HU180202B - Insecticide and acaricide compositions containing halogenated esters of benzyl-alkohol and cyclopropane carboxylic acid as active agents,and process for producing the active agents - Google Patents

Abstract

Cyclopropane carboxylic esters of formula (I) are new:-(R=F, Cl, Br, and when R=F or Br, then m=0-5, n=0-5 but m and n are not both 0. When R=Cl, m=0-4; n=1-5. When m=0 and n=5, R can also be CH3). (I) have low toxicity to warm-blooded animals, excellent residual activity on wood and clay, and are stable on white-washed surfaces. In an example, reaction of pentafluorobenzyl alcohol with 2,2-dimethyl-3-dichlorovinyl-cyclopropane carboxylic acid gave pentafluorobenzyl 2,2-dimethyl-3-dichlorovinyl-cyclopropanecarboxylate.

Description

Insecticidal and acaricidal compositions containing cyclopropanecarboxylic acid esters of halogenated benzyl alcohol as active ingredient and process for their preparation

FIELD OF THE INVENTION The present invention relates to insecticidal and acaricidal compositions which contain as active ingredient 0.1 to 95% by weight of a carboxylic acid ester of a cyclopropanoyl halogenated benzyl alcohol in admixture with excipients and / or surfactants.

In the formula (1):

- R and R '

- m

- n is independently chlorine or bromine; means 0-3:

1-5; provided that / rn + n / max

The invention further relates to a process for the preparation of the new compounds of formula (I).

The active compounds of formula (I) are prepared by reacting a compound of formula (11) - R and R ^r are as defined above, and R 1 is hydroxy, C 1-4 alkoxy or halogen according to formula (111). compound

n and m are as defined above at -20 ° C to 120 ° C, optionally in the presence of an inert diluent; or b) a salt of Formula IV, wherein R * of R is as defined above and l1 * is an alkali metal, alkaline earth metal cation or ammonium ion, m or n is a above, at a temperature of 20-100 ° 0 in a polar solvent;

-1 '! 180 202

Esters of 2,2-dimethyl-3- (2-methylbuten-1-yl) -cyclopropanecarboxylic acid with polychlorinated benzyl alcohol are known to have insecticidal properties (see French Patent No. 2,271,196). However, the speed, magnitude and duration of action of these compounds are not always satisfactory.

The benzyl ester derivatives of the present invention have surprisingly potent and rapid insecticidal and acaricidal activity. Thus, the active compounds of the invention represent a valuable extension of the range.

The novel active compounds of the invention are generally defined by formula (I). In the formula (1):

R and R * are preferably chlorine or bromine;

m is preferably 2-3;

n is preferably 3-5;

with the proviso that / m + n / „„ _v = 5 · ul .iX

The active compounds of the present invention form several stereoisomers. The substituents on the cyclopropane ring may be cis or trans with respect to one another. Each of the carbon atoms 1 and 3 can be R-. or S-configuration may give the vegyü- formulas ¹ · optically active in and racemic cis and trans isomers.

Examples of compounds of the invention include:

2,2-Dimethyl-3- (dibromo-vinyl) -cyclopropanecarboxylic acid pentafluorobenzyl ether;

2,2-Dimethyl-3- (dichloro-vinyl) -cyclopropanecarboxylic acid pentafluorobenzyl ester;

2.2-Dimethyl-3- (dichloro-vinyl) -cyclopropanecarboxyl-2,3,5,6-

-tetrafluor benzyl éazter; '· ............

2,2-dimethyl-3- (dichloro-vinyl) -cyclopropanecarboxylic acid 2,4,6-trifluorobenzyl-ether;

2,2-Dimethyl-3- (dichloro-vinyl) -cyclopropanecarboxylic acid 2,3,5-trifluorobenzyl ester;

2,2-dimethyl-3- (dichloro-vinyl) -cyclopropanecarboxylic acid 2,4-difluorobenzyl ester;

2,2-dimethyl-3- (dichloro-vinyl) -cyclopropanecarboxylic acid 2,6-difluorobenzyl ester; .... ............... . .............................. ..................... ...

2,2-Dimethyl-3- (dichloro-vinyl) -cyclopropanecarboxylic acid tetrafluoro-3-chloro-benzyl ester;

2,2-Dimethyl-3- (dichloro-vinyl) -cyclopropanecarboxylic acid 2,3,6-trifluorobenzyl ester;

2.2-Dimethyl-3- (dichloro-vinyl) -cyclopropanecarboxylic acid trifluoro-3,5-dichloro-benzyl ester;

2,2-Dimethyl-3- (dichloro-vinyl) -cyclopropanecarboxylic acid 2,6-difluoro-3,5-dichloro-benzyl ester;

2,2-Dimethyl-3- (dichloro-vinyl) -cyclopropanecarboxylic acid 2,3-difluoro-5-chloro-benzyl ester;

2.2-Dimethyl-3- (dichloro-vinyl) -cyclopropanecarboxylic acid 2-fluoro-

-3,5-dichlorobenzyl ester and the corresponding 3-dibromo-vinyl compounds.

The esters listed herein may be racemic or optically active, cis, and trans isomers.

a / procedure

If 2,2-2180202; -dimethyl-3- (dichloro-vinyl) -cyclopropanecarboxylic acid chloride is used as starting material (11), pentafluorobenzyl alcohol is used as benzyl alcohol derivative (111), and the reaction is carried out. illustrated in Scheme a /.

The compounds of formula (11) - R, R * and R 4 are as defined - are known / 1. German Patent Publication No. 2,439,177 /.

