DD208755A5 - PESTICIDE COMPOSITION - Google Patents

Abstract

The invention relates to novel pesticidal compositions based on fluorophenoxybenzyl esters. Preferred active substances are: α-Aethynyl-2-fluoro-3-phenoxybenzyl-2,2-dimethyl-3 - ((propargyloxyimino) methyl) cycloporpane carboxylate, α-cyano-3 fluoro-5-phenoxybenzyl-2,2-dimethyl-3 - ((isobutoxyimino) methyl) cyclopropanecarboxylate, 3- (4-fluorophenoxy) -4-fluorobenzyl-2,2-dimethyl-3 - ((cyclopropylmethoxyimino) methyl) cyclopropanecarboxylate ,

Description

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24,674

Pesticidal composition

Field of application of the invention:

The invention relates to a novel pesticidal composition.

Characteristic of the known technical solutions:

From the European patent application 5882 it is known that, among other Phenoxyvwnzylester of Oximinoäthylcyclopropancarbonsäuren possess insecticidal and acaricidal properties. A new class of esters has been found, namely fluorophenoxybenzyl esters, which have better insecticidal and acaricidal properties, especially over cotton budworm and mites.

Object of the invention:

The invention is intended to provide a novel pesticidal composition.

Explanation of the essence of the invention:

According to the invention, the new composition contains as active ingredient a compound of the following general formula (I):

-2.N0Y198-3 * i. ^l '-Ü472

H _v CH β N (H-OR- ¹ -T) / V 7

wherein R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a (cycloalkyl) alkyl group having 3 to 7 ring carbon atoms and a total of 4 to 9 carbon atoms, a cycloalkyl group having 3 to 7 ring carbon atoms, an alkenyl or alkynyl group having 2 to 4 carbon atoms an aryl group having fi to 12 carbon atoms or an aralkyl group having 7 to 11 carbon atoms; m and η are each independently 0 or 1 and m + η is 1 or 2; and D represents a hydrogen atom, a cyano group or a Äthynylgrupps "under uer proviso that when D is cyano or ethynyl, then the R, S ~ racemic or S-optical configuration comprises the alcohol component.

Specific examples of these esters are:

U, -ethylnyl-2-fluoro-3-phenoxybenzyl-2,2-dimethyl-3 - ((p-ropygyloxyimino) methyl) cyclopropanecarboxylate,

~6β-cyano-3-fluoro-5 »-phenoxybenzyl-2- _t 2-dimethyl-3 - ((isobutoxyimino-methyl) -cycloproply carboxylate,

ük / 3- (4-fluorophenoxy) -4-fluorobenzyl-2,2-dimethyl-5 - ((cyclopropylmethoxyimino) methyl) cyclopropanecarboxylate

In the compounds of the invention, R is preferably an alkyl group having 1 to 6 carbon atoms, a (cycloalkyl) alkyl group having 3 to 6 ring carbon atoms and a total of 4 to 8 carbon atoms, a cycloalkyl group having 3 to 6 ring carbon atoms,

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an alkenyl or alkynyl group having 2 to 4 carbon atoms, an aryl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 11 carbon atoms.

It is even better if R is an alkyl group having 2 to 6 carbon atoms, such as ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, amyl, isoamyl, tert-amyl, neopentyl, and n-hexyl; a (cycloalkyl) alkyl group having 3 to 5 ring carbon atoms and a total of 4 to 8 carbon atoms such as cyclopropylmethyl,! - (cyclopropyl) ethyl, cyclpbutylmethyl and cyclohexylmethyl, a cycloalkyl group having 3 to 6 ring carbon atoms such as cyclopropylethyl, cyclobutyl, cyclopentyl and cyclohexyl; an alkenyl or alkynyl group having 2 to 4 carbon atoms such as alkyl or propargyl; an aryl group having 6 to 10 carbon atoms, such as phenyl and naphthyl; or an alkyl group having 7 to 10 carbon atoms such as benzyl or phenethyl.

Most preferred is that R is an alkyl group of 3 to 6 carbon atoms, a (cycloalkyl) alkyl or cycloalkyl group of 4 to 5 carbon atoms, allyl, phenyl or benzyl. Particularly useful are those compounds in which R is an alkyl, (cycloalkyl) alkyl or cycloalkyl group each having 4 or 5 carbon atoms, especially isobutyl, tert-butyl, sec-butyl, neo-pentyl, cyclopropylmethyl, 1-methylcyclopropylmethyl and Cyclobutylmethyl is.

