JPS62145046A - Novel derivatives of bromine-substituted cyclopropanecarboxylic acid, manufacture, parasiticidal use for plants ans animals and composition - 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 subject of the present invention is that all stereoisomeric forms or stereoisomeric It is a compound in the form of a mixture.

Chlorinated or brominated derivatives corresponding to compounds of general formula (I) are known and are known from French Patent No. λ185,612.
listed in the number.

The present inventor has now discovered that the iodinated compound of general formula (I) is endowed with remarkable pesticidal (pesticide) properties.

Prior art methods did not encourage chemists to produce diiodinated derivatives.

This is because the starting material carbon tetraiodide used is not very stable and is therefore a difficult reagent to handle. Furthermore, it was anticipated that the final product obtained would be too unstable to be used for agricultural purposes. But there was no such thing at all.

It has now been unexpectedly found that short vinyl compounds of formula (I) can be prepared, which are stable and which are endowed with excellent besticidal properties.

However, the Wittzig reaction described for carbon tetrachloride or carbon tetrabromide in 7 Reims Patent No. 2,185,612 could not be used for tetraiodinated derivatives.

In fact, until very recently, tl-short alkenes were a largely unknown group of compounds. This is because short methylene cyclohexane was only produced intermediately with boron (F
, Ganina et al., J. Chem.

Soe, Commun, p. 296 (1985)
). F. Ganina et al. were the first to convert aliphatic and aromatic aldehydes to tl-short alkenes by the Wittig reaction using triphenylphosphine and carbon tetraiodide. However, this reaction is extremely delicate.
However, it can only be carried out using very pure carbon tetraiodide at temperatures close to 0°C.

Here, the present inventor applied the reaction of Mr. F. Ganina et al. to 3-formyl-2,2-dimethylcyclopropanecarboxaldehyde to obtain 2,2-dimethyl-3-(2,2-short ethynyl)cyclo It was discovered that propanecarboxylic acid can be provided.

More particularly, the subject of the invention provides that R is a) 1-8
a linear or branched alkyl group containing m carbon atoms, or b) a benzyl group, or a group in which R1 represents a hydrogen atom or a methyl group,
or d) where R3 is an aliphatic organic group containing 2 to 6 carbon atoms and one or more carbon-carbon unsaturations, especially -
CHz=CH=CH1, -CR2-CH=CH-CH
a, -C1(2-C)(=CH-C2I!, -CH2
-CH=CH-CH=C) (represents 2, CH2-CMMCH), or e) the following formula (where B represents a C=0 group or an oxygen atom, R4 is a hydrogen atom, a methyl group, - CIWN group, -CMMCH group or -C-NH* group), or f) a group of the following formula, or g) a group of the following formula, or h) a group of the following formula [where R is a hydrogen atom or - Represents a CN group, RεR
.

■ is a thiazolyl group (in this group, the bond -CH- is m+
ihmtr-+-, am, b+--s-7%, /+1-
L+1-p-klD- represents -CH, - group or oxygen atom], or l) a group of the following formula, or j) a group of the following formula (where R8 represents a hydrogen atom or a =CH group) basis,
or k) a group of the following formula (where R group represents a hydrogen atom or a -CN group),
or l) a group of the following formula (where Rtz represents a hydrogen atom, a methyl group, an ethynyl group or a cyano group, and RIO and R11 may be the same or different and represent a hydrogen, fluorine, chlorine or bromine atom), or m) a group of the following formula (where Rts represents a hydrogen atom, a methyl group, an ethynyl group, or a cyano group, and B/ represents an oxygen or sulfur atom), or n) a group of the following formula (where R14 represents a halogen atom, RIS represents an alkyl group containing 1 to 6 carbon atoms or a trifluoromethyl group; RIS represents a halogen atom, an alkyl group containing 1 to 6 carbon atoms, an alkoxy group containing 1 to 6 carbon atoms; or represents a trifluoromethyl group, and a is 0, 1 .
2.3 or 4, and b is 0.1.2.3.4 or 5
The compound is a compound having the general formula (I) according to claim 1, characterized in that it represents a group of (I) in the form of all stereoisomers or in the form of a mixture of stereoisomers.

In the compounds according to the invention, when R represents a linear or branched alkyl group containing 1 to 8 carbon atoms, it stands in particular for methyl, ethyl, linear or branched privyl,
It can represent a linear or branched butyl, linear or branched pentyl, linear or branched hexyl or linear or branched octyl group.

More particularly, the subject of the invention provides that R is of the formula (where B
represents a C=0 group or an oxygen atom, R4 is a hydrogen atom, a methyl group, -(:xN group, -CmCH group or -C-NH2
compounds of the general formula (I), characterized in that they represent a group of the formula (I), in particular a group of the formula where R represents a hydrogen atom, a methyl group, a cyclotinyl group, or a cyano group, and R1 (1 and R11 may be the same or different and represent hydrogen, fluorine, chlorine, or bromine), especially Compounds in the form of all stereoisomers or mixtures of stereoisomers having the general formula (I), characterized in that they represent a group of the formula; R is a hydrogen atom, a methyl group, represents an ethynyl group or a cyano group, B' represents an oxygen or sulfur atom), in particular a group of Compounds in the form of mixtures; R is a halogen atom, an alkyl group containing 1 to 6 carbon atoms or a trifluoromethyl group; Rti is a halogen atom, an alkyl group containing 1 to 6 carbon atoms; represents an alkyl group containing atoms, an alkoxy group containing 1 to 6 carbon atoms or a trifluoromethyl group, and the island is 0.1
．． 2.3 or 4, and b is 0.1.2.3.4 or 5
It concerns compounds in all stereoisomeric forms or in the form of mixtures of stereoisomers of the general formula (I), characterized in that they represent a radical of the formula (I), in particular a radical of the formula:

More specifically, the subject matter of the present invention relates to compounds in which the compound owner is as follows.

