HU184087B - Insecticide compositions containing perhalo-alkyl-vinyl-cyclopropane-carboxylates - Google Patents

Abstract

SUMMARY OF THE INVENTION The present invention relates to insecticidal compositions comprising perhalogenalkyl vinyl cyclopropanecarboxylates as active ingredients, liquid or solid diluents or carriers, surfactants or emulsifiers, preferably octylphenoxy polyethoxyethanol, calcium dodecylbenzene sulfonate. , ethoxylated nonylphenol or octylphenol, together with at least one of the compounds. The active ingredients of the formulations are perhalogenalkyl vinylcyclopropanecarboxylates of formula I wherein one of Y and Z substituents is C 1 -C 4 perhalogenalkyl and the other is hydrogen. , halogen, lower alkyl, phenyl, phenylthio or benzyl, with the proviso that Y and Z may form a perhalogenocyclopentylidene group and R1 represents an alcohol residue which forms an insecticidal ester with chrysanthemic acid or a 3- (2,2-dihalo-vinyl) -2-dimethyl-cyclopropane-carbo acid t. -1-

Description

The present invention relates to insecticidal compositions which contain perhalogenalkyl vinylcyclopropane carboxylates as active ingredients.

The preparation of intermediates of the active compounds and the use of insecticidal compositions are also described herein.

Pyrethrins are extracts of naturally occurring chrysanthemum flowers that have long been used as active ingredients in insecticidal compositions. Since the discovery of the structure of these compounds, the syntheses have been directed towards the production of related compounds with enhanced insecticidal activity and good resistance to air and light. Significant progress in this field has been the discovery by Elliott et al. Of certain high-potency compounds, such as dihalovinylcyclopropane carboxylates such as permethrin, also known as 3-phenoxybenzyl-3 - ([1, 5-dichlorvinyl). ) -2,2-dimethyl-cyclopropane-carboxylate. Such compounds, which are described in U.S. Patent 4,024,163, exhibit a significantly enhanced luminous stability in the composition compared to previously used cyclopropanecarboxylates, such as chrysanthenamates, i.e. compounds of formula (Γ) in which Y and Z each substituent is methyl.

Previously known cyclopropane carboxylates, such as those described in the above-mentioned United States Patent, show great activity against insects of the order Lepidoptera but do not exhibit satisfactory activity against insects of the order Homoptera such as aphids.

The present invention relates to novel insecticidal compositions containing new cyclopropane carboxylates, namely perhalogenalkyl vinyl cyclopropane carboxylates, which are particularly effective against insects of the order Homoptera, such as aphidids, and have excellent light stability.

In addition to the active ingredients, the following describes their preparation, insecticidal compositions, methods of insect control, and novel intermediates for use in the manufacture of the active ingredients.

In the following, the term "lower alkyl" refers to alkyl groups having 1 to 6 carbon atoms, preferably 14 carbon atoms. The term "halogen" refers to bromine, chlorine or fluorine. In the case of the perhalogenalkyl group, the halogen atoms may be the same or different and are predominantly fluorine and chlorine, with fluorine being preferred. The names mentioned above are valid throughout the specification and the claim series unless otherwise noted.

The cyclopropane carboxylates which form the active ingredient of the insecticidal compositions of the present invention have the formula (I). In this formula

One of the substituents Y and Z is C 1-4, preferably C 1 or C 2 -haloalkyl, and the other is hydrogen, halogen, lower alkyl, phenyl, phenylthio or benzyl, provided that Y and Z are taken together it forms a perhalogenocyclopentylidene group, preferably a perfluorocyclopentylidene group.

Particularly preferred compounds are trihalogenpropenyl, preferably trifluoropropenyl, cyclopropanecarboxylates of the formula I wherein one of Y and Z is trihalomethyl, in particular trifluoromethyl, and the other is halogen.

R ¹ represents an alcohol residue which described krizanténsavval [3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropane-carboxylate] or No. 4,024,163, U. S. Patent dihalovinyl cyclopropane carboxylic acids such as permethrin, they are capable of forming insecticidal esters. Thus, R ^{1 is} a group which can be used to form cyclopropanecarboxylates as an active ingredient in an insecticidal composition when combined with a suitable known pyrethroid acid. R ¹ is alletrolonyl, tetrahydrophthalimidomethyl, or a group of formula (a) or (b) wherein R ^{2 is} hydrogen, lower alkyl, ethynyl, cyano or trihalomethyl, R ³ divalent oxygen, divalent sulfur or vinylene, ^{R4, R5} and ^R6 are independently hydrogen, lower alkyl, halogen, lower ilkenil-, phenyl, phenoxy, benzyl or phenylthio group, or R ⁴ , Each of R ⁵ and R ⁶ together form a divalent methylenedioxy group bound to two adjacent carbon atoms of a phenyl ring, provided that when R ⁴ , R ⁵ or R ⁶ contains a phenyl ring, then the phenyl ring is 1-3. "May be substituted with a substituent selected from the group consisting of halogen and lower alkyl, R ^{8 is} hydrogen, lower alkyl, lower alkoxy, lower alkenyl, lower alkenyloxy, phenyl or benzyl, and R ⁹ is hydrogen, halogen, lower alkyl, lower alkoxy, lower alkenyl, lower alkenyloxy, lower alkenyloxy, lower alkenyloxy , lower alkylsulfinyl, lower alkylsulfonyl, phenyl, phenoxy, benzoyl, nitro or cyano.

Among the said alcohol residues, those in which R ^{13 is} 3-phenoxybenzyl, -cyano-3-phenoxybenzyl, 3-phenylbenzyl or 5-benzyl-3-furylmethyl are readily available or readily available. can be synthesized at low cost from readily available starting materials. In addition, compounds of formula I containing these alcohol residues in combination with an acid component wherein one of Y and Z is trihalomethyl, preferably trifluoromethyl, and the other is halogen, exhibit very good activity against insects in general. , and are particularly effective against afidides as active ingredients of insecticides, except for the 5-benzyl-3-furylmethyl compound, and, moreover, their light stability to conventional 3

-2184,087 excellent.

The compounds of formula I and certain intermediates thereof exist in the form of cis and trans geometric isomers. The carboxyl and substituted vinyl groups at positions 1 and 3 of the cyclopropane ring are in cis or trans position with respect to each other. The preparation of such compounds typically results in mixtures of cis and trans isomers, designated as cis, trans compounds, in which the cis / trans ratio may vary within wide limits. In this specification, the cis and trans designations are described by P.E. Búrt et al. Pestic, Sci., 5, 791-799 (1974).

The compounds of formula (I) may exist in the form of E or Z isomers or mixtures of E and Z isomers, designated as Ε, Ζ isomers, depending on the CX carbon atom of the vinyl group and the β carbon atom of the vinyl group. the substituents in space are spatially spaced relative to one another.

Cyclopropanecarboxylates are known to have a significant difference between the insecticidal activity of the cis and trans isomers. For a given cyclopropane carboxylate, one of the cis and trans isomers is generally more active than the other and much more active than the cis, trans isomer mixture. In the case of the active compounds of the formula I, the cis isomer is more active. Similar differences exist between the E and Z isomers.

Unless otherwise noted, the invention includes all compounds wherein the carboxylic and substituted vinyl groups at the 1 and 3 positions of the cyclopan ring are in cis or trans position with respect to each other, but excluding cis and trans and mixtures of compounds with the same configuration. Similarly, since Formula I represents a mixture of E and Z isomers as well as individual isomers, the present invention includes both individual isomers and mixtures thereof. Enantiomers of isomers are also within the scope of the invention.

Compounds of formula (I) useful as insecticidal agents may be prepared from alkanoates of formula (II). In this formula, Y and Z are as defined above, R is lower alkoxy such as methoxy or ethoxy, R ^{7 is} hydrogen, lower alkylcarbonyl, lower alkoxycarbonyl or cyano, preferably H, and X is chlorine. - or my bromine. Example 1 illustrates the preparation of intermediates of formula II. The preparation consists of reacting a lower alkyl 3,3-dimethyl-4-pentenoate with a compound of the formula X ₂ -C (Y) (Z) wherein X, Y and Z are as defined above.

This alkanoate is then converted to a compound of formula (III) wherein R is a lower alkoxy, hydroxy or halogen atom, Y, Z and R ⁷ are as defined above. The conversion is carried out using the formula (II). compound dehydrohalogenated. This reaction may be carried out via intermediates (IV), (V), (VI). The reaction may be carried out in one step, with the halogen cleavage, or it may be carried out stepwise. These intermediates or mixtures thereof may, if desired, be isolated. The compounds of formula (III) are then converted to the compounds of formula (I) by methods known in the art. The conversion is carried out, for example, removing the R ⁷ group (where meanings other than hydrogen) and transesterifying compound HOR ^1. Other methods for converting R to -OR ¹ are also known.

The following examples illustrate the preparation of the active compounds of the present invention and their novel intermediates according to the general method described above. In the examples, the temperature is given in degrees Celsius and the pressure in mmHg, while the reduced pressure, unless otherwise stated, is achieved by a water air pump.

In Example 1, the preparation of compounds of formula (II) was novel.

Example 1

Preparation of ethyl 3,3-dimethyl-N, 6,6-trichloro-7,7,7-trifluoroheptanoate

44.6 g (0.267 mol) of ethyl 3,3-dimethyl-4-pentenoate, 100 g (0.533 mol) of 1,1,1-trichlorotrifluoroethane, 0.27 g (0.0027 mol) of cupric chloride and A solution of ethanolamine (2 g, 0.134 mol) in tert-butyl alcohol (270 ml) was heated at reflux under nitrogen for 16 hours. The reaction mixture was cooled to ambient temperature and extracted three times with 100 ml of diethyl ether. The precipitate formed in the extracts was removed by vacuum filtration. The filter cake was washed twice with 25 ml of diethyl ether. The ether extracts were combined with the washings and concentrated under reduced pressure to an oily residue. The residual volatiles were removed from the residue under reduced pressure, which was established using a vacuum pump. The residue was distilled under reduced pressure. 78.3 g of ethyl 3,3-dimethyl-4,6,6-trichloro-7,7,7-trifluoroheptanoate are obtained.

Fp. 85-87 ° (0.12-0.15 mm Hg).

The nmr spectrum confirmed the structure.

Other compounds of formula II are prepared as described in Example 1 and are listed in Table I below.

Examples 2 and 3 illustrate the preparation of lower alkyl esters of the formula (Γ). 2 illustrates a two-step process via Formula IV, and 3 describes a one-step process.

-3184 087

Example 2

Methyl cis, trans -3- [2-chloro-3,3,3-trifluoropropyl] -2,2-dimethylcyclopropanecarboxylate

A) Preparation of methyl cis, trans -3- [2,2-dichloro-3,3,3-trifluoropropyl] -2,2-dimethylcyclopropanecarboxylate intermediate

A solution of 37.0 g (0.112 mol) of methyl 3,3-dimethyl-4,6,6-trichloro-7,7,7-trifluoroheptanoate, 50 ml of tert-butyl alcohol, 50 ml of dimethylformarmide and 50 ml of hexane was stirred under argon. and cooled to -5 ° C. A solution of potassium tert-butoxide (16.4 g, 0.14 mol) in tert-butyl alcohol (200 ml) was added dropwise with stirring at such a rate as to maintain the reaction temperature between -3 ° C and -5 ° C. After the addition was complete, the reaction mixture was stirred for 4 hours at -3 ° C to -5 ° C and then poured into a solution of 8.0 g of ammonium chloride in 250 ml of water. The mixture is extracted twice with 200-200 ml of diethyl ether and the combined ether extracts are washed twice with 200-200 ml of water. The ether layer was dried over sodium sulfate and filtered, and the filtrate was concentrated under reduced pressure. The oily residue was distilled under reduced pressure to give 19.8 g of methyl cis-trans-3- [2,2-dichloro-3,3,3-trifluoropropyl] -2,2-dimethylcyclopropanecarboxylate.

Fp. 55-57 ° C / 0.09 mmHg.

Irish and nmr spectra confirm the structure.

Elemental analysis for C H

Calculated: C 40.98; H4.47 9?

Found: C, 41.50; H, 4.41 T

B) Synthesis of methyl cis, trans-3- [2-chloro-3,3,3-trifluoropropenyl] 2,2-dimethylcyclopropanecarboxylate

30.6 g (0.105 mol) of methyl cis, trans -3- [2,2-dichloro-3- ₍ 3,3-trifluoropropyl] -2,2-dimethylcyclopropanecarboxylate) and 17.6 g (0.116 mol) A solution of 1,5-diazabicyclo [5.4.0] undec-5-ene in 100 ml of dimethylformamide was stirred and refluxed at 100 ° C for 4 hours, then the reaction mixture was cooled and 37.2 ml of concentrated hydrochloric acid in 300 ml of water. The mixture was extracted three times with 200 ml of diethyl ether, the combined ethereal extracts were washed with saturated aqueous sodium chloride solution, and the ether layer was dried over sodium sulfate and then filtered.

The filtrate was concentrated under reduced pressure and the oily residue was dissolved in hexane. The hexane solution was decolorized by treatment with carbon and filtered. The filtrate was concentrated under reduced pressure and the resulting oily residue was distilled under reduced pressure. Methyl cis, trans-3- [2-chloro-3,3,3-trifluorophenyl] -2,2-dimethylcyclopropanecarboxylate (10.0 g) was obtained in three fractions.

Fp. 40-60 ° C / 0.05 mmHg.

Irish and nmr spectra confirm the structure. The nmr spectrum showed the product to be an 88:12 mixture of cis / trans isomers.

Analysis: _θ Hj _{2 for} C ₁ F ₃ O ₂

Calculated: C, 46.80; H, 4.71%

Found: C, 46.91; H4,79%

Example 3

Preparation of ethyl cis, trans-3- {2-chloro-3,3,3-trifluorophenyl} -2,2-dimethylcyclopropanecarboxylate

To a solution of ethyl 3,3-dimethyl-4,6,6-trichloro-7,7,7-trifluoroheptanoate (78.3 g, 0.228 mol) in distilled ethanol (200 ml) was added dropwise a solution of sodium ethoxide in ethanol (500 ml) at ambient temperature. 11.5 g (0.50 mole) of sodium metal are prepared while the solution is stirred. After the addition is complete, the reaction mixture is stirred for one hour at ambient temperature and then allowed to stand for 18 hours. The cloudy reaction mixture was filtered and the filtrate was concentrated under reduced pressure. The residue thus obtained is slurried in 200 ml of water and the mixture is extracted three times with 50 ml each of diethyl ether. The combined extracts were dried over sodium sulfate and filtered. The filtrate was concentrated under reduced pressure to give 58.5 g of an oily product, which was ethyl cis, trans -3- [2-chloro-3,3,3-trifluorophenyl] -2,2-dimethylcyclopropanecarboxylate. . The nmr and Irish spectra confirm the structure shown. The product consists of approximately equal proportions of the cis and trans isomers.

