DE3032617A1 - CYCLOPROPANIC CARBONIC ACID ESTER, METHOD FOR THE PRODUCTION THEREOF AND THE PESTICIDAL COMPOSITIONS CONTAINING IT - Google Patents

Description

ROUSSEL-UCLAF, Paris / France

ei ss ss zs s; ss ssssssfss rsrsÄSsrsssrssss — rsssss - ssssss - ss - c:

Cyclopropanecarboxylic acid esters, processes for their preparation and those containing them pestisid compositions

description

The invention relates to cyclopropanecarboxylic acid esters and their production process and the pesticidal compositions containing them.

From DE-OS 28 10 881 (RS) -a-cyano-6-phenoxy-2-pyridylmethyl-dl-cis-trans-2,2-dimethyl-3- (2,2-dihalovinyl) -cyclopropane- l-carboxylate, endowed with insecticidal properties are known.

The invention relates to the compounds of the general formula I:

(D

wherein X ^ and X ~, which can be the same or different, a Fluorine, chlorine or bromine atom mean, the acidic linkage component lR-cis or lR-trans structure and the alcoholic one Linking component (R), (S) or (RS) configurations can have.

13001S / 0765

The invention relates in particular to compounds of the formula I, which are described below in the experimental part, compounds of the formula I in which X. and Xp are identical and mean a fluorine, chlorine or bromine atom.

The compounds of formula I are pesticidal with, in particular Insecticidal and acaricidal properties, e.g. through experiments on the house fly, the cockroach, the Spodoptera larva, the Epilachna larva, on Aphis fabae or on Tetranychus urticae can be illustrated.

Such experiments are described below in the experimental section described.

The compounds according to the invention are also acaricidal Properties with regard to parasitic mites of warm-blooded animals, particularly with regard to ixodids and sarcoptides.

The activity of the compounds of the invention is unexpected Characteristics.

The results of tests in the experimental part show that for a given acidic linkage component the esters of (R) -alcohol and (S) -alcohol are essentially one show equal activity, which is in contrast to the results obtained for the majority of analogous known molecules such as, in particular, those of the corresponding α-cyano-3-phenoxybenzyl alcohol esters.

They also have an alcoholic linking component certain configuration in certain tests the invention Esters of the IR-cis series and those of the IR-trans series similar activities, and on other tests, the esters of the IR-trans series show activities similar to those of the IR-cis series are superior. These results, which are confirmed in the experimental section below, are in contrast to "u the results, which for the majority of known analogous molecules

130015/0765

BATH

küle received v / earth.

The invention also relates to a process for the preparation of the compounds of general formula I, which thereby is characterized in that in an aqueous medium 6-phenoxy-2-picolinaldehyde with a CN ~ -ion-forming compound and with an IR-cis- or IR-trans-2,2-dimethyl-3- (2,2-dihalo-. vinylJ-cyclopropane-1-carboxylic acid, in which Halo is a fluorine, Means chlorine or bromine atom, or reacts with a functional derivative of this acid to form a (RS) -a ~ cyano-6-pher.oxy-2-pyridylmebhyl-2,2-dimerhyl-3- (2,2-dihalovinyl} -cyclopropane-1-carboxylate, whose acidic linking component has the same structure as that of the starting acid. obtain, then, if desired, with the aid of a physical method, the two diastereomers of the ester of the alcohol with (RS) configuration separates to a (R) -a-cyano-6-phenoxy-2-pyridylmethyl-2,2-dimethy1-3- (2,2-dihalovinyl) -cyclopropane-1-carboxylate and an (S) -a-cyano-6-phenoxy-2-pyridylmethyl-2,2-dimethyl-3- (2,2-dihalovinyl) -cyclopropane-1-carboxylate to obtain whose acidic linking component has the same structure as that of the starting acid.

According to a preferred embodiment of the invention Process is the implementation of the aldehyde of the CN ~ ions forming Compound and the acid or its functional derivative with the aid of what is known as phase transfer catalysis Method in an aqueous medium in the presence of + - a basic agent and a water-immiscible solvent carried out.

In the method according to the invention, the functional derivative can of the acid, in particular, the chloride or an anhydride. The basic agent used is then preferred the tetradecyltrimethylammonium bromide, and not that with water The miscible solvent is toluene.

130015/0766

In the inventive process the means for BiIdU ₁ Kj of CN ~ ions preferably an alkali metal cyanide such as sodium or potassium cyanide.

