CS209935B2 - Insecticide or/and acaricide means and method of making the active substance - Google Patents

Abstract

1. Fluoroalkenyl-substituted cyclopropane compounds of the formula (I) see diagramm : EP0009709,P11,F1 in which R**1 represents chlorine, R**2 represents chlorine, R**3 represents Cl or Br, X represents see diagramm : EP0009709,P11,F2 and R represents C1-4 -alkyl and the radicals of the formula see diagramm : EP0009709,P11,F3 or in the case where R**3 represents Cl, represents see diagramm : EP0009709,P11,F4

Description

The present invention relates to insecticidal and / or acaricidal compositions which contain novel fluoroalkenyl esters as active ingredients, and they are also suitable for use as arbocyanides. The invention furthermore relates to a process for the preparation of these new active substances as well as to intermediates for the production of these active substances.

Fluoralkenyl substituted cyclopropanecarboxylic acid esters are already known from DOS 2 802 962.

However, the compounds known from this publication have the disadvantage of too low potency. Especially at low applied concentrations, the effect, duration of action and spectrum of activity is not satisfactory.

The new fluoroalkenylsubstituted cyclopropanecarboxylic acid esters, on the other hand, can be prepared cheaper because fluorine-containing starting materials are more readily available.

We have now found novel fluoroalkenyl substituted cyclopropanecarboxylic acid esters of formula I,

in which it means

R @ ^{1 is} hydrogen, chlorine, bro. alkyl. (C 1 -C 4) group, (C 1 -C 4) haloalkyl group;

R ^{2 is} chloro, bromo, alkyl. a group having from 1 to 4 carbon atoms or a haloalkyl group having from 1 to 4 carbon atoms,

R ^{3 is} halogen, preferably chloro and bromo, trifluoromethyl or a group of the formula

R ¹ —CF — R ² a

R is a pentafluorobenzyl group or a group of formula i

CF

...... \

COOR (I)

where it means

R ^{9 is} fluorine or hydrogen,

X is —CIIs— or —O—,

R ^{10 is} phenyl, -CH 2, or-CF 3, and

R ^{11 is} hydrogen or cyano.

The novel fluoroalkenyl substituted cyclopancanecarboxylic acid esters of formula (I) are obtained by reacting an acid or a reactive derivative of formula (II),

in which

R ^1, R ² and R ³ are as defined above and

Z ¹ is halogen, preferably chlorine or hydroxy, reacted with an alcohol or a reactive derivative of formula III,

R - Z ² (III) wherein

R is as defined above and

Z ² is hydroxy, chloro or bromo, optionally in the presence of solvents, acid binding agents and / or phase transfer catalysts at 0 to 120 ° C.

Acids or their reactive derivatives of the general formula II,

R ¹ , R ² , R ³ and Z ¹ are as defined above, are new.

These novel acids or their reactive derivatives of the general formula (II) are obtained by reacting the compounds of the general formula (IV).

in which

R ⁴ is -COO-alkyl of 1 to C atoms in alkyl, CN or -COCH 3 and

R 1, R ² and R ³ are as defined above (when R ⁴ is a group

O dl - <CO-alkyl of 1 to 4 carbon atoms in the alkyl group CN, saponified when R ⁴ represents a group

O

II -? -? -, are optionally oxidized and optionally the acid in which R ⁴ is --COOH is reacted with a halogenating agent.

Compounds of formula IV

in which

R ^1, R ² and R ³ are as defined above and R ⁴ represents CN,

O —С — СНз or

O-CO-alkyl wherein the alkyl contains 1 to 4 carbon atoms are new.

The novel compounds of formula (IV) are obtained by:

R ² R ³ Hal СНз СНз

II II /

Rl-CF-С-CH2-CH-C-CH 2 R ⁴

Hal (V) in which

R ^1, R ^2, R ³ and R ⁴ are as defined above and

Hal represents halogen, preferably chlorine or bromine, which halogen may be the same or different from each other, dehydrohalogenating.

Compounds of Formula V

R ² R ³ Hal Hal з r r c f С - — - CH 2 - 'CH - C - CH ² R ⁴

I I

Hal CH ₃ (A)

F F

in which

R 1, R ² , R ³ and R ⁴ are as defined above and

Hal has the meaning given above, they are new.

These novel compounds of formula (V) are obtained by halogenating derivatives of formula (VI),

R ³

R1-CF-C (Hal) 2

R ² (VI) in which

Hal is the same or different from each other and is halogen, preferably chlorine or bromine and

R @ ¹ , R @ ² and R @ ³ , as defined above, add to the olefins of formula (VII) wherein R @ 1 is R @ 1

R ^{11 is} hydrogen or CN,

R ^{9 is} hydrogen or fluoro; and

R ¹⁰ -CHF 2, -CF 3, or phenyl.

Very particularly preferred are those compounds of formula (I) wherein:

R is a radical of formula

in which

R ⁴ is as defined above, after the case-in the presence of a catalyst.

The compounds of general formula (I) exhibit good insecticidal properties.

Surprisingly, the novel active compounds of the formula I according to the invention show a considerably higher activity than the compounds known in the art. .

Among the compounds of formula I of the invention, those in which they are preferred are those

R ¹ and R ² are chlorine, bromine or trifluoromethyl,

R ^{3 is} chlorine or bromine;

R is a pentafluorobenzyl group or a group of formula

where R ^{9 is} fluorine or hydrogen,

X is CHa— or —0—,

R ^{10 is} phenyl, - CHF? or —CF3 a

R ^{11 is} hydrogen or cyano.

