JP2007238570A - Phosphor compound, process for producing the same, and cyclic phosphor compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a novel phosphole compound and cyclic phosphole compound. <P>SOLUTION: The phosphole compound according to the present invention is represented by general formula (1) [wherein Ar represents an aryl group or a hetero-aryl group; X represents an oxygen atom or a sulfur atom; Y represents an aryl group, a hetero-aryl group, or -COOR<SP>4</SP>(R<SP>4</SP>is an alkyl group); R<SP>1</SP>and R<SP>2</SP>each represent an oxygen atom, -S(O)<SB>m</SB>- (m is 0 to 2), or an alkylene group; and R<SP>3</SP>represents an alkyl group]. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention is easily converted into a non-linear optical material that can be used in an optical integrated circuit and the like, a phosphole compound useful as a starting material such as a cyclic phosphole compound that can also be used as a metal ligand, a simple production method thereof, and the like The present invention relates to a cyclic phosphole compound produced using this phosphole compound as a starting material.

  Phosphor is a heterocyclic compound in which the nitrogen of pyrrole is replaced by phosphorus, but its electronic state is very different from that of pyrrole. That is, pyrrole is a typical aromatic compound, whereas phosphole has little aromaticity, but rather behaves as a conjugated diene. In addition, the basicity of the unshared electron pair on nitrogen of pyrrole is extremely small, whereas the unshared electron pair on phosphorous of phosphorus has a relatively high basicity. Such properties of phosphole are strongly reflected in its structure, physical properties and reactivity. For example, the HOMO-LUMO gap of phosphole is much smaller than that of pyrrole, and its absorption spectrum and emission spectrum often appear in the visible region. In addition, phosphole can form a transition metal complex as a neutral phosphorus ligand, and chemical modification on phosphorus can be easily performed.

  In recent years, in the field of material chemistry and synthetic chemistry, much attention has been paid to the development of functional materials and the development of catalysts utilizing the characteristics of phosphole. For example, use as a nonlinear optical material and use as a phosphorus ligand for constructing a homogeneous metal catalyst have been studied, and it is known to exhibit characteristics different from pyrrole and thiophene. In order to control the physical properties of phosphole and make the most of its functions, the introduction of functional groups such as ester groups into the phosphole skeleton is an important synthesis issue. Several methods for solving this problem have been reported so far (see, for example, Non-Patent Document 1 to Non-Patent Document 3). (2) the chemical species generated in the middle are extremely unstable, and (3) the types and number of functional groups that can be introduced are limited.

Patent Document 1 describes a method for producing a phosphole compound by reacting a metallacyclopentadiene compound prepared from a diyne compound and an organic transition metal compound with phosphine. However, Patent Document 1 only describes a method of introducing an aryl group at the α-position of the phosphole skeleton, and introduction of a functional group into the phosphole skeleton has not been studied.
Japanese Patent Laid-Open No. 2003-261585 Angew. Chem., Int. Ed. Engl. 1997, 36, 98. Angew. Chem., Int. Ed. Engl. 1994, 33, 1158. Tetrahedron Lett. 1981, 22, 3533.

  Therefore, the present invention provides a phosphole compound useful as a starting material such as a cyclic phosphole compound that can be easily chemically converted into a nonlinear optical material that can be used in an optical integrated circuit or the like and can also be used as a metal ligand, and a simple method for producing the same. And it aims at providing the cyclic phosphole compound manufactured by using this phosphole compound as a starting material.

  As a result of intensive studies in view of the above points, the inventors of the present invention have made it easy to obtain a phosphole compound having an ester group introduced at the α-position of the phosphole skeleton by reacting an organic titanium compound with a diyne compound having an ester group. If a phosphole compound produced by this method is found and a phosphole compound produced by this method is used, it has a unique coordination space and π conjugation compared to known cyclic phosphole compounds, and it can be used for intermediates and metal coordination of nonlinear optical materials. It has been found that cyclic phosphole compounds useful as ligands can be synthesized.

  That is, the present invention is a phosphole compound represented by the following general formula (1) as described in claim 1.

[In the formula, Ar represents an aryl group which may have a substituent or a heteroaryl group which may have a substituent. X represents an oxygen atom or a sulfur atom. [] Indicates that it may not be present. Y represents an aryl group which may have a substituent, a heteroaryl group which may have a substituent, or —COOR ⁴ (R ⁴ represents an alkyl group). R ¹ and R ² together are optionally an oxygen atom, -S (O) m- (m represents an integer of 0 to 2), -NR ^5- (R ⁵ represents a hydrogen atom or an alkyl group) Represents an alkylene group which may be interrupted by. R ³ represents an alkyl group)

Further, as described in claim 2, the phosphoric compound according to claim 1, wherein Y is -COOR ⁴ and R ³ and R ⁴ are the same alkyl group.

Further, as described in claim 3, a method for producing a phosphole compound represented by the following general formula (1), wherein a diyne compound represented by the following general formula (2) is reacted with an organic transition metal compound. Thus, a metallacyclopentadiene compound represented by the following general formula (3) is obtained, and ArPX ¹ X ² (X ¹ and X ² are the same or different from each other and represents a halogen atom in the obtained metallacyclopentadiene compound. Is the same as the above, and if desired, further P-sulfidation or P-oxidation.

[Wherein Ar, X, [], Y, R ¹ , R ² , R ³ are as defined above.]

[Wherein, Q represents an alkylene group formed by R ¹ and R ² . Y and R ³ are as defined above.

[Wherein, M represents a transition metal atom. L ¹ and L ² are the same or different and each represents an anionic ligand or a neutral ligand. Y, R ¹ , R ² and R ³ are as defined above.

  Further, as described in claim 4, the production method according to claim 3, wherein the transition metal atom is a titanium atom.

  Further, as described in claim 5, the production method according to claim 3 or 4, wherein titanium tetraisopropoxide is reacted with the diyne compound represented by the general formula (2) in the presence of isopropyl magnesium halide.

  Further, as described in claim 6, it is a phosphole compound represented by the following general formula (4).

[In the formula, T is an aryl group which may have a substituent, a heteroaryl group which may have a substituent, -CR ¹³ R ¹⁴ OH (R ¹³ and R ¹⁴ are the same or different, Any one of an alkyl group which may have a substituent, an aryl group which may have a substituent, and a heteroaryl group which may have a substituent. R ¹¹ and R ¹² are the same or different and each represents a hydrogen atom, an alkyl group that may have a substituent, an aryl group that may have a substituent, or a heteroaryl group that may have a substituent. Indicates either. Ar, X, [], R ¹ and R ² are as defined above.

  Further, as described in claim 7, it is a method for producing a phosphole compound represented by the following general formula (4), which is bonded to the α-position of the phosphole skeleton of the phosphole compound represented by the following general formula (1). This is a production method by reducing or alkylating the ester group.

[In the formula, Ar, X, [], T, R ¹ , R ² , R ¹¹ , R ¹² are as defined above.]

[Wherein Ar, X, [], Y, R ¹ , R ² , R ³ are as defined above.]

  Further, as described in claim 8, it is a cyclic phosphole compound represented by the following general formula (5).

[In the formula, ring A is constituted by an arylene group which may further have three or more substituents in addition to the indicated phosphole and / or a heteroarylene group which may have a substituent. The ring structure in which part or all may form a π-electron conjugated system is shown. Ar, X, [], R ¹ and R ² are as defined above.

  Further, as described in claim 9, the cyclic phosphole compound according to claim 8, which is represented by the following general formula (6).

[Wherein, U, V and W are the same or different and each represent an arylene group which may have a substituent or a heteroarylene group which may have a substituent. R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ are the same or different and have a hydrogen atom, an alkyl group which may have a substituent, or a substituent. Or a heteroaryl group which may have a substituent. Any of R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , and R ²⁸ may form a double bond with adjacent U, V, and W. Ar, X, [], R ¹ and R ² are as defined above.

Further, as described in claim 10, a method for producing a cyclic phosphole compound represented by the following general formula (6), the phosphole compound represented by the following general formula (7) having a substituent. The phosphole compound represented by the following general formula (8) is obtained by dehydration condensation reaction with the aryl compound which may be substituted and / or the heteroaryl compound which may have a substituent, and the obtained phosphole compound is converted into HOR ^{33 R 34 CV-CR 35 R 36} OH (R 33, R 34, R 35, R 36 are each converted to ^{R 23, R 24, R 25} , R 26 as synonymous or ^{R 23, R 24, R 25} , R 26 And V is a production method by dehydration condensation reaction with V).

[In the formula, Ar, X, [], U, V, W, R ¹ , R ² , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ are as defined above. ]

[Wherein, R ³¹ , R ³² , R ³⁷ and R ³⁸ have the same meanings as R ²¹ , R ²² , R ²⁷ and R ²⁸ , respectively, and represent groups which can be converted to R ²¹ , R ²² , R ²⁷ and R ²⁸ . Ar, X, [], R ¹ and R ² are as defined above.

[Wherein, U ′ and W ′ each represents an aryl group which may have a substituent corresponding to U or W, or a heteroaryl group which may have a substituent. Ar, X, [], R ¹ , R ² , R ³¹ , R ³² , R ³⁷ , R ³⁸ are as defined above.

  Further, as described in claim 11, it is a complex compound of a cyclic phosphole compound represented by the following general formula (5) and a transition metal.

[Wherein, ring A, Ar, X, [], R ¹ and R ² are as defined above.]

  If a phosphole compound having an ester group introduced at the α-position of the phosphole skeleton of the present invention is used, this ester group may be substituted with an alkyl group which may have a substituent or an aryl group which may have a substituent. After conversion to a hydroxymethyl group which may be substituted with an optionally substituted heteroaryl group, it is subjected to a dehydration condensation reaction with pyrrole, thiophene, furan, etc., and 2,5-bis (1-hydroxyalkyl) ) High yields of cyclic phosphole compounds that can be easily converted into non-linear optical materials and used as metal ligands by dehydration condensation reaction with thiophene or 2,5-bis (1-hydroxyalkyl) furan. Can be manufactured at a rate.

  The phosphole compound provided by the present invention is represented by the following general formula (1).

[Wherein Ar, X, [], Y, R ¹ , R ² , R ³ are as defined above.]

  In the phosphole compound represented by the above general formula (1), examples of the aryl group in the aryl group which may have a substituent in Ar and Y include, for example, a phenyl group, a naphthyl group, and an ortho-fused two group. Examples of the cyclic group include groups having 8 to 10 ring atoms and at least one ring being an aromatic ring (for example, an indenyl group). Examples of the heteroaryl group in the heteroaryl group which may have a substituent include, for example, a 5- to 6-membered ring group having carbon and 1 to 4 heteroatoms (oxygen, sulfur, nitrogen), and the like. Ortho-fused bicyclic heteroaryl groups having 8 to 10 ring atoms derived, in particular benz derivatives, or those derived by fusing a propenylene group, trimethylene group, tetramethylene group thereto, and its stable N -Oxides and the like, specifically, pyrrolyl group, furyl group, thienyl group, oxazolyl group, isoxazolyl group, imidazolyl group, thiazolyl group, isothiazolyl group, pyrazolyl group, triazolyl group, tetrazolyl group, 1,3, 5-Oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,4-thiadiazolyl, pyridyl, pyranyl, pyrazinyl, Midinyl group, pyridazinyl group, 1,2,4-triazinyl group, 1,2,3-triazinyl group, 1,3,5-triazinyl group, benzoxazolyl group, benzothiazolyl group, benzoimidazolyl group, thianaphthenyl group, isothianaphthenyl group, Examples include benzofuranyl group, isobenzofuranyl group, chromenyl group, isoindolyl group, indolyl group, indazolyl group, isoquinolyl group, quinolyl group, phthalazinyl group, quinoxalinyl group, quinazolinyl group, cinnolinyl group, and benzoxazinyl group.

