JP5122799B2 - Benzoylpyrazole compounds and herbicides containing them - Google Patents

Description

  The present invention relates to a novel benzoylpyrazole compound useful as an active ingredient of a herbicide.

  Patent Documents 1 to 4 disclose benzoylpyrazole compounds, respectively. However, they have a different chemical structure from the benzoylpyrazole compounds represented by the following formula (I).

International Publication WO 96/26206 JP-A-50-126830 JP 2-288866 JP-A-2-173

  Conventionally, there has been a demand for a herbicide that has excellent herbicidal performance against weeds and safety for cultivated crops in order to save labor in controlling weeds and improve productivity of agricultural and horticultural crops. Yes. However, the search for new compounds suitable for such purposes relies on trial and error.

  The inventors of the present invention have completed the present invention as a result of various studies on benzoylpyrazole compounds in order to find better herbicides that solve the above problems. That is, the present invention relates to the formula (I):

{Wherein R ¹ is alkyl or cycloalkyl, R ² is a hydrogen atom or alkyl, R ³ is alkyl; cycloalkyl; haloalkyl; alkoxyalkyl; alkoxycarbonylalkyl; alkenyl; or R ⁸ it is also an arylalkyl, R ⁴ is alkyl; a or alkylsulfonyl, R ⁵ is a hydrogen atom; haloalkyl; alkoxy; halogen; nitro; cyano; alkylthio; alkylsulfinylalkyl; alkenyl; alkynyl, halogen, cyano, cyano alkyl; cyanoalkenyl; haloalkyl; alkoxyalkyl; haloalkoxyalkyl; alkyl, cyano, cyanoalkyl, (alkylthio) carbonyl, alkyl (thiocarbonyl) alkyl, -C (O) oR ⁷ and -C (O) SR ⁷ Amino (thiocarbonyl) alkyl optionally substituted with at least one substituent selected from: thiocyanatoalkyl; alkoxy; alkenyloxy; alkynyloxy; haloalkoxy; alkoxyalkoxy; haloalkoxyalkoxy; Alkoxyalkoxyalkyl; alkylthio; alkoxyalkylthio; haloalkoxyalkylthio; alkoxyhaloalkylthio; haloalkoxyhaloalkylthio; alkylthioalkylthio; haloalkylthioalkylthio; alkylthiohaloalkylthio; haloalkylthiohaloalkylthio; Alkoxycarbonylalkyl; alkoxycal Niruarukokishi; heterocyclylalkyl; heterocyclyloxy; heterocyclylalkoxy; heterocyclylalkyl alkoxyalkyl; heterocyclyloxyalkyl; ^{cycloalkyloxy; -OC (O) SR 7;} -OC (O) OR 7; -C (O) OR 7; -C ^{(O) SR 7; -C (} S) oR 7; -C (S) SR 7; alkyl, cyano, cyanoalkyl, (alkylthio) carbonyl, alkyl (thiocarbonyl) alkyl, -C (O) oR ⁷ and Aminoalkyl optionally substituted with at least one substituent selected from —C (O) SR ⁷ ; or 4,5-dihydroisoxazol-3-yl optionally substituted with R ⁹ , R ⁶ Is haloalkyl; halogen; nitro; cyano; alkylthio; alkylsulfinyl; or alkylsulfonyl, R ⁷ is alkyl; haloalkyl; alkoxyalkyl; Alkenyl; haloalkenyl; alkynyl; or arylalkyl optionally substituted with R ¹⁰ , wherein R ⁸ , R ⁹ and R ¹⁰ are each independently halogen; alkyl; or alkoxy} Or a salt thereof, a production method thereof, a herbicide containing them as an active ingredient, and an effective herbicidal amount thereof are applied to an undesired plant or a place where it grows to control or inhibit the growth of the undesired plant. Regarding the method.

  The compound represented by the formula (I) exhibits an excellent herbicidal effect.

The alkyl or alkyl moiety in R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ or R ¹⁰ may be either linear or branched, and specific examples thereof As methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, neopentyl, tert-pentyl, n-hexyl, iso And C _1-9 such as -hexyl, n-heptyl, n-octyl, n-nonyl.
Examples of the cycloalkyl or cycloalkyl moiety in R ¹ , R ³ or R ⁵ include those of C _3-6 such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
The alkenyl or alkenyl moiety in R ³ , R ⁵ or R ⁷ may be linear or branched, and specific examples thereof include vinyl, 1-propenyl, 2-propenyl, iso-propenyl, allyl, 1- Butenyl, 2-butenyl, 3-butenyl, 1,3-butadienyl, 2-pentenyl, 4-pentenyl, 2-hexenyl, 4-hexenyl, 2-heptenyl, 4-heptenyl, 2-octenyl, 6-octenyl, 2- Examples include C _2-9 such as nonenyl.

The alkynyl or alkynyl moiety in R ⁵ or R ⁷ may be linear or branched, and specific examples thereof include ethynyl, propargyl, 1-propynyl, 1-pentynyl, 3-pentynyl, 1-heptynyl, 1 -C _2-9 such as noninyl.
Examples of the halogen in R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ or R ¹⁰ or the halogen as a substituent include each atom of fluorine, chlorine, bromine or iodine.
The number of substitutions of halogen as a substituent in R ³ , R ⁴ , R ⁵ , R ⁶ or R ⁷ may be 1 or 2 or more, and in the case of 2 or more, they may be the same or different. The halogen substitution position may be any position.

The number of alkoxy or alkoxy moieties substituted as substituents in R ³ , R ⁵ or R ⁷ may be 1 or 2 or more, and in the case of 2 or more, they may be the same or different. Moreover, those positions may be any positions.
The aryl or aryl moiety as a substituent in R ³ or R ⁷ includes phenyl, naphthyl and the like. The number of substitutions of the aryl or aryl moiety may be 1 or 2 or more, and in the case of 2 or more, they may be the same or different. Moreover, those positions may be any positions.

The number of substitution of R ⁸ for substituting the arylalkyl of R ³ may be 1 or 2 or more, and in the case of 2 or more, they may be the same or different. In addition, the substitution position of each substituent may be any position.
The number of substitution of R ¹⁰ substituting the arylalkyl of R ⁷ may be 1 or 2 or more, and in the case of 2 or more, they may be the same or different. In addition, the substitution position of each substituent may be any position.

The number of substitution of R ⁹ substituting 4,5-dihydroisoxazol-3-yl of R ⁵ may be 1 or 2 or more, and in the case of 2 or more, they may be the same or different. In addition, the substitution position of each substituent may be any position.

The alkoxyalkoxy of R ⁵ means that the same or different alkoxy moiety is bonded to the alkoxy group. Any position may be sufficient as the substitution position of the alkoxy part which substitutes an alkoxy group. The same applies to haloalkoxyalkoxy, alkoxyhaloalkoxy, alkoxyalkoxyalkyl, alkylthioalkylthio, alkylsulfonylalkyl, alkoxycarbonylalkyl and the like.

The heterocyclyl moiety in R ⁵ is, for example, a 5-membered or 6-membered ring containing 1 to 4 heteroatoms arbitrarily selected from O, S or N, and saturated. These may be either unsaturated or unsaturated, and specific examples include oxolanyl, 1,3-dioxolanyl, tetrahydrofuranyl, tetrahydro-2H-pyranyl and the like. In addition, the number of substitutions of the heterocyclyl moiety may be 1 or 2 or more, and in the case of 2 or more, they may be the same or different. The substitution position of the heterocyclyl moiety may be any position.

  The salt of the benzoylpyrazole compound represented by the above formula (I) includes any agriculturally acceptable salt, for example, alkali metal salts such as sodium salt and potassium salt; magnesium salt Alkaline earth metal salts such as calcium salts; amine salts such as dimethylamine salts and triethylamine salts; inorganic acid salts such as hydrochlorides, perchlorates, sulfates and nitrates; acetates and methanesulfonates Organic acid salts such as

The benzoylpyrazole compound represented by the above formula (I) or a salt thereof (hereinafter abbreviated as the compound of the present invention) can be produced according to the following reactions [A] to [AG] and a general salt production method. .
The compound of the present invention represented by the above formula (I) can be produced according to the following reaction [A].

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are as described above, and Z is a leaving group such as halogen).
That is, the compound of the present invention represented by the above formula (I) can be produced by reacting the compound represented by the formula (II) with the compound represented by the formula (III).

  The above reaction can be carried out in the presence of a solvent, if necessary. Any solvent may be used as long as it is inert to the reaction. For example, halogenated hydrocarbons such as methylene chloride, chloroform, dichloroethane, and trichloroethane; aromatic hydrocarbons such as benzene, toluene, and xylene. Esters such as methyl acetate, ethyl acetate, propyl acetate; aprotic polar solvents such as acetonitrile, N, N-dimethylformamide, dimethyl sulfoxide, sulfolane, dimethoxyethane; diethyl ether, dioxane, tetrahydrofuran, etc. And ethers. As the solvent, one or more of these can be appropriately selected.

  The above reaction can be performed in the presence of a base, if necessary. The base may be either an inorganic base or an organic base. Examples of the inorganic base include alkali metal hydrides such as sodium hydride and potassium hydride; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate. An alkali metal hydrogen carbonate such as sodium hydrogen carbonate or potassium hydrogen carbonate; an alkaline earth metal hydroxide such as calcium hydroxide; an alkaline earth metal carbonate such as calcium carbonate; Examples of the organic base include tertiary amines such as triethylamine and diisopropylethylamine; pyridine, 4- (dimethylamino) pyridine, 2,6-lutidine and the like. As the base, one or more of these may be appropriately selected and mixed for use.

The reaction temperature for the above reaction is usually from 0 ° C to 150 ° C, and the reaction time is usually from 1 minute to 48 hours.
The reaction can also be carried out in a two-phase system of water and a solvent insoluble in water in the solvent in the presence of a phase transfer catalyst such as a quaternary ammonium salt.

Thus, the compound represented by the above formula (II) is useful as a synthetic intermediate for the compound represented by the formula (I). Some of the compounds represented by the formula (II) are novel and are exemplified below.
Formula (II-x):

{Wherein R ¹ is alkyl or cycloalkyl, R ² is a hydrogen atom or alkyl, R ⁴ is alkyl; haloalkyl; alkoxy; halogen; nitro; cyano; alkylthio; alkylsulfinyl; or alkylsulfonyl; R ^5-x is alkyl substituted with 2 or more alkoxy; alkyl substituted with 2 or more haloalkoxy; alkyl, cyano, cyanoalkyl, (alkylthio) carbonylalkyl, alkyl (thiocarbonyl) alkyl, —C (O ) Amino (thiocarbonyl) alkyl optionally substituted with at least one substituent selected from OR ⁷ and —C (O) SR ⁷ ; thiocyanatoalkyl; alkoxy substituted with 2 or more alkoxy; Alkoxy substituted with haloalkoxy; alkoxyhaloalkoxy; haloalkoxy Haloalkoxy; alkoxyalkyl substituted with 2 or more alkoxy; alkylthio substituted with 2 or more alkoxy; alkylthio substituted with 2 or more haloalkoxy; alkoxyhaloalkylthio; haloalkoxyhaloalkylthio; alkylthioalkylthio; haloalkylthioalkylthio Alkylthiohaloalkylthio; haloalkylthiohaloalkylthio; alkylthioalkoxy; alkyl substituted with two or more alkylsulfonyls; alkyl substituted with two or more alkoxycarbonyls; alkoxy substituted with two or more alkoxycarbonyls; two or more heterocyclyls in substituted alkyl; more heterocyclyl alkoxy substituted; more heterocyclylalkoxy in substituted ^alkyl; -OC (O) SR ^7; or sheer , Cyano alkyl, (alkylthio) carbonyl, alkyl (thiocarbonyl) alkyl, -C (O) OR ⁷ and -C (O) at least one substituted amino alkyl optionally substituted with a substituent selected from SR ⁷ , R ⁶ is haloalkyl; halogen; nitro; cyano; alkylthio; alkylsulfinyl; or alkylsulfonyl, R ⁷ is alkyl; haloalkyl; alkoxyalkyl; alkenyl; haloalkenyl; alkynyl; or aryl optionally substituted with R ¹⁰ A benzoylpyrazole compound or a salt thereof, which is alkyl, and R ¹⁰ is halogen; alkyl; or alkoxy.

In addition, among the compounds of the present invention represented by the above formula (I), a compound in which R ³ is R ^3-a can be produced according to the following reaction [B-1].

(Wherein R ¹ , R ² , R ⁴ , R ⁵ and R ⁶ are as defined above, and R ^3-a is alkyl; cycloalkyl; haloalkyl; alkoxyalkyl; alkoxycarbonylalkyl; alkenyl; or R ⁸ An arylalkyl which may be substituted.)
That is, the compound of the present invention represented by the above formula (Ia) is obtained by reacting a compound represented by the formula (IV-a) or (Va) with a compound represented by the formula (VI-a) or It can be produced by reacting a compound represented by formula (IV-a) and a mixture of compounds represented by formula (Va) with a compound represented by formula (VI-a).

