HU176198B - Insecticide and acaricide preparations containing substituted phenoxy-benzyloxy-carbonyl-derivatives and process for preparing the substituted phenoxy-benzyloxy-carbonyl-derivatives - Google Patents

Description

OFFICE

Date of announcement: 1977. IV. 77. (BA-3530)

Priority: 1976. IV. 09., (P 26 15 435.8)

Federal Republic of Germany

Published: 1980. VII. 28th

Published in 1987 II. 18th

International Class:

A 01 N 9/00,

C 07 C 69/76,

C 07 C 69/74,

C 07 C 121/75,

C 07 C 43/20

Inventor)

Dr. Fuchs Rainer Alois, chemist, Dr. Stendel Wilhelm, veterinarian, Wuppertal, Dr. Hammann Ingeborg, zoologist, Cologne, Dr. Behrenz Wolfgang, zoologist, Overath, Dr. Homeyer Berhard, biologist, Leverkusen (DE)

Owner:

Bayer AG, Leverkusen (DE) / 7

Insecticidal and acaricidal compositions containing substituted phenoxybenzyloxycarbonyl derivatives and methods for the preparation of substituted phenoxybenzyloxycarbonyl derivatives

The present invention relates to insecticidal and acaricidal compositions comprising novel substituted phenoxybenzyloxycarbonyl derivatives and to a process for the preparation of novel compounds.

It is known that phenoxybenzylacetates or carboxylates such as 3'-phenoxybenzyl-α-isopropyl (3,4-dimethyloxy or 4-bromo, 4-fluoro and 3,4-dioxymethylene) phenyl) acetate and 3'-phenoxybenzyl- [2, 2-dimethyl-3 (2,2-dichloro-vinyl) -cyclopropane] -carboxylate, insecticidal and acaricidal properties (see German Federal Patent No. 2,335,347). and the Belgian Patent Application 801 946).

It has been found that the novel substituted phenoxybenzyloxycarbonyl derivatives of the formula I show strong insecticidal and acaricidal activity. In formula (1):

R is fluoro or bromo;

-R ¹ is hydrogen;

- R ^J is cyano or ethynyl or hydrogen;

-R ³ represents a group of formula (VII): wherein: R ⁴ and R * are as defined above are chlorine or bromine or methyl or a group of the formula wherein R ^{6 is} optionally halogen, 1-4; alkyl group or a methylenedioxy group, a substituted phenyl group, with the proviso that if R ² is hydrogen, in formula (VII), ^R4 and ^R5 always represents a chlorine atom and the formula (VIII) R ⁶ is always unsubstituted phenyl different meanings.

Formula (I) includes various possible stereoisomers, optical isomers, and mixtures of these isomers.

It has also been found that the novel substituted phenoxybenzyl oxocarbonyl derivatives of formula (I) can be prepared by the carbonyl halides of formula (II) represented by the formula "Hal" being halogen, preferably chlorine; -R ^{3 is} reacted with the specified meaning of substituted phenoxybenzyl alcohols of formula III in formula (ΙΠ)

R, R ¹ and R ² are as defined above - optionally in the presence of an acid acceptor and optionally in the presence of a solvent.

The substituted phenoxybenzyloxy-catbonyl derivatives of the present invention exhibit improved insecticidal and acaricidal properties as well as insecticidal and acaricidal compounds of known chemical structure. The tai.iim'íny chin seats enrich the technique.

for example, 3 (3-fluorophenoxy) -cyanobenzylalkolol and β-isepropyl-eloxyphenylacetic acid kyride are used as starting material, the reaction is illustrated in the accompanying Reaction Scheme A.

The range of compounds that can be used as starting materials is clearly defined by formulas (II) and (111). In the formula, the preferred meanings of the substituents are:

-R fluorine or bromine; -R ^{1 is} hydrogen;

-R ^{2 is} hydrogen, cyano or ethynyl, and -R ³

2,2-Dimethyl-3- (2,2-dichloro) and 2,2-dimethyl-3 (2,2-dibromo) and 2,2- (dimethyl-vinyl) cyclopropanyl, α-isopropyl benzyl, optionally substituted on the ring singly or multiply by one of the following groups, wherein the substituents may be the same or different: fluoro, chloro, bromo, methylenedioxy, straight or branched C1-3 carbon atoms alkyl.

The carbonyl halides which can be used as starting materials are known and can be prepared by generally known methods (see, for example, 2 365 555;

926 433 and 2 231 312 of the Federal Republic of Germany).

By way of example, the following compounds of formula II are mentioned:

2,2-Dimethyl-3- (2,2-dichloro-vinyl) -cyclopropanecarboxylic acid chloride,

2,2-dimethyl-3- (2,2-dibromo-vinyl) -cyclopropanecarboxylic acid chloride

2,2-Dimethyl-3- (2,2-diroethyl vinyl) cyclopropanecarboxylic acid chloride, α-isopropylphenylacetic acid chloride, α-isopropyl-4-fluorophenylacetic acid chloride; isopropyl 4-chlorophenylacetic acid chloride,? -isopropyl-4-bromophenylacetic acid chloride,? -isopropyl-4-methylphenylacetic acid chloride,? -isopropyl-4-ethylphenyl acetic acid chloride, Q-isopropyl-4-n-propylphenylacetic acid chloride,? -isopropyl-4-isopropylphenylacetic acid chloride,? -isopropyl-4-methoxyphenylacetic acid chloride, or -isopropyl-4-ethoxyphenylacetic acid chloride, α-isopropyl-4-methylthiophenylacetic acid chloride, α-isopropyl-4-ethylthiophenylacetic acid chloride,? -isopropyl-4 -nitrophenylacetic acid chloride,? -isopropyl-3-fluorophenylacetic acid chloride,? -isopropyl-3-bromophenylacetic acid chloride,? -isopropyl-3-chlorophenylacetic acid chloride , e-isopropyl-3-methylphenylacetic acid chloride,? -isopropyl-3-ethylphenylacetic acid chloride,? -isopropyl-3-methoxyphenylacetic acid chloride, space-isopropyl-3-ethoxy -phenylacetic acid chloride,? -isopropyl-3-methylthiophenylacetic acid chloride,? -isopropyl -3-Ethyl-thiophenylacetic acid chloride, isopropyl-3,4-methylenedioxyphenylacetic acid chloride.