It can also be used advantageously as a cyanidizing agent Tetraethylammonium cyanide, 1-methyl-l-ethylethanonitrile and Use cuprocyanide.

In the method according to the invention, the separation of the two Diastereomers of a (RS) -a-cyano-6-phenoxy-2-pyridylmethyl-2.2-dimethyl-3- (2,2-dihalovinyl) -cyclopropane-carboxylate be effected by chromatography.

The separation of one of the two diastereomers of an (RS) -Ot-cyano-6-phenoxy-2-pyridylmethyl-2,2-dimethyl-3- (2,2-dihalovinyl ) -cyclopropane-1-carboxylate can also be brought about by crystallization.

The invention particularly relates to a method as above defined, which is characterized in that the ester of the racemic alcohol obtained is either the (RS) -a-Cyrr.o-6-phenoxy-2-pyridylmethyl-IR-trans-2,2-dimethyl-3- (2.2 -dichlorovinyl J-cyclopropane-1-carboxylate, the (RS) -a-cyano-6-pheno: <y-2-pyridylmethyl-lR-trans-2,2-dimethyl-3- (2,2-dibromovinyl) -cyclopropane- 1-carboxylate or the (RS) '- a -cyano-6-phenoxy-2-pyr'idylmethyl-IR-trans-2,2-dimethyl-3- (2,2-difluorovinyl) -cyclopropane-1-carboxylate and that the dias.tereomer isolated by crystallization is the (R) -a-cyano-6-phenoxy-2-pyridylmethyl-lR-trans-2,2-dimethyl-3- (2,2-dichlorovinylJ-cyclopropane-l- carboxlyat, the (R) -cc-cyano-6-phenoxy-2-pyridylmethyl-IR-tranG ~ 2,2-dimethyl-3- (2,2-dibromovinyl) -cyclopropsn-1-carhoxylate BSW. the (R) -a-cyano-6-phenoxy-2-pyridylmethyl-IR-trans-2,2-dimethyl-3- (2,2-difluorovinyl) -cyclopropane-1-carboxylate is.

The invention further relates to pesticidal and especially insecticidal and acaricidal compositions, characterized the o ^e ~ are features that they defined above as active ingredient at least one of the compounds of general formula I x ^ / ie

130015/0765

contain, as well as acaricidal compositions for veterinary medicine Use which contain at least one of the compounds of general formula I as active ingredient.

The compositions of the invention can be in the form of Powders, granules, suspensions, emulsions, solutions, solutions for aerosols, incense tapes, baits or other preparations, which are used in classic form for the application of this type of compounds are available.

In addition to the active ingredient, these compositions can generally be a carrier and / or a nonionic surfactant Agent which also ensures a uniform dispersion of the substances forming the mixture contain. The carrier used can be a liquid such as water, alcohol, hydrocarbons or other organic solvents, a mineral oil, an animal or vegetable oil or a powder such as talc, clays, silicates and diatomaceous earth.

In order to increase the insecticidal activity of the compounds according to the invention, classic synergists, as used in similar cases, such as 1- (2 _S 5, S-trioxadodecyl) -2-propyl-4, 5-methylene ioxy benzene ( or piperonyi ^ ut oxide), N- (2- = ethylheptyl) -bicyclo-i2.2.1.] 5-hepten-2, 3-dicarboximide etc., add.

The insecticidal or acaricidal compositions according to the invention preferably contain 0.2 to 90 % active ingredient.

The following examples illustrate the invention.

130015/0765

example 1

(RS) -α-Cyano-6-phenoxy-2-pyridy! Methyl-IR-trans-2,2-d! Methyl- 3- (2,2-dichlorovinyl) cyclopropane-1-carboxylate

19.9 g of sodium cyanide, 0.360 g of tetradecyltrimethylammonium bromide and then slowly at 23 ° C. are placed in 21 g cm of water a solution ■ of 72 g of 6-phenoxy-2-picolinalcehydrate, 0.360 π tetradecyltrimethylammonium bromide and 84.7 g of IR-trans-2,2-dimethyl-3- (2, 2-dichlorovinyl) -cycloprcpan-1-carboxylic acid chloride in 290 cm of toluene (with the acid chloride last in the solution is introduced), 'stirs for 21 hours at 23 ° C under an inert atmosphere, separates the organic phase by decanting off, wash them with water, dry them, concentrate to dryness by distillation under reduced pressure, add isopropanol to, concentrated to dryness and recovered 158 g of (RS) -a-cyano-6-phenoxy-2-pyridylmethyl-IR-trans-2,2 ~ dimethyl-3- (2,2 « dichlorovinylJ-cyclopropane-1-carboxyiate.