Other intermediates of general formula (VT) are illustrated in Scheme 2A. Prepared in the same manner as in Example 1A and summarized in Table T.

The lower alkyl esters of formula (Γ) prepared as described in Examples 2 and 3 above are listed in Table III (after Examples) as compounds 3.1 to 3.8. Compounds 3.1-3.7 are prodruged as in Example 2 and Compound 3.8 as in Example 3.

Example 4

Preparation of trans and cis, trans-3- [2-chloro-3,3,3-trifluoropropenyl] -2,2-dimethylcyclopropanecarboxylic acid

Ethyl cis, trans-3- [2-chloro-3,3,3-trifluoropropenyl] -2,2-dimethylcyclopropanecarboxylate (16.2 g, 0.06 mol) 94 nd (0.078 mol) A solution of a stock solution of 3.34 g of sodium hydroxide, 94 ml of ethanol and 6 ml of water is stirred and refluxed for 18 hours. The reaction mixture is reduced5

After concentration at 4184,087, water was added to the residue and the mixture was acidified to pH 1 with 6N hydrochloric acid. The acidic mixture was extracted twice with 50 ml of diethyl ether. The combined extracts were dried over magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure and the residue was heated with 50 ml of hexane. The hot hexane was decanted from the tarry residue, cooled, and the precipitated solid precipitated by filtration and dried. this way

3.3 g of a solid are obtained, m.p. 97-103 ° C. The mother liquor was concentrated to give a second fraction of solid (0.8 g). m.p. 97-103 ° C.

The nmr spectrum showed that both fractions were trans-3- [2-chloro-3,3,3-trifluoropropenyl] -2,2-dimethylcyclopropanecarboxylic acid. The mother liquor was evaporated to dryness and the residue was taken up in 50 ml of hexane and the solution was cooled in a freezer for 18 hours. The precipitated solid was collected by filtration to give 4.3 g, m.p. 64-74 ° C. The nmr spectrum indicates that the solid is a 50/50 mixture of cis and trans isomers of 3- [2-chloro-3,3,3-trichlorophenyl] -2,2-dimethylcyclopropanecarboxylic acid.

Further free acids corresponding to the general formula (Γ), prepared according to Example 4, are exemplified in Examples 4.1 to 4.7.

III. is given in the table.

Example 5

Preparation of Trans-3- (2-chloro-3,3,3-trifluoropropemyl) -2,2-dimethylcyclopropanecarbonyl chloride

To a solution of 4.1 g (0.173 mol) of trans-3- [2-chloro-3,3,3-trifluoropropenyl] -2,2-dimethylcyclopropanecarboxylic acid in 40 ml of toluene is added with stirring at ambient temperature. pyridine (0.022 mol) was added followed by a solution of thionyl chloride (2.6 g, 0.022 mol) in toluene (25 ml). After the addition was complete, the reaction mixture was stirred at ambient temperature for 17 hours. The reaction mixture was then filtered through diatomaceous earth and the filtrate was concentrated under reduced pressure. 3.8 g of trans-3- [2-chloro-3,3,3-trifluoropropenyl] -2,2-dimethylcyclopropanecarbonyl chloride are thus obtained. The Irish spectrum confirms the structure.

Further compounds of Example 5, which are represented by Formula I ', may be prepared as described in Example III. Table 5.1 to 5.8 are examples.

6-10. Examples 1 to 6 illustrate the preparation of compounds of formula (I).

Example 6

Preparation of 3-phenoxybenzyl trans-3- \ 2-chloro-3,3,3-trifluoropropenyl] -2,2-dimethylcyclopropanecarboxylate

To a solution of trans-3- [2-chloro-3,3,3-trifluoropropenyl] -2,2-dimethylcyclopropanecarbonyl chloride (1.8 g, 0.007 mol) in methylene chloride (10 ml) was added with stirring at ambient temperature. A solution of 3-phenoxybenzyl alcohol (1.6 g, 0.008 mol) and pyridine (0.73 g, 0.009 mol) in methylene chloride (5 ml) was added. After the addition was complete, the reaction mixture was stirred at ambient temperature for 3 hours and then poured into water (50 mL). The organic layer was separated and the aqueous layer was extracted three times with 50 ml of methylene chloride. The combined extracts were dried over sodium sulfate, filtered and the filtrate was concentrated under reduced pressure. In this way, an oily residue is obtained, the volatile components of which are removed at 125 ° C / 0.05 mm Hg by a ball-cooled distillation system. The residue in the vessel was found to be 99% 3-phenoxybenzyl trans-3- [2-chloro-3,3,3-trifluoropropenyl] -2,2-dimethylcyclopropanecarboxylate. The determination is carried out by gas chromatography. The amount of material obtained was 2.0 g. The nmr spectrum confirmed the structure.

Analysis for C ₂₂ H 2 _q ClF ₃ O ₃

Calculated: C, 62.05; H4,73%

Found; C, 62.29; H4,80%.

Example 7 Preparation of o (. Cyano-3-phenoxybenzyl trans-3- [2-chloro-3,3,3-trifluoropropenyl] dimethylcyclopropanecarboxylate

This compound was prepared as described in Example 6. In the preparation, 4.8 g (0.007 mol) of trans-3- [2-chloro-3,3,3-trifluoropropenyl] -2,2-dimethylcyclopropanecarbonyl chloride, prepared according to Example 4, 1.7 g (0.008 mol) were obtained. mole) (X-cyano-3-phenoxybenzyl alcohol and pyridine (0.73 g, 0.009 mole) in methylene chloride (15 mL) was used. The residue was analyzed and analysis showed that 98.9% ( cyano-3-phenoxybenzyl trans-3- [2-chloro-3,3,3-trifluoropropenyl] -2,2-dimethylcyclopropanecarboxylate Analysis by gas chromatography (2.4 g) The nmr and Irish spectra indicate that the structures are as given.

Analysis calculated for C ₂₃ H _to ClF ₃ NO ₃ Calcd: C 61.27; H4,25%

Found: C, 61.57; H, 4.38%.

Example 8

Preparation of 3-phenoxybenzyl cis, trans-3- [2-chloro-3,3,3-trifluoropropenyl] -2,2-dimethylcyclopropanecarboxylate

This compound was prepared as described in Example 6. 1.8 g (0.006 mol) of cis, trans-3- [2-chloro-3,3,3-trifluoropropenyl] -2,2-dimethylcyclopropanecarbonyl chloride were used as in Example 4. 1.4 g (0.007 mol) were obtained.

