JPS5850209B2 - 2 2-dimethyl-3-(2 2-dihalovinyl)-cyclopropanecarbonyl - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides 2,2 dimethyl-
The present invention relates to a method for producing a 3-(2,2-dihalobinyl)-cyclopropanecarboxylic acid derivative.

[In the formula, R1 represents a lower alkyl group, and X represents the same or different halogen atoms.

] More specifically, the reaction formula is shown below.

[In the above formula, X and R1 represent the same meanings as above,
R2 represents a lower alkyl group.

] At present, there is a group of insecticidal ester compounds collectively called pyrethroids, but when the carboxylic acid obtained by the present invention forms the acid component, it is more effective than tertiary chrysanthemum acid ester, which is conventionally considered to be the most effective. It exhibits approximately twice the efficacy of insecticidal properties and maintains the low toxicity to warm-blooded animals that is characteristic of pyrethroids (M, Elliott Nature 2).
44 456 (August 17-1973)).

Furthermore, the aldehyde of general formula (IV) used in the present invention can be prepared, for example, by the method of L. Crombie et al. (J.

Chem, Soc, 1970 1076) and provides an inexpensive method for the synthesis of compounds of general formula CI).

The addition of a trihalogen hydrocarbon to an aldehyde group represented by reaction formula (1) is described, for example, in Jikken Kagaku Koza Vol. 20, 199.
This is a well-known reaction as shown on page 1, but it is an example of a reaction when the same molecule contains a carboxylic acid derivative, which is a group that is easily affected by alkali, as in compound (IV) of the present invention. is not very well known.

Examples of polyhalogenated hydrocarbons used here include carbon tetrachloride, chloroform, trichlorobromide hydrocarbon, bromoform, and the like.

Further, as the base used, caustic alkali, alkali alkoxide, alkali metal amide, alkaline earth metal amide, etc. are used.

Any inert solvent may be used as the solvent, but methylal and dimethylformamide, which have high polarizability, are preferable.

The reaction temperature is preferably from room temperature to -30°C.

The acylation of reaction scheme (2) is accomplished with conventional acylating reagents, ie, acid halides or acid anhydrides, in the presence of deoxidizing agents such as pyridine, or catalyzed by mineral acids.

The reduction reaction of reaction formula (3) is usually easily accomplished with excess zinc powder in the presence of lower alcohols or lower fatty acids in the temperature range from room temperature to the boiling point of the solvent used, and the desired compound CI) is obtained. It can be obtained in high yield.

Note that the intermediate (In) and [■] included in the present invention are new compounds that have not been described in any literature.

The present invention will be explained below with reference to Examples.

Example 1 24 ml of methylal was cooled to -20°C, and 10 g of chloroform and 2.41 g of powdered caustic potassium were added.

6.32 g of 2,2-dimethyl-3-formylcyclopropanecarboxylic acid methyl ester was added and stirred for 1 hour.

The reaction solution was poured into diluted hydrochloric acid, and the resulting oil was extracted with ether and concentrated.

From the N, M, R, and findings of the concentrate, the proton peak derived from the aldehyde of the raw material aldehyde was δ9.62 (IH, d,
J2.5Hz) became smaller, and a peak at δ5.0 (I H,m ) (the hydroxyl group is the proton peak of the root) appeared instead, and the ratio of these peak areas was about 1:1 ( Approximately 50% responded.

) Furthermore, no hydrolysis of the carboxylic acid ester occurred.

Example 2 To the above reaction mixture were added 10 f of acetic anhydride and 51 g of pyridine, and the mixture was left at room temperature overnight.

Water was added and the mixture was allowed to stand for 1 hour to decompose excess acetic anhydride, extracted with ether, washed with aqueous sodium bicarbonate and diluted hydrochloric acid, and concentrated.

The concentrated liquid was distilled under reduced pressure of 0.3 mmHg to obtain about 31 unreacted aldehydes as a distillate at a boiling point of 50 to 60°C, and the internal temperature was further raised to 100°C to remove the distillate.

2,2-dimethyl-3-(1-acetoxy-1-trichloromethyl)cyclopropanecarboxylic acid methyl ester 4.51 was obtained as a residue.

■, R61765CrrL-11735CrrL-1,
N0M, R0δ5.2 (IH, m), 3.65 (3H,
s) 2.15 (3H, s) Example 3 25 ml of ether, 4.61 acetic acid and 4.61 zinc dust
into a flask, and add 4.52% of the above acetate while stirring.
was added and heated under reflux for 1 hour.

After the reaction, the zinc was filtered off and washed with water and ether.

The ether solution was washed with aqueous sodium bicarbonate to give a neutral fraction of 2.92.

This was nearly pure 2,2-dimethyl-3(2,2-dichlorovinyl)-cyclopropanecarboxylic acid methyl ester.

The yield was 32% (from aldehyde).

Claims (1)

[Claims] 1 General formula [wherein X is the same or different] Represents a rogene atom, and R1 and R2 represent a lower alkyl group. [In the formula, X and R1 has the same meaning as above. ] A method for producing a 2,2-dimethyl-3-(2,2-dihalobinyl)-cyclopropanecarboxylic acid derivative. 2 General formula [wherein, X and R1 have the same meanings as described in claim 1]. ] The 2,2-dimethyl-3-(1-hydroxy-1-)1,1 halomethyl)-cyclopropanecarboxylic acid derivative represented by the general formula [wherein, X, R1 and R2, has the same meaning as stated in Section 1. 2,2-dimethyl-3-(1-acyloxy-1-trihalomethylmethyl)-cyclopropanecarboxylic acid derivative represented by the general formula [ In the formula, X and R1 have the same meanings as above. ] A method for producing a 2,2-dimethyl-3-(2,2-dihalobinyl)-cyclopropanecarboxylic acid derivative. 3 General formula [wherein R1 represents the same meaning as described in claim 1]. 2,2-dimethyl-3-formylcyclopropanecarboxylic acid derivative represented by the general formula % [wherein, X has the same meaning as described in claim 1]. ] is reacted with a polyhalogenated hydrocarbon represented by the formula in the presence of a strong base to form a compound of the general formula [wherein X and R1 have the same meanings as above. A 2,2-dimethyl-3-(1-hydroxy-1-trihalomethyl)-cyclopropanecarboxylic acid derivative represented by , has the same meaning as stated in claim 1. 2,2-dimethyl-3-(1-acyloxy-1-trihalomethylmethyl)-cyclopropanecarboxylic acid derivative represented by the general formula [ In the formula, X and R1 have the same meanings as above. ] A method for producing a 2,2-dimethyl-3-(2,2-dihalobinyl)-cyclopropanecarboxylic acid derivative.