As a result of their pesticidal properties, a preferred class of compounds of the invention has the general formula I, wherein D is a hydrogen atom or a cyano group and m is 1 "and η is 0, especially if the fluorine atoms in the 4-position of the ring with respect on the BenzylkohLenstöffatom stand.

Thus, examples of particularly active compounds are those when R is an alkyl, (cycloalkyl) alkyl or cycloalkyl group having 4 or 5 carbon atoms, D is a cyano group and the fluorine atom is at the 4-position; d "h.

^ - cyano-3-phoenoxy-4-fluorobenzyl 2,2-dimethyl-3-bis ((oxypropylmethoxyimino) methyl) cyclopropanecarboxylate,

.L-cyano-3-phenoxy-4-fluorobenzyl 2,2-dimethyl-3 - ((neopentoxyimino-methyl-cyclopropanecarboxylate,

A, ~ cyano-3-phenoxy-4-fluorobenzyl 2,2-dimethyl ~ 3 - ((eyelobutmethoxyimino) methyl) cyclopropanecarboxylate,

• (, - Cyano-3-phenoxy-4-fluorobenzyl 2,2-dimethyl-3 - ((isobutoxyimino) methyl) cyclopropanecarboxylate »

Examples of other very active compounds arise when R is an alkyl, (cycloalkyl) alkyl or cycloalkyl group having 4 or 5 carbon atoms, D is a hydrogen atom and the fluorine atom is in the 4-position;

3 "phenoxy-4-fluorobenzyl 2, 2-dimethyl-3- ((cyclopropyl)

methoxyimino-methyl-cyclopropanecarboxylate,

3-phenoxy-4-fluorobenzyl 2,2-dimethy1-3 - ((neopentoxyimino) -methyl) cyclopropanecarboxylate,

3-phenoxy-4-fluorobenzyl 2,2-dimethyl-3 - ((cyclobutmethoxyimino) methyl) cyclopropanecarboxylate,

3-phenoxy-4-fluorobenzyl 2, 2-dime thy 1-3- (isobutoxyimino) -methyl) eyelopropanecarboxylate.

The oxime substituent group d & r of the invention results in geometric isomerism due to the presence of an asymmetrically substituted double bond. These isomers are usually described as follows:

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H OR R OR

C = N and C = N

R H

Anti or syn or

Ε isomers Z isomer

A useful embodiment of the invention relates to esters in which the oxime substituent is present in the Z-isomeric form, since such isomers may be many times more pesticidally effective than when the oxime substituent is in the E-isomeric form or is a mixture of the E and Z isomer forms.

Formula I includes all possible configurations of the acid component as well as individual configurations or mixtures.

The invention includes all pesticidally active esters of the acid forms resulting from the synthesis and mixtures formed by mistake. A useful embodiment of the invention relates to esters in which the acid component has the ice or (IR cic ) isomer configuration, whether fairly enriched or relatively pure in such isomer configuration.

A particularly preferred embodiment of the invention is when the oxime substituent is present in the Z isomeric form and the acid component is enriched or relatively pure in the ice or IR cis configuration.

The fluorochemical oxyiminocyclopropanecarboxylates of this invention can be prepared by esterification involving the reaction of a fluorochemical phenoxybenzyl alcohol or reactive derivative thereof with an oxyiminocyclopropanecarboxylic acid or a reactive derivative thereof in the presence of triethylamine, preferably the reaction is carried out in a solvent such as refluxing ethyl acetate. The alcohols and their reactive derivatives are known from US Pat. Nos. 4,218,469 and 4,276,306. The acids are generally known from U.S. Patent Nos. 3,922,269, 4,282,249, and 4,292,325 and European Patent 5,882, and are prepared by the treatment of caronaldehyde carboxylic acid or a reactive derivative thereof (as disclosed in U.S. Patent No. 3,922,269 ) with hydroxylamine or an O-substituted hydroxylamine R CNH ₂ , wherein R is as hereinbefore defined, and in the case where R represents hydrogen, subsequent hydrocarbylation of the resulting oxime, if desired, with an alkyl (or alkenyl) halide or the like for obtaining an alkoxime (or alkenyl) halide or the like, for obtaining an alkoxime (or alkenyl oxime), etc.