Example 2

(R) -q-Cyano-6-phenoxy-2-pyridylmethyl-1R-trans-2 ₁ 2-diinethv.l-3- (2,2-dichlorovinylj-cyclopropane-1-carboxylate

158 g of (RS) -a-cyano-6-phenoxy-2-pyridylmethyl-1R-trans-2,2-dimethyl-3- (2,2-dichlorovinyl) -cyclopropane-1-carJ-doxylate, which in Example 1 was obtained from isopropanol and receives 75 ^ 2 g of (R) -a-Cyaho-6-phenoxy-2-pyridylmethyllR-trans-2,2-dimethyl-3- (2,2-dichlorovinyl) -cyclopropane-1-carboxylate . F --- 102 ° C, [a] _D = -8 ° (c = 3%, toluene).

Analysis: ^c ₂ i ^H ₁ 3 ^O 3 ^N 2 ^C1 2 ⁽⁴¹⁷ » ²⁹ )

Calculated: C 60.44 H 4.34 N 6.71 Cl 16.99 % Found: 60.6 4.3 6.7 17.3

O / / O

130015/0765

NMR spectrum (deuterium chloroform)

Peaks at 1.23-1.32 ppm, assigned to the hydrogen atoms geminal methyl groups,

Peaks at 1.65 - 1.73 ppm, assigned to the hydrogen atom in the 1 ~ position of the cyclopropyl group,

Peaks at 2.17 - 2.25 - 2.30 - 2.38 ppm, assigned to the hydrogen atom in the 3-position of the cyclopropyl group, peaks at 5.53-5.67 ppm, assigned to the ethylenic hydrogen,

Peak at 6.32 ppm assigned to that of the same carbon atom hydrogen atom carried as the CN group.

Example 3

(S) -a-Cyano-6-phenoxy-2-pyridylmethyl-IR-trans-2,2-dimethyl-3- (2,2-dichlorovinyl) -cyclopropane-1-carboxylate

The crystalline mother of the 158 g of the (RS) -a-cyano-6-phenoxy-2-pyridylmethyl-IR-trans-2,2-dimethyl-3- (2,2-dichlorovinyl) obtained in Example 2 is concentrated ) -cyclcpropane-l-carboxlyats to dryness under reduced pressure, chroma to - graphs the residue under pressure while eluting with petroleum ether (boiling point 35 to 70 ° C) and isopropyl ether and receives 38.68 g (S) -a- Cyano-6-phenoxy-2-pyridylmethyl-IR-trans-2,2-dimethyl-3- (2,2-dichlorovinyl) -cyclopropane-1-carboxylate. [a] _D «+ 20.5 ° (c = 4%, toluene).

NMR spectrum (deuterochloroform)

Peaks at 1.20 - 1.24 ppm, assigned to the hydrogen atoms ■ the geminal methyl groups,

Peaks at 1.65-1.74 ppm, assigned to the hydrogen atom in l ~ position of the cyclopropyl group,

Peaks at 2.2 - 2.28 - 2.40 - 2.42 ppm, assigned to hydrogen atom in 3-position of the cyclopropyl group, peaks at 5.55 - 5.68 ppm, assigned to the ethylene hydrogen atom,

Peak at 6.32 ppm assigned to that of the same carbon atom like the CN group carried hydrogen atom peaks at 6.83 - 7.9 ppm, assigned to the aromatic nuclei.

130015/0765

Example 4

'(RS) -g-Cyano-6-phenoxy-2-pyridylmethyl-1R-cis-2,2-dimethyl ~ 3- (2,2-dichlorovinyl) cyclopropane-1-carboxylate

3
1.352 g of sodium cyanide and 0.025 g of tetradecyltrimethylammonium bromide are introduced into 15 cm of water, a solution of 4.9 g of δ-phenoxy - ^ - picolinaldehyde, 0.025 g of tetradecyltrimethylammonium bromide and; 6.15 g of lR-cis-2, is slowly added at 27 ° C. 2-Dimeth'y] -3- (2,2-dichlorovinyl / cyclopropane-1-carboxylic acid chloride in 20 ecm of toluene, stirred under an inert atmosphere for 15 hours at 23 ° C, left, separates the organic P ¹ phase by decanting, Washed with water, the aqueous phases combined, washed with toluene, concentrated to dryness by distillation under reduced pressure and obtained 10.8 g of (RS) -a-cyano-6-phenoxy-2-pyridylmethyl-IR-cis-2 , 2-dimethyl-3- (2,2-dichloro-vinyl) -eyelopropane-1-carboxylate as crude product.