The compounds of formula (III) which can be used as starting materials are new. They can be prepared by the reaction of the phenoxybenzaldehydes of formula IV with R and R ^{1 in} the formula (IV) as defined above.

A) in the case where R ² is hydrogen, a complex metal hydride is reduced in an inert solvent;

B) when R ² is cyano, reacted with an alkali metal cyanide such as sodium or potassium cyanide in the presence of an acid, optionally with the addition of a solvent, or

C) when R ² is ethynyl, reacted with a compound of formula V wherein "Hal" represents a halogen atom in a suitable solvent.

For example, in process variant A) 3- (3-fluorophenoxy) benzaldehyde and lithium aluminum hydride, in process variant B, 3- (2-fluorophenoxy) benzaldehyde and potassium cyanide and process variant C).

2- (4-Bromophenoxy) benzaldehyde and ethinylmagnesium bromide are used as starting materials and the reactions can be illustrated in Scheme B below.

The range of compounds that can be used as starting materials is clearly defined by the formulas (II) and (III). The preferred meanings of the substituents are:

-R fluorine or bromine;

—R * hydrogen; and - "Fish" bromine.

Ethinyl compounds of formula (V) as well as alkali cyanides and complex metal hydrides have been described in the literature.

The phenoxybenzaldehyde of formula (IV) may be prepared by generally known methods, for example by reacting the corresponding phenoxybenzyl halides of formula (VI), which may be prepared from the corresponding phenoxy toluenes by conventional means, with hexamethylenetetramine. Scheme C). In the scheme, R and R * are as defined above and Hal is halogen. As an example of the phenoxybenzaldehyde to be reacted in the process, the following compounds are mentioned:

3- (4-fluorophenoxy) -benzaldehyde,

3- (3-Fluorophenoxy) benzaldehyde,

3- (2-Fluoro-phenoxy) -benzaldehyde,

3- (4-Bromophenoxy) benzaldehyde

3- (3-bromophenoxy) enzaldehyde,

3- (2-Bromophenoxy) benzaldehyde,

3-Phenoxy-6-fluorobenzaldehyde.

In the preparation of the compounds of formula (III), the reaction is preferably carried out in the presence of a suitable solvent diluent.

In process variant A, ethers such as diethyl ether, tetralydofuran, dioxane, and hydrocarbons such as toluene or petrol are particularly suitable. If sodium borohydride is used as the reducing agent, water, alcohols such as methanol, ethanol, are also added. Nitriles such as acetonitrile or propionitrile can also be used. In carrying out process variant B), the use of water, alcohols such as methanol, ethanol or ethers such as diethyl ether, tetrahydrofuran or nihil such as acetonitrile is particularly preferred. Process variant C) is particularly preferably carried out in the presence of ethers such as diethyl ether, tetrahydrofuran and dioxane.

Preferred complex metal hydrides useful in carrying out process variant C) are lithium aluminum and sodium borohydride.

In reaction B, the acid may be inorganic acids such as hydrochloric acid or sulfuric acid, or organic acids such as acetic acid or formic acid.

The reaction temperature can be varied within wide ranges for all process variants. Generally, the reaction is carried out at -10 to 110 ° C.

The preferred temperature range is

In process variant A) from 0 to 60 ° C, a

In process variant B) -5 to 20 ° C and a

C) from 0 to 80 ° C.

The reaction is generally carried out under normal pressure.

According to the variant A), the reactants are preferably reacted in equimolar amounts. The use of one or the other reagent in excess does not lead to any advantage. In process variant B, the cyanide is added in an excess of 100 to 150%. In process variant C, the ethinyl compound is reacted with an excess of 20 to 50%. The reaction is preferably carried out under reflux in any of the above solvents or diluents. After several hours of reaction, which is usually carried out at elevated temperatures, the reaction mixture is worked up by generally known methods.

The new compounds are obtained in oily form, which may either be distilled or so-called "distillation", i.e., under reduced pressure, at slightly elevated temperature, released by prolonged heating from the last volatile constituents. The refractive index or boiling point is used to characterize the compounds.

The novel phenoxybenzyl alcohols used to prepare the novel phenoxybenzyloxycarbonyl derivatives of the present invention include the following compounds:

- (4-fluorophenoxy) -6-fluorobenzylalcohol,

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- (2-Bromophenoxy) benzyl alcohol

3- (4-Fluorophenoxy) -α-cyanobenzyl alcohol,

3- (3-fluorophenoxy) -a-cyano-benzyl alcohol,

3- (4-Bromophenoxy) α-cyanobenzyl alcohol

3- (3-Bromophenoxy) -α-cyanobenzyl alcohol,

3- (2-Fluoro-phenoxy) -α-cyano-benzyl;

3 (2-Bromophenoxy) - cyanobenzyl alcohol

344 41-Phenoxy) -α-ethinylbenzyl alcohol,

3- {3-fluoro-phenoxy) -a-ethynyl-benzyl alcohol,

3 (4-Bromophenoxy) -? - ethinylbenzyl alcohol

343-bromophenoxy) acetylbenzyl alcohol,

342-fluorophenoxy) α-ethinylbenzyl alcohol,

3- (2-Bromophenoxy) -α-ethynylbenzyl alcohol.

In the process of the present invention, all conventional acid binding agents can be used as acid receptors. Particularly preferred are alkali carbonates and alcoholates such as sodium and potassium carbonate, sodium night potassium methylate and ethylate, and.

aliphatic, aromatic or heterocyclic amines such as triethylamine, trimethylamine, dimethylaniline, dimethylbenzylamine and pyridine. .

The reaction temperature can be varied within wide limits. Usually we work between 0 and 100, preferably between 15 and 40 ° C.

The reaction is generally carried out under normal pressure.

The process according to the invention is preferably carried out using suitable solvents and diluents. For this purpose virtually all of the organic solvents for the solvent can be taken into account. This includes, in particular, aliphatic and aromatic, optionally chlorinated hydrocarbons such as benzene, toluene, xylene, petrol, methylene chloride, chloroform, carbon tetrachloride, chlorobenzene or ethers such as diethyl and dibutyl ether, dtoxane, and ketones, such as acetone, methyl ethyl, methyl isopropyl, and methyl isobutyl ketone, in addition to these nitriles such as acetone and propionitrile.

In carrying out the process, the starting materials are preferably reacted in equimolar amounts. The use of one or the other reaction partner in excess does not result in substantial benefits. The reagents are usually added to one of the solvents indicated, and the resulting mixture is usually stirred at elevated temperature until completion of the reaction, usually for one to several hours. The reaction mixture was finally poured into water, the organic phase was separated and washed with water. After drying, the solvent was distilled off under reduced pressure.

The new compounds are obtained in oily form, some of which may not be distilled without decomposition. The separation of these can be accomplished by so-called "distillation", i.e. the material is heated under reduced pressure at moderate high temperatures for a long time. The last traces of volatile constituents are then removed so that the process results in the purification of the material. The refractive index is used to characterize the result.

As mentioned several times, the substituted phenoxybenzyloxycarbonyl derivatives of the present invention exhibit excellent insecticidal and acaricidal activity. The compounds do not damage the plants and, due to their low warm-blood toxicity, are excellent for destroying animal pests, especially insects, spiders and nematodes in agriculture, forestry, stock protection and material protection, as well as hygiene. The compounds are also active against normally sensitive and resistant varieties at all stages of development. __

Examples of compounds that can be killed with compounds include:

From the order of Isopoda, Oniscus asellus, ArmadilJidium vulgare, Porcellio scaber; from the Diplopoda order to Blaniulis guttulatus; from Chilopoda order to Geophilus carpophagus, Scutígera spec .;

from the Symphyla order to Scutigerella immaculata; from the order of Thysanura to Lepisma saccharina; from the Collembola order to the Onychiurus armatus; from the Orthoptera order Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattelia germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differential, Schistocerca gregaria: from the Dermaptera to Forficula auricularia;

from the order of Isoptera to Reticulitermes spp., from the order of Anoplura to Phylloxera vastatrix, Pfemphigus spp.,

Pediculus humanus corporis, Haematopinus spp., Linognathus spp .;

from the order of Mallophaga to Trichodcctes spp., Damalinea ^S PP;

from the order of Thysanopicra to Hercinothrips femoralis, Thrips tabaei;

from the order of Heleroptera to Eurygaster spp., Dysdercus intermediiis, Piesma qudrata, Cimex lectularius, Rlioduiiis prolixus, Triatoma spp .;

from the order of Homoptera, Aleurodes brassicae, Bemisia labaci, Trialeurodes vaporatiorum, Aphis gossypii, Bievicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopierus anmdiiiis, Macrosiphum avenae, Myzus spp. , Euseelis bilobatus, Nephotettix cincticeps, Lecaniu corni, Saissetia oleae, Laodelphax striatum, Nílaparvata lugens, Aonidiella aurantii, Aspidiotus nederae, Pseudococeus spp., Psylla spp .;

from the order of Lepidoptera, Pectinophora gossypieüa, Bualus pinlarius, Cheimatobia brumata, Lithocolletis lancardeila, Hyponomeuta padella, Plutclla maculipenn's, Malacosoma neustria, Euproctis chrysorrhoea,

Lymantria spp., Bucculatrix thurberiella, Phyllocnistis citrate, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp. Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehnieÚa, Galleria rnellonella, Cacoecia podana, Capua reticulana, Choristoneura rumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana;

from Coleoptera order, Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Pylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna, Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp. spp., Tenebrio molitor Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Cstelytra zealandica .;

from the Hymenoptera order, Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa ^s pp;

from the Diptera order, Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp.,

Sobosca spp., Stomoxys spp., Oestrus spp., Hyma spp., Tabanus spp., Tannia spp., Bibio lanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitits capitata, Dacus oleae, Tipula paludosa; ^{r from} the order of the Siphonaptera to Xenopsylla cheopis, Ceratophyllus spp .;

from the order of Arachnida to Scorpio_maurus, Latrodectus mactans;

from Acarina order Acarus siro, Argas spp.,. Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp. frying pan, Panonychus spp., Tetranychus spp.

The nematodes that can be killed using the compounds include Pratylenchus spp., Radophoius similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp., Trichodorus spp.

The compounds of the present invention exhibit strong ectoparasiticidal or anti-inflammatory properties, particularly effective against ticks that are present in domestic animals such as oxen and sheep. At the same time, the compounds have favorable properties for warm-blooded toxicity. Due to their favorable properties, they are excellent for killing animal ectoparasites, especially ticks.

These types of agriculturally important ectoparasites, which are particularly problematic in tropical and subtropical countries, include: the Australian and South American monocotyledon, the Boophilus microplus, the South African ox tick, the Boophilus decoloratus, which belong to the íxodidae family. include African, multi-farmed ox and sheep ticks, such as Rhipicephalus appendiculatus, Rhipicephalus evertsi, Amblyomma hebraeum, Hyalomma auncatum, and South American multipurpose oxen such as Amblyomma cajennense and Amblyomma americanum.

Over time, many areas have developed ticks that are resistant to the use of phosphoric esters and carbarates used in pest control so that the success of protection against them is increasingly questioned in many areas. The requirement for cost-effective livestock farming requires urgent action against agents that can successfully kill resistant strains such as Genus Boophilus at all stages of development, such as larvae, metal larvae, nympha, metanympha and adult individuals. For example, in Australia, the strains of Boophilus microplus Mackay, Mt-Alfort and Biarra are highly resistant to phosphoric acid esters.

The compounds of the present invention can be used to treat ticks that are normally sensitive and resistant to ticks, such as all strains of Boophilus. By treating the host animal in the usual manner, these compounds directly kill all parasitic forms by interrupting the developmental cycle of parasites that parasite on the host.

Treatment prevents the larvae from escaping.

The use is, for example, in the form of dipping baths in which the compounds of the present invention, despite being contaminated and subjected to microbiological attack, have to stop for at least 6 months. Other forms of formulation include premeters and irrigation agents.

The compounds of the present invention are completely stable in all forms of application, i.e. no loss of effect after 6 months.

Compounds are in conventional forms such as solutions, emulsions, spray powders, suspensions, powders, dusts, foams, pastes, soluble powders, granules, aerosols, suspension emulsion concentrates, dressing powders, impregnated natural and synthetic materials, fine capsules, polymeric materials and coatings for dressing purposes, preparations for use in the form of incineration, such as smoke cartridges, dosages, spirals, and ULV cold and tincture formulations.

The formulations are prepared in a manner known per se, for example, by treating the compound having a pest control with fillers, i.e., liquid solvents, pressurized liquefied gases, and / vay solid carriers, optionally surfactants, such as emulsifiers and / or dispersants and / or foaming agents. combined use. Suitable liquid solvents include essentially the following solvents: aromatic compounds such as xylene, toluene or alkyl naphthalenes; chlorinated aromatic and chlorinated aliphatic hydrocarbons such as chlorobenzene, chloroethylene or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins such as petroleum fractions, alcohols such as butanol or glycol, and ethers and esters thereof, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, highly polar solvents such as dimethylformamide and dimethylsulfoxide, water. Liquid gaseous fillers or carriers are gaseous substances at normal pressure and temperature, such as aerosol carrier gases such as halogenated hydrocarbons, butane, propane, nitrogen and carbon dioxide. Solid carriers include natural calcareous minerals such as kaolin, clay, talc, chalk, quartz, attapulgite, montmorrillonite, diatomaceous earth and synthetic calcareous, such as high dispersed silicas, alumina and silicates.

Solid granules for granules include, for example, crushed and fractionated natural rocks such as calcite, marble, gypsum, sepiolite, dolomite, and granules of inorganic and organic flours, as well as granules of organic materials such as coconut shell, corn and tobacco fiber.

Emulsifying and / or foaming agents include non-ionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers such as alkylaryl poly (glycol ethers), alkyl- sulfonates, alkyl sulfates, arylsulfonates, and protein hydrolysates are contemplated.

Examples of suitable dispersants include lignin, sulphite soaps and methylcellulose.

Binders such as carboxymethylcellulose, natural and synthetic powdery, granular or latex polymers such as gum arabic, polyvinyl alcohol, polyvinyl acetate can also be used.

Coloring agents such as inorganic pigments such as iron oxide, titanium oxide, ferrocyanide and organic colors such as alizarin or azo-metal phthalocyanine dyes and trace amounts of nutrients such as iron, manganese, boron, copper, cobalt , molybdenum and zinc salts may also be used.

The compositions generally contain from 0.05 to 95% by weight of active ingredient, preferably from 0.5 to 90% by weight of the active ingredient.

The compounds are used in the form of the formulation and / or in the formulation of the formulation.

For use in the field of hygiene and the protection of stored stocks, the compounds exhibit excellent residual activity on wood and clay surfaces and exhibit excellent alkaline stability on calcified surfaces.

Further details of the invention will be described in the following non-limiting examples.

Examples of packaging

I. Dust Coating

For the preparation of a suitable active ingredient, 0.05 parts by weight of the active compound of Formula 16 is mixed with 99.95 parts by weight of natural calcine, and the mixture is milled into porphine. The resulting composition is applied to the plants or their foreskin by dusting.

II. Pennetpor (dispersible powder)

To prepare a suitable drug formulation, 25 parts by weight of the active compound of Formula 18 are mixed with 1 part by weight of dibutylnaphthalenesulfonate. 4 parts by weight of lingin sulfonate, 8 parts by weight of high dispersion silica, and 62 parts by weight of natural stone slurry, and the mixture is ground to powder. Before use, the wettable powder is mixed with water to obtain the desired concentration of the active ingredient.

III. Emulsifiable concentrate

To prepare a suitable drug formulation, 25 parts by weight of active ingredient 21 are dissolved in a mixture of 55 parts by weight of xylene and 10 parts by weight of cyclohexane. To this solution was added an amount of 10 parts by weight of a mixture of dodecylbenzenesulfonic acid calcium and nonylphenol polyglycol ether as emulsifiers. Prior to use, the emulsion concentrate is diluted with as much water as the resulting mixture contains the active ingredient at the desired concentration.

ARC. Granulate

To prepare a suitable drug formulation, 1 part by weight of the active compound of Formula 40 is sprayed onto 9 parts by weight of granulated suction clay. The resulting granules are expressed in the desired amount in the plants or living areas.

V. ULV preparation

To prepare a suitable drug formulation, 3 parts by weight of a polyoxyethylene oxide emulsifier is added to 90 parts by weight of the active ingredient, and the mixture is dissolved in 7 parts by weight of an aromatic mineral oil fraction. The resulting composition was applied by ULV (ULV = ultra low volume).

Examples of Application Techniques Example A)

Myzus Test (Contact Effect)

Solvent: 3 parts by weight of acetone Emulsifier: 1 part of alkyl aryl poly (glycol ether)

To prepare a suitable composition, 1 part by weight of the compound of the present invention is mixed with the amount of solvent indicated above, containing the given amount of emulsifier and diluted with water to give the desired concert.

Λ Spray cabbage plants (Brassica oleracea), which are thoroughly infected with peach aphids (Mycus persicae), and spray with water.

After a certain time, we determine the% mortality rate. 100% means that all aphids have died while 0% have been killed if no aphids have died.

The active ingredients, drug concentrations, evaluation times and results obtained are shown in Table 1 below.

Table 1 (herb pests)

Myzus test

Number of active ingredient formula Drug Concentration Destruction case After 1 people <%) 1. (known) 0.1 100 0.01 90 0,001 0 2. (known) 0.1. 100 0.01 95 0,001 0 3. (known) 0.1 100 0.01 100 0,001 0 4th 0.1. 100 0.01 100 0,001 95 & 0.1 100 0.01 100 0,001 95 6th 0.1 100 0.01 100 0,001 100 7th 01 100 0.01. 100 0,001 100 8th 0.1 100 0.01. 100 0,001 80 9th 0.1 100 0.01 100 0,001 95 10th 0.1 100 0.01 100 0,001 99 11th 0.1 100 0.01 100 0,001 100 12th 0.1 100 0.01 100 0,001 100 13th 011 100 0.01 100 0,001 100

14th 15th 0.1. 0.01 0,001 0.1 0.01 0,001 100 100 100 100 100 100 16th 0.1 100 0.01 100 0,001 100 17th 0.1 100 0.01. 100 0,001 100 18th 0.1 100 0.01 100 0,001 100 19th 0.1. 100 0.01 100 0,001 95 20th 0.1 100 0.01. 100 0,001 100 21st 0.1 · 100 0.01 100 0,001 98 22nd 0.1. 100 0.01. 100 0,001 100 23rd 0.1 100 0.01. 100 0001 100 24th 0.1 100 0.01. 100 0,001 98 25th 0.1 100 0.01 100 0,001 100 26th 0.1 - 100 0.01. 100 0,001 80 27th 0.1 100 0.01 0,001 100

Example B)

Laphygma-test

Solvent: 3 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl poly (elicolyte)

To prepare a suitable drug formulation, 1 part by weight of the compound of the invention is mixed with the above amount of solvent containing the particular amount of emulsifier and diluted with water to the desired concentration.

sypium hirsutum) is sprayed with dripping water, and then the leaves are infected with owl larvae (Laphygma exigua).

After a certain time, we determine the% mortality rate. 100% means that all larvae have died while 0% have been killed if no larva has died.

The active ingredients, drug concentrations, evaluation times, and results obtained are shown in Table 2 below.

Table 2 (plant insect pests) Laphygma test

Formula Number: Drug Concentration (%) Degree of destruction 3 days after expiration (%) 1. (known) 0.1. 100 0.01. 80 0,001 0 28. (Ismén) 0.1 100 0.01. 95 0,001 0 29. (known) 0.1 100 0.01 100 0,001 0 30. (known) 0.1 · 100 0.01 100 0,001 0 10th 0.1 100 0.01. 100 0,001 100 12th 0.1 100 0.01. 100 0,001 100 13th 0.1 · 100 0.01. 100 0,001 100 16th 0.1 100 0.01. 100 0,001 100 18th 0.1 100 0.01. 100 0,001 100 22nd 0.1 100 0:01 100 0,001 100 23rd 0.1 · 100 0.01. 100 0,001 100 24th 0.1 100 0.01. 100 0,001 100 25th 0.1 100 0.01. 100 0,001 100

Example C)

Tetranychus Test (Resistant)

Solvent: 3 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl poly (glycol ether)

In order to prepare a suitable active ingredient composition, 1 part by weight of the compound of the invention is mixed with the above amount of solvent, and contains a given amount of emulsifier.

The resulting concentrate is diluted with water to the desired concentration.

The resulting composition is used to spray botanicals (Phaseolus vulgaris) heavily infected with specimens at all stages of development of the common spider or bean cage (Tetranychus erticae).

After a specified time, we determine the% mortality rate. 100% is the degree of death if all spinach kills, while 0% means that no spinner has died.

The active compounds, drug concentrations, evaluation times and results obtained are given in the following table.

Table 3 (plant mite pests) Tetranychus test

Formula of the active substance Active ingredient destruction rate 2 days centering (%) after expiration (%) 2. (known) 0.1 0 4th 0.1 100 6th 0.1 100 7th 0.1 98 9th 0.1 100 10th 0.1 99 11th 0.1 98 12th 0.1 99 13th 0.1 00 14th 0.1 99 15th 0.1 100 16th 0.1 100 17th 0.1 100 18th 0.1 100 20th 0.1 100 23rd 0.1 99 24th 0.1 100 25th 0.1 99 26th 0.1 100 27th 0.1 100

Example D)

Critical concentration test / soil pests

Pests tested: Tenebrio molitor larvae in soil

Solvent: 3 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl poly (glycol ether)

To prepare a suitable composition, 1 part by weight of the active ingredient is mixed with the given amount of solvent, the amount of emulsifier is added and the concentrate is diluted with water to the desired concentration. The preparation is intimately mixed with the soil. Thus, the active ingredient concentration of the composition is practically non-active, only the amount of active ingredient per unit volume of soil is decisive, expressed in ppm (e.g. mg / liter). The soil is filled into pots, _x and the dishes are left at room temperature. After 24 hours, the treated pests are applied to the treated soil and after a further 2 to 7 days, the potency of the drug is determined by counting the dead and live pests and calculating the% values. 100% is the efficiency if all the pests tested are dead, while 0% if the same amount of pests are alive as in the control vessel.

The active ingredients, the amounts used and the results obtained are shown in Table 4 below.

{TaLii'un live insect pests) ftuebriu uiohíi larvae in soil

Formula of active ingredient

Decrease case (%) at 2.5 ppm drug concentration

28. (know) 0

1. 0 te. 100

16. 100

Example E)

Boundary concentration-test / soil-borne insect pests Phorbia antiqua-worms in soil Solvent: 3 parts by weight acton

Emulsifier: 1 part by weight of alkylaryl poly (glycol ether)

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

The composition is intimately mixed with the soil. Thus, the active ingredient concentration of the composition does not play any role, only the amount of active ingredient per unit volume of soil is decisive, given in pjpm (mg / l). The soil is filled into containers and allowed to stand at room temperature.

hours later, the test pests are added to the treated soil, and after two to seven days, the efficacy of the drug is determined by counting the dead and live pests and calculating the %_ values. 100% efficiency is when all pests are 'dead, while 0% if there are as many pests alive as in untreated controls.

The active ingredients, the amounts used and the results are shown in Table 5 below.

_5. Table (Soil Pests)

Phorbia antiqua-worms in the soil

Formula number of the active substance

Degree of destruction (%) at 2.5 ppm drug concentration

28. (tmertl 0 1. (known) 0 21st 100 16th 100 TASTE 100 13th 100 20th 100 14th 100 11th 100 19th 100 6th ιοσ 9th 100

Examinated pest; Blatta orientalis

Solvent: acetone weight fraction The compound of the present invention is dissolved in 100 volumes of solvent.

The resulting solution is diluted with additional solvent to the desired concentration.

Pipette 2.5 ml of this solution into a Petri dish. The bottom of the Petri dish is about 9.5 cm in diameter. filter paper envelope. The Petri dish is left open until the solvent evaporates completely. Depending on the concentration of the solution, the active ingredient layer of different thickness is retained on 1 m _{2 of} filter paper. Approximately 25 pests are then added to the Petri dish and the cup is sealed with a glass lid.

check their condition after the introduction of pests. Determine the degree of death in%. 100% means that all pests have been killed while 0% have been killed if no pests have died.

The active compounds are shown in the following table for drug concentrations, test pests and results.

Table 6

Formula number of the active substance Concentration of active ingredient (s% solution) decay <% T 1. (known) 0.2 0 2. (known) 0.2 0 28. (known) 0.2 0 3. (known) 0.2 0 18th 0.02 100 20th 0.2 100 17th 0.2 100 22nd 0.2 100

Example G)

LT _t ο o-test (Pests of the Diptera order) Pests tested: Musca domestica Solvent: Acetone weight fraction is taken up in 1000 volumes of solvent. The resulting solution is diluted with additional solvent to the desired lower concentration.