  The above reaction can be performed in the presence of a solvent, if necessary. Any solvent may be used as long as it is inert to the reaction. For example, halogenated hydrocarbons such as methylene chloride, chloroform, dichloroethane, and trichloroethane; aromatic hydrocarbons such as benzene, toluene, and xylene. Esters such as methyl acetate, ethyl acetate, propyl acetate; aprotic polar solvents such as acetonitrile, N, N-dimethylformamide, dimethyl sulfoxide, sulfolane, dimethoxyethane; diethyl ether, dioxane, tetrahydrofuran, etc. And ethers. As a solvent, these 1 type (s) or 2 or more types can be selected suitably.

  The above reaction can be performed in the presence of a base, if necessary. The base may be either an inorganic base or an organic base. Examples of the inorganic base include alkali metal hydrides such as sodium hydride and potassium hydride; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate. An alkali metal hydrogen carbonate such as sodium hydrogen carbonate or potassium hydrogen carbonate; an alkaline earth metal hydroxide such as calcium hydroxide; an alkaline earth metal carbonate such as calcium carbonate; Examples of the organic base include tertiary amines such as triethylamine and diisopropylethylamine; pyridine, 4- (dimethylamino) pyridine, 2,6-lutidine and the like. As the base, one or more of these may be appropriately selected and mixed for use.

The reaction temperature for the above reaction is usually from 0 ° C to 150 ° C, and the reaction time is usually from 1 minute to 48 hours.
Among the compounds of the present invention represented by the above formula (I), a compound in which R ³ is R ^3-b can be produced according to the following reaction [B-2].

(Wherein R ¹ , R ² , R ⁴ , R ⁵ and R ⁶ are as described above, and R ^3-b is alkenyl.)
That is, the compound of the present invention represented by the formula (Ib) is reacted with a compound represented by the formula (IV-b) or the formula (Vb) and a compound represented by the formula (VI-b) It can be produced by reacting a compound represented by formula (IV-b) and a mixture of compounds represented by formula (Vb) with a compound represented by formula (VI-b).

  The above reaction can be performed in the presence of a solvent, if necessary. Examples of the solvent include halogenated hydrocarbons such as methylene chloride, chloroform, dichloroethane, and trichloroethane; aromatic hydrocarbons such as benzene, toluene, and xylene; esters such as methyl acetate, ethyl acetate, and propyl acetate; Examples include aprotic polar solvents such as acetonitrile, N, N-dimethylformamide, dimethyl sulfoxide, sulfolane and dimethoxyethane; ethers such as diethyl ether, dioxane and tetrahydrofuran. As the solvent, one or more of these can be appropriately selected.

  The above reaction can be performed in the presence of a base, if necessary. The base may be either an inorganic base or an organic base. Examples of the inorganic base include alkali metal hydrides such as sodium hydride and potassium hydride; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate. An alkali metal hydrogen carbonate such as sodium hydrogen carbonate or potassium hydrogen carbonate; an alkaline earth metal hydroxide such as calcium hydroxide; an alkaline earth metal carbonate such as calcium carbonate; Examples of the organic base include tertiary amines such as triethylamine and diisopropylethylamine; pyridine, 4- (dimethylamino) pyridine, 2,6-lutidine and the like. As the base, one or more of these may be appropriately selected and mixed for use.

The reaction temperature for the above reaction is usually from 0 ° C to 150 ° C, and the reaction time is usually from 1 minute to 48 hours.
The compound represented by the above formula (IV-a) or formula (Va) or a mixture thereof can be produced according to the following reaction [C-1].

(Wherein R ¹ , R ² , R ⁴ , R ⁵ and R ⁶ are as described above.)
That is, the compound represented by the formula (IV-a) or the formula (Va) or a mixture thereof can be produced by reacting the compound represented by the formula (II) with phosgene (COCl ₂ ). it can.

  The above reaction can be performed in the presence of a solvent, if necessary. Any solvent may be used as long as it is inert to the reaction. For example, halogenated hydrocarbons such as methylene chloride, chloroform, dichloroethane, and trichloroethane; aromatic hydrocarbons such as benzene, toluene, and xylene. Esters such as methyl acetate, ethyl acetate, propyl acetate; aprotic polar solvents such as acetonitrile, N, N-dimethylformamide, dimethyl sulfoxide, sulfolane, dimethoxyethane; diethyl ether, dioxane, tetrahydrofuran, etc. And ethers. As the solvent, one or more of these can be appropriately selected.

  The above reaction can be performed in the presence of a base, if necessary. The base may be either an inorganic base or an organic base. Examples of the inorganic base include alkali metal hydrides such as sodium hydride and potassium hydride; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate. An alkali metal hydrogen carbonate such as sodium hydrogen carbonate or potassium hydrogen carbonate; an alkaline earth metal hydroxide such as calcium hydroxide; an alkaline earth metal carbonate such as calcium carbonate; Examples of the organic base include tertiary amines such as triethylamine and diisopropylethylamine; pyridine, 4- (dimethylamino) pyridine, 2,6-lutidine and the like. As the base, one or more of these may be appropriately selected and mixed for use.

The reaction temperature for the above reaction is usually from -10 ° C to 150 ° C, and the reaction time is usually from 1 minute to 48 hours.
The compound represented by the above formula (IV-b) or formula (Vb) or a mixture thereof can be produced according to the following reaction [C-2].

(Wherein R ¹ , R ² , R ⁴ , R ⁵ and R ⁶ are as described above.)
That is, the compound represented by formula (IV-b) or formula (Vb), or a mixture thereof is produced by reacting the compound represented by formula (II) with thiocarbonyl chloride (CSCl ₂ ). be able to.

  The above reaction can be performed in the presence of a solvent, if necessary. Any solvent may be used as long as it is inert to the reaction. For example, halogenated hydrocarbons such as methylene chloride, chloroform, dichloroethane, and trichloroethane; aromatic hydrocarbons such as benzene, toluene, and xylene. Esters such as methyl acetate, ethyl acetate, propyl acetate; aprotic polar solvents such as acetonitrile, N, N-dimethylformamide, dimethyl sulfoxide, sulfolane, dimethoxyethane; diethyl ether, dioxane, tetrahydrofuran, etc. And ethers. As the solvent, one or more of these can be appropriately selected.

  The above reaction can be performed in the presence of a base, if necessary. The base may be either an inorganic base or an organic base. Examples of the inorganic base include alkali metal hydrides such as sodium hydride and potassium hydride; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate. An alkali metal hydrogen carbonate such as sodium hydrogen carbonate or potassium hydrogen carbonate; an alkaline earth metal hydroxide such as calcium hydroxide; an alkaline earth metal carbonate such as calcium carbonate; Examples of the organic base include tertiary amines such as triethylamine and diisopropylethylamine; pyridine, 4- (dimethylamino) pyridine, 2,6-lutidine and the like. As the base, one or more of these may be appropriately selected and mixed for use.

The reaction temperature for the above reaction is usually from -10 ° C to 150 ° C, and the reaction time is usually from 1 minute to 48 hours.
Some compounds among the compounds represented by the above formula (II), for example, R ⁴ is alkyl, R ⁵ is alkoxyalkyl, alkoxycarbonyl, alkoxyalkoxycarbonyl or haloalkoxycarbonyl, and R ⁶ is alkyl. Compounds that are sulfonyl are described on pages 36-41 of European Publication No. 282944, compounds in which R ⁴ is halogen, R ⁵ is alkoxyalkoxy or heterocyclylalkoxy, and R ⁶ is alkylsulfonyl. A compound described in pages 16 to 20 of publication No. 352543, wherein R ⁴ is halogen, R ⁵ is alkoxyalkoxyalkyl or alkoxy, and R ⁶ is alkylsulfonyl is disclosed in European Publication No. 344775 25 ~ 27 is described in a page, R ⁴ is halogen, R ⁵ is 4,5-dihydroisoxazol zone A-3-yl, compounds wherein R ⁶ is halogen or alkylsulfonyl is a known compound such as described in the 121 to 127 pages of International Publication WO 98/31681, which are described in this publication Or a similar method.
The compound represented by the above formula (II) can be produced according to the following reaction [D].

(Wherein R ¹ , R ² , R ⁴ , R ⁵ and R ⁶ are as described above.)
That is, the compound represented by the formula (II) can be produced by a rearrangement reaction of the compound represented by the formula (VII).
The above reaction can be performed in the presence of a solvent, if necessary. Any solvent may be used as long as it is inert to the reaction. For example, halogenated hydrocarbons such as methylene chloride, chloroform, dichloroethane, and trichloroethane; aromatic hydrocarbons such as benzene, toluene, and xylene. Esters such as methyl acetate, ethyl acetate and propyl acetate; aprotic polar solvents such as acetonitrile, N, N-dimethylformamide, dimethyl sulfoxide, sulfolane and dimethoxyethane; ethers such as diethyl ether, dioxane and tetrahydrofuran And the like. As the solvent, one or more of these can be appropriately selected.

  The above reaction can be performed in the presence of a base, if necessary. The base may be either an organic base or an inorganic base. Examples of the organic base include tertiary amines such as triethylamine and diisopropylethylamine; pyridine, 4- (dimethylamino) pyridine, 2,6-lutidine and the like. Examples of the inorganic base include alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal cyanides such as sodium cyanide and potassium cyanide. It is done. These bases can be used by appropriately selecting and mixing one or more of them in an amount of 0.01 to 100 equivalents with respect to the compound of formula (VII).

In the above reaction, a catalyst can be added as necessary. As the catalyst, 0.01 to 10 equivalents of acetone cyanohydrin can be used with respect to the compound of formula (VII).
The reaction temperature for the above reaction is usually from 0 ° C to 150 ° C, and the reaction time is usually from 1 minute to 48 hours.
The compound represented by the above formula (VII) can be produced according to the following reaction [E].

(Wherein R ¹ , R ² , R ⁴ , R ⁵ and R ⁶ are as described above.)
That is, the compound represented by the formula (VII) is reacted with the compound represented by the formula (VIII) or a salt thereof, for example, hydrochloride, sulfate, nitrate, etc., and the compound represented by the formula (IX). Can be manufactured.

  The above reaction can be carried out in the presence of a solvent, if necessary. Any solvent may be used as long as it is inert to the reaction. For example, halogenated hydrocarbons such as methylene chloride, chloroform, dichloroethane, and trichloroethane; aromatic hydrocarbons such as benzene, toluene, and xylene. Esters such as methyl acetate, ethyl acetate and propyl acetate; aprotic polar solvents such as acetonitrile, N, N-dimethylformamide, dimethyl sulfoxide, sulfolane and dimethoxyethane; ethers such as diethyl ether, dioxane and tetrahydrofuran And the like. As the solvent, one or more of these can be appropriately selected.

  The above reaction can be performed in the presence of a base, if necessary. As the base, the base may be either an inorganic base or an organic base. Examples of the organic base include tertiary amines such as triethylamine and diisopropylethylamine; pyridine, 4- (dimethylamino) pyridine, 2,6-lutidine and the like. Examples of the inorganic base include alkali metal carbonates such as sodium carbonate and potassium carbonate; alkaline earth metal carbonates such as calcium carbonate and magnesium carbonate; alkali metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate; Examples include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. These bases can be used by appropriately selecting and mixing one or more of them in an amount of 1 to 100 equivalents with respect to the compound of formula (IX).

The reaction temperature for the above reaction is usually from 0 ° C to 150 ° C, and the reaction time is usually from 1 minute to 48 hours.
The compound represented by the above formula (IX) can be produced according to the following reaction [F].

(Wherein R ⁴ , R ⁵ and R ⁶ are as described above.)
That is, the compound represented by the formula (IX) can be produced by reacting the compound represented by the formula (X) with a halogenating agent. This reaction is, for example, a method known in the literature (Organic Syntheses, Collective Volume 4, page 715, Collective Volume 9, page 516, etc.).
In the above reaction, 1 to 100 equivalents of a halogenating agent such as thionyl chloride or oxalyl chloride can be reacted with the compound represented by the formula (X).

  The above reaction can be performed in the presence of a solvent, if necessary. Any solvent may be used as long as it is inert to the reaction. For example, halogenated hydrocarbons such as methylene chloride, chloroform, dichloroethane, and trichloroethane; aromatic hydrocarbons such as benzene, toluene, and xylene. Esters such as methyl acetate, ethyl acetate, propyl acetate; aprotic polar solvents such as acetonitrile, N, N-dimethylformamide, dimethyl sulfoxide, sulfolane, dimethoxyethane; diethyl ether, dioxane, tetrahydrofuran, etc. And ethers. As the solvent, one or more of these can be appropriately selected.

In the above reaction, a catalyst can be used as necessary. Examples of the catalyst include DMF.
The reaction temperature for the above reaction is usually from 0 ° C to 150 ° C, and the reaction time is usually from 1 minute to 48 hours.
In addition to the above method, the compound represented by the formula (VII) can be produced according to the following reaction [G].

(Wherein R ¹ , R ² , R ⁴ , R ⁵ and R ⁶ are as described above.)
That is, the compound represented by the formula (VII) is obtained by dehydrating a compound represented by the formula (VIII) or a salt thereof such as hydrochloride, sulfate, nitrate, and the compound represented by the formula (X). It can manufacture by making it react using an agent.
Examples of the dehydrating agent used in the above reaction include DCC (dicyclohexylcarbodiimide) and 1-ethyl 3- (3-dimethylaminopropyl) -carbodiimide hydrochloride.