NMR spectrum (deuterochloroform)

Peaks at 1.80 - 1.90 - 1.93 ppm, assigned to the hydrogen atoms the geminal methyl groups and the hydrogen atoms the methyl group,

Peaks at 2.83 - 3.5 ppm, assigned to the hydrogen atoms of the Cyclopropyl group,

Peaks at 9.17 - 9.36 ppm, assigned to the ethylene hydrogen atom the vinyl chain,

Peak at 9.48 ppm assigned to that of the carbon atom in α-position to the CN group, assigned to hydrogen atom, peaks at 10.3-10.46-11.5-11.7-11.8 ppm the pyridine ring,

Peaks at 10.7 - 11.3 ppm, assigned to the other aromatic Hydrogen atoms.

Example 5

(R) -g-Cyano-6-phenoxy-2-pyridylmethyl-1R-cis-2 _T 2-dimethyl-3-C2,2-dichlorovinyl) -cyclopropane-1-carboxalate

Chromatographie ^ t under pressure on silica gel 10.4 g of (RS) -a-cyano-6-phenoxy-2-pyridylmethyl-lR-cis-2,2-dimethyl-3-

130015/0765

(2,2-dichlorovinyl ^ cyclopropane-1-carboxylate eluting with a mixture of petroleum ether (boiling point 35 to 70 ° C.) and isopropyl ether (80/20) and gives 4.812 g of (R) -a-cyano-6-phenoxy-2 Pyridylmethyl-IR-cis-2,2-dimethyl-3- (2,2-dichlorovinyl) -cyclopropane-1-carboxylate. Ca] _β = -17 ° (c = 4%, toluene).

NMR spectrum (deuterochloroform)

Peak at 1.29 ppm, assigned to the hydrogen atoms of the geminal methyl groups,

Peak at 6.32 ppm assigned to that of the same carbon atom hydrogen atom carried as the CN group.

4.75 g of the product obtained are chromatographed again Silicon dioxide, eluting with methylene chloride, and giving 3.993 g of (R) -a-cyano-6-phenoxy-2-pyridylmethyl-lR-cis-2,2-dimethyl-3- (2,2-dichlorovinyl) -cyclopropane- l-carboxylate in purified form.

Analysis: C ₂₁ H ₁₈ O ₃ N ₂ Cl ₂ (417.89)

Calculated: C 60.44 H 4.34 N 6.71 Cl 16.99% Found: 60.3 4.3 6.5 17.2 %

Example 6

(S) -a-Cyano-6-phenoxy-2-pyridylmethyl-IP-cis-2 ₅ 2-dimethyl 3- (2,2-dichlorovinyl) -cyclopropane-1-carboxylate

The chromatography of the 10.49 of the (RS) -a-cyano-6-phenoxy-2-pyridylmethyl-lR-cis-2,2-dimethyl-3- (2,2-dichlorovinyl) - described in Example 5 - cyclopropane-l-carboxylate continues and receives 2.9 7 g (S) -a-cyano-6-phenoxy-2-pyridylmeth / l-lR-cis-2, 2-dimethyl-3- (2,2-dichlorovinyl) -cyclopropane-1-carboxylate. Ca] ₀ = + 24 ° (c = 4%, toluene).

NMR spectrum (deuterochloroform)

Peaks at 1.20 - 1.27 ppm, assigned to the hydrogen atoms of the geminal methyl groups,

Peak at 6.3 ppm, assigned to that of the same carbon

130015/0765

atom like the CN group carried hydrogen atom, peaks at 6.14 - 6.23 ppm, assigned to the ethylenic hydrogen atom,

Peaks at 1.87 - 1.97 ppm, assigned to the hydrogen a + -om in ! Position of the cyclopropyl group,

Peaks at 6.89 - 7.88 ppm, assigned to the hydrogen atoms of the aromatic kernels.

