CS241132B2 - Insecticide and acaricide and method of its active substance production - Google Patents

Description

(54) An insecticidal and acaricidal composition and a process for the manufacture of an active ingredient thereof

The subject of the invention is an insecticidal and acaricidal composition comprising an active ingredient and at least one surfactant or carrier, characterized in that it contains a compound as active ingredient.

, Wherein R represents an alkyl group of up to 6 carbon atoms,

D represents a hydrogen atom or a cyano group and each man independently of one another represents 0 or 1 and the sum of m and n is 1 or 2, with the proviso that when D represents cyano, the alcohol moiety is in the RS-racemic or S-optical configuration a process for the manufacture of an active ingredient therefor.

The invention relates to an insecticidal and acaricidal composition and to a process for the manufacture of an active ingredient thereof which is an alkoxyiminomethylcyclopropanecarboxylic acid derivative.

It is known from European Patent No. 5882 that phenoxybenzyl esters of alkyoxyiminomethylcyclopropanecarboxylic acid have insecticidal and acaricidal properties. The Applicant has discovered a new class of esters, namely fluorophenoxybenzyl esters, which exhibit improved insecticidal and acaricidal properties, in particular against Heliothis zea and mites.

SUMMARY OF THE INVENTION The present invention provides an insecticidal and acaricidal composition comprising an active ingredient and at least one surfactant or carrier, wherein the active ingredient comprises a compound of formula I

where

R ¹ represents an alkyl group of up to 6 carbon atoms,

D represents a hydrogen atom or a cyano group and each of m and n independently of one another is or 1 and the sum of m + n is 1 or 2, provided that when

D is cyano, then the alcohol moiety is in the RS-racemic or S-optical configuration.

A particular example of this ester is, for example, alpha-cyano-3-fluoro-5-phenoxybenzyl (2,2-dimethyl-3 - [isobutoxyimino] methyl) cyclopropanecarboxylate.

In the compounds of the invention, R ¹ is preferably an alkyl group having 1 to 6 carbon atoms. In a particularly preferred embodiment, R ¹ is a C 2-6 alkyl group such as ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, amyl, isoaiftyl, tert-amyl , neopentyl and n-hexyl.

Furthermore, R ^{1 may} suitably be an alkyl group having 3 to 6 carbon atoms. Particularly suitable are compounds in which R @ ¹ denotes a alkyl group having 4 or 5 carbon atoms, in particular isobutyl, tert-butyl, sec-butyl and neopentyl.

Particularly favorable insecticidal and acaricidal properties are represented by the group of compounds of the invention represented by formula (I) in which D is hydrogen or cyano, m is 1 and n is 0, especially when the fluorine atoms are bonded at the 4-position relative to the benzylic carbon atom.

Examples of particularly suitable active compounds according to the invention are those compounds of the formula I in which R @ ¹ represents an alkyl group having 4 or 5 carbon atoms, D is cyano and the fluorine atom is in the 4-position, i.e.:

alpha-cyano-3-phenoxy-4-fluorobenzyl (2,2-dimethyl-3 - [neopentoxyimino (methyl) cyclopropanecarboxylate) and alpha-cyano-3-phenoxy-4-fluorobenzyl (2,2-dimethyl-3-) (isobutoxyimino) methyl (cyclopropanecarboxylate).

Examples of other very active compounds are those compounds of formula (I) wherein:

3 *

R ¹ is an alkyl group containing 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- (neopentoxyimino) methyl) cyclopropanecarboxylate

3-Phenoxy-4-fluorobenzyl (2,2-dimethyl-3 - [(isobutoxyimino) methyl] cyclopropanecarboxylate).

The oxime substituent group of the compounds of the invention gives rise to geometric isomerism due to the presence of an asymmetrically substituted double bond. These isomers are typically described as follows:

the anti- or E-isomer of the syn- or Z-isomer

A preferred embodiment of the invention includes esters in which the oxime substituent is in the form of the Z-isomer, as such isomers are several times more potent than those in which the oxime substituent is in the form of the E-isomer or mixtures of the E- and Z-isomeric forms.

