WO2002076962A1 - Process for producing 3-oxo-2-(2-thiazolyl)propanenitrile and intermediate - Google Patents

Abstract

A process for producing a 3-oxo-2-(2-thiazolyl)propanenitrile useful as an intermediate for agricultural chemicals, medicines, etc., especially as an intermediate for an acrylonitrile derivative which is an active ingredient for insecticides or acaricides. Provided are: a novel compound represented by the formula (2); a process for producing the compound (2) which comprises reacting a compound represented by the formula (3) with a compound represented by the formula (4); and a process for producing a compound represented by the formula (1) which comprises causing ammonia to act on the compound (2). (In the formulae, Z represents nitro, cyano, etc.; Y represents halogeno, C1-6 alkyl, etc.; R represents hydrogen, C1-6 alkyl, etc.; X represents halogeno; and n and m each independently is an integer of 0 to 5.) (4) (3) → (2) (2) → (1).

Description

 Specification

 Method for producing 3-oxo 2- (2-thiazolyl) propanenitrile and intermediates

 The present invention relates to a method for producing 3-oxo-l2- (2-thiazolyl) propanenitrile, which is useful as an intermediate for producing agricultural chemicals and the like, particularly an intermediate for producing an acrylonitrile derivative which is an active ingredient of insecticides and acaricides. For new intermediates. Background technology:

 Formula (I)

(Wherein, Y ′ and Z ′ each represent an alkyl group or the like, and m ′ and η ′ each represent 0 or an integer of 1 to 5). It is useful as an intermediate material for insecticides described in 74 and the like, and is a compound that is expected to have physiological activities such as agricultural chemicals and pharmaceuticals by itself. Conventionally, as a method for producing the compound of formula (I), as shown in the following reaction formula, cyanothioacetamide (Π) is reacted with phenacyl halide (m) to obtain cyanomethylthiazane. There is known a method in which benzoyl (IV) is obtained, and further benzoylation of cyanomethylthiazole (IV) is performed using benzoyl halide (V) (EP. 82602031). And WO97 / 40909, etc.).

(In the formula, Y ′, Z ′, m ′ and n ′ have the same meaning as described above, and X ′ represents a halogen atom.) According to this method, the target compound (I) can be obtained in a relatively high yield. Although it can be obtained, the cyanothioacetamide (II) used as a reaction raw material is expensive and disadvantageous for industrial mass production. It is.

DISCLOSURE OF THE INVENTION:

 An object of the present invention is to provide a production method capable of industrially producing 3-oxo-1- (2-thiazolyl) propane nitrile in an industrially advantageous manner.

 The present inventors have diligently studied a production method capable of obtaining 3-oxo-1- (2-thiazolyl) propane nitrile in high yield without using expensive cyanothioacetamide, and as a result, (2)

(Wherein, Z is a nitro group, Shiano group, a halogen atom, Ji alkyl group, Ji Le ₆ Haroaruki group, an alkoxy group, which may have an optionally substituted Fuweniru group or a substituted group Represents a good phenoxy group, n represents 0 or an integer of 1 to 5, Y represents a halogen atom, a C _x - ₆ alkyl group, a C i- ₆ alkoxy group or a substituent which may have a substituent. And m represents 0 or an integer of 1 to 5, R represents a hydrogen atom, an ^ alkyl group or a metal atom.) A compound represented by the following formula: By applying the above, the yield can be improved by the formula (1)

 (Wherein, Y, Z, m and η have the same meanings as described above).

 In addition, the present inventors have prepared a dithiocarboxy group-introduced dithiocarboxy group of the formula (3)

(式中、 Y、 mは、 前記と同じ意味を表し、 Xはハロゲン原子を表す。） で表される化合物 とを反応させることにより前記式 （2) で表される化合物とした後、 このものにアンモニ ァを作用させることにより、 目的物が高収率で得られることを見出し、 本発明を完成する に到った。 (Wherein, Z, n and R represent the same meaning as described above), and a compound represented by the formula (4):

(Wherein, Y and m represent the same meaning as described above, and X represents a halogen atom.) The compound represented by the formula (2) is reacted with It has been found that the desired product can be obtained in high yield by reacting ammonia on the product, and the present invention has been completed.

 That is, first, the present invention provides a method for producing a compound represented by the above formula (1), wherein ammonia is allowed to act on the compound represented by the above formula (2).

 The present invention secondly provides a compound represented by the above formula (3).

 Thirdly, the present invention provides a method for producing a compound represented by the formula (2), comprising reacting a compound represented by the formula (3) with a compound represented by the formula (4). Provide a way. A fourth aspect of the present invention is a step of obtaining a compound represented by the formula (2) by reacting a compound represented by the formula (4) with a compound represented by the formula (3); There is provided a method for producing a compound represented by the above formula (1), comprising a step of reacting the obtained compound represented by the formula (2) with ammonia.

 ADVANTAGE OF THE INVENTION According to this invention, 3-oxo-1-2- (2-thiazolyl) propane nitrile can be obtained in high yield, without using expensive cyanothioacetamide. Further, according to the present invention, a production intermediate of the production method of the present invention and a production method thereof are provided. Embodiment of the invention:

 Hereinafter, the present invention will be described in detail.

