CS208136B2 - Means for suppression of the soil insects - Google Patents

Abstract

The substituted benzyl cyclopropanecarboxylates, some of which are known, of the general formula I <IMAGE> in which R represents CH3, Cl, Br or F; X represents Cl, Br or I; Y represents Cl or F; and m and n represent integers from 0 to 5, with the condition that m and n are not simultaneously zero, are suitable for the control of soil insects. The novel compounds among the compounds of the general formula I can be prepared by reaction of an appropriate reactive acid derivative with the corresponding alcohol or its reactive derivative.

Description

(54) Soil control product

The present invention relates to a composition for controlling soil insects which contains, as an active ingredient, partially known cyclopropanecarboxylic acid esters.

It is already known that esters of 2,2-dimethyl- (3-substituted vinylcyclopropemarboxylic acids with substituted benzyl alcohols) have insecticidal properties (cf. Pestic. Sci. 1975, pp. 537-542; Agr. Biol. Chem. 40, p. 8). 247-249 (1976); French Patent No. 2,290,415 (French Patent No. 2,271,196; DOS 2,658,074).

thoroughly explored, interesting pyrethroids are known not to be suitable as soil insecticides (Pestic. Sci. 1977, p. 241, Pestic. Sci. _1977. p. 267, Proceedings 1977 Brit Crop. Protéct. Coitf *., Vol. 2, 647 and 655). On this basis, it was concluded that pyrethroids are generally not suitable as soil insecticides (Pestic. Sci. 1977, p. 267; Nach. Chem. Techn. Lab. 26/1978 / No 3, p. 121).

It has now been found that the substituted cycluprupanecarboxylic acid esters of formula I are substituted

in which

R is chlorine and bromine, (I)

2061

X is eel, bromine, iodine

Ϊ means ChLoir, fluorine and man mean integers from 0 to 5, provided that m and n cannot simultaneously represent zero, they are highly effective soil insecticides.

This surprising finding, which could not be expected from the prior art, is therefore a valuable enrichment of the state of the art.

Substituted cyclopropanecarboxylic acid esters of formula (I) are known in part from DOS 2,658,074 and French Patent Specification No. 2,290,415.

The substituted cyclopropanecarboxylic acid esters of formula (I) wherein:

R is as defined above,

X is bromine, iodine,

Ϊ represents chlorine, fluorine, m represents an integer from 1 to 3 and n represents an integer from 0 to 4, are novel compounds.

These compounds are produced by:

a) to the acid chloride of formula XI

(II) in which:

R is as defined above, with an alcohol of formula III

x _m HOCH, - * n (III) in which X, Y, m and n. mm as defined above,

at temperatures between 20 ° C and 100 ° C, optionally in the presence of a diluent or acid-binding agent;

b) to a salt of formula IV

^H 3 ^C _X , ^CH 3 R (IV) ,> COO 'M + in which R is as defined above and

11 * is an alkali metal or alkaline earth metal cation, or a primary, secondary or tertiary ammonium ion, acts with a benzyl halide of formula V

HalCH ₂

^x m

Yn (V) in which

Hal is chlorine or bromine and

X, Y, m and n are as defined above, in a polar solvent at temperatures between 20 and 120 ° C.

Compounds useful in the invention are generally defined by Formula 1. In this formula, R is preferably the same or different substituents represented by chlorine or bromine, m is preferably an integer from 0 to 5, n is preferably an integer from 0 to 5.

These compounds are present in the form of their stereoisomers. The substituents on the cyclopropane ring may have a cis or trans position relative to each other. C atoms and Cj may in each case have the R and / or S configuration and thus lead to optically active, optionally racemic cis and / or trans isomers.