Formula I encompasses all possible configurations of the acid moiety as well as individual configurations or mixtures. The present invention encompasses all insecticidally and acaricidally active acid esters which have been formed by synthesis and obtained from mixtures.

A preferred embodiment of the invention includes esters in which the acid moiety has a cis- or (IR) -isomeric configuration, and it is irrelevant whether they are enriched or relatively pure compounds with said isomeric configuration. A particularly preferred form of the invention is when the oxime substituent is in the Z-isomeric form and the acid moiety is enriched or is of relatively pure cis- or IR, cis-configuration.

The alkoxyiminocyclopropane oxaroxy fluorides of the invention can be prepared by esterification.

The process for the preparation of the active ingredient for the insecticidal and acaricidal composition according to the invention is characterized in that

(II), is reacted with a compound of formula III

H CH = N-OR ¹

(III), where

R ^1, D, m and n have ^the meanings indicated above ^EA

P and Q are functional groups capable of reacting with each other to form an ester bond.

The reaction generally proceeds expediently in the presence of triethylamine, preferably in a solvent such as ethyl acetate at reflux temperature. Alcohols and their reactive derivatives are known from U.S. Patent Nos. 4,218,469 and 4,276,306.

Acids are generally known from U.S. Patent Nos. 3,922,269, 4,282,249 and 4,292,325 and European Patent No. 5,882 and are prepared by reaction of a carboxylic acid or a reactive derivative thereof (as disclosed in U.S. Patent No. 3,922,269). with hydroxylamine or an O-substituted hydroxylamine of the formula r ^x onh ₂ , wherein

R ^X m ^and the above Uve ^d Eny meaning, and ^possibly and ^DE that R ¹ brand ^whose VOCl ^ n ^{with an L} Edna introduction ^d en ^s him ^hl ovo ^thanks s ^eh oz ^would t ^k u ^d of the resulting oxime, if desired by reaction with an alkyl halide and the like to form an alkoxide halide. Oxime formation can be effected by treating equimolar amounts of aldehyde and hydroxylamine or / a hydrocarbon residue / oxyamine in a polar solvent such as an alkanol, for example, ethanol or dioxane.

If the aldehyde is converted to the oxime by reaction with hydroxylamine and it is desired to convert the resulting oxime to its alkylated derivative, this reaction may be carried out by conventional methods used to alkylate phenols.

Thus, the oxime can be reacted in a polar solvent such as ethanol with an alkyl halide, especially an alkyl bromide, in the presence of a hydrogen halide acceptor, while heating the reaction mixture until completion of the reaction.

Oxime formation is conveniently performed using hydroxylamine or (hydrocarbon residue) oxyamine in the form of acid addition salts, for example in the form of the hydrochloride. In cases where m ^{and possibly} rav ^it a ^{compound to} ter ^{s rX} brand ^or me ^th yl, given к ^d axis ^t with ^p nose ^t ih ^yd roc ^hl chloride methoxylamine common to conduct the reaction in one step using methoxylamine hydrochloride.

In ^a case-that the ^p ot ^of EBN Get ready ^{e p} s ^{l i} n ^y compound act ^{in kt} erých ^R1 brand ^or sentences ^with ^ ^ pin is usually preferable to first prepare an oxime of the oxime and subsequently to introduce hydrocarbyl.

Alternatively, the compounds of the invention can be prepared by reacting the acid described in U.S. Patent No. 3,723,469.

The reaction is usually carried out in the liquid phase with stirring of the mixture of reactants. The resulting product is further processed in a conventional manner such as filtration, extraction and the like.

The reaction temperature is not critical and may range from room temperature to the reflux temperature of the solvent used at normal pressure.

The reaction medium may contain a small amount of additional solvent.

The invention includes insecticidal and acaricidal compositions comprising an insecticidally and acaricidally acceptable adjuvant, for example at least one surfactant carrier, and an active ingredient in the form of at least one insecticidally and acaricidally active ester of the invention.

The composition according to the invention causes the control of insects, mites or other harmful arthropod insects at the locus, comprising applying an insecticidally and acaricidally effective amount of at least one compound of the invention to the pest or locus thereof.

In terms of the spectrum of insecticidal and acaricidal activity, the compounds of the invention have a selective or non-selective effect on the orders of coleoptera, lepidoptera (especially in the larval stage), diptera, orthoptera, hemiptera, homoptera and acarina. .

The compositions according to the invention are very suitable for controlling disease-transmitting insects such as mosquitoes, flies, cockroaches, cereal pests such as rice weevil (Sitophilus oryzae) and mites, as well as harmful insects in agriculture such as flea beetles, lightning beetles Nephotettix bipuntatus cinticeps Uhler Plutella maculipennis Curtis, Pieris rapae Linne, Chilo supressalis Walker, larvae of Hellothis zea Boddie, mosquitoes, aphids, spider mites, weevils and the like.

Esters are used for field crops, gardens, forest stands and greenhouse crops.

The term carrier refers to an inert material, inorganic or organic and of a synthetic or natural nature, with which the active ingredient is mixed or formulated for better application to plants, seeds, soil and other objects to be treated or to facilitate storage, transport or treatment. The carrier may be solid or liquid.

Suitable solid carriers may be natural and synthetic clays and silicates, for example silicon oxides such as diatomaceous earth, magnesium silicates, for example talc). magnesium aluminum silicates such as attapulgites and vermiculites aluminum silicates such as kaolins, montmorillonites and mica, calcium carbonate, calcium sulfate, synthetic hydrated silicon oxides and synthetic calcium or aluminum silicates, elements such as carbon and sulfur, natural and synthetic resins such as coumaric resins, polyvinyl chloride and styrene polymers and copolymers, solid polychlorophenols, resins, waxes such as beeswax, paraffin wax and chlorinated mineral waxes, degradable organic solids such as ground corn flakes and nut shells and solids fertilizers such as superphosphate.

Suitable liquid carriers include solvents of the active agent of the invention and liquids in which the toxic agent is insoluble or sparingly soluble.

Examples of such solvents and liquid carriers are generally water, alcohols such as isopropyl alcohol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ethers, aromatic hydrocarbons such as benzene, toluene and xylene, petroleum distillation fractions such as kerosene, light mineral oils, chlorinated hydrocarbons such as methylene chloride, perchlorethylene, trichloroethane, including liquefied gaseous compounds that are normally in the gas phase. Mixtures of different liquids are also suitable.

If a surfactant is used, it may be an emulsifying or dispersing agent or a wetting agent. This may be of a non-ionic or ionic nature or preferably a mixture of both. Surfactants which are commonly used in the preparation of insecticides and acaridides may be used.

Examples of surfactants are the sodium or calcium salts of polyacrylic and lignin sulphonic acids, the condensation products of aliphatic acids or aliphatic amines or amides containing at least 12 carbon atoms in the molecule with ethylene oxide and / or propylene oxide, aliphatic acid esters of glycerol, sorbitan, sucrose or pentaerythritol low molecular weight aliphatic acids, mono-, di- and trialkylanines, condensation products of these compounds with ethylene oxide and / or propylene oxide, condensation products of aliphatic 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 metal or alkaline earth metal salts, preferably sodium sulfonated castor oil, and sodium alkylarylsulfonates such as sodium dodecylbenzene sulfonate and polymers and copolymers of ethylene oxide and propylene oxide. ’

The compositions of the invention may be formulated as wettable powders, dusts, granules, solutions, emulsifiable concentrates, emulsions, suspension concentrates or aerosols. To the extent

The invention also includes encapsulated and controlled release compositions such as bait formulations. Wettable powders are generally formulated to contain 25, 50, or 75% by weight of the active ingredient, and usually contain, in addition to a solid carrier, 3 to 10% by weight of a stabilizer or stabilizers and / or other additives such as penetration or sticking agents.

Dusts are typically formulated so that the dust concentrates have approximately the same content as the wettable powders, but without the dispersant. These are ranked in the field by another solid carrier to provide a composition containing about 0.5 to 10% by weight of the toxic compound.

The granules can be made by extrusion from plastic, by agglomeration or by impregnation techniques. Generally, the granules comprise 0.5 to 25% by weight of the toxic component and 10% by weight of additives such as stabilizers, slow release modifiers and binders.

Emulsifiable concentrates generally contain, in addition to the solvent and, if necessary, a co-solvent, 10-15% by weight of the toxic compound, 2-20% (w / v) emulsifier and up to 20% (w / v) suitable additives such as stabilizers, penetration corrosion inhibitors.

Suspension concentrates are formulated to provide stable, non-sedating, liquid products, typically containing 10 to 75% by weight of the toxic component, up to 5% by weight of dispersants, 0.1 to 10% by weight of suspending agents, as protective agents and thixotropic agents. up to 10% by weight of suitable additives, such as suds suppressors, corrosion inhibitors, stabilizers, penetration and adhesion promoters, and as a carrier a water or organic liquid in which the toxic component is substantially insoluble, wherein certain organic additives or inorganic salts are they can dissolve in a carrier to prevent sedimentation or as water-repellent agents.

Aqueous dispersions and emulsions, for example compositions obtained by diluting a wettable powder or an 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 exhibiting pesticidal, herbicidal or fungicidal properties, or attractants, such as pheromones, lure-inducing feed ingredients and the like, for use in bait and lure compositions.

Particularly suitable compositions are obtained by using a mixture of two or more kinds of compounds according to the invention or by using synergistic agents, such as those generally used with a group of pyrethroid compounds, in particular alpha- (2- (2-butoxyethoxy) ethoxy) -4 _of 5 methylenedioxy-2-propyltoluene, also referred to as pipexonyl butoxide, 1,2-methylenedioxy-4- [2- (octylsulfinyl) propyl] benzene, 4- (3,4-methylenedioxyphenyl) -5-ethyl-1,3-dioxane; _{<označovaný'rovněž} as safroxan N- / 2-ethylhexyl / bicyclo / 2.2 l / hept-5-ene-2,3-dikarboxanld, oktachlordipropylether, isobornylthiokyanoacetát and synerglcké other agents used to allethrln · and pyrethrin.

Suitable formulations may include other biologically active chemicals, including other cyclopropanecarboxylates, phosphate and carbamate type organic insecticides.

The compositions of the invention are used in an amount sufficient to provide an effective dose of the toxic agent at the site to be protected. This dose depends on many circumstances, including the carrier used, the method and conditions of application, and it is important whether the composition is present at the site of use in the form of aerosol, coating or discrete particles, coating thickness or particle size, insect species or mites. to be suppressed and the like

Only the person skilled in the art can make his own consideration and decide on all the above circumstances to ensure the necessary dose of the active substance at the site of use. In general, however, the effective dose of the toxic agent of the invention at the site of use - i.e. the application rate - is of the order of 0.01 to 0.5% based on the total weight of the composition, although in some cases the effective concentration is less than 0.001% or higher. than 2%, on the same basis.

The excellent activity of the cis- or (1R, cis) -form esters of the invention is particularly useful when such ester form is present in a substantially higher amount than is usually present in the alkoxyimino-substituted ester racemate.

It is preferred to use the cis- or (IR) cis -form esters of the invention in such a form substantially free of other stereoisomers, for example at a purity of the cis- or (IR) cis -isomer greater than about 70-85%, preferably with a purity of cis- or / lR, cis / -isomex greater than about 90%, or even greater than 95%.

The invention is illustrated by the following examples, which are given for illustrative purposes.

Example 1

^PU with ^b productions ^{by 3} - ^{phenoxy y} - ^{4-fluoro- b} enz ^y l / ^(L R, C ^{and S) -2,} ^ - ^ i ^ d ⁱ et ^hyl-3- ffisobutoxyimino) meth- ^hyl) cyclopropanecarboxylate /

^Mixtures of the reaction 1.0 ^g Selin ^{ky y} / R, cis / ^{-2, 2-di methylcarbazole} -3- (with ^s u ^{b t} ox ^{y imino)} met ^hyl) c o ^{p YKL} ropankarboxylové, 1.32 g of 3 phenoxy-4-fluorobenzyl ^b perfluorooctyl bromide and 0.48 g of triethylamine in 40 ml of ethyl acetate was heated to reflux.

After 17 hours, the reaction mixture is 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, then 100 ml of aqueous sodium chloride, dried and stripped to give 1.4 g of a viscous yellow oil.

This oil was chromatographed on silica eluting with 30% diethyl ether in hexane. 670 mg of the desired product are obtained.

Example 2.

OF^preindeer^y and^lfand-^kyano-3-^Fenox^y-4-^Fluor^benyl / (1R, c^andwith)-²,²-d^andme^thyl-³-^ff isobutox ^ i ^ no} methyl) cyclopropanecarboxylate /

To a solution ^of 1 ^g to ^y in ^{y l} (lR ^^ ^{i) -2,} 2- ^{dimethylphenyl yl} - ³ - ^{((i yi} utox with ^b m ^{i no) methylcarbazole) YKL} c o ^p ro ^{p to} an r ^b oxyl in 12 ml of toluene was added 0.33 g of potassium carbonate, 38 mg of tetrabutylammonium hydrogen sulfate and 20 mg of benzyltriethylammonium chloride in 8 ml of water and then 1.2 g of alpha-cyano-3-phenoxy-4-fluorobenzyl ^y lbromidu dissolved in 5 ml toluene.

D e ^AL can be ^at 3 m ^{y l} water and the mixture rea ^{CZK E} are ^H, and m ^ and ^{gro-IV and T} e ^pl ol ⁶⁰ ° ^C at night Res. 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 combined extracts were washed with brine, dried and stripped to give 1.5 g of a yellow oil. The oil was chromatographed on silica and 25% diethyl ether in hexane as eluent.

The product is re-chromatographed on silica eluting with a toluene / hexane / diethyl ether (42: 54: 2) mixture to give 700 mg of the desired product as an oil.

Example 3

Preparation of ^{3-phenoxy-3-fluorobenzyl} / ^{cis-2, 3-dimethyl-3} - ffneopentoxyimino) methyl) cyclopropanecarboxylate /

К extended ^h o ^and u tyseUny 0.47 g of cis-2,2-dimethyl-yl ³³ 3 ^{y f} (NNO ^p nnhoy ieino ^s) EET ^y y].) O ^p r ^s aiopro ^and rrOoyylové in 10 ml toluene was added 0 2 ^y gu polymeric meta potassium, 50 mg hetraOutyil ^ r oniuesuUfáhu 50mg Oenz ltrehyy ^{y y} lmioniimchloridu in 6 ml of water, then 0.58 g R 3-4-fenoyy fluorbenzylOromidu in 10 mi of toluene.

^r rakční mixture MIC ^Ya r zshřív pulsation ^and NS 55 RA 70 ° C overnight ocyirdí NR TE ^p) ol mu ^ s ^ i ^ Noos., poured into 150 mi water, NR r extracted. three times with 100 ml diethyl ether. The combined extracts are washed with aqueous sodium chloride solution, dried with magnesium sulfate and stripped.

0.98 g of a seamless oil is obtained. The crude oil was chromatographed over silica using 15 liters of heyr ether ether. 0.86 g of a solid product is obtained, which is free from viscous oil.

Example 4

Process for producing t) FT-altno- ^{3-phenoxy-4-yl} f) uxrbenz ^yl / cis-2,2-dmetУl1-3з ^(s fnnxpentoyyieinoχeet yl) cykloproptnkarboxylátu /

К solution of 0.47 g of cis22,3-diIneУh 3зЗ- ^y ¢ ^y nxPpentox ieinx) eeth ^y i) cyaУophoptmarrOoxy "LOVE toyuenu in 10 ml was added 0.5 g of potassium carbonate, 50 mg OenzyltrieУ ^y yt.mxniwecCУxX ^± з du with 50 mg of hetrabutyl-nitrile hydrophene in 6 ml of water followed by 0.89 g of .alpha.-cl-3-phenyl-4-fluorobenzyl (midu in 10 ml of toluene).

Reetoční mixture zt ^y iv ^and overnight NR ^l ep ^t x ^t at 75 ° C, O-Ra! м ta ^ ol ^eíítnxoSi, VyUje na · 100 ml of water, extracted three times with 50 ml R dávkrmi dietУl) etУeru. The combined extracts were dried with magnesium sulphate and stripped.

1.15 g of an oil is obtained, and the crude oil is chromatographed on silica, eluting with diethyl ether. 1.02 g of a clear product of a viscous yellow oil is obtained.

P Example 5.

Method of productions ^would enxx 3- ^f 4- ^{f y} luxR ^about NNZ ^yl / ^(lR, cis) - ^{2, 2} - ^d ieethhl- ³ - ((NTO nn ^{p h y} ieino Oy) EET ^{hy l) 3} cya) xproptnkarbeoylate /

Pxstupem ^p o ^p san ^{characterized} mv BC ^ LSDU ^3, the NEC ^YA R gov ^ a mixture of O, ^{65 g} kfseHny ^{(lR, cis)} 3 ^{2, 3} DI3 neo ^p entox ^y ieinx) ee ^nt l ^h l ^l) C ^YKi x> ^p ro ^p tn ^to srbxx ^y LXVe ^{0.6 g} u ^y if ^no Itin a potassium ^ s ^ o, ⁶⁰ 'm ^g. hntrabutytmxniueУhdrrχennslfáhu R 60 m ^g OenzylhrneУ tenoniιec ^{yy y} lxridu in water with 0.81 grams of toluene-3-fnnχyyз4 flxeebenzyebroeidu.

Following the procedure of Example 3, 1.42 g of crude product was obtained. After chromatographic purification, 0.77 g of a clear product is obtained.

P Example 6

Process for producing t) FT-altnx ^з FEN-xx ^3-yl-4-yl fluxr0enz / · (iR CLS) - ² 2ddientУyl- ^Зff, nexopnntχyl ^з imino-ethyl) cyaУxproptnkarboxylátu /

К solution of 0.82 ^g ^ 861 ^ ^{(lR, cis)} з ^{2 2} - ^d ieet yl ^{H 3} - ^{P fn} neo ^entoxyieinx) EET ^h y ^{y) y CY} lxprxptnatroxx LXVe in 10 ml toluene was added 0.62 60 mg of triphenylmethylammonium sulfate and 60 mg of benzyltriethylammonium chloride in 8 ml of water and then 1.1 g of alpha-cyano-3-phenoxy-4-fluorobenzyl bromide in 10 ml of toluene. The reaction mixture was heated at 75-80 ° C for 18 hours, cooled to room temperature, poured into 300 mL of water, and extracted three times with 100 mL portions of diethyl ether. The combined extracts were washed with brine, dried over magnesium sulfate and stripped.

1.44 g of a yellow oil are obtained. This oil was chromatographed on silica eluting with 25% diethyl ether in hexane. 1.22 g of the expected product is obtained in the form of a yellow oil.

The NMR peaks of the compounds of Examples 1-6 are summarized in the table below. The values represent the chemical shift reported in ppm relative to tetramethylsilane as a standard in CDCl 3 solution.

Table 1

The compound of Example no.