  The above reaction can be performed in the presence of a solvent, if necessary. Any solvent may be used as long as it is inert to the reaction. For example, halogenated hydrocarbons such as methylene chloride, chloroform, dichloroethane, and trichloroethane; aromatic hydrocarbons such as benzene, toluene, and xylene. Esters such as methyl acetate, ethyl acetate, propyl acetate; aprotic polar solvents such as acetonitrile, N, N-dimethylformamide, dimethyl sulfoxide, sulfolane, dimethoxyethane; diethyl ether, dioxane, tetrahydrofuran, etc. And ethers. As the solvent, one or more of these can be appropriately selected.

The above reaction can be performed in the presence of a base, if necessary. Examples of the base include tertiary amines such as triethylamine and diisopropylethylamine; pyridine, 4- (dimethylamino) pyridine, 2,6-lutidine and the like. These bases can be used by appropriately selecting and mixing one or more of them in an amount of 1 to 100 equivalents with respect to the compound represented by the formula (X).
The reaction temperature for the above reaction is usually from 0 ° C to 150 ° C, and the reaction time is usually from 1 minute to 48 hours.

Among the compounds represented by the formula (X), a compound in which R ⁴ is alkyl, R ⁵ is haloalkoxy, and R ⁶ is alkylthio or alkylsulfonyl is, for example, International Publication WO96 / 14285, 31-32 It is a known compound described on pages. These can be produced according to the method described in the publication or the like or a method similar thereto.
The compound represented by the above formula (X) can be produced according to the following reaction [H].

(In the formula, R ⁴ , R ⁵ and R ⁶ are as described above, and L is a protecting group such as alkyl.)
The compound represented by the formula (X) can be produced by hydrolyzing the compound represented by the formula (XI).
The above reaction can be carried out in the presence of a solvent, if necessary. For example, aromatic hydrocarbons such as benzene, toluene and xylene; aprotic polar solvents such as acetonitrile, N, N-dimethylformamide, dimethyl sulfoxide, sulfolane and dimethoxyethane; such as diethyl ether, dioxane and tetrahydrofuran Ethers; alcohols such as methanol and ethanol; water and the like. As a solvent, these 1 type (s) or 2 or more types can be selected suitably.

  The above reaction can be performed in the presence of a base or an acid, if necessary. The base may be either an inorganic base or an organic base. Examples of the inorganic base include alkali metal hydroxides such as lithium hydroxide and sodium hydroxide; alkali metal carbonates such as potassium carbonate and sodium carbonate; alkaline earth metal carbonates such as calcium carbonate and barium carbonate. Can be mentioned. Examples of the organic base include tertiary amines such as triethylamine and diisopropylethylamine. Examples of the acid include hydrochloric acid, sulfuric acid, perchloric acid and the like. These bases or acids can be used by appropriately selecting and mixing one or more of them in an amount of 1 to 100 equivalents with respect to the compound represented by the formula (XI).

The reaction temperature for the above reaction is usually from 0 ° C to 150 ° C, and the reaction time is usually from 1 minute to 48 hours.
Among the compounds represented by the formula (XI), the compound represented by the formula (XI-a-1) in which R ⁵ is R ^5-a-1 can be produced according to the following reaction [I]. .

Wherein R ⁴ , R ⁶ and L are as described above, and R ^5-a-1 is alkoxy, haloalkoxy, alkoxyalkoxy, haloalkoxyalkoxy, alkoxyhaloalkoxy, haloalkoxyhaloalkoxy, heterocyclyloxy, heterocyclyl. Alkoxy, cycloalkyloxy, —OC (O) SR ⁷ , —OC (O) OR ⁷ , alkylthioalkoxy, alkoxycarbonylalkoxy, alkenyloxy or alkynyloxy, R ^α is alkyl, haloalkyl, alkoxyalkyl, haloalkoxyalkyl a alkoxyhaloalkyl, halo alkoxyhaloalkyl, heterocyclyl, heterocyclylalkyl, ^{cycloalkyl, -C (O) SR 7,} -C (O) oR 7, alkylthioalkyl, alkoxycarbonylalkyl, alkenyl or alkynyl.
That is, the compound represented by the formula (XI-a-1) can be produced by reacting the compound represented by the formula (XII) with the compound represented by the formula (XIII) using a dehydrating agent. it can.

Examples of the dehydrating agent used in the above reaction include DCC (dicyclohexylcarbodiimide), 1-ethyl 3- (3-dimethylaminopropyl) -carbodiimide hydrochloride, diethyl azodicarboxylate, and the like.
The above reaction can be performed in the presence of a solvent, if necessary. Any solvent may be used as long as it is inert to the reaction. For example, halogenated hydrocarbons such as methylene chloride, chloroform, dichloroethane, and trichloroethane; aromatic hydrocarbons such as benzene, toluene, and xylene. Esters such as methyl acetate, ethyl acetate, propyl acetate; aprotic polar solvents such as acetonitrile, N, N-dimethylformamide, dimethyl sulfoxide, sulfolane, dimethoxyethane; diethyl ether, dioxane, tetrahydrofuran, etc. And ethers. As the solvent, one or more of these can be appropriately selected.

The above reaction can be performed in the presence of a base, if necessary. Examples of the base include tertiary amines such as triethylamine and diisopropylethylamine; pyridine, 4- (dimethylamino) pyridine, 2,6-lutidine and the like. These bases can be used by appropriately selecting and mixing one or more of them in an amount of 1 to 100 equivalents with respect to the compound represented by the formula (XII).
The reaction temperature for the above reaction is usually from 0 ° C to 150 ° C, and the reaction time is usually from 1 minute to 48 hours.

Among the compounds represented by the above formula (XII), compounds in which R ⁴ is alkyl, R ⁶ is alkylthio, and alkylsulfonyl are known compounds described in, for example, International Publication WO97 / 35851, pages 54 to 55 It is. These can be produced according to the method described in the publication or the like or a method similar thereto.
In addition to the above method, the compound represented by the formula (XI-a-1) can also be produced according to the following reaction [J].

(In the formula, R ⁴ , R ^5-a-1 , R ⁶ , R ^α and L are as described above. X represents a leaving group such as halogen or a methanesulfonyloxy group.)
That is, the compound represented by the formula (XI-a-1) can be produced by reacting the compound represented by the formula (XII) and the compound represented by the formula (XIV) in the presence of a base. it can.

  The above reaction can be carried out in the presence of a solvent, if necessary. Any solvent may be used as long as it is inert to the reaction. For example, halogenated hydrocarbons such as methylene chloride, chloroform, dichloroethane, and trichloroethane; aromatic hydrocarbons such as benzene, toluene, and xylene. Esters such as methyl acetate, ethyl acetate and propyl acetate; aprotic polar solvents such as acetonitrile, N, N-dimethylformamide, dimethyl sulfoxide, sulfolane and dimethoxyethane; ethers such as diethyl ether, dioxane and tetrahydrofuran And the like. As the solvent, one or more of these can be appropriately selected.

  The base used in the above reaction may be either an inorganic base or an organic base. Examples of the organic base include triethylamine, diisopropylethylamine, pyridine, 4- (dimethylamino) pyridine, 2,6-lutidine and the like. Examples of the inorganic base include alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal hydrides such as sodium hydride and potassium hydride. Is mentioned. These bases can be used by appropriately selecting and mixing one or two or more of them in an amount of 0.5 to 100 equivalents with respect to the compound of the formula (XII).

The above reaction can be carried out in the presence of a catalyst, if necessary. Examples of the catalyst include potassium iodide and tetranormal butyl ammonium iodide.
The reaction temperature for the above reaction is usually from 0 ° C to 150 ° C, and the reaction time is usually from 1 minute to 48 hours.
The compound represented by the above formula (XII) can be produced according to the following reaction [K].

(Wherein R ⁴ , R ⁶ and L are as described above.)
That is, the compound represented by the formula (XII) can be produced by reacting the compound represented by the formula (XV) with a Lewis acid such as BBr ₃ .

  The above reaction can be carried out in the presence of a solvent, if necessary. Any solvent may be used as long as it is inert to the reaction. For example, halogenated hydrocarbons such as methylene chloride, chloroform, dichloroethane, and trichloroethane; aromatic hydrocarbons such as benzene, toluene, and xylene. An ester such as methyl acetate, ethyl acetate or propyl acetate; As the solvent, one or more of these can be appropriately selected.

The reaction temperature for the above reaction is usually from 0 ° C to 150 ° C, and the reaction time is usually from 1 minute to 48 hours.
The compound represented by the above formula (XV) can be produced according to the following reaction [L].

(Wherein R ⁴ , R ⁶ and L are as described above.)
That is, the compound represented by the formula (XV) can be produced by a reaction in which the protective group L is introduced into the compound represented by the formula (XVI).
The above reaction can be carried out in the presence of a solvent, if necessary. Examples of solvents include alcohols such as methanol and ethanol; aromatic hydrocarbons such as benzene, toluene and xylene; esters such as methyl acetate, ethyl acetate and propyl acetate; methylene chloride, chloroform, dichloroethane and trichloroethane. Halogenated hydrocarbons such as: aprotic polar solvents such as acetonitrile, N, N-dimethylformamide, dimethyl sulfoxide, sulfolane, and dimethoxyethane. As the solvent, one or more of these can be appropriately selected.

The above reaction can be performed in the presence of an acid, if necessary. Examples of the acid that can be used in the above reaction include hydrochloric acid and sulfuric acid.
The reaction temperature for the above reaction is usually from 0 ° C to 150 ° C, and the reaction time is usually from 1 minute to 48 hours.

The compound represented by the above formula (XVI) can be produced by a known method. For example, among the compounds represented by the formula (XVI), a compound in which R ⁴ is alkyl and R ⁶ is alkylsulfonyl is described on page 4 of International Publication WO 93/13060, wherein R ⁴ is halogen, R ⁶ A compound in which is alkylsulfonyl is a known compound described in JP-A-2-45448, page 6, and can be produced according to the method described in the publication or a method similar thereto.
Among the compounds represented by the above formula (XI), a compound in which R ⁵ is R ^5-a-2 can be produced according to the following reaction [M].

(Wherein R ⁴ , R ⁶ and L are as described above, and R ^5-a-2 is alkylthiocarbonyl.)
That is, the compound represented by the formula (XI-a-2) can be produced by reacting the compound represented by the formula (XVIII) with an alkylthiol.
The above reaction can be carried out in the presence of a solvent, if necessary. The solvent may be any solvent as long as it is inert to the reaction. For example, ethers such as diethyl ether, dioxane and tetrahydrofuran; aromatic hydrocarbons such as benzene, toluene and xylene; methyl acetate; Examples include esters such as ethyl acetate and propyl acetate; halogenated hydrocarbons such as methylene chloride, chloroform, dichloroethane, and trichloroethane. As the solvent, one or more of these can be appropriately selected.

  In the said reaction, it can be made to react in presence of a base as needed. The base may be either an inorganic base or an organic base. Examples of the organic base include triethylamine, diisopropylethylamine, pyridine, 4- (dimethylamino) pyridine, 2,6-lutidine and the like. Examples of the inorganic base include alkali metal carbonates such as potassium carbonate and sodium carbonate; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal hydrides such as sodium hydride and potassium hydride. It is done. As the base, one or more of these may be appropriately selected and mixed for use.

The reaction temperature for the above reaction is usually from 0 ° C to 150 ° C, and the reaction time is usually from 1 minute to 48 hours.
The compound represented by the above formula (XVIII) can be produced according to the following reaction [N].

(Wherein R ⁴ , R ⁶ and L are as described above.)
That is, the compound represented by the formula (XVIII) can be produced by reacting the compound represented by the formula (XIX) with a halogenating agent. This reaction can be carried out in the same manner as the above-mentioned reaction [F].
The compound represented by the above formula (XIX) can be produced according to the following reaction [O].

(Wherein R ⁴ , R ⁶ and L are as described above.)
That is, the compound represented by the formula (XIX) can be produced by oxidizing the compound represented by the formula (XX).
Examples of the oxidizing agent in the above reaction include potassium permanganate and chromium trioxide.

The above reaction can be performed in the presence of a solvent, if necessary. The solvent may be any solvent as long as it is inert to the reaction. For example, ketones such as acetone and methyl ethyl ketone; esters such as methyl acetate, ethyl acetate and propyl acetate; diethyl ether, dioxane and tetrahydrofuran Such ethers. As the solvent, one or more of these can be appropriately selected.
The reaction temperature for the above reaction is usually from 0 ° C to 150 ° C, and the reaction time is usually from 1 minute to 48 hours.
The compound represented by the above formula (XX) can be produced according to the following reaction [P].

(Wherein R ⁴ , R ⁶ and L are as described above.)
That is, the compound represented by the formula (XX) can be produced by reacting the compound represented by the formula (XXI) with an oxidizing agent in the presence of a solvent.
Examples of the oxidizing agent used in the above reaction include N-methylmorpholine oxide.

The solvent used in the above reaction may be any solvent as long as it is inert to the reaction. For example, an aprotic polar solvent such as acetonitrile, N, N-dimethylformamide, dimethyl sulfoxide, sulfolane, dimethoxyethane; Examples include ethers such as diethyl ether, dioxane and tetrahydrofuran. As the solvent, one or more of these can be appropriately selected.
The reaction temperature for the above reaction is usually from 0 ° C to 150 ° C, and the reaction time is usually from 1 minute to 48 hours.

The compound represented by the above formula (XX) or formula (XXI) can be produced by a known method. For example, among the compounds represented by the formulas (XX) and (XXI), compounds in which R ⁴ is alkyl and R ⁶ is alkylsulfonyl are described on page 9 of JP-A-11-240872, wherein R ⁴ is halogen, The compound in which R ⁶ is alkylsulfonyl is a known compound such as described in International Publication WO 98/29392, page 264, and can be produced according to the method described in the publication or a method similar thereto. .
Among the compounds represented by the formula (XI), a compound in which R ⁵ is represented by R ^5-a-3 can be produced according to the following reaction [Q].

(Wherein R ⁴ , R ⁶ and L are as described above, and R ^5-a-3 is alkylsulfonylalkyl.)
That is, the compound represented by the formula (XI-a-3) can be produced by reacting the compound represented by the formula (XXII) with an oxidizing agent in the presence of a solvent.

Examples of the oxidizing agent used in the above reaction include hydrogen peroxide, peracetic acid, metachloroperbenzoic acid, and the like.
The solvent used in the above reaction may be any solvent as long as it is inert to the reaction. For example, halogenated hydrocarbons such as methylene chloride, chloroform, dichloroethane, and trichloroethane; acetone, dimethylethylketone Ketones such as: ethers such as diethyl ether, dioxane and tetrahydrofuran; acetic acid and the like. As the solvent, one or more of these can be appropriately selected.

The reaction temperature for the above reaction is usually from 0 ° C to 150 ° C, and the reaction time is usually from 1 minute to 48 hours.
The compound represented by the above formula (XXII) can be produced according to the following reaction [R].

(Wherein R ⁴ , R ⁶ and L are as described above.)
That is, the compound represented by the formula (XXII) can be produced by reacting the compound represented by the formula (XXIII) with an alkylthiol in the presence of a solvent.
The solvent used in the above reaction may be any solvent that is inert to the reaction, such as halogenated hydrocarbons such as methylene chloride, chloroform, dichloroethane, and trichloroethane; ketones such as acetone and dimethylethylketone. Ethers such as diethyl ether, dioxane and tetrahydrofuran; acetic acid; water; N, N-dimethylformamide, dimethyl sulfoxide, sulfolane, dimethoxyethane and the like. As the solvent, one or more of these can be appropriately selected.

  In the said reaction, reaction can be performed in presence of a base as needed. The base may be either an inorganic base or an organic base. Examples of the organic base include triethylamine, diisopropylethylamine, pyridine, 4- (dimethylamino) pyridine, 2,6-lutidine and the like. Examples of inorganic bases include alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate; alkaline earth metal carbonates such as calcium carbonate and magnesium carbonate; water Examples thereof include alkali metal hydroxides such as sodium oxide; alkali metal hydrides such as sodium hydride and potassium hydride. As the base, one or more of these may be appropriately selected and mixed for use.

The reaction temperature for the above reaction is usually from 0 ° C to 150 ° C, and the reaction time is usually from 1 minute to 48 hours.
The compound represented by the above formula (XXIII) can be produced by a known method. For example, a compound in which R ⁴ is alkyl and R ⁶ is alkylsulfonyl is described on page 9 of JP-A-11-240872, and a compound in which R ⁴ is halogen and R ⁶ is alkylsulfonyl is disclosed in WO 98/29392. And the like, and can be produced according to the method described in the publication or a method similar thereto.
Among the compounds represented by the formula (XI), the compound in which R ⁵ is R ^5-a-4 can be produced according to the following reaction [S].

(Wherein R ⁴ , R ⁶ and L are as described above, and R ^5-a-4 is cyano.)
That is, the compound represented by the formula (XI-a-4) is produced by reacting the compound represented by the formula (XXIV) with an acid anhydride such as acetic anhydride or a sulfonyl chloride such as methanesulfonyl chloride. can do.

  The above reaction can be performed in the presence of a solvent, if necessary. The solvent may be any solvent as long as it is inert to the reaction. For example, halogenated hydrocarbons such as methylene chloride, chloroform, dichloroethane, and trichloroethane; ketones such as acetone and dimethylethylketone; diethyl ether, Examples include ethers such as dioxane and tetrahydrofuran; pyridine and the like. As the solvent, one or more of these can be appropriately selected.

In the said reaction, it can be made to react in presence of a base as needed. Examples of the base include triethylamine, N, N-dimethylaminopyridine, diisopropylaminopyridine and the like. As the base, one or more of these may be appropriately selected and mixed for use.
The reaction temperature for the above reaction is usually from 0 ° C to 150 ° C, and the reaction time is usually from 1 minute to 48 hours.
The compound represented by the above formula (XXIV) can be produced according to the following reaction [T].

(Wherein R ⁴ , R ⁶ and L are as described above.)
That is, the compound represented by the formula (XXIV) can be produced by reacting the compound represented by the formula (XX) with hydroxyamine or hydroxyamine hydrochloride in the presence of a solvent.

  The solvent used in the above reaction may be any solvent as long as it is inert to the reaction. For example, alcohols such as methanol and ethanol; halogenated hydrocarbons such as methylene chloride, chloroform, dichloroethane and trichloroethane; Examples include ketones such as acetone and dimethyl ethyl ketone; ethers such as diethyl ether, dioxane and tetrahydrofuran. As the solvent, one or more of these can be appropriately selected.

In the said reaction, it can be made to react in presence of an acid or a base as needed. Examples of the acid include p-toluenesulfonic acid. Examples of the base include sodium acetate.
The reaction temperature for the above reaction is usually from 0 ° C to 150 ° C, and the reaction time is usually from 1 minute to 48 hours.
Among the compounds represented by the formula (XI), a compound in which R ⁵ is represented by R ^5-a-5 can be produced according to the following reaction [U].

(Wherein R ⁴ , R ⁶ and L are as described above, and R ^5-a-5 is cyanoalkyl.)
That is, the compound represented by the formula (XI-a-5) is produced by reacting the compound represented by the formula (XXV) with an acid anhydride such as acetic anhydride or a sulfonyl chloride such as methanesulfonyl chloride. can do. This reaction can be carried out in the same manner as the above-mentioned reaction [S].
The compound represented by the above formula (XXV) can be produced according to the following reaction [V].

(Wherein R ⁴ , R ⁶ and L are as described above.)
That is, the compound represented by the formula (XXV) can be produced by reacting the compound represented by the formula (XXVI) with hydroxyamine or hydroxyamine hydrochloride in the presence of a solvent. This reaction can be carried out in the same manner as the above-mentioned reaction [T].
The compound represented by the above formula (XXVI) can be produced according to the following reaction [W].

(Wherein R ⁴ , R ⁶ and L are as described above, and A is alkyl.)
That is, the compound represented by the formula (XXVI) can be produced by reacting the formula (XXVII) with an acid such as hydrochloric acid.
The above reaction can be performed in the presence of a solvent, if necessary. The solvent may be any solvent as long as it is inert to the reaction. Examples thereof include water; alcohols such as methanol and ethanol; ethers such as diethyl ether, dioxane and tetrahydrofuran. As the solvent, one or more of these can be appropriately selected.

The reaction temperature for the above reaction is usually from 0 ° C to 150 ° C, and the reaction time is usually from 1 minute to 48 hours.
The compound represented by the above formula (XXVII) can be produced according to the following reaction [X].

(Wherein R ⁴ , R ⁶ , L and A are as described above.)
That is, the compound represented by the formula (XXVII) can be produced by reacting the compound represented by the formula (XXVIII) with an alcohol in the presence of an acid.
Examples of alcohols used in the above reaction include methanol and ethanol. Examples of the acid include hydrochloric acid and toluenesulfonic acid.

The reaction temperature for the above reaction is usually from 0 ° C to 150 ° C, and the reaction time is usually from 1 minute to 48 hours.
The compound represented by the above formula (XXVIII) can be produced according to the following reaction [Y].

(Wherein R ⁴ , R ⁶ and L are as defined above, T is a halogen, Ph represents phenyl, and Me represents methyl.)
That is, the compound represented by the formula (XXVIII) can be produced by the Wittig reaction of the compound represented by the formula (XX) in the presence of a solvent.

The solvent used in the above reaction may be any solvent that is inert to the reaction. For example, ethers such as diethyl ether, dioxane, and tetrahydrofuran; aromatic hydrocarbons such as benzene, toluene, and xylene. Aprotic polar solvents such as acetonitrile, N, N-dimethylformamide, dimethyl sulfoxide, sulfolane, dimethoxyethane, and the like.
The above reaction can be performed in the presence of a base as necessary. Examples of the base include sodium hydride (NaH); an alkali lithium reagent such as normal butyl lithium; a metal amide such as sodium amide (NaNH ₂ ), and the like.

The reaction temperature for the above reaction is usually from -80 ° C to 150 ° C, and the reaction time is usually from 1 minute to 48 hours.
Among the compounds represented by the formula (XI), a compound in which R ⁵ is R ^5-a-6 can be produced according to the following reaction [Z].

(In the formula, R ⁴ , R ⁶ and L are as described above, and R ^5-a-6 is alkoxyalkoxyalkyl.)
That is, the compound represented by the formula (XI-a-6) can be produced by reacting the compound represented by the formula (XXIII) with an alkoxy alcohol.

  The above reaction can be performed in the presence of a solvent, if necessary. Any solvent may be used as long as it is inert to the reaction. Examples thereof include alcohols such as methanol and ethanol; esters such as methyl acetate, ethyl acetate and propyl acetate; diethyl ether, dioxane and tetrahydrofuran. Ethers such as: aprotic polar solvents such as acetonitrile, N, N-dimethylformamide, dimethyl sulfoxide, sulfolane, dimethoxyethane, and the like. As the solvent, one or more of these can be appropriately selected.

The above reaction can be performed in the presence of a base, if necessary. Examples of the base include alkali metal hydrides such as sodium hydride and potassium hydride.
The reaction temperature for the above reaction is usually from 0 ° C to 150 ° C, and the reaction time is usually from 1 minute to 48 hours.

The compound represented by the above formula (XXIII) can be produced by a known method. For example, a compound in which R ⁴ is alkyl and R ⁶ is alkylsulfonyl is described on page 9 of JP-A-11-240872, and a compound in which R ⁴ is halogen and R ⁶ is alkylsulfonyl is disclosed in WO 98/29392. And the like, and can be produced according to the method described in the publication or a method similar thereto.
Among the compounds represented by the formula (XI), a compound in which R ⁵ is R ^5-a-7 can be synthesized according to the following reaction [AA].

Wherein R ⁴ , R ⁶ and L are as defined above, and R ^5-a-7 is alkylthio, alkoxyalkylthio, haloalkoxyalkylthio, alkoxyhaloalkylthio, haloalkoxyhaloalkylthio, alkylthioalkylthio, haloalkylthioalkylthio, Alkylthiohaloalkylthio or haloalkylthiohaloalkylthio.)
That is, the compound represented by the formula (XI-a-7) can be produced by reacting the thiol corresponding to R ^5-a-7 with the compound represented by the formula (XXIX).

  The above reaction can be performed in the presence of a solvent, if necessary. The solvent may be any solvent as long as it is inert to the reaction. For example, alcohols such as methanol and ethanol; ethers such as diethyl ether, dioxane and tetrahydrofuran; acetonitrile, N, N-dimethylformamide , Aprotic polar solvents such as dimethyl sulfoxide, sulfolane and dimethoxyethane; water and the like. As the solvent, one or more of these can be appropriately selected.

The above reaction can be performed in the presence of a base, if necessary. Examples of the base include alkali metal hydrides such as sodium hydride and potassium hydride; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide and the like. .
The reaction temperature for the above reaction is usually from 0 ° C to 250 ° C, and the reaction time is usually from 1 minute to 48 hours.

The compound represented by the above formula (XXIX) can be produced by a known method. For example, a compound in which R ⁴ is halogen and R ⁶ is alkylsulfonyl is described on page 8 of European Patent Publication No. 195247, and a compound in which R ⁴ is alkyl and R ⁶ is alkylsulfonyl is described in Pest Management Science ( 2002), 58 (12), 1175-1186, and the like, and can be produced according to the method described in the publication or a method similar thereto.

Among the compounds represented by the formula (XI), a compound in which R ⁵ is R ^5-a-8 can be synthesized according to the following reaction [AB].

(Wherein R ⁴ , R ⁶ and L are as described above, and R ^5-a-8 is heterocyclylalkyl containing two oxygen atoms.)
That is, the compound represented by the formula (XI-a-8) can be produced by reacting an alkylene glycol and a compound represented by the formula (XXVI) in the presence of a solvent and an acid catalyst.
The solvent used in the above reaction may be any solvent as long as it is inert to the reaction. For example, halogenated hydrocarbons such as methylene chloride, chloroform, dichloroethane, and trichloroethane; benzene, toluene, xylene Aromatic hydrocarbons such as; esters such as methyl acetate, ethyl acetate, propyl acetate; aprotic polar solvents such as acetonitrile, N, N-dimethylformamide, dimethyl sulfoxide, sulfolane, dimethoxyethane; diethyl ether; And ethers such as dioxane and tetrahydrofuran. As the solvent, one or more of these can be appropriately selected.
Examples of the acid catalyst used in the above reaction include p-toluenesulfonic acid and pyridium p-toluenesulfonate.
In the above reaction, it is preferable that water generated by the reaction is azeotroped with the solvent or moisture is removed using a desiccant, as necessary.
The reaction temperature for the above reaction is usually from 0 ° C to 150 ° C, and the reaction time is usually from 1 minute to 48 hours.

Among the compounds represented by the above formula (II), a compound in which R ⁵ is R ^5-a-9 can be synthesized according to the following reaction [AC].

(Wherein R ¹ , R ² , R ⁴ and R ⁶ are as described above, and R ^5-a-9 is thiocyanatoalkyl.)
That is, the compound represented by the formula (II-a-9) can be produced by reacting NaSCN with a compound represented by the formula (II-a-10).
The above reaction can be performed in the presence of a solvent, if necessary. The solvent used in the above reaction may be any solvent as long as it is inert to the reaction. For example, halogenated hydrocarbons such as methylene chloride, chloroform, dichloroethane, and trichloroethane; benzene, toluene, xylene Aromatic hydrocarbons such as; esters such as methyl acetate, ethyl acetate, propyl acetate; aprotic polar solvents such as acetonitrile, N, N-dimethylformamide, dimethyl sulfoxide, sulfolane, dimethoxyethane; diethyl ether; Examples include ethers such as dioxane and tetrahydrofuran; alcohols such as methanol, ethanol and propanol. As the solvent, one or more of these can be appropriately selected.
The reaction temperature for the above reaction is usually from 0 ° C to 150 ° C, and the reaction time is usually from 1 minute to 48 hours.

Among the compounds represented by the formula (XI), a compound in which R ⁵ is R ^5-a-10 can be synthesized according to the following reaction [AD].

(In the formula, R ⁴ , R ^5-a-5 , R ⁶ and L are as defined above, and R ^5-a-10 is alkyl, cyano, cyanoalkyl, (alkylthio) carbonylalkyl, alkyl (thiocarbonyl). An amino (thiocarbonyl) alkyl optionally substituted with at least one substituent selected from alkyl, —C (O) OR ⁷ and —C (O) SR ⁷ .
That is, the compound represented by the formula (XI-a-10) can be produced by reacting P ₂ S ₅ with a compound represented by the formula (XI-a-5) in the presence of a solvent. it can.
The solvent used in the above reaction may be any solvent as long as it is inert to the reaction. For example, alcohols such as methanol, ethanol, and propanol: halogenated compounds such as methylene chloride, chloroform, dichloroethane, and trichloroethane. Hydrocarbons; aromatic hydrocarbons such as benzene, toluene, xylene; esters such as methyl acetate, ethyl acetate, propyl acetate; acetonitrile, N, N-dimethylformamide, dimethyl sulfoxide, sulfolane, dimethoxyethane, etc. And aprotic polar solvents; ethers such as diethyl ether, dioxane and tetrahydrofuran. As the solvent, one or more of these can be appropriately selected.
The reaction temperature for the above reaction is usually from 0 ° C to 250 ° C, and the reaction time is usually from 1 minute to 48 hours.

Among the compounds represented by the above formula (XI), a compound in which R ⁵ is R ^5-a-11 can be synthesized according to the following reaction [AE].

(Wherein R ⁴ , R ⁶ and L are as defined above, and R ^5-a-11 is alkyl, cyano, cyanoalkyl, (alkylthio) carbonylalkyl, alkyl (thiocarbonyl) alkyl, —C (O) Aminoalkyl optionally substituted with at least one substituent selected from OR ⁷ and —C (O) SR ^7. )
That is, the compound represented by the formula (XI-a-11) is alkyl, cyano, cyanoalkyl, (alkylthio) carbonylalkyl, alkyl (thiocarbonyl) alkyl, —C (O) OR ⁷ and —C (O). It can be produced by reacting an amine which may be substituted with at least one substituent selected from SR ⁷ or ammonia and a compound represented by the formula (XXIII).
The above reaction can be performed in the presence of a solvent, if necessary. The solvent used in the above reaction may be any solvent as long as it is inert to the reaction. For example, halogenated hydrocarbons such as methylene chloride, chloroform, dichloroethane, and trichloroethane; benzene, toluene, xylene Aromatic hydrocarbons such as; esters such as methyl acetate, ethyl acetate, propyl acetate; aprotic polar solvents such as acetonitrile, N, N-dimethylformamide, dimethyl sulfoxide, sulfolane, dimethoxyethane; diethyl ether; And ethers such as dioxane and tetrahydrofuran. As the solvent, one or more of these can be appropriately selected.
The above reaction can be performed in the presence of a base as necessary. The base may be either an inorganic base or an organic base. Examples of inorganic bases include alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate; alkaline earth metal carbonates such as calcium carbonate and magnesium carbonate; hydrogen Sodium hydroxide (NaH); alkaline lithium reagents such as normal butyl lithium; metal amides such as sodium amide (NaNH ₂ ), and the like. Examples of the organic base include triethylamine, N, N-dimethylaminopyridine, diisopropylaminopyridine, amines such as DBU (diazabicycloundecene), and the like.
The above reaction can be performed in the presence of a catalyst as necessary. Examples of the catalyst include TBAI (tertiary butyl ammonium iodide).
The reaction temperature for the above reaction is usually from 0 ° C to 150 ° C, and the reaction time is usually from 1 minute to 48 hours.

Among the compounds represented by the above formula (XI), a compound in which R ⁵ is R ^5-a-12 can be synthesized according to the following reaction [AF-1].

(In the formula, R ⁴ , R ⁶ , R ^5-a-11 and L are as described above, and R ^5-a-12 is an amino part of R ^5-a-11 substituted with alkyl or cyanoalkyl. .)
That is, the compound represented by the formula (XI-a-12) can be produced by reacting the compound represented by the formula (XI-a-11) with an alkyl halide or a cyanohalogenated alkyl. it can.
The said reaction can be performed in presence of a solvent as needed. The solvent may be any solvent as long as it is inert to the reaction. For example, alcohols such as methanol, ethanol, and propanol: halogenated hydrocarbons such as methylene chloride, chloroform, dichloroethane, and trichloroethane; benzene, Aromatic hydrocarbons such as toluene and xylene; esters such as methyl acetate, ethyl acetate and propyl acetate; aprotic polar solvents such as acetonitrile, N, N-dimethylformamide, dimethyl sulfoxide, sulfolane and dimethoxyethane An ether such as diethyl ether, dioxane or tetrahydrofuran; As the solvent, one or more of these can be appropriately selected.
The above reaction can be performed in the presence of a base as necessary. The base may be either an inorganic base or an organic base. Examples of inorganic bases include alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate; alkaline earth metal carbonates such as calcium carbonate and magnesium carbonate. Can be mentioned. Examples of the organic base include triethylamine, N, N-dimethylaminopyridine, diisopropylaminopyridine, amines such as DBU (diazabicycloundecene), and the like.
The reaction temperature for the above reaction is usually from 0 ° C to 150 ° C, and the reaction time is usually from 1 minute to 48 hours.

Among the compounds represented by the above formula (I), a compound in which R ⁵ is R ^5-a-13 can be synthesized according to the following reaction [AF-2].

(In the formula, R ¹ , R ² , R ⁴ , R ⁶ , R ^5-a-11 and Z are as described above, and R ^5-a-13 represents (alkylthio) on the amino moiety of R ^5-a-11. ) Substituted by carbonyl.)
That is, the compound represented by the formula (Ia-13) is produced by reacting the compound represented by the formula (II-a-11) with the compound represented by the formula (III-a). Can do. This reaction can be carried out in the same manner as the above-mentioned reaction [A].

Among the compounds represented by the above formula (XI), a compound in which R ⁵ is R ^5-a-14 can be synthesized according to the following reaction [AG].

(In the formula, R ⁴ , R ⁶ , L, T and Ph are as described above, and R ^5-a-14 is cyanoalkenyl.)
That is, the compound represented by the formula (XI-a-15) can be produced by the Wittig reaction of the compound represented by the formula (XX) in the presence of a solvent. This reaction can be carried out in the same manner as the above-mentioned reaction [Y].

  The compound of the present invention exhibits an excellent herbicidal effect when used as an active ingredient of a herbicide. The range of application ranges widely from agricultural fields such as paddy fields, upland fields, orchards, mulberry fields, and non-agricultural land such as forests, farm roads, grounds, and factory sites. You can choose.

  The compound of the present invention includes, for example, Inobie, Tainubie, Agaricus, Enokorogusa, Akinoenokorogusa, Oshiba, Oats, Oats, Sobamue, Shibamugi, Velvet Mill, Paragrass, Azegaya, Itozegaya, Prunus japonicus, Echinoptera Weeping weeds such as firefly, Weeping weeping weeds such as Cyperus weeds such as firefly, Weeping weeping weeping, Weeping weeds such as Urikawa, Omodaka and Heramoda Family weeds, other broad-leaved weeds, for example, Ichibi, Maruba morning glory, Shiroza, American king deer, Purslane, Aobiu, Aogay C, can be sicklepod, Inuhouzuki, Sanaetade, chickweed, Elatine triandra Schk, cocklebur, Cardamine flexuosa, henbit, ragweed, cleavers, field bindweed, white Bana Datura, Ezo Roh fox thistle, be used to control a variety of harmful weeds of such Enokigusa. Therefore, it selectively controls harmful weeds in useful crops such as corn, soybean, cotton, wheat, rice, barley, oat, sorghum, rape, sunflower, sugar beet, sugar cane, turf, peanut, flax, tobacco and coffee. It is used effectively in the case of controlling harmful harmful weeds. In particular, the compound of the present invention is used for the cultivation of corn, soybean, cotton, wheat, rice, rape, sunflower, sugar beet, sugar cane, turf, peanut, flax, tobacco, coffee, etc., among them, the cultivation of corn, soybean, wheat, rice, etc. Effectively used when selectively controlling harmful weeds.

The compounds of the present invention are usually mixed with various agricultural adjuvants, powders, granules, granule wettable powders, wettable powders, tablets, pills, capsules (including forms packaged in water-soluble films), aqueous suspensions. It can be formulated and applied in the form of a suspension, oily suspension, microemulsion formulation, suspoemulsion formulation, aqueous solvent, emulsion, solution, paste, etc. It can be in any formulation form commonly used in the art.
Adjuvants used in the formulation include solid carriers such as diatomaceous earth, slaked lime, calcium carbonate, talc, white carbon, kaolin, bentonite, kaolinite and sericite, clay, sodium carbonate, sodium bicarbonate, sodium sulfate, zeolite, starch, etc. Solvent such as water, toluene, xylene, solvent naphtha, dioxane, acetone, isophorone, methyl isobutyl ketone, chlorobenzene, cyclohexane, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, alcohol; fatty acid salt, benzoic acid Acid salt, alkylsulfosuccinate, dialkylsulfosuccinate, polycarboxylate, alkylsulfate, alkylsulfate, alkylarylsulfate, alkyldiglycolethersulfate, alcohol Sulfate ester salt, alkyl sulfonate salt, alkyl aryl sulfonate salt, aryl sulfonate salt, lignin sulfonate salt, alkyl diphenyl ether disulfonate salt, polystyrene sulfonate salt, alkyl phosphate ester salt, alkyl aryl phosphate salt, styryl aryl Phosphate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl aryl ether sulfate, polyoxyethylene alkyl aryl ether sulfate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl aryl phosphate Such as polyoxyethylene aryl ether phosphate ester salt, naphthalene sulfonate formalin condensate, alkyl naphthalene sulfonate formalin condensate Surfactants and spreading agents: sorbitan fatty acid ester, glycerin fatty acid ester, fatty acid polyglyceride, fatty acid alcohol polyglycol ether, acetylene glycol, acetylene alcohol, oxyalkylene block polymer, polyoxyethylene alkyl ether, polyoxyethylene alkylaryl Ether, polyoxyethylene styryl aryl ether, polyoxyethylene glycol alkyl ether, polyethylene glycol, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene hydrogenated castor oil, polyoxypropylene fatty acid Nonionic surfactants and spreading agents such as esters; olive oil, kapok oil, sunflower Examples thereof include vegetable oil, palm oil, coconut oil, coconut oil, sesame oil, corn oil, rice bran oil, peanut oil, cottonseed oil, soybean oil, rapeseed oil, flaxseed oil, linseed oil, liquid paraffin and other vegetable oils and mineral oils. These adjuvants can be used by appropriately selecting one or two or more kinds without departing from the object of the present invention. For example, extenders, thickeners, anti-settling agents, antifreeze agents, dispersion agents Various commonly used adjuvants such as stabilizers, safeners, antifungal agents, foaming agents, disintegrants, binders and the like can also be used. The compounding ratio of the compound of the present invention and various adjuvants is 0.1: 99.9 to 95: 5, preferably 0.2: 99.8 to 85:15.