Particularly preferred are compounds in which

R is a radical of formula

with

R ^{11 is} hydrogen or CN,

R ^{9 is} hydrogen or fluoro; and

R ^{10 is} phenyl.

The following compounds of formula I may be mentioned individually:

pentafluorobenzyl 2,2-dimethyl-3- (2 ‘, 3‘, 3‘-triohloro-3‘-fluoropropenyl) cyclopropanecarboxylate,

3‘-phenoxybenzyl-2,2-dimethyl-3- (2 2, 3‘, 3‘-trichloro-3‘-fluoropropenyl) cyclopropanecarboxylate,

3'-phenoxy-2,2-cyanobenzyl'dimethyl-3- (2 ', 3 ^T, 3'-trichloro-3'-fluoropropenyl jcyklopropankarboxylát,

3 ^{<-fe.noxy-4'-fluoro- <-kyanbenzyl-2,2-dimethyl-3-} (2 ^', 3', 3'-trichloro-3'-fluoropropenyl] cyclopropanecarboxylate,

3'-fluoro-.beta; and ^< 'cyanobenzyl 2,2-dimethyl-3- (2'-chloro-34rifhiormethyl-3', 4 ', ^4', 4'-tetrafluorobut-l-enyl) cyklopropankaTboxylát,

3'-phenoxybenzyl 2,2-dimethyl-3- (2'-chloro-3'-trifluoromethyl-3 ', 4', 4 ^{<4 s} -tetrafluorbut-l-enyl) cykloprO'pankarboxylát, pentafluoro luorbenzyl- 2,2-dimethyl-1-3- (2'-chloro-3-3Mrifluormethyl \ 4 ^4, 4 ', 4'-tetrafluorobut-Γ-enyl) cyclopropanecarboxylate.

The preparation of the fluoroalkenyl substituted cycl-o-propanecarboxylic acid esters of the present invention can be illustrated by the following reaction scheme:

an acid binding agent

---------> I

For example, chloride is used in the process of the present invention. 2,2-dimethyl-3- (2 ‘, 3‘, 3‘-trichloro-3-fluorophinyl) -cyclopropanecarboxylic acid and 3‘-benzoxybenzyl alcohol as starting materials, as shown by the following reaction scheme:

The cyclopropanecarboxylic acids or their reactive derivatives of the formula (II) which are used as starting materials are novel and preferably acid chlorides are used as reactive derivatives.

Examples of compounds of formula II which are used as starting materials are:

N dift1éthy 2-one 3- (2 ', 3 \ 3 ^of -tricliloir-3'-fluoro-lucrpřOpenylJ cyclopropanecarboxylic acid chloride thereof,

2 _? 2-diethyl-3- (2'-chloro-3'-trifluoromethyl-3,4,4,4,4-trifluorobut-1-enyl) cyclopropanecarboxylic acid and its chloride.

The novel compounds of the formula mohou can be prepared as described above.

The alcohols or their reactive derivatives of formula (III), which are also used as starting materials, are known and can be prepared by conventional methods described in the literature (cf., for example, DAS or DOS 2,554,883, 1,926,433, 2,612,115, 2,615) 435,

436 178, 2 436 46.2 and Monatshefte 67, p. 35 (1936).

Preference is given to compounds of the formula III in which R has the above-mentioned preferred or particularly preferred meanings.

Examples of compounds of formula III which are used as starting materials are:

pentafluorobenzyl alcohol.

3-trifluoromethoxybenzyl alcohol,

-fen o xy b e n.zy 1 and 1 coc o 1,

3-phenyl-α-cyanobenzyl alcohol,

3-phenoxy-4-fluoirbenzylalko ^and alcohol. 3-phenoxy-4-fluoro-α-cyanobenzyl alcohol, 3- (4'-fluorophenoxy) -benzyl alcohol, 3-difluoromethoxybenzyl chloride, 3-phenoxybenzyl bromide, pentafluorobenzyl chloride.

For the preparation of the compounds of the formula I according to the invention from the carboxylic acids or carboxylic acid halides of the formula II and the alcohols or chlorides or bromides of the formula III, all conventional acid-binding agents can be used as acid-binding agents.

Particular mention should be made of alkali metal hydroxides, carbonates and alkoxides, such as potassium hydroxide, sodium hydroxide, sodium methoxide, potassium carbonate, sodium ethoxide, as well as 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 by reacting the acid halides with alcohols at temperatures between 0 and 100 ° C, preferably at 15 to 40 ° C, and at the reaction of the carboxylic acid with halides between 50 and 150 ^° C, preferably at 80 to 120 ° C . In the latter case, it preferably operates in the presence of a catalyst.

Suitable catalysts are phase-transfer catalysts, such as crown ethers or, for example, quaternary ammonium or phosphonium salts. Preferred are quaternary ammonium salts, such as tetrabutyutylammonium chloride, tetrabutylammonium bromide, benzyltriethylammonium chloride or methyltrioctylammonium chloride.