IR, eim-2,2-dimethyl-5-(2,2-di1
-doethenyl)cyclopropanecarboxylic acid (S)cyano-(3-phenoxy-4-fluorophenyl)methyl, I R,clm -2,2-dimethyl-3-(2,2-
cyclopropanecarboxylic acid (S)cyano-1-(3-phenoxy-4-fluorophenyl)
Methyl and IS, elm-2,2-dimethyl-5
-(2,2-dirodethenyl)cyclopropanecarboxylic acid (R) 50-50i compound with cyano-1-(3-phenoquine-4-fluorophenyl)methyl.

The subject of the invention is also a process for preparing compounds of the general formula (I) as defined above in all stereoisomeric forms or in the form of a mixture of stereoisomers, which method comprises the following formula (If ) with tetraiodomethane and triphenylphosphine, and the resulting compound of formula (II) is reacted with p-) in an organic solvent. The following formula (
IV), optionally converting this compound into a functional derivative such as an acid chloride, acid anhydride or mixed acid anhydride, and then converting the compound to an acid of formula (II/) or a functional derivative thereof. The present invention relates to a process for the preparation of compounds of general formula (I), characterized in that an alcohol of the formula or a functional derivative of this alcohol is reacted to obtain a corresponding compound of general formula CI).

In a preferred method of the production method of the present invention, formula (If)
When the compound of formula (III) is reacted with tetraiodomethane and triphenylphosphine, the organic solvent is a chlorinated aliphatic solvent such as methylene chloride, and the compound of formula (III) is reacted with p-
) The organic solvent in which the acid is reacted is an organic solvent such as benzene, toluene or xylene, the functional derivative of the acid of formula (■) is an acid chloride, and this acid chloride is Alcohol R-OT in the presence of three bases
The acid of formula (■) is reacted with alcohol R-OH in the presence of dicyclohexylcarbodiimide or diisopropylcarbodiimide and dimethylaminopyridine.

The invention is also characterized in that a compound of formula (If) is reacted with tetraiodomethane, triphenylphosphine and zinc in an organic solvent to obtain a compound of formula (If) and then the synthesis is continued as described above. The object of the present invention is to provide a method for producing a compound of general formula (I).

In a preferred method for carrying out the above manufacturing method,
The organic solvent for reacting the compound of formula (It) with tetraiodomethane, triphenylphosphine and zinc is a chlorinated aliphatic solvent such as methylene chloride.

The compounds of formula (I) exhibit beneficial properties that make it possible to use them for combating parasites. For example, this includes the control of plant parasites, house parasites and bleeding animal parasites. Therefore, the compound of formula (I) is
It can be used to exterminate pests, nematodes, and mites that are parasites of plants and animals.

The subject of the invention is therefore the use of the compounds of formula CI) as defined above for the control of plant parasites, house parasites and bloodworm parasites.

The subject of the invention is therefore the general formula CI as defined above.
A pesticide composition for exterminating parasites of infected animals, house parasites, and plants, characterized by containing at least one compound of the following as an active ingredient.

In the case of agricultural and domestic compositions, one or more other besticides can be added to them. These compositions can be provided in the form of powders, granules, suspensions, emulsions, solutions, aerosol solutions, combustion strips, baits or other formulations commonly used for the use of compounds of this type. .

In addition to the active ingredients, these compositions generally contain, among other things:
Contains a vinyl and/or nonionic surfactant that enables uniform dispersion of the components that make up the mixture.

The vehicles used may be water, alcohols, hydrocarbons or other organic solvents, liquids such as mineral oil, animal or vegetable oils, powders such as talc, clay, silicates or diatomaceous earth, or combustible solids. It's fine.

The compounds of formula (I) can therefore be used, in particular, for the control of pests in the agricultural field, such as larvae of the Aphids, Lepidoptera and Coleoptera. They are used in dosages of between 10 and 300 grams per hectare of active substance.

Compounds of formula CI) can also be used to combat pests in houses, especially flies.
It can be used to control mosquitoes and cockroaches, as well as animal parasitic pests such as cattle, sheep and poultry lice.

In particular, the subject of the invention is insecticidal compositions containing as active ingredient at least one compound of the general formula CI) as defined above.

More specifically, the present invention provides compounds whose active ingredients are as follows: I R, C1m -
2,2-dimethyl-3-(Z2-jodoethyl)cyclopropanecarboxylic acid (S) cyano-(3-phenoxy-4-fluorophenyl)methyl, I R, aim -2,2-dimethyl-3- (2,2-
short ethynyl) cyclopropanecarboxylic acid (S)cyano-1-(3-7dynoxy4-fluorophenyl)
Methyl and IS, eig-42-dimethyl-5-(2,2
- short ethynyl) Schifta propanecarvone @ (R
) Cyano-1-(3-7 dynoxy-4-fluorophenyl)methyl and a 5o-so mixture.

The insecticide composition according to the invention preferably has o, oos to
Contains 10% by weight of active substance.

For domestic use, in a useful embodiment the compositions of the invention are used in the form of smokable compositions.

Thus, the insecticide composition according to the invention may consist of a flammable insecticide coil or a non-flammable fibrous substrate for the non-active part. In the latter case, the smoke agent obtained after incorporating the active substance is placed on a heating device, such as an electric emitter.

When insecticide coils are used, inert carriers can be used, for example, pyrethrum lees, machilusthu powder, etc.
mbergil leaf powder), pyrethrum stem powder,
It may consist of cedar needle powder, wood flour (pine sawdust), starch and coconut shell powder.

In that case, the dosage of active substance is, for example, α03-1% by weight.

If a non-combustible fibrous material carrier is used, the dosage of active substance may be 1, for example 103 to 95% by weight.

The compositions of the invention for domestic use can also be obtained by preparing a spray oil based on the active ingredient and impregnating a lamp wick with this oil, which is then combusted.

The concentration of active ingredient incorporated into this oil is preferably 103 to 95% by weight.

The compounds of formula (I) can also be used to combat parasitic mites on plants. The biological tests presented in the experimental section below demonstrate, inter alia, the pronounced acaricidal properties of the compound of Example 4.

The compounds of the invention can also be used to combat parasitic nematodes on plants.

Therefore, the present invention provides an acaricide composition containing at least one compound of formula (I) as an active ingredient as well as a nematicide composition containing at least one compound of formula (I) as an active ingredient. The composition is the subject matter.