Di oximation can be achieved by treatment of substantial equimolar amounts of aldehyde and hydroxylamine or hydrocarbyloxyamine in a polar solvent such as an alkanol, e.g. Ethanol or dioxane, going on. When the aldehyde is converted to the oxime by reaction with hydroxylamine, and if it is desired to convert the resulting oxime to an alkylated or alkenylated derivative or the like, then this reaction can be carried out by methods commonly used for the alkylation of phenols be applied. The oxime can therefore be dissolved in a polar solvent.

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agent such as ethanol with an alkyl halide, generally the bromide, in the presence of a hydrogen halide acceptor and the mixture is heated until the reaction is complete.

Oxime formation is normally carried out using an acid addition salt of hydroxylamine or the hydrocarbyloxyamine, e.g. of the hydrochloride. In cases where the preparation of a compound wherein R represents methyl is contemplated, it is generally more convenient, through the availability of methoxyamine hydrochloride, to conduct the reaction in one step using methoxylamine hydrochloride, but where compounds are required in which R represents a larger group, then it is usually more convenient to first form the oxime and then to hydrocarbylate the oxime.

Alternatively, according to a further modification, the compounds of the invention are prepared by treatment of cis - or (IR, ice ) - caronaldehydecarboxylic acid recently described in U.S. Patent 3,723,469 and the formula

= 0

CH ₃

has, with an O-substituted hydroxylamine salt of the formula R -ONH ₃ -W, wherein R ^{1 is} as defined above and W is the anion of the salt-forming inorganic acid prepared. Suitable inorganic acids are hydrogen halides such as hydrochloric and hydrobromic acid

acid, sulfuric acid such as sulfuric acid, fluorosulfonic acid, phosphoric acids such as phosphoric acid and nitrogen-containing acids such as nitric acid or boric acids such as boric or fluoroboric »

The reaction is preferably carried out in an aqueous medium in the presence of a buffer such as an alkali metal salt of a polybasic acid including sodium hydrogencarbonate, potassium hydrogen tartrate, disodium hydrogenphosphate and the like. Generally, at least one mole of buffer is used for each mole of caronaldehydecarboxylic acid.

The molar ratio of the reactants is not critical and can be varied widely; In general, a molar ratio of the O-substituted hydroxylamine salt to caronaldehyde carboxylic acid is from about 1.0 to about 1.5, and preferably from about 1.02 to 1.3.

The reaction is generally carried out in the liquid phase by agitation, e.g. Stirring, a mixture of the reactants made. The resulting product is recovered using conventional techniques such as filtration, extraction, or the like. «

The reaction temperature is not critical and can easily range from the ambient temperature to the reflux temperature of any solvent used at normal pressure. In general, the temperature is between about O ⁰ C and about 50 ⁰ C ₀

A minor amount of co-solvent can be used in the reaction medium. Suitable cosolvents are lower alcohols having 1 to 6 carbon atoms such as methanol, esthanol and the like.

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2.4 67

The resulting ice or (IR, ε is_) acids are converted to the ester compounds of the present invention, for example as described above, by reaction with the arylmethyl halide in the presence of triethylamine in a solvent such as refluxing ethyl acetate.

The invention includes within its scope pesticidal compositions of a pesticidally acceptable adjuvant - i. at least one carrier or a surfactant - and as an active ingredient at least one pesticidally active ester of the invention. The invention also relates to a method of controlling insect, mite or other arthropod pests on a site consisting in applying a pesticidally effective amount of at least one compound of the invention to the pests or the site.

With regard to the spectrum of pesticidal activity, the compounds of the present invention exhibit selective or non-selective activity in species such as CoIeoptera, Lepidoptera (especially larvae), Diptera, Orthoptera, Hemiptera, Homoptera and Acarina, depending on the specific combination of acid and alcohol of the present invention , The compositions according to the invention are very useful for the control of disease-transmitting insects such as mosquitoes, flies and cockroaches, cereal beetles such as rice beetles ( Sitophilus oryzee ) and mites and of insects harmful to agriculture such as lantern carriers, green rice leaf beetles ( Neophotettix bipuntatus cinticeps, Uhler ), Cabbage ( Plutelle maculipennis Curtis ), small cabbage white ( Pieris rapae Linne ) rice hammer ( Chilo suppressalis, Walker ) cotton boll larvae ( Heliothis zea Boddie ), aphids, clove winders, leafminers and

like.

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The esters are used for harvested plants, in horticulture, in foraging and in greenhouses.

As used herein, "carrier" means an inert material which may be inorganic or organic and of synthetic or natural origin, with which the active compound is mixed or formulated to be applied to the plant, seed, soil or other object to be treated or storage, transport or handling. The carrier may be a solid or a liquid.

Suitable solid carriers can be natural or synthetic clays and silicates, for example natural silicas such as datum; Magnesium silicates, for example talcs; Magnesium aluminum silicates, for example attapulgites and vermiculites; Aluminum silicates, for example kaolinites, montmorillonites and mica types; Calcium carbonate; Calcium sulfate; synthetic hydrated silicas and synthetic calcium or aluminum silicates, elements such as carbon and sulfur; natural and synthetic resins such as coumarone resins, polyvinyl chloride and styrenic polymers and copolymers; solid polychlorophenols; Bitumen, waxes such as beeswax, paraffin wax and chlorinated mineral waxes; degradable organic solids such as ground corn cobs and walnut shells; and solid fertilizers, for example superphosphates «

Suitable liquid carriers include solvents for the compound of the invention and liquids in which the toxin is insoluble or only slightly soluble.

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Examples of such solvents and liquid carriers are generally water, alcohols, for example isopropyl alcohol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; Ether; aromatic hydrocarbons such as benzene, toluene and xylene; Petroleum fractions such as petroleum, light mineral oils, chlorinated hydrocarbons such as methylene chloride, perchlorethylene, trichloroethane / including liquefied, normally vaporous compounds. Mixtures of different liquids are often suitable.

When used, the surfactant may be an emulsifier or a dispersant or wetting agent. It may be non-ionic, ionic or, preferably, a mixture of both. The surfactants normally used for the formulation of pesticides can be used. Examples of such surfactants are the sodium or calcium salts of polyacrylic acids and lignosulfonic acids; the condensation products of fatty acids or aliphatic amines or amides containing at least 12 carbon atoms in the molecule with ethylene oxide and / or propylene oxide; Solid acid esters of glycerol, sorbitol, sucrose or pentaerythritol; Low molecular weight fatty acid salts, mono-, di- or trialkylamines; Kodensate this with Äthylenöxid and / or propylene oxide; Condensation products of fatty alcohols or alkylphenols, for example p-octylphenol or p-octylcresol, with ethylene oxide and / or propylene oxide; Sulfates or sulfonates of these condensation products; Alkali or alkaline earth metal salts, preferably sodium salts of sulfonated castor oil and sodium alkylarylsulfonates such as sodium dodecylbenzenesulfonate; and polymers of ethylene oxide and copolymers of ethylene oxide and propylene oxide.

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The compositions of the present invention may be formulated in the form of surfactant powders, dusts, granules, solutions, emulsifiable concentrations, emulsions, suspension concentrates or aerosols. Encapsulated formulations and controlled release formulations are also contemplated, as are bait formulations. Surface-active powders are usually mixed to contain 25, 50 or 75 % by mass of toxicant and usually contain from 3 to 10 % by weight stabilizer and / or other additives such as penetrants or adhesives in addition to the solid carrier. Dust is commonly used as a dust concentrate of a composition similar to a surface active powder but formulated without dispersing agent, and they are diluted on site with further carrier to obtain a composition which normally contains from 0.5 to 10 % by mass of the toxicant. Granules can be made by plastic extrusion, agglomeration or impregnation techniques. Normally granules of 0.5 to 25 % by weight of toxicant and 0 to 10 % by weight of additives such as stabilizers, slow release modifiers and binders are obtained. Emulsifiable concentrates normally contain, in addition to the solvent, and, if necessary, co-solvent, 10 to 50 % by mass / volume of toxicant, 2 to 20% by mass / volume. Emulsifier and 0 to 20% by mass / vol. equivalent additives such as stabilizers, penetrants and corrosion inhibitors, suspension concentrates are prepared to yield a durable, non-precipitable, flowable product, usually containing 10 to 75 % by weight of toxicant, 0 to 5 % by weight of dispersant, 0.1 to 10 % by weight of suspending agent Protective colloids and thioxotropic agents, 0 to 10 % by weight of appropriate additives such as antidegradants, anticorrosion agents ₄ stabilizers, penetrants and

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Adhesive and as a carrier water or an organic liquid in which the toxicant is substantially insoluble; Certain organic additives or inorganic salts may be dissolved in the vehicle to aid in preventing sedimentation or as antifreeze for the water.

Aqueous dispersions and emulsions, for example compositions obtained by diluting a surface active powder or emulsifiable concentrate according to the invention with water, are also within the scope of the invention.

