JPH059151A - Cyclopropanecarboxylic acid derivative - Google Patents

Abstract

PURPOSE:To obtain a new cyclopropanecarboxylic asid derivative useful as a production intermediate for N-benzylcyclopropanecarboxamide derivative useful as a germicide. CONSTITUTION:A cyclopropanecarboxylic acid derivative expressed by formula I (R<1> is H or halogen; R<2> is lower alkyl or halogen-substituted lower alkyl, provided that when R<1> is H, R<2> is halogen-substituted lower alkyl and when R<1> is halogen, R<2> is lower alkyl; R<3> is lower alkyl; A is OH or halogen), (e.g. 2,2-dichloro-(trans)-3-chloromethyl-(cis)-3-methylcyclopropanecarboxylic acid chloride. A compound expressed by formula III [ (R<2>)' is halogen-substitutited lower alkyl; Hal' is halogen] which is one compound among the compound expressed by formula I is obtained e.g. by reacting a compound expressed by formula IV with a compound expressed by the formula NaBrO2 to afford a compound expressed by sormula V and further reacting the nessltant compound expressed by formula V with a compound expressed by the formula SO (Hal<1>)2.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel cyclopropanecarboxylic acid derivative useful as an intermediate for a bactericide.

[0002]

2. Description of the Related Art The specification of JP-A-55-66555, which is a publicly known publication before the filing date of the present application, has the general formula:

[0003]

[Chemical 4]

[In the formula, R ₁ represents a hydrogen atom or a lower alkyl group, R ₂ represents an alkyl group or a cycloalkyl group, and R ₁ and R ₂ may form a ring. ] It is described that the N-benzyl-acetamide derivative represented by the formula has herbicidal activity, and the specification describes, for example,

[0005]

[Chemical 5]

Compounds of the formula ## STR1 ## have been described.

[0007]

DISCLOSURE OF THE INVENTION The present inventors have made the following general formula

[0008]

[Chemical 6]

In the formula, X represents a halogen atom, n represents 1 or 2, R ¹ represents a hydrogen atom or a halogen atom, R ² represents a lower alkyl group or a halogen-substituted-lower alkyl group, wherein , When R ¹ is a hydrogen atom, R ² is a halogen-substituted-lower alkyl group, when R ¹ is a halogen atom, R ² is a lower alkyl group, and R ³ is a lower alkyl group. It was found that the N-benzyl-cyclopropanecarboxamide derivative described above is novel and useful as a fungicide for agriculture and horticulture. The present invention provides a cyclopropanecarboxylic acid derivative which is an intermediate for producing the N-benzyl-cyclopropanecarboxamide derivative.

[0010]

The present invention provides the following formula (I):

[0011]

[Chemical 7]

In the formula, R ¹ represents a hydrogen atom or a halogen atom, R ² represents a lower alkyl group or a halogen-substituted-lower alkyl group, and when R ¹ is a hydrogen atom, R ²
Represents a halogen-substituted-lower alkyl group, when R ¹ is a halogen atom, R ² represents a lower alkyl group, and R ³
Represents a lower alkyl group, and A represents a hydroxyl group or a halogen atom.

The compound of the formula (I) of the present invention can be produced, for example, by the following method.

Manufacturing method i)

[0015]

[Chemical 8]

[In the formula, (R ² ) 'represents a halogen-substituted-lower alkyl group, and Hal ¹ represents a halogen atom. ] Manufacturing method ii)

[0017]

[Chemical 9]

[In the formula, R ² , R ³ and Hal ¹ are the same as defined above, and Hal ² is a halogen atom. In the above reaction formula, Hal ¹ and Hal ² represent halogen atoms such as fluoro, chloro, bromo and iodo, and R ² is, for example, methyl, ethyl, propyl, isopropyl, n-
A lower alkyl group such as (iso-, sec-, or tert-) butyl and the like, or a lower alkyl group such as the above exemplified substituted with a halogen atom similar to the above exemplified, for example,
Mono- (di- or tri-) chloromethyl, mono- (di-
Or tri-) fluoromethyl, mono- (di- or tri-) bromomethyl, 1- (or 2-) chloro (bromo,
Or fluoro) ethyl, 1,1- (1,2 or 2,2)
Di-chloro (bromo or fluoro) ethyl, 1,1,1
-(1,1,2-, 1,2,2- or 2,2,2-) tri-chloro (bromo or fluoro) ethyl and the like are shown.