  The application rate of the herbicide containing the compound of the present invention cannot be defined unconditionally due to differences in weather conditions, soil conditions, formulation forms, types of target weeds, application time, etc., but generally the compound of the present invention is 0.5 to 5,000 per hectare. g, preferably 1 to 1,000 g, more preferably 10 to 500 g. The present invention includes a method for controlling harmful weeds by application of such a herbicide.

  In addition, the herbicide containing the compound of the present invention can be mixed or used in combination with other agricultural chemicals, fertilizers, safeners and the like, and in this case, more excellent effects and functions may be exhibited. Other pesticides include herbicides, fungicides, antibiotics, plant hormones, insecticides and the like. In particular, a mixed herbicidal composition in which the compound of the present invention and one or more active ingredient compounds of other herbicides are mixed or used in combination has a range of applicable herb species, timing of chemical treatment, herbicidal activity, etc. It is possible to improve in the preferred direction. In addition, the compound of the present invention and other herbicidal active ingredient compounds may be prepared separately and mixed at the time of spraying, or both may be used together. The above-described mixed herbicidal composition is also included in the present invention.

  The mixing ratio of the compound of the present invention and the active ingredients of other herbicides cannot be defined unconditionally due to differences in weather conditions, soil conditions, drug formulation, application time, application method, etc. On the other hand, other herbicides contain 0.001 to 10,000 parts by weight, preferably 0.01 to 1,000 parts by weight of the active ingredient per one kind. In addition, the appropriate amount to be applied is 0.1 to 10,000 g, preferably 0.2 to 5,000 g, more preferably 10 to 3,000 g as the total amount of active ingredient compounds per hectare. The present invention also includes a method for controlling harmful weeds by application of such a mixed herbicidal composition.

Examples of the active ingredients of other herbicides include those listed below (generic names; including those for which some ISO applications have been filed), but salts, alkyl esters, etc. exist in these compounds even if not specifically described. Of course, they are also included.
(1) 2,4-D, 2,4-DB, 2,4-DP, MCPA, MCPB, MCPP, naproanilide, phenoxy type such as clomeprop, 2,3,6-TBA, Aromatic carboxylic acids such as dicamba, dichlobenil, picloram, triclopyr, clopyralid, aminopyralid, other naptalam, benazolin, quinro It is said that herbicidal activity is shown by disrupting the hormonal action of plants such as quinclorac, quinmerac, diflufenzopyr, thiazopyr.

  (2) urea systems such as chlorotoluron, diuron, fluometuron, linuron, isoproturon, metobenzuron, tebuthiuron, simazine, Atrazine, atratone, simetrin, promethrin, dimethametryn, hexazinone, metribuzin, terbuthylazine, cyanazine, ametrine, ametrine Triazines such as cybutryne, triaziflam, propazine, uracils such as bromacil, lenacil, terbacil, propanil, cypromid A Carbamates such as lido, swep, desmedipham, phenmedipham, hydroxybenzo such as bromoxynil, bromoxynil-octanoate, ioxynil Nitriles, other pyridates, bentazone, amicarbazone, methazole, etc. that are said to show herbicidal efficacy by inhibiting plant photosynthesis.

  (3) Quaternary ammonium salt systems such as paraquat and diquat, which are said to themselves become free radicals in the plant body and generate active oxygen to show rapid herbicidal efficacy.

  (4) Nitrofen, Chlomethoxyfen, bifenox, acifluorfen-sodium, fomesafen, oxyfluorfen, lactofen, ethoxyphenethyl Diphenyl ethers such as (ethoxyfen-ethyl), chlorphthalim, flumioxazin, flumiclorac-pentyl, cyclic imides such as fluthiacet-methyl, and other oxadiargyl ( oxadiargyl), oxadiazon, sulfentrazone, carfentrazone-ethyl, thidiazimin, pentoxazone, azafenidin, isopropazol Isopropazole, pyraflufen-ethyl, benzfendizone, benzfendizone, butafenacil, metobenzuron, cinidon-ethyl, flupoxam, fluazolate, Inhibits plant chlorophyll biosynthesis, such as profluazol, pyrachlonil, flufenpyr-ethyl, and bencarbazone, and provides photosensitized peroxides in plants It is said to show herbicidal efficacy by accumulating abnormally.

  (5) Pyridazinones such as norflurazon, chloridazon, metflurazon, pyrazolate, pyrazoxifene, benzofenap, topramezone, BAS-670H) Pyrazoles such as pyrasulfotole, other amitrol, fluridone, flurtamone, diflufenican, methoxyphenone, clomazone, sulcotrione , Mesotrione, tembotrione, tefuryltrione (AVH-301), isoxaflutole, difenzoquat, isoxachlortole, beoxatritol Zobishikuron (benzobicyclon), picolinafen (picolinafen), Bifurubutamido (beflubutamid) inhibiting dye biosynthesis of plants, such as carotenoids, such as, what is showing a herbicidal activity characterized by whitening effect.

  (6) Diclohopop-methyl, flamprop-M-methyl, pyriphenop-sodium, fluazifop-butyl, haloxyhop-methyl ( Aryloxyphenoxy such as haloxyfop-methyl, quizalofop-ethyl, cyhalofop-butyl, fenoxaprop-ethyl, metamifop-propyl Propionic acid, alloxydim-sodium, clethodim, sethoxydim, tralkoxydim, butroxydim, tepraloxydim, caloxydim, clefoxydim , Cyclohexanedione such as profoxydim What is specifically herbicidal activity to grasses are found strongly, such as.

  (7) Chlorimuron-ethyl, sulfometuron-methyl, primisulfuron-methyl, bensulfuron-methyl, chlorsulfuron, methos Methylsulfuron-methyl, Cinosulfuron, pyrazosulfuron-ethyl, azimsulfuron, flazasulfuron, rimsulfuron, nicosulfuron, imazosulfuron imazosulfuron, cyclosulfamuron, prosulfuron, flupirsulfuron, triflusulfuron-methyl, halosulfuron-methyl, thifensulfuron- methyl) Ethoxysulfuron, oxasulfuron, ethametsulfuron, iodosulfuron, sulfosulfuron, triasulfuron, tribenuron-methyl ), Tritosulfuron, foramsulfuron, trifloxysulfuron, mesosulfuron-methyl, orthosulfamuron, flucetosulfuron, amidos Amidosulfuron, TH-547, sulfonylureas such as the compounds described in International Publication WO2005092104, flumetsulam, metosulam, diclosulam, cloransulam-methyl, Florasla Triazolopyrimidinesulfonamides such as florasulam, metosulfam, penoxsulam, imazapyr, imazethapyr, imazaquin, imazamox, imazamox, imazamox, imazameth (imazameth) (Imazamethabenz), imidazolinones such as imazapic, pyrithiobac-sodium, bispyribac-sodium, pyriminobac-methyl, pyribenzoxim ), Pyriftalid, pyrimidinylsalicylic acid such as pyrimisulfan, KUH-021, flucarbazone, sulfonylaminocarbonyl such as procarbazone-sodium Azorinone, other glyphosate, glyphosate sodium salt (glyphosate-sodium), glyphosate potassium salt (glyphosate-potassium), glyphosate ammonium salt (glyphosate-ammonium), glyphosate isopropylamine salt (glyphosate-isopropylamine), sulfosate (sulfosate) , Glufosinate, glufosinate ammonium salt (glufosinate-ammonium), vilanafos (bilanafos), etc. that are said to show herbicidal efficacy by inhibiting plant amino acid biosynthesis.

  (8) Dinitroaniline series such as trifluralin, oryzalin, oryzalin, nitraline, pendimethalin, ethalfluralin, benfluralin, prodiamine, benzulide (Bensulide), amides such as napronamide, pronamide, amiprofos-methyl, butamifos, anilofos, organic phosphorus such as piperophos, Propham, chlorpropham, phenyl carbamates such as barban, daimuron, cumyluron, cumylamines such as bromobutide, other aslam, dithiopyr (Dithiopyr), thiazopyr (Thiazopyr), etc. that are said to show herbicidal efficacy by inhibiting cell mitosis of plants.

  (9) alachlor, metazachlor, butachlor, pretilachlor, metolachlor, S-metolachlor, tenylchlor, petoxamide , Chloroacetamides such as acetochlor, propachlor, propisochlor, molinate, dimepiperate, carbamates such as pyributicarb, and other etobenzanid ), Mefenacet, flufenacet, tridiphane, cafenstrole, fentrazamide, oxaziclomefone, indanofan , Dimethenamid (dimethenamid), benfuresate (benfuresate), pyroxasulfone (pyroxasulfone, KIH-485) What is showing a herbicidal activity by inhibiting protein biosynthesis or lipid biosynthesis of plants, such as.

  (10) EPTC, butyrate, vernolate, pebulate, cycloate, prosulfocarb, esprocarb, thiobencarb, diallate, triarate Thiocarbamate such as (triallate), other MSMA, DSMA, endothal, etofumesate, sodium chlorate, pelargonic acid, fosamine, pinoxaden, HOK-201 etc.

(11) What is said to show herbicidal efficacy by infesting plants such as Xanthomonas campestris , Epicoccosurus nematosurus , Exserohilum monoseras , Drechsrela monoceras .

Next, although an example of the desirable aspect of the present invention is described, the present invention is not limited to these.
(1) In the above formula (I), R ¹ is alkyl or cycloalkyl, R ² is a hydrogen atom or alkyl, and R ³ is alkyl; cycloalkyl; haloalkyl; alkoxyalkyl; alkenyl; or substituted with R ⁸ has been is also an arylalkyl, R ⁴ is alkyl; a or alkylsulfonyl, R ⁵ is a hydrogen atom; haloalkyl; alkoxy; halogen; nitro; cyano; alkylthio; alkylsulfinylalkyl, halogen, cyano, cyanoalkyl; Haloalkyl; alkoxyalkyl; haloalkoxyalkyl; alkoxy; haloalkoxy; alkoxyalkoxy; haloalkoxyalkoxy; alkoxyhaloalkoxy; alkoxyalkoxyalkyl; Kiruchio; alkylthioalkyl thio; haloalkylthio alkylthioalkyl; alkylthioalkoxy; alkylsulfonyl; alkylsulfonylalkyl; alkoxycarbonylalkyl; alkoxycarbonylalkoxy; heterocyclyloxy; heterocyclylalkoxy; heterocyclylalkyl ^{alkoxyalkyl; -OC (O) SR 7;} -OC (O) ^{oR 7; -C (O) oR} 7; a or R ⁹ may dihydro-isoxazol-3-yl which may be substituted by, R ⁶ is ^haloalkyl;; -C (O) SR ⁷ halogen; Nitro; cyano; alkylthio; alkylsulfinyl; or alkylsulfonyl, wherein R ⁷ is alkyl; haloalkyl; alkoxyalkyl; alkenyl; haloalkenyl; alkynyl; or arylalkyl optionally substituted with R ¹⁰ , R ⁸ , R ⁹ and R Benzoylpyrazole compounds or salts thereof, wherein ¹⁰ is independently halogen, alkyl, or alkoxy, their production method, herbicides containing them as active ingredients, their herbicidally effective amount, undesired plants or their growth The method of applying to the place to control and controlling an undesirable plant or suppressing the growth.

(2) In the above formula (I), R ¹ is alkyl or cycloalkyl, R ² is a hydrogen atom or alkyl, and R ³ is alkyl; cycloalkyl; haloalkyl; alkoxyalkyl; or R ⁸ it is also an arylalkyl, R ⁴ is alkyl; a or alkylsulfonyl, R ⁵ is alkyl; haloalkyl; alkoxy; halogen; nitro; cyano; alkylthio; alkylsulfinyl haloalkyl; alkoxyalkyl; haloalkoxyalkyl; alkoxy; halo alkoxy; alkoxyalkoxy; halo alkoxyalkoxy; heterocyclyloxy; heterocyclylalkoxy; heterocyclylalkyl ^{alkoxyalkyl; -OC (O) SR 7;} -OC (O) OR 7; -C (O) OR 7; -C (O) SR 7 ; or R ⁹ may be substituted 4,5-dihydroisoxazol An Lumpur-3-yl, R ⁶ is haloalkyl; a or alkylsulfonyl, R ⁷ is alkyl; halogen; nitro; cyano; alkylthio; alkylsulfinyl haloalkyl; alkoxyalkyl; alkenyl; haloalkenyl; alkynyl; or R ^A benzoylpyrazole compound or a salt thereof, an arylalkyl which may be substituted with ¹⁰ and R ⁸ , R ⁹ and R ¹⁰ are each independently halogen; alkyl; or alkoxy, a production method thereof, and an active ingredient thereof A method of controlling or inhibiting the growth of an undesirable plant by applying the herbicides contained therein and their herbicidally effective amount to an undesirable plant or a place where it grows.