2.92 g of the product are chromatographed again on silica while eluting with methylene chloride and obtained 2.307 g (b) -a-Cyano-6-phenoxy-2-pyridylmethyl-IR-cis-2,2-dimethyl-3- (2,2-dichlorovinyl) -cyc. lopropane-1-carboxylate in purified form.

Analysis: C ₃₁ H ₁₃ O ₃ N ₂ Cl ₂ (417.89)

Calculated: C 60.44 H 4.34 N 6.71 Cl 16.99% Found: 60.2 4.4 6.6 17.1%

Example 7

(RS) -a-Cyano-6-phenoxy-2-pyridylmethyl-IR-cis-2,2-dimethyl-3- (2,2-dibromovinylj-cyclopropane-1-carboxylate

The procedure is as indicated in Example 1, starting from 5.55 g of sodium cyanide, 0.22 g of tetradecyltrimethylammonium bromide, 20 g 6-phenoxy-2-picolinaldehyde and 33.1 g of lR-cis-2,2-dimethyl-3- (2,2-dibromovinylJ-cyclopropane-1-carboxylic acid chloride, and receives 51 g of the expected product.

Analysis: C ₀ .H " _Q 0, N ₀ Br ₀ (506.20)

"* ' / Li. Io OtLtL'

Calculated: C 49.82 H 3.58 N 5.53 Br 31.57% Found: 49.7 3.6 5.4 31.6 %

Example 8

(R) -g-Cyar: o-6-phenoxy-2-pyridylmethyl-1R-cis-2, 2-dimethyl-3 ~ . (2,2-dibromovinyl) cyclopropane-1-carboxylate

10 g of the product obtained in Example 7 are chromatographed under pressure on silica gel using a mixture of petroleum ether (boiling point 35 to 70 ° C) and isopropyl ether

130015/0765

(80/20) elutes, yielding 4.2 g of the expected (R) -isomer (Rf = 0.68), [a] _D = -17.5 ° - 1.5 ° (c = 1%, toluene ). F = 78 ° C

Analysis; ^C 2i ^H 18 ° 3 ^N 2 ^Br 2

Calculated: C 49.82 H 3.58 N 5.53 Br 31.57 % Found: 49.9 3.5 5.6 31.5 % '

Example 9

(S) -a-Cyano - S-phenoxy - ^ -pyridylmethyl-1R-cis-ä, 2-dimethyl-3 ~ (2,2-dibromovinyl) -cyclopropane-1-carboxylate

The chromatography described in Example 8 is continued and 3.85 g of the expected (S) -isomer is recovered. (Rf = 0.59), Ca] ₀ = + 20.5 ° i 1.5 ° (c = 1%, toluene).

Analysis: C ₃₁ H ₁₈ O ₃ N ₂ Br ₂ (506.20)

Calculated: C 49.82 H 3.58 N 5.53 Br 31.57% Found: 50.0 3.7 5.5 31.5 %

Example 10

(RS) -a-Cyano-6-phenoxy-2-pyridylmethyl-IR-trans-2,2-dimethyl ~ 3- (2,2 ~ dibromovinylj-cyclopropane-1-carboxylate

The procedure is as indicated in Example 7, starting from 33.1 g IR-trans-2,2-dimethyl-3- (2,2-dibromvinYl) -cyclopropane-1-carboxylic acid chloride and receives 54.5 g of the expected product.

Example 11

(R> - «- Cyano-6-phenoxy-2-pyridylmethyl-IR-trans-2,2-dimethyl-3- (2,2-dibromovinyl) -cyclopropane-1-carboxylate

The product obtained in Example 10 is crystallized from 200 cm of isopropanol by cooling after dissolving under reflux. The crystals formed are filtered off with suction, washed with isopropanol and 21.75 g of the following are obtained:
Ca] _n »+7.5 + 1 ° (c = 1 % toluene)

panol and receives 21.75 g of the expected product. F = 110 ° C.

136015/0765 '

ORIGINAL INSPECTED

Analysis; C ^ H ^ CU ^ Br ^ (506.20)

Calculated: C 49.82 H 3.58 N 5.53 Br 31.57 % Found: 49.9 3.5 5.6 31.4 %

Example 12

(S) -a-cyano-6 - phenoxy-2-pyridvlmethvl-lR-trans - 2,2-dimethyl - 3- (2,2-dibromovinyl) cyclopropane-1-carboxylate

The crystallization mother liquors obtained in Example 11 are collected, evaporated to dryness and the residue is chromatographed under pressure on silica, eluting with a mixture of petroleum ether (boiling point 35 to 70 ° C.) and isopropyl ether (80/20), and wins 5.9 g of the expected product (Rf = 0.55). [a] _D = + 27.5 ° (c = 1%, toluene).

