Pyrethroid compounds containing double bonds and cyano groups, their synthesis methods, and applications.

Abstract

The present invention discloses a pyrethroid compound having a double bond containing a cyano group, a synthesis method and applications. When synthesizing, tert-butyl 3-formyl-2,2-dimethyl-cyclopropionate and cyanomethyl phosphate are used as raw materials. Through the Witting-Horner reaction and column chromatography separation, tert-butyl (Z)-3-(2-cyanovinyl)-2,2-dimethyl-cyclopropionate is obtained. After deprotection, (Z)-3-(2-cyanovinyl)-2,2-dimethyl-cyclopropionic acid is obtained. Through an acyl group chlorination reaction, (Z)-3-(2-cyanovinyl)-2,2-dimethyl-cyclopropane acid chloride is generated, and further esterification with the corresponding alcohol gives a pyrethroid compound. The said compound is used as an insecticide to kill pests such as mosquitoes, flies, and cockroaches.

Description

Technical Field

[0001] The present invention relates to pyrethroid compounds that can be used for insecticidal purposes, specifically to a method for synthesizing a pyrethroid compound containing a double bond and a cyano group, and to the application thereof in controlling pests such as mosquitoes and flies. The present invention belongs to the field of chemical synthesis technology.

Background Art

[0002] Pyrethroids are active ingredients of mosquito-repellent incense and aerosol preparations, and are mainly used for controlling household pests such as mosquitoes and flies. Since pyrethroid products have been used for a long time, mosquitoes have developed varying degrees of resistance to most commercially available products. The development of pyrethroids with novel structures helps to partially solve the resistance problem and extend the service life of this type of insecticide.

[0003] Momfluorothrin (US2012 / 29227, EP2241551) is a novel pyrethroid insecticide developed by Sumitomo Corporation of Japan. It has good contact killing activity against insects and spiders, but there are no reports regarding its effect on household pests. Tests have shown that while it has good knockdown activity against mosquitoes when formulated as an aerosol in a canister, its activity when used in mosquito-repellent incense is inferior. This is possibly because the nitrogen contained in its structure reduces the vapor pressure, making it difficult to volatilize by heating to achieve the contact killing effect.

[0004] The present invention increases the vapor pressure of the compound by simplifying the structure of momfluorothrin, further enhances the effect when used in mosquito-repellent incense, and lays a foundation for the application of pyrethroid compounds having a cyano group on the double bond in mosquito control.

Summary of the Invention

[0005] The technical problem that this invention aims to solve is to provide a pyrethroid compound containing a double bond and a cyano group, which can be used as an insecticide to control pests such as mosquitoes, flies, and German cockroaches, and to provide a method for synthesizing the same compound and its applications, taking into account the shortcomings of the prior art.

[0006] To achieve the above objective, the present invention employs the following technical approach.

[0007] The present invention first relates to the following general formula I: [ka] I The present invention provides a pyrethroid compound containing a double bond and a cyano group, represented by the formula, where n is 3 or 4.

[0008] In the above embodiment, when n is 3, the compound is 2,3,5-trifluorobenzyl(Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropanecarboxylate or 2,3,6-trifluorobenzyl(Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropanecarboxylate.

[0009] In the above embodiment, when n is 4, the compound is 2,3,5,6-tetrafluorobenzyl(Z)-3(2-cyanovinyl)-2,2-dimethylcyclopropanecarboxylate.

[0010] In the above embodiment, the compound is preferably 2,3,5-trifluorobenzyl(Z)-3(2-cyanovinyl)-2,2-dimethylcyclopropanecarboxylate, the structural formula of which is shown in formula II: [ka] II

[0011] The present invention also provides a method for synthesizing a pyrethroid compound containing the double bond and cyano group, comprising the following steps.

[0012] (1) Synthesis of Z-configuration products: The process involves reacting tert-butyl 3-formyl-2,2-dimethylcyclopropionate with cyanomethyl phosphate or cyanomethyltriphenylphosphine under basic action in solvent I to produce tert-butyl 3-(2-cyanovinyl)-2,2-dimethylcyclopropionate, and obtaining (Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropionate tert-butyl by column chromatography;

[0013] (2) Detert-butylation Step (1) involves removing tert-butyl from (Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropionic acid tert-butyl under acid action to obtain (Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropionic acid;

[0014] (3) Acyl chlorination reaction: The (Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropionic acid obtained in step (2) is subjected to an acyl chlorination reaction to obtain (Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropionyl chloride;

[0015] (4) Esterification reaction: The (Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropionyl chloride obtained in step (3) is subjected to an esterification reaction with benzyl alcohol under the action of a base to obtain a pyrethroid compound containing a double bond and a cyano group.