Benzyl alcohol derivatives of formula (111)

m and n are as defined in the. J. Chem. Soc. C, 293 (1967); J. Chem Soc., 3227 (1962); J. Wow. Soc., 808 (1961); J. Chem. Soc., 166 (1959); J. Med.Chem »11, 814/1968 /.

Novel benzyl alcohol derivatives of formula (111)

m and n are as defined in a manner known per se, such as the corresponding carbonyl derivatives of formula VIII: m and n are as defined and Y is hydroxy, alkoxy, chloro, fluoro or by reduction of a hydrogen complex with a metal hydride.

For example, when excess lithium aluminum hydride is used, one or two fluorines may be cleaved from the ring at the same time as the reduction.

The carbonyl derivatives of formula VIII, the starting materials for the reduction - m and n and Y are as defined in the above section. The new compounds can be prepared in an analogous manner to known methods. Synthesis 1976, 652 /.

The reduction of aldehydes or acid halides of formula VIII is illustrated in the following scheme - 2,4,6-trifluorobenzaldehyde-ad /.

In Scheme d /, Scheme 1 illustrates the reduction of the carbonyl functionality with metal hydrides such as sodium borohydride or lithium aluminum hydride. The reduction is carried out in the presence of an inert organic diluent at 0-100 ° C.

For example, in addition to the sodium borohydride reduction, water may be used as a diluent, in addition to the inert organic diluents, such as ethers (such as diethyl ether, dioxane, tetrahydrofuran), alcohols such as ethyl or methyl alcohol, and aqueous mixtures thereof.

Aprotic inert organic diluents such as ethers (such as ethyl ether, dioxane, tetrahydrofuran) may be used as diluents for other complex metal hydrides such as lithium aluminum hydride.

The compounds of Formula VIII to be reduced, m, h, and Ϊ are as defined, are dissolved in one of the diluents mentioned and the reducing agent is added to the solution, however, at low temperatures, 7-30 / - / - 50 The reducing agent is added at / ° C in a solvent and the reduction is carried out by slowly raising the temperature (optionally to 50-60 ° C).

The reaction is carried out in the usual manner at atmospheric pressure.

The reaction mixture is optionally worked up by adding the same amount of water as the reducing agent added, separating the phases and distilling the organic phase.

If lithium aluminum hydride is used as the reducing agent, then only the carbonyl-swept reduction is applied3

-3180202, only the stoichiometric amount of lithium aluminum hydride is added. When a reducing metal hydride, such as a weaker one, is used, the excess metal hydride does not affect the course of the reaction.

Scheme 2 of Reaction Scheme d / shows the reductive removal of the p-position fluorator with simultaneous reduction of carbonyl. Lithium aluminum hydride is used as the reducing agent for this reaction. Carbon! In addition to the lithium aluminum hydride required for the sweep reduction, a further stoichiometric amount of lithium aluminum hydride must be added to each fluorine substituent to be removed.

Particularly suitable diluents for this reaction are ethers, especially tetrahydrofuran.

The reduction of lithium aluminum hydride is carried out at a temperature of from 20 ° C to 100 ° C, preferably from 50 ° C to 70 ° C. Set up the reaction conditions as described above and process the reaction mixture.

Examples of compounds of formula (III) wherein m and n are as defined are: pentafluorobenzyl alcohol; 2,3,5,6-tetrafluoro-benzyl alcohol;

2.4.6-trifluorobenzyl alcohol; 2,3,5 ^"fc xifluor-benzyl alcohol;

1,4-difluorobenzyl alcohol; 3,5-difluoro-benzyl alcohol:

2,6-difluorobenzyl alcohol; tetrafluoro-3-chlorobenzyl alcohol; , 2,4,6-trifluoro-3,5-üiklór benzi1-alcohol; 2,3-difluoro-5-chloro-benzyl alcohol; 2-fluoro-3,5-dichlorobenzyl alcohol.

When R and / or R * is bromine, the following benzyl alcohol derivatives are preferably used in addition to the above:

2.3.5.6-tetrachlorobenzyl alcohol; 2,3,4,5-tetrachloro-benzyl alcohol; 2,3,4,6-tetrachloro-benzyl alcohol; 2,3, ^ - trichloro-benzyl alcohol; 2,4,5-trichloro-benzyl alcohol; 3,5-dichloro-benzi1 alcohol; 2,4-dichlorobenzyl alcohol; 2,6-dichloro-benzi1 alcohol.

As mentioned above, some of the benzyl alcohol derivatives of formula (111) are new compounds. A more specific group of the novel compounds of formula (III) are the benzyl alcohol derivatives of formula (III) - m 'is 0-2 and n' is 1-4, provided that when m 'is 0 and n * represents 2, then the 6-position of the phenyl ring must be unsubstituted - represent.

The following novel benzyl alcohol derivatives are particularly preferred:

2.3.5.6-tetrafluorobenzyl alcohol; 2,4,6-trifluoro-benzyl alcohol; 2,3,5-trifluoro-benzyl alcohol; 2,4-difluorobenzyl alkoholf

3.5-difluorobenzyl alcohol; 3-chloro-tetrafluoroethane benzi1 alcohol;

2.4.6-Trifluoro-3,5-dichlorobenzyl alcohol; 2,6-difluoro-3,5-dichlorobenzyl alcohol; . 2,3-difluoro-5-chlorobenzyl alcohol; 2-fluoro, 5-dichlorobenzyl alcohol.