Analysis: ^c ₂ i ^H i8 ° 3 ^N 2 ^Br 2 ^(5O6 > ² °)

Calculated: C 49.82 H 3.58 N 5.53 Br 31.57% Found: 49.9 3.5 5.6 31.4 %

Io

Example 13

(R, S) -oc-cyano-6-phenoxy-2-pyridy.imethyl-lR-cis-2,2-dimethyl-3- (2,2-difluorvinyD-cyclopropane-1-carboxylate

The procedure is as indicated in Example 1, starting from 2.1 g of sodium cyanide, 0.08 g of tetradecyltrimethylammonium bromide, 7.6 g ä-Phenoxy - ^ - picolinaldehyde and 8.2 g of lR-cis-2,2-dimethyl-3- (2,2-difluorvinyD-cyclopropane-1-carboxylic acid chloride, and receives 15.1 g of the expected product.

Example 14

(R) -a-Cyano-6-phenoxy-2-pyridylmethyl-IR-cis-2,2-dimethyl-3- (2,2-difluorovinyl) -cyclopropane-1-carboxylate

chromatographed under pressure on silica gel the 15.1 g of product obtained in Example 13, eluting with a mixture of petroleum ether (boiling point 35 to 70 ° C.) and isopropyl ether (80/20), and 6.5 g of the expected (R. ) Isomers (Rf = 0.39). [a] _D = -16.5 ° (c = 1.5 % toluene). ·

130015/0765

(384.38)

Calculated: C 65.62 H 4.72 N 7.29 %
Found: 65.5 4.7 7.2%

Example 15

(S) -a-Cyano-6-phenoxy-2-pyridylmethyl-1R-cis-2,2-dimethyl-3- (2,2-difluorovinyl-cyclopropane-1-carboxylate

The chromatography described in Example 14 is continued and 3.8 g of the expected (S) -isomer are recovered. (Rf = 0.33). Cuc] _D «+ 19 ° (c = 1.5% toluene).

Analysis; ^c ₂ i ^H i 8 ° 3 ^N 2 ^F 2 ⁽³⁸⁴ > ³⁸ >
Calculated: C 65.62 H 4.72 N 7.29 %
Found: 65.5 4.7 7.1%

Example 16

(RS) -cx -cyano-6-phenoxy-2-pyridylmethyl-IR-trans-2 ^ 2-dimethyl-3- (2,2-difluorovinyl) -cyclopropane-1-carboxylate

The procedure is as indicated in Example 1, starting from 2.3 g of sodium cvanide, 0.08 g of tetradecyltrimethylammonium bromide, 8.85 g 6-phenoxy-2-picolinaldehyde and 8.85 g of 1R-trans-2,2-dimethyl-3- (2,2-difluorovinyl) -cyclopropane-1-carboxylic acid, and receives 16.7 g of the expected product.

Example 17

(R) -oc-Cyano-6-phenoxy-2-pyridylmethyl-IR-trans- 2,2-dimethyl- ' 3- (2,2-difluorovinyl) -cyclopropane-1-carboxylate

Is chromatographed under pressure on Siliciumdioxidrel obtained in Example 16 16.7 g of product, eluting with a mixture of petroleum ether (boiling point 35 to 70 ⁰ C) erluiert and isopropyl ether (80/20), and 8 g of the expected (R) Isomers. (Rf = 0.75). Ca] ₀ = -22 ° + 1.5 ° (c = 1 %, toluene).

13001S / 076S

Analysis: ^C 2i ^H 18 ° 3 ^N 2 ^F 2 " ³⁸⁴ > ³⁸ >

Calculated: C 65.62 H 4.72 N 7.29 F 9.88% Found: 65.5 4.9 7.3 9.8%

Example 18

(S) -g-Cyano-6-phenoxy-2-pyridylmethyl-1R-trans -2, 2-dimethy 1-3- (2 _y 2-difluorovinyl) -cyclopropane-1-carboxylate

The chromatography described in Example 17 is continued and 5.8 g of the expected (S) -isomer are obtained. ιRf = 0.70). CiX] ₀ = 0 ° (c = 1 %, toluene).