[0016] The chemical equation is as follows: [ka]

[0017] In the above embodiment, step (1) is performed as follows for the synthesis of the Z configuration product: A base is suspended in solvent I at -5 to -30°C, cyanomethyl phosphate or cyanomethyltriphenylphosphine is added dropwise to the system at -5 to -30°C, and then tert-butyl 3-formyl-2,2-dimethylcyclopropionate is added dropwise; the system is incubated at -5 to -30°C for 1 hour, and after confirming that the conversion of the starting materials is complete by GC analysis, the pH of the system is neutralized to 7 to 8 with 10% hydrochloric acid, followed by liquid-liquid extraction, and the aqueous layer is extracted with an extraction solvent to obtain the organic phase. The organic phase is desolvated and subjected to column chromatography to obtain (Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropionate tert-butyl.

[0018] In the above embodiment, in step (1), the cyanomethyl phosphate ester is dimethyl cyanomethyl phosphate, diethyl cyanomethyl phosphate, or isopropyl cyanomethyl phosphate, and preferably dimethyl cyanomethyl phosphate.

[0019] In the above embodiment, in step (1), the molar ratio of the cyanomethyl phosphate ester or cyanomethyltriphenylphosphine to tert-butyl 3-formyl-2,2-dimethylcyclopropionic acid is 0.5 to 1.5:1.

[0020] In the above embodiment, in step (1), the solvent I is a mixture of one of tetrahydrofuran, 2-methyltetrahydrofuran, acetonitrile, and toluene, or two or more of these in any proportion, preferably tetrahydrofuran; the solvent I is used in an amount of 3 to 15 times the weight of tert-butyl 3-formyl-2,2-dimethylcyclopropionate.

[0021] In the above embodiment, in step (1), the base is any one of sodium methoxide, sodium ethoxide, sodium amide, sodium tert-butoxide and potassium tert-butoxide, or a mixture of two or more of the foregoing mixed at any ratio; the base is used in an amount of 1 to 5 molar equivalents, preferably 1.2 molar equivalents, relative to cyanomethyl phosphate or cyanomethyltriphenylphosphine.

[0022] In the above embodiment, in step (1), the extraction solvent is any one of ethyl acetate, methyl acetate, dichloromethane, dichloroethane, chloroform, toluene, xylene and benzene, or a mixture of two or more of the foregoing mixed at any ratio, with ethyl acetate being preferable; the extraction solvent is used in an amount of 1 to 5 times the weight of tert-butyl 3-formyl-2,2-dimethyl-cyclopropionate.

[0023] In the above embodiment, in step (2), the specific operation for removing said tert-butyl group is as follows. Dissolve tert-butyl Z-3-(2-cyanovinyl)-2,2-dimethyl-cyclopropionate in solvent II, allow the reaction to proceed at the normal pressure reflux temperature (61~140°C) of the reaction solvent used under the catalysis of an acid to remove the tert-butyl group. After confirming by TLC that the conversion of the starting material is completed, after the system is cooled, wash the system with water until the pH reaches 6~7, remove the solvent to obtain (Z)-3-(2-cyanovinyl)-2,2-dimethyl-cyclopropionic acid.

[0024] In the above embodiment, in step (2), the solvent II is any one of toluene, xylene, benzene, dichloroethane, chloroform and tetrahydrofuran, or a mixture of two or more of the foregoing mixed at any ratio, with toluene being preferable; the solvent II is used in an amount of 3 to 10 times the weight of tert-butyl Z-3-(2-cyanovinyl)-2,2-dimethyl-cyclopropionate.

[0025] In the above embodiment, in step (2), the acid is one of p-toluenesulfonic acid, methanesulfonic acid, hydrochloric acid, or hydrobromic acid, or a mixture of two or more of these in any proportion, with p-toluenesulfonic acid being preferred; the amount of the acid used is 0.01 to 1 molar equivalent of (Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropionate t-butyl, preferably 0.03 molar equivalents.