The compositions of the invention may also contain other ingredients, for example other compounds having pesticidal, herbicidal or substantive properties, or attractants such as pheromones, attractant feed ingredients and the like for use as bait and trap formulations.

Particularly nutritive compositions can be achieved by the use of a mixture of two or more types of compounds of the invention or by the use of synergists, such as those known for use with the general class of "pyrethroid" compounds, especially - (2 2-butoxyethoxy) ethoxy-4- _t- 5-methylenedioxy-2-propyltoluene, also known as piperphenyl butoxide, 1,2-methylenedioxy-4- (2- (octylsulfinyl) propylbenzene, 4- (3,4-methylenedioxyphenyl) 5-methyl-1,3-dioxane, also known as safroxan, N ^, (2-ethylhexyl) bicyclo-2,2,2,7-hept-5-ene-2,3-dicarboxamide, octachlorodipropyl ether, isobornyl thiocyanoacetate, and others for AlIeth. synergists used in r'in and pyrethrin. Useful compositions may be combined with other biological chemicals, including other cyclopropanecarboxylates,

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phosphate type organic insecticides and carbamate type insecticides.

The compositions of the invention are applied in an amount sufficient to provide the effective amount of toxin at the site to be protected. This amount depends on many factors, such as the carrier used, the method and conditions of application / whether the formulation is applied on-site in the form of an aerosol or as a film or in the form of single particles, the thickness of the film or the size of the film Particles, the insect or mite species to be controlled, and the like, the proper assessment and evaluation of these factors for the choice of the amount of active material required at the site being left to the skill of the artisan. In general, the effective amount of toxicants of the present invention will be at the site to be protected, ie, the amount applied, but on the order of 0.01 % to 0.5 % of the total weight of the formulation, although in some circumstances the effective concentration on the same basis only O ₄ OOl % or even 2 % can be »

The superior efficacy of the cos or (IR, cis ) forms of the esters of this invention is fully exploited when such ester form is present in an amount significantly greater than that normally present in the racemate of the oxyimino substituted ester. Therefore, the use of the cjLji or (IR, cjLsJ forms of the esters of the present invention in such a substantially free form of other stereoisomers is preferred, for example, in a cjLs_ or (IR, cjLsJ isomer purity greater than about 70 %. to about 85 %, preferably in a C ₁ Is ₁ "or (IR ₄ , cjLsJ isomer purity of greater than about 90% or even greater than 95 % *

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2.4 67 4

Ausführungsbeisplel;

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The invention will be explained with reference to the following examples which are intended to illustrate *

example 1

3-Phenoxy-4-fluorobenzyl (IR, cis ) -2,2-dimethyl-3 - ((isobutoxyimino) methylcyclopropanecarboxylate

A reaction mixture formed from 1.0 g of (IR, cis ) -2,2-dimethyl-3 - ((isobutoxyimino) methylcyclopropanecarboxylic acid, 1.32 g of 3-phenoxy-4-fluorobenzylbromide and 0.48 g of triethylamine in 40 ml of ethyl acetate After 17 hours, the reaction mixture was poured into 100 ml of water and extracted three times with 50 ml portions of diethyl ether. The combined extracts were washed with 100 ml of water and then with 100 ml of aqueous sodium chloride, dried and stripped to give 1, 4 g of a viscous yellow DI This Dl was chromatographed on silica and eluted with 30% diethyl ether in hexane to yield 670 g of the required product.

Example 2

(T, cyano-S-phenoxy) -fluorobenzyl (IR, cis ) -2,2-dimethyl-3 - ((isobutoxyimino) methylcyclopropanecarboxylate

To a solution of 1 g (lR ₁ cis ) -2,2-dimethyl-3 - ((isobutoxyimino) methyl) cyclopropanecarboxylic acid in 12 ml of toluene, 0.33 g of potassium carbonate, 38 mg of tetrabutylammonium hydro gensulfat and 20 mg Benzyltriäthylammoniumchlorid in 8 ml of water followed by 1.2 g of oC-cyano-3-phenoxy-4-fluorobenzylbromide dissolved in 5 ml of toluene followed. There were some

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3 ml of water were added and the reaction mixture was kept at 60 ^° C. with stirring overnight. The reaction mixture was cooled to room temperature, poured into 100 ml of water and extracted four times with 50 ml portions of diethyl ether. The pooled extracts were washed with aqueous sodium chloride solution, dried and stripped to yield 1.5 g of yellow oil Chromatographed with 25% diethyl ether in hexane as Aluierungsrnittel, and the product was rechromatographed on silica using 42: 54: 2 toluene / hexane / diethyl ether as the eluent to recover 700 g of the required product in the form of an oil "

3-phenoxy-4 ~ f £ luorbenzyl is_-2 _e 3-dimethyl ~ 3 ~ ((neopentoxyiminomethy1) cyclopropanecarboxylate

2 _{e of} a solution of 0.47 g of ejU ^ -2,2-dimethyl-3- ((neopentoxyiminomethyl) cyclopropanecarboxylic acid in 10 ml of toluene were added 0 _e 2 g of potassium carbonate, 50 mg of tetrabutylammonium sulfate and 50 mg of benzyliriethylammonium chloride in 6 ml of water, whereupon 0, The reaction mixture was kept with stirring overnight at 55 to 70 ⁰ C, cooled to room temperature, poured into 150 ml of water and extracted three times with 100 ml portions of diethyl ether, 58 g of 3 ™ phenoxy "4 ~ fluorberizylbromid in 10 ml of toluene, The combined extracts were washed with aqueous sodium chloride solution, dried (MgSO 4), and stripped to give 0.98 g of colorless oil. Data crude oil was chromatographed on silica using a 15: 1 diethyl ether-hexane eluant to give 0.86 g of the product requested in Forrr's a colorless and viscous oil.

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6 * 7/1 4

Example 4

-Cyano-3-phosphoryloxy-4-fluorobenzyl cis -2,2-dimethyl-3 - ((neopentoxyimino) methyl) eyepropropanearboxylate

To a solution of 0.47 g of cis -2,2-dimethyl-3 - ((neopentoxyimino) methylcyclopropanecarboxylic acid in 10 ml of toluene was added 0.5 g of potassium carbonate, 50 mg of benzyltriethylammonium chloride and 50 mg of tetrabutylammonium hydrogensulfate in 6 ml of water followed by 0.89 g of cxÜ phenoxy-4-fluorobenzyl bromide in 10 ml of toluene. The reaction mixture was kept overnight at 75 ⁰ C, cooled to room temperature, poured into 100 ml water and extracted three times with 50-ml portions of diethyl ether. The extracts taken together were dried (MgSO and the crude oil was chromatographed on silica-diobide using a diethyl ether-hexane eluant to give 1.02 g of the expected product as a viscous yellow oil.

Example 5

3-Phenoxy-4-fluorobenzyl (IR, cis ) -2,2-dimethyl-3 - ((neopentoxyimino) methylcyclopropanecarboxylate

As described in Example 3 above, a mixture of 0.65 g of (IR, cis ) -2,2-dimethyl-3 - ((neopentoxyimino) methyl) cyclopropanecarboxylic acid, 0.6 g of potassium carbonate, 60 mg of tetrabutylammonium hydrogensulfate and 60 mg of benzyltriethylammonium chloride reacted in water and toluene with 0.81 g of 3-phenoxy-4-fluorobenzyl bromide. Recovery of the product according to the procedure described in Example 3 gave 1.42 g of crude product. After chromatographic purification, 0.77 g of the required product was recovered.

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Example 6

uO-cyano-3-phenoxy-4-fluorobenzyl (IR, ice ) -2 , 2, dimethyl-3 - ((neopentoxyimino) methylcyclopropanecarboxylate

To a solution of 0.82 g (IR, cJLs) -2,2-dimethyl-3- ((neopentoxyimino) methylcyclopropanecarboxylic acid in 10 ml of toluene was added 0.62 g of potassium carbonate, 60 mg of tetrabutylammonium hydrogensulfate and 60 mg of benzyltriethylammonium chloride in 8 ml of water and then 1 1 g of gi / cyano-3-phenoxy-4-fluorobenzyl bromide in 10 ml of toluene The reaction mixture was kept at 75-80 ° C for 18 hours, cooled to room temperature, poured into 300 ml of water and washed three times with 100 ml of water. The combined extracts were washed with aqueous sodium chloride solution, dried (MgSO ₄ ) and stripped to give 1.44 g of yellow oil This oil was chromatographed on silica using 25% diethyl ether in hexane as eluent to give 1, 22 g of the required product in the form of a yellow oil.