Examples of materials useful in the present invention include:

pentafluorobenzyl esters of 2,2-dimethyl-3-dichloro-vinyl-cyclopropanecarboxylic acid, tetrafluoro-2-chlorobenzyl ester, 2,2-dimethyl-3-dichloro-vinyl-cyclopropanecarboxylic acid, tetrafluoro-2-chlorobenzyl ester, 2,2-dimethyl-3-dichloro-vinyl-cyclopropanecarboxylic acid chlorobenzyl ester, 2,2-dimethyl-3-dichloro-vinyl-cyclopropanecarboxylic acid tetrafluoro-3-bromobenzyl ester,

2,2,6-Dimethyl-3-dichloro-vinyl-cyclopropanecarboxylic acid 2,4,6-trifluoro-dichlorobenzyl ester,

2,2,6-Dimethyl-3-dichloro-vinyl-cyclopropanecarboxylic acid trifluoro-dichlorobenzyl ester,

2,2,5-Dimethyl-3-dichloro-vinylcyclopropanecarboxylic acid 2,4,5-trifluorodichlorobenzyl ester,

2,2.5-Dimethyl-3-dichloro-vinyl-cyclopropanecarboxylic acid trifluoro-dichlorobenzyl ester,

2,2.6-Dimethyl-3-dichloro-vinylcyclopropanecarboxylic acid 2,4,6-trifluorodibromobenzyl ester,

2,2,6-Dimethyl-3-dichloro-vinyl-cyclopropanecarboxylic acid 2,4,6-trichlorodifluorobenzyl ester,

2,2,6-Dimethyl-3-dichloro-vinyl-cyclopropanecarboxylic acid 2,3,6-trichlorodifluorobenzyl ester,

2,4-Dimethyl-3-dichlorvinylcyclopropanecarboxylic acid trichlorodifluorobenzyl ester,

3,4.5-2,2-dimethyl-3-dichloro-vinylcyclopropanecarboxylic acid trichlorodifluorobenzyl ester,

206136 2,2-Dimethyl-3-dichloro-vinyl-cyclopropanecarboxylic acid trachlor-2-fluoro-benzyl ester, 2,2-Dimethyl-3-dichloro-vinyl-cyclopropanecarboxylic acid tetrachloro-3-fluoro-benzyl ester, 2,2-Dimethyl-3-fluoro-benzyl ester 2,2-dimethyl-1-3 -dichlorvinylcyclopropanecarboxylic acid,

2,2,5-Dimethyl-3-dichloro-vinyl-cyclopropanecarboxylic acid 2,3,5,6-tetrafluorobenzyl ester,

2.3.4.5-Tetrafluorobenzyleater of 2,2-dimethyl-3-dichlorvinylcyclopropanecarboxylic acid,

2,3.5.6-Tetrachlorobenzyl ester of 2,2-dimethyl-3-dlchlorvinylcyclopropanecarboxylic acid,

2,2-dimethyl-3-dichloro-vinylcyclopropanecarboxylic acid 2, 3,4,5-tetrachlorobenzyl ester,

2,2-Dimethyl-3-dichloro-vinyl-cyclopropanecarboxylic acid 2,4,6-trifluorobenzyl ester,

2,2,6-Dimethyl-3-dichlorvinyl-cyclopropanecarboxylic acid 2,3,6-trifluorobenzyl ester,

2,2,5-Dimethyl-3-dichlorvinyl-cyclopropanecarboxylic acid trifluorobenzyl ester,

3,4.5-2,2-dimethyl-3-dichloro-vinylcyclopropanecarboxylic acid trifluorobenzyl ester,

2,2.6-Dimethyl-3-dichloro-vinylcyclopropanecarboxylic acid trichlorobenzyl ester,

2,2-dimethyl-3-dichloro-vinylcyclopropanecarboxylic acid 2,3,6-trichlorobenzyl ester,

2,2-Dimethyl-3-dichloro-vinyl-cyclopropanecarboxylic acid 2,4,5-trichlorobenzyl ester,

2,2,5-Dimethyl-3-dichloro-vinyl-cyclopropanecarboxylic acid 3,4,5-trichlorobenzyl ester »