[0026] In the above embodiment, the specific operation of the acyl chlorination reaction in step (3) is as follows: Dissolve Z-3-(2-cyanovinyl)-2,2-dimethylcyclopropionic acid in solvent III, heat to the atmospheric reflux temperature (39~140°C) of the reaction solvent used, add thionyl chloride dropwise under reflux, and after the addition is complete, maintain the temperature at 10~60°C for 0.5~2 hours to completely convert the starting material in the gas phase, then remove the solvent to obtain (Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropionyl chloride.

[0027] In the above embodiment, in step (3), solvent III is a mixture of one or more of n-hexane, cyclohexane, methylcyclohexane, dichloromethane, chloroform, dichloroethane, benzene, toluene, and xylene in any proportion, with n-hexane being preferred; solvent III is used in an amount of 3 to 10 times the weight of Z-3-(2-cyanovinyl)-2,2-dimethylcyclopropionic acid.

[0028] In the above embodiment, in step (3), the thionyl chloride is used in an amount of 1 to 3 molar equivalents, preferably 1.2 molar equivalents, of (Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropionic acid.

[0029] In the above embodiment, step (4) is carried out as follows for the esterification reaction: After dissolving benzyl alcohol in toluene, an acid binding agent is added, and (Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropionyl chloride is added dropwise under conditions of 0 to 10°C. After the addition is complete, the mixture is incubated at 0 to 10°C for 0.5 to 2 hours to completely convert the benzyl alcohol in the gas phase. Then, the pH of the system is neutralized to 6 to 7 with dilute hydrochloric acid and the system is separated into layers. The organic phase is then desolvated, separated by column chromatography, and desolvated again to obtain a pyrethroid compound containing a double bond and a cyano group.

[0030] In the above embodiment, in step (4), the benzyl alcohol is 2,3,6-trifluorobenzyl alcohol, 2,3,5-trifluorobenzyl alcohol, or 2,3,5,6-tetrafluorobenzyl alcohol.

[0031] In the above embodiment, in step (4), the acid binding agent is triethylamine, pyridine, or a liquid base (aqueous solution of sodium hydroxide).

[0032] In the above embodiment, in step (4), the molar ratio of benzyl alcohol, acid binding agent, and (Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropionyl chloride is 0.9 to 1.2:1.0 to 1.3:1.

[0033] In the above embodiment, in step (4), the toluene is used in an amount of 3 to 10 times the weight of (Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropionyl chloride.

[0034] The present invention also provides an application for using pyrethroid compounds containing the double bond and cyano group as insecticides for pest control.

[0035] In the above embodiment, when a pyrethroid compound containing the double bond and cyano group is used as an insecticide for pest control, the pyrethroid compound containing the double bond and cyano group represented by formula I is used as a mosquito repellent aerosol (content 0.3%) or an electric mosquito coil (content 0.04%) to kill mosquitoes, flies, German cockroaches, etc.

[0036] Compared to conventional technologies, the present invention provides a pyrethroid compound having a novel structure. This pyrethroid compound is mildly toxic to mammals; for example, the median lethal dose (LD50) for acute oral toxicity in rats of 2,3,5,6-tetrafluorobenzyl(Z)-3(2-cyanovinyl)-2,2-dimethylcyclopropanecarboxylate, a compound of the present invention, exceeds 5000 mg / kg, indicating mild toxicity; and the median lethal dose (LD50) for acute dermal toxicity in rats also exceeds 5000 mg / kg, indicating mild toxicity. It is significantly lower in acute toxicity in rats than dimefluthrin and metofluthrin, which are commonly found on the market, is safer for non-target organisms, and has excellent preventive effects against certain specific pest targets. Furthermore, it has the characteristic of high vapor pressure, making it suitable for various room-temperature volatile sanitary formulations. [Modes for carrying out the invention]

[0037] Specific embodiments of the present invention will be described in detail below, but the present invention is not limited to the following description.

[0038] The raw materials used in the examples of the present invention, tert-butyl 3-formyl-2,2-dimethylcyclopropionate, cyanomethyl phosphate or cyanomethyltriphenylphosphine, 2,3,6-trifluorobenzyl alcohol, 2,3,5-trifluorobenzyl alcohol, 2,3,5,6-tetrafluorobenzyl alcohol, and monfluorothrin, can be purchased. [Examples]

[0039] The present invention will be described below based on specific examples.