Pipette 2.5 ml of the solution into a Petri dish, the bottom of which is covered with a 9.5 cm diameter filter paper disc. Allow the Petri dish to remain open until the total amount of solvent evaporates. Depending on the concentration of the solution, the active agent layer of various thicknesses remains at 1 m ² of filter paper. Finally, 25 pests are placed in the Petri dish and the cup is covered with a glass lid. We are constantly checking the condition of the pests tested. Determine the time required to achieve 100% destruction of pests This is referred to as "LT, oo" in the literature.

The test pests, active ingredients, drug concentrations, and times required to achieve 100% destruction are given in Table 7 below.

Table 7

LT, oo test for pests of the Diptera order Musca eomestica

Formula number of the active substance 'Active ingredient concentration of the solution {*%) ut ... 28 (ttmart) 0.2 * 70 0.02 6 hours-0% . 1. (for my account) 0.2 150 * 0.02 6 hours «0% 23rd 0.2 30 ' 0.02 60 ' 0,002 6 hours 16th 0.2 80 ' 0.02 6 hours TASTE 0.2 * 40 0.02 6 hours - 70% 20th 0.2 30 ' 0.02 100 ' 18th 0.2 55 ' 0.02 6 hours 17th 0.2 55 ' 0.02 6 hours - 60% 22nd 0.2 55 ' 0.02 90 ' 0,002 6 hours - 60% 15th 0.2 140 ' 0.02 160 '

Example H)

Aesiosol examination

Pests tested: Musca domestica (resistant to phosphoric acid ester:

Solvent: Acetone Amount of admixture: 2 cm ³

For the preparation of a suitable drug formulation, 2 mg of the active ingredient is mixed with the above amount of solvent,

There are four cage cages in an air-tight, 1m ³ -sized glass chamber with about 25 investigated pests. After sealing the chamber, it is sprayed with 2 ml of the above solution. Throughout the glass wall, we constantly check the condition of the pests tested and determine the time required for 95% death of the animals. This is referred to as "LT _9S " in the literature.

The active ingredients, drug concentrations, and time required to achieve 95% destruction are shown in Table 8 below.

Table 8

Aerosol test

Formula number of the active substance Concentration of active substance (mg / m3 air) LT " 31. (Known) 30. 23rd r 1 2 2 t hours · 50% horse-20% lyso

Example L)

Examination of ticks

Solvent: 35 parts by weight of ethylene glycol mono-methyl ether inonylphenol poly (glycol ether)

In order to prepare a suitable composition, 3 parts by weight of the active ingredient are mixed with the above-mentioned adjuvant emulsifier mixture and the resulting concentrate is diluted with water to the desired concentration.

The resulting active ingredient formulation was immersed for 1 minute in adult, fully-eradicated female of resistant Boophilus microplus species. After immersion of about 10 representatives of the different species, each stall was placed in Petri dishes, the bottom of which was previously covered with a filter paper of suitable size.

After a day, the effectiveness of the preparation is determined, i.e., the extent to which it inhibits the laying of eggs compared to untreated (control) ticks. Efficiency is expressed in%. 100% means no egg laying at all, but 0% efficiency when ticks are laying a normal amount of eggs.

The test compounds, concentrations, parasites, and results obtained are shown in Table 9 below.

Table 9

Tick Test (Boophilus microplus Biarra strain, resistant)

The active ingredient formula number Active ingredient concentration (ppm) Destructive effect (%) 32. (known) 10,000 0 20th 10,000 100 1000 100 100 0

Examples of production

Example 1

Preparation of Compound 16

8 g / 0.033 mole of 2- (4-fluorophenoxy) -α-cyanobenzyl alcohol and 7.6 g (0.033 mole) of? -Isopropyl-4-chlorophenylacetic acid chloride are dissolved in anhydrous toluene (150 ml). and a solution of 2.64 g (0.033 mol) of pyridine in 50 ml of toluene is added dropwise at 25-30 ° C with constant stirring. Finally, the solution was stirred for an additional 3 hours at 25 ° C. The reaction mixture was poured into 150 ml of water, the organic layer was separated and washed with another 100 ml of water. The toluene phase was finally dried over sodium sulfate and the solvent was distilled off in a vacuum jet pump. The last solvent residues were removed by short distillation at 60 ° C under 1 torr. 13.2 g (91% of theory) of 3 '- (4-fluorophenoxy) -α'-cyanobenzylisopropyl-4-chlorophenylacetate as a yellow oil with refractive index: η θ = 1.5549.

Example 2:

Preparation of Compound 18

In anhydrous toluene (100 mL), 7.6 g (0.035 mole) of 3-24-fluorophenoxy) benzyl alcohol and 7.95 g (0.035 mole) of 2,2-dimethyl-3- (2.2 dichloro-vinyl) cyclopropane are dissolved. hydrochloric acid chloride and added dropwise with stirring at 25 to 30 ° C. A solution of pyridine (2.8 g, 0.035 mol) in toluene (50 ml) was prepared. The resulting mixture was stirred for 3 hours at 25 ° C, poured into water (150 ml), the toluene phase separated and washed again with water (100 ml). The effluent phase was dried over sodium sulfate and the toluene was finally distilled off under a water jet pump. The last solvent residues were removed at 60 ° C under 1 torr pressure in a bath. 11 g (77% of theory ¹ ) of 3 '- (4-fluorophenoxy) benzyl-2,2-dinyl-3- (2,2-dichloro-vinyl-cyclopropanecarboxylate as a yellow oil, refractive index : nj, '- 1.5559.

The following compounds of formula (I) can be prepared analogously to the methods described in Examples 1 and 2:

KitarPólda RR * R ¹ R ^J Physical data molding number (refractive index) (% of theoretical value)

3 4-F H H the · 1.5585 85 4 4-F H H b njf - 1.5668 70 5 4-F H H c nf) * - 1.5499 83 6 4-F H CN c njf »1.5452 83 7 4-F H CN b n ⁴ - 1.5658 71 8 4-F H CN d  1.5447 81 8 3-F H CN β ntf - 1.5510 81 10 4-Br H CN c n = ⁴ - 1.5688 96 11 4-Br H H the - 1.5778 95 12 4-Br H H b nfr · - 1.5880 87 13 4-Br H H c n # - 1.5707 81 14 4-Br H CN b φ - 1.5840 77 15 4-Br H CN the π £ · - 1.5757 85 16 4-F H CN d ntf 1.5574 68 17 3-F H CN e πβ '- 1.5513 88 18 4-F H CN • nfc ¹ · 1.5505 89 18 4-Br H CN f ie # - 1.5578 77 21 4-F H CN f nfc ¹ 1.5348 78 23 4-Br H CN the rhymes, '- 1.5596 88 24 4-F H H d njj ⁴ - 1.5448 2 25 4-F H H FL2 26 4-F H H h 27 4-F H -CCH the nj, ⁴ - 1.6613 83 28 4-F H OCH c 28 3-F H OCH the 30 3-F H OCH I 31 4-F H CN 8 32 4-F H CN I 33 3-F H CN c 34 3-F H CN 1 35 3-F H CN .9 36 3-F H i -CN 1

KlttrPetó R R * R 'R' Physical data elevation number formula (fractional value)

37 4-F H H d 38 3-F H CN k 39 4-F - H H k 40 4-F H OCH β ⁿ D 1.5573 77 41 4-F H CN k ⁿ D 9 1.5630 84 42 4-F - H CN 1 D s 1.5519 83 43 3-F - H H k 44 3-F H H e 45 3-F H C = CH β 46 3-F H -CeCH Θ 47 4-F H OCH 9 48 2-F H CN 9 ⁿ Ö 1.5564 84 49 2-F H CN m ⁿ D the 1.5571 74 50 - H 6-F CN 0 ⁿ o 9 1.5435 71 51 H 6-F CN (You D 1.5473 76 52 H 6-F H e ⁿ D - 1.5555 68 53 H 6-F - H m ⁿ D - 1.5601 72

The starting phenoxybenzyl alcohols can be prepared as follows;

a) Ret'erene Example: Preparation of Compound A A solution of 3- (3-fluorophenoxy) toluene (90 g, 0/145 mol) and N-bromosuccinimide (79.3 g) in refluxing 300 ml of 300 ml of anhydrous tetrachloride was refluxed. boil in a well-equipped dish. After reaching a temperature of 70 ° C, 5 g of azo diisovacetic acid nitrile were added, after about 10-20 minutes, the exothermic reaction started, after which the reflux was continued for 4 hours. The reaction mixture was cooled to 10 ° C, succinimide was filtered off and the carbon tetrachloride was distilled off under reduced pressure. The residual oil was distilled at 143-150 ° C under 1 torr. 72.9 g (58.2% of theory) of 3- (3-fluorophenoxy) benzyl bromide are obtained.

The following compounds can be prepared analogously:

Boiling point: 145-150 ° C / 1 torr

Yield: 61% of theory

Compound C

Boiling point: 160-165 ° C / 3 torr Yield: 54.5% of theory.

b) Reference Example

Preparation of Compound D

47.8 g of hexamethylenetetramine and 48 g (0.17 mol) of 3- (3-fluoro-phenoxylbenzyl bromide) were dissolved in 250 ml of methylene chloride and refluxed for 3 hours. This was washed with 100 ml of methylene chloride, sucked dry, and then refluxed in 100 ml of 50% aqueous acetic acid for 5 hours, followed by the addition of concentrated hydrochloric acid (25 ml) for a further 30 minutes. The reaction mixture was then heated to reflux and finally cooled to 10-20 ° C. To the reaction mixture was added 200 ml of water, extracted with ether (2.times.150 ml) and the combined ether layers were washed with sodium bicarbonate solution and dried over sodium sulfate. 3- (3-Fluorophenoxy) benzaldehyde was obtained by distillation in vacuo to give the following compounds as a source (142-148 ° C).

Melting point: 48 ° C

Yield: 62% of theory

Compound F

Refractive index: n ^ = 1.6109 Yield: 67% of theoretical value c,) Reference Example

21.6 g (0.1 mol) of 3- (4-fluorophenoxy) benzaldehyde are dissolved in 25 ml of glacial acetic acid and 5 ° C, with a solution of 10.2 g of sodium cyanide in 25 ml of water are added dropwise with stirring. Finally, the mixture was stirred for 8 hours at 20 ° C, poured into water (100 ml), extracted with ether (200 ml) and the ether phase separated. To remove the glacial acetic acid, the ether layer was washed with dilute aqueous sodium hydrogen carbonate solution and dried over sodium sulfate. . The ether was distilled off under reduced pressure to give 17 g (70% of theory) of 33- (4-fluorophenoxy) -cyanobenzyl alcohol, with refractive index n = ³ = 1.5643.

The following compounds can be prepared analogously: Compound H

Our refractive index = 1.5561

Yield: 93% of theory: Compound I

Refractive index n k = 1, 5700 Yield: 69% of the theoretical value of Compound J

The yield is 88% of the theoretical value. Reference Example c, 2.4 g (0.1 mole) of magnesium chips mixed in anhydrous tetrahydrofuran, dropwise, 14 g (0.13 mole) of bromoethane are added dropwise with stirring and the resulting mixture is stirred at 50 ° C for 30 minutes. stir over. The resulting Grignard solution was poured into a drip funnel under a nitrogen atmosphere and dropwise added to a solution of acetylene in 40 ml of anhydrous tetrahydrofuran at 20 ° C in small portions. At the same time, further acetylene is introduced and the addition is continued after a drop of 30 to 45 pounds. A solution of 3- (4-fluorophenoxy) -benzaldehyde (10.8 g, 0.05 mol) in absolute tetrahydrofuran (50 ml) and the resulting mixture was added dropwise to the resulting suspension of ethinylmercum bromide at 25-30 ° C (0.05 mol). for 40 hours. The reaction mixture was then cooled to 10 ° C, poured into 500 ml of ice-water and the resulting precipitate was dissolved by the addition of concentrated hydrochloric acid. The resulting solution was extracted with ether (2 x 150 mL), the ether layers were dried over sodium sulfate, and the ether was distilled off under reduced pressure, 7.3 g (61% of theory) of 3- (4-fluorophenoxy) -ethynyl. - benzyl alcohol is obtained in the form of a yellow oil having a boiling point of 160-180 ° C / 3 torr. c ₃ ) Refraction example

A solution of 3- (4-fluorophenoxy) benzaldehyde (50 g, 0.25 mol) in 50 µl of anhydrous ether was added dropwise to a solution of 3.8 g of lithinuminium hydride in 100 µl of anhydrous ether at constant boiling temperature. The resulting mixture was stirred at 22 ° C for 10 hours, then cooled to 0 ° C and, with stirring, dropwise addition of glacial acetic acid until hydrogen evolution was observed. The resulting precipitate was dissolved by the addition of 10% by weight sulfuric acid, and the reaction mixture was extracted with 2x100 ml of food. The ether layers were separated, washed with saturated aqueous sodium chloride solution and dried over sodium sulfate. The ether was distilled off in vacuo to give 41.5 g (76.1% of theory) of 3- (4-fluorophenoxy) benzyl alcohol having a refractive index of n = 1.5725.

