CS196210B2 - Insecticide and acaricide and process for preparing effective compounds - Google Patents

Description

The present invention relates to an insecticidal and acaricidal composition comprising as active ingredient novel substituted phenoxybenzyloxycarbonyl derivatives. The invention further relates to a process for the preparation of these novel insecticidal and caricidal active compounds, as well as to novel intermediates used for the preparation of these active compounds.

It is already known that phenoxybenzyl acetates or carboxylates, for example. 3'-phenoxybenzyl-α-isopropyl (3,4-dimethoxy- or 4-bromo-, 4-fluoro- and 3,4-dioxymethylenophenyl acetate); and 3'-phenoxybenzyl [2,2-dimethyl-3- ( 2,2-bis (cyclopropane) carboxylate have insecticidal and acaricidal properties (cf. DOS 2,335,347 and Belgian patent specification 801946).

It has now been found that the novel substituted phenoxybenzylcarbonyl derivatives of formula (I)

O-CO-R ³ wherein

R 1 and R 1 are different from each other and are hydrogen, fluoro or bromo,

R2 is cyano or ethyl

R ³ is a residue.

where

R 4 and R ⁵ are the same and represent chloro, bromo or methyl, or a radical of the formula -CH-R 6

I CH of \

H3C · CH3 where

R6 is optionally halogen, alkyl, alkylthio, C1-C4alkoxy,

198210

nitro, methylenedioxy · substituted phenyl radical, and R ² represents hydrogen, if. .

R ³ represents a radical

whereas

R ⁴ and R ⁵ are the same and are chlorine or bromine or a radical of the formula -CH-R ⁶

I CH / \ СНз CH3 where

R ⁶ has the meaning indicated above, are distinguished by a powerful insecticidal and acaricidal activity. . '

Preferred are the substituted phenoxybenzyloxycarbonyl derivatives of the general formula I in which:

R is fluorine or bromine,

R ¹ represents hydrogen or fluorine,

R2 is cyano or ethynyl; and

R 3 is 2,2-dimethyl-3- (2,2-dichloro- or 2,2-dibromo) and 2,2 - ((R) - (R) - (R) - (R) - (R) - (R) - (R) -I)] a cyclopropane radical, an α-isopropylbenzyl radical which is optionally substituted one or more times in the ring by the same or different radicals selected from the group consisting of fluorine, chlorine, bromine, methylenedioxy, methoxy, ethoxy, methylthio, ethylthio, straight or branched (C1-C3) alkyl and / or nitro, and

R2 is hydrogen if

R 3 represents a 2,2-dimethyl-3- (2,2-dichloro- and 2,2-dibromvinyl) cyclopropane radical, an α-isopropylbenzyl radical which is optionally substituted one or more times in the ring by the same or different radicals selected from from the group consisting of fluorine, chlorine, bromine, methylenedioxy,. methoxy, ethoxy, methylthio, ethylthio, straight or branched (C 1 -C 3) alkyl and / or nitro.

The general formula (I) here comprises various possible stereoisomers, optical isomers. and mixtures thereof.

According to the invention, the novel substituted phenoxybenzyloxycarbonyl derivatives of the formula I are obtained by reacting the carbonyl halides of the formula II

Hal — CO — R ⁵ (Π) in which

R 3 is as defined above, and

Hal means halogen; preferably chloro, with substituted phenoxybenzyl alcohols of formula III

in which

R 1, R 1 and R 2 are as defined above, optionally in the presence of an acid binding agent and optionally in the presence of a solvent at temperatures between 0 and 100 ° C.

Surprisingly, the substituted phenoxybenzyloxycarbonyl derivatives exhibit. according to the invention. better insecticidal and acaricidal activity than the corresponding known products of analogous structure and the same type of action. Thus, the products of the present invention represent a true enrichment of the prior art.

. For example, if 3- (3-fluorophenoxy) -α-cyanobenzyl alcohol and diisopropyl-4-ethoxyphenylacetic acid chloride are used as starting materials, the reaction scheme may be illustrated as follows:

CH

Cl-COCH

oc _z h _p

9 '6' -2Г0

The starting materials used for this reaction are generally defined by Formula II '. and III. In these formulas, the general symbols have the following preferred meanings:

Ø means. fluorine or bromine,

R 1 is hydrogen · or fluoro, ·

R ² represents vqdík, cyano or ethynyl 'group and

R ³ is 2,2-dimethyl-3- (2,2-dichloro- or 2,2-dibromo and 2,2-dimethyl-cyclopropane). a radical, an α-isopropylbenzyl radical, which is optionally substituted in the ring one or more times by the same or different. . residues selected from the group consisting of fluorine, bromine, bromine, methylenedioxy, .beta.-oxy, ethoxycycline (methyl) (quinine). ethylthio, straight or branched alkyl having 1. . up to 3 carbon atoms and / or nitro group. . '. . - v. ··

Carbones - halides - specimen. II used as starting materials. are ·. ' They are known and can be prepared according to generally conventional methods described in the literature (cf., for example, DOS 2,365,555; 1,926,433 and 2,231,312). ’

Examples of such compounds are: 2,2-dimethyl-3-cyclopropanecarboxylic acid, 6-chloro acid, 2,2-dimethyl-3- (2,2-dibromvinyl) cyclopropanecarboxylic acid chloride. acid, 2,2-dimethyl-3 - ((2) (2-dimethylvinyl) cyclopropanecarboxylic acid chloride), isoisopropylphenylacetic acid chloride; chloride, .alpha.-isopropyl-4-fluorophenyl '''acetic _acid: \ ioopropyl chloride α-4-chloгfenyIOctové acid -.,. <> ·· chloride and isopropyl-4-rrrmfenyloctové. α-isopropyl-4-methylphenylacetic acid chloride α-isopropyl-4-ethylphenylacetic acid α-isopropyl-4-n-propylphenylacetic acid chloride. Α-SSprprprp chlor chlor chlor 4 4 4 4 4 4 4 4 4 4 4. ,.

α-CsQp-ΌpyM-methoxyphenylacetic chloride. α-isopropyl-4-alkoxyphenylacetic acid chloride,. ., <·.

α-Csoproryl-4-deadlythiophenylacetic acid chloride:%, α-isopropyl-4-ethylthiophenylacetic acid chloride. acids,. . .:. . Α-isopropyl-4-nitrophenylacetic acid chloride,. w. ·. <. Α-α-β-propyl- 3 3 -fluorophenylacetic acid chloride,. α-Isopropyl-3-b'-phenylacetic acid chloride. Α-Csopropyl-3-chloro-phenylacetic acid chloride, α-Co-propyl-3-methyl-phenylacetic acid chloride, α-10-propyl-3-ethyl-phenylacetic acid chloride, C1-iso-propyl-3-methoxy-phenylacetic acid chloride , .alpha.-isopropyl-3-ethoxyphenylacetic acid chloride, (.alpha.-propyl-3-methylthiophenylacetic acid chloride), .alpha.-iso-propyl-3-ethylthiophenylacetic acid, .alpha.-Cs-propyl-3,4-methylenedioxyphenylacetic acid.