Process b) When the sodium salt of 2,2-dimethyl-3- (dichloro-vinyl) -cyclopropanecarboxylic acid is used as the salt of formula (IV) and the pentafluorobenzyl chloride is used as the benzyl chloride derivative of formula (V), the progress of the reaction is illustrated by b / scheme *.

A / IV / starting salts of formula - R, R * and M ^{+ 1} je-

Save as specified - known / German Federal Publication No. 2,436,178! document /. The benzyl halide reaction partners of formula (V) - m and n are as defined - are known in part to 55 · Ohem. Soc., J227 / 1962 /}.

The benzyl chloride derivatives of the formula V can be prepared in a manner analogous to known procedures, for example by halogenation of the corresponding toluene derivatives or by chlorination of the corresponding benzyl alcohol derivatives 111, for example by treatment with thionyl chloride. An example of a benzyl chloride derivative for use in the process of the invention is pentafluorobenzyl chloride.

The reaction of process b) is carried out in polar organic diluents such as ketones (such as acetone), nitriles (such as acetonitrile), acid amides (such as dimethylformamide), hexamethylphosphoric triamide or aqueous mixtures thereof. The reaction temperature is 20-100 ° C.

The reaction is carried out in the presence or absence of a suitable catalyst. Suitable catalysts include polyalkylated polyarrides (e.g., tetramethylethylenediamine). The reaction conditions are described in Synthesis (1975, 805).

The active compounds of the present invention are well tolerated by plants and have no significant toxicity to warm-blooded animals, and can therefore be used against animal pests, particularly insects and arachnids, for the protection of stored products and for health. They are effective against pests that are normally sensitive and resistant at various stages of development.

Pests which can be controlled by the compositions of the invention include:

from the order Isopoda, for example, Oniscus acellus, Armadillidium volgare, Porcellio scaber; ~, —For example, from the order of the Diplopoda, Blaniulus guttulatus; from the order of Ohilopoda, e.g., Geophilus carpophagus, Scutigera spec .;

from the order of the Symphyla, for example Scutigerella immaculata; from the order of Thysanura, for example Lepisma saccharina; from the order of the Oollembole, for example Onychiurus armatus;

from the order of Orthoptera, such as Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spec., Losusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria; from the order of the Dermaptera, for example Forficula auricularia; from the order of Isoptera, for example Reticulitermes Spec .;

from the order of Anoplura, e.g., Phylloxera vastatrix, Pemphigus spec., Pediculus humanus corporis, Haematopinus spec., linognathús spec .;

from the order of Mallophaga, e.g. Teichodestes spec., Damalinea spec .;

from the order of the Thysanoptera, for example Herinothrips femoralis, Thrips tabaci; ----------------------------------------------- from the Order of Heteroptera , e.g., Eurygaster spec., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spec .;

from the order of Homoptera, such as aleurodes brassicae. Bemisia, tabaci, Trialeurodes vaporariorum, Aphis goseypii, Brevicoryne 'brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eroisoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzusi spas, Phorodon humuli,

-5180202 spec., Euscelis bilobatug, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax stritellus, Nílaparvata lugens, Aonidiella aurantii, Aspidiotus Hederae, Pseudococcug gpec · .. Psy 11a spec »;

from the order of Lepidoptera, e.g. Pectinophora gossyplella, Bupalus piniarius, Oheimatobia brumata, Lithocellctis bíancerdella, Hyponoraeuta padella, Plutella maculipennis, Malacosoma neugtria, Euprectiis chrysorrhoea, Iymantria gpec. ., Earisa insulans, Heliothig spec., Iaphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spdoptera gpec., Trichoplusiani, Carposapsa pomonella, Pieris spec., Chilo spec., Pyrausta nubilalis, Ephestia kuehniella, Capua reticulans, Choristoneura fumiferana, Clysis ambiguella, Homona magnanima, Tortrix viridana;

from the order of the Goleoptera, e.g., Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Laptinotarsa decemlineata * Phaedon cochleariae, Diabrotica specia, Psylliodes chroysys, , Sitopilus spec., Otiorrhynchus sulcatus, Cosmepolites sordidus, Ceuth.orrhynch.us assimilis, Hypera postica, Dermestes spec., Trogoderha spec., Anthernus spec., Attagenus spec., Lyctus spec., Meligethes aeneus, Ptinas spec. , Gibbium payllodiea, Tribolium spec., Tenebrio molitor, Agriotes gpec., Gonoderus gpec., Melolontha melolontha, Amphimallon solstitualis, Costelytra zealandica;

from the order of Hytnenoptera, e.g., Diprion spec., Hoplocampa spec., lasius gpec., Monomorium pharonis, Vespa apec .; from the order of Diptera, e.g., Aedes spec., Anopheies spec., - Culex apec., Drosophila melanogaster, Musca spec., Fannié spec., Oalliphora erythrocephala, Lacilia gpec., Chryaotnyia spec., Cuterebra apec., Gastrophilus. spec., Hyppobosca spec., Stomoxys spec., Oestrus spec., Hypoderma spec., Tabanus spec ;, Tannia spec., Bibio hortulanug, Ogcinella frit, Phorbia spec., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae ,, Tipula paludosa;

from the order of the Siphonaptera, e.g., Xenopsylla cheopie, Ceretőphyllus spec .;

from the order of -Arachnida, such as Scorpio maupus, Latrodectus mactans;

from the order of Acarina, for example, Acarus crying, Argag spec., Ornithodoros spec., Dermanyssus gallinae, Eriophes ribis, Phylloceoptruta oleivora, Boophilus spec., Rhipicephalus spec., Amblyomma spéci, Hyalomma spec., Ixodes spec., Phoroptes spec. , Sar'coptes spec. , Tarsomenus spec., Bryobia praetiosa, Panonyohus epeo., Tetranyohus spec.