Specific examples of the compound of the formula (I) of the present invention include 2,2-dichloro- (trans) -3-chloromethyl- (cis) -3-methylcyclopropanecarboxylic acid, 1,2,2. 2-trichloro-3,3-dimethylcyclopropanecarboxylic acid, 1,2,2-trichloro-
3,3-diethylcyclopropanecarboxylic acid, 2,2-
Dichloro- (trans) -3-bromomethyl- (cis)
-3-Methylcyclopropanecarboxylic acid, 2,2-dichloro- (trans) -3-trifluoromethyl- (cis) -3-methylcyclopropanecarboxylic acid, 1-bromo-2,2-dichloro-3,3 -Dimethylcyclopropanecarboxylic acid, 2,2-dichloro-1-fluoro-3,
3-Dimethylcyclopropanecarboxylic acid, 2,2-dichloro- (trans) -3- (2,2,2-trifluoroethyl)-(cis) -3-methylcyclopropanecarboxylic acid, 2,2-dichloro- Examples thereof include (trans) -3- (2-chloroethyl)-(cis) -3-methylcyclopropanecarboxylic acid. Further, instead of the above-mentioned carboxylic acid, those acid halides such as acid chloride and acid bromide can be exemplified.

Specific examples of the compound of the general formula (II) which is the starting material in the above production method i) include 2,2-dichloro- (trans) -3-chloromethyl- (cis) -3-.
Methylcyclopropane methanol, 2,2-dichloro-
(Trans) -3-Bromomethyl- (cis) -3-methylcyclopropanemethanol, 2,2-dichloro- (trans) -3-trifluoromethyl- (cis) -3-methylcyclopropanemethanol, 2,2- Dichloro-
(Trans) -3- (2,2,2-trifluoroethyl)-(cis) -3-methylcyclopropanemethanol, 2,2-dichloro- (trans) -3- (2-chloroethyl)-(cis) Examples include 3-methylcyclopropanemethanol and the like.

Further, specific examples of the compound of the general formula (III) which is the starting material in the above production method ii) include, for example, methyl 2-chloro-crotonate, methyl 2-bromo-crotonate and 2-fluoro-croton. Methyl acid, 2-
Examples include methyl chloro-3-ethyl-2-pentenoate. Further, instead of the methyl ester represented by the general formula (III), other alkyl ester can be mentioned.

In process ii), instead of sodium trichloroacetate which reacts with the compound of the general formula (III), it is also possible to react a phase transfer catalyst such as 50% sodium hydroxide and triethylbenzylammonium chloride in chloroform. .

A representative example is shown below, wherein the above production methods i) and i
i) will be described respectively.

[0024]

[Chemical 10]

The above-mentioned manufacturing method can be preferably carried out by using a solvent or a diluent. For this all inert solvents,
Diluents can be used.

Examples of such solvents or diluents include
Water; Aliphatic, cycloaliphatic and aromatic hydrocarbons (optionally chlorinated), eg hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride , Ethylene chloride and trichloroethylene, chlorobenzene; other ethers such as diethyl ether, methyl ethyl ether, di-i
so-propyl ether, dibutyl ether, propylene oxide, dioxane, tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methyl-i
So-propyl ketone, methyl-iso-butyl ketone; nitriles such as acetonitrile, propionitrile, acrylonitrile; alcohols such as methanol, ethanol, iso-propanol, butanol, ethylene glycol; esters such as ethyl acetate, amyl acetate; Examples thereof include acid amides such as dimethylformamide and dimethylacetamide; sulfones and sulfoxides such as dimethylsulfoxide and sulfolane; and bases such as pyridine.

The method of the present invention can be carried out within a wide temperature range. Generally it can be carried out between about -20 ° C and the boiling point of the mixture, preferably between about 0 and about 100 ° C. Further, the reaction is preferably carried out under normal pressure, but it is also possible to operate under increased pressure or reduced pressure.

Next, the contents of the present invention will be specifically described with reference to examples, but the present invention should not be limited to these.

[0029]

Example 1 2,2-Dichloro- (trans) -3-chloromethyl- (cis) -3-methylcyclopropanemethanol (8 g) was suspended in a mixed solvent of acetic acid (30 ml) and water (6 ml). , Sodium bromate hydrate [containing about 60% as sodium bromate] (16 g) at room temperature. After the addition, raise the reaction temperature to 40 ° C. After 8 hours total reaction time, the reaction mixture is poured into ice water, adjusted to pH 5 with dilute hydrochloric acid and extracted with ether. The ether layer is washed with aqueous hypo solution and dried over anhydrous sodium sulfate. The ether was distilled off under reduced pressure, and the residue was recrystallized from hexane,
The target 2,2-dichloro- (trans) -3-chloromethyl- (cis) -3-methylcyclopropanecarboxylic acid (3.2 g) represented by the following formula is obtained. mp. 1
18-120 ° C

[0030]

[Chemical 11]

[0031]

Example 2 Compound No. 1 synthesized in Example 1 above I-
1 (3.0 g) is reacted with thionyl chloride (1.0 ml) at 60 ° C. When vacuum distillation is carried out from the reaction mixture,
The target 2,2-dichloro- (trans) -3-chloromethyl- (cis) -3-methylcyclopropanecarboxylic acid chloride represented by the following formula (2.8 g) is obtained. bp. 105-107 ° C / 20mmHg

[0032]

[Chemical 12]

[0033]

Example 3 The compounds of the general formula (I) of the present invention shown in Table 1 below were synthesized in the same manner as in Examples 1 and 2 above.