[0040] Example 1: (1) Synthesis of tert-butyl (Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropionate In a 250 mL four-necked flask with a stirring mechanism, 3.51 g (90 mmol) of sodium amide and 80 mL of tetrahydrofuran were added and stirred. The mixture was cooled to -20°C, and 6.7 g (45 mmol) of dimethyl cyanomethyl phosphate was added dropwise. After the addition was complete, the mixture was stirred for 15 minutes. At this temperature, 8 g (40 mmol) of tert-butyl 3-formyl-2,2-dimethylcyclopropionate was added dropwise. After the addition was complete, the mixture was incubated for 0.5 hours. After the complete conversion of tert-butyl 3-formyl-2,2-dimethylcyclopropionate in the gas phase, 5% hydrochloric acid was added dropwise until the pH of the system reached 7-8, and the system was separated. The aqueous layer was extracted with 2 x 20 mL of ethyl acetate, and the organic phases were combined and desolvated. 8 g of brown liquid was recovered, and 4.32 g of white solid (Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropionate tert-butyl was obtained by column chromatography using ethyl acetate:n-hexane = 1:10 (V / V) (yield = 54%).

[0041] (2) Synthesis of (Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropionic acid In a 250 mL four-necked flask with a stirrer, 4.32 g (19.5 mmol) of tert-butyl (Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropionic acid, 0.13 g of p-toluenesulfonic acid, and 25 mL of toluene were added and stirred. The mixture was then heated to 110°C under reflux and reacted for 1.5 hours under reflux. The reaction was monitored by TLC, and after the starting materials had completely converted, the mixture was cooled to room temperature, washed with water until the pH of the system was 6-7, and desolvated to obtain 3 g of a pale yellow solid of (Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropionic acid (yield = 93%).

[0042] (3) Synthesis of (Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropionyl chloride In a 250 mL four-necked flask with a stirring mechanism, 3 g (18.2 mmol) of (Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropionic acid and 20 mL of n-hexane were added. Two drops of DMF were added, the mixture was stirred, and the mixture was heated to reflux. 2.6 g (21.8 mmol) of thionyl chloride was added dropwise. After the addition was complete, the mixture was incubated for 0.5 hours until the starting material was completely converted in the gas phase. The solvent was then removed to obtain 3.2 g (17.5 mmol) of a dark green oily liquid of (Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropionyl chloride (yield = 96%).

[0043] (4) Synthesis of 2,3,5-trifluorobenzyl(Z)-3(2-cyanovinyl)-2,2-dimethylcyclopropanecarboxylate 2.7 g (16.7 mmol) of 2,3,5-trifluorobenzyl alcohol, 4.7 g (35 mmol) of 30% sodium hydroxide aqueous solution, and 20 mL of toluene were added to a 250 mL four-necked flask. The mixture was stirred and cooled to 0-5°C. 3.2 g (17.5 mmol) of (Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropionyl chloride was slowly added dropwise, and the mixture was kept warm after the addition was complete. After the benzyl alcohol was completely converted in the gas phase, the pH was adjusted to 6-7 with hydrochloric acid, the mixture was separated, the organic phase was desolvated, and the mixture was separated by column chromatography using ethyl acetate:n-hexane = 1:15 (V / V). Desolvation was performed to obtain 4.7 g of a colorless oily liquid of 2,3,5-trifluorobenzyl(Z)-3(2-cyanovinyl)-2,2-dimethylcyclopropanecarboxylate (yield = 92%).

[0044] Example 2: (1) Synthesis of tert-butyl (Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropionate In a 250 mL four-necked flask with a stirring mechanism, 6.8 g (100 mmol) of sodium ethoxide and 50 mL of tetrahydrofuran were added and stirred. The mixture was then cooled to -20°C, and 8.95 g (50 mmol) of diethyl cyanomethyl phosphate was added dropwise. After the addition was complete, the mixture was stirred for 15 minutes. At this temperature, 9 g (45 mmol) of tert-butyl 3-formyl-2,2-dimethylcyclopropionate was added dropwise. After the addition was complete, the mixture was incubated for 0.5 hours. After completely converting tert-butyl 3-formyl-2,2-dimethylcyclopropionate in the gas phase, 5% hydrochloric acid was added dropwise until the pH of the system reached 7-8, followed by liquid-liquid extraction. The aqueous layer was extracted with 2 x 20 mL of ethyl acetate, and the organic phase was combined and desolvated. 9.5 g of the brown liquid was recovered, and 5.17 g of the white solid (Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropionate tert-butyl was obtained by column chromatography using ethyl acetate:n-hexane = 1:10 (V / V) (yield = 52%).