 A first aspect of the present invention is a method for producing a compound represented by the formula (1), wherein ammonia is allowed to act on the compound represented by the formula (2).

式 （1) 及び （2) において、 Ζは、 ニトロ基；シァノ基；フッ素、 塩素、 臭素、 ヨウ 素等のハロゲン原子；メチル、 ェチル、 η—プロピル、 イソプロピル、 η—プチル、 s e c—ブチル、イソブチル、 t—プチル、 n—ペンチル、 n—へキシル等の Ci_₆アルキル基； クロロメチル、 フルォロメチル、 プロモメチル、 ジクロロメチル、 ジフルォロメチル、 ジ プロモメチル、 トリクロロメチル、 トリフルォロメチル、 トリブロモメチル、 トリクロ口 ェチル、 トルフルォロェチル、ペンタフルォロェチル等の Ci一 ₆ハロアルキル基；メトキシ、 エトキシ、 n_プロボキシ、 イソプロボキシ、 n—ブトキシ、 s e c—ブトキシ、 イソブ トキシ、 t—ブトキシ等の C ₆アルコキシ基；置換基を有していてもよいフエニル基又は 置換基を有していてもよいフヱノキシ基を表す。

In the formulas (1) and (2), Ζ represents a nitro group; a cyano group; a halogen atom such as fluorine, chlorine, bromine, or iodine; methyl, ethyl, η-propyl, isopropyl, η-butyl, sec-butyl, isobutyl, t-heptyl, n- pentyl, CI_ ₆ alkyl cyclohexyl, etc., to n-; chloromethyl, Furuoromechiru, Promo methyl, dichloromethyl, Jifuruoromechiru, di promo, trichloromethyl, triflumizole Ruo Russia, tribromomethyl, Ci- ₆ haloalkyl groups such as trichloroethyl, tolufluoroethyl, and pentafluoroethyl; C such as methoxy, ethoxy, n_propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, and t-butoxy ₆ alkoxy group; which may have an optionally substituted phenyl group or a substituted group It represents a Fuwenokishi group.

Examples of the substituent of the phenyl group and the phenyl group include halogen atoms such as fluorine, chlorine, bromine, and iodine; methyl, ethyl, n-propyl, isopropyl, n-butyl, and t_butyl. And c- ₆ alkyl groups; chloromethyl, trifluoromethyl, trifluorofluoryl, pentafluoroethyl and the like; 6 haloalkyl groups; methoxy, ethoxy and the like d-6 alkoxy groups; and the like. Further, the phenyl group and the phenoxy group may have the same or different plural substituents.

 n represents 0 or an integer of 1 to 5.

 R represents a hydrogen atom; an alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isoptyl, t-butyl, n-pentyl, n-hexyl; or a metal atom. Examples of the metal atom include: alkali metal atoms such as lithium, potassium, and sodium; alkaline earth metals such as magnesium and potassium; transition metals such as copper, zinc, iron, cobalt, nickel, and manganese; and aluminum and tin. Typical metals; and the like, with preference given to alkali metals.

Y is a halogen atom such as fluorine, chlorine, bromine and iodine; C such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, n-pentyl and n-hexyl ₆ alkyl group; ( ₆ alkoxy group such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, t-butoxy, etc .; or a phenyl group optionally having a substituent.

Examples of the substituent of the phenyl group include halogen atoms such as fluorine, chlorine, bromine and iodine; ( ₆ alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl and t-butyl; chloromethyl, trifluoromethyl) A Ci-e haloalkyl group such as chloromethyl, trifluoroethyl and pentafluoroethyl; a C-i-s alkoxy group such as methoxy and ethoxy; It may have a plurality of different substituents.

 m represents 0 or an integer of 1 to 5. As a method of reacting ammonia with the compound represented by the formula (2), any method can be used in which the compound represented by the formula (1) can be obtained by reacting the compound represented by the formula (2) with ammonia. There are no particular restrictions. For example, a method of blowing ammonia gas into a solution of the compound represented by the formula (2) with stirring, a method of adding aqueous ammonia to a solution of the compound represented by the formula (2), and the like can be given.

 Examples of the solvent used in the reaction include water; alcohol solvents such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, and t-butyl alcohol; getyl ether, tetrahydrofuran, Ether solvents such as 1,2-dimethoxyethane and dioxane; nitrile solvents such as acetonitrile and benzonitrile; and aromatic hydrocarbon solvents such as benzene, toluene and xylene. These solvents can be used alone or in combination of two or more. Among these, in the present invention, the use of alcoholic solvents such as methanol and ethanol is preferred. The amount of the solvent to be used is generally in the range of 1 to 100 ml, preferably 3 to 2 Oml, per 1 g of the compound represented by the formula (2).

The reaction proceeds smoothly in the range of 0 to 50 ° C, preferably 10 to 20 ° C. After completion of the reaction, the desired compound represented by the above formula (1) can be obtained by performing ordinary post-treatment.

 The resulting tautomer represented by the formula (1) may have, for example, the following tautomers. These are all included in the present invention.

 Next, a method for producing the compound represented by the above formula (2), which is the third invention, which is a raw material for the above reaction, will be described.

 The compound represented by the formula (2) can be produced by reacting a compound represented by the formula (3) with a compound represented by the formula (4).

式 （2 )、 （3 ) 及び （4 ) において、 Z、 Y、 R、 m及び nは、 前記と同じ意味を表す。

In the formulas (2), (3) and (4), Z, Y, R, m and n have the same meaning as described above.

X represents a halogen atom such as fluorine, chlorine, bromine and iodine.

 As a method of reacting the compound represented by the formula (3) with the compound represented by the formula (4), the compound represented by the formula (3) is reacted with the compound represented by the formula (4). The method is not particularly limited as long as it can obtain the compound represented by the formula (2). In the present invention, from the viewpoint of performing the reaction efficiently, a compound represented by the formula (4) is added at a predetermined reaction temperature to a solution of the compound represented by the formula (3) dissolved in an appropriate solvent. After dropping, a method of stirring at a predetermined temperature for a predetermined time is preferable. The amount of the compound represented by the formula (4) to be used is generally in the range of 0.5 to 5 mol, preferably 1 to 3 mol, per 1 mol of the compound represented by the formula (3).

Examples of the solvent to be used include water; alcohol solvents such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, and t-butyl alcohol; getyl ether, tetrahydrofuran, Ether solvents such as 1,2 dimethyloxetane and dioxane; nitrile solvents such as acetonitrile and benzonitrile; and aromatic hydrocarbon solvents such as benzene, toluene and xylene; I can do it. These solvents can be used alone or in combination of two or more. Among these, in the present invention, use of acetonitrile is preferred. The amount of the solvent to be used is generally 1-100 ml, preferably 10-40 ml, per 1 g of the compound represented by the formula (3).

 The reaction proceeds smoothly in the range of usually 0 to 50 ° C, preferably 5 to 15 ° C, and is completed usually in several minutes to 10 hours, preferably in 1 to 5 hours.

 In this reaction, hydrogen halide is generated. If hydrogen halide adversely affects the reaction system, use an organic base such as triethylamine or an inorganic base such as sodium hydroxide or sodium bicarbonate to remove (neutralize) the hydrogen halide as necessary. You can also. After completion of the reaction, the compound represented by the formula (2) can be obtained by performing ordinary post-treatments, if necessary.

 The compounds represented by the formula (2) which can be produced in this way are exemplified in Table 1. Abbreviations in the table have the following meanings.

Me: methyl, Et: ethyl, Pr: propyl, iPr: isopropyl, Ph: phenyl

Table 1

Zn Ym R Zn Ym R Zn Ym R-N0 ₂ 2-FH 2-F 2- CI H 2-F 2-O'Pr H-N0 ₂ 2-F Me 2-F 2- CI Me 2-F 2- 0 ^ Me-N0 ₂ 2-F Na 2-F 2-CI Na 2-F 2-O'Pr Na-N0 ₂ 2— Me H 2-F 2-Br H 2-F 2-OCF3 H-N0 ₂ 2-Me Me 2-F 2-Br Me 2-F 2-OCF3 Me-N0 ₂ 2-Me Na 2-F 2-Br Na 2-F 2-OCF3 Na-N0 ₂ 2-CF ₃ H 2-F 2-Me H 2-F 2-Ph H-N0 ₂ 2-CF ₃ Me 2-F 2-Me Me 2-F 2-Ph Me-N0 ₂ 2-CF3 Na 2-F 2-Me Na 2-F 2-Ph Na-N0 ₂ 2-OMe H 2-F 2-Et H 2-F 3-Me H-N0 ₂ 2-OMe Me 2-F 2-Et Me 2-F 3-Me Me- 0 ₂ 2 -OMe Na 2-F 2-Et Na 2-F 3-Me Na-CN 2-FH 2-F 2-Pr H 2-F 3-CI H -CN 2-F Me 2-F 2- Pr Me 2 -F 3- CI Me -CN 2-F Na 2-F 2-Pr Na 2-F 3- CI Na-CN 2-Me H 2-F 2-CF ₃ H 2-F 3-CF3 H -CN 2 -Me Me 2-F 2-CF3 Me 2-F 3-CF ₃ Me -CN 2-Me Na 2-F 2-CF ₃ Na 2-F 3-CF3 Na -CN 2-CF3 H 2-F 2- CH ₂ CF ₃ H 2-F 3- OMe H -CN 2-CF3 Me 2-F 2 F3 Me 2-F 3-OMe Me -CN 2-CF ₃ Na 2-F 2-CH ₂ CF ₃ Na 2- F 3- OMe Na -CN 2-OMe H 2-F 2-OMe H 2-F 4-Me H -CN 2-OMe Me 2-F 2-OMe Me 2-F 4-Me Me -CN 2-OMe Na 2-F 2-OMe Na 2-F 4-Me Na

2-F 2-F H 2-F 2-OEt H 2-F 4-F H

2-F 2-F Me 2-F 2-OEt Me 2-F 4-F Me

2-F 2-F Na 2-F 2-OEt Na 2-F 4-F Na Table 1 (continued)

Zn Ym R Zn Ym R Zn Ym -F 4-CI H 2-F 3,5-F ₂ H 2-Me 2-Br -F 4-CI Me 2-F 3, 5-F ₂ Me 2-Me 2 -Br -F 4-CI Na 2-F 3, 5-F ₂ Na 2-Me 2-Br -F 4-CF3 H 2-CI 2-FH 2-Me 2-Me -F 4-CF3 Me 2- CI 2-F Me 2-Me 2-Me -F 4-CF3 Na 2-CI 2-F Na 2-Me 2-Me -F 4-OMe H 2-CI 2— Me H 2-Me

-F 4-OMe Me 2-CI 2-Me Me 2-Me 2-Et -F 4-OMe Na 2-CI 2-Me Na 2-Me 2-Et -F 2,4-Me ₂ H 2-CI 2-CF ₃ H 2-Me 2-ipr -F 2, 4-Me ₂ Me 2-CI 2-CF3 Me 2-Me

-F 2, 4- e ₂ Na 2-CI 2-CFg Na 2-Me

-F 2, 4-F ₂ H 2-CI 2-OMe H 2-Me 2-CF3 -F 2,4- F ₂ Me 2-CI 2-OMe Me 2-Me 2-CF3 -F 2, 4- F ₂ Na 2-CI 2-OMe Na 2-Me 2-CF3 -F 2, 4-Cl ₂ H 2-Br 2-FH 2-Me 2-CH ₂ CF ₃ -F 2, 4-CI ₂ Me 2 -Br 2-F Me 2-Me 2-CH ₂ CF ₃

 M C

-F 2, 4-CI ₂ Na 2-Br 2-F Na 2-Me 2- CH ₂ CF ₃

 UJ

2-F 2, 6-Me ₂ H 2-Br 2-Me H 2-Me 2-O ~ T3Me -F 2, 6-Me ₂ Me 2-Br 2-Me Me 2-Me 2-OMe

2-F 2, 6-Me ₂ Na 2-Br 2-Me Na 2-Me 2-OMe

2-F 2, 6-F2 H 2-Br 2-CF ₃ H 2-Me 2-OEt

2-F 2, 6-F2 Me 2-Br 2-CFg Me 2-Me 2-OEt

2-F 2, 6-F2 Na 2-Br 2-CF3 Na 2-Me 2-OEt

2-F 2, 6-CI2 H 2-Br 2-OMe H 2-Me 2-0 ^! Pr

2-F 2, 6-CI2 Me 2-Br 2-OMe Me 2-Me 2-O ⁱ Pr

2-F 2, 6-CI2 Na 2-Br 2-OMe Na 2-Me 2-o'Pr

2-F 2, 6-(GF3) 2 H 2— Me 2-F H 2-Me 2-OCF3

2-F 2, 6- (CF3) 2 Me 2 -Me, 2-F Me 2-Me 2-OCF ₃

2-F 2,6--(GF3) 2 Na 2-Me 2-F Na 2-Me 2-OCF3

2-F 3, 5-Me2 H 2-Me 2-CI H 2-Me 2-Ph

2-F 3, 5-Me2 Me 2-Me 2-CI Me 2-Me 2-Ph

2-F 3, 5-Me2 Na 2-Me 2-CI Na 2-Me 2-Ph Table 1 (continued)

2-OMe Me- Me 3-Me Na 2 - Me 2, 4 - Cl₂ Na 2-Et 2-OMe Na - Me 3-CI H 2-Me 2， 6-Me₂ H 2- 2-F H - Me 3-CI Me 2-Me 2, 6- e₂ Me 2^JPr 2-F Me - Me 3-CI Na 2M C-Me 2, 6- Me₂ Na 2^JPr 2-F Na - Me 3-CF₃ H 2-M m me 2， 6— F₂ H 2^JPr 2-Me H- Me 3-CF₃ Me 2-Me 2， 6-F₂ Me 2^JPr 2-Me Me-Me 3-CF3 Na 2-Me 2, 6-F₂ Na 2^JPr 2-Me Na - Me 3-OMe H 2-Me 2, 6-CI₂ H 2^JPr 2-CF3 H-Me 3-OMe Me 2-Me 2, 6-Cl₂ Me 2- 2-CF3 Me-Me 3-OMe H 2 - Me 2, 6-CI₂ Na 2^JPr 2-CF3 Na-Me 4-Me Me 2 - Me 2, 6-(CF₃)₂ H 2 - 2-OMe H-Me 4 - Me Me 2-Me 2, 6-(CF₃) ₂ Me 2- 2-OMe Me-Me 4-Me Na 2-Me 2, 6-(CF₃)₂ Na 2^JPr 2-OMe Na-Me 4-F H 2-Me 2-Cト 6-F H 2-CF3 2-F H-Me 4 - F Me 2-Me 2-CI-6-F Me 2-CF3 CM 2-F Me-Me 4-F Na 2-Me 2-CI-6-F Na 2-CF3 2-F Na Zn Ym R Zn Ym R Zn Ym R-Me 3-Me H 2-Me 2, 4-CI ₂ H 2-Et 2-OMe H- Me 3-Me Me 2-Me 2, 4-CI ₂ Me

2-OMe Me- Me 3-Me Na 2-Me 2, 4--Cl ₂ Na 2-Et 2-OMe Na-Me 3-CI H 2-Me 2, 6-Me ₂ H 2- 2-FH-Me 3-CI Me 2-Me 2, 6- e ₂ Me 2 ^J Pr 2-F Me-Me 3-CI Na 2M C-Me 2, 6- Me ₂ Na 2 ^J Pr 2-F Na-Me 3-CF ₃ H 2-M mm 2, 6—F ₂ H 2 ^J Pr 2-Me H-Me 3-CF ₃ Me 2-Me 2, 6-F ₂ Me 2 ^J Pr 2-Me Me-Me 3-CF3 Na 2-Me 2, 6-F ₂ Na 2 ^J Pr 2-Me Na-Me 3-OMe H 2-Me 2, 6-CI ₂ H 2 ^J Pr 2-CF3 H-Me 3-OMe Me 2-Me 2, 6-Cl ₂ Me 2- 2-CF3 Me-Me 3-OMe H 2-Me 2, 6-CI ₂ Na 2 ^J Pr 2-CF3 Na-Me 4-Me Me 2-Me 2, 6- ( CF ₃ ) ₂ H 2-2-OMe H-Me 4-Me Me 2-Me 2, 6- (CF ₃ ) ₂ Me 2- 2-OMe Me-Me 4-Me Na 2-Me 2, 6- ( CF ₃ ) ₂ Na 2 ^J Pr 2-OMe Na-Me 4-FH 2-Me 2-C 6-FH 2-CF3 2-F H-Me 4-F Me 2-Me 2-CI-6-F Me 2-CF3 CM 2-F Me-Me 4-F Na 2-Me 2-CI-6-F Na 2-CF3 2-F Na

 m

-Me 3-CI H 2-Me 3,5- Me ₂ H 2-CF3 2-CI H-Me 3-CI Me 2-Me 3,5- Me ₂ Me 2-CF3 2-CI Me-Me 3- CI Na 2-Me 3,5-Me ₂ Na 2-CF3 2-CI Na-Me 4-CF3 H 2-Me 3,5- F ₂ H 2-CFg 2-Br H-Me 4-CF3 Me 2- Me 3,5- F ₂ Me 2-CF3 2-Br Me-Me 4-CF ₃ Na 2-Me 3,5- F ₂ Na 2-CFg 2-Br Na-Me 4-OMe H 2- Et 2- FH 2-CF3 2-Me H-Me 4-OMe Me 2-F Me 2-CFg 2-Me Me-Me 4-OMe Na 2- Et 2-F Na 2-CF3 2-Me Na-Me 2, 4 One Me ₂ H 2-Me H 2-CF3 H-Me 2, 4- Me ₂ Me 2- Et 2-Me Me 2-CF3 2-Et Me- Me 2, 4-Me ₂ Na 2-Et 2-Me Na 2-CF ₃ Na-Me 2, 4-F ₂ H 2-CF ₃ H 2-CF3 2- Pr H-Me 2, 4-F ₂ Me 2-Et 2- CF ₃ Me 2-CFg 2- Pr Me-Me 2, 4-F ₂ Na 2-Et 2-CF3 Na 2-CF ₃ 2- Pr Na Table 1 (continued)

Zn Ym R Zn Ym R Zn Ym-CF ₃ 2-CF3 H 2-CF3 4 Me H 2-CFg 2-CI-6-F- CF ₃ 2-CFg Me 2-CF3 4— Me Me 2-CFg 2 _{-CI-6-F-CF 3} 2 - C OF 3 Na 2-CF3 4 one Me Na 2-CFg 2-CI -6-F m

-CF ₃ 2-CH ₂ CF ₃ H 2-CFg 4-FH 2-CF ₃ 2, 6-CI ₂ -CF ₃ 2-CH ₂ CF ₃ Me 2-CFg 4-F Me 2-CF ₃ 2, 6 -CI ₂ -CF3 2-CH ₂ CF ₃ Na 2-CF3 4-F Na 2-CF3 2, 6-CI ₂ -CF3 2-OMe H 2-CF3 4- CI H 2-CFg 2, 6- (CF ₃ ) ₂ -CF3 2-OMe Me 2-CF3 4- CI Me 2-CFg 2, 6- (CF ₃ ) ₂ -CF ₃ 2-OMe Na 2-CF3 4-CI Na 2-CF ₃ 2, 6- (CF ₃ ) ₂ -CF3 2-OEt H 2-CF3 4-CF ₃ H 2-CF ₃ 3,5-Me ₂ -CFg 2-OEt e 2-CF3 4-CF3 Me 2-CFg 3,5-Me ₂ -CF3 Na 2-CFg 4-CF3 Na 2-CF3 3,5-Me ₂ -CF3 2-O'Pr H 2-CF3 4-OMe H 2-CF3 3,5-F ₂ -CFg 2-0 Me 2-CF3 4-OMe Me 2-CF3 3,5- F ₂ -CFg 2-O'Pr Na 2-CFg 4-OMe Na 2-CFg 3,5-F ₂ -CF3 2-OCF3 H 2-CF3 2 _{, 4-Me 2 H 2-} CH 2 CF 3 2-F-CFg 2-OCF3 Me 2-CF3 2, 4-Me 2 Me 2-CH 2 CF 3 2 - F-CFg 2-OCF3 Na 2-CFg 2 , 4-Me ₂ Na 2-CH ₂ CF ₃ 2-F-CF ₃ 2-Ph H 2-CFg 2, 4-F ₂ H 2-GH2CF3 2-Me-CF3 2-Ph Me 2-CF3 2, 4 -F ₂ Me 2 ^— CH2CF3 2-Me-CFg 2-Ph Na 2-CF3 2, 4-F ₂ Na 2-CH ₂ CF ₃ 2— Me-CF ₃ 3-Me H 2-CFg 2, 4-CI _{2 H 2-CH 2 CF 3} 2-CFg-CFg 3 - Me Me 2-CFg 2, 4-CI 2 Me 2-CH 2 CF 3 2 - CF 3 -CFg 3- Me Na 2-CF3 2, 4- Cl ₂ Na 2-CH ₂ CF ₃ 2-CFg- CF ₃ 3-CI H 2-CF3 2, 6-Me ₂ H 2-CH ₂ CF ₃ 2-OMe-CFg 3-CI Me 2-CF3 2, 6-Me ₂ Me 2-CH ₂ CF ₃ 2-OMe-CF ₃ 3-CI Na 2-CFg 2, 6-Me ₂ Na 2 ^— CH Crs 2-OMe-CF3 3- CF ₃ H 2-CF ₃ 2, 6-F ₂ H 2-OMe 2-F-CFg 3-CFg Me 2-CFg 2, 6-F ₂ Me 2-OMe 2-F-CF ₃ 3-CF ₃ Na 2-CF ₃ 2, 6-F ₂ Et 2 -OMe 2-F-CFg 3-0 Me H 2-CFg 2, 6- F ₂ Pr 2-OMe 2-CI-CF3 3-OMe Me 2-CFg 2, 6-F ₂ Na 2-OMe 2-CI -CF3 3-OMe Na 2-CFg 2, 6-F ₂ K 2-OMe 2-CI Table 1 (continued)

Zn Ym R Zn Ym R, Zn Ym R-OMe 2-Br H 2-OMe 3- CI H 2-OMe 2, 6-Me ₂ H-OMe 2- Br Me 2-OMe 3- CI Me 2-OMe 2 , 6-Me ₂ Me m

-OMe 2-Br Na 2-OMe 3- CI Na 2-OMe 2, 6-Me ₂ Na-OMe 2-Me H 2-OMe 3-CF3 H 2-OMe 2, 6- F ₂ H-OMe 2- Me Me 2-OMe 3-CF ₃ Me 2-OMe 2, 6-F ₂ Me-OMe 2-Me Na 2-OMe 3-CF ₃ Na 2-OMe 2, 6-F ₂ Na-OMe H 2-OMe 3-OMe H 2-OMe 2, 6- Cl ₂ H-OMe 2- Et Me 2-OMe 3-OMe Me 2-OMe 2, 6-CI ₂ Me-OMe 2-Et Na 2-OMe 3-OMe Na 2-OMe 2, 6-CI ₂ Na-OMe 2-ipr H 2-OMe 4-Me H 2-OMe 2, 6-(CF ₃ ) ₂ H-OMe 2 ^J Pr Me 2-OMe 4-Me Me 2 -OMe 2, 6- (CF ₃ ) ₂ Me-OMe 2 ^J Pr Na 2-OMe 4-Me Na 2-OMe 2, 6- (CF ₃ ) ₂ Na-OMe 2-CF ₃ H 2-OMe 4- FH 2-OMe 3,5-Me ₂ H-OMe 2-CF3 Me 2-OMe 4-F Me 2-OMe 3,5-Me ₂ Me-OMe 2-CF3 Na 2-OMe 4-F Na 2-OMe 3,5-Me ₂ Na-OMe H 2-OMe 4-CI H 2-OMe 3,5-F ₂ Me-OMe 2-CH ₂ CF ₃ Me 2-OMe 4- CI Me 2-OMe 3,5- F ₂ Na-OMe 2-CH ₂ CF ₃ Na 2-OMe 4-CI Na 2-OEt 2-F Me-OMe 2-OEt H 2-OMe 4-CF3 H 2-OEt 2-F Na-OMe 2- OEt Me 2-OMe 4-CF ₃ Me 2-OEt 2-Me Me-OMe 2-OEt Na 2-OMe 4-CF3 Na 2-OEt 2-Me Na-OMe 2- 0H 2-OMe 4-OMe H 2-OEt 2-CF3 Me-OMe 2-0 Me 2-OMe 4-OMe Me 2-OEt 2-CF3 Na-OMe 2-o'Pr Na 2-OMe 4-OMe Na 2-OEt 2-OMe Me-OMe 2-OCF3 H 2-OMe 2, 4-Me ₂ H 2-OEt 2-OMe Na-OMe 2-OCF3 Me 2-OMe 2, 4-Me ₂ Me 2-. 2-F Me-OMe 2-OCF3 Na 2-OMe 2, 4-Me ₂ Na 2- 0 2-F Na-OMe 2-Ph H 2-OMe 2, 4-F ₂ H 2-O ^j Pr 2- Me Me-OMe 2-Ph Me 2-OMe 2, 4- F ₂ Me 2-2-Me Na-OMe 2-Ph Na 2-OMe 2, 4-F ₂ Na 2-O 2-CF ₃ Me-OMe 3- Me H 2-OMe 2, 4-CI ₂ H 2- O 2-CF3 Na-OMe 3-Me Me 2-OMe 2, 4-CI ₂ Me 2-O'Pr 2-OMe Me-OMe 3- Me Na 2-OMe 2, 4-CI ₂ Na 2-. ! "2-OMe Na

Table 1 (continued)

Zn Ym R Zn Ym R Zn Ym-OMe 2, 6-Me ₂ Me 4-Me 2-CF3 Na 4-OMe 2-F-OMe 2, 6- F ₂ Me 4-Me 2-CF ₃ Me 4-OMe 2-Me-OMe 2, 6-F ₂ Na 4-Me 2-OMe Na 4-OMe 2-Me-OMe 2, 6-CI ₂ Me 4-Me 2-OMe Me 4-OMe 2-CF3-OMe 2 , 6-Cl ₂ Na 4-F 2-F Na 4-OMe 2-OMe-OMe 2, 6- (CF ₃ ) ₂ Me 4-F 2-F e 4-OMe 2-OMe-OMe 2, 6- _{(CF 3) 2 Na 4-} F 2 - Me Na 2, 4-Me 2 2-F-OMe 2-CI-6-F Me 4-F 2-Me Me 2, 4-Me 2 2-F-OMe 2-CI-6-F Na 4-F 2-CF ₃ Na 2, 4-Me ₂ 2-Me-OMe 3,5-Me ₂ Me 4-F 2-CF ₃ Me 2, 4-Me ₂ 2- Me-OMe 3,5-Me ₂ Na 4-F 2-OMe Na 2, 4-Me ₂ 2-CFg-OMe 3,5-F ₂ Me 4-F 2-OMe Me 2, 4-Me ₂ 2- _{CF3-OMe 3,5-F 2 Na} 4-CI 2-F Na 2, 4 - Me 2 2-OMe-OMe 2-F Me 4 - CI 2-F Me 2, 4-Me 2 2-OMe-OMe 2 - F Na 4-CI 2 -Me Na 2, 4-F 2 2-F-OMe 2- Me Me 4-CI 2-Me Me 2, 4-F 2 2-F-OMe 2-Me Na 4- CI 2-CF3 Na 2, 4 -F 2 2-Me-OMe 2-CF 3 Me 4-CI 2-CF3 Me 2, 4-F 2 2-Me-OMe 2-CF3 Na 4-CI 2-OMe Na _{2, 4-F 2 2-} CF3-OMe 2-OMe Me 4-CI 2-OMe Me 2, 4- F 2 2 - CF 3 -OMe 2-OMe Na 4-CI 2-CI-6-F Na 2 , 4-F ₂ 2-OMe

3-OEt 2-F Me 4-CI 2-C 6-F Me 2, 4-F ₂ 2-OMe

3-OEt 2-F Na 4-CI 2, 6-F ₂ Na 2, 4- Cl ₂ 2-F

3-OEt 2-Me Me 4-CI 2, 6-F ₂ Me 2, 4- Cl ₂ 2-F

3-OEt 2-Me Na -CF3 2-F Na 2, 4- Cl ₂ 2-Me

3-OEt 2 ~ CF ₃ Me 4-CF3 2-F Me 2, 4- Cl ₂ 2-Me

3-OEt 2-CF3 Na 4-CF3 2-Me Na 2, 4-CI ₂ 2-CF ₃

3-OEt 2-OMe Me 4-CF ₃ 2-Me Me 2, 4- Cl ₂ 2-CF3

3-OEt 2-OMe Na 4-CF3 2-CF3 Na 2, 4-Cl ₂ 2-OMe

4-Me 2-F Me 4-CF ₃ 2-CF3 Me 2, 4- Cl ₂ 2-OMe

4-Me 2-F Na -CF3 2-OMe Na 2, 6-Me 2 2-F

4-Me 2-Me Me -CF3 2-OMe Me 2, 6-Me ₂ 2-F

4-Me 2-Me Na 4-OMe 2-F Na 2, 6-Me ₂ 2-Me Table 1 (continued)

本発明においては、 式 （1) で表されるィ匕合物は、 式 （3) で表される化合物と式 （4) で表される化合物とを反応させて式 （2) で表される化合物を得た後、 単離することなく そのままアンモニアを作用させることによって製造することもできる。 すなわち、 式 （3) で表される化合物と式 （4) で表される化合物との反応と、 反応後、 反応液中の式 （2) で表される化合物にアンモニアを作用させる一連の操作を、 連続して行うことにより、 簡 便、 かつ効率よく式 （1) で表される化合物を得ることができる。

In the present invention, the compound represented by the formula (1) is represented by the formula (2) by reacting the compound represented by the formula (3) with the compound represented by the formula (4). The compound can also be produced by reacting ammonia without isolation after obtaining the compound. That is, a reaction between the compound represented by the formula (3) and the compound represented by the formula (4), and after the reaction, a series of operations for reacting ammonia with the compound represented by the formula (2) in the reaction solution. The compound represented by the formula (1) can be obtained simply and efficiently by performing the reaction continuously.

 As shown in the following reaction formula, the conjugated compound represented by the formula (1) produced as described above is reacted with an acid halide to form a more stable agricultural chemical active compound represented by the formula (5). The acrylonitrile derivative represented can be derived.

 (1) (5)

(In the formula, Υ, τ m and η represent the same meaning as described above, R ² represents an alkyl group, a phenyl group which may have a substituent, and the like, and X ″ represents a halogen atom.) BEST MODE FOR CARRYING OUT THE INVENTION:

 Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to only the following examples.

 Example 1 3-oxo-1- [4- (2,6-difluorophenyl) 1-1,3-thiazol-1-yl] —3-—2- (trifluoromethyl) [Fanil] Production of propane nitrile

 1) Production of 2- (2-trifluoromethylbenzoyl) -3- (2,6-difluorobenzoylmethylthio) -1-3-methylthioacrylonitrile

To a solution of 1 g of methyl 2-propanoate [2- (trifluoromethyl) phenyl] propanedithioate in 2 Oml of acetonitrile, 0.29 g of sodium hydrogen carbonate was added. The mixture was cooled to 10 ° C., and 0.82 g of 2,6-difluorobenzoyl bromide was added dropwise with stirring, and the mixture was further stirred at room temperature for 2 hours. The reaction solution was poured into ice water and extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure, and the obtained oil was purified by silica gel column chromatography to obtain 1 g of the title compound. Yield: 66.3%

Melting point: 163.0-166.0 ° C 2) 3-oxo-1-2- [4- (2,6-difluorophenyl) -1-1,3-thiazonole-2-yl] -3- [2- (trifluoromethyl) phenyl] propanenitrile Manufacturing of

 2— (2-Trifluoromethylbenzoyl) -3- (2,6-diph benzoylmethylthio) 1-3-Methylthioacrylonitrile 3 g of ethanol 2 Om 1 solution of ammonia gas at room temperature 10 After blowing for minutes, the mixture was further stirred for 3 hours. Dilute hydrochloric acid was added to the residual oil obtained by evaporating the solvent from the reaction solution, and the mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated to obtain crystals. The obtained crystals were washed with a small amount of ethyl ether to obtain 1.6 g of the title compound. Yield: 60%

 Melting point: 170.0-172.0 ° C Industrial applicability:

 As described above, according to the present invention, 3-oxo-1- (2-thiazolyl) is useful as an intermediate for producing agricultural chemicals and the like, particularly as an intermediate for producing an acrylonitrile derivative which is an active ingredient of insecticides and acaricides. ) Propane nitrile can be produced industrially advantageously.

Claims

The scope of the claims  1. Equation (2)

(In the formula, Z is a nitro group, a cyano group, a halogen atom, a C-s alkyl group, a d-6 haloalkyl group, an alkoxy group, a phenyl group which may have a substituent or a substituent Represents a phenoxy group which may be substituted, n represents 0 or an integer of 1 to 5, and Y represents a halogen atom, a C _{x 16} alkyl group, a C- ₆ alkoxy group or a substituent. Represents a good phenyl group, m represents 0 or an integer of 1 to 5, and R represents a hydrogen atom, a Cis-s alkyl group or a metal atom.) Equation (1) characterized by

 (In the formula, Y, Z, m and η represent the same meaning as described above.) A method for producing a compound represented by the formula: 2. Equation (2)

(Wherein, the Zeta, nitro group, Shiano group, a halogen atom, an alkyl group, C ^ - e Haroaruki group, - ₆ alkoxy groups, have an optionally substituted phenyl group or a substituted group Represents a phenoxy group, n represents 0 or an integer of 1 to 5, and Y may have a halogen atom, a C ₆ -alkyl group, a Ci ₆ alkoxy group or a substituent. represents phenylene Le group, m represents an integer of 0 or. 1 to 5, R represents a C doctor ₆ alkyl group or a metal atom.) represented by reduction compounds with. 3. Equation (3)

(Wherein, Z is a nitro group, Shiano group, a halogen atom, an alkyl group, d ₆ Haroaruki group, - ₆ alkoxy group, which may have an optionally substituted phenyl group or a substituted group Represents a good phenoxy group, n represents an integer of 0 or 15, and R represents a ₆ alkyl group or a metal atom. And a compound represented by the formula (4)

(In the formula, Y represents a halogen atom, an alkyl group, a C- ₆ alkoxy group or a phenyl group which may have a substituent, m represents an integer of 0 or 15, and X represents a halogen atom. Wherein the compound is reacted with a compound represented by the formula:

 (In the formula, Z, Y, R, m and n represent the same meaning as described above.) A method for producing a compound represented by the formula: 4. Equation (3)

(Wherein, Z is a nitro group, Shiano group, a halogen atom, - 6 alkyl group, C ^ - s Haroaruki group, _ ₆ alkoxy groups, have a good phenyl group or a substituted group may have a substituent And n represents an integer of 0 or 15; R represents a C i ₆ alkyl group or a metal atom; and a compound represented by the formula (4)

(Wherein, Y represents a halogen atom, a —6 alkyl group, a C i ₆ alkoxy group or a phenyl group which may have a substituent, m represents 0 or an integer of 1 to 5, and X represents Represents a halogen atom.) By reacting with the compound represented by the formula (2)

(Wherein, Z, Y, R, m and n represent the same meaning as described above), and reacting the obtained compound represented by the formula (2) with ammonia Formula with process (1)

 (Wherein, Z, Y, m and η have the same meanings as described above).