Analysis: C, "H" _Q 0-N _o P _o (384.38)

'Calculated: C 65.62 H 4.72 N 7.29 P 9.88 % Found: 65.5 4.8 7.3 9.6%

Example 19

Composition according to the invention 0.02 G (R) -a-Cyano-6-phenoxy-2-pyridylmethyl-lR-trans- 5.0 r 2,2-dimethyl-3- (2,2-dichlorovinyl) -cyclopropane- 0.1 G l-carbo: cylate 94.88 G Tween 80 Topanol A * Xylene

• Merck Index, 9th Edition, page 7361 ** or 2,4-dimothyl-6-tert-butylphenol

Example 20 Composition according to the invention

(S) -a-Cyano-e-phenoxy ^ -pyridylmethyl-IR-cis- · ^, 2-dimethyl-3- (2,2-dichlorovinyl) -cyclopropane-1-carboxylate 0.03 g Atlox 4851 *. 6.0 g

Atlox 4855 3.0 g

Xylene 90.97 g

* Mixture of alkaryl aryl sulfonate and polyethoxylated Triglyceride with a viscosity at 25 ° C of 300 to 700 cP

130015/0765

5 G 25th G 10 G 25th G 1 G 100 ml

Mixture of alkylarylsulphonate and polyethanol: ylated triglyceride with a viscosity at 25 ° C of 1500 to 1900 cP,

Example 21

Acaricidal composition according to the invention for veterinary use

Solutions of the following formulation were prepared:

(R) -Oi-Cyano- 6-phenoxy-2-pyridylmethyl-lR-cis-2,2-dimethyl-3- (r: _y 2-dichlorovinyl) -cyclopropane-1-carboxylate

Piperonyl butoxide polysorbate 80

Triton X 100 ■■ - ■. ·

Tocopherol acetate Ethyl alcohol quantum satis ad

This gives a solution which is diluted in 5 liters of water at the time of use.

Investigation of the insecticidal activity of the invention links

The tests described below are performed with:

(S) -a-Cyano-6-phenoxy-2-pyridylmethyl-lR-cis-2,2-dimethyl-3- (2, 2-dichlorovinyl) - cyclopropane-l-carboxylate (compound A),

(R) -a-Cyano-6-phenoxy-2-pyridylmethyl-iR-cis-2,2-dimethyl-3- (2,2-dichlorovinyl) -cyclopropane-1-carboxylate (Connection B),

(S) -a-Cyano-6-phenoxy-2-pyridylmethyl-lR - trans-2, 2-r-diiaethyl-3- (I ^J , 2-dichlorovinyl) -cyclopropane-1-carboxylate (compound C) and

(R) -a-Cyano-6-phenoxy-2-pyridylmethyl-IR-trans-2,2-dimethyl-3- (2,2-dichlorovinyl) -cyclopropane-1-carboxylate (Compound D).

130015 / 076S

BATH ORIGINAL

A. Investigation of the legal effect on the housefly

The insects used for the tests are female house flies that are 4 days old. Man leads a topical application of 1 ^ ul acetone solution to the dorsal thorax of the insect using an Arnold Mijcromanipulator by. 50 individuals are used per treatment. Mortality monitoring is carried out 24 hours after treatment by.

The experimental results given in the table below are expressed as the LD ₅₀ or the dose required to kill 50% of the insects:

^LD 50 Connection A 8 mg / 1 Connection B 8 mg / 1 Compound C 18 mg / 1 Connection D 17 mg / 1

Conclusion: The pre-compounds A, B, C and D have an interesting insecticidal activity with regard to the house fly.

B. Investigation of shock activity in the house fly

The insects used in the tests are female house flies with an age of & days. Direct atomization is carried out in a Kearns and March chamber using a mixture of equal volumes of acetone and kerosene as the solvent (amount of solution used

3
2 χ 0.2 cm). About 50 insects are used per treatment. The controls are carried out every minute for up to 10 minutes and then at 15 minutes, and the KT ₅₀ value is determined by conventional methods.

130015/0785

The test results are given in the following table. *

- ·· ^ 5O ^) Connection A .. ,.: - 3 Wed «.-: Connection B i Compound C ■ _ \ ~ ^ 27: M.in ^ Connection D "3.30" min.

Conclusion: The compounds A, B, C and D 'have a depressing effect on the house fly.

. H

C. Investigation of the insecticidal activity in defe- --- Blatellä Germanica '''' ^ :: .-- * r. .- .; . : