JPH0212941B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel class of pyrethroids,
More specifically, novel esters of 2,2-dimethylcyclopropanecarboxylic acid in which an unsaturated polyhalogenated chain with 3 carbon atoms is substituted in the 3-position of the cyclopropane ring and their use as insecticides. Regarding. Furthermore, the present invention relates to novel above-mentioned cyclopropanecarboxylic acids, lower alkyl esters thereof and methods for their synthesis. Pyrethrins (or pyrethrum), namely chrysanthemum acid (2,2-dimethyl-3-isobutenylcyclopropanecarboxylic acid) and letronolone (2-alkenyl-3-methylcyclopent-2-ene-4-
Oron) is a naturally occurring insecticide characterized by fast-acting, high insecticidal activity and low toxicity to animals. However, pyrethrum easily decomposes in the atmosphere, and this behavior makes it unsuitable for crop protection and limits its use to indoor use only. Moreover, this requires high outlays, on the one hand due to the complexity of the extraction process, and on the other hand, due to the forced combination with suitable synergistic substances. In order to overcome all of these problems and to obtain a molecule that retains insecticidal action and low toxicity to animals, and at the same time is more resistant to atmospheric substances, structurally similar to pyrethrum (pyrethroid) Many substances have been synthesized [e.g. "synthetic pyrethroids" (written by M.Elliott; ACS Symposium
Series No. 42, Washington (1977)]. The research focuses on the synthesis of new derivatives of 2,2-dimethylcyclopropanecarboxylic acid and similar substances,
It was directed to the synthesis of alcohols similar to cyclopentenolone and to new groups with an alcohol function to be esterified with derivatives or analogs of 2,2-dimethylcyclopropanecarboxylic acid. Among them, 2, which has a substituent at the 3-position,
There are many derivatives of 2-dimethylcyclopropanecarboxylic acid. Among these, the most promising compounds from the viewpoint of stability are those having a β,β-dihalobinyl group at the 3-position [J. Farkas et al., Chem.Listy.
52, 688 (1958); M.Elliott et al., Nature (London)
246, 169 (1973); M.Elliott et al., J.Chem.Soc.
Perkin 1, 1974 , 2470]. Some of the synthetic pyrethroids that have shown beneficial properties are shown in Table 1 below. [Table] [Table] Here, the inventor has calculated the following formula A 3-phenoxybenzyl ester of 2,2-dimethyl-3-(β-fluoro-β-trifluoromethylvinyl)cyclopropanecarboxylic acid has been found. The compounds of formula are endowed with high insecticidal and acaricidal activity. Furthermore, the inventor has determined that the following general formula We have found new derivatives of 2,2-dimethylcyclopropanecarboxylic acid encompassed by (where R' is H, C ₁ -C ₄ alkyl). This serves another purpose of the invention. Compounds of the general formula are useful intermediates in the synthesis of new pyrethroids of the general formula. One of the methods for preparing derivatives of the general formula, which is another object of the present invention, starts from polyfluorohalogenated ethane of the formula CF ₃ -C(F)Y ₂ , where Y is Cl or Br. The reaction is carried out according to Reaction Formula 1. Reaction route diagram 1 (R' and Y have the meanings described above) (1) Addition of a CF ₃ -C(F)Y ₂ compound to the double bond of 3,3-dimethyl-4-pentenoate ester in the presence of a radical reaction promoter according to the following method. (2) Cyclization of the adduct so obtained in the presence of a base. (3) Dehydrohalogenation by further treatment with base. Conditions for carrying out the last two reactions and halogen Y
Based on the nature of step (3), step (3) may be accomplished when step (2) proceeds or may also proceed by the following order: All of the starting compounds of type CF ₃ -C(F)Y ₂ are known compounds easily obtained from commercially available halogenated polyfluoroethane by known substitution reactions. Examples of compounds of type CF ₃ -C(F)Y ₂ are as follows. Suitable promoters for the _{CF3- CFBr2} addition reaction (1) are organic peroxides such as t-butyl peroxide, benzoyl peroxide or diacetyl peroxide, azo derivatives such as azobisisobutyronitrile, These are transition metal-containing complexes, such as those formed from iron or copper salts and aliphatic amines, or redox transfer systems. Reaction (1) involves the reaction of polyhalogenoethane with 3,3-