The following compounds can be prepared analogously: Compound M

Yield: 76% of theory

Compound N

Yield: 71% of theory

Refractive index n = 1,6009.

Claims (7)

SEQ ID NO: 1: An insecticidal and acaricidal composition comprising, as active ingredient, a substituted phenoxybenzyloxy derivative of the formula I in the formula (I). -R is fluoro or bromo; -R * is hydrogen; -R ² is cyano or ethinyl or hydrogen: R ³ represents a group of formula (VII) are those wherein: - - R ⁴ and R ^{s has} the same meaning chlorine or bromine atom or a methyl group, or a group of formula (VIII): wherein - - R ^& optionally substituted by halogen, substituted by C1-4 alkyl or methylene dioxy phenyl group, __ with the proviso that if R ² is hydrogen, in formula (VII), R ^{4 and} R always represents a chlorine atom and a compound of formula (VUI) R ⁶ different meanings of unsubstituted phenyl groups - From 0.005 to 90% by weight, with solid carriers commonly used in plant protection, suitably natural or synthetic calcareous, and / or liquid diluents, preferably aromatic hydrocarbons, their derivatives and / or alcohols, and optionally surfactants, suitably nonionic or anionic emulsifiers and / or or dispersing agents. 2. A process for the preparation of a substituted phenoxybenzyloxy derivative of the formula (1) for use as an active ingredient of the composition of claim 1 - wherein R, R ¹ , R ² R ³ R ⁴ , R ^s and R ⁶ are 1 in the formula 1 as defined in claim 1, characterized in that a halogen of formula (II) in the formula (II): "Hal" represents a halogen atom, preferably a chlorine atom; -R ³ is reacted with the indicated meaning of a substituted phenoxybenzyl alcohol of formula III in the formula III; R, R * and R ^{1 are} as defined in the specification, optionally in the presence of an acid acceptor and optionally a solvent. Published by: National Office of Invention, Budepest The walls of the Fall: Zoltán Hlmer Head of Department /. / 1 drawing 176 198 International classification: A 01 N 9/00 C 07 C 69/76, C 07 C 69/74, C 07 C 121/75 C 07 C 43/20 Scheme CHO + 3 NH3 + 51 ^ 00 + [CH3NH3] ® Hal® R (IV) 11/2 176 198 International classification: A 01 N 9/00 C 07 C 69/76, C 07 C 69/74, C 07 C 121/75 C 07 C 43/20 Scheme B D + L1AIH 4 2) + 2 H 2 O LiA 10 and C = CH CH-OH Br ^ Q 0 1X / 3 176 198 International classification: A 01 N 9/00 C 07 C 09/76, C 07 C 69/74, C 07 C 121/75 C 07 C 43/20 (1, ^CH / ^CH \ t CH3 CH ₃ CHj — 0— (2) CH2-0 - co X CH ₃ ch ₃ CH = C CH ₃ CH3 0) CI + 3 CH ₃ (4) .xra CH2-0— CO — CH — α THE CH3 CH3 ( 5) 11/4 cl Br ( 6) (7) C (O-CO-r _HH 0> _Br . CH / ch ₃ ch ₃ (10)) 176 198 International classification; A 01 N 9/00 7o. C 07 C 69/74, C 07 C 121/1 C 07 C 43/20 11/5 CN CH < ^ 0-CO-CH ' THE CH3 CH3 CH3 (11) CN ^x 0 —CO-CH- ^ _ ^ -CH ₃ CH CH ₃ ^X CH3 (12) O-CO-CH- [23] Br, CH / \ t CH3 _CH3 (13) -CO-CH - / V-CI | rT CH ch ₃ ch ₃ (14) _X CN% —CO — CH — QC. Λ 0¾ XHy (15) 176 198 International classification: A 01 N 9/00 C 07 C 69/76. C 07 C 69/74, C 07 C 121/75 C 07 C 43/20 11/6 CO-CH I Z ^CH \ t CH3, CH3 (16) O-CO-CH- / ^C ₃ ch ₃ (17) ch ₂ -O-co CH = C cl Cl (18, o-co.) CH? CN CH "C 0¾ (19, _F xr XX 0 + 3 Cl *, CH = C CH3 CMj (20) 176 198 International classification: A 01 N 9/00 C 07 C 69/76, C 07 C 69/74, C 07 C 121/75 C 07 C 43/20 tt / 7 CN cl CH o-co CH3 CH3 CH = C (22) CsCH, χζσ CH 2 O-CO-CH-CH-CH = C 2 Z \ t CH3 CH3 (23) cl Cl (24, CN 0CO-CH — CH-Oi CH3 ch ₃ (25) 11/8 176 198 International classification: A 01 N 9/00 C 07 C 69/76, C 07 C 69/74, C 07 C 121/75 C 07 C 43/20 CN CH3 CH3 (26) Cl (27) CH? -0-C0-CH I% CH2 XH3 Br (28) (29) (30) 176.198 lX / 9 International classification: A 01 N 9/00 C 07 C 69/76, C 07 C 69/74, C 07 C 121/76 C 07 C 43/20 CH-00C-CH CH3 (31) (32) (a) H3C _z CH ₃ (d) 176 198 International classification: A 01 N 9/00 C 07 C 69/76, C 07 C 69/74, C 07 C 121/75 C 07 C 43/20 11/10 176 198 International classification: A 01 N 9/00 C 07 C 69/76. C 07 C 69/74. C 07 C 121/75 C07 C 43/20 12, 11 (N) 12/12 176 198 International classification: A 01 N 9/00 C 07 C 69/76, C 07 C 69/74, C 07 C 121/76 C 07 C 43/20 (II) (IV) HCsC-MgHal X CH3 CH3 CH = C * RS (VII) (Fruit)