(3) In the above formula (I), R ¹ is alkyl, R ² is a hydrogen atom, R ³ is alkyl, R ⁴ is alkyl, R ⁵ is alkoxy; haloalkoxy; O) OR ⁷ ; or 4,5-dihydroisoxazol-3-yl, wherein R ⁶ is alkylsulfonyl, or a benzoylpyrazole compound or a salt thereof, a production method thereof, a herbicide containing them as an active ingredient And a method of applying an effective amount of these herbicidal substances to an undesirable plant or a place where it grows to control or suppress the growth of the undesirable plant.

(4) A mixed herbicidal composition containing the benzoylpyrazole compound of the above formula (I) or a salt thereof and one or more active ingredient compounds of other herbicides, and an herbicidally effective amount thereof is not desirable. A method of applying to a plant or a place where it grows to control or suppress the growth of an undesirable plant.

  Next, examples of the present invention will be described, but the present invention is not limited thereto. Hereafter, the synthesis example of this invention compound is described.

Synthesis example 1
Synthesis of 5- (ethylthio) carbonyloxy-1-methylpyrazol-4-yl 3- (methoxycarbonyl) -2-methyl-4- (methylsulfonyl) phenyl ketone (Compound No. 1 below)
5-Hydroxy-1-methylpyrazol-4-yl 3- (methoxycarbonyl) -2-methyl-4- (methylsulfonyl) phenyl ketone (290 mg, 0.82 mmol) was dissolved in dry tetrahydrofuran (15 mL). Triethylamine (166 mg, 1.64 mmol) was added. Thereto was added a solution (4 mL) of 96% chlorothioformate S-ethyl (107 mg) in dry tetrahydrofuran in small portions while cooling with ice water, and the mixture was stirred for 90 minutes while gradually raising the reaction temperature to room temperature. The reaction solution was poured into ice water and extracted with ethyl acetate. The extract was dried over anhydrous sodium sulfate and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane: ethyl acetate = 6: 4) to obtain the desired product (202 mg, 0.46 mmol) (yield 56%) as an amorphous solid.

Synthesis example 2
Synthesis of 1-ethyl-5- (ethylthio) carbonyloxypyrazol-4-yl 3- (methoxycarbonyl) -2-methyl-4- (methylsulfonyl) phenyl ketone (Compound No. 2 below)
5-Hydroxy-1-ethylpyrazol-4-yl 3- (methoxycarbonyl) -2-methyl-4- (methylsulfonyl) phenyl ketone (510 mg, 1.39 mmol) was dissolved in dry tetrahydrofuran (20 mL). Triethylamine (281 mg, 2.78 mmol) was added. Thereto was added a solution (4 mL) of 96% chlorothioformate S-ethyl (217 mg) in dry tetrahydrofuran in small portions while cooling with ice water, and the mixture was stirred for 90 minutes while gradually raising the reaction temperature to room temperature. The reaction mixture was poured into ice water and extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane: ethyl acetate = 6: 4) to obtain an oily target product (417 mg, 0.92 mmol) (yield 66%).

Synthesis example 3
Synthesis of 5- (ethylthio) carbonyloxy-1-methylpyrazol-4-yl 3- (methoxy) -2-methyl-4- (methylsulfonyl) phenyl ketone (Compound No. 35 below)
(1) 3-Methoxy-2-methyl-4- (methylsulfonyl) benzoic acid (340 mg, 1.39 mmol) and 5-hydroxy-1-methylpyrazole hydrochloride (230 mg) in anhydrous methylene chloride (10 mL) Then, DCC (dicyclohexylcarbodiimide) (315 mg) and triethylamine (260 mg) were added at room temperature with stirring for 2 hours. The reaction mixture was filtered through celite, and the filtrate was concentrated. The residue was dissolved in 10 mL of anhydrous acetonitrile, a catalytic amount of triethylamine (260 mg) and acetone cyanohydrin were added, and the reaction solution was stirred at room temperature overnight. 150 mL of ethyl acetate was added, and the mixture was washed once with 1N aqueous hydrochloric acid and once with saturated brine. The organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel column chromatography (ethyl acetate: methanol = 9: 1) to give 5-hydroxy-1-methylpyrazole- 4-yl 3-methoxy-2-methyl-4- (methylsulfonyl) phenyl ketone (115 mg) was obtained.
¹ H-NMR (400 MHz CDCl ₃ δ ppm): 2.31 (s, 3H), 3.20 (s, 3H), 3.66 (s, 3H), 3.92 (s, 3H), 7.1 (br s, 1H), 7.29 (d , 1H, J = 7.6Hz), 7.30 (s, 1H), 7.85 (d, 1H, J = 7.6Hz).

(2) 5-hydroxy-1-methylpyrazol-4-yl 3-methoxy-2-methyl-4- (methylsulfonyl) phenyl ketone (100 mg, 0.3 mmol) was dissolved in dry tetrahydrofuran (5 mL) and triethylamine was dissolved. (61 mg) was added, followed by 96% S-ethyl chlorothioformate (50 mg) at room temperature. After the reaction solution was stirred for 1 hour, 150 mL of ethyl acetate was added. The mixture was washed twice with saturated brine, the organic layer was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane: ethyl acetate = 2: 1) to obtain an oily target product.

Synthesis example 4
Synthesis of 5- (ethylthio) carbonyloxy-1-methylpyrazol-4-yl 2-methyl-4- (methylsulfonyl) -3- (4,5-dihydroisoxazol-3-yl) phenyl ketone No.39)
5-hydroxy-1-methylpyrazol-4-yl 3- (4,5-dihydroisoxazol-3-yl) -2-methyl-4- (methylsulfonyl) phenyl ketone (100 mg, 2.75 × 10 ^-4 mol) was dissolved in anhydrous tetrahydrofuran (5 mL), and triethylamine (55 mg) was added, followed by 96% S-ethyl chlorothioformate (45 mg) at room temperature. The reaction solution was stirred for 1 hour, 150 mL of ethyl acetate was added, and the mixture was washed twice with saturated brine. The organic layer was dried over anhydrous sodium sulfate and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane: ethyl acetate = 6: 4) to obtain the desired product (82 mg) as an oil.

Synthesis example 5
Synthesis of 5- (ethylthio) carbonyloxy-1-methylpyrazol-4-yl 3- (difluoromethoxy) -2-methyl-4- (methylsulfonyl) phenyl ketone (Compound No. 38 below)
(1) 3- (Difluoromethoxy) -2-methyl-4- (methylsulfonyl) benzoic acid (500 mg, 1.78 mmol) and 5-hydroxy-1-methylpyrazole hydrochloride (288 mg) in anhydrous acetonitrile (10 mL 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (443 mg), triethylamine (360 mg) and dimethylaminopyridine (217 mg) were added at room temperature with stirring for 12 hours. The reaction mixture was concentrated under reduced pressure and the residue was dissolved in 100 mL of methylene chloride. After washing this solution with 100 mL of water, the organic layer was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The residue was dissolved in 10 mL of anhydrous acetonitrile, a catalytic amount of triethylamine (260 mg) and acetone cyanohydrin were added, and the mixture was stirred overnight at room temperature. 150 mL of methylene chloride was added and extracted with 1N aqueous potassium carbonate solution, and the aqueous layer was acidified with 2N hydrochloric acid. The obtained acidic aqueous solution was extracted twice with methylene chloride (100 mL), and the organic layers were combined and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the resulting crude product was purified by silica gel column chromatography (ethyl acetate: hexane = 1: 1 to 9: 1) to give oily 5-hydroxy-1-methylpyrazole- 4-yl 3- (difluoromethoxy) -2-methyl-4- (methylsulfonyl) phenyl ketone was obtained.
¹ H-NMR (400 MHz acetone-d ₆ δppm): 2.37 (s, 3H), 3.28 (s, 3H), 3.61 (s, 3H), 6.90 (d, 1H, J = 75.2Hz), 7.27 (s, 1H), 7.59 (d, 1H, J = 8.4Hz), 7.96 (d, 1H, J = 8.4Hz).

(2) 5-hydroxy-1-methylpyrazol-4-yl 3- (difluoromethoxy) -2-methyl-4- (methylsulfonyl) phenyl ketone (89 mg) was dissolved in dry tetrahydrofuran (5 mL) and triethylamine was dissolved. (50 mg) Subsequently, 96% S-ethyl chlorothioformate (40 mg) was added at room temperature. After the reaction solution was stirred for 1 hour, 150 mL of ethyl acetate was added. The mixture was washed twice with saturated brine, the organic layer was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane: ethyl acetate = 2: 1) to obtain an oily target product.

Synthesis Example 6
Synthesis of 5- (ethylthio) carbonyloxy-1-methylpyrazol-4-yl 3- (2-methoxyethoxy) -2-methyl-4- (methylsulfonyl) phenyl ketone (Compound No. 55 below)
(1) Under a nitrogen gas atmosphere, sodium hydride (60%, 220 mg, 5.32 mmol) was suspended in anhydrous N, N-dimethylformamide (10 mL), and 3-hydroxy-2-methyl-4- ( Methylsulfonyl) methyl benzoate (1 g, 4.09 mmol) was added at room temperature. After stirring for 30 minutes, 2-bromoethyl methyl ether (1.13 g, 8.18 mmol) and a catalytic amount of potassium iodide were added, and the reaction solution was stirred at 60 ° C. for 12 hours. To the reaction solution, 200 mL of ethyl acetate was added and washed twice with saturated brine. The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane: ethyl acetate = 1: 2) to give oily methyl 3- (2-methoxyethoxy) -2-methyl-4- (methylsulfonyl) benzoate (680 mg )
¹ H-NMR 400 MHz (CDCl ₃ δppm): 2.53 (s, 3H), 3.26 (s, 3H), 3.46 (s, 3H), 3.78 (m, 2H), 3.91 (s, 3H), 4.19 (m, 2H), 7.71 (d, 1H, J = 8.4Hz), 7.84 (d, 1H, J = 8.4Hz).

(2) Methyl 3- (2-methoxyethoxy) -2-methyl-4- (methylsulfonyl) benzoate (680 mg, 2.25 mmol) was dissolved in methanol (10 mL), and 20% strength aqueous sodium hydroxide solution was added. (2 mL) was added at room temperature. After stirring for 30 minutes, 100 mL of 1N hydrochloric acid was added to the reaction solution, and the mixture was extracted with ethyl acetate (200 mL). The organic layer was washed twice with saturated brine and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 3- (2-methoxyethoxy) -2-methyl-4- (methylsulfonyl) benzoic acid (570 mg) as a white solid.
¹ H-NMR 400MHz (acetone-d ₆ δppm): 2.56 (s, 3H), 3.31 (s, 3H), 3.41 (s, 3H), 3.80 (m, 2H), 4.21 (m, 2H), 7.81 ( s, 2H).

(3) 3- (2-methoxyethoxy) -2-methyl-4- (methylsulfonyl) benzoic acid (195 mg, 6.76 mmol) dissolved in chloroform (15 mL), oxalyl chloride (0.5 mL) and catalyst An amount of DMF was added. The reaction mixture was stirred at room temperature for 30 minutes and the solvent was removed under reduced pressure. The residue was dissolved in anhydrous THF (20 mL), 5-hydroxy-1-methylpyrazole hydrochloride (136 mg, 1.01 mmol), triethylamine (136 mg) and N, N-dimethylaminopyridine (250 mg) were added, Heated to reflux for 1 hour. The reaction mixture was cooled to room temperature, ethyl acetate (200 mL) was added, and the mixture was washed twice with saturated brine. The organic layer was dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The residue was dissolved in anhydrous acetonitrile (10 mL), triethylamine (136 mg) and a catalytic amount of acetone cyanohydrin were added, and the mixture was stirred at room temperature for 12 hours. The solvent was distilled off under reduced pressure to obtain crude 5-hydroxy-1-methylpyrazol-4-yl 3- (2-methoxyethoxy) -2-methyl-4- (methylsulfonyl) phenyl ketone.
¹ H-NMR (400MHz CDCl ₃ δppm): 2.39 (s, 3H), 3.29 (s, 3H), 3.46 (s, 3H), 3.71 (s, 3H), 3.81 (m, 2H), 4.24 (m, 2H), 7.34 (s, 1H), 7.35 (d, 1H, J = 7.6Hz), 7.92 (d, 1H, J = 7.6Hz).

(4) The crude 5-hydroxy-1-methylpyrazol-4-yl 3- (2-methoxyethoxy) -2-methyl-4- (methylsulfonyl) phenyl ketone obtained in the above step (3) is treated with anhydrous THF (10 To the mixture was added triethylamine (190 mg) and 96% S-ethyl chlorothioformate (151 mg), and the mixture was stirred at room temperature for 1 hour. Ethyl acetate (200 mL) was added to the obtained reaction mixture, and the mixture was washed twice with saturated brine. The organic layer was dried over anhydrous sodium sulfate and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane: ethyl acetate = 1: 1) to obtain the desired product (250 mg).