Acaricides and nematocides are provided in particular in the form of powders, granules, suspensions, emulsions or solutions.

For acaricide applications, preferably foliar spray wettable powders containing from 1 to 80% active ingredient, or from 1 to 500% active ingredient.
A foliar spray solution containing 9/A of active ingredient is used. Foliar powders containing from 3% O,OS active substance can also be used.

As a nematocide, a soil treatment solution containing 300 to 7 tons of active ingredients is used.

The acaricidal and nematocidal compounds according to the invention are used in dosages of 1 to 100 g of active substance per hectare.

The compound of formula CI) can also be used to exterminate parasitic mites in animals,
For example, ticks (tlck L, especially Boophilus)
philua) species mite, Hyal elA (Hyal
omnlm) 81 mites, Amblyomnia (Am
blyomnlm) species, Ribice 77#s (Ph
Control of mites of species 1piephalu+s) or all types of mites, especially aareoptic mites, pgoroptic mites
) and Kryobchitsk Might (chorlopt)
ic m1ta).

The subject of the present invention is therefore a composition for combating parasitic mites in mixed-breed animals, which is characterized in that it contains at least one compound of formula CI).

These compositions can be administered externally, by vaporization, by shampooing, by bathing, or by application. They can also be administered by application onto the spine by the so-called "pour-on" method. They can also be administered by the gastrointestinal route.

When the control of parasitic mites on animals is a problem, the compounds of the invention can be incorporated into feeding compositions in combination with nutrient mixtures for animal fattening. The nutrient mixture can vary depending on the species of animal. These are grains, sugars,
It can contain grains, soybean cake, peanut cake, sunflower cake, animal powders such as fishmeal, synthetic amino acids, inorganic salts, vitamins, antioxidants, etc.

The subject of the invention is therefore a composition for animal husbandry which contains as active ingredient at least one compound of the general formula (I) as defined above.

To increase the biological activity of the compounds of the invention, standard synergists used in analogous cases, such as 1-(2,
5,8-)rioxadodecyl)-2-propyl-4,5
-Methylenedioxybenzene (biperonyl butoxide)
, or N-(2-ethylhbutyl)bicyclo(2,2,
1) -5-hebutene-23-dicarboxamide or biperonyl bis-2-(2'-n-butoxyethoxy)
Ethyl acetal (trobital) can be added.

The subject of the invention also provides as active substance on the one hand the general formula (
at least one of the compounds of I), and on the other hand, chrysanthemum acid and arethrolone, 3,4,5,6-titrahydrophthalimidomethyl alcohol, 5-benzyl-3-furylmethyl alcohol, 3-phenoxybenzyl alcohol and α - Each ester with cyano-3-phenoxybenzyl alcohol; z2-dimethyl-3-(2-oxo-3-
ester of cyclopropane-1-carboxylic acid (tetrahydrothiophenylidenemethyl) and 5-benzyl-3-7lyl methyl alcohol;
Each ester of 2,2-dichlorovinylcyclopropane-1-carboxylic acid and 3-phenoxybenzyl alcohol and α-cyano-3-phenoxybenzyl alcohol;
ester of 2,2-dimethyl-3-(2゜2-dibromvinyl)cyclopropane-1-carboxylic acid with α-cyano-3-phenoxybenzyl alcohol) 2-P-chlorophenyl-2-isopropylacetic acid and 3- Esters with phenoxybenzyl alcohol; 2,2-dimethyl-3
-(t2.2.2-?trahaloethyl)cyclopropane-1-carboxylic acid (where halo represents a fluorine, chlorine or bromine atom) and arethrolone, & 4.5° 6-tetrahydrophthalimidomethyl alcohol, 5-benzyl - containing at least one pyrethrinoid ester selected from the group consisting of 3-furyl methyl alcohol, 3-phenoxybenzyl alcohol, and esters with α-cyano-3-phenoxybenzyl alcohol (herein, formula CI); compositions endowed with insecticidal, acaricidal or nematicidal activity, characterized in that the acid and alcohol linking moieties of the pyrethrinoid esters are in all possible stereoisomeric forms thereof. It is in.

The mixed composition according to the invention is particularly advantageous in that it provides multimodal action against a wide range of parasites and in some cases exhibits a synergistic effect.

The following examples are illustrative of the invention and do not limit the invention in any way.

Mix 10 and 19 of triphenylphosphine and 180 CC of methylene chloride, introduce 10 of tetraiodomethane at 0°C, and stir at 0°C for 20 minutes. Then t
99 IR, trans -3-formyl-2,2-
t-butyl dimethylcyclopropanecarboxylate 21c
Gradually add a solution of c dissolved in methylene chloride, +
Stir at 20°C for 20 hours. After concentration by vacuum distillation, the residue was eluted on silica, eluting with a mixture of methylene chloride and ethyl acetate (1/1) and then with a mixture of methylene chloride and hexane (5/7),
2.5 expected compounds were obtained.

t 2-15 ppm peak: attributed to methyl hydrogen; 147 ppm peak: attributed to t-butyl hydrogen; t
55-t 65 ppm peak: Attributable to hydrogen at position 1 of cyclopropane, 'L83~2.05 ppm peak: Attributable to hydrogen at position 3 of cyclopropane, 6,75-6.87 ppm peak : Attributable to hydrogen of ethynyl.

10. Mix 19 of triphenylphosphine and 180 CC of methylene chloride, add 109 of tetraiodomethane at 0°C, and stir at 0°C for 15 minutes. Then 1
A solution of 99 IR, aim -3-formyl-λ2-dimethylcyclopumapancarboxylic acid t-butyl dissolved in 20 CC of methylene chloride was gradually added to +20
After filtering and concentrating solution F by vacuum distillation, the residue was chromatographed on silica and mixed with a mixture of ethyl acetate and methylene chloride (1/1).
Then, a mixture of methylene chloride and hexane (3/7
) to obtain the desired compound of tolg.

1! L568m-': attributed to methyl of t-butyl,
11601M: Attributed to c-o-c.