-511

3-Phenoxybenzyl alcohol and 0.66 g (0.008 mol) of pyridine are used in 15 ml of methylene chloride. The residue from the vessel was analyzed and analysis showed that 99% of the bane is 3-phenoxybenzylcis, trans-3- [2-chloro-3,3,3-trifluoropropenyl] -2,2-dimethylcyclopropane. carboxylate. Analysis by gas chromatography afforded 1.0 g of product.

The nmr and Irish spectra show that the product corresponds to the structure given.

Analysis for the formula 2222 ^ 20 ^^ 3 ^ 3

Calculated: C, 62.01; H4,49%

Found: C, 62.11; H4,58%.

Example 9 Preparation of ocyano-3-phenoxybenzylcis, trans-3- [2-chloro-3,3,3-trifluoropropenyl] -2,2-dimethylcyclopropanecarboxylate

This compound was prepared as described in Example 6. In the preparation, 1.8 g (0.006 mol) of the cis, trans-3- [24-doro-3,3,3-trifluorophenyl] -2,2-dimethylcyclopropanecarbonyl chloride prepared according to Example 4, 1.6 g (m.p. P-cyano-3-phenoxybenzyl alcohol (0.007 mol) and pyridine (0.66 g, 0.008 mol) in methylene chloride (15 ml) were reacted. Analysis of the residue showed 99% ck-cyano-3-phenoxybenzylcis, trans-3- [2-chloro-3,3,3-trifluoropropenyl] -2,2-dimethyl. cyclopropanecarboxylate. The analysis is carried out by gas chromatography. 0.9 g of product is obtained.

The nmr and Irish spectra show the product to have the structure shown.

Analysis for C ₂₃ H ₁₉ ClF ₃ NO ₃

Calculated: C, 61.46; H4,26%

Found: C, 61.47; H4,48%.

The compounds of the present invention may also be prepared by reacting a diene of formula VII wherein Y and Z are as defined above with a compound of formula n ₂ chco ₂ r, i.e., a diazoacetic acid ester, wherein R is lower alkyl. or an R ¹ group as defined above.

The following examples illustrate this variant of the preparation.

Example 10

Preparation of 3-phenoxybenzyl cis, trans-3- [2-trifluoromethyl-1-propenyl] -2,2-dimethylcyclopropanecarboxylate

A) Preparation of 3-methyl-2-butenyl / triphenylphosphonium chloride

3-methyl-2-butenyl chloride (52.3 g, 0.5 mol) and triphenylphosphine (144.1 g, 0.55 mol) in toluene (400 ml) were heated at 100 ° C. heat for an hour. Does the resulting white colored material collect by filtration? g = 147 0 g (5 methyl T-butenyldiphenylphosphonium chloride is obtained)

Preparation of B / 2-methyl-tert-trifluoromethyl-2,4-hexadiene

A solution of 144.3 g (after 0.39) of 3-methyl-2-butenyl) triphenylphosphonium chloride in 300 ml of methylene chloride was cooled to 0 ° C under nitrogen with stirring. To the cooled solution was added dropwise a solution of 84.2 g (0.39 mol) of sodium methoxide in 25% methanol at such a rate as to maintain the reaction temperature below 4 ° C. After completion of the addition (40 minutes), a solution of 1,1,1-trifluoroacetone (50.4 g, 0.45 mol) in methylene chloride (5 mL) was added dropwise to the reaction mixture at a temperature below 6 ° C. After the addition was complete (40 minutes), the reaction mixture was allowed to warm to ambient temperature and stirred for 18 hours. The reaction mixture is then washed twice with 150 ml to 150 ml of water and then dried over magnesium sulfate. The mixture is then filtered and the filtrate is concentrated by distillation. Pentane was added to the residue to precipitate triphenylphosphinoxide. The mixture was filtered and the filtrate was concentrated by distillation. Diglyme is added to the residue and additional triphenylphosphinoxide can be collected by filtration. The filtrate was fractionally distilled using a rotary evaporator to give 14.2 g (98%) of 2-methyl-5-trifluoromethyl-2,4-hexadiene in sixteen fractions.

Fp. 122-124 ° C. The nmr spectrum confirmed the structure.

C) Preparation of ethyl cis, trans -3- [2-trifluoromethyl-1-propenyl] -2,2-dimethylcyclopropanecarboxylate

A solution of 11.9 g (0.073 mol) of 2-methyl-5-trifluoromethyl-2,4-hexadiene and 80 ml of radium diacetate in Mitchell, Rempel et al. (JACS A, 3322 (1970)), 8.3 g (0.073 mol) of ethyldiazzoacetate are added via syringe under nitrogen atmosphere. The total addition takes 16.5 hours. After the addition was complete, the reaction mixture was stirred and analyzed for 30.5 hours. Gas chromatography (GC) analysis indicated that the reaction mixture contained 44% hexadiene starting material. An additional 6.5 g of ethyl diazoacetate was then added dropwise over 18 hours. Analysis of the reaction mixture by gas chromatography after 60 hours shows that the reaction mixture contains 20% hexadiene starting material. The reaction mixture was distilled under reduced pressure (95-12 mmHg) to give 10.2 g of crude product.

Fp. 80-85 ° C / 5 mm Hg. The crude product was applied to a chromatography column containing 300 g of silica gel, eluting first with pure hexane and then with 3% ethyl acetate in hexane. Chromatography 75

-6184,087 or 150 mL of 20 fractions. The appropriate fractions were subjected to gas chromatography and nuclear magnetic resonance analysis. The nmr analysis shows that fraction 9 is pure cis. E, Z isomer, 10-12. and fraction C is pure cis, trans isomer. 9-12. Fraction 1 was combined to give 4.3 g of ethyl cis, trans -3- [2-trifluoromethyl-1-propenyl] -2,2-dimethylcyclopropanecarboxylate.

D) Preparation of 3-phenoxybenzyl cis, trans-3- [2-trifluoromethyl-1-propenyl] -2,2-dimethylcyclopropanecarboxylate

Ethyl cis, trans-3- [2-trifluoromethyl-1-propenyl] -2,2-dimethylcyclopropanecarboxylate (4.2 g, 0.017 mol), 3-phenoxy- (5.0 g, 0.025 mol). of benzyl alcohol and 3 drops of titanium isopropylate in 6 ml of nonane and heated under nitrogen atmosphere at 140 ° C for 67 hours in a reaction vessel equipped with a short-stage distillation head to remove the ethanol by-product. GC analysis showed that the reaction was almost complete. The reaction mixture was applied to a chromatography column containing 300 ml of silica gel in hexane. Elution was carried out with 1 L of 3% eric acetate in hexane followed by 5% ethyl acetate in hexane to give 500 mL of 14, fractions and 250 mL of 5-9. fractions. Fractions 4 and 5 were combined and distilled using a ball-cooled distillation system. First, the low-boiling impurities are removed at 95 ° C / 0.05 mmHg and then, at 105 ° C / 0.05 mmHg, 5.6 g of 3-phenoxybenzyl-cis, trans-3- [2-trifluoro- methyl 1-propenyl] -2,2-dimethylcyclopropanecarboxylate was removed.

The Irish and nmr spectra confirm the structures given.

Analysis for C ₂₃ H ₂₃ F ₃ O ₃

Calculated: C68.31; H5,73%

Found: C, 68.21; H 5.85%.

The compounds of the present invention, prepared as the active compounds of the insecticidal compositions of the present invention, are prepared as described in Table IV. table.

An effective amount of the insecticidal compositions of the present invention is applied to the site where the insect is to be controlled, such as applied to the insect itself or to the leaves or seeds of the plants. The compositions of the invention are used as a technical preparation or as a formulated product for controlling domestic insects, animal insects and plants or fruits.

The formulations contain the active ingredient in admixture with an agriculturally acceptable carrier or excipient, preferably a surfactant or other ingredients and optionally other active ingredients. Suitable formulations include granules, powders, or liquid formulations that are used depending upon the species of pest to be controlled and the environmental factors of the infected site. Thus, the compositions are prepared in the form of granules, powders, wettable powders, emulsifiable concentrates, solutions, dispersions, slow release formulations and the like, of various sizes. The individual formulations may vary within wide limits as to the active ingredient concentration, depending on the active ingredient itself, the additives and carriers, other active ingredients and the mode of administration. Taking all of these factors into account, the active ingredient may, for example, be present in a concentration range of from 0.00025% to 5.0% by weight. A compatible surfactant, when used, may be present in various concentrations in the compositions, preferably from 1 to 30% by weight of the surfactant.

The composition may be used in the form of a formulation or dilution to the desired extent. Suitable diluents or carriers for dilution are preferably xylene, isopropanol, water, or mixtures thereof, to facilitate dispersion of the active ingredients. The concentration of the active compound in the diluted composition may vary from 0.0001% to 15% by weight. In addition to the active compounds of formula (I), other known active ingredients may be included in some of the sprayable, sprayable formulations and slow release agents.

The compositions of the invention may also contain other compatible active ingredients such as nematocides, other insecticides, acaricides, fungicides, plant growth regulators, herbicides, fertilizers and the like.

When the insecticidal compositions of the present invention are used alone or in combination with other agents, care should be taken to use an effective amount of insecticidal agents. Because the amount that can be used can vary widely, depending on the active ingredient itself, the form of application, the mode of application, the plant species to be protected and the density of the plant, the appropriate amount has been determined experimentally. It has been found that a suitable application rate is from 0.005 to 3 kg / ha, preferably from 0.01 to 1 kg / ha.

The insecticidal activity of the insecticidal compositions of the invention is given in the following examples.

Example 11

Initial contact activity

0.0512 g of the test compound is dissolved in 10 ml (7.9 g) of acetone and 1 drop (0.025 g) of octylphenoxy polyethoxyethanol is added as the surfactant. Dilute the solution to 100 ml (100 g) to obtain a test solution containing 512 ppm (0.0512% w / w) of active ingredient, 7.9% w / w acetone, 0.0025% w / w surfactant and 92.0463% w / w water. and provides complete kill of treated insects. Further dilution of the aliquot portion of the solution gives a test solution containing 2.5 ppm (0.00025% w / w) of active ingredient, 0.039% by weight of acetone, 0.000012% by weight of surfactant and 99.9997% by weight of water.

The insects tested and used in the test

-7184 087 methods include:

The activity against the Mexican bean borer beetle (Epilachna varivestis, Muls.) And the southern spotted beetle (Spodoptera eridania, Cram.) Is determined by dipping the leaves of bean sprouts in the solution of the test substance or by spraying the leaves with the solution and infecting the leaves with insect specimens in an appropriate underdeveloped state. The activity against the pea aphid (Acyrthosiphon pisum, Harris) is determined on a pig bean, the leaves of which are weighed in a solution of the active ingredient or sprayed with the solution before being infected with adult aphids. The activity against the two-spotted baby spit mite (Tetranychus urticae, Koch) is determined on the leaves of kidney beans, the leaves of which are dipped in or sprayed with the active ingredient after being infected with adult individuals. The action against canine milk bug (Oncopeltus faciatus Dallas) and prune aphid (Conatrachelus nenuphar, Herbst) is determined by spraying a solution of the test substance on adult insects in glass jars or bowls. Following treatment and infection, the materials are stored in a container at 26.7 ° C and 50% RH for at least 48 hours. After the storage period, dead and still live insects and mites are counted and then the percentage of deaths is determined. The results of these experiments are summarized in Table V. If more than one test is performed, the number in parentheses indicates the result of the second test. Table V also includes data for commercial insecticides at 156, 39 and 10 ppm. Such agents include permethrin as active ingredient, i.e., 3-phenoxybenzyl-6) cis, trans-3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropane-1-carboxylate. which are active compounds of the formula I exhibit excellent activity against the comparator.

Example 12

The insecticidal activity of the active compounds of the formula I is tested by treating the insects with a solution of 5 mg / l of acetone in the active ingredient. The results of the experiments were determined 24 hours after treatment with the active compound solution and the percent mortality was calculated by comparing the well-known commercial product, permethrin, i.e. 3-phenoxybenzyl ( ⁺ ) -cis, trans-3- (2). , 2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate is used. A relative effect based on 1.0 permethrin was determined relative to the standard compound and the percent mortality was calculated. The insects used were the southern beetle (Spodoptera eridania, Cram.), The cabbage butterfly (Trichoplusia ni (Hubner), the beetle beetle (Spodoptera exigua, Hubner), and the cereal owl moth (Heliothis zea, Boddie), Mexican bean spurge tis Muls.) and dog milk bug (Oncopeltus faciatus, Dallas).

The results reported in Table VI. Table 1 shows that formulations containing the active compounds of formula I are much more effective than the comparative agent against the pests tested. Agents containing the active compounds of formula (I) wherein Y and Z are the preferred groups and the alcohol moieties are the above preferred groups have surprisingly good activity relative to permethrin. These agents are at least as effective as permethrin, but in most cases they outperform its action.

The insecticidal compositions of the present invention are mutated against the aphids by the following example.

Example 13

In this experiment, the actual effect of the agents of the invention is shown in comparison with the expected effect. The expected effect relative to permethrin was determined by the following equation:

lepidopteran effect afferent effect permethrin permethrin lepidopteran effect expected test substance afferent effect test substance

The following table shows the application of this formula to two known compounds (A and B), in which the expected affinity range is calculated, and the results actually obtained for these two compounds. The measured activity of these two compounds is in the expected range or very close to it. Compound A is 3-phenoxybenzyl cis-3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropane-1-carboxylate (about 95% cis isomer). Compound B is -cyano-3-phenoxybenzyl-3- (2,2-dichlorobenzyl) -2,2-dimethylcyclopropane-1-carboxylate having a cis isomer content of about 40%. This formula was also applied to the active ingredients of the insecticidal compositions of the invention.

It has been found that the actual LC ₉₀ value for most compounds is several times lower than the expected value. For example, the expected LC _9Q value for aphids for compound 6.1 is in the range of 27-32 ppm. The actual value obtained is 3 ppm. Thus, this compound is about 10 times more potent than expected. Similarly, compound 6.2 was Ιϋ-20 times more potent than expected, compound 6.3 was 2-3 times more than expected, and compound 6.8 was 45-65 times more potent than expected. that was to be expected. Some compounds, such as 6.21 and 6.22, do not show more than expected activity, but show a greater affinity for permethrin.