The phenoxyrenzylalcohol (III) used below as starting materials is novel.

These compounds are prepared by the use of the phenoxybenzaldehydes of formula IV

CHO

v. which

R and R ¹ have the abovementioned meanings,

a) v. event,. that R2 is hydrogen reduced with a complex metal hydride in an inert solvent,

(b) in the case where R 2 is cyanocurine, reacted with an alkali metal cyanide, for example sodium cyanide or potassium cyanide, in the presence of an acid, optionally with the addition of a solvent; or

c) in the case where R2 is an ethynyl group, react with an ethynyl derivative of the formula V;

HC = C — MgHal '(V) in which

Hal is halogen,. in a suitable solvent.

If, for example, 3- (3-fluorophenoxy) benzaldehyde and lithium aluminum hydride are used in the process of Alternative a), in the process of Alternative b) 3- (2-fluorophenoxy) benzaldehyde and potassium cyanide and in the process of Alternative c) 3- (4-rgomphenoxy) benzaldehyde a. ethCnylmagneoium bromide, then the reaction sequence can be illustrated by the following reaction schemes:

19821V &), 4X

F

1.) ₊ ^ _L h h y, y

· 2 + _2Η ζ ϋ

(b)

F

CHO

СНзСО-ОН + KCN —----->

~ _CH3 O (O) K

CH 2 OH + 11ALO 4 ^{/ C} CH-OH

C = CH CH-OH

CHO

The starting materials used are unambiguously defined by formulas II and III. In these formulas, the general symbols have the following preferred meanings:

R is fluorine or bromine,

R ¹ represents hydrogen or fluorine and

HaI means bromine.

Ethylderivatives of formula V are described in the literature, as are alkali metal cyanides and complex metal hydrides.

The phenoxybenzaldehydes of the formula IV can be prepared in general. by conventional methods, for example by reacting the corresponding phenoxybenzyl halides of formula (VI), which are prepared by conventional methods from the corresponding phenoxytoluenes, with hexamethylenetetramine according to the following reaction scheme:

RR ¹

CHO> Θ

НеЛ

+ 3 NH3b 5 H _Z CO

HC 1 NH 4 H & L (IV) wherein R and R 1 are as defined above and

Hal is halogen.

As . examples of the phenoxybenzaldehydes used for the reaction according to the invention can be individually mentioned:

3- (4-fluorophenoxy) benzaldehyde,

3- (3-fluorophenoxy) benzaldehyde,

3- (2-fluorophenoxy) benzaldehyde,

3- (4-bromophenoxy) benzaldehyde, 3- (3-bromophenoxy) benzaldehyde,

3- (2-bromophenoxy) benzaldehyde, 3-phenoxy-6-fluorobenzaldehyde. ·

Process variants a) to cj for the preparation of the compounds according to the invention are preferably carried out using suitable solvents and diluents. .

In carrying out variant (a), suitable solvents are preferably ethers, such as diethyl ether, tetrahydrofuran, dioxane, as well as hydrocarbons, such as toluene and petrol. When using sodium borohydride as a reducing agent, water, alcohols such as methanol, ethanol, nitriles such as acetonitrile or propionitrile may additionally be used. In carrying out variant b), suitable solvents are preferably water, alcohols such as methanol, ethanol or ethers such as diethyl ether, tetrahydrofuran or nitriles such as acetonitrile. Ethers such as diethyl ether, tetrahydrofuran and dioxane are preferably suitable for variant (c).

Complex metal hydrides in process variant c) are preferably lithium aluminum hydride and sodium borohydride.

As acids in process variant bj, inorganic acids such as hydrochloric acid or sulfuric acid or organic acids such as acetic or formic acid may be used.

The reaction temperature can be varied over a wide range in all processes. In general, temperatures of from -10 ° C to 110 ° C;

in variant a) preferably at 0 to 60 ° C, in variant b) preferably at -5 to 20 ° C, in variant c) preferably at 0 to 80 ° C.

The reaction is usually allowed to proceed at atmospheric pressure.

In carrying out variant a), the reactants are preferably used in equimolar amounts. Excess of one or the other component brings no advantage. In variant b), cyanide is used in an ICU of up to 15U% excess. In variant c), the ethynyl derivative is used in a 20 to 50% excess. The reaction is preferably carried out in one of the above solvents or diluents at the indicated temperatures under stirring. After a reaction time of one to several hours, usually at elevated temperature, the reaction mixture is worked up by generally conventional methods.

The novel compounds are obtained in the form of oils, which can either be distilled off or, by so-called "distillation", i.e., by longer heating under reduced pressure to slightly elevated temperatures, free of the last volatiles and in this way purified. Refractive index or boiling point serve for their characterization.

Examples of novel phenoxybenzyl alcohols which are useful in the preparation of the phenoxybenzyloxycarbonyl derivatives of the invention are individually mentioned.

3- (4-fluorophenoxy) -6-fluorobenzyl alcohol

3- (4-fluorophenoxy) benzyl alcohol 3- (3-fluorophenoxy) benzyl alcohol 3- (4-bromophenoxy) benzyl alcohol 3- (3-bromophenoxy) benzyl alcohol 3- (2-fluorophenoxy) benzyl alcohol 3- (4-fluorophenoxy) 3'-cyanobenzyl alcohol 3- (3-fluorophenoxy) 3'-cyanobenzyl alcohol 3- (4-bromophenoxy) -a-cyanobenzyl alcohol 3- (3-bromophenoxy) -a-cyanobenzyl alcohol 3- (2-fluorophenoxy) -a- 3- (2-bromophenoxy) -α-cyanobenzyl alcohol 3- (4-fluorophenoxy) -of-ethynylbenzyl alcohol 3- (3-fluorophenoxy) -ethynylbenzyl alcohol 3- (4-bromophenoxy) -a 3- (3-bromophenoxy) -α-ethynylbenzyl alcohol 3- (2-fluorophenoxy) -α-ethinynylbenzyl alcohol 3- (2-bromophenoxy) -α-ethinylbenzyl alcohol.

In the preparation of the phenoxybenzyloxycarbonyl derivatives of the invention, all conventional acid binding agents can be used as acid binding agents. Of particular note are alkali carbonates and alkoxides. metals such as sodium and potassium carbonate, sodium and potassium ethoxide and optionally ethoxide, and also aliphatic, aromatic or heterocyclic amines, for example triethylamine, trimethylamine, dimethylaniline, dimethylbenzylamine and pyridine.