It is carried out by reacting dimethylpentenoic acid ester, preferably in a polyhalogenoethane/ester molar ratio greater than 1, at a temperature between 50 and 200°C. This reaction may conveniently be carried out in an autoclave under autogenous or atmospheric pressure in an inert solvent at reflux temperature. The cyclization reaction (2) takes place in a polar solvent at temperatures between -20°C and +50°C under the action of a strong base such as an alkali alcoholate or sodium hydride. By prolonged treatment with the same base or under slightly more aggressive temperature conditions, dehydrohalogenation according to reaction (3) can occur. Alternatively, the HY acid removal reaction can be carried out by the action of an inorganic base or an acid-accepting amine before and after the cyclization step. The compound prepared according to the above method is an ethyl ester or a methyl ester, from which the acid to be reacted can be easily obtained by a common hydrolysis reaction. When the HY acid removal reaction is carried out with an inorganic base such as sodium or potassium hydroxide, hydrolysis of the ester group occurs simultaneously so that subsequent acidification directly yields the compound in the free acid form. It will be done. Compounds of the formula are also other objects of the invention and can be prepared by other methods. As a first step, this method uses the following formula It consists of adding a compound of the formula CF ₃ -CFY ₂ to 2-alkoxycarbonyl-3,3-dimethyl-4-pentenoic acid ester and carrying out the reaction by various methods. The raw material compound - alkoxycarbonyl-3,3-dimethyl-4-pentenoic acid ester can be easily obtained by the reaction of 3-chloro-3-methylbutene and malonic acid ester (Belgian Patent No. 851524) . The steps for producing compounds of the general formula according to this second method are summarized in Reaction Route Diagram 2 below. Reaction route diagram 2 (where R' and Y have the meanings given above) The various steps summarized in Reaction Pathway Figure 2 will now be described in detail. Reaction (1) (Route Diagram 2) Reaction (1) is an organic peroxide such as t-butyl peroxide, benzoyl peroxide or diacyl peroxide; an azo derivative such as azobisisobutyronitrile, e.g. It is carried out in the presence of a radical reaction promoter, such as a complex containing a salt of a transition metal, such as a complex of an iron or copper salt with an aliphatic amine, or a redox transfer system. Reaction (1) involves the reaction between polyhalogenoethane of the formula CF ₃ -CXY ₂ and 2-alkoxycarbonyl-3,3-dimethyl- in the presence of a catalytic amount of the radical reaction promoter described above.
4-pentenoate ester preferably in a polyhalogenoethane/ester molar ratio greater than 1 50
It is carried out by reacting at temperatures between -200°C. This reaction may conveniently be carried out in an autoclave under autogenous pressure or at atmospheric pressure in an inert solvent at reflux temperature. Examples of compounds of type CF ₃ -C(F)Y ₂ are as follows. CF ₃ -CFBr ₂ reaction (2) In reaction (2), the adduct (B) obtained in reaction (1) is
equivalent amount of alkali base (NaHCO ₃ , Na ₂ CO ₃ ,
K ₂ CO ₃ , KOH, NaOH, C ₂ H ₅ ONa) in an organic solvent. As a result, 1, indicated by (C) in route diagram 2,
1-cyclopropanedicarboxylic acid diester is obtained. Reaction (3) The cyclopropane derivative obtained in reaction (2) is 1
It is dehydrohalogenated by treatment with an equivalent amount of alkali base, which is preferably a sodium alcoholate. Optionally, the homologous intermediate can be obtained directly by treating the adduct described in step 1 with 2 equivalents of alkali base. As a result, a cyclopropanedicarboxylic acid ester represented by (D) is obtained. Reaction (4) Intermediate (D) is subjected to decarboxylation under any of the following conditions. (a) Complete or partial hydrolysis with acids or alkalis in alcohols followed by heating of the corresponding acids in neutral or basic organic solvents at temperatures between 100 and 250°C. (b) Hydrolysis as in (a) above followed by heating in quinoline in the presence of copper at a temperature between 100 and 250°C. (c) Heating in an aprotic polar solvent such as dimethyl sulfoxide in the presence of an alkali halide or cyanide and a stoichiometric amount of water (2 equivalents). This gives a compound of the general formula as a carboxylic acid (R'=H). If desired, this can be converted into the corresponding ester by conventional esterification reactions, from which the corresponding acids can be prepared, if