The reaction is generally allowed to proceed at atmospheric pressure. The process for the preparation of the compounds according to the invention is preferably carried out using suitable solvents and diluents. Virtually all inert organic solvents are suitable as such. These include, in particular, aliphatic and aromatic or chlorinated hydrocarbons, such as benzene, toluene, xylene, petrol, methylene chloride, chloroform, dichloroethane, chlorobenzene, o-dichlorobenzene, or ethers such as diethyl ether, diisopropyl ether or dibutyl ether, nitriles such as acetonitrile and propionitrile.

In the process, the starting materials are preferably used in equimolar ratios. The reactants are generally contacted in one of the solvents mentioned, and usually at elevated temperature after addition of the acid binding agent and optionally the catalyst, the reaction mixture is stirred for one or several hours to complete the reaction. The reaction mixture is then poured into water, the organic phase is separated and washed with water until neutral. 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 longer heating under reduced pressure to slightly elevated temperatures, the last volatiles are freed and purified in this way. Refractive index is used to characterize them.

New acids or halides of acids of petroleum jelly ^lake of the formula II can be prepared from compounds of formula IV with the procedure mentioned above.

In variant a) when R is -COalkyl,

Wherein the alkyl contains 1 to 4 carbon atoms, saponification is carried out in a manner known per se under acidic or basic conditions. Preferably the saponification is carried out under basic conditions.

In the case where R is cyano, the nitrile is converted to an ester group by dissolving the nitrile in the corresponding alcohol of formula alkyl-OH, where the alkyl contains 1 to 4 carbon atoms, and the solution is saturated with hydrogen chloride, usually at about 0-20 ° C. After a period of standing, the imide chloride forms from which the ester is formed by the action of water.

Suitable saponification agents are all customary saponification agents, such as, for example, sulfuric acid, acetic acid or alkali metal hydroxides. Particularly preferred is potassium hydroxide in an alcoholic solution, for example methanol.

The saponification can be carried out at an elevated temperature, for example between 20 and 100 ° C, but preferably at 20 to 40 ° C.

The acids are liberated by acidification with aqueous acidic solutions and separated from the salts by extraction and optionally purified by distillation.

The acid halides may be prepared by conventional methods using conventional halogenating agents, such as SOCl 2, COCl ₂ , PCl 3, PCl 5, oxalyl chloride or oxalylibromide, Rvgз.

In process variant b), R represents a group

O

II —С — СНз.

The acid is obtained by oxidation, preferably with hypochlorite or hypobromite. Examples of such agents include sodium hypochlorite, potassium hypochlorite, calcium hypochlorite, sodium hypobromite, potassium hypobromite and calcium hypobromite. Furthermore, this reaction can also be carried out by introducing the halogen into an aqueous alkali metal hydroxide solution containing the starting material. The reaction temperature is generally -20 to 100 ° C, preferably 0 to 70 ^Q C is generally used as water · solvent, but may be added as auxiliary solvents, organic solvents.

By adding phase transfer catalysts, such as quaternary ammonium salts, the reaction can be accelerated. Suitable quaternary ammonium salts are the compounds mentioned above.

Examples of novel compounds of formula IV are:

2,2-dimethyl-3- (2 ', 3', 3'-trichloro-3'-fluoropropenyl) cyclopropanecarboxylic acid methyl ester, 2,2-dimethyl-3- (2 ', 3', 3'-trichloroethyl ester) 3'-fluoropropenyl) cyclopropanecarboxylic acid, 2,2-dimethyl-3- (2 ', 3', 3'-trichloro-3'-fluoropropenyl) cyclopropanecarboxylic acid butyl ester, 1-cyano-2,2-dimethyl- 3- (2 ', 3', 3'-trichloro-3'-fluoropropenyl) cyclopropane, methyl ester or 2,2-dimethyl-3- (2'-chloro-3'-trifluoromethyl-3 ', 4', ethyl ester) 4 ', 4'4'-tetrafluoro-but-1'-enyl) cyclopropainecarboxylic acid, 1-acetyl-2,2-dimethyl-3- (2', 3 ', 3'-trichloro-3'-fluoropropenyl) cyclopropane, 1-Acetyl-2,2-dimethyl-3- (2'-chloro-3'-trifluoromethyl-3,4,4,4'4-tetrafluoro-but-1-enyl) cyclopropane.

The novel compounds of formula (IV) may be prepared as described above from compounds of formula (V) by dehydrohalogenation. This reaction can be illustrated by the following reaction scheme:

2О »9 3 5

RI - CF - C (Hal ·) - CH 2 - CH (Hal) - C - CH 2 - R ⁴ IL / \

R2 R3 НзС СНз base

—2HHal

thereafter a compound of formula V to be deihydrohalogenated (slowly) is added, first at about 0 to 30 ° C and then to terminate the reaction at 40 to 100 ° C, preferably at 50 to 80 ° C,

Examples of compounds of formula V include:

The dehydrohalogenation is carried out by treatment with bases in the presence of diluents. Suitable bases are: sodium hydroxide, potassium hydroxide, potassium carbonate, alkoxides, such as sodium methoxide, sodium isopropoxide or potassium tert-butoxide. Suitable solvents are, in particular, alcohols, such as, for example, methanol, ethanol, n- or isopropanol, butanol, tert-butanol, glycol or glycol monomethyl ether. Possible chlorinated hydrocarbons or ethers such as benzene, toluene, xylene, chlorobenzene, dichlorobenzene, methylene chloride, tetrahydrofuran, dioxane, dimethoxyethane are also suitable. It can also be carried out, in particular using sodium hydroxide or potassium hydroxide, in a two-phase system, such as in toluene / water. Optionally, a phase transfer catalyst such as a quaternary ammonium salt may be added. This does not only make sense when working in a two-phase system, but is also advantageous when working in an anhydrous environment, for example, when potassium carbonate is used as the base.