NMR spectrum (deuterochloroform) 125
Attributable to methyl hydrogen in two pairs of ppm peaks, 147 p
PM peak: attributed to t-butyl hydrogen, t58 and t
85 ppm peak: attributed to the hydrogens at positions 1 and 3 of cyclopropane; 7,32-7.4 ppm peak: attributed to the hydrogens of ethyl.

Step AI: I R, trans -2,2-dimethyl-3-(λ2-short ethynyl)cyclopropanecarboxylic acid 1α Mix 1 g of triphenylphosphine and 200 CC of methylene chloride, and add 10.25 g of tetraiodo at 0°C. Add methane and stir at 0°C for 15 minutes. Gradually add a solution of t1-dimethylethyl 3-formyl-2,2-dimethylcyclopropanecarboxylate dissolved in methylene chloride of 20 (:C) and stir at +20°C for 17 hours. Electrolysis of 125 Add zinc, stir for 10 minutes, then filter and concentrate the p-liquid by vacuum distillation.

The residue was chromatographed on silica, eluting with methylene chloride and then with a mixture of methylene chloride and ethyl acetate (1/1) to give 2.67 of the expected compound. m
p=100℃.

IR spectrum (chloroform) & 505 cfR absorption knee OH, attributed to monomer and dimer, 1,737 cM: -C- attributed to monomer acid, peak pair of It 22- t 55 ppm Attributable to hydrogen of methyl, 'L64-'L73 ppm peak: Attributable to hydrogen at position 1 of cyclopropane, t90-199 ppm and 2.02-2.12 ppm
Beak of m: Attributable to hydrogen at position 5 of cyclopropane; Beak of &74-&85 ppm: Attributable to hydrogen of ethynyl; Beak of 155 ppm: attributable to hydrogen of carboxyl.

Step A2: IR,trans-212-dimethyl-3-(2,2-short ethynyl)cyclopropanecarmenic acid'L2g of IR,trans-2,2-dimethyl-
Mix 3-(2,2-short ethynyl)cyclopropanecarbon[1,1-dimethylethyl and 20 CC of toluene, reflux, then introduce 200 IIP of p-)luenesulfonic acid and keep stirring the whole for 15 minutes. . It was then cooled and concentrated by vacuum distillation and the residue was chromatographed on silica, eluting with a mixture of hexane and ethyl acetate (6/4) to give the expected compound of t6y. mp=101°C.

Step B: IR, trams -2,2-dimethyl-
3-(2,2-short ethynyl)cyclopropanecarbon[(S)cyano-(phenoxyphenyl)methyl 19 g of I R, trans -2,2-dimethyl-3
-(2,2--/iodoethynyl)cyclopropanecarboxylic acid, 1.39 of (S)cyano-3-phenoxybenzyl alcohol, 20 WII of dimethylaminopyridine and 20- of methylene chloride are mixed, then 145 g of dicyclo A solution of hexylcarbodiimide in 1 occ of methylene chloride is slowly introduced at +5°C. +
After bringing to 20° C. and filtration, the p-liquid was concentrated by distillation under reduced pressure and the residue was chromatographed on silica, eluting with a mixture of hexane and ethyl acetate (9/1), 19
5 g of the expected compound were obtained.

Absorption of 15850 and 1485G: following formula (% formula %) Peak at t 2 - t 25 ppm: Attributable to the hydrogen of the methyl pair, Peak at t 67 - t 76 ppm: Attributable to the hydrogen at the 1st position of cyclopropane, 195-2.15 ppm peak: attributed to hydrogen at position 3 of cyclopropane; 658 ppm peak: attributed to hydrogen on the same carbon as CN; &75- & 87 ppnl peak: attributed to ethynyl hydrogen. Peak of 6-92-7.58 ppm: Attributable to hydrogen of aromatic nucleus.

1R of t51, trans -2,2-dimethyl-3-
(2,2-Short ethynyl)cyclopropanecarboxylic acid, (S)cyano-3-phenoxy-4 of 85511P
- Fluorophenylmethyl alcohol
Introduce at °C. The mixture is stirred at +20° C. for 2 hours, then filtered and Part F is concentrated under reduced pressure. The residue was chromatographed on silica, eluting with a mixture of methylene chloride and hexane (45155) to give 14 g of the expected compound.

Attributable to absorption knee C- of t740cW1, t19-1
22 ppm peak: attributed to the hydrogen in the methyl pair, t 65-174 ppm peak: attributed to the hydrogen in the 1st position of cyclopropane, t92-2.12 ppm peak: attributed to the hydrogen in the 3rd position of the cyclopropane Attributable to, & 53PPm peak: Attributable to hydrogen on the same carbon as CN, 6, 75-6.85 ppm peak: Attributable to ethynyl hydrogen, 6.88-7.5 ppm peak: Aromatic Attributable to nuclear hydrogen.

Step A: I Rs cig -2+ 2-dimethyl-
IR of 3-(Z2-short ethynyl)cyclopropanecarboxylic acid 9501P R,clg -2,2-dimethyl-3
tert-butyl -(2,2-short ethynyl)cyclopropanecarboxylate, 90 cc of p-)luenesulfonic acid and 10 cc of toluene were mixed, the reaction mixture was refluxed and 1
Continue to reflux for 5 minutes, then cool.

After concentration by vacuum distillation, the residue was chromatographed on silica and chromatographed with a mixture of ethyl acetate and hexane (3/3).
7), yielding 770 μ of the desired compound. mp”1
40℃.

IR spectrum (chloroform) & 505 cm absorption knee OH, attributed to monomer and dimer, t735z-” knee (- attributed to monomer acid, 0% 697 cm: -C- attributed to dimer acid) Cause.

NMR spectrum (deuterochloroform) t 3p
Peak of pm: attributed to the hydrogen of the pair of methyls, t63 and t
98 Ppm peak: attributed to hydrogens at positions 1 and 3 of cyclopropane; 713-7: 42 ppm peak: attributed to hydrogens of ethynyl.

