a), Formula (23a ′), Formula (23b), Formula R ³ in (23b ′), formula (24) and formula (24 ′) is a C _6-18 aryl group or, when two R ³ together form a ring, C _3-5 A divalent group,
Formula (21a), Formula (21a ′), Formula (21b), Formula (21b ′), Formula (22), Formula (22 ′), Formula (23a), Formula (23a ′), Formula (23b), Formula (23b ') or ^{R 4} in the formula (24) and (24') are each independently a hydrogen atom, a halogen _{atom, C 1-4} alkyl group (said alkyl group is unsubstituted, or Substituted with a halogen atom), a C _1-4 alkoxy group, a nitro group or a cyano group,
Formula (21a), Formula (21a ′), Formula (21b), Formula (21b ′), Formula (22), Formula (22 ′), Formula (23a), Formula (23a ′), Formula (23b), Formula M in (23b ′), formula (24) and formula (24 ′) is TiJ ¹ J ² (in TiJ ¹ J ² , Ti is a titanium atom, and J ¹ and J ² are each independently , A hydroxyl group, a halogen atom, a C _1-4 alkoxy group, J ¹ and J ² together represent an oxygen atom, or J ¹ and J ² together form a ring Formula (25), which is an optically active titanium complex

(The partial structural formula OEOO in the formula (25) includes the following formula (26a), the following formula (26a ′), the following formula (26b), the following formula (26b ′), the following formula (27), and the following formula (27). Formula (27 ′), Formula (28a), Formula (28a ′), Formula (28b), Formula (28b ′), Formula (29), Formula (29 ′) and Formula (29 ′)

(Formula (26a), Formula (26a ′), Formula (26b), Formula (26b ′), Formula (27), Formula (27 ′), Formula (28a), Formula (28a ′), Formula (28b), R ¹ , R ² , R ^3, and R ⁴ in formula (28b ′), formula (29), and formula (29 ′) are the same as described above. At this time, two partial structural formulas in formula (25) are used. O-EO is the same as each other). The case where the titanium binuclear complex represented by this is formed is shown. ). An optically active titanium complex represented by any one of

[10]
R ¹ is partial structural formula (AA) (X in partial structural formula (AA) is an oxygen atom, Y in partial structural formula (AA) is a methylene group (the methylene group is unsubstituted) Or Z in the partial structural formula (AA) is a C _6-22 aryl group (the aryl group is unsubstituted or a halogen atom, C _{1 -4} alkyl group (the alkyl group is unsubstituted or substituted with a halogen atom or a C _6-16 aryl group), a C _6-16 aryl group (the aryl group is unsubstituted Or optionally substituted with a C _1-4 alkoxy group) or a C _2-9 heteroaryl group (wherein the heteroaryl group is unsubstituted) Or substituted with a halogen atom. , ^{R 2} in the partial structural formula (AA) is a hydrogen atom, or a methoxy group, ^{R 4} in the partial structural formula (AA) is a hydrogen atom, or a methoxy group.), ^{R 2} is , A hydrogen atom, R ³ is a tetramethylene group which is a divalent group, and R ⁴ is a hydrogen atom [9], the formula (21a), the formula (21a ′) and the formula (21b ), An optically active titanium complex represented by any one of formula (21b ′), formula (22) and formula (22 ′).

[11]
R ¹ is a partial structural formula (AB) (X in the partial structural formula (AB) is an oxygen atom, Y in the partial structural formula (AB) is a methylene group (the methylene group is unsubstituted) Or Z in the partial structural formula (AB) is a C _6-22 aryl group (the aryl group is unsubstituted or a halogen atom, C _{1 -4} alkyl group (the alkyl group is unsubstituted or substituted with a halogen atom or a C _6-16 aryl group), a C _6-16 aryl group (the aryl group is unsubstituted Or optionally substituted with a C _1-4 alkoxy group) or a C _2-9 heteroaryl group (wherein the heteroaryl group is unsubstituted) Or substituted with a halogen atom. And R ² in the partial structural formula (AB) is a hydrogen atom, R ⁴ in the partial structural formula (AB) is a hydrogen atom), R ² is a hydrogen atom, and R ³ Is a tetramethylene group that is a divalent group, and R ⁴ is a hydrogen atom. The formula (23a), formula (23a ′), formula (23b), formula (23b ′), An optically active titanium complex represented by any one of formula (24) and formula (24 ′).

[12]
Formula (1a), Formula (1a ′), Formula (1b), Formula (1b ′), Formula (2), Formula (2 ′), Formula (3a), Formula (3a ′), Formula (3b), Formula (3b ′), formula (4) and formula (4 ′)

(Formula (1a), Formula (1a ′), Formula (1b), Formula (1b ′), Formula (2), Formula (2 ′), Formula (3a), Formula (3a ′), Formula (3b), R ¹ in formula (3b ′), formula (4), and formula (4 ′) represents partial structural formula (AA) and partial structural formula (AB).

(X in the partial structural formula (AA) and the partial structural formula (AB) is an oxygen atom or a sulfur atom, and Y in the partial structural formula (AA) and the partial structural formula (AB) is a single bond or a methylene group. (The methylene group is unsubstituted or substituted with a fluorine atom.), An ethylene group (the ethylene group is unsubstituted or substituted with a fluorine atom), -SO _2- , a carbonyl group, —CH (C _1-4 alkyl group) — (the alkyl group in —CH (C _1-4 alkyl group) — is unsubstituted or substituted with a halogen atom. Or the aryl group in —CH (C _6-14 aryl group) — (the —CH (C _6-14 aryl group) — is unsubstituted or substituted with a halogen atom. Z in the partial structural formula (AA) and the partial structural formula (AB) is C _3-12 alkyl group (said alkyl group is substituted or unsubstituted, or a halogen _{atom.), C 3-8} cycloalkyl _{group, C 6-22} aryl group (the aryl group is unsubstituted Substituted or halogen atom, C _1-4 alkyl group (the alkyl group is unsubstituted or substituted with a halogen atom or C _6-16 aryl group), C _6-16. An aryl group (the aryl group is unsubstituted or substituted with a halogen atom), or optionally substituted with a C _1-4 alkoxy group) or a C _2-9 heteroaryl group ( The heteroaryl group is unsubstituted or substituted with a halogen atom.), And R ² in the partial structural formula (AA) and the partial structural formula (AB) is a hydrogen atom, a halogen atom, C _1-4 alkyl Group (the alkyl group is substituted or unsubstituted, or a halogen atom.), Or C _1-4 alkoxy group, the partial structural formula (AA) and a partial structural formulas (AB) R ⁴ each independently represents a hydrogen atom, a halogen atom, a C _1-4 alkyl group (the alkyl group is unsubstituted or substituted with a halogen atom), a C _1-4 alkoxy group, a nitro group; Group or a cyano group).
Formula (1a), Formula (1a ′), Formula (1b), Formula (1b ′), Formula (2), Formula (2 ′), Formula (3a), Formula (3a ′), Formula (3b), Formula (3b ') ^{R 2} of formula (4) and formula (4') in a hydrogen atom, a halogen _{atom, C 1-4} alkyl group (said alkyl group is unsubstituted or substituted with a halogen atom Or a C _1-4 alkoxy group,
Formula (1a), Formula (1a ′), Formula (1b), Formula (1b ′), Formula (2), Formula (2 ′), Formula (3a), Formula (3a ′), Formula (3b), Formula R ³ in (3b ′), formula (4), and formula (4 ′) is a C _6-18 aryl group or, when two R ³ together form a ring, C _3-5 Valent group,
Formula (1a), Formula (1a ′), Formula (1b), Formula (1b ′), Formula (2), Formula (2 ′), Formula (3a), Formula (3a ′), Formula (3b), Formula (3b ') or ^{R 4} of the formula (4) and formula (4') during each independently represent a hydrogen atom, a halogen _{atom, C 1-4} alkyl group (said alkyl group is unsubstituted, Or a C _1-4 alkoxy group, a nitro group, or a cyano group. An optically active ligand represented by any one of

[13]
R ¹ is partial structural formula (AA) (X in partial structural formula (AA) is an oxygen atom, Y in partial structural formula (AA) is a methylene group (the methylene group is unsubstituted) Or Z in the partial structural formula (AA) is a C _6-22 aryl group (the aryl group is unsubstituted or a halogen atom, C _{1 -4} alkyl group (the alkyl group is unsubstituted or substituted with a halogen atom or a C _6-16 aryl group), a C _6-16 aryl group (the aryl group is unsubstituted Or optionally substituted with a C _1-4 alkoxy group) or a C _2-9 heteroaryl group (wherein the heteroaryl group is unsubstituted) Or substituted with a halogen atom. , ^{R 2} in the partial structural formula (AA) is a hydrogen atom, or a methoxy group, ^{R 4} in the partial structural formula (AA) is a hydrogen atom, or a methoxy group.), ^{R 2} is , R ³ is a tetramethylene group which is a divalent group, and R ⁴ is a hydrogen atom [12], the formula (1a), the formula (1a ′) and the formula (1b ), An optically active ligand represented by any one of formula (1b ′), formula (2) and formula (2 ′).

[14]
R ¹ is a partial structural formula (AB) (X in the partial structural formula (AB) is an oxygen atom, Y in the partial structural formula (AB) is a methylene group (the methylene group is unsubstituted) Or Z in the partial structural formula (AB) is a C _6-22 aryl group (the aryl group is unsubstituted or a halogen atom, C _{1 -4} alkyl group (the alkyl group is unsubstituted or substituted with a halogen atom or a C _6-16 aryl group), a C _6-16 aryl group (the aryl group is unsubstituted Or optionally substituted with a C _1-4 alkoxy group) or a C _2-9 heteroaryl group (wherein the heteroaryl group is unsubstituted) Or substituted with a halogen atom. And R ² in the partial structural formula (AB) is a hydrogen atom, R ⁴ in the partial structural formula (AB) is a hydrogen atom), R ² is a hydrogen atom, and R ³ Is a tetramethylene group that is a divalent group, and R ⁴ is a hydrogen atom. The formula (3a), formula (3a ′), formula (3b), formula (3b ′), An optically active ligand represented by any one of formula (4) and formula (4 ′).

[15]
Formula (1a), Formula (1a ′), Formula (1b), Formula (1b ′), Formula (2), Formula (2 ′), Formula (3a), Formula (3a ′), Formula (3b), Formula (3b ′), formula (4) and formula (4 ′)

(Formula (1a), Formula (1a ′), Formula (1b), Formula (1b ′), Formula (2), Formula (2 ′), Formula (3a), Formula (3a ′), Formula (3b), R ¹ in formula (3b ′), formula (4), and formula (4 ′) represents partial structural formula (AA) and partial structural formula (AB).

(X in the partial structural formula (AA) and the partial structural formula (AB) is an oxygen atom or a sulfur atom, and Y in the partial structural formula (AA) and the partial structural formula (AB) is a single bond or a methylene group. (The methylene group is unsubstituted or substituted with a fluorine atom.), An ethylene group (the ethylene group is unsubstituted or substituted with a fluorine atom), -SO _2- , a carbonyl group, —CH (C _1-4 alkyl group) — (the alkyl group in —CH (C _1-4 alkyl group) — is unsubstituted or substituted with a halogen atom. Or the aryl group in —CH (C _6-14 aryl group) — (the —CH (C _6-14 aryl group) — is unsubstituted or substituted with a halogen atom. Z in the partial structural formula (AA) and the partial structural formula (AB) is C _3-12 alkyl group (said alkyl group is substituted or unsubstituted, or a halogen _{atom.), C 3-8} cycloalkyl _{group, C 6-22} aryl group (the aryl group is unsubstituted Substituted or halogen atom, C _1-4 alkyl group (the alkyl group is unsubstituted or substituted with a halogen atom or C _6-16 aryl group), C _6-16. An aryl group (the aryl group is unsubstituted or substituted with a halogen atom), or optionally substituted with a C _1-4 alkoxy group) or a C _2-9 heteroaryl group ( The heteroaryl group is unsubstituted or substituted with a halogen atom.), And R ² in the partial structural formula (AA) and the partial structural formula (AB) is a hydrogen atom, a halogen atom, C _1-4 alkyl Group (the alkyl group is substituted or unsubstituted, or a halogen atom.), Or C _1-4 alkoxy group, the partial structural formula (AA) and a partial structural formulas (AB) R ⁴ each independently represents a hydrogen atom, a halogen atom, a C _1-4 alkyl group (the alkyl group is unsubstituted or substituted with a halogen atom), a C _1-4 alkoxy group, a nitro group; Group or a cyano group).
Formula (1a), Formula (1a ′), Formula (1b), Formula (1b ′), Formula (2), Formula (2 ′), Formula (3a), Formula (3a ′), Formula (3b), Formula (3b ') ^{R 2} of formula (4) and formula (4') in a hydrogen atom, a halogen _{atom, C 1-4} alkyl group (said alkyl group is unsubstituted or substituted with a halogen atom Or a C _1-4 alkoxy group,
Formula (1a), Formula (1a ′), Formula (1b), Formula (1b ′), Formula (2), Formula (2 ′), Formula (3a), Formula (3a ′), Formula (3b), Formula R ³ in (3b ′), formula (4), and formula (4 ′) is a C _6-18 aryl group or, when two R ³ together form a ring, C _3-5 Valent group,
Formula (1a), Formula (1a ′), Formula (1b), Formula (1b ′), Formula (2), Formula (2 ′), Formula (3a), Formula (3a ′), Formula (3b), Formula (3b ') or ^{R 4} of the formula (4) and formula (4') during each independently represent a hydrogen atom, a halogen _{atom, C 1-4} alkyl group (said alkyl group is unsubstituted, Or a C _1-4 alkoxy group, a nitro group, or a cyano group. The optically active titanium complex obtained by reacting the optically active ligand represented by any of the above and a titanium compound (the optically active titanium complex is an optically active titanium salen complex, an optically active titanium salalene complex, or an optically active titanium salen). Is used as a catalyst, and the following formula (30)

(R ²² and R ^{23 in} formula (30) are different substituents, and each independently represents a C _6-12 aryl group (the aryl group is unsubstituted or a halogen atom, C _{1- 4} alkyl group, C _1-4 alkoxy group, C _2-5 alkylcarbonyloxy group, C _2-5 alkoxycarbonyl group, nitro group, or cyano group.), C _6-12 arylmethyl group ( The arylmethyl group is unsubstituted or a halogen atom, a C _1-4 alkyl group, a C _1-4 alkoxy group, a C _2-5 alkylcarbonyloxy group, a C _2-5 alkoxycarbonyl group, a nitro group, Or substituted with a cyano group), 2-pyridyl, 3-pyridyl, 4-pyridyl, or C _1-6 alkyl group (the alkyl group is unsubstituted or Are is substituted by a halogen atom, a nitro group, a hydroxyl group, or a cyano group.). ^{However, R 22} is _{C 6-12} aryl groups, _C in the ortho position of the _{C 6-12} aryl group _{1- 4} alkyl group, or _{C 1-4} when an alkoxy group is ^substituted, _{C 2-4} ^{R 23} may form a ring together with the _{C 1-4} alkyl group, or the _{C 1-4} alkoxy group The sulfide compound represented by formula (31) is asymmetrically oxidized with an oxidizing agent:

(R ²² and R ²³ in the formula (31) are the same as described above, and the absolute configuration of the sulfur atom indicated by * means (R) or (S).) Compound production method.

[16]
Formula (1a), Formula (1a ′), Formula (1b), Formula (1b ′), Formula (2), Formula (2 ′), Formula (3a), Formula (3a ′), Formula (3b), Formula (3b ′), Formula (4) and Formula (4 ′) (Formula (1a), Formula (1a ′), Formula (1b), Formula (1b ′), Formula (2), Formula (2 ′), Formula (3a), formula (3a '), formula (3b), wherein ^{(3b'), R 1,} R 2, R 3 and ^{R 4} in the formula (4) and formula (4 ') includes a [15] The optically active titanium complex obtained by reacting the optically active ligand represented by any of the above and a titanium compound (the optically active titanium complex is an optically active titanium salen complex, an optically active titanium salalene complex, or An optically active titanium-saran complex) as a catalyst.

(R ²² and R ²³ in the formula (32) are the same as those in [15].) One optical isomer of the racemic or sulfoxide compound having a low optical purity represented by the formula is selectively oxidized with an oxidizing agent. By doing the following formula (33)

(R ²² and R ²³ in the formula (33) are the same as those in [15].)

(R ²² and R ²³ in the formula (31) are the same. And [15]) The process for producing an optically active sulfoxide compound, characterized by obtaining an optically active sulfoxide compound represented by the.

[17]
R ¹ is partial structural formula (AA) (X in partial structural formula (AA) is an oxygen atom, Y in partial structural formula (AA) is a methylene group (the methylene group is unsubstituted) Or Z in the partial structural formula (AA) is a C _6-22 aryl group (the aryl group is unsubstituted or a halogen atom, C _{1 -4} alkyl group (the alkyl group is unsubstituted or substituted with a halogen atom or a C _6-16 aryl group), a C _6-16 aryl group (the aryl group is unsubstituted Or optionally substituted with a C _1-4 alkoxy group) or a C _2-9 heteroaryl group (wherein the heteroaryl group is unsubstituted) Or substituted with a halogen atom. , ^{R 2} in the partial structural formula (AA) is a hydrogen atom, or a methoxy group, ^{R 4} in the partial structural formula (AA) is a hydrogen atom, or a methoxy group.), ^{R 2} is , R ³ is a tetramethylene group which is a divalent group, and R ⁴ is a hydrogen atom [15], the formula (1a), the formula (1a ′) and the formula (1b ), An optically active titanium complex obtained by reacting an optically active ligand represented by any one of formula (1b ′), formula (2) and formula (2 ′) with a titanium compound (optically active titanium salen complex, The method for producing an optically active sulfoxide compound according to [15] or [16], wherein an optically active titanium salalene complex or an optically active titanium salane complex) is used as a catalyst.

[18]
R ¹ is a partial structural formula (AB) (X in the partial structural formula (AB) is an oxygen atom, Y in the partial structural formula (AB) is a methylene group (the methylene group is unsubstituted) Or Z in the partial structural formula (AB) is a C _6-22 aryl group (the aryl group is unsubstituted or a halogen atom, C _{1 -4} alkyl group (the alkyl group is unsubstituted or substituted with a halogen atom or a C _6-16 aryl group), a C _6-16 aryl group (the aryl group is unsubstituted Or optionally substituted with a C _1-4 alkoxy group) or a C _2-9 heteroaryl group (wherein the heteroaryl group is unsubstituted) Or substituted with a halogen atom. And R ² in the partial structural formula (AB) is a hydrogen atom, R ⁴ in the partial structural formula (AB) is a hydrogen atom), R ² is a hydrogen atom, and R ³ Is a tetramethylene group that is a divalent group, and R ⁴ is a hydrogen atom. The formula (3a), formula (3a ′), formula (3b), formula (3b ′), An optically active titanium complex (an optically active titanium salen complex, an optically active titanium salalene complex, or an optically active titanium) obtained by reacting an optically active ligand represented by any one of formula (4) and formula (4 ′) with a titanium compound The method for producing an optically active sulfoxide compound according to [15] or [16], wherein a (saran complex) is used as a catalyst.

[19]
The method for producing an optically active sulfoxide compound according to any one of [15] to [18], wherein the oxidizing agent is a hydrogen peroxide solution or a urea-hydrogen peroxide adduct.

  According to the present invention, an unsaturated compound having a prochiral carbon-carbon double bond in the molecule is epoxidized with high enantioselectivity, and an optically active epoxy compound is economical in higher quality and higher yield than conventional techniques. Can be manufactured. Furthermore, the optically active epoxy compound obtained by the production method of the present invention is useful as an optically active pharmaceutical intermediate of a compound effective for the treatment of hypertension, asthma and the like. ADVANTAGE OF THE INVENTION According to this invention, the optically active sulfoxide compound useful as a synthetic intermediate or raw material of physiologically active substances, such as a pharmaceutical, can be economically manufactured with high quality and a high yield. Furthermore, according to the present invention, the amount of the catalyst used can be reduced, and an industrially useful solvent such as toluene can be used as the solvent.

  As used herein, “n” is normal, “i” is iso, “s” is secondary, “t” is tertiary, “c” is cyclo, “o” is ortho, “m” Means meta, “p” means para, and “TMEDA” means N, N, N ′, N′-tetramethylethylenediamine. R and S described in the chemical structural formulas indicate absolute configurations.

  The present invention is described in detail below. The production method of the optically active epoxy compound of the present invention includes formula (1a), formula (1a ′), formula (1b), formula (1b ′), formula (2), formula (2 ′), formula (3a), Formula (3a ′), Formula (3b), Formula (3b ′), Formula (4), and Formula (4 ′)

(Formula (1a), Formula (1a ′), Formula (1b), Formula (1b ′), Formula (2), Formula (2 ′), Formula (3a), Formula (3a ′), Formula (3b), R ¹ in formula (3b ′), formula (4), and formula (4 ′) represents partial structural formula (AA) and partial structural formula (AB).

(X in the partial structural formula (AA) and the partial structural formula (AB) is an oxygen atom or a sulfur atom, and Y in the partial structural formula (AA) and the partial structural formula (AB) is a single bond or a methylene group. (The methylene group is unsubstituted or substituted with a fluorine atom.), An ethylene group (the ethylene group is unsubstituted or substituted with a fluorine atom), -SO _2- , a carbonyl group, —CH (C _1-4 alkyl group) — (the alkyl group in —CH (C _1-4 alkyl group) — is unsubstituted or substituted with a halogen atom. Or the aryl group in —CH (C _6-14 aryl group) — (the —CH (C _6-14 aryl group) — is unsubstituted or substituted with a halogen atom. Z in the partial structural formula (AA) and the partial structural formula (AB) is C _3-12 alkyl group (said alkyl group is substituted or unsubstituted, or a halogen _{atom.), C 3-8} cycloalkyl _{group, C 6-22} aryl group (the aryl group is unsubstituted Substituted or halogen atom, C _1-4 alkyl group (the alkyl group is unsubstituted or substituted with a halogen atom or C _6-16 aryl group), C _6-16. An aryl group (the aryl group is unsubstituted or substituted with a halogen atom), or optionally substituted with a C _1-4 alkoxy group) or a C _2-9 heteroaryl group ( The heteroaryl group is unsubstituted or substituted with a halogen atom.), And R ² in the partial structural formula (AA) and the partial structural formula (AB) is a hydrogen atom, a halogen atom, C _1-4 alkyl Group (the alkyl group is substituted or unsubstituted, or a halogen atom.), Or C _1-4 alkoxy group, the partial structural formula (AA) and a partial structural formulas (AB) R ⁴ each independently represents a hydrogen atom, a halogen atom, a C _1-4 alkyl group (the alkyl group is unsubstituted or substituted with a halogen atom), a C _1-4 alkoxy group, a nitro group; Group or a cyano group).
Formula (1a), Formula (1a ′), Formula (1b), Formula (1b ′), Formula (2), Formula (2 ′), Formula (3a), Formula (3a ′), Formula (3b), Formula (3b ') ^{R 2} of formula (4) and formula (4') in a hydrogen atom, a halogen _{atom, C 1-4} alkyl group (said alkyl group is unsubstituted or substituted with a halogen atom Or a C _1-4 alkoxy group,
Formula (1a), Formula (1a ′), Formula (1b), Formula (1b ′), Formula (2), Formula (2 ′), Formula (3a), Formula (3a ′), Formula (3b), Formula R ³ in (3b ′), formula (4), and formula (4 ′) is a C _6-18 aryl group or, when two R ³ together form a ring, C _3-5 Valent group,
Formula (1a), Formula (1a ′), Formula (1b), Formula (1b ′), Formula (2), Formula (2 ′), Formula (3a), Formula (3a ′), Formula (3b), Formula (3b ') or ^{R 4} of the formula (4) and formula (4') during each independently represent a hydrogen atom, a halogen _{atom, C 1-4} alkyl group (said alkyl group is unsubstituted, Or a C _1-4 alkoxy group, a nitro group, or a cyano group. The optically active titanium complex obtained by reacting the optically active ligand represented by any of the above and a titanium compound (the optically active titanium complex is an optically active titanium salen complex, an optically active titanium salalene complex, or an optically active titanium salen). Is used as a catalyst, and the following formula (5), formula (6), formula (7), formula (8), formula (9) and formula (10) are used.

(In formula (5) and formula (6), R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, cyano group, nitro group, amino group (the amino group is a protecting group) Unprotected or protected.), C _1-4 alkylamino group (the alkylamino group is unprotected or protected by a protecting group), halogen atom, C _{1 -4} alkyl group (the alkyl group is unsubstituted or substituted with a halogen atom), C _1-4 alkoxy group, carboxyl group, formyl group, C _1-4 alkylcarbonyl group (the alkyl The carbonyl group is unsubstituted or substituted with a halogen atom.), A C _6-12 arylcarbonyl group (the arylcarbonyl group is unsubstituted or substituted with a halogen atom). ), Cal Moil _{group, C 1-4} alkylsulfinyl _{group, C 6-7} arylsulfinyl _{group, C 1-4} alkylsulfonyl _{group, C 6-12} arylsulfonyl group, a sulfamoyl group, a mono _{C 1-3} alkylaminosulfonyl group, or a di A C _1-3 alkylaminosulfonyl group,
R ⁹ in formula (5), formula (6), formula (9) and formula (10) is a hydrogen atom, a C _1-4 alkyl group (the alkyl group is unsubstituted or a halogen atom) Or a C _1-4 alkoxy group, and R ¹⁰ in formula (5), formula (6), formula (9) and formula (10) is a hydrogen atom, C _1-22 alkyl. Group, C _1-4 alkoxy group, C _6-10 aryl group (the aryl group is unsubstituted or substituted by a halogen atom, a C _1-4 alkyl group, or a C _1-4 alkoxy group) .) However, R ⁹ and R ¹⁰ in Formula (5), Formula (6), Formula (9), and Formula (10) are combined with each other, and the following Formula (11), Formula (12), and Formula (13) And formula (14)

(R ¹² in formula (11), formula (12), formula (13) and formula (14) is each independently a hydrogen atom or a C _1-4 alkyl group). Divalent groups may be formed. R ¹¹ in Formula (6) is a C _1-4 alkyl group (the alkyl group is unsubstituted or substituted with a halogen atom).
R ^a and R ^{b in} formula (7) and formula (8) are each independently a hydrogen atom, a C _1-22 alkyl group (the alkyl group is unsubstituted or a halogen atom, C _{1 -4} alkyl group, C _6-10 aryl group (the aryl group is unsubstituted or substituted with a halogen atom, a C _1-4 alkyl group, or a C _1-4 alkoxy group), benzoyl. An oxy group, a benzyloxy group, or a pivaloyloxy group), a C _3-8 cycloalkyl group (the cycloalkyl group is unsubstituted or a halogen atom, a C _1-4 alkyl group, benzoyloxy group, benzyloxy group, or is substituted with pivaloyloxy group.), C _1-4 alkoxy groups, C _6-22 aryl group (the aryl group is unsubstituted, and Halogen _{atom, C 1-4} alkyl group (said alkyl group is substituted by unsubstituted or substituted with halogen atom, or a _{C 6-16} aryl _{group.), C 6-16} aryl group (the aryl group Is unsubstituted or substituted with a halogen atom), or optionally substituted with a C _1-4 alkoxy group.
The ring partial structure A in the formula (9) and the formula (10) is a 5-membered ring, 6-membered ring or 7-membered ring condensed with a benzene ring. Or h substituents R ¹³ (wherein R ¹³ is a halogen atom, a hydroxyl group, a C _1-6 alkyl group (the alkyl group is unsubstituted or a halogen atom, a hydroxyl group, A cyano group, an amino group, a nitro group, a C _1-4 alkoxy group (the alkoxy group is unsubstituted or substituted with a halogen atom), a C _1-4 alkylcarbonyloxy group (the alkylcarbonyl The oxy group is unsubstituted or substituted with a halogen atom.), A C _1-4 alkylcarbonylamino group (the alkylcarbonylamino group is unsubstituted or substituted with a halogen atom) there.), or _{C 1-} Alkoxycarbonyl group (the alkoxy group is unsubstituted or substituted by substituted by halogen atom.) Are replaced by.), C _1-6 alkoxy group (said alkoxy group is unsubstituted Or a halogen atom, a hydroxyl group, a cyano group, an amino group, a nitro group, a C _1-4 alkoxy group (the alkoxy group is unsubstituted or substituted with a halogen atom), C _1-4. An alkylcarbonyloxy group (the alkylcarbonyloxy group is unsubstituted or substituted with a halogen atom), a C _1-4 alkylcarbonylamino group (whether the alkylcarbonylamino group is unsubstituted) or substituted with a halogen atom.), or C _1-4 alkoxycarbonyl group (the alkoxy group is unsubstituted, or Substituted with a halogen atom))), nitro group, cyano group, formyl group, formamide group, carbamoyl group, sulfo group, sulfoamino group, sulfamoyl group, sulfonyl group, amino group, carboxyl group, C _1-6 alkylamino group (the alkylamino group is unsubstituted or substituted with a halogen atom), diC _1-6 alkylamino group (the dialkylamino group is unsubstituted) Or a C _1-6 alkylcarbonylamino group (the alkylcarbonylamino group is unsubstituted or substituted with a halogen atom), C _1-6. An alkylsulfonamido group (the alkylsulfonamido group is unsubstituted or substituted with a halogen atom). ), A C _6-14 arylsulfonamido group (the arylsulfonamido group is unsubstituted or substituted with a halogen atom), a C _1-6 alkylaminocarbonyl group (the alkylaminocarbonyl group is , Unsubstituted or substituted with a halogen atom), a di-C _1-6 alkylaminocarbonyl group (the dialkylaminocarbonyl group is unsubstituted or substituted with a halogen atom). ), C _1-6 alkylcarbonyl group (the alkylcarbonyl group is unsubstituted or substituted with a halogen atom), C _1-6 alkoxycarbonyl group (the alkoxycarbonyl group is unsubstituted) substituted with some or halogen atom.), C _1-4 alkylsulfonyl group (the alkylsulfonyl group is unsubstituted der Or substituted with halogen atoms.), C _6-14 arylsulfonyl group (the aryl sulfonyl group is substituted or unsubstituted, or a halogen atom.), Or C _6-14 aryl A carbonyl group (the arylcarbonyl group is unsubstituted or substituted with a halogen atom), h is an integer of 1 to 6, and when h is 2 to 6, R ¹³ is It can be the same or different. ) And can contain 1 to 3 oxygen atoms, nitrogen atoms or sulfur atoms as ring constituents, alone or in combination, and the number of unsaturated bonds in the ring is One, two or three carbon atoms including a ring unsaturated bond may be carbonyl or thiocarbonyl. ). The following formula (15), formula (16), formula (17), formula (18), formula (19), wherein the unsaturated compound represented by any one of And equation (20)

(In formula (15), formula (16), formula (17), formula (18), formula (19) and formula (20), R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ^a , R ^b and the ring partial structure A are the same as described above, except for the case where R ¹⁰ is a hydrogen atom, the absolute configuration of the carbon atom indicated by * is (R) or (S The optically active epoxy compound represented by any one of the above) can be produced.

  Formula (1a), Formula (1a ′), Formula (1b), Formula (1b ′), Formula (2), Formula (2 ′), Formula (3a), Formula (3a ′), Formula (3b), Each substituent in Formula (3b ′), Formula (4), and Formula (4 ′) will be described.

Formula (1a), Formula (1a ′), Formula (1b), Formula (1b ′), Formula (2), Formula (2 ′), Formula (3a), Formula (3a ′), Formula (3b), R ¹ in Formula (3b ′), Formula (4), and Formula (4 ′) is Partial Structural Formula (AA) and Partial Structural Formula (AB).

  X in the partial structural formula (AA) and the partial structural formula (AB) is an oxygen atom or a sulfur atom. X in the partial structural formula (AA) and the partial structural formula (AB) is preferably an oxygen atom.

Y in the partial structural formula (AA) and the partial structural formula (AB) is a single bond, a methylene group (the methylene group is unsubstituted or substituted with a fluorine atom), an ethylene group (the The ethylene group is unsubstituted or substituted with a fluorine atom.), —SO ₂ —, a carbonyl group, —CH (C _1-4 alkyl group) — (the —CH (C _1-4 alkyl) The alkyl group in the group)-is unsubstituted or substituted with a halogen atom.), Or -CH (C _6-14 aryl group)-(the -CH (C _6-14 aryl group) The aryl group in-) is unsubstituted or substituted with a halogen atom.

Y in the partial structural formula (AA) and the partial structural formula (AB) will be specifically described. Examples of the methylene group include a methylene group and a difluoromethylene group. Examples of the ethylene group include an ethylene group and a tetrafluoroethylene group. The —CH (C _1-4 alkyl group) — represents —CH (methyl group) —, —CH (ethyl group) —, —CH (n-propyl group) —, —CH (i-propyl group) —, -CH (n-butyl group)-, -CH (i-butyl group)-, -CH (s-butyl group)-, -CH (t-butyl group)-, -CH (trifluoromethyl group)-, And divalent substituents such as —CH (pentafluoroethyl group) —. The —CH (C _6-14 aryl group) — represents —CH (phenyl group) —, —CH (o-biphenylyl group) —, —CH (m-biphenylyl group) —, —CH (p-biphenylyl group). -, -CH (1-naphthyl group)-, -CH (2-naphthyl group)-, -CH (1-anthryl group)-, -CH (2-anthryl group)-, -CH (9-anthryl group) -, -CH (1-phenanthryl group)-, -CH (2-phenanthryl group)-, -CH (3-phenanthryl group)-, -CH (4-phenanthryl group)-, -CH (9-phenanthryl group) And divalent substituents such as-.

  Y in the partial structural formula (AA) and the partial structural formula (AB) is preferably a methylene group, a difluoromethylene group, —CH (methyl group) —, —CH (trifluoromethyl group) —, and a methylene group, difluoromethylene. The group is particularly preferred.

Z in the partial structural formula (AA) and the partial structural formula (AB) is a C _3-12 alkyl group (the alkyl group is unsubstituted or substituted with a halogen atom), C _{3- 8} cycloalkyl group, C _6-22 aryl group (the aryl group is unsubstituted or halogen atom, C _1-4 alkyl group (the alkyl group is unsubstituted, halogen atom, or is substituted with C _6-16 aryl _{group.), C 6-16} aryl group (the aryl group is substituted or unsubstituted, or a halogen atom.), or _{C 1-4} alkoxy group Or a C _2-9 heteroaryl group (the heteroaryl group is unsubstituted or substituted with a halogen atom).

Z in the partial structural formula (AA) and the partial structural formula (AB) will be specifically described. The C _3-12 alkyl group includes an n-propyl group, an i-propyl group, an n-butyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-perfluoropropyl group, i-perfluoropropyl group, n-perfluorobutyl group, t-perfluorobutyl group, n- Perfluoropentyl group, n-perfluorohexyl group, n-perfluoroheptyl group, n-perfluorooctyl group, n-perfluorononyl group, n-perfluorodecyl group, n-perfluoroundecyl group, and Examples include an n-perfluorododecyl group. The C _3-8 cycloalkyl group includes a c-propyl group, a c-butyl group, a 1-methyl-c-propyl group, a 2-methyl-c-propyl group, a c-pentyl group, and a 1-methyl-c-butyl group. Group, 2-methyl-c-butyl group, 3-methyl-c-butyl group, 1,2-dimethyl-c-propyl group, 2,3-dimethyl-c-propyl group, 1-ethyl-c-propyl group 2-ethyl-c-propyl group, c-hexyl group, c-heptyl group, c-octyl group, 1-methyl-c-hexyl group, 2-methyl-c-hexyl group, 3-methyl-c-hexyl Group, 1,2-dimethyl-c-hexyl group, 2,3-dimethyl-c-propyl group, 1-ethyl-c-propyl group, 1-methyl-c-pentyl group, 2-methyl-c-pentyl group 3-methyl-c-pentyl group, 1-ethyl-c-butyl Group, 2-ethyl-c-butyl group, 3-ethyl-c-butyl group, 1,2-dimethyl-c-butyl group, 1,3-dimethyl-c-butyl group, 2,2-dimethyl-c -Butyl group, 2,3-dimethyl-c-butyl group, 2,4-dimethyl-c-butyl group, 3,3-dimethyl-c-butyl group, 1-n-propyl-c-propyl group, 2- n-propyl-c-propyl group, 1-i-propyl-c-propyl group, 2-i-propyl-c-propyl group, 1,2,2-trimethyl-c-propyl group, 1,2,3- Trimethyl-c-propyl group, 2,2,3-trimethyl-c-propyl group, 1-ethyl-2-methyl-c-propyl group, 2-ethyl-1-methyl-c-propyl group, 2-ethyl- 2-methyl-c-propyl group and 2-ethyl-3-methyl-c-propyl Etc. The.

The C _6-22 aryl group includes 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2,6-difluorophenyl group, 3,5-difluorophenyl group, 3,4,5-tri Fluorophenyl group, 2,3,4,5,6-pentafluorophenyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2,6-dichlorophenyl group, 3,5-dichlorophenyl group, 2- Bromophenyl group, 3-bromophenyl group, 4-bromophenyl group, 2,6-dibromophenyl group, 3,5-dibromophenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2,6-dimethylphenyl group, 2,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,4,6-trimethylphenyl group 2-trifluoromethylphenyl group, 3-trifluoromethylphenyl group, 4-trifluoromethylphenyl group, 2,6-bis (trifluoromethyl) phenyl group, 2,4-bis (trifluoromethyl) phenyl group 3,5-bis (trifluoromethyl) phenyl group, 2,4,6-tris (trifluoromethyl) phenyl group, 2-ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group, 2,6 -Diethylphenyl group, 3,5-diethylphenyl group, 2,4,6-triethylphenyl group, 2-pentafluoroethylphenyl group, 3-pentafluoroethylphenyl group, 4-pentafluoroethylphenyl group, 2,6 -Di (pentafluoroethyl) phenyl group, 3,5-di (pentafluoroethyl) phenyl group, 2,4,6-tri Pentafluoroethyl) phenyl group, 2-n-propylphenyl group, 3-n-propylphenyl group, 4-n-propylphenyl group, 2,6-di-n-propylphenyl group, 3,5-di-n -Propylphenyl group, 2,4,6-tri-n-propylphenyl group, 2-i-propylphenyl group, 3-i-propylphenyl group, 4-i-propylphenyl group, 2,6-di-i -Propylphenyl group, 3,5-di-i-propylphenyl group, 2,4,6-tri-i-propylphenyl group, 2-n-butylphenyl group, 3-n-butylphenyl group, 4-n -Butylphenyl group, 2,6-di-n-butylphenyl group, 3,5-di-n-butylphenyl group, 2,4,6-tri-n-butylphenyl group, 2-t-butylphenyl group 3-t-butylphenyl 4-t-butylphenyl group, 2,6-di-t-butylphenyl group, 3,5-di-t-butylphenyl group, 2,4,6-tri-t-butylphenyl group, 2-methoxy Phenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2,6-dimethoxyphenyl group, 3,5-dimethoxyphenyl group, 2,4,6-trimethoxyphenyl group, 2-ethoxyphenyl group, 3- Ethoxyphenyl group, 4-ethoxyphenyl group, 2,6-diethoxyphenyl group, 3,5-diethoxyphenyl group, 2,4,6-triethoxyphenyl group, 2-n-propoxyphenyl group, 3-n -Propoxyphenyl group, 4-n-propoxyphenyl group, 2,6-di-n-propoxyphenyl group, 3,5-di-n-propoxyphenyl group, 2,4,6-tri-n-propo Xiphenyl group, 2-i-propoxyphenyl group, 3-i-propoxyphenyl group, 4-i-propoxyphenyl group, 2,6-di-i-propoxyphenyl group, 3,5-di-i-propoxyphenyl group 2,4,6-tri-i-propoxyphenyl group, 2-n-butoxyphenyl group, 3-n-butoxyphenyl group, 4-n-butoxyphenyl group, 2,6-di-n-butoxyphenyl group 3,5-di-n-butoxyphenyl group, 2,4,6-tri-n-butoxyphenyl group, 2-t-butoxyphenyl group, 3-t-butoxyphenyl group, 4-t-butoxyphenyl group 2,6-di-t-butoxyphenyl group, 3,5-di-t-butoxyphenyl group, 2,4,6-tri-t-butoxyphenyl group, 2-benzyloxyphenyl group, 3-benzyloxy Siphenyl group, 4-benzyloxyphenyl group, 2,6-di-benzyloxyphenyl group, 3,5-di-benzyloxyphenyl group, 3,4-di-benzyloxyphenyl group, 2,4,6-tri -Benzyloxyphenyl group, 1-naphthyl group, 2-methyl-1-naphthyl group, 2-trifluoromethyl-1-naphthyl group, 2-phenyl-1-naphthyl group, 2-methoxy-1-naphthyl group, 2 -[3,5-dimethylphenyl] -1-naphthyl group, 2- [4-methylphenyl] -1-naphthyl group, 2- (o-biphenylyl) -1-naphthyl group, 2- (m-biphenylyl)- 1-naphthyl group, 2- (p-biphenylyl) -1-naphthyl group, 2-naphthyl group, 2-biphenylyl group, 3-biphenylyl group, 4-biphenylyl group, 1-anthryl group, 2- Enthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, 1-pyrenyl group, 2,6-diphenylphenyl group, and 3,5 -A diphenylphenyl group etc. are mentioned.

The C _2-9 heteroaryl group is a C _2-6 monocyclic heterocycle having 1 to 3 oxygen atoms, nitrogen atoms or sulfur atoms, which may contain 5 to 7 membered ring alone or in combination. C _5-9 fused bicyclic heterocyclic groups having up to 8-10 groups and constituent atoms are included. Examples of the C _2-6 monocyclic heterocyclic group having 5 to 7 members include a 2-thienyl group, a 3-thienyl group, a 2-furyl group, a 3-furyl group, a 2-pyranyl group, and a 3-pyranyl group. 4-pyranyl group, 1-pyrrolyl group, 2-pyrrolyl group, 3-pyrrolyl group, 1-imidazolyl group, 2-imidazolyl group, 4-imidazolyl group, 1-pyrazolyl group, 3-pyrazolyl group, 4-pyrazolyl group 2-thiazolyl group, 4-thiazolyl group, 5-thiazolyl group, 3-isothiazolyl group, 4-isothiazolyl group, 5-isothiazolyl group, 2-oxazolyl group, 4-oxazolyl group, 5-oxazolyl group, 3-isoxazolyl group 4-isoxazolyl group, 5-isoxazolyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-pyrazinyl group, 2-pyrimidinyl group, 4-pyridinyl group Midinyl group, 5-pyrimidinyl group, 3-pyridazinyl group, 4-pyridazinyl group, 2-1,3,4-oxadiazolyl group, 2-1,3,4-thiadiazolyl group, 3-1,2,4-oxadiazolyl group 5-1, 2, 4-oxadiazolyl group, 3-1, 2, 4-thiadiazolyl group, 5-1, 2, 4-thiadiazolyl group, 3-1, 2, 5-oxadiazolyl group, and 3-1, 2 , 5-thiadiazolyl group and the like, and the C _5-9 condensed bicyclic heterocyclic group having 8 to 10 constituent atoms includes 2-benzofuranyl group, 3-benzofuranyl group, 4-benzofuranyl group, 5 -Benzofuranyl group, 6-benzofuranyl group, 7-benzofuranyl group, 1-isobenzofuranyl group, 4-isobenzofuranyl group, 5-isobenzofuranyl group, 2-benzothienyl group, 3- Benzothienyl group, 4-benzothienyl group, 5-benzothienyl group, 6-benzothienyl group, 7-benzothienyl group, 1-isobenzothienyl group, 4-isobenzothienyl group, 5-isobenzothienyl group, 2 -Chromenyl group, 3-chromenyl group, 4-chromenyl group, 5-chromenyl group, 6-chromenyl group, 7-chromenyl group, 8-chromenyl group, 1-indolidinyl group, 2-indolidinyl group, 3-indolidinyl group, 5 -Indolidinyl group, 6-indolidinyl group, 7-indolidinyl group, 8-indolidinyl group, 1-isoindolyl group, 2-isoindolyl group, 4-isoindolyl group, 5-isoindolyl group, 1-indolyl group, 2-indolyl group, 3 -Indolyl group, 4-Indolyl group, 5-Indolyl group, 6-Indolyl group, 7-I Drill group, 1-indazolyl group, 2-indazolyl group, 3-indazolyl group, 4-indazolyl group, 5-indazolyl group, 6-indazolyl group, 7-indazolyl group, 1-purinyl group, 2-purinyl group, 3- Purinyl group, 6-purinyl group, 7-purinyl group, 8-purinyl group, 2-quinolyl group, 3-quinolyl group, 4-quinolyl group, 5-quinolyl group, 6-quinolyl group, 7-quinolyl group, 8- Quinolyl group, 1-isoquinolyl group, 3-isoquinolyl group, 4-isoquinolyl group, 5-isoquinolyl group, 6-isoquinolyl group, 7-isoquinolyl group, 8-isoquinolyl group, 1-phthalazinyl group, 5-phthalazinyl group, 6- Phthalazinyl group, 1-2,7-naphthyridinyl group, 3-2,7-naphthyridinyl group, 4-2,7-naphthyridinyl group, 1-2,6-naphth Ridinyl group, 3-2,6-naphthyridinyl group, 4-2,6-naphthyridinyl group, 2-1,8-naphthyridinyl group, 3-1,8-naphthyridinyl group, 4-1,8-naphthyridinyl group, 2- 1,7-naphthyridinyl group, 3-1,7-naphthyridinyl group, 4-1,7-naphthyridinyl group, 5-1,7-naphthyridinyl group, 6-1,7-naphthyridinyl group, 8-1,7-naphthyridinyl group Group, 2-1,6-naphthyridinyl group, 3-1,6-naphthyridinyl group, 4-1,6-naphthyridinyl group, 5-1,6-naphthyridinyl group, 7-1,6-naphthyridinyl group, 8-1 , 6-Naphthyridinyl group, 2-1,5-naphthyridinyl group, 3-1,5-naphthyridinyl group, 4-1,5-naphthyridinyl group, 6-1,5-naphthyridinyl group, 7-1,5-naphthyridinyl group Group, 8-1,5-naphthyridinyl group, 2-quinoxalinyl group, 5-quinoxalinyl group, 6-quinoxalinyl group, 2-quinazolinyl group, 4-quinazolinyl group, 5-quinazolinyl group, 6-quinazolinyl group, 7-quinazolinyl group Group, 8-quinazolinyl group, 3-cinnolinyl group, 4-cinnolinyl group, 5-cinnolinyl group, 6-cinnolinyl group, 7-cinnolinyl group, 8-cinnolinyl group, 2-pteridinyl group, 4-pteridinyl group, 6-pteridinyl group Group, 7-pteridinyl group and the like.

  Z in partial structural formula (AA) and partial structural formula (AB) is t-butyl group, n-perfluorononyl group, n-perfluorodecyl group, n-perfluoroundecyl group, n-perfluorododecyl. Group, c-propyl group, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2,6-difluorophenyl group, 3,5-difluorophenyl group, 3,4,5-trifluorophenyl Group, 2,3,4,5,6-pentafluorophenyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2,6-dichlorophenyl group, 3,5-dichlorophenyl group, 2-bromophenyl Group, 3-bromophenyl group, 4-bromophenyl group, 2,6-dibromophenyl group, 3,5-dibromophenyl group, 2-methylphenyl 3-methylphenyl group, 4-methylphenyl group, 2,6-dimethylphenyl group, 2,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,4,6-trimethylphenyl group, 2-triphenyl Fluoromethylphenyl group, 3-trifluoromethylphenyl group, 4-trifluoromethylphenyl group, 2,6-bis (trifluoromethyl) phenyl group, 2,4-bis (trifluoromethyl) phenyl group, 3,5 -Bis (trifluoromethyl) phenyl group, 2,4,6-tris (trifluoromethyl) phenyl group, 4-i-propylphenyl group, 2,4,6-tri-i-propylphenyl group, 4-t -Butylphenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2-i-propoxyphenyl group, 3-i-propyl Poxyphenyl group, 4-i-propoxyphenyl group, 2,6-di-i-propoxyphenyl group, 3,5-di-i-propoxyphenyl group, 2,4,6-tri-i-propoxyphenyl group, 2-benzyloxyphenyl group, 3-benzyloxyphenyl group, 4-benzyloxyphenyl group, 2,6-di-benzyloxyphenyl group, 3,5-di-benzyloxyphenyl group, 3,4-di-benzyl Oxyphenyl group, 1-naphthyl group, 2-methyl-1-naphthyl group, 2-trifluoromethyl-1-naphthyl group, 2-phenyl-1-naphthyl group, 2-methoxy-1-naphthyl group, 2-naphthyl Group, 2-biphenylyl group, 3-biphenylyl group, 4-biphenylyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, 1-pyrenyl group, 2,6-diphenylphenyl group, and 3,5-diphenylphenyl group are preferable.

  Z in partial structural formula (AA) and partial structural formula (AB) is 2-fluorophenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2,6-dimethylphenyl group, 2,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,4,6-trimethylphenyl group, 4-bromophenyl group, 2-trifluoromethylphenyl group, 3-trifluoromethylphenyl group, 4- Trifluoromethylphenyl group, 2,6-bis (trifluoromethyl) phenyl group, 2,4-bis (trifluoromethyl) phenyl group, 3,5-bis (trifluoromethyl) phenyl group, 2,4,6 -Tris (trifluoromethyl) phenyl group, 4-i-propylphenyl group, 2,4,6-tri-i-propylphenyl group, 4-t-butylphenyl group 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2-i-propoxyphenyl group, 3-i-propoxyphenyl group, 4-i-propoxyphenyl group, 2,6-di-i- Propoxyphenyl group, 3,5-di-i-propoxyphenyl group, 2,4,6-tri-i-propoxyphenyl group, 2-benzyloxyphenyl group, 3-benzyloxyphenyl group, 4-benzyloxyphenyl group 2,6-di-benzyloxyphenyl group, 3,5-di-benzyloxyphenyl group, 3,4-di-benzyloxyphenyl group, 1-naphthyl group, 2-methyl-1-naphthyl group, 2- Trifluoromethyl-1-naphthyl group, 2-phenyl-1-naphthyl group, 2-methoxy-1-naphthyl group, 2-naphthyl group, 2-biphenylyl group 3-biphenylyl group, 4-biphenylyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, A 1-pyrenyl group, a 2,6-diphenylphenyl group, and a 3,5-diphenylphenyl group are more preferable.

Formula (1a), Formula (1a ′), Formula (1b), Formula (1b ′), Formula (2), Formula (2 ′), Formula (3a), Formula (3a ′), Formula (3b), In formula (3b ′), formula (4) and formula (4 ′), and in partial structural formula (AA) and partial structural formula (AB), R ² represents a hydrogen atom, a halogen atom, or a C _1-4 alkyl group. (The alkyl group is unsubstituted or substituted with a halogen atom.) Or a C _1-4 alkoxy group.

Formula (1a), Formula (1a ′), Formula (1b), Formula (1b ′), Formula (2), Formula (2 ′), Formula (3a), Formula (3a ′), Formula (3b), R ² in Formula (3b ′), Formula (4), and Formula (4 ′), and in Partial Structural Formula (AA) and Partial Structural Formula (AB) will be specifically described. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The C _1-4 alkyl group includes a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and an i-butyl group, an s-butyl group, a t-butyl group, and a trifluoromethyl group. And pentafluoromethyl group. Examples of the C _1-4 alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, an s-butoxy group, and a t-butoxy group.

Formula (1a), Formula (1a ′), Formula (1b), Formula (1b ′), Formula (2), Formula (2 ′), Formula (3a), Formula (3a ′), Formula (3b), R ² in formula (3b ′), formula (4) and formula (4 ′), and partial structural formula (AA) and partial structural formula (AB) is a hydrogen atom, a methyl group, a trifluoromethyl group, methoxy Group is preferable, and a hydrogen atom and a methoxy group are more preferable.

Formula (1a), Formula (1a ′), Formula (1b), Formula (1b ′), Formula (2), Formula (2 ′), Formula (3a), Formula (3a ′), Formula (3b), R ³ in formula (3b ′), formula (4) and formula (4 ′) is a C _6-18 aryl group or, when two R ³ together form a ring, C _3-5 It is a divalent group.

Formula (1a), Formula (1a ′), Formula (1b), Formula (1b ′), Formula (2), Formula (2 ′), Formula (3a), Formula (3a ′), Formula (3b), R ³ in Formula (3b ′), Formula (4), and Formula (4 ′) will be specifically described. Examples of the C _6-18 aryl group include a phenyl group, a 3,5-dimethylphenyl group, a 2,4,6-trimethylphenyl group, and a 4-methylphenyl group. _Examples of the C _3-5 divalent group in the case where two R ³ are combined to form a ring include a trimethylene group and a tetramethylene group.

Formula (1a), Formula (1a ′), Formula (1b), Formula (1b ′), Formula (2), Formula (2 ′), Formula (3a), Formula (3a ′), Formula (3b), R ³ in formula (3b ′), formula (4), and formula (4 ′) is a phenyl group, 3,5-dimethylphenyl group, 2,4,6-trimethylphenyl group, and two R ³ groups together. A tetramethylene group which is a divalent group when a ring is formed is preferable, and a tetramethylene group is more preferable.

Formula (1a), Formula (1a ′), Formula (1b), Formula (1b ′), Formula (2), Formula (2 ′), Formula (3a), Formula (3a ′), Formula (3b), R ⁴ in formula (3b ′), formula (4) and formula (4 ′), and in partial structural formula (AA) and partial structural formula (AB) each independently represents a hydrogen atom, a halogen atom, C _{1 A -4} alkyl group (the alkyl group is unsubstituted or substituted with a halogen atom), a _C1-4 alkoxy group, a nitro group, or a cyano group.

Formula (1a), Formula (1a ′), Formula (1b), Formula (1b ′), Formula (2), Formula (2 ′), Formula (3a), Formula (3a ′), Formula (3b), R ⁴ in Formula (3b ′), Formula (4), and Formula (4 ′), and Partial Structural Formula (AA) and Partial Structural Formula (AB) will be specifically described. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The C _1-4 alkyl group includes a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, a trifluoromethyl group, And a pentafluoromethyl group. Examples of the C _1-4 alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, an s-butoxy group, and a t-butoxy group.

Formula (1a), Formula (1a ′), Formula (1b), Formula (1b ′), Formula (2), Formula (2 ′), Formula (3a), Formula (3a ′), Formula (3b), R ⁴ in formula (3b ′), formula (4) and formula (4 ′), and partial structural formula (AA) and partial structural formula (AB) is a hydrogen atom, a methyl group, a trifluoromethyl group, methoxy Group is preferable, and a hydrogen atom and a methoxy group are more preferable.

  Formula (5), Formula (6), Formula (7), Formula (8), Formula (9), Formula (10), Formula (11), Formula (12), Formula (13), Formula (14) Each substituent in formula (15), formula (16), formula (17), formula (18), formula (19) and formula (20) will be described.

R ⁵ , R ⁶ , R ⁷ and R ⁸ in the formula (5), formula (6), formula (15) and formula (16) are each independently a hydrogen atom, cyano group, nitro group, amino A group (the amino group is not protected or protected by a protecting group), a C _1-4 alkylamino group (the alkylamino group is not protected or protected by a protecting group); A halogen atom, a C _1-4 alkyl group (the alkyl group is unsubstituted or substituted with a halogen atom), a C _1-4 alkoxy group, a carboxyl group, a formyl group, A C _1-4 alkylcarbonyl group (the alkylcarbonyl group is unsubstituted or substituted with a halogen atom), a C _6-12 arylcarbonyl group (whether the arylcarbonyl group is unsubstituted) Or a halogen atom Is substituted.), Carbamoyl _{group, C 1-4} alkylsulfinyl _{group, C 6-7} arylsulfinyl _{group, C 1-4} alkylsulfonyl _{group, C 6-12} arylsulfonyl group, a sulfamoyl group, a mono _{C 1-3} An alkylaminosulfonyl group, or a di-C _1-3 alkylaminosulfonyl group.

R ⁵ , R ⁶ , R ⁷ and R ⁸ in Formula (5), Formula (6), Formula (15) and Formula (16) will be specifically described. The amino group includes an amino group, a mesylamino group, a dimesylamino group, a trifluoromethylsulfonylamino group, a ditrifluoromethylsulfonylamino group, a tosylamino group, a benzylamino group, a C _2-7 acylamino group, and a C _2-5 alkoxycarbonylamino. Groups and the like. Examples of the C _2-7 acylamino group include an acetylamino group, a propionylamino group, and a benzoylamino group. The C _2-5 alkoxycarbonylamino group includes a methoxycarbonylamino group and an ethoxycarbonylamino group. N-propoxycarbonylamino group, i-propoxycarbonylamino group, n-butoxycarbonylamino group, i-butoxycarbonylamino group, s-butoxycarbonylamino group, t-butoxycarbonylamino group and the like. The C _1-4 alkylamino group includes a methylamino group, an ethylamino group, an n-propylamino group, an n-butylamino group, a tosylmethylamino group, a tosylethylamino group, a tosyl-n-propylamino group, a tosyl- n-butylamino group, benzylmethylamino group, benzylethylamino group, benzyl-n-propylamino group, benzyl-n-butylamino group, _C2-7 acyl _C1-4 alkylamino group, and _C2-5 An alkoxycarbonyl _C1-4 alkylamino group etc. are mentioned. The C _2-7 acyl C _1-4 alkylamino group includes an acetylmethylamino group, an acetylethylamino group, an acetyl-n-propylamino group, an acetyl-n-butylamino group, a propionylmethylamino group, and propionylethyl. Amino group, propionyl-n-propylamino group, propionyl-n-butylamino group, benzoylmethylamino group, benzoylethylamino group, benzoyl-n-propylamino group, benzoyl-n-butylamino group, etc. The C _2-5 alkoxycarbonyl C _1-4 alkylamino group includes a methoxycarbonylmethylamino group, a methoxycarbonylethylamino group, a methoxycarbonyl-n-propylamino group, a methoxycarbonyl-n-butylamino group, and an ethoxycarbonyl group. Methylamino Group, ethoxycarbonylethylamino group, ethoxycarbonyl-n-propylamino group, ethoxycarbonyl-n-butylamino group, i-propoxycarbonylmethylamino group, i-propoxycarbonylethylamino group, i-propoxycarbonyl-n-propyl Amino group, i-propoxycarbonyl-n-butylamino group, n-butoxycarbonylmethylamino group, n-butoxycarbonylethylamino group, n-butoxycarbonyl-n-propylamino group, n-butoxycarbonyl-n-butylamino group Group, t-butoxycarbonylmethylamino group, t-butoxycarbonylethylamino group, t-butoxycarbonyl-n-propylamino group, t-butoxycarbonyl-n-butylamino group and the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The C _1-4 alkyl group includes a methyl group, a trifluoromethyl group, a monochloromethyl group, an ethyl group, a pentafluoroethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s -Butyl group, t-butyl group, etc. are mentioned. Examples of the C _1-4 alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, an s-butoxy group, and a t-butoxy group. The C _1-4 alkylcarbonyl group includes a methylcarbonyl group, a trifluoromethylcarbonyl group, a monochloromethylcarbonyl group, an ethylcarbonyl group, a pentafluoroethylcarbonyl group, an n-propylcarbonyl group, an i-propylcarbonyl group, and n-butyl. Examples include a carbonyl group, i-butylcarbonyl group, s-butylcarbonyl group, and t-butylcarbonyl group. The C _6-12 arylcarbonyl group includes a phenylcarbonyl group, an o-toluoylcarbonyl group, an m-toluoylcarbonyl group, a p-toluoylcarbonyl group, an o-biphenylylcarbonyl group, an m-biphenylylcarbonyl group, p -Biphenylyl carbonyl group, 1-naphthyl carbonyl group, 2-naphthyl carbonyl group, etc. are mentioned. The C _1-4 alkylsulfinyl group includes methylsulfinyl group, ethylsulfinyl group, n-propylsulfinyl group, i-propylsulfinyl group, n-butylsulfinyl group, i-butylsulfinyl group, s-butylsulfinyl group, and t -A butylsulfinyl group etc. are mentioned. Examples of the C _6-7 arylsulfinyl group include a benzenesulfinyl group, an o-toluenesulfinyl group, an m-toluenesulfinyl group, and a p-toluenesulfinyl group. The C _1-4 alkylsulfonyl group includes a methanesulfonyl group, an ethanesulfonyl group, an n-propanesulfonyl group, an i-propanesulfonyl group, an n-butanesulfonyl group, an i-butanesulfonyl group, an s-butanesulfonyl group, and t. -A butanesulfonyl group etc. are mentioned. The C _6-12 arylsulfonyl group includes a benzenesulfonyl group, a p-toluenesulfonyl group, an o-biphenylsulfonyl group, an m-biphenylsulfonyl group, a p-biphenylsulfonyl group, a 1-naphthalenesulfonyl group, and a 2-naphthalenesulfonyl group. Etc. Examples of the mono C _1-3 alkylaminosulfonyl group include a methylaminosulfonyl group, an ethylaminosulfonyl group, an n-propylaminosulfonyl group, and an i-propylaminosulfonyl group. Examples of the di-C _1-3 alkylaminosulfonyl group include a dimethylaminosulfonyl group, a diethylaminosulfonyl group, a di-n-propylaminosulfonyl group, and a di-i-propylaminosulfonyl group.

R ⁵ , R ⁶ , R ⁷ and R ⁸ in the formula (5), formula (6), formula (15) and formula (16) are each independently a hydrogen atom, cyano group, nitro group, amino Group, mesylamino group, dimesylamino group, trifluoromethylsulfonylamino group, ditrifluoromethylsulfonylamino group, tosylamino group, benzylamino group, acetylamino group, propionylamino group, benzoylamino group, methoxycarbonylamino group, ethoxycarbonylamino group N-propoxycarbonylamino group, i-propoxycarbonylamino group, t-butoxycarbonylamino group, methylamino group, ethylamino group, n-propylamino group, n-butylamino group, tosylmethylamino group, tosylethylamino Group, tosyl-n-propylamino group, tosyl-n-butyl Ruamino group, benzylmethylamino group, benzylethylamino group, benzyl-n-propylamino group, benzyl-n-butylamino group, acetylmethylamino group, acetylethylamino group, acetyl-n-propylamino group, benzoylmethylamino Group, benzoylethylamino group, benzoyl-n-propylamino group, benzoyl-n-butylamino group, ethoxycarbonylmethylamino group, ethoxycarbonylethylamino group, ethoxycarbonyl-n-propylamino group, ethoxycarbonyl-n-butyl Amino group, i-propoxycarbonylmethylamino group, i-propoxycarbonylethylamino group, i-propoxycarbonyl-n-propylamino group, i-propoxycarbonyl-n-butylamino group, t-butoxycarbonyl Methylamino, t-butoxycarbonylethylamino, t-butoxycarbonyl-n-propylamino, t-butoxycarbonyl-n-butylamino, fluorine, chlorine, bromine, iodine, methyl, tri Fluoromethyl group, monochloromethyl group, ethyl group, pentafluoroethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, methoxy group, ethoxy Group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, s-butoxy group, t-butoxy group, methylcarbonyl group, trifluoromethylcarbonyl group, monochloromethylcarbonyl group, ethylcarbonyl group , Pentafluoroethylcarbonyl group, n-propylcarbonyl group, i-propylcarbo Nyl group, n-butylcarbonyl group, i-butylcarbonyl group, s-butylcarbonyl group, t-butylcarbonyl group, phenylcarbonyl group, o-toluoyl group, m-toluoyl group, p-toluoyl group, o-biphenylyl Carbonyl group, m-biphenylylcarbonyl group, p-biphenylylcarbonyl group, 1-naphthylcarbonyl group, 2-naphthylcarbonyl group, methylsulfinyl group, ethylsulfinyl group, n-propylsulfinyl group, i-propylsulfinyl group, n -Butylsulfinyl group, i-butylsulfinyl group, s-butylsulfinyl group, t-butylsulfinyl group, benzenesulfinyl group, o-toluenesulfinyl group, m-toluenesulfinyl group, p-toluenesulfinyl group, methylsulfonyl group, ethylsulfo group Group, n-propylsulfonyl group, i-propylsulfonyl group, n-butylsulfonyl group, i-butylsulfonyl group, s-butylsulfonyl group, t-butylsulfonyl group, methylaminosulfonyl group, ethylaminosulfonyl group, n -Propylaminosulfonyl group, i-propylaminosulfonyl group, dimethylaminosulfonyl group, diethylaminosulfonyl group, di-n-propylaminosulfonyl group, di-i-propylaminosulfonyl group are preferred.

R ⁵ , R ⁶ , R ⁷ and R ⁸ in the formula (5), formula (6), formula (15) and formula (16) are each independently a hydrogen atom, cyano group, nitro group, mesylamino Group, dimesylamino group, trifluoromethylsulfonylamino group, ditrifluoromethylsulfonylamino group, tosylamino group, benzylamino group, acetylamino group, propionylamino group, benzoylamino group, methoxycarbonylamino group, ethoxycarbonylamino group, n- Propoxycarbonylamino group, i-propoxycarbonylamino group, t-butoxycarbonylamino group benzylmethylamino group, benzylethylamino group, benzyl-n-propylamino group, benzyl-n-butylamino group, acetylmethylamino group, acetyl Ethylamino group, acetyl-n-propyl Pyramino group, benzoylmethylamino group, benzoylethylamino group, benzoyl-n-propylamino group, benzoyl-n-butylamino group, t-butoxycarbonylmethylamino group, t-butoxycarbonylethylamino group, t-butoxycarbonyl- n-propylamino group, t-butoxycarbonyl-n-butylamino group, fluorine atom, chlorine atom, bromine atom, iodine atom, methyl group, trifluoromethyl group, monochloromethyl group, ethyl group, pentafluoroethyl group, n -Propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, s-butoxy group, t-butoxy group, methylcarbonyl group, tri Fluoromethylcarbonyl group, monochloromethylcarbonyl group, ethylcarbonyl group, pentafluoroethylcarbonyl group, n-propylcarbonyl group, i-propylcarbonyl group, n-butylcarbonyl group, i-butylcarbonyl group, s-butylcarbonyl group T-butylcarbonyl group, phenylcarbonyl group, o-toluoyl group, m-toluoyl group, p-toluoyl group, o-biphenylylcarbonyl group, m-biphenylylcarbonyl group, p-biphenylylcarbonyl group, 1-naphthyl Carbonyl group, 2-naphthylcarbonyl group, methylsulfonyl group, ethylsulfonyl group, n-propylsulfonyl group, i-propylsulfonyl group, n-butylsulfonyl group, i-butylsulfonyl group, s-butylsulfonyl group, t-butyl Sulfonyl group, Tylaminosulfonyl group, ethylaminosulfonyl group, n-propylaminosulfonyl group, i-propylaminosulfonyl group, dimethylaminosulfonyl group, diethylaminosulfonyl group, di-n-propylaminosulfonyl group, di-i-propylaminosulfonyl group Is more preferable.

In Formula (5), Formula (6), Formula (9), Formula (10), Formula (15), Formula (16), Formula (19), and Formula (20), R ⁹ is a hydrogen atom, C _{A 1-4} alkyl group (the alkyl group is unsubstituted or substituted with a halogen atom), or a C _1-4 alkoxy group.

R ⁹ in Formula (5), Formula (6), Formula (9), Formula (10), Formula (15), Formula (16), Formula (19), and Formula (20) will be specifically described. . The C _1-4 alkyl group includes a methyl group, a trifluoromethyl group, a monochloromethyl group, an ethyl group, a pentafluoroethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s -Butyl group, t-butyl group, etc. are mentioned. Examples of the C _1-4 alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, an s-butoxy group, and a t-butoxy group.

In Formula (5), Formula (6), Formula (9), Formula (10), Formula (15), Formula (16), Formula (19), and Formula (20), R ⁹ is a hydrogen atom, methyl Group, trifluoromethyl group, monochloromethyl group, ethyl group, pentafluoroethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, methoxy Group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, s-butoxy group and t-butoxy group are preferred.

In Formula (5), Formula (6), Formula (9), Formula (10), Formula (15), Formula (16), Formula (19), and Formula (20), R ¹⁰ is a hydrogen atom, C _{A 1-22} alkyl group, a C _1-4 alkoxy group, a C _6-10 aryl group (the aryl group is unsubstituted or a halogen atom, a C _1-4 alkyl group, or a C _1-4 alkoxy group; Has been replaced.)

However, R ⁹ and R ^{10 in} Formula (5), Formula (6), Formula (9), Formula (10), Formula (15), Formula (16), Formula (19), and Formula (20) Are combined with each other, and R ^{12 in the} formula (11), formula (12), formula (13), and formula (14) (formula (11), formula (12), formula (13), and formula (14) Are each independently a hydrogen atom or a C _1-4 alkyl group).

R ¹⁰ in Formula (5), Formula (6), Formula (9), Formula (10), Formula (15), Formula (16), Formula (19), and Formula (20) will be specifically described. . The C _1-22 alkyl group is a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, a pentyl group, or an isopentyl group. , Neopentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, isotridecyl, myristyl, palmityl, stearyl, icosyl Group, docosyl group and the like. Examples of the C _1-4 alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, an s-butoxy group, and a t-butoxy group. The C _6-10 aryl group includes a phenyl group, an o-fluorophenyl group, an m-fluorophenyl group, a p-fluorophenyl group, an o-chlorophenyl group, an m-chlorophenyl group, a p-chlorophenyl group, and an o-bromophenyl group. M-bromophenyl group, p-bromophenyl group, o-tolyl group, m-tolyl group, p-tolyl group, o-ethylphenyl group, m-ethylphenyl group, p-ethylphenyl group, o- (t -Butyl) phenyl group, m- (t-butyl) phenyl group, p- (t-butyl) phenyl group, 3,5-dimethylphenyl group, o-methoxyphenyl group, m-methoxyphenyl group, and p-methoxy A phenyl group etc. are mentioned.

R ¹⁰ in Formula (5), Formula (6), Formula (9), Formula (10), Formula (15), Formula (16), Formula (19), and Formula (20) is independently , Hydrogen atom, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, pentyl group, isopentyl group, neopentyl group, Xyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, isotridecyl, myristyl, palmityl, stearyl, icosyl, docosyl, Methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, s-butoxy group, t-butoxy group, phenyl group, o-fluorophenyl group, m-fluorophenol Nyl group, p-fluorophenyl group, o-chlorophenyl group, m-chlorophenyl group, p-chlorophenyl group, o-bromophenyl group, m-bromophenyl group, p-bromophenyl group, o-tolyl group, m-tolyl Group, p-tolyl group, o-ethylphenyl group, m-ethylphenyl group, p-ethylphenyl group, o- (t-butyl) phenyl group, m- (t-butyl) phenyl group, p- (t- (Butyl) phenyl group, 3,5-dimethylphenyl group, o-methoxyphenyl group, m-methoxyphenyl group and p-methoxyphenyl group are preferred.

R ¹⁰ in Formula (5), Formula (6), Formula (9), Formula (10), Formula (15), Formula (16), Formula (19), and Formula (20) is independently , Hydrogen atom, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, pentyl group, isopentyl group, neopentyl group, Xyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, isotridecyl, myristyl, palmityl, stearyl, icosyl, docosyl, Phenyl group, o-fluorophenyl group, m-fluorophenyl group, p-fluorophenyl group, o-chlorophenyl group, m-chlorophenyl group, p-chlorophenyl group, o-bromophenyl group, m- Bromophenyl group, p-bromophenyl group, o-tolyl group, m-tolyl group, p-tolyl group, o-ethylphenyl group, m-ethylphenyl group, p-ethylphenyl group, o- (t-butyl) More phenyl group, m- (t-butyl) phenyl group, p- (t-butyl) phenyl group, 3,5-dimethylphenyl group, o-methoxyphenyl group, m-methoxyphenyl group, p-methoxyphenyl group preferable.

R ¹¹ in the formulas (6) and (16) is a C _1-4 alkyl group (the alkyl group is unsubstituted or substituted with a halogen atom).

R ¹¹ in Formula (6) and Formula (16) will be specifically described. Examples of the C _1-4 alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, and a t-butyl group.

R ¹¹ in the formula (6) and the formula (16) is preferably a methyl group.

R ¹² in the formula (11), formula (12), formula (13) and formula (14) is each independently a hydrogen atom or a C _1-4 alkyl group.

R ¹² in Formula (11), Formula (12), Formula (13), and Formula (14) will be specifically described. Examples of the C _1-4 alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, and a t-butyl group.

In formula (11), formula (12), formula (13) and formula (14), R ¹² is preferably independently a hydrogen atom, a methyl group or an ethyl group.

R ¹² in the formula (11), formula (12), formula (13) and formula (14) is more preferably a methyl group.

R ⁹ and R ^{10 in} Formula (5), Formula (6), Formula (9), Formula (10), Formula (15), Formula (16), Formula (19), and Formula (20) are Together, they may form a divalent group. When R ⁹ and R ¹⁰ are combined with each other to form a group represented by the formula (11), a 6-membered ring is formed. Thus, examples of the compound include benzopyran and derivatives thereof. Further, when R ⁸ and R ⁹ are combined with each other to form a group represented by the above formula (12), a 5-membered ring is formed. Thus, examples of the compound include indene and derivatives thereof. . Further, when R ⁸ and R ⁹ are combined with each other to form a group represented by the above formula (13), a 6-membered ring is formed. Therefore, the compound includes 1,2-dihydronaphthalene and its Derivatives and the like. Further, when R ⁸ and R ⁹ are combined with each other to form a group represented by the above formula (14), a 7-membered ring is formed. Examples include 1,3-cycloheptadiene and its derivatives.

The compound of the formula (5) and the formula (15) is a compound that can be described in a combination selected from the formula (11), the formula (12), the formula (13), and the formula (14) that are divalent groups. preferable. The substitution position of the formula (11), R ⁹ side is an oxygen atom, R ⁹ side is preferably when located carbon atoms.

  The compound of the formula (6) and the formula (16) is preferably a compound that can be described in one combination selected from the formula (12) and the formula (13).

The compound of the formula (9), the formula (10), the formula (19) and the formula (20) is preferably a compound that can be described by a combination of the formula (11) which is a divalent group. The substitution position of the formula (11), R ⁹ side is an oxygen atom, R ⁹ side is preferably when located carbon atoms.

R ¹⁰ in formula (7), formula (8), formula (17) and formula (18) is each independently a hydrogen atom or a C _1-22 alkyl group (the alkyl group is unsubstituted). Or a halogen atom, a C _1-4 alkyl group, a C _6-10 aryl group (the aryl group is unsubstituted or a halogen atom, a C _1-4 alkyl group, or a C _1-4 alkoxy group). Substituted), a benzoyloxy group, a benzyloxy group, or a pivaloyloxy group), a C _3-8 cycloalkyl group (the cycloalkyl group is unsubstituted or a halogen atom) , C _1-4 alkyl group, benzoyloxy group, benzyloxy group, or pivaloyloxy group.), C _1-4 alkoxy group, C _6-10 aryl group (the aryl group is , Unsubstituted or substituted with a halogen atom, a C _1-4 alkyl group, or a C _1-4 alkoxy group.

R ¹⁰ in Formula (7), Formula (8), Formula (17), and Formula (18) will be specifically described. The C _1-22 alkyl group is a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, a pentyl group, or an isopentyl group. , Neopentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, isotridecyl group, myristyl group, palmityl group, stearyl group, icosyl group Group, docosyl group and the like. The C _3-8 cycloalkyl group includes a c-propyl group, a c-butyl group, a 1-methyl-c-propyl group, a 2-methyl-c-propyl group, a c-pentyl group, and a 1-methyl-c-butyl group. Group, 2-methyl-c-butyl group, 3-methyl-c-butyl group, 1,2-dimethyl-c-propyl group, 2,3-dimethyl-c-propyl group, 1-ethyl-c-propyl group 2-ethyl-c-propyl group, c-hexyl group, c-heptyl group, c-octyl group, 1-methyl-c-hexyl group, 2-methyl-c-hexyl group, 3-methyl-c-hexyl Group, 1,2-dimethyl-c-hexyl group, 2,3-dimethyl-c-hexyl group, 1-ethyl-c-propyl group, 1-methyl-c-pentyl group, 2-methyl-c-pentyl group 3-methyl-c-pentyl group, 1-ethyl-c-butyl Group, 2-ethyl-c-butyl group, 3-ethyl-c-butyl group, 1,2-dimethyl-c-butyl group, 1,3-dimethyl-c-butyl group, 2,2-dimethyl-c -Butyl group, 2,3-dimethyl-c-butyl group, 2,4-dimethyl-c-butyl group, 3,3-dimethyl-c-butyl group, 1-n-propyl-c-propyl group, 2- n-propyl-c-propyl group, 1-i-propyl-c-propyl group, 2-i-propyl-c-propyl group, 1,2,2-trimethyl-c-propyl group, 1,2,3- Trimethyl-c-propyl group, 2,2,3-trimethyl-c-propyl group, 1-ethyl-2-methyl-c-propyl group, 2-ethyl-1-methyl-c-propyl group, 2-ethyl- 2-methyl-c-propyl group and 2-ethyl-3-methyl-c-propyl Etc. is Ageraru. Examples of the C _1-4 alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, an s-butoxy group, and a t-butoxy group. The C _6-10 aryl group includes a phenyl group, an o-fluorophenyl group, an m-fluorophenyl group, a p-fluorophenyl group, an o-chlorophenyl group, an m-chlorophenyl group, a p-chlorophenyl group, and an o-bromophenyl group. M-bromophenyl group, p-bromophenyl group, o-tolyl group, m-tolyl group, p-tolyl group, o-ethylphenyl group, m-ethylphenyl group, p-ethylphenyl group, o- (t -Butyl) phenyl group, m- (t-butyl) phenyl group, p- (t-butyl) phenyl group, 3,5-dimethylphenyl group, o-methoxyphenyl group, m-methoxyphenyl group, and p-methoxy A phenyl group etc. are mentioned.

The ring partial structure A in Formula (9), Formula (10), Formula (19), and Formula (20) will be described. The ring partial structure A is a 5-membered ring, 6-membered ring or 7-membered ring fused with a benzene ring (the 5-membered ring, the 6-membered ring or the 7-membered ring are either unsubstituted or h R ¹³ (wherein R ¹³ is a halogen atom, a hydroxyl group, a C _1-6 alkyl group (the alkyl group is unsubstituted or a halogen atom, a hydroxyl group, a cyano group, an amino group, a nitro group, C _{1 -4} alkoxy group (the alkoxy group is unsubstituted or substituted with a halogen atom), C _1-4 alkylcarbonyloxy group (the alkylcarbonyloxy group is unsubstituted, or Substituted with a halogen atom), a C _1-4 alkylcarbonylamino group (the alkylcarbonylamino group is unsubstituted or substituted with a halogen atom), or a C _1-4 alkoxycarbonyl Group ( Alkoxycarbonyl group is substituted by either unsubstituted or substituted with a halogen atom.).), C _1-6 alkoxy group (said alkoxy group is unsubstituted, or a halogen atom , A hydroxyl group, a cyano group, an amino group, a nitro group, a C _1-4 alkoxy group (the alkoxy group is unsubstituted or substituted with a halogen atom), a C _1-4 alkylcarbonyloxy group ( The alkylcarbonyloxy group is unsubstituted or substituted with a halogen atom.), A C _1-4 alkylcarbonylamino group (the alkylcarbonylamino group is unsubstituted or substituted with a halogen atom. it is substituted.), or C _1-4 alkoxycarbonyl group (the alkoxy group is unsubstituted or substituted by a halogen atom That.) Are replaced with.), A nitro group, a cyano group, a formyl group, formamide group, a carbamoyl group, a sulfo group, sulfoamino group, a sulfamoyl group, a sulfonyl group, an amino group, a carboxyl group, C _1-6 alkylamino A group (the alkylamino group is unsubstituted or substituted with a halogen atom), a diC _1-6 alkylamino group (the dialkylamino group is unsubstituted or substituted with a halogen atom); Substituted), C _1-6 alkylcarbonylamino group (the alkylcarbonylamino group is unsubstituted or substituted with a halogen atom), C _1-6 alkylsulfonamido group (the substituted The alkylsulfonamido group is unsubstituted or substituted with a halogen atom.), A C _6-14 arylsulfonamido group The arylsulfonamido group is unsubstituted or substituted with a halogen atom. ), A C _1-6 alkylaminocarbonyl group (the alkylaminocarbonyl group is unsubstituted or substituted with a halogen atom), a diC _1-6 alkylaminocarbonyl group (the dialkylaminocarbonyl group). Is unsubstituted or substituted with a halogen atom), a C _1-6 alkylcarbonyl group (the alkylcarbonyl group is unsubstituted or substituted with a halogen atom), C _1-6 alkoxycarbonyl group (the alkoxycarbonyl group is unsubstituted or substituted with a halogen atom), C _1-4 alkylsulfonyl group (whether the alkylsulfonyl group is unsubstituted) or substituted with a halogen atom.), C _6-14 arylsulfonyl group (the aryl sulfonyl group is unsubstituted, or Substituted with halogen atoms.), Or C _6-14 arylcarbonyl group (the arylcarbonyl group is unsubstituted or substituted by substituted by halogen atom.), H is 1 to 6 An integer is meant, and when h is 2 to 6, R ¹³ may be the same or different. ) And can contain 1 to 3 oxygen atoms, nitrogen atoms or sulfur atoms as ring constituents, alone or in combination, and the number of unsaturated bonds in the ring is One, two or three carbon atoms including a ring unsaturated bond may be carbonyl or thiocarbonyl. ).

The R ¹³ will be specifically described. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The C _1-6 alkyl group includes a methyl group, a trifluoromethyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, 1-pentyl group, 2-pentyl group, 3-pentyl group, i-pentyl group, neopentyl group, 2,2-dimethylpropyl group, 1-hexyl group, 2-hexyl group, 3-hexyl group, 1-methyl- n-pentyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 3,3-dimethyl-n-butyl group, methylcarbonyloxymethyl group, ethylcarbonyl Oxymethyl group, methylcarbonyloxyethyl group, ethylcarbonyloxyethyl group, methylcarbonylaminomethyl group, trifluoromethylcarbonylaminomethyl group, ethylcarbo Examples include nylaminomethyl group, methylcarbonylaminoethyl group, ethylcarbonylaminoethyl group, methoxycarbonylmethyl group, trifluoromethoxycarbonylmethyl group, ethoxycarbonylmethyl group, methoxycarbonylethyl group, and ethoxycarbonylethyl group. The C _1-6 alkoxy group includes a methoxy group, a trifluoromethoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, an s-butoxy group, a t-butoxy group, 1-pentyloxy group, 2-pentyloxy group, 3-pentyloxy group, i-pentyloxy group, neopentyloxy, 2,2-dimethylpropoxy group, 1-hexyloxy group, 2-hexyloxy group, 3- Hexyloxy group, 1-methyl-n-pentyloxy group, 1,1,2-trimethyl-n-propoxy group, 1,2,2-trimethyl-n-propoxy group, 3,3-dimethyl-n-butoxy group Methylcarbonyloxymethoxy group, ethylcarbonyloxymethoxy group, methylcarbonyloxyethoxy group, ethylcarbonyloxyethoxy group, Methylcarbonylaminomethoxy group, trifluoromethylcarbonylaminomethoxy group, ethylcarbonylaminomethoxy group, methylcarbonylaminoethoxy group, ethylcarbonylaminoethoxy group, methoxycarbonylmethoxy group, trifluoromethoxycarbonylmethoxy group, ethoxycarbonylmethoxy group, methoxy A carbonylethoxy group, an ethoxycarbonylethoxy group, etc. are mentioned. The C _1-6 alkylamino group includes a methylamino group, a trifluoromethylamino group, an ethylamino group, an n-propylamino group, an i-propylamino group, a c-propylamino group, an n-butylamino group, an i- Butylamino group, s-butylamino group, t-butylamino group, c-butylamino group, 1-pentylamino group, 2-pentylamino group, 3-pentylamino group, i-pentylamino group, neopentylamino group T-pentylamino group, c-pentylamino group, 1-hexylamino group, 2-hexylamino group, 3-hexylamino group, c-hexylamino group, 1-methyl-n-pentylamino group, 1,1 , 2-trimethyl-n-propylamino group, 1,2,2-trimethyl-n-propylamino group, 3,3-dimethyl-n-butylamino group, etc. Is mentioned. The di-C _1-6 alkylamino group includes a dimethylamino group, a bis (trifluoromethyl) amino group, a diethylamino group, a di-n-propylamino group, a di-i-propylamino group, and a di-c-propylamino group. Di-n-butylamino group, di-i-butylamino group, di-s-butylamino group, di-t-butylamino group, di-c-butylamino group, di-1-pentylamino group, di- 2-pentylamino group, di-3-pentylamino group, di-i-pentylamino group, di-neopentylamino group, di-t-pentylamino group, di-c-pentylamino group, di-1- Hexylamino group, di-2-hexylamino group, di-3-hexylamino group, di-c-hexylamino group, bis (1-methyl-n-pentyl) amino group, bis (1,1,2-trimethyl) -N-p (Lopyl) amino group, bis (1,2,2-trimethyl-n-propyl) amino group, bis (3,3-dimethyl-n-butyl) amino group, (methylethyl) amino group, (ethyl) trifluoromethyl Amino group, methyl-n-propylamino group, methyl-i-propylamino group, methyl-c-propylamino group, n-butylmethylamino group, i-butylmethylamino group, s-butylmethylamino group, t- Butylmethylamino group, c-butylmethylamino group, ethyl-n-propylamino group, ethyl-i-propylamino group, ethyl-c-propylamino group, n-butylethylamino group, i-butylethylamino group, s-butylethylamino group, t-butylethylamino group, c-butylethylamino group, n-propyl-i-propylamino group, n-pro Ru-c-propylamino group, n-butyl-n-propylamino group, i-butyl-n-propylamino group, s-butyl-n-propylamino group, t-butyl-n-propylamino group, c- Butyl-n-propylamino group, i-propyl-c-propylamino group, n-butyl-i-propylamino group, i-butyl-i-propylamino group, s-butyl-i-propylamino group, t- Butyl-i-propylamino group, c-butyl-i-propylamino group, n-butyl-c-propylamino group, i-butyl-c-propylamino group, s-butyl-c-propylamino group, t- Butyl-c-propylamino group, c-butyl-c-propylamino group, n-butyl-i-butylamino group, n-butyl-s-butylamino group, n-butyl-t-butylamino group n-butyl-c-butylamino group, i-butyl-s-butylamino group, i-butyl-t-butylamino group, i-butyl-c-butylamino group, s-butyl-t-butylamino group, Examples thereof include s-butyl-c-butylamino group and t-butyl-c-butylamino group. The C _1-6 alkylcarbonylamino group includes a methylcarbonylamino group, a trifluoromethylcarbonylamino group, an ethylcarbonylamino group, an n-propylcarbonylamino group, an i-propylcarbonylamino group, an n-butylcarbonylamino group, i -Butylcarbonylamino group, s-butylcarbonylamino group, t-butylcarbonylamino group, 1-pentylcarbonylamino group, 2-pentylcarbonylamino group, 3-pentylcarbonylamino group, i-pentylcarbonylamino group, neopentyl Examples include carbonylamino, t-pentylcarbonylamino group, 1-hexylcarbonylamino group, 2-hexylcarbonylamino group, and 3-hexylcarbonylamino group.

The C _1-6 alkylsulfonamide group includes a methanesulfonamide group, a trifluoromethanesulfonamide group, an ethanesulfonamide group, an n-propanesulfonamide group, an i-propanesulfonamide group, an n-butanesulfonamide group, an i- Butanesulfonamide group, s-butanesulfonamide group, t-butanesulfonamide group, n-pentanesulfonamide group, 2-pentanesulfonamide group, 3-pentanesulfonamide group, i-pentanesulfonamide group, neopentanesulfone group Examples include an amide group, a t-pentanesulfonamide group, an n-hexanesulfonamide group, a 2-hexanesulfonamide group, and a 3-hexanesulfonamide group. The C _6-14 arylsulfonamide group includes a benzenesulfonamide group, a p-toluenesulfonamide group, an o-biphenylsulfonamide group, an m-biphenylsulfonamide group, a p-biphenylsulfonamide group, and a 1-naphthalenesulfonamide group. 2-naphthalenesulfonamide group, 1-anthracenesulfonamide group, 2-anthracenesulfonamide group, 9-anthracenesulfonamide group, 1-phenanthrenesulfonamide group, 2-phenanthrenesulfonamide group, 3-phenanthrenesulfonamide group, 4-phenanthrenesulfonamide group, 9-phenanthrenesulfonamide group and the like can be mentioned. The C _1-6 alkylaminocarbonyl group includes a methylaminocarbonyl group, a trifluoromethylaminocarbonyl group, an ethylaminocarbonyl group, an n-propylaminocarbonyl group, an i-propylaminocarbonyl group, an n-butylaminocarbonyl group, i -Butylaminocarbonyl group, s-butylaminocarbonyl group, t-butylaminocarbonyl group, 1-pentylaminocarbonyl group, 2-pentylaminocarbonyl group, 3-pentylaminocarbonyl group, i-pentylaminocarbonyl group, neopentyl Examples thereof include an aminocarbonyl group, a t-pentylaminocarbonyl group, a 1-hexylaminocarbonyl group, a 2-hexylaminocarbonyl group, and a 3-hexylaminocarbonyl group. The diC _1-6 alkylaminocarbonyl group includes a dimethylaminocarbonyl group, a bis (trifluoromethyl) aminocarbonyl group, a diethylaminocarbonyl group, a di-n-propylaminocarbonyl group, a di-i-propylaminocarbonyl group, a di- -C-propylaminocarbonyl group, di-n-butylaminocarbonyl group, di-i-butylaminocarbonyl group, di-s-butylaminocarbonyl group, di-t-butylaminocarbonyl group, di-c-butylamino Carbonyl group, di-1-pentylaminocarbonyl group, di-2-pentylaminocarbonyl group, di-3-pentylaminocarbonyl group, di-i-pentylaminocarbonyl group, di-neopentylaminocarbonyl group, di-t -Pentylaminocarbonyl group, di-c-pentylaminocarbo Nyl group, di-1-hexylaminocarbonyl group, di-2-hexylaminocarbonyl group, di-3-hexylaminocarbonyl group, di-c-hexylaminocarbonyl group, bis (1-methyl-n-pentyl) amino Carbonyl group, bis (1,1,2-trimethyl-n-propyl) aminocarbonyl group, bis (1,2,2-trimethyl-n-propyl) aminocarbonyl group, bis (3,3-dimethyl-n-butyl) ) Aminocarbonyl group, (methylethyl) aminocarbonyl group, (ethyl) trifluoromethylaminocarbonyl group, methyl-n-propylaminocarbonyl group, methyl-i-propylaminocarbonyl group, methyl-c-propylaminocarbonyl group, n-butylmethylaminocarbonyl group, i-butylmethylaminocarbonyl group, s Butylmethylaminocarbonyl group, t-butylmethylaminocarbonyl group, c-butylmethylaminocarbonyl group, ethyl-n-propylaminocarbonyl group, ethyl-i-propylaminocarbonyl group, ethyl-c-propylaminocarbonyl group, n -Butylethylaminocarbonyl group, i-butylethylaminocarbonyl group, s-butylethylaminocarbonyl group, t-butylethylaminocarbonyl group, c-butylethylaminocarbonyl group, n-propyl-i-propylaminocarbonyl group, n-propyl-c-propylaminocarbonyl group, n-butyl-n-propylaminocarbonyl group, i-butyl-n-propylaminocarbonyl group, s-butyl-n-propylaminocarbonyl group, t-butyl-n- Propylaminocarbo Group, c-butyl-n-propylaminocarbonyl group, i-propyl-c-propylaminocarbonyl group, n-butyl-i-propylaminocarbonyl group, i-butyl-i-propylaminocarbonyl group, s-butyl -I-propylaminocarbonyl group, t-butyl-i-propylaminocarbonyl group, c-butyl-i-propylaminocarbonyl group, n-butyl-c-propylaminocarbonyl group, i-butyl-c-propylaminocarbonyl group Group, s-butyl-c-propylaminocarbonyl group, t-butyl-c-propylaminocarbonyl group, c-butyl-c-propylaminocarbonyl group, n-butyl-i-butylaminocarbonyl group, n-butyl- s-butylaminocarbonyl group, n-butyl-t-butylaminocarbonyl group, n- Butyl-c-butylaminocarbonyl group, i-butyl-s-butylaminocarbonyl group, i-butyl-t-butylaminocarbonyl group, i-butyl-c-butylaminocarbonyl group, s-butyl-t-butylamino Examples include a carbonyl group, a s-butyl-c-butylaminocarbonyl group, and a t-butyl-c-butylaminocarbonyl group. The C _1-6 alkylcarbonyl group includes a methylcarbonyl group, a trifluoromethylcarbonyl group, an ethylcarbonyl group, an n-propylcarbonyl group, an i-propylcarbonyl group, an n-butylcarbonyl group, an i-butylcarbonyl group, an s- Butylcarbonyl group, t-butylcarbonyl group, 1-pentylcarbonyl group, 2-pentylcarbonyl group, 3-pentylcarbonyl group, i-pentylcarbonyl group, neopentylcarbonyl group, t-pentylcarbonyl group, 1-hexylcarbonyl group , 2-hexylcarbonyl group, 3-hexylcarbonyl group and the like.

The C _1-6 alkoxycarbonyl group includes a methoxycarbonyl group, a trifluoromethoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an i-propoxycarbonyl group, an n-butoxycarbonyl group, an i-butoxycarbonyl group, an s- Butoxycarbonyl group, t-butoxycarbonyl group, 1-pentyloxycarbonyl group, 2-pentyloxycarbonyl group, 3-pentyloxycarbonyl group, i-pentyloxycarbonyl group, neopentyloxycarbonyl group, t-pentyloxycarbonyl group 1-hexyloxycarbonyl group, 2-hexyloxycarbonyl group, 3-hexyloxycarbonyl group and the like. The C _1-4 alkylsulfonyl group includes a methanesulfonyl group, a trifluoromethanesulfonyl group, an ethanesulfonyl group, an n-propanesulfonyl group, an i-propanesulfonyl group, an n-butanesulfonyl group, an i-butanesulfonyl group, and an s-butane. A sulfonyl group, a t-butanesulfonyl group, etc. are mentioned. The C _6-14 arylsulfonyl group is a benzenesulfonyl group, p-fluorobenzenesulfonyl group, p-toluenesulfonyl group, o-biphenylsulfonyl group, m-biphenylsulfonyl group, p-biphenylsulfonyl group, 1-naphthalenesulfonyl group. 2-naphthalenesulfonyl group, 1-anthracenesulfonyl group, 2-anthracenesulfonyl group, 9-anthracenesulfonyl group, 1-phenanthrenesulfonyl group, 2-phenanthrenesulfonyl group, 3-phenanthrenesulfonyl group, 4-phenanthrenesulfonyl group, and Examples include 9-phenanthrenesulfonyl group. The C _6-14 arylcarbonyl group includes a phenylcarbonyl group, a p-fluorophenylcarbonyl group, an o-biphenylylcarbonyl group, an m-biphenylylcarbonyl group, a p-biphenylylcarbonyl group, a 1-naphthylcarbonyl group, 2- Naphthylcarbonyl group, 1-anthrylcarbonyl group, 2-anthrylcarbonyl group, 9-anthrylcarbonyl group, 1-phenanthrylcarbonyl group, 2-phenanthrylcarbonyl group, 3-phenanthrylcarbonyl group, 4 -Phenanthrylcarbonyl group, 9-phenanthrylcarbonyl group, etc. are mentioned.

With respect to R ¹³ , preferred atoms and substituents will be specifically described. R ¹³ is a fluorine atom, chlorine atom, bromine atom, hydroxyl group, methyl group, trifluoromethyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, n-pentyl group, i-pentyl group. 3,3-dimethyl-n-butyl group, methylcarbonyloxymethyl group, ethylcarbonyloxymethyl group, methylcarbonyloxyethyl group, ethylcarbonyloxyethyl group, methylcarbonylaminomethyl group, trifluoromethylcarbonylaminomethyl group, Ethylcarbonylaminomethyl group, methylcarbonylaminoethyl group, ethylcarbonylaminoethyl group, methoxycarbonylmethyl group, trifluoromethoxycarbonylmethyl group, ethoxycarbonylmethyl group, methoxycarbonylethyl group, ethoxycarbonylethyl group, methoxy group, Trifluoromethoxy group, ethoxy group, n-propoxy group, i-propoxy group, 3,3-dimethyl-n-butoxy group, methylcarbonyloxymethoxy group, ethylcarbonyloxymethoxy group, methylcarbonyloxyethoxy group, ethylcarbonyloxy Ethoxy group, methylcarbonylaminomethoxy group, trifluoromethylcarbonylaminomethoxy group, ethylcarbonylaminomethoxy group, methylcarbonylaminoethoxy group, ethylcarbonylaminoethoxy group, methoxycarbonylmethoxy group, trifluoromethoxycarbonylmethoxy group, ethoxycarbonylmethoxy Group, methoxycarbonylethoxy group, ethoxycarbonylethoxy group, nitro group, cyano group, formyl group, formamide group, carbamoyl group, sulfoamino group, Rufamoyl group, amino group, carboxyl group, methylamino group, trifluoromethylamino group, ethylamino group, n-propylamino group, i-propylamino group, n-butylamino group, dimethylamino group, bis (trifluoromethyl ) Amino group, diethylamino group, di-n-propylamino group, di-i-propylamino group, di-n-butylamino group, methylcarbonylamino group, trifluoromethylcarbonylamino group, ethylcarbonylamino group, n- Propylcarbonylamino group, i-propylcarbonylamino group, n-butylcarbonylamino group, methanesulfonamide group, trifluoromethanesulfonamide group, ethanesulfonamide group, n-propanesulfonamide group, i-propanesulfonamide group, n -Butanesulfone Group, benzenesulfonamide group, p-toluenesulfonamide group, methylaminocarbonyl group, trifluoromethylaminocarbonyl group, ethylaminocarbonyl group, n-propylaminocarbonyl group, i-propylaminocarbonyl group, n-butylaminocarbonyl Group, dimethylaminocarbonyl group, bis (trifluoromethyl) aminocarbonyl group, diethylaminocarbonyl group, di-n-propylaminocarbonyl group, di-i-propylaminocarbonyl group, di-c-propylaminocarbonyl group, di- n-butylaminocarbonyl group, ethylmethylaminocarbonyl group, (ethyl) trifluoromethylaminocarbonyl group, methylcarbonyl group, trifluoromethylcarbonyl group, ethylcarbonyl group, n-propylcarbonyl group, i-propylcarbonyl group, n-butylcarbonyl group, methoxycarbonyl group, trifluoromethoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, i-propoxycarbonyl group, n-butoxycarbonyl group, i-butoxycarbonyl group, s-butoxycarbonyl group, t-butoxycarbonyl group, methanesulfonyl group, trifluoromethanesulfonyl group, ethanesulfonyl group, benzenesulfonyl group, o-biphenylsulfonyl group, m-biphenylsulfonyl group, p-biphenylsulfonyl group, 1-naphthalene Sulfonyl group, 2-naphthalenesulfonyl group, phenylcarbonyl group, o-biphenylylcarbonyl group, m-biphenylylcarbonyl group, p-biphenylylcarbonyl group, 1-naphthylcarbonyl group, 2-naphthyl group Chill carbonyl group is preferred.

  The ring partial structure A in the formula (9), formula (10), formula (19) and formula (20) is represented by the following formula (a), formula (b), formula (c), formula (d), formula (E), Formula (f), Formula (g), Formula (h), Formula (i), Formula (j), Formula (k), Formula (l), Formula (m), Formula (n), Formula (O), formula (p), formula (q), formula (r), formula (s), formula (t), formula (u), formula (v), formula (w), formula (x), formula (Y), Formula (z), Formula (aa), Formula (ab), Formula (ac), Formula (ad), Formula (ae), Formula (af), Formula (ag), and Formula (ah)

It is expressed by either.

  The ring partial structure A in the formula (9), formula (10), formula (19) and formula (20) is represented by the following formula (a), formula (b), formula (i), formula (k), formula (O), Formula (p), Formula (s), Formula (v), Formula (y), Formula (ae), Formula (ag), Formula (ah)

Is preferred.

Formula (a), Formula (b), Formula (c), Formula (d), Formula (e), Formula (f), Formula (g), Formula (h), Formula (i), Formula (j) , Formula (k), Formula (l), Formula (m), Formula (n), Formula (o), Formula (p), Formula (q), Formula (r), Formula (s), Formula (t) , Formula (u), Formula (v), Formula (w), Formula (x), Formula (y), Formula (z), Formula (aa), Formula (ab), Formula (ac), Formula (ad) The substituents of R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ in formula (ae), formula (af), formula (ag) and formula (ah) will be described.

Formula (a), Formula (b), Formula (e), Formula (f), Formula (g), Formula (h), Formula (i), Formula (j), Formula (k), Formula (l) , Formula (m), Formula (n), Formula (p), Formula (q), Formula (v), Formula (w), Formula (x), Formula (ab), Formula (ae), Formula (af) And R ¹⁴ and R ^{15 in} formula (ag) are each independently a hydrogen atom, a C _1-6 alkyl group (the alkyl group is unsubstituted or a halogen atom, a C _1-6 alkoxy group). (The alkoxy group is unsubstituted or substituted with a halogen atom.), An amino group, a hydroxyl group, a C _6-14 aryl group (the aryl group is unsubstituted or q Substituent R ²⁰ (wherein R ²⁰ represents the same meaning as R ¹³ , q represents an integer of 1 to 3, and when q is 2 or 3, R ²⁰ may be the same or different). C _2-9 heteroaryl group (the heteroaryl group is unsubstituted or q substituents R ²⁰ (the R ²⁰ represents the same meaning as R ¹³ , q is 1 to Represents an integer of 3, and when q is 2 or 3, R ²⁰ may be the same or different.)), C _1-6 alkylaminocarbonyl group, diC _1-6 alkylamino A carbonyl group, a C _1-6 alkylcarbonyloxy group (the alkylcarbonyloxy group is unsubstituted or substituted with a halogen atom), a C _1-6 alkylcarbonyl group (the alkylcarbonyl group is either unsubstituted or substituted with a halogen atom.), C _1-6 alkylcarbonylamino group, C _3-8 cycloalkyl group (said cycloalkyl group is unsubstituted der Or substituted with halogen atoms.), C _1-6 alkoxycarbonyl group (the alkoxy group is substituted or unsubstituted, or a halogen atom.), C _1-4 alkylsulphonyl A group (the alkylsulfonyl group is unsubstituted or substituted with a halogen atom), a carboxyl group, a C _6-14 arylcarbonyl group (the arylcarbonyl group is unsubstituted or halogenated); Substituted with an atom) or a C _2-9 heteroarylcarbonyl group), a C _6-14 aryl group (the aryl group is unsubstituted or q substituents R ²⁰ (wherein R ²⁰ represents the same meaning as R ¹³ , q represents an integer of 1 to 3, and when q is 2 or 3, R ²⁰ may be the same or different. ). ), C _2-9 heteroaryl group (the heteroaryl group is unsubstituted or q substituents R ²⁰ (the R ²⁰ represents the same meaning as R ¹³ , q is an integer of 1 to 3) And when q is 2 or 3, R ²⁰ may be the same or different.)), A C _1-6 alkylaminocarbonyl group, a diC _1-6 alkylaminocarbonyl group, C _1-6 alkylcarbonyl group, C _3-8 cycloalkylcarbonyl group, C _1-6 alkoxycarbonyl group, C _1-4 alkylsulfonyl group (the alkylsulfonyl group is unsubstituted or substituted with a halogen atom) C _6-14 arylsulfonyl group (the arylsulfonyl group is unsubstituted or q substituents R ²⁰ (wherein R ²⁰ has the same meaning as R ¹³ , q is 1 ~ 3 Represents an integer, and when q is 2 or 3, R ²⁰ is substituted with or.) To be the same or different.), C _2-9 heteroarylsulfonyl group (the hetero arylsulfonyl group, an unsubstituted Or q substituents R ²⁰ (wherein R ²⁰ represents the same meaning as R ¹³ , q represents an integer of 1 to 3, and when q is 2 or 3, R ²⁰ is the same or different. Substituted), a carboxyl group, a C _6-14 arylcarbonyl group (the arylcarbonyl group is unsubstituted or q substituents R ²⁰ (the R ²⁰ is R) represents the same meaning as ^13, q represents an integer of 1 to 3, when q is 2 or ^{3, R 20} is substituted with or.) to be the same or different. or _{C 2-9} heteroaryl A carbonyl group (the heteroarylcarbonyl group is Or is unsubstituted, or q substituents, ^{R 20} (wherein ^{R 20} has the same meaning as ^{R 13,} q represents an integer of 1 to 3, when q is 2 or ^3, also ^{R 20} is the same May be different.) Is substituted with.

Formula (a), Formula (b), Formula (e), Formula (f), Formula (g), Formula (h), Formula (i), Formula (j), Formula (k), Formula (l) , Formula (m), Formula (n), Formula (p), Formula (q), Formula (v), Formula (w), Formula (x), Formula (ab), Formula (ae), Formula (af) And each substituent of R ¹⁴ and R ^{15 in} formula (ag) will be specifically described. The C _1-6 alkyl group includes a methyl group, a trifluoromethyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, n-pentyl group, 2-pentyl group, 3-pentyl group, i-pentyl group, neopentyl group, 2,2-dimethylpropyl group, n-hexyl group, 2-hexyl group, 3-hexyl group, 1-methyl- n-pentyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 3,3-dimethyl-n-butyl group, methylcarbonyloxymethyl group, ethylcarbonyl Oxymethyl group, methylcarbonyloxyethyl group, ethylcarbonyloxyethyl group, methylcarbonylaminomethyl group, trifluoromethylcarbonylaminomethyl group, ethylcarbo Examples include nylaminomethyl group, methylcarbonylaminoethyl group, ethylcarbonylaminoethyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, methoxycarbonylethyl group, and ethoxycarbonylethyl group. The C _6-14 aryl group is phenyl, o-biphenylyl, m-biphenylyl, p-biphenylyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl. Group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group and the like.

The C _2-9 heteroaryl group is a C _2-6 monocyclic heterocycle having 1 to 3 oxygen atoms, nitrogen atoms or sulfur atoms, which may contain 5 to 7 membered ring alone or in combination. C _5-9 fused bicyclic heterocyclic groups having up to 8-10 groups and constituent atoms are included. Examples of the C _2-6 monocyclic heterocyclic group having 5 to 7 members include a 2-thienyl group, a 3-thienyl group, a 2-furyl group, a 3-furyl group, a 2-pyranyl group, and a 3-pyranyl group. 4-pyranyl group, 1-pyrrolyl group, 2-pyrrolyl group, 3-pyrrolyl group, 1-imidazolyl group, 2-imidazolyl group, 4-imidazolyl group, 1-pyrazolyl group, 3-pyrazolyl group, 4-pyrazolyl group 2-thiazolyl group, 4-thiazolyl group, 5-thiazolyl group, 3-isothiazolyl group, 4-isothiazolyl group, 5-isothiazolyl group, 2-oxazolyl group, 4-oxazolyl group, 5-oxazolyl group, 3-isoxazolyl group 4-isoxazolyl group, 5-isoxazolyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-pyrazinyl group, 2-pyrimidinyl group, 4-pyridinyl group Midinyl group, 5-pyrimidinyl group, 3-pyridazinyl group, 4-pyridazinyl group, 2-1,3,4-oxadiazolyl group, 2-1,3,4-thiadiazolyl group, 3-1,2,4-oxadiazolyl group 5-1, 2, 4-oxadiazolyl group, 3-1, 2, 4-thiadiazolyl group, 5-1, 2, 4-thiadiazolyl group, 3-1, 2, 5-oxadiazolyl group, and 3-1, 2 , 5-thiadiazolyl group and the like, and the C _5-9 condensed bicyclic heterocyclic group having 8 to 10 constituent atoms includes 2-benzofuranyl group, 3-benzofuranyl group, 4-benzofuranyl group, 5 -Benzofuranyl group, 6-benzofuranyl group, 7-benzofuranyl group, 1-isobenzofuranyl group, 4-isobenzofuranyl group, 5-isobenzofuranyl group, 2-benzothienyl group, 3- Benzothienyl group, 4-benzothienyl group, 5-benzothienyl group, 6-benzothienyl group, 7-benzothienyl group, 1-isobenzothienyl group, 4-isobenzothienyl group, 5-isobenzothienyl group, 2 -Chromenyl group, 3-chromenyl group, 4-chromenyl group, 5-chromenyl group, 6-chromenyl group, 7-chromenyl group, 8-chromenyl group, 1-indolidinyl group, 2-indolidinyl group, 3-indolidinyl group, 5 -Indolidinyl group, 6-indolidinyl group, 7-indolidinyl group, 8-indolidinyl group, 1-isoindolyl group, 2-isoindolyl group, 4-isoindolyl group, 5-isoindolyl group, 1-indolyl group, 2-indolyl group, 3 -Indolyl group, 4-Indolyl group, 5-Indolyl group, 6-Indolyl group, 7-I Drill group, 1-indazolyl group, 2-indazolyl group, 3-indazolyl group, 4-indazolyl group, 5-indazolyl group, 6-indazolyl group, 7-indazolyl group, 1-purinyl group, 2-purinyl group, 3- Purinyl group, 6-purinyl group, 7-purinyl group, 8-purinyl group, 2-quinolyl group, 3-quinolyl group, 4-quinolyl group, 5-quinolyl group, 6-quinolyl group, 7-quinolyl group, 8- Quinolyl group, 1-isoquinolyl group, 3-isoquinolyl group, 4-isoquinolyl group, 5-isoquinolyl group, 6-isoquinolyl group, 7-isoquinolyl group, 8-isoquinolyl group, 1-phthalazinyl group, 5-phthalazinyl group, 6- Phthalazinyl group, 1-2,7-naphthyridinyl group, 3-2,7-naphthyridinyl group, 4-2,7-naphthyridinyl group, 1-2,6-naphth Ridinyl group, 3-2,6-naphthyridinyl group, 4-2,6-naphthyridinyl group, 2-1,8-naphthyridinyl group, 3-1,8-naphthyridinyl group, 4-1,8-naphthyridinyl group, 2- 1,7-naphthyridinyl group, 3-1,7-naphthyridinyl group, 4-1,7-naphthyridinyl group, 5-1,7-naphthyridinyl group, 6-1,7-naphthyridinyl group, 8-1,7-naphthyridinyl group Group, 2-1,6-naphthyridinyl group, 3-1,6-naphthyridinyl group, 4-1,6-naphthyridinyl group, 5-1,6-naphthyridinyl group, 7-1,6-naphthyridinyl group, 8-1 , 6-Naphthyridinyl group, 2-1,5-naphthyridinyl group, 3-1,5-naphthyridinyl group, 4-1,5-naphthyridinyl group, 6-1,5-naphthyridinyl group, 7-1,5-naphthyridinyl group Group, 8-1,5-naphthyridinyl group, 2-quinoxalinyl group, 5-quinoxalinyl group, 6-quinoxalinyl group, 2-quinazolinyl group, 4-quinazolinyl group, 5-quinazolinyl group, 6-quinazolinyl group, 7-quinazolinyl group Group, 8-quinazolinyl group, 3-cinnolinyl group, 4-cinnolinyl group, 5-cinnolinyl group, 6-cinnolinyl group, 7-cinnolinyl group, 8-cinnolinyl group, 2-pteridinyl group, 4-pteridinyl group, 6-pteridinyl group Group, 7-pteridinyl group and the like.

The C _1-6 alkylaminocarbonyl group includes a methylaminocarbonyl group, an ethylaminocarbonyl group, an n-propylaminocarbonyl group, an i-propylaminocarbonyl group, an n-butylaminocarbonyl group, an i-butylaminocarbonyl group, an s -Butylaminocarbonyl group, t-butylaminocarbonyl group, 1-pentylaminocarbonyl group, 2-pentylaminocarbonyl group, 3-pentylaminocarbonyl group, i-pentylaminocarbonyl group, neopentylaminocarbonyl group, t-pentyl Examples include an aminocarbonyl group, 1-hexylaminocarbonyl group, 2-hexylaminocarbonyl group, and 3-hexylaminocarbonyl group. The diC _1-6 alkylaminocarbonyl group includes a dimethylaminocarbonyl group, a bis (trifluoromethyl) aminocarbonyl group, a diethylaminocarbonyl group, a di-n-propylaminocarbonyl group, a di-i-propylaminocarbonyl group, a di- -C-propylaminocarbonyl group, di-n-butylaminocarbonyl group, di-i-butylaminocarbonyl group, di-s-butylaminocarbonyl group, di-t-butylaminocarbonyl group, di-c-butylamino Carbonyl group, di-1-pentylaminocarbonyl group, di-2-pentylaminocarbonyl group, di-3-pentylaminocarbonyl group, di-i-pentylaminocarbonyl group, di-neopentylaminocarbonyl group, di-t -Pentylaminocarbonyl group, di-c-pentylaminocarbo Nyl group, di-1-hexylaminocarbonyl group, di-2-hexylaminocarbonyl group, di-3-hexylaminocarbonyl group, di-c-hexylaminocarbonyl group, bis (1-methyl-n-pentyl) amino Carbonyl group, bis (1,1,2-trimethyl-n-propyl) aminocarbonyl group, bis (1,2,2-trimethyl-n-propyl) aminocarbonyl group, bis (3,3-dimethyl-n-butyl) ) Aminocarbonyl group, (methylethyl) aminocarbonyl group, (ethyl) trifluoromethylaminocarbonyl group, methyl-n-propylaminocarbonyl group, methyl-i-propylaminocarbonyl group, methyl-c-propylaminocarbonyl group, n-butylmethylaminocarbonyl group, i-butylmethylaminocarbonyl group, s Butylmethylaminocarbonyl group, t-butylmethylaminocarbonyl group, c-butylmethylaminocarbonyl group, ethyl-n-propylaminocarbonyl group, ethyl-i-propylaminocarbonyl group, ethyl-c-propylaminocarbonyl group, n -Butylethylaminocarbonyl group, i-butylethylaminocarbonyl group, s-butylethylaminocarbonyl group, t-butylethylaminocarbonyl group, c-butylethylaminocarbonyl group, n-propyl-i-propylaminocarbonyl group, n-propyl-c-propylaminocarbonyl group, n-butyl-n-propylaminocarbonyl group, i-butyl-n-propylaminocarbonyl group, s-butyl-n-propylaminocarbonyl group, t-butyl-n- Propylaminocarbo Group, c-butyl-n-propylaminocarbonyl group, i-propyl-c-propylaminocarbonyl group, n-butyl-i-propylaminocarbonyl group, i-butyl-i-propylaminocarbonyl group, s-butyl -I-propylaminocarbonyl group, t-butyl-i-propylaminocarbonyl group, c-butyl-i-propylaminocarbonyl group, n-butyl-c-propylaminocarbonyl group, i-butyl-c-propylaminocarbonyl group Group, s-butyl-c-propylaminocarbonyl group, t-butyl-c-propylaminocarbonyl group, c-butyl-c-propylaminocarbonyl group, n-butyl-i-butylaminocarbonyl group, n-butyl- s-butylaminocarbonyl group, n-butyl-t-butylaminocarbonyl group, n- Butyl-c-butylaminocarbonyl group, i-butyl-s-butylaminocarbonyl group, i-butyl-t-butylaminocarbonyl group, i-butyl-c-butylaminocarbonyl group, s-butyl-t-butylamino Examples include a carbonyl group, a s-butyl-c-butylaminocarbonyl group, and a t-butyl-c-butylaminocarbonyl group. The C _1-6 alkylcarbonyl group includes methylcarbonyl group, ethylcarbonyl group, n-propylcarbonyl group, i-propylcarbonyl group, n-butylcarbonyl group, i-butylcarbonyl group, s-butylcarbonyl group, t- Butylcarbonyl group, 1-pentylcarbonyl group, 2-pentylcarbonyl group, 3-pentylcarbonyl group, i-pentylcarbonyl group, neopentylcarbonyl group, t-pentylcarbonyl group, 1-hexylcarbonyl group, 2-hexylcarbonyl group , And 3-hexylcarbonyl group. The C _3-8 cycloalkylcarbonyl group includes a c-propylcarbonyl group, a c-butylcarbonyl group, a 1-methyl-c-propylcarbonyl group, a 2-methyl-c-propylcarbonyl group, a c-pentylcarbonyl group, 1 -Methyl-c-butylcarbonyl group, 2-methyl-c-butylcarbonyl group, 3-methyl-c-butylcarbonyl group, 1,2-dimethyl-c-propylcarbonyl group, 2,3-dimethyl-c-propyl Carbonyl group, 1-ethyl-c-propylcarbonyl group, 2-ethyl-c-propylcarbonyl group, c-hexylcarbonyl group, c-heptylcarbonyl group, c-octylcarbonyl group, 1-methyl-c-hexylcarbonyl group 2-methyl-c-hexylcarbonyl group, 3-methyl-c-hexylcarbonyl group, 1,2-di Methyl-c-hexylcarbonyl group, 2,3-dimethyl-c-propylcarbonyl group, 1-ethyl-c-propylcarbonyl group, 1-methyl-c-pentylcarbonyl group, 2-methyl-c-pentylcarbonyl group, 3-methyl-c-pentylcarbonyl group, 1-ethyl-c-butylcarbonyl group, 2-ethyl-c-butylcarbonyl group, 3-ethyl-c-butylcarbonyl group, 1,2-dimethyl-c-butylcarbonyl Group, 1,3-dimethyl-c-butylcarbonyl group, 2,2-dimethyl-c-butylcarbonyl group, 2,3-dimethyl-c-butylcarbonyl group, 2,4-dimethyl-c-butylcarbonyl group, 3,3-dimethyl-c-butylcarbonyl group, 1-n-propyl-c-propylcarbonyl group, 2-n-propyl-c-propyl group Bonyl group, 1-i-propyl-c-propylcarbonyl group, 2-i-propyl-c-propylcarbonyl group, 1,2,2-trimethyl-c-propylcarbonyl group, 1,2,3-trimethyl-c -Propylcarbonyl group, 2,2,3-trimethyl-c-propylcarbonyl group, 1-ethyl-2-methyl-c-propylcarbonyl group, 2-ethyl-1-methyl-c-propylcarbonyl group, 2-ethyl -2-methyl-c-propylcarbonyl group, 2-ethyl-3-methyl-c-propylcarbonyl group and the like. The C _1-6 alkoxycarbonyl group includes a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an i-propoxycarbonyl group, an n-butoxycarbonyl group, an i-butoxycarbonyl group, an s-butoxycarbonyl group, a t- Butoxycarbonyl group, 1-pentyloxycarbonyl group, 2-pentyloxycarbonyl group, 3-pentyloxycarbonyl group, i-pentyloxycarbonyl group, neopentyloxycarbonyl group, t-pentyloxycarbonyl group, 1-hexyloxycarbonyl Group, 2-hexyloxycarbonyl group, 3-hexyloxycarbonyl group and the like.

The C _1-4 alkylsulfonyl group includes a methanesulfonyl group, a trifluoromethanesulfonyl group, an ethanesulfonyl group, an n-propanesulfonyl group, an i-propanesulfonyl group, an n-butanesulfonyl group, an i-butanesulfonyl group, and an s-butane. A sulfonyl group, a t-butanesulfonyl group, etc. are mentioned. The C _6-14 arylsulfonyl group includes a benzenesulfonyl group, an o-biphenylsulfonyl group, an m-biphenylsulfonyl group, a p-biphenylsulfonyl group, a 1-naphthalenesulfonyl group, a 2-naphthalenesulfonyl group, and a 1-anthracenesulfonyl group. 2-anthracenesulfonyl group, 9-anthracenesulfonyl group, 1-phenanthrenesulfonyl group, 2-phenanthrenesulfonyl group, 3-phenanthrenesulfonyl group, 4-phenanthrenesulfonyl group, 9-phenanthrenesulfonyl group, and the like. The C _2-9 heteroarylsulfonyl group may contain 1 to 3 oxygen atoms, nitrogen atoms or sulfur atoms, alone or in combination up to 5 to 7 membered C _2-6 monocyclic heterocycle Ring sulfonyl groups and C _5-9 fused bicyclic heterocyclic sulfonyl groups with up to 8-10 constituent atoms are included. Examples of the C _2-6 monocyclic heterocyclic sulfonyl group up to 5 to 7-membered ring include 2-thienylsulfonyl group, 3-thienylsulfonyl group, 2-furylsulfonyl group, 3-furylsulfonyl group, 2-pyranyl. Sulfonyl group, 3-pyranylsulfonyl group, 4-pyranylsulfonyl group, 1-pyrrolylsulfonyl group, 2-pyrrolylsulfonyl group, 3-pyrrolylsulfonyl group, 1-imidazolylsulfonyl group, 2-imidazolylsulfonyl group, 4-imidazolylsulfonyl group, 1-pyrazolylsulfonyl group, 3-pyrazolylsulfonyl group, 4-pyrazolylsulfonyl group, 2-thiazolylsulfonyl group, 4-thiazolylsulfonyl group, 5-thiazolylsulfonyl group, 3- Isothiazolylsulfonyl group, 4-isothiazolylsulfonyl group, 5-isothiazolylsulfonyl group Group, 2-oxazolylsulfonyl group, 4-oxazolylsulfonyl group, 5-oxazolylsulfonyl group, 3-isoxazolylsulfonyl group, 4-isoxazolylsulfonyl group, 5-isoxazolyl Sulfonyl group, 2-pyridylsulfonyl group, 3-pyridylsulfonyl group, 4-pyridylsulfonyl group, 2-pyrazinylsulfonyl group, 2-pyrimidinylsulfonyl group, 4-pyrimidinylsulfonyl group, 5-pyrimidinylsulfonyl group, 3-pyridinylsulfonyl group Dazinylsulfonyl group, 4-pyridazinylsulfonyl group, 2-1,3,4-oxadiazolylsulfonyl group, 2-1,3,4-thiadiazolylsulfonyl group, 3-1,2,4 -Oxadiazolylsulfonyl group, 5-1,2,4-oxadiazolylsulfonyl group, 3-1,2,4-thiadiazolyl group Examples include phonyl group, 5-1,2,4-thiadiazolylsulfonyl group, 3-1,2,5-oxadiazolylsulfonyl group, 3-1,2,5-thiadiazolylsulfonyl group, and the like. Examples of the C _5-9 condensed bicyclic heterocyclic sulfonyl group having 8 to 10 atoms include 2-benzofuranylsulfonyl group, 3-benzofuranylsulfonyl group, 4-benzofuranylsulfonyl group, 5- Benzofuranylsulfonyl group, 6-benzofuranylsulfonyl group, 7-benzofuranylsulfonyl group, 1-isobenzofuranylsulfonyl group, 4-isobenzofuranylsulfonyl group, 5-isobenzofuranylsulfonyl group, 2 -Benzothienylsulfonyl group, 3-benzothienylsulfonyl group, 4-benzothienylsulfonyl group, 5-benzothienylsulfonyl group, 6- Nzothienylsulfonyl group, 7-benzothienylsulfonyl group, 1-isobenzothienylsulfonyl group, 4-isobenzothienylsulfonyl group, 5-isobenzothienylsulfonyl group, 2-chromenylsulfonyl group, 3-chromenylsulfonyl group 4-chromenylsulfonyl group, 5-chromenylsulfonyl group, 6-chromenylsulfonyl group, 7-chromenylsulfonyl group, 8-chromenylsulfonyl group, 1-indolidinylsulfonyl group, 2-indolidinylsulfonyl group Group, 3-indolidinylsulfonyl group, 5-indolidinylsulfonyl group, 6-indolidinylsulfonyl group, 7-indolidinylsulfonyl group, 8-indolidinylsulfonyl group, 1-isoindolylsulfonyl group, 2-isoindolylsulfonyl group, 4-isoindo Rusulfonyl group, 5-isoindolylsulfonyl group, 1-indolylsulfonyl group, 2-indolylsulfonyl group, 3-indolylsulfonyl group, 4-indolylsulfonyl group, 5-indolylsulfonyl group, 6-in Drillsulfonyl group, 7-indolylsulfonyl group, 1-indazolylsulfonyl group, 2-indazolylsulfonyl group, 3-indazolylsulfonyl group, 4-indazolylsulfonyl group, 5-indazolylsulfonyl group 6-indazolylsulfonyl group, 7-indazolylsulfonyl group, 1-prinylsulfonyl group, 2-prinylsulfonyl group, 3-prinylsulfonyl group, 6-purinylsulfonyl group, 7-prinylsulfonyl group Group, 8-purinylsulfonyl group, 2-quinolylsulfonyl group, 3-quinolylsulfonyl group, 4- Quinolylsulfonyl group, 5-quinolylsulfonyl group, 6-quinolylsulfonyl group, 7-quinolylsulfonyl group, 8-quinolylsulfonyl group, 1-isoquinolylsulfonyl group, 3-isoquinolylsulfonyl group, 4 -Isoquinolylsulfonyl group, 5-isoquinolylsulfonyl group, 6-isoquinolylsulfonyl group, 7-isoquinolylsulfonyl group, 8-isoquinolylsulfonyl group, 1-phthalazinylsulfonyl group, 5-phthal Razinylsulfonyl group, 6-phthalazinylsulfonyl group, 1-2,7-naphthyridinylsulfonyl group, 3-2,7-naphthyridinylsulfonyl group, 4-2,7-naphthyridinylsulfonyl group, 1 -2,6-naphthyridinylsulfonyl group, 3-2,6-naphthyridinylsulfonyl group, 4-2,6-naphthyridinylsulfonyl group, -1,8-naphthyridinylsulfonyl group, 3-1,8-naphthyridinylsulfonyl group, 4-1,8-naphthyridinylsulfonyl group, 2-1,7-naphthyridinylsulfonyl group, 3-1 , 7-naphthyridinylsulfonyl group, 4-1,7-naphthyridinylsulfonyl group, 5-1,7-naphthyridinylsulfonyl group, 6-1,7-naphthyridinylsulfonyl group, 8-1,7 -Naphthyridinylsulfonyl group, 2-1,6-naphthyridinylsulfonyl group, 3-1,6-naphthyridinylsulfonyl group, 4-1,6-naphthyridinylsulfonyl group, 5-1,6-naphthy Lydinylsulfonyl group, 7-1,6-naphthyridinylsulfonyl group, 8-1,6-naphthyridinylsulfonyl group, 2-1,5-naphthyridinylsulfonyl group, 3-1,5-naphthyridinyl Sulfonyl group, 4-1,5-naphthyridinylsulfonyl group, 6-1,5-naphthyridinylsulfonyl group, 7-1,5-naphthyridinylsulfonyl group, 8-1,5-naphthyridinylsulfonyl group 2-quinoxalinylsulfonyl group, 5-quinoxalinylsulfonyl group, 6-quinoxalinylsulfonyl group, 2-quinazolinylsulfonyl group, 4-quinazolinylsulfonyl group, 5-quinazolinylsulfonyl group Group, 6-quinazolinylsulfonyl group, 7-quinazolinylsulfonyl group, 8-quinazolinylsulfonyl group, 3-cinnolinylsulfonyl group, 4-cinnolinylsulfonyl group, 5-cinnolinylsulfonyl group, 6-cinnolinylsulfonyl group, 7-cinnolinylsulfonyl group, 8-cinnolinylsulfonyl group, 2-pteridinylsulfonyl group, 4-pte Examples thereof include a lysinylsulfonyl group, a 6-pteridinylsulfonyl group, and a 7-pteridinylsulfonyl group.

The C _6-14 arylcarbonyl group is a phenylcarbonyl group, o-biphenylylcarbonyl group, m-biphenylylcarbonyl group, p-biphenylylcarbonyl group, 1-naphthylcarbonyl group, 2-naphthylcarbonyl group, 1-anthone. Tolylcarbonyl group, 2-anthrylcarbonyl group, 9-anthrylcarbonyl group, 1-phenanthrylcarbonyl group, 2-phenanthrylcarbonyl group, 3-phenanthrylcarbonyl group, 4-phenanthrylcarbonyl group, And 9-phenanthrylcarbonyl group. The C _2-9 heteroarylcarbonyl group may contain 1 to 3 oxygen atoms, nitrogen atoms or sulfur atoms, alone or in combination up to 5 to 7 membered C _2-6 monocyclic heterocycle A ring carbonyl group and a C _5-9 fused bicyclic heterocyclic carbonyl group having 8 to 10 member atoms are included. Examples of the C _2-6 monocyclic heterocyclic carbonyl group having 5 to 7 members include 2-thienylcarbonyl group, 3-thienylcarbonyl group, 2-furylcarbonyl group, 3-furylcarbonyl group, 2-pyranyl. Carbonyl group, 3-pyranylcarbonyl group, 4-pyranylcarbonyl group, 1-pyrrolylcarbonyl group, 2-pyrrolylcarbonyl group, 3-pyrrolylcarbonyl group, 1-imidazolylcarbonyl group, 2-imidazolylcarbonyl group, 4-imidazolylcarbonyl group, 1-pyrazolylcarbonyl group, 3-pyrazolylcarbonyl group, 4-pyrazolylcarbonyl group, 2-thiazolylcarbonyl group, 4-thiazolylcarbonyl group, 5-thiazolylcarbonyl group, 3- Isothiazolylcarbonyl group, 4-isothiazolylcarbonyl group, 5-isothiazolylcarbonyl group Group, 2-oxazolylcarbonyl group, 4-oxazolylcarbonyl group, 5-oxazolylcarbonyl group, 3-isoxazolylcarbonyl group, 4-isoxazolylcarbonyl group, 5-isoxazolyl Carbonyl group, 2-pyridylcarbonyl group, 3-pyridylcarbonyl group, 4-pyridylcarbonyl group, 2-pyrazinylcarbonyl group, 2-pyrimidinylcarbonyl group, 4-pyrimidinylcarbonyl group, 5-pyrimidinylcarbonyl group, 3-pyridinylcarbonyl group Dazinylcarbonyl group, 4-pyridazinylcarbonyl group, 2-1,3,4-oxadiazolylcarbonyl group, 2-1,3,4-thiadiazolylcarbonyl group, 3-1,2,4 -Oxadiazolylcarbonyl group, 5-1,2,4-oxadiazolylcarbonyl group, 3-1,2,4-thiadiazolylca Bonyl group, 5-1,2,4-thiadiazolylcarbonyl group, 3-1,2,5-oxadiazolylcarbonyl group, 3-1,2,5-thiadiazolylcarbonyl group, etc. Examples of the C _5-9 condensed bicyclic heterocyclic carbonyl group having 8 to 10 constituent atoms include 2-benzofuranylcarbonyl group, 3-benzofuranylcarbonyl group, 4-benzofuranylcarbonyl group, 5 -Benzofuranylcarbonyl group, 6-benzofuranylcarbonyl group, 7-benzofuranylcarbonyl group, 1-isobenzofuranylcarbonyl group, 4-isobenzofuranylcarbonyl group, 5-isobenzofuranylcarbonyl group, 2-benzothienylcarbonyl group, 3-benzothienylcarbonyl group, 4-benzothienylcarbonyl group, 5-benzothienylcarbonyl group, 6 Benzothienylcarbonyl group, 7-benzothienylcarbonyl group, 1-isobenzothienylcarbonyl group, 4-isobenzothienylcarbonyl group, 5-isobenzothienylcarbonyl group, 2-chromenylcarbonyl group, 3-chromenylcarbonyl group, 4-chromenylcarbonyl group, 5-chromenylcarbonyl group, 6-chromenylcarbonyl group, 7-chromenylcarbonyl group, 8-chromenylcarbonyl group, 1-indolidinylcarbonyl group, 2-indolidinylcarbonyl group 3-indolidinylcarbonyl group, 5-indolidinylcarbonyl group, 6-indolidinylcarbonyl group, 7-indolidinylcarbonyl group, 8-indolidinylcarbonyl group, 1-isoindolylcarbonyl group, 2 -Isoindolylcarbonyl group, 4-isoin Rylcarbonyl group, 5-isoindolylcarbonyl group, 1-indolylcarbonyl group, 2-indolylcarbonyl group, 3-indolylcarbonyl group, 4-indolylcarbonyl group, 5-indolylcarbonyl group, 6-in Drillcarbonyl group, 7-indolylcarbonyl group, 1-indazolylcarbonyl group, 2-indazolylcarbonyl group, 3-indazolylcarbonyl group, 4-indazolylcarbonyl group, 5-indazolylcarbonyl group 6-indazolylcarbonyl group, 7-indazolylcarbonyl group, 1-purinylcarbonyl group, 2-prinylcarbonyl group, 3-prinylcarbonyl group, 6-purinylcarbonyl group, 7-prinylcarbonyl group Group, 8-purinylcarbonyl group, 2-quinolylcarbonyl group, 3-quinolylcarbonyl group, 4 -Quinolylcarbonyl group, 5-quinolylcarbonyl group, 6-quinolylcarbonyl group, 7-quinolylcarbonyl group, 8-quinolylcarbonyl group, 1-isoquinolylcarbonyl group, 3-isoquinolylcarbonyl group, 4-isoquinolylcarbonyl group, 5-isoquinolylcarbonyl group, 6-isoquinolylcarbonyl group, 7-isoquinolylcarbonyl group, 8-isoquinolylcarbonyl group, 1-phthalazinylcarbonyl group, 5- Phthalazinylcarbonyl group, 6-phthalazinylcarbonyl group, 1-2,7-naphthyridinylcarbonyl group, 3-2,7-naphthyridinylcarbonyl group, 4-2,7-naphthyridinylcarbonyl group, 1-2,6-naphthyridinylcarbonyl group, 3-2,6-naphthyridinylcarbonyl group, 4-2,6-naphthyridinylcarbonyl group 2-1,8-naphthyridinylcarbonyl group, 3-1,8-naphthyridinylcarbonyl group, 4-1,8-naphthyridinylcarbonyl group, 2-1,7-naphthyridinylcarbonyl group, 3- 1,7-naphthyridinylcarbonyl group, 4-1,7-naphthyridinylcarbonyl group, 5-1,7-naphthyridinylcarbonyl group, 6-1,7-naphthyridinylcarbonyl group, 8-1, 7-naphthyridinylcarbonyl group, 2-1,6-naphthyridinylcarbonyl group, 3-1,6-naphthyridinylcarbonyl group, 4-1,6-naphthyridinylcarbonyl group, 5-1,6- Naphthyridinylcarbonyl group, 7-1,6-naphthyridinylcarbonyl group, 8-1,6-naphthyridinylcarbonyl group, 2-1,5-naphthyridinylcarbonyl group, 3-1,5-naphthyridinyl group Carbonyl group, 4-1,5-naphthyridinylcarbonyl group, 6-1,5-naphthyridinylcarbonyl group, 7-1,5-naphthyridinylcarbonyl group, 8-1,5-naphthyridinylcarbonyl group 2-quinoxalinylcarbonyl group, 5-quinoxalinylcarbonyl group, 6-quinoxalinylcarbonyl group, 2-quinazolinylcarbonyl group, 4-quinazolinylcarbonyl group, 5-quinazolinylcarbonyl group Group, 6-quinazolinylcarbonyl group, 7-quinazolinylcarbonyl group, 8-quinazolinylcarbonyl group, 3-cinnolinylcarbonyl group, 4-cinnolinylcarbonyl group, 5-cinnolinylcarbonyl group, 6-cinnolinylcarbonyl group, 7-cinnolinylcarbonyl group, 8-cinnolinylcarbonyl group, 2-pteridinylcarbonyl group, 4-propyl Teridinylcarbonyl group, 6-pteridinylcarbonyl group, 7-pteridinylcarbonyl group and the like can be mentioned.

Formula (a), Formula (b), Formula (e), Formula (f), Formula (g), Formula (h), Formula (i), Formula (j), Formula (k), Formula (l) , Formula (m), Formula (n), Formula (p), Formula (q), Formula (v), Formula (w), Formula (x), Formula (ab), Formula (ae), Formula (af) And R ¹⁴ and R ^{15 in} formula (ag) are each independently a hydrogen atom, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, n-pentyl group, i- Pentyl group, methylcarbonyloxymethyl group, ethylcarbonyloxymethyl group, methylcarbonyloxyethyl group, ethylcarbonyloxyethyl group, methylcarbonylaminomethyl group, ethylcarbonylaminoethyl group, methylcarbonylaminoethyl group, ethylcarbonylaminoethyl group , Methoxycarbonylmethyl group, ethoxy Rubonylmethyl group, methoxycarbonylethyl group, ethoxycarbonylethyl group, phenyl group, o-biphenylyl group, m-biphenylyl group, p-biphenylyl group, 1-naphthyl group, 2-naphthyl group, 2-pyridyl group, 3-pyridyl group Group, 4-pyridyl group, methylaminocarbonyl group, ethylaminocarbonyl group, n-propylaminocarbonyl group, i-propylaminocarbonyl group, n-butylaminocarbonyl group, dimethylaminocarbonyl group, diethylaminocarbonyl group, di-n -Propylaminocarbonyl group, di-i-propylaminocarbonyl group, di-c-propylaminocarbonyl group, di-n-butylaminocarbonyl group, methylcarbonyl group, ethylcarbonyl group, n-propylcarbonyl group, i-propyl Carbonyl group, n- Butylcarbonyl group, c-pentylcarbonyl group, c-hexylcarbonyl group, methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, i-propoxycarbonyl group, n-butoxycarbonyl group, i-butoxycarbonyl group, s- Butoxycarbonyl group, t-butoxycarbonyl group, methanesulfonyl group, trifluoromethanesulfonyl group, benzenesulfonyl group, o-biphenylsulfonyl group, m-biphenylsulfonyl group, p-biphenylsulfonyl group, 1-naphthalenesulfonyl group, 2-naphthalene Sulfonyl group, 2-pyridylsulfonyl group, 3-pyridylsulfonyl group, 4-pyridylsulfonyl group, phenylcarbonyl group, o-biphenylylcarbonyl group, m-biphenylylcarbonyl group, p-biphenylyl Carbonyl group, 1-naphthyl group, 2-naphthyl group, 2-pyridylcarbonyl group, 3-pyridylcarbonyl group, 4-pyridylcarbonyl group.

Formula (a), Formula (b), Formula (e), Formula (f), Formula (g), Formula (h), Formula (i), Formula (j), Formula (k), Formula (l) , Formula (m), Formula (n), Formula (p), Formula (q), Formula (v), Formula (w), Formula (x), Formula (ab), Formula (ae), Formula (af) And R ¹⁴ and R ^{15 in} formula (ag) are each independently a hydrogen atom, a methyl group, a trifluoromethyl group, a methoxymethyl group, an ethyl group, an n-propyl group, an i-propyl group, or n-butyl. A group, n-pentyl group, i-pentyl group, amino group and hydroxyl group are more preferred.

Formula (a), Formula (b), Formula (c), Formula (d), Formula (f), Formula (g), Formula (h), Formula (j), Formula (k), Formula (m) , Formula (n), Formula (o), Formula (p), Formula (q), Formula (r), Formula (s), Formula (t), Formula (u), Formula (v), Formula (w) R ¹⁶ , R ¹⁷ , R ¹⁸ in formula (y), formula (z), formula (aa), formula (ab), formula (ac), formula (ad), formula (ae), and formula (af). And R ¹⁹ are each independently a hydrogen atom, a halogen atom, a C _1-6 alkyl group (the alkyl group is unsubstituted or a halogen atom, a C _1-6 alkoxy group (the alkoxy group is Substituted, or substituted with a halogen atom), an amino group, a hydroxyl group, a C _6-14 aryl group (the aryl group is unsubstituted or r substituents R ²¹ (the R ²¹ is the same as R ¹³ And r represents the same meaning as q.)), A C _2-9 heteroaryl group (the heteroaryl group is unsubstituted or r substituents R ^21. (Wherein R ²¹ represents the same meaning as R ¹³ and r represents the same meaning as q).), A C _1-6 alkylaminocarbonyl group, a diC _1-6 alkylaminocarbonyl group, A C _1-6 alkylcarbonyloxy group (the alkylcarbonyloxy group is unsubstituted or substituted with a halogen atom), a C _1-6 alkylcarbonyl group (the alkylcarbonyl group is unsubstituted) substituted with some or halogen atom.), C _1-6 alkylcarbonylamino group, C _3-8 cycloalkyl group (said cycloalkyl group is unsubstituted, or Substituted with halogen atoms.), C _1-6 alkoxycarbonyl group (the alkoxy group is substituted or unsubstituted, or a halogen atom.), C _1-4 alkylsulfonyl group (the The alkylsulfonyl group is unsubstituted or substituted with a halogen atom.), A carboxyl group, a C _6-14 arylcarbonyl group (the arylcarbonyl group is unsubstituted or substituted with a halogen atom) Or substituted with a C _2-9 heteroarylcarbonyl group), a C _3-8 cycloalkyl group (the cycloalkyl group is unsubstituted or a halogen atom, C _1-6 An alkoxy group (the alkoxy group is unsubstituted or substituted with a halogen atom), substituted with an amino group or a hydroxyl group . ), C _1-6 alkoxy group (the alkoxy group is unsubstituted or substituted with a halogen atom, C _1-6 alkoxy group (the alkoxy group is unsubstituted or substituted with a halogen atom) ), A carboxyl group, an amino group, a hydroxyl group, a C _6-14 aryl group (the aryl group is unsubstituted or r substituents R ²¹ (the R ²¹ represents the same meaning as R ¹³ ; r represents the same meaning as q.) or a C _2-9 heteroaryl group (the heteroaryl group is unsubstituted or has r substituents R ²¹ (the R ²¹ Represents the same meaning as R ^13, and r represents the same meaning as q).)), C _1-6 thioalkoxy group (the thioalkoxy group is unsubstituted) or is, or halogen _{atom, C 1-6} Al Alkoxy group (said alkoxy group is unsubstituted or substituted by halogen atom.), A carboxyl group, a hydroxyl group, or a C _6-14 aryl group (the aryl group is unsubstituted, or r Or a C _2-9 heteroaryl group (the heteroaryl group is substituted with R ²¹ (the R ²¹ has the same meaning as R ¹³ and r has the same meaning as q)). Is unsubstituted or substituted with r substituents R ²¹ (wherein R ²¹ has the same meaning as R ¹³ and r has the same meaning as q). ), A hydroxyl group, a C _6-14 aryl group (the aryl group is unsubstituted or r substituents R ²¹ (the R ²¹ has the same meaning as R ¹³ , r is the same as q) is substituted in the sense represents _{a.).), C 2-9} heteroaryl group The heteroaryl group is unsubstituted, or the r substituents R ^{21 (wherein} R ²¹ has the same meaning as R ^13, r represents. The same meaning as q) is substituted with.) , C _1-6 alkylcarbonyloxy group, nitro group, cyano group, formyl group, formamide group, amino group, sulfo group, C _1-6 alkylamino group, diC _1-6 alkylamino group, C _6-14 aryl An amino group (the arylamino group is unsubstituted or substituted with r substituents R ²¹ (the R ²¹ has the same meaning as R ¹³ and r has the same meaning as q)); C _2-9 heteroarylamino group (the heteroarylamino group is unsubstituted or r substituents R ²¹ (wherein R ²¹ has the same meaning as R ¹³ , r is q Means the same. ). ), C _1-6 alkylcarbonylamino group, C _1-6 alkylsulfonamido group, carbamoyl group, C _1-6 alkylaminocarbonyl group, diC _1-6 alkylaminocarbonyl group, C _1-6 alkylcarbonyl group, C _6-14 arylcarbonyl group (the arylcarbonyl group is unsubstituted or r substituents R ²¹ (wherein R ²¹ represents the same meaning as R ^13, and r represents the same meaning as q). ), A C _2-9 heteroarylcarbonyl group (the heteroarylcarbonyl group is unsubstituted or r substituents R ²¹ (the R ²¹ has the same meaning as R ^13). represents, r is substituted with representing.) the same meaning as _{q.), C 1-6} alkoxycarbonyl group, a sulfamoyl _{group, C 1-4} alkylsulfonyl group (the alkyl Ruhoniru group is substituted or unsubstituted, or a halogen atom.), C _6-14 arylsulfonyl group (the aryl sulfonyl group is unsubstituted, or the r substituents R ²¹ ( R ²¹ represents the same meaning as R ^13, and r represents the same meaning as q.)), C _2-9 heteroarylsulfonyl group (the heteroarylsulfonyl group is unsubstituted) Or r substituents R ²¹ (wherein R ²¹ represents the same meaning as R ¹³ and r represents the same meaning as q)), a carboxyl group, or C _2-9 non- Aromatic heterocyclyl group (the non-aromatic heterocyclyl group is unsubstituted or is a halogen atom or a C _1-6 alkyl group (the alkyl group is unsubstituted or is a halogen atom, C _1-6 Alkoxy group ( Alkoxy groups are substituted or unsubstituted, or a halogen atom.), An amino group is substituted with a carboxyl group or a hydroxyl group.), C _1-6 alkoxy group (said alkoxy group is unsubstituted Or substituted with a halogen atom), a C _6-14 aryl group (wherein the aryl group is unsubstituted or r substituents R ²¹ (the R ²¹ is the same as R ¹³⁾⁾ And r represents the same meaning as q.), C _2-9 heteroaryl group (the heteroaryl group is unsubstituted or r substituents R ^21. (Wherein R ²¹ represents the same meaning as R ¹³ and r represents the same meaning as q).), Hydroxyl group, nitro group, cyano group, formyl group, formamide group, amino group, C _{1 -6} alkylamino group, di _{C 1-6} Alkylamino _{group, C 1-6} alkylcarbonylamino _{group, C 1-6} alkyl sulfonamido group, a carbamoyl _{group, C 1-6} alkylaminocarbonyl group, di _{C 1-6} alkylaminocarbonyl _{group, C 1-6} alkylcarbonyl group , A C _1-6 alkoxycarbonyl group, a sulfamoyl group, a C _1-4 alkylsulfonyl group, a carboxyl group, or a C _6-14 arylcarbonyl group. )

Formula (a), Formula (b), Formula (c), Formula (d), Formula (f), Formula (g), Formula (h), Formula (j), Formula (k), Formula (m) , Formula (n), Formula (o), Formula (p), Formula (q), Formula (r), Formula (s), Formula (t), Formula (u), Formula (v), Formula (w) R ¹⁶ , R ¹⁷ , R ¹⁸ in formula (y), formula (z), formula (aa), formula (ab), formula (ac), formula (ad), formula (ae), and formula (af). And each atom and each substituent of R ¹⁹ will be specifically described. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The C _1-6 alkyl group includes a methyl group, a trifluoromethyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, n-pentyl group, 2-pentyl group, 3-pentyl group, i-pentyl group, neopentyl group, 2,2-dimethylpropyl group, n-hexyl group, 2-hexyl group, 3-hexyl group, 1-methyl- n-pentyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 3,3-dimethyl-n-butyl group, methylcarbonyloxymethyl group, ethylcarbonyl Oxymethyl group, methylcarbonyloxyethyl group, ethylcarbonyloxyethyl group, methylcarbonylaminomethyl group, trifluoromethylcarbonylaminomethyl group, ethylcarbo Examples include nylaminomethyl group, methylcarbonylaminoethyl group, ethylcarbonylaminoethyl group, methoxycarbonylmethyl group, trifluoromethoxycarbonylmethyl group, ethoxycarbonylmethyl group, methoxycarbonylethyl group, and ethoxycarbonylethyl group. The C _3-8 cycloalkyl group includes a c-propyl group, a c-butyl group, a 1-methyl-c-propyl group, a 2-methyl-c-propyl group, a c-pentyl group, and a 1-methyl-c-butyl group. Group, 2-methyl-c-butyl group, 3-methyl-c-butyl group, 1,2-dimethyl-c-propyl group, 2,3-dimethyl-c-propyl group, 1-ethyl-c-propyl group 2-ethyl-c-propyl group, c-hexyl group, c-heptyl group, c-octyl group, 1-methyl-c-hexyl group, 2-methyl-c-hexyl group, 3-methyl-c-hexyl Group, 1,2-dimethyl-c-hexyl group, 2,3-dimethyl-c-propyl group, 1-ethyl-c-propyl group, 1-methyl-c-pentyl group, 2-methyl-c-pentyl group 3-methyl-c-pentyl group, 1-ethyl-c-butyl Group, 2-ethyl-c-butyl group, 3-ethyl-c-butyl group, 1,2-dimethyl-c-butyl group, 1,3-dimethyl-c-butyl group, 2,2-dimethyl-c -Butyl group, 2,3-dimethyl-c-butyl group, 2,4-dimethyl-c-butyl group, 3,3-dimethyl-c-butyl group, 1-n-propyl-c-propyl group, 2- n-propyl-c-propyl group, 1-i-propyl-c-propyl group, 2-i-propyl-c-propyl group, 1,2,2-trimethyl-c-propyl group, 1,2,3- Trimethyl-c-propyl group, 2,2,3-trimethyl-c-propyl group, 1-ethyl-2-methyl-c-propyl group, 2-ethyl-1-methyl-c-propyl group, 2-ethyl- 2-methyl-c-propyl group and 2-ethyl-3-methyl-c-propyl Etc. is Ageraru. The C _1-6 alkoxy group is a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, an s-butoxy group, a t-butoxy group, or a 1-pentyloxy group. 2-pentyloxy group, 3-pentyloxy, i-pentyloxy, neopentyloxy, 2,2-dimethylpropoxy, 1-hexyloxy, 2-hexyloxy group, 3-hexyloxy group, 1-methyl-n -Pentyloxy group, 1,1,2-trimethyl-n-propoxy group, 1,2,2-trimethyl-n-propoxy group, 3,3-dimethyl-n-butoxy group and the like. The C _1-6 thioalkoxy group includes methylthio, ethylthio, n-propylthio, i-propylthio, c-propylthio, n-butylthio, i-butylthio, s-butylthio, t-butylthio, n-pentylthio, i-pentylthio, Neopentylthio, t-pentylthio, n-hexylthio, c-hexylthio and the like can be mentioned.

The C _6-14 aryl group is phenyl, o-biphenylyl, m-biphenylyl, p-biphenylyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl. Group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group and the like. The C _2-9 heteroaryl group is a C _2-6 monocyclic heterocycle having 1 to 3 oxygen atoms, nitrogen atoms or sulfur atoms, which may contain 5 to 7 membered ring alone or in combination. C _5-9 fused bicyclic heterocyclic groups having up to 8-10 groups and constituent atoms are included. Examples of the C _2-6 monocyclic heterocyclic group having 5 to 7 members include a 2-thienyl group, a 3-thienyl group, a 2-furyl group, a 3-furyl group, a 2-pyranyl group, and a 3-pyranyl group. 4-pyranyl group, 1-pyrrolyl group, 2-pyrrolyl group, 3-pyrrolyl group, 1-imidazolyl group, 2-imidazolyl group, 4-imidazolyl group, 1-pyrazolyl group, 3-pyrazolyl group, 4-pyrazolyl group 2-thiazolyl group, 4-thiazolyl group, 5-thiazolyl group, 3-isothiazolyl group, 4-isothiazolyl group, 5-isothiazolyl group, 2-oxazolyl group, 4-oxazolyl group, 5-oxazolyl group, 3-isoxazolyl group 4-isoxazolyl group, 5-isoxazolyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-pyrazinyl group, 2-pyrimidinyl group, 4-pyridinyl group Midinyl group, 5-pyrimidinyl group, 3-pyridazinyl group, 4-pyridazinyl group, 2-1,3,4-oxadiazolyl group, 2-1,3,4-thiadiazolyl group, 3-1,2,4-oxadiazolyl group 5-1, 2, 4-oxadiazolyl group, 3-1, 2, 4-thiadiazolyl group, 5-1, 2, 4-thiadiazolyl group, 3-1, 2, 5-oxadiazolyl group, and 3-1, 2 , 5-thiadiazolyl group and the like, and the C _5-9 condensed bicyclic heterocyclic group having 8 to 10 constituent atoms includes 2-benzofuranyl group, 3-benzofuranyl group, 4-benzofuranyl group, 5 -Benzofuranyl group, 6-benzofuranyl group, 7-benzofuranyl group, 1-isobenzofuranyl group, 4-isobenzofuranyl group, 5-isobenzofuranyl group, 2-benzothienyl group, 3- Benzothienyl group, 4-benzothienyl group, 5-benzothienyl group, 6-benzothienyl group, 7-benzothienyl group, 1-isobenzothienyl group, 4-isobenzothienyl group, 5-isobenzothienyl group, 2 -Chromenyl group, 3-chromenyl group, 4-chromenyl group, 5-chromenyl group, 6-chromenyl group, 7-chromenyl group, 8-chromenyl group, 1-indolidinyl group, 2-indolidinyl group, 3-indolidinyl group, 5 -Indolidinyl group, 6-indolidinyl group, 7-indolidinyl group, 8-indolidinyl group, 1-isoindolyl group, 2-isoindolyl group, 4-isoindolyl group, 5-isoindolyl group, 1-indolyl group, 2-indolyl group, 3 -Indolyl group, 4-Indolyl group, 5-Indolyl group, 6-Indolyl group, 7-I Drill group, 1-indazolyl group, 2-indazolyl group, 3-indazolyl group, 4-indazolyl group, 5-indazolyl group, 6-indazolyl group, 7-indazolyl group, 1-purinyl group, 2-purinyl group, 3- Purinyl group, 6-purinyl group, 7-purinyl group, 8-purinyl group, 2-quinolyl group, 3-quinolyl group, 4-quinolyl group, 5-quinolyl group, 6-quinolyl group, 7-quinolyl group, 8- Quinolyl group, 1-isoquinolyl group, 3-isoquinolyl group, 4-isoquinolyl group, 5-isoquinolyl group, 6-isoquinolyl group, 7-isoquinolyl group, 8-isoquinolyl group, 1-phthalazinyl group, 5-phthalazinyl group, 6- Phthalazinyl group, 1-2,7-naphthyridinyl group, 3-2,7-naphthyridinyl group, 4-2,7-naphthyridinyl group, 1-2,6-naphth Ridinyl group, 3-2,6-naphthyridinyl group, 4-2,6-naphthyridinyl group, 2-1,8-naphthyridinyl group, 3-1,8-naphthyridinyl group, 4-1,8-naphthyridinyl group, 2- 1,7-naphthyridinyl group, 3-1,7-naphthyridinyl group, 4-1,7-naphthyridinyl group, 5-1,7-naphthyridinyl group, 6-1,7-naphthyridinyl group, 8-1,7-naphthyridinyl group Group, 2-1,6-naphthyridinyl group, 3-1,6-naphthyridinyl group, 4-1,6-naphthyridinyl group, 5-1,6-naphthyridinyl group, 7-1,6-naphthyridinyl group, 8-1 , 6-Naphthyridinyl group, 2-1,5-naphthyridinyl group, 3-1,5-naphthyridinyl group, 4-1,5-naphthyridinyl group, 6-1,5-naphthyridinyl group, 7-1,5-naphthyridinyl group Group, 8-1,5-naphthyridinyl group, 2-quinoxalinyl group, 5-quinoxalinyl group, 6-quinoxalinyl group, 2-quinazolinyl group, 4-quinazolinyl group, 5-quinazolinyl group, 6-quinazolinyl group, 7-quinazolinyl group Group, 8-quinazolinyl group, 3-cinnolinyl group, 4-cinnolinyl group, 5-cinnolinyl group, 6-cinnolinyl group, 7-cinnolinyl group, 8-cinnolinyl group, 2-pteridinyl group, 4-pteridinyl group, 6-pteridinyl group Group, 7-pteridinyl group and the like.

The C _1-6 alkylcarbonyloxy group includes a methylcarbonyloxy group, an ethylcarbonyloxy group, an n-propylcarbonyloxy group, an i-propylcarbonyloxy group, an n-butylcarbonyloxy group, an i-butylcarbonyloxy group, an s -Butylcarbonyloxy group, t-butylcarbonyloxy group, 1-pentylcarbonyloxy group, 2-pentylcarbonyloxy group, 3-pentylcarbonyloxy group, i-pentylcarbonyloxy group, neopentylcarbonyloxy group, t-pentyl Carbonyloxy group, 1-hexylcarbonyloxy group, 2-hexylcarbonyloxy group, 3-hexylcarbonyloxy group, 1-methyl-n-pentylcarbonyloxy group, 1,1,2-trimethyl-n-propylcarbonyloxy group 1 2,2-trimethyl-n-propylcarbonyloxy group, 3,3-dimethyl-n-butylcarbonyloxy group, and the like. The C _1-6 alkylamino group includes a methylamino group, an ethylamino group, an n-propylamino group, an i-propylamino group, a c-propylamino group, an n-butylamino group, an i-butylamino group, an s- Butylamino group, t-butylamino group, c-butylamino group, 1-pentylamino group, 2-pentylamino group, 3-pentylamino group, i-pentylamino group, neopentylamino group, t-pentylamino group C-pentylamino group, 1-hexylamino group, 2-hexylamino group, 3-hexylamino group, c-hexylamino group, 1-methyl-n-pentylamino group, 1,1,2-trimethyl-n -Propylamino group, 1,2,2-trimethyl-n-propylamino group, 3,3-dimethyl-n-butylamino group and the like. The di-C _1-6 alkylamino group includes a dimethylamino group, a bis (trifluoromethyl) amino group, a diethylamino group, a di-n-propylamino group, a di-i-propylamino group, and a di-c-propylamino group. Di-n-butylamino group, di-i-butylamino group, di-s-butylamino group, di-t-butylamino group, di-c-butylamino group, di-1-pentylamino group, di- 2-pentylamino group, di-3-pentylamino group, di-i-pentylamino group, di-neopentylamino group, di-t-pentylamino group, di-c-pentylamino group, di-1- Hexylamino group, di-2-hexylamino group, di-3-hexylamino group, di-c-hexylamino group, bis (1-methyl-n-pentyl) amino group, bis (1,1,2-trimethyl) -N-p (Lopyl) amino group, bis (1,2,2-trimethyl-n-propyl) amino group, bis (3,3-dimethyl-n-butyl) amino group, (methylethyl) amino group, (ethyl) trifluoromethyl Amino group, methyl-n-propylamino group, methyl-i-propylamino group, methyl-c-propylamino group, n-butylmethylamino group, i-butylmethylamino group, s-butylmethylamino group, t- Butylmethylamino group, c-butylmethylamino group, ethyl-n-propylamino group, ethyl-i-propylamino group, ethyl-c-propylamino group, n-butylethylamino group, i-butylethylamino group, s-butylethylamino group, t-butylethylamino group, c-butylethylamino group, n-propyl-i-propylamino group, n-pro Ru-c-propylamino group, n-butyl-n-propylamino group, i-butyl-n-propylamino group, s-butyl-n-propylamino group, t-butyl-n-propylamino group, c- Butyl-n-propylamino group, i-propyl-c-propylamino group, n-butyl-i-propylamino group, i-butyl-i-propylamino group, s-butyl-i-propylamino group, t- Butyl-i-propylamino group, c-butyl-i-propylamino group, n-butyl-c-propylamino group, i-butyl-c-propylamino group, s-butyl-c-propylamino group, t- Butyl-c-propylamino group, c-butyl-c-propylamino group, n-butyl-i-butylamino group, n-butyl-s-butylamino group, n-butyl-t-butylamino group n-butyl-c-butylamino group, i-butyl-s-butylamino group, i-butyl-t-butylamino group, i-butyl-c-butylamino group, s-butyl-t-butylamino group, Examples thereof include s-butyl-c-butylamino group and t-butyl-c-butylamino group. The C _6-14 arylamino group includes a phenylamino group, an o-biphenylylamino group, an m-biphenylylamino group, a p-biphenylylamino group, a 1-naphthylamino group, a 2-naphthylamino group, and a 1-anne. Tolylamino group, 2-anthrylamino group, 9-anthrylamino group, 1-phenanthrylamino group, 2-phenanthrylamino group, 3-phenanthrylamino group, 4-phenanthrylamino group and Examples include 9-phenanthrylamino group.

The C _2-9 heteroarylamino group may contain 1 to 3 oxygen atoms, nitrogen atoms or sulfur atoms, alone or in combination up to 5 to 7 membered C _2-6 monocyclic heterocycle Ring amino groups and C _5-9 fused bicyclic heterocyclic amino groups having up to 8 to 10 member atoms are included. Examples of the C _2-6 monocyclic heterocyclic amino group having 5 to 7 members include a 2-thienylamino group, a 3-thienylamino group, a 2-furylamino group, a 3-furylamino group, and a 2-pyranylamino group. 3-pyranylamino group, 4-pyranylamino group, 1-pyrrolylamino group, 2-pyrrolylamino group, 3-pyrrolylamino group, 1-imidazolylamino group, 2-imidazolylamino group, 4-imidazolylamino group, 1-pyrazolylamino group, 3-pyrazolylamino group, 4-pyrazolylamino group, 2-thiazolylamino group, 4-thiazolylamino group, 5-thiazolylamino group, 3-isothiazolylamino group, 4-isothiazolylamino group, 5-isothiazolylamino group 2-oxazolylamino group, 4-oxazolylamino group, 5-oxazolylamino group, 3-isoo Xazolylamino group, 4-isoxazolylamino group, 5-isoxazolylamino group, 2-pyridylamino group, 3-pyridylamino group, 4-pyridylamino group, 2-pyrazinylamino group, 2-pyrimidinylamino group, 4-pyrimidinyl Amino group, 5-pyrimidinylamino group, 3-pyridazinylamino group, 4-pyridazinylamino group, 2-1,3,4-oxadiazolylamino group, 2-1,3,4-thia Diazolylamino group, 3-1,2,4-oxadiazolylamino group, 5-1,2,4-oxadiazolylamino group, 3-1,2,4-thiadiazolylamino group, 5-1 2,4-thiadiazolylamino group, 3-1,2,5-oxadiazolylamino group, 3-1,2,5-thiadiazolylamino group, etc., and the number of constituent atoms is 8-10. Until As the C _5-9 fused bicyclic heterocyclic amino group, 2-benzofuranyl group, 3-benzofuranyl group, 4-benzofuranyl group, 5-benzofuranyl group, 6- Benzofuranylamino group, 7-benzofuranylamino group, 1-isobenzofuranylamino group, 4-isobenzofuranylamino group, 5-isobenzofuranylamino group, 2-benzothienylamino group, 3- Benzothienylamino group, 4-benzothienylamino group, 5-benzothienylamino group, 6-benzothienylamino group, 7-benzothienylamino group, 1-isobenzothienylamino group, 4-isobenzothienylamino group, 5 -Isobenzothienylamino group, 2-chromenylamino group, 3-chromenylamino group, 4-chromenylamino group, 5-chromenylamino 6-chromenylamino group, 7-chromenylamino group, 8-chromenylamino group, 1-indolidinylamino group, 2-indolidinylamino group, 3-indolidinylamino group, 5-indolidinyl group Ruamino group, 6-indolidinylamino group, 7-indolidinylamino group, 8-indolidinylamino group, 1-isoindolylamino group, 2-isoindolylamino group, 4-isoindolylamino group Group, 5-isoindolylamino group, 1-indolylamino group, 2-indolylamino group, 3-indolylamino group, 4-indolylamino group, 5-indolylamino group, 6-indolylamino group Group, 7-indolylamino group, 1-indazolylamino group, 2-indazolylamino group, 3-indazolylamino group, 4-indazolylamino group, 5-inda Rylamino group, 6-indazolylamino group, 7-indazolylamino group, 1-purinylamino group, 2-purinylamino group, 3-prinylamino group, 6-purinylamino group, 7-purinylamino group, 8-prinylamino group, 2 -Quinolylamino group, 3-quinolylamino group, 4-quinolylamino group, 5-quinolylamino group, 6-quinolylamino group, 7-quinolylamino group, 8-quinolylamino group, 1-isoquinolylamino group, 3-isoquinolylamino group, 4-isoquinolylamino group, 5-isoquinolylamino group, 6-isoquinolylamino group, 7-isoquinolylamino group, 8-isoquinolylamino group, 1-phthalazinylamino group, 5- Phthalazinylamino group, 6-phthalazinylamino group, 1-2,7-naphthyridinylamino group, 3-2,7-naphthi Lydinylamino group, 4-2,7-naphthyridinylamino group, 1-2,6-naphthyridinylamino group, 3-2,6-naphthyridinylamino group, 4-2,6-naphthyridinylamino group 2-1,8-naphthyridinylamino group, 3-1,8-naphthyridinylamino group, 4-1,8-naphthyridinylamino group, 2-1,7-naphthyridinylamino group, 3 -1,7-naphthyridinylamino group, 4-1,7-naphthyridinylamino group, 5-1,7-naphthyridinylamino group, 6-1,7-naphthyridinylamino group, 8-1 , 7-naphthyridinylamino group, 2-1,6-naphthyridinylamino group, 3-1,6-naphthyridinylamino group, 4-1,6-naphthyridinylamino group, 5-1,6 -Naphthyridinylamino group, 7-1,6-naphthyridinylamino group, -1,6-naphthyridinylamino group, 2-1,5-naphthyridinylamino group, 3-1,5-naphthyridinylamino group, 4-1,5-naphthyridinylamino group, 6-1 , 5-naphthyridinylamino group, 7-1,5-naphthyridinylamino group, 8-1,5-naphthyridinylamino group, 2-quinoxalinylamino group, 5-quinoxalinylamino group 6-quinoxalinylamino group, 2-quinazolinylamino group, 4-quinazolinylamino group, 5-quinazolinylamino group, 6-quinazolinylamino group, 7-quinazolinylamino group, 8-quinazolinylamino group, 3-cinnolinylamino group, 4-cinnolinylamino group, 5-cinnolinylamino group, 6-cinnolinylamino group, 7-cinnolinylamino group, 8- Cinnolinylamino group, 2-pteridinyl group Amino group, 4-pteridinylmethyl amino group, 6-pteridinylmethyl amino group, and 7-pteridinylmethyl amino group and the like.

The C _1-6 alkylcarbonylamino group includes a methylcarbonylamino group, an ethylcarbonylamino group, an n-propylcarbonylamino group, an i-propylcarbonylamino group, an n-butylcarbonylamino group, an i-butylcarbonylamino group, an s -Butylcarbonylamino group, t-butylcarbonylamino group, 1-pentylcarbonylamino group, 2-pentylcarbonylamino group, 3-pentylcarbonylamino group, i-pentylcarbonylamino group, neopentylcarbonylamino group, t-pentyl Examples include carbonylamino group, 1-hexylcarbonylamino group, 2-hexylcarbonylamino group, and 3-hexylcarbonylamino group. The C _1-6 alkylsulfonamide group includes a methanesulfonamide group, an ethanesulfonamide group, an n-propanesulfonamide group, an i-propanesulfonamide group, an n-butanesulfonamide group, an i-butanesulfonamide group, an s -Butanesulfonamide group, t-butanesulfonamide group, 1-pentanesulfonamide group, 2-pentanesulfonamide group, 3-pentanesulfonamide group, i-pentanesulfonamide group, neopentanesulfonamide group, t-pentane Examples thereof include a sulfonamide group, a 1-hexanesulfonamide group, a 2-hexanesulfonamide group, and a 3-hexanesulfonamide group. The C _1-6 alkylaminocarbonyl group includes a methylaminocarbonyl group, an ethylaminocarbonyl group, an n-propylaminocarbonyl group, an i-propylaminocarbonyl group, an n-butylaminocarbonyl group, an i-butylaminocarbonyl group, an s -Butylaminocarbonyl group, t-butylaminocarbonyl group, 1-pentylaminocarbonyl group, 2-pentylaminocarbonyl group, 3-pentylaminocarbonyl group, i-pentylaminocarbonyl group, neopentylaminocarbonyl group, t-pentyl Examples include an aminocarbonyl group, 1-hexylaminocarbonyl group, 2-hexylaminocarbonyl group, and 3-hexylaminocarbonyl group. The diC _1-6 alkylaminocarbonyl group includes a dimethylaminocarbonyl group, a bis (trifluoromethyl) aminocarbonyl group, a diethylaminocarbonyl group, a di-n-propylaminocarbonyl group, a di-i-propylaminocarbonyl group, a di- -C-propylaminocarbonyl group, di-n-butylaminocarbonyl group, di-i-butylaminocarbonyl group, di-s-butylaminocarbonyl group, di-t-butylaminocarbonyl group, di-c-butylamino Carbonyl group, di-1-pentylaminocarbonyl group, di-2-pentylaminocarbonyl group, di-3-pentylaminocarbonyl group, di-i-pentylaminocarbonyl group, di-neopentylaminocarbonyl group, di-t -Pentylaminocarbonyl group, di-c-pentylaminocarbo Nyl group, di-1-hexylaminocarbonyl group, di-2-hexylaminocarbonyl group, di-3-hexylaminocarbonyl group, di-c-hexylaminocarbonyl group, bis (1-methyl-n-pentyl) amino Carbonyl group, bis (1,1,2-trimethyl-n-propyl) aminocarbonyl group, bis (1,2,2-trimethyl-n-propyl) aminocarbonyl group, bis (3,3-dimethyl-n-butyl) ) Aminocarbonyl group, (methylethyl) aminocarbonyl group, (ethyl) trifluoromethylaminocarbonyl group, methyl-n-propylaminocarbonyl group, methyl-i-propylaminocarbonyl group, methyl-c-propylaminocarbonyl group, n-butylmethylaminocarbonyl group, i-butylmethylaminocarbonyl group, s Butylmethylaminocarbonyl group, t-butylmethylaminocarbonyl group, c-butylmethylaminocarbonyl group, ethyl-n-propylaminocarbonyl group, ethyl-i-propylaminocarbonyl group, ethyl-c-propylaminocarbonyl group, n -Butylethylaminocarbonyl group, i-butylethylaminocarbonyl group, s-butylethylaminocarbonyl group, t-butylethylaminocarbonyl group, c-butylethylaminocarbonyl group, n-propyl-i-propylaminocarbonyl group, n-propyl-c-propylaminocarbonyl group, n-butyl-n-propylaminocarbonyl group, i-butyl-n-propylaminocarbonyl group, s-butyl-n-propylaminocarbonyl group, t-butyl-n- Propylaminocarbo Group, c-butyl-n-propylaminocarbonyl group, i-propyl-c-propylaminocarbonyl group, n-butyl-i-propylaminocarbonyl group, i-butyl-i-propylaminocarbonyl group, s-butyl -I-propylaminocarbonyl group, t-butyl-i-propylaminocarbonyl group, c-butyl-i-propylaminocarbonyl group, n-butyl-c-propylaminocarbonyl group, i-butyl-c-propylaminocarbonyl group Group, s-butyl-c-propylaminocarbonyl group, t-butyl-c-propylaminocarbonyl group, c-butyl-c-propylaminocarbonyl group, n-butyl-i-butylaminocarbonyl group, n-butyl- s-butylaminocarbonyl group, n-butyl-t-butylaminocarbonyl group, n- Butyl-c-butylaminocarbonyl group, i-butyl-s-butylaminocarbonyl group, i-butyl-t-butylaminocarbonyl group, i-butyl-c-butylaminocarbonyl group, s-butyl-t-butylamino Examples include a carbonyl group, a s-butyl-c-butylaminocarbonyl group, and a t-butyl-c-butylaminocarbonyl group. The C _1-6 alkylcarbonyl group includes methylcarbonyl group, ethylcarbonyl group, n-propylcarbonyl group, i-propylcarbonyl group, n-butylcarbonyl group, i-butylcarbonyl group, s-butylcarbonyl group, t- Butylcarbonyl group, 1-pentylcarbonyl group, 2-pentylcarbonyl group, 3-pentylcarbonyl group, i-pentylcarbonyl group, neopentylcarbonyl group, t-pentylcarbonyl group, 1-hexylcarbonyl group, 2-hexylcarbonyl group , And 3-hexylcarbonyl group.

The C _6-14 arylcarbonyl group is a phenylcarbonyl group, o-biphenylylcarbonyl group, m-biphenylylcarbonyl group, p-biphenylylcarbonyl group, 1-naphthylcarbonyl group, 2-naphthylcarbonyl group, 1-anthone. Tolylcarbonyl group, 2-anthrylcarbonyl group, 9-anthrylcarbonyl group, 1-phenanthrylcarbonyl group, 2-phenanthrylcarbonyl group, 3-phenanthrylcarbonyl group, 4-phenanthrylcarbonyl group, And 9-phenanthrylcarbonyl group. The C _2-9 heteroarylcarbonyl group may contain 1 to 3 oxygen atoms, nitrogen atoms or sulfur atoms, alone or in combination up to 5 to 7 membered C _2-6 monocyclic heterocycle A ring carbonyl group and a C _5-9 fused bicyclic heterocyclic carbonyl group having 8 to 10 member atoms are included. Examples of the C _2-6 monocyclic heterocyclic carbonyl group having 5 to 7 members include 2-thienylcarbonyl group, 3-thienylcarbonyl group, 2-furylcarbonyl group, 3-furylcarbonyl group, 2-pyranyl. Carbonyl group, 3-pyranylcarbonyl group, 4-pyranylcarbonyl group, 1-pyrrolylcarbonyl group, 2-pyrrolylcarbonyl group, 3-pyrrolylcarbonyl group, 1-imidazolylcarbonyl group, 2-imidazolylcarbonyl group, 4-imidazolylcarbonyl group, 1-pyrazolylcarbonyl group, 3-pyrazolylcarbonyl group, 4-pyrazolylcarbonyl group, 2-thiazolylcarbonyl group, 4-thiazolylcarbonyl group, 5-thiazolylcarbonyl group, 3- Isothiazolylcarbonyl group, 4-isothiazolylcarbonyl group, 5-isothiazolylcarbonyl group Group, 2-oxazolylcarbonyl group, 4-oxazolylcarbonyl group, 5-oxazolylcarbonyl group, 3-isoxazolylcarbonyl group, 4-isoxazolylcarbonyl group, 5-isoxazolyl Carbonyl group, 2-pyridylcarbonyl group, 3-pyridylcarbonyl group, 4-pyridylcarbonyl group, 2-pyrazinylcarbonyl group, 2-pyrimidinylcarbonyl group, 4-pyrimidinylcarbonyl group, 5-pyrimidinylcarbonyl group, 3-pyridinylcarbonyl group Dazinylcarbonyl group, 4-pyridazinylcarbonyl group, 2-1,3,4-oxadiazolylcarbonyl group, 2-1,3,4-thiadiazolylcarbonyl group, 3-1,2,4 -Oxadiazolylcarbonyl group, 5-1,2,4-oxadiazolylcarbonyl group, 3-1,2,4-thiadiazolylca Bonyl group, 5-1,2,4-thiadiazolylcarbonyl group, 3-1,2,5-oxadiazolylcarbonyl group, 3-1,2,5-thiadiazolylcarbonyl group, and the like Examples of the C _5-9 condensed bicyclic heterocyclic carbonyl group having 8 to 10 atoms include 2-benzofuranylcarbonyl group, 3-benzofuranylcarbonyl group, 4-benzofuranylcarbonyl group, 5- Benzofuranylcarbonyl group, 6-benzofuranylcarbonyl group, 7-benzofuranylcarbonyl group, 1-isobenzofuranylcarbonyl group, 4-isobenzofuranylcarbonyl group, 5-isobenzofuranylcarbonyl group, 2 -Benzothienylcarbonyl group, 3-benzothienylcarbonyl group, 4-benzothienylcarbonyl group, 5-benzothienylcarbonyl group, 6- Nzothienylcarbonyl group, 7-benzothienylcarbonyl group, 1-isobenzothienylcarbonyl group, 4-isobenzothienylcarbonyl group, 5-isobenzothienylcarbonyl group, 2-chromenylcarbonyl group, 3-chromenylcarbonyl group 4-chromenylcarbonyl group, 5-chromenylcarbonyl group, 6-chromenylcarbonyl group, 7-chromenylcarbonyl group, 8-chromenylcarbonyl group, 1-indolidinylcarbonyl group, 2-indolidinylcarbonyl group Group, 3-indolidinylcarbonyl group, 5-indolidinylcarbonyl group, 6-indolidinylcarbonyl group, 7-indolidinylcarbonyl group, 8-indolidinylcarbonyl group, 1-isoindolylcarbonyl group, 2-isoindolylcarbonyl group, 4-isoindo Rucarbonyl group, 5-isoindolylcarbonyl group, 1-indolylcarbonyl group, 2-indolylcarbonyl group, 3-indolylcarbonyl group, 4-indolylcarbonyl group, 5-indolylcarbonyl group, 6-in Drillcarbonyl group, 7-indolylcarbonyl group, 1-indazolylcarbonyl group, 2-indazolylcarbonyl group, 3-indazolylcarbonyl group, 4-indazolylcarbonyl group, 5-indazolylcarbonyl group 6-indazolylcarbonyl group, 7-indazolylcarbonyl group, 1-purinylcarbonyl group, 2-prinylcarbonyl group, 3-prinylcarbonyl group, 6-purinylcarbonyl group, 7-prinylcarbonyl group Group, 8-purinylcarbonyl group, 2-quinolylcarbonyl group, 3-quinolylcarbonyl group, 4- Quinolylcarbonyl group, 5-quinolylcarbonyl group, 6-quinolylcarbonyl group, 7-quinolylcarbonyl group, 8-quinolylcarbonyl group, 1-isoquinolylcarbonyl group, 3-isoquinolylcarbonyl group, 4 -Isoquinolylcarbonyl group, 5-isoquinolylcarbonyl group, 6-isoquinolylcarbonyl group, 7-isoquinolylcarbonyl group, 8-isoquinolylcarbonyl group, 1-phthalazinylcarbonyl group, 5-phthal Razinylcarbonyl group, 6-phthalazinylcarbonyl group, 1-2,7-naphthyridinylcarbonyl group, 3-2,7-naphthyridinylcarbonyl group, 4-2,7-naphthyridinylcarbonyl group, 1 -2,6-naphthyridinylcarbonyl group, 3-2,6-naphthyridinylcarbonyl group, 4-2,6-naphthyridinylcarbonyl group, -1,8-naphthyridinylcarbonyl group, 3-1,8-naphthyridinylcarbonyl group, 4-1,8-naphthyridinylcarbonyl group, 2-1,7-naphthyridinylcarbonyl group, 3-1 , 7-naphthyridinylcarbonyl group, 4-1,7-naphthyridinylcarbonyl group, 5-1,7-naphthyridinylcarbonyl group, 6-1,7-naphthyridinylcarbonyl group, 8-1,7 -Naphthyridinylcarbonyl group, 2-1,6-naphthyridinylcarbonyl group, 3-1,6-naphthyridinylcarbonyl group, 4-1,6-naphthyridinylcarbonyl group, 5-1,6-naphthy Lydinylcarbonyl group, 7-1,6-naphthyridinylcarbonyl group, 8-1,6-naphthyridinylcarbonyl group, 2-1,5-naphthyridinylcarbonyl group, 3-1,5-naphthyridinyl Rubonyl group, 4-1,5-naphthyridinylcarbonyl group, 6-1,5-naphthyridinylcarbonyl group, 7-1,5-naphthyridinylcarbonyl group, 8-1,5-naphthyridinylcarbonyl group 2-quinoxalinylcarbonyl group, 5-quinoxalinylcarbonyl group, 6-quinoxalinylcarbonyl group, 2-quinazolinylcarbonyl group, 4-quinazolinylcarbonyl group, 5-quinazolinylcarbonyl group Group, 6-quinazolinylcarbonyl group, 7-quinazolinylcarbonyl group, 8-quinazolinylcarbonyl group, 3-cinnolinylcarbonyl group, 4-cinnolinylcarbonyl group, 5-cinnolinylcarbonyl group, 6-cinnolinylcarbonyl group, 7-cinnolinylcarbonyl group, 8-cinnolinylcarbonyl group, 2-pteridinylcarbonyl group, 4-pte Examples include lysinylcarbonyl group, 6-pteridinylcarbonyl group, and 7-pteridinylcarbonyl group.

The C _1-6 alkoxycarbonyl group includes a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an i-propoxycarbonyl group, an n-butoxycarbonyl group, an i-butoxycarbonyl group, an s-butoxycarbonyl group, a t- Butoxycarbonyl group, 1-pentyloxycarbonyl group, 2-pentyloxycarbonyl group, 3-pentyloxycarbonyl group, i-pentyloxycarbonyl group, neopentyloxycarbonyl group, t-pentyloxycarbonyl group, 1-hexyloxycarbonyl Group, 2-hexyloxycarbonyl group, 3-hexyloxycarbonyl group and the like. The C _1-4 alkylsulfonyl group includes a methanesulfonyl group, a trifluoromethanesulfonyl group, an ethanesulfonyl group, an n-propanesulfonyl group, an i-propanesulfonyl group, an n-butanesulfonyl group, an i-butanesulfonyl group, and an s-butane. A sulfonyl group, a t-butanesulfonyl group, etc. are mentioned. The C _6-14 arylsulfonyl group is a benzenesulfonyl group, o-biphenylsulfonyl group, m-biphenylsulfonyl group, p-biphenylsulfonyl group, 1-naphthalenesulfonyl group, 2-naphthalenesulfonyl group, 1-anthracenesulfonyl group, Examples include 2-anthracenesulfonyl group, 9-anthracenesulfonyl group, 1-phenanthrenesulfonyl group, 2-phenanthrenesulfonyl group, 3-phenanthrenesulfonyl group, 4-phenanthrenesulfonyl group, and 9-phenanthrenesulfonyl group. The C _2-9 heteroarylsulfonyl group may contain 1 to 3 oxygen atoms, nitrogen atoms or sulfur atoms, alone or in combination up to 5 to 7 membered C _2-6 monocyclic heterocycle Ring sulfonyl groups and C _5-9 fused bicyclic heterocyclic sulfonyl groups with up to 8-10 constituent atoms are included. Examples of the C _2-6 monocyclic heterocyclic sulfonyl group up to 5 to 7-membered ring include 2-thienylsulfonyl group, 3-thienylsulfonyl group, 2-furylsulfonyl group, 3-furylsulfonyl group, 2-pyranyl. Sulfonyl group, 3-pyranylsulfonyl group, 4-pyranylsulfonyl group, 1-pyrrolylsulfonyl group, 2-pyrrolylsulfonyl group, 3-pyrrolylsulfonyl group, 1-imidazolylsulfonyl group, 2-imidazolylsulfonyl group, 4-imidazolylsulfonyl group, 1-pyrazolylsulfonyl group, 3-pyrazolylsulfonyl group, 4-pyrazolylsulfonyl group, 2-thiazolylsulfonyl group, 4-thiazolylsulfonyl group, 5-thiazolylsulfonyl group, 3- Isothiazolylsulfonyl group, 4-isothiazolylsulfonyl group, 5-isothiazolylsulfonyl group Group, 2-oxazolylsulfonyl group, 4-oxazolylsulfonyl group, 5-oxazolylsulfonyl group, 3-isoxazolylsulfonyl group, 4-isoxazolylsulfonyl group, 5-isoxazolyl Sulfonyl group, 2-pyridylsulfonyl group, 3-pyridylsulfonyl group, 4-pyridylsulfonyl group, 2-pyrazinylsulfonyl group, 2-pyrimidinylsulfonyl group, 4-pyrimidinylsulfonyl group, 5-pyrimidinylsulfonyl group, 3-pyridinylsulfonyl group Dazinylsulfonyl group, 4-pyridazinylsulfonyl group, 2-1,3,4-oxadiazolylsulfonyl group, 2-1,3,4-thiadiazolylsulfonyl group, 3-1,2,4 -Oxadiazolylsulfonyl group, 5-1,2,4-oxadiazolylsulfonyl group, 3-1,2,4-thiadiazolyl group Examples include phonyl group, 5-1,2,4-thiadiazolylsulfonyl group, 3-1,2,5-oxadiazolylsulfonyl group, 3-1,2,5-thiadiazolylsulfonyl group, and the like. Examples of the C _5-9 condensed bicyclic heterocyclic sulfonyl group having 8 to 10 atoms include 2-benzofuranylsulfonyl group, 3-benzofuranylsulfonyl group, 4-benzofuranylsulfonyl group, 5- Benzofuranylsulfonyl group, 6-benzofuranylsulfonyl group, 7-benzofuranylsulfonyl group, 1-isobenzofuranylsulfonyl group, 4-isobenzofuranylsulfonyl group, 5-isobenzofuranylsulfonyl group, 2 -Benzothienylsulfonyl group, 3-benzothienylsulfonyl group, 4-benzothienylsulfonyl group, 5-benzothienylsulfonyl group, 6- Nzothienylsulfonyl group, 7-benzothienylsulfonyl group, 1-isobenzothienylsulfonyl group, 4-isobenzothienylsulfonyl group, 5-isobenzothienylsulfonyl group, 2-chromenylsulfonyl group, 3-chromenylsulfonyl group 4-chromenylsulfonyl group, 5-chromenylsulfonyl group, 6-chromenylsulfonyl group, 7-chromenylsulfonyl group, 8-chromenylsulfonyl group, 1-indolidinylsulfonyl group, 2-indolidinylsulfonyl group Group, 3-indolidinylsulfonyl group, 5-indolidinylsulfonyl group, 6-indolidinylsulfonyl group, 7-indolidinylsulfonyl group, 8-indolidinylsulfonyl group, 1-isoindolylsulfonyl group, 2-isoindolylsulfonyl group, 4-isoindo Rusulfonyl group, 5-isoindolylsulfonyl group, 1-indolylsulfonyl group, 2-indolylsulfonyl group, 3-indolylsulfonyl group, 4-indolylsulfonyl group, 5-indolylsulfonyl group, 6-in Drillsulfonyl group, 7-indolylsulfonyl group, 1-indazolylsulfonyl group, 2-indazolylsulfonyl group, 3-indazolylsulfonyl group, 4-indazolylsulfonyl group, 5-indazolylsulfonyl group 6-indazolylsulfonyl group, 7-indazolylsulfonyl group, 1-prinylsulfonyl group, 2-prinylsulfonyl group, 3-prinylsulfonyl group, 6-purinylsulfonyl group, 7-prinylsulfonyl group Group, 8-purinylsulfonyl group, 2-quinolylsulfonyl group, 3-quinolylsulfonyl group, 4- Quinolylsulfonyl group, 5-quinolylsulfonyl group, 6-quinolylsulfonyl group, 7-quinolylsulfonyl group, 8-quinolylsulfonyl group, 1-isoquinolylsulfonyl group, 3-isoquinolylsulfonyl group, 4 -Isoquinolylsulfonyl group, 5-isoquinolylsulfonyl group, 6-isoquinolylsulfonyl group, 7-isoquinolylsulfonyl group, 8-isoquinolylsulfonyl group, 1-phthalazinylsulfonyl group, 5-phthal Razinylsulfonyl group, 6-phthalazinylsulfonyl group, 1-2,7-naphthyridinylsulfonyl group, 3,2,7-naphthyridinylsulfonyl group, 4-2,7-naphthyridinylsulfonyl group, 1 -2,6-naphthyridinylsulfonyl group, 3-2,6-naphthyridinylsulfonyl group, 4-2,6-naphthyridinylsulfonyl group, -1,8-naphthyridinylsulfonyl group, 3-1,8-naphthyridinylsulfonyl group, 4-1,8-naphthyridinylsulfonyl group, 2-1,7-naphthyridinylsulfonyl group, 3-1 , 7-naphthyridinylsulfonyl group, 4-1,7-naphthyridinylsulfonyl group, 5-1,7-naphthyridinylsulfonyl group, 6-1,7-naphthyridinylsulfonyl group, 8-1,7 -Naphthyridinylsulfonyl group, 2-1,6-naphthyridinylsulfonyl group, 3-1,6-naphthyridinylsulfonyl group, 4-1,6-naphthyridinylsulfonyl group, 5-1,6-naphthy Lydinylsulfonyl group, 7-1,6-naphthyridinylsulfonyl group, 8-1,6-naphthyridinylsulfonyl group, 2-1,5-naphthyridinylsulfonyl group, 3-1,5-naphthyridinyl Sulfonyl group, 4-1,5-naphthyridinylsulfonyl group, 6-1,5-naphthyridinylsulfonyl group, 7-1,5-naphthyridinylsulfonyl group, 8-1,5-naphthyridinylsulfonyl group 2-quinoxalinylsulfonyl group, 5-quinoxalinylsulfonyl group, 6-quinoxalinylsulfonyl group, 2-quinazolinylsulfonyl group, 4-quinazolinylsulfonyl group, 5-quinazolinylsulfonyl group Group, 6-quinazolinylsulfonyl group, 7-quinazolinylsulfonyl group, 8-quinazolinylsulfonyl group, 3-cinnolinylsulfonyl group, 4-cinnolinylsulfonyl group, 5-cinnolinylsulfonyl group, 6-cinnolinylsulfonyl group, 7-cinnolinylsulfonyl group, 8-cinnolinylsulfonyl group, 2-pteridinylsulfonyl group, 4-pte Examples thereof include a lysinylsulfonyl group, a 6-pteridinylsulfonyl group, and a 7-pteridinylsulfonyl group.