The active compounds of the present invention are formulated into conventional formulations such as solutions, emulsions, sprays, suspensions, powders, dusts, foams, pastes, soluble powders, granules, aerosols, emulsifiers, suspensions, emulsifiers, and synthetic materials, capsules encapsulated in polymeric materials, seed coatings, combustible formulations such as incense cartridges, cans, spirals, and ultra-small volume / ÜLV / 'cold' and hot mist formulations,

These formulations are prepared in a known manner, for example, by mixing the active compounds with excipients, such as liquid solvents, pressurized liquid bound gases and / or solid carriers, optionally using surfactants such as emulsifiers and / or dispersants and / or or foaming agents. When water is used as a filler, auxiliary solvents such as organic solvents may be used.

Liquid solvents include: aromatic hydrocarbons such as xylene, toluene, benzene or alkylnaphthalenes and chlorinated aromatic or aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride and aliphatic hydrocarbons such as cyclohexane or paraffin, e.g. alcohols such as butanol or glycol; and ethers or esters of these alcohols: ketones such as acetone, methyl ethyl ketone, methyl 1-isobutyl ketone. or cyclohexanone: highly polar solvents such as dimethylformamide, dimethylsulfoxide and water.

Liquid fillers or carriers which are gaseous at ordinary temperatures, such as aerosol propellants, such as halogenated hydrocarbons such as freon, butane, propane, nitrogen and carbon dioxide may be used.

Solid carriers include natural rock flour such as kaolins, clays, talc, chalk, quartz, attapulgite, Mont Moron Honit or diatomaceous earth, and synthetic rock flour such as highly dispersed silica, alumina and silicate; solid carriers for granules of crushed or fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite, and synthetic granules of inorganic or organic rock flour, and granules of organic materials such as sawdust, coconut shells and tobacco stalks.

Nonionic and anionic emulsifiers, such as polyoxyethylene / fatty acid esters, polyoxyethylene / fatty alcohol ethers, such as, for example, alkylaryl, can be used as emulsifying and / or foaming agents. polyglycol ethers, alkyl ulphonates. alkyl sulfates, aryl sulfonates, and protein hydrolysates: lignin, sulfite alkali and methyl cellulose as dispersants.

The compositions may also contain adhesives such as carboxymethylcellulose, natural and synthetic powder, lump or latex-like polymers, gum arabicum, polyvinyl alcohol, polyvinyl acetate.

In addition, inorganic pigments such as iron oxide may also be used. titanium (II) oxide, ferrocyanic blue and organic dyes such as alizarin, azo-metal phthalocyanine dyes and biological trace elements such as iron, manganese, boron, copper cobalt, molybdenum and zinc.

The compositions according to the invention generally contain from 0.1 to 95% by weight, preferably from 0.5 to 90% by weight, of the active ingredient.

The active compounds of the present invention may be used in the form of commercially available formulations and / or as ready-to-use formulations prepared from these formulations.

Occasionally made from commercial formulations

The active ingredient concentration of the -7180202 ready-to-use formulations ranges from 0.0000001 to 95% by weight, preferably 0.01 to 10% by weight.

Ready-to-use formulations are used in any suitable form.

When used in health care and stockpile storage, the active ingredients are distinguished by their excellent residual activity on wood and clay as well as their good alkaline stability on whitewashed surfaces.

The example

Aerosol test

Experimental animals: Phosphoric ester resistant Musca domestica

Solvent: acetone

The active compounds are dissolved in the desired amount of acetone to form a suitable formulation.

A wire cage was hung in the middle of a gas-impermeable glass canister, in which 25 experimental animals were placed. The chamber was then resealed and sprayed with 2 ml of the drug formulation. Are the conditions of the experimental animals constantly monitored through the glass walls and determined? the time needed for the 100% destructive effect. *

Table I lists the active compounds tested, the amounts applied and the time required for the 100% killing effect:

Table I

Aerosol test / Musca domeetica, resistant /

Formula number of active ingredient in 2 ml acetone / mg /

/ 1 / 1 55 ' / 2 / and / 3/1: 1  15 * 55 / 4 / 5 * 25 / 7 / 15 6Ο'χ »47% / S / Aransz isomer / 1 26 »

Example B

Laphygma test

Solvent: 3 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

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

The cotyledon composition is sprayed on cotton leaves / Gossypium hirsutum / dew-damp and introduced with owl moth caterpillars / laphygma exigua.

After a given time, the efficiency is determined as a percentage. 100% means that all caterpillars are dead, 0% means that “no caterpillars are destroyed.

-8180202

The active ingredients ;, the concentration of the active ingredient, the evaluation times and the results obtained are shown in Table II. in the table below:

II. Table 5 The formula number of the active ingredient / insect pests / ha Concentration of material /% / Efficiency 3 days later /%/ / 4 / 0.1 100 0.01 100 / 1 / . o, i 100 0.01 100 / 16 / 0.1 100 0.01 100 / 8 / and / 15 / Isi 0.1 100 0.01 100 0,001 90 / 2 / and / 3/1: 1 0.1 100 0.01 100 0,001 100

Example 0

Limit concentration test / soil insects /

Experimental animal: Tenebrio molitor larvae in soil Solvent: 3 parts by weight of acetone

Elution agent: 1 part by weight of alkylaryl polyglycol ether

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

The active compound formulation is thoroughly mixed with the soil. The active ingredient concentration of the preparation is practically irrelevant here, only the amount of active ingredient per unit volume of soil, which is given in ppm / mg / l, is decisive. The soil is filled into pots and allowed to stand at room temperature.

After 1 hour, add the experimental animals to the treated soil and add 2 to 2 hours. days later, determine the efficacy of the active ingredient by counting the number of dead and living animals. The efficacy is 100% if all experimental animals are killed and 0% if the same number of animals as the untreated control survived.

The active ingredients, the amounts of the active ingredients and the results obtained are shown in Annex III. in the table below:

III. spreadsheet

Old Test / Tenebrio molitor larvae in soil /

Effectiveness in% 1, 2> ppm drug concentration

The active compound has the formula number / structure / / 1 / / - / cis

100/1/100/20 / / - / R trans100 / 20 / / - / cis / trans100 / 13 / - - / cis / tranaz 100

Example D>

Boundary contamination test / soil insects / Experimental animal: Agrotis segetum 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 formulation, 1 part by weight of the active ingredient is mixed with the indicated amount of solvent and emulsifier and the concentrate is diluted with water to the desired concentration * - ------ ----- The active ingredient formulation is thoroughly mixed with ground. The active ingredient concentration of the preparation is practically irrelevant here, only the amount of active ingredient per unit volume of soil, which is given in ppm / mg / l, is decisive. The soil is filled into pots and allowed to stand at room temperature.

after one hour, add experimental animals to the treated soil and, after a further 2-7 days, determine the percentage of active ingredient by counting the number of dead and living experimental animals; The efficacy is 100% when all experimental animals are killed and 0% if the same amount of untreated control animals is alive.

The active ingredients, the amounts of active ingredients and the results obtained are shown in Table IV. in the table below:

ARC. spreadsheet

Limit concentration test / Agrolis segetum larvae in soil /

Active ingredient% Effectiveness at 1.25 ppm formula / structure / active ingredient concentration

/ 1 / / - / / cis 100 / V 100 / 20 / / - / R trans 100 / 20 / - - / cis / trans 100 / 13 / - - / cis / trans 100

This is an example

Limit concentration test / soil insects /

Experimental animal: Biorbia antiqua 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 formulation, 1 part by weight of the active ingredient is admixed with the indicated amount of solvent and emulsifier and the concentrate

-10180202 is diluted with water to the desired concentration.

The active compound formulation is thoroughly mixed with the soil. The concentration of the active ingredient is practically irrelevant here, only the amount of active ingredient per unit volume of the soil, which is given in ppm / mg / l, is decisive. The soil is filled into pots and allowed to stand at room temperature after after a further 2 to 7 days, determining the efficacy of the active ingredient by counting the number of dead and living experimental animals. The efficacy is 100% when all experimental animals are killed and 0% if the same amount of untreated control animals is alive.

The active ingredients, the amounts of active ingredients and the results obtained are given in Table V:

Table V.

Limit concentration test / Phorbia antiqua larvae in soil /

The formula of the active ingredient- number / structure / —---------------------------- Efficiency% at 1.25 ppm active ingredient- / 1 / / - / / cis 100 / V 100 / 20 / / - / R trans 100 / 20 / - - / cis / trans 100 / 15 / - - / cis / trans 100

Example P

Tetranychus Test / Resistant / Solvent: 3 parts by weight acetone Emulsifier: 1 parts by weight alkyl aryl polyglycol ether

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

The bean plants (Phaseolus vulgaris), which are highly contaminated with individuals of all stages of the development of the common horse mackerel (Tetranychus urticae), are immersed in the desired concentration of active ingredient.

After the desired time, the percentage efficacy of the formulation is determined. Here, 100% means that all mites have been killed and 0% means that no mites have been killed.

In this assay, the following compounds are significantly more potent than those known in the art: Table VI

Tetranychus Test / Pest Control /

Formula of active ingredient- Concentration of active ingredient- Efficiency after 2 days /% / structure /% in% / 1 / cis 0.1 100/1 / / - / trans 0 »l 9 °

-11180202

Formula number / structure / Active ingredient concentration:% Percentage after 2 days in% / 20 / 0.1 100 / 13 / cis / trans 0.1 100 / 1 / 0.1 . 95 / 4 / 0.1 95

Example G ·

Laphygma test

Solvent: 3 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable formulation of the active ingredient, one part by volume of the active ingredient is mixed with the specified amount of solvent and the specified amount of emulsifier and the concentrate is diluted with water to the desired concentration.

Cabbage leaves (Brassica oleracea) are immersed in the desired concentration of the active ingredient and the leeks filled with owl moth caterpillars (Laphygma frugiperda) before drying.

After the desired time, the percent efficiency is determined. Here 100% means that all caterpillars are dead and 0% means that no caterpillars are dead.

In this test, the following compounds are significantly more potent than the active compounds known in the art:

VII. spreadsheet

Laphygma Trial / Plant Pest Insects /

Formula of active ingredient- Concentrate of active ingredient- Effectiveness% after 3 days / structure / ration%

/ 1 / cis 0.1 100 0.01 100 0,001 100 / 1 / / - / trans 0.1 10o 0.01 - .......-. .. 100 ----------- 0,001 100 / 20 / cis 0.1 100 0.01 100 0,001 100 / 13 / cis / trans 0.1 100 0.01 100 0,001 100 / 12 / trans 0.1 ......... 100 0.01 100 0,001 100 / 11 / trans 0.1 100 0.01 100 • 0,001 100 / A / / known / 0.1 100 0.01 100 0,001 .0

-12180202

Example H

Ι / Γ

The ΙΟθ-test on a double-winged beaker was taken up in 1000 parts by volume of solvent. The resulting solution is diluted with additional solvent to the desired concentration.