Chemical shift / ppm /

0.9 (d, 6H / 1.21 / d, 6H / 1.6-2.5 / m, 3H)

3.75 (dd, 2H) (4.9), 2H (6.7-7.7 (m, 9H))

0.9 / d, 6H / 1.21 / dd, 6H / 1.6-2.5 / ш, ЗН /

3.75 / т, 2Н / 6.2 / d, 1H / 6.7-7.7 / т, 9Н /

3 0.9 (s, 9H) 3.7 (d, 2H) 4 0.9 (s, 9H) 3.7 / t, 2Н / 5 0.9 (s, 9H) 3.7 / t, 2Н / 6 0.9 (d, 9H) 3.7 / t, 2Н /

1.2 / dd, 6H / 1.6-2.0 / т, 2Н /

4.95 / s, 2H / 6.7-7.7 / т, 9Н /

1.2 / m, 6H / 1.6-2.0 / t, 2N /

6.2 / т, 1Н / 6.6-7.6 / т, 9Н /

1.2 / dd, 6H / 1.6-2.0 / т, 2N /

4.95 / s, 2H / 6.7-7.7 / t, 9N / <

1.2 / т, 6Н / 1.6-2.0 / т, 2Н /

6.2 / d, 1H / 6.6-7.6 / т, 9Н /

Example 7

Insecticidal and acaricidal effect

The effect of the compounds of the invention in controlling insects and mites was determined by the following procedure:

I. House flies (Musea domestica) were tested by placing 50 5 day old house flies in a dusting chamber and spraying with 0.6 ml of test compound solution. After spraying, the flies were anesthetized with CO ₂ and transferred to a recovery chamber containing the milk crust as food.

After 18 to 20 hours, the number of dead flies was determined. This included dead and paralyzed flies. Assays were performed using several different doses of the test compound.

II. Pea Aphids (Acyrthosiphon pisum / Haris //) were tested by placing about 100 aphids on bean plants. Plants were sprayed with dilute acetone solutions of the test compound in water and containing an emulsifier and left under laboratory conditions for 18-20 hours, after which live aphids were counted in reservoirs. Assays were performed using different doses of each of the test compounds.

III. Adult female mites (Tetranychus urticae / Koch) were placed 50 to 75 individuals on the underside of bean leaves. The leaves were sprayed with dilute acetone solutions of the test compound in water containing an emulsifier and maintained under laboratory conditions for about 20 hours, after which mortality was determined. The tests were repeated with different doses of the active compound.

IV. Heliothis zea (Boddie) larvae were tested by spraying the bean plants with dilute acetone solutions of the test compound in water containing an emulsifier. Immediately after spraying, 5 larvae were transferred to the plant and left for 44 to 46 hours, after which the sum of dead and paralyzed larvae was determined. Assays were performed with different doses of each of the test compounds.

The toxicity of the compounds of the invention was compared to the toxicity of the standard pesticide (Parathion), wherein the relative toxicity was expressed as the relationship between the amount of the compound of the invention and the amount of standard pesticide needed to achieve the same percent (50) mortality of test insects and mites.

The dose of the standard pesticide was designated as 100 and the toxicity of the compounds of the invention was expressed in relative values comparing the toxicity of the compounds of the invention with that of the standard resticide.

This means that a test compound with a toxicity index of 50 will have half the potency, while a compound with an index of 200 will be twice as potent as the standard pesticide. The toxicity indices are given in Table II.

It has been found that the compounds of the present invention have unexpectedly greater potency in controlling certain insects, especially Helithis zea (Boddie) larvae and mites than the corresponding, structurally very similar compounds described in U.S. Patent Nos. 3,922,269, 4,211,792, 4,282,249 and 4,292,325.

Claims (1)

SUBJECT OF THE INVENTION Insecticidal and acaricidal composition comprising an active ingredient and at least one surfactant or carrier, characterized in that it comprises as active ingredient a compound of the general formula I wherein: R ^{1 BC} e ^d st.avuje Al ^alkyl with ^the nominal ^pi nu u ^{t o} 6 carbon uh!. ^^ represents hydrogen or cyano and each of that when m and n each independently is 0 or 1 and the sum of m and n is 2, with the proviso, is cyano, then the alcohol moiety. it is in RS-racemic or S-optical config2. A process for the preparation of an active compound of the formula I as described in 1, characterized in that (11) is reacted with a compound of formula III H CH = N-OR ¹ _CH3 H ^kd e R ^{3, D,} m and n have the meanings Uve ^{d b} of said preceding and ^{DE 1/111} /, P and Q are functional groups capable of reacting with each other to form an ester bond.