Examples of the substituent in the aryl group which may have a substituent and the heteroaryl group which may have a substituent include an alkyl group, a hydroxyl group, an alkoxy group, a halogen atom, a nitro group, a cyano group, and trifluoromethyl. Group, alkylthio group, formyl group, acyloxy group, aryl group, arylalkyl group, -COORa, -CH ₂ COORb, -OCH ₂ COORc, -CONRdRe, -CH ₂ CONRfRg, -OCH ₂ CONRhRi, -NRjRk, etc. . The alkyl group is preferably a linear or branched lower alkyl group having 1 to 6 carbon atoms, specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, n -Butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, n-hexyl group and the like. The alkoxy group is preferably a linear or branched lower alkoxy group having 1 to 6 carbon atoms, specifically, a methoxy group, an ethoxy group, an isopropoxy group, an n-butoxy group, An isopentyloxy group, n-hexyloxy group, etc. are mentioned. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The alkylthio group is preferably a linear or branched lower alkylthio group having 1 to 6 carbon atoms, and specifically includes a methylthio group, an ethylthio group, an n-propylthio group, and an n-butylthio group. , Isopentylthio group, n-hexylthio group and the like. The acyloxy group is preferably a linear or branched lower acyloxy group having 1 to 6 carbon atoms, specifically, a formyloxy group, an acetyloxy group, an n-propionyloxy group, n -Butyryloxy group, valeryloxy group, pivaloyloxy group, hexanoyloxy group and the like can be mentioned. The aryl group has the same meaning as described above. As the arylalkyl group, the aryl part has the same meaning as described above, and the alkyl part is preferably a linear or branched chain having 1 to 3 carbon atoms, such as a benzyl group, a phenethyl group, a 3-phenylpropyl group. 1-naphthylmethyl group, 2-naphthylmethyl group, 2- (1-naphthyl) ethyl group, 2- (2-naphthyl) ethyl group, 3- (1-naphthyl) propyl group, 3- (2-naphthyl) Specific examples include a propyl group. Ra to Rk may be the same or different and include a hydrogen atom, an alkyl group (as defined above), an arylalkyl group (as defined above), and the like.

  The halogen atom in X is as defined above.

The alkylene group formed by combining R ¹ and R ² is preferably a lower alkylene group having 3 to 6 carbon atoms, and any one of the carbon atoms is optionally an oxygen atom, -S (O) m- (m Is replaced with -NR ^5- (R ⁵ is as defined above), and the carbon chain may be interrupted.

The alkyl group in R ³ , R ⁴ and R ⁵ has the same meaning as described above.

The phosphole compound represented by the general formula (1) is obtained by reacting, for example, a diyne compound represented by the following general formula (2) with an organic transition metal compound, for example, an organic titanium compound. 3) is obtained, and the resulting metallacyclopentadiene compound is reacted with ArPX ¹ X ² (Ar, X ¹ and X ² are as defined above), and if desired, further P-sulfidation or It can be produced by P-oxidation. The halogen atoms in X ¹ and X ² are as defined above.

[Wherein Q, Y and R ³ are as defined above]

[Wherein, M, L ¹ , L ² , Y, R ¹ , R ² , R ³ are as defined above]

In the metallacyclopentadiene compound represented by the general formula (3), the anionic ligand in L ¹ and L ² is an alkoxy group having 1 to 20 carbon atoms exemplified by an isopropoxy group. In addition, a delocalized cyclic η ⁵ -coordinated ligand exemplified by a cyclopentadienyl group can be used. Further, examples of the neutral ligand in L ¹ and L ² include a carbonyl ligand and a carbene ligand.

  Examples of the organic titanium compound to be reacted with the diyne compound represented by the general formula (2) include titanium tetraisopropoxide in the presence of isopropyl magnesium chloride as a reducing agent. Needless to say, a functional group that needs to be protected during the production process may be protected by a publicly known protective group and then deprotected.

  The phosphole compound represented by the general formula (1) is converted into the phosphole compound represented by the following general formula (4) by reducing or alkylating the ester group bonded to the α-position of the phosphole skeleton. be able to.

[In the formula, Ar, X, [], T, R ¹ , R ² , R ¹¹ , R ¹² are as defined above.]

The phosphole compound represented by the general formula (4) has an aryl group which may have a substituent in T, R ¹¹ , R ¹² , R ¹³ and R ¹⁴ , and a substituent. The preferred heteroaryl group has the same meaning as described above. Further, the alkyl group in the alkyl group which may have a substituent in R ¹¹ , R ¹² , R ¹³ and R ¹⁴ has the same meaning as described above, and the substituent in the alkyl group which may have a substituent also includes It is synonymous with the above.

  The reduction of the ester group at the α-position of the phosphole skeleton of the phosphole compound represented by the general formula (1) can be performed using, for example, an excessive amount of a reducing agent such as diisobutylaluminum hydride. In addition, alkylation of the ester group can be performed, for example, using 4 or more equivalents of a Gourillard reagent with respect to 1 equivalent of the phosphole compound represented by the general formula (1). Needless to say, a functional group that needs to be protected during the production process may be protected by a publicly known protective group and then deprotected.

  The phosphole compound represented by the above general formula (4) is useful as a starting material for producing the cyclic phosphole compound represented by the following general formula (5).

[Wherein, ring A, Ar, X, [], R ¹ and R ² are as defined above.]

  In the cyclic phosphole compound represented by the general formula (5), the arylene group in the arylene group which may have a substituent constituting the ring A is, for example, an arylene having 6 to 10 carbon atoms. Specific examples include 1,3-phenylene, 1,4-phenylene, naphthalene-1,3-diyl, naphthalene-1,4-diyl, and the like. Examples of the heteroarylene group in the heteroarylene group which may have a substituent include, for example, a 5- to 6-membered heteroarylene group having carbon and 1 to 4 heteroatoms (oxygen, sulfur, nitrogen). And ortho-fused bicyclic heteroarylene groups having 8 to 10 ring atoms, specifically, pyridine-diyl group, pyrimidine-diyl group, pyrazine-diyl group, pyridazine-diyl group, triazine- Diyl group, thiophene-diyl group, furan-diyl group, pyrrole-diyl group, imidazole-diyl group, pyrazole-diyl group, thiazole-diyl group, oxazole-diyl group, isothiazole-diyl group, isoxazole-diyl group, Indole-diyl group, isoindole-diyl group, indolizine-diyl group, indazole-diyl group, purine-diyl group, 4-H-quino Gin-diyl, quinoline-diyl, isoquinoline-diyl, phthalazine-diyl, naphthyridine-diyl, quinoxaline-diyl, quinazoline-diyl, benzthiazole-diyl, benzoxazole-diyl, benzofuran-diyl Group, benzothiophene-diyl group and the like. The arylene group which may have a substituent and the substituent in the heteroarylene group which may have a substituent are as defined above.

For example, when the cyclic phosphole compound represented by the general formula (5) is a cyclic phosphole compound represented by the following general formula (6), the phosphole compound represented by the following general formula (7) is substituted. A phosphole compound represented by the following general formula (8) was obtained by dehydration condensation reaction with an aryl compound optionally having a group and / or a heteroaryl compound optionally having a substituent. the phosphole compounds ^{HOR 33 R 34 CV-CR 35} R 36 OH (R 33, R 34, R 35, R 36 are each R ^23, R ^24, R ^25, R ²⁶ as synonymous or R ^23, R ^24, R ²⁵ , R represents a group that can be converted to R ^26. V is as defined above, and can be produced by a dehydration condensation reaction.

[In the formula, Ar, X, [], U, V, W, R ¹ , R ² , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ are as defined above. ]

In the cyclic phosphole compound represented by the above general formula (6), substituents in U, V, W, R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ An arylene group which may have a heteroaryl group which may have a substituent has the same meaning as described above. In addition, the alkyl groups in R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ are as defined above.

[In the formula, Ar, X, [], R ¹ , R ² , R ³¹ , R ³² , R ³⁷ , R ³⁸ are as defined above.]

[Wherein, Ar, X, [], U ′, W ′, R ¹ , R ² , R ³¹ , R ³² , R ³⁷ , R ³⁸ have the same meanings as described above]

The phosphole compound represented by the general formula (7) is a compound included in the phosphole compound represented by the general formula (4), and the phosphole compound represented by the general formula (1). Can be manufactured from. The dehydration condensation reaction for producing the phosphole compound represented by the general formula (8) can be carried out using a Lewis acid such as an ether complex of trifluoroborane. HOR ³³ R ³⁴ CV-CR ³⁵ R ³⁶ OH can be produced, for example, by the method described in J. Chem. Soc., Pekin Trans. 1 1977, 877 and Tetrahedron Lett. 2000, 41, 2919. The dehydration condensation reaction for producing the cyclic phosphole compound represented by the general formula (6) can be carried out using a Lewis acid such as an ether complex compound of trifluoroborane as described above. The dehydration condensation reaction is preferably performed after P-sulfidation (X = S) in order to facilitate subsequent chemical modification on phosphorus. It goes without saying that functional groups that need to be protected during the production process may be protected by a known protecting group and then deprotected.

  The cyclic phosphole compound represented by the above general formula (5) is calixarene and is active against chemical modification with various functional functional groups. Therefore, the compound is useful as an intermediate that can be easily chemically converted into a nonlinear optical material. Further, since the P-sulfide body has an action of taking in heavy metals, it is useful as a heavy metal recognition sensor material. Further, when this cyclic phosphole compound has only one phosphorus atom, the compound can be coordinated to a transition metal or the like as a monodentate ligand, and can contribute to an improvement in catalytic activity by the transition metal. Among the compounds in which Y of the phosphole compound represented by the general formula (1) is an aryl group which may have a substituent or a heteroaryl group which may have a substituent, There are those that exhibit excellent absorption characteristics and emission characteristics (especially a compound in which Y is a thiophene which may have a substituent), and the compound itself has applicability as a functional optical material, Further, it has applicability as a starting material of a phosphole compound that is an excellent functional material.

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is limited to the following description and is not interpreted at all.

Example 1:
The phosphole compounds having an ester group at the α-position of the phosphole skeleton of the present invention shown in Table 1 below were produced. The details of the manufacturing method are as follows.

(Method for producing diyne compound as raw material)
The diyne compound (1a-1h) was produced from 1,7-octadiyne for 1a, 1,6-heptadiine for 1b, c, eh, and dipropargyl ether for 1d according to the following scheme.