The C _2-9 non-aromatic heterocyclyl group is composed of one or more atoms freely selected from a nitrogen atom, an oxygen atom, and a sulfur atom, and monocyclic and condensed ring groups composed of 2 to 9 carbon atoms. A cyclic heterocyclic group, specifically,

Etc. In the above formula,-(meaning a bond) described in each ring structure indicates that an arbitrary position where chemical substitution is possible can be taken, and does not mean specifying a substitution site.

Formula (a), Formula (b), Formula (c), Formula (d), Formula (f), Formula (g), Formula (h), Formula (j), Formula (k), Formula (m) , Formula (n), Formula (o), Formula (p), Formula (q), Formula (r), Formula (s), Formula (t), Formula (u), Formula (v), Formula (w) R ¹⁶ , R ¹⁷ , R ¹⁸ in formula (y), formula (z), formula (aa), formula (ab), formula (ac), formula (ad), formula (ae), and formula (af). And R ¹⁹ are each independently a hydrogen atom, fluorine atom, chlorine atom, bromine atom, methyl group, trifluoromethyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, n- Pentyl group, i-pentyl group, 3,3-dimethyl-n-butyl group, methylcarbonyloxymethyl group, ethylcarbonyloxymethyl group, methylcarbonyloxyethyl group, ethylcarbonyloxy Cyethyl group, methylcarbonylaminomethyl group, ethylcarbonylaminomethyl group, methylcarbonylaminoethyl group, ethylcarbonylaminoethyl group, methoxycarbonylmethyl group, trifluoromethoxycarbonylmethyl group, ethoxycarbonylmethyl group, methoxycarbonylethyl group, ethoxy Carbonylethyl group, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, hydroxyl group, phenyl group, o-biphenylyl group, m-biphenylyl group, p-biphenylyl group, 1-naphthyl group, 2-naphthyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, methylcarbonyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, i-propylcarbonyloxy group, n-butylcarbonyloxy group, t-butyl Rucarbonyloxy group, nitro group, cyano group, formyl group, formamide group, amino group, methylamino group, ethylamino group, n-propylamino group, i-propylamino group, n-butylamino group, dimethylamino group, Diethylamino group, di-n-propylamino group, di-i-propylamino group, di-n-butylamino group, phenylamino group, o-biphenylylamino group, m-biphenylylamino group, p-biphenylylamino Group, 1-naphthylamino group, 2-naphthylamino group, 2-pyridylamino group, 3-pyridylamino group, 4-pyridylamino group, methylcarbonylamino group, ethylcarbonylamino group, n-propylcarbonylamino group, i-propylcarbonyl Amino group, n-butylcarbonylamino group, methanesulfonamide group, Tansulfonamide group, n-propanesulfonamide group, i-propanesulfonamide group, n-butanesulfonamide group, methylaminocarbonyl group, ethylaminocarbonyl group, n-propylaminocarbonyl group, i-propylaminocarbonyl group, n-butylaminocarbonyl group, dimethylaminocarbonyl group, diethylaminocarbonyl group, di-n-propylaminocarbonyl group, di-i-propylaminocarbonyl group, di-c-propylaminocarbonyl group, di-n-butylaminocarbonyl group Group, methylcarbonyl group, ethylcarbonyl group, n-propylcarbonyl group, i-propylcarbonyl group, n-butylcarbonyl group, phenylcarbonyl group, o-biphenylylcarbonyl group, m-biphenylylcarbonyl group, p-biphenylyl Carbonyl group, 1-naphthylcarbonyl group, 2-naphthylcarbonyl group, 2-pyridylcarbonyl group, 3-pyridylcarbonyl group, 4-pyridylcarbonyl group, methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, i-propoxy group Carbonyl group, n-butoxycarbonyl group, i-butoxycarbonyl group, s-butoxycarbonyl group, t-butoxycarbonyl group, methanesulfonyl group, trifluoromethanesulfonyl group, benzenesulfonyl group, o-biphenylsulfonyl group, m-biphenylsulfonyl Group, p-biphenylsulfonyl group, 1-naphthalenesulfonyl group, 2-naphthalenesulfonyl group, 2-pyridylsulfonyl group, 3-pyridylsulfonyl group, 4-pyridylsulfonyl group, carbamoyl group, carboxy group Group,

Is preferred. In the above formula,-(meaning a bond) described in each ring structure indicates that an arbitrary position where chemical substitution is possible can be taken, and does not mean specifying a substitution site.

Formula (a), Formula (b), Formula (c), Formula (d), Formula (f), Formula (g), Formula (h), Formula (j), Formula (k), Formula (m) , Formula (n), Formula (o), Formula (p), Formula (q), Formula (r), Formula (s), Formula (t), Formula (u), Formula (v), Formula (w) R ¹⁶ , R ¹⁷ , R ¹⁸ in formula (y), formula (z), formula (aa), formula (ab), formula (ac), formula (ad), formula (ae), and formula (af). And R ¹⁹ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, a trifluoromethyl group, an ethyl group, an n-propyl group, an i-propyl group, a methylcarbonyloxymethyl group, or an ethylcarbonyloxymethyl group. Group, methylcarbonylaminoethyl group, ethylcarbonylaminoethyl group, methoxycarbonylmethyl group, trifluoromethoxycarbonylmethyl group methoxy , Ethoxy group, hydroxyl group, methylcarbonyloxy group, ethylcarbonyloxy group, methylamino group, ethylamino group, dimethylamino group, diethylamino group, methylcarbonylamino group, ethylcarbonylamino group, methanesulfonamide group, ethanesulfonamide group More preferred are methoxycarbonyl group, ethoxycarbonyl group, methanesulfonyl group, trifluoromethanesulfonyl group, nitro group, cyano group, formyl group, formamide group, amino group, carbamoyl group, and carboxyl group.

Q in the formula (c), formula (d), formula (p), formula (q), formula (v), formula (w), formula (ab), formula (ac) and formula (ad) is O (oxygen atom), S (sulfur atom), SO (sulfur group) or SO ₂ (sulfonyl group) is meant. Q is preferably O (oxygen atom) or S (sulfur atom).

  The method for producing the optically active sulfoxide compound of the present invention includes formula (1a), formula (1a ′), formula (1b), formula (1b ′), formula (2), formula (2 ′), formula (3a), Formula (3a ′), Formula (3b), Formula (3b ′), Formula (4), and Formula (4 ′)

(Formula (1a), Formula (1a ′), Formula (1b), Formula (1b ′), Formula (2), Formula (2 ′), Formula (3a), Formula (3a ′), Formula (3b), R ¹ in formula (3b ′), formula (4), and formula (4 ′) represents partial structural formula (AA) and partial structural formula (AB).

(X in the partial structural formula (AA) and the partial structural formula (AB) is an oxygen atom or a sulfur atom, and Y in the partial structural formula (AA) and the partial structural formula (AB) is a single bond or a methylene group. (The methylene group is unsubstituted or substituted with a fluorine atom.), An ethylene group (the ethylene group is unsubstituted or substituted with a fluorine atom), -SO _2- , a carbonyl group, —CH (C _1-4 alkyl group) — (the alkyl group in —CH (C _1-4 alkyl group) — is unsubstituted or substituted with a halogen atom. Or the aryl group in —CH (C _6-14 aryl group) — (the —CH (C _6-14 aryl group) — is unsubstituted or substituted with a halogen atom. Z in the partial structural formula (AA) and the partial structural formula (AB) is C _3-12 alkyl group (said alkyl group is substituted or unsubstituted, or a halogen _{atom.), C 3-8} cycloalkyl _{group, C 6-22} aryl group (the aryl group is unsubstituted Substituted or halogen atom, C _1-4 alkyl group (the alkyl group is unsubstituted or substituted with a halogen atom or C _6-16 aryl group), C _6-16. An aryl group (the aryl group is unsubstituted or substituted with a halogen atom), or optionally substituted with a C _1-4 alkoxy group) or a C _2-9 heteroaryl group ( The heteroaryl group is unsubstituted or substituted with a halogen atom.), And R ² in the partial structural formula (AA) and the partial structural formula (AB) is a hydrogen atom, a halogen atom, C _1-4 alkyl Group (the alkyl group is substituted or unsubstituted, or a halogen atom.), Or C _1-4 alkoxy group, the partial structural formula (AA) and a partial structural formulas (AB) R ⁴ each independently represents a hydrogen atom, a halogen atom, a C _1-4 alkyl group (the alkyl group is unsubstituted or substituted with a halogen atom), a C _1-4 alkoxy group, a nitro group; Group or a cyano group).
Formula (1a), Formula (1a ′), Formula (1b), Formula (1b ′), Formula (2), Formula (2 ′), Formula (3a), Formula (3a ′), Formula (3b), Formula (3b ') ^{R 2} of formula (4) and formula (4') in a hydrogen atom, a halogen _{atom, C 1-4} alkyl group (said alkyl group is unsubstituted or substituted with a halogen atom Or a C _1-4 alkoxy group,
Formula (1a), Formula (1a ′), Formula (1b), Formula (1b ′), Formula (2), Formula (2 ′), Formula (3a), Formula (3a ′), Formula (3b), Formula R ³ in (3b ′), formula (4), and formula (4 ′) is a C _6-18 aryl group or, when two R ³ together form a ring, C _3-5 Valent group,
Formula (1a), Formula (1a ′), Formula (1b), Formula (1b ′), Formula (2), Formula (2 ′), Formula (3a), Formula (3a ′), Formula (3b), Formula (3b ') or ^{R 4} of the formula (4) and formula (4') during each independently represent a hydrogen atom, a halogen _{atom, C 1-4} alkyl group (said alkyl group is unsubstituted, Or a C _1-4 alkoxy group, a nitro group, or a cyano group. The optically active titanium complex obtained by reacting the optically active ligand represented by any of the above and a titanium compound (the optically active titanium complex is an optically active titanium salen complex, an optically active titanium salalene complex, or an optically active titanium salen). Is used as a catalyst, and the following formula (30)

(R ²² and R ^{23 in} formula (30) are different substituents, and each independently represents a C _6-12 aryl group (the aryl group is unsubstituted or a halogen atom, C _{1- 4} alkyl group, C _1-4 alkoxy group, C _2-5 alkylcarbonyloxy group, C _2-5 alkoxycarbonyl group, nitro group, or cyano group.), C _6-12 arylmethyl group ( The arylmethyl group is unsubstituted or a halogen atom, a C _1-4 alkyl group, a C _1-4 alkoxy group, a C _2-5 alkylcarbonyloxy group, a C _2-5 alkoxycarbonyl group, a nitro group, Or a C _1-6 alkyl group (the alkyl group is unsubstituted, a halogen atom, a nitro group, a hydroxyl group, or However, R ²² is a C _6-12 aryl group, and a C _1-4 alkyl group or a C _1-4 alkoxy group is located at the ortho position of the C _6-12 aryl group. When the group is substituted, R ²³ may be a C _2-4 divalent group that forms a ring together with the C _1-4 alkyl group or the C _1-4 alkoxy group. )) Is asymmetrically oxidized with an oxidizing agent, the following formula (31)

(R ²² and R ²³ in the formula (31) are the same as described above, and the absolute configuration of the sulfur atom indicated by * means (R) or (S).) A compound can be produced.

Formula (1a), Formula (1a ′), Formula (1b), Formula (1b ′), Formula (2), Formula (2 ′), Formula (3a), Formula (3a ′), Formula (3b), Formula (3b ′), Formula (4) and Formula (4 ′) (Formula (1a), Formula (1a ′), Formula (1b), Formula (1b ′), Formula (2), Formula (2 ′), Formula In formula (3a), formula (3a ′), formula (3b), formula (3b ′), formula (4) and formula (4 ′), R ¹ , R ² , R ³ and R ⁴ are the same as above. An optically active titanium complex obtained by reacting an optically active ligand represented by any of the above and a titanium compound (the optically active titanium complex is an optically active titanium salen complex, an optically active titanium salalene complex, or an optically active compound). A titanium-saran complex) is used as a catalyst, and the following formula (32)

(R ²² and R ^{23 in} Formula (32) are the same as described above.) One of the optical isomers of the racemic or sulfoxide compound having a low optical purity is selectively oxidized with an oxidizing agent. According to the following formula (33)

(R ²² and R ²³ in the formula (33) are the same as those described above), and the optically active sulfoxide compound represented by the formula (31) is obtained by kinetic resolution. It is characterized in that an optically active sulfoxide compound can be produced.

  Each substituent in Formula (30), Formula (31), Formula (32), and Formula (33) will be described.

R ²² and R ²³ in Formula (30), Formula (31), Formula (32) and Formula (33) are different substituents, and each independently represents a C _6-12 aryl group (the aryl group). Is unsubstituted or by a halogen atom, a C _1-4 alkyl group, a C _1-4 alkoxy group, a C _2-5 alkylcarbonyloxy group, a C _2-5 alkoxycarbonyl group, a nitro group, or a cyano group. Substituted), C _6-12 arylmethyl group (the arylmethyl group is unsubstituted or halogen atom, C _1-4 alkyl group, C _1-4 alkoxy group, C _2-5 alkyl) Substituted with a carbonyloxy group, a C _2-5 alkoxycarbonyl group, a nitro group, or a cyano group.), 2-pyridyl, 3-pyridyl, 4-pyridyl, or C _1-6 alkyl (The alkyl group is unsubstituted or substituted by a halogen atom, a nitro group, a hydroxyl group, or a cyano group). However, when R ²² is a C _6-12 aryl group and a C _1-4 alkyl group or a C _1-4 alkoxy group is substituted at the ortho position of the C _6-12 aryl group, R ²³ is It may be a C _1-4 alkyl group or a C _2-4 divalent group that forms a ring together with the C _1-4 alkoxy group.

R ²² and R ²³ in Formula (30), Formula (31), Formula (32), and Formula (33) will be specifically described. The C _6-12 aryl group includes a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, o-nitrophenyl, m-nitrophenyl, p-nitrophenyl, o-chlorophenyl, m-chlorophenyl, p-chlorophenyl, o-bromophenyl, p-bromophenyl, m-bromophenyl, o-methoxyphenyl, m-methoxyphenyl, p-methoxyphenyl, 1-naphthyl group, 2-naphthyl group, 2-biphenylyl group etc. are mentioned. Examples of the C _6-12 arylmethyl group include benzyl group, 1′-methylphenylmethyl group, 1′-naphthylmethyl group, 2′-naphthylmethyl group, 2′-biphenylmethyl group and the like. The C _1-6 alkyl group is a methyl group, ethyl group, n-propyl group, c-propyl group, i-propyl group, c-propyl group, n-butyl group, i-butyl group, s-butyl group, Examples include t-butyl group, n-pentyl group, i-pentyl group, n-hexyl group, c-hexyl group and the like. When R ²² is a C _6-12 aryl group and a C _1-4 alkyl group or a C _1-4 alkoxy group is substituted at the ortho position thereof, R ²³ is the C _1-4 alkyl group, or C _{Examples of} the C _2-4 divalent group that forms a ring together with a _1-4 alkoxy group include a dimethylene group, a dimethyleneoxy group, a trimethylene group, a trimethyleneoxy group, a tetramethylene group, and a tetramethyleneoxy group. Etc.

R ²² and R ²³ in formula (30), formula (31), formula (32) and formula (33) are different substituents, and each independently represents a phenyl group, a 2-naphthyl group, a benzyl group. A 1′-naphthylmethyl group, a methyl group, and an ethyl group are preferred. R ²³ is a C _2-4 divalent group that forms a ring together with the C _1-4 alkyl group or C _1-4 alkoxy group, and includes a dimethylene group, a dimethyleneoxy group, and a trimethylene group. preferable.

Among the sulfide compounds represented by the formula (30), as a particularly preferable sulfide compound by a combination of the substituents R ²² and R ²³ , methyl phenyl sulfide,
Ethyl phenyl sulfide, methyl 2-methylphenyl sulfide,
Methyl 4-methylphenyl sulfide, methyl o-nitrophenyl sulfide,
Methyl p-nitrophenyl sulfide, methyl o-chlorophenyl sulfide, methyl p-chlorophenyl sulfide, methyl o-bromophenyl sulfide, methyl p-bromophenyl sulfide, methyl o-methoxyphenyl sulfide, methyl p-methoxyphenyl sulfide, ethyl o-nitrophenyl sulfide, methyl 1-naphthyl sulfide, methyl 2-naphthyl sulfide,
Methyl 2-pyridyl sulfide, methyl benzyl sulfide,
And ethyl benzyl sulfide.

  Next, Formula (1a), Formula (1a ′), Formula (1b), Formula (1b ′), Formula (2), Formula (2 ′), Formula (3a), Formula (3a ′), Formula (3b) ), Formula (3b ′), Formula (4), and Formula (4 ′)

The manufacturing method of the optically active ligand described in 1 is demonstrated.

  Formula (1a), Formula (1a ′), Formula (3a), and Formula (3a ′) are optically active salen ligands. For example, they can be produced by the method represented by the following reaction formula.

R ¹ , R ² , R ³ and R ⁴ in the above reaction formula are the same as described above. The aldehyde compound represented by the above formula (40) or the formula (41) and the diamine compound represented by the above formula (42) or the formula (43) (compound (40) or compound (41) per mol) 5 to 0.6 mol) is mixed in an organic solvent to produce the imine compound (1a), (1a ′), (3a) or (3a ′) which is a salen ligand. Examples of the organic solvent to be used include alcohol solvents, nitrile solvents, halogen solvents, aromatic hydrocarbon solvents, ether solvents, hydrocarbon solvents, amide solvents, or solvents obtained by mixing the above. I-propanol, ethanol, methanol, acetonitrile, propionitrile, dichloromethane, chloroform, benzene, toluene, tetrahydrofuran, diethyl ether, hexane, heptane, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like. Among these, preferred solvents are i-propanol, ethanol, methanol, acetonitrile, dichloromethane, toluene, dimethylformamide, and a mixture of the above solvents.

  Formula (42) and formula (43) of the diamine compound to be used can use the diamine compound which forms a salt with a free diamine compound. Specific examples include diamine sulfate, diamine hydrochloride, and diamine tartrate. As a diamine compound used when manufacturing the imine compound which is a salen ligand, a free diamine compound, a diamine sulfate, and a diamine tartrate are preferable.

  When these salen ligands are produced, they can be produced in the presence of a dehydrating agent for 1 mol of the formula (40) or the formula (41) of the 2-hydroxyarylaldehyde compound. Examples of the dehydrating agent include anhydrous magnesium sulfate, anhydrous sodium sulfate, anhydrous boric acid, and molecular sieves. It can be produced by coexisting 1 to 10 mol of a dehydrating agent with respect to 1 mol of the formula (40) or the formula (41) of the 2-hydroxyaryl aldehyde compound. In the case of molecular sieves, 2-hydroxyaryl aldehyde It can be produced in the presence of 1 to 10 times the weight of the dehydrating agent relative to the weight of the compound of formula (40) or formula (41). As the dehydrating agent, anhydrous magnesium sulfate, anhydrous boric acid, and molecular sieves are preferable. Further, as a dehydration operation, a Dean-Stark type dehydration reactor or a Soxhlet type dehydration reactor can be used while removing water produced by azeotropic dehydration with a solvent.

  The reaction temperature for producing the salen ligand can be from -78 ° C to the boiling point of the solvent used, but is preferably in the range of 0 ° C to 50 ° C.

  The formula (40) or formula (41) of the 2-hydroxyarylaldehyde compound is described in J. Chem. Soc. Perkin Trans 1. (1980), 1862-1865. Can be produced by heating and stirring the corresponding phenol compound (P40) or compound (P41) and paraformaldehyde in toluene in the presence of tin chloride and a base. The production method is shown in the following reaction formula.

  Specific examples of the production of 2-hydroxyaryl aldehyde compounds will be described. For example, as for 2-hydroxyaryl aldehyde compounds (44) and (44 '), Japanese Patent Application Laid-Open No. 7-285983 and non-patent document Tetrahedron (1994), 50, 11827-11838. It can be synthesized by the method described in 1. An example of the production method is shown in the following reaction formula.

Compound (44 ') can be produced from compound (45') by the same production method as described above.

In the above reaction formula, Ph is a phenyl group, Tf ₂ NPh is N-phenyltrifluoromethanesulfonimide, PhMgBr is a Grignard reagent, NiCl ₂ (dppe) is [1,2-bis (diphenylphosphino) ethane chloride. ] Nickel (II) chloride, MOMCl is chloromethyl methyl ether, (i-Pr) ₂ NEt is ethyl diisopropylamine, t-BuLi is tertiary butyllithium, DMF is dimethylformamide, TMSBr is trimethylsilyl bromide Means. In Reaction Scheme 4, the 2-hydroxyaryl aldehyde compound (44) is obtained from the starting material (45), and the 2-hydroxyaryl aldehyde compound (44) is obtained from the starting material (45 ′) using the same method as described above. ') Can get.

As for the diamine compound, for example, (1S, 2S)-(+)-1,2-diaminocyclohexane and (1R, 2R)-(−)-1,2-diaminocyclohexane are Aldr.
available from Ich, Tokyo Chemical Industry Co., Ltd., etc., (1S, 2S)-(-)-1,
2-diphenylethylenediamine and (1R, 2R)-(+)-1,2-diphenylethylenediamine are available from Aldrich.

  Formula (1b), Formula (1b ′), Formula (3b), and Formula (3b ′) are optically active salalene ligands, and are described in Adv. Synth. Catal. (2007), 349, 2385-2391. It can be synthesized by the method described in 1.

  Formula (2), Formula (2 '), Formula (4), and Formula (4') are optically active Saran ligands, and are disclosed in WO2006 / 087874A1 in patent literature and Angew. Chem. Int. Ed. (2006), 45, 3478-3480. It can be synthesized by the method described in 1.

  Formula (21a), Formula (21a ′), Formula (23a), and Formula (23a ′) are optically active titanium-salen complexes, JP2002-308845A in patent literature, and Tetrahedron Letters (2001), 42 in nonpatent literature. , 3873-3876. It can be synthesized by the method described in 1.

  Formula (21b), Formula (21b '), Formula (23b), and Formula (23b') are optically active titanium salalene complexes, and are described in Adv. Synth. Catal. (2007), 349, 2385-2391. A titanium complex is formed by reducing one of the two imino bonds of the salen ligand from the optically active salen ligand and the Meerwein-Pondorf-Verley (MPV) reduction reaction from the optically active salen ligand. Patent Document JP 2007-284438A, and Non-patent Document Angew. Chem. Int. Ed. (2005), 44, 4935-4939. The synthesis method described in 1 is known.

  Formula (22), Formula (22 '), Formula (24), and Formula (24') are optically active titanium-saran complexes and are described in WO2006 / 087874A1 in the patent document and Angew. Chem. Int. Ed. (2006), 45, 3478-3480. Eur. J. et al. Org. Chem. (2008), 3369-3376. It can be synthesized by the method described in 1.

In the production of an optically active titanium compound (the optically active titanium complex is an optically active titanium salen complex, an optically active titanium salalene complex, or an optically active titanium salen complex), titanium tetramethoxide, titanium tetra Examples include ethoxide, titanium tetra n-propoxide, titanium tetra i-propoxide, titanium tetra n-butoxide, titanium tetra t-butoxide, titanium tetrachloride, etc. Among these, titanium tetra i-propoxide and titanium tetra t-Butoxide is preferable, and titanium tetra i-propoxide [Ti (Oi-Pr) ₄ ] is more preferable.

  The procurement of the olefin compound represented by the formula (5), formula (6), formula (7), formula (8), formula (9) or formula (10), which is the starting material, will be described.

  For example, 1,2-dihydronaphthalene, indene, styrene and 2-vinylnaphthalene are available from Aldrich, Tokyo Chemical Industry Co., Ltd., etc., and 1,2-dihydro-4-methylnaphthalene is a non-patent document. Synthetic Communications (2003), 33 (21), 3653-3660. It can be synthesized by the method described in 1.

R ⁹ and R ^{10 in the} formula (9) and the formula (10) are combined with each other, and the formula (11) (R ¹² in the formula (11) which is a divalent group is a methyl group) The substitution position of the formula (11) is as follows. The compound having a benzopyran ring, which is a divalent group represented by R ⁹ side is an oxygen atom and R ¹⁰ side is a carbon atom. It can be synthesized using a general synthesis method. Furthermore, the synthesis of the condensed ring in the formulas (9) and (10) can be achieved by appropriately combining and utilizing the following heterocycle synthesis methods with the benzopyran ring synthesis method.

Benzopyran ring general synthesis known method Med. Chem. (1984), 27, 1127. ,
J. et al. Med. Chem. (1986), 29, 2194. ,
J. et al. Org. Chem. (1995), 60, 3397. ,

JP-A-56-57785, JP-A-56-57786,
JP-A-58-188880, JP-A-2-141,
They can be synthesized according to the methods described in JP-A-10-87650, JP-A-11-209366, and the like.

Indole and Oxyindole Synthesis Methods Known Methods Heterocycles, (1986), 24, 31. ,
Synthesis (2001), 222. ,
J. et al. Chem. Soc. (1961), 2714.
Etc. can be synthesized according to the method described in the above.

Methods for Synthesis of Imidazolinone Known Methods Synthetic Commun. (2000), 30, 1937.
Etc. can be synthesized according to the method described in the above.

Methods for Synthesizing Quinolines Known Methods Synthetic Commun. (1996), 26, 2197. ,
Tetrahedron (1997), 53, 6001. ,
J. et al. Chem. Soc. Perkin Trans. (1993), 1,181. ,
J. et al. Org. Chem. (1990), 55, 738. ,
Chem. Pharm. Bull. (1981), 29, 2485. ,
J. et al. Org. Chem. (1987), 52, 1673. ,
J. et al. Heterocyclic Chem. (1993), 30, 17.
Etc. can be synthesized according to the method described in the above.

Synthetic Commun. (2000), 30,427. ,
Tetrahedron Lett. (1999), 40, 4505. ,
Synthesis, (1997), 1249. ,
J. et al. Heterocyclic Chem. (1989), 26, 917. ,
Heterocycles, (1986), 24, 2169. ,
Synthesis, (1995), 1362.
Method described in etc.

Can be synthesized according to

Methods for Synthesizing Benzothiazole and Triazole Known Methods Synthetic Commun. (1997), 27, 1487. ,
J. et al. Chem. Soc (C). (1968), 1268.
Etc. can be synthesized according to the method described in the above.

Methods for synthesizing quinoxaline and quinoxalinone Org. Chem. , (2000), 65, 3395. ,
Tetrahedron Lett. (1999), 40, 4507. ,
Bull. Chem. Soc. Jpn. , (1987), 60, 1145.
Etc. can be synthesized according to the method described in the above.

Methods for synthesizing benzoxazinones Med. Chem. , (1987), 30, 295. ,
J. et al. Med. Chem. (2000), 43, 3408. ,
J. et al. Heterocyclic Chem. (1995), 32, 395.
Etc. can be synthesized according to the method described in the above.

The compounds represented by the following formulas (52) and (53) can be obtained by reacting the compound (50) with the compound (51).
(Reference J. Org. Chem., (1987), 52, 1673.)

The compounds represented by the following formulas (52) and (53) can also be obtained by reacting the compound (50) and the compound (54) in the presence of an acid catalyst.
(Reference Tetrahedron (1997), 53, 6001.,
J. et al. Heterocyclic Chem. (1993), 30, 17. )

  The chromene compound represented by the following formula (57) can be synthesized from the compound (55) and obtained by performing mesylation via the compound (56) obtained by reducing the nitro group to an amine with a platinum carbon catalyst. Can do. Pt / C in the following formula is a platinum carbon catalyst, and MsCl means mesyl chloride.

  It describes about the solvent used by the asymmetric epoxidation reaction of an olefin compound, and the asymmetric oxidation reaction of a sulfide compound, using an optically active titanium complex as a catalyst. The aprotic organic solvent is a halogen solvent, an aromatic hydrocarbon solvent, an ester solvent, an ether solvent or a nitrile solvent, and the protic organic solvent is an alcohol solvent. Examples of the halogen solvent include dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene, the aromatic hydrocarbon solvent includes benzene, toluene, and the like, and the ester solvent includes ethyl acetate and the like. Examples of the ether solvent include tetrahydrofuran and diethyl ether, and examples of the nitrile solvent include butyronitrile, propionitrile, acetonitrile, and the like. Examples of the alcohol solvent include methanol, ethanol, i-propanol, and a mixed solvent in which the above solvents are arbitrarily selected and mixed. In addition, when an aqueous solution of hydrogen peroxide (hydrogen peroxide solution) is used in this reaction, the organic layer and the aqueous layer may be separated by mixing with an organic solvent that does not dissolve in water. A two-phase solvent can also be used as the reaction solvent of the present invention. Preferred solvents are aprotic organic solvents such as dichloromethane, 1,2-dichloroethane, chlorobenzene, toluene, ethyl acetate, or a mixture of these solvents. More preferred are dichloromethane, toluene, and ethyl acetate.

  Specific examples of the oxidizing agent used in the reaction include iodosobenzene, sodium hypochlorite, m-chloroperbenzoic acid, oxone (registered trademark of DuPont), hydrogen peroxide, urea-hydrogen peroxide adduct ( UHP), oxaziridine, N-methylmorpholine oxide (NMO), t-butyl hydroperoxide (TBHP), cumene hydroperoxide (CHP), and a mixture obtained by arbitrarily selecting and mixing the above oxidizing agents. Among these, hydrogen peroxide solution and urea-hydrogen peroxide adduct (UHP) are preferable. In the case where the oxidizing agent is hydrogen peroxide solution, the concentration is in the range of 1 to 100% (% by weight), but the range of 5 to 60% (% by weight) is preferable.

  Although the range of 1-10 equivalent is mentioned as an usage-amount of the oxidizing agent used by reaction with respect to the olefin compound or sulfide compound which is a starting material, The range of 1-3 equivalent is preferable.

  As a method for adding the oxidizing agent, divided addition and continuous addition can be mentioned in addition to batch addition. In the case of continuous addition, the addition rate is preferably in a range in which the internal temperature in the reaction solvent system does not increase rapidly, specifically in the range of 0.01 to 1000 equivalents per hour, more preferably 0.05 to 0. The range is 3 equivalents. The divided addition is a method in which the oxidizing agent to be used is added in p times (p is an arbitrary integer). The division may be equally divided or unequal, and p is preferably in the range of 2 to 100.

  With respect to the reaction temperature, a range of −78 ° C. to solvent reflux temperature or a solvent melting point temperature to solvent reflux temperature to be used can be mentioned, but a range of −20 to 50 ° C. is preferred, and a range of 0 to 35 ° C. is more preferred.

  In order to improve the reactivity, a reagent for adjusting the pH in the reaction system can be added. For details, see Synlett (2007), 25, 2445-2447. There is a description.

  When adding the buffer or buffer to be used to the reaction system, there are a method of adding it to the reaction solution as it is, a method of adding it after dissolving it in an oxidizing agent to be used, for example, 30% hydrogen peroxide, etc. It can be appropriately selected depending on the raw materials and reaction conditions.

  The components used in the buffer include boric acid, phosphoric acid, alkaline phosphoric acid, alkaline hydrogen phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium dihydrogen phosphate, dipotassium hydrogen phosphate, pyrophosphoric acid Disodium dihydrogen, tetrasodium diphosphate, ammonium phosphate, ammonium hydrogen phosphate, ammonium nitrate, sodium acetate, ammonium acetate, sodium bicarbonate, ammonium bicarbonate, nitrilotriacetic acid (NTA) and its alkali salts, ethylenedinitriloacetic acid (EDTA) or an alkali salt thereof, triethylenetetraminehexaacetic acid (TTHA), (N- (2-hydroxyethyl) -ethylenediamine-N, N, N′-triacetic acid trisodium salt, ethylene glycol-bis (β-aminoethyl) Ether) -N, N-tetraacetic acid (E TA), 3-aza-3- (carboxymethyl) -pentamethylenedinitrilotetraacetic acid (DTPA), 1,2-cyclohexanediamine-N, N, N, N′-tetraacetic acid, tris (hydroxymethyl) aminomethane (Tris) and the like, and disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium dihydrogen phosphate, dipotassium hydrogen phosphate, and tris (hydroxymethyl) aminomethane (Tris) are preferable.

The buffer solution is a non-patent document D.I. D. Perrin. B. Dempsey. "Buffers for pH and Metal Ion Control" Ed. by CHAPMAN AND HALL, London, (1974) or non-patent literature edited by the Chemical Society of Japan, 3rd edition; Chemical Handbook; Fundamentals II (1984), pages 354-357. Examples of the buffer include citrate / NaOH buffer, citrate / sodium citrate buffer, phosphate buffer, KH ₂ PO ₄ / NaOH buffer, Tris / HCl buffer, borate / NaOH buffer, boron Examples include acid Na / HCl buffer, and citric acid / NaOH buffer, citric acid / sodium citrate buffer, boric acid / NaOH buffer, phosphate buffer, and KH ₂ PO ₄ / NaOH buffer are preferable. .

  In order to improve the reactivity, a reagent for adjusting the pH in the reaction system can be added. The pH range to be adjusted is pH 4-11, preferably pH 6-9, more preferably pH 7-8. As a reagent for pH adjustment, an inorganic salt or a buffer solution can be used. Examples of the salt include carbonates, hydrochlorides, sulfates, phosphates, borates, acetates, phthalates, and the like, preferably phosphates. The concentration of the buffer solution is in the range of 0.1 mM to 1000 mM, preferably 10 mM to 100 mM.

  Hereinafter, although an Example demonstrates in more detail, this invention is not limited to these.

Example 1
The synthesis of the optically active titanium-saran complex (65) is described below.

(Monoether synthesis)
Synthesis of 2 ′-(9-anthrylmethoxy) -1,1′-biphenyl-2-ol (62):
2,2-Biphenol (4.10 g, 22 mmol), potassium carbonate (3.04 g, 22 mmol), potassium iodide (3.66 g, 22 mmol) and 26 mL of acetone were added to the reaction vessel and stirred to 60 ° C. Heated. To this mixed solution was added 9-chloromethylanthracene (61) (5.01 g, 22 mmol), and the mixture was stirred at 60 ° C. for 20 hours. After confirming the reaction conversion rate by HPLC, a saturated aqueous ammonium chloride solution was added to stop the reaction. After liquid separation, the aqueous layer was extracted with ethyl acetate, combined and concentrated to obtain a crude product. The crude product was purified by silica gel column chromatography to obtain monoether (62) (3.01 g) as white crystals in a yield of 36.3% and a HPLC relative area percentage of 96.3%.
¹ H-NMR (300 MHz, CDCl ₃ ) δ; 5.92 (s, 2H, —OCH ₂ —), 6.46 (s, 1H, —OH), 6.80 (dd, J = 8.0, 1.2 Hz, 1H), 6.94 (dt, J = 7.3, 1.2 Hz, 1H), 7.14-7.28 (m, 3H), 7.34-7.49 (m, 7H) ), 7.93 to 8.03 (m, 2H), 8.03 to 8.13 (m, 2H), 8.45 (s, 1H).
HPLC analysis conditions:
Column name Inertsil ODS-3 4.6 mmφ × 150 mm × 3 μm,
Eluent acetonitrile / 20 mM aqueous sodium acetate solution (v / v) = 96/4
Flow rate 1.0 mL / min, column temperature 40 ° C., retention time 2.4 minutes Analytical wavelength 254 nm

(Hydroxy aryl aldehyde synthesis)
Synthesis of 2-hydroxy-2 ′-(9-anthrylmethoxy) -1,1′-biphenyl-3-carbaldehyde (63):
Paraformaldehyde (0.72 g, 31 mmol), anhydrous magnesium chloride (1.5 g, 31 mmol), N, N, N ′, N′-tetramethylethylenediamine (TMEDA) (2.4 mL, 16 mmol) and acetonitrile (27 mL). The reaction vessel was charged and the temperature was maintained at 85 ° C. To this mixed solution was added monoether (62) (3.0 g, 8 mmol), and the mixture was washed with acetonitrile (3.0 g). After stirring at 85 ° C. for 17 hours, 2 mol / L hydrochloric acid was added to stop the reaction. After neutralization, the aqueous layer from which acetonitrile was distilled off was extracted with ethyl acetate, the organic layer was washed with water (100 mL) three times, and then ethyl acetate was distilled off to obtain pale brown crystals. The crude product crystals were suspended and washed with isopropyl alcohol to give hydroxyaryl aldehyde (63) (1.86 g) as a pale yellow powder in a yield of 57.5% and a HPLC relative area percentage of 89.2%. Obtained.
¹ H-NMR (300 MHz, CDCl ₃ ) δ; 5.90 (s, 2H, —O—CH ₂ —), 6.65 (t, J = 7.7 Hz, 1H), 7.08 to 7.20. (M, 2H), 7.25 to 7.32 (m, 2H), 7.35 to 7.50 (m, 6H), 7.87 to 7.97 (m, 2H), 8.12 to 8 .23 (m, 2H), 8.35 (s, 1H), 9.64 (s, 1H, -CHO), 11.15 (s, 1H, -OH).
HPLC analysis conditions:
Column name Inertsil ODS-3 4.6 mmφ × 150 mm × 3 μm
Eluent acetonitrile / 20 mM aqueous sodium acetate solution (v / v) = 96/4
Flow rate 1.0 mL / min, column temperature 40 ° C., retention time 2.5 minutes Analytical wavelength 280 nm

(Optically active Saran ligand synthesis)
Synthesis of optically active salen ligand (64):
(S, S) -cyclohexanediamine (58) (0.228 g, 2.00 mmol), aldehyde (63) (1.62 g, 4.00 mmol) and toluene (9 mL) were charged into a reaction vessel and heated to 50 ° C. And stirred for 1 hour. Methanol (4 mL) was added to the reaction solution, and the mixture was further stirred for 2 hours, and then sodium borohydride (0.189 g, 4.00 mmol) was added little by little while paying attention to foaming. The reaction solution was stirred at 50 ° C. for 3 hours and at room temperature for 12 hours, and then water was added to stop the reaction. After toluene (9 mL) was added for liquid separation, the organic layer was washed with water and the solvent was distilled off to obtain a crude product as a pale yellow solid. Recrystallization with isopropyl alcohol gave Saran ligand (64) as light yellow crystals (1.37 g) in a yield of 76.3% and a relative HPLC area percentage of 80.6%.
¹ H-NMR (300 MHz, CDCl ₃ ) δ; 0.55 to 0.78 (br, 2H), 0.78 to 1.00 (br, 2H), 1.18 to 1.47 (br, 2H) , 1.61~1.84 (br, 2H), 1.88~2.09 (br, 2H), 3.51 (d, J = 13.5Hz, 2H, -N-CH 2 -), 3 .67 (d, J = 13.5 Hz, 2H, —N—CH ₂ —), 5.74 (s, 4H, —O—CH ₂ —), 6.64 (t, J = 7.4 Hz, 2H) ), 6.75 (dd, J = 7.4, 1.2 Hz, 2H), 7.05 to 7.20 (m, 4H) 7.29 to 7.47 (m, 16H), 7.83. 7.92 (m, 4H) 8.00 to 8.09 (m, 4H) 8.31 (s, 2H).
HPLC analysis conditions:
Column name Inertsil ODS-3 4.6 mmφ × 150 mm × 3 μm
Eluent acetonitrile / 20 mM aqueous sodium acetate solution (v / v) = 96/4
Flow rate 1.0 mL / min, column temperature 40 ° C., retention time 7.8 minutes Measurement wavelength 254 nm

(Synthesis of optically active titanium-saran complex)
Synthesis of optically active titanium-saran complex (65):
To a mixed solution of optically active Saran ligand (64) (0.446 g, 0.500 mmol) in acetonitrile (5.7 mL) and toluene (1.0 mL), titanium tetraisopropoxide [Ti (Oi-Pr) ₄ ] (0.148 mL, 0.500 mmol) was added dropwise at 40 ° C. The reaction solution was stirred at 40 ° C. for 1 hour, water (27 mg, 1.5 mmol) was added dropwise, and the mixture was further stirred at 40 ° C. for 3 hours. The reaction temperature was set to 20 to 25 ° C., and the mixture was stirred for 15 hours. The reaction solution was concentrated, and acetonitrile (10 mL) was added to precipitate a solid. After filtering the solid, the cake was washed twice with acetonitrile (3 mL, 2 mL). By drying under reduced pressure while heating to 40 ° C., the optically active titanium-saran complex (65) (0.429 g) was obtained as a yellow powder in a yield of 90.0%.
¹ H-NMR (300 MHz, CDCl ₃ ) δ; −3.00 to −2.75 (m, 2H), −1.46 to −1.25 (m, 2H), −0.60 to −0. 40 (m, 2H), -0.37 to -0.06 (m, 4H), 0.72 to 1.13 (m, 4H), 1.48 to 1.93 (m, 2H), 2. 24 (t, J = 11.9 Hz, 2H), 2.54 (d, J = 11.0 Hz, 2H), 2.93 (d, J = 12.2 Hz, 2H), 3.17 (t, J = 11.5 Hz, 2H), 3.58 to 3.73 (m, 2H), 3.82 (d, J = 11.3 Hz, 2H), 5.09 (d, J = 10.4 Hz, 2H) , 5.15 (d, J = 10.4 Hz, 2H), 5.53 (d, J = 10.4 Hz, 2H), 5.60 (d, J = 10.4 Hz, 2H), 6.29 ( dd, J = .9, 1.6 Hz, 2H), 6.51 (dd, J = 7.7, 1.2 Hz, 2H), 6.68 to 7.53 (m, 40H), 7.63 to 7.76 ( m, 4H), 7.76-7.83 (m, 4H), 7.97 (t, J = 9.2 Hz, 8H), 8.23 (s, 2H), 8.40 (s, 2H) .
ESI-HRMS; C ₁₂₄ H ₁₀₅ N ₄ O ₁₀ Ti ₂ ⁺ :
m / z Measured value = 1906.6825, Theoretical value = 19066.6823

(Example 2)
The synthesis of the optically active titanium-saran complex (75) is described below.