The reaction temperature can be varied within a wide range. In general, the reaction is carried out at temperatures between 0 and 100 ° C, preferably at 15 to 40 ° C.

The reaction is usually allowed to proceed at atmospheric pressure.

The process for preparing the compounds of the invention is preferably carried out using suitable solvents and diluents. As such, virtually all inert organic solvents are suitable. These include in particular aliphatic and aromatic or chlorinated hydrocarbons such as benzene, toluene, xylene, petrol, methylene chloride, chloroform, carbon tetrachloride, chlorobenzene, or ethers such as diethyl ether and dibutyl ether, dioxane, ketones such as acetone, methyl ethyl ketone, methylisopropyl ketone; methylisobutylketone, and nitriles such as acetonitrile and propionitrile.

In carrying out the process, the starting materials are preferably used in equimolar ratios. Excess of one or the other reactant does not bring any significant advantages. The reactants are generally reacted in one of the above solvents, and mostly at elevated temperature, the reaction mixture is stirred for one or several hours to complete the reaction. The reaction mixture is poured into water, the organic phase is separated and washed with water. After drying, the solvent was distilled off in vacuo.

The novel compounds are obtained in the form of oils, which in part cannot be distilled without decomposition, but by so-called "distillation", i.e. by heating under reduced pressure to moderately elevated temperatures, the last volatiles are freed and purified in this way. Refractive index is used for their characteristics.

As mentioned several times, the substituted phenoxybenzyloxycarbonyl derivatives of the invention exhibit excellent insecticidal and acaricidal activity.

The active compounds according to the invention have good plant compatibility and favorable warm-blood toxicity and are suitable for controlling pests, in particular insects, spider mites and nematodes in agriculture, forestry, in the protection of stocks and materials, as well as in hygiene. They are effective against normally susceptible and resistant species as well as against all or only individual stages of development of pests. The above mentioned pests include:

from the order of the Isopods, for example Oniscus asellus, Armadillidium vulgare, Porcellio scaber;

from the class of the Diplopoda, for example Blaniulus guttulatus;

from the class of the Chilopoda, for example Geophilus carpophagus, Scutigera spec.

from the class of the Centipede (Sympbyla), for example, Scutigerella immaculata;

from the order of scales. . . (Thysanura), for example, fish (Lepisma saccharina);

from the order of the Collembola, for example:

larva. (Onychiurus armatus);

from the order of the Orophoptera, such as the cockroach (Blatta orientalls), the cockroach (Periplaneta americana), Leucophaea madérae,.

Domestic Russian (Blattella. germanica),. House cricket (Acheta domesticus), n «+ u-nurib«, t 11 ^ + nl i-u o, OX ~. «^ CL \

Ml HJllUijnu U1 У nuiuipu ppCb.Jj Locusta migratoria migratorioides,

Melanoplus differentialis, Schlstocerca gregaria;

from the order of the Dermaptera, for example Forficula auricularia;

from the order of the term of term. (Isoptera), for example, Reticulitermes spec.

from the order of the Anoplura, for example Phylloxera vastatrix, Pemphigus spec., Pediculus humanus corporis, Haematopinus spec., Linognathus spec .;

from the order of the Mallophaga, for example, Trichodectes spec., Damalinea spec .; .

from the order of the Thysanoptera, for example Hercinothrips femoralis, Thrips tahaci;

from the order of the Heteroptera, for example Eurygaster spec. Dysdercus intermedius, Beetle (Piesma. Quadrata), Bed Bug (Cimex lectularius), Rhodnius prolixus, Triatoma spec .;

from the order of the winged hens (Aleurodes brassicae), Bemisia tabaci, greenhouse aphid (Trialeurodes vaporariorum), cotton aphid (Aphis gossypii), green aphid (Brevicoryne brasszica), fish aphid Cryptomyzus ribis), poppy aphids (Doralis fabae), apple aphids (Doralis pomi), bloody aphids (Eriosoma lanigerum), aphids (Hyalopterus arundinis),

Macro.siphum avenae,. Myzus spec.

hop aphids (Phorodon humuli), bird aphids (Rhopalosiphum padi), peacock (Empoasca spec.), leafhopper (Euscelis bilobatus), Nephotettix cincticeps, Lecanium. corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spec., Psylla spec.

from the order of the butterflies (Lepldoptera), for example TI o r4-4 va ovxVx rsvxn crorr v vxA rx 11 λ 4 t / U UllUJXlUl UL r j piu Dark-spot Pug (Bupalus piniarius),

Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea ^ m. ), Bucculatrix thurberiella, Phyllocnistis' citrella, Agrotis spec., Euxoa .spec.,

Feltia spec.,

Earias insulana, * Heliothis spec., Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia litura,

Spodoptera spec., Trichoplusia ni, Carpocapsa pomonella, White (Pieris spec.), Chilo spec. carnation (Cacoecia podana),

Capua reticulana, Choristoneura fumiferana

Clysia ambiguella, Homona magnanima, Tortrix viridana;

- of the order of the beetles (Coleoptera), for example, Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastelotea ala, ), Colorado beetle (Phaedon-coch leariae),

Diabrotica spec. Oilseed flea beetle (Psylliodes chrysocephala),

Epilachna varivestis, Atomaria spec., Oryzaephilus surinamensis, Anthonomus spec., Sitophilus spec., Otiorrhynchus sulcatus,

Cosmopolites sordidus, Ceu.thorrhynchus assimilis,

Hypera postica,. Dermestes spec., Trogoderma spec.,:

Towel (Auílireuus spec.), Skin-beetle (Attagenus spec.), Lumpfish (Lyctus spec.), Rape (Meligethes aeneus), Helicopter (Ptinus spec.), Helicopter (Niptus hololeucus), Gibbium psylloides, Darkworm (Tribolium spec.). ), Tenebrio molitor, Agriotes spec.