Step B: IR, cis-2,2-dimethyl-3-(Z2
-Short ethynyl)cyclopropanecarboxylic acid (S)
IR of cyano-1-(3-phenoxy-4-fluorophenyl)methyl 750yHi R,aim -2,2-dimethyl-
3-(2,2-short ethynyl)cyclopropanecarboxylic acid, 440q of (S)cyano-(3-phenoxy-
4-Fluorophenyl) methyl alcohol, 7,41+
9 of 4-dimethylaminopyridine and 7.5 CC of methylene chloride are mixed and then a solution of 430 cap of dicyclohexylcarbodiimide dissolved in 2.5 CC of methylene chloride is slowly added at +5°C.

The whole is stirred at +20° C. for 2 hours, then filtered and Part F is concentrated by vacuum distillation. The residue was chromatographed on silica and chromatographed with a mixture of methylene chloride and hexane (1
/1) and washed with hexane, 70011P
The desired compound was obtained. m p =98°C.

IR spectrum /I/(chloroform) 1,742 cm Attributable to absorption knee C-, NMR spectrum (deuterochloroform) t 17-125
Peaks of 178 and 1.98 ppm: attributed to the hydrogens in the 1 and 3 positions of cyclopropane; 6,54 ppm peaks: attributed to the hydrogens on the same carbon as CN; Attribution, L 9-7.55 ppm peak: Attributable to aromatic nucleus hydrogen and ethynyl hydrogen.

It is carried out as shown in Example 3, Step B, except that at the start t99 IR, eig-2,2-dimethyl-
Starting from 3-(2,2-short ethynyl)cyclopropanecarboxylic acid (obtained as described in Example 5), t
A crude product of 95% was obtained which was chromatographed on silica and chromatographed on silica using a mixture of methylene chloride and ethyl acetate (1/i
) and then washed by trituration in acetonitrile.

After filtration, washing with ether and recrystallization from ethyl acetate, 17 g of the expected compound were obtained. mp-130°C.

1.587 tan and 1,487cm: following formula 'L 22-
129 ppm peak attributed to two pairs of methyl hydrogens, t 82-2.09 ppm peak: attributed to hydrogens at positions 1 and 3 of cyclopropane, 6,45 ppm peak: located on the same carbon as CN Attributable to hydrogen; 698-7.6 ppm peak: Attributable to aromatic nucleus hydrogen and ethynyl hydrogen.

α839 IR, trans -2,2-dimethyl-
3-(2,2-short ethynyl)cyclopropanecarboxylic acid, 10 cc of methylene chloride-10 cm of dimethylaminopyridine and 0.459 of [2-methyl-(t
Mix the 1'-biphenyl)-3-ylcomethyl alcohol and then add 0.4479 dicyclohexylcarbodiimide in one portion at 20°C.

The resulting urea was separated, the F solution was concentrated by vacuum distillation, and the residue was chromatographed on silica, eluting with a mixture of hexane and ethyl acetate (9/1) to give C1,959
The desired compound was obtained.

1.590CM and 1,498cm” attributed to aromatics.

NMR spectrum (CDCl3) t 22-152 ppm peak: pair of methyl hydrogens, t 71-18 ppm peak: 1 of cycloprovir
Hydrogen at position 199-2.13 ppm peak: Hydrogen at 1 and 3 positions of cycloprovir, peak 6, 77-6.88 ppm: Hydrogen of ethylene, peak 7, 22-7.56 ppm: aromatic hydrogen.

IR of methyl 1 R, cls -2,2-dimethyl-5-(2
゜2-cy-)'ethynyl)cyclopropanecarbon W
i, 2 o cc of methylene chloride, 10 cm of dimethylaminopyridine and α55 of 2-methyl-(11/-biphenyl)-3-ylcomethyl alcohol were mixed, and then 0.589 of dicyclohexylcarbodiimide was added. Add at once. After stirring for 2 hours at 0°C, the resulting urea is distributed door to door. The organic phase is washed with water and concentrated by vacuum distillation.

The residue was chromatographed on silica, eluting with a mixture of hexane and methyl acetate (9/1), yielding 15 g of the expected compound.

1,585eyn and 1495cm: attributed to aromatics.

t 26-128 ppm peak: Hydrogen of the methyl pair 1 155-2.02 ppm peak: Hydrogens at positions 1 and 5 of cycloprovir, 2,5 lppm peak: Hydrogen at position 2 of methyl, 7.
15-7.48 ppm peak: aromatic hydrogen and ethylene protons.

Analysis: 572.228 = CzzH2z(h lz
C% H% 1% Calculation: 46.18 587 44.55 Actual measurement:
47.2 4.0 42.41111L To a solution containing 1 g of triphenylphosphine and 180 d of methylene chloride is placed 10 g of tetraiodomethane at 0°C. After continuing to stir this at 0°C for 20 minutes, the IS of 199, aim-2°2-dimethyl-3-formylcyclopropanecarbon I! 1! i, 1-dimethylethyl and 2
0 CC of methylene chloride is introduced and stirring is continued for 17 hours. After washing, drying and evaporation, a residue is obtained, which is dissolved with 250 cc of isopropyl ether, then filtered and the filtrate is evaporated. 5859 product is obtained which is chromatographed on silica, eluting with a mixture of methylene chloride and hexane. In this way 2.39
The desired compound was obtained. m p = 54°C.

Step A: IS, cim-2.2-dimethyl-3-(2°2-short ethynyl)cycloprepanecarboxylic acid 2.159 compound prepared in Step A, 10 CC toluene and 200111P p-)luenesulfone The solution containing the acid is heated to reflux, then cooled and diluted with 30 CC of ethyl acetate. The organic phase is then washed, dried and evaporated under reduced pressure. A product of 1859 is obtained which is chromatographed on silica and eluted with a mixture of hexane and ethyl acetate (7/3). The desired compound of t55Ii was obtained. mp=139°C.