desired, by conventional hydrolysis reactions. Compounds of general formula were prepared according to the method described above and are summarized in Table 2 below. Table: Pyrethroids of the general formula can be easily obtained from cyclopropane carboxylic acids and esters of the general formula by methods quite common in the field of organic chemistry. For example, compounds of the general formula can be produced by converting acids and esters of the general formula to the corresponding acyl halides, which are reacted with 3-phenoxybenzyl alcohol. The specific structure of the acids and esters of the general formula allows for the existence of various geometric and stereoisomers. Their existence is due to the presence of the following factors. (a) the asymmetry of carbon atoms 1 and 3 of the cyclopropane ring (enantiomers); (b) the relative spatial configuration of the COOR′ group and the substituent [formula] with respect to the plane defined by the cyclopropane ring (cis or trans), (c) cis or trans isomerism of the substituent present on the double bond of [Formula]. The separation of the various stereoisomers and their enantiomers from the various isomer mixtures is achieved by applying known chemical methods, such as chromatography and salt precipitation with optically active bases. be able to. The scope of the present invention includes all the stereoisomeric and/or configurational isomeric forms obtainable from the mixture of compounds of the formula prepared by the process described above. Included are separation and use as well as the use of the mixture itself and those derived by partially or completely separating it into stereoisomers. Similarly, the novel pyrethroids of the general formula may also be mixtures of isomers due to the presence of asymmetric centers and the possibility of cis-trans isomerism. A unique feature of these mixtures is the fact that the separation of the components can be carried out by simple chemical methods, such as column chromatography or thin layer chromatography. The scope of the invention also includes the isolation and use as pesticides of each stereoisomer or configurational isomer and the direct use of the mixture obtained by the synthesis of the isomers or their incomplete separation. . The compounds of the general formula which form the object of the present invention are useful for pests belonging to the most important classes in terms of their toxicity in the agricultural and household fields, such as Hemiptera, Lepidoptera, Coleoptera,
Besides a very high activity against Diptera and Blattoidea, it also showed a satisfactory acaricidal activity, clearly superior to many known pyrethroids. The benefits of the compounds of the present invention are demonstrated by their high levels of insecticidal activity, as evidenced by the data set forth below in Table 4 (where a comparison is made with two known synthetic pyrethroids) and from Example 8, respectively. This becomes especially clear when considering its low acute toxicity. Furthermore, the pyrethroids that are the object of the present invention are
As demonstrated in Example 9, the requirement of good stability is met. The following examples are provided to better illustrate the invention. Example 1 3,3-dimethyl-4,6-dibrome-6,
Preparation of ethyl ester of 7,7,7-tetrafluoroheptanoic acid In an autoclave with a holding capacity of 200 ml, under nitrogen atmosphere, add 17 g of 3,3-dimethyl-4
-Ethyl ester of pentenoic acid (0.105 mol), 55
g of 1,1,1,2-tetrafluorodibromomethane (0.21 mol) and 0.5 ml of tert-butyl peroxide were charged. The autoclave was then immersed in an oil bath and mechanically shaken for 5 hours at a temperature of 120°C.
After cooling, the contents were diluted with 100 ml of CH ₂ Cl ₂ . This solution was then dissolved in H ₂ O containing a small amount of FeSO ₄
(3 x 50ml), dried with anhydrous _CaCl2 and the solvent was evaporated under vacuum. Due to this
43.3 g of crude product was obtained, which was vacuum distilled to collect a fraction with a boiling point of 97-99°C at 0.25 mmHg.
39g of 3,3-dimethyl-4,6-dibrome
Ethyl 6,7,7,7-tetrafluoroheptanoate was obtained. Elemental analysis Bromine Theoretical value 38.41% Actual value 37.83% Example 2 2,2-dimethyl-3-(β-fluoro-β-
Preparation of ethyl ester of (trifluoromethylvinyl)cyclopropanecarboxylic acid and its free acid 3,3-dimethyl-4,6-dibromo-6,7,7,7-tetra obtained as described in Example 1 A solution of ethyl fluoroheptanoate (25 g, 0.06 mol) in ethanol (50 ml) was heated at 23-32°C.
