JPS6221776B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel intermediate compound for producing a novel cyclopropane derivative useful as an insecticide and acaricide, and a method for producing the same. Although it has been known for many years that certain naturally occurring cyclopropane carboxylic acid esters have insecticidal properties, such esters are very easily degraded by ultraviolet light and are therefore not very useful in the agricultural field. Therefore, in an attempt to find compounds with sufficient photostability for use as general agricultural insecticides, several synthetic compounds based on cyclopropanecarboxylic acid (e.g., as described in British Patent Nos. 1,243,858 and 1,413,491) have been developed. Compounds described) have been evaluated. The present inventor has now proposed the following formula: [In the formula, one of R ¹ and R ² is a group W-(CF ₂ ) _n-
(Here, W is hydrogen, fluorine, or chlorine, and m is 1
or 2), and the other of R ¹ and R ² is fluorine, chlorine, bromine or a group.

[Formula] (where X, Y and Z each represent hydrogen, fluorine or chlorine)
and R ³ represents hydrogen, cyano or ethynyl] has been found to have extremely excellent insecticidal and acaricidal activity and good resistance to photodegradation. We have created a compound useful as a raw material or intermediate for the production of propane derivatives. New useful intermediate compounds which can be directly converted into cyclopropane derivatives of formula (A) (hereinafter referred to as insecticidal final ester compounds or simply compounds of formula (A)) have the following formula: [In the formula, one of R ¹ and R ² is a group W-(CF ₂ ) _n-
(Here, W is hydrogen, fluorine, or chlorine, and m is 1
or 2), and the other of R ¹ and R ² is fluorine, chlorine, bromine or a group.

[Formula] (where X, Y and Z each represent hydrogen, fluorine or chlorine)
and Q represents a hydroxy group, a lower alkoxy group containing up to 6 carbon atoms, or a chlorine or bromine atom. A preferred group of intermediate compounds of formula (B) are:
One of R ¹ and R ² represents the group WCF ₂ --(W has the meaning above), and the other represents the group

[Formula] (X, Y and Z have the above meanings), and Q
represents hydroxy, lower alkoxy having 1 to 3 carbon atoms, chlorine or bromine, and particularly preferred is a compound in which both R ¹ and R ² are trifluoromethyl. Another preferred group of intermediate compounds of formula (B) is one in which R ¹ and R ² are groups WCF ₂
- (where W is hydrogen, fluorine or chlorine), the other represents fluorine, chlorine or bromine, Q is hydroxy, lower alkoxy having 1 to 3 carbon atoms,
A compound representing chlorine or bromine, inter alia:
Preference is given to compounds in which one of R ¹ and R ² represents trifluoromethyl and the other represents chlorine or bromine. A compound in which Q is hydroxy in formula (B) is
obtained by hydrolysis of a compound of formula (B) in which Q is lower alkoxy, which is converted into a compound of formula (B) in which Q is chlorine or bromine, respectively, by reaction with thionyl chloride or thionyl bromide, for example. Therefore, the preparation of compounds of formula (B) in which Q is a lower alkoxy group is important for the preparation of insecticidal final ester compounds. The object of the present invention is to provide a novel intermediate compound useful for the production of a compound of formula (B) in which Q is a lower alkoxy group, and a method for producing the same. That is, the present invention is based on the following formula: [In the formula, one of R ¹ and R ² is a group W-(CF ₂ ) _n-
(Here, W is hydrogen, fluorine, or chlorine, and m is 1
or 2), and the other of R ¹ and R ² is fluorine, chlorine, bromine or a group.

[Formula] (where X, Y and Z each represent hydrogen, fluorine or chlorine)
, Q represents a lower alkoxy group containing up to 6 carbon atoms, W' and W'' represent fluorine, chlorine or bromine, respectively, provided that if R ² is bromine, then W' is It represents bromine]
It provides a 3,3-dimethylpolyhaloalkanoic acid ester represented by: Representative examples of intermediate compounds of formula () according to the present invention include the following compounds. 3,3-dimethyl-4,6,6-trichloro-
Ethyl 7,7,7-trifluoroheptanoate; 3,3-dimethyl-7,7-difluoro-4,
Ethyl 6,6,7-tetrachloroheptanoate; Ethyl 3,3-dimethyl-6,7,7-trifluoro-4,6,7-trichloroheptanoate; 3,3-dimethyl-4,6,6, -ethyl tribromo-7,7,7-trifluoroheptanoate; ethyl 3,3-dimethyl-7,7,8,8,8-pentafluoro-4,6,6-trichlorooctanoate; 3,3-dimethyl -Ethyl 7,7,8,8-tetrafluoro-4,6,6,8-tetrachlorooctanoate. According to the invention, the compound of formula () has the following formula: (wherein Q has the above meaning) and the following formula: (wherein R ¹ , R ² , W′ and W″ have the meanings given above) in the presence of a free radical initiator. The free radical initiator is It can be a physical initiator, such as irradiation with a suitable light source (e.g. an ultraviolet source), or a conventional chemical free radical catalyst, such as benzoyl peroxide or azobisisobutyronitrile. It is convenient to carry out the reaction using an excess of the compound of formula () at a temperature of 50 to 150 °C, preferably 80 to 120 °C, optionally in a closed vessel and under free reaction pressure for 1 to 20 hours. A particularly useful compound is ethyl 3,3-dimethyl-4-pentenoate, although other lower alkyl esters may also be used.
Instead of esters of 4-pentenoic acid, it is also possible to use other compounds whose carboxylate functions are replaced by other equivalent functions. By "equivalent functional group" is meant here a functional group, such as a nitrile, acetyl or formyl group, which can subsequently be converted chemically by oxidation or hydrolysis into a carboxylic acid group without interfering with the aforementioned process. Alternatively,
Instead of the compound of formula (), the following formula: (wherein Q′ is alkoxycarbonyl, cyano or acetyl and Q″ is cyano or alkoxycarbonyl). Examples of compounds of formula () useful in the above process include hexafluoro Ethane, chloropentafluoroethane, 1,1-dichlorotetrafluoroethane,
1,2-dichlorotetrafluoroethane, 1,
1,1-trichlorotrifluoroethane, 1,
1,2-trichlorotrifluoroethane, 1,
1,1-tribromotrifluoroethane, 1,
1,1,3-tetrachlorotetrafluoropropane and 1,1,3-trichloropentafluoropropane. Next, a novel cyclopropane derivative, which is a useful intermediate compound of formula (B), is prepared from the compound of formula () according to the present invention, and further, the insecticidal final ester of formula (A) is prepared from the intermediate compound of formula (B). The method for producing the compound will be explained. First, the intermediate compound of formula (B) in which Q represents a lower alkoxy group is easily produced by a ring-closing reaction induced by treating the compound of formula () according to the present invention with a base. Suitable bases for carrying out this process are tertiary amines such as pyridine, triethylamine, diethylaniline and N-methylpiperidine and alkali metal lower alkoxides (having up to 6 carbon atoms) such as sodium methoxide, sodium ethoxy sodium t-butoxide and potassium t-butoxide. The process is conveniently carried out in a diluent or solvent of the reactants and base used. A particularly convenient way of carrying out this process is to treat a solution of a compound of formula () dissolved in an alcohol corresponding to the alkali metal alkoxide used for 0.5 to 20 hours. A compound of formula () is a compound of formula (B) in which R is alkoxy
At least 2 moles of base are required for the conversion to the compound, and the process involves two steps: cyclization and β-elimination of the hydrogen halide, but in what order do these two steps proceed? Or it is unclear whether they will proceed at the same time. When this process is carried out using only 1 molar equivalent of base, three different products of the following formulas () to () are obtained. Further treatment of each of these products with a molar equivalent of base provides a compound of formula (B), thus converting at least one compound of formula (), () or () into
A method is provided for preparing compounds of formula (B) where Q is alkoxy by treatment with a molar equivalent of base. This method can be used for the preparation of all compounds of formula (B) in which Q is alkoxy, but especially
It is useful for producing compounds where one of R ¹ and R ² is halogen. In formula (B), the compound in which Q is a hydroxy group and the compound in which Q is a base or bromine can be easily produced starting from the compound in which Q is an alkoxy group, as described above. When carrying out various methods of preparing intermediate compounds of formula (B), the products usually result in mixtures of various geometric isomers. For example, mixtures of cis and trans isomers (often with a predominance of monoisomers) are obtained, and when R ¹ is different from R ² both the cis and trans Z- and E-isomers (this In some cases, the monoisomer often predominates). If these isomers are not separated by physical methods, e.g. by fractional crystallization of carboxylic acids, formula (A)
The final ester compound will also consist of a mixture of various isomers containing two or more compounds. The insecticidal ester compound of formula (A), which is the final object, is produced by a conventional esterification method as described below using the intermediate compound of formula (B) derived as described above from the compound of formula () according to the present invention. can. (a) The following formula: The acid of is given by the following formula: can be directly reacted with alcohol. This reaction is preferably carried out in the presence of an acid catalyst, such as dry hydrogen chloride. (b) The following formula: The acid halide (wherein Q is halogen, preferably chlorine) is expressed by the following formula: can be reacted with alcohol. This reaction is preferably carried out in the presence of a base, such as pyridine, an alkali metal hydroxide, carbonate or alkoxide. Alternatively, when R ³ is a cyano group, an alkali metal cyanide and 3
- It is also possible to use mixtures with phenoxybenzaldehyde. (c) The following formula: or preferably its alkali metal salt, of the following formula: (wherein Q' is a halogen, preferably chlorine) or a quaternary halide derived from such a halide and a tertiary amine, such as a trialkylamine such as pyridine or triethylamine.
can be reacted with grade ammonium salts. (b) The following formula: The lower alkyl ester of (wherein R ⁴ is lower alkyl having 6 or less carbon atoms, preferably methyl or ethyl) is expressed by the following formula: The transesterification reaction is carried out by heating with alcohol. The process is preferably carried out in the presence of a suitable catalyst, for example an alkali metal alkoxide such as sodium methoxide or an alkylated titanium derivative such as tetramethyl titanate. All of these conventional ester preparation processes can be carried out using solvents or diluents of the various reactants, if appropriate, and the reaction can be accelerated at elevated temperatures or in the presence of suitable catalysts, such as phase transfer catalysts. Product yield can be increased. The preparation of the individual isomers can be carried out analogously starting from the corresponding individual isomers of the intermediate compounds of formula (B). Such isomers are obtained from mixtures of isomers by conventional isomer separation methods. For example, cis and trans isomers can be separated by fractional crystallization of a carboxylic acid or its salt, while various optically active forms can be separated by fractional crystallization of a carboxylic acid and an optically active amine, followed by regeneration of the optically pure acid. The resulting optically pure isomer of the acid (or its acid chloride or ester) is then converted into 3
- Can be reacted with phenoxybenzyl alcohol to produce the final ester compound of formula (A) in individually pure isomeric form. α-cyano-3-
In the case of phenoxybenzyl alcohol, the reaction of optically pure α-cyano-3-phenoxybenzyl alcohol with a carboxylic acid or its functional derivative is carried out without racemization of the alcohol. cannot, so it will be a mixture of two isomers. Typical products of this method include: (±)-α-cyano-3-phenoxybenzyl (1R,3R)-3-(3,3,3-trifluoro-
2-trifluoromethyl-1-propen-1-yl)-2,2-dimethylcyclopropane carboxylate and (±)-α-cyano-3-phenoxybenzyl (1R,3S)-3-(2- Chloro-3,3,3-trifluoro-1-propen-1-yl)-2,2
-Dimethylcyclopropane carboxylate.
These final ester compounds of formula (A) are particularly useful as insecticides. The production of single isomers of these final ester compounds of formula (A) is accomplished by creating an optically pure acid chloride and reacting it with (±)-3-phenoxymandelamide (±)-α-carboxylic acid chloride. This can be achieved by obtaining an amide ester. These two isomeric esters are separated by fractional crystallization, and the individual esters are dehydrated to give the corresponding α-cyano-3-
It can be phenoxybenzyl ester. It is thus possible to obtain the following single isomers, which are considered to be the most effective insecticidal isomers of the individual compounds: (S)-α-cyano-3-phenoxybenzyl (1R,3R )-3-(3,3,3-trifluoro-
2-trifluoromethyl-1-propen-1-yl)-2,2-dimethylcyclopropane carboxylate and (S)-α-cyano-3-phenoxybenzyl (1R,3S)-3-(2- Chloro-3,3,3-trifluoro-1-propen-1-yl)-2,2
-Dimethylcyclopropane carboxylate.
A preferred group of final ester compounds is one in which in formula (A), one of R ¹ and R ² represents a group WCF ₂ -- (where W is hydrogen, fluorine or chlorine), and R ¹ and
The other side of R ² is the base

[Formula] (wherein X, Y and Z are each hydrogen, fluorine or chlorine), and R ₃ is hydrogen or cyano. Among this preferred group of compounds, those in which both R ¹ and R ² are trifluoromethyl groups are particularly preferred. Another preferred group of final ester compounds has the formula
In (A), one of R ¹ and R ² represents the group WCF ² -- (where W is hydrogen, fluorine or chlorine), the other represents fluorine, chlorine or bromine, and R ³ represents hydrogen or cyano. It is a compound. Particularly preferred are compounds in which one of R ¹ and R ² represents trifluoromethyl and the other represents chlorine or bromine. The final ester compound of formula (A) may exist in various geometric and stereoisomeric forms. For example, cis and trans isomers resulting from the type of substitution on the cyclopropane ring and E- and Z-isomers resulting from substituted vinyl groups when R ¹ is different from R ² may exist. Furthermore, 2 of the three carbon atoms of cyclopropane
are asymmetrically substituted, so R configuration or S
and, if R ³ is not hydrogen, the carbon atom to which it is attached may also exist in the R or S configuration. Therefore, for compounds of formula (A) in which R ¹ and R ² are the same and R ³ is hydrogen, there may be four isomers resulting from the substitution of the cyclopropane ring. These are (1R, 3R), (1R, 3S), (1S, 3S) and (1S, 3S) with reference to their absolute configurations.
3R). If R ³ is not hydrogen, each of the four possible cyclopropane ring configurations exists in two forms corresponding to the S and R configurations of the carbon atom bearing the group R ³ ,
Eight isomers are possible. Separately, even when R ³ is hydrogen and R ¹ is different from R ² , each of the four possible cyclopropane ring configurations has two forms corresponding to the Z and E configurations of the vinyl group. Therefore, eight isomers are possible. After all, if R ¹ is different from R ² and R ³ is not hydrogen, each compound can exist as 16 isomers. Representative examples of the final ester compound of formula (A) are shown in Table 1. Although the compounds shown are racemic mixtures of (+) and (-) isomers, respectively, a distinction is made between cis and trans substitutions on the cyclopropane ring and E and Z substitutions on the vinyl group (if present). . All compounds shown in the table follow the formula:

【table】

【table】

Table: Particularly useful final ester compounds include: (±)-α-cyano-3-phenoxybenzyl (+)-cis/trans-3-(2-chloro-
3,3,3-trifluoro-1-propene-1-
yl)-2,2-dimethylcyclopropane carboxylate, (±)-α-cyano-3-phenoxybenzyl (±)-cis/trans-3-(3,3,3-trifluoro-2-tri Fluoromethyl-1-propen-1-yl)-2,2-dimethylcyclopropane carboxylate, (±)-α-cyano-3-phenoxybenzyl (+)-cis/trans-3-(3-chloro ―
2,3,3-trifluoro-1-propene-1-
(±)-α-cyano-3-phenoxybenzyl (+)-cis/trans-3-(2-bromo-
3,3,3-trifluoro-1-propene-1-
yl)-2,2-dimethylcyclopropane carboxylate, 3-phenoxybenzyl(+)-cis/trans-3-(2-chloro-3,3,3-trifluoro-1-propen-1-yl )-2,2-dimethylcyclopropane carboxylate, and 3-phenoxybenzyl (±)-cis/trans-3-(3,3,3-trifluoro-2-trifluoromethyl-1-propene-1 -il)-
2,2-dimethylcyclopropane carboxylate. The final ester compounds of formula (A) prepared from compounds of formula () according to the invention via compounds of formula (B) can be used for the control of insects and other invertebrate pests, such as mites. Pests that can be controlled using the final ester compounds include agriculture (this term encompasses the cultivation of food and textile crops, horticulture and farming);
Includes pests associated with forestry and the preservation of plant products such as fruits, grains or timber, as well as those associated with the transmission of human and animal diseases. To apply the final ester compound of formula (A) to a pest-infested area, it is usually prepared in a composition containing the final ester compound as the insecticidal active ingredient and a suitable inert diluent or carrier and/or surfactant. Formulated. Such compositions may further contain other pest control agents, such as other insecticides or acaricides or fungicides, and may also contain insecticidal synergists such as, for example, dodecylimidazole, safroxan or piperonyl butoxide. It's okay. The compositions may be in the form of powders for dispersion, in which the active ingredient is mixed with a solid diluent or carrier, such as kaolin, bentonite, diatomaceous earth or talc, or in granules, in which the active ingredient is absorbed in porous particulate material, such as pumice. The compositions can also be used in liquid form for use as a dipping liquid or as a spray liquid, which is usually an aqueous dispersion or emulsion containing the active ingredient in the presence of one or more wetting agents, dispersing agents or emulsifying agents (surfactants). It can also be in the form of a formulation. Such drugs are cationic,
It can be an anionic or nonionic active agent. Suitable cationic activators are quaternary ammonium compounds such as cetyltrimethylammonium bromide. Suitable anionic active agents are soaps, salts of aliphatic monoesters of sulfuric acid, such as sodium lauryl sulfate, salts of sulfonated aromatic compounds, such as sodium, calcium or ammonium lignosulfonate, butylnaphthalene.
It is a mixture of sodium salts of sulfonate and diisopropyl and triisopropylnaphthalene sulfonic acids. Suitable nonionic surfactants are condensation products of ethylene oxide with aliphatic alcohols such as oleyl alcohol or cetyl alcohol or alkyl phenols such as octylphenol, nonylphenol or octylcresol. Other nonionic surfactants are partial esters derived from long chain fatty acids and hexitol anhydride, condensation products of the partial esters with ethylene oxide, and lecithin. The composition comprises dissolving the active ingredient in a suitable solvent, for example a ketone solvent such as diacetone alcohol or an aromatic solvent such as trimethylbenzene;
The resulting mixture can be prepared by adding to water which may contain known wetting agents, dispersing agents or emulsifying agents. Other suitable organic solvents are dimethylformamide, ethylene dichloride, isopropyl alcohol,
Propylene glycol and other glycols, diacetone alcohol, toluene, kerosene, white oil, methylnaphthalene, xylene, trichlorethylene, N-methyl-2-pyrrolidone and tetrahydrofurfuryl alcohol (THFA)
It is. Spray compositions can also be in the form of an aerosol, in which the formulation is held under pressure in a container in the presence of a propellant, such as fluorotrichloromethane or dichlorodifluoromethane. Compositions used in the form of aqueous dispersions or emulsions are usually supplied in the form of concentrates containing a high proportion of the active ingredient and are diluted with water before use. Such concentrates often need to be capable of withstanding long-term storage and, when diluted with water after such long-term storage, to form an aqueous formulation that remains homogeneous long enough to be applied with conventional spray equipment. It is. Such concentrates may contain from 10 to 85% by weight of active ingredient. When diluted to prepare aqueous formulations, such formulations may contain varying amounts of active ingredient depending on their intended use. Aqueous formulations containing 0.0001 to 0.1% by weight of active ingredient are particularly useful for agricultural and horticultural applications. In use, the composition can be applied using any known method of pesticide application;
It is applied, for example by dusting or spraying, to the pest itself, to the location or habitat of the pest, or to growing plants susceptible to attack by the pest. The compounds and compositions of the present invention are extremely harmful to a wide range of insects and other invertebrate pests, including the following pests: black aphid (Aphis fabae) green aphid (Megoura viceae) mosquito (Aedes aegypti) Dysdercus fuasciatus
(Dysdercus fasciatus) House fly (Musca domestica) Pieris brassicae Plutella maculipennis Phaedon cochleariae Red spider mite (Telarius cinnabarinus) Scale insect (Aonidiella spp.) Whitefly (Trialeuroides spp.) Cockroach (Blattella germanica) Spodoptera littoralis (Chortiocetes terminifera) The final ester compounds of formula (A) and compositions containing them are particularly effective against lepidopterous pests of cotton, such as Spodoptera spp. and Heliothis spp. It is useful for controlling pests and mites on livestock, such as the sheep fly (Lucilia sericata) and Boophilus spp., Ixodes spp.
spp.), Amblyomma, Rhipicephalus spp. and Dermaceutor spp.). Such compounds and compositions are effective in controlling sensitive and resistant strains of the above pests in adult, larval and intermediate stages and may be applied to host animals infested with the pest by topical, oral or parenteral administration. . Next, Examples 1 and 2 show examples of producing the compound of formula () of the present invention by the method of the present invention. Furthermore, in order to prove the usefulness of the compound of formula () of the present invention as an intermediate, examples 3 to 4 of producing an intermediate compound of formula (B) from the compound of formula () are shown.
In addition, the production of the corresponding free acid and the production of acid chloride from the compound of formula (B) are shown in Examples 5 to 9.
Examples 10 to 12 show examples of the preparation of insecticidal final ester compounds of formula (A) from intermediates of (B), and test examples illustrating the effectiveness of compounds of formula (A) as insecticides and acaricides. are shown in Examples 13-15. Example 1 This example shows 3,3-dimethyl-4,6,6-trichloro- of the formula: CF ₃ CCl ₂ CH ₂ CHClC(CH ₃ ) ₂ CH ₂ CO ₂ C ₂ H ₅
The production of ethyl 7,7,7-trifluoroheptanoate is shown. Ethyl 3,3-dimethyl-4-pentenoate (7.0g), 1,1,1-trichloro-2,2,2
- A mixture of trifluoroethane (20.0 g) and benzoyl peroxide (0.1 g) in a closed glass tube.
It was heated at 100°C for 5 hours. The reaction mixture thus obtained was carefully distilled to give 3,3-dimethyl-4,
Ethyl 6,6-trichloro-7,7,7-trifluoroheptanoate was collected as a fraction with a boiling point of 112-114°C/2 mmHg, and this was confirmed by infrared absorption spectroscopy and nuclear magnetic resonance spectroscopy. Example 2 The following various halogenated esters were produced by reacting the following haloalkanes with ethyl 3,3-dimethyl-4-heptenoate in the same manner as in Example 1: (i) 1,1 -Difluorotetrachloroethane to 3,3-dimethyl-7,7-difluoro-
Ethyl 4,6,6,7-tetrachloroheptanoate. NMR (CDCl ₃ ): ppm1.10-1.35 (m,
9H): 2.10-3.00 (m, 4H); 4.12 (q,
2H); 4.52 (dd, 1H). (ii) Ethyl 3,3-dimethyl-6,7,7-trifluoro-4,6,7-trichloroheptanoate from 1,1,2-trifluorotrichloroethane. Boiling point of product, 75-76°C/0.05mmHg. (iii) 1,1,1-tribromotrifluoroethane to ethyl 3,3-dimethyl-4,6,6-tribromo-7,7,7-trifluoroheptanoate. NMR (CDCl ₃ ): ppm1.16-1.44 (m,
9H); 2.50 (q, 2H); 3.04 (q,
2H); 4.18 (q, 2H); 460−4.74 (m,
1H). (iv) 1,1,1-trichloropentafluoropropane to 3,3-dimethyl-7,7,8,
Ethyl 8,8-pentafluoro-4,6,6-trichlorooctanoate. NMR (CCl ₄ ): ppm1.13-1.40 (m, 9H);
2.14 2.92 (m, 4H); 3.96-4.25 (q,
2H); 4.5-4.62 (m, 1H). (v) 1,1,1,3-tetrachlorotetrafluoropropane to 3,3-dimethyl-7,7,
Ethyl 8,8-tetrafluoro-4,6,6,8-tetrachlorooctanoate. Example 3 This example shows (±)-cis/trans-3-(E/Z
-2-chloro-3,3,3-trifluoro-1-
This figure shows the production of ethyl propen-1-yl)-2,2-dimethylcyclopropane carboxylate. 3,3-dimethyl-4 obtained in Example 1,
Ethyl 6,6-trichloro-7,7,7-trifluoroheptanoate was dissolved in anhydrous tetrahydrofuran (30
ml) and this solution was dissolved in a suspension of sodium t-butoxide (2.75 g, prepared in situ from sodium hydride and t-butyl alcohol) in anhydrous tetrahydrofuran (120 ml) at 0°C. dripped. After the addition, the mixture was stirred at 0°C for 2 hours,
The mixture was then made acidic with an ethanolic solution of hydrochloric acid.
The mixture was diluted with diethyl ether, washed with water, dried over anhydrous magnesium sulfate and concentrated by evaporating the solvent under reduced pressure. The residual yellow oil was carefully distilled under reduced pressure to give (±)-cis/trans-3-(2-chloro-3,3,3-trifluoro-1-propen-1-yl)-2,2 -Dimethylcyclopropane Ethyl carboxylate (boiling point
70℃/0.5mmHg). From the results of nuclear magnetic resonance analysis, this product consists of a mixture of about 60% cis-isomer and about 40% trans-isomer (relative to the cyclopropane ring), and each of the above isomers. The isomer in which the trifluoromethyl group is in the trans position with respect to the double bond with respect to the cyclopropane ring (Z-isomer) accounts for about 90 to 95%
and the isomer in which the trifluoromethyl group is in the cis position with respect to the cyclopropane ring (E-isomer) is about 5
It was found that ~10% of Example 4 In the same manner as in Example 3, formula (B) was prepared as follows.
Other ethyl esters were prepared. (i) 3,3-dimethyl-7,7-difluoro-
From ethyl 4,6,6,7-tetrachloropentanoate, (±)-cis/trans-3-(E/
Z-2,3-dichloro-3,3-difluoro-
Ethyl 1-propen-1-yl)-2,2-dimethylcyclopropanecarboxylate. NMR (CDCl ₃ ): ppm1.15-1.55 (m,
9H); 1.55-2.50 (m, 2H); 4.00-4.33
(m, 2H); 6.13 and 6.95 (dd, 1H). (ii) From ethyl 3,3-dimethyl-6,7,7-trifluoro-4,6,7-trichloroheptanoate, (±)-cis/trans-3-(E/Z
-3-chloro-2,3,3-trifluoro-1
-propen-1-yl)-2,2-dimethylcyclopropane ethyl carboxylate. NMR ( _CCl4 ): ppm1.20-1.58 (m, 9H)
1.58-2.33 (m, 2H); 4.15 (q, 2H);
5.10, 5.41, 5.91 and 6.25 (4d, 1H). (iii) From ethyl 3,3-dimethyl-4,6,6-tribromo-7,7,7-trifluoroheptanoate, (±)-cis/trans-3-(2-bromo-3,3,3 Ethyl -trifluoro-1-propen-1-yl)-2,2-dimethylcyclopropanecarboxylate. NMR (CCl ₄ ): ppm1.10-1.40 (m, 9H);
1.60-2.44 (m, 2H); 3.96-4.28 (m,
2H); 5.96-7.26 (m, 1H). (iv) From ethyl 3,3-dimethyl-7,7,8,8,8-pentafluoro-4,6,6-trichlorooctanoate, (±)-cis/trans-3
-(2-chloro-3,3,4,4,4-pentafluoro-1-buten-1-yl)-2,2-
Ethyl dimethylcyclopropanecarboxylate. NMR (CCl ₄ ): ppm1.15-2.53 (complex peak, 11H); 3.92-4.30 (m, 2H); 6.12
and 6.92 (dd, 1H). (v) From ethyl 3,3-dimethyl-7,7,8,8-tetrafluoro-4,6,6,8-tetrachlorooctanoate, (±)-cis/trans-
3-(2,4-dichloro-3,3,4,4-tetrachloro-1-buten-1-yl)-2,2
-Ethyl dimethylcyclopropanecarboxylate. Example 5 This example shows (±)-cis/trans-3-(3,
The production of 3,3-trifluoro-2-trifluoromethyl-1-propen-1-yl)-2,2-dimethylcyclopropanecarboxylic acid is shown. (±)-cis/trans-3-(3,3,3-
Ethyl trifluoro-2-trifluoromethyl-1-propen-1-yl)-2,2-dimethylcyclopropanecarboxylate (0.52 g), glacial acetic acid (2.52 ml), hydrobromic acid (48 W/V%, A mixture of 3.36ml) and water (1.12ml) was heated at reflux for 10 hours. After cooling the reaction mixture, it was diluted with water (50 ml) and extracted several times with diethyl ether. The extracts were combined, washed with water, dried over anhydrous sodium sulphate and then concentrated by evaporating the ether under reduced pressure. Based on the results of spectral analysis, the residual oil is mainly composed of (±)-cis/trans-3
-(3,3,3-trifluoro-2-trifluoromethyl-1-propen-1-yl)-2,2-
It was found to consist of dimethylcyclopropanecarboxylic acid. Example 6 In this example, (±)-cis/trans-3-(3,
Figure 2 shows the conversion of 3,3-trifluoro-2-trifluoromethyl-1-propen-1-yl)-2,2-dimethylcyclopropanecarboxylic acid to acid chloride. (±)-cis/trans-3-(3,3,3-
Trifluoro-2-trifluoromethyl-1-propen-1-yl)-2,2-dimethylcyclopropanecarboxylic acid (0.4 g) and thionyl chloride (5.0 g)
ml) was heated at reflux temperature for 2 hours, excess thionyl chloride was removed by vacuum distillation,
(±)-cis/trans-1-chlorocarbonyl-3-(3,3,3-trifluoro-2-trifluoromethyl-1-propen-1-yl)2,2
-Dimethylcyclopropane was obtained. Example 7 This example describes the production of (±)-cis/trans-3-(2-chloro-3,3,3-trifluoro-1-propen-1-yl)-2,2-dimethylcyclopropanecarboxylic acid. shows. (±)-cis/trans-3-(2-chloro-
3,3,3-trifluoro-1-propene-1-
yl)-2,2-dimethylcyclopropanecarboxylate (0.52 g), glacial acetic acid (2.52 ml), hydrobromic acid (48 W/V%, 3.36 ml) and water (1.12 ml)
The mixture was heated at reflux temperature for 10 hours. After cooling the reaction mixture, it was diluted with water (50 ml) and extracted several times with diethyl ether. The extracts were combined, washed with water, dried over anhydrous sodium sulfate and then concentrated by evaporating the ether under reduced pressure. Based on the results of spectral analysis, the residual oil is mainly composed of (±)-cis/trans-3-(2-chloro-3,3,3-trifluoro-1-propene-1).
-yl)-2,2-dimethylcyclopropanecarboxylic acid. Example 8 This example shows (±)-cis/trans-3-(2-
Figure 2 shows the conversion of chloro-3,3,3-trifluoro-1-propen-1-yl)-2,2-dimethylcyclopropanecarboxylic acid to acid chloride. (±)-cis/trans-3-(2-chloro-
3,3,3-trifluoro-1-propene-1-
After heating a mixture of 2,2-dimethylcyclopropanecarboxylic acid (0.4 g) and thionyl chloride (5.0 ml) at reflux temperature for 2 hours, excess thionyl chloride was removed by vacuum distillation to give (±) -Sith/
Trans-1-chlorocarbonyl-3-(2-chloro-3,3,3-trifluoro-1-propen-1-yl)2,2-dimethylcyclopropane was obtained. Example 9 The following carboxylic acids were prepared from the corresponding ethyl esters using methods similar to those described in Examples 5 and 7. (i) (±)-cis/trans-3-(3,3-difluoro-2-trifluoromethyl-1-propen-1-yl)-2,2-dimethylcyclopropane carboxylic acid. IR (liquid film): 3500 to 2500, 1700 ^{, 1665cm -1} . (ii) (±)-cis/trans-3-(3,3-difluoro-2-difluoromethyl-1-propen-1-yl)-2,2-dimethylcyclopropane carboxylic acid. NMR ( _CCl4 ): ppm1.30-1.50 (m, 6H);
1.70~2.60 (complex peak, 2H); 5.70~
7.13 (complex peak, 3H). (iii) (±)-cis/trans-3-(E/Z-2
-trifluoromethyl-1-propen-1-yl)-2,2-dimethylcyclopropane carboxylic acid. NMR ( _CCl4 ): ppm1.22-1.44 (m, 6H);
1.6-2.3 (m, 5H); 5.36-6.6 (m,
1H); 11.9 (s, 1H). (iv) (±)-cis/trans-3-(3-chloro-3,3-difluoro-2-chlorodifluoromethyl-1-propen-1-yl)-2,2-
Dimethylcyclopropane carboxylic acid. NMR ( _CCl4 ): ppm1.24-1.42 (m, 6H);
1.80-2.68 (m, 2H); 6.16 and 7.12
(dd, 1H); 11.6 (S, 1H). (v) (±)-cis/trans-3-(E/Z-
3,3-difluoro-2-chlorodifluoro-
Methyl-1-propen-1-yl)-2,2-
Dimethylcyclopropane carboxylic acid. IR ( _CHCl3 ): 3450~2500, 1705, 1675 ^{cm -1} . (vi) (±)-cis/trans-3-(2-promo-3,3,3-trifluoro-1-propene-
1-yl)-2,2-dimethylcyclopropane carboxylic acid. IR ( _CHCl3 ): 3400~2450, 1700, 1650,
1275, 1140cm ^-1 . (vii) (±)-cis/trans-3-(3-chloro-2,3,3-trifluoro-1-propene-
1-yl)-2,2-dimethylcyclopropane carboxylic acid. IR (oil film); 3400-2200, 1700, 1450,
1140, 1070cm ^-1 . (viii) (±)-cis/trans-3-(2,3-dichloro-3,3-difluoro-1-propene-
1-yl)-2,2-dimethylcyclopropane carboxylic acid. IR ( _CHCl3 ): 3400-2200, 1700cm ^-1 . (ix) Pure (±)-cis-3-(2,3-dichloro-3,3-difluoro-1-propen-1-yl)- on cooling from a concentrated solution of mixed cis and trans acids in hexane. 2,2-dimethylcyclopropane carboxylic acid precipitates. NMR ( _CDCl3 ): ppm1.25 (S, 6H): 1.80
~2.25 (m, 2H): 6.73 (d, 1H). (x) (±)-cis/trans-3-(2-chloro-3,3,4,4,4-pentafluoro-1-
buten-1-yl)-2,2-dimethylcyclopropanecarboxylic acid. NMR ( _CDCl3 ): ppm1.10-1.50 (m,
6H): 1.68-2.58 (m, 2H); 6.14 and
6.85 (dd, 1H). () (±)-cis/trans-3-(2,4
-dichloro-3,3,4,4-tetrafluoro-1-buten-1-yl)-2,2-dimethylcyclopropane carboxylic acid. Example 10 This example shows (±)-α-cyano-3-phenoxybenzyl (±)-cis/trans-3-(3,3,
3-trifluoro-2-trifluoromethyl-1
The production of -propen-1-yl)-2,2-dimethylcyclopropanecarboxylate (hereinafter referred to as compound No. 1) will be described. (±)-cis/trans-1-chlorocarbonyl-3-(3,3,3-trifluoro-2-trifluoromethyl-1-propen-1-yl)-
To the residue consisting of 2,2-dimethylcyclopropane (see Example 6) was added a mixture of pyridine (0.12 g) and (±)-α-cyano-3-phenoxybenzyl alcohol (0.33 g), The mixture thus obtained was stirred at ambient temperature for 16 hours. Water (20
After adding ml), extraction was performed with diethyl ether (10 ml x 3). The extracts were combined, washed successively with water, saturated aqueous sodium carbonate solution and water, and then dried over anhydrous sodium sulfate. After removing the ether by vacuum distillation, the residual oil was subjected to preparative thick-layer chromatography using 2 mm thick silica on glass and chloroform as eluent to yield approximately 20% cis-isomers and approximately 80% cis-isomers. (±)-α-cyano- containing trans-isomer
3-phenoxybenzyl (±)-cis/trans-3-(3,3,3-trifluoro-2-trifluoromethyl-1-propen-1-yl)-2,
2-dimethylcyclopropanecarboxylate (Rf0.53) was obtained. Spectral analysis: Infrared spectrum, 1755, 1680, 1600, 1490,
1300, 1160: NMR, 0.9-2.5τ, 6.0-6.15τ,
6.35−7.2τ: Mass spectrometry spectrum, M ⁺ 483
(275, 259, 231, 209, 208, 181). Example 11 This example shows (±)-α-cyano-3-phenoxybenzyl (±)-cis/trans-3-(2-chloro-3,3,3-trifluoro-1-propene-
The production of 1-yl)-2,2-dimethylcyclopropanecarboxylate (hereinafter referred to as compound No. 6) will be described. A residue consisting of (±)-cis/trans-1-chlorocarbonyl-3-(2-chloro-3,3,3-trifluoro-1-propen-1-yl)-2,2-dimethylcyclopropane ( (see Example 8), pyridine (0.12 g) and (±)-α-cyano-3-phenoxybenzyl alcohol (0.33 g)
g) was added and the mixture thus obtained was stirred at ambient temperature for 16 hours. After adding water (20 ml), extraction was performed with diethyl ether (10 ml x 3
times). The extracts were combined, washed successively with water, saturated aqueous sodium carbonate solution, and water, and then dried over anhydrous sodium sulfate. After removing the ether by vacuum distillation, the residual oil was deposited on glass to a thickness of 2 mm.
Preparative thick layer chromatography using silica and chloroform as eluent (±)-
α-Cyano-3-phenoxybenzyl (±)-cis-3-(2-chloro-3,3,3-trifluoro-1-propen-1-yl)-2,2-dimethylcyclopropanecarboxylate (Rf0.52) and the corresponding trans isomer (Rf0.42) were obtained.
Each of the above isomers contained about 90-95% Z-isomer. Spectral analysis: Infrared spectrum (CHCl ₃ )
1740, 1660, 1590, 1480, 1460cm ^-1 :NMR
(CCl ₄ ): 6.90―7.50τ, 1.60―2.70τ, 1.50―
1.00τ and a special peak, 6.3τ (benzylic H), are believed to belong to Z-cis, E-cis, Z-trans and E-trans, respectively. 6.85, 6.50, 6.11 and 5.84τ (vinyl H) Example 12 3-Phenoxybenzyl alcohol, (±) -
Various carboxylic acids of Example 9 were prepared with the formula
(A) is converted to an ester product with insecticidal activity. These reaction products (hereinafter referred to as product No. 2~
5 and 7-29) are mostly mixtures of two or more of the compounds in Table 1, as shown below. Product No. 2: (±)-α-cyano-3-phenoxybenzyl (±)-cis/trans-3-(3,3,3-trifluoro-2-trifluoromethyl-1-propene- 1-yl)-2,2-dimethylcyclopropane carboxylate, which is a mixture of one part of Compound No. 1 and one part of Compound No. 2. NMR ( _CCl4 ): ppm1.20-1.40
(m, 6H): 1.80~2.30 (m,
2H): 6.17~6.37 and 6.85~7.42
(mm, 11H). Product No. 3: (±)-α-cyano-3-phenoxybenzyl (±)-trans-3-
(3,3,3-trifluoro-2-
Trifluoromethyl-1-propen-1-yl)-2,2-dimethylcyclopropanecarboxylate, which is Compound No. 2 alone. Product No. 4: (±)-α-cyano-3-phenoxybenzyl (±)-cis-3-
(3,3,3-trifluoromethyl-1-propen-1-yl)-2,
2-dimethylcyclopropane carboxylate, which is Compound No. 1 alone. Product No. 5: (±)-α-cyano-3-phenoxybenzyl (±)-cis-3-(2
-Chloro-3,3,3-trifluoro-1-propen-1-yl)-
2,2-dimethylcyclopropane
Carboxylate, this is compound no.
It is a mixture of 19 parts of Compound No. 31 and 1 part of Compound No. 32. Product No. 7: 3-Phenoxybenzyl (±)-cis/trans-3-(3,3,3-
trifluoro-2-trifluoromethyl-1-propen-1-yl)-
2,2-dimethylcyclopropane
Carboxylate, this is compound no.
It is a mixture of 11 parts of Compound No. 3 and 14 parts of Compound No. 4. NMR ( _CCl4 ): ppm1.18~1.40
(m, 6H): 1.75-2.55 (m,
2H): 5.15 (s.2H): 6.30 and 6.70
~7.40 (dm, 10H). Product No. 8: (±)-α-cyano-3-phenoxybenzyl (±)-cis/trans-3-(3,3-difluoro-2-
trifluoromethyl-1-propen-1-yl)-2,2-dimethylcyclopropane carboxylate,
This is a mixture of compounds No. 15, 16, 17 and 18 (composition not measured). IR (liquid film): 1745, 1655, 1595cm
^-1 . Product No. 9: 3-Phenoxybenzyl (±)-cis/trans-3-(Z-2,3-
Dichloro-3,3-difluoro-1
-propene-1-yl)-2,2-
Dimethyl cyclopropane carboxylate, which is a mixture of one part of Compound No. 39 and one part of Compound No. 41. NMR ( _CDCl3 ): ppm1.20~1.37
(m, 6H): 1.73-2.50 (m,
2H): 5.10 (d, 2H): 6.12 and
6.88-7.48 (dm, 10H). Product No. 10: (±)-α-cyano-3-phenoxybenzyl (±)-cis/trans-3-(Z/E-2,3-dichloro-3,3-difluoro-1-propene -1-yl)-2,2-dimethylcyclopropane carboxylate, which consists of 19 parts of Compound No. 43, 1 part of Compound No. 44, and 19 parts of Compound No. 45.
1 part of Compound No. 46. NMR ( _CCl4 ): ppm1.18~1.45
(m, 6H): 1.73~2.50 (m,
2H): 6.32 (m, 1H): 6.08 and
6.81 (dd, 1H): 6.90~7.44 (m,
9H). Product No. 11: (±)-α-cyano-3-phenoxybenzyl (±)-cis-3-
(Z/E-2,3-dichloro-3,
3-difluoro-1-propene-1
-yl)-2,2-dimethylcyclopropane carboxylate, which is a mixture of 19 parts of Compound No. 43 and 1 part of Compound No. 44. NMR ( _CCl4 ): ppm1.18~1.40
(m, 6H): 1.92-2.32 (m,
2H): 6.31 (d, 1H): 6.81
(d, 1H): 6.90-7.45 (m,
9H). Product No. 12: 3-phenoxybenzyl (±)-cis-3-(Z/E-2,3-dichloro-3,3-difluoro-1-propen-1-yl)-2,2- Dimethyl cyclopropane carboxylate, which is a mixture of 19 parts of Compound No. 39 and 1 part of Compound No. 40. NMR ( _CCl4 ): ppm1.05~1.48
(m, 6H): 1.84-2.38 (m,
2H): 5.02 (s, 2H): 6.72-7.45
(m, 10H). Product No. 13: (±)-α-cyano-3-phenoxybenzyl (±)-cis/trans-3-(Z/E-2-trifluoromethyl-1-propen-1-yl)
-2,2-dimethylcyclopropane carboxylate, which is a compound
It is a mixture of 1 part of Compound No. 19, 9 parts of Compound No. 20, 1 part of Compound No. 21, and 9 parts of Compound No. 22. NMR ( _CCl4 ): ppm1.22-1.40
(m, 6H): 1.60~2.30 (m,
5H): 5.2-6.45 (m, 1H). Product No. 14: 3-Phenoxybenzyl (±)-cis/trans-3-(Z/E-2-
trifluoromethyl-1-propen-1-yl)-2,2-dimethylcyclopropane carboxylate,
This is part of compound No. 23 and compound
It is a mixture of 9 parts of No. 24, 1 part of Compound No. 25, and 9 parts of Compound No. 26. NMR ( _CCl4 ): ppm1.22-1.40
(m, 6H): 1.58~2.2 (m,
5H): 5.02 (s, 2H): 5.2~6.45
(m, 1H): 6.85-7.42 (m,
9H). Product No. 15: (±)-α-cyano-3-phenoxybenzyl (±)-cis/trans-3-(Z-3-chloro-2,3,
3-trifluoro-1-propene-
1-yl)-2,2-dimethylcyclopropane carboxylate, which is one part of compound No. 47 and one part of compound No. 48
It is a mixture with one part of. NMR ( _CCl4 ): ppm1.15-1.40
(m, 6H): 1.65 ~ ~ 2.40 (m,
2H): 5.08, 5.39, 5.80 and 6.12
(4d.1H): 6.35 (m, 1H): 6.92
~7.50 (m, 9H). Product No. 16: (±)-α-cyano-3-phenoxybenzyl (±)-cis-3-(Z
-3-chloro-2,3,3-trifluoro-1-propen-1-yl)
-2,2-dimethylcyclopropane carboxylate, which is a compound
It is No.47. NMR ( _CCl4 ): ppm1.18~1.40
(m, 6H): 1.85-2.33 (m,
2H): 5.80 and 6.11 (dd, 1H):
6.35 (d, 1H): 6.95-7.60 (m,
9H). Product No. 17: 3-Phenoxybenzyl (±)-cis/trans-3-(Z-3-chloro-2,3,3-trifluoro-1
-propene-1-yl)-2,2-
Dimethyl cyclopropane carboxylate, which is a mixture of one part of Compound No. 49 and one part of Compound No. 50. NMR ( _CCl4 ): ppm1.15-1.30
(m, 6H): 1.65-2.40 (m,
2H): 5.10, 5.40, 5.92 and 6.23
(m, 3d, 3H): 6.90-7.45 (m,
9H). Product No. 18: (±)-α-cyano-3-phenoxybenzyl (±)-cis/trans-3-(3,3,3-trifluoro-2-trifluoromethyl-1-propene- 1-yl)-2,2-dimethylcyclopropane carboxylate, which is a mixture of 1 part of Compound No. 1 and 2 parts of Compound No. 2. Product No. 19: 3-Phenoxybenzyl (±)-cis/trans-3-(3,3-difluoro-2-difluoromethyl-1
-propene-1-yl)-2,2-
Dimethyl cyclopropane carboxylate, which is a mixture of 3 parts of Compound No. 5 and 2 parts of Compound No. 6. NMR ( _CCl4 ): ppm1.18~1.37
(m, 6H): 1.60~2.45 (m,
2H): 5.03~5.1 (m, 2H): 5.15
~7.47 (complex peak, 12H). Product No. 20: (±)-α-cyano-3-phenoxybenzyl (±)-cis/trans-3-(3,3-difluoro-2-
Difluoromethyl-1-propene-
1-yl)-2,2-dimethylcyclopropane carboxylate, which is 3 parts of Compound No. 7 and Compound No. 8
It is a mixture with 2 parts of NMR ( _CCl4 ): ppm: 1.20-1.40
(m, 6H): 1.80-2.47 (m,
2H): 6.17~6.37 and 6.85~7.43
(mm, 13H). Product No. 21: 3-Phenoxybenzyl (±)-cis/trans-3-(Z/E-2-
chloro-3,3,3-trifluoro-1-propen-1-yl)-2,
2-dimethylcyclopropane carboxylate, which consists of 9 parts of compound No. 35, 1 part of compound No. 36, and the compound
It is a mixture of 6 parts of No. 37 and 4 parts of Compound No. 38. Product No. 22: (±)-α-cyano-3-phenoxybenzyl (±)-cis/trans-3 (Z-2,4-dichloro-3,
3,4,4-tetrafluoro-1-
buten-1-yl)-2,2-dimethylcyclopropane carboxylate, which is a mixture of 9 parts of Compound No. 51 and 1 part of Compound No. 52. Product No. 23: (±)-α-cyano-3-phenoxybenzyl (±)-trans-3-
(Z-2-chloro-3,3,4,
4,4-pentafluoro-1-buten-1-yl)-2,2-dimethylcyclopropane carboxylate, which is compound No. 53. NMR ( _CCl4 ): ppm1.16-1.42
(m, 6H): 1.74-2.60 (m,
2H): 5.98~6.40 and 6.77~7.55
(mm, 11H). Product No. 24: 3-Phenoxybenzyl (±)-cis/trans-3-(3-chloro-
3,3-difluoro-2-chlorodifluoromethyl-1-propene-1
-yl)-2,2-dimethylcyclopropane carboxylate, which consists of 7 parts of Compound No. 9 and 7 parts of Compound No. 10.
It is a mixture with 13 parts. NMR ( _CCl4 ): ppm1.24-1.42
(m, 6H): 1.76-2.60 (m,
2H): 5.02 (s, 2H): 6.16 and
7.12 (dd, 1H) 6.76-7.40 (m,
9H). Product No. 25: (±)-α-cyano-3-phenoxybenzyl (±)-cis/trans-3-(3-chloro-3,3-difluoro-2-chloro-difluoromethyl-1- Propen-1-il)-
2,2-dimethylcyclopropane
Carboxylate, this is compound no.
It is a mixture of 7 parts of Compound No. 11 and 13 parts of Compound No. 12. NMR ( _CCl4 ): ppm1.24-1.42
(m, 6H): 1.84-2.70 (m,
2H): 6.16 and 7.12 (dd, 1H):
6.36 (ss, 1H): 6.90~7.50 (m,
9H). Product No. 26: (±)-α-cyano-3-phenoxybenzyl (±)-cis/trans-3-(Z/E-3,3-difluoro-2-chloro-difluoromethyl-1- Propen-1-yl)-2,
2-dimethylcyclopropane carboxylate, this is compound No. 27,
It is a mixture of undetermined composition containing 28, 29 and 30. NMR ( _CCl4 ): ppm1.24-1.52
(m, 6H): 1.76-2.70 (m,
2H): 5.6-7.6 (m, 12H). Product No. 27: (±)-α-cyano-3-phenoxybenzyl (±)-cis/trans-3 (Z/E-2-bromo-3,
3,3-trifluoro-1-propen-1-yl)-2,2-dimethylcyclopropane carboxylate, consisting of 10 parts of compound No. 54, 1 part of compound No. 55, and compound No. 56 10 of
1 part of Compound No. 57. NMR ( _CCl4 ): ppm1.24~1.50
(m, 6H): 1.75-2.55 (m,
2H): 5.96-7.26 (m, 1H): 6.36
~6.56 (m, 1H): 7.0 ~ 7.6 (m,
9H). Product No. 28: (±)-α-ethynyl-3-phenoxybenzyl (±)-cis/trans-3-(Z/E-2-chloro-
3,3,3-trifluoro-1-propen-1-yl)-2,2-dimethylcyclopropane carboxylate, which is 10 parts of compound No. 58,
One part of compound No. 59 and one part of compound No. 60
It is a mixture of 10 parts and 1 part of Compound No. 61. NMR ( _CCl4 ): ppm1.16-1.44
(m, 6H): 1.64-2.56 (m,
3H): 5.7~7.0 (m, 1H): 6.28~
6.40 (m, 1H): 6.70~7.40 (m,
9H). Product No. 29: (±)-α-ethynyl-3-phenoxybenzyl (±)-cis/trans-3-(3,3,3-trifluoro-2-trifluoromethyl-2-
Propen-1-yl)-2,2-dimethylcyclopropane carboxylate, which is a mixture of 2 parts of Compound No. 13 and 3 parts of Compound No. 14. NMR ( _CCl4 ): ppm1.16-1.44
(m, 6H): 1.76-2.56 (m,
3H): 6.12-7.40 (m, 1H): 6.24
~6.40 (m, 1H): 6.76~7.36
(m, 9H). Example 13 This example uses (±)-α-cyano-3-phenoxybenzyl (±)-cis/trans-3-(2-chloro-
3,3,3-trifluoro-2-trifluoromethyl-1-propen-1-yl)-2,2-dimethylcyclopropane carboxylate (containing 60% cis isomer - product no. 6) and ( ±)―α―
Cyano-3-phenoxybenzyl (±)-cis/
trans-3-(3,3,3-trifluoro-2
-Trifluoromethyl-1-propen-1-yl)-2,2-dimethylcyclopropane carboxylate (contains 20% cis isomer) - Product No.
The insecticidal activity of 1) will be explained. The activity of the above products was tested against various insects and other invertebrate pests. Each product is Product No.1
In the case of 1000, 500, 125 and
In the case of product No. 6 it was used in the form of a liquid formulation containing 62.5 ppm and 50, 25, 12.5 and 6.25 ppm. These formulations are made by dissolving each compound in a solvent mixture consisting of 4 volumes of acetone and 1 volume of diacetone alcohol, and then adding the solution to water containing 0.01% by weight of a wetting agent sold under the trade name "Lisapol" NX. It was prepared by dilution until a liquid formulation containing the required concentration of active compound was obtained. The test method employed for each test pest was essentially the same and consisted of supporting a large number of pests on a medium, usually its host plant or some type of food for which it feeds, and either infesting the pest or in the medium. It consists of treating one or both with the test formulation. Mortality of the pests was then evaluated at appropriate times, 1-3 days after treatment. The test results are shown in Tables 1 and 2. In these tables, the first column indicates the species and common name of the pest tested, and the following columns indicate the host plant or medium that supported the pest, the number of days elapsed after treatment and before assessment of pest mortality, and the following columns indicate the species and common name of the pest tested. The results obtained for each concentration of test compound are shown. The evaluation is expressed by the following numerical value from 0 to 3. 0 Killing rate 30% or less 1 Killing rate 30-49% 2 Killing rate 50-90% 3 Killing rate 90% or more In the table, a dash (-) indicates that the test was not conducted. A "contact test" indicates that both pest and media were treated, and a "residue test" indicates that the media was treated before infesting the media with pests. The results for product No. 1 are shown in Table 1.
The results for No. 6 are shown in Table 1.

【table】

Table: Example 14 This example illustrates the insecticidal activity of the product of Example 12. The test was conducted under the same conditions as Example 13.
The test results are shown in the table as % pest mortality at a single application rate for each product. The application rate is expressed as the ppm concentration of the active ingredient in the test formulation. The symbols used for the test pests in the table have the following meanings: “A”—Tetranychus telarius (red spider mite, adult) “B”—Tetranychus telarius (red spider mite, adult)
“C”—Aphis fabae (black aphid) “D”—Megoura viceae (green aphid) “E”—Aedes aegypti (mosquito) “F”—Musca domestica (contact active) “G”—Musca domestica (House fly - residual activity) "H" - Plutella xylostella (residual activity 3 days) "I" - Plutella xylostella (residual activity 10 days) "J" - Phaedon cochleariae (mustard beetle) "K" - Calandra qranaria ) "L" - Tribolium castaheum (flour beetle) "M" - Spodptora littoralis (cotton star beetle) The asterisk (*) in the table indicates that in addition to the indicated mortality rate, surviving pests were also severely affected during the test period. This means that if it were extended, he would probably have died.

[Table] Example 15 This example illustrates the acaricidal activity of products No. 2 and No. 6 against cattle ticks (Boophilus microplus). 10 parts of each product with 985 parts of water and “Teric”N9
(“Teric” is a registered trademark and “Teric” N9 is a nonionic surfactant obtained by condensing nonylphenol and ethylene oxide in a molar ratio of 1:9). A suspension containing 1.0% of the active ingredient was prepared. A portion of this suspension was diluted with water to obtain compositions containing 0.1% and 0.01% of active ingredient. The efficacy of each test product against adult (female) ticks of the strain "Yeerongpilly" was tested by applying a small amount of the suspension to each of about 20 ticks. After 14 days, adult tick mortality was assessed by calculating the number of eggs laid and the percentage of hatched eggs. The results are shown in Table 1. The efficacy of each test product against mite larvae of the "Yeerongpilly" strain was tested as follows. The paper was immersed in a suspension of the above concentration and then dried, the treated paper was shaped into a wrapper, and about 100 larvae of the above mite were wrapped in the wrapper. The number of dead tick larvae was calculated 48 hours after packaging, and the kill rate was expressed on a scale of 0 to 5: 0 Kill rate 0 to 20% 1 〃 20 to 50% 2 〃 50 to 80% 3 〃 80-95% 4 〃 95-99% 5 〃 100% The results are shown in the table. In another test, 25 parts of the test compound were mixed with 75 parts of cyclohexanone and 25 parts of "Teric"N9;
Emulsions of each test product were prepared by diluting this mixture with water to give 10,000 parts by volume of emulsion. The emulsion thus obtained was sprayed in drops onto calves infested with cattle ticks of the resistant "Biana" strain at various stages of growth. The efficacy of each test product was evaluated as follows. (i) All adult mites (female) that were fully mature at the time of spraying were collected immediately after spraying and placed in a Petri dish in an incubator, and the mortality rate was calculated as egg production capacity and surviving larvae if eggs were laid. Evaluation was based on egg viability as indicated by hatching. Mature adults (if present) were similarly collected 24 and 48 hours after spraying to assess mortality. This assessment is based on “mortality – engorged adults.”
The results are shown in Table 1. (ii) Every other day, scheduled sampling areas on each calf were examined for the effect of the active ingredient on immature adults and nymphs. This evaluation is expressed on the scale 0 to 5 described above and is referred to as "mortality rate - immature worms" and "mortality rate - nymphs." The results are shown in Table 1. In the table, the symbol "-" indicates that there were no mature adults. In these tests, permethrin, i.e. 3-phenoxybenzyl (±)
-cis/trans-3(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate was used. From the results in Table 1, it can be seen that the novel cyclopropane derivatives of the present invention having at least one fluoroalkyl group bonded to a vinyl group compared with the comparative drug permethrin, a known insecticidal and acaricide compound with similar structure. It is recognized that significantly lower doses are required to achieve the desired effect.

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Claims (1)

[Claims] Primary formula: [In the formula, one of R ¹ and R ² is a group W-(CF ₂ ) _n-
(Here, W is hydrogen, fluorine, or chlorine, and m is 1
or 2), and the other of R ¹ and R ² is fluorine, chlorine, bromine or a group [Formula] (where X, Y and Z each represent hydrogen, fluorine or chlorine)
, Q represents a lower alkoxy group containing up to 6 carbon atoms, W' and W'' represent fluorine, chlorine or bromine, respectively, provided that if R ² is bromine, then W' is It represents bromine]
3,3-dimethylpolyhaloalkanoic acid ester represented by: Quadratic formula: (In the formula, Q has the meaning below) and the following formula: in the ^presence of a free ^radical initiator: [In the formula, one of R ¹ and R ² is a group W-(CF ₂ ) _n-
(Here, W is hydrogen, fluorine, or chlorine, and m is 1
or 2), and the other of R ¹ and R ² is fluorine, chlorine, bromine or a group [Formula] (where X, Y and Z each represent hydrogen, fluorine or chlorine)
, Q represents a lower alkoxy group containing up to 6 carbon atoms, W' and W'' represent fluorine, chlorine or bromine, respectively, provided that if R ² is bromine, then W' is It represents bromine]
A method for producing a 3,3-dimethylpolyhaloalkanoic acid ester represented by 3 The compound of formula () is hexafluoroethane,
Chloropentafluoroethane, 1,1-dichlorotetrafluoroethane, 1,2-dichlorotetrafluoroethane, 1,1,1-trichlorotrifluoroethane, 1,1,2-trichlorotrifluoroethane, 1,1,1 3. The manufacturing method according to claim 2, wherein the compound is selected from -tribromotrifluoroethane, 1,1,1,3-tetrachlorotetrafluoropropane, and 1,1,3-trichloropentafluoropropane.