Step B: IS, cig-2,2-dimethyl-5-(2°2-short ethynyl) Schiff's party prepane carboxylic acid (R
) Cyano-1-(3-phenoxy-4-fluorophenyl)methyl 0.82 IS, elg-2,2-dimethyl-3
-(2,2-short ethynyl)cyclopropanecarmene[,458■(R)cyano-(3-phenoxy-4
-fluorophenyl) methyl alcohol, 9 vq of dimethylaminopyridine, and 8 CC of methylene chloride, 4.6019 dihexylcarbodiimide dissolved in 5 CC of methylene chloride was heated to 0°C.
will be introduced. After filtration, the solvent is distilled under reduced pressure. The product obtained is chromatographed on silica and eluted with a mixture of methylene chloride and hexane (1/1). A resin-like substance was obtained, which was again subjected to four-mudography, 78 (l
The desired compound of v was obtained. m p = 95°C.

(ff) D=-25'±1° (-=19%, CHC1s
).

Attributable to absorption knee C- of 1,742 cm, t 2-1
26 ppm peak: paired methyl H1t66~2
Beak of ppm; Hl at the 1st and 3rd positions of Schiff-Roshi propyl 695-7.57 Beak of ppm: Hydrogen of ethylene,
& 58 PPn1l beak; H150 mixture i R,cls -212-dimethyl-5-(2,2-
di-doethynyl) cyclopropanecarboxylic acid and its i
! 88-elm-mixture and (R8) Schiff/
-1-(3-phenoxy-4-fluoro, II/7 x
carried out as in the above method starting from methyl alcohol and after chromatographic separation,
A racemate (1R, elm, S and 18°cts, R) was obtained. n5p=104°C.

(R3) The desired compound was obtained by working as in Example 11 starting from cyano-1-(3-phenoxyphenyl)methyl alcohol.

The following compounds were prepared according to the method of the present invention.

I R, trans -Z2-dimethyl-5-(2,2
-Short ethynyl) cyclopropanecarboxylic acid pentafluoro722methyl.

[α] D = +450i-Q, 5° (e = 15%, c
Hcxs).

I R, trans -2,2-dimethyl-5-(2,
2-Short ethynyl)cyclopropanecarboxylic acid 1-
(3-phenoxyphenyl)methyl.

[α]D=+a50-1:l1lL5o(c=15%,
CHCl).

I R, trans -2,2-dimethyl-3-(2,
2-Short ethynyl)cyclopropanecarboxylic acid (S
) 3-(2-Pudaben, A/)-2-methyl-4-oxo-2-cyclopentenyl.

[α) D=-2°±1° (c=1%, CHCl,).

I R, trans -2,2-dimethyl-5-(2,
Methyl-1-(6-7 dinoxy-2-pyridyl) Schiff tetrapropanecarboxylate.

[α) D = + 25.5° ± 1° (c = 1%, CHCl
5).

IR, trana-2,2-dimethy-5-(2,
Cyano-1-(6-phenoxy-2-pyridyl)methyl 2-short ethynyl)cyclopropanecarboxylate.

[α]D=+16°±α! 5° (a = 15%, CH
CIg).

1 R,clg -2,2-dimethyl-3-(2,2-
di-doethynyl)cyclopropanecarboxylic acid (S)3
-(2-propenyl)-2-methyl-4-oxo-2-
Cyclopentenyl.

[α] D = +13° +15° (C = α6%, CHCIg
).

j R, aim -212-dimethyl-5-(ZZ-short ethynyl)cyclopropanecarboxylic acid cyano-1
-(6-7dinoxy2-pyridyl)methyl O [a) D=5°±1'(c=(L9%, CHCl,)
.

I R,eis -2,2-dimethyl-3-(2,2-
methyl cyclopropanecarboxylate
1-(6-7 dinoxy 2-pyridyl) methyl O [α] D = +7° ± 1° (e = 15 J, CHCl5
).

IR, clm-λ2-dimethyl-3-(2,2-shortethynyl)cyclopropanecarboxylic acid 1-(5-phenoxyphenyl)methyl.

(g) D=-11°±1' (e=1%, CHCl3)
.

I R, aim -2,2-dimethyl-5-(2,2-
Pentafluorophenylmethyl (di-10-doethynyl)cyclopropanecarboxylate.

(a) D=-14°±15° (c=2%, CHCl5
).

Example 23: Preparation of soluble concentrate Make a homogeneous mixture of the following ingredients.

Compound of Example 5 α259 Piperonyl Butoxide 1g Tween 80 125g Dopanol A
11g water
9 &4 g Example 24: Preparation of emulsifiable concentrate Mix the following ingredients intimately.

Compound of Example 5 α015 Cubiperonyl ptoxide 0.5g Dopanol A
Q, 19 xylene 95.88
59 Tween 80 55g Example 2: Preparation of emulsifiable concentrate The following ingredients are mixed homogeneously.

Compound of Example 5 tsp Tween 80 209 Dopanol A a2g xylene
7a4g Example 26: Preparation of smoke composition The following ingredients are mixed homogeneously.

Compound of Example 5 (L25 Cutap powder
25g Cedar Leaf Powder 409 Pine Tree Powder 35751 Brilliant Green α5g p-Nitrophenol 0.59 Example 27: Preparation of Soluble Concentrate A homogeneous mixture is prepared from the following ingredients.

Compound of Example 11 Q, 25g Piperonyl Butoxide 1g Tween 80 0.259 Dopanol A α1 Water
9 &49 Example 28: Preparation of emulsifiable concentrate The following ingredients are mixed intimately.

Compound of Example 7 α015 Kubipeinylbutoxide Q, 59 Dopanol A
Q, 1g xylene 95.98
59 Tween 80 55g Example 29: Preparation of emulsifiable concentrate The following ingredients are mixed homogeneously.

Compound of Example 8 tsg Tween 80 209 Dopanol A Q, 2g xylene
78.49 Test insects shall be female house flies 4 to 5 days after emergence.

This is carried out by locally applying 1 μt of an acetone solution of the test compound to the dorsal thorax of one insect using an Arnold type Mikuta manipulator. Fifty animals are used for each treatment. Mortality is determined 24 hours after treatment.

The experimental results are summarized in the table below and are expressed as LD5°, ie the medicated t (fig) required to kill 50% of the insects.

4 58 5 t6 62.0 11 t92 Conclusion The compounds of Examples 4.5.6 and 11 showed significant activity in the tests used.