Synthesis example 7
Synthesis of 5- (ethylthio) carbonyloxy-1-ethylpyrazol-4-yl 3- (2-methoxyethoxy) -2-methyl-4- (methylsulfonyl) phenyl ketone (Compound No. 16 below)
(1) 3- (2-methoxyethoxy) -2-methyl-4- (methylsulfonyl) benzoic acid (200 mg, 6.90 × 10 ⁻⁴ mol) was dissolved in chloroform (15 mL), and oxalyl chloride (0.5 mL) was dissolved. mL) and a catalytic amount of DMF. The reaction mixture was stirred at room temperature for 30 minutes and the solvent was removed under reduced pressure. The residue was dissolved in anhydrous THF (20 mL), 5-hydroxy-1-ethylpyrazole hydrochloride (134 mg, 9.01 × 10 ^-4 mol), triethylamine (139 mg) and N, N-dimethylaminopyridine (170 mg). ) And heated to reflux for 1 hour. The reaction mixture was cooled to room temperature, ethyl acetate (200 mL) was added, and the mixture was washed twice with saturated brine. The organic layer was dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The residue was dissolved in anhydrous acetonitrile (10 mL), triethylamine (139 mg) and a catalytic amount of acetone cyanohydrin were added, and the mixture was stirred at room temperature for 12 hours. The solvent was distilled off under reduced pressure to obtain crude 5-hydroxy-1-ethylpyrazol-4-yl 3- (2-methoxyethoxy) -2-methyl-4- (methylsulfonyl) phenyl ketone.
¹ H-NMR (400MHz CDCl ₃ δppm): 1.40 (t, 3H, J = 7.0Hz), 2.39 (s, 3H), 3.25 (s, 3H), 3.42 (s, 3H), 3.76 (m, 2H) , 4.02 (q, 2H, J = 7.0Hz), 4.20 (m, 2H), 7.28 (s, 1H), 7.31 (d, 1H, J = 7.6Hz), 7.87 (d, 1H, J = 7.6Hz) .

(2) The crude 5-hydroxy-1-ethylpyrazol-4-yl 3- (2-methoxyethoxy) -2-methyl-4- (methylsulfonyl) phenyl ketone obtained in the step (1) is treated with anhydrous THF (10 To the mixture was added triethylamine (139 mg) and 96% S-ethyl chlorothioformate (111 mg), and the mixture was stirred at room temperature for 1 hour. Ethyl acetate (200 mL) was added to the obtained reaction mixture, and the mixture was washed twice with saturated brine. The organic layer was dried over anhydrous sodium sulfate and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane: ethyl acetate = 1: 1) to obtain the desired product (170 mg).

Synthesis Example 8
Synthesis of 5- (ethylthio) carbonyloxy-1-methylpyrazol-4-yl 3- (2,2-dimethoxyethoxy) -2-methyl-4- (methylsulfonyl) phenyl ketone (Compound No. 209 below)
(1) 3-hydroxy-2-methyl-4- (methylsulfonyl) benzoic acid (300 mg, 1.30 mmol) was dissolved in N, N-dimethylformamide (10 mL), and potassium carbonate (360 mg, 2.72 mmol) and bromo Acetaldehyde dimethyl acetal (660 mg, 3.90 mmol) was added at room temperature. The reaction mixture was heated to 80 ° C. and stirred for 32 hours. The reaction mixture was cooled to room temperature and 100 mL of water and 0.5 N aqueous sodium hydroxide (10 mL) were added. Thereafter, the mixture was extracted with ethyl acetate (200 mL), and the organic layer was dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain oily 2,2-dimethoxyethyl 3- (2,2-dimethoxyethoxy) -2-methyl-4- (methylsulfonyl) benzoate.
¹ H-NMR 400MHz (CDCl ₃ δppm): 2.54 (s, 3H), 3.31 (s, 1H), 3.39 (s, 6H), 3.44 (s, 6H), 4.06 (d, 2H, J = 5.4Hz) , 4.31 (d, 2H, J = 5.4Hz), 4.73 (t, 1H, J = 5.4Hz), 4.87 (t, 1H, J = 5.4Hz), 7.76 (d, 1H, J = 8.4Hz), 7.82 (d, 1H, J = 8.4Hz).

(2) Dissolve 2,2-dimethoxyethyl 3- (2,2-dimethoxyethoxy) -2-methyl-4- (methylsulfonyl) benzoate obtained in the step (1) in methanol (20 mL), A 20% strength aqueous sodium hydroxide solution (2 mL) was added at room temperature. After stirring for 30 minutes, 100 mL of 1N hydrochloric acid was added to the reaction solution, and the mixture was extracted with ethyl acetate (200 mL). The organic layer was washed twice with saturated brine and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 3- (2,2-dimethoxyethoxy) -2-methyl-4- (methylsulfonyl) benzoic acid (390 mg) as a white solid.
¹ H-NMR 400MHz (acetone-d ₆ δppm): 2.56 (s, 3H), 3.31 (s, 3H), 3.44 (s, 6H), 4.06 (d, 2H, J = 5.2Hz), 4.88 (t, 1H, J = 5.2Hz), 7.82 (br s, 2H).

(3) 3- (2,2-dimethoxyethoxy) -2-methyl-4- (methylsulfonyl) benzoic acid (390 mg, 1.23 mmol) was dissolved in chloroform (15 mL), and oxalyl chloride (0.5 mL) and A catalytic amount of DMF was added. The reaction mixture was stirred at room temperature for 30 minutes and the solvent was removed under reduced pressure. Dissolve the residue in anhydrous THF (20 mL), add 5-hydroxy-1-methylpyrazole (132 mg, 1.35 mmol), triethylamine (250 mg) and N, N-dimethylaminopyridine (300 mg) for 1 hour. Heated to reflux. The reaction mixture was cooled to room temperature, ethyl acetate (200 mL) was added, and the mixture was washed twice with saturated brine. The organic layer was dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The residue was dissolved in anhydrous acetonitrile (10 mL), triethylamine (250 mg) and a catalytic amount of acetone cyanohydrin were added, and the mixture was stirred at room temperature for 12 hours. The solvent was distilled off under reduced pressure to obtain crude 5-hydroxy-1-methylpyrazol-4-yl 3- (2,2-dimethoxyethoxy) -2-methyl-4- (methylsulfonyl) phenyl ketone.
¹ H-NMR (400MHz CDCl ₃ δppm): 2.38 (s, 3H), 3.29 (s, 3H), 3.47 (s, 6H), 3.70 (s, 3H), 4.09 (d, 2H, J = 5.2Hz) , 4.1 (br s, 1H), 4.83 (t, 1H, J = 5.2Hz), 7.32 (s, 1H), 7.35 (d, 1H, J = 8.4Hz), 7.91 (d, 1H, J = 8.4Hz ).

(4) The crude 5-hydroxy-1-methylpyrazol-4-yl 3- (2,2-dimethoxyethoxy) -2-methyl-4- (methylsulfonyl) phenyl ketone obtained in the step (3) is treated with anhydrous THF. (10 mL), triethylamine (250 mg) and 96% S-ethyl chlorothioformate (200 mg) were added, and the mixture was stirred at room temperature for 1 hour. Ethyl acetate (200 mL) was added to the obtained reaction mixture, and the mixture was washed twice with saturated brine. The organic layer was dried over anhydrous sodium sulfate and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane: ethyl acetate = 1: 1) to obtain the desired product (150 mg).

Next, typical examples of the compounds of the present invention represented by the formula (I) are listed in Table ¹ , and their ¹ H-NMR spectral data are listed in Table 2. Further, representative examples of the compound represented by the formula (II) as the synthetic intermediate are listed in Table 3, and their ¹ H-NMR spectral data are listed in Table 4. These compounds can be synthesized based on the above synthesis examples or various production methods of the above-described compounds of the present invention. In Tables 1 to 4, No. represents a compound number. In Tables 1 and 3, Me is a methyl group, Et is an ethyl group, n-Pr group is a normal propyl group, i-Pr is an isopropyl group, c-Pr is a cyclopropyl group, s-Bu represents a secondary butyl group, t-Bu represents a tertiary butyl group, Ph represents a phenyl group, and Bn represents a benzyl group.

Next, test examples are described.
Test example 1
A field crop soil was filled in a 1 / 170,000 hectare pot and seeds of various plants were sown. After that, the plant has a certain leaf age ((1) Nobier: 0.8-2.5 leaf stage, (2) Barnyard grass: 0.5-3.0 leaf stage, (3) Enokorogusa: 1.0-3.0 leaf stage, (4) Aogaeto: cotyledon-2.0 Leaf stage, (5) American king deer: cotyledon-1.1 leaf stage, (6) citrus: cotyledon-1.5 leaf stage, (7) rice: 1.0-2.5 leaf stage, (8) wheat: 1.7-3.4 leaf stage, ( 9) Corn: 2.0 to 3.5 leaf stage, (10) Soybean: primary leaf to 0.3 leaf stage), and a wettable powder or emulsion prepared according to a conventional formulation method is used as the predetermined amount of active ingredient. And was diluted with water equivalent to 500 liters per hectare. Further, 0.1% by volume of an agricultural spreading agent was added to the diluted solution, and the leaves were treated with a small spray.
From 17 to 23 days after drug treatment, the growth state of various plants was observed with the naked eye, and the herbicidal effect was evaluated with a growth inhibition rate (%) of 0 (equivalent to the untreated group) to 100 (completely killed). The table results were obtained.

Test example 2
A field crop soil was filled in a 1 / 170,000 hectare pot, and seeds of various plants (Nobie, mosquito, Enocologosa, Aogaeto, American golden deer, Ichibi, rice, wheat, corn and soybean) were sown. On the day after sowing, the wettable powder or emulsion prepared according to the usual formulation method of the compound of the present invention is weighed so as to have a predetermined active ingredient amount, diluted in water equivalent to 500 liters per hectare, and treated with a small spray. did.
From 19 to 24 days after drug treatment, the growth state of various plants was observed with the naked eye, and the herbicidal effect was evaluated with a growth inhibition rate (%) of 0 (equivalent to the untreated group) to 100 (completely killed). The table results were obtained.

Next, formulation examples of the present invention will be described.
Formulation Example 1
(1) Compound of the present invention 75 parts by weight (2) Geropone T-77 (trade name; manufactured by Rhone-Poulenc) 14.5 parts by weight (3) NaCl 10 parts by weight (4) dextrin 0.5 parts by weight or more The ingredients are put into a high-speed mixing fine granulator, 20% water is further added thereto, and granulated and dried to obtain a granulated wettable powder.

Formulation Example 2
(1) Kaolin 78 parts by weight (2) Labelin FAN (trade name; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 2 parts by weight (3) Solpol 5039 (trade name; manufactured by Toho Chemical Industry Co., Ltd.) 5 parts by weight (4 ) Carplex (trade name; manufactured by DSL Japan Co., Ltd.) 15 parts by weight or more, the mixture of the components (1) to (4) and the compound of the present invention are mixed at a weight ratio of 9: 1 to obtain a wettable powder. can get.

Formulation Example 3
(1) High filler No. 10 (trade name; manufactured by Matsumura Sangyo Co., Ltd.) 33 parts by weight (2) Solpol 5050 (trade name; manufactured by Toho Chemical Co., Ltd.) 3 parts by weight (3) Solpol 5073 (trade name; Toho Chemical Industries, Ltd.) Product) 4 parts by weight (4) Compound of the present invention 60 parts by weight or more of (1) to (4) are mixed to obtain a wettable powder.

Formulation Example 4
(1) Compound of the present invention 4 parts by weight (2) bentonite 30 parts by weight (3) calcium carbonate 61.5 parts by weight (4) Toxanone GR-31A (trade name; manufactured by Sanyo Chemical Industries, Ltd.) 3 parts by weight (5 ) Calcium lignin sulfonate 1.5 parts by weight Premixed (1), (2) and (3), mixed with (4), (5) and water, and extruded Grain. Thereafter, the granules are obtained by drying and sizing.

Formulation Example 5
(1) Compound of the present invention 30 parts by weight (2) Siegrite (trade name; manufactured by Siegrite Co., Ltd.) 60 parts by weight (3) New Calgen WG-1 (trade name; manufactured by Takemoto Yushi Co., Ltd.) 5 parts by weight (4) New Calgen FS-7 (trade name; manufactured by Takemoto Yushi Co., Ltd.) 5 parts by weight (1), (2) and (3) are mixed, passed through a pulverizer, and (4) is added. After kneading, extrusion granulation is performed. Thereafter, it is dried and sized to obtain a granulated wettable powder.

Formulation Example 6
(1) Compound of the present invention 28 parts by weight (2) Sopropol FL (trade name; manufactured by Rhone-Poulein) 2 parts by weight (3) Solpol 355 (trade name; manufactured by Toho Chemical Co., Ltd.) 1 part by weight (4) IP solvent 1620 (trade name; manufactured by Idemitsu Petrochemical Co., Ltd.) 32 parts by weight (5) ethylene glycol 6 parts by weight (6) water 31 parts by weight or more of components (1) to (6) are mixed and wet pulverized An aqueous suspension is obtained by pulverization using a machine (Dyno-Mill).

Claims (2)

  5-hydroxy-1-ethylpyrazol-4-yl 3- (2-methoxyethoxy) -2-methyl-4- (methylsulfonyl) phenyl ketone.   3- (2-methoxyethoxy) -2-methyl-4- (methylsulfonyl) benzoic acid.