(Monoether synthesis)
Synthesis of 2 ′-(4-methylbenzyloxy) -1,1′-biphenyl-2-ol (72):
2,2-Biphenol (3.72 g, 20 mmol), potassium carbonate (1.38 g, 10 mmol), potassium iodide (3.72 g, 20 mmol) and 23.5 mL of acetone were charged into the reaction vessel and stirred for 60 hours. Heated to ° C. To this mixed solution, p-methylbenzyl chloride (71) (2.81 g, 20 mmol) was added dropwise and stirred at 60 ° C. for 17 hours. After confirming the reaction conversion rate by HPLC, a saturated aqueous ammonium chloride solution was added to stop the reaction. After liquid separation, the aqueous layer was extracted with ethyl acetate, combined and concentrated to obtain a crude product. Purification by silica gel column chromatography (hexane / ethyl acetate (v / v) = 90/10, Rf value = 0.25) gave monoether (72) (4.30 g) as white crystals in a yield of 74.0. %, HPLC relative area percentage> 99.9%.
¹ H-NMR (300 MHz, CDCl ₃ ) δ; 2.32 (s, 3 H, —CH ₃ ), 5.07 (s, 2 H, —OCH ₂ —), 6.41 (s, 1 H, —OH) 6.97-7.05 (m, 2H), 7.07-7.19 (m, 6H), 7.23-7.38 (m, 4H).
HPLC analysis conditions:
Column name Inertsil ODS-3 4.6 mmφ × 150 mm × 3 μm
Eluent acetonitrile / 20 mM aqueous sodium acetate solution (v / v) = 96/4
Flow rate 1.0 mL / min, column temperature 40 ° C., retention time 2.0 minutes Measurement wavelength 254 nm

(Hydroxy aryl aldehyde synthesis)
Synthesis of 2-hydroxy-2 ′-(4-methylbenzyloxy) -1,1′-biphenyl-3-carbaldehyde (73):
Paraformaldehyde (0.93 g, 31 mmol), anhydrous magnesium chloride (2.0 g, 31 mmol), N, N, N ′, N′-tetramethylethylenediamine (TMEDA) (3.1 mL, 21 mmol) and tetrahydrofuran (30 mL). The reaction vessel was charged and the temperature was kept at 65 ° C. To this mixed solution was added monoether (72) (3.0 g, 10 mmol), and the mixture was washed with tetrahydrofuran (3.0 g). After stirring at 65 ° C. for 17 hours, 2 mol / L hydrochloric acid was added to stop the reaction. After separation, the aqueous layer was extracted with tetrahydrofuran, and the organic layers were combined and concentrated. The concentrate was dissolved in ethyl acetate (200 mL), washed three times with water (100 mL), and then ethyl acetate was distilled off to obtain pale brown crystals. The crystals were suspended and washed with isopropyl alcohol to obtain hydroxyarylaldehyde (73) (2.21 g) as a white powder in a yield of 67.4%.
¹ H-NMR (300 MHz, CDCl ₃ ) δ; 2.31 (s, 3H, —CH ₃ ), 5.04 (s, 2H, —OCH ₂ —), 7.01 to 7.12 (m, 5H) ), 7.13 to 7.18 (m, 2H), 7.29 to 7.37 (m, 2H), 7.53 to 7.59 (m, 4H), 9.95 (s, 1H, − CHO), 11.34 (s, 1H, -OH).

(Optically active Saran ligand synthesis)
Optically active salen ligand synthesis (74):
(S, S) -cyclohexanediamine (58) (0.285 g, 2.50 mmol), hydroxyarylaldehyde (73) (1.59 g, 5.00 mmol) and toluene (9 mL) were added to the reaction vessel, and this reaction was performed. The solution was heated to 50 ° C. and stirred for 1 hour. Methanol (2 mL) was added to the reaction solution, and the mixture was further stirred for 2 hours, and then sodium borohydride (0.189 g, 5.00 mmol) was added little by little while paying attention to foaming. After stirring at 50 ° C. for 3 hours and at room temperature for 12 hours, water was added to stop the reaction. After toluene (9 mL) was added for liquid separation, the organic layer was washed with water and the solvent was distilled off to obtain a crude product. Purification by column chromatography gave the Saran ligand (74) as a white solid (1.73 g) in a yield of 96.3%.
¹ H-NMR (300 MHz, CDCl ₃ ) δ; 0.98 to 1.28 (br, 4H), 1.50 to 1.70 (br, 2H), 1.94 to 2.15 (br, 2H) _{, 2.25~2.41 (br, 2H),} 2.29 (s, 6H, -CH 3), 3.86 (d, J = 13.4Hz, 2H, -N-CH2 -), 3. 99 (d, J = 13.4 Hz, 2H, —N—CH ₂ —), 4.98 (s, 4H, —O—CH ₂ —), 6.81 (t, J = 7.4 Hz, 2H) , 6.92-7.45 (m, 22H).
HPLC analysis conditions:
Column name Inertsil ODS-3 4.6 mmφ × 150 mm × 3 μm
Eluent acetonitrile / 20 mM aqueous sodium acetate solution (v / v) = 96/4
Flow rate 1.0 mL / min, column temperature 40 ° C
Retention time Saran compound; 4.6 minutes, (salen compound; 5.2 minutes)
Measurement wavelength 254nm

(Synthesis of optically active titanium-saran complex)
Synthesis of optically active titanium-saran complex (75):
To a solution of optically active Saran ligand (74) (0.359 g, 0.500 mmol) in acetonitrile (4.6 mL), titanium tetraisopropoxide [Ti (Oi-Pr) ₄ ] (0.148 mL, 0.500 mmol). ) Was added dropwise at 40 ° C. The reaction solution was stirred at 40 ° C. for 1 hour, water (27 mg, 1.5 mmol) was added dropwise, and the mixture was further stirred at 40 ° C. for 3 hours. The reaction temperature was set to 20 to 25 ° C., and the mixture was stirred for 15 hours. The precipitated solid was filtered, and the cake was washed twice with acetonitrile (3 mL, 2 mL). By drying under reduced pressure while heating to 40 ° C., the optically active titanium-saran complex (75) (0.286 g) was obtained as a pale yellow powder in a yield of 73.3% and a relative area percentage of HPLC of> 99%. .
¹ H-NMR (300 MHz, CDCl ₃ ) δ; −1.20 to −0.99 (br, 2H), 0.27 to 0.46 (br, 2H), 0.46 to 0.82 (br, 4H), 1.16 (d, J = 11.0 Hz, 4H), 1.48 to 1.87 (br, 6H), 2.20 (s, 6H, -CH3), 2.23 to 2.31. (M, 2H), 2.33 (s, 6H, -CH3), 2.37 to 2.58 (m, 2H), 2.91 (d, J = 13.7 Hz, 2H), 3.34 ( d, J = 11.0 Hz, 2H), 3.67 (t, J = 12.5 Hz, 4H), 4.06 (d, J = 10.7 Hz, 4H), 4.40 (d, J = 11 .9 Hz, 2H), 4.52 (d, J = 11.9 Hz, 2H), 4.86 (d, J = 12.5 Hz, 2H), 4.96 (d, J = 11.9 Hz, H), 6.11 (dd, J = 7.7, 1.2 Hz, 2H), 6.31 (dd, J = 7.6, 1.6 Hz, 2H), 6.59 to 7.19 (m 38H), 7.30 (dd, J = 7.4, 1.8 Hz, 2H).
HPLC analysis conditions:
Column name Inertsil ODS-3 4.6 mmφ × 150 mm × 3 μm
Eluent acetonitrile / 20 mM aqueous sodium acetate solution (v / v) = 96/4
Flow rate: 1.0 mL / min, column temperature: 40 ° C., retention time: 73.5 minutes Measurement wavelength: 254 nm

(Example 3)
The synthesis of the optically active titanium-saran complex (105) is described below.

(Monoether synthesis)
Synthesis of 2 ′-(mesitylmethoxy) -1,1′-biphenyl-2-ol (102):
2,2-Biphenol (3.72 g, 20 mmol), potassium carbonate (2.76 g, 20 mmol), potassium iodide (3.32 g, 20 mmol), and 24 mL of acetone were charged into the reaction vessel and stirred to 60 ° C. Heated. 2,4,6, -Trimethylbenzyl chloride (101) (3.37 g, 20 mmol) was added to the mixed solution, and the mixture was stirred at 60 ° C. for 17 hours. After confirming the reaction conversion rate by HPLC, a saturated aqueous ammonium chloride solution was added to stop the reaction. After liquid separation, the aqueous layer was extracted with ethyl acetate, combined and concentrated to obtain a crude product. The crude product was recrystallized from 2-propanol to obtain monoether (102) (5.93 g) as white crystals in a yield of 93.1%.
¹ H-NMR (300 MHz, CDCl ₃ ) δ; 2.17 (s, 6 H, —CH ₃ ), 2.24 (s, 3 H, —CH ₃ ), 5.01 (s, 2 H, —OCH ₂ —) ), 6.70 (s, 1H, —OH), 6.80 (s, 2H), 6.89 to 7.02 (m, 2H), 7.16 to 7.28 (m, 4H), 7 .32-7.43 (m, 2H).

(Hydroxy aryl aldehyde synthesis)
Synthesis of 2-hydroxy-2 ′-(2-mesitylmethoxy) -1,1′-biphenyl-3-carbaldehyde (103):
Paraformaldehyde (4.76 g, 159 mmol), anhydrous magnesium chloride (10.06 g, 106 mmol), N, N, N ′, N′-tetramethylethylenediamine (TMEDA) (12.3 mL, 106 mmol) and tetrahydrofuran (153 mL). The reaction vessel was charged and the temperature was kept at 70 ° C. To this mixed solution was added monoether (102) (17.0 g, 53 mmol). After stirring at 70 ° C. for 91 hours, 2 mol / L hydrochloric acid was added to stop the reaction. After neutralization, the aqueous layer from which tetrahydrofuran was distilled off was extracted with chloroform. The organic layer was washed with water (100 mL) three times, and then chloroform was distilled off to obtain a crude product. This crude product was crystallized from hexane and suspended and washed with 2-propanol to give hydroxyarylaldehyde (103) (13.1 g) as white crystals, yield 71.5%, HPLC relative area percentage 99. Obtained at 2%.
¹ H-NMR (300 MHz, CDCl ₃ ) δ; 2.19 (s, 6 H, —CH ₃ ), 2.21 (s, 3 H, —CH ₃ ), 4.97 (s, 2 H, —O—CH _2- ), 6.76 (s, 2H), 6.94 (t, J = 7.4 Hz, 1H), 6.75 (td, J = 7.3, 1.3 Hz, 1H), 7.18. ˜7.33 (m, 2H), 7.35 to 7.49 (m, 3H), 9.84 (s, 1H, —CHO), 11.21 (s, 1H, —OH).
HPLC analysis conditions:
Column name Inertsil ODS-3 4.6 mmφ × 150 mm × 3 μm
Eluent acetonitrile / 20 mM aqueous sodium acetate solution (v / v) = 96/4
Flow rate 1.0 mL / min, column temperature 40 ° C., retention time 2.5 minutes Analytical wavelength 254 nm

(Optically active Saran ligand synthesis)
Synthesis of optically active Saran ligand (104):
(S, S) -cyclohexanediamine (58) (0.229 g, 2.01 mmol), hydroxyarylaldehyde (103) (1.39 g, 4.01 mmol) and toluene (8 mL) were added to the reaction vessel, and this reaction was performed. The solution was heated to 50 ° C. and stirred for 1 hour. Methanol (4 mL) was added to the reaction solution and the mixture was further stirred for 1 hour, and then sodium borohydride (0.152 g, 4.01 mmol) was added little by little while paying attention to foaming. After stirring at 50 ° C. for 4 hours, the mixture was allowed to cool to room temperature, and water was added to stop the reaction. After toluene (8 mL) was added for liquid separation, the organic layer was washed with water and the solvent was distilled off to obtain a crude product. The crude product was recrystallized from isopropyl alcohol to obtain Saran ligand (104) as white crystals (1.24 g) in a yield of 79.6% and HPLC relative area percentage of 98.1%.
¹ H-NMR (300 MHz, CDCl ₃ ) δ; 0.87 to 1.39 (m, 4H), 1.48 to 1.72 (m, 2H), 1.89 to 2.08 (m, 2H) _{, 2.17 (s, 12H, -CH} 3), 2.21 (s, 6H, -CH 3), 2.16~2.37 (m, 4H), 3.79 (d, J = 13. 7 Hz, 2H, —N—CH ₂ —), 3.92 (d, J = 13.4 Hz, 2H, —N—CH ₂ —), 4.91 (s, 4H, —O—CH ₂ —), 6.73 (td, J = 4.5, 2.1 Hz, 2H), 6.75 (s, 4H), 6.92 (d, J = 7.4 Hz, 2H), 7.02 to 7.15 (M, 4H), 7.18 (d, J = 8.0 Hz, 2H), 7.27-7.38 (m, 4H).
HPLC analysis conditions:
Column name Inertsil ODS-3 4.6 mmφ × 150 mm × 3 μm
Eluent acetonitrile / 20 mM aqueous sodium acetate solution (v / v) = 96/4
Flow rate 1.0 mL / min, column temperature 40 ° C., retention time 6.5 minutes Measurement wavelength 254 nm

(Synthesis of optically active titanium-saran complex)
Synthesis of optically active titanium-saran complex (105):
To a solution of optically active Saran ligand (104) (0.388 g, 0.500 mmol) in acetonitrile (5.0 mL) was added titanium tetraisopropoxide [Ti (Oi-Pr) ₄ ] (0.148 mL,. 500 mmol) was added dropwise at 40 ° C. The reaction solution was stirred at 40 ° C. for 1 hour, water (27 mg, 1.5 mmol) was added dropwise, and the mixture was further stirred at 40 ° C. for 3 hours. The reaction temperature was 20 to 25 ° C., and the mixture was stirred for 15 hours. The reaction solution was concentrated, and acetonitrile (5.0 mL) was added to precipitate a solid. After filtering the solid, the cake was washed twice with acetonitrile (3 mL, 3 mL). By drying under reduced pressure while heating to 40 ° C., the optically active titanium-saran complex (105) (0.332 g) was obtained as a pale yellow solid in a yield of 79.4%.
¹ H-NMR (300 MHz, CDCl ₃ ) δ; -1.21 to -0.93 (m, 2H), 0.17 to 0.89 (m, 6H), 0.98 to 1.30 (m, _{4H), 1.49~1.80 (m, 6H} ), 1.93 (s, 12H, -CH 3), 2.15 (s, 6H, -CH 3), 2.22 (s, 12H, _{-CH 3), 2.24 (s,} 6H, -CH 3), 2.33~2.48 (m, 2H), 2.54 (t, J = 11.8Hz, 2H), 2.95 ( d, J = 14.6 Hz, 2H), 3.31 (d, J = 10.7 Hz, 2H), 3.63 (t, J = 11.5 Hz, 2H), 3.72 (d, J = 14 .3 Hz, 2H), 4.02 (d, J = 10.7 Hz, 2H), 4.27 (d, J = 10.4 Hz, 2H), 4.30 (d, J = 10.7 Hz, 2H) , 4.78 (d, J = 10.1 Hz, 2H), 4.82 (d, J = 10.4 Hz, 2H), 6.21 (d, J = 7.7 Hz, 2H), 6.28 (d , J = 7.1 Hz, 2H), 6.59 (t, J = 7.3 Hz, 2H), 6.63 to 6.85 (m, 8H), 6.67 (s, 4H), 6.80. (S, 4H), 6.88 (d, J = 7.1 Hz, 2H), 6.93 (d, J = 7.4 Hz, 2H), 7.00 to 7.22 (m, 10H).
_{ESI-HRMS; C 104 H 113} N 4 O 10 Ti 2 +:
m / z Measured value = 11674.7449, Theoretical value = 16.74.7449

Example 4
The synthesis of the optically active titanium-saran complex (115) is described below.

(Monoether synthesis)
Synthesis of 2 ′-(2-naphthylmethoxy) -1,1′-biphenyl-2-ol (112):
2,2-Biphenol (3.72 g, 20 mmol), potassium carbonate (2.8 g, 20 mmol) and 24 mL of acetone were charged into a reaction vessel and heated to 60 ° C. with stirring. To this mixed solution was added 2- (bromomethyl) naphthalene (111) (4.42 g, 20 mmol), and the mixture was stirred at 60 ° C. for 17 hours. After confirming the reaction conversion rate by HPLC, a saturated aqueous ammonium chloride solution was added to stop the reaction. After liquid separation, the aqueous layer was extracted with ethyl acetate, combined and concentrated to obtain a crude product. The crude product was recrystallized from 2-propanol to obtain monoether (112) (4.75 g) as white crystals in a yield of 72.8%.
¹ H-NMR (300 MHz, CDCl ₃ ) δ; 5.27 (s, 2H, —OCH ₂ —), 6.31 (s, 1H, —OH), 6.97 to 7.08 (m, 2H) , 7.08-7.18 (m, 2H), 7.25-7.41 (m, 5H), 7.41-7.50 (m, 2H), 7.67-7.84 (m, 4H).

(Hydroxy aryl aldehyde synthesis)
Synthesis of 2-hydroxy-2 ′-(2-naphthylmethoxy) -1,1′-biphenyl-3-carbaldehyde (113):
Paraformaldehyde (0.90 g, 30 mmol), anhydrous magnesium chloride (1.9 g, 20 mmol), N, N, N ′, N′-tetramethylethylenediamine (TMEDA) (3.0 mL, 20 mmol) and tetrahydrofuran (33 mL). The reaction vessel was charged and the temperature was kept at 65 ° C. Monoether (112) (3.26 g, 10.0 mmol) was added to this mixed solution, and the mixture was washed with tetrahydrofuran (3.3 g). After stirring at 70 ° C. for 15 hours, 2 mol / L hydrochloric acid was added to stop the reaction. After neutralization, the aqueous layer from which acetonitrile was distilled off was extracted with ethyl acetate, the organic layer was washed with water (100 mL) three times, and then ethyl acetate was distilled off to obtain a crude product. The crude product was suspended and washed with isopropyl alcohol to give hydroxyarylaldehyde (113) (2.63 g) as white crystals in a yield of 74.1% and a HPLC relative area percentage of 99.0%.
¹ H-NMR (300 MHz, CDCl ₃ ) δ; 5.17 (s, 2H, —O—CH ₂ —), 6.93 to 7.08 (m, 3H), 7.25 to 7.49 (m 6H), 7.55 (dd, J = 7.4, 1.8 Hz, 1H), 7.61-7.78 (m, 4H), 9.84 (s, 1H, -CHO), 11. 42 (s, 1H, -OH).
HPLC analysis conditions:
Column name Inertsil ODS-3 4.6 mmφ × 150 mm × 3 μm
Eluent acetonitrile / 20 mM aqueous sodium acetate solution (v / v) = 96/4
Flow rate 1.0 mL / min, column temperature 40 ° C., retention time 2.5 minutes Analytical wavelength 254 nm

(Optically active Saran ligand synthesis)
Synthesis of optically active salen ligand (114):
(S, S) -cyclohexanediamine (58) (0.285 g, 2.50 mmol), hydroxyarylaldehyde (113) (1.77 g, 5.00 mmol) and toluene (10 mL) were charged into a reaction vessel, and this reaction was performed. The solution was heated to 50 ° C. and stirred for 1 hour. Methanol (4 mL) was added to the reaction solution, and the mixture was further stirred for 1 hour, and then sodium borohydride (0.189 g, 5.00 mmol) was added little by little while paying attention to foaming. After stirring at 50 ° C. for 4 hours, the mixture was allowed to cool to room temperature, and water was added to stop the reaction. After toluene (10 mL) was added for liquid separation, the organic layer was washed with water and the solvent was distilled off to obtain a crude product. Recrystallization from isopropyl alcohol gave Saran ligand (114) as white crystals (1.75 g) in a yield of 88.2% and a HPLC relative area percentage of 95.9%.
¹ H-NMR (300 MHz, CDCl ₃ ) δ; 0.61 to 1.00 (m, 6H), 1.12 to 1.49 (m, 4H), 1.66 to 1.90 (m, 2H) , 1.90~2.10 (m, 2H), 3.70 (d, J = 13.7Hz, 2H, -N-CH 2 -), 3.81 (d, J = 13.4Hz, 2H, _{-N-CH 2 -), 5.06} (d, J = 13.4Hz, 2H, -O-CH 2 -), 5.11 (d, J = 13.4Hz, 2H, -O-CH 2 - ), 6.82 (t, J = 7.4 Hz, 2H), 6.86 to 7.10 (m, 6H), 7.15 to 7.48 (m, 12H), 7.53 to 7.82. (M, 8H).
HPLC analysis conditions:
Column name Inertsil ODS-3 4.6 mmφ × 150 mm × 3 μm
Eluent acetonitrile / 20 mM aqueous sodium acetate solution (v / v) = 96/4
Flow rate 1.0 mL / min, column temperature 40 ° C., retention time 5.0 minutes Measurement wavelength 254 nm

(Synthesis of optically active titanium-saran complex)
Synthesis of optically active titanium-saran complex (115):
To a solution of optically active Saran ligand (114) (0.395 g, 0.500 mmol) in acetonitrile (5.0 mL) was added titanium tetraisopropoxide [Ti (Oi-Pr) ₄ ] (0.148 mL, .0. 500 mmol) was added dropwise at 40 ° C. The reaction solution was stirred at 40 ° C. for 1 hour, water (27 mg, 1.5 mmol) was added dropwise, and the mixture was further stirred at 40 ° C. for 3 hours. The reaction temperature was 20 to 25 ° C., and the mixture was stirred for 15 hours. The reaction solution was concentrated, and acetonitrile (5.0 mL) was added to precipitate a solid. After filtering the solid, the cake was washed twice with acetonitrile (3 mL, 3 mL). By drying under reduced pressure while heating to 40 ° C., the optically active titanium-saran complex (115) (0.354 g) was obtained as a pale yellow solid in a yield of 83.0%.
¹ H-NMR (300 MHz, CDCl ₃ ) δ; -1.79 to -1.57 (m, 2H), -0.54 to 0.30 (m, 2H), 0.00 to 0.41 (m , 4H), 0.41 to 0.62 (m, 2H), 1.10 to 1.33 (m, 2H), 1.40 to 1.82 (m, 6H), 2.15 to 2.35. (M, 4H), 2.92 (d, J = 14.3 Hz, 2H), 3.28 (d, J = 11.3 Hz, 2H), 3.60 (t, J = 11.0 Hz, 2H) 3.62 (d, J = 14.0 Hz, 2H), 4.03 (d, J = 11.3 Hz, 2H), 4.60 (d, J = 12.2 Hz, 2H), 4.74 ( d, J = 12.2 Hz, 2H), 5.03 (d, J = 12.5 Hz, 2H), 5.16 (d, J = 12.5 Hz, 2H), 6.18 (d, J = 7). .4Hz, H), 6.38 (dd, J = 7.4,1.3Hz, 2H), 6.68~7.90 (m, 52H).

(Example 5)
The synthesis of the optically active titanium-saran complex (125) is described below.

(Monoether synthesis)
Synthesis of 2 ′-(4-bromobenzyloxy) -1,1′-biphenyl-2-ol (122):
2,2-Biphenol (3.72 g, 20 mmol), potassium carbonate (2.76 g, 20 mmol), potassium iodide (3.32 g, 20 mmol), and 24 mL of acetone were charged into the reaction vessel and stirred to 60 ° C. Heated. 4-Bromobenzyl bromide (121) (4.99 g, 20 mmol) was added to this mixed solution, and the mixture was stirred at 60 ° C. for 17 hours. After confirming the reaction conversion rate by HPLC, a saturated aqueous ammonium chloride solution was added to stop the reaction. After liquid separation, the aqueous layer was extracted with ethyl acetate, combined and concentrated to obtain a crude product. The crude product was recrystallized from 2-propanol to obtain monoether (122) (4.78 g) as white crystals in a yield of 67.3%.
¹ H-NMR (300 MHz, CDCl ₃ ) δ; 5.05 (s, 2H, —OCH ₂ —), 6.11 (s, 1H, —OH), 6.97 to 7.19 (m, 6H) , 7.20-7.47 (m, 6H).

(Hydroxy aryl aldehyde synthesis)
Synthesis of 2-hydroxy-2 ′-(4-bromobenzyloxy) -1,1′-biphenyl-3-carbaldehyde (123):
Paraformaldehyde (0.98 g, 33 mmol), anhydrous magnesium chloride (2.1 g, 22 mmol), N, N, N ′, N′-tetramethylethylenediamine (TMEDA) (3.3 mL, 22 mmol) and tetrahydrofuran (36 mL). The reaction vessel was charged and the temperature was kept at 65 ° C. To this mixed solution was added monoether (122) (3.6 g, 11 mmol), and the mixture was washed with tetrahydrofuran (3.6 g). After stirring at 70 ° C. for 15 hours, 2 mol / L hydrochloric acid was added to stop the reaction. After neutralization, the aqueous layer from which acetonitrile was distilled off was extracted with ethyl acetate, the organic layer was washed with water (100 mL) three times, and then ethyl acetate was distilled off to obtain crystals of the crude product. . This crude product was suspended and washed with isopropyl alcohol to obtain hydroxyarylaldehyde (123) (2.64 g) as white crystals in a yield of 62.6% and a HPLC relative area percentage of 98.9%.
¹ H-NMR (300 MHz, CDCl ₃ ) δ; 5.01 (s, 2H, —O—CH ₂ —), 6.92 to 7.18 (m, 5H), 7.27 to 7.45 (m , 3H), 7.51 to 7.61 (m, 3H), 9.95 (s, 1H, —CHO), 11.37 (s, 1H, —OH).
HPLC analysis conditions:
Column name Inertsil ODS-3 4.6 mmφ × 150 mm × 3 μm
Eluent acetonitrile / 20 mM aqueous sodium acetate solution (v / v) = 96/4
Flow rate 1.0 mL / min, column temperature 40 ° C., retention time 2.5 minutes Analytical wavelength 254 nm

(Optically active Saran ligand synthesis)
Synthesis of optically active salen ligand (124):
(S, S) -cyclohexanediamine (58) (0.285 g, 2.50 mmol), hydroxyarylaldehyde (123) (1.92 g, 5.00 mmol) and toluene (11 mL) were added to the reaction vessel, and this reaction was performed. The solution was heated to 50 ° C. and stirred for 1 hour. Methanol (5 mL) was added to the reaction solution and the mixture was further stirred for 1 hour, and then sodium borohydride (0.189 g, 5.00 mmol) was added little by little while paying attention to foaming. After stirring at 50 ° C. for 4 hours, the mixture was allowed to cool to room temperature, and water was added to stop the reaction. After adding toluene (11 mL) for liquid separation, the organic layer was washed with water and the solvent was distilled off to obtain a crude product. Recrystallization with isopropyl alcohol gave Saran ligand (124) as pale yellow crystals (1.85 g) in a yield of 86.9% and a HPLC relative area percentage of 95.2%.
¹ H-NMR (300 MHz, CDCl ₃ ) δ; 0.74 to 1.37 (m, 6H), 1.41 to 1.72 (m, 2H), 1.85 to 2.10 (m, 2H) , 2.17~2.37 (m, 2H), 3.79 (d, J = 13.4Hz, 2H, -N-CH 2 -), 3.92 (d, J = 13.4Hz, 2H, _{-N-CH 2 -), 4.88} (s, 4H, -O-CH 2 -), 6.77 (t, J = 7.4Hz, 2H), 6.82~7.10 (m, 10H ), 7.10-7.39 (m, 10H).
HPLC analysis conditions:
Column name Inertsil ODS-3 4.6 mmφ × 150 mm × 3 μm
Eluent acetonitrile / 20 mM aqueous sodium acetate solution (v / v) = 96/4
Flow rate: 1.0 mL / min, column temperature: 40 ° C., retention time: 4.8 minutes Measurement wavelength: 254 nm

(Synthesis of optically active titanium-saran complex)
Synthesis of optically active titanium-saran complex (125):
To a solution of optically active salen ligand (124) (0.424 g, 0.500 mmol) in acetonitrile (5.0 mL) was added titanium tetraisopropoxide [Ti (Oi-Pr) ₄ ] (0.148 mL,. 500 mmol) was added dropwise at 40 ° C. The reaction solution was stirred at 40 ° C. for 1 hour, water (27 mg, 1.5 mmol) was added dropwise, and the mixture was further stirred at 40 ° C. for 3 hours. The reaction temperature was 20 to 25 ° C., and the mixture was stirred for 15 hours. The reaction solution was concentrated, and acetonitrile (5.0 mL) was added to precipitate a solid. After filtering the solid, the cake was washed twice with acetonitrile (3 mL, 3 mL). By drying under reduced pressure while heating to 40 ° C., the optically active titanium-saran complex (125) (0.396 g) was obtained as a pale yellow solid in a yield of 87.0%.
¹ H-NMR (300 MHz, CDCl ₃ ) δ; −1.14 to −0.88 (m, 2H), 0.18 to 0.90 (m, 6H), 1.04 to 1.95 (m, 10H), 2.19 (t, J = 11.9 Hz, 2H), 1.37 to 1.62 (m, 2H), 2.89 (d, J = 14.6 Hz, 2H), 3.36 ( d, J = 11.3 Hz, 2H), 3.56 to 3.80 (m, 4H). 4.09 (t, J = 11.0 Hz, 2H), 4.38 (d, J = 12.2 Hz, 2H), 4.52 (d, J = 12.5 Hz, 2H), 4.84 (d , J = 12.2 Hz, 2H), 4.94 (d, J = 12.5 Hz, 2H), 6.11 (d, J = 7.4 Hz, 2H), 6.32 (d, J = 7. 4, 1.3 Hz, 2H), 6.64 (t, J = 7.4 Hz, 2H), 6.68-7.15 (m, 30H), 7.26 (d, J = 8.6 Hz, 4H) ), 7.40 (d, J = 8.6 Hz, 4H).

(Example 6)
The synthesis of the optically active titanium-saran complex (135) is described below.

(Monoether synthesis)
Synthesis of 2 ′-(2-methoxybenzyloxy) -1,1′-biphenyl-2-ol (132):
2,2-Biphenol (3.72 g, 20 mmol), potassium carbonate (2.8 g, 20 mmol) and 24 mL of acetone were charged into a reaction vessel and heated to 60 ° C. with stirring. To this mixed solution was added 2-methoxybenzyl chloride (131) (3.13 g, 20 mmol), and the mixture was stirred at 60 ° C. for 17 hours. After confirming the reaction conversion rate by HPLC, a saturated aqueous ammonium chloride solution was added to stop the reaction. After liquid separation, the aqueous layer was extracted with ethyl acetate, combined and concentrated to obtain a crude product. The crude product was recrystallized from 2-propanol to obtain monoether (132) (5.58 g) as white crystals in a yield of 91.0%.
¹ H-NMR (300 MHz, CDCl ₃ ) δ; 3.81 (s, 3 H, —OCH ₃ ), 5.15 (s, 2 H, —OCH ₂ —), 6.60 (s, 1 H, —OH) , 6.82 to 6.93 (m, 2H), 6.95 to 7.03 (m, 2H), 7.05 to 7.18 (m, 2H), 7.18 to 7.31 (m, 4H), 7.31-7.40 (nm, 2H).

(Hydroxy aryl aldehyde synthesis)
Synthesis of 2-hydroxy-2 ′-(2-methoxybenzyloxy) -1,1′-biphenyl-3-carbaldehyde (133):
Paraformaldehyde (0.90 g, 30 mmol), anhydrous magnesium chloride (1.9 g, 20 mmol), N, N, N ′, N′-tetramethylethylenediamine (TMEDA) (3.0 mL, 20 mmol) and tetrahydrofuran (31 mL). The reaction vessel was charged and the temperature was kept at 65 ° C. To this mixed solution was added monoether (132) (3.06 g, 10.0 mmol), and the mixture was washed with tetrahydrofuran (3.1 g). After stirring at 70 ° C. for 15 hours, 2 mol / L hydrochloric acid was added to stop the reaction. After neutralization, the aqueous layer from which acetonitrile was distilled off was extracted with ethyl acetate, the organic layer was washed with water (100 mL) three times, and then ethyl acetate was distilled off to obtain crystals of the crude product. . This crude product was suspended and washed with isopropyl alcohol to obtain hydroxyarylaldehyde (133) (2.08 g) as white crystals in a yield of 62.2% and a HPLC relative area percentage of 99.2%.
¹ H-NMR (300 MHz, CDCl ₃ ) δ; 3.81 (s, 2H, —O—CH ₃ ), 5.12 (s, 2H, —O—CH ₂ —), 6.74 to 6.89 (M, 2H), 6.97-7.13 (m, 3H), 7.13-7.26 (m, 2H), 7.26-7.39 (m, 2H), 7.49-7 .67 (m, 2H), 9.94 (s, 1H, -CHO), 11.29 (s, 1H, -OH).
HPLC analysis conditions:
Column name Inertsil ODS-3 4.6 mmφ × 150 mm × 3 μm
Eluent acetonitrile / 20 mM aqueous sodium acetate solution (v / v) = 96/4
Flow rate 1.0 mL / min, column temperature 40 ° C., retention time 2.5 minutes Analytical wavelength 254 nm

(Optically active Saran ligand synthesis)
Synthesis of optically active salen ligand (134):
(S, S) -cyclohexanediamine (58) (0.285 g, 2.50 mmol), hydroxyaryl aldehyde (133) (1.67 g, 5.00 mmol) and toluene (10 mL) were added to the reaction vessel, and this reaction was performed. The solution was heated to 50 ° C. and stirred for 1 hour. Methanol (4 mL) was added to the reaction solution, and the mixture was further stirred for 1 hour, and then sodium borohydride (0.189 g, 5.00 mmol) was added little by little while paying attention to foaming. After stirring at 50 ° C. for 4 hours, the mixture was allowed to cool to room temperature, and water was added to stop the reaction. After toluene (10 mL) was added for liquid separation, the organic layer was washed with water and the solvent was distilled off to obtain a crude product as a pale yellow solid. Recrystallization from isopropyl alcohol gave Saran ligand (134) as white crystals (1.56 g) in a yield of 83.1% and a HPLC relative area percentage of 97.1%.
¹ H-NMR (300 MHz, CDCl ₃ ) δ; 0.78 to 1.38 (m, 8H), 1.42 to 1.65 (m, 2H), 1.85 to 2.08 (m, 2H) _{, 2.17~2.36 (m, 4H),} 3.75 (s, 6H, -O-CH 3) 3.79 (d, J = 13.7Hz, 2H, -N-CH 2 -), 3.92 (d, J = 13.1 Hz, 2H, —N—CH ₂ —), 5.09 (s, 4H, —O—CH ₂ —), 6.72 to 6.87 (m, 6H) 6.89-7.17 (m, 6H), 7.21-7.47 (m, 10H).
HPLC analysis conditions:
Column name Inertsil ODS-3 4.6 mmφ × 150 mm × 3 μm
Eluent acetonitrile / 20 mM aqueous sodium acetate solution (v / v) = 96/4
Flow rate 1.0 mL / min, column temperature 40 ° C., retention time 3.6 minutes Measurement wavelength 254 nm

(Synthesis of optically active titanium-saran complex)
Synthesis of optically active titanium-saran complex (135):
To a solution of optically active salen ligand (134) (0.375 g, 0.500 mmol) in acetonitrile (5.0 mL) was added titanium tetraisopropoxide [Ti (Oi-Pr) ₄ ] (0.148 mL, .0. 500 mmol) was added dropwise at 40 ° C. The reaction solution was stirred at 40 ° C. for 1 hour, water (27 mg, 1.5 mmol) was added dropwise, and the mixture was further stirred at 40 ° C. for 3 hours. The reaction temperature was 20 to 25 ° C., and the mixture was stirred for 15 hours. The reaction solution was concentrated, and acetonitrile (5.0 mL) was added to precipitate a solid. After filtering this solid, the cake was washed twice with acetonitrile (3 mL, 3 mL). By drying under reduced pressure while heating to 40 ° C., the optically active titanium-saran complex (135) (0.328 g) was obtained as a pale yellow solid in a yield of 80.7%.
¹ H-NMR (300 MHz, CDCl ₃ ) δ; −0.81 to −0.55 (m, 2H), 0.30 to 0.82 (m, 6H), 0.97 to 1.37 (m, 6H), 1.55 to 1.97 (m, 6H), 2.27 to 2.61 (m, 4H), 2.92 (d, J = 14.0 Hz, 2H), 3.40 (d, J = 11.3Hz, 2H), 3.64~3.78 (m, 2H), 3.81 (s, 6H, -O-CH 3), 3.87 (s, 6H, -O-CH 3 ), 4.11 (d, J = 11.3 Hz, 2H), 4.42 (d, J = 13.1 Hz, 2H), 4.83 (d, J = 13.4 Hz, 2H), 4.97. (D, J = 13.7 Hz, 2H), 5.11 (d, J = 13.7 Hz, 2H), 6.14 (d, J = 7.4 Hz, 2H), 6.38 (dd, J = 7.4,1. Hz, 2H), 6.54 to 6.92 (m, 20H), 6.94 to 7.15 (m, 12H), 7.15 to 7.27 (m, 6H), 7.32 (dd, J = 7.4, 1.2 Hz, 2H).

(Example 7)
The synthesis of the optically active titanium-saran complex (145) is described below.

(Monoether synthesis)
Synthesis of 2 ′-(2-fluorobenzyloxy) -1,1′-biphenyl-2-ol (142):
2,2-Biphenol (24.21 g, 130 mmol), potassium carbonate (8.98 g, 65 mmol), potassium iodide (4.32 g, 26 mmol) and 120 g of acetone were added to the reaction vessel and stirred at 20-25 ° C. did. 2-Fluorobenzyl bromide (141) (24.57 g, 130 mmol) was added to the reaction solution, and the mixture was stirred at a reaction temperature of 60 ° C. for 23 hours. After cooling to 20 to 25 ° C., a saturated aqueous solution of ammonium chloride is added to the reaction solution to stop the reaction, and after separation, the aqueous layer is extracted with chloroform, the organic layers are combined and concentrated, and then silica gel column chromatography. Purification by chromatography (hexane / ethyl acetate (v / v) = 80/20) gave monoether (142) (26.55 g) as light brown crystals in a yield of 69.4%.
¹ H-NMR (300 MHz, CDCl ₃ ) δ; 5.17 (s, 2 H, —OCH ₂ —), 6.17 (s, 1 H, —OH), 6.97 to 7.20 (m, 7 H) , 7.22-7.43 (m, 5H).

(Hydroxy aryl aldehyde synthesis)
Synthesis of 2-hydroxy-2 ′-(2-fluorobenzyloxy) -1,1′-biphenyl-3-carbaldehyde (143):
A flask equipped with a stirrer and a reflux tube was purged with nitrogen, and then paraformaldehyde (4.62 g, 154 mmol), anhydrous magnesium chloride (10.2 g, 107 mmol), monoether (142) (15.1 g, 51.2 mmol) And acetonitrile (100 mL) was added and it stirred at 20-25 degreeC. N, N, N ′, N′-tetramethylethylenediamine (TMEDA) (11.84 g, 102 mmol) was added dropwise to the reaction solution. The reaction solution was stirred at a reaction temperature of 75 to 80 ° C. for 16 hours, cooled to 15 to 20 ° C., and 2 mol / L hydrochloric acid was added to stop the reaction. After neutralizing the reaction solution, the aqueous layer from which acetonitrile was distilled off was extracted with ethyl acetate, the organic layers were combined, and then the solvent was distilled off to obtain a crude product. The crude product was recrystallized in a chloroform-hexane-ethyl acetate system to obtain hydroxyarylaldehyde (143) (10.3 g) as a pale white yellow crystal in a yield of 62.7%.
¹ H-NMR (300 MHz, CDCl ₃ ) δ; 5.15 (s, 2H, —OCH ₂ —), 6.95 to 7.12 (m, 5H), 7.17 to 7.41 (m, 4H) ), 7.53-7.61 (m, 2H), 9.94 (s, 1H, -CHO), 11.32 (s, 1H, -OH).

(Optically active Saran ligand synthesis)
Synthesis of optically active salen ligand (144):
Hydroxyaryl aldehyde (143) (3.59 g, 11.3 mmol) and toluene (21 g) were added to the reaction vessel and then dissolved in methanol (9 g) (S, S) -cyclohexanediamine (58) (0. 637 g, 5.57 mmol) was added, and the reaction temperature was then raised to 40 ° C. and stirred for 7 hours. Next, sodium borohydride (0.632 g, 16.7 mmol) is added to the reaction solution, the reaction temperature is 50 ° C. and the mixture is stirred for 6 hours, and then cooled to 20 to 25 ° C. Stopped. After adding toluene and liquid-separating, the organic layer was washed with water and the solvent was distilled off to obtain a crude product. The crude product was purified by silica gel column chromatography (hexane / ethyl acetate (v / v) = 70/30 → 40/60) to give pale yellow crystals (3.04 g) as saran ligand (144 ) Was obtained in a yield of 75.0%.
¹ H-NMR (300 MHz, CDCl ₃ ) δ; 1.05 to 1.24 (m, 2H), 1.40 to 1.90 (br, 4H), 1.99 to 2.13 (m, 2H) , 2.33 to 2.45 (m, 2H), 3.87 (d, J = 13.7 Hz, 2H), 4.00 (d, J = 13.7 Hz, 2H), 5.11 (s, 4H), 6.78 to 6.88 (m, 2H), 6.94 to 7.09 (m, 10H), 7.13 to 7.24 (m, 4H), 7.25 to 7.38 ( m, 6H).

(Synthesis of optically active titanium-saran complex)
Synthesis of optically active titanium-saran complex (145):
To a solution of optically active salen ligand (144) (0.729 g, 1.00 mmol) in toluene (4.4 mL) was added titanium tetraisopropoxide [Ti (Oi-Pr) ₄ ] (0.281 g, 0.988 mmol). ) Was added dropwise at 25-30 ° C. The reaction solution was stirred at 40 ° C. for 1 hour, water (54 mg, 3.0 mmol) was added dropwise, and the mixture was further stirred at 40 ° C. for 1 hour. After the reaction temperature was 20 to 25 ° C. and the mixture was stirred for 13 hours, hexane (5 mL) was added to the reaction solution to precipitate a solid. The solid was collected by filtration, and the cake was washed with hexane (3 mL). The obtained wet product was dried under reduced pressure at 40 ° C. to obtain an optically active titanium-saran complex (145) (0.461 g) as a pale yellow solid in a yield of 59.2%.
¹ H-NMR (300 MHz, CDCl ₃ ) δ; −0.77 to −0.57 (m, 2H), 0.32 to 0.65 (m, 4H), 0.66 to 0.84 (m, 2H), 1.08 to 1.33 (m, 4H), 1.70 to 1.93 (m, 6H), 2.32 to 2.45 (m, 2H), 2.46 to 2.62 ( m, 2H), 2.87-2.98 (m, 2H), 3.46 (d, J = 11.1 Hz, 2H), 3.66-3.81 (m, 4H), 4.12 ( d, J = 11.1 Hz, 2H), 4.43 (d, J = 13.2 Hz, 2H), 4.83 (d, J = 12.6 Hz, 2H), 4.97 (d, J = 12. .6 Hz, 2H), 5.07 (d, J = 12.9 Hz, 2H), 6.11 (dd, J = 7.8, 1.5 Hz, 2H), 6.35 (dd, J = 7. 8, 1.8Hz, H), 6.57~7.37 (m, 40H).

(Example 8)
The synthesis of the optically active titanium-saran complex (155) is described below.

(Monoether synthesis)
Synthesis of 2 ′-(2-phenylbenzyloxy) -1,1′-biphenyl-2-ol (152):
2,2-Biphenol (18.62 g, 100 mmol), potassium carbonate (6.91 g, 50.0 mmol), potassium iodide (3.32 g, 20.0 mmol) and 90 g of acetone are added to the reaction vessel and 20-25. Stir at ° C. 2-Phenylbenzyl bromide (151) (24.71 g, 100 mmol) was added to the reaction solution, and the mixture was stirred at a reaction temperature of 55 ° C. for 27 hours. After cooling to 20 to 25 ° C., the reaction was stopped by adding saturated aqueous ammonium chloride solution to the reaction solution, and after separation, the aqueous layer was extracted with chloroform, the organic layers were combined, concentrated, and then ethyl acetate-diisopropyl. Monoether (152) (34.38 g) was obtained as a yellow oil in a yield of 97.6% by purification by recrystallization in an ether-hexane system.
¹ H-NMR (300 MHz, CDCl ₃ ) δ; 4.97 (s, 2H, —OCH ₂ —), 6.30 (s, 1H, —OH), 6.84 to 6.90 (m, 1H) 6.96-7.05 (m, 2H), 7.06-7.14 (m, 1H), 7.19-7.43 (m, 13H).

(Hydroxy aryl aldehyde synthesis)
Synthesis of 2-hydroxy-2 ′-(2-phenylbenzyloxy) -1,1′-biphenyl-3-carbaldehyde (153):
A flask equipped with a stirrer and a reflux tube was purged with nitrogen, and then paraformaldehyde (4.61 g, 154 mmol), anhydrous magnesium chloride (9.73 g, 102 mmol), monoether (152) (18 g, 51 mmol) and acetonitrile (144 g). ) Was added and stirred at 20-25 ° C. N, N, N ′, N′-tetramethylethylenediamine (TMEDA) (11.86 g, 102 mmol) was added dropwise to the reaction solution. The reaction solution was stirred at a reaction temperature of 80 ° C. for 24 hours, cooled to 20 to 25 ° C., and 2 mol / L hydrochloric acid was added to stop the reaction. The reaction solution was neutralized and extracted with chloroform, and the organic solvent was distilled off to obtain a crude product. The crude product was recrystallized in a chloroform-hexane-ethyl acetate system to obtain hydroxyarylaldehyde (153) (10 g) as white crystals in a yield of 54%.
¹ H-NMR (300 MHz, CDCl ₃ ) δ; 4.96 (s, 2H, —OCH ₂ —), 6.81 to 6.86 (m, 1H), 6.98 to 7.08 (m, 2H) ), 7.20-7.43 (m, 11H), 7.50-7.57 (m, 2H), 9.95 (s, 1H, -CHO), 11.33 (s, 1H, -OH) ).