A solution of sodium ethylate (0.132 mol) dissolved in ethanol (150 ml) was added at a temperature of . Upon completion of the addition, the resulting solution was maintained at room temperature for 3 hours. Then remove that 50ml from the solution and
It was then concentrated to reduced volume. The resulting solution was then poured into water and ice. Then,
The solution was extracted with CH ₂ Cl ₂ (50 ml) and the organic phase was washed with water until a neutral pH was reached, after which it was dried
Dry with CaCl ₂ and remove the solvent under vacuum. This gave 3.6 g of crude reaction product, which, as analyzed by gas chromatography combined with mass spectrometry, was 2,2-dimethyl-3-(β-fluoro-β- ethyl ester of (trifluoromethylvinyl)cyclopropanecarboxylic acid (compound a, Table 2) (which can be separated from the crude product by column chromatography)
and 2,2-dimethyl-3-(β-bromo-β,
It was found to consist mainly of the ethyl ester of γ,γ,γ-tetrafluoropropyl)cyclopropanecarboxylic acid (approximately 20% of the crude product) (compound b, Table 2). A portion of the remaining ethanol solution from which the 50 ml portion was taken was added to the
of KOH. The reaction mixture was then heated at reflux temperature for 2 hours to effect hydrolysis of the ester and complete dehydrobromination of the β-bromo-β,γ,γ,γ-tetrafluoropropyl group. The reaction mixture was then concentrated to reduced volume before pouring into water and ice. The mixture was acidified with dilute H ₂ SO ₄ and then
Extract with CH ₂ Cl ₂ (3 x 50 ml) and remove the organic phase.
Wash with an aqueous solution of NaCl (2 x 100 ml) and dry
Dry with _CaCl2 . By removing the solvent under vacuum, 8 g of 2,2-dimethyl-3-
(β-fluoro-β-trifluoromethylvinyl)
Cyclopropanecarboxylic acid (compound c, Table 2) was obtained. Example 3 CF ₃ −CFBr−CH ₂ −CHBr−C(CH ₃ ) ₂ −CH
Production of (CO ₂ C ₂ H ₅ ) ₂ In a 250 ml Hastelloy C autoclave equipped with a balance rocker, 208
g of CF ₃ CFBr ₂ (0.8 mol), 91.2 g of CH ₂ =CH−
C( _CH3 ) ₂ -CH( _CO2Et ) ₂ (0.4 mol) and 6 ml of di-tert-butyl peroxide were introduced. The autoclave was heated to 140°C and maintained at this temperature for a period of time. After cooling, take out the contents,
After removing excess _CF3 − _CFBr2 by evaporation,
The contents of the autoclave are subjected to molecular distillation to reduce the boiling point.
The fraction at 90°C (10 ^-3 mmHg) was collected. This is 120
g of (1,1-dimethyl-2,4-dibromo-
It consisted of ethyl 4,5,5,5-tetrafluoropentylmaloate (n ²² _D =1.4513). IR analysis was consistent with the given structure. Elemental analysis C actual value = 34.9% C theoretical value = 34.5% H actual value = 4.2% H theoretical value = 4.1% F actual value = 15.4% F theoretical value = 15.6% Br actual value = 31.9% Br theoretical value = 32.8% Example 4 Preparation of [Formula] and [Formula] Into an ethanolic solution of sodium ethylate prepared from 2.4 g of sodium and 100 ml of absolute ethanol, 48.8 g prepared as described in Example 4
A solution of (0.1 mol) of ethyl (1,1-dimethyl-2,4-dibromo-4,5,5,5-tetrafluoro)pentylmalonate dissolved in 100 ml of absolute ethanol was added dropwise with stirring. Once the addition was complete, a sample was taken from the mixture and then gas mass spectrometry showed that the cyclization reaction was already complete producing the next compound. Mass fragmentation (C ₁₄ H ₁₉ F ₄ BrO ₄ ): 406 (M ⁺ ) 327 (M ⁺ −Br) 361 (M ⁺ C ₂ H ₅ O) 213 (M ⁺ −C ₃ F ₄ BrH ₂ ) 315 314 185 167 43 At this point, more sodium ethylate in ethanol was added and the reaction mixture was stirred.
It was kept at 40°C for 5 hours. After neutralization with HCl (1:1) and subsequent filtration, the solution was concentrated to a small volume, 200 ml of water was added and extracted with CHCl ₃ (2×150 ml). Then,
The chloroform extract was dried over CaCl ₂ and evaporated to give 31.4 g of diethyl ester of 2,2-dimethyl-3-(β-fluoro-β-trifluoromethylvinyl)cyclopropane-1,1-dicarboxylic acid (n ²² _D = 1.4303) was obtained. Mass fragmentation (C ₁₄ H ₁₈ F ₄ O ₄ ): 326 (M ⁺ ) 281 (M ⁺ −C ₂ H ₅ O) 253 (M ⁺ −C ₃ H ₅ O ₂ ) 225 (253−C ₂ H ₄ ) 235 207 179 167 160 115 Example 5 Preparation of Formula In a flask immersed in an oil bath and equipped with a reflux condenser, under a nitrogen atmosphere, 5 g of the following material prepared as described in Example 4 were added: of 1 g NaCl, 12 ml dimethyl sulfoxide and
0.6 ml of water was introduced. The reaction mixture was then heated at reflux for 9 hours at 165-167°C. After cooling, gas chromatographic analysis shows that the compound has a degree of conversion of 75% and a ratio of approximately 1:1 in the ring.
It is shown that it was produced with a cis/trans ratio. Example 6 (±)-cis,trans2,2-dimethyl-3-(β
-Fluoro-β-trifluoromethylvinyl)
Production of m-phenoxybenzyl ester of cyclopropanecarboxylic acid and partial separation of geometric isomers 9.5 g of 2,2-dimethyl-3-(β-fluoro-β-trifluoromethylvinyl)cyclopropanecarboxylic acid , 23 ~ in 200 ml CCl ₄
The acid was converted to the chloride by treatment with 9.7 g of PCl ₅ at 24°C. By vacuum distillation,
6.2 g of acid chloride (elemental analysis: actual value Cl = 14.29
%, theoretical value Cl = 14.49%). 2.2 g of the acid chloride thus obtained were dissolved in 100 ml of anhydrous benzene containing 2 ml of pyridine.
Esterification was carried out by treatment with 2.2 g of 3-phenoxybenzyl alcohol at a temperature of 18-24°C. After filtration of the pyridium salt, the solution was washed with 80 ml of aqueous HCl and then with water at 0° C. to neutral pH. After dehydration, by evaporating the solvent in vacuum,
Crude (±)-cis,trans-2,2-dimethyl-
4.1 g of 3-phenoxybenzyl ester of 3-(β-fluoro-β-trifluoromethylvinyl)cyclopropanecarboxylic acid was obtained. To achieve partial separation of the geometric isomers, the product thus obtained was passed through a silica gel column [filling material:
Silica gel Kieselgel G (type 10) manufactured by Merck & Co. and C-Elba code 453332
1:2 weight ratio mixture of similar products according to Column length: 20 cm, Column diameter: 2.4 cm, Eluent:
Chromatographed with n-hexane/benzene (2:1), room temperature] and collected the following fractions: Fraction: Sample 1-A (1 g) Fraction: Sample 1-M (0.6 g) Fraction: Sample 1-B (1.2 g) Based on nuclear magnetic resonance (NMR) analysis, sample 1
-A is (±)-cis-2,2-dimethyl-3-
It was found to consist primarily (at least 90%) of the 3-phenoxybenzyl ester isomer of (β-fluoro-β-trifluoromethyl(E)vinyl)cyclopropanecarboxylic acid. Sample 1-B is from the 3-phenoxybenzyl ester isomer of (±)-trans-2,2-dimethyl-3-(β-fluoro-β-trifluoromethyl(E)vinyl)cyclopropanecarboxylic acid. It turned out to be mainly (mainly at least 80%). Sample 1-M is approximately 1:3 of the above two isomers.
It was found that it consists of a mixture of cis:trans ratios. The properties of these samples are described below. NMR (δ.ppm) (*) 2 (m, H _A + H _B ) 6.1 (dd, H _C ) 1.23 (s, gem-methyl) 5.06 (s, CH ₂ ) 6.8-7.5 (m, aromatic proton) J (H _C , Ftrans) = 33Hz J (H _C , H _A ) = 9Hz 1.7 (d, H _B ) 2.33 (dd, H _A ) 5.23 (dd, H _C ) 1.16 (s, CH ₃ ) 1.25 (s, CH ₃ ) 5.05 (s, CH ₂ ) 6.8−7.4 (m, aromatic Proton) J (H _C , H _A ) = 9 Hz J (H _A , H _B ) = 5 Hz J (H _C , Ftrans) = 31 Hz ‐‐‐‐‐‐‐‐‐‐ (*) s = singlet; d = doublet; dd = doublet of doublets; m = triplet; J = binding constant Example 7 Insecticidal activity of the compound of the present invention The compound of the present invention was prepared according to the method shown below.
Tests were conducted on larvae and adults of herbivorous pests of the following species and genera. The data are shown in Table 3. A. Biological activity against Macrosiphum euphorbiae (aphid beetle) Small needle-grown potato trees were infested with female adult aphid beetles and then sprayed several hours later with an aqueous dispersion of the test compound. (See Table 3). Mortality was assessed 24 hours after treatment (regarding the mortality of aphids on untreated plants as 0). B Pieris Bratusicae
Biological activity against (Lepidoptera) Cut cauliflower leaves were sprayed with an aqueous dispersion of the test compound (see Table 3). After drying, the leaves were infested with 5-day-old larvae. Larval mortality was determined 48 hours after treatment (mortality on untreated leaves was taken as 0). C. Biological activity against Leptinotarsa decemlineata (Coleoptera) Small needle-grown potato trees were infested with 4-day-old larvae and then sprayed with an aqueous dispersion of the test compound (see Table 3). ). Mortality was determined 48 hours after treatment (mortality of untreated plants was taken as 0). D Musca domestica
Biological activity against (Diptera) Four-day-old adult insects were treated by topical application of an acetone solution of the test compound with a microsyringe (see Table 3). Mortality was determined 24 hours after treatment (mortality of insects treated with acetone alone was taken as 0). E Culex pipiens
Biological activity against adults of (Diptera) A rectangular strip of Whatman paper No. 1 was uniformly treated with an acetone solution of the test compound (see Table 3). After evaporation of the solvent, Perspex cylinders (model OMS) were lined with each treated paper and closed with netting. A 2-3 day old female adult was then placed in the cylinder. One hour after the start of contact, the insects were transferred to identical cylinders similarly lined with untreated paper and given the sugar solution. Mortality was determined 24 hours after the start of treatment (mortality of untreated insects was taken as 0). F. Blatta orientalis
Biological activity against (Orthoptera) The bottom and walls of a glass crystallization dish (cylinder) were treated homogeneously with an acetone solution of the test compound (Table 3
). After evaporation of the solvent, add 80 to 100 microns to each crystallization dish.
Neanide was introduced and the crystallization dish was then covered with a metal net cover. 24 hours after starting treatment, worms were transferred to similar untreated crystal dishes;
I was fed properly. Mortality was determined 48 hours after the start of treatment (mortality of untreated insects was taken as 0). G. Biological activity against adults of Tetranychus urticae (mites).
Subsequently, an aqueous dispersion of the test compound was sprayed (Table 3
). Mortality was calculated 24 hours after treatment (deeming mortality of mites on untreated leaves as 0). [Table] [Table] Example 8 Acute toxicity by oral administration to rats Test animals: White rats, Wistar breed, 50% male and 50% female. Animals were fasted from 2 hours before to 2 hours after treatment after the fattening period and subsequently kept under observation for 14 days. During this period, the animals were provided with constant pellets and water. Treatment was carried out by introducing a fixed amount of compound into the animal's stomach via a gastric probe connected to a pressurized syringe. Mortality and all possible signs of poisoning were recorded during the entire observation period. Compound 1-B was also tested on rats according to the method described above at a dose of 200 mg of active substance per kg of body weight, and no mortality of the test animals was observed after the test. Example 9 Testing the activity and duration of action against mites in the field The activity and duration of action of a number of representative compounds against mites (Tetranychus urticae) that are resistant to conventional insecticides were tested. The test was conducted outdoors in a field. The compounds were applied as a dispersion in aqueous acetone with the addition of a wetting agent ("Fitofil" from Montegisson, 0.5% concentration) and sprayed uniformly over the crop to the drop limit (concentration of active ingredient = 0.3%). Data is collected at regular intervals from the start of processing.
Adult mites present on randomly sampled leaves were counted and recorded. It is well known that under the above conditions all of the pyrethroids listed in Table 1, with the exception of mermethrin, cypermethrin and decamethrin, undergo rapid degradation and become completely inactive after a very short time. In this example test, mermethrin and cypermethrin were observed to become completely inactive after 14 days. In contrast, the compounds of the invention still showed significant activity after this same period. Example 10 Comparative Tests A series of experiments were conducted to compare the insecticidal and acaricidal activities of the compounds listed below. The compound tested has the general formula: (Here, X represents a fluorine, chlorine or bromine atom) The compounds used are as follows. I-F-m: (±)-cis,trans-2,2-dimethyl-3-(β-fluoro-β-trifluoromethylvinyl)cyclopropanecarboxylic acid 3
-Phenoxybenzyl ester (formula, X=
F, approximately 1:1 cis-trans isomer mixture) I-F-t: (±)-trans-2,2-dimethyl-3-(β-fluoro-β-trifluoromethylvinyl)cyclopropanecarboxylic acid 3-phenoxybenzyl ester (formula, X=F,
trans isomer) I-Cl-m: (±)-cis,trans-3- of 2,2-dimethyl-3-(β-chloro-β-trifluoromethylvinyl)cyclopropanecarboxylic acid
Phenoxybenzyl ester (formula, X=Cl,
approximately 1:1 cis-trans isomer mixture) I-Cl-t: (±)-trans-2,2-dimethyl-3-(β-chloro-β-trifluoromethylvinyl)cyclopropanecarboxylic acid -Phenoxybenzyl ester (formula, X=Cl,
trans isomer) I-Br-m: (±)-cis,trans-3- of 2,2-dimethyl-3-(β-bromo-β-trifluoromethylvinyl)cyclopropanecarboxylic acid
Phenoxybenzyl ester (formula, X=Br,
approximately 1:1 cis-trans isomer mixture) I-Br-t: (±)-trans-2,2-dimethyl-3-(β-bromo-β-trifluoromethylvinyl) 3 of cyclopropanecarboxylic acid -Phenoxybenzyl ester (formula, X=Br,
trans isomer) A Spodoptera litoralis
Relative efficacy of insecticidal activity against A. littoralis) The insecticidal activity of the test compound was expressed as relative efficacy as shown below. For each test compound, the LD ₅₀ value (50
%lethal dose) was determined. In a series of compounds, the activity (LD ₅₀ value) of the compound with the formula where X=F was set as 100, and the relative potency of the compounds with the formula where X=Cl and Br was determined by the following formula. Relative potency = (LD ₅₀ ) _X=F / (LD ₅₀ ) _X=Cl or _Br ×1
00 The results obtained are shown in Table 4. [Table] B Tetranyus urticae (Tetrany-
chus urticae) The relative potency of the test compound was determined in the same manner as in A) above. The results are shown in Table 5. 【table】

Claims (1)

[Claims] Linear formula 2,2-dimethyl-3-(β-fluoro-β-
3-Phenoxybenzyl ester of trifluoromethylvinyl)cyclopropanecarboxylic acid. 2 (±)-cis-2,2-dimethyl-3-(β
-Fluoro-β-trifluoromethyl(E)vinyl)
The compound according to claim 1, which is 3-phenoxybenzyl ester of cyclopropanecarboxylic acid. 3 (±)-trans-2,2-dimethyl-3-
The compound according to claim 1, which is 3-phenoxybenzyl ester of (β-fluoro-β-trifluoromethyl(E)vinyl)cyclopropanecarboxylic acid. 4. The compound according to claim 1, which is a mixture of two isomeric compounds according to claims 2 and 3. Quintic formula (where R′ is H or C ₁ -C ₄ alkyl) into the corresponding acyl halide,
The following formula is characterized by reacting this with 3-phenoxybenzyl alcohol in the presence of a hydrogen halide-accepting base in an inert solvent. 2,2-dimethyl-3-(β-fluoro-β-
A method for producing 3-phenoxybenzyl ester of (trifluoromethylvinyl)cyclopropanecarboxylic acid. 6th order equation 2,2-dimethyl-3-(β-fluoro-β-
An insecticidal and acaricide composition containing 3-phenoxybenzyl ester of (trifluoromethylvinyl)cyclopropanecarboxylic acid as an active ingredient.