Physicochemical data of deca-2,8-diynediethyl ester (1a)
¹ H NMR (CDCl ₃ , 400 MHz) δ 1.31 (t, 6H, J = 7.1 Hz, OCH ₂ CH ₃ ), 1.86 (quin, 2H, J = 7.1 Hz, CH ₂ CH ₂ CH ₂ ), 2.49 (t , 4H, J = 7.1 Hz, CH ₂ CH ₂ CH ₂ ), 4.22 (q, 4H, J = 7.1 Hz, OCH ₂ CH ₃ ).

Physicochemical data of nona-2,7-diynediethyl ester (1b)
¹ H NMR (CDCl ₃ , 400 MHz) δ 1.31 (t, 6H, J = 7.2 Hz, OCH ₂ CH ₃ ), 1.72 (m, 4H, CH ₂ CH ₂ CH ₂ ), 2.39 (m, 4H, CH ₂ CH ₂ CH ₂ ), 4.22 (q, 4H, J = 7.2 Hz, OCH ₂ CH ₃ ).

Physicochemical data of nona-2,7-diynedimethyl ester (1c)
¹ H NMR (CDCl ₃ , 400 MHz) δ 1.86 (quin, 2H, J = 7.0 Hz, CH ₂ CH ₂ CH ₂ ), 2.50 (t, 4H, J = 7.0 Hz, CH ₂ CH ₂ CH ₂ ), 3.77 (s, 4H, OCH ₃ ).

Physicochemical data of bis [3- (ethoxycarbonyl) propargyl] ether (1d)
¹ H NMR (CDCl ₃ , 400 MHz) δ 1.32 (t, 6H, J = 7.2 Hz, OCH ₂ CH ₃ ), 4.25 (q, 4H, J = 7.2 Hz, OCH ₂ CH ₃ ), 4.41 (s, 4H, CH ₂ OCH ₂ ).

Physicochemical data of 1-ethoxycarbonyl-7-phenyl-1,6-heptadiyne (1e)
¹ H NMR (CDCl ₃ , 400 MHz) δ 1.31 (t, 3H, J = 7.1 Hz, OCH ₂ CH ₃ ), 1.89 (tt, 2H, J = 7.1, 7.1 Hz, CH ₂ CH ₂ CH ₂ ), 2.54 (t, 2H, J = 7.1 Hz, EtOCO-CC-CH ₂ CH ₂ ), 2.56 (t, 2H, J = 7.1 Hz, Ph-CC-CH ₂ CH ₂ ), 4.22 (q, 4H, J = 7.1 Hz, OCH ₂ CH ₃ ), 7.28 (m, 3H, m, pH Ph), 7.39 (m, 2H, oH Ph); ¹³ C { ¹ H} NMR (CDCl ₃ , 75 MHz) δ 14.0 ( OCH ₂ CH ₃ ), 17.8 (CH ₂ CH ₂ CH ₂ ), 18.6 (Ph-CC-CH ₂ ), 26.7 (EtOCO-CC-CH ₂ ), 61.9 (OCH ₂ CH ₃ ), 73.7 (EtOCO-CC) , 81.7 (PhCC), 88.2 and 88.3 (EtOCO-CC and Ph-CC), 123.6 (ipso-C Ph), 127.8 (pC Ph), 128.2 (mC Ph), 131.6 (oC Ph), 153.7 (C = O ); IR (KBr) ν _max 1712 (C = O) cm ^-1 ; MS (MALDI-TOF) m / z 241 (M ⁺ ). Anal.Calcd for C ₁₆ H ₁₆ O ₂ : C, 79.97; H, 6.71. Found: C, 79.72; H, 6.68.

Physicochemical data of 1-ethoxycarbonyl-7- (2-pyridyl) -1,6-heptadiyne (1f)
¹ H NMR (CDCl ₃ , 400 MHz) δ 1.31 (t, 3H, J = 7.2 Hz, OCH ₂ CH ₃ ), 1.92 (tt, 2H, J = 7.0,7.0 Hz, CH ₂ CH ₂ CH ₂ ), 2.55 (t, 2H, J = 7.0 Hz, Py-CC-CH ₂ CH ₂ ), 2.60 (t, 2H, J = 7.0 Hz, Py-CC-CH ₂ CH ₂ ), 4.22 (q, 4H, J = 7.2 Hz, OCH ₂ CH ₃ ), 7.20 (ddd, 1H, J = 7.6, 4.9, 1.6 Hz H5 Py), 7.38 (dd, 1H, J = 7.6, 1.6 Hz, H3 Py), 7.63 (ddd, 1H, J = 7.6, 7.6, 1.8 Hz H4 Py), 8.55 (dd, 1H, J = 4.9, 1.8 Hz, H6 Py); ¹³ C { ¹ H} NMR (CDCl ₃ , 68 MHz) δ 14.1 (s, OCH ₂ CH ₃ ), 18.0 (s, CH ₂ CH ₂ CH ₂ ), 18.6 ( s, Py-CC-CH ₂ ), 26.4 (s, EtOCO-CC-CH ₂ ), 61.9 (s, OCH ₂ CH ₃ ), 73.8 (s, EtOCO-CC), 81.4 (s, Py-CC), 87.9 (s, EtOCO-CC), 88.8 (s, Py-CC), 122.4 (s, C5 Py), 126.8 (s, C3 Py), 136.0 (s, C4 Py), 143.4 (s, C2 Py), 149.8 (s, C6 Py), 153.6 (s, C = O); IR (KBr) ν _max 1709 (C = O) cm ^-1 ; MS (MALDI-TOF) m / z 242 (M ⁺ ). Anal. Calcd for C ₁₅ H ₁₅ NO ₂ : C, 74.67; H, 6.27; N, 5.81. Found: C, 74.68; H, 6.22; N, 5.63.

Physicochemical data of 1-ethoxycarbonyl-7- (2-thienyl) -1,6-heptadiyne (1g)
¹ H NMR (CDCl ₃ , 400 MHz) δ 1.31 (t, 3H, J = 7.1 Hz, OCH ₂ CH ₃ ), 1.88 (tt, 2H, J = 7.1, 7.1 Hz, CH ₂ CH ₂ CH ₂ ), 2.52 (t, 2H, J = 7.1 Hz, EtOCO-CC-CH ₂ CH ₂ ), 2.55 (t, 2H, J = 7.1 Hz, Th-CC-CH ₂ CH ₂ ), 4.22 (q, 4H, J = 7.1 Hz, OCH ₂ CH ₃ ), 6.94 (dd, 1H, J = 5.2, 3.7 Hz, H4 Th), 7.13 (dd, 1H, J = 3.7, 1.1 Hz, H3 Th), 7.19 (dd, 1H , J = 5.2, 1.1 Hz, H5 Th); ¹³ C { ¹ H} NMR (CDCl ₃ , 75 MHz) δ 14.2 (OCH ₂ CH ₃ ), 17.9 (CH ₂ CH ₂ CH ₂ ), 18.9 (Th-CC -CH ₂ ), 26.6 (EtOCO-CC-CH ₂ ), 61.8 (OCH ₂ CH ₃ ), 73.7 (EtOCO-CC), 74.8 (Th-CC), 87.9 (EtOCO-CC), 92.2 (Th-CC) , 123.5 (C2 Th), 126.1 (C4 Th), 126.7 (C5 Th), 131.2 (C3 Th), 153.5 (C = O); IR (KBr) ν _max 1710 (C = O) cm ^-1 ; MS ( MALDI-TOF) m / z 246 (M ⁺ ). Anal.Calcd for C ₁₄ H ₁₉ O ₂ PS: C, 68.26; H, 5.73. Found: C, 68.23; H, 5.52.

Physicochemical data of 1- (9-anthryl) -7- (2-thienyl) -1,6-heptadiyne (1h)
Mp 42-43 ° C; ¹ H NMR (CDCl ₃ , 300 MHz) δ 1.31 (t, 3H, J = 7.1 Hz, OCH ₂ CH ₃ ), 2.10 (tt, 2H, J = 7.0, 7.0 Hz, CH ₂ CH ₂ CH ₂ ), 2.70 and 2.91 (each t, 2H, J = 7.0 Hz, CH ₂ CH ₂ CH ₂ ), 4.23 (q, 4H, J = 7.1 Hz, OCH ₂ CH ₃ ), 7.46-7.58 (m, 4H, H2,3 An), 7.99 (d, 2H, J = 8.4 Hz, H4 An), 8.39 (s, 1H, H10 An), 8.51 (d, 2H, J = 8.4 Hz, H1 An); ¹³ C { ¹ H} NMR (CDCl ₃ , 75 MHz) δ 14.0 (OCH ₂ CH ₃ ), 18.1 (CH ₂ CH ₂ CH ₂ ), 19.4 ( An-CC-CH ₂ ), 27.0 (EtOCO-CC-CH ₂ ), 61.8 (OCH ₂ CH ₃ ), 73.8 (EtOCO-CC-CH ₂ ), 78.2 (An-CC-CH ₂ ), 87.9 (EtOCO- CC-CH ₂ ), 99.6 (An-CC-CH ₂ ), 117.6, 125.4, 126.2, 126.5, 126.9, 128.5, 131.0, 132.5 (each An) 153.5 (C = O); IR (neat) ν _max 1708 ( C = O) cm ^-1 ; MS (MALDI-TOF) m / z 340 (M ⁺ )

(Production of phosphole compound of the present invention)
The phosphole compound (4a) was produced as follows. A mixture of diyne compound (1a) (1.25 g, 5.0 mmol), titanium tetraisopropoxide (1.5 mL, 5.0 mmol) and diethyl ether (75 mL) was added to a diethyl ether solution of isopropylmagnesium chloride (2.0 MX 5.0 mL, 10 mmol). ) At -78 ° C and stirred at -50 ° C for 2 hours. Thereafter, dichlorophenylphosphine (0.68 mL, 5.0 mmol) was added at −50 ° C., the temperature of the resulting suspension was raised to room temperature, and further stirred at room temperature for 2 hours. Thereafter, a saturated aqueous solution of ammonium chloride (30 mL) was poured into the reaction solution, and insoluble matters were removed by filtration through Celite.The filtrate was separated into oil and water, and the aqueous layer was extracted with diethyl ether ( 15 mL X 2) and the organic layers were combined, washed with brine (50 mL), dried over magnesium sulfate, and concentrated in vacuo to give an oil. The oily substance was crystallized from cold methanol at −78 ° C. to obtain the desired phosphole compound (4a) as a light yellow solid (560 mg, 31%). The phosphole compound (4b-4h) was also basically produced by the same method as above (however, the phosphole compound (4h) could not be produced by this method).