The male test insect (Blatalla germa)
nicm). Operation is 20cm in diameter! This was done by depositing an acetone solution of a known concentration on the bottom of a vetri dish. After drying, the cockroaches were left there for 1 hour at a rate of -20 animals per concentration, after which the cockroaches were moved to a healthy place and the mortality rate was determined at 24 hours, 48 hours, 3 and 5 hours.
I checked it the other day.

Results are expressed as lethal concentration 50 (LC50).

3 CL15 4 α152 5 (LO25·6 α062 11 α121 Conclusion The compounds of Examples 3.4.5.6 and 11 showed significant activity in the tests used.

The test insects are female house flies that are 4 to 5 days old.

The operation was carried out by direct spraying into the Kern-March chamber using an equal volume mixture of acetone and Isovar L (solution used ff12Xα2α3) as the solvent. Approximately 50 insects are used per treatment. 1 up to 10 minutes
Check every minute, then check at 15 minutes, KTs
The following results were obtained by combining o and f in a conventional manner.

3&9 45.3 56.1 11 &9 Conclusion The compounds of Examples 3.4.5.6 and 11 show good activity in the tests used.

The test was conducted by locally applying an acetone solution of the test compound to the dorsal thorax of the larva using an Arnold-type Mikuwa manipulator. A ratio of 15 larvae was used for each concentration of test compound. The larvae used were fourth instar stage larvae.
That is, about 10 days had passed since they were grown at 24° C. and in a 65% relative condensation chamber. After treatment, the individual larvae were transferred onto an artificial nutrient medium (Boitou medium).

1. 14.8 Conclusion The compounds of Examples 5 and 11 were endowed with significant activity in the tests used ◇ The research tests were carried out by topical application in a manner similar to that used on the larvae of Subodoplara litoralis. .

The following results were obtained.

4 1t7 5 6・16
The compounds of Examples 4.5.6 and 11 showed significant activity when tested using 1 t 5.

The following results (lethal concentration 5
o (expressed as LCso)) was obtained.

11 α4’611i/ conclusion The compound of Example 11 showed good activity in the tests used.

Claims (1)