The base, preferably sodium methoxide or sodium ethoxide, is introduced in a solvent, after the methyl ester of 3,5-dimethyl-6,6,7,7-pentachloro-7-fluorenantic acid, ethyl ester 3,3-dimethyl-4,6,6, 7,7-pentachloro-7-fluorenantic acid, 3,3-dimethyl-4,6,6,7,7-pentachloro-7-fluorenantic acid butyl ester, 3,3-dimethyl-4,6,6,7,7-nitrile -pentachlor-7-fluorenantic acid, 3,3-dimethyl-4,6,6-tribromo-7,7,7-trifluorenantic acid methyl ester,

2,2-diinethyl-3,5,5,6,6-pentachloro-4- (41-fluoromethylmethyl) ketone, 3,3-dimethyl-4,6,6-trichloro-6- (trifluoromethyl) -7,8,8, etetrafluorooctanoic acid methyl ester, ethyl ester 3,3 - _{<4,6-dimethyl)} -6-trichloro-7-trifluoromethyl-7,8,8,8-tetrafluoro> ktanové acid

2,2-dimethyl-3,5,5-trichloro-6-trifluoromethyl-6,7,7,7-tetrafluoroheptylmethylketone.

The novel compounds of formula V are obtained as described above from compounds of formulas VI and VII. The compounds of formulas VI and VII are known.

This process can be illustrated by the following reaction scheme:

R ^Z R ^Z © I

R CF ~ C (

R *

R ¹ CF C (Haj к £

Hal ICHrCH (Hni JC-CH, ? ² *)

H ₃ c CH ₃

If, for example, methyl ester of 3,3-dimethyl-4-pentenoic acid and 1-fluoro-1,1,2,2,2-pentachloroethane is used as the starting material, the reaction sequence can be illustrated by the following reaction scheme:

СГС ^ СС ^ +

HX CH

F i fy ^-

СН ^ СО + СН +> cfo ^ ci-S ^ chci-cchhcccc ^

- Hf ^СН ₅

By way of example, the following starting materials of formula VI are:

pentachlorofluoropentane, pentabromfluoropentane, 1,1,1-triohloro-2, 3,3fetrafluoro-2-trl ·

-fluoromethylpropane,

1.U-DifluoгtelracУlrretУan, llfluorllUUltfichlofll, 2-dtbrrmethane,

1.1 U Ut.elfac hlrrfluoretha ^ι ^ n, fluo-rheptachlorpropan,

1. U-diorrhea x achlorpropane, pentachlorol, 1,2 ^; 1-Dibromo-2-chloropentafluoropropane, 1,2-dibromo-2-chloropentafluoropropane, 1, 2'-Dibromo-2-chloropentafluoropropane, 1'-Dibromo-2-chloropentafluoropropane, 1'-dibromo-2-chloropentafluoropropane, l, l, l, U-tetfafluofpfrpan

1.1, U-trichloro-1,2-difluoro-U-iodomethane.

As examples. the following starting materials of formula VII may be mentioned:

2,3-dimethyl-4-pentenoic acid methyl ester, 2 ', 3-dimethyl-4-pentenoic acid ethyl ester, 2,3-dimethyl-4-pentenoic acid butyl ester, niltril 2,2 - ((R, R) -phenyl) -. N, N-Dimethyl-3-methyl-3-methylmethyl-ketone.

. The process is preferably carried out under pressure, but can also be carried out using high boiling compounds of the formula VI at atmospheric pressure.

The pressure range can vary within wide limits, approximately between 0.1 and 2 MPa, preferably between 0.2 and 1.5 MPa. The overpressure can be achieved by forcing an inert gas such as nitrogen into the reaction vessel.

The reaction temperature may be between 50 and 100 ° C, but preferably between 100 and 150 ° C. Optionally, a diluent is added to both starting materials.

Suitable diluents are: aliphatic or aromatic hydrocarbons, such as benzine or toluene, alcohols such as methanol, ethanol, propanol or tert-butanol, nitriles such as acetonitrile or propionitrile, dimethylformamide. Alcohols, acetonitrile and dimethylformamide are preferred.

In order to carry out the reaction, catalysts are needed, either

(a) free radical-providing catalysts such as azobisisobutyronitrile, benzoyl peroxide or dil-tert-butyl peroxide; the compounds of formula VI are used in equimolar amounts or preferably in excess;

or

b) catalyst mixtures consisting of a metal salt, an amine and optionally a small amount of benzoin. The metal salt may also be present in the form of a hydrate, the amine may be present as a -salt, for example as a hydrochloride.

Examples of metal salts include: copper (I) chloride, copper (I) chloride, iron (II) chloride, iron (III) chloride, copper (II) sulfate, cobalt (II) chloride, zinc chloride, iron (II) sulfate, iron (II) acetate, copper or iron acetylacetonate.

Examples of amines include: - dimethylamine, diethylamine, trimethylamine, - methylamine, - ditsopropylamine, n-butylamine, benzylamine, ethanolamine, aniline, pyridine. Preferred are dimethylamine, diethylamine (such as hydrochloride) and n-butylamine.