[0045] (2) Synthesis of (Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropionic acid In a 250 mL four-necked flask with a stirrer, 5.17 g (23.4 mmol) of tert-butyl (Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropionic acid, 0.16 g of p-toluenesulfonic acid, and 25 mL of dichloroethane were added and stirred. The mixture was then heated to 84°C under reflux and reacted for 6 hours under reflux. The reaction was monitored by TLC, and after the starting materials had completely converted, the mixture was cooled to room temperature, washed with water until the pH of the system was 6-7, and desolvated to obtain 3.7 g of a pale yellow solid of (Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropionic acid (yield = 96%).

[0046] (3) Synthesis of (Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropionyl chloride In a 250 mL four-necked flask with a stirring mechanism, 3.7 g (22.4 mmol) of (Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropionic acid and 20 mL of dichloromethane were added, 2 drops of DMF were added, the mixture was stirred, and the mixture was heated under reflux to 40°C. 3.2 g (26.9 mmol) of thionyl chloride was added dropwise, and after the addition was complete, the mixture was kept warm for 0.5 hours to completely convert the starting material in the gas phase. After desolvation, 4.16 g (20.8 mmol) of (Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropionyl chloride was obtained as a dark green oily liquid (yield = 93%).

[0047] (4) Synthesis of 2,3,6-trifluorobenzyl(Z)-3(2-cyanovinyl)-2,2-dimethylcyclopropanecarboxylate 3.0 g (18.7 mmol) of 2,3,6-trifluorobenzyl alcohol, 2.95 g (37.4 mmol) of pyridine, and 20 mL of toluene were added to a 250 mL four-necked flask. The mixture was stirred and cooled to 0-5°C. 4.16 g (20.8 mmol) of (Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropionyl chloride was slowly added dropwise, and the mixture was kept warm after the addition was complete. After the benzyl alcohol was completely converted in the gas phase, the pH was adjusted to 6-7 with hydrochloric acid, the mixture was separated, the organic phase was desolvated, and the mixture was separated by column chromatography using ethyl acetate:n-hexane = 1:15 (V / V). Desolvation yielded 5.14 g of a colorless oily liquid of 2,3,6-trifluorobenzyl(Z)-3(2-cyanovinyl)-2,2-dimethylcyclopropanecarboxylate (yield = 89%).

[0048] Example 3: (1) Synthesis of tert-butyl (Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropionate In a 250 mL four-necked flask with a stirring mechanism, 4.86 g (90 mmol) of sodium methoxide and 60 mL of acetonitrile were added and stirred. The mixture was then cooled to -20°C, and 6.7 g (45 mmol) of dimethyl cyanomethylphosphate was added dropwise. After the addition was complete, the mixture was stirred for 15 minutes. At this temperature, 8 g (40 mmol) of tert-butyl 3-formyl-2,2-dimethylcyclopropionate was added dropwise. After the addition was complete, the mixture was incubated for 0.5 hours. After completely converting tert-butyl 3-formyl-2,2-dimethylcyclopropionate in the gas phase, 5% hydrochloric acid was added dropwise until the pH of the system reached 7-8, and the mixture was separated. The aqueous layer was extracted with 2 x 20 mL of ethyl acetate, and the organic phase was combined and desolvated. 8.4 g of the brown liquid was recovered, and 5.22 g of the white solid (Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropionate tert-butyl was obtained by column chromatography using ethyl acetate:n-hexane = 1:10 (V / V) (yield = 59%).

[0049] (2) Synthesis of (Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropionic acid In a 250 mL four-necked flask with a stirrer, 5.22 g (23.6 mmol) of tert-butyl (Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropionic acid, 0.16 g of p-toluenesulfonic acid, and 30 mL of xylene were added and stirred. The mixture was heated to 140°C under reflux and reacted under reflux for 2 hours. The reaction was monitored by TLC, and after the starting materials had completely converted, the mixture was cooled to room temperature. The system was washed with water until the pH reached 6-7, and the solvent was removed to obtain 3.66 g of a pale yellow solid of (Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropionic acid (yield = 94%).