Physicochemical data of phosphole compound (4a)
Mp 71-72 ° C; ¹ H NMR (CDCl ₃ , 400 MHz) δ 1.10 (t, 6H, J = 6.8 Hz, OCH ₂ CH ₃ ), 1.76 (br, 4H, CH ₂ CH ₂ CH ₂ CH ₂ ), 3.03 and 3.21 (each br, 2H, CH ₂ CH ₂ CH ₂ CH ₂ ), 4.11 (br, 4H, OCH ₂ CH ₃ ), 7.25-7.35 (m, 5H, Ph); ¹³ C { ¹ H} NMR (CDCl ₃ , 75 MHz) δ 14.1 (s, OCH ₂ CH ₃ ), 22.2 (s, CH ₂ CH ₂ CH ₂ CH ₂ ), 29.0 (s, CH ₂ CH ₂ CH ₂ CH ₂ ), 60.3 (s, OCH ₂ CH ₃ ), 128.3 (d, ³ J _PC = 8.7 Hz, mC Ph), 129.8 (d, ⁴ J _PC = 1.9 Hz, pC Ph), 134.0 (d, ² J _PC = 19.9 Hz, oC Ph), 136.9 (s, PC = C), 158.8 (d, ² J _PC = 10.6 Hz, PC = C), _{^{164.8 (d, 2 J PC =}} 18.8 Hz, C = O); 31 P {1 H} NMR (CDCl 3, 162 MHz) δ + 8.7; IR (KBr) ν max 1701, 1696 (C = O) cm - ¹ ; MS (MALDI-TOF) m / z 358 (M ⁺ ). Anal. Calcd for C ₁₂ H ₂₃ O ₄ P: C, 67.03; H, 6.47; P, 8.64. Found: C, 67.21; H, 6.51 ; P, 8.44.
The ipsocarbon of the phenyl group is not clearly detectable by ^13C NMR

Physicochemical data of phosphole compound (4b)
Mp 75-76 ° C; ¹ H NMR (CDCl ₃ , 400 MHz) δ 1.17 (t, 6H, ¹ J = 6.4 Hz, OCH ₂ CH ₃ ), 2.33 (br, 2H, CH ₂ CH ₂ CH ₂ ), 2 , 80 and 3.13 (each br, 4H, CH ₂ CH ₂ CH ₂ ), 4.15 (br, 4H, OCH ₂ CH ₃ ), 7.27-7.42 (m, 5H, Ph); ¹³ C { ¹ H} NMR (CDCl ₃ , 75 MHz) δ 14.1 (s, OCH ₂ CH ₃ ), 28.3 (s, CH ₂ CH ₂ CH ₂ ), 30.1 (s, CH ₂ CH ₂ CH ₂ ), 60.5 (s, OCH ₂ CH ₃ ), 128.4 (d, ³ J _PC = 8.7 Hz, mC Ph), 129.8 (d, ⁴ J _PC = 1.9 Hz, pC Ph), 132.9 (s, PC = C), 133.7 (d, ² J _PC = 19.9 Hz, oC Ph), 164.7 (d, ² J _PC = 20.4 Hz, C = O), 167.3 (d, ² J _PC = 10.6 Hz, PC = C); ³¹ P NMR (162 MHz) δ + 32.7; IR (KBr) ν _max 1703, 1689 (C = O) cm ^-1 ; MS (MALDI-TOF) m / z 345 ([M + H] ⁺ ). Anal. Calcd for C ₁₁ H ₂₁ O ₄ P: C, 66.27; H, 6.15; P, 9.00. Found: C, 66.13; H, 6.36; P, 8.75.
The ipsocarbon of the phenyl group is not clearly detectable by ^13C NMR
Fig. 1 shows the X-ray crystallographic analysis results (ORTEP diagram).

Physicochemical data of phosphole compound (4c)
Mp 107-108 ° C; ¹ H NMR (CDCl ₃ , 400 MHz) δ 2.33 (br, 2H, CH ₂ CH ₂ CH ₂ ), 2,81 and 3.13 (each br, 2H, CH ₂ CH ₂ CH ₂ ), 3.69 (s, 4H, OCH ₃ ), 7.28-7.40 (m, 5H, Ph); ¹³ C { ¹ H} NMR (CDCl ₃ , 75 MHz) δ 28.3 (s, CH ₂ CH ₂ CH ₂ ), 30.1 ( s, CH ₂ CH ₂ CH ₂ ), 51.7 (s, OCH ₃ ), 128.6 (d, ³ J _PC = 8.7 Hz, mC Ph), 129.8 (s, pC Ph), 129.9 (d, ¹ J _PC = 8.7 Hz, ipso-C Ph), 132.5 (d, ¹ J _PC = 3.1 Hz, PC = C), 133.6 (d, ² J _PC = 19.9 Hz, oC Ph), 165.1 (d, ² J _PC = 20.5 Hz, C = O), 167.6 (d, ² J _PC = 9.9 Hz, PC = C); ³¹ P { ¹ H} NMR (CDCl ₃ , 162 MHz) δ + 32.6; IR (KBr) ν _max 1699 (C = O ) cm ^-1 ; MS (MALDI-TOF) m / z 317 (M ⁺ ). Anal.Calcd for C ₉ H ₁₇ O ₄ P: C, 64.56; H, 5.42; P, 9.79. Found: C, 64.44; H, 5.57; P, 9.65.

Physicochemical data of phosphole compound (4d)
Mp 89-90 ° C; ¹ H NMR (CDCl ₃ , 400 MHz) δ 1.19 (t, 6H, J = 7.1 Hz, OCH ₂ CH ₃ ), 4.17 (q, 4H, J = 7.1 Hz, OCH ₂ CH ₃ ), 4.97 (m, 4H, CH ₂ OCH ₂ ), 7.31-7.45 (m, 5H, Ph); ¹³ C { ¹ H} NMR (CDCl ₃ , 75 MHz) δ 14.1 (s, OCH ₂ CH ₃ ), 61.0 (s, OCH ₂ CH ₃ ), 69.6 (s, CH ₂ OCH ₂ ), 128.7 (d, ³ J _PC = 9.3 Hz, mC Ph), 130.3 (s, pC Ph), 132.1 (s , PC = C), 133.9 (d, ² J _PC = 20.5 Hz, oC Ph), 161.6 (d, ¹ J _PC = 10.6 Hz, PC = C), 163.8 (d, ² J _PC = 15.6 Hz, C = O); ³¹ P { ¹ H} NMR (CDCl ₃ , 162 MHz) δ + 40.5; IR (KBr) ν _max 1690 (C = O) cm ^-1 ; MS (MALDI-TOF) m / z 347 ([M + H] ⁺ ). Anal. Calcd for C ₁₀ H ₁₉ O ₅ P: C, 62.43; H, 5.53; P, 8.94. Found: C, 62.16; H, 5.73; P, 8.66.
The ipsocarbon of the phenyl group is not clearly detectable by ^13C NMR

Physicochemical data of phosphole compound (4e)
Mp 135-136 ° C; ¹ H NMR (CDCl ₃ , 400 MHz) δ 1.20 (t, 3H, J = 7.3 Hz, OCH ₂ CH ₃ ), 2.35 (m, 2H, CH ₂ CH ₂ CH ₂ ), 2, 65- 3.15 (m, 4H, CH ₂ CH ₂ CH ₂ ), 4.14 (m, 2H, OCH ₂ CH ₃ ), 7.17-7.24 (m, 4H, m, pH 1-Ph, pH 5-Ph), 7.27-7.31 (m, 2H, mH 5-Ph), 7.39 (m, 2H, oH 1- Ph), 7.49 (m, 2H, oH 5-Ph); ¹³ C { ¹ H} NMR (CDCl ₃ , 75 MHz) δ 14.3 (s, OCH ₂ CH ₃ ), 29.1 (s, CH ₂ CH ₂ CH ₂ ), 29.2 (s, PC (CO ₂ Et) = CCH ₂ ), 30.0 (s, C (Ph) = CCH ₂ ), 60.0 (s, OCH ₂ CH ₃ ), 126.1 (s, PC (CO ₂ Et) = CCH ₂ ), 127.4 (s, pC 5-Ph), 128.0 (d, ³ J _PC = 10.6 Hz, oC 5-Ph), 128.5 (d, ³ J _PC = 8.8 Hz, mC 1-Ph), 128.6 (s, mC 5-Ph), 129.3 (s, pC 1-Ph), 131.7 (d, ¹ J _PC = 12.3 Hz, ipso-C 1-Ph), 133.6 (d, ² J _PC = 19.3 Hz, oC 1-Ph), 136.2 (d, ² J _PC = 17.4 Hz, ipso-C 5-Ph), 144.6 (s, PC (Ph) = CCH ₂ ), 153.1 (d, ² J _PC = 8.1 Hz, PC ( Ph) = CCH ₂ ), 165.1 (d, ² J _PC = 21.7 Hz, C = O), 170.1 (d, ² J _PC = 11.8 Hz, PC (CO ₂ Et) = CCH ₂ ); ³¹ P { ¹ H } NMR (CDCl ₃ , 162 MHz) δ + 32.0; IR (KBr) ν _max 1690 (C = O) cm ^-1 ; MS (MALDI-TOF) m / z 348 (M ⁺ ). Anal. Calcd for C ₂₂ H ₂₁ O ₂ P: C, 75.85; H, 6.08; P, 8.89. Found: C, 75.55; H, 6.25; P, 8.86.

Physicochemical data of phosphole compound (4f)
Mp 135-136 ° C; ¹ H NMR (CDCl ₃ , 300 MHz) δ 1.19 (t, 3H, J = 7.2 Hz, OCH ₂ CH ₃ ), 2.37 (m, 2H, CH ₂ CH ₂ CH ₂ ), 2.75- 3.25 (m, 4H, CH ₂ CH ₂ CH ₂ ), 4.15 (m, 2H, OCH ₂ CH ₃ ), 7.06 (m, 1H, H5 Py), 7.19-7.28 (m, 3H, m, p-Ph), 7.41-7.46 (m, 2H, o-Ph), 7.47 (m, 1H, H3 Py), 7.56 (m, 1H, H4 Py), 8.53 (m, 1H, H6 Py); ¹³ C NMR (CDCl ₃ , 68 MHz) δ 14.3 (s, OCH ₂ CH ₃ ), 28.9 (s, CH ₂ CH ₂ CH ₂ ), 29.8 (s, PC (CO ₂ Et) = CCH ₂ ), 30.0 (s, PC (Py) = CCH ₂ ), 60.1 (s, OCH ₂ CH ₃ ), 121.4 (s, C5 Py), 122.1 (d, ³ J _PC = 7.2 Hz, C3 Py), 128.2 (d, ³ J _PC = 8.4 Hz, mC Ph), 129.2 (d, ⁴ J _PC = 1.7 Hz, pC Ph), 131.8 ( d, ¹ J _PC = 12.8 Hz, ipso-C Ph), 133.6 (d, ² J _PC = 19.5 Hz, oC Ph), 136.2 (d, ⁴ J _PC = 1.1 Hz, C4 Py), 143.7 (s, PC (Py) = CCH ₂ ), 149.6 (s, C6 Py), 154.5 (d, ² J _PC = 17.8 Hz, C2 Py), 156.3 (d, ² J _PC = 8.4 Hz, PC (Py) = CCH ₂ ) , 165.0 (d, ² J _PC = 21.2 Hz, C = O), 169.2 (d, ² J _PC = 11.7 Hz, PC (CO ₂ Et) = CCH ₂ ); ³¹ P NMR (CDCl ₃ , 162 MHz) δ + 32.6; IR (KBr) ν _max 1695 (C = O) cm ^-1 ; MS (MALDI-TOF) m / z 350 (M ⁺ ). Anal.Calcd for C ₂₁ H ₂₀ NO ₂ P: C, 72.20; H, 5.77; N, 4.01; P, 8.89. Found: C, 72.10; H, 5.79; N, 3.97; P, 8.76.
Alpha carbon is not clearly detectable by ¹³ C NMR