Preferably, at least 1.5 mol, preferably U-10, mol of organic amine is used per mole of metal salt. The metal salt is used in an amount of from 0.01 to 15 mole - ° / o, preferably between ^0, 05 ^and 10 molmmcli ^0% based on the compound of formula VII.

Often the addition of an equimolar amount of benzoin based on the metal salt is preferred.

Since the compounds of the formula (VI) according to the invention, in particular pentachloroflurflethane, are so well additive to the olefins of the formula (VII), it must be particularly surprisingly indicated that one cannot assume that hexachloroethane cannot be added to olefins.

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

с ..: · ..... ‘from the order of -opods (Isopoda) -for example, the Common Woodlouse (Oniscus -asellus), Common Pigs - (Armadillidium vulgare), Common Woodlouse (Porcellio scabor);

from the class of the Diplopoda, for example, the blind millipede (Bla-niulus guttulatus);

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

from the class of - scorpions (Symphyla) - for example, Scutigerella immaculata;

from the order of the Thysanura, for example Lepisma saccharina;

from the order of the Collembola, for example Onychiurus -armatus;

z - order Orthoptera eg Blatta oriontalis, Periplaneta -americana, Leu.copihaoa- madorae, Blattella germanica, Acheta domesticus, Gryllotalpa spec .), Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca caogogaria;

from the order of the Dermaptera., e.g., Forficula auricularia;

from the order of the Isoptera, for example Reticulitermes spec.

from the order of the lice (AnoiDlura), for example Phylloxera vastatrix, Pemphigus spec., Pediculus humanus corporis, Haematoplnus sp., 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 tabaci;

from the order of the Heteroptera, for example, Eurygaster spec., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spec .;

from the order of the Homoptera, for example Aleurodeis brassicae, Bemisrn tabaci, greenhouse sapweed (Trialeurodes vaporarioum), cotton aphid (Aphis gossypii), green aphid (Brevicoryne brassicae), green aphid (Cryptic aphid) (Doralis fabae), apple aphid (Doralis pomi), bloody aphid (Eriosoma. Lanigorum), aphid (Hyalopterus - arundinis), .MMcrossphum avenae,

Phylon humuli, Rhopalosiphum worm, Empoasca spec., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni.

Saissetia oleas, Laodelphax striatollus, Nilaparvata lugens, A. curantii, Aspidiotus hodorao, Pseudococcus spec., Psylla spec.

from the order of the butterflies (Lepldopt-era), for example, Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletiís blancardella, Hyponomeuta padolla, Plutcosoma -neustria), musk moth (Euproctis chrysorrhooa), moth (Ly ^ é ^^ rt-ría spec.), Bucculatrix thurberiella, broadleaf (PliyHomistis citroUa), Agrotis spec. insulana, Heliothis -spec., Laphygma exigua, Cabbage moth, Panolis flammea, Prodenia litura, Spodoptera spec., Trichoplusia, C ^ jrpocapsa pomonella , White (Pieris -spec.), Chilo -spec., Pyraustanubilalis, Ephestia kuhniollá, Galleria mellonella, Caocoocia podana, Capua Choristonoura fumiforana, Clysia ambiguella Homona magnanima, Tortrix viridana;

from the order of the beetles (Coleoptera), for example, Anobium punctatum, Rhizopertha 'dominica, B.ruchidius obtectus, Acanthoscelide-s-obtoctus, Hylotrupes bajulus, Age ^ ca alni), potato tangerine (Lepti-notarsa do ^ mUno ^.), cucumber tangerine (Phaedon cochloariao), Diabrotica -spoc., white pea (Psylliodes ^^ 0 ^ h.ala), Epilachna varivostis .), Oryzaephilus surinamensis, Anthon-omus spec., Sitophilus spec., Otlorrhynohus sulcatus, Sordidus, Ceuthorrhynchus assimilis,

Hyipera postica, Dermestes spec., Trogoderma spec., Anthrenus spec., Attagenus spec., Lyctus spec., Meligethes aeneus, Ptinus spec. fern (Niptus hololeucus), Gibbium psylloides, darkling beetle (Tribolium spec.), darkling beetle (Tenebrio molitor), click beetle (Agriotes spec.),

Conoderus spec., Common Cockchafer (Melolontha melolontha), Common Cockchafer (Amphimallon solstitiaBs) zealandica;

from the order of the Hymenoptera · eg Diprion spec., Hoplocampa ¹ spec., Lasius spec.

Monomaria pharaonis, Hornet (Vespa spec.);

from the order Diptera. for example, mosquito (Aedes spec.), anofeles (Anopheles spec.), mosquito (Culex spec.), fruit fly (Drosophila melanogaster), fly (Musea spec.), sunflower (Fannia spec.), buzzard (Calliphora erythrocephala) , buzzer (Lucil.ia spec.),

Chrysomyia spec., Cuterebra spec., Hamster (Gastrophilus spec.), Hyppobosca spec., Thistle (Stomoxys spec.), Wednesday. (Oestrus spec.), Middle (Hypoderma spec.), Horsefly (Tabanus spec.), Tannia spec., Flycatch (Bi-bio · hortulanus), Barberry (Oscinella frit),

Phorbia spec., Pegomyia hyoscyami, • Ceratitis capitata

Dacus oleae, Tipula paludosa;

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

from the order of the Arachnida, for example, Scorpio · maurus, Latrodectus mactans;

from the order of the mites (Acarinaj, for example Acarus broad), Argas spec., Ornithodoros spec., Dermanussus gallinae, Eriophyes ribis, Boylus spec. (Rhipicephalus spec.), Drinker (Amblyomma spec.), Yalomma spec., Tick (Ixodes spec.), Flesh (Psoroptes spec.), Scab (Chorioptes spec.), Sarcoptes · spec., Mite (T ^ rsonemus spec.) .), Currant Spider (Bryobia praetiosa), Spider Mite (Panonychus spec.), Spider Mite (Tetranychus spec.).

