JPS61191640A - 5-fluoromethyl-6-fluoro-5-hydroxy-2-methylhexene-2 and manufacture - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is a novel intermediate compound for the production of a novel cyclopropane crocodile conductor useful as an insecticide and acaricide.

and its manufacturing method.

Although it has been known for many years that the naturally occurring cyclopropane carzenate esters of certain seaweeds 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 cyclopropanecarzenic acid (e.g. British Watch No. 1 Co. 4I311) were used.
No. 1 and No. 1≠i3p (compounds described in Specification No. 1) have been evaluated.

The present inventors have now discovered the following formula:
n- (where W is hydrogen, fluorine or chlorine, mt!/
or λ), the other of R1 and R2 is fluorine,
Cyclopropane derivatives represented by chlorine, bromine or the group Y (wherein X, Y and -C- and 2 represent hydrogen, fluorine or chlorine, respectively) and R3 represents hydrogen, cyano or ethynyl are very superior. The compound was found to have insecticidal and acaricidal activity and good resistance to photodegradation, and furthermore, a compound useful as a raw material or intermediate for producing a useful cyclopropane derivative of the above formula (4) was created.

A novel useful intermediate compound which can be directly converted into the primary cyclopropane derivative (hereinafter referred to as the insecticidal final ester compound or simply the primary compound) has the following formula 20 [wherein one of R1 and R2 is a group W-( OF2)m-
(where W is hydrogen, fluorine or chlorine, and m is l or co], and the other of R1 and R2 is fluorine, chlorine,
bromine or the group Y (where X, Y and 2 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 tB) are cyclopropane derivatives represented by: 2-a- has the above-mentioned meaning), and Q represents hydroxy, lower alkoxy having 7 to 3 carbon atoms, chlorine or bromine, and especially, both 几 and 几2 are trifluoromethyl. Certain compounds are particularly preferred. Formula (B)
Another preferred group of intermediate compounds is such that one of R and R2 represents a group WOF2- (where W is hydrogen, fluorine or chlorine, the other represents fluorine, chlorine or bromine, and Q is hydroxy, lower alkoxy having 7 to 3 carbon atoms,
Compounds representing chlorine or bromine, particularly compounds in which one of a1 and rJR2 represents trifluoromethyl and the other represents chlorine or bromine are preferred.

A compound in which Q is hydroxy in formula (B) has the formula (
B) is obtained by hydrolysis of a compound in which Q is lower alkoxy, which can be converted, for example by reaction with thionyl chloride or thionyl bromide, into a compound of formula (B) in which Q is chlorine or bromine, respectively. The preparation of a compound of formula (B) in which Q is a lower alkoxy group is necessary for the preparation of the final insecticidal ester compound of formula (4).

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 provides j-fluoromethyl-1-fluoro-j represented by the following formula: (wherein one of B1 and B2 is a trifluoromethyl group, and the other is a trifluoromethyl or difluoromethyl group) -hydroxy-2-methylhexene-2.

Representative compounds of the unsaturated alcohol of formula (1) according to the present invention are: -Hydroxy-comethyl-6. A, 4-) Lifluoro-1-) Lifluoromethylhexene-2: and! -hydroxy-comethyl-4.4-,)fluoro-! -trifluoromethylhexene-2.

The present invention further provides a compound of the following formula consisting of reacting a ketone of the formula: and R2 is a trifluoromethyl group, and the other is a trifluoromethyl or difluoromethyl group. do.

The above reaction is preferably carried out under pressure.

Next, a process for producing a novel cyclopropane derivative of the formula (which is a recently useful intermediate compound) from an unsaturated alcohol compound of formula (1) according to the present invention, and a method for producing a novel cyclopropane derivative of formula (4) from an intermediate compound of formula (B) according to the present invention. The method for producing the final insecticidal ester compound will be explained.

First, the formula (
The intermediate compound of B) can be obtained by reacting an unsaturated alcohol compound of formula (1) according to the invention with a lower alkyl ester of diazoacetic acid to give a compound of formula: which is then dehydrated with a chemical dehydrating agent. Can be manufactured. An example of a chemical dehydrating agent is phosphorus pentoxide.

Alternatively, a compound of formula (!) of the invention may be treated directly with a chemical dehydrating agent, such as phosphorus pentoxide, to give the following formula:
1 and R2 are defined for K in formula (1) and have the same meaning as 9], and then this diene compound is reacted with a lower alkyl ester of diazoacetic acid to obtain the same formula ( An intermediate compound of B) can be obtained.

This final reaction step uses an excess of diene as a solvent for the alkyl diazoacetate and a metal catalyst, such as steel or! Conveniently it is carried out in the presence of copper powder.

In addition, the diene compound of the formula (goods) obtained as an intermediate product in the above-mentioned alternative method is an alkyl malonate and, optionally, in the presence of a reducing copper salt, lithium chloride or calcium chloride, etc. The reaction in the presence of another salt selected from metal halides gives the following formula: t- Conventional hydrolysis and esterification lead to an initial product with the formula (
It can also be converted into the desired intermediate compound of B).

A compound in which Q is a hydroxy group and a compound in which Q is chlorine or bromine in formula (B) can be easily produced starting from a 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, a mixture of cis and trans isomers (often with a predominance of the -isomer is obtained, and if l- is different from R2, both the cis and trans forms of the 2- and E-isomers (in this case Sometimes a predominance of isomers is obtained.

If these isomers are not separated by physical methods, such as fractional crystallization of calzenic acid, the resulting final ester compound will also consist of a mixture of isomers containing two or more compounds. .

The insecticidal ester compound of formula (4), which is the final object, can be produced from the intermediate compound of formula (B) derived as described above from the compound of formula (1) according to the present invention by a conventional esterification method as described below. .

(a) An acid of formula: can be reacted directly with an alcohol of formula: This reaction is preferably carried out in the presence of an acid catalyst 1, such as dry hydrogen chloride.

(b) An acid halide P''Ik of the formula: (wherein Q is a halogen, preferably chlorine) can be reacted with an alcohol of the formula: carried out in the presence of a hydroxide, carbonate or alkoxide.B
Alternatively, when 3 is a cyano group, α-cyano-3
- Instead of phenoxybenzyl alcohol, a mixture of an alkali metal cyanide and 3-phenoxypenzaldehye P can also be used.

(c) An acid of the formula: or preferably an alkali metal salt thereof, is combined with a halide of the formula: (wherein Q/ is halogen, preferably chlorine) or such a halide and a tertiary amine, such as pyridine or triethylamine. It can be reacted with a primary ammonium salt derived from a trialkylamine.

(b) A lower alkyl ester of the following formula: % formula % (wherein R is a lower alkyl having 6 or less carbon atoms, preferably methyl or ethyl) is heated with an alcohol of the following formula to perform a transesterification reaction. Let's do it. The process is preferably carried out in the presence of a suitable catalyst, for example an alkali such as sodium methoxide, a metal alkoxide or an alkylated titanium conductor such as tetramethyl titanate.

All of these conventional ester preparation processes can be carried out using various solvents or diluents of the reactants, if appropriate, and the reactions can be carried out at elevated temperatures or in the presence of suitable catalysts, e.g. phase transfer catalysts. or increase product yield.

The preparation of the individual 7 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 calzenic acid or its salts, and -1 various optically active forms can be separated by fractional crystallization of cald7 acid and optically active amines, followed by regeneration of the optically pure acid. Can be separated.

The resulting acid (or its acid chloride or ester)
The optically pure isomer of can then be reacted with 3-phenoxybenzyl alcohol to produce the final ester compound of formula (4) in individually pure isomeric form. In the case of α-cyano-3-phenoxybenzyl alcohol, the reaction of optically pure α-cyano-3-phenoxybenzyl alcohol with carzenic acid or its functional derivative is used to cause racemization of the alcohol. Since it cannot be done without it, it will result in a mixture of the two isomers. Typical products of this process include: (to)-α-cyano-3-phenoxybenzyl ('as
JR)-J-(J,j,J-)-trifluoro-trifluoromethyl-t-f-ropen-l-yl)-λ, coco-methylcyclopropane cal-l-xylate and (to)-α-cyano-3- Phenoxybenzyl (/R2
33) -j-(J-chloro-j, J, J-trifluoro-7-propen-7-yl)-2, cordimethylcyclopropane carboxylate. The final ester compounds of these agents are particularly useful as insecticides.

The preparation of the single isomer of these final ester compounds of formula (4) involves preparing an optically pure acid chloride and reacting it with the corresponding ()-α-calzexyl This can be achieved by obtaining an amide ester. These one type of isomeric esters are separated by fractional crystallization, and the individual esters are dehydrated to obtain the corresponding α
-cyano-3-phenoxybenzyl ester.

It is thus possible to obtain the following single isomer, which is considered to be the most effective insecticidal isomer of the individual compounds: (8)-α-cyano-3-phenoxybenzyl (/R.

JR) -J- (J, J, J-) Refluoro-λ-
trifluoromethyl-7-propen-/-yl)-λ,
2-dimethylcyclopropane calxylate and (8)-α-cyano-3-phenoxybenzyl (' R
*38) -j-(Cau Chloro J,!,!-Trifluoro-7-propen-7-yl)-2, Codimethylcyclopropane Calxylate.

The final ester compound may exist in a number of geometric and stereoisomeric forms. For example, cis and trans isomers resulting from the type of substitution on the cyclopropane ring and E- and 2 resulting from substituted vinyl groups when R1 is different from R2.
- Isomers may exist.

Additionally, two of the three carbon atoms of cyclopropane are asymmetrically substituted so that they can exist in the S configuration or in the S configuration;
Furthermore, when the reactor is not hydrogen, the carbon atom to which it is bonded can also exist in the R configuration and the S configuration.

Therefore, for compounds in which R1 and R2 are identical in origin and R3 is hydrogen, different isomers resulting from substitution of the cyclopropane ring may exist. These are (/R, jI'L), (/R,
j8), (/8.38) and (/8, J R). If R3 is not hydrogen, each of the various possible cyclopropane ring configurations
Since it exists in two forms corresponding to the 8-configuration and the R-configuration of the carbon atoms with 3, j isomers are possible. Separately, even when FL3 is hydrogen and R is different from R, each of the possible configurations of the cyclopropane ring exists in two forms corresponding to the Z configuration and the E configuration of the vinyl group. Therefore, j isomers are possible.

After all, if R1 is different from 几2 and R3 is not hydrogen, each compound can exist as 16 isomers.

Representative examples of the final ester compound of formula (4) are shown in Table 1. The compounds shown are racemic mixtures of isomers, respectively, but with cis and trans substitutions on the cyclopropane ring and E in the vinyl group (if present).
A distinction is made between and two permutations.

The compounds shown in Table 1 all follow the formula: OH50H3 Table I Table I (Continued) Table I (Continued) Table 7 (Continued) Particularly useful final ester compounds are: Including: (t)-α-cyano-3-phenoxybenzyl(t)-
Cis/trans-3-(cochloro-3°J, J-trifluoro-7-propen-7-yl)-2,J-dimethylcyclopropanecarboxylate.

(e)-α-cyano-3-phenoxybenzyl (1)-
cis/trans-3-(3,J,J-trifluoro-2
−) +7fluoromethyl-l-propen-7-yl)
-'eCodimethylcyclopropane carboxylate.

(t)-α-cyano-j-phenoxybenzyl (1)-
cis/trans-J-(J-chloroco.

3,! -trifluoro-7-propene-l-iA/)
-J, 2-')) f cyclopropane carboxylate.

(1)-α-cyano-3-phenoxybenzyl (7)-
cis/trans-J-(copromo 3°J, J-trifluoro-1-propen-l-yl)-'e coco-methylcyclopropane carboxylate.

3-phenoxybenzyl (1)-cis/trans-3
-(λ-chloroJ,J,J-)lifluoro-l-propen-l-yl)-2,2-dimethylcyclopropane
carboxylate, and j-phenoxybenzyl (ho)-cis/trans-J
-(J, 3.J-)rifluoro-cotrifluoromethyl-/-7'lopen-/-yl)-2, cordimethylcyclopropane carboxylate.

The final ester compound of formula (2) prepared from a compound of formula I according to the invention via a compound of formula I can be used for the control of insects and other pests such as mites. Pests that can be controlled using the final ester compounds are used in agriculture (this term includes the cultivation of food and textile crops, horticulture and animal husbandry), forestry and the preservation of plant products such as fruits, grains or timber. Related Pests and Transmission of Human and Animal Diseases Kr1a includes related pests.

In order to apply the final ester compound to a pest-infested area, it is usually formulated into a composition containing the final ester compound as the insecticidal active ingredient and a suitable inert diluent or carrier and/or surfactant. Such compositions may further contain other pest control agents, such as other insecticides or acaricides or fungicides, such as insecticides such as dodecylimidazole, afroxan or piperonyl butoxide. It may contain a synergist.

The compositions can be prepared as 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 the active ingredient is mixed with a porous granular material, such as! It is available in the form of granules that have been absorbed into the stone.

The composition can also be used as a liquid solution for use as a dipping or spraying solution, 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 agents may be cationic, anionic or nonionic active agents. Suitable cationic activators include graded ammonium (
E compound, for example 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 sulfonate and diisopropyl- and triisopropyl. Naphthalene is a mixture of sodium salts of sulfonic acid. 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 is prepared by dissolving the active ingredient in a suitable solvent, for example a ketone solvent such as diacetone alcohol or an aromatic solvent such as trimethylbenzene, and adding the resulting mixture to a known wetting agent, dispersing agent or emulsifying agent. It can be prepared by adding it to the water it may contain. Other suitable organic solvents are dimethylformamide, tyrene dichloride, inopropyl alcohol, propylene glycol and other glycols, diacetone alcohol, toluene, kerosene, white oil, methylnaphthalene, xylene, trichlorethylene, N-methyl-2- with pyrrolidone and tetrahydrofurfuryl alcohol (THFA).

The nebulizing composition can also be an aerosol, in which the formulation is held under pressure in a container under pressure in the presence of a propellant, such as, for example, fluorotrifluoromethane 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 are often capable of resisting static electricity for long periods of time and forming aqueous formulations that, when diluted with water after such long-term storage, remain homogeneous long enough to be applied with conventional spray equipment. It is necessary. Such a concentrated liquid is 10~rjxx
x active ingredients. When diluted to prepare aqueous formulations, such formulations may contain varying amounts of active ingredient depending on their intended use.

Aqueous formulations containing 0.000/0.1% by weight of active ingredient are particularly useful for agricultural and horticultural applications.

In use, the compositions are applied to the pest itself, to the locus or habitat of the pest, or to growing plants susceptible to the pest, by any known agrochemical application method, such as by dusting or spraying.

The final ester compounds and compositions of formula (g) are extremely harmful to a wide range of insects and other vertebrate pests, including the following: : Black Aphid (Aphls fabae) Final ester compound of formula (4) and a composition containing them
In particular, cotton lepidopteran pests 1 such as Spodoptera (8p
odoptera spp,) and Helionus (He
lio-this spp, );
There are also pests and mites on livestock, such as the green fly (on sheep).
Luclliasericata) and Boophilus spp.
des spp. ), Amblyo
mma), Libicephalus 1j4 (几hipice-p
halus sp9. ) and Dermahuta spp. (1)
It is extremely useful for controlling ixodidticks such as the pests of Erma-ceutor spp. Such compounds and compositions are effective in controlling susceptible and resistant strains of the above pests in their adult, larval and intermediate stages of growth.

It can be applied topically, orally or parenterally to the infested host animal.

Next, examples of the production of the compounds in the formula according to the present invention are shown in Examples.

Furthermore, in order to prove the usefulness of the compound of formula (1) of the present invention as an intermediate, an example of the production of an intermediate compound of formula (B) from the compound of formula (81) is shown in Example 3.6. The production of the corresponding free acid and the production of acid chloride are shown in Examples 7 to 1, and examples of the production of the insecticidal final ester compound of formula (4) from the intermediate of formula (B1) are shown in Examples 1 to 1. and a test example illustrating the effectiveness of the compound of formula (AJ) as an insecticide and acaricide is shown in Example/j-77.

Example 1 Book? lJ frame j-hydroxy-comethyl-4,4, A trifluoro-! -Production of trifluoromethylhexeneco will be explained.

A stirred mixture of hexafluoroacetone (<23 ft) and 3-methylbutene-/(1001) was heated at 100° C. at 17 atmospheres for 20 hours. The obtained n7 was obtained by vacuum distillation of the product to give the title compound Compound lA3°C//jm
Obtained as a free-flowing colorless liquid of mHg.

NMR (00t4): p, p, m, /, 77 (
d, 6H) ;22! −JL O(7(m, J
H) : j O-j 4' (m*/H)Example 7- to pentafluoro-7- to t-hydroxy-cortacyl-6,6-difluorocr-j-) by a method similar to Example 1. Fluoromethylhexene-2 was produced.

NMR (00t4): p, p, m, /, 7t
(d, 6H): JLj~-1'7-t(m-j
H):J:/ff(me/H):j:r(70,/H)
.

Example 3 In this example, cis/trans-3-(cohydroxy-J
, j , J-trifluoro-J-trifluoromethylpropyl-7)-2,2-dimethylcyclopropane The production of ethyl cyclopropane carboxylate will be described.

A solution of ethyl diazoacetate in dichloromethane is diluted with hydroxy-2-methyl-4.
4, A-trifluoro-j-trifluoromethylhexene-J (/r, rit) was added dropwise to A-trifluoro-j-trifluoromethylhexene-J (/r, rit) in the presence of a catalytic amount of anhydrous sulfuric acid at 10-720°C over an hour. .

The resulting mixture was washed with water, dried over anhydrous magnesium sulfate, and distilled to a boiling point of 61r~Otl:/01! mm
Several fractions in the Hg range were obtained. NMR4IR
and M8 Spectral analysis revealed that these fractions were identified as 3-(cohydroxy-J,J,J-trifluoro-J-to13fluoromethylglobin-/)-2,codimethylcyclopropane in ethyl carboxylate. f'Lfc was found to consist of a mixture of cis and trans isomers in varying proportions.

NMR (00t!S): p, p, m, /, Ou
~/, Hiro0 (m, riH): tl! -24'
J (m s reference H); u, 00-44.77 (m, ko H
)6 Example Gal By the same method as Example 3, j-hydroxy-2-
Methyl-4,4-difluoro-trifluoromethyl to (t)-cis/trans-3-(λ-hydroxy-J, J-difluoro-trifluoromethylglobil-1-yl)-'t '-Dimethyl cycloglopane was converted to ethyl carboxylate.

NMR (OO24): p-p, m, /, J-2"
(m e / J H) e.

p, o-hiro, j j (m, 2H): 4',
6-u, r (m, /H): Yocomb≠(m, /
H).

”1-1,! This example shows (t)-cis/trans-J(J,J,J-trifluoro-quatrifluoromethyl-7-propene-/
-(ru)-2, Kodimethylsiglopropane Cal/y
The production of ethyl acid will be explained.

(t)-cis/trans-3-(cohydroxy-J,
J, J-) Trifluoro-coated trifluoromethylpropyl-7)-2, Kodimethylcyclopropane Ethyl carzenate (4A4Jf), Phosphorus oxychloride (712t)
and dry pyridine (YoJ+d) at 6°C.
The mixture was heated for j hours, then poured into ice water and stirred for 5 hours. The resulting fL7 mixture was washed with diethyl ether and the extract was dried over anhydrous sodium sulfate. After removing the ether by evaporation under reduced pressure, the residual oil was distilled under reduced pressure to yield the title compound with a boiling point of t O-6j °C/0. j mm
Obtained as a colorless oil of HH.

NMFL (ODO43): p, p, m, /, /
j −/, j ta (m, riH):/, 74cm,
t4(7(m, koH): @OJ -4J#(m, koH
): A, J4 and 774 (dd, /H).

An example of an example! By the same method as above, cis/trans-3-(J,J-difluoro-2-trifluoromethyl-7-zoαpe/-!-zul)-2, cordimethyl was obtained from the product of the working gal. Ethyl cyclopropane carmenate was obtained.

PJMR (00t4): p, p, m, /, 2-
/, 4k (m,riH):/, 4--16 (m
*koH): IAO-@44 (m,koH):J:
Reference-22 (mtcoH).

Example 7 This example -cis/trans-3-(J,J,J-trifluoro-quatrifluoromethyl-/-bropene-7-
Figure 2 shows the production of codimethylcyclopronozenecargenic acid.

(t)-cis/trans-J-(J, J, J-trifluoro-2-trifluoromethyl-l-prope7-1
-yl)-'*Ethyl coco-methylcyclopropanecarboxylate (0,12f), glacial acetic acid (Jjλ-), hydrobromic acid (4crW/VK, J, JAm) and water (/
, /co1) was heated at reflux temperature for 10 hours.

After cooling the reaction mixture, it was diluted with water (!Owd) and extracted several times with diethyl ether. The extracts were combined, washed with water, dried over anhydrous sulfuric acid and concentrated by evaporating the ether under reduced pressure. From the results of spectral analysis of the residual oil, it was found that (t)-cis/trans-3-(J,J,J-)lifluoro-2-trifluoromethyl-l-propen-l-yl)-2, 2
-dimethylcyclopropane carbonate sister.

Example j In this example, (t)-cis/trans-3-(3,!).

Figure 2 shows the conversion of 3-trifluoro-trifluoromethyl-l-propen-l-yl)-2,2-dimethylcyclopropanecargenic acid to acid chloride.

(t)-cis/trans-J-(J,J,J-trifluoro-cotrifluoromethyl-7-propen-l-yl)-2,2-dimethylcyclopropanecarzenic acid 10
．． After heating a mixture of .mu.t) and thionyl chloride (J:01Rt) at reflux temperature for 2 hours, excess thionyl chloride was removed by vacuum distillation to obtain cyclo-cis/trans-l-chlorocarbonyl-J-(J).

J, J-! p-refluorocoat trifluoromethyl-7
-10pen-)-yl)kott 2-dimethylsicucpropane was obtained.

Examples and exceptions are (to)-cis/trans-3-(Caucro a-J
,J,! -trifluoro-7-propen-l-yl)-
J, J--7ff shows the production of methylcyclopropanecarmenic acid.

(t)-cis/trans-3-(cochloro-3°J,
J-trifluoro-l-propene-/-1l)-J,J
--7 Ethyl methylcyclopropanecarboxylate (QJ Kot), wood vinegar tll (Yu! Ko), hydrogen bromide @ (see rW/
VN,! , 34m) and water (/, /Jd) was heated at reflux temperature for 10 hours. The reaction mixture was diluted with cold vk1 water (!Od) 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 of the residual oil, mainly (
to)-cis/trans-3-(cochloro-3゜3.3
-trifluoro-7-propen-7-yl)-2,2-
It was found that dimethyl cycloglonocenecal & y acid ip.

Example IO In an exceptional case, I-cis/trans-J-(cochloro-J,
J, J-)lifluoro-1-pen-7-yl)"'
Figure 3 shows the conversion of codimethylcyclocarzenic acid to acid chloride.

Mountain-cis/trans-3-(Kokrok-3゜3.3-
A mixture of trifluoro-7-propen-7-yl)-co,dimethylcyclopropanecarboxylic acid (o, hirof) and thionyl chloride (yoo-) was heated at reflux temperature for 2 hours, and then the excess Thionyl chloride was removed by vacuum Kurobe and (
g)-cis/tranx-t-prolocarbonyl-J-(
Cork Roro J, J,! -trifluoro-l-yl)J
, J-dimethylcyclopropane was obtained.

Example/1 Rather than using a method similar to that described in Example 7 and Example 1, the corresponding ethyl ester was
y@f: II was built.

(1) Se-cis/trans-J-(J,J-difluoro-quatrifluoromethyl-l-propen-7-yl)-J,J-dimethylcyclopropane Caly'17
ell@IR (liquid film): JJOO-Kohiro 00, 1700,
/441〆-.

(M) (1)-cis/trans-J-(J,J-difluoro-2-difluoromethyl-7-propene-7-
yl)-co-dimethylcyclobronocene caruneic acid.

NMatootsu: p, p, m, /, j O~
/, j O(m, 6H): /, 70~26Q
(Complex peak, 2H): 170-2/J (Complex peak, 38).

(ffD Cf)-VX/to57su J-(g
/z -J -trifluoromethyl-l-propene-1
-yl)-2, cordimethylcyclopropane carboxylic acid.

NMR (OOt4): p, p, m, /, here~t4
4 Reference (m, 4H): 7 A ~ JL J (
m @ j H) :Ma36〜4,4 (to, /
H): / /,? (St'H) *phrase ψ (g) -
cis/trans-J-(J-chloro-J, J--)fluoro-2-chlorodifluoromethyl-/-7'lopen-l-yl)-2, cordimethylcyclopropane carboxylic acid.

NMR (OOA4): p, p, m, /, J 44
~/, 4' J (m, 6H):/, r(7~,
tAr (m, JH): A, /A and z/ko (dd, /
H): //, 4 (8, /H).

M palanquin-cis/trans-J-(1!f/Z-3゜3-
Difluoro-coke c10 difluoromethyl-7-propen-7-yl)-1, cordimethylcyclopropane cardiphosphoric acid.

IR (CHOLJ): J4cJO~2100,
/701. /A7rm-”.

q-(To)-Sith/Tora/Sue 3-(Kobromo J
, J, J-trifluoro-7-propeno-7-yl)
-2,λ-dimethylcyclopropane carboxylic acid.

■几(OH0L3)=3u00~2810, /
700, /410゜l core 1, //80
m-C11) (t)-cis/trans-3-(3-chloro-J,J,J-trifluoro-1-propen-l-yl)-2, cordimethylcyclopropane carboxylic acid.

IR (oil film): 3 da 00 ~ here 00, /700
,,/Hiroshi 10.

// Reference 0, 107051-0 & 11th generation-cis/trans-3-(Kots 3-Jiku o
o-3,3-difluoro-l-propene-/-(l)-
2. Kodimethylcyclopropane carboxylic acid.

IR (OHOj!$): WOO~2ko00, /
700 aw-hot.

When cooled from a concentrated bath of mixed cis and trans acids in a medium-sized bath, pure (t)-cis-3-(2,!
-dichloro-3,3-difluoro-7-propene-7-
yl)-2, codimethylcyclopropane carboxylic acid precipitates.

NMR (CD(M3): p, p, m, /, 2k
(8, 6H) ;/, 10 N, t2t(m,, 2H
): 4.7J (d.

/H). '(capital)(t)-cis/trans-3-(2-chloro-J
,! , 4c, Hiro゛, Derpentafluoro-l-butene-
7-i5r)-2, cordimethylcyclopropanecaldic acid.

NMR (OD Ot!3): p, p, m, /, /
0・~/, j O(m, AH); t+ r−yuj
J' (yn e J H): Murohiro and A, rj
(dd, /H).

(X) (to)-cis/trans-J-(,2,4C
-dikuoo-J,J,lL,4c,lL-tetrafluoro-7-buten-l-yl)-2,cordimethylcycloprono7/calzyea.

Example/2 ゛In this example, (t)-α-cyano-3-phuninoΦdibenzyl
(1)-cis/trans-3-(J,J,J-trifluoro-cotrifluoromethyl-7-propen-7-yl)-2,2-dimethylcycloglonocalcexylate (hereinafter referred to as compound (referred to as AI).

(1)-cis/trans-l-chlorocarbonyl J
-(J, j, J-17 fluoro-quatrifluoromethyl-/--j'lopen-/-1)-2
, pyridine (0,72f) and (to)-α
-Cyano-3-phenoxybenzyl alcohol (QJJ
The mixture of f) was added and the mixture thus obtained was stirred at ambient temperature for 16 hours. After adding water (0,1), extraction was performed with diethyl ether (3 times / Otl). The extracts were combined, washed successively with water, saturated aqueous carbonate solution, and water, and then dried over anhydrous sodium sulfate. After removal of the ether in vacuum, the residual oil was subjected to preparative thick-layer chromatography on glass with a thickness of silica and chloroform as the eluent to give about 20'x of the cis-isomer and about tO (t)-α-cyano-3- containing % trans-isomer
Fuenogishipenzil (t)-cis/trans-! −(
J, J, J-trifluoro-2-trifluoromethyl-
7-propen-l-yl)-2,2-dimethylcyclopropa7carboxylate) (RfO,Jj)'e was obtained.

Spectral analysis: infrared spectrum, /711. /4
10, /600. /4490°/300. /
/40: NMR, 0.9-11τ, 6.
0-Ano! τ, 4#j−72τ; Mass spectrometry spectrum M+4(r J (j7j, 2!Y
, 231. 209. 201. /II)
.

Example 13 This example flffl-α-cyano-3-phenoxybenzyl (1)-cis/trans-3-(cochloric 3°3
．． 3-trifluoro-7-propen-7-yl)-2,
The production of 2-dimethylcyclopropanecarboxylate (hereinafter referred to as compound 166) will be described.

(t)-cis/trans-7-chlorocarbonyl-3-
(2-Chloro-J,J,!-Triple Oro/-10pen-7-yl)-J,! -To the residue consisting of dimethylcyclopropane (see Example 10), pyridine (0,
Jf) and (t)-α-cyano-3-phenoxybenzyl alcohol (0#Jf) CD mixture was added and the resulting mixture was stirred at ambient temperature for 76 hours. water(
After adding 0 dl).

Extraction was performed with diethyl ether ( / OmtxJ
times).

The extracts were combined, washed successively with water, saturated carbonic acid, +7 ml of aqueous solution, and water *vk, dried over anhydrous [8 sl-+7 ml of 7 ml of water, and after removing the ether under reduced pressure, the remaining Preparation of an oil on glass using thick silica and chloroform as eluent: 1 Madograph 1
-, (t)-α-cyano-3-phinino-dibenzyl out-cis-3-(cochloro-3,!, J-t
-Refluoro-7-zolopene-/-(ru)-J,J-dimethylcyclopropa7carboxyle) (Rf O,
j2 ) and the corresponding trans isomer (Rf O, Hiroλ) were obtained. Each of the above isomers contains about 20 to 70 IX of the 2-isomer. .

Spectral analysis; infrared spectrum (OHOLa):
t7≠Q.

/140. /j90. /4110. /u4
0 51-': NMR (OOt4):t,ri0-7
1Or, 1.6O-27Or, /, jo -t00τ
and special peaks, t, 3τ (benzylic H), son
zon, 'l-shix, B-shix, Z-trans and E-
It is thought that it belongs to trance. t, rz, t, z
Example 74C' 3-phenoxybenzyl alcohol, α-cyano-
Example 11om'
Each Cal/y Ill is converted into a final ester compound with insecticidal activity. These reaction products (hereinafter referred to as products NIL2-J and 7-λ) are mostly as shown below.

This is a mixture of 281 or more of the compounds in Table 1.

Product A: (t)-α-cyano-3-phenoxybenzyl (t)-cis/trans-3-(J,3.!-trifluoro-quatrifluoromethyl-l'-propen-l-yl) -2,2-dimethylcyclopropane caldexylate, which is a mixture of 7 fl of compound B and one part of compound II.

NMR (OOt4): p', p, m, /, 20~
/, u O(m, 6 H): /,'t O~
230 (m, koH): &/ 7~A, j 7 and it
j ~74CJ (mm, / /H).

Product sJ: Se-alpha-cyano-3-phenoxybenzyl (t)-trans-3- (J, J, j-trifluoro-2-trifluoromethyl-l-zolopen-l-yl)-2,co. -dimethylcyclopropanecar Np plate, plus compound I & λ alone.

Product JKu: (1)-α-cyano-3-phenoxybenzyl (t)-cis-s-(J.

J,! -trifluoromethyl-l -propennyl-yl)-2,2 monodimethylcyclopropane cal boxylate, which is compound I61 Alone.

Product I6! : (1) -α-Sibuno-3-phenoxybenzyl (E)-Cis-3-(Co-Roroj, J, j-trifluoro-7-propen-7-yl) -a,X-dimethylcyclopropane Carboxylate, which is a mixture of one part of compound AJ/ and one part of compound AjJ.

Product A7: 3-7 Mitsuki dibenzyl (1)
-cis/trans-J-(J,J.

3-trifluoro-coat rifle Offmethyl-l-propene-l- yl)-2,-1 dimethylcyclo Propane carboxylate, This is 11 parts of compound A3 and the compound It is a mixture with I6 Hiro's /Ic part.

NMR (CCL4): p, p, m, to/r
~Hehiro O (m, AH): /, 7j ~2.11 (m,
KoH)-: ! , / j (s, JH): 4. j
O and 170-7.4 CO (dm, 10H).

Product 16r: (e)-α-cyano-3-phenoxybenzyl (e)-cis/trans-J-(j,J-difluoro-quatrifluoromethyl-l-propen-1-yl)-2,- Monodimethylcyclopropane carboxylate, which is a chemical compound /! , /1°/7 and /r (composition not measured).

IR (liquid film): 17 hiroz, 14j1°/J'rijcf
lIo Product A: 3-phenoxybenzyl (→-cis/trans-3-(z-2゜3-dichloro-3,3-difluoro-1-propen-7-yl)-2, cordimethylcyclopropanecarboxy rate, which is a mixture of 1 part of compound AJ and 1 part of compound All/.

NMR (CDCj3): p, p, m, heko0~/,
J 7 (m, 4H): /, 7J ~ J, R
) (m, JH): J, 10 (d, , zn); 4. /
J and 6. lr t ~7. Reference 1 (dm.

toH).

Product sio', to)-α-cyano-3-phenoxybenzyl (1)-cis/trans-J-(Z/E-2,3-dichloroJ,J-difluorol-propen-l-yl)-2 , Coates methyl cyclopropane carboxylate, which consists of one part of Compound A Hiro 3, one part of Compound I64c Hiro, and compound 5uzo
It is a mixture of 1 part of compound Set and 1 part of compound Set.

NMR (C('j4): p, p, m, /, /
t ~1, reference j (m, 4H): /, 77~ko, j
O(m, JH): 4. Jco (m.

/H);bu,or andhi4. t / (dd.

/H):4. 0 to 7.8% (m, taH).

Product A//', (e)-α-cyano-3-phenoxybenzyl (to)-cis-J-(Z /E-2,3-dikutetra-J, J-difluoro-7-propen-I-yl )-2, cordimethylcyclopropane carboxylate, which is a mixture of one part of compound 5 and one part of compound Am-.

NMR (CCl2): p, p, m, /, /l ~
Hesan〇 (m, AH): /, F Kolko, JJ (m, koH): 4. J/(d.

/H): t, tt (d, /H): A, fO~? , $j(m, taH).

Product Azx: J-phenoxybenzyl (e)-
cis-i-(Z/E-a, s-dichloro-J,!-difluoro-7-propen-I-yl)-2, cordimethylcyclopropane carboxylate, which is 12 parts of compound AJ de and compound A It is a mixture with 1 part of O.

NMR (CC24): p, p, m, 1.01~/,
4AI(m, AH): /, If 4'-J,
3r (ms2H): j, 02 (s, JH): 6.72-7.4Aj (m, /OH).

Product &13: (e)-α-cyano-3-phenoxybenzyl (e)-cis/trans-j-(Z/E-,2-)lifluoromethyl-l-propen-l-yl)-J, J-dimethylcyclopropane carboxylate, which is a mixture of 1 part of Compound I61, 2 parts of Compound A-0, 1 part of Compound A21, and 2 parts of Compound A6.

NMR (CCja): p, p, m, 822-I
, uO (m, AH): 8toN2.30 (m, jH): j, J ~4jCj (m, /
H).

Product Mu/Hiro: J-phenoxybenzyl (e)-
cis/trans-J-(Z/E-2-trifluoromethyl-l-prone-1-yl)-J,J-dimethylcyclopropane carboxylate, which is a combination of one part of compound A6co3 and one part of compound Mucosin. 12,501 parts of compound A26 and 2 parts of compound A26.

NMR (CCA4): p, p, m, he2ko~84!0 (m, AM): /, jlA-ko,ko (m.

jH): J, 0ko(s,koH); ! , 2-6.411 (m, /H): tJj-7. Hiro J (
m, PH).

Product A/j: (e)-α-cyano-J-phenoxybenzyl (1)-cis/trans-3-(Z-3-chloro-2,3°3-trifluoro-7-propene 1/- yl)-2, Codimethyl cyclopropane carboxylate, which is a mixture of 1 part of Compound A 7 and 1 part of Compound A#t.

NMR (CCl2): p, p, m, /, /j ~/
, #0 (m, AH): /jJ~ Ko, $ 0 (m, JH): j, Or
,j,Jri.

z, to and 4. /J (da d, zH); 4, JJ (m,
/H): 4. Octopus ~7, IO (m, PH).

Product A/, 4: (e)-α-cyano-3-phenoxybenzyl (t)nisis-3-(z-3-chloro-u,J,J-trifluoro-7-propen-/-yl)- 2, Kodimethylcyclopropane carboxylate, which is compound 164c7.

NMR (CCl2): p, p, m, /, / r
~ to 4cO (m, AH): /, t j~ko, j
j (m, JH): j, I O and 4, / /
(dd, /H): & 31(d, /H): t
, f j ~7.60 (m, riH).

Product A/7: J-phenoxybenzyl (e)-
cis,/trans-J-(Z-J- chloroco, J,J-)lifluorol-l-propen-7-yl)-J,x-dimethylcyclopropanecarboxylate, which is one part of compound I6 and one part of compound AjO It is a mixture with 1 part of

NMR (CCl2): p, p, m, /, /j~/,
JO (m, AH): /jj~ko, (40 (m.

-H); t, IO, t, san〇,! , Octopus and t, Koj (
m, Jd, JH): 6, riQ~7. Hiro! (m,riH).

Product J/t: (e)-a-cyano-3-phenoxybenzyl (e)-cis/trans-J-(j,j,J-trifluoroquattrifluorotetramethyl-l-propen-!-yl)- Co,-1 dimethylcyclopropane carboxylate, which is a mixture of one part of compound A/ and one part of compound Aj.

Product A/R: 3-phenoxybenzyl (e)-cis/trans-! -(J,J-difluorocordifluoromethyl-1-propen-1-yl)-2,-1 dimethylcyclopropane carboxylate, which is a mixture of 3 parts of compound Aj and 2 parts of compound Aj.

NMR (CCA4): p, pom, /, /If ~
/, J7 (m, AH): /, 60A-2, pt (m
, JH): ! , OJ~! , / (m, JH)
: Yo 13-2 Hiro 7 (complex peak, /JH).

Product A20: (to)-α-cyano-3-phenoxybenzyl (f)-cis/trans-j-(j,j-difluorocordifluoromethyl-l-propenol-l-yl)-2,2-dimethyl Cyclopropane carboxylate, which is a mixture of 3 parts of compound 7 and 1 part of compound 16.

NMR (CCl2): p, p, m, /, ko~/,
uO(m, 4H); /, tO~,
t#7 (m, koH): 4. /7~t, 37 and 6. I j ~7.44 J (mm.

/JH).

Product I6: 3-phenoxybenzyl (e)-
cis/trans-3-(Z/E-cochloro-j,J,J-)refluoro-7-propen-1-yl)-2, codimethylcyclopropane carboxylate, which is two parts of compound 16Jj and compound A 36 It is a mixture of 1 part of compound A37, 4 parts of compound A37, and the first part of compound AJt.

Product AJJ: (e)-α-cyano-J-phenoxybenzyl (to)-cis/trans-J (Z-a, dichloro-3°3, μ, ←-titrafluoro-7 monobutene-1- yl)-2, codimethylcyclopropane carboxylate, which is a mixture of two parts of the compound AJ/ and one part of the compound At.

Product/16.2j: (e)-α-cyano-J-phenoxybenzyl (t)-trans-3-(z-2-chloro-J,j,!.

Hiro, Hiro - Pentafluoro L-B (ten-7-yl)-λ1.2-dime Chilcyclopropane Carboxy・ rate, this is the compound Ajj Ru.

NMR (CCj4): p, p, m, /, /6~/,
4'ko (m, AH): /, 744~2.40
(m, koH); 1-1 〇 and 177-7. j J (mm, / / H).

Product A-4c: J-phenoxybenzyl (e)
-cis/trans-3-(3-chloro-J,J-difluoro-2-chlorodifluoromethyl-/-7'lopen-l-yl)-2, cordimethylcyclopropane carboxylate, which is the 7th part of compound A2 and 73 parts of compound sio.

NMR (CCj4): p, p, m, /, J Hiro~/,
4C Ko(m, AH): /, 74~JLt O(m, J
H); YoOko (s, KoH) : &/4 and 7: /J (dd, /H) 474~7. Hiro 17 (m, taH).

Product 427: (e)-α-cyano-3-phenoxybenzyl (e)-cis/trans-J-(J-chloro-3,3-difluoro-cochlorodifluorot-tyl-l-propene-l -il) -J,! -dimethylcyclopropane carboxylate, which is a mixture of 7 parts of compound A// and 13 parts of compound A/J.

NMR (CCl4): p, p, m, /, Kohiro ~/
, u2 (m, AH): /,! Hiro ~ 170 (m, J
H): A, / and 7, /2 (dd, /H): A
, J4 (ss.

/H): &ri 0-7. ! 0 (m, taH).

Product 1621. : (1) -α-cyano-3-phenoxybenzyl (ho)-cis/trans-J-(Z/E-j, j-difluoro-cochlorodifluoromethyl-l-propen-7-yl) -a , 2-dimethylcyclopropane carboxylate, which is compound A27. It is a mixture of unmeasured composition containing Jr, JP and 3°.

NMR (CCl2): p, p, m, /, 2 u
-4! Ko (m, 4H): /, 74~JL
70 (m, JH): J:j ~7.4 (m, /
JH).

Product A27 = (e)-α-cyano-3-phenoxybenzyl (→-cis/trans-J(Z/E-2-promo3°3,3-trifluoro-7-propen-7-yl)-2 , 2-dimethylcyclopropane carboxylate, which is a mixture of the io part of compound Arhi, 1 part of compound 41, 101 parts, the to part of compound 474, and 1 part of compound Ar7.

NMR (CC24): p, p, m, /, 24'
~/,! 0 (m, AH): /, 7j ~ JLj
j (m, koH): from t~7, J t (m, /H): 436~4,
j4 (m, /H) Near 0-76 (m, TaH)
.

Product I6: (e)-α-ethynyl-3-phenoxybenzyl (e)-cis/trans-J-(Z/E-cochloroj,J,j-)lifluoro-7-propen-7-yl )-2, cordimethylcyclopropane carboxylate, which is a mixture of io parts of compound 11, 7 parts of compound I6j, 10 parts of compound IfL60, and 1 part of compound 447.

NMR (CO24) p, p, m, /, / t ~
/, 4cu (m, AH):/, t#~LJ&(m,
JH): jnear~z0(m,/.

H): 62t~&, uO(m,/H): 4.7 (
7-7: #0 (m, taH).

Product 711Ii25P: (1)-α-ethynyl-
3-phenoxybenzyl (ho)-cis/trans-J-(J,J,J-)trifluoro-quatrifluoromethyl-7-propen-7-yl)-2,2-dimethylcyclopropane carboxylate, which is It is a mixture of 2 parts of Compound A 13 and 3 parts of Compound A/μ.

NMR (CC24): p, p, m, /, / 4~/
, reference μ(m, 4H);/, 76~2.14 (m, JH): 6. / 2 ~ zO Hiroshi (
m, /H): Mu λhiro ~ L4AO (m, /H): 1. ．． 76～z3. g(m, taH).

Example 1! In this example, (o)-α-cyano-3-phenoxybenzyl (o)-cis/t'y-n-su-3-(,z-chloro-J, j, J -trifluoro-quatrifluoromethyl-/-7'lopen-l-yl)-,2,J-dimethylcyclopropane carboxylate (10% cis isomer)
Containing active acids AA) and (t)-α-cyano-3-phenoxybenzyl (ho)-cis/trans-j-(J,
J, j-trifluoro-2-to IJ fluoromethyl-/
-7'Lopen-l-yl)-2,2-dimethylcyclopropane carboxylate (contains 20% cis isomer)-
This illustrates the insecticidal activity of product A/).

The activity of the above products was tested against various insects and other vertebrate pests. Each product weighs 1000. ! 00゜ko! and 6Ljpp
m, and in the case of product A, it is added to 10. Kot, /11 and 6.2! It was used in the form of a liquid preparation containing p-p-m-. These formulations involve dissolving each compound in a mixture of solvents consisting of 77 tons of alcohol and 1 volume of diacetone alcohol, and then adding 0.07% by weight of a wetting agent sold under the trade name "Lisapol" NX to the solution. The formulation was prepared by diluting with water containing 100% of the active compound until a liquid formulation containing the required concentration of active compound was obtained.

The test method employed for each test pest is essentially the same and involves supporting a large number of pests on a medium, usually their host plant or some type of food on which they feed, and then or both are treated with the test preparation. Then, the mortality rate of pests was measured from 1 to 3 after treatment.
Evaluations were made at appropriate times of the day.

The test results are shown in Tables ■ and 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.

O Killing rate 30% or lessl Killing rate 30~V-2% K Killing rate! O~riO% 3R failure rate oX 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 A/IC are shown in Table 2, and the results for product 44 are shown in Table 2.

Example/4 This example illustrates the insecticidal activity of the product of Example/4C. The test is Example 1! A friend who does it under the same conditions. The test results are shown in Table 1 as pest mortality at a single application rate for each product. Application rates are expressed in degrees p, p, m, a of the active ingredient in the tested formulation.

The symbols used for the test pests in Table 2 have the following meanings: 0" - Tetranychus telari
us (Red Gumoda=, gmushi) @0# -muph
is fabae (black aphid) D”-M
egoura viceae (green aphid)
G” -Musca domestica (house/knee residual activity) @J' -Phaedon co
chleariae (mustard beetle)-L”
-Triboliumcastaheum (flour beetle) -M” -8podop tora eyestt
oralis (Bollworm) The asterisk in the table means that in addition to the mortality rates shown, surviving pests were also severely affected and would have died if the test period was extended.

Example 17 This example demonstrates how products 4u and S6 were tested against bovine ticks (Booph).
The acaricidal activity against illus m1croplus) will be explained.

10 parts of each product was diluted with rz parts of water and "Teric"("Teric" is a registered trademark, "Teric"
-N is nonylphenol and ethylene oxide:
A suspension containing 1.0% of the active fraction was prepared by milling in a Zeel mill with 5 parts of a nonionic surfactant obtained by condensation in a molar ratio of 1. A portion of this suspension was diluted with water to obtain compositions containing 0.1% and 0.101% of the active fraction.

The efficacy of each test product was tested by micro-applying the suspension to each of about 40 ticks. Mortality of convergent mites after lμB was assessed by calculating the number of eggs laid and the percentage of eggs that became infected. The results are shown in Table 7.

= The efficacy of each test product against mite larvae of the Yeerongpilly' strain was tested as follows. p
The paper is immersed in a suspension of the above concentration and then dried, the treated P paper is shaped into a wrapping paper, and the wrapping paper is used for about io.

of the above mite larvae. After packaging ≠ j The number of dead tick larvae after the waiting time was calculated and expressed on the scale of killing rate t-0-j: O killing rate Q#koO% l KoO~yo0
Person in charge l jO~r
0%3 10~rij%≠
Tata ~ Tatachiz
ioo% The results are shown in Table 7.

In a separate test, each test product was prepared by mixing Jj parts of test compound with 7j parts of cyclohexanone and 2j parts of "Teric" N2 and diluting this mixture with water to give an emulsion of t-1oooo parts by volume. emulsion gold was prepared. The emulsion obtained by smelling
Cattle of the resistant "Biana" strain at various stages of growth were sprayed to a drip onto calves infested with ticks.

The efficacy of each test product was evaluated as follows.

(1) Immediately after spraying, all adult mites (female) that were fully mature at the time of spraying were collected and placed in a Petri dish in an egg evaluation device. Learn more about the larva! The evaluation was based on the viability of the eggs shown. Mature adults (if present) were similarly collected at 2 hrs and tar hrs after spraying to assess mortality.
ultg)' and the results are shown in Table 3.

Every (li)/day, scheduled sampling areas on each calf were examined for the effect of the active ingredient on immature adults and nymphs. This review 1iIIlt-The above nine scales O~
! and are referred to as "mortality rate - immature adult" and 1 mortality - nymph 2. The results are shown in Table ■.

In the table, the symbol "-#" indicates that the insect had matured and no next adult was present.

In these tests, permethrin,
Immediately? +j-2 enoxybenzyl (to)-cis/trans-J (w, w-J chlorovinyl]-W, W-)
Next using methyl cyclozolonocarboxylate.

From the results in Table 2, the novel cyclozolonogne derivative of the present invention having at least one fluoroalkyl group bonded to a vinyl group was compared with the comparative drug permethrin, which is a known insecticide and acaricide compound with a similar structure. It is recognized that the desired effect can be achieved with significantly lower doses.

Claims (1)

[Claims] 1. The following formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, one of R^1 and R^2 is a trifluoromethyl group, and the other is a trifluoromethyl group. or difluoromethyl group) 5-fluoromethyl-6-
Fluoro-5-hydroxy-2-methylhexene-2. 2,5-hydroxy-2-methyl-6,6,6-trifluoro-5-trifluoromethylhexene-2 and 5-
A compound according to claim 1 selected from hydroxy-2-methyl-6,6-difluoro-5-trifluoromethylhexene-2. 3. The following formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R^1 and R^2 have the meanings given below) consisting of reacting the ketone with 3-methylbutene-1 The following formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the formula, one of R^1 and R^2 is a trifluoromethyl group, and the other is a trifluoromethyl or difluoromethyl group) 5-fluoromethyl-6-
Method for producing fluoro-5-hydroxy-2-methylhexene-2. 4. The production method according to claim 3, wherein the reaction is carried out under pressure.