2,2-Dimethyl-3-dichloro-vinylcyclopropanecarboxylic acid 2,4,6-trichloro-3-bromobenzyl ester,

2,2-Dimethyl-3-dichloro-vinylcyclopropanecarboxylic acid 2,4,6-trichloro-3-iodobenzyl ester,

2,4-dichloro-6-bromobenzyl ester of 2,2-dimethyl-3-dichlorvinylcyclopropanecarboxylic acid,

2,2-Dimethyl-3-dichloro-vinyl-cyclopropanecarboxylic acid 3,5-dichloro-4-bromobenzyl ester,

2,4-dichloro-5-iodobenzyl ether of 2,2-dimethyl-3-dichlorvinylcyclopropanecarboxylic acid,

2,2-dimethyl-3-dlchlorvinylcyclopropanecarboxylic acid 2,4-dichlorobenzyl ester,

2,2-dimethyl-3-dichloro-vinylcyclopropanecarboxylic acid 3,4-dichlorobenzyl ester,

2,2-Dimethyl-3-dichloro-vinylcyclopropanecarboxylic acid 3,5-dichlorobenzyl ester,

2,2,6-Dimethyl-3-dichloro-vinyl-cyclopropanecarboxylic acid 2,4,6-tribromo-benzyl ester,

2,4,5-tribromobenzyleater 2,2-dimethyl-3-dichloro vinyl cyclopropanecarboxylic acid,

2,2-Dimethyl-3-dichloro-vinylcyclopropanecarboxylic acid 2,4-dibromo-6-chlorobenzyl ester,

2,2-Dimethyl-3-dichloro-vinylcyclopropanecarboxylic acid 2,4-dibromobenzyl ester,

2,2-Dimethyl-3-dichloro-vinylcyclopropanecarboxylic acid dibromobenzyl ester,

2,2-Dimethyl-3-dichlorvinyl-cyclopropanecarboxylic acid 3,5-dibromobenzyl ester,

2,2-Dimethyl-3-dichloro-vinylcyclopropanecarboxylic acid 2,6-dibromobenzyl ester,

2,2-Dimethyl-3-dichlorvinyl-cyclopropanecarboxylic acid 2,4-difluorobenzyl ester,

2,2-Dimethyl-3-dichloro-vinylcyclopropanecarboxylic acid 3,5-difluorobenzyl ester,

2,2-Dimethyl-3-dichloro-vinyl-cyclopropanecarboxylic acid 2-fluoro-3-iodobenzyl ester,

2,2-Dimethyl-3-dichloro-vinyl-cyclopropanecarboxylic acid 4-fluoro-3-iodobenzyl ester, 2,2-dimethyl-3-dichloro-vinyl-cyclopropanecarboxylic acid 4-chloro-2-iodo-benzyl ester,

2,6-Difluoro-3-chloro-5-iodobenzyl 2,2-dimethyl-3-dichlorvinylcyclopropanecarboxylic acid,

2,2-Dimethyl-3-dichloro-vinyl-cyclopropanecarboxylic acid 2-bromo-4-iodobenzyl ester,

3-bromo-4-iodo-benzyl-2,2-dimethyl-3-dichloro-vinyl-cyclopropanecarboxylic acid,

2,2-Dimethyl-3-dichloro-vinylcyclopropanecarboxylic acid 3-bromobenzyl ester,

2,2-Dimethyl-3-dichloro-vinylcyclopropanecarboxylic acid 3-iodo-4-chlorobenzyl ester,

2,2-Dimethyl-3-dichloro-vinylcyclopropanecarboxylic acid 3-iodo-4-fluorobenzyl ester,

2,2-dimethyl-3-dichloro-vinylcyclopropanecarboxylic acid 3-iodobenzyl ether, and the corresponding 2,2-dimethyl-3- (2-methylbuten-1-yl) cyclopropnicarboxylic acid esters as well as 2,2-dimethyl-3-dibvinylmethylcyclopropanecarboxylic acid.