Conoderus spec ,, Melolontha melolontha, Amphimallon · solstitialis,

Cosielytra zealandica;

from the order of the Hymenoptera, for example Diprion spec., Hoplocampa spec., Lasius spec., Monomorium pharaonis, Vespa spec.

of the order Diptera, for example, the mosquito (Aedes spec.), anofeles (Anopheles spec.), mosquito (Culex spec.), fruit fly (Drosophila melanogaster), fly (Musea spec.), sunflower (Fannia spec.). ), the buzzer. (Calliphora erythrocephala), buzz (Lucilia spec.),,

Chrysomyia spec., Cuterebra spec., Gastrophilus spec., Hyppobosca spec., Stomoxys spec., Oestrus spec., Hypoderma spec., Tabanus spec., Tannia spec. ., 'Garden Flycatcher' (Bibio hortulanus), Barberry (Oscinella frit),

Phorbia spec., Beetle (Pegomyia hyoscyami), Propeller (Ceratitis capitata),. Dacus oleae, Tipula paludosa; ?

from the order of the Slphonaptera, for example, Xenopsylla cheopis, Ceratophyllus spec.

from the order of Arachnida, for example

Scorpio maurus, Weaver (Latrodectus mactans);

from the order of the mites (Acarina.), for example Acarus broad;

Argas (spec.), Ornithodoros spec., Dermanyssus gallinae, Currant (Erlophyes ribis), Phyllocoptruta oleivora, Eat (Boophilus spec.), Rhipicephalus spec., Amblyomma spec. .),

Hyalomma spec., Ixodes spec., JPsoroptes spec., Chorioptes spec., Sarcoptes spec., Tarsonemus spec., Bryobia praetiosa, Panonychus spec., Spider mite. (Tetranychus spec.).

Phytopathogenic nematodes include Pratylenchus spec., Radopholus similis, Ditylehchus dipsaci, Tylenchus semipenetrans, Heterodera spec., Meloidogyne spec., Aph. Xiphinema spec., Trichodorus.

The substances according to the invention have potent ectoparasiticidal or tickicidal properties, in particular against ticks which, as animal ectoparasites, attack domestic animals such as cattle and sheep. At the same time, the active compounds according to the invention have a favorable warm-blooded toxicity. It is therefore well suited for combating animal ectoparasites, especially ticks.

As economically important ectoparasites of this type, who in particular. tropical and subtropical countries' are of great importance, for example: Australian and South American tick (Boophilus microplus), South African tick (Boophilus decoloratus), both of the Ixodidae family, an African polyvalent tick that attacks cattle and sheep such as for example, a drinker (Rhipicephalus appendiculatus), a drinker (Rhipicephalus evertsi), Amblyomma hebraeum, Hyalomma aruncatum, as well as South American polyvalent ticks that attack cattle such as Amblyomma cajennense and Amblyomma americanum.

Over time, such ticks have become consistent with phosphoric acid esters and carbamates, used hitherto as pest control agents, so that the outcome of this control has become increasingly illusory in many areas. In order to ensure economical livestock farming, there is an urgent need for means to combat all developmental stages, ie larvae, metalarva, nymphs, metanymphs and adults, as well as resistant strains such as the genus Boophilus. Mackay, Mt-Alfort and Biarra tick strains (Boophilus microplus) are highly resistant to existing phosphoric acid ester compositions in Australia, for example.

The active compounds according to the invention are equally effective against both normally sensitive and resistant strains of, for example, tick (Boophilus j. Lyto substances, when applied to a livestock animal, cause direct killing of all forms parasitic in the animal. the animal interrupts.

The laying of fertile eggs and thus the development and removal of larvae is inhibited.

The application is carried out, for example, in the form of. The active substances must remain stable for 6 months or more in the contaminated and microbial attack exposed to the water bath. Other application forms are sprays and baths.

In all dosage forms, the compounds according to the invention have perfect stability, i.e. no decrease in activity was observed after 6 months.

The active ingredients may be converted into the customary formulations such as solutions, emulsions, wettable powders, suspensions, powders, dusts, foams, pastes, soluble powders, granules, aerosols, concentrates based on suspensions and emulsions, seed dressing powders, natural and synthetic active substances impregnated, small particles coated with polymeric substances and seed coatings, furthermore compositions with flammable additives such as smoke cartridges, smoke trays, smoke spirals and the like, as well as formulations of active substance concentrates for mist dispersion cold or hot.

These compositions are prepared in known manner, for example by mixing the active ingredient with fillers, i.e. liquid solvents, liquefied gases under pressure and / or solid carriers, optionally using surfactants, i.e. emulsifiers and / or dispersants and / or foaming agents. If water is used as a filler, it is also possible to use, for example, organic solvents as co-solvents. Basically suitable liquid solvents are: aromatics such as xylene, toluene or alkyl naphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, for example petroleum fractions, alcohols such as butanol or glycol and their ethers and esters; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; strongly polar solvents such as dimethylformamide and dimethyl sulfoxide; and water. By liquefied gaseous fillers or carriers is meant those liquids which are gaseous at normal temperature and pressure, for example aerosol propellants such as halogenated hydrocarbons, as well as butane, propane, nitrogen and carbon dioxide. Suitable solid carriers are: natural stone meal, such as kaolins, alumina, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and synthetic stone meal, such as highly disperse silica, aluminum oxide and silicates. Crushed and fractionated natural stone materials, such as limestone, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic flours, and granules of organic material such as sawdust, coconut shells, are suitable solids for the preparation of granules. nuts, corn sticks and tobacco stalks. Suitable emulsifiers and / or foaming agents are non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g.

The compositions of the invention may include adhesives such as carboxymethylcellulose, natural and synthetic powdered, granular or latex polymers such as gum arabic, polyvinyl alcohol and polyvinyl acetate.

In addition, these compositions may contain coloring agents such as inorganic pigments, for example iron oxide, titanium dioxide and ferrocyanide blue, and organic dyes such as alizarin dyes and metallic azo-phthalocyanine dyes, as well as trace elements such as iron, manganese, boron, copper, cobalt, molybdenum and zinc.

The concentrates generally contain between 0.1 and 95% by weight, preferably between 0.5 and 90% by weight, of the active ingredient.

The active compounds according to the invention can be used in the form of commercial preparations and / or in dosage forms prepared from these preparations.

The content of active ingredient in dosage forms prepared from commercial preparations can vary within wide limits. The concentration of the active ingredient in the dosage forms can range from 0.0000001 to 100% by weight, preferably from 0.01 to 10% by weight.

The application is being performed. in a conventional manner adapted to the application form used.

When used against hygiene pests and against storage pests, the active compounds according to the invention are distinguished by excellent

В 210 by residual effect on wood and clay and good stability to alkalis on lime substrates.

Example A

Test for peach aphid (Myzus persicae) - contact effect

Solvent: 3 parts by weight of acetone. 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable active ingredient, 1 part by weight of the active ingredient is mixed with the indicated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.

Cabbage (Brassica oleracea) plants heavily infested with peach aphids (Myzus persicae) are sprayed with the prepared active ingredient until dripping.

After a period of time below, mortality was found in%. 100% means that all aphids have been killed, 0% means that no aphids have been killed.