(Optically active Saran ligand synthesis)
Synthesis of optically active salen ligand (154):
Hydroxyaryl aldehyde (153) (4.27 g, 11.2 mmol) and toluene (21 g) were added to the reaction vessel and then dissolved in methanol (9 g) (S, S) -cyclohexanediamine (58) (0. 640 g, 5.61 mmol) was added, followed by heating to 40 ° C. and stirring for 2 hours. Next, sodium borohydride (0.913 g, 24.1 mmol) was added to the reaction solution, the reaction temperature was 40 ° C. and the mixture was stirred for 6 hours, cooled to 20 to 25 ° C., and water added to react. Stopped. After adding toluene and liquid-separating, the organic layer was washed with water and the solvent was distilled off to obtain a crude product. The crude product was purified by silica gel column chromatography (hexane / ethyl acetate (v / v) = 80/20 → 65/35) to obtain a pale yellow white crystal (2.16 g) as a Saran ligand (2.16 g). 154) was obtained in a yield of 45.7%.
¹ H-NMR (300 MHz, CDCl ₃ ) δ; 1.00 to 1.30 (m, 4H), 1.46 to 1.69 (m, 2H), 1.95 to 2.10 (m, 2H) , 2.30-2.43 (m, 2H), 3.85 (d, J = 13.5 Hz, 2H), 3.97 (d, J = 13.5 Hz, 2H), 4.92 (s, 4H), 6.75 to 6.85 (m, 4H), 6.89 to 7.04 (m, 4H), 7.12 to 7.48 (m, 16H).

(Synthesis of optically active titanium-saran complex)
Synthesis of optically active titanium-saran complex (155):
To a solution of optically active salen ligand (154) (0.600 g, 0.712 mmol) in toluene (1.6 mL) was added titanium tetraisopropoxide [Ti (Oi-Pr) ₄ ] (0.218 g,. 767 mmol) was added dropwise at 25-30 ° C., followed by toluene (1 mL). The reaction solution was stirred at 45 ° C. for 1 hour, water (38 μL, 2.11 mmol) was added dropwise, and the mixture was further stirred at 45 ° C. for 2 hours. After the reaction temperature was set to 20 to 25 ° C. and the mixture was stirred for 10 hours, the organic solvent of this reaction solution was distilled off to obtain a crude product. The crude product was purified by silica gel column chromatography (hexane / ethyl acetate (v / v) = 80/20 → 70/30) to obtain Saran complex (155) as yellow crystals (0.221 g). Obtained at a rate of 34.3%.
ESI-HRMS; C ₁₁₆ H ₁₀₅ N ₄ O ₁₀ Ti ₂ ⁺ :
m / z Measured value = 1810.6824, Theoretical value = 1810.6823

Example 9
The synthesis of the optically active titanium-saran complex (165) is described below.

(Monoether synthesis)
Synthesis of 2 ′-(2,4,6-triisopropylbenzyloxy) -1,1′-biphenyl-2-ol (162):
2,2-Biphenol (7.36 g, 39.5 mmol), potassium carbonate (2.84 g, 20.5 mmol), potassium iodide (1.32 g, 7.95 mmol) and 35 g of acetone were added to the reaction vessel, Stir at ~ 25 ° C. 2,4,6-Triisopropylbenzyl chloride (161) (9.99 g, 39.5 mmol) was added to the reaction solution, and the mixture was stirred at a reaction temperature of 55 ° C. for 39 hours. After cooling to 20 to 25 ° C., the reaction was stopped by adding a saturated aqueous solution of ammonium chloride to the reaction solution, and after separation, the aqueous layer was extracted with ethyl acetate, and the combined organic layer was dried over magnesium sulfate. Concentration gave monoether (162) (13.9 g) as pale orange white crystals in a yield of 87.2%.
¹ H-NMR (300 MHz, CDCl ₃ ) δ; 1.10 (d, J = 6.9 Hz, 12H), 1.24 (d, J = 6.9 Hz, 6H), 2.86 (qq, J = 6.9 Hz, 1H), 3.04 (qq, J = 6.9 Hz, 2H), 5.06 (s, 2H), 6.45 (s, 1H), 6.87 to 7.01 (m, 4H), 7.14-7.29 (m, 4H), 7.34-7.46 (m, 2H).

(Hydroxy aryl aldehyde synthesis)
Synthesis of 2-hydroxy-2 ′-(2,4,6-triisopropylbenzyloxy) -1,1′-biphenyl-3-carbaldehyde (163):
A flask equipped with a stirrer and a reflux tube was purged with nitrogen, and then paraformaldehyde (3.13 g, 104 mmol), anhydrous magnesium chloride (6.62 g, 69.6 mmol), monoether (162) (14.0 g, 34.34). 8 mmol) and acetonitrile (100 mL) were added, and the mixture was stirred at 20 to 25 ° C. N, N, N ′, N′-tetramethylethylenediamine (TMEDA) (8.08 g, 69.6 mmol) was added dropwise to the reaction solution. The reaction solution was stirred at a reaction temperature of 80 ° C. for 37 hours, cooled to 20 to 25 ° C., and 2 mol / L hydrochloric acid was added to stop the reaction. The reaction solution was neutralized and extracted with dichloromethane, and the organic solvent was distilled off to obtain a crude product. The crude product was recrystallized in a chloroform-hexane-ethyl acetate system to obtain hydroxyarylaldehyde (163) (11.8 g) as white crystals in a yield of 78.5%.
¹ H-NMR (300 MHz, CDCl ₃ ) δ; 1.10 (d, J = 6.9 Hz, 12H), 1.22 (d, J = 6.9 Hz, 6H), 2.84 (qq, J = 6.9 Hz, 1H), 3.13 (qq, J = 6.9 Hz, 2H), 4.99 (s, 2H), 6.90-6.99 (m, 3H), 7.04-7. 12 (m, 1H), 7.20-7.31 (m, 2H), 7.39-7.49 (m, 3H), 9.85 (s, 1H), 11.20 (s, 1H) .

(Optically active Saran ligand synthesis)
Synthesis of optically active salen ligand (164):
Hydroxyaryl aldehyde (163) (3.00 g, 6.90 mmol) and toluene (36 mL) were added to the reaction vessel and then dissolved in methanol (18 mL) (S, S) -cyclohexanediamine (58) (0. (39 g, 3.45 mmol) was added, and the reaction temperature was then raised to 60 ° C. and stirred for 4 hours. Next, sodium borohydride (6.91 g, 183 mmol) and toluene (80 mL) were added to the reaction solution, the reaction temperature was 65 ° C., and the mixture was stirred for 17 hours. In addition, the reaction was stopped. Toluene and methanol were distilled off, followed by extraction with chloroform, and the organic solvent was distilled off to obtain a crude product. The crude product was purified by silica gel column chromatography (hexane / ethyl acetate (v / v) = 80/20) to obtain Saran ligand (164) as pale yellowish white crystals (1.92 g). Obtained at a rate of 59%.
¹ H-NMR (300 MHz, CDCl ₃ ) δ; 0.94 to 1.34 (br, 4H), 1.10 (dd, J = 6.9, 2.0 Hz, 24H), 1.22 (d, J = 7.2 Hz, 12H), 1.45 to 1.65 (m, 2H), 1.90 to 2.04 (m, 2H), 2.24 to 2.36 (m, 2H), 2. 84 (qq, J = 6.9 Hz, 2H), 3.09 (qq, J = 6.9 Hz, 4H), 3.79 (d, J = 13.8 Hz, 2H), 3.91 (d, J = 13.8 Hz, 2H), 4.86 to 5.01 (m, 4H), 6.71 (t, J = 7.5 Hz, 2H), 6.85 to 6.99 (m, 6H), 7 .01-7.15 (m, 4H), 7.16-7.41 (m, 6H).

(Synthesis of optically active titanium-saran complex)
Synthesis of optically active titanium-saran complex (165):
To a solution of optically active Saran ligand (164) (0.50 g, 0.53 mmol) in acetonitrile (2.3 mL) was added titanium tetraisopropoxide [Ti (Oi-Pr) ₄ ] (0.15 g,. 53 mmol) was added dropwise at 40 ° C., and the mixture was stirred at 40 ° C. for 2 hours and 30 minutes. After adding water (29 μL, 1.6 mmol) dropwise, acetonitrile was added and the precipitate was collected by filtration to give a yellow solid as a crude product Got. The crude product was purified by silica gel column chromatography (hexane / ethyl acetate (v / v) = 90/10 → 80/20) to give Saran complex (165) as pale yellow crystals (0.35 g). Obtained in 66% yield.
ESI-HRMS; C ₁₂₈ H ₁₆₁ N ₄ O ₁₀ Ti ₂ ⁺ :
m / z measured value = 2011.1205, theoretical value = 2011.1205

(Example 10)
The synthesis of the optically active titanium salen complex (168 ′) is described below.

(Optically active salen ligand synthesis)
Synthesis of optically active salen ligand (168 ′):
(R, R) -cyclohexanediamine sulfate (69) (1.23 g, 5.80 mmol), aldehyde (163) (5.00 g, 11.61 mmol), potassium carbonate (0.8 g, 5.80 mmol) and ethanol (60 mL) was added to the reaction vessel, heated to 50 ° C., and stirred for 17 hours. After the reaction mixture was brought to 20-25 ° C., the produced pale yellow solid was filtered, and the resulting cake was washed with a mixed solvent of ethanol and water and ethanol to obtain a pale yellow solid (5.53 g) as a yield. 99% of the salen ligand was obtained as a yellow solid.
¹ H-NMR (300 MHz, CDCl ₃ ) δ; 1.06 (dd, J = 6.9 Hz, 24H), 1.17 (d, J = 6.9 Hz, 12H), 1.33-1.42 ( m, 2H), 1.50 to 1.69 (m, 2H), 1.74 to 1.93 (br, 2H), 2.80 (qq, J = 6.9 Hz, 2H), 3.10 ( qq, J = 6.9 Hz, 4H), 3.08-3.19 (s, 2H), 4.92 (s, 4H), 6.59 (t, J = 7.5 Hz, 2H), 6. 83 (d, J = 7.2 Hz, 2H), 6.83 (s, 4H) 7.03 to 7.31 (m, 8H), 7.34 to 7.43 (m, 2H), 8.35 (S, 2H).

(Example 11)
(Synthesis of optically active epoxy compounds)
The synthesis of (3R, 4R) -3,4-epoxy-3,4-dihydro-2,2-dimethyl-6-nitro-2H-1-benzopyran (301) is described.

Optically active titanium-saran complex (145)

To a toluene solution (4 mL) (14 mg, 0.0087 mmol, 0.54 mol% with respect to the substrate), 2,2-dimethyl-6-nitro-2H-1-benzopyran (0.33 g, 1.6 mmol) was added. In addition, while stirring the reaction solution at 40 ° C., 30% aqueous hydrogen peroxide (0.27 g, 2.4 mmol) was added, and the mixture was stirred at a reaction temperature of 40 ° C. for 6 hours. After cooling the reaction solution to 20 to 25 ° C., toluene (3 mL) and distilled water (3 mL) were added to the reaction solution, the organic layer was separated, and further extracted from the aqueous layer with toluene (3 mL). The layers were combined and concentrated to give the crude product. The obtained crude product was purified by column chromatography to obtain an epoxy compound (301) (0.35 g, yield 98%, optical purity 99% ee or higher) as pale yellow crystals.
¹ H-NMR (300 MHz, CDCl ₃ ) δ; 1.33 (s, 3H), 1.62 (s, 3H), 3.58 (d, J = 4.4 Hz, 1H), 4.00 (d , J = 4.4 Hz, 1H), 6.89 (d, J = 8.6 Hz, 1H), 8.14 (dd, J = 8.6, 3.0 Hz, 1H), 8.30 (d, J = 3.0 Hz, 1H).
HPLC analysis conditions:
Column name CHIRALPAK AD-RH
4.6 mmφ × 150 mm × 5 μm 3 continuous eluent acetonitrile / 20 mM (pH 8) phosphate buffer (v / v) = 60/40
Flow rate 1.0 mL / min, column temperature 40 ° C
Retention time Target product of this reaction: 12.6 minutes (3R, 4R),
Enantiomer: 15.8 min (3S, 4S)
Measurement wavelength 330nm

(Example 12)
(Synthesis of optically active epoxy compounds)
The synthesis of (3R, 4R) -3,4-epoxy-3,4-dihydro-2,2-dimethyl-6-nitro-2H-1-benzopyran (301) is described.
Optically active titanium-saran complex (75)

(10 mg, 0.0065 mmol, 0.10 mol% with respect to the substrate) in a toluene solution (8 mL) at 25 ° C., 2,2-dimethyl-6-nitro-2H-1-benzopyran (1.3 g, 6. 5 mmol) was added. While stirring the reaction solution at 40 ° C., 30% aqueous hydrogen peroxide (1.1 g, 9.8 mmol) was added, and the mixture was stirred at a reaction temperature of 40 ° C. for 24 hours. After cooling the reaction solution to 20 to 25 ° C., toluene (5 mL) and distilled water (5 mL) are added to the reaction solution, the organic layer is separated, and the aqueous layer is further separated with toluene (2 × 5 mL). The extracted organic layers were combined and concentrated to obtain a crude product. The obtained crude product was purified by column chromatography to obtain an epoxy compound (301) (1.2 g, yield 84%, optical purity 99% ee or more) as pale yellow crystals.
¹ H-NMR (CDCl ₃ ) δ; 1.33 (s, 3H), 1.62 (s, 3H), 3.58 (d, J = 4.4 Hz, 1H), 4.00 (d, J = 4.4 Hz, 1H), 6.89 (d, J = 8.6 Hz, 1H), 8.14 (dd, J = 8.6, 3.0 Hz, 1H), 8.30 (d, J = 3.0 Hz, 1 H).
HPLC analysis conditions:
Column name CHIRALPAK AD-RH
4.6 mmφ × 150 mm × 5 μm 3 continuous eluent acetonitrile / 20 mM (pH 8) phosphate buffer (v / v) = 60/40
Flow rate 1.0 mL / min, column temperature 40 ° C
Retention time Target product of this reaction: 12.6 minutes (3R, 4R),
Enantiomer: 15.8 min (3S, 4S)
Measurement wavelength 330nm

(Example 13)
(Synthesis of optically active epoxy compounds)
(3R ^* , 4R ^* )-3,4-epoxy-3,4-dihydro-2,2-dimethyl-7-nitro-6-methoxy-2H-1-benzopyran (302) ( ^* indicates relative configuration) .)) Is described.

Optically active titanium-saran complex (75) (16 mg, 0.010 mmol, 0.50 mol% based on substrate) in toluene (3 mL) at 25 ° C., 2,2-dimethyl-7-nitro-6-methoxy- 2H-1-benzopyran (0.47 g, 2.0 mmol) was added. While stirring the reaction solution at 40 ° C., 30% aqueous hydrogen peroxide (0.34 g, 3.0 mmol) was added, and the mixture was stirred at a reaction temperature of 40 ° C. for 6 hours. After cooling the reaction solution to 20-25 ° C., toluene (3 mL) and distilled water (3 mL) are added to the reaction solution to separate the organic phase, and the aqueous phase is further washed twice with toluene (3 mL, 3 mL). The crude product obtained by combining and concentrating the extracted organic phases was purified by column chromatography, and the epoxy compound (302) or (302 ′) (0.46 g, yield 92%, optical purity 99% ee or higher) was yellow. Obtained as an oil.
¹ H-NMR (CDCl ₃ ) δ; 1.26 (s, 3H), 1.59 (s, 3H), 3.53 (d, J = 4.4 Hz, 1H), 3.90 (d, J = 4.4 Hz, 1H), 3.95 (s, 3H), 7.08 (s, 1H), 7.33 (s, 1H)
HPLC analysis conditions:
Column name CHIRALPAK AD-RH
4.6 mmφ × 150 mm × 5 μm 3 continuous eluent acetonitrile / 20 mM (pH 8) phosphate buffer (v / v) = 60/40
Flow rate 0.8mL / min, column temperature 40 ℃
Retention time Target product of this reaction: 12.1 minutes, Enantiomer: 11.3 minutes Measurement wavelength: 225 nm

(Example 14)
(Synthesis of optically active epoxy compounds)
The synthesis of (R)-(+)-styrene oxide (303) is described.

Optically active titanium-saran complex (65)

(19.1 mg, 0.010 mmol, catalyst amount 0.5 mol%, ligand amount 1.0 mol%), toluene (1.0 mL) and starting styrene (0.21 g, 2.0 mmol) 20-20 The mixture was added to the reaction vessel at a temperature and stirred. To this reaction solution, 30% aqueous hydrogen peroxide (0.23 mL, 2.2 mmol) was added at a reaction temperature of 25 ° C. After stirring at 25 ° C. for 22 hours, a part of the reaction solution (5 μL) was sampled, and the conversion rate and optical purity were confirmed by HPLC. there were.
HPLC analysis conditions:
Column name CHIRALCEL OD-H 4.6 mmφ × 250 mm × 5 μm
Eluent hexane / isopropyl alcohol (v / v) = 999/1
Flow rate 1.0 mL / min, column temperature 40 ° C
Retention time Target product of this reaction; 13.1 min (R), enantiomer; 12.4 min (S)
Measurement wavelength 220nm

(Comparative Example 1)
(Synthesis of optically active epoxy compounds)
Non-patent literature Synlett (2006), 20, 3545-3547. The optically active titanium-saran complex was synthesized and isolated from the saran ligand described in (1) (corresponding to saran ligand (2j) in the non-patent document). A comparative experiment in which an epoxidation reaction of styrene was performed using this complex will be described. The reaction conditions for the asymmetric epoxidation reaction were the same as in Example 13, except that the catalyst used was changed from the titanium-saran complex (65) to the titanium-saran complex (85). Optically active titanium-saran complex as catalyst (85)

(15.1 mg, 0.010 mmol, catalyst amount 0.5 mol%, ligand amount 1.0 mol%), toluene (1.0 mL) and starting styrene (0.21 g, 2.0 mmol) in 20 to 25 The mixture was added to the reaction vessel at a temperature and stirred. To this reaction solution, 30% aqueous hydrogen peroxide (0.23 mL, 2.2 mmol) was added at a reaction temperature of 25 ° C. After stirring at 25 ° C. for 22 hours, a part of the reaction solution (5 μL) was sampled and the conversion and optical purity were confirmed by HPLC. The conversion was 34% (HPLC relative area ratio) and the optical purity was 85%. It was ee.

(Synthesis of optically active titanium-saran complex (85))
Optically active Saran ligand (84)

0.35 g (0.50 mmol) was charged into a reaction vessel, dissolved in 2.2 mL of acetonitrile, stirred at 40 ° C. under a nitrogen atmosphere, and 0.14 g (0.50 mmol) of titanium tetra i-propoxide [Ti (Oi -Pr) ₄ ] was added dropwise at 40C. Stirred at 40 ° C. for 1 hour under nitrogen atmosphere, then 27 mg (1.5 mmol) of water (H ₂ O) was added at 40 ° C. After the addition of water, the mixture was stirred at 25 ° C. for 14 hours. The resulting precipitate was filtered off with filter paper, and the cake was washed with 10 mL of acetonitrile. The cake was placed in an eggplant-shaped flask and dried using an evaporator and a vacuum dryer until a constant weight was reached. 0.29 g (yield 77%) of an optically active titanium-saran compound (85) was obtained as a pale yellow powder. The relative area percentage (%) of the complex by HPLC was 99%.
HPLC analysis conditions:
Column name Inertsil ODS-3 4.6 mmφ × 150 mm × 3 μm
Eluent acetonitrile / 20 mM aqueous sodium acetate solution = 96/4 (v / v)
Flow rate 1.0 mL / min, column temperature 40 ° C
Retention time 45.2 minutes, measurement wavelength 254 nm
¹ H-NMR (CDCl ₃ ): δ 7.41-6.58 (m, 44H), 6.34 (dd, J = 7.4, 1.5 Hz, 2H), 6.13 (dd, J = 7 .9, 1.0 Hz, 2H), 5.01 (d, J = 12.5 Hz, 2H), 4.91 (d, J = 12.5 Hz, 2H), 4.56 (d, J = 12. 2 Hz, 2H), 4.46 (d, J = 12.5 Hz, 2H), 4.08 (d, J = 10.7 Hz, 2H), 3.72 (d, J = 12.5 Hz, 2H), 3.68 (d, J = 11.0 Hz, 2H), 3.36 (d, J = 11.3 Hz, 2H), 2.91 (d, J = 13.1 Hz, 2H), 2.58-2 .36 (m, 2H), 2.28 (t, J = 11.8 Hz, 2H), 1.91-1.47 (m, 6H), 1.23 (t, J = 14.9 Hz, 4H) , .82-0.24 (m, 6H), - 0.89--1.13ppm (m, 2H).

(Example 15)
(Synthesis of optically active epoxy compounds)
The synthesis of (R)-(+)-styrene oxide (303) is described.
Optically active titanium-saran complex (105)

(13 mg, 0.008 mmol, catalyst amount 0.25 mol%, ligand amount 0.50 mol%) was dissolved in dichloromethane (1.0 mL), and then this reaction solution was placed in a thermostat at 20 ° C. Styrene (0.31 g, 3.0 mmol) as a starting material and biphenyl (100 mg) as an internal standard substance were added and stirred. Once a part of the reaction solution (5 μL) was sampled, the ratio of the starting material (styrene) to the internal standard substance (biphenyl) was measured using HPLC. Next, 30% aqueous hydrogen peroxide (0.46 mL, 4.5 mmol) was added to the reaction solution at a temperature of 20 ° C., and the mixture was stirred at a reaction temperature of 20 ° C. for 40 hours. A part (5 μL) of the reaction solution was sampled, and the ratio of the starting material (styrene), the internal standard substance (biphenyl) and the target product (styrene oxide) was measured by HPLC, and the yield and optical purity were calculated. The yield was 92% and the optical purity was 94% ee.
HPLC analysis conditions:
Column name CHIRALCEL OD-H 4.6 mmφ × 250 mm × 5 μm 2-linked eluent hexane / isopropyl alcohol (v / v) = 999/1
Flow rate 1.2 mL / min, column temperature 40 ° C,
Retention time Target product of this reaction; 13.1 min (R), enantiomer; 12.4 min (S)
Measurement wavelength 220nm

(Example 16)
(Synthesis of optically active epoxy compounds)
The synthesis of (R)-(+)-styrene oxide (303) is described.
Optically active titanium-saran complex (165)

(10 mg, 0.005 mmol, catalyst amount 0.25 mol%, ligand amount 0.50 mol%) was dissolved in dichloromethane (1.6 mL), and then this reaction solution was placed in a thermostat at 20 ° C. Styrene (0.21 g, 2.0 mmol) as a starting material and biphenyl (50 mg) as an internal standard substance were added and stirred. Once a part of the reaction solution (5 μL) was sampled, the ratio of the starting material (styrene) to the internal standard substance (biphenyl) was measured using HPLC. Next, 30% aqueous hydrogen peroxide (0.31 mL, 3.0 mmol) was added to the reaction solution at a temperature of 20 ° C., and the mixture was stirred at a reaction temperature of 20 ° C. for 27 hours. A part (5 μL) of the reaction solution was sampled, and the ratio of the starting material (styrene), the internal standard substance (biphenyl) and the target product (styrene oxide) was measured by HPLC, and the yield and optical purity were calculated. The yield was 62% and the optical purity was 97% ee.
HPLC analysis conditions:
Column name CHIRALCEL OD-H 4.6 mmφ × 250 mm × 5 μm 2-linked eluent hexane / isopropyl alcohol (v / v) = 999/1
Flow rate 1.2 mL / min, column temperature 40 ° C,
Retention time Target product of this reaction; 13.1 min (R), enantiomer; 12.4 min (S)
Measurement wavelength 220nm

(Example 17)
(Synthesis of optically active epoxy compounds)
It describes about the synthesis | combination of (S)-(-)-styrene oxide (303 ').

  Saran ligand (90 ')

(3.0 mg, 0.005 mmol, ligand amount 0.5 mol%) and 2-bromonaphthalene (21.3 mg) were dissolved in dichloromethane (0.80 mL), and the concentration of 0.020 mol / L dichloromethane solution of titanium tetra Isopropoxide [Ti (Oi-Pr) ₄ ] (0.20 mL, 0.004 mmol, titanium compound amount 0.4 mol%) was added, and the mixture was stirred at room temperature for 40 minutes. When starting material styrene (11.5 μL, 0.10 mmol) was added to the reaction solution and stirred, a part of the reaction solution (about 20 μL) was once extracted and analyzed by ¹ H-NMR. And the standard substance (2-bromonaphthalene) were measured. Thereafter, 30% hydrogen peroxide solution (12.5 μL, 0.11 mmol) was added to the reaction solution, and the reaction was performed by stirring at room temperature. After 9 hours, a part of the reaction solution (about 20 μL) was withdrawn, and ¹ H-NMR was measured to calculate the conversion rate and yield. As a result, the conversion rate of styrene oxide was 60% and the yield was 60%. Met. A part of the obtained styrene oxide was purified by silica gel chromatography (pentane / diethyl ether (v / v) = 20/1), subjected to HPLC analysis, and (S)-(−)-styrene oxide (303 ′ ) Was determined to be 93% ee.
HPLC analysis conditions:
Column name DAICEL CHIRALCEL OD-H
Eluent hexane / isopropyl alcohol (v / v) = 999/1

  The Saran ligand (90 ') of the above example is changed to the Saran ligand (91').

Instead of, a similar synthesis study on (S)-(−)-styrene oxide (303 ′) was conducted. The conversion of styrene oxide was 50%, the yield was 47%, and the optical purity of (S)-(−)-styrene oxide (303 ′) was 92% ee.

  Non-patent literature Synlett (2006), 20, 3545-3547. Saran ligand (92 ') described in

The optical purity of (S)-(−)-styrene oxide (303 ′) in the case of using was described as 89% ee. Therefore, when Saran ligand (90 ') and Saran ligand (91') are used in the asymmetric epoxidation reaction of styrene, Nonlettlement Synlett (2006), 20, 3545-3547. The optical purity was higher than that of using the Saran ligand (92 ') described in 1).

(Example 18)
(Synthesis of optically active epoxy compounds)
The synthesis of (R) -2-naphthyloxirane (304) is described.

Optically active titanium-saran complex (65)

(38 mg, 0.020 mmol, catalyst amount 0.50 mol%, ligand amount 1.0 mol%) was dissolved in dichloromethane (5 mL), and then this reaction solution was placed in a constant temperature apparatus at 20 ° C. 2-vinylnaphthalene (0.62 g, 4.0 mmol) was added. Next, 30% aqueous hydrogen peroxide (0.61 mL, 6.0 mmol) was added at 20 ° C. while stirring the reaction solution. After stirring at a reaction temperature of 20 ° C. for 24 hours, an aqueous sodium hydrogen carbonate solution was added to stop the reaction. The reaction solution is separated, the organic layer is concentrated, and purified by column chromatography (hexane / ethyl acetate (v / v) = 95/5 → 0/100) to give the target epoxy compound as white crystals. (304) was obtained in an amount of 0.50 g, an isolation yield of 74%, and an optical purity of 94%.
HPLC analysis conditions:
Column name CHIRALCEL OB-H (4.6 mmφ × 250 mm × 5 μm) and
CHIRALCEL OB (4.6 mmφ × 250 mm × 5 μm) and ligated eluent hexane / isopropyl alcohol (v / v) = 99/1
Flow rate 1.5 mL / min, column temperature 40 ° C
Retention time Target product of this reaction; 16.2 min (R), enantiomer; 18.6 min (S)
Measurement wavelength 230nm

(Example 19)
(Synthesis of optically active epoxy compounds)
The synthesis of (R) -2-naphthyloxirane (304) is described.

Optically active titanium-saran complex (105)

(34 mg, 0.020 mmol, catalyst amount 0.50 mol%, ligand amount 1.0 mol%) was dissolved in dichloromethane (5 mL), and then this reaction solution was placed in a thermostat at 20 ° C. 2-vinylnaphthalene (0.62 g, 4.0 mmol) was added. Next, 30% aqueous hydrogen peroxide (0.61 mL, 6.0 mmol) was added at 20 ° C. while stirring the reaction solution. After stirring at 20 ° C. for 24 hours, an aqueous sodium hydrogen carbonate solution was added to stop the reaction. The reaction solution is separated, the organic layer is concentrated, and purified by column chromatography (hexane / ethyl acetate (v / v) = 97/3 → 0/100) to give the target epoxy compound as white crystals. 0.64 g of (304) was obtained with an isolation yield of 89% and an optical purity of 94%.
HPLC analysis conditions:
Column name CHIRALCEL OB-H (4.6 mmφ × 250 mm × 5 μm) and
CHIRALCEL OB (4.6 mmφ × 250 mm × 5 μm) and ligated eluent hexane / isopropyl alcohol (v / v) = 99/1
Flow rate 1.5 mL / min, column temperature 40 ° C
Retention time Target product of this reaction; 16.2 min (R), enantiomer; 18.6 min (S)
Measurement wavelength 230nm

(Example 20)
(Synthesis of optically active epoxy compounds)
The synthesis of (R) -2-naphthyloxirane (304) is described.
Saran ligand (104)

(4.7 mg, 0.006 mmol, ligand amount 0.6 mol%) was dissolved in dichloromethane, and then titanium tetraisopropoxide [Ti (Oi-Pr) ₄ ] (concentration 0.10 mol / L dichloromethane solution) (50 μL of solution, 0.005 mmol, titanium compound amount 0.5 mol%) was added, and the mixture was stirred at room temperature for 10 minutes. To this reaction solution, starting materials 2-vinylnaphthalene (154.2 mg, 1.0 mmol), 2-bromonaphthalene (207.1 mg, 1.0 mmol) and phosphate buffer (100 μL, concentration 0.067 mol / L, pH 7.4) was sequentially added and stirred. Once a part of the reaction solution (about 40 μL) was extracted, the ratio of the starting material (2-bromonaphthalene) to the standard substance (2-bromonaphthalene) was measured by ¹ H-NMR. Thereafter, the reaction solution was placed in a thermostatic device having a reaction temperature of 40 ° C., 30% aqueous hydrogen peroxide (136.1 μL, 1.2 mmol) was added to the reaction solution, and the reaction was performed by stirring at a reaction temperature of 40 ° C. After 10 hours, a part of the reaction solution (about 40 μL) was extracted, and ¹ H-NMR was measured to calculate the conversion rate and yield. As a result, the conversion rate of 2-naphthyloxirane was 86% and the yield was It was 84%. A part of the obtained 2-naphthyloxirane was purified by basic silica gel chromatography (hexane / diethyl ether (v / v) = 20/1) and subjected to HPLC analysis, and (R) -2-naphthyloxirane ( The optical purity of 304) was determined to be 92% ee.
HPLC analysis conditions:
Column name DAICEL CHIRALCEL OJ-H
Eluent hexane / isopropyl alcohol (v / v) = 999/1

(Example 21-Example 29)
(Synthesis of optically active epoxy compounds)
The Saran ligand (104) of the above example is changed to the Saran ligand (164).

And Saran ligand (64)

Instead of, the synthesis of (R) -2-naphthyloxirane (304) was studied. Furthermore, the reaction temperature and reaction time were also examined using the Saran ligand (104), Saran ligand (164), and Saran ligand (64), respectively. About implementation operations other than the kind of ligand, reaction temperature, and reaction time, (Example 20) was followed. Saran ligand (164) is 5.7 mg (0.006 mmol, ligand amount 0.6 mol%), and Saran ligand (64) is 5.3 mg (0.006 mmol, ligand amount is 0.00 mol). 6 mol%) was used to study each synthesis. The results are listed in Table 1 below for each condition and result.

(Example 30)
The synthesis of the optically active salalene ligand (166) is described below.

(Amine compound synthesis)
Synthesis of amine compound (170):
t-butyl ((1S, 2S) -2-aminocyclohexyl) carbamate (70) (2.13 g, 10.0 mmol), aldehyde (163) (4.30 g, 10.0 mmol) and methanol (70 mL) with tetrahydrofuran ( 30 mL) was added to the reaction vessel and stirred at room temperature for 12 hours. After the reaction solution was cooled to 0 ° C., sodium borohydride (0.912 g, 24.0 mmol) was added little by little while paying attention to foaming. The reaction solution was stirred at room temperature for 2 hours, and then the reaction was stopped by adding an aqueous ammonium chloride solution. After ethyl acetate was added for liquid separation, the organic layer was washed with water, and the solvent was distilled off to obtain a crude product. Purification by silica gel column chromatography (hexane / ethyl acetate = 10/1 to 4/1) gave the amine compound (170) (5.16 g) in a yield of 82%.
¹ H-NMR (300 MHz, CDCl ₃ ) δ; 1.04 to 1.14 (m, 3H), 1.11 (d, J = 6.9 Hz, 6H), 1.12 (d, J = 6. 9 Hz, 6H), 1.22 (d, J = 7.2 Hz, 6H), 1.36 (s, 9H), 1.54 to 1.71 (m, 2H), 1.80 to 1.98 ( m, 1H), 2.05 to 2.14 (m, 1H), 2.15 to 2.28 (m, 1H), 2.84 (sep, J = 7.2 Hz, 1H), 3.11 ( sep, J = 6.9 Hz, 4H), 3.23 to 3.39 (m, 1H), 3.89 (d, J = 13.5 Hz, 1H), 4.03 (d, J = 13.5 Hz) , 1H), 4.30-4.46 (m, 1H), 4.87 (d, J = 10.2 Hz, 1H), 4.93 (d, J = 10.2 Hz, 1H), 6.71 (T, J 7.5 Hz, 1H), 6.88 to 6.93 (m, 1H), 6.83 (s, 1H) 7.04 to 7.23 (m, 3H), 7.30 to 7.38 (m , 2H).

(Optically active salalene ligand synthesis)
Synthesis of optically active salalene ligand (166):
Amine compound (170) (1 g, 1.59 mmol), triethylamine (1.76 mL, 12.7 mmol), trimethylsilyl triflate (1.76 mL, 9.54 mmol), and dichloromethane (5 mL) were charged into a reaction vessel at room temperature. After stirring for 20 hours, the reaction was stopped by adding an aqueous ammonium chloride solution. After ethyl acetate was added for liquid separation, the organic layer was washed with water, and the solvent was distilled off to obtain a crude product as compound (261). This crude product was subjected to the next reaction without purification.
Crude product (261), aldehyde (163) (0.582 mg, 1.35 mmol), and ethanol (10 mL) were added to the reaction vessel, and the mixture was stirred at room temperature for 1 hour and 30 minutes. After distilling off the solvent, purification by silica gel column chromatography (hexane / ethyl acetate = 10/1 to 5/1) yielded salarene ligand (166) (1.19 g) as a yellow crystal in a yield. Obtained at 80%.
¹ H-NMR (300 MHz, CDCl ₃ ) δ; 1.07 (d, J = 6.9 Hz, 6H), 1.08 (d, J = 6.9 Hz, 12H), 1.09 (d, J = 6.9 Hz, 6H), 1.19 (d, J = 6.9 Hz, 6H), 1.20 (d, J = 6.9 Hz, 6H), 1.24-1.32 (m, 1H), 1.42-1.79 (m, 6H), 1.99-2.14 (m, 1H), 2.58-2.71 (m, 1H), 2.82 (sep, J = 6.9 Hz) , 2H), 2.97 to 3.02 (m, 1H), 3.09 (sep, J = 6.9 Hz, 4H), 3.81 (d, J = 4.5 Hz, 1H), 3.95. (D, J = 4.5 Hz, 1H), 4.83 to 4.96 (m, 4H), 6.65 (dd, J = 7.2, 7.8 Hz, 1H), 6.56-6. 75 (m, 2H , 6.91 (s, 2H), 6.92 (s, 2H) 7.02~7.44 (m, 11H), 8.34 (s, 1H).

By the production method of the present invention, an optically active epoxy compound can be produced by epoxidizing a prochiral unsaturated compound having a carbon-carbon double bond in the molecule with high enantioselectivity. Furthermore, the optically active epoxy compound obtained by the production method of the present invention is useful as an optically active pharmaceutical intermediate of a compound effective for the treatment of hypertension, asthma and the like.
Furthermore, according to the present invention, an optically active sulfoxide compound useful as a synthetic intermediate or raw material for physiologically active substances such as pharmaceuticals can be economically produced with high quality and high yield.
Furthermore, according to the present invention, the amount of the catalyst used can be reduced, and an industrially useful solvent such as toluene can be used as the solvent.

Claims (19)

Formula (1a), Formula (1a ′), Formula (1b), Formula (1b ′), Formula (2), Formula (2 ′), Formula (3a), Formula (3a ′), Formula (3b), Formula (3b ′), formula (4) and formula (4 ′)

(Formula (1a), Formula (1a ′), Formula (1b), Formula (1b ′), Formula (2), Formula (2 ′), Formula (3a), Formula (3a ′), Formula (3b), R ¹ in formula (3b ′), formula (4), and formula (4 ′) represents partial structural formula (AA) and partial structural formula (AB).

(X in the partial structural formula (AA) and the partial structural formula (AB) is an oxygen atom or a sulfur atom, and Y in the partial structural formula (AA) and the partial structural formula (AB) is a single bond or a methylene group. (The methylene group is unsubstituted or substituted with a fluorine atom.), An ethylene group (the ethylene group is unsubstituted or substituted with a fluorine atom), -SO _2- , a carbonyl group, —CH (C _1-4 alkyl group) — (the alkyl group in —CH (C _1-4 alkyl group) — is unsubstituted or substituted with a halogen atom. Or the aryl group in —CH (C _6-14 aryl group) — (the —CH (C _6-14 aryl group) — is unsubstituted or substituted with a halogen atom. Z in the partial structural formula (AA) and the partial structural formula (AB) is C _3-12 alkyl group (said alkyl group is substituted or unsubstituted, or a halogen _{atom.), C 3-8} cycloalkyl _{group, C 6-22} aryl group (the aryl group is unsubstituted Substituted or halogen atom, C _1-4 alkyl group (the alkyl group is unsubstituted or substituted with a halogen atom or C _6-16 aryl group), C _6-16. An aryl group (the aryl group is unsubstituted or substituted with a halogen atom), or optionally substituted with a C _1-4 alkoxy group) or a C _2-9 heteroaryl group ( The heteroaryl group is unsubstituted or substituted with a halogen atom.), And R ² in the partial structural formula (AA) and the partial structural formula (AB) is a hydrogen atom, a halogen atom, C _1-4 alkyl Group (the alkyl group is substituted or unsubstituted, or a halogen atom.), Or C _1-4 alkoxy group, the partial structural formula (AA) and a partial structural formulas (AB) R ⁴ each independently represents a hydrogen atom, a halogen atom, a C _1-4 alkyl group (the alkyl group is unsubstituted or substituted with a halogen atom), a C _1-4 alkoxy group, a nitro group; Group or a cyano group).
Formula (1a), Formula (1a ′), Formula (1b), Formula (1b ′), Formula (2), Formula (2 ′), Formula (3a), Formula (3a ′), Formula (3b), Formula (3b ') ^{R 2} of formula (4) and formula (4') in a hydrogen atom, a halogen _{atom, C 1-4} alkyl group (said alkyl group is unsubstituted or substituted with a halogen atom Or a C _1-4 alkoxy group,
Formula (1a), Formula (1a ′), Formula (1b), Formula (1b ′), Formula (2), Formula (2 ′), Formula (3a), Formula (3a ′), Formula (3b), Formula R ³ in (3b ′), formula (4), and formula (4 ′) is a C _6-18 aryl group or, when two R ³ together form a ring, C _3-5 Valent group,
Formula (1a), Formula (1a ′), Formula (1b), Formula (1b ′), Formula (2), Formula (2 ′), Formula (3a), Formula (3a ′), Formula (3b), Formula (3b ') or ^{R 4} of the formula (4) and formula (4') during each independently represent a hydrogen atom, a halogen _{atom, C 1-4} alkyl group (said alkyl group is unsubstituted, Or a C _1-4 alkoxy group, a nitro group, or a cyano group. The optically active titanium complex obtained by reacting the optically active ligand represented by any of the above and a titanium compound (the optically active titanium complex is an optically active titanium salen complex, an optically active titanium salalene complex, or an optically active titanium salen). Is used as a catalyst, and the following formula (5), formula (6), formula (7), formula (8), formula (9) and formula (10) are used.

(In formula (5) and formula (6), R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, cyano group, nitro group, amino group (the amino group is a protecting group) Unprotected or protected.), C _1-4 alkylamino group (the alkylamino group is unprotected or protected by a protecting group), halogen atom, C _{1 -4} alkyl group (the alkyl group is unsubstituted or substituted with a halogen atom), C _1-4 alkoxy group, carboxyl group, formyl group, C _1-4 alkylcarbonyl group (the alkyl The carbonyl group is unsubstituted or substituted with a halogen atom.), A C _6-12 arylcarbonyl group (the arylcarbonyl group is unsubstituted or substituted with a halogen atom). ), Cal Moil _{group, C 1-4} alkylsulfinyl _{group, C 6-7} arylsulfinyl _{group, C 1-4} alkylsulfonyl _{group, C 6-12} arylsulfonyl group, a sulfamoyl group, a mono _{C 1-3} alkylaminosulfonyl group, or a di A C _1-3 alkylaminosulfonyl group,
R ⁹ in formula (5), formula (6), formula (9) and formula (10) is a hydrogen atom, a C _1-4 alkyl group (the alkyl group is unsubstituted or a halogen atom) Or a C _1-4 alkoxy group, and R ¹⁰ in formula (5), formula (6), formula (9) and formula (10) is a hydrogen atom, C _1-22 alkyl. Group, C _1-4 alkoxy group, C _6-10 aryl group (the aryl group is unsubstituted or substituted by a halogen atom, a C _1-4 alkyl group, or a C _1-4 alkoxy group) .) However, R ⁹ and R ¹⁰ in Formula (5), Formula (6), Formula (9), and Formula (10) are combined with each other, and the following Formula (11), Formula (12), and Formula (13) And formula (14)

(R ¹² in formula (11), formula (12), formula (13) and formula (14) is each independently a hydrogen atom or a C _1-4 alkyl group). Divalent groups may be formed. R ¹¹ in Formula (6) is a C _1-4 alkyl group (the alkyl group is unsubstituted or substituted with a halogen atom).
R ^a and R ^{b in} formula (7) and formula (8) are each independently a hydrogen atom, a C _1-22 alkyl group (the alkyl group is unsubstituted or a halogen atom, C _{1 -4} alkyl group, C _6-10 aryl group (the aryl group is unsubstituted or substituted with a halogen atom, a C _1-4 alkyl group, or a C _1-4 alkoxy group), benzoyl. An oxy group, a benzyloxy group, or a pivaloyloxy group), a C _3-8 cycloalkyl group (the cycloalkyl group is unsubstituted or a halogen atom, a C _1-4 alkyl group, benzoyloxy group, benzyloxy group, or is substituted with pivaloyloxy group.), C _1-4 alkoxy groups, C _6-22 aryl group (the aryl group is unsubstituted, and Halogen _{atom, C 1-4} alkyl group (said alkyl group is substituted by unsubstituted or substituted with halogen atom, or a _{C 6-16} aryl _{group.), C 6-16} aryl group (the aryl group Is unsubstituted or substituted with a halogen atom), or optionally substituted with a C _1-4 alkoxy group.
The ring partial structure A in the formula (9) and the formula (10) is a 5-membered ring, 6-membered ring or 7-membered ring condensed with a benzene ring. Or h substituents R ¹³ (wherein R ¹³ is a halogen atom, a hydroxyl group, a C _1-6 alkyl group (the alkyl group is unsubstituted or a halogen atom, a hydroxyl group, A cyano group, an amino group, a nitro group, a C _1-4 alkoxy group (the alkoxy group is unsubstituted or substituted with a halogen atom), a C _1-4 alkylcarbonyloxy group (the alkylcarbonyl The oxy group is unsubstituted or substituted with a halogen atom.), A C _1-4 alkylcarbonylamino group (the alkylcarbonylamino group is unsubstituted or substituted with a halogen atom) there.), or _{C 1-} Alkoxycarbonyl group (the alkoxy group is unsubstituted or substituted by substituted by halogen atom.) Are replaced by.), C _1-6 alkoxy group (said alkoxy group is unsubstituted Or a halogen atom, a hydroxyl group, a cyano group, an amino group, a nitro group, a C _1-4 alkoxy group (the alkoxy group is unsubstituted or substituted with a halogen atom), C _1-4. An alkylcarbonyloxy group (the alkylcarbonyloxy group is unsubstituted or substituted with a halogen atom), a C _1-4 alkylcarbonylamino group (whether the alkylcarbonylamino group is unsubstituted) or substituted with a halogen atom.), or C _1-4 alkoxycarbonyl group (the alkoxy group is unsubstituted, or Substituted with a halogen atom))), nitro group, cyano group, formyl group, formamide group, carbamoyl group, sulfo group, sulfoamino group, sulfamoyl group, sulfonyl group, amino group, carboxyl group, C _1-6 alkylamino group (the alkylamino group is unsubstituted or substituted with a halogen atom), diC _1-6 alkylamino group (the dialkylamino group is unsubstituted) Or a C _1-6 alkylcarbonylamino group (the alkylcarbonylamino group is unsubstituted or substituted with a halogen atom), C _1-6. An alkylsulfonamido group (the alkylsulfonamido group is unsubstituted or substituted with a halogen atom). ), A C _6-14 arylsulfonamido group (the arylsulfonamido group is unsubstituted or substituted with a halogen atom), a C _1-6 alkylaminocarbonyl group (the alkylaminocarbonyl group is , Unsubstituted or substituted with a halogen atom), a di-C _1-6 alkylaminocarbonyl group (the dialkylaminocarbonyl group is unsubstituted or substituted with a halogen atom). ), C _1-6 alkylcarbonyl group (the alkylcarbonyl group is unsubstituted or substituted with a halogen atom), C _1-6 alkoxycarbonyl group (the alkoxycarbonyl group is unsubstituted) substituted with some or halogen atom.), C _1-4 alkylsulfonyl group (the alkylsulfonyl group is unsubstituted der Or substituted with halogen atoms.), C _6-14 arylsulfonyl group (the aryl sulfonyl group is substituted or unsubstituted, or a halogen atom.), Or C _6-14 aryl A carbonyl group (the arylcarbonyl group is unsubstituted or substituted with a halogen atom), h is an integer of 1 to 6, and when h is 2 to 6, R ¹³ is It can be the same or different. ) And can contain 1 to 3 oxygen atoms, nitrogen atoms or sulfur atoms as ring constituents, alone or in combination, and the number of unsaturated bonds in the ring is One, two or three carbon atoms including a ring unsaturated bond may be carbonyl or thiocarbonyl. ). The following formula (15), formula (16), formula (17), formula (18), formula (19), wherein the unsaturated compound represented by any one of And equation (20)

(In formula (15), formula (16), formula (17), formula (18), formula (19) and formula (20), R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ^a , R ^b and the ring partial structure A are the same as described above). R ¹ is partial structural formula (AA) (X in partial structural formula (AA) is an oxygen atom, Y in partial structural formula (AA) is a methylene group (the methylene group is unsubstituted) Or Z in the partial structural formula (AA) is a C _6-22 aryl group (the aryl group is unsubstituted or a halogen atom, C _{1 -4} alkyl group (the alkyl group is unsubstituted or substituted with a halogen atom or a C _6-16 aryl group), a C _6-16 aryl group (the aryl group is unsubstituted Or optionally substituted with a C _1-4 alkoxy group) or a C _2-9 heteroaryl group (wherein the heteroaryl group is unsubstituted) Or substituted with a halogen atom. , ^{R 2} in the partial structural formula (AA) is a hydrogen atom, or a methoxy group, ^{R 4} in the partial structural formula (AA) is a hydrogen atom, or a methoxy group.), ^{R 2} is The formula (1a), the formula (1a ′), the formula (1b) according to claim 1, wherein R ³ is a tetramethylene group that is a divalent group, and R ⁴ is a hydrogen atom. ), An optically active titanium complex obtained by reacting an optically active ligand represented by any one of formula (1b ′), formula (2) and formula (2 ′) with a titanium compound (the optically active titanium complex) Is an optically active titanium-salen complex, an optically active titanium-salen complex, or an optically active titanium-saran complex). The formula (15), formula (16), formula (17), formula ( 18), an optically active epoxidation represented by any one of formulas (19) and (20) Method of manufacturing a thing. R ¹ is a partial structural formula (AB) (X in the partial structural formula (AB) is an oxygen atom, Y in the partial structural formula (AB) is a methylene group (the methylene group is unsubstituted) Or Z in the partial structural formula (AB) is a C _6-22 aryl group (the aryl group is unsubstituted or a halogen atom, C _{1 -4} alkyl group (the alkyl group is unsubstituted or substituted with a halogen atom or a C _6-16 aryl group), a C _6-16 aryl group (the aryl group is unsubstituted Or optionally substituted with a C _1-4 alkoxy group) or a C _2-9 heteroaryl group (wherein the heteroaryl group is unsubstituted) Or substituted with a halogen atom. And R ² in the partial structural formula (AB) is a hydrogen atom, R ⁴ in the partial structural formula (AB) is a hydrogen atom), R ² is a hydrogen atom, and R ³ Is a tetramethylene group which is a divalent group, and R ⁴ is a hydrogen atom. The formula (3a), the formula (3a ′), the formula (3b), the formula (3b ′), An optically active titanium complex obtained by reacting an optically active ligand represented by any one of formula (4) and formula (4 ′) with a titanium compound (the optically active titanium complex is an optically active titanium salen complex, optical Active titanium salalene complex or optically active titanium-saran complex) is used as a catalyst. The formula (15), formula (16), formula (17), formula (18), formula (19) and The manufacturing method of the optically active epoxy compound represented by either of Formula (20). Following formula (5) and formula (6)

(R ⁵ , R ⁶ , R ⁷ and R ⁸ in the formula (5) and the formula (6) are each independently a hydrogen atom, a cyano group, a nitro group, a mesylamino group, a dimethylylamino group, or a trifluoromethylsulfonyl group. Amino group, ditrifluoromethylsulfonylamino group, tosylamino group, benzylamino group, acetylamino group, propionylamino group, benzoylamino group, methoxycarbonylamino group, ethoxycarbonylamino group, n-propoxycarbonylamino group, i-propoxycarbonyl Amino group, t-butoxycarbonylamino group benzylmethylamino group, benzylethylamino group, benzyl-n-propylamino group, benzyl-n-butylamino group, acetylmethylamino group, acetylethylamino group, acetyl-n-propyl Amino group, benzo Rumethylamino group, benzoylethylamino group, benzoyl-n-propylamino group, benzoyl-n-butylamino group, t-butoxycarbonylmethylamino group, t-butoxycarbonylethylamino group, t-butoxycarbonyl-n-propylamino group T-butoxycarbonyl-n-butylamino group, fluorine atom, chlorine atom, bromine atom, iodine atom, methyl group, trifluoromethyl group, monochloromethyl group, ethyl group, pentafluoroethyl group, n-propyl group, i -Propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, s-butoxy group, t-butoxy group, methylcarbonyl group, trifluoromethylcarbonyl Group, monochloromethylcarbonyl group, ethylcarbonyl group, pentafluoroethylcarbonyl group, n-propylcarbonyl group, i-propylcarbonyl group, n-butylcarbonyl group, i-butylcarbonyl group, s-butylcarbonyl group, t-butyl Carbonyl group, phenylcarbonyl group, o-toluoyl group, m-toluoyl group, p-toluoyl group, o-biphenylylcarbonyl group, m-biphenylylcarbonyl group, p-biphenylylcarbonyl group, 1-naphthylcarbonyl group, 2 -Naphtylcarbonyl group, methylsulfonyl group, ethylsulfonyl group, n-propylsulfonyl group, i-propylsulfonyl group, n-butylsulfonyl group, i-butylsulfonyl group, s-butylsulfonyl group, t-butylsulfonyl group, methyl Aminosulfonyl group , Ethylaminosulfonyl group, n-propylaminosulfonyl group, i-propylaminosulfonyl group, dimethylaminosulfonyl group, diethylaminosulfonyl group, di-n-propylaminosulfonyl group, or di-i-propylaminosulfonyl group. R ⁹ in the formulas (5) and (6) is a hydrogen atom, a methyl group, a trifluoromethyl group, a monochloromethyl group, an ethyl group, a pentafluoroethyl group, an n-propyl group, an i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, s-butoxy group , or a t- butoxy group, the formula (5) and ^{R 10} in the formula (6) is a hydrogen atom, a methyl group, an ethyl group, n- Propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, 2- Ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, isotridecyl group, myristyl group, palmityl group, stearyl group, icosyl group, docosyl group, phenyl group, o-fluorophenyl group, m-fluoro Phenyl group, p-fluorophenyl group, o-chlorophenyl group, m-chlorophenyl group, p-chlorophenyl group, o-bromophenyl group, m-bromophenyl group, p-bromophenyl group, o-tolyl group, m-tolyl Group, p-tolyl group, o-ethylphenyl group, m-ethylphenyl group, p-ethylphenyl group, o- (t-butyl) L) phenyl group, m- (t-butyl) phenyl group, p- (t-butyl) phenyl group, 3,5-dimethylphenyl group, o-methoxyphenyl group, m-methoxyphenyl group, or p-methoxy It may be a phenyl group, or R ⁹ and R ^{10 in the} formulas (5) and (6) may be combined with each other to form a divalent group. The compound of the formula (5) is a divalent group of the formula (11), formula (12), formula (13) or formula (14).

(Equation (11), equation (12), ^{R 12} in the formula (13) and (14) is a methyl group.) Is a compound which can be described by combinations of one selected from the formula (11) Regarding the substitution position, the R ⁹ side is an oxygen atom, and the R ⁹ side is a carbon atom. The compound of the formula (6) is a compound that can be described in one combination selected from the formula (12) and the formula (13), and R ¹¹ in the formula (6) is a methyl group. ), Wherein the unsaturated compound represented by any one of the following formulas (15) and (16)

(R < ⁵ >, R < ⁶ >, R < ⁷ >, R < ⁸ >, R <^9> , R < ¹⁰ > and R < ¹¹ > in Formula (15) and Formula (16) are the same as described above). The method for producing an optically active epoxy compound according to any one of claims 1 to 3. Following formula (7) and formula (8)

(In the formulas (7) and (8), ^Ra represents a methyl group, a benzoyloxymethyl group, a benzyloxymethyl group, a phenylmethyl group, an ethyl group, a 2-benzoyloxyethyl group, and a 2-benzyloxyethyl group. Phenylethyl group, n-propyl group, 3-benzoyloxy-n-propyl group, 3-benzyloxy-n-propyl group, n-butyl group, 4-benzoyloxy-n-butyl group, 4-benzyloxy- n-butyl group, t-butyl group, n-pentyl group, 5-benzoyloxy-n-pentyl group, 5-benzyloxy-n-pentyl group, n-hexyl group, 6-benzoyloxy-n-hexyl Group, 6-benzyloxy-n-hexyl group, n-heptyl group, 7-benzoyloxy-n-heptyl group, 7-benzyloxy-n-heptyl group, octyl Group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group, c-propyl group, c-butyl group, c-pentyl group, 3-benzoyl-c-pentyl group, 3-benzyloxy -C-pentyl group, c-hexyl group, 3-benzoyl-c-hexyl group, 3-benzyloxy-c-hexyl group, 4-benzoyl-c-hexyl group, 4-benzyloxy-c-hexyl group, phenyl Group, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2-bromophenyl group, 3-bromophenyl group, 4-bromo Phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2-ethylphenyl group, 3-ethylphenyl group, -Ethylphenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2-naphthyl group, 6-bromo-2-naphthyl group, 6-methoxy-2-naphthyl group, 2-biphenylyl group , 3-biphenylyl group, or 4-biphenylyl group, and R ^{b in} formula (7) and formula (8) is a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, t -Butyl group, c-propyl group, c-butyl group, c-pentyl group, c-hexyl group)), and asymmetric epoxidation with an oxidizing agent. The following formula (17) and formula (18)

4. The optical activity according to claim 1, wherein R ^a and R ^{b in} formula (17) and formula (18) are the same as those described above. A method for producing an epoxy compound. Following formula (9) and formula (10)

(The ring partial structure A in the formula (9) and the formula (10) has the formula (a), formula (b), formula (c), formula (d), formula (e), formula (f), formula (G), Formula (h), Formula (i), Formula (j), Formula (k), Formula (l), Formula (m), Formula (n), Formula (o), Formula (p), Formula (Q), formula (r), formula (s), formula (t), formula (u), formula (v), formula (w), formula (x), formula (y), formula (z), formula (Aa), formula (ab), formula (ac), formula (ad), formula (ae), formula (af), formula (ag), and formula (ah)

(Formula (a), Formula (b), Formula (e), Formula (f), Formula (g), Formula (h), Formula (i), Formula (j), Formula (k), Formula (l ), Formula (m), formula (n), formula (p), formula (q), formula (v), formula (w), formula (x), formula (ab), formula (ae), formula (af) And R ¹⁴ and R ^{15 in} formula (ag) are each independently a hydrogen atom, a C _1-6 alkyl group (the alkyl group is unsubstituted or a halogen atom, C _1-6 alkoxy) A group (the alkoxy group is unsubstituted or substituted with a halogen atom), an amino group, a hydroxyl group, a C _6-14 aryl group (the aryl group is unsubstituted or q Substituted with R ²⁰ (wherein R ²⁰ represents the same meaning as R ¹³ , q represents an integer of 1 to 3, and when q is 2 or 3, R ²⁰ may be the same or different). The C _2-9 heteroaryl group (the heteroaryl group is unsubstituted or q substituents R ²⁰ (the R ²⁰ represents the same meaning as R ¹³ , q is 1 Represents an integer of ˜3, and when q is 2 or 3, R ²⁰ may be the same or different.)), C _1-6 alkylaminocarbonyl group, diC _1-6 alkyl An aminocarbonyl group, a C _1-6 alkylcarbonyloxy group (the alkylcarbonyloxy group is unsubstituted or substituted with a halogen atom), a C _1-6 alkylcarbonyl group (the alkylcarbonyl group is is substituted or unsubstituted, or a halogen atom.), C _1-6 alkylcarbonylamino group, C _3-8 cycloalkyl group (said cycloalkyl group is unsubstituted Luke, or substituted with a halogen atom.), C _1-6 alkoxycarbonyl group (the alkoxy group is substituted or unsubstituted, or a halogen atom.), C _1-4 alkyl A sulfonyl group (the alkylsulfonyl group is unsubstituted or substituted with a halogen atom), a carboxyl group, a C _6-14 arylcarbonyl group (the arylcarbonyl group is unsubstituted, or Substituted with a halogen atom) or a C _2-9 heteroarylcarbonyl group), a C _6-14 aryl group (the aryl group is unsubstituted or q substituents) R ²⁰ (wherein R ²⁰ represents the same meaning as R ¹³ , q represents an integer of 1 to 3, and when q is 2 or 3, R ²⁰ may be the same or different. ). ), C _2-9 heteroaryl group (the heteroaryl group is unsubstituted or q substituents R ²⁰ (the R ²⁰ represents the same meaning as R ¹³ , q is an integer of 1 to 3) And when q is 2 or 3, R ²⁰ may be the same or different.)), A C _1-6 alkylaminocarbonyl group, a diC _1-6 alkylaminocarbonyl group, C _1-6 alkylcarbonyl group, C _3-8 cycloalkylcarbonyl group, C _1-6 alkoxycarbonyl group, C _1-4 alkylsulfonyl group (the alkylsulfonyl group is unsubstituted or substituted with a halogen atom) C _6-14 arylsulfonyl group (the arylsulfonyl group is unsubstituted or q substituents R ²⁰ (wherein R ²⁰ has the same meaning as R ¹³ , q is 1 ~ 3 Represents an integer, and when q is 2 or 3, R ²⁰ is substituted with or.) To be the same or different.), C _2-9 heteroarylsulfonyl group (the hetero arylsulfonyl group, an unsubstituted Or q substituents R ²⁰ (wherein R ²⁰ represents the same meaning as R ¹³ , q represents an integer of 1 to 3, and when q is 2 or 3, R ²⁰ is the same or different. Substituted), a carboxyl group, a C _6-14 arylcarbonyl group (the arylcarbonyl group is unsubstituted or q substituents R ²⁰ (the R ²⁰ is R) represents the same meaning as ^13, q represents an integer of 1 to 3, when q is 2 or ^{3, R 20} is substituted with or.) to be the same or different. or _{C 2-9} heteroaryl A carbonyl group (the heteroarylcarbonyl group is Or is unsubstituted, or q substituents, ^{R 20} (wherein ^{R 20} has the same meaning as ^{R 13,} q represents an integer of 1 to 3, when q is 2 or ^3, also ^{R 20} is the same And may be different from each other.), And the above formula (a), formula (b), formula (c), formula (d), formula (f), formula (g), formula ( h), formula (j), formula (k), formula (m), formula (n), formula (o), formula (p), formula (q), formula (r), formula (s), formula ( t), formula (u), formula (v), formula (w), formula (y), formula (z), formula (aa), formula (ab), formula (ac), formula (ad), formula ( ae) and R ¹⁶ , R ¹⁷ , R ¹⁸ and R ^{19 in} formula (af) are each independently a hydrogen atom, a halogen atom or a C _1-6 alkyl group (the alkyl group is unsubstituted or or halogen _{atom, C 1-6} alkoxy group (該A Kokishi group is substituted or unsubstituted, or a halogen atom. ), An amino group, a hydroxyl group, a C _6-14 aryl group (the aryl group is unsubstituted or has r substituents R ²¹ (the R ²¹ has the same meaning as R ¹³ , r is q and Substituted with a C _2-9 heteroaryl group (the heteroaryl group is unsubstituted or r substituents R ²¹ (the R ²¹ is R ¹³ and The same meaning, and r is the same meaning as q.)), A C _1-6 alkylaminocarbonyl group, a di C _1-6 alkylaminocarbonyl group, a C _1-6 alkylcarbonyloxy group. (The alkylcarbonyloxy group is unsubstituted or substituted with a halogen atom.), A C _1-6 alkylcarbonyl group (the alkylcarbonyl group is unsubstituted or substituted with a halogen atom. Has been.) C _1-6 alkylcarbonylamino _{group, C 3-8} cycloalkyl group (the cycloalkyl group is substituted or unsubstituted, or a halogen _{atom.), C 1-6} alkoxycarbonyl group ( The alkoxycarbonyl group is unsubstituted or substituted with a halogen atom.), A C _1-4 alkylsulfonyl group (the alkylsulfonyl group is unsubstituted or substituted with a halogen atom) ), A carboxyl group, a C _6-14 arylcarbonyl group (the arylcarbonyl group is unsubstituted or substituted with a halogen atom) or a C _2-9 heteroarylcarbonyl group. Yes. ), A C _3-8 cycloalkyl group (the cycloalkyl group is unsubstituted or substituted with a halogen atom, a C _1-6 alkoxy group (the alkoxy group is unsubstituted or substituted with a halogen atom) Substituted with an amino group or a hydroxyl group), a C _1-6 alkoxy group (the alkoxy group is unsubstituted, or a halogen atom, a C _1-6 alkoxy group (the alkoxy group is , Unsubstituted or substituted with a halogen atom), a carboxyl group, an amino group, a hydroxyl group, a C _6-14 aryl group (the aryl group is unsubstituted or r substituents) Substituted with R ²¹ (wherein R ²¹ represents the same meaning as R ¹³ and r represents the same meaning as q)) or a C _2-9 heteroaryl group (the heteroaryl group is unsubstituted) Is or r substituents, ^{R 21} (wherein ^{R 21} has the same meaning as ^{R 13,} r represents. the same meaning as q) is substituted with.) which is substituted _{with.), C 1-6} thio An alkoxy group (the thioalkoxy group is unsubstituted or a halogen atom, a C _1-6 alkoxy group (the alkoxy group is unsubstituted or substituted with a halogen atom), a carboxyl group; , A hydroxyl group, a C _6-14 aryl group (the aryl group is unsubstituted or r substituents R ²¹ (the R ²¹ represents the same meaning as R ^13, and r represents the same meaning as q). ), Or a C _2-9 heteroaryl group (the heteroaryl group is unsubstituted or r substituents R ²¹ (wherein R ²¹ has the same meaning as R ^13). And r represents the same meaning as q). ), A hydroxyl group, a C _6-14 aryl group (the aryl group is unsubstituted or r substituents R ²¹ (wherein R ²¹ represents the same meaning as R ¹³⁾ , r represents the same meaning as q.)), a C _2-9 heteroaryl group (the heteroaryl group is unsubstituted or r substituents R ²¹ (the R ²¹ Represents the same meaning as R ^13, and r represents the same meaning as q).), C _1-6 alkylcarbonyloxy group, nitro group, cyano group, formyl group, formamide group, amino group , A sulfo group, a C _1-6 alkylamino group, a di C _1-6 alkylamino group, a C _6-14 arylamino group (the arylamino group is unsubstituted or r substituents R ²¹ ( the ^{R 21} are as defined ^{R 13,} r is equal and q Meaning represents a. ). ), C _2-9 heteroarylamino group (the heteroarylamino group is unsubstituted or r substituents R ²¹ (the R ²¹ represents the same meaning as R ¹³ , r is the same as q) Represents a meaning.)), C _1-6 alkylcarbonylamino group, C _1-6 alkylsulfonamido group, carbamoyl group, C _1-6 alkylaminocarbonyl group, di-C _1-6 alkylamino A carbonyl group, a C _1-6 alkylcarbonyl group, a C _6-14 arylcarbonyl group (the arylcarbonyl group is unsubstituted or r substituents R ²¹ (the R ²¹ has the same meaning as R ¹³⁾ ; And r represents the same meaning as q.)), A C _2-9 heteroarylcarbonyl group (the heteroarylcarbonyl group is unsubstituted or r substituents) Substituted with R ²¹ (wherein R ²¹ has the same meaning as R ¹³ and r has the same meaning as q)), C _1-6 alkoxycarbonyl group, sulfamoyl group, C _1-4 alkylsulfonyl. A group (the alkylsulfonyl group is unsubstituted or substituted with a halogen atom), a C _6-14 arylsulfonyl group (the arylsulfonyl group is unsubstituted or substituted with r substituents); Substituted with a group R ²¹ (wherein R ²¹ has the same meaning as R ¹³ and r has the same meaning as q)), a C _2-9 heteroarylsulfonyl group (the heteroarylsulfonyl group is It is unsubstituted or substituted with r substituents R ²¹ (wherein R ²¹ has the same meaning as R ¹³ and r has the same meaning as q)), a carboxyl group, or C _2-9 non Aromatic heterocyclyl group (non-aromatic heterocyclyl group is unsubstituted, or halogen atom, C _1-6 alkyl group (said alkyl group is unsubstituted, or halogen atom, C _1-6 An alkoxy group (the alkoxy group is unsubstituted or substituted with a halogen atom), an amino group, a carboxyl group, or a hydroxyl group), a C _1-6 alkoxy group (the alkoxy group Is unsubstituted or substituted with a halogen atom.), A C _6-14 aryl group (the aryl group is unsubstituted or r substituents R ²¹ (the R ²¹ is R ¹³ represents the same meaning as R ^13, and r represents the same meaning as q.)), A C _2-9 heteroaryl group (the heteroaryl group is unsubstituted or r substituents ^{R 21} (wherein ²¹ has the same meaning as ^{R 13,} r represents the same meaning as q. ). ), Hydroxyl group, nitro group, cyano group, formyl group, formamide group, amino group, C _1-6 alkylamino group, diC _1-6 alkylamino group, C _1-6 alkylcarbonylamino group, C _1-6 alkyl Sulfonamide group, carbamoyl group, C _1-6 alkylaminocarbonyl group, diC _1-6 alkylaminocarbonyl group, C _1-6 alkylcarbonyl group, C _1-6 alkoxycarbonyl group, sulfamoyl group, C _1-4 alkyl Substituted with a sulfonyl group, a carboxyl group, or a C _6-14 arylcarbonyl group. In the formula (c), formula (d), formula (p), formula (q), formula (v), formula (w), formula (ab), formula (ac) and formula (ad) Q in the formula means O (oxygen atom), S (sulfur atom), SO (sulfyl group) or SO ₂ (sulfonyl group). And R ⁹ and R ¹⁰ in formula (9) and formula (10) are combined together to form the following formula (11):

(R ¹² in the formula (11) which is a divalent group is a methyl group, and the substitution position of the formula (11) is located on the oxygen atom on the R ⁹ side and on the carbon atom on the R ¹⁰ side.) It is a bivalent group represented by these. ), Wherein the unsaturated compound represented by any one of the following formulas (19) and (20)

The ring partial structure A, R ⁹ and R ¹⁰ in the formula (19) and the formula (20) are the same as those described above. A method for producing the optically active epoxy compound according to 1. The ring partial structure A in formula (9) or formula (10) is represented by formula (a), formula (b), formula (i), formula (k), formula (o), formula (p), formula (s ), Formula (v), formula (y), formula (ae), formula (ag) and formula (ah)

(Formula (a), Formula (b), Formula (i), Formula (k), Formula (o), Formula (p), Formula (s), Formula (v), Formula (y), Formula (ae ), Formula (ag) or formula (ah), formula (a), formula (b), formula (i), formula (k), formula (p), formula (v), formula (ae) and formula R ¹⁴ and R ^{15 in} (ag) are a hydrogen atom and a methyl group, and the formula (a), formula (b), formula (k), formula (o), formula (p), formula (s), formula (V), R ¹⁶ , R ¹⁷ and R ¹⁸ in formula (y) and formula (ae) are each independently a hydrogen atom, a halogen atom, or a C _1-6 alkyl group (the alkyl group is a halogen atom) , C _1-6 alkoxy group (the alkoxy group may be optionally substituted with a halogen atom), amino group, hydroxyl group, C _1-6 alkylaminocarbonyl group, di-C _1-6 alkylaminocarbonyl. Group, C _1-6 alkylcarbonyloxy group (the alkylcarbonyloxy group may be optionally substituted with a halogen atom), C _1-6 alkylcarbonyl group (the alkylcarbonyloxy group is a halogen atom) Optionally substituted with a C _1-6 alkylcarbonylamino group, a C _3-8 cycloalkylcarbonyl group, or a C _1-6 alkoxycarbonyl group. , Q is O (oxygen atom).) An unsaturated compound represented by any one of the following formulas (19) and (20) (formula (19)): And the ring partial structure A, R ⁹ and R ¹⁰ in the formula (20) are the same as defined above.) The optical activity according to any one of claims 1 to 3 Of epoxy compounds Production method.   The method for producing an optically active epoxy compound according to any one of claims 1 to 7, wherein the oxidizing agent is a hydrogen peroxide solution. Formula (21a), Formula (21a ′), Formula (21b), Formula (21b ′), Formula (22), Formula (22 ′), Formula (23a), Formula (23a ′), Formula (23b), Formula (23b ′), formula (24) and formula (24 ′)

(Formula (21a), Formula (21a ′), Formula (21b), Formula (21b ′), Formula (22), Formula (22 ′), Formula (23a), Formula (23a ′), Formula (23b), R ¹ in formula (23b ′), formula (24), and formula (24 ′) represents partial structural formula (AA) and partial structural formula (AB).

(X in the partial structural formula (AA) and the partial structural formula (AB) is an oxygen atom or a sulfur atom, and Y in the partial structural formula (AA) and the partial structural formula (AB) is a single bond or a methylene group. (The methylene group is unsubstituted or substituted with a fluorine atom.), An ethylene group (the ethylene group is unsubstituted or substituted with a fluorine atom), -SO _2- , a carbonyl group, —CH (C _1-4 alkyl group) — (the alkyl group in —CH (C _1-4 alkyl group) — is unsubstituted or substituted with a halogen atom. Or the aryl group in —CH (C _6-14 aryl group) — (the —CH (C _6-14 aryl group) — is unsubstituted or substituted with a halogen atom. Z in the partial structural formula (AA) and the partial structural formula (AB) is C _3-12 alkyl group (said alkyl group is substituted or unsubstituted, or a halogen _{atom.), C 3-8} cycloalkyl _{group, C 6-22} aryl group (the aryl group is unsubstituted Substituted or halogen atom, C _1-4 alkyl group (the alkyl group is unsubstituted or substituted with a halogen atom or C _6-16 aryl group), C _6-16. An aryl group (the aryl group is unsubstituted or substituted with a halogen atom), or optionally substituted with a C _1-4 alkoxy group) or a C _2-9 heteroaryl group ( The heteroaryl group is unsubstituted or substituted with a halogen atom.), And R ² in the partial structural formula (AA) and the partial structural formula (AB) is a hydrogen atom, a halogen atom, C _1-4 alkyl Group (the alkyl group is substituted or unsubstituted, or a halogen atom.), Or C _1-4 alkoxy group, the partial structural formula (AA) and a partial structural formulas (AB) R ⁴ each independently represents a hydrogen atom, a halogen atom, a C _1-4 alkyl group (the alkyl group is unsubstituted or substituted with a halogen atom), a C _1-4 alkoxy group, a nitro group; Group or a cyano group).
Formula (21a), Formula (21a ′), Formula (21b), Formula (21b ′), Formula (22), Formula (22 ′), Formula (23a), Formula (23a ′), Formula (23b), Formula R ² in (23b ′), formula (24), and formula (24 ′) is a hydrogen atom, a halogen atom, or a C _1-4 alkyl group (the alkyl group is unsubstituted or substituted with a halogen atom) Or a C _1-4 alkoxy group,
Formula (21a), Formula (21a ′), Formula (21b), Formula (21b ′), Formula (22), Formula (22 ′), Formula (23a), Formula (23a ′), Formula (23b), Formula R ³ in (23b ′), formula (24) and formula (24 ′) is a C _6-18 aryl group or, when two R ³ together form a ring, C _3-5 A divalent group,
Formula (21a), Formula (21a ′), Formula (21b), Formula (21b ′), Formula (22), Formula (22 ′), Formula (23a), Formula (23a ′), Formula (23b), Formula (23b ') or ^{R 4} in the formula (24) and (24') are each independently a hydrogen atom, a halogen _{atom, C 1-4} alkyl group (said alkyl group is unsubstituted, or Substituted with a halogen atom), a C _1-4 alkoxy group, a nitro group or a cyano group,
Formula (21a), Formula (21a ′), Formula (21b), Formula (21b ′), Formula (22), Formula (22 ′), Formula (23a), Formula (23a ′), Formula (23b), Formula M in (23b ′), formula (24) and formula (24 ′) is TiJ ¹ J ² (in TiJ ¹ J ² , Ti is a titanium atom, and J ¹ and J ² are each independently , A hydroxyl group, a halogen atom, a C _1-4 alkoxy group, J ¹ and J ² together represent an oxygen atom, or J ¹ and J ² together form a ring Formula (25), which is an optically active titanium complex

(The partial structural formula OEOO in the formula (25) includes the following formula (26a), the following formula (26a ′), the following formula (26b), the following formula (26b ′), the following formula (27), and the following formula (27). Formula (27 ′), Formula (28a), Formula (28a ′), Formula (28b), Formula (28b ′), Formula (29), Formula (29 ′) and Formula (29 ′)

(Formula (26a), Formula (26a ′), Formula (26b), Formula (26b ′), Formula (27), Formula (27 ′), Formula (28a), Formula (28a ′), Formula (28b), R ¹ , R ² , R ^3, and R ⁴ in formula (28b ′), formula (29), and formula (29 ′) are the same as described above. At this time, two partial structural formulas in formula (25) are used. O-EO is the same as each other). The case where the titanium binuclear complex represented by this is formed is shown. ). An optically active titanium complex represented by any one of R ¹ is partial structural formula (AA) (X in partial structural formula (AA) is an oxygen atom, Y in partial structural formula (AA) is a methylene group (the methylene group is unsubstituted) Or Z in the partial structural formula (AA) is a C _6-22 aryl group (the aryl group is unsubstituted or a halogen atom, C _{1 -4} alkyl group (the alkyl group is unsubstituted or substituted with a halogen atom or a C _6-16 aryl group), a C _6-16 aryl group (the aryl group is unsubstituted Or optionally substituted with a C _1-4 alkoxy group) or a C _2-9 heteroaryl group (wherein the heteroaryl group is unsubstituted) Or substituted with a halogen atom. , ^{R 2} in the partial structural formula (AA) is a hydrogen atom, or a methoxy group, ^{R 4} in the partial structural formula (AA) is a hydrogen atom, or a methoxy group.), ^{R 2} is The hydrogen atom, R ³ is a tetramethylene group which is a divalent group, and R ⁴ is a hydrogen atom. The formula (21a), the formula (21a ′) and the formula (21b ), An optically active titanium complex represented by any one of formula (21b ′), formula (22) and formula (22 ′). R ¹ is a partial structural formula (AB) (X in the partial structural formula (AB) is an oxygen atom, Y in the partial structural formula (AB) is a methylene group (the methylene group is unsubstituted) Or Z in the partial structural formula (AB) is a C _6-22 aryl group (the aryl group is unsubstituted or a halogen atom, C _{1 -4} alkyl group (the alkyl group is unsubstituted or substituted with a halogen atom or a C _6-16 aryl group), a C _6-16 aryl group (the aryl group is unsubstituted Or optionally substituted with a C _1-4 alkoxy group) or a C _2-9 heteroaryl group (wherein the heteroaryl group is unsubstituted) Or substituted with a halogen atom. And R ² in the partial structural formula (AB) is a hydrogen atom, R ⁴ in the partial structural formula (AB) is a hydrogen atom), R ² is a hydrogen atom, and R ³ Is a tetramethylene group which is a divalent group, and R ⁴ is a hydrogen atom. The formula (23a), formula (23a ′), formula (23b), formula (23b ′), An optically active titanium complex represented by any one of formula (24) and formula (24 ′). Formula (1a), Formula (1a ′), Formula (1b), Formula (1b ′), Formula (2), Formula (2 ′), Formula (3a), Formula (3a ′), Formula (3b), Formula (3b ′), formula (4) and formula (4 ′)

(Formula (1a), Formula (1a ′), Formula (1b), Formula (1b ′), Formula (2), Formula (2 ′), Formula (3a), Formula (3a ′), Formula (3b), R ¹ in formula (3b ′), formula (4), and formula (4 ′) represents partial structural formula (AA) and partial structural formula (AB).

(X in the partial structural formula (AA) and the partial structural formula (AB) is an oxygen atom or a sulfur atom, and Y in the partial structural formula (AA) and the partial structural formula (AB) is a single bond or a methylene group. (The methylene group is unsubstituted or substituted with a fluorine atom.), An ethylene group (the ethylene group is unsubstituted or substituted with a fluorine atom), -SO _2- , a carbonyl group, —CH (C _1-4 alkyl group) — (the alkyl group in —CH (C _1-4 alkyl group) — is unsubstituted or substituted with a halogen atom. Or the aryl group in —CH (C _6-14 aryl group) — (the —CH (C _6-14 aryl group) — is unsubstituted or substituted with a halogen atom. Z in the partial structural formula (AA) and the partial structural formula (AB) is C _3-12 alkyl group (said alkyl group is substituted or unsubstituted, or a halogen _{atom.), C 3-8} cycloalkyl _{group, C 6-22} aryl group (the aryl group is unsubstituted Substituted or halogen atom, C _1-4 alkyl group (the alkyl group is unsubstituted or substituted with a halogen atom or C _6-16 aryl group), C _6-16. An aryl group (the aryl group is unsubstituted or substituted with a halogen atom), or optionally substituted with a C _1-4 alkoxy group) or a C _2-9 heteroaryl group ( The heteroaryl group is unsubstituted or substituted with a halogen atom.), And R ² in the partial structural formula (AA) and the partial structural formula (AB) is a hydrogen atom, a halogen atom, C _1-4 alkyl Group (the alkyl group is substituted or unsubstituted, or a halogen atom.), Or C _1-4 alkoxy group, the partial structural formula (AA) and a partial structural formulas (AB) R ⁴ each independently represents a hydrogen atom, a halogen atom, a C _1-4 alkyl group (the alkyl group is unsubstituted or substituted with a halogen atom), a C _1-4 alkoxy group, a nitro group; Group or a cyano group).
Formula (1a), Formula (1a ′), Formula (1b), Formula (1b ′), Formula (2), Formula (2 ′), Formula (3a), Formula (3a ′), Formula (3b), Formula (3b ') ^{R 2} of formula (4) and formula (4') in a hydrogen atom, a halogen _{atom, C 1-4} alkyl group (said alkyl group is unsubstituted or substituted with a halogen atom Or a C _1-4 alkoxy group,
Formula (1a), Formula (1a ′), Formula (1b), Formula (1b ′), Formula (2), Formula (2 ′), Formula (3a), Formula (3a ′), Formula (3b), Formula R ³ in (3b ′), formula (4), and formula (4 ′) is a C _6-18 aryl group or, when two R ³ together form a ring, C _3-5 Valent group,
Formula (1a), Formula (1a ′), Formula (1b), Formula (1b ′), Formula (2), Formula (2 ′), Formula (3a), Formula (3a ′), Formula (3b), Formula (3b ') or ^{R 4} of the formula (4) and formula (4') during each independently represent a hydrogen atom, a halogen _{atom, C 1-4} alkyl group (said alkyl group is unsubstituted, Or a C _1-4 alkoxy group, a nitro group, or a cyano group. An optically active ligand represented by any one of R ¹ is partial structural formula (AA) (X in partial structural formula (AA) is an oxygen atom, Y in partial structural formula (AA) is a methylene group (the methylene group is unsubstituted) Or Z in the partial structural formula (AA) is a C _6-22 aryl group (the aryl group is unsubstituted or a halogen atom, C _{1 -4} alkyl group (the alkyl group is unsubstituted or substituted with a halogen atom or a C _6-16 aryl group), a C _6-16 aryl group (the aryl group is unsubstituted Or optionally substituted with a C _1-4 alkoxy group) or a C _2-9 heteroaryl group (wherein the heteroaryl group is unsubstituted) Or substituted with a halogen atom. , ^{R 2} in the partial structural formula (AA) is a hydrogen atom, or a methoxy group, ^{R 4} in the partial structural formula (AA) is a hydrogen atom, or a methoxy group.), ^{R 2} is The hydrogen atom, R ³ is a tetramethylene group which is a divalent group, and R ⁴ is a hydrogen atom. The formula (1a), the formula (1a ′) and the formula (1b ), An optically active ligand represented by any one of formula (1b ′), formula (2) and formula (2 ′). R ¹ is a partial structural formula (AB) (X in the partial structural formula (AB) is an oxygen atom, Y in the partial structural formula (AB) is a methylene group (the methylene group is unsubstituted) Or Z in the partial structural formula (AB) is a C _6-22 aryl group (the aryl group is unsubstituted or a halogen atom, C _{1 -4} alkyl group (the alkyl group is unsubstituted or substituted with a halogen atom or a C _6-16 aryl group), a C _6-16 aryl group (the aryl group is unsubstituted Or optionally substituted with a C _1-4 alkoxy group) or a C _2-9 heteroaryl group (wherein the heteroaryl group is unsubstituted) Or substituted with a halogen atom. And R ² in the partial structural formula (AB) is a hydrogen atom, R ⁴ in the partial structural formula (AB) is a hydrogen atom), R ² is a hydrogen atom, and R ³ Is a tetramethylene group which is a divalent group, and R ⁴ is a hydrogen atom. The formula (3a), the formula (3a ′), the formula (3b), the formula (3b ′), An optically active ligand represented by any one of formula (4) and formula (4 ′). Formula (1a), Formula (1a ′), Formula (1b), Formula (1b ′), Formula (2), Formula (2 ′), Formula (3a), Formula (3a ′), Formula (3b), Formula (3b ′), formula (4) and formula (4 ′)

(Formula (1a), Formula (1a ′), Formula (1b), Formula (1b ′), Formula (2), Formula (2 ′), Formula (3a), Formula (3a ′), Formula (3b), R ¹ in formula (3b ′), formula (4), and formula (4 ′) represents partial structural formula (AA) and partial structural formula (AB).

(X in the partial structural formula (AA) and the partial structural formula (AB) is an oxygen atom or a sulfur atom, and Y in the partial structural formula (AA) and the partial structural formula (AB) is a single bond or a methylene group. (The methylene group is unsubstituted or substituted with a fluorine atom.), An ethylene group (the ethylene group is unsubstituted or substituted with a fluorine atom), -SO _2- , a carbonyl group, —CH (C _1-4 alkyl group) — (the alkyl group in —CH (C _1-4 alkyl group) — is unsubstituted or substituted with a halogen atom. Or the aryl group in —CH (C _6-14 aryl group) — (the —CH (C _6-14 aryl group) — is unsubstituted or substituted with a halogen atom. Z in the partial structural formula (AA) and the partial structural formula (AB) is C _3-12 alkyl group (said alkyl group is substituted or unsubstituted, or a halogen _{atom.), C 3-8} cycloalkyl _{group, C 6-22} aryl group (the aryl group is unsubstituted Substituted or halogen atom, C _1-4 alkyl group (the alkyl group is unsubstituted or substituted with a halogen atom or C _6-16 aryl group), C _6-16. An aryl group (the aryl group is unsubstituted or substituted with a halogen atom), or optionally substituted with a C _1-4 alkoxy group) or a C _2-9 heteroaryl group ( The heteroaryl group is unsubstituted or substituted with a halogen atom.), And R ² in the partial structural formula (AA) and the partial structural formula (AB) is a hydrogen atom, a halogen atom, C _1-4 alkyl Group (the alkyl group is substituted or unsubstituted, or a halogen atom.), Or C _1-4 alkoxy group, the partial structural formula (AA) and a partial structural formulas (AB) R ⁴ each independently represents a hydrogen atom, a halogen atom, a C _1-4 alkyl group (the alkyl group is unsubstituted or substituted with a halogen atom), a C _1-4 alkoxy group, a nitro group; Group or a cyano group).
Formula (1a), Formula (1a ′), Formula (1b), Formula (1b ′), Formula (2), Formula (2 ′), Formula (3a), Formula (3a ′), Formula (3b), Formula (3b ') ^{R 2} of formula (4) and formula (4') in a hydrogen atom, a halogen _{atom, C 1-4} alkyl group (said alkyl group is unsubstituted or substituted with a halogen atom Or a C _1-4 alkoxy group,
Formula (1a), Formula (1a ′), Formula (1b), Formula (1b ′), Formula (2), Formula (2 ′), Formula (3a), Formula (3a ′), Formula (3b), Formula R ³ in (3b ′), formula (4), and formula (4 ′) is a C _6-18 aryl group or, when two R ³ together form a ring, C _3-5 Valent group,
Formula (1a), Formula (1a ′), Formula (1b), Formula (1b ′), Formula (2), Formula (2 ′), Formula (3a), Formula (3a ′), Formula (3b), Formula (3b ') or ^{R 4} of the formula (4) and formula (4') during each independently represent a hydrogen atom, a halogen _{atom, C 1-4} alkyl group (said alkyl group is unsubstituted, Or a C _1-4 alkoxy group, a nitro group, or a cyano group. The optically active titanium complex obtained by reacting the optically active ligand represented by any of the above and a titanium compound (the optically active titanium complex is an optically active titanium salen complex, an optically active titanium salalene complex, or an optically active titanium salen). Is used as a catalyst, and the following formula (30)

(R ²² and R ^{23 in} formula (30) are different substituents, and each independently represents a C _6-12 aryl group (the aryl group is unsubstituted or a halogen atom, C _{1- 4} alkyl group, C _1-4 alkoxy group, C _2-5 alkylcarbonyloxy group, C _2-5 alkoxycarbonyl group, nitro group, or cyano group.), C _6-12 arylmethyl group ( The arylmethyl group is unsubstituted or a halogen atom, a C _1-4 alkyl group, a C _1-4 alkoxy group, a C _2-5 alkylcarbonyloxy group, a C _2-5 alkoxycarbonyl group, a nitro group, Or a C _1-6 alkyl group (the alkyl group is unsubstituted, a halogen atom, a nitro group, a hydroxyl group, or However, R ²² is a C _6-12 aryl group, and a C _1-4 alkyl group or a C _1-4 alkoxy group is located at the ortho position of the C _6-12 aryl group. When the group is substituted, R ²³ may be a C _2-4 divalent group that forms a ring together with the C _1-4 alkyl group or the C _1-4 alkoxy group. )) Is asymmetrically oxidized with an oxidizing agent, the following formula (31)

(R ²² and R ²³ in the formula (31) are the same as described above, and the absolute configuration of the sulfur atom indicated by * means (R) or (S).) Compound production method. Formula (1a), Formula (1a ′), Formula (1b), Formula (1b ′), Formula (2), Formula (2 ′), Formula (3a), Formula (3a ′), Formula (3b), Formula (3b ′), Formula (4) and Formula (4 ′) (Formula (1a), Formula (1a ′), Formula (1b), Formula (1b ′), Formula (2), Formula (2 ′), Formula (3a), formula (3a '), formula (3b), wherein ^{(3b'), R 1,} R 2, R 3 and ^{R 4} in the formula (4) and formula (4 ') includes a claim 15 The optically active titanium complex obtained by reacting the optically active ligand represented by any of the above and a titanium compound (the optically active titanium complex is an optically active titanium salen complex, an optically active titanium salalene complex, or An optically active titanium-saran complex) as a catalyst.

(R ²² and R ²³ in the formula (32) are the same as those in claim 15.) One of the optical isomers of the racemic or sulfoxide compound having a low optical purity is selectively oxidized with an oxidizing agent. By doing the following formula (33)

(R ²² and R ²³ in the formula (33) are the same as those in claim 15), and the kinetic resolution is applied to formula (31).

(R ²² and R ^{23 in} formula (31) are the same as in claim 15). A method for producing an optically active sulfoxide compound, comprising obtaining an optically active sulfoxide compound represented by formula (31). R ¹ is partial structural formula (AA) (X in partial structural formula (AA) is an oxygen atom, Y in partial structural formula (AA) is a methylene group (the methylene group is unsubstituted) Or Z in the partial structural formula (AA) is a C _6-22 aryl group (the aryl group is unsubstituted or a halogen atom, C _{1 -4} alkyl group (the alkyl group is unsubstituted or substituted with a halogen atom or a C _6-16 aryl group), a C _6-16 aryl group (the aryl group is unsubstituted Or optionally substituted with a C _1-4 alkoxy group) or a C _2-9 heteroaryl group (wherein the heteroaryl group is unsubstituted) Or substituted with a halogen atom. , ^{R 2} in the partial structural formula (AA) is a hydrogen atom, or a methoxy group, ^{R 4} in the partial structural formula (AA) is a hydrogen atom, or a methoxy group.), ^{R 2} is The hydrogen atom, R ³ is a tetramethylene group which is a divalent group, and R ⁴ is a hydrogen atom. The formula (1a), the formula (1a ′) and the formula (1b ), An optically active titanium complex (optically active titanium salen complex, The method for producing an optically active sulfoxide compound according to claim 15 or 16, wherein an optically active titanium salalene complex or an optically active titanium salane complex) is used as a catalyst. R ¹ is a partial structural formula (AB) (X in the partial structural formula (AB) is an oxygen atom, Y in the partial structural formula (AB) is a methylene group (the methylene group is unsubstituted) Or Z in the partial structural formula (AB) is a C _6-22 aryl group (the aryl group is unsubstituted or a halogen atom, C _{1 -4} alkyl group (the alkyl group is unsubstituted or substituted with a halogen atom or a C _6-16 aryl group), a C _6-16 aryl group (the aryl group is unsubstituted Or optionally substituted with a C _1-4 alkoxy group) or a C _2-9 heteroaryl group (wherein the heteroaryl group is unsubstituted) Or substituted with a halogen atom. And R ² in the partial structural formula (AB) is a hydrogen atom, R ⁴ in the partial structural formula (AB) is a hydrogen atom), R ² is a hydrogen atom, and R ³ Is a tetramethylene group which is a divalent group, and R ⁴ is a hydrogen atom. The formula (3a), the formula (3a ′), the formula (3b), the formula (3b ′), An optically active titanium complex (an optically active titanium salen complex, an optically active titanium salalene complex, or an optically active titanium) obtained by reacting an optically active ligand represented by any one of formula (4) and formula (4 ′) with a titanium compound The method for producing an optically active sulfoxide compound according to claim 15 or 16, wherein a (saran complex) is used as a catalyst.   The method for producing an optically active sulfoxide compound according to any one of claims 15 to 18, wherein the oxidizing agent is a hydrogen peroxide solution or a urea-hydrogen peroxide adduct.