CN114426485B

CN114426485B - Synthetic method of dichlorochrysanthemic acid compound

Info

Publication number: CN114426485B
Application number: CN202011173593.3A
Authority: CN
Inventors: 胡向平; 陈修帅
Original assignee: Dalian Institute of Chemical Physics of CAS
Current assignee: Dalian Institute of Chemical Physics of CAS
Priority date: 2020-10-28
Filing date: 2020-10-28
Publication date: 2023-06-13
Anticipated expiration: 2040-10-28
Also published as: CN114426485A

Abstract

The invention provides a synthesis method of a dichlorochrysanthemic acid compound, which takes 3- (2, 2-dichloro-1-hydroxyethyl) -2, 2-dimethylcyclopropane-1-methyl formate as a raw material to generate dichlorochrysanthemate through dehydration reaction under the condition of an acid catalyst, and then sodium hydroxide is used for hydrolysis to generate dichlorochrysanthemic acid, so that the yield of the dichlorochrysanthemic acid is up to 86%. Compared with the traditional method, the method greatly reduces the reaction cost, greatly shortens the synthesis steps and has high industrial application value.

Description

Synthetic method of dichlorochrysanthemic acid compound

Technical Field

The invention belongs to the field of organic synthesis, and particularly relates to a synthesis method of a dichlorochrysanthemic acid compound.

Background

Dichlorochrysanthemic acid is an important intermediate for the synthesis of pyrethroid insecticides. The cypermethrin synthesized by the cypermethrin is one of important varieties of pyrethroid insecticide, has the advantages of quick acting, low toxicity, high efficiency, broad spectrum, no residual toxicity and the like, and is deeply favored by people [ (a) Showcase, xiong Jianping, changsha electric university report, 1995,3 (10) ]. The domestic demand for the intermediate permethric acid is increasing.

At present, the industrialized production of the dichlorochrysanthemic acid mainly has two process routes: cyclopropane addition of ethyl diazoacetate to olefins and phase molding with cardiac acid esters as starting materials [ (b) Wang Qingmin, ma Junan, huang Runqiu, modern pesticides, 2003,6 (2); (c) Aratani T.pure & appl.chem.1985,57 (12): 1839-1844; (d) Kondo k., matsui k., negishi a., ACS Symposium series 1977, 42:128-136 ]. As the environmental pollution problem is more and more prominent, the national importance is more and more attached to the environmental protection, so that the exploration of a new synthetic route and the enrichment of the synthetic method of the dichlorochrysanthemic acid have important practical significance.

Disclosure of Invention

The invention aims to provide a synthesis method of a dichlorochrysanthemic acid compound (I), which does not need to add a large amount of alkali and acid, has the advantages of simple operation, easily available raw materials, high reaction activity, greatly reduced reaction cost, greatly shortened synthesis steps and high industrial application value.

The invention provides a synthesis method of a permethrin compound (I), which takes 3- (2, 2-dichloro-1-hydroxyethyl) -2, 2-dimethylcyclopropane-1-methyl formate (II) as a raw material, and in a proper reaction medium, the permethrin compound (III) is generated through dehydration reaction under the action of an acid catalyst, and then the permethrin compound (I) is generated through hydrolysis by a normal method. The method comprises the following specific steps:

first step, the synthesis of permethrin (III)

Adding 3- (2, 2-dichloro-1-hydroxyethyl) -2, 2-dimethylcyclopropane-1-carboxylic acid methyl ester (II) into a solvent, and carrying out dehydration reaction under the condition of an acid catalyst, wherein the mass percent of the acid catalyst accounts for 0.01-30% of the mass percent of the 3- (2, 2-dichloro-1-hydroxyethyl) -2, 2-dimethylcyclopropane-1-carboxylic acid methyl ester based on the 3- (2, 2-dichloro-1-hydroxyethyl) -2, 2-dimethylcyclopropane-1-carboxylic acid methyl ester; the reaction temperature is 20-130 ℃, the reaction time is 2-24h, and the permethrin (III) is synthesized. The synthetic route of the permethrin is as follows:

the acid catalyst comprises Lewis acid and protonic acid, wherein the Lewis acid is one or more than two of ferric trichloride, aluminum trichloride, zinc chloride, cupric chloride, chromium chloride, niobium pentachloride, boron trifluoride diethyl ether and copper trifluorosulfonate; the protonic acid is one or more of concentrated sulfuric acid, concentrated hydrochloric acid, phosphoric acid, hydrofluoric acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid and methanesulfonic acid. Preferably concentrated sulfuric acid.

The reaction medium is at least one of toluene, benzene, xylene, methylene dichloride, dichloroethane, carbon tetrachloride, ethyl acetate, diethyl ether, tetrahydrofuran, dimethyl sulfoxide or N, N-dimethylformamide. Toluene is preferred.

Second, synthesizing the dichlorochrysanthemic acid (I)

Adding the permethrin (III) synthesized in the first step into a solvent, and carrying out hydrolysis reaction under the action of alkali to obtain the permethrin (I) through acidification. The synthetic route of the dichlorochrysanthemic acid is as follows:

the invention has the following advantages:

1. high reaction activity and mild reaction condition.

2. The starting materials are cheap and readily available.

3. Compared with the traditional method, the method greatly reduces the reaction cost, greatly shortens the synthesis steps and has high industrial application value.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.

FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of permethric acid prepared in example 6.

Detailed Description

The following examples further illustrate the invention, but are not intended to limit it.

Example 1

2.4g of methyl 3- (2, 2-dichloro-1-hydroxyethyl) -2, 2-dimethylcyclopropane-1-carboxylate was weighed, 10mL of toluene was added, 0.024g of concentrated hydrochloric acid was reacted at room temperature for 12h, and the conversion was monitored by GC.

Example 2

2.4g of methyl 3- (2, 2-dichloro-1-hydroxyethyl) -2, 2-dimethylcyclopropane-1-carboxylate was weighed, 10mL of toluene was added, 0.024g of concentrated hydrochloric acid was added, the reaction was refluxed for 12 hours, and the conversion was monitored by GC for 50%.

Example 3

2.4g of methyl 3- (2, 2-dichloro-1-hydroxyethyl) -2, 2-dimethylcyclopropane-1-carboxylate was weighed out, 10mL of toluene was added, 0.024g of concentrated sulfuric acid was added, the reaction was refluxed for 12 hours, and the conversion was monitored by GC for 55%.

Example 4

2.4g of methyl 3- (2, 2-dichloro-1-hydroxyethyl) -2, 2-dimethylcyclopropane-1-carboxylate was weighed out, 10mL of tetrahydrofuran was added, 0.024g of concentrated sulfuric acid was added, the reaction was refluxed for 12 hours, and the conversion was monitored by GC for 36%.

Example 5

2.4g of methyl 3- (2, 2-dichloro-1-hydroxyethyl) -2, 2-dimethylcyclopropane-1-carboxylate was weighed out, 10mL of N, N-dimethylformamide was added, 0.36g of concentrated sulfuric acid was added, the reaction was refluxed for 12 hours, and the conversion was monitored by GC.

Example 6

2.4g of methyl 3- (2, 2-dichloro-1-hydroxyethyl) -2, 2-dimethylcyclopropane-1-carboxylate were weighed, 10mL of toluene was added, 0.24g of concentrated sulfuric acid was added, the reaction was refluxed for 12 hours, and the conversion was monitored by GC for 95%. Cooled to room temperature, washed with water and the solvent was spun off under reduced pressure to give crude permethrin 2.1g.

2.1g of permethrin is added into 10mL of toluene, 0.4g of sodium hydroxide is subjected to reflux reaction for 2h, GC is used for monitoring complete conversion, the reaction is cooled to room temperature, 10mL of water is added, the reaction is acidified by concentrated hydrochloric acid, white solid is separated out, 1.8g of permethrin is obtained through filtration and drying, and the yield of the two steps is 86%. The nuclear magnetic resonance hydrogen spectrum of the dichlorochrysanthemic acid is shown in figure 1,

¹ H NMR(400MHz,CDCl ₃ )δ7.80(s,1H),5.59(d,1H),2.16(m,1H),1.55(d,1H),1.25(s,3H),1.17(s,3H).

example 7

2.4g of methyl 3- (2, 2-dichloro-1-hydroxyethyl) -2, 2-dimethylcyclopropane-1-carboxylate was weighed, 10mL of toluene was added, 0.36g of anhydrous aluminum chloride was added, the reaction was refluxed for 12 hours, and the conversion was monitored by GC for 5%.

Example 8

2.4g of methyl 3- (2, 2-dichloro-1-hydroxyethyl) -2, 2-dimethylcyclopropane-1-carboxylate was weighed, 10mL of toluene, 0.36g of anhydrous ferric chloride was added, the reaction was refluxed for 12 hours, and the conversion was monitored by GC for 90%. Treatment as in example 6 gave 1.75g of permethric acid in 82% yield in two steps.

Example 9

2.4g of methyl 3- (2, 2-dichloro-1-hydroxyethyl) -2, 2-dimethylcyclopropane-1-carboxylate was weighed out, 10mL of toluene was added, 0.42g of copper triflate was added, the reaction was refluxed for 12 hours, and the conversion was monitored by GC. Treatment as in example 6 gave 1.7g of permethric acid in 80% yield in two steps.

The above-described embodiments represent only embodiments of the present invention, but are not to be construed as limiting the scope of the patent of the invention, it being noted that several variations and modifications can be made by a person skilled in the art without departing from the inventive concept.

Claims

1. A synthesis method of a dichloro chrysanthemic acid compound is characterized in that: taking 3- (2, 2-dichloro-1-hydroxyethyl) -2, 2-dimethylcyclopropane-1-methyl formate as a raw material, generating a dehydration reaction in a reaction medium through the action of an acid catalyst to generate dichlorochrysanthemate, and then generating a dichlorochrysanthemic acid compound through hydrolysis by sodium hydroxide; the method comprises the following specific steps:

first step, the synthesis of permethrin (III)

Adding 3- (2, 2-dichloro-1-hydroxyethyl) -2, 2-dimethylcyclopropane-1-methyl formate (II) into a toluene solvent, and carrying out dehydration reaction under the condition of an acid catalyst, wherein the mass percent of the acid catalyst is 10% -30% of the mass percent of the 3- (2, 2-dichloro-1-hydroxyethyl) -2, 2-dimethylcyclopropane-1-methyl formate based on the 3- (2, 2-dichloro-1-hydroxyethyl) -2, 2-dimethylcyclopropane-1-methyl formate; reflux reaction is carried out for 12 hours to synthesize the permethrin (III), wherein the synthetic route of the permethrin is as follows:

the acid catalyst is concentrated sulfuric acid or anhydrous ferric chloride or copper triflate;

second, synthesizing the dichlorochrysanthemic acid (I)

Adding the permethrin (III) synthesized in the first step into a solvent, and carrying out hydrolysis reaction under the action of alkali to obtain permethrin (I), wherein the synthetic route of the permethrin is as follows:

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