Pipette 2.5 ml of the active ingredient solution into a petri dish. A 9.5 cm diameter filter paper was previously applied to the bottom of the pet * rice. The petri dish remains open until the solvent is completely evaporated. Depending on the concentration of the active ingredient solution, 1m ^{2 of} the filter paper contains different amounts of the active ingredient. Finally, the required amount of experimental animal is added to the petri dish and covered with a glass lid.

The condition of the experimental animals is constantly monitored and the time required for a 100% knock-down effect is measured.

In this test, the following compounds are significantly more potent than those known in the art:

. ............. ........... VIII. spreadsheet Iff ₁₀₀ test on double wings ^M 100 Formula number / structure / If the concentration of the material in the solution is /% / / A / / known / 0.02 6 ^h / 1 / / + / cis 0,002 25 ' / 11 / / + / trans '0.02 20 ' / 1 / / - / trans 0,002 15 ' / 15 / / + / cis 0.02 20 ' / 15 / / + / cis / trans 0.02 50 '

Preparation Examples

1 / Dusting agent

For the purpose of preparing the active ingredient formulation, 0.5 parts by weight of the active ingredient are mixed with 99.5 parts by weight of natural stone flour and ground to a powder. The resulting composition is sprayed on the plants or their habitat in the desired amount. 2 / Spray powder / Diaperspirable powder /

To prepare a suitable active ingredient formulation, 25 parts by weight of the active ingredient are mixed with 1 part by weight of tibutyl naphthalene sulphonate, 4 parts by weight of lignin sulphonate, 6 parts by weight of highly dispersed silica and 62 parts by weight of natural stone meal and powdered. Before use, the wettable powder is mixed with water so that the resulting mixture contains the active ingredient in the desired concentration.

3 / Emulsifiable concentrate

To prepare the active ingredient formulation, 25 parts by weight of the active ingredient are dissolved in a mixture of 55 parts by weight of xylene and 10 parts by weight of cyclohexanone. As the emulsifier, 10 parts by weight of a mixture of dodecylbenzenesulfonic acid calcium and nonylphenol polyglycol ether were added. Prior to use, the emulsion concentrate is diluted with sufficient water to form the resulting mixture

-13180202 contains the active ingredient in the desired concentration.

4 / Granules

To prepare the active ingredient formulation, 1 mg of active ingredient is sprayed onto 9 parts by weight of granulated, absorbent clay. The resulting granules are sprayed as desired on the plants or their habitat,

5 / ULV preparation

To prepare a suitable active ingredient formulation, 90 parts by weight of the active ingredient are added with 3 parts by weight of the polyethylene oxide / emulsifier and the mixture is dissolved in 7 parts by weight of the aromatic petroleum fraction. This mixture is used in the ULV process. Production examples

Example 1/1. formula/

2,2-Dimethyl-3- (dichloro-vinyl) -cyclopropanecarboxylic acid pentafluorobenzyl ester

0.1 M 2,2-Dimethyl-3- (dichloro-vinyl) -cyclopropanecarboxylic acid chloride was added dropwise at 0 ° C to 1 * 1 mole of pentafluorobenzyl alcohol at / cis / trans. The reaction mixture was then heated to 120 ° C for a few minutes, until gas evolution had ceased. The title product is obtained as a pure oil by TLC (quantitative yield). Spectroscopic data:

IR / cm ^-1 : 2900, 1740, 1660, 1510, 1460, 1415, 1385, 1355, 1310, 1220, 1161, 1130, 1080, 1050, 995, 970, 940, 850, 810, 780.

MS (m / e): 181, 163, 165-191, 127, 109, 191, 207, 353, 388 (M).

(ppm): 6.6 & 5.6 (1H, doublet), 5.2 (2H, singlet), 0.8-2.4 (8H, multiplet).

In an analogous manner, other esters (I) of the same acid, otherwise designated by formula (XI), wherein R 'is as defined below, may be prepared.

Example 2

2,2-Dimethyl-3- (di-chloro-vinyl) -cyclo-pr opone orb-av-2,3,5,6-tetrafluorobenzyl ester | 7xi, R " is a group of formula a

Spectroscopic data:

IR (cm ^-1 ): 1730, 1630

MS (m / e): 163, 91, 127, 207, 335, 570 (M).

NMR (ppm): 7 (18), 6.2 and 5.6 (1H), doublet (5.2), 2H, singlet, 0.9-2.5 (8H, multiplet).

Example 3

2,2-Dimethyl-3- / dichlorovinyl / -cyclopropanecarboxylic acid 2,3,5-trifluoro-benzyl ester

E is a compound of formula 7X1, R 'is a powder of formula b

Spectroscopic data:

IR (cm ^-1 ): 1730, 1630

MS (m / e); 145, 163, 165, 129, 191, 317, 352 / M /.

-14180202

NMR (ppm): 7 (2H, multiplet), 5.6 (1H, doublet), 5.1 ₍ (2H, singlet), 0.9-2.5 (8H, multiplet).

Example 4

2.2-Dimethyl-3- (dichloro-vinyl) -cyclopropanecarboxylic alpha-2,4,5,6-tetrafluoro-3-chlorobenzyl ester [7X1, R is ac / group

Spectroscopic data:

IR / sm ¹ /: 2950, 1740, 1650, 1630, 1500, 1420, 1390, 1350, 1280, 1230i 1160, 1135, 1100, 1020, 940, 870, 820, 780.

Example 5

2.2-Dimethyl-3-dichloro-1H-cyclopropanecarboxylic acid 2,6-diphthyl-3,5-dichloro-benzyl ester (7X1, R is a moiety of formula d)

Spectroscopic data:

IR (cm ^-1 ): 1735, 1630

MS (m / e): 195, 163, 165, 127, 91, 191, 207, 367, 402 (M).

Example 6

2.2-Dimethyl-3- (dichloro-vinyl) -cyclopropanecarboxylic acid 2,4-difluorobenzyl ester

QXI (" compound of formula R " refers to group e)

Spectroscopic data:

IR / cm ^-1 : 2950, 1735, 1620, 1515, 1460, 1350, 1280, 1230, 1160, 1140, 1100, 1090, 1055, 990, 965, 920, 885, 850, 820.

MS (m / e): 127, 109, 163, 165, 91, 191, 207, 251, 299 (M-Cl).

Example 7

2.2-Dimethyl-3- (dichloro-vinyl) -cyclopropanecarboxylic acid 2,6-difluoro-biphenyl ester (compound of formula XI, R 'is a compound of formula f)

Spectroscopic data:

IR / cm ^-1 : 2950. 1735, 1635, 1600, 1485, 1280, 1230, 1170, 1140, 1120, 1055, 920.

MS (m / e): 127, 109, 163, 165, 91, 191, 207, 251, 299, 344 (M +).

NMR (ppm): 6.7-7.6 (3H, multiplet), 6.2 and 5.6 (1H, doublet).

5.2 (2H, singlet), 0.7-2.4 (8H, multiplet).

Example 8

2.2-Dimethyl-3- (dichloro-vinyl) -cyclopropanecarboxylic acid 2,5,6-trifluoro-3-chloro-benzyl ester

Γ / ΧΙ (R '= g)]

Spectroscopic data: ·

IR / ^cm-1/1730, 1620th

MS (m / e): 163, 165, 179, 127, 91, 191, 207, 351, 386 (M).

-15180202

9 · Example

2.2-Dimethyl-3- (dichloro-vinyl) -cyclopropanecarboxylic acid 2,5-difluoro-3-chloro-benzyl ester (Txi, R ') is a moiety of formula h

Spectroscopic data: IR / cm-1: 1730, 1620.

MS (m / e) 161, 163, 165, 91, 191, 207, 333, 363 (M).

The following compound can be prepared analogously:

Example 10/11. formula/

2.2-Dimethyl-3- (dibromo-vinyl) -cyclopropanecarboxylic acid pentafluorobenzyl ester

Example 11 / Example 12 formula/

2.2-Dimethyl-3- (dibromo-vinyl) -cyclopropanecarboxylic acid pentachlorobenzyl boiling point: 130-140 DEG / 0.133 mbar

Example 12 .............................................. ' ................................ '

2.2-Di-11β-3- (dichloro-vinyl) -cyclopropanecarboxylic acid 2,4,6-trifluoro-3,5-dichloro-benzyl ester

Example 13/14. formula/

2.2-Dimethyl-3- (di-chloro-vinyl) -cyclopropanecarboxyl α-2,4,6-trifluorobenzyl ester

Example 14 / Formula 15/

2.2- Dimθtil-3- / ^dichloro-v, ihil / -öiklop! Rőpánkarböaΐ'ϊV-5,6-difltíöϊ -3τklór · benzyl ester

Example 15/16. Formula / / + / Trans-2,2-Dimethyl-3- (dichloro-vinyl) -cyclopropanecarboxylic acid pentafluorobenzyl ester

0.1 M Potassium salt of (+) - trans -2,2-dimethyl-3- (dichloro-vinyl) -cyclopropanecarboxylic acid burns 0.1 moles of pentafluorobenzyl chloride in acetonitrile until the reaction is complete. The reaction mixture is then concentrated, dissolved in a little water / petroleum ether, the phases are separated, the organic phase is concentrated to give the title compound as a colorless oil, which lacks the cis ester of Example 1 in its NMR spectrum. vinyl doublet and.

Preparation of Polyfluorobenzoyl Alcohols / General Procedure /? / Reduction of Polyfluorobenzoyl Fluorides With the Phenyl Substituted

Polyfluorobenzoyl fluoride (0.1 mol) and sodium borobaride (0.08 mol) in absolute dloxane (80 ml) were heated at 50 ° C for 5 hours with vigorous stirring. The reaction mixture was poured into water and extracted with ether to give the desired benzyl alcohol derivatives in 95% yield as the base oil, the halogen content of the aromatic ring being unchanged.

By this method, the following polyfluoro-benzyl alcohol derivatives can be prepared for which the spectroscopic data are also given:

-16180202

Pentafluorobenzyl alcohol / III a compound of Formula ¹ / IR / cm ^"1/3400, 3900, 1670, 1510, 1310, 1300, 1220, 1120, 1050, 1030, 950, 930, 870th

1 H NMR (ppm): CDCly: 4.7 (2H, singlet), 2.4 (1H, ³ singlet).

Compound 2.4.5.6- tetrafluoro-3-chlorobenzyl alcohol · / ² of formula III /

IR / cm 3: 3300, 1650, 1490, 1380, 1280, 1230, 1130, 1090, 1030, 1000, 930, 860, 750.