[0034]

[Table 1]

[0035]

[Table 2]

[0036]

Example 4 Methyl 1,2,2-trichloro-3,3-dimethylcyclopropanecarboxylate (10 g) is dissolved in formic acid (20 ml), and concentrated sulfuric acid (0.1 g) is added.
The mixture is gently heated to reflux for 12 hours. After cooling, water (60 ml) is added to this thread, and the precipitated crystals are collected by filtration. When this crystal is recrystallized from hexane, the target 1,2,2-trichloro-3,3-dimethylcyclopropanecarboxylic acid (3.4 g) represented by the following formula is obtained. mp. 148-150 ° C

[0037]

[Chemical 13]

1, used as a raw material in Example 4 above
A synthetic reference example of methyl 2,2-trichloro-3,3-dimethylcyclopropanecarboxylate is shown below.

[0039]

[Synthesis Reference Example 1] Sodium trichloroacetate (55 g) is added to methyl 2-chloro-3-methyl-2-butenoate (15.5 g) at 100 to 120 ° C over 5 hours. After the addition, stirring is continued for another 2 hours at the same temperature. After cooling, the reaction mixture is extracted with ether, the ether layer is washed with water and dried over anhydrous sodium sulfate. After distilling off the ether under reduced pressure, the residue is distilled under reduced pressure to obtain the desired methyl 1,2,2-trichloro-3,3-dimethylcyclopropanecarboxylate represented by the following formula (10.3 g). bp. 156 ~ 159 ℃ / 23mmHg

[0040]

[Chemical 14]

[0041]

Example 5 1,2,2-Trichloro-3,3-dimethylcyclopropanecarboxylic acid (3.0 g) synthesized in Example 4 above was mixed with thionyl chloride (1.0 ml) and the mixture was mixed at 60 ° C. React. When the reaction mixture is distilled under reduced pressure, the desired 1,2,2-trichloro-3,3-dimethylcyclopropanecarboxylic acid chloride represented by the following formula (2.8 g) is obtained. bp. 100 ° C / 20mm
Hg

[0042]

[Chemical 15]

[0043]

[Sixth Embodiment] By the same method as in the fourth and fifth embodiments,
The compounds of the general formula (I) of the present invention shown in Table 2 below were synthesized.

[0044]

[Table 3]

A synthetic reference example of a compound having bactericidal activity, which is prepared from 1,2,2-trichloro-3,3-dimethylcyclopropanecarboxylic acid chloride synthesized in Example 5, is shown below.

[0046]

[Synthesis Reference Example 2] 4-chloro-α-methylbenzylamine (15.6 g), triethylamine (10.1 g)
Was dissolved in toluene (150 ml) and stirred at 0 to 10 ° C with 1,2,2-trichloro-3,3-.
Dimethylcyclopropanecarboxylic acid chloride (23.
A solution of 6 g) in toluene (30 ml) is added dropwise. After completion of dropping, the mixture is stirred at room temperature for 2 hours. The reaction solution is poured into ice water, and the aqueous layer is extracted with toluene. The toluene layers are combined, washed successively with a 1% aqueous hydrochloric acid solution, a 1% aqueous sodium hydroxide solution and water, and dried over anhydrous sodium sulfate. When toluene is distilled off under reduced pressure, N of the target colorless crystal represented by the following formula is obtained.
-(4-Chloro-α-methylbenzyl) 1,2,2-trichloro-3,3-dimethylcyclopropanecarboxamide (32g) is obtained. mp. 138-139 ° C

[0047]

[Chemical 16]

[0048]

INDUSTRIAL APPLICABILITY The compound of the formula (I) of the present invention is useful as an intermediate for the production of N-benzylcyclopropanecarboxamide derivatives useful as fungicides.

Claims (3)

[Claims] 1. A general formula: In the formula, R ¹ represents a hydrogen atom or a halogen atom, R ² represents a lower alkyl group or a halogen-substituted-lower alkyl group, and when R ¹ is a hydrogen atom, R ² represents a halogen-substituted-lower alkyl group. Wherein R ¹ represents a halogen atom, R ² represents a lower alkyl group, R ³ represents a lower alkyl group, and A represents a hydroxyl group or a halogen atom. 2. The formula: The 2,2-dichloro- (trans) -3-chloromethyl- (cis) -3-methylcyclopropanecarboxylic acid chloride according to claim 1, represented by 3. The formula: 1,2,2-trichloro-of claim 1 represented by
3,3-Dimethylcyclopropanecarboxylic acid chloride.