Said esters include both racemic and optically active isomers as well as cis and / or trans isomers.

When H is used as the acid chloride of formula II, the chloride of (.beta.-dimethyl-4-dichloro-vinylcyclic acid) and as the alcohol of formula III is 3'-joalemolecanol, then the reaction sequence - in process a) is shown by the following reaction scheme:

The compounds of formula (II) are known (BOS 2,439,177). ⁷

The A-alcohols of formula (III) are partially known (BUstein, 5th major, Volume 446,447).

The novel alcohols of formula III can be prepared by methods known in the art, for example by reduction of the corresponding aromatic compounds of formula VIII

in which

X, Y, m and n are as defined above and

Z stands for hy (aproxy) caffeine, α-oxysupupin, chlorine, fluorine or hydrogen, by complex metal hydrides.

The compounds of formula VIII necessary for the reduction are known compounds (Beiste®,

9th main volume, Syst. No. 938, pp. 355-3618; 9. dílo Syst. No. 938, pp. 1,378, 1,427-1,431, pp. 1,452-1,415).

Examples of alcohols of formula III are:

2- or 3- or 4-benzoyl-alcohol

2- or 3- or 4-benzoyl alcohol

4-fluoro-3-V &apos;

4-chloro-3-joaenzylalcohol

4-bpvo-3-iodobenzyl alcohol and dichlorobenzoyl alcohol ethanol and dibromocarbonyl alcohol and dibromobenzyl alcohol and lithium benzyl alcohol.

H-sodium 2,2-dimethyl-3-dichloro-vinylcyclopropane-1-carboxylate and as a bansyl halide of formula V 3 &apos; 5-dibronobutyl chloride are used as salts of the formula IV, followed by a process. reactions in process b) to depict the non-following reaction scheme B:

Salts of the formula IV which are used as starting materials in process b) are known (DOS 2,436,178). The compounds of formula (V) which are necessary as the reactant are partially known (B-IsI-I, 5th main volume, 3. supplemented with Vol. No. 466, 717-720, 726-727).

The novel benzyl chlorides of the formula (V) can be prepared in a manner known per se by the halogenation of the corresponding toluenes (Vo-I-1β, 5th major edition, 3 rd supplement, system No. 466, pp. 719-720, p. 725). As an example for the banzylculorides useful in the present invention, 3,5-dibromo-mesylate may be mentioned.

Process b) is carried out in polar organic solvents such as cation (e.g. acetone), nitrates (e.g. acetonitrile), tyzaline amides (such as dimethylformamide, hexameyltriamide phosphoric acid) or mixtures thereof with water. at temperatures between 20 and 100 ° C.

The process is carried out in the primitive or in the absence of suitable catalysts. Such catalysts. are peralkylated polyamide such as pentamethyldiethyl ether lamin. The reaction is carried out as described in Sylthia 1975, p. 805.

The active compounds are suitable for controlling animal pests, especially insects which live in the invasion. They are active against normally sensitive and resistant species as well as against all or individual developmental stages.

The active ingredients have a good herbicide and favorable theolocrine toxicity and are suitable for controlling animal pests, in particular fog, in agriculture. They are active against normally dUA-resistant species as well as against all or only uniform developmental stages of pests.

The above mentioned pests include:

from the order of the Isopods, for example On.scus asellus, Ar ^ addili ^ clitm, Poocc-ΙΙγ scaber ;,

Ί from the millipedes class <D ^] ^ JLop <^ c ^ c ^), for example BlunLulus guttuLatus;

from the class of the Chilopoda, for example Geophilua carpophiapis, Sulfur spec.

From the class of the Centipede (Syrnphyla), for example

Scutigerella imaculata;

from the order of the Tailfish (Cooieabooaa, for example, Lemongrass (ОпгсЫшч) armaCus);

from the order of the Otopterer, such as mole cricket (Ог ^ Шс ^) spec.), locusta migratoric.,

Mellaioplus differenttaCis, Grasshopper (Schistocercc greg ^^ ic);

from the order of the Dermaatela, for example

Common earwig (Fooficulc au: · icutacra);

from the order of the Isoptera, for example, the reptile (Specter spec.);

from the order of the Anopuua, for example Ptylloxera vacSaCrix, Pemphigus spec, Linognathus from the order Leetdoottla, e.g. Arrtis spee., Euxoa spec.

