DD143849A6 - INSECTICIDES, ACARICIDES AND NEMATICIDES - Google Patents

Abstract

The invention relates to novel esters of cyclopropanecarboxylic acids which contain a polyhalogenated substituent according to main patent 135,152. The compounds are used as insecticides, acaricides, nernatides. According to the invention, compounds in the form of isomer A, isomer B or of geinics of these isomers are prepared, for example (S. ) α-Cyano-3-phenoxybenzyl (IR, trans) -2,2-dichloro-3- (2 ', 2-dichloro-1 *, 2-dibromoethyl) -cyclopropane-1-carboxylate, (S) -t -Cyano-3-phenoxybenzyl- (1R, cis) -2, 2-dimethyl-3- (2 ♦, 2'-dibromo-1 *, 2'-dichloroethyl) -eyopropan-1-carboxylate and others having the general Formula I *, in which X ,, X2r X3

Description

- Λ-

Insecticides, acaricides and nematicides

Field of application of the invention

The invention relates to insecticidal, acaricidal and nematicidal compositions according to patent / 135 "ΛS" λ containing esters of cyclopropanecarboxylic acids with a polyhalogenated substituent as an active ingredient in addition to conventional additives.

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Gen characteristics of known technically en Lösun

No. Haffie44 ¥ yag entitled "Process for the Preparation of Novel Esters of Cyclopropanecarboxylic Acids Containing a Polyhalogenated Substituent", filed on September 21, 1977 No. 2-Q4-44, was a process for preparing the compounds of the general Formula I is described in all its possible isomeric forms.

, _f

and X ~ wv all a fluorine, chlorine or

in the X p

Bromatom represent and R especially;

- a benzy! radical that may be substituted

a 5-benzyl-3-furyl-methyl group or related groups

a 2-methyl-3-alkyl-4-oxo-cyclopentenyl (2) group or. related groups ·

3-phenoxybenzyl groups, c-cyano-3-phenoxybenzyl or -äthynyl-3-phenoxybenzyl groups or related groups

129 1 129 - ³

a 3,4,5,6-tetrahydro-methylphtaliraid group or one of the related groups.

Iia main patent has been stated that the esters of formula I can exist in many isomeric forms "And indeed have the cyclopropanecarboxylic acids, the acid part of the. Esters of the formula I form, usually 3 asymmetric carbon atoms, ie the asymmetric carbons in the positions 1 and 3 of the cyclopropane ring and the asymmetric carbon in the position A 'of the polyhalogenated ethyl side chain fixed in position 3 *

It has also been stated in the main patent that the ROH alcohol which is the alcoholic portion of the esters of formula I may contain one or more asymmetric carbon atoms and / or one or more double bonds giving rise to an E / Z isomerism.

In the main patent was also noted that in the case of v / o, the substituents X and X ₂ are the same at a specific steric configuration of the asymmetric carbon atoms in position 1 and 3 of the cyclopropane ring and at a unique stereochemical structure of the alcoholic part, two diastereoisomeric forms of the esters (i) or the corresponding acids due to the presence of the asymmetric carbon atom may be present in 1.

These isomers can usually be separated or isolated in a pure state; they are here and below called isomers (A) and (B).

In the main patent, the insecticidal compositions have been described which contain as active ingredient at least one of the compounds of formula (i), and the acaricidal or nematicidal compositions containing at least one of the compounds of general formula I.

AP C 07 C / 211 129 54 844 11

The main patent also described the pharmaceutical compositions for the veterinary. Use primarily intended for the control of diseases caused by mites, mixtures containing at least one of the compounds of general formula I, and compositions intended for feeding animals and consisting of a composite, balanced feed, - Which also contains at least one of the compounds of general formula I.

The main patent also describes the fungicidal compositions containing some products of general formula I.

Object of the invention

The aim of the invention is the provision of insecticidal, acaricidal and nematicidal agents with improved efficacy.

Outline of the essence of the invention

The invention is based on the object, suitable compounds for use in the o. G. To locate funds.

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The compounds used according to the invention correspond to the general formula I in the form of isomer A, isomer B or a mixture of isomers A and B whose names are listed below:

- (S), X - cyano-3-phenoxybenzyl- (1R, trans) -2,2-dimethyl-3-

(2 ', 2'-dichloro-1'2'-dibromoethyl) -cyclopropane-1-carboxylate,

- (S) c-cyano-3-phenoxybenzyl (1R, cis) -2.2-dimethyl-3-

(2 ', 2'-dibromo-1 · ¹ , 2' -dichloroethyl) -cyclopropane-1-carboxy-

3j 4,5,6-Tetrahydro-methyl-phthalimide (1R, trans) -2,2-dimethyl-3- (1 ', 2', 2 ', 2' -tetrabromethyl) -dicyclopropane-icarboxylate,

3,4,5,6-Tetrahydromethylphtalimid- (1R, cis) -2,2-dimethyl-3- (1 ', 2', 2 ', 2'-tetrabromäthyD-cyclopropane-T-carboxylate,

(S) 0C_Cyano-3-phenoxybenzyl- (1R, cis) -2,2-dimethyl-3- (1 ', 2', 2 ', 2'-tetrachloroethyl-cyclopropane-1-carboxylate,

20/80, 50/50 or 80/20.

The additional patent application thus includes a process for the preparation of the compounds "ö" of the mixtures of cis- and trans-isomers according to what has been stated above, compounds which are represented by the general formula I ¹ :

- (R) <u- cyano- »3-phenoxybenzyl- (1R _i trans) -2,2-dimethyl-3" - (2 ^f 2 ^f -dichloro-1 ^t _s 2 ^t -dibromoethyl) cyclopropane-1 carboxylates

These connections are called "" connections in the following. "

The (S) o -cyano-3-phenoxybenzyl- (1R, cis) -2,2-dimethyl-3- (2 *, ^2f -dibhloro-1 ', 2'-dibromoethyl) -cyclopropane-i carboxylate has already been described in the main patent: (S) sC-cyano-3-phenoxybenzyl (1R, trans) -2,2-dimethyl-3 (2 ^l , 2'-dibromo-1 ') - ^ ^ i dicIiXora'thy -cyclopropane-carboxylate and the. (S) c <= 3-cyano-phenoxybenzyl (1R _s tran3) -2,2-diiaethyl-3- ^(1!, 2 ^f, 2 ', 2'-tetrachloroethyl) -cyclopropane-1-carboxylate can be prepared by esterification of the corresponding acids described in the main patent by (S) C 1 -C-cyano-3-phenoxybenzyl alcohol by a process analogous to that described in Example 3 below. R) o <-cyano-3-phenoxybenzyl- (1R, cis) -2,2-dimethyl-3- (2 ', 2 * -dichloro-1' _S 2 '»''dibromoethyl) -cyclopropane-1-carboxylate by esterification of the corresponding acid described in the main patent, by which (R) x-cyano-3-phenoxybenzyl ™ alcohol is prepared by a process analogous to that described below in Example 6

In particular, the application for an additional patent relates to a process for the preparation of the compounds "" in the form of a mixture of stereoisomers with cis structure and trans structure in any ratio *

Among these compound mixtures, there are mentioned in particular those consisting of mixtures of stereoisomers having a cis structure and a trans structure in the weight ratios

1 1 1

αο

X * and R may be summarized in which X, X _2, the substituent of the "^" - compounds have corresponding meanings, method characterized in that a suitable ester of the formula II:

! -OR

in which X _-1 , X ₂ and R have the meanings corresponding to the substituents of the "^" compounds, is reacted with a chlorinating or brominating agent capable of attaching Cl ₉ 'or Br ₉ to the To fix double bond of the side chain of cyclopropanecarboxylic acid.

As the halogenating agent of the ester II, especially chlorine or bromine is used, and the halogenation of the ester II is carried out in an organic solvent which does not react with chlorine or bromine, for. As acetic acid, Kohienstofftetrachlorid, chloroform, methylene chloride.

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The additional patent application also includes a process for the preparation of the "" compounds or the previously defined geras, characterized in that a suitable acid of the formula Uli

3H

C-OH

in which 2L and X ₂ have the meanings corresponding to the "" compounds, are reacted with a chlorinating or brominating agent which is able to 'fix' Cl ₂ or Br ₂ to the side chain of the acid III and that then the resulting acid of the formula IV:

in the

the halo added to the double bond

;

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or a functional derivative of this acid is reacted with a ROH alcohol or one of its functional derivatives, wherein R has the meaning of the corresponding "/ '" - compounds.

The halogenating agent of acids II is mainly chloro or bromo, and the halogenation of the acids

21112 9 - ίο - .-

II now takes place in an organic solvent which does not react with chlorine or bromine, for. Acetic acid, carbon tetrachloride, chloroform, methylene chloride.

The functional derivative of the acid II which is used for esterification with the ROH alcohol or with a functional derivative of this alcohol is especially the chloride, the anhydride, a mixed anhydride, a lower alkyl ester, a metal salt or an organic basic salt Acid II, wherein the functional derivative of the alcohol may be a chloride, a bromide or sulfonate of this alcohol.

The '/' "- compounds have a high insecticidal activity, especially by testing on flies, larvae of Spodoptera littoralis, on larvae of Epilachna Varivestris, on larvae of Aedes Aegypti, on Blatella Germanica, Dysdercus Fasciatus, Sitophilus Granarius and Tribolium Castaneum can be demonstrated »

Yerbindungen well to combat insects in the agricultural sector - thanks to their photochemical stability, the ¹¹ J '"own.

For example, they enable effective control of aphids, lepidopteran larvae, coleopterans.

They are preferably used in dosages between 1 g and 100 g of active ingredient per hectare. Due to their rapid action, these compounds can also be used as insecticides in the household.

Thus, the compounds of formula I can be used in the preparation of insecticidal compositions containing as active ingredient at least one of said compounds or at least one of the stereoisomeric mixtures described above.

21112

In these compositions, the active ingredient or agents may optionally be supplemented with one or more pesticidal agents. These compositions may be in the form of powders, granules, suspensions, emulsions, solutions, solutions for aerosols, hides, baits or other preparations traditionally used to prepare this type of compound.

In addition to the active ingredient, these compositions generally contain a carrier and / or a surface-active, non-ionic agent, which also ensures a uniform dispersion of the components of the mixture. The carrier used may be a liquid such as water, alcohol, hydrocarbons or other organic solvents, a mineral oil, animal or vegetable oil, a powder such as talc, clays, silicates, kieselguhr or a solid fuel such as tabu powder (or pyrethrum marc).

In order to enhance the insecticidal activity of the compounds of the patent application, synergistic enhancers traditionally used in such a case, such as 1- (2,5, ε-trioxadocedyl-2-propyl-4,5-methylenedioxy) -benaol (or piperonyl butoxide), N - (2-ethyl-heptyl) -bicyclo / 2,2-i / -5-heptene-2,3-dicarboximide, piperonyl-bis-2- (2'-n-butoxy) -ethoxy). ~ Ethyl-acetal ( or tropital).

The insecticidal compositions according to the invention preferably contain between 0.005 and 10% by weight of iron.

The above-mentioned insecticidal compositions may thus contain, in addition to the active substance (s), a synergistic enhancer and in particular piperonyl butoxide.

Among the above-mentioned compositions, those selected as the active compound "S" d (-cyano-3-phenoxybenzyl-iR, trans-2,2-dimethyl-3- ( ^2f , 2'-dichloro-1 ♦ , 2'-dibromoethyl ^ cyclopropane-1-carboxylate in the form of isomer A,

Isomer B or a mixture of these isomers A and B included.

The "^" compounds likewise have an acaricidal activity, which can be detected above all by tests on Tetranychus urticae, as well as a nematicidal activity.

The "/ '" compounds can thus be used for the preparation of akarlziden and nematicidal compositions containing as active ingredient at least one of the "^' - compounds or at least one of the Stereoisomerge.mische described above"

For acaricidal application, wettable powder for foliar spraying containing 1 to 80% by weight of the active ingredient or liquid for foliar spraying containing 1 to 500 g / l of the active ingredient are preferably used. It is also possible to use powder for foliar spraying containing 0.05 to 3 $ of active ingredient.

For nematocidal application, soil treatment fluids containing from 300 to 500 g / l of active ingredient are preferably used.

The acaricidal and nematicidal compounds according to the invention are preferably used in dosages of between .1 to 100 g of active ingredient per hectare.

The antiperspirant properties of the compounds of the invention mentioned above also allow the use of these products in the form of pharmaceutical compositions for veterinary use in the fight against spider mite parasites of animals and especially in the fight against the Ixodiden- and Sarcoptidae parasites of the animals.

The compounds of the invention can be used in animals, especially to combat all types of scabies, such as

the Sarcoptidae, Psoroptidae and Chorioptidae scabies.

By means of the compounds according to the invention it is also possible to combat all types of ticks, for example the species Boophilus, Hyalomnia, Amblyoma and Rhipicephalus.

Accordingly, the invention also relates to a method of combating the spider mite parasites of the animals, characterized in that veterinary compositions are used which as active ingredient comprise at least one of the "/" "compounds or contain at least one of the previously described steroid isomeric preparations ,

The compositions mentioned can be applied externally, but can also be administered by parenteral or digestive route.

A synergetic enhancer from the pyrethrinoid group may also advantageously be added to the said compositions. Such agent has been described above. These compositions are prepared by conventional methods.

Finally, it may be convenient for veterinary use if the compounds of the invention are mixed with the composite, balanced animal feeds.

For example, compound feeds containing from 0.002 to 0.4% by weight of (S) oi-cyano-3-phenoxybenzyl-iR, trans-2,2-dimethyl-3- (2 ^t , 2'-dichloro) can be used. 1 ·, 2'-dibromoethyl) ~ cyclopropane ~ 1-carboxylate.

These animal feeding compositions are characterized in that they consist of a compound, balanced feed, and moreover at least

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contain one of the compounds with the general formula "/" "or at least one of the stereoisomer mixtures described above"

embodiment

The following examples serve to illustrate the invention without, however, limiting it.

211129 -

_? Example 1: 3 • _{"<4 <5 <6-Tetrahyd} romethyl.Ohtali in id-CiR c is) -2-.2 dimeth yl-5- (i '.2 .2 * * ^' - tetrabr- omat hylO-c ycloprouan-i-carboxy lat

Stage A; (1R, ice) ~ 2,2-dimethyl-3- (i 'x, 2'.2', ^2f -tetrabromethyl) -

There are introduced in 150 cm ⁵ carbon tetrachloride 19.4 g (iR, cis) -2,2-dimethyl-3- (2 ·, 2 * -dibronrvinyl) -cyclopropan-1-Carboxylsäiire, 10.4 g of bromine, the dissolved in 22 cm carbon tetrachloride, added, stirred for one hour at 20 ⁰ G, concentrated by distillation under reduced pressure to dryness, and obtained 31.4 g of crude product (mp = 145 ⁰ C). This crude product is crystallized from ilO cm of carbon tetrachloride to give 22.12 g (iR, cis-2,2-dimethyl-3- (i, 2 ', 2', 2'-tetrabromethyl) -cyclopropane-1-carboxylic acid. = 150 ⁰ C.

This product is a mixture of two isomers (A) and (B), which are detected by the nuclear magnetic resonance spectrum. Namely, the nuclear resonance spectrum can detect a compound (which accounts for about 2/3 of the mixture) having peaks at 1.31-1.43 ppm corresponding to the hydrogens of the methyl pair, and peaks at 5.33 to 5, 66 ppm corresponding to the hydrogen bonded to the asymmetric monobrominated carbon and another compound (representing about 1/3 of the mixture) having peaks at 1.28-1.48 ppm corresponding to the hydrogens of the paired ones Correspond to methyls, and peaks at 4.24 to 5.34 ppm corresponding to hydrogen bound to the asymmetric monobrominated carbon.

In the mixture, peaks at 1.67 to 2.17 ppm (hydrogens in positions 1 and 3 of the cyclopropane) and a peak at 11.25 ppm (acidic acid mobile oxygen) are further detected.

The analysis of the recovered mixture (F. = 150 ⁰ C) is the following:

Ah-

^e 8 ^H i0 ^Br 4 ° 2 C (457 , 804 K. % 2 20 Br ° h 69, 82 calculated: % 20 99 2 2 70 2 Gefundens 20

_z ; D ^^

In 179 cm of ⁵ petroleum ether (bp. 35-75 ⁰ C) 0.2 cm ^{3 of} dimethylformamide, 8.5 cm of thionyl chloride, the mixture was refluxed, 35.76 g (iR, cis) -2.2 ~ Diraethyl-3- (i ^f , 2 ¹ j2'j2 ^l -tetrabromäthyl) cyclopropane-1-carboxylsä rre added in 150 cm methylene chloride _s stirred for 2 hours under reflux, cooled, distilled to dryness, toluene was added, again by distillation under reduced pressure to dryness eingeeng-p and there is obtained 38 g of crude acid chloride (mp = 88 ⁰ C) so ^as! it is used for the next stage.

There are mixed 7.7 g of the acid chloride prepared in the previous stage with 2.97 g .Neopynaminol in 50 cm of anhydrous benzene, cooled to 0 ⁰ C, with stirring 3 g of pyridine were added, under 18 ~ hours of stirring, the ambient temperature is again reached, the The reaction mixture was poured into a dilute acid solution, extracted with benzene, washed with an aqueous sodium bicarbonate solution, rinsed to neutrality with water, the organic phase was isolated, dried over magnesium sulfate, filtered and concentrated under reduced pressure to give 10 g of crude product which is purified by chromatography on silica (elution agent: benzyl ethyl acetate 95/5), there are 3.3 g of 3,4,5,6-tetrahydro-methyl-phthalimide (iR, cis) -2s2-dimethyl-3- ( i ', 2 ^f , 2 ^s , 2'-tetrabromethyl) -cyclopropane-1-carboxylate in the form of a mixture of isomers A and B and 0.5 g in the form of isomer (B) «

Characteristic value e of the product obtained in the form of a mixture of isomeric A and B:

/ af / _D ²⁰ = - 21.5 ° + 1 ° (c = 1 #, benzene) Anal yse; C ₁₇ H ₁₉ Br ₄ NO ₄ MW = ^620.982:

Calculated: C ° h 32.88 H <$> 3.08 N # 2.25 Br % 51.47 Found: 33.8 3.2 2.1 50.2

UV-S-pectrum (ethanol)

Turning point = 218 nm E ^ J = 243.

Maximum = 223 nra E ₁ = 275 f. = 17 100

Maximum = 229 nm E ₁ = 269 I = 16 700

Turning point ^! = 238 nm E ₁ = 170 pounds = 10 500 -

Turning point = 295 nm E ₁ = 8 ·

Nuclear resonance spectrum (Deutrochloroform)

Peaks at 4.98-5.17 ppm, characteristic of the hydrogen in position 1 of the islet B of the islet

Peaks "at 1.2-1.45 ppm ·, characteristic of the hydrogens of the methyl pairs of the isomer B

Peaks at 5.17-5.38 ppm, characteristic of the hydrogen in position 1 'of the ethyl side chain of the isomer A.

Peaks at 1.2-1.38 ppm, characteristic of the hydrogens of the methyl pairs of the isomer (A).

Peaks at 1.58-2.08 ppm, characteristic of the hydrogens of the cyclopropyl and the methylenes of the cyclohexyl.

Massive at 2.33 ppm. characteristic of the hydrogens of the methylenes of the cyclohexyl.

Peaks at 5.33-5 »70 ppm, characteristic of the yers of the

Characteristics of the product obtained in the form of the isomer (B)

D ²⁰ = - * - 72.5 ° + 2.5 ° (c = 0.5 % benzene)

Analy ^ sej. C ₁₇ H ₁₉ Br ₄ NO ₄ MG «620.982

Calculated: C % 32.88 H % 3.08 Έ% 2.25 Br % 51.47

Found: 33.5 3.3 2.2 50.1

UV spectrum

Wendep. j? 18 nm E ^ «248

Max «223 nm e]« 278

Max · 228-229 nm e] £ 272

Turning angle 238 nm e] = 172

Vfendep «, at 295 nm e! J = 7

(Deuterochlor of orm)

Peaks at 4.98-5.16 ppm, characteristic of the hydrogen in position 1 ^{f of} the ethyl side chain.

Peaks at 1.21-1.45 ppm, characteristic of the hydrogens of the methylpairs »

Peaks at 1.5-2 ppm, characteristic for the hydrogens of cyclopropyl and for the methylenes in position in the cyclohexyl.

Massive at 2.38 ppm, characteristic of the hydrogens of the methylenes of cyclohexylo

Peaks at 5.38-5 * 57 and 5.57-5.75 ppm, characteristic of the C0OCII ₂ W hydrogens

129 - "" -

Example 2: 3. 4 * 5,6-Tetrahydro-methyl-phthalimide-f-IR. trans V2.2- · dirnethvl-3-d ' _? 2 ^f , 2 *, 2 '-tetyabromethyl) -c ₁ -propan-1-carboxylate

This compound is obtained by bromination of the (iR, trans) -2,2-di-ethyl-3- (2- ^f ''-dibromovinyl) -cyclopropane-1-carboxylic acid, a geroisclic acid of isomers (A) and (B).

Nuclear magnetic resonance spectrum

Pealcs at 1.30 to 1.40 ppm (hydrogens of the methyls in position 2 of the cyclopropane);

Pjeaks at 1.65-1.74 and 1.97 to 2.37 ppm (hydrogens in positions 1 and 3 of the cyclopropane);

Peaks at 4.30-4.47 and 4.47-4.65 ppm (ethanol in position 1 'of the ethyl);

Peak at 9.63 ppm (hydrogen of carbonyl).

By action of the thionyl chloride on the prepared in stage A (iR _s trans) ' _r 2,2-dimethyl-3- (i', 2 ', 2', 2'-tetrabromethyl) -cyclopropane-1-carboxylic acid, the acid chloride is gewon which is used as such in the following stage.

Infrared spectrum (chloroform) absorption at 1778 cm

£ 1_Σα1.ι2j.6-Te_trahy_drorae thylOhtalimide -_ (i P ^ trans) -2_, 2 dirne th.2l-3 £ i_ ^f j. 2 ^ 2. ^ 2 ^ - · t 2. ί-Ε §ίΐ £ 2 ^ ί ^ -Zi 2ζ £

7.7 g of the acid chloride obtained in the preceding stage are treated according to a procedure identical to that used in the stage C of Example 1.

There are obtained 9.2 g of crude product, which is purified by chromatography on silica (eluent: Athylazetat-benzene 1/9). After crystallization, the crude product is taken up in petroleum ether (40 ° C-70 ⁰ C), spun, dried, and you get 5.4 g of 3,4,5,6-Tetrahydromethylphtalimid- (iR, trans) -2,2-dimethyl -3 '(i', ^f 2, 2 ', 2 ¹ -tetrabrornäthyl) -cyclopropane-1-car "boxylat. Mixture of isomers A and BF = 124 ⁰ C.

/ 5 ° = -1 ° + 1 °. (c = 1 #, Benaol) Anales «! ^c i η & _Λ 9Br ₄ NO ₄ MW = 620.982

Calculated: C # 32.88 H # 3jO8 Br? 6 51.47 N * 2.25 Found: 33.1 3.2 51.1 2.1

W-Sp ectrpm (ethanol)

Max. 224 nm Max. 228 nm turn ρ. 235 nm V / end p. 280 nm

Kernel ona nzs' spectrum (Deuterochloroforiii)

Peaks at 1.25 - 1.30 - 1.31 ppm, - characteristic of the hydrogens of the methylpairs »

Peaks at 1.58 to 2.16 ppm, characteristic of the hydrogens of the cyclopropyl and the methylenes in the / ^ - position in the

= 274 £ = 17 000 ej = 269 ε = 16 700 A = 167 10 400 ε " ^{1 Λ} 1 = 9

• 21 ί129 - μ-

Cyclohexyl.

Peaks at 2.16 to 2.5 ppm, characteristic of the hydrogens of the methylenes in the U. position in the cyclohexyl.

Peaks at 4.24 to 4.41 and 4.43 - 4.61 ppm, characteristic of the hydrogen in position 1 ^{1 of} the A'thylseitenkette.

Peaks at 5.51 and 5.55 ppm, characteristic of the COOCHoN group. ,

Example 3? (S ^ v ^ I cyano - 'P henoxybenzyl CIR trans.) -2,2-dimethyl-3 - C2' ^ '- dichloro-i' .2 ^t -dibromäthyl) -cycloriropan-1-carbox _T ylat

By action of the bromine on the (iR, trans) -2,2-dimethyl-3- (2 '-' - dichlorovinyl ^ -cyclopropane-i-carboxylic acid gives the (1R, trans) -2,2-dimethyl-3 - (2 ^f , 2'dichloro-1 ·, 2'-dibromoethyl) -cyclopropane-1-carboxylic acid, a mixture of isomers (A) and (B).

Nuclear resonance spectrum . .. -

Peaks at 1.17-1.37 ppm (hydrogens of the methyls in position 2 'of the cyclopropane); '''.

Peaks of 1.65-1.73 ppm to 1.93-2.03 ppm (hydrogens in position 1 of the cyclopropane);

Peaks at 4.23-4.45 and at 4.45-4.62 ppm (hydrogens in position 1 ^{1 of} the ethyl in position 3 of the cyclopropane).

By the action of thionyl chloride on previous ^ Stadiumvhergestellte acid yields the chloride of (1R, trans) -2 ₉ 2 ~ dimethyl-3- (2 ', 2 ^f »dichloro-1', 2'-dibromäthyl) · cyclopropane-carboxy !acid"

Infrared spectrum (chloroform) absorption at 1777 cm ^-1 .

Ct stage (S) ⁶ C-cyano ~ 3 ~ phen _{i i} O7y benzyl-OR, trans) -2,2-dime thy 1-3- (2 ^f, 2 'Dichloro-1', 2 ^{-dibromät. hyl) -cyclopropane-1 '

There are 4 $ 45 g of the acid chloride prepared in the previous stage with 2.6 g of (S) &quot; cyano-3-phenoxybenzyΙo

ο alcohol mixed in 100 cm anhydrous benzene.

It is cooled to + 15 ⁰ C, a solution of 5 car pyridine added in 20 cur anhydrous benzene. It will be 3

Stirred at ambient temperature for hours and the beak 's

The organic phase was isolated, washed with water and concentrated to dryness under reduced pressure => After chromatography on silica (eluent: benzene) is obtained 4.9 (S) et-cyano-3 ~ phenoxybenzyl - (1R, trans) -2,2 ~ dimethyl ~ 3 ~ ( ^2f , ^2f -dichloro-1 ', 2'-dibromoethyl-cyclopropane-icarboxylate in the form of a mixture of isomers A and B »

| = 0 ° (benzene) Analysis: C ₂₂ H ₁₉ Cl ₃ N ₂ O -. MG = 576.12

Calculated: C % 45 * 86 H ^ 3 _S 32 Br % 27.74 Cl % 12.31

2,4% 2.43

Found: 46 _? O '-3.4 27.5 1.2.2

21 ί ί O @ T ^ III £ > -Vh-

Circular dichroism;

Max. At 287 nm £ € = + 0,12 Max.-hei 282 nm 4 £ = + 0,11 Max. Hei 265 nm 4 £ = + 0,042 ....

Nuclear magnetic resonance spectrum

Peaks at 1.20-1.26-1.31 ppm, characteristic of the water molecules of the methyl pairs.

Peaks at 4.20-4.35 and at 4.36-4.52 ppm, characteristic of the hydrogen in position 1 'of the iithine chain.

Peaks at 1.68-1.78, at 1.97-2.07, and at 1.97-2.42 ppm, characteristic of the hydrogens of cyclopropyl.

Peak at 6.42 ppm, characteristic of the hydrogen of the COOCHCN group.

Peaks τοη 6.92 to 7.58 ppm, characteristic of the hydrogens of the aromatic nuclei.

4.69 g of the mixture of isomers A and B of (S) ^1- cyano-3-phenoxybenzyl (iE, trans) -2,2-dimethyl-3- (2 ') obtained in stage C are obtained on silica. , 2'-dichloro-1 ·, 2'-dibromoethyl) -cyclopropane-1-carboxylate chromatograph eluted by passing through a hexane-pentane-Xther-acetonitrile-isopropanol mixture (30 12 0.4 1.2 0.03) and you get:

- 1.385 g of isomer A / ^ | g ° = + 35.5 + 2.5 ° (c = $ 0.5 benzene) and

- 0.980 g isomer B IU \ ° = 17.5 + 2 ° (c = 0.8 % benzene)

The (S) -cyano-3-phenoxybenzyl alcohol used in stage C of example 3 is described in the patent application filed by the applicant company on January 31, 1978 under the number 78.02.621 and entitled "Optically Active, substituted benzyl alcohol and process for its preparation "carries. An example of the preparation of this alcohol is given below:

There are 22.5 g of (R, S) o-cyano-phenoxybenzyl alcohol, 9.46 g of lactone of (iR, 3S) -cis-2,2-dimethyl-3- (dihydroxymethyl) -cyclopropane-1 carboxylic acid, 0.150 g of paratoluene sulfonic acid in the form

-2

of monohydrate and heated under a vacuum of 10 mm of mercury at 80 ⁰ C, the reaction mixture for 2 hours under these conditions, the resulting water is distilled off. It is cooled to 20 ⁰ C and gives 30.7 g of crude mixture of (iR, 5S) -6,6-dimethyl-4 (R) - { (S) -cyano- (3 ^f -; phenoxyphenyl) -methoxy} 3-oxabicyclo- (3 1 0) -hexanone (2) and from (iR, 5S) -6,6-dimethyl-4 (R) ^ (R) -cyano- (3'-phenoxyphenyl) -methoxy} 3 -oxa-bicyclo- (3 1 0) -hexanone (2) (containing as impurities mainly the starting products which did not react) (A). ·

χ ^

The mixture obtained in stage A is chromatographed on silica gel eluting with a mixture of benzene and ethyl acetate (95/5) to give 10.9 g of (iR, 5S) -6,6-dimethyl. 4 (R) / (S) -cyano - "(3'-phenoxyphenyl) methoxy / ~ 3-oxa, -bicyclo- (3 1 0) -hexanone (2).

⁰ C U / ^ ⁰ = 71 °

F. = 126 ⁰ C, U / ^ ⁰ = - 71 ° (.c - 1 %, benzene)

~ 25-

In a mixture of 100 cm dioxane and 50 cm ^{-1 of} water are added 10 g (1R, 5S) of 6,6-dimethyl-4 (R) - ((S) -cyano-1'-phenoxyphenyl) -methyl) -3- oxabicyclo- (3 1 0) -hex.anone (2), which was recovered in Stage B above, further 1 g of iv-hydohydrate of paratoluene-sulfonic acid, the reaction mixture is refluxed, and left in this state for 23 hours it is concentrated by distillation under reduced pressure until half the initial volume is obtained, ethyl ether is added, stirred, the organic phase is separated by decantation, washed with water, dried, concentrated to dryness by distillation under reduced pressure, the residue (9.5 g) is chromatographed on silica gel eluting with a mixture of benzene and ethyl acetate (9/1) to give 6.1 g of (S) c> i-cyano-3-phenoxybenzyl alcohol (o0p ° = - 16.5 ° + 1.5 ° (c = 0.8 # benzene)

Nuclear resonance spectrum (deuterochloroform)

Peak at 3.25 ppm, characteristic of the hydrogen, alcohol function.

Peak at 5.42 ppm, characteristic of. the hydrogen that. is bound to the same carbon as the nitrile group.

Example 4 : (S) ol-Cyano-3-Ohenoxybenzyl-CiR _? cis) -2,2-dimethyl- 3-C2 * ,, 2'-dibromo-i ', 2'- dichloroethyl) -cyclopr QP an-j-carboxyl at

2 ± s> 2 ₂ 2 _z dimeth2l ₌ 3 _z (2 ^ _A 2j_-dibromo _:: 1_J_ _a 2 ^ _:: dichloro _::

In 30 cm ⁵ Kohlenstofftetrachloricl · allowed at - 15 ⁰ C bubbled 11.8 g of chlorine are then slowly added at - 10 ⁰ C. 24 g of (IR, cis) -2,2-dimethyl-3- (2 '^' dibromovinyl ^ cyclopropanecarboxalic acid solution in 37 cm methylene chloride, a

Stirred for hour and 30 minutes "ü at ⁰ C and 2 hours at 25 ⁰ C j · under reduced pressure concentrated, purified by crystallization from carbon tetrachloride and 7.4 g (IR, cis) ~ 2,2-dimethyl ~ 3- ( 2, ^t 2 ^f ~ dibromo-1 •, 2 * -diohloräthyl) -oyclopropan-1-carboxylic acid obtained. ·

F. = 134 ⁰ C (mixture of isomers (A) and (B). Kernre sonansspektrum

Peaks at 1.32-1.44 and at 1.28-1.48 ppm (hydrogens of the methyl in position 2 of the cyclopropane).

Peaks at 5.08 to 5.45 and from 4.67 to 5 ₅ 0 ppm (hydrogen in position 1 of the ^f Äthylkette in position 3 of the cyclopropane).

Peak at 10.1 ppm (hydrogen of the carboxyl). ,

1'aB ^ -dichloräth ^ l ^ c ^ clojropan - ^ - ^ L acid carbox £

The action of the thionyl chloride in the presence of pyridine on the acid obtained in the preceding stage A, the chloride of (iR, cis) ~ 2,2-dimethyl-3- (2 ^!, 2'-dibromo-1 *, 2'- dichloroethyl) -cyclopropane-1-carboxylic acid ₅ which is used as it is in the following stage.

3 ^

There are mixed 3.8 g of the acid chloride obtained in the preceding stage · 2.5 g (s) o (-cyano ^ -rphenoxybsnzylalkohol in 100 cm of anhydrous benzene. It is cooled to + 15 ⁰ C and a solution of 4 cm pyridine in 20 cm of anhydrous benzene is stirred for 4 hours at ambient temperature, and the reaction medium is poured onto 100 cm hydrochloric acid 2N

- Inorganic phase is isolated, washed with water, dried and concentrated under reduced pressure to dryness. Wake up chromatography on silica. Eluent: petroleum ether (40 ° - 70 ⁰ C) isopropyl ether (100 20) / one obtains the (S) ^ Cyano-3-phenoxybenzyl (IR, cis) -2,2 - dimethyl-3 - (2 ^f, 2 ^l -dibromo-1 '^' - dichloroethyl-cyclopropane-i-carboxylate in the form of 1.8 g of isomer A ₁ rf = 0.30 and 1. 4 g of isomer B, rf = 0.25.

Physical value of the isomer s A / o £ / J3 ° = -21 ° + 1 ° (c = 1 0, benzene) Circular dichroism

Max. "At 300 nm Λ <f = - 0.003

Max. At 288 nm Ä C = + 0.29

Max. At 264 nm 4 £ = + 0.11

Max. At 232 nm Af = - 1 »8

Nuclear resonance spectrum (deuterochloroform)

Peaks at 1.28-1.37 ppm, characteristic of the yers of the methyl pairs.

Peaks at 5.05 to 5.10 - 5.18 to 5.23 ppm, characteristic for the 'hydrogen in position 1 of ¹ Äthylseitenkette.

Peaks at 1.83-2.10 ppm, characteristic of the hydrogens of cyclopropyl.

Peaks at 6.38 ppm characteristic of the COOCHCN group hydrogen. , ,

Peaks at 6.92 to 7.55 ppm, characteristic of the Y seeds of the aromatic nuclei.

Physical tests of the isomer B

/ ca / ^ ⁰ = + 80 ° + 2.5 ° (c = 1 ^, benzene)

Circular dichroism.

Max. At 288 nm A € = + o, 22 turning p. at 263 nra AC = + 0.62 max · at 220 nm AE = + 3.7

Nuclear resonance spectrum (deuterochloroform)

Peaks at 1.23-1.38 ppm, characteristic of the hydrogens of the methyl pairs ·

Peaks at 4.6 to 4.95 ppm ₅ characteristic of the hydrogen in position 1 'of the Äthylseitenkette.

Peaks at 1.75 to 2.16 ppm, characteristic of the hydrogens of cyclopropyl «

Peak at 6.38 ppm, characteristic of the hydrogen of the COOCHCN group.

Peaks at 6.88 to 7.57 ppm, characteristic of hydrogens of aromatic nuclei »

Example 5 ^ _ (S) o _(f -G ya'no-3,, r "Phenox, ybenz, yl- _(iR? Cis) -2, 2 ~ dim eth, yl

feft P hl ο r th, y Ι ^ -, ο XP- Ip P ro · ρ an-1 - c ar b ο xy 1 at

jt2 ₌ D ^

In 30 cm of carbon tetrachloride, the chlorine is bubbled to saturation (11.8 g of chlorine are dissolved), and a solution of 16.7 g (iR, cis) -2 5 2-dimethyl-3- is added in about 30 minutes. (2 ♦, 2 ^s -dichloro-ylinyl) -cyclopropane-1-carboxylic acid

in 40 cm of methylene chloride at a temperature below 0 ⁰ C, stirred for 24 hours at 0 ⁰ C, the temperature of the reaction mixture brought to + 25 ⁰ C, stirred at this temperature for 3 hours, expelled the excess chlorine by passing nitrogen, concentrated to dryness by distillation under reduced pressure, the residue is purified by chromatography on silica gel by eluting with a mixture of cyclohexane and ethyl acetate (8/2), crystallized in petroleum ether (bp 35-75 ⁰ C), and we obtain 3 , 1-4 g (iR, cis) -2,2-dimethyl-3 (i ^f , 2 », 2", 2'-tetrachloroethyl) -cyclopropane-1-carboxylic acid. F. = 144 ^° C.

Analysis: _Cn H. _n Cl, 0 _? (279.98)

calculated:

C % 34.3 H 96 3.6 Cl # 50.6

Found ^:! 34.4 3.7 50.3 - ·

j

Kernresonan zspektr um (deuterochloroform)

Peaks at 1.26-1.42 ppm, and at 1.30-1.42 ppm, characteristic of the hydrogens of the methyl pairs;

Peaks at 4.67-5.17 ppm and at 5.08 to 5.43 ppm, character. hydrogen for the position 1 · the substituted ethyl side chain;

Peaks of 1.67 to 2.0 ppm, characteristic of the hydrogens of cyclopropyl;

Peak at 10.2 ppm, characteristic of the hydroxide of the carboxyl, ¹

In a mixture of 60 cnr petroleum ether (bp. 35-70 ⁰ C) and 8.7 cm- ⁵ thionyl chloride are 6.75 g (iR, cis) -2,2-dimethyl-3 ~ (i ·, · 2 ' , 2 ', 2 ^l -tetrachloroethyl) -cyclopropane-1-carboxyic acid.

The reaction mixture is refluxed, left to stand for 4 hours and 30 minutes, concentrated to dryness by distillation under reduced pressure, benzene is added, evaporated to dryness to give the chloride of (iR, cis) -2 2-Dimethyl-3- (i ^f , 2 ", 2", 2'-tetrachloroethyl) -cyclopropane-1-carboxy-crude acid which is used as it is for the following stage.

That is, 3.19 g of the acid chloride prepared in the previous stage is mixed with 2.6 g of (S) -i-cya, no-3-phenoxybenzyl alcohol in 30 cm of anhydrous benzene. 3s is cooled in an ice bath and slowly 3 cm of pyridine are added. It is stirred for 24 hours at ambient temperature, then the reaction medium is poured onto cold, dilute hydrochloric acid. It is extracted with benzene, the organic phases are isolated, washed with a sodium bicarbonate solution, rinsed with water, dried over sodium sulfate, filtered and concentrated under reduced pressure. It is purified by chromatography on silica (eluent: benzene cyclohexane 7 3) to give the (S) - cyano-3-phenoxybenzyl (iR, cis) -2,2 dime--. thy1-3 ^O'j-2 ', 2' ₅ 2 ^l -tetrachloräthyl) -cyclopropane-1-carboxylate in the form of 2.258 g of isomer (A) and 1.48 g of a mixture of isomers A and B.

Physical analysis of the isomer (A)

/ vl / 2 ° = + 35.5 ° + 2 ° (c = 0.6 % benzene)

Analysis: C ₂₂ H ₁₉ Cl ₄ NO ₃ = 487.213

Calculated: C # 54.23 H # 3.93 N ⁰ Io 2.87 Cl % 29.1 Found: 54.4 3.8. 2.8. 28.5

J - 3-f

Nuclear Magnetic Resonance (deuterochloroform)

Peaks at 1.28-1.37 ppm, characteristic of the hydrogens of the methyl pairs.

Peaks at 1.75 to 2.08 ppm, characteristic of the hydrogens of cyclopropyl.

Peaks at 5.07 to 5.25 ppm, characteristic of the hydrogen in position 1 'of the iithyl side chain.

Peak at 6.35 ppm, characteristic of the hydrogens of the COOCHCN group. , '

Peaks at 6.92 to 7.58 ppm, characteristic of the hydrogens of the aromatic nuclei.

Physics alische analysis of the mixture of isomers A and B / oil / 2 ° = -33.5 ° + 2.5 ° (c = 0.4 # benzene) Analysis: C ₂₂ H ₁₉ Cl ₄ NO = 487.213

Calculated: C ° h 54.23 H # 3.93 N <f> 2.87 Cl # 29.1 Found: 54.5 3.9 2.8 28.8

Ke r nr es 0 nan.zs ρ e k tr (deuterochloroform)

Peaks at 1.2-1, 35 ppm, characteristic of the hydrogens of the methyl pairs of the isomer R.

Peaks at 1.27-1.35 ppm, characteristic of the hydrogens of the methyl pairs of the isomer S.

Peaks at 1.75-2.08 ppm, characteristic of the hydrogens of cyclopropyl.

• S i & »« ^

Peaks at 4.77 to 4.94 ppm, characteristic of the hydrogen in position 1 ^{of the iithyl side chain.

Peaks at 5.08 to 5.26 ppm, characteristic of the hydrogen in position 1 'of the Äthylseitenkette.

Peaks at 6.35 and 6.37 ppm, characteristic of the hydrogen of the COOCHCN group. '

Peaks at 7.93 to 7.58 ppm, characteristic of the aromatic nuclei.

Example, 6: (R) cä- cyano-5-T) henoy.yben g ₁ vl - CiR _? tran 5) - 2,2-ditneth, vl 7-3- (2 *, 2'-dichloro-1 ' _- 2'-dibromoethyl) oxyol) ro ~ ~ ~ ca_rboory_lat _-

By proceeding as in Stage C of Example 3, starting from 2 g of (1R, trans) -2'-2,2-dimethyl-3- (2 ', 2'-dichloro-1, obtained in Stage B' of Example 3, ·, 2'-dibromoethyl) -cyclopropane-1-carboxylic acid chloride and 1.1 g of (R) c * -cyano-3-phenoxybenzyl alcohol 1.4 g of (R) ö-cyano-3-phenoxybenzyl ( irt, trans) -2 ", 2-dimethyl-3- (2- ^t , 2'-dichloro-1 ', 2'-dibromoethyl) -cyclopropane-1-carboxylate in the form of a mixture of isomers A and B.

° - 28 ° + 2 ° (C = 0,7? O, benzene)

^C 22 ^H 19 ^Br 2 ^C1 2 ^N0 3 ^{MW = 576 5122}

Calculated: C Io 45.87 H % 3.32 N ° h 2.43 Cl # 12.31 Br ^c fo 27.74 Found: 46.3 3.3 2.4 12.4 27.4

Nuclear resonance spectrum (deuterochloroform)

peaks at 1.31-1.35 ppm, characteristic of the hydrogens of the methyl pairs.

Peaks at 1.66-2.42 ppm, characteristic of the hydrogens of cyclopropyl.

1 1 ί

Peaks at 4 ₅ .23-4.42 ppm and at 4.42-4.58 ppm, characteristic of the hydrogen in position 1 of the ethyl side chain.

Peak at 6.47 ppm, characteristic of the hydrogen of the COOCHCN group.

Peaks at 6.92 to 7.58 ppm, characteristic of the hydrogens of the aromatic nuclei.

Zirkulardic. hrō i sinus. (Dioxane)

Maximum at 219 nm £ = - 5.4 maximum at 280 nm t = - 0.28 inflection point at 285 "nm C = - 0.27

The mixture of isomers A and B prepared above is chromatographed on silica by elution with a hexane-pentane-ether mixture (7, 2.8, 0.17) and the isomers A and B are obtained separately.

Iso mer A

Nuclear resonance spectrum (deuterochloroform)

Peaks at 1.32-1.37 ppm, characteristic of the hydrogens of the methyl pairs,

Peaks at 1.66-1.76 ppm, at 2.08-2.17 ppm and at 2.26-2.35 ppm, characteristic of the hydrogens of the cyclopropane.

Peaks at 4.2-4.37 ppm: characteristic of the hydrogen in position 1 'of the ethyl side chain.

Peak at 6.42 ppm, characteristic of the hydrogen of the COOCHCN group.

Peaks at 6.92 to 7.58 ppm, characteristic of the hydrogens of the aromatic nuclei »

Isomer B. ·

Nuclear resonance spectrum (deuterochloroform)

Peaks hei 4.37-4.53 ppm, characteristic of the hydrogen in position 1 'of Äthylseitenkette »·.

The (R) c <-cyano-3-phenoxybenzyl alcohol used at the beginning of Example 6 was prepared as follows:

Chromatography, begun at stage B of the preparation described in Example 3, is continued and 7.32 g of the expected product are obtained. / Ei / _D = -20 + 2.5 ° (c = 0.9 #, benzene).

The procedure is analogous to that used in stage C of the preparation described in example 3 starting from 12.8 g of the product described in the previous stage, and the same chromatographic purification gives -5 g of the expected product M / I ° = '+ 11 ° + 2 ° (Conc * = 0.5. #, Benzene).

Example 7: Untersucl ^ IIK, the insecticides Vvirkunff: there d _t C vano-3-phenpyybengyl _{ri (i} 1 R _{i tra.ns?).} "2 ₁ 2-di met hy_l _r ^ 3 ..- _{C2.? '?} 2 ^t - _i diohlpr _1'? _ 2 '"diBr ^ ma, thjl ^ _-_ c, y.clojpropjin-1 -carbοxylats Q / Getting Connected _t, A),...?

of isomer A of (S) ^ -C ^ γanor ^ .- phenoyybenz.yl. ~ C _ι j _ι R _ιί , .c _ι is) - _ι 2 _? 2-dimethy 1-3 ^ ( 2 ' , 2'- dibromo-i ! , 2'-dichloroethyl ) -cyclopropane-ica rbox ylats (Compound B ) .... and "isomer s B d he ,, same connection ^ (Jerbindun

1) ITnteyspnliiirig; .. d.or. töfli.i p.hfin T / i rlainp d> p.-r Verbj nflnnn; en., A .., BC ₁ b ui the St-ubenflie ^ e

The experimental insects are 4 day old female houseflies.

1 ί ί

1 , -η 1 Acetone solution is locally applied to the back of the insects using the Arnold micromanipulator. "50 animals are used for treatment. Twenty-four hours after treatment, mortality control is performed.

The experiments are carried out without synergetic enhancer or with the addition of piperonyl butoxide (10 parts synergetic enhancer to 1 part of the compound to be tested).

The experimental results summarized in the following table are given in DL 50 or the dose (in nanograms) necessary to achieve 5Q #. to kill the insects:

A without synerg. Reinforced. DL 50 in ng / insect connection A with synerg. Enhancement. 5.75 connection 3, without synerg , Reinforced. 0.91 connection B with synerg. Enhancement. 1.67 connection C ₅ without synerg , amplifier 0.88. connection c, with synerg. amplifier 2,95. connection 0.82

Conclusion : The compounds A, B and C have a strong insecticidal activity against houseflies.

2) Investigation of the linock-down effect of compounds A _{i? I} B and C in the housefly

The experimental animals are 4 day old female houseflies. There is a direct pollination in the IiSARNS and IvIARCH's chamber, using as solvent a mixture of equal parts by volume of acetone and kerosene (amount of solution 2 × 0.2 cm used). There are about 50 insects taken per treatment. The controls are performed every minute up to 10 minutes, then up to 15 minutes, and the IiT 50 (knock-down time) is determined by the usual methods.

The obtained Yersuch results are summarized in the following table:

KT ^ ₀ in minutes Connection A 6 _Λ 00 · Compound B 6 ^ 12 Compound C 6.02

Conclusion; The extensions A, B and C have an interesting Knock ™ do v / n effect on houseflies.

3) monitoring the investi _ti In sektiziden Wirkun g of e Bonds in the form of a total set Incense Ver g A on houseflies' fly

Neutral carriers of incense spirals are impregnated with active ingredient dissolved in acetone. In a closed glass cylinder of 13.50 dm 20 houseflies are brought in, and it leads for 2 minutes a smoke spiral: a, which burns at one end. After each minute, the knock-down control is carried out and the experiment is stopped after 5 minutes, after all insects have sunk. For each dose, three series of experiments are carried out.

Cans in weight active ingredient on spiral weight 0 ^ 4 # KT ^ 50 KT ₅₀ ^ J- ₅₀ Κ "Φ ^χ 50 Average Connection A 0.2 # _ §JL§ _ 6 _Λ 6 7 ^ 75 _ "_ "11.8 10.2 9.2 10,22.

S chlu ßfolgerung;., Are used In Käucherform, the compound A shows a good insecticidal action.

4) Investigation of the insecticidal activity of compounds k_, B and C on the caterpillars of Spodoptera littoralis

In. In the experiments, the active ingredient is administered locally. 1 / U 1 of an acetone solution of the product to be tested is applied to the back thorax of each animal. For each dose applied, 15 caterpillars of Spodoptera littoralis are taken in the fourth instar. After treatment, the test animals are placed on an artificial nutrient medium (Poitoitsches medium). The efficacy control (mortality rate considering an untreated control lot) is performed 24 hours, and then 48 hours after the treatment, and the lethal dose 50 (DL ^ ₀ ) in nanograms per caterpillar is determined.

The test results are summarized in the following table:

DL ₅₀ in ng / per caterpillar Connection A 0 ^ 22- Compound B Compound C 0.65

Conclusion: The compounds A, B and C have a strong insecticidal activity against the caterpillars of Spodoptera littoralis.

5) Examination of the insecticidal activity on the larvae of Epilochna varivestries

In the experiments, the compounds are applied locally analogous to the larvae of Spodoptera. In the second instar larvae larvae are used, and after the treatment the larvae are fed with bean plants. The mortality control is performed 72 hours after the treatment. The test results are summarized in the following table:

1 1 2 9 " ^3a ~

DL ^ Q in ng / per experimental animal Connection A 0 ^ 1 8. Compound B 4.26 Compound C 6.95

'Conclusion;. The compounds A, B and C have a strong insecticidal activity against the larvae of Epilachna varivestries. Compound A is particularly effective in this field.

6) Examination of insecticides, effect of compound A on larvae of Aedes Aegypti

The 370 ml glass jar is used, into which 200 ml of water are introduced. The water in each tube is treated with 1 ml of acetone solution containing the product to be tested. Each vessel is infected with 10 larvae of Aedes Aegypti (last larval stage). The larvae are transferred from their whereabouts into 49 ml of water. Efficacy controls are performed 24 hours to 48 hours * after the infection. During the test, the vessels are stored at 25 ^° C. in a drying oven.

The results obtained here are summarized in the following table (CL = lethal concentration) ί

in ppm

^r Getting Connected A

3.24 χ 10 "

Finally, he successfully clothes: The connection A'besitz.t a strong insecticidal action against La; RVen Aedes Aegypti from.

7) Investigation of the insecticidal activity of Compound A against Blattella germanica

This test is carried out by topical application. The adult male Blattella germanica specimens selected according to the length criterion receive two microliters of an acetone solution of the product to be tested between the second and third leg pairs. After the treatment you keep the "test insects" at 20 ⁰ C in the semi-darkness and feed them. Bs are administered doses of 10-7.5-5-3.75-2.5 ng / insect. The controls were performed twenty-four hours, forty-eight hours and six days after treatment. The experimental results expressed in DL ₅₀ per nanogram per insect are summarized in the following table:

in ng per insect

Connection A

1.06

Conclusion : Compound A has a strong insecticidal activity against Blattella germanica.

8) Supervision ; the insecticidal activity of Compound A against D.ysdercus f asciatus.

One microliter of an acetone solution of the product to be tested is applied to the abdominal thorax of each test animal. It uses doses of 3.75-2.5-1.25-1-0.625 nanograms per insect. Efficacy controls are performed 24 hours, 48 hours and 5 days after treatment.

The results obtained are shown in the following table:

DL ₅ Q in nanograms per insect Connection A 1.06

Conclusion: ' Compound A has a strong insecticidal activity against Dysdercus fasciatus.

9) investigation of the insecticidal activity of the compound ; A opposite Sito'philus Granarius and Tribolium Castaneum

The test is carried out by direct pollination of the infested wheat. Bs are atomized 5 ml of an acetone solution of the product to be tested and 0.1 cm of water onto 100 g of wheat, which is in a 1 liter flask of a (moving) rotary evaporator. There is an artificial attack by 50 animals made (Sitophilus or Tribolium). For each dose, the mortality rate and then the lethal concentrations (CL) in ppm are determined after 7 days, taking into account a non-treated reference lot and by averaging to 100 specimens.

Cans in PPm SITOPHILUS GRANARIUS CL ₅₀ in ppm TRIBOLIUM CASTANEUM CL ₅₀ in ppm -J Λ _. ⁰ Jo mortality 0.80 ° h mortality 0.19 90 ^ 0 100 66 _Λ 70 96 ^ 9 0 ^ 5 35 _λ3 89 _Λ 5 0.25 18 _Λ 2 85.2,3 2.0. 62.0

Conclusion:. Compound A has a good insecticidal activity against Sitophilus granarius and Tribolium castaneum.

Beispiel_ J3 t Unt e rs \ xchung of akari cides n effect he ..d Ve rbindung A "on Te.trany.ch.us" .Urticae.

Bean leaves are used which are infested by 10 female specimens of Tetranychus urticae per leaf and are covered in glue at their periphery; one lets the females while. lay eggs for four and twenty hours, then they are taken off,

and the leaves covered with eggs are divided into two groups. '

a) a first group is treated with the compound to be tested: 0.5 cm of an aqueous solution is sputtered onto each leaf, using concentrations τοη 50 and 25 g of compound to be tested per hectare.

b) A second group of leaves is left untreated and serves as a reference lot.

The census of live adult animals, live eggs and live larvae takes place nine days after the start of treatment. The results, which are expressed in mortality rates of adult animals, eggs and larvae, are summarized in the following table (taking into account the untreated comparative lot):

^c h mortality of adult. animals ^c / o mortality of eggs not hatched # Mortality of the larvae Connection A 52.3 , .54,3 47.6 '

Conclusion: Compound A has a favorable acaricidal activity against Tetranychus urticae.

Example 9: Insecticidal Composition ;: An emulsifiable concentrate is prepared by intimate dissolution of:

) CN4-cyano-3-phenoxybenzyl 1R, trans-2,2-dimethyl-3- (2 ^l, 2'-dichloro-1 ', 2'-dibromäthyl) -cyclopropane-1-carboxylate:

-Piperonyl butoxide .0.5 g

-Topanol A 0.1 g

-Xylene '. 99.385 g

manufactured.

Example 10; Insecticidal composition.: Sg _ri y / ird bares Konzen occurred in the following manner, manufactured !.

It becomes a homogeneous mixture of:

(S) ^ '~ Cyano-3-phenoxy'benzyl-1R, trans-2,2-dimethyl-3- (2 ^t, 2'-dichloro-1', 2 -di ^f "Dromäthyl) -cyclopropane-1 cart) oxylate:

··· 1.5 g

- Tween 80 20 g

- Topanol A 0.1 g

Xylene 78.4 g

manufactured.

Example 11; Acari zide composition ;

There was an emulsifiable concentrate prepared containing 20 # (S) o. (^ -Cyano--phenoxybenzyl IRjtrans ^^ - dimethyl-O- ^ ^1, 2'-dichloro-1 ', 2'-dibromäthyl) -cyclopropan- 1-carboxylate, 6.5% by weight of Atlox 485.1 (oxyethylenated glyceride combined with a sulphonate, acid number 1.5), 3.3% by weight of Atlox 4855 (oxyethylenated triglyceride, as with a sulphonate , Acid number 3, combined, and containing 70.2 wt. ^ Xylene.

Example 12; nematicidal composition;

An emulsifiable concentrate for soil treatment was prepared containing 45% by weight of (S) oi-cyano-3-phenoxy-1-benzyl-1R, trans-2,2-dimethyl-3- (2 ', 2'-dichloro-1', 2 '-dibromoethyl) -cyclopropane-1-carboxylate, 6.4% by weight of Atlox 4851 (oxyethylenated triglyceride combined with a sulfonate, acid number 1.5), 3.2% of Atlox 4855 and 45.4% of xylene,

pe ispiel 13: Ixod izide Composition etzun g :;

A solution with the following composition was prepared:

- (S) c <~ cyano-3-phenoxybenzyl-1R, trans-2,2-dimethyl-3 »(2 ^l , 2'-

211129 - ^ -

dichloro-1 ', 2 ^l -di'bromoethyl) -cyciopropane-1-car'boxylate 0.5 g

- polysorbate SO 10 g

- Triton X 100 25g

- o / tocopherola did 1 g

- Ethanol sufficient amount for .100 ml.

This solution is used after 50-fold dilution of its volume in water for external use.

Example 14: Ixodicidal Composition;

It is made a sprayable solute, the

- (S) -ol-cyano-3-phenoxybenzyl-1R, trans ~ 2,2-dimethyl-3- ~ (2 ', 2 · - dichloro-1', 1'-dibromoethylcyclopropane-1-carboxylate 2 g

- Piperonyl butoxide '.6,65 g

O-tocopherol acetate 0.33 g _t

- contains oily.

- Oily binder sufficient amount for 100 m

* This oily binder consists of 29 g of benzyl benzoate and peanut oil in sufficient quantity to complete a total volume of 100 cm.

Example 15: Composite food

A feed containing corn, dehydrated alfalfa, wheat straw, molasses palm kernel cake, urea, a mineral vitaminized condiment is used as a balanced basic feed.

This feed contains at least 11 # raw proteins (of which 2.8 ^cf from urea), '2.5 percent fats and a maximum of 15 percent cellulose, 6 percent mineral and 13 percent moisture'. The feed used is 82 feed units per 100 kilos and contains 100 kilos: 910 000 IU of vitamin A, 91 000 IU of vitamin D ₃ - 156 mg of vitamin E and 150 mg of vitamin C.

This feed will be .0.04 kg. (S) oC-Cyano-O-phenoxybenzyl-1R, trans-2,2-dimethyl-3 "(2 ^f ₎ 2'-dichloro-1 ·, 2'-dibromoethyl) -cyclopropane-1-carboxylate.

Claims (2)

Claim for invention. .. - 1-carboxylate, - 3,4,5,6-Tetrahydromethylphtalimid- (1R, cis) -2,2-dimethyl-3-0 ', 2 ^ ^{1 1,} 2'-tetrabromäthyl) -cyclopropane-1-carboxylate, - (S) 06-Cyano-3-phenoxybenzyl - ( '1R, cis) -2,2-dimethyl-3- (1', 2 ', 2 ^' - ^{tetrachloräthyD-cyclopropane-icarboxylat:} - (R) c6-Cyano-3-phenoxybenzyl- (1R, trans) -2,2-dimethyl-3- (2 ', 2'-dichloro-11,2'-dibromoethyl) -cyclopropane-1-carboxylate, or mixtures of stereoisomers with ice and trans structure in any ratios. Compounds which combine under the general formula I ¹ -ffc- can be: in the X have the meaning that -, _?? xo correspond to the substituents of the above-mentioned compounds, together with suitable additives. 1. Insecticides, acaricides and nematicides according to. ··. Patent AhS ^ ASI4 marked in that it contains one or more compounds in the form of isomer A, isomer B or in the form of a mixture of these isomers, with the following designations: - (S) (X - Cyano-3-phenoxybenzyl- (1R, trans) -2,2-dimethyl-3- (2 ', 2'-dichloro-1', 2'-dibromoethyl) -cyclopropan-1 carboxylate, - (S) c6-Cyano-3-phenoxybenzyl- (1R, cis) -2,2-dimethyl-3- (2 ', 2'-dibromo-1', 2 ^l -dichloroethyl) -cyclopropane-1-carboxylate, 3,4,5-β-tetrahydro-methyl-phthalimide (1R, trans) -2,2-dimethyl-3- (1 ', 2', 2 ', 2'-tetrabromethyid-cydopropane) 2. Composition according to item 1, characterized in that the active ingredient "S" £-cyano-3-phenoxybenzyl-1R, trans-2,2-dimethyl-3- (2 ', 2'-dichloro-1', 2'-dibromoethyld-cyclopropane-T-carboxylate in the form of isomer A, isomer B or in the form of a mixture of these A and B. '-a! ARi 19 ä ü' * 8 4 ti 4 6 3 '