[0050] (3) Synthesis of (Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropionyl chloride In a 250 mL four-necked flask with a stirring mechanism, 3.66 g (22.2 mmol) of (Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropionic acid and 20 mL of cyclohexane were added, 2 drops of DMF were added, the mixture was stirred, and the mixture was heated under reflux to 81°C. 3.96 g (33.3 mmol) of thionyl chloride was added dropwise, and after the addition was complete, the mixture was incubated for 0.5 hours to allow the starting material to be completely converted in the gas phase. The solvent was then removed to obtain 4.34 g (21.76 mmol) of (Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropionyl chloride as a dark green oily liquid (yield = 98%).

[0051] (4) Synthesis of 2,3,5,6-tetrafluorobenzyl(Z)-3(2-cyanovinyl)-2,2-dimethylcyclopropanecarboxylate 3.33 g (18.5 mmol) of 2,3,5,6-tetrafluorobenzyl alcohol, 4.7 g (35 mmol) of 30% sodium hydroxide aqueous solution, and 20 mL of toluene were added to a 250 mL four-necked flask. The mixture was stirred and cooled to 0-5°C. 4.34 g (21.76 mmol) of (Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropionyl chloride was slowly added dropwise, and the mixture was kept warm after the addition was complete. After the benzyl alcohol was completely converted in the gas phase, the pH was adjusted to 6-7 with hydrochloric acid, the mixture was separated, the organic phase was desolvated, and the solution was separated by column chromatography using ethyl acetate:n-hexane = 1:20 (V / V). Desolvation yielded 5.32 g of a colorless oily liquid of 2,3,5,6-tetrafluorobenzyl(Z)-3(2-cyanovinyl)-2,2-dimethylcyclopropanecarboxylate (yield = 88%).

[0052] Pyrethroid compounds 1 to 3 containing the double bond and cyano group of the present invention were prepared according to the synthesis methods of Examples 1 to 3, and their structural formulas are shown in Formula I. [ka] Equation I In the formula, n is either 3 or 4. [Table 1]

[0053] The following test examples demonstrate that the pyrethroid compound of the present invention is effective as an insecticide.

[0054] Test Example 1: 99.96 parts by weight of corn starch, a mixture of carbon powder and wood flour (1:5:4), and 120 parts by weight of water were added, kneaded and molded, and dried to form mosquito coil bases (12.0 cm in diameter, 4 mm thick, 40 g per pair).

[0055] On the other hand, a 0.4 w / v% solution of compound 1 in kerosene was prepared. Four ml of this solution was uniformly sprayed onto a mosquito coil base using a microsyringe, and then left to dry at room temperature for three hours to obtain one set of mosquito coils W1 containing 0.04 w / w% compound 1.

[0056] Similarly, compounds 2-3 of the present invention, as well as monfluorothrin and tetramethylfluthrin, were prepared in the same manner as shown in Table 1 to obtain the corresponding mosquito coils W2-W5.

[0057] The mosquito-repelling effects of mosquito coils W1 to W5 were measured and compared according to GB / T13917.4-2009. The test insects were Culex pipiens, specifically female mosquitoes that had not bitten blood for 2-3 days after emergence. The specific process was as follows: Twenty test mosquitoes were taken using a mosquito trap tube and placed in a sealed cylindrical test apparatus. A portion of the test mosquito coil was taken, placed in the coil rack, lit, and timed. After 1 minute, the mosquito coil was moved, and the number of knocked-down test mosquitoes was recorded at regular intervals. The experimental results are shown in Table 2. The mosquito-repelling efficacy of mosquito coils produced with compounds 1-3 of the present invention, synthesized by simplifying the structure of monfluorothrin, was clearly superior to that of monfluorothrin, and also clearly superior to that of the control compound, tetrafluoromethyl ether, a commercially available pyrethroid. [Table 2]

[0058] Test Example 2: After uniformly heating and mixing 0.3 parts by weight of compound 1 and 59.7 parts by weight of kerosene, an insecticide was prepared. The resulting formulation was placed in an aerosol tank, which was fitted with a valve. Under pressurized conditions, 40.0 parts by weight of propane and butane were injected through this valve to obtain an insecticide aerosol containing 0.3% of compound 1.

[0059] The efficacy of this insecticide aerosol against mosquitoes, flies, and German cockroaches was measured according to GB / T13917.2-2009, using a sealed cylindrical apparatus. The specific procedure was as follows: Test insects were placed in a tank, and after the test insects recovered to normal activity, 1 g of the insecticide aerosol was quantitatively sprayed from the tank. After 1 minute, the baffle was removed to allow the test insects to come into contact with the insecticide, and timing was immediately started. Recording was then initiated, recording the number of knocked-down test insects at regular intervals. After 20 minutes, all test insects were transferred to a clean insect rearing cage, and the number of dead test insects was examined after 24 hours. Among these, the 72-hour mortality rate of German cockroaches was examined.

[0060] Aerosol formulations of compounds 1-3, monfluorothrin, and tetramethylfluthrin were prepared according to Test Example 2, and efficacy tests were conducted. The comparative results are shown in Table 3. [Table 3]

[0061] As is clear from the results, the aerosol prepared with compound 1 of the present invention has a relatively good control effect against mosquitoes, flies, and German cockroaches, and its effect is clearly better than that of other compounds.

[0062] The present invention also includes the following aspects and embodiments. [Item 1] A pyrethroid compound containing a double bond and a cyano group, wherein the structure of the pyrethroid compound is of general formula I [ka] I A pyrethroid compound represented by the formula, where n is 3 or 4. [Item 2] The pyrethroid compound according to Item 1, characterized in that when n is 3, the compound is 2,3,5-trifluorobenzyl(Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropanecarboxylate or 2,3,6-trifluorobenzyl(Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropanecarboxylate. [Item 3] The pyrethroid compound according to Item 1, characterized in that when n is 4, the compound is 2,3,5,6-tetrafluorobenzyl(Z)-3(2-cyanovinyl)-2,2-dimethylcyclopropanecarboxylate. [Item 4] The compound is 2,3,5-trifluorobenzyl(Z)-3(2-cyanovinyl)-2,2-dimethylcyclopropanecarboxylate, and its structural formula is formula II [ka] II A pyrethroid compound according to item 1, characterized by being represented by [the specified symbol]. [Item 5] A method for synthesizing a pyrethroid compound containing a double bond and a cyano group as described in any of Items 1 to 4, comprising the following steps (1) to (4): (1) Synthesis of Z-configuration products The process involves reacting tert-butyl 3-formyl-2,2-dimethylcyclopropionate with cyanomethyl phosphate or cyanomethyltriphenylphosphine under basic action in solvent I to produce tert-butyl 3-(2-cyanovinyl)-2,2-dimethylcyclopropionate, and obtaining (Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropionate tert-butyl by column chromatography. (2) Detert-butylation The tert-butyl of (Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropionic acid obtained in step (1) is removed under acid action to obtain (Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropionic acid. (3) Acyl chlorination reaction The (Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropionic acid obtained in step (2) is subjected to an acyl chlorination reaction to obtain (Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropionyl chloride. (4) Esterification reaction The (Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropionyl chloride obtained in step (3) is subjected to an esterification reaction with benzyl alcohol under basic action to obtain a pyrethroid compound containing a double bond and a cyano group. A synthesis method characterized by including the following. [Item 6] In step (1), the base is suspended in solvent I at -5 to -30°C, cyanomethyl phosphate or cyanomethyltriphenylphosphine is added dropwise at -5 to -30°C, and then tert-butyl 3-formyl-2,2-dimethylcyclopropionate is added dropwise and reacted to obtain (Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropionate tert-butyl. The synthesis method according to claim 5, characterized in that the solvent I is one of tetrahydrofuran, 2-methyltetrahydrofuran, acetonitrile, and toluene, or a mixture of two or more of these in any proportion. [Item 7] In step (2), tert-butyl Z-3-(2-cyanovinyl)-2,2-dimethylcyclopropionic acid is dissolved in solvent II, and (Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropionic acid is obtained under the catalytic action of an acid. The synthesis method according to claim 5, characterized in that the solvent II is one of toluene, xylene, benzene, dichloroethane, chloroform, and tetrahydrofuran, or a mixture of two or more of these in any proportion. [Item 8] In step (3), Z-3-(2-cyanovinyl)-2,2-dimethylcyclopropionic acid is dissolved in solvent III, thionyl chloride is added dropwise under normal pressure reflux, and the reaction is carried out to obtain (Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropionyl chloride. The synthesis method according to claim 5, characterized in that the solvent III is one of n-hexane, cyclohexane, methylcyclohexane, dichloromethane, chloroform, dichloroethane, benzene, toluene, and xylene, or a mixture of two or more of these in any proportion. [Item 9] In step (4), after dissolving benzyl alcohol in toluene, an acid binding agent is added, and (Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropionyl chloride is added dropwise under conditions of 0 to 30°C to react and obtain a pyrethroid compound containing a double bond and a cyano group represented by formula I. The synthesis method according to claim 5, characterized in that the acid binding agent is triethylamine, pyridine, or a liquid base. [Item 10] The use of a pyrethroid compound containing a double bond and a cyano group as described in any of Items 1 to 4 as an insecticide for pest control, characterized in that the pyrethroid compound containing a double bond and a cyano group represented by Formula I is prepared as a mosquito repellent aerosol or electric mosquito coil and used to kill mosquitoes, flies, and German cockroaches. The above examples are for illustrative purposes only and do not limit the scope of protection of the present invention. Equivalent transformations or modifications based on the substance of the present invention should be included within the scope of protection of the present invention.

Claims

1. A pyrethroid compound containing a double bond and a cyano group, 【Chemistry 1】 2,3,5-trifluorobenzyl(Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropanecarboxylate, and 【Chemistry 2】 A pyrethroid compound selected from 2,3,6-trifluorobenzyl(Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropanecarboxylate, represented by .

2. A method for synthesizing a pyrethroid compound containing a double bond and a cyano group as described in claim 1, comprising the following steps (1) to (4): (1) Synthesis of Z-configuration products A step comprising reacting tert-butyl 3-formyl-2,2-dimethylcyclopropionate with cyanomethyl phosphate or cyanomethyltriphenylphosphine under basic action in solvent I to produce tert-butyl 3-(2-cyanovinyl)-2,2-dimethylcyclopropionate, and obtaining (Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropionate tert-butyl by column chromatography, wherein solvent I is one of tetrahydrofuran, 2-methyltetrahydrofuran, acetonitrile, or toluene, or a mixture of two or more of these in any proportion, (2) Detert-butylation The tert-butyl of (Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropionic acid obtained in step (1) is removed under acid action to obtain (Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropionic acid. (3) Acyl chlorination reaction The (Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropionic acid obtained in step (2) is subjected to an acyl chlorination reaction to obtain (Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropionyl chloride. (4) Esterification reaction The (Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropionyl chloride obtained in step (3) is subjected to an esterification reaction with 2,3,5-trifluorobenzyl alcohol or 2,3,6-trifluorobenzyl alcohol under basic action to obtain a pyrethroid compound containing a double bond and a cyano group. A synthesis method characterized by including the following.

3. The synthesis method according to claim 2, wherein in step (1), the base is suspended in solvent I at -5 to -30°C, cyanomethyl phosphate ester or cyanomethyltriphenylphosphine is added dropwise at -5 to -30°C, and then tert-butyl 3-formyl-2,2-dimethylcyclopropionate is added dropwise and reacted to obtain (Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropionate tert-butyl.

4. In step (2), tert-butyl Z-3-(2-cyanovinyl)-2,2-dimethylcyclopropionic acid is dissolved in solvent II, and (Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropionic acid is obtained under the catalytic action of an acid. The synthesis method according to claim 2, characterized in that the solvent II is one of toluene, xylene, benzene, dichloroethane, chloroform, and tetrahydrofuran, or a mixture of two or more of these in any proportion.

5. In step (3), Z-3-(2-cyanovinyl)-2,2-dimethylcyclopropionic acid is dissolved in solvent III, thionyl chloride is added dropwise under normal pressure reflux, and the reaction is carried out to obtain (Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropionyl chloride. The synthesis method according to claim 2, characterized in that the solvent III is one of n-hexane, cyclohexane, methylcyclohexane, dichloromethane, chloroform, dichloroethane, benzene, toluene, and xylene, or a mixture of two or more of these in any proportion.

6. In step (4), after dissolving 2,3,5-trifluorobenzyl alcohol or 2,3,6-trifluorobenzyl alcohol in toluene, an acid binding agent is added, and (Z)-3-(2-cyanovinyl)-2,2-dimethylcyclopropionyl chloride is added dropwise under conditions of 0 to 30°C to react and obtain a pyrethroid compound containing a double bond and a cyano group represented by formula I. The synthesis method according to claim 2, characterized in that the acid binding agent is triethylamine, pyridine, or a liquid base.

7. An insecticide comprising a pyrethroid compound according to claim 1 for use in controlling a pest selected from mosquitoes, flies, and German cockroaches, wherein the insecticide is an aerosol for controlling mosquitoes, flies, or German cockroaches, or an electric mosquito coil for controlling mosquitoes.

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