The active substances can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, natural substances and synthetic substances impregnated with the active substances, small particles coated with polymeric substances and coatings. seed compositions, further flammable additive formulations such as smoke cartridges, smoke jars, smoke spirals and the like, as well as formulations in the form of active ingredient concentrates. for cold or hot fog dispersion. .

These funds are. They are prepared in a known manner, for example by mixing the active ingredient with fillers, i.e. liquid solvents, with liquefied gases under pressure and / or with solid carriers, optionally using surfactants, i.e. emulsifiers and / or dispersants and / or foaming agents. If water is used as a filler, it is possible. organic solvents, for example, can also be used 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 as well as their ethers and esters, ketones such as acetone, methyl ethyl ketone, methylisobutyl ketone or cyclohexanone, strongly polar. solvents such as dimethylformamide and dimethyl sulfoxide; and water. By liquefied gaseous fillers or carriers is meant those liquids that are normal. temperature and normal pressure gaseous, 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 silicic acid, nitrous oxide and silicates. Suitable solid carriers for the preparation of granulates are 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 , corn sticks and tobacco stalks. Suitable emulsifiers and / or foaming agents are nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid ethers, polyoxyethylene ethers of fatty alcohols, e.g.

The compositions of the invention may contain 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 ferrocyanamide 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 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 carried out 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 an excellent residual effect on wood and clay and good stability to alkali on lime substrates.

The application of the active compounds according to the invention in the veterinary sector is carried out in a known manner, such as orally in the form of, for example, tablets, capsules, drinks, granules, dermally, in the form of e.g. baths, sprays, pour-on and spot-on and powdering, parenterally in the form of, for example, injection.

The biological activity of the compositions of the invention is illustrated by the following examples.

Example A

Test for leaf beetle larvae (Phaedon cochleariae) solvent:

parts by weight of dimethylformamide emulsifier:

part by weight of alkylarylipolyglycol 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.

Leaves of cabbage (Brassica oleracea) are treated by immersion in the active preparation of the desired concentration and the leaves thus treated are occupied by larvae of the leaf beetle (Phaedon cochleariae) while still wet.

After the required time, mortality is determined in%. 100% means that all larvae have been killed, and 0% means that no larvae have been killed.

In this test, for example, the following compounds of the examples illustrating the method of manufacture of the active ingredient show a higher effect than the compounds of the prior art: the compounds of Examples 2, 6, 10.

Example В

Test for resistant strain of spider mite (Tetranychus urticae) solvent:

parts by weight of dimethylformamide emulsifier:

part by weight of alkylaryl polyglycol ether

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

Bean plants (Phaseolus vulgaris), heavily contaminated with all developmental stages of the spider mite (Tetranychus urticae), are treated by immersion in a preparation containing the active ingredient at the desired concentration.

After a given period of time, mortality was found in%; 100% means that all spider mites have been killed, 0% means that none of the mites have been killed.

In this test, for example, the following compounds of the invention show a better effect than the compounds of the prior art: the compounds of Examples 2, 6.

Example C

Limit concentration test (soil insects) experimental insects:

Mealworm (Tenebrio molitor] - larvae in soil

parts by weight of acetone emulsifier:

part by weight of alkylaryipolyglycol 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 given in ppm (= mg / l), is decisive. The treated soil is filled with pots and the filled pots are allowed to stand at room temperature.

After 24 hours, the test insects were transferred to the treated soil and after a further 2 to 7 days the percentage of active compound activity was determined by counting dead and living specimens of the test insects. At sacrifice, all the specimen ^{W teaches} NEK 100 ^-% -0% and ^p is the number of live insects are - as in the comparative test.

the following compounds show in this test. from the examples illustrating the method of production of the active ingredient a higher effect compared to the state of the art: the compounds of examples 1, 2.

Example D

LDioodest experimental insects:

Common Cockroach [Blatta orientalis] Number of test insect samples: 10 Solvent: Acetone swelling (l - Effective substances are dissolved in 1000 parts by volume of solvent. Dilute the solution so obtained to the desired concentration with additional solvent.

The 2.5 - m effective solution is piped into a Petri dish. At the bottom of the Petri dish there is a filter paper with a diameter of about 9.5 cm. The petri dish is left open until the solvent is completely evaporated. Depending on the concentration of the active substance solution, the amount of active substance per 1 m 2 of filter paper varies. The indicated number of specimens of the test insect is 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. Determines -se mortality in%. Even ^00% means the killing of all exemP ^{à la} experimental ru er zu ^y, 0% ^means that none of Z ^e test insects -nebyl -usmrcen.

In this test, for example, the following compounds of the invention exhibit a higher effect than those known in the art: compounds of Examples 1, 2, 6.

Example 1 E

LTO test for double-winged insects: mosquito [Aedes aegypti) number of specimens: 25 solvent: acetone 2 parts by weight of the active substance are dissolved in 1000 parts by volume of solvent. The solution thus obtained is diluted with additional solvent to the desired lower concentration.

Pipette 2.5 ml of the drug solution into a petri dish. At the bottom of the Petri dish there is a filter paper of about

9,5 cm. Leave the petri- tal open until the solvent has evaporated completely. Depending on the concentration of the active substance solution, the amount of active substance per 1 m 2 of filter psipir is different. The indicated number of specimens of test insects is then added to the Petri dish and the Petri dish is covered with a glass lid.

The condition of the test insects is continuously monitored. The time required for 100% insect paralysis (konck -dówn-effect) is determined.

In this test, for example, the following compounds of the invention show a greater effect than those known in the art: the compounds of Examples 1, 2, 5:

Example F

Field Witch Test [Plutella maculipennisj Solvent:

parts by weight of acetone emulsifier:

part by weight of alkylaryl polyglycol ether.

To make 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 leaves of cabbage (Brassica oleracea) are treated by immersion in the active agent of the desired concentration and occupied by caterpillars of the plutella maculipennis while the leaves are still wet.

After the required mortality time is determined in%. Om declared unto ^{the gloom} with ^{a 100%} and ^{when -Have} all the caterpillars were killed, -zatímco 0% means that none of the caterpillars were killed.

In this test, for example, the following compounds of the Examples exhibit a higher effect than the prior art: the compounds of Examples 2, 5, 6.

23 209935 24 Table Test for field embroidery Plutella maculipennis active substance concentration of active substance in '% mortality in ° / o after 3 days

100 ALIGN!

100 ALIGN!

100 ALIGN!

100 ALIGN!

Example 1

Example 2

5.88 g of 2,2-dimethyl-3- (2 ', 3', 3'-trichloro-3'-fluoropropenyl) cyclopropanecarboxylic acid chloride are mixed with 100 ml of toluene and 4.0 g of 3-phenO '. Xybenzyl alcohol. 1.8 g of pyridine in 50 ml of toluene are then added dropwise at room temperature with stirring, and the reaction mixture is stirred for 4 hours at room temperature. The reaction mixture is then treated with 100 ml of water, the organic phase is separated and washed with 100 ml of water. The organic phase is dried over sodium phosphate, filtered and evaporated to a residue. rotary evaporator and distilled at 60 ° C under high vacuum (about 1 hour). The residue weighs 8.0 g and consists of 2,2-dimethyl-3- (2,3,3-dichloro-3‘-fluoropropenyl) cyclopropanecarboxylic acid (3‘-phenoxy) -benzyl ester.

5.88 g of 2,2-dimethyl-3- (2‘, 3‘, 3‘-trichloro-3‘-fluoropropenyl) cyclopropanecarboxylic acid chloride were mixed with 100 ml of toluene and 4.5 g of 3-phenoxybenzaldehyde cyanohydrin. 1.8 g of pyridine in 50 ml of toluene are then added dropwise with stirring at room temperature and the mixture is stirred for 4 hours at room temperature. 150 ml of water are then added to the reaction mixture, the organic phase is separated and washed with 100 ml of water. The organic phase is dried over sodium sulphate, filtered, the filtrate is evaporated on a rotary evaporator and distilled under high vacuum at 60 ° C (about 1 hour). The residue weighs 9.1 g and consists of 2,2-dimethyl-3- (2 ‘, 3‘, ЧЧЫЫprЫ-ZЧ-fluoropropenyl) cyclopropanecarboxylic acid (3‘-phenoxy) -2-cyanobenzyl ester.

The following compounds were prepared in an analogous manner to those described in Examples 1 and 2:

Example compound

^(CFf t ^CF h ₃ c ch ₃

Cl 2 CH _t

OCF ₃

209933 Example compound

Example 13

Production of compound of formula

g of 2,2-dimethyl-3- (2 ', 3', 3'-trichloro-3 '· -fluoropropenyl) cyclopropanecarboxylic acid is dissolved in 150 ml of methylene chloride, a few drops of dimethylformamide are added and phosgene is introduced at room temperature until The reaction is complete (infrared control), then excess phosgene and methylene chloride are distilled off to give 2,2-dimethyl-3- (2 ', 3', 3 ', - trichloro-3'-f) chloride by distillation. (fluoropropenyl) cyclopropanecarboxylic acid, b.p. 82-86 ° C;

Example 1 a d 14

g 2,2-Dimethyl-3- (2'-chloro-3'-trifluoromethyl-3 ', 4', 4 ', 4'-tetrafluorobut-1-enyl) cyclopropanecarboxylic acid was dissolved in 100 ml thionyl chloride and the solution was heat for one hour to boil. After excess thionyl chloride was distilled off, the residue was distilled under high vacuum. There was obtained 2,2-dimethyl-3- (2'-chloro-3'-trifluoromethyl-3 ', 4', 4 ', 4'-tetrafluorobut-1-enyl) cyclopropanecarboxylic acid chloride, b.p. 73-76 ° C. / 106 Pa.

Example 1 a d 15

M C ru

299935

To 30.35 g of ethyl 2,2rdimethyl 3 - (. 2 ', 3', ^{3 <-tFichlor} 5 ^<-f luorpropenylJcyklop.rOpankarboxylové acid was added 200 ml of 2N methanolic potassium hydroxide solution and the mixture was stirred for 6 hours at Then 300 ml of ice water are added and the pH is adjusted to 1 by addition of concentrated hydrochloric acid. Extraction with petroleum ether gives 23.5 g of carboxylic acid which only partially solidifies (mixture of isomers).

Example 16

Analogously as described in Example 15 to afford 2 ^ - ^^ l ^ t ^ .mu.m] ^] yl-3- (2 ^t -C ^] ^ l ^{^^,} 3'-trifluoromethyl-3 ', ^4', 4 ^{<4 <,} -tetrafluor -but-l ^<-tnylCcykl · opropankaгboxylová acid.

Example 17

To a solution of 16.1 g of sodium in 800 ml of ethanol was added dropwise 120 g of 3,3- (ethyl) -ethyl-4,66,7,77-entachlorofluorenenoic acid ethyl ester. The reaction mixture was stirred at room temperature for 1 hour and then heated at 45-50 ° C for 7 hours. After cooling, the precipitated sodium chloride is filtered off, the filtrate is concentrated in vacuo, added to 500 ml of water and the reaction is brought to neutral pH. Extraction of methylene chloride and fractional distillation gave 82 g of ethyl ester

-3- (2 ^s, 3 ^s, 3'-trichloro-3 ^I -f fluoropropenyl jcykiopropankarboxylové acid b.p. 92-97 ° C / 40 mbar.

Example 18

CH3

FC1C-CCl2-CH2-CHCl-C-CH2CO2C2H5

CH3

168 g of ethyl 3: ^ - ^ (^ i ^ i ^ (^ 1 ^^^ diyl-4 - ^] ^ i ^ ^NTE! Boronic acid and 624 g · pentachlorlluorethanu is heated together with 2.4 g of benzoyl peroxide under agitation At a bath temperature of 100 ° C, the internal temperature is increased to 118 ° C.

After about 2.5 hours, the exothermic reaction is complete.

Excess pentachlorofluoroethane and untreated 3,3-dimethyl-4-pentenoic acid ethyl ester are readily separated by distillation from the resulting 3,3-dimethyl-4,6,6,7,7,7-pytaaC] -or-7-ethyl ester. fluorinic acids (refractive index no ²⁰ - 1.487).

Example 19

HC * ^CF CH ^ N <

Analogously as described in Example · 17 · from ethyl 3,3-dimethyl-4,6,63nchlor-7-trifluoromethyl-8,8,8-7 ₅ tetrafluoroktanové acid and sodium ethoxide give 2,2-di- Methyl-3- (2'-chloro-3'-trifluoromethyl-3 ', 4', 4 ', 4'-trifluorobutyl) phenyl) cyclopropanecarboxylic acid boiling point 68-72 ° C / 40 Pa.

The following compounds were obtained in an analogous manner to that described in Example 18:

example · compound boiling point (° C / Pa)

CH3 l ·

CFC2CCC2CHCHCl - C - CH2CO2CH5 122-130/40

CH3 ........................... .....................

CH3 l · -

CFCI2CCl2CH2CHCl — C — CH2CO — CH3 103 to 107/33 '

CH3

Example 22

CH3 (CF3J2CFCCl2CH2CHCl — C — CH2CO2C2H5)

AND

CHs g of 3- ₍ 3-dimethyl-4-pentenoic acid ethyl ester, 287.5 g, 11-trichloro-2,3,3-tetrahydro-2-trifluoromethylpr (rpan), 50 g acetonitrile, 0.65 g FeCl3. 6H2O 0.51 g of benzoin and 0.4 g of dimethylamine hydrochloride were heated in an autoclave under nitrogen pressure of 0.6 MPa for 7 hours at 100-120 ° C, and after cooling and depressurization, the reaction mixture was distilled through a Vlgreux column. with 3,3-dimethyl-4,6-trichloro-7,8,8,8-tettafluoro-7-trifluoromethyloctanoic acid ethyl ester, b.p. 115-118 ° C / 33 Pa.

Claims (2)

SUBJECT Insecticidal and / or acaricidal compositions, characterized in that they contain, as active ingredient, at least one fluoralkenyl-substituted cyclopropanecarboxylic acid ester of the formula I, in which: R ^{1 is} hydrogen, chloro, bromo, (C 1 -C 4) alkyl, (C 1 -C 4) haloalkyl, R2 is chloro, bromo, (C1-C4) alkyl or (C1-C4) haloalkyl, R ^{3 is} halogen, trifluoromethyl or a group of formula R1-CF-R2 a R is a pentafluorobenzyl group or a group of formula of the invention wherein is R ^{9 is} fluorine or hydrogen, X is —CH2— or —Ο—, R10 is phenyl, - CHF2, or —CF3, and R 11 is hydrogen or. cyano. 2. A process for producing an active ingredient according to item. A compound according to claim 1, characterized in that the acid or its reactive derivative of the general formula (II) in which: R ¹ , R 2 and R ³ are as defined in 1 a Z ¹ is halogen or hydroxy, reacted with an alcohol or a reactive derivative of formula III, R-Z2 (III) wherein R is as defined in 1 a Z 2 is hydroxy, chlorine or bromine, optionally in the presence of solvents, acid binding agents and / or phase transfer catalysts at a temperature of 0 to 120 ° C.