NMR (ppm): 4.7 (2H, singlet), 2.8 (1H, singlet).

2.4.6- Trifluoro-3,5-dichlorobenzyl alcohol / m? of the formula / ~~ ~

NMR (ppm in ODCK: 4.7 (2H, singlet), 2.6 (1H), singlet (MS / m / e): 230 (M).

2.4-Difluorobenzyl alcohol / Compound III ⁴ /

IR / cm ^-1 : 3300, 2900, 1620, 1510, 1430, 1280, 1230, 1140, 1100, 1040, 1010. 960, 860, 820,

Nuclear Magnetic Resonance Spectrum: 6.5-7.5 (3H, multiplet), 4.6 (2H, singlet)

3.0 (1H, singlet).

2.6-Difluorobenzene-alcohol (compound of formula III)

IR / cm ^"1 /: 3300, 2950, 2870, 1630, 1600, 1470, 1380, 1270, 1220, 1200, 1190, 1110, 1020, 910, 830, 790th

NMR (ppm): 6.7-7.5 (3H). multiplet /, 4.7 / 2H, singlet /,

3.2 (1H, singlet).

The following compounds may be prepared analogously! g

2.4.6-trifluorobenzyl alcohol (compound of formula III),

3.5-difluorobenzyl alcohol / III? compound of formula.

b / Reduction of Polluorobenzoyl Fluorides with Reductive Cleavage of Part of the Fluoro Substituents of the Phenyl Group

Polyfluorobenzoyl fluoride (1 / 0.01 mol) and lithium aluminum hydride (0.0075 µL) were heated in 80 ml of absolute tetrahydrofuran for 5 hours. After completion of the reaction, the resulting complex is decomposed with slightly more than the calculated amount of water and the resulting p-defluorinated benzyl alcohol derivatives are isolated in 80-90% yield.

In this way, the following compounds can be prepared from the following starting materials:

Starting materials

2,3,4,6-tetrafluoro-3-chlorobenzene-1-fluoride (formula VIII ¹ )

2,4,6-trifluoro-3,5-áiklór-

Benzyl alcohol derivatives

2.3.6-Trifluoro-3-chlorobenzyl alcohol (Formula III ⁸ )

Nuclear Magnetic Resonance Spectrum (CDC3) 7 (1H, multiplet), 4.65 (2H),

3.3 (1H).

MS (m / e): 196, 75-142, 147, 161, 167, 178, 113, 98, 71.

2,6-Difluoro-3,5-dichlorobenzyl · '' 0202

benzene-1-fluoride (formula VIII ² )

-alcohol (formula 111) /

Nuclear Magnetic Resonance Spectrum (ppm in ODCl 2): 7.2 (IR),

4.6 (2H), 2.9 (IR).

2 / 0.01 mol of polifluorobenzoyl fluoride and 0.12 mol of lithium aluminum hydride are heated in 100 ml of absolute tetrahydrofuran for 5 hours. The work-up described in Example b / 1 isolates the resulting benzoyl alcohol in the azo and p-positions.

In this way, the following compounds can be prepared from the following starting materials:

Starting materials pentafluorobenzene-1-fluoride (formula VIII ³ )

2.4.5.6-Tetrafluoro-3-chlorobenzene-1-fluoride (Formula VIII ⁴ )

2.4.6- trifluoro-3,5- <3iklórbenzoi1 fluoride / VIII ^O5 /

Benzyl alcohol derivatives

2.3.5-Trifluorobenzyl alcohol (III ¹⁰ )

Nuclear Magnetic Resonance Spectrum (CDC3 / bpm, 7H, 2H, 4.6 / 2H, singlet, 2.8).

2.5-Difluoro-3-chlorobenzyl alcohol (III ¹¹ )

MS (m / e): 178, 11, 115, 143, 148, 161, 129, 125.

2-fluoro-3,5-dichlorobenzyl alcohol (III ¹² )

NMR (ppm in CDCl3: 7.2 (2H, multiplet), 4.7 '(2Η), 2.8 (1H, singlet).

Claims (2)

Patent claims Insecticidal and acaricidal compositions, characterized in that they contain from 0.1 to 95% by weight, as active ingredient, of a carboxylic acid ester of the formula (1) which is a halogenated benzyl alcohol, wherein: R and R * are each independently chlorine or bromine; - m is 0-3; n is 1 to 5, with the proviso that = 5, solid carriers, preferably natural or artificial stone flours, and / or liquid diluents, preferably aromatic and / or polar organic solvents, and optionally surfactants, are preferably nonionic. or anionic. emulsifying and / or dispersing agents. A process for the preparation of cyclopropanecarboxylic acid esters of halogenated benzyl alcohols of the formula (I) as an active ingredient of the insecticidal or acaricidal compositions of claim 1, wherein: R and R * are the same or different and can be chlorine or bromine; - m is 0-3 -18180202 n is 1-5; with the proviso that / ^{+ n} / _m ax = 5, characterized in that the compound of formula (11) wherein R and R * are as defined above and R 1 is hydroxy-substituted C 1 -C 4 alkoxy. or a halogen atom, by reaction with a compound of formula (III): wherein m and n are as defined in the foregoing at a temperature of from 20 to 120 ° C and optionally in the presence of an inert diluent; or b) a salt of formula IV wherein R and R * are as defined in the scope and NT is an alkali metal, alkaline earth metal cation or ammonium ion, with a compound of formula V wherein m and - 20-100 ° G in the presence of a polar solvent.