-8184 087

Expected and actual aficid effect

LD 'values 5 0 LC ₉₀ values (ppm) -afidida (Ng / insect) Compound* SAW ¹ CL ² BAW ³ expected province actual value permethrin 20 100 650 64 THE 9 120 350 30-77 80 B 22 110 300 30-70 50 6.1 9 50 275 27-32 3 6.2 25 200 600 59-128 6 6.3 38 150 1100 96-122 40 6.8 10 50 230 23-32 05 6.9 14 53 260 26-45 1 6:10 19 70 380 38-61 40 6:15 12 33 21-38 5 6:17 11 83 232 24-53 12 6:21 1.6 83 27 3-5 6 6:22 3 12 82 8- 10 32

⁺ The structure is shown in Annex IV. table.

1. Spodoptera eridania (Cram.)

2. Trichoplusia ni (Hubner)

3. Spodoptera exigua (Hubner)

The following example illustrates the unexpected light and air stability of the compounds of the present invention in the presence of light and air.

Example 14

An emulsifiable concentrate of (X-cyano-3-phenoxybenzyl-cis, trans-3- (2-chloro-3,3,3-trifluoropropenyl) -2,2-dimethylcyclopropanecarboxylate (Compound 6.9) with toluene Dilute to obtain a solution of 220 mghath / l volume and place in one hundred µl aliquots of six 5.0 cm diameter Petri dishes and leave the solvent to evaporate, leaving 1.1 g / cm ^{2 of} sediment in the dish. and three were illuminated with 275 watts of sunlight at a distance of 26 cm, and the residue at the bottom of the cups was removed from each of the six cups after 24 hours and the remaining active ingredient determined by high performance liquid chromatography. The following table shows the permethrin and the other two compounds disclosed in Elliott et al., U.S. Pat. No. 4,024,163. U.S. Pat.

% remaining after 24 hours

Compound in the dark With 275 watts of sunlight 6.1 100 41.1, 39.2 ^a 6:16 100 41.6 permethrin 100 19.1 NRDC 148 ^b 100 21,2,24,0 ³ NRDC 160 ^c 100 20.2

the. results of duplicate experiments, three or three dishes per test

b. the cis isomer component of permethrin

c. cis-isomeric component of a cxi-cyano compound analogous to permethrin

Table I Compounds of formula (Ha)

Example X Y z R ll ^a Br ^CF 3 Br OCH 1.2 ^a cl ^CF 3 F and ₃ 1.3 ^a cl cf ₃ H and ₃ 1.4 ^a cl CF ₂ C1 cl OCH 1.5 ^a cl cf ₂ ci F and ₃ 1.6 ^a cl cfci ₂ F ^0CH 3 1.7 ^a cl cf ₂ cf ₂ ci cl OCH 1.8 ^b cl c F cl and ₃

boiling points (° C / mmHg): 1.1: 63 / 0.08; 1.2;

71 / 0.09 mmHg; 1/3: 112-115 / 7; 1.4: 95-106 / 0.1 to 0.125; 1.5: 58-60 / 0.005; 1.6: 103 / 0.2-0.3;

1.7: 98-102 / 0.05 b, confirmed by nmr spectra

Π. Table IIb Compounds of Formula IIb

Example X Y z R 2.1 ^a Br ^CF 3 Br and ₃ 2.2 cl CF F OCH, 2.3 ^b cl 3 ^CF 3 H and ₃ 2.4 cl CF ₂ d cl OCH 2.5 ^a cl CF ₂ C1 F and ₃ 2.6 2.7 ^b cl cl cfci ₂ cf ₂ cf ₂ ci F cl OCH and ₃

% remaining after 24 hours

In the dark, ^{275 watts}

Compound with sunlight

6.9 100 48.7,43.5 ³ a Boiling points (C ^& mmHg): 2.1: 100-113 / 0.09-0.1; 2.5: 45-47 / 0.02 ba structure confirmed by nmr spectrum

-9184 087

III. Table Compound (Γ)

Example Y z R isomer 3.1 ^{b CF} 3 Br and ₃ c / t 3.2 ^{b CF} 3 F OCH c / t 3.3 ^CF 3 H and ₃ c / t 3.4 ^b cf ₂ ci cl and ₃ c / t 3.5 ^b cf ₂ ci F and ₃ c / t 3.6 ^b cfci ₂ F and ₃ c / t 3.7 ^b cf ₂ cf ₂ ci cl and ₃ c / t 3.8 ^{b C} 2 ^F 5 cl ^0CH 3 c / t 4.1 ^{c CF} 3 Br OH c / t 4.2 ^{d CF} 3 F OH c / t 4.3 ^{a CF} 3 H OH c / t 4.4 ^a cf ₂ ci cl OH c / t 4.5 ^C CF ₂ Cl F OH c 4.6 ^C cf ₂ cf ₂ ci cl OH c / t 4.7 ^C 2 ^F 5 cl OH c / t 5.1 ^{e CF} 3 Br cl c / t 5.2 ^e 5.3 ^{f CF} 3 F cl c / t ^CF 3 H cl c / t 5.4 ^e cf ₂ ci cl cl W 5.5 ^d , e CF ₂ C1 F cl c 5.6 ^{d, e} cf ₂ cf ₂ ci cl cl c (t, z 5.7 ^{b C} 2 ^F 5 cl cl c / t, z 5.8 ^{d, e} CF, cl cl c / t and E /

³ the structure is confirmed by the nmr spectrum ^b bp (C ° / mmHg): 3.1: 44-47 / 0.07-0.08; 3.2: 71/29; 3.4: 84-88 / 1.25-1.4; 3.5: 90-92 / 11; 3.6: 60-71 / 0.08; 3.7: 59-65 / 0.07; 3.9: 98-110 / 7; 5.7: 42-51 / 0.1 ^c melting points (° C): 4.1: 110-116; 4.5: 80-87;

4.6: 67-69 ^d the structure of the Irish spectrum is confirmed by ^this liquid, cannot be separated f

semi-solid, not separable

ARC. Table I Compounds of formula (I)

Compound ^a Y z R ¹ isomer 6.1 ^CF 3 cl (C) c 6.2 ^CF 3 cl (C) c / t 6.3 ^CF 3 cl (C) t 6.4 ^Cp 3 Br (C) c 6.5 ^CF 3 Br (C) c / t 6.6 ^CF 3 Br (C) t 6.7 ^CF 3 F (C) c 6.8 ^CF 3 cl (D) c 6.9 ^CF 3 cl (D) c / t

(Continuation of Table IV)

Compound ³ Y z R ¹ isomer 6:10 ^CF 3 cl > (D) t 6:11 ^CF 3 Br (D) c / t 6:12 ^CF 3 Br (D) t 6:13 ^CF 3 F (D) + c 6:14 ^CF 3 F (D) + c 6:15 ^CF 3 F (D) t 6:16 ^CF 3 cl (E) c 6:17 ^CF 3 Br (E) c 6:18 ^CF 3 Br (E) t 6:19 ^CF 3 F (E) c 6:20 ^CF 3 F (E) t 6:21 ^CF 3 cl (0 c 6:22 ^CF 3 cl (0 c / t 6:23 cf ₂ ci cl (C) c 6:24 cf ₂ ci F (C) c 6:25 cfci ₂ F (C) c 6:26 C F 2 5 cl (C) c 6:27 CF ₂ CF ₂ C1 cl (C) c / t 6:28 ^CF 3 H (C) c 6:29 ^CF 3 Φ (C) c 6:30 ^CF 3 ch ₃ (C) c / t 6:31 ^CF 3 ^CF 3 (C) c / t 6:32 ^CF 2 ^C1 cl (D) c ".33 cf ₂ ci F (D) c 6:34 ^C 2 ^p 5 cl (D) c 6:35 cf ₂ cf ₂ ci cl (D) c / t 6:36 ^CF 3 H (D) c 6:37 ^CF 3 H (D) t 6.38 ^b cf ₂ ci cl (E) c 6.39 ^b cf ₂ ci F (C) c 6:40 ^C 2 ^F 5 cl (E) c 6:41 ^d cf ₂ ci ₂ ci cl (E) c 6:42 ^CF 3 H (E) c 6:43 ^CF 3 cl (G) c / t 6:44 ^CF 3 cl (H) t 6:45 ^CF 3 cl (I) c / t 6:46 ^CF 3 cl SHE) c / t 6:47 ^CF 3 cl (K) c / t 6:48 ^CF 3 cl (1) c / t 6:49 ^CF 3 cl (M) c / t 6:50 ^CF 3 cl (N) c / t 6:51 ^CF 3 cl (She) c / t 6:52 ^CF 3 cl (P) c / t 6:53 ^CF 3 cl (Q) c / t 6:54 ^CF 3 cl (R) c 6:55 ^CF 3 cl (S) c 6:56 ^CF 3 cl (T) c 6:57 ^CF 3 cl (U) c 6:58 cf ₃ cl (V) c 6:59 cf ₃ cl (W) c

⁺ Separated diastereoisomers ^a The structure is confirmed by nmr and elemental analysis ^b Fp. 100-102 ° C / 0.005 mmHg

-10184 087

Fp. 110C ° / 0.9 mmHg Only nmr analysis phenyl group

Table V.

Initial activity

Percentage death

Compound ^a Conc. ^b MWB ¹ MBB ² SAW ³ PA ⁴ SM ⁵ PC ⁶ 6.1 39 6 100 100 70 87 100 6.2 39 30 100 100 100 6 100 6.3 39 (10) ^c 5 (100) ^c (100) ^c 100 7 90 6.4 64 - 100 100 100 36 - 6.5 78 40 100 100 100 54 - 6.6 64 - 100 100 100 0 6.7 20 40 100 100 100 85 50 6.8 39 90 100 100 100 41 15 6.9 39 90 100 100 100 15 45 6:10 39 (2.5) 75 (100) (100) (92) 36 100 6:11 78 100 100 100 100 17 - 6:12 64 - 100 100 100 53 - 6:14 78 50 100 100 100 92 1 6:16 20 (39) 10 100 100 100 (50) 10 6:17 64 - 100 100 100 0 - 6:18 64 (512) - 95 100 71 (0) __ 6:19 78 (5) 41 (100) (100) 100 100 55 6:21 64 - 100 100 100 0 - 6:22 64 - 100 100 100 0 __ 6:23 78 45 100 100 100 100 5 6:24 20 70 100 100 100 29 10 6:26 20 100 100 82 100 100 20 6:27 78 (312) 10 100 10 100 29 (40) 6:28 78 25 100 100 100 96.5 5 6:29 64 - 100 5 0 0 - 6:30 64 - 100 100 100 48 6:31 64 (512) - 100 65 100 (0) 6:32 78 (2) 10 100 100 0 (55) 0 0 6:33 78 100 100 100 100 42 10 6:35 78 (312) 30 100 100 100 18 (25) 6:39 78 95 100 100 100 94 25 6:40 78 25 100 100 100 80 0 6:41 78 (312) 10 100 100 90 58 (0) 6:42 78 55 100 100 90 92 0 6:43 20 (312) 5 100 100 92 (31) 6:44 20 (312) 10 95 100 100 19 6:45 78 22 100 100 100 _ 15 6:46 78 10 100 100 100 _ 15 6:47 78 5 100 100 100 5 6:48 39 0 100 28 90 0 0 6:49 39 10 100 0 0 0 0 ' 6:50 64 - 65 100 65 0 6:51 64 - 45 0 0 0 - 12

-1 123

184 087 (Continuation of Table V)

Percentage death

Compound ³ Conc. ' ³ MWB ¹ MBB ² SAW ³ PA ⁴ SM ⁵ PC ⁶ 6:52 64 45 20 0 0 6:53 64 - 100 30 0 0 6:55 512 - 100 100 43 0 __ 6:56 512 - 85 100 100 0 __ 6:57 512 100 100 100 0 6:58 64 - 100 100 50 65 - 6:59 64 - 80 0 20 0 - permethrin 156 71 - - 94 36 100 permethrin 39 30 100 100 93 - 33 10 10 75 100 54 - 15 CHECK ^d - 0 0 5 10 0 0

^a IV. b Concentration in ppm ^c Data in parentheses are given for concentrations in parentheses ^d Untreated sample

Oncopeltus fadatus (Dallas)

Epilachna varivestis (Muls.)

Spodoptera eridania (Cram.)

Acyrthosiphon pisum (Harris)

Tetranychus urticae (Koch)

Conatrachelus nenuphar (Herbst)

VI. Spreadsheet

Relative effect against pests

Compound SAW ¹ CL ² BAW ³ CEW ⁴ MBB ⁵ MWB ⁶ 6.1 2.3-2.6 1.0-2.7 1.9-2.8 1.5-1.8 7.1 2.4 6.2 0.9-1.0 0.5-0.9 1.0 1.2 - - 6.3 0.5-0.7 0.7-1.1 0.6 0.9 - - 6.4 2.5 3.4 1.3 - 5.1 4.9 6.5 1.8 1.1 1.5 1.0 - - 6.6 0.1 0.5 0.6 - 0.4 1.5 6.7 2.4 1.8 1.3 - - - 6.8 2.1-2.3 2.1-3.0 2.5 1.8 - - 6.9 1.4-1,9 2.4-3.6 2.1 6.0 5.6 6:10 1.0-1.7 1.8-2.0 1.7 2.0 - - 6:11 1.3 1.7 1.8 1.1 - - 6:12 0.01 - - - 1.88 1.6 6:13 0.6 3.1 - __ - - 6:14 0.3 0.1 - - - - 6:15 1.7 3.0 - - - - 6:16 1.0 0.8 1.6 0.7 0.7 3.6 6:17 1.8 1.7 2.8 - 1.6 1.6 6:18 0.1 0.06 - - - - 6:19 0.9 0.5 - - -