Example 7

3-phenoxy-4-fluorobenzyl-CjLs_-2,2-dimethyl-3- ((isobutoxy-amino-methyl) -cyclopropanecarboxylate

A solution of 22 parts of cis -2,2-dimethyl-3 - ((isobutoxyimino) methyl) cyclopropanecarboxylic acid, 28 parts of acid, 28 parts of 3-phenoxy-4-fluorobenzyl bromide, 11 parts of triethylamine and 200 parts of ethyl acetate was added for 3 hours Reflux cooked. The reaction mixture was diluted with methylene chloride, washed with water, dried over magnesium sulfate and stripped to give an oil product. Chromatography on a silica column with ether-pentane as the eluent yielded the desired product as an oil.

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Example 8

By following similar procedures to those described in Examples 1-7, the following further compounds can be prepared in Table I which have an E-Z configuration in the oxime substituent.

Table I Fluorine-containing oxyiminocyclopropanecarboxylates

H CH = N-QR ¹

O D

11 I

ο C OCH *

"m

Example R -CH ₃ -CH (CH ₃ ) ₂ -CH ₀ CH = CH ₀ D CN H 2 2 2 2 2 m and n Fluoro-ring-acid positions isomeric 1 R, trans 1 R, ice cis-trans 8 9 10 benzyl H 0.1 1.0 0.1 3 2 2 trans 11 -C ₂ H ₅ H 0.1 3 trans 12 -CH (CH ₃ ) C ₂ H ₃ -phenyl CN -CSTCH 0.1 4 ice cis-trans 13 14 -nC, H ₇ H 1,0 1,1 4 2.2 cis-trans 15 -nC ₄ H _g H 1.1 3.4 trans 16 -C _(CH3 J ₃ -CH ₂ (CH ₂ J ₄ CH ₃ -CH ₂ CH (CH _{3) 2} -CH ₂ CH ₂ CH (CH ₃₎ -CH _{2 0} CH (CH ₇₎ CH ₀ CH, 1.1 2.4 ice ice ice ice ice 17 18 19 20 21 1.0 1.0 1.0 1.0 1.0 3 4 4 4 4

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2A67A1 Ί

Continuation Table I

Example R ¹ -CH ₂ - _A D m and η Fluorine ring positions Acid-isomer configura- tion 22 "CH ₂ - ₀ CN 1.0 4 ice 23 -Δ CN 1.0 4 CiS ₁ 24 -CH (CH ₃ J ₂ CN I ₁ O 4 IR, ice 25 -CH ₂ - ₀ -C = CH 1.1 3.3 trans 26 -CH ₂ - ₀ H 1.1 2.2 ice 27 -CH ₂ C (CH ₃ J = CH ₂ CH l ", 0 4 IR ₁ CiS 28 -CH ₂ CH ₂ CH = CHCH ₃ H 0.1 2 cis-trans 29 -CH (CH ₃ YES H 1.1 3.3 trans 30 -CH ₂ C (CH ₃ J ₃ CN 1.0 4 IR, CJLS, 31 -CH (CH ₃ YES • CN 1.0 4 trans 32 -CH ₀ C (CH _x ), H 1.0 4 £ JS 33 -CH ₂ - 0 CN 1.0 4 IR, trans 34 -CH (CH ₃ JQ CN 1.0 4 IR, ice 35 -CH ₂ (CH ₃ J ₃ H 1.0 4 ice 36 -CH ₂ -φ H 1.0 4 cis-trans 37 H 1.0 4 cis-trans

Example 38 Pesticidal activity

The effectiveness of the compounds according to the invention in insects and mite pests was determined as follows using test methods for toxicity testing:

I. Experiments with Stune flies ( Musca do mestica (Linne) J were carried out in such a way that 50 five-day-old house flies were placed in a spray cage and filled with 0.6 ml

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a solution of the test compound were sprayed. After spraying, the flies were pollinated with CO ₂ and placed in a recovery cage with a milk sponge as feed. The flies were kept in the cages for 18 to 20 hours, after which the mortality counts were made. Dead and dying animals were counted. The experiments were performed with several different dosages of each test compound.

II. Experiments with green pea aphids ( Acyrthosiphon pisum (Harris)) were carried out so that about 100 aphids were placed on broad bean plants. The plants were sprayed with dilutions of acetone solution of the test compound in water containing an emulsifier and kept in containers under laboratory conditions for 18 to 20 hours, whereupon the live aphids in the containers were counted. The experiments were done with several different doses of each test compound.

Experiments with adult female spider mites ( Tetranychus urticae (Koch)) were carried out by placing 50 to 75 mites on the underside of the leaves of spotted cowpeas. The leaves were sprayed with dilutions of acetone solution of the test compound in water containing an emulsifier and held under laboratory conditions for about 20 hours, after which the mortality counts were made. The experiments were performed using several different dosages of the test compounds.

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24 67 Λ 1 1

The experiments on larvae of bollworms (HeIiot his ea (Boddie)) were carried out by spraying a broad bean plant with dilutions of acetone solution of the test compound in water containing an emulsifying agent. Immediately after spraying, 5 larvae were placed on the plant and left there for 44 to 46 hours, whereupon the dead and dying larvae were counted. The experiments were performed using several different doses of each test compound.

In each case, the toxicity of the compound of the invention was compared with that of a standard pesticide (parathion), the relative toxicity of which was then expressed as the ratio between the amount of compound of the invention and the amount of standard pesticide used to produce the same percentage (50th) ) of mortality among the test insects or mites. Since an arbitrary rating of 100 was assigned to the standard pesticide, the toxicities of the compounds of this invention were expressed in terms of toxicity indexes, comparing the toxicity of the compounds of the present invention with that of the standard pesticide. That is, a test compound with a toxicity index of 50 would be only half as effective, while one with a toxicity index of 200 would be twice as effective as the standard pesticide. The toxicity indices are listed in Table II.

Moreover, contrary to expectation, the compounds of the present invention have been more effective in controlling certain pests, especially larvae of cotton bollworm and mites, than the corresponding structurally almost similar compounds described in U.S. Patent Nos. 3,922,269, 4,211,792, 4,282,249 and U.S. Pat 4,292,325.

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246741 1

Table II Pesticidal efficacy, expressed as the toxicity index relative to that of parathyme as a standard equals 100

Cotton capsule - Common example housefly Pea aphid worm Spinnmil

1 500 70 200 2 - 400 - 3 140 160 4 940 1650 5 280 6 6200

2000 270 2300 1100 2300 540 1000 670 1050 880 4600 1650

means "no attempt"

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Claims (8)

Claim claim: ^1: 1 in the compound of the formula (I), R is an alkyl group having 1 to 6 carbon atoms, a (cycloalkyl) alkyl group having 3 to 6 ring carbon atoms and a total of 4 to 8 carbon atoms, a cycloalkyl group having 3 to 6 ring carbon atoms, an alkenyl or alkynyl group with 2 to 4 coal I - 25 - atoms, an aryl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 11 carbon atoms. ¹ ^. -0- // V ^CH 3 HF _m • contains -wherein R is a hydrogen atom; an alkyl group having 1 to 10 carbon atoms, a (cycloalkyl group) alkyl group having 3 to 7 ring carbon atoms and a total number of 4 to 9 carbon atoms, a cyclic alkyl group having 3 to 7 ring carbon atoms, an alkenyl group or alkynyl group having 2 to 4 carbon atoms, · an aryl group having 6 to 12 carbon atoms · or an aralkyl group having 7 to 11 carbon atoms; rn and η are each independently 0 or 1 and m + η is 1 or 2; and D is a hydrogen atom, a cyano group or an ethynyl group, provided that when D is cyano or x-thynyl then the alcohol component is present in the R, S racemic or S optical configuration. 1. Pesticidal composition, characterized in that. at least one surfactant or carrier and, as active ingredient, a pesticidally effective amount of a compound of formula (I) H, CH = N-OR 2. Composition according to. Point 1, characterized by 3. Composition according to item 1 or 2, characterized in that in the compound of formula (I) R is an alkyl group having 3 to 6 carbon atoms, a (cycloalkyl) alkyl group having 4 to 5 carbon atoms or an allyl, phenyl or benzyl group , 4. The composition of item 4, characterized in that in the compound of formula I D is a hydrogen atom or a cyano group, m is 1 and η is 0 and the fluorine atom is in the 4-position of the ring with respect to the benzyl carbon atom. 'Collabora on 5- to 4, characterized in that -]
R is an alkyl, (cycloalkyl) alkyl or cycloalkyl group each having 4 or 5 carbon atoms. 6. A composition according to item 1, characterized in that in the compound of formula (I) the oxime substituent in the Z-isomeric form, substantially free of other stereoisomers. 7. Composition according to one of the preceding points, characterized in that in the compound of formula (I) the acid component in the c_is_ isomer form or in the (1R, _i c_iS.) ~ I ^{soiner orra} each substantially free of other stereoisomers, is present, 8. A method for controlling pests in a location, characterized in that a pesticidal / effective amount of a compound of formula (I) is applied to the pest or the location.