[Claims] (1) All solids having the following formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (Here, R represents an alcohol residue used in the field of pyrethrinoids) Compounds in the form of isomers or mixtures of stereoisomers. (2) R is a) a linear or branched alkyl group containing 1 to 8 carbon atoms, or b) a benzyl group, or c) the following formula ▲ Numerical formula, chemical formula, table, etc. ▼ (where R_1 represents a hydrogen atom or a methyl group), or d) the following formula ▲ Numerical formula, chemical formula, table, etc. ▼ (where R_3 is 2 to 6 carbon atoms and one or more carbon-carbon atoms) Aliphatic organic groups containing saturation, especially -CH_2=CH=CH_2, -CH_2-CH=CH
-CH_3, -CH_2-CH=CH-C_2H_5,
-CH_2-CH=CH-CH=CH_2, CH_2-
C≡CH), or e) the following formula ▲ Numerical formula, chemical formula, table, etc. ▼ (Here, B represents a C=O group or an oxygen atom, and R_4 is a hydrogen atom, a methyl group, -C≡ N group, -C≡CH group or ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ Representing groups), or f) The following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Groups, or g) The following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ of group, or h) The following formula ▲ There are numerical formulas, chemical formulas, tables, etc. ▼ [Here, R_5 represents a hydrogen atom or -CN group, and R_
6 represents a thiazolyl group (in this group, the bond ▲a mathematical formula, a chemical formula, a table, etc. may be located at any valid position), and R_7 represents a -CH_2- group or an oxygen atom], or i) A group of the following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, or j) A group of the following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (where R_8 represents a hydrogen atom or -CN group), or k) The following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (Here, R_9 represents a hydrogen atom or -CN group) Group, or l) The following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (Here R_1_2 represents a hydrogen atom, a methyl group, an ethynyl group, or a cyano group, and R_1_0 and R_1_1 may be the same or different and represent a hydrogen, fluorine, chlorine, or bromine atom), or m) a group of the following formula ▲ formula, There are chemical formulas, tables, etc. ▼ (where R_1_3 represents a hydrogen atom, methyl group, ethynyl group, or cyano group, and B' represents an oxygen or sulfur atom), or n) the following formula ▲ Numerical formula, chemical formula, table etc. ▼ (Here, R_1_4 represents a halogen atom, an alkyl group containing 1 to 6 carbon atoms, or a trifluoromethyl group, and R_1_5 represents a halogen atom, an alkyl group containing 1 to 6 carbon atoms, represents an alkoxy group or a trifluoromethyl group containing 1 to 6 carbon atoms, a is 0, 1, 2, 3 or 4, and b is 0, 1, 2, 3, 4
or 5), in all stereoisomeric forms or in the form of a mixture of stereoisomers, having the general formula (I) according to claim 1. 3) R is the following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (Here, B represents a C=O group or an oxygen atom, and R_4 is a hydrogen atom, a methyl group, a -C≡N group, a -C≡CH group) Or ▲
There are mathematical formulas, chemical formulas, tables, etc. All stereoisomeric forms or stereoisomerisms having the general formula (I) according to claim 1 or 2, which is characterized by representing the group Compounds in the form of body mixtures. (4) R is the following formula ▲ Numerical formula, chemical formula, table, etc. ▼ (Here, R_1_2 represents a hydrogen atom, methyl group, ethynyl group, or cyano group, R_1_0 and R_1_1 may be the same or different, and hydrogen, (representing a fluorine, chlorine or bromine atom) All stereoisomeric forms or mixtures of stereoisomers having the general formula (I) according to claim 1 or 2, characterized in that Compounds in the form of. (5) R represents a group of the following formula ▲ Numerical formula, chemical formula, table, etc. ▼ (Here, R_1_3 represents a hydrogen atom, methyl group, ethynyl group, or cyano group, and B' represents an oxygen or sulfur atom) Compounds of the general formula (I) according to claim 1 or 2, characterized in that they are in the form of all stereoisomers or in the form of mixtures of stereoisomers. (6) R is the following formula ▲ Numerical formula, chemical formula, table, etc. ▼ (Here, R_1_4 represents a halogen atom, an alkyl group containing 1 to 6 carbon atoms, or a trifluoromethyl group, and R_1_5 represents a halogen atom, represents an alkyl group containing 1 to 6 carbon atoms, an alkoxy group containing 1 to 6 carbon atoms or a trifluoromethyl group, a is 0, 1, 2, 3 or 4, and b is 0 , 1, 2, 3, 4
or 5), in all stereoisomeric forms or in the form of a mixture of stereoisomers, having the general formula (I) according to claim 1 or 2. (7) R is a group of the following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Claims 1 to 6 are characterized in that
Compounds of the general formula (I) as defined in any of the following paragraphs, in all stereoisomeric forms or in the form of mixtures of stereoisomers. (8) Claim 1 in which the compound name is as follows:
Compounds described in Section. 1R, cis-2,2-dimethyl-3-(2,2-diiodoethenyl)cyclopropanecarboxylic acid (S) cyano-(3-phenoxy-4-fluorophenyl)methyl, 1R, cis-2,2-dimethyl -3-(2,2-diiodoethenyl)cyclopropanecarboxylic acid (S)cyano-1-(3-phenoxy-4-fluorophenyl)methyl and 1S, eis-2,2-dimethyl-3-(2,2 −
diiodoethenyl) cyclopropanecarboxylic acid (R)cyano-1-(3-phenoxy-4-fluorophenyl)
50-50 mixture with methyl. (9) A method for producing a compound in the form of all stereoisomers or a mixture of stereoisomers having the general formula (I) according to claim 1, the method comprising: (I
I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) The compound obtained by reacting the compound in the form of all stereoisomers or the form of a mixture of stereoisomers with tetraiodomethane and triphenylphosphine. The following formula (IV) is obtained by reacting the compound of (III) with p-toluenesulfonic acid in an organic solvent. There are mathematical formulas, chemical formulas, tables, etc. IV), optionally converting this compound into a functional derivative such as an acid chloride, acid anhydride or mixed acid anhydride, then converting the acid of formula (IV) or its functional derivative to the acid of formula (IV) or its functional derivative by formula A general formula (I) characterized by reacting an R-OH alcohol or a functional derivative of this alcohol to obtain a compound of the corresponding general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) A method for producing the compound. (10) When the compound of formula (II) is reacted with tetraiodomethane and triphenylphosphine, the organic solvent is a chlorinated aliphatic solvent such as methylene chloride, and the compound of formula (III) is reacted with p-toluenesulfone. The organic solvent in which the acid is reacted is an organic solvent such as benzene, toluene or xylene, the functional derivative of the acid of formula (IV) is an acid chloride, and this acid salt compound is treated in the presence of a tertiary base. Alcohol R-O below
The method according to claim 9, characterized in that the acid of formula (IV) is reacted with alcohol R-OH in the presence of dicyclohexylcarbodiimide or diisopropylcarbodiimide and dimethylaminopyridine. (11) The following formula (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ The compound of (II) is reacted with tetraiodomethane, triphenylphosphine and zinc in an organic solvent to form the following formula (IV) ▲ Formula, A manufacturing method according to claim 9, characterized in that the compound of (IV) is obtained, and the synthesis is then continued as described in claim 9. (12) The production method according to claim 11, wherein the organic solvent used is a chlorinated aliphatic solvent such as methylene chloride. (13) A compound of formula (I) according to any one of claims 1 to 8 for use in the extermination of plant parasites, house parasites, and warm-blooded animal parasites. (14) Plant parasites, house parasites, and warm-blooded animal parasites, characterized by containing at least one compound according to any one of claims 1 to 8 as an active ingredient. Pesticide composition for the extermination of. (15) An insecticide composition containing at least one compound described in any one of claims 1 to 8 as an active ingredient. (16) An acaricidal composition for exterminating parasitic mites on plants, which contains at least one compound according to any one of claims 1 to 8 as an active ingredient. (17) A nematocide composition containing at least one compound described in any one of claims 1 to 8 as an active ingredient. (18) An acaricidal composition for exterminating parasitic mites on animals, which contains at least one compound according to any one of claims 1 to 8 as an active ingredient. (19) An animal breeding composition containing at least one compound as set forth in any one of claims 1 to 8 as an active ingredient. (20) on the one hand at least one compound of the general formula (I) as active substance and on the other hand chrysanthemum acid and arethrolone, 3,4,5,6-tetrahydrophthalimidomethyl alcohol, 5-benzyl-3-furyl Each ester with methyl alcohol, 3-phenoxybenzyl alcohol and α-cyano-3-phenoxybenzyl alcohol;
Ester of 2,2-dimethyl-3-(2-oxo-3-tetrahydrothiophenylidenemethyl)cyclopropane-1-carboxylic acid and 5-benzyl-3-furylmethyl alcohol; 2,2-dimethyl-3 -(esters of 2,2-dichlorovinylcyclopropane-1-carboxylic acid and 3-phenoxybenzyl alcohol and α-cyano-3-phenoxybenzyl alcohol; 2,2-dimethyl-3-( 2,2-dipromvinyl)cyclopropane-
Ester of 1-carboxylic acid with α-cyano-3-phenoxybenzyl alcohol; 2-p-chlorophenyl-2
-Ester of isopropylacetic acid and 3-phenoxybenzyl alcohol; 2,2-dimethyl-3-(1,2,2
, 2-tetrahaloethyl) cyclopropane-1-carboxylic acid (where halo represents a fluorine, chlorine or bromine atom) and arethrolone, 3,4,5,6-tetrahydrophthalimidomethyl alcohol, 5-benzyl-3 - Contains at least one pyrethrinoid ester selected from the group consisting of esters with furyl methyl alcohol, 3-phenoxybenzyl alcohol, and α-cyano-3-phenoxybenzyl alcohol (herein, the formula (
I) and the acid and alcohol bonding moieties of the above-mentioned pyrethrinoid esters are in all possible stereoisomeric forms). composition.