-12184 087 (Continuation of Table VI) ____Relative effect against pests

Compound* SAW ¹ CL ² BAW ³ CEW ⁴ MBB ⁵ MWB ⁶ 6:20 0.08 0,001 6:21 12.2 11.8 24.1 - 7.9 67.6 6:22 6.4 8.2 7.9 3.8 55.7 6:23 0.6 0.8 - - 6:24 1.1 0.4 - - - 6:25 0.1 0.1 - - 6:26 0.02 0.1 0.2 0.1 6:27 0.01 0.6 - - - 6:28 0.5 0.3 6:29 0,001 0,001 - 0.1 0,001 6:30 0.9 1.0 - - 6:31 0.06 0,001 - 6:32 0.04 0,001 - - __ 6:33 0.4 0.3 - - 6:34 0.08 0.2 - - __ - 6:35 0.04 0.05 - - - - 6:36 0.3 0.2 - - - - 6:37 0.8 0.5 - - 6:38 1.3-1.6 0.9 - - - 6:39 0.4 0.1 - 6:40 0.03 0,001 __ - - - 6:41 0.01 0,001 - - - - 6:42 0.1 0,001 - - - 6:43 0.08 0.09 - - - - 6:44 0.2 0.05 - - 6:45 0.2 0.6 - - - - 6:46 0.05 0.3 - - - - 6:47 0.06 0.05 - - - - 6:48 0,001 0,001 - __ .. 6:49 0,001 0,001 - - - _ 6:50 0.06 - - - 0.06 0.6 6:51 0.05 - - - 0.01 0.4 6:52 0.01 - - 1.0 0.07 6:53 0.04 - - - 0.5 0,001 6:54 0.05 0.06 - - - 6:55 0.03 0.04 - - - - 6:57 0.01 - - - - - 6:58 0.4 0.2 - - - - 6:59 0.2 0.2 - __ - -

Spodoptera eridania (Cram)

Trichoplusia ni (Hubner)

Spodoptera exigua (Hubner)

Heliothis zea (Boddie)

Epilachna varivestis (Muls.)

Oncopeltus faciatus (Dallas) + A IV. corresponds to the structure given in Table

-13184 087

Example 75

The emulsifiable concentrate of the following is the active ingredient of IV. Table 6.9.

Ingredients Weight% Active ingredient (90%) 11.7 emulsifier 6.0 Xylene (solvent / carrier) 82.3 100.0

The emulsifier used in the formulation is a mixture of anionic calcium dodecylbenzene sulfonate, nonionic ethoxylated nonylphenol and nonionic ethoxylated octylphenol.

The preparation is all. Using the procedure described in Example 1A, complete killing of insects is achieved. The above formulation is diluted with water into test solutions containing 0.3.0.15% and 0.0075% by weight of the active ingredient and treated (sprayed) on apple trees that have been previously infected with the following insects: Tetranyhus urticae, RSM, apple aphid (Aphis pomi, GA), pink apple aphid (Dysaphis plantaginea, RA), and white apple aphid (Typhlocylia pomar, WAL). The efficacy of the preparations is shown in the table below:

Concentration Percentage death

(weight%) TSM GA RA WAL 0.3 95.2 98.2 96.9 97.9 0.15 59.1 94.5 93.7 98.9 0.0075 60.4 90.9 90.6 98.9

Example 16

The active ingredient of the following microencapsulated preparation is shown in Table IV. Table 6.21.

Composition Weight%

active ingredient (90%) 5.00 ethyl cellulose (encapsulant) polyalkylene glycol ether 1.25 (Emulsifier) 1.75 xylene (solvent / carrier) 5.00 isopropanol (solvent / vehicle) 12.00 water (solvent / vehicle) 75.00 100.00

The preparation is all. Further dilutions were made as described in Example 1 and were used at various concentrations against Mexican Beetroot (HBB), Southern Star Beetle (SAW) and Cabbage Butterfly (Cl).

From the data in the table below, it can be seen that the "break point" at which death is less than 100% can be achieved with a formulation having a concentration of about 6.5 ppm.

Concentration Death (%)

(Ppm) MBB SAW CL 6.5 100 85 80 4.5 100 65 75 3.2 100 40 80 2.1 90 25 70

Claims (6)

Claims 1. An insecticidal composition comprising as an active ingredient 0.00025-15% by weight of a perhalogenalkyl vinylcyclopropanecarboxylate of the formula I in which One of the substituents Y and Z is a C 1-4 perhalogenalkylpowder and the other is hydrogen, halogen, lower alkyl, phenyl, phenylthio or benzyl, provided that Y and Z can form a perhalogenocyclopentylidene group, and ^R1 alletrolonil group, an a-methyl group of either (a) or (b) a radical of formula wherein R ^{2 is} hydrogen, lower alkyl, ethynyl, cia. no- or trihalomethyl, R ^{3 is a} divalent oxygen, divalent sulfur or vinylene group, R ⁴ , R ⁵ and R ⁶ are each independently hydrogen, lower alkyl, halogen, lower alkenyl, phenyl, phenoxy, benzyl or phenylthio, or any two of R ⁴ , R ⁵ and R ⁶ together form a divalent inetiléndioxi-group attached to a phenyl ring with two adjacent carbon atoms, with the proviso that, if R contains ^4, R ^s or R ⁶ phenyl ring, then the phenyl ring 1 to 3, leaving substituents include halo and lower alkyl groups can be replaced, R * is hydrogen, lower alkyl, lower alkoxy, lower alkenyl, lower alkenyloxy, phenyl or benzyl, and R ^{5 is} hydrogen, halogen, lower alkyl, lower alkoxy, lower alkenyl, lower alkenyloxy, lower alkyl thio, lower alkylsulfinyl, lower alkylsulfonyloxy, phenyl or phenyl; cyanide tube powders, liquid or solid diluents or carriers, preferably xylene, isopropanol, water or mixtures thereof, and surfactants or emulsifiers, preferably octylphenoxypolyethoxyethanol, calcium dodencylbenzene sulfonate, ethoxylated nonylphenol or -octylphenol, together with at least one. (Priority: July 24, 1978) -14184 087 An embodiment of the insecticidal composition according to claim 1, wherein the active ingredient is a compound of formula (I) wherein R ^{1 is} (a) wherein R ^{2 is} hydrogen, lower alkyl, ethynyl, dano or trihalomethyl, R ^{3 is} divalent oxygen, divalent sulfur or vinylene, R ⁴ and R ^{5 are} hydrogen, lower alkyl, lower alkenyl, phenyl, phenoxy, benzyl or phenylthio and R ⁶ hydrogen atoms, provided that when one of the substituents R ⁴ and R ⁵ is phenoxy, then R ^{2 is a} trihalomethyl group or R ^{4 is} other than hydrogen. (Priority: January 20, 1978) Third embodiment of the insecticidal composition according to claim 1, characterized in that it contains as active substance (I) compound wherein R ¹ 5-benzyl-3-furylmethyl radical. (Priority: January 20, 1978) An embodiment of the insecticidal composition according to claim 1, wherein the active ingredient is a compound of formula (I) wherein R ^{1 is} a group of formula (a) wherein R ^{2 is} hydrogen, R ^{3 is} vinylene, R ^{One of 4} , R ⁵ and R ⁶ is optionally substituted with halogen or lower alkyl 5 substituted phenyl groups and the other two are independently hydrogen, halogen or lower alkyl. (Priority: July 24, 1978) An embodiment of the insecticidal composition according to claim 4, wherein the active ingredient is a compound of formula (I) wherein R ^{1 is} 3-phenylbenzyl, (Preferred January 20, 1978). An embodiment of the insecticidal composition according to claim 1, wherein the active ingredient is a compound of formula (I) wherein R ^{1 is} an alcohol moiety of formula (b). Represents 20, wherein R ^{8 is} hydrogen and R ^{9 is} nitro or phenyl.