□ The active substances, active substance concentrations, evaluation time and results obtained are given in Table 1 below:

Table 1

Aphid test (Myzus) - contact effect

Active substance Concentration of active substance in%

Mortality in% after 1 day

100 ALIGN!

(Х.И & М1)

0.1

0.01

0.001

100 ALIGN!

0

100 100 *

100 ALIGN!

100 ALIGN!

100 ALIGN!

100 ALIGN!

0.1

0.01

0.001

100 ALIGN!

100 ALIGN!

100 ALIGN!

Mortality in% after 1 day

Concentration of the active substance in ° / o

Active substance

/ ^CN CH o-co

0.001

CH ₃ CH,

/ \ CH. CH

CN

O-CO-CH

100 ALIGN!

100 ALIGN!

100 ALIGN!

100 ALIGN!

100 ALIGN!

100 ALIGN!

100 ALIGN!

100 ALIGN!

100 ALIGN!

100 '

100 ALIGN!

100 ALIGN!

100 ..

100 ALIGN!

100 ALIGN!

100 ALIGN!

100 ALIGN!

100 ALIGN!

100 ALIGN!

100 ALIGN!

100 ALIGN!

Mortality in% after 1 day

Active substance concentration in%

Active substance

0.1

0.01

0.001

100 ALIGN!

100 ALIGN!

100 ALIGN!

0.1

0.01

0.001

100 ALIGN!

100 ALIGN!

100 ALIGN!

CW3 'cm ₃

0.1

0.01

0.001

0.1

0.01

0.001

100 ALIGN!

100 ALIGN!

100 ALIGN!

100 ALIGN!

100 ALIGN!

100 ALIGN!

0.1

0.01

0.001

100 ALIGN!

100 ALIGN!

100 ALIGN!

0.1

0.01

0.001

100 ALIGN!

100 ALIGN!

100 / CN

H ₃ c CH ₃

0.1

0.01

0.001

100 ALIGN!

100 ALIGN! 95

0.1

0.01

0.001

100 ALIGN!

100 ALIGN!

100 ALIGN!

196210 20

Concentration Mortality in% of active substance in% after 1 day

Active substance

C = CH

CH

100 ALIGN!

100 ALIGN!

^X-CO-CH = CH-C ^H

Cl = c

Cl

0.1

0.01

0.001

100 ALIGN!

100 ALIGN!

CH, CH,

O-CO-CH-CH-CH =

CN

CN

CH ₂ CH ₂ .

O-CO-CH

CH C = CH

& 0.1 100 ALIGN! / 0.01 100 ALIGN! C 0.001 100 ALIGN! 0.1 0.01 100 ALIGN! 100 ALIGN! 0.001 80 0.1 100 ALIGN! 0.01 100 ALIGN! IN- 0.001 95

Example B

Laphygma exigua

Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable active ingredient, 1 part by weight of the active ingredient is mixed with the indicated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.

The prepared active ingredient is sprayed until wetted with cotton leaves (Gossypium hirsutum), which are then contaminated with caterpillars of the Laphygma exigua.

After the time below, the percent mortality was evaluated, with 100% indicating that all caterpillars were killed, while 0% means that no caterpillar was killed.

The active substances, active substance concentrations, evaluation time and results obtained are given in Table 2 below:

- 'Mortality- .- in% after. 3 days

T a b at 1 k and 2

Test na. · Laphygma exigua

Active substance Concentration of active substance in. %

Br

0.1

0.01

0.001

100 ALIGN!

0

(brand)

0.1

0.01

0.001

100 ALIGN!

(Xhima,)

F

0.1

0.01

0.001

100 ALIGN!

100 0

0.1

0.01

0.001

100 ALIGN!

100 fxMáími; CH ₃ ⁴ CH ₃

/ \

CH ₃

0.1

0.01

0.001

100 ALIGN!

100 ALIGN!

100 о-со-сн-'Ус ^ / ^с \ CN ₃ CH ₂

0.1

0.01

0.001

100 ALIGN!

100 ALIGN!

100 ALIGN!

CN /

Btr

0.1

0.01

0.001

100 ALIGN!

100 ALIGN!

100 ALIGN!

0.1

0.01

0.001

100 ALIGN!

100 ALIGN!

100 ALIGN!

Active substance concentration in%

Active substance

Mortality in% by days

0.1

0.01

0.001

100 ALIGN!

100 ALIGN!

100 ALIGN!

0.1

0.01

0.001

100 ALIGN!

100 ALIGN!

100 ALIGN!

100 ALIGN!

100 ALIGN!

100 ALIGN!

0.1

0.01

0.001

100 ALIGN!

100 ALIGN!

100 ALIGN!

/ CN CM \ ссо-сн-сн-с1-1 = с

X

CH ₃ CH ₃

0.1

0.01

0.001

100 ALIGN!

100 ALIGN!

100 ALIGN!

Example C

Tesil for resistant spider mite (Tetranychus urticae)

Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaoylyplyglycol ether

1 part by weight of the respective active ingredient is mixed to prepare a suitable active agent. of the active ingredient with said amount of solvent and said amount of emulsifier, and the concentrate obtained is diluted with water to the desired concentration.

The bean plants (Phaseolus vulgarisj.) Are sprayed with the prepared active ingredient until dew-rays.

After this time, the efficacy of the applied composition is determined by counting dead insect specimens. The observed mortality is expressed in o / o. 100% means all bugs have been killed, 0% means none of the bugs have been killed.

The active substances, active substance concentrations, evaluation time and results obtained are given in Table 3 below:

Mortality in · ·% after 2 days

Table 3

Test for resistant spider mite (Tetranychus)

Active substances Concentration of active substance in%

CHO-CO-CH * from ^C \

0.1 (acquaintances)

CH ₃ CH ₃

0.1

100 ALIGN!

CH ₃ CH ₃

0.1

0.1

100 ALIGN!

0.1

100 CH3

/ \ ch, CM ₃

0,1 / ^CN

BrO Ό ~ O-co-ch £ ^ -ch ₃

Mortality in% after 2 days

Active substance concentration in%

Active substance

0.1100 from ^cw

CH 10 -CO-CH

I /

0.1

CH ₃ CH ₂

CN

CH ₃ CH ₃

0.1

100 ALIGN!

C.N

/ ^Cl \

CH ₃ CH ₃

100 ALIGN!

0.1

100 ALIGN!

0.1

100 _Z CN

H ₃ c. CH ₂

0.1

100 ALIGN!

198210

Mortality in ° / o after 2 days

Active substance concentration in%

Active substance

Cl = c

Cl

0.1

100 ALIGN!

0.1

0.1

100 ch ₃ ch ₃

CzCH

CH ^X O-CO-CH- / -cl

Čh / \

CH ₃ CM ₃

100 ALIGN!

Example D

Limit concentration test (soil insects)

Experimental insects: Mealworm (Těnebrio molitor) - larvae in soil

Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable active ingredient, 1 part by weight of active ingredient is mixed with the indicated amount of solvent, the indicated amount of emulsifier is added, and the concentrate is diluted with water to the desired concentration.

The active ingredient is thoroughly mixed with the soil. The concentration of the active ingredient in the composition plays practically no role, only the amount of active ingredient per unit volume of soil, which is reported in ppm (mg / liter); The treated soil is filled with flower pots and left to stand at room temperature after filling. After 24 hours, the test insects are transferred to the treated soil and after a further 2 to 7 days the percentage of action of the active compound is determined by counting the dead and living specimens of the test insects. At killing of all specimens, the efficacy is 100%, 0% means that the number of live insect specimens is the same as in the control.

The active substances, the amounts of active substances used and the results obtained are given in Table 4 below;

Table 4

Limiting concentration test - Tenebrio molitor larvae in soil

Active substance Mortality in% at active substance concentration 2.5 ppm

CN

Cl

Cl

O ~ CO ~

CH.CH

/ ^CH x CH, (

Example E

Limit concentration test (insects living in soil)

Experimental. · Insects: Phorbia. antlqua - larvae living in soil

Solvent: 3 parts by weight of acetone Emulsifier: .1 parts by weight of alkylaryl polyglycol ether

To prepare a suitable active ingredient, 1 part by weight of the active ingredient is mixed with the indicated amount of solvent, the indicated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

The active ingredient is thoroughly mixed with the soil. Concentration of active substance in pro100

There is practically no role in the middle, only the amount of active substance per unit volume of soil, which is given in ppm (e.g. mg / Htr), is decisive. The treated soil is filled with flower pots and allowed to stand after filling. at room temperature. After 24 hours, the test insects are transferred to the treated soil and after a further 2 to 7 days the percentage of action of the active compound is determined by counting the dead and living specimens of the test insects. At killing of all specimens, the efficacy is 100%, 0% means that the number of live insects is the same as in the control.

The active substances, the amounts of active substances used and the results obtained are given in Table 5 below:

T a b u lk а 5

Limiting concentration test (Phorbia antiqua larvae in soil)

Active substance Mortality in% at active substance concentration 2.5 ppm.

(internal)

/ CN CH ^x o-co

100 ALIGN!

/ ^CH x ^сн з ^c h

100 ALIGN!

CN

100 / CN с ₃ сн _э

100 ALIGN!

100 ALIGN!

Cl

100 ALIGN!

Active substance

1’9 6 '21 O

Mortality in% at an active substance concentration of 2.5 ppm

Br

yCN

CH ^X Oi

, CN CH \) - co

100 ALIGN!

BT100 ° _F XX In ^{CHí0 <CH} CH, and ^R

CH 5 O-CO-CH

100 ALIGN!

100 ALIGN!

Example F

LD100 - test

Experimental insects: Cockroach (Blatta orientalis)

Solvent: acetone parts by weight of the active substance are dissolved in 1000 parts by volume of solvent and the solution is diluted with additional solvent to the desired concentration.

2.5 ml of the active substance solution is pipetted into a Petri dish, on the bottom of which a circular filter paper with a diameter of approx.

9,5 cm. The petri dish is left uncovered until the solvent is completely steamed. Depending on the concentration of the active substance solution, the amount of active substance, based on the m2 of filter paper, varies. About 25 specimens of test insects are then transferred to a Petri dish and the dish is covered with a glass lid.

The condition of the test insects is checked 3 days after the experiment and the% mortality is found.

In this case, 100% means that all specimens of the test insect have been killed; 0% means that none of the test animals were killed.

The active substances, active substance concentrations, experimental insects and results obtained are given in Table 6 below:

Active substance

LDioo - Test

Concentration of active substance in solution in%

Mortality in%

19В210

Table 6

(Z NAR)

CHrOCOC-CH * I

CH

0.2

0.2 (Xhifibi) (~ H ₃ CMj

0.2

(zhúnáj

0.2

0.02

100 ALIGN!

0.2

100 ALIGN!

0.2

100 ALIGN!

100 ALIGN!

190'210

Example G.

LTioo - double-wing test

Experimental insects: house fly (Musea domestica)

Solvent: acetone δ parts by weight of the active substance are dissolved in 1000 parts by volume of solvent and the solution is diluted with additional solvent to the desired lower concentration.

2.5 ml of the drug solution was pipetted into a petri dish, at the bottom of which a circular filter paper with a diameter of about 9.5 centimeters was placed. Leave the petri dish exposed to stand until the solvent is completely evaporated. Depending on the concentration of the active substance solution, the amount of active substance, based on the m2 of filter paper, varies greatly. About 25 specimens of test insects are then transferred to a Petri dish and the dish is covered with a glass lid.

The condition of the test insects is 'continuously checked' and the time required to achieve 100% mortality is determined.

The test insects, the active substances, the active substance concentrations and the times at which 100% mortality occurs are given in Table 7 below:

Table 7

LTioo - Double-winged Test (Musea domestica]

Active substance Concentration of active substance in solution in%

LTioo

(from n & has.)

CH 2 -CO-CH ** I

0.2

0.02

70 'h = 0%

(xtiahia) h

CH ₃ CH ₃

CH 2 O-CO-CH

0.2

0.02

150 * h '= 0%

CN

CN

0.2

0.02

0,002

30 '

60 '

P

0.2

0.02

80 'h

O-CO-CM

O-CO / CN

0.2

0.02

0.2

0.02

40 'h = 70%

30 '

100 '

Active substance

Concentration of the active LT 10 O in solution in ° / o

0.2

0.02

55 * h

Example H

Aerosol test

55 ‘h = 60%

55 *

90 * h = 60%

140 *

160 *

Tested animal: house fly (Musea domestica)

(resistant to phosphoric esters)

Solvent: acetone Amount: 2 ml

To prepare a suitable active ingredient, 2 mg of active ingredient is mixed with the indicated amount of solvent.

A wire cage containing about 25 test animals is suspended in the center of a 1 m ³ gas-tight chamber. After the chamber has been closed, 2 ml of the active product are sprayed therein. The condition of the test animals is constantly checked with glass walls from outside and the time required to achieve 95% mortality of the animals is determined.

The following table 8 shows the active substances, active substance concentrations and mortality times:

Table 8

Active substance:

Aerosol test:

Concentration of active LT95 in mg per m ^{3 of} air

h = 20%

F

19 * 30 “

Example · L

Tesf on ^ ticks

Solvent: 35 parts by weight of ethylene glycolmonomethylether

Emulsifier: · 35 parts by weight of nonylphenol polyglycol ether

To prepare a suitable formulation, 3 parts by weight of the active ingredient are mixed with 7 parts of a mixture of the above solvent and emulsifier, and the emulsifiable concentrate obtained is diluted with water to the desired concentration.

Fully aspirated adult female Boophilus micrpylus (resistant) ticks are immersed for 1 minute in the above formulation. After immersion. always 10 females of different ticks species. the treated specimens are transferred to Petrjho dishes whose bottom is. covered with 'filter' paper of appropriate size. .

After 10 days, the efficacy of the composition is determined by detecting egg clutch suppression against untreated control ticks. The observed effect is expressed in%, with 100% indicating that no egg has been laid and 0% means that the ticks lay eggs in the normal amount.

The active substances to be tested, the active substance concentrations, the test parasite and the results obtained are given in Table 9 below:

T a b at 1 k and 9

Test for ticks (resistant strain Biarra Boophilus microplus)

Active substance Effective Mortality Concentration substances in ppm in%

(known.)

000

CH ₃ CH ₃

000

1000

100 ALIGN!

100 ALIGN!

100 o

Examples illustrating the method of production of active ingredients:

Example 1

F CH ₃ \ / CH ³

CL g (0.033 mol) of 3- (4-fluorophenoxy) -α-cyanobenzyl alcohol and 7.6 g (0.033 mol) of α-isopoopyl-4-chlorophenyl PCC acid chloride are dissolved in 150 ml of anhydrous toluene at 25 to 30 ° 2.64 g (0.033 mol) of pyridine dissolved in 25 DEG C. are added dropwise. The reaction mixture is poured into 150 ml of water, the organic phase is separated and washed again with 100 ml of water. The toluene phase is then dried over sodium sulfate and the solvent is distilled off under a water pump vacuum. The last residual solvent was removed by brief distillation at a bath temperature of 60 ° C under a vacuum of 133 Pa. 13.2 g (91%) of 3'- (4-fluorophenoxy) - « '- cyanobenzyl--isopi'opyl N-4-chlorophenyl acetate as a yellow' oil of refractive index and? ^5: 1.5549 .

Example 2

w, c CWj

7.6 g (0.035 mol) of 3- (4-fluorophenoxy) benzyl alcohol and 7.95 g (0.035 mol) of 2,2-di-methyl-3- (2,2-dichlorvinyl) cycloproyanecarboxylic acid chloride are dissolved in 100 ml of 'anhydrous toluene' and 2.8 g (0.035 mol) of pyridine dissolved in 50 ml of toluene are added dropwise with stirring at 25-30 ° C. The reaction mixture was then stirred for an additional 3 hours at 25 ° C. The reaction mixture is poured into 150 ml of water, the toluene phase is separated and washed again with 100 ml of water. The organic phase is dried over sodium sulphate and the toluene is then distilled off under a water pump vacuum. The last residues were dissolved in 50 ml of toluene, with stirring. Thereafter, the reaction mixture was stirred for an additional 3 hours at a bath temperature of 60 ° C / 133 Pa. There are obtained 11 g (77% of theory) of 3 ‘- (4sflupophenol) benzy-2,2sdime-

In 210 thyl-3- (2,2-dichlorinyl) cyclopropanecarboxylate as a yellow oil with an index Analogous to the examples of lard, they were removed by "distillation" at thermo no ²² : 1,5559.

or 2 compounds of formula I may be prepared:

6210

л cd

CD it oo CD CM OO what Three it it what in uo in t — 1 νγ гЧ rH r-T -4 * ’ - * 5 ’’ OJ OJ OJ OJ Q O O O and tí Д Й

what it is

О 'i O O

CD 4t ω

QQ

/ oo About ¹ rO

X

it

it it it it 4 4 4 4

what

Example R R1 R ² R3 Physical data Yield number · (refractive index) (% of theory) f — IWD

CO CO D © o oo rH t-ч ©

O 00 '00 O O г — 1 00 00. . O © WHAT O WHAT WHAT ιτγ rH © ^ . гЧ © r4 © © ~ r4 © ~ гЧ © ~ гЧ cm ‘ CM CM 'O** CM OJ xj <’ OJ 4ι * OJ Q Q Q Q Q Q Q ti ti ti ti ti ti ti

X

s

/ oo About ¹ m

X

z ω z ω z o X  X x Z O

X X X X X X X the 1 the 1 m P pq ¢ -1 pq P pq P PQ WHAT 1 4 1 • Φ 4 ’ 1 4

196210.

Example RR ¹ R ² R ³ Physical data Yield number (refractive index) (% of theory)

Zс _z ch.

it OO oo CD !>. WHAT OO what 00 oo Гх O

LS xtl oo it WHAT oo it rH. ‘ O Γχ- it it it it oo iq it iq. iq it iq rH ’RH rH rH rH · rH Til 'OJ oi * ⁱⁿ OJ ·: 8 and' and' Q Q Q · Q and O Й and Д Й tí Й

OF OF of Bye it 1 4 oó

what гЧ г- <

И · 'д

oo  CD * 4 rH rH CM

6 210

Example RR ¹ R ² R ³ Physical data Yield number (refractive index) (% of theory)

CO oo

3-F H C = H

6.210

Example RR ¹ R ² R ³ Physical data Yield number (refractive index) (% of theory)

III

Pq

I co

Pq r

OF OF of O O at

pq Pq Pq pq Pq 4 1 WHAT what WHAT what

126210

Example RR ¹ R ² R ³ Physical data Yield number (refractive index) (% of theory)

HCČ CL

tM WHAT WHAT 00

WHAT O CD oo Y ”H it CD it it it 1Л rH. rH rH 4 * OJ * oj. OJ OJ 0 Q Q tí Й Й

OF Z O TO OF OF OF the the the 4 what TM

Γχ

WHAT

WHAT.

O)

-CH-

OF Ш o z ω Z o of OF TO the it the 4 4 4

tM

M TM

CM tM

Example RR ¹ R ² R ³ Physical data Yield number (refractive index) (% of theory) n _D ²² : 1,5564

Example RR ¹ R ² R ³ Physical data Yield number ______________________________________________________'____ (refractive index) (% of theory)

Me rH what 00 CM

rH ID what Ю rH O WHAT O Ю O ID ME Me ID WHAT ID Ю Ю ID • ID

2 O § 2 o я Я W fa Í4 ЬН what ώ со со fa CM Я Я Я Я

o in

ID

CM cn tn

1-9-8-.2-10.

The phenoxybenzyl alcohols required as starting materials can be prepared by the following procedures:

g (0.445 mol) of 3- (3-fluorophenoxy) toluene are dissolved in 300 ml of anhydrous carbon tetrachloride and the solution is heated together with 79.3 g of N-bromosuccinimide to reflux and after reaching 70 DEG C. 5 g of azodiisobutyric acid nitrile is added, after about 10 to 20 minutes the reaction develops under heat, and after the exothermic reaction has elapsed, the reaction mixture is refluxed for 4 hours, then cooled to 10 ° C, succinimide is filtered off and the carbon tetrachloride is distilled off under vacuum, and the residual oil is distilled at a temperature of 143-150 ° C / 1 mm Hg to give 72.9 g (58.2 percent of theory) of 3- (3-fluoroperioxy) benzyl bromide. · +.

The following compounds can be prepared in an analogous manner:

CH ^ §

Boiling point: 145-150 ° C / 1 mm Hg, yield: 61% of theory.

Boiling point: 160-165 ° C / 400 Pa, yield: 54.5% of theory.

3- (3-fluorophenoxy) benzyl bromide (0.17 mol) and hexamethylenetetramine (47.8 g) in methylene chloride (250 ml) were heated at reflux for 3 hours. The mixture was cooled to 5-10 ° C and the precipitate formed. filtered. The precipitate is washed with 100 ml of methylene chloride and dried. The mixture was filtered and then heated to reflux in 100 ml of 50% aqueous acetic acid for 5 hours. Concentrated hydrochloric acid (25 ml) was then added, the mixture was again heated to reflux for 30 minutes and then cooled to room temperature. 10-20 ° C. Water (200 ml) was added to the reaction mixture and extraction was performed twice with 150 ml each. of ether and the combined ether phases are then washed with sodium bicarbonate solution and dried over sodium sulfate. The ether was distilled off in vacuo. It is obtained in 31% yield. 3- (3-Fluorophenoxy) benzaldehyde, b.p. 142-148 DEG C./0.1 mbar;

The following compounds can be prepared in an analogous manner:

CHO

Melting point: 48 DEG C. Yield: 62%.

Refractive index: nD ²² : 1.6109, yield: 67% of theory.

21.6 g (0.1 mol of 3- (4-fluorophenoxy) benzaldehyde) are dissolved in 25 ml of glacial acetic acid and, at 5 DEG C., 10.2 g of sodium cyanide dissolved in 25 ml of water are added dropwise with stirring. The reaction mixture is poured into 100 ml of water, extracted with 200 ml of ether and the ether phase is separated, and the ether phase is washed with a dilute solution of hydrogen carbonate to remove glacial acetic acid. After the ether was distilled off in vacuo, 17 g (70% of theory) of 3- (4-fluorophenoxy) -α-cyanobenzyl alcohol having a refractive index n _D ^{2 of} 3: 1 were obtained. 5643. {

The following compounds can be prepared in an analogous manner: i

Refractive index n _D ²¹ = 1.5561, yield: 93% of theory.

19'6 2'10

CN CH-OH • ^F ....

Refractive index . [Delta] = 1.5700, yield: 69% of theory.

2 x 150 ml ether each, ether. phase is dried over sodium sulphate and the ether is then distilled off in vacuo. 7.3 g (61% of theory) of 3- (4-fluorophenoxy) -α-ethynyl-benzyl alcohol are obtained in the form of a yellow oil. 160 [deg.] C./400. Bye.

CH-OM

Refractive index n D ² 2 ^: yield: 88% of theory.

K 2,4. g. (0.1 mol). . Magnesium shavings in the 1970s. ml of anhydrous tetrahydrofuran. ·. is slowly added at 30 to 40 ° C. 14 g (0.13 mol) of bromoethane was added dropwise with stirring, and the mixture was further stirred at 50 ° C for 30 minutes. The Grignard solution thus prepared is poured into a dropping funnel under a nitrogen atmosphere and added dropwise to the acetylene solution in 40 ml. ml of anhydrous tetrahydrofuran, saturated at room temperature. Deň: 18 ° C. Acetylene was then continuously introduced and acetylene was continued for 30 to 45 minutes after the dropwise addition of the Grignard solution. Ethynylmagnesium bromide suspension was added dropwise at 25-30 ° C

10.8 g (0.05 mol) of 3- (4-fluorophenoxy) benzaldehyde dissolved in 50 ml of absolute tetrahydrofuran and then heated to 40 ° C for 4 hours. Reaction. the mixture is then cooled. Pour into 500 ml of ice-water and dissolve the precipitate. by adding concentrated hydrochloric acid. Extraction is then carried out. .K. 3.8 g of lithium aluminum hydride in 100 ml of anhydrous ether. at boiling temperature with good stirring was added dropwise 54 g (0.25 mole) of ₃ - s 4-flu _{Rf phenoxy} jb nz _e ld _{and e} hydn US _{margin assured of} eh in 50 ml _of absolute ether. Thereafter, the mixture was further stirred for 10 hours at 22 ° C, the reaction mixture was cooled to 0 ° C and ice water was added dropwise with stirring until no further evolution of hydrogen was observed. The resulting precipitate was dissolved by the addition of 10% sulfuric acid and then reacted. the mixture was extracted twice with 100 ml of ether each time. Etheric. phases are separated, washed with saturated chloride solution. sodium. and dried over sulfate. sodium. After. distilling off the ether in vacuo afforded 41.5. g (76.1% of theory) of 3- (4-fluoro-phenoxy) -benzyl alcohol. with refractive index nD ²¹ : 1.5725.

The following compounds can be prepared analogously:

Yield:. 76. % theory.

ch _z oh

Yield: 71% of theory. Refractive index nD ²⁴ : 1.6009.

Claims (2)

An insecticidal and acaricidal composition, characterized in that it contains at least one substituted phenoxybenzylcarbonyl derivative of the general formula I as an active ingredient. R дм. CH-O-CO-R ⁹ wherein R ¹ and R ¹ are different from each other and are hydrogen, fluoro or bromo, R ² represents kyanQokupinu or ethynyl group and R ³ represents a radical H ^C CH 19 9 210 where R ⁴ and R ⁵ are the same and represent chloro, bromo or methyl, or the radical -CH-R ⁸ CH / \ НзС СНз taking R ⁸ is optionally halogen, C 1 -C 4 alkyl, C 1 -C 4 alkylthio, C 1 -C 4 alkoxy, nitro, methylenedioxy substituted phenyl ring, and R ² is hydrogen if R ³ represents a radical H ₃ c ch ₂ wherein R ⁴ and R ⁵ are the same and represent chlorine or bromine, or the radical -CH-R ⁸ AND CH OF\ НзС .СНз taking R ⁸ is as defined above. 2. A process for the preparation of substituted phenoxybenzyloxycarbonyl derivatives of the formula I as claimed in claim 1, which comprises reacting the carbonyl halides of the formula II. Hal — CO — R ³ , (П) wherein R ³ is as defined above, and Hal represents halogen, preferably chlorine, with substituted phenoxybenzyl alcohol of the general formula III in which R ¹ , R ¹ and R ² are as defined above, optionally in the presence of an acid binding agent and optionally in the presence of a solvent at a temperature between 0 to 100 ° C.