Feltic spec

Escurts insulcnc, ftrodenia Mturc, ^f

Spodoppera spec

Chilo spec corn moth (Pyrausta тЮ-аНе);

from the order of the beetles (Coteeottla), for example

Diabrotica spec., Oilseed flea beetle (Atomria spec.), Small weevil (Atommria spec.), Weevil (SlpnUus spec.), Ragged lobe (Otiorrhynchls s ^ lc ^ i ^ - ^ ^ Si, Cotmoptlit18 sopO-nit, Seululean Cryothrush (Ceuthprrhynchls cssimiiis), European Mealworm (Tenebrio шоМ-ог), Quartz (Arictes spec.), Conoderus spp. (Meeolontha, Summer (AnaPiLmllpn) 0 ^) 1 tidis), ^ oSely ^ a zealand;

208136 t of Diptera, for example Blblo hortulanus, OscCnaeia frit, Piorbia cpac Pegomria hyoaccaeD, Tlpula paludoaa.

The active substances can be converted into customary formulations, such as solutions, emulsions, drinkable powders, suspensions, powders, dusts, soluble powders, grams, baits, bait concentrates! suspensions and eaults, seed dressing powders, active substances impregnated with natural and synthetic substances, small particles of polymeric substances and seed coatings.

These compositions are prepared in a manner known per se, for example by effective mixing. substance-with extenders, that is liquid rozpouHšdly, liquefied gases nacCházjícími under too and / or solid carriers, agents, optionally pooHtí surface active agents, that emugátorů and / meta-sperg ^ ORU and / No ^b oz ^p ěnovacích ^No ini ^d el . In at ^p and ^DE potóití water Pinl as ^y ^ and It is possible to "used as auxiliary solvents such organic rospouštšdla example. Suitable liquid solvents are, in principle, aromatics, such as xylene, toluene or alkanepthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorine. ethylene or ethylene glycol, aliphatic hydrocarbons, such as cyclohexane or particles, for example petroleum fractions, alcohols, such as butanol or glycol, as well as their ethers and esters; ,. as . . ^ο ^ ι ^ ιοοοΙΙ. . a. as well as water. .

By liquefied gaseous fillers or carriers is meant liquids which are gaseous at normal temperature and pressure, for example aerosol burns, such as halogenated hydrocarbons such as butane, propane, nitrogen and carbon dioxide. Possible solid carriers are: natural stone flours such as kaolins, alumina, talc, chalk, quartz, attapuugit), or silica and synthetic stone flours such as highly dispersed silica, rotten oxide and silicates. Suitable solid carriers for the preparation of granulates are crushed and fractured natural stone materials, such as limestone, marble, pumice, seeiool and dolomite, as well as synthetic granules of organic material such as sawdust, coconut shells, corn. ic and tobacco stems.

Suitable emulsifiers and / or foaming agents are nonionic and anionic emulsifiers; fatty alcohol alcohols, for example .alpha.-arylalkyl polyol glycol ether, sterol, alkenyl sulfonates, alkali metal, arlyl sulfoates and hydrolysates of proteins, and as dispersants, for example, lignin, diolites and methylesters.

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

In addition, these compositions may contain coloring agents such as inorganic pigments, for example iron (III) oxide, titanium dioxide and the like. errolyanide blue and organic dyes such as alizarin dyes and metallic azo-phthalocyanine dyes, as well as trace elements such as iron, manganese, boron, ear, cobalt, molybdenum and zinc salts.

In general, between 0.1 and 95% by weight of the active ingredient is present, preferably between 0.5 and 90% by weight.