Physicochemical data of phosphole compound (4g)
Mp 131-132 ° C; ¹ H NMR (CDCl ₃ , 400 MHz) δ 1.18 (t, 3H, J = 7.1 Hz, OCH ₂ CH ₃ ), 2.39 (m, 2H, CH ₂ CH ₂ CH ₂ ), 2.65- 3.20 (m, 4H, CH ₂ CH ₂ CH ₂ ), 4.12 (m, 2H, OCH ₂ CH ₃ ), 6.93 (m, 1H, H4 Th), 7.04 (m, 1H, H3 Th), 7.27 (m, 1H, H5 Th), 7.29 (m, 3H, m, p-Ph), 7.45 (m, 2H, o-Ph); ¹³ C { ¹ H} NMR (CDCl ₃ , 75 MHz) δ 14.2 (s, OCH ₂ CH ₃ ), 28.7 (s, CH ₂ CH ₂ CH ₂ ), 29.1 (s , PC (CO ₂ Et) = CCH ₂ ), 30.2 (s, PC (Th) = CCH ₂ ), 60.0 (s, OCH ₂ CH ₃ ), 125.1 (s, PC (CO ₂ Et) = CCH ₂ ), 126.2 (d, ⁵ J _PC = 1.9 Hz, C5 Th), 126.4 (d, ³ J _PC = 8.0 Hz, C3 Th), 127.7 (s, C4 Th), 128.6 (d, ³ J _PC = 8.8 Hz, mC Ph), 129.7 (s, pC Ph), 132.0 (d, ¹ J _PC = 13.7 Hz, ipso-C Ph), 133.8 (d, ² J _PC = 19.9 Hz, oC Ph), 137.9 (d, ¹ J _PC = 3.7 Hz, PC (Th) = CCH ₂ ), 139.5 (d, ² J _PC = 21.2 Hz, C2 Th), 152.1 (d, ² J _PC = 8.1 Hz, PC (Th) = CCH ₂ ), 165.0 ( d, ² J _PC = 21.7 Hz, C = O), 170.3 (d, ² J _PC = 10.6 Hz, PC (CO ₂ Et) = CCH ₂ ); ³¹ P { ¹ H} NMR (CDCl ₃ , 162 MHz) δ + 33.4; IR ν _max 1690 (C = O) cm ^-1 ; MS (MALDI-TOF) m / z 354 (M ⁺ ). Anal.Calcd for C ₂₂ H ₁₉ O ₂ PS: C, 67.78; H, 5.40; P, 8.74. Found: C, 67.63; H, 5.46; P, 8.45.

Example 2:
According to the scheme shown below, reduction, alkylation, and P-sulfidation of an ester group of a phosphole compound having an ester group at the α-position of the phosphole skeleton of the present invention were performed. The details of the manufacturing method are as follows.

(Production of phosphole compound (6) and phosphole compound (7))
The phosphole compound (4b) (300 mg, 0.87 mmol) prepared in Example 1 dissolved in 10 mL of hexane was added to a hexane solution of diisobutylaluminum hydride (1.0 M, 3.5 mL, 3.5 mmol) at −78 ° C. After stirring at −50 ° C. for 1 hour, elemental sulfur (40 mg, 1.3 mmol) was added and the temperature of the resulting mixture was slowly raised to room temperature. Saturated aqueous ammonium chloride (5 mL) was then added, the mixture was filtered through celite, and the organic layer was separated from the filtrate. The aqueous layer was extracted with diethyl ether (5 mL x 3), and the organic layers were combined, washed with brine (20 mL), dried over sodium sulfate, and concentrated to give a crude product. I got a thing. The crude product was crystallized using a mixed solvent of ethyl acetate and hexane to obtain the desired phosphole compound (7) as a pale yellow solid (160 mg, 0.55 mmol, 63%). When the reaction was stopped without adding elemental sulfur in the above process, the phosphole compound (6), which was a σ ³ -phosphine compound, was obtained as a substance that was considerably unstable to air. The chemical structure of the phosphole compound (6) was confirmed by ¹ H NMR and MS.

Physicochemical data of phosphole compound (6)
¹ H NMR (CDCl ₃ , 400 MHz) δ 1.77 (br, 2H, OH), 2.14 (m, 1H, CH ₂ CH ₂ CH ₂ ), 2.28 (m, 1H, CH ₂ CH ₂ H ₂ ), 2.45 ( m, 2H, PC = CCH ₂ ), 2.64 (m, 2H, PC = CCH ₂ ), 4.38 (m, 2H, CH ₂ OH), 4.52 (m, 2H, CH ₂ OH), 7.28-7.40 (m, 5H, Ph); MS (MALDI-TOF) m / z 503 ([2M-OH] ⁺ ).

Physicochemical data of phosphole compound (7)
Mp 131-132 ° C; ¹ H NMR (CDCl ₃ , 400 MHz) δ 2.03 (t, 2H, J = 6.0 Hz, OH), 2.10-2.27 (m, 2H, CH ₂ CH ₂ CH ₂ ), 2.58-2.73 (m, 4H, PC = CCH ₂ ), 4.38-4.52 (m, 4H, CH ₂ OH), 7.43-7.55 (m, 3H, m, p-Ph), 7.82-7.88 (m, 2H, o-Ph ); ¹³ C { ¹ H} NMR (CDCl ₃ , 75 MHz) δ 27.0 (d, ⁴ J _PC = 1.8 Hz, CH ₂ CH ₂ CH ₂ ), 27.4 (d, ³ J _PC = 11.2 Hz, PC = CCH ₂ ), 57.6 (d, ² J _PC = 15.6 Hz, CH ₂ OH), 127.6 (d, ¹ J _PC = 70.3 Hz, PC = C), 128.9 (d, ² J _PC = 12.4 Hz, oC Ph), 130.0 (s, ipso-C Ph), 130.3 (d, ³ J _PC = 11.9 Hz, mC Ph), 132.2 (d, ⁴ J _PC = 2.4 Hz, pC Ph), 157.3 (d, ² J _PC = 23.0 Hz , PC = CCH ₂ ); ³¹ P { ¹ H} NMR (CDCl ₃ , 162 MHz) δ + 67.5; IR (KBr) ν _max 3390 (OH) cm ^-1 ; MS (MALDI-TOF) m / z 292 ( M ⁺ ).

(Production of phosphole compound (8))
The phosphole compound (4b) prepared in Example 1 (4b) (1.17 g, 3.40 mmol) dissolved in 7 mL of THF was added to a THF solution of methylmagnesium bromide (0.96 M, 15 mL, 14 mmol) at −78 ° C. The temperature of the mixture was slowly raised to room temperature over 30 minutes and stirred for an additional 30 minutes at 50 ° C. The resulting mixture was then acidified by adding saturated aqueous ammonium chloride (3 mL) at 0 ° C., followed by elemental sulfur (160 mg, 5.0 mmol) under this temperature condition. After stirring for 30 minutes, the aqueous layer was extracted with diethyl ether, the organic layers were combined, washed with brine, dried over sodium sulfate, and concentrated to give an oily substance. The oily substance was subjected to silica gel column chromatography (hexane / EtOAc = 2/1: R _f = 0.2) to obtain the desired phosphole compound (8) as a pale yellow solid (475 mg, 1.36 mmol, 40%).

Physicochemical data of phosphole compound (8)
Mp 133-134 ° C; ¹ H NMR (CDCl ₃ , 400 MHz) δ 1.28 (s, 6H, Me), 1.43 (s, 6H, Me), 2.12-2.18 (m, 2H, CH ₂ CH ₂ CH ₂ ) , 2.64-2.69 (m, 4H, CH ₂ CH ₂ CH ₂ ), 3.03 (s, 2H, OH), 7.26-7.49 (m, 3H, m, p-Ph), 7.85-7.91 (m, 2H, o -Ph); ¹³ C NMR (CDCl ₃ , 75 MHz) δ 27.1 (d, ⁴ J _PC = 1.7 Hz, CH ₂ CH ₂ CH ₂ ), 28.5 (d, ³ J _PC = 12.3 Hz, PC = CCH ₂ ), 29.8 (d, ³ J _PC = 1.6 Hz, Me), 31.3 (d, ³ J _PC = 2.5 Hz, Me), 72.9 (d, ² J _PC = 11.5 Hz, COH), 128.6 (d, ¹ J _PC = 71.8 Hz, ipso-C Ph), 128.6 (d, ² J _PC = 12.3 Hz, oC Ph), 130.0 (d, ³ J _PC = 11.5 Hz, mC Ph), 131.5 (d, ⁴ J _PC = 3.3 Hz, pC Ph), 136.8 (d, ¹ J _PC = 75.9 Hz, PC = C), 157.3 (d, ² J _PC = 23.0 Hz, PC = CCH ₂ ); ³¹ P { ¹ H} NMR (CDCl ₃ , 162 MHz) δ + 68.9; IR (KBr) ν _max 3390 (OH) cm ^-1 ; MS (MALDI-TOF) m / z 314 ([M-2 (OH)] ⁺ ).

(Production of phosphole compound (9))
A mixture of the phosphole compound (4 g) (53 mg, 0.15 mmol) prepared in Example 1 and elemental sulfur (24 mg, 0.75 mmol) and dichloromethane (2 mL) was stirred at room temperature for 5 days, and the solvent was removed. The obtained crude product was subjected to silica gel column chromatography using dichloromethane as an eluent (R _f = 0.2) to obtain the desired phosphole compound (9) as a yellow solid (20 mg, 35% ).

Physicochemical data of phosphole compound (9)
Mp 111-112 ° C; ¹ H NMR (CDCl ₃ , 400 MHz) δ 1.16 (t, 3H, J = 7.1 Hz, OCH ₂ CH ₃ ), 2.35 (m, 2H, CH ₂ CH ₂ CH ₂ ), 2.91 and 3.10 (each m, 2H, CH ₂ CH ₂ CH ₂ ), 4.14 (m, 2H, OCH ₂ CH ₃ ), 7.00 (m, 1H, H4 Th), 7.38 (m, 1H, H3 Th), 7.42 (m, 1H, H5 Th), 7.42 (m, 3H, m-Ph), 7.50 (m , 1H, p-Ph), 7.86 (m, 2H, o-Ph); ¹³ C { ¹ H} NMR (CDCl ₃ , 100 MHz) δ 14.0 (s, OCH ₂ CH ₃ ), 27.0 (d, ⁴ J _PC = 1.7 Hz, CH ₂ CH ₂ CH ₂ ), 29.4 (d, ³ J _PC = 9.9 Hz, PC (CO ₂ Et) = CCH ₂ ), 30.9 (d, ³ J _PC = 9.1 Hz, PC (Th) = CCH ₂ ), 60.5 (s, OCH ₂ CH ₃ ), 120.4 (d, ¹ J _PC = 81.3 Hz, PC = C), 128.0 (s, C5 Th), 128.4 (s, C4 Th), 128.6 (d , ² J _PC = 13.2 Hz, oC Ph), 129.1 (d, ³ J _PC = 4.1 Hz, C3 Th), 129.2 (d, ¹ J _PC = 82.5 Hz, PC = C), 130.5 (s, ipso-C Ph), 130.5 (d, ³ J _PC = 12.4 Hz, mC Ph), 132.1 (d, ⁴ J _PC = 2.8 Hz, pC Ph), 135.1 (d, ² J _PC = 18.2 Hz, C2 Th), 149.7 ( d, ² J _PC = 19.8 Hz, PC (Th) = CCH ₂ ), 162.0 (d, ² J _PC = 17.4 Hz, C = O), 173.6 (d, ² J _PC = 19.8 Hz, PC (CO ₂ Et ) = CCH ₂ ); ³¹ P NMR (CDCl ₃ , 162 MHz) δ + 66.2; IR ν _max 1692 (C = O) cm ^-1 ; MS (MALDI-TOF) m / z 387 (M ⁺ ).

(Production of phosphole compound (10))
The phosphole compound (4 g) (200 mg, 0.56 mmol) prepared in Example 1 dissolved in 10 mL of hexane was added to a hexane solution of diisobutylaluminum hydride (1.0 M, 1.12 mL, 1.12 mmol) at −78 ° C. After stirring at −50 ° C. for 1 hour, elemental sulfur (27 mg, 0.85 mmol) was added and the temperature of the resulting mixture was slowly raised to room temperature. Saturated aqueous ammonium chloride (5 mL) was then added, the mixture was filtered through celite, and the organic layer was separated from the filtrate. The aqueous layer was extracted with diethyl ether (10 mL X 2), and the organic layers were combined, washed with brine (20 mL), dried over magnesium sulfate, and concentrated to give a crude product. I got a thing. The crude product was subjected to silica gel column chromatography using a mixed solvent of ethyl acetate and hexane (2: 1) as an eluent (R _f = 0.3) to obtain the desired phosphor compound (10) as a yellow solid. (160 mg, 83%).

Physicochemical data of phosphole compound (10)
Mp 170-171 ° C; ¹ H NMR (CDCl ₃ , 400 MHz) δ 2.09 (br, 1H, CH ₂ OH), 2.31 (m, 2H, CH ₂ CH ₂ CH ₂ ), 2.72 and 2.87 (each m, 2H , CH ₂ CH ₂ CH ₂ ), 4.48 (m, 2H, CH ₂ OH), 6.95 (m, 1H, H4 Th), 7.25 (m, 1H, H3 Th), 7.29 (m, 1H, H5 Th), 7.43 (m, 2H, mH Ph), 7.50 (m, 1H, pH Ph), 7.88 (m, 2H, oH Ph); ¹³ C { ¹ H} NMR (CDCl ₃ , 68 MHz) δ 27.2 (d, ⁴ J _PC = 1.7 Hz, CH ₂ CH ₂ CH ₂ ), 27.5 (d, ³ J _PC = 11.7 Hz, PC (CH ₂ OH) = CCH ₂ ), 29.7 (d, ³ J _PC = 11.1 Hz, PC (Th ) = CCH ₂ ), 57.7 (d, ² J _PC = 15.0 Hz, CH ₂ OH), 125.0 (d, ¹ J _PC = 81.3 Hz, PC = C), 126.4 (s, C5 Th), 126.7 (d, ³ J _PC = 4.5 Hz, C3 Th), 127.6 (s, ipso-C Ph), 127.8 (s, C4 Th), 128.4 (d, ¹ J _PC = 71.4 Hz, PC = C), 128.9 (d, ² J _PC = 12.8 Hz, oC Ph), 130.4 (d, ³ J _PC = 11.7 Hz, mC Ph), 132.1 (d, ⁴ J _PC = 2.8 Hz, pC Ph), 135.2 (d, ² J _PC = 19.5 Hz , C2 Th), 151.9 (d, ² J _PC = 22.8 Hz, PC (Th) = CCH ₂ ), 158.2 (d, ² J _PC = 21.7 Hz, PC (CH ₂ OH) = CCH ₂ ); ³¹ P { ¹ H} NMR (CDCl ₃ , 162 MHz) δ + 68.0; IR (KBr) ν _max 3475 (OH) cm ^-1 ; MS (MALDI-TOF) m / z 3 44 (M ⁺ ). Anal. Calcd for C ₁₈ H ₁₇ OPS ₂ : C, 62.77; H, 4.97; P, 8.99. Found: C, 62.58; H, 5.02; P, 8.73.

(Optical properties of phosphole compounds)
The ultraviolet absorption and fluorescence properties (excitation wavelength: 365 nm) of phosphole compounds were measured in THF. As a result, the ultraviolet absorption maximum (λ _max ) of the phosphole compound (4g) is 382 nm (log ε 4.17), which is longer than 355 nm (log ε 4.12), which is the ultraviolet absorption maximum (λ _max ) of the phosphole compound (4e). I found that it was on the side. The phosphor compound (4e) and the phosphor compound (4g) emit yellowish green fluorescence, and the emission band of the phosphor compound (4g) is λ _max of 475 nm, which is larger than 453 nm, which is the λ _max of the phosphor compound (4e). It was found to be on the long wavelength side. On the other hand, the phosphole compound (4b), the phosphole compound (9), and the phosphole compound (10) hardly emitted fluorescence. From the above results, in order to exhibit high emission characteristics, the substituents at the 2-position and 5-position of the phosphole skeleton of the phosphole compound are preferably a combination of π electron donating type and π electron withdrawing type. It was found that CT interaction in the molecule contributed greatly to the optical properties.

Example 3:
The cyclic phosphole compound of the present invention was produced according to the scheme shown below. The details of the manufacturing method are as follows.

(Production of phosphole compound (12))
A solution of the phosphole compound (8) prepared in Example 2 dissolved in 60 cm ³ (870 mmol) of pyrrole (8) (2.1 g, 6.0 mmol) was bubbled with nitrogen for 30 minutes, and then a diethyl ether complex of trifluoroborane ( 0.77 cm ³ , 6.0 mmol) was added. After stirring at room temperature for 4 hours, dichloromethane (100 cm ³ ) and saturated aqueous sodium hydrogen carbonate solution (50 cm ³ ) were added. The aqueous layer was extracted with dichloromethane, the organic layers were combined, washed with brine, dried over sodium sulfate, and concentrated. The obtained product was subjected to silica gel column chromatography using a mixed solvent of dichloromethane and ethyl acetate (50: 1) as an eluent, and the eluate with R _f = 0.6 was concentrated and washed with methanol to obtain the target phosphole. Compound (12) was obtained as a colorless solid (650 mg, 24%).

Physicochemical data of phosphole compound (12)
Mp 154-155 ° C (Found: C, 72.60; H, 6.99; N, 6.27; P, 6.89.Calc. For C ₂₇ H ₃₁ N ₂ PS: C, 72.61; H, 7.00; N, 6.27; P, 6.94 ¹ H NMR (400 MHz; CDCl ₃ ) 1.38 (6H, s), 1.41 (6H, s), 1.54-1.62 (1H, m), 1.90-1.94 (1H, m), 2.09-2.25 (4H , m), 5.88-5.90 (2H, m), 5.99-6.01 (2H, m), 6.70-6.71 (2H, m), 7.48-7.59 (3H, m), 7.97 (2H, m) and 9.12 (2H , br s); ¹³ C { ¹ H} NMR (68 MHz; CDCl ₃ ) 26.6, 27.6, 27.7, 27.9, 28.0, 28.7, 28.8, 37.7, 37.9, 102.5, 106.4, 117.2, 128.8, 129.8, 131.7, 131.8 , 134.6, 135.0, 136.1, 138.3, 158.0 and 158.4; ³¹ P { ¹ H} NMR (162 MHz; CDCl ₃ ) 69.3; m / z (MALDI-TOF) 447 (M ⁺ ).

(Production of cyclic phosphole compound (15) and cyclic phosphole compound (16))
Phosphor compound (12) and 2,5-bis (1-hydroxy-1-methylethyl) prepared by referring to, for example, J. Chem. Soc., Pekin Trans. 1 1977, 877 and Tetrahedron Lett. 2000, 41, 2919 Thiophene (13) (22 mg, 0.11 mmol) was dissolved in dichloromethane (80 cm ³ ), nitrogen was bubbled into the resulting solution for 40 minutes, and then diethyl ether complex of trifluoroborane (0.014 cm ³ , 0.11 mmol). ) Was added. After stirring at room temperature for 3.5 hours, it was washed with distilled water (3 × 80 cm ³ ), dried using sodium sulfate, and concentrated. The obtained pale yellow solid was subjected to silica gel column chromatography using a mixed solvent of hexane and dichloromethane (2: 1) as an eluent, and the desired cyclic phosphole, the σ ⁴ -P, S, N ₂ -hybrid form Compound (15) was obtained as a yellow solid (R _f = 0.4; 41 mg, 61%). In the same manner, the desired σ ⁴ -P, O, N ₂ -hybrid form is obtained from the phosphole compound (12) and 2,5-bis (1-hydroxy-1-methylethyl) thiophene (14). Cyclic phosphole compound (16) was obtained as a yellow solid (R _f = 0.4; 39%).

Physicochemical data of cyclic phosphole compound (15)
Mp 241-242 ° C (Found: C, 72.85; H, 7.10; N, 4.47; P, 5.12. Calc. For C ₃₇ H ₄₃ N ₂ PS ₂ : C, 72.75; H, 7.10; N, 4.59; P, 5.07%); ¹ H NMR (400 MHz; CDCl ₃ ) 1.27 (1H, m), 1.32 (6H, s), 1.36 (6H, s), 1.65 (6H, s), 1.72 (6H, s), 1.86 (1H, m), 2.10 (4H, m), 5.79 (4H, s), 6.78 (2H, s), 7.50 (3H, m), 7.90 (2H, m) and 9.09 (2H, s); ¹³ C { ¹ H} NMR (75 MHz; CDCl ₃ ) 26.7, 27.2, 28.0, 28.2, 31.4, 31.7, 37.4, 37.6, 38.1, 99.8, 101.7, 101.8, 123.6, 128.6, 129.1, 129.5, 131.8, 135.5, 136.5, 137.0, 141.3, 152.0, 158.4 and 158.7; ³¹ P { ¹ H} NMR (162 MHz; [D ₈ ] toluene) 69.6; m / z (FAB) 610 (M ⁺ ).
Fig. 2 shows the X-ray crystallographic analysis results (ORTEP diagram).

Physicochemical data of cyclic phosphole compound (16)
Mp 177-178 ° C; ¹ H NMR (400 MHz; CDCl ₃ ) 1.27 (1H, m), 1.39 (6H, s), 1.40 (6H, s), 1.60 (6H, s), 1.67 (6H, s) , 1.82 (1H, m), 2.11 (4H, m), 5.76 (2H, m), 5.78 (2H, m), 6.05 (2H, s), 7.51 (3H, m), 7.96 (2H, m) and 9.57 (2H, s); ¹³ C { ¹ H} NMR (75 MHz; CDCl ₃ ) 22.6, 22.8, 23.3, 23.6, 23.7, 24.4, 24.6, 25.4, 25.7, 25.8, 25.9, 29.0, 29.2, 29.7, 29.8 , 34.1, 36.0, 36.1, 37.6, 37.7, 60.2, 60.5, 100.2, 100.3, 100.9, 103.6, 103.8, 104.2, 130.1, 131.1, 131.2, 131.3, 133.5, 133.7, 134.4, 134.9, 137.9, 138.9, 139.2, 146.8 , 147.0, 159.6, 159.7, 168.8 and 169.0; ³¹ P { ¹ H} NMR (162 MHz; CDCl ₃ ) 69.4; m / z (MALDI-TOF) 594 (M ⁺ ).

Example 4:
A complex compound of the cyclic phosphole compound of the present invention and platinum (II) was produced according to the scheme shown below. The details of the manufacturing method are as follows.

(Production of cyclic phosphole compound (17))
Tris (dimethylamino) phosphine (0.040 cm ³ , 0.22 mmol) was added to a toluene solution (5 cm ³ ) of the cyclic phosphole compound (15) (47 mg, 0.077 mmol) prepared in Example 3, and the mixture was refluxed. Stir for hours. The obtained mixture was concentrated under reduced pressure and subjected to silica gel column chromatography using a mixed solvent of hexane and dichloromethane (2: 1) as an eluent to obtain the desired σ ³ -P, S, N ₂ -hybrid form. A cyclic phosphole compound (17) was obtained as a colorless solid (R _f = 0.5; 41 mg, 92%). The ¹ H NMR spectrum of this cyclic phosphole compound (17) showed that the compound was present in a ratio of 4: 1 with two conformers.

Physicochemical data of cyclic phosphole compound (17) Main conformers: ¹ H NMR (400 MHz; CDCl ₃ ) 1.23 (6H, s), 1.38 (6H, s), 1.66 (6H, s), 1.71 (6H , s), 1.5-2.4 (6H, m), 5.76 (2H, m), 5.83 (2H, m), 6.79 (2H, s) and 7.1-7.4 (7H, m); ³¹ P { ¹ H} ( 162 MHz; [D ₈ ] toluene) 32.1.
Secondary conformers: ¹ H NMR (CDCl ₃ , 400 MHz) 1.16 (6H, s), 1.52 (6H, s), 1.66 (12H, s), 1.5-2.4 (6H, m), 5.65 (2H , m), 5.79 (2H, m), 6.84 (2H, s) and 7.1-7.4 (7H, m); ³¹ P { ¹ H} (162 MHz; [D ₈ ] toluene) 31.4; m / z (MALDI -TOF) 578 (M ⁺ ).

(Production of complex compound of cyclic phosphole compound (17) and platinum (II))
Toluene (2 cm ³ ) was added to a flask containing the cyclic phosphole compound (17) (42 mg, 0.073 mmol) and PtCl ₂ (COD) (18) (27 mg, 0.073 mmol), and heated at reflux for 6 hours. The obtained solution was concentrated under reduced pressure to obtain an oily substance. This oily substance was subjected to silica gel column chromatography using a mixed solvent of hexane and dichloromethane (2: 1) as an eluent, and further chloroform as an eluent. GPC separation was performed to obtain the target platinum-phosphine complex compound (19) as light yellow crystals (41 mg, 62%). Further, a platinum-phosphine complex compound (20) (2 mg, 4%) and a platinum-phosphine complex compound (21) (3 mg, 5%) were obtained. From the above results, it was found that the cyclic phosphole compound (17), which is a phosphorus-containing hybrid calic spirol, functions as a monodentate ligand for transition metals and the like.

Physicochemical data of platinum-phosphine complex compound (19)
Mp ca. 160 ° C (decomp) (Found: C, 53.95; H, 5.57; N, 2.70; P, 2.72.Calc. For C ₄₆ H ₅₅ Cl ₄ N ₂ PPtS (19 ・ CHCl ₃ ): C, 53.34; H, 5.35; N, 2.70; P, 2.99%); ¹ H NMR (400 MHz; CDCl ₃ ) 0.81 (1H, m), 0.91 (3H, s), 1.15 (1H, m), 1.51-1.88 (7H , m), 1.61 (3H, s), 1.68 (3H, s), 1.70 (3H, s), 1.77 (3H, s), 1.82 (3H, s), 1.85 (3H, s), 1.93 (3H, s), 2.06-2.21 (3H, m), 2.89 (1H, m), 5.50-6.01 (3H, m), 5.66 (1H, m), 5.73 (1H, m), 5.85 (1H, m), 5.88 (1H, m), 6.30-6.56 (1H, m), 6.56 (1H, s), 7.36-7.44 (3H, m), 7.70-7.74 (2H, m) and 9.21 (2H, s); ¹³ C { ¹ H} (75 MHz; CDCl ₃ ) 23.9, 25.5, 25.8, 25.9, 27.0, 27.1, 28.1, 29.8, 30.6, 31.1, 31.4, 31.7, 34.1, 36.1, 36.2, 37.2, 37.4, 37.5, 37.7, 37.8, 40.5, 99.1, 99.8, 101.8, 102.3, 105.3, 105.5, 109.2, 109.3, 124.2, 124.4, 128.4, 128.6, 129.2, 129.5, 130.5, 131.6, 131.7, 134.1, 134.2, 134.8, 141.6, 141.7, 142.3, 142.5, 142.6, 143.2, 150.0, 151.0, 160.1, 160.3, 166.9 and 167.1; ³¹ P { ¹ H} (162 MHz; CDCl ₃ ) 51.1 (J _Pt-P 4281); m / z (FAB) 916 (M ⁺ ).
Fig. 3 shows the X-ray crystallographic analysis results (ORTEP diagram) of the platinum-phosphine complex compound (19) ・ (CHCl ₃ ) ₂

Physicochemical data of platinum-phosphine complex compound (20)
¹ H NMR (300 MHz; CDCl ₃ ) 0.92-1.04 (4H, m), 1.23 (12H, s), 1.60-1.72 (28H, m), 1.88-2.05 (4H, m), 2.09 (12H, s) , 5.76-5.79 (8H, m), 6.41 (4H, s), 7.34-7.38 (4H, m), 7.45-7.49 (2H, m), 7.86-7.90 (4H, m) and 8.85 (4H, s) ; ³¹ P { ¹ H} (162 MHz; CDCl ₃ ) 46.7 (J _Pt-P 2476); m / z (MALDI-TOF) 1388 (M ⁺ -Cl).

Physicochemical data of platinum-phosphine complex compound (21)
¹ H NMR (400 MHz; CDCl ₃ ) 1.28 (6H, s), 1.45 (6H, s), 1.62 (6H, s), 1.65 (6H, s), 1.67 (18H, s), 1.77-2.10 (8H , m), 2.25 (6H, s), 2.43-2.48 (2H, m), 5.66-5.68 (2H, m), 5.80-5.82 (6H, m), 6.55 (2H, s), 6.84 (2H, s ), 7.19-7.26 (2H, m), 7.35-7.46 (6H, m), 7.53 (2H, m), 7.92 (2H, s) and 8.91 (2H, s); ³¹ P { ¹ H} (162 MHz ; CDCl ₃ ) 45.5 (J _Pt-P 2400), 46.5 (J _Pt-P 2560); m / z (MALDI-TOF) 1424 (M ⁺ ).

Example 5:
A complex compound of the cyclic phosphole compound of the present invention and palladium (0) was produced according to the scheme shown below. The details of the manufacturing method are as follows.

(Production of cyclic phosphole compound (24) and cyclic phosphole compound (25))
The phosphole compound (12) was obtained from the phosphole compound (8) produced in Example 2 in the same manner as in Example 3. Next, nitrogen was bubbled into a dichloromethane solution (600 mL) of this phosphole compound (12) (530 mg, 1.2 mmol) and the thiophenediol compound (23) (360 mg, 1.2 mmol), and then trifluoroborane was added. Of diethyl ether complex (0.17 mL, 1.2 mmol) was added. After stirring at room temperature for 2 hours, 2,3-dichloro-5,6-dicyanobenzoquinone (600 mg, 2.6 mmol) was added, and the mixture was further stirred for 1 hour. Saturated aqueous sodium carbonate solution (200 mL) was poured into the obtained reaction mixture, and the organic layer was washed with saturated aqueous sodium carbonate solution (200 mL X 3), further washed with brine (200 mL), and sodium sulfate was used. Dried and concentrated. The product was subjected to silica gel column chromatography using a mixed solvent of hexane, dichloromethane and ethyl acetate (10: 3: 1) as an eluent, and an _Rf = 0.5 fraction (partially oxidized) showing an orange band and grapes. Collect the fraction (complete oxidation) of R _f = 0.3 that shows a wine-colored band, concentrate both fractions, wash with methanol, and remove the cyclic phosphole compound (25) from the former fraction as a reddish orange solid. Obtained (40 mg, 5%). Further, from the latter fraction, a cyclic phosphole compound (24) was obtained as a red solid (200 mg, 24%).

Physicochemical data of cyclic phosphole compound (24)
Mp 190 ° C (dec); ¹ H NMR (CDCl ₃ , 400 MHz) δ 1.45 (s, 6H, CH ₃ ), 1.56 (s, 6H, CH ₃ ), 1.90-2.15 (m, 2H, CH ₂ CH ₂ CH ₂ ), 2.35-2.60 (m, 4H, CH ₂ CH ₂ CH ₂ ), 6.55 and 6.66 (each d, 2H, J = 4.4 Hz, β-pyrrole), 6.64 (s, 2H, β-thiophene), 7.35-7.50 (m, 10H, meso-Ph), 7.40-7.55 (m, 3H, m, pH P-Ph), 8.14 (m, 2H, oH P-Ph); ¹³ C { ¹ H} NMR (CDCl ₍₃ , 68 MHz) δ 24.8, 24.9, 26.0, 28.4, 30.7, 30.9, 41.7, 41.8, 125.6, 127.5, 128.2, 128.3, 128.5, 130.4, 130.6, 130.8, 133.3, 133.8, 134.4, 136.0, 138.3, 141.8, 152.5, 152.6, 180.4; ³¹ P { ¹ H} NMR (CDCl ₃ , 162 MHz) δ + 67.9; UV / Vis (CH ₂ Cl ₂ ) λ _max (ε): 330 (34200), 496 (18400), 524 (15700); MS (FAB) m / z 703 ([M + H] ⁺ ).

Physicochemical data of cyclic phosphole compound (25)
Mp 218-220 ° C; ¹ H NMR ([D ₈ ] toluene, 343 K, 400 MHz) δ 1.30-1.50 (br, 2H, CH ₂ CH ₂ CH ₂ ), 1.45 (s, 6H, CH ₃ ), 1.61 (s, 6H, CH ₃ ), 1.82-2.00 (m, 4H, CH ₂ CH ₂ CH ₂ ), 5.97 and 6.02 (each m, 2H, β-pyrrole), 6.51 (s, 2H, β-thiophene), 7.08-7.14 (m, 10H, meso-Ph), 7.28-7.34 (m, 3H, m, pH P-Ph), 7.97 (m, 2H, oH P-Ph), 10.06 (m, 2H, NH); ³¹ P { ¹ H} NMR (d ₈ toluene, 343 K, 162 MHz) δ + 70.0; IR (KBr) ν _max 3297 (NH) cm ^-1 ; UV / Vis (CH ₂ Cl ₂ ) λ _max (ε): 306 (19900), 480 (sh, 25000), 508 (28000); MS (FAB) m / z 704 (M ⁺ ).

(Production of cyclic phosphole compound (26) and cyclic phosphole compound (27))
After bubbling nitrogen into a toluene solution (20 mL) of cyclic phosphoric compound (24) (200 mg, 0.28 mmol) which is σ ⁴ -P, S, N ₂ -hybrid calixphyrin, tris (dimethylamino) Phosphine (0.13 mL, 0.71 mmol) was added and stirred for 20 hours at reflux. The resulting mixture was concentrated under reduced pressure and subjected to silica gel column chromatography using a mixed solvent of hexane, dichloromethane and ethyl acetate (15: 5: 1) as eluent, and a fraction of R _f = 0.3 showing a purple band. After being collected and concentrated, it was washed with methanol to obtain a cyclic phosphole compound (26) as a σ ³ -P, S, N ₂ -hybrid form as a wine-colored solid (125 mg, 66%). In addition, a small amount of a cyclic phosphole compound (27), which was a reduction product of a tripyran unit, was obtained as an orange solid (R _f = 0.5, 9 mg, 5%).

Physicochemical data of cyclic phosphole compound (26)
¹ H NMR (CDCl ₃ , 400 MHz) δ 1.33 (s, 6H, CH ₃ ), 1.52 (s, 6H, CH ₃ ), 2.00-2.10 and 2.24 (each m, 1H, CH ₂ CH ₂ CH ₂ ), 2.20-2.32 and 2.45-2.55 (each m, 2H, CH ₂ CH ₂ CH ₂ ), 6.60 (s, 2H, β-thiophene), 6.60 and 6.64 (each d, 2H, J = 4.5 Hz, β-pyrrole) , 7.26-7.30 (m, 3H, m, pH P-Ph), 7.32-7.50 (m, 10H, meso-Ph), 7.57 (m, 2H, oH P-Ph); ¹³ C { ¹ H} NMR ( (CDCl ₃ , 100 MHz) δ 26.5, 26.6, 28.7, 28.8, 29.5, 41.6, 41.8, 126.0, 127.4, 127.8, 127.9, 128.0, 128.4, 130.4, 130.5, 130.6, 133.5, 134.1, 134.4, 135.3, 135.5, 138.1 , 140.9, 141.3, 152.2, 152.7, 155.5, 155.6, 182.4; ³¹ P { ¹ H} NMR (CDCl ₃ , 162 MHz) δ + 26.7; MS (FAB) m / z 671 ([M + H] ⁺ ).

Physicochemical data of cyclic phosphole compound (27)
¹ H NMR (CDCl ₃ , 400 MHz) δ 1.35 (s, 6H, CH ₃ ), 1.72-1.83, 2.02-2.13 and 2.40-2.50 (each m, 2H, CH ₂ CH ₂ CH ₂ ), 5.76 (br, 2H, β-thiophene), 5.98 and 6.41 (each m, 2H, β-pyrrole), 7.27-7.48 (m, 13H, m, pH P-Ph and meso-Ph), 7.53 (m, 2H, oH P- Ph), 8.68 (m, 2H, NH); ³¹ P { ¹ H} NMR (CDCl ₃ , 162 MHz) δ + 31.0; IR (KBr) ν _max 3414 (NH) cm ^-1 ; MS (FAB) m / z 672 (M ⁺ ).

(Production of complex compound of cyclic phosphole compound (26) and palladium (0))
A mixture of the cyclic phosphole compound (26) (6.7 mg), Pd (dba) ₂ (5.8 mg) and dichloromethane was stirred at room temperature for 3 hours and then concentrated under reduced pressure.The eluent was hexane, dichloromethane and ethyl acetate ( 10: 3: 1) silica gel column chromatography using a mixed solvent, and the fraction of R _f = 0.5 showing a purple band was collected, concentrated, washed with methanol, and the desired palladium-phosphine complex compound ( 28) was obtained as a reddish purple solid (80%).

Physicochemical data of palladium-phosphine complex compound (28)
¹ H NMR (CDCl ₃ , 400 MHz) δ 1.22 (s, 6H, CH ₃ ), 1.67 (s, 6H, CH ₃ ), 2.12-2.27 and 2.30 -2.44 (each m, 1H, CH ₂ CH ₂ CH ₂ ), 2.48-2.64 and 2.77-2.90 (each m, 2H, CH ₂ CH ₂ CH ₂ ), 6.10 and 6.34 (each br, 2H, J = 3.2 Hz, β-pyrrole), 6.22 (br, 2H, β- thiophene), 7.26-7.29 (m, 3H, m, pH, P-Ph), 7.29-7.32 (m, 4H, oH meso-Ph), 7.32-7.38 (m, 6H, m, pH meso-Ph), 7.39-7.44 (m, 2H, oH P-Ph); MS (MALDI-TOF) m / z 777 (M ⁺ ).

  The present invention is easily converted into a nonlinear optical material that can be used in an optical integrated circuit and the like, and is useful as a starting material such as a cyclic phosphole compound that can also be used as a metal ligand, a simple production method thereof, and the like The present invention has industrial applicability in that a cyclic phosphole compound produced using this phosphole compound as a starting material can be provided.

Results of X-ray crystallographic analysis of phosphole compound (4b) (ORTEP diagram) Results of X-ray crystallographic analysis of cyclic phosphole compound (15) (ORTEP diagram) Results of X-ray crystallographic analysis of platinum-phosphine complex compound (19) ・ (CHCl ₃ ) ₂ (ORTEP diagram)

Claims (11)

A phosphole compound represented by the following general formula (1).

[In the formula, Ar represents an aryl group which may have a substituent or a heteroaryl group which may have a substituent. X represents an oxygen atom or a sulfur atom. [] Indicates that it may not be present. Y represents an aryl group which may have a substituent, a heteroaryl group which may have a substituent, or —COOR ⁴ (R ⁴ represents an alkyl group). R ¹ and R ² together are optionally an oxygen atom, -S (O) m- (m represents an integer of 0 to 2), -NR ^5- (R ⁵ represents a hydrogen atom or an alkyl group) Represents an alkylene group which may be interrupted by. R ³ represents an alkyl group) 2. The phosphole compound according to claim 1, wherein Y is —COOR ⁴ and R ³ and R ⁴ are the same alkyl group. A method for producing a phosphole compound represented by the following general formula (1), wherein a diyne compound represented by the following general formula (2) is reacted with an organic transition metal compound and the following general formula (3): And the resulting metallacyclopentadiene compound is reacted with ArPX ¹ X ² (X ¹ and X ² are the same or different and each represents a halogen atom. Ar is as defined above), A production method by further P-sulfidation or P-oxidation.

[Wherein Ar, X, [], Y, R ¹ , R ² , R ³ are as defined above.]

[Wherein, Q represents an alkylene group formed by R ¹ and R ² . Y and R ³ are as defined above.

[Wherein, M represents a transition metal atom. L ¹ and L ² are the same or different and each represents an anionic ligand or a neutral ligand. Y, R ¹ , R ² and R ³ are as defined above.   4. The production method according to claim 3, wherein the transition metal atom is a titanium atom.   5. The production method according to claim 3, wherein titanium tetraisopropoxide is reacted with the diyne compound represented by the general formula (2) in the presence of isopropylmagnesium halide. A phosphole compound represented by the following general formula (4).

[In the formula, T is an aryl group which may have a substituent, a heteroaryl group which may have a substituent, -CR ¹³ R ¹⁴ OH (R ¹³ and R ¹⁴ are the same or different, Any one of an alkyl group which may have a substituent, an aryl group which may have a substituent, and a heteroaryl group which may have a substituent. R ¹¹ and R ¹² are the same or different and each represents a hydrogen atom, an alkyl group that may have a substituent, an aryl group that may have a substituent, or a heteroaryl group that may have a substituent. Indicates either. Ar, X, [], R ¹ and R ² are as defined above. A method for producing a phosphole compound represented by the following general formula (4), wherein the ester group bonded to the α-position of the phosphole skeleton of the phosphole compound represented by the following general formula (1) is reduced or alkylated. Manufacturing method.

[In the formula, Ar, X, [], T, R ¹ , R ² , R ¹¹ , R ¹² are as defined above.]

[Wherein Ar, X, [], Y, R ¹ , R ² , R ³ are as defined above.] The cyclic phosphole compound represented by the following general formula (5).

[In the formula, ring A is constituted by an arylene group which may further have three or more substituents in addition to the indicated phosphole and / or a heteroarylene group which may have a substituent. The ring structure in which part or all may form a π-electron conjugated system is shown. Ar, X, [], R ¹ and R ² are as defined above. 9. The cyclic phosphole compound according to claim 8, represented by the following general formula (6):

[Wherein, U, V and W are the same or different and each represent an arylene group which may have a substituent or a heteroarylene group which may have a substituent. R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ are the same or different and have a hydrogen atom, an alkyl group which may have a substituent, or a substituent. Or a heteroaryl group which may have a substituent. Any of R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , and R ²⁸ may form a double bond with adjacent U, V, and W. Ar, X, [], R ¹ and R ² are as defined above. A method for producing a cyclic phosphole compound represented by the following general formula (6), wherein the phosphole compound represented by the following general formula (7) may have an aryl compound and / or substitution A phosphole compound represented by the following general formula (8) is obtained by dehydration condensation reaction with a heteroaryl compound which may have a group, and the obtained phosphole compound is converted to HOR ³³ R ³⁴ CV-CR ³⁵ R ³⁶ OH (R ³³ , R ³⁴ , R ³⁵ and R ³⁶ are the same as R ²³ , R ²⁴ , R ²⁵ and R ²⁶ , respectively, or represent a group which can be converted to R ²³ , R ²⁴ , R ²⁵ and R ^26. And a production method by dehydration condensation reaction.

[In the formula, Ar, X, [], U, V, W, R ¹ , R ² , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ are as defined above. ]

[Wherein, R ³¹ , R ³² , R ³⁷ and R ³⁸ have the same meanings as R ²¹ , R ²² , R ²⁷ and R ²⁸ , respectively, and represent groups which can be converted to R ²¹ , R ²² , R ²⁷ and R ²⁸ . Ar, X, [], R ¹ and R ² are as defined above.

[Wherein, U ′ and W ′ each represents an aryl group which may have a substituent corresponding to U or W, or a heteroaryl group which may have a substituent. Ar, X, [], R ¹ , R ² , R ³¹ , R ³² , R ³⁷ , R ³⁸ are as defined above. A complex compound of a cyclic phosphole compound represented by the following general formula (5) and a transition metal.

[Wherein, ring A, Ar, X, [], R ¹ and R ² are as defined above.]

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