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

«

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

The application is carried out in a manner adapted to the application forms, usually by spraying, sprinkling or dusting, or they are applied to the soil or applied in the form of baits which are placed in the presence of pests.

Example 'A

Limit concentration test - soil insects

Experimental insects: Mealworm (Tenebrio molitor) - larvae in soil Solvent: 3 parts by weight of acetone Qnulgátor: 1 part by weight of alkylaryl polyglycol ether

A suitable active agent is prepared by mixing 1 part by weight of the active compound 8 with said amount of solvent, adding said amount of emulsifier and diluting the concentrate with water to the desired concentration.

The active ingredient is thoroughly mixed with the soil. The concentration of the active substance in the composition plays practically no role, the decisive factor being the amount of active substance per unit volume of soil, which is given in ppm (= mg / liter). The soil ее filled into pots and they are left at room temperature.

After 24 hours, the test insects are added to the soil treated as described above and after a further 2 to 7 days the degree of action of the active compound is determined by counting the dead and live specimens of the test insects and expressed as a percentage. The degree of action is 100% when all insects are killed and 0% if exactly as many specimens of the test insects survived as in the control.

The active substance, the amounts used and the results are shown in the following table:

Table

Soil insect limit test (Tenebrio molitor larvae in soil)

Active substance (formula) known

Mortality in% at active substance concentration in ppm

2.5 ppm

Permethrin

continued table

Active substance (formula)

Mortality in% at active substance concentration in ppm

2.5 ppm

Sumicidin

CH ₃ CH ₃ (known)

(±) trans-isomer of continuation table

Active substance (formula)

Mortality in% at active substance concentration in ppm

2.5 ppm

cis

Example В

Limit concentration test - soil insects

Trial insects: 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, 1 part by weight of active ingredient is mixed with the indicated amount of solvent, the said amount of emulsifier is added, and the concentrate is diluted with water to the desired concentration. The active agent is thoroughly mixed with the soil. The concentration of the active ingredient in the composition has virtually no role, only the moiety of the active ingredient per unit volume of soil, which is expressed in ppm (= m / l), is decisive. .

After 24 hours, the test insects are transferred to the treated soil and the percentage of action of the active compound, calculated on the dead and live specimens of the test insect, is determined in 2 to 7 days. The effect is 100% when all insects have been killed, and 0% if the live number of live insects of the test insects is exactly the same as in the control (untreated soil).

The active ingredients used and the results are obtained from the table below.

Table

Limit concentration test - soil insects (A / oois se / eUm larvae in soil)

Active substance (formula) The percentage in% at the rate of active ingredient in ppm 0.5 ppm

H3C CH3

Su ^ msci ^ in (known substance)

continued table

Active substance (formula)

Moottlity in% at active substance concentration in ppm

0.5 ppm

100%

208136 14

Example 1

2,2-Dimethyl-3-dichloro-cyclopropanecarboxylic acid 3-iodobenzyl ester

0.01 mol of 2,2-dimethyl-3-dichloroyl-glycolopanecarboxylic acid chloride and 0.02 mol of 3-iodobenzyl alcohol are heated together at 100 ° C until the evolution of hydrogen chloride is complete. Zby-

The oil is then distilled in a flask at a temperature 160 ° C and 13.3 Pa. iC spectrum: 2,950, 1 790, , 1 630, 1 610, 1 580, 1 460, 1 420, 1 390, 1 350 1 290, 1 270, , t 230, 1 180, 1 170, 1 140, 1 120, 1 090, 1 060 1 000 930, 890, 870 , 810, 785,735 , 700 cm ''.

Claims (1)

SUBJECT OF THE INVENTION An insect retardant composition comprising, as an active ingredient, at least one substituted C18-copolymer of the acid of the formula I (I) in which: R is chlorine or bromine, X is chlorine, bromine, iodine, Y is chlorine, fluorine, and man substitute integers from 0 to 5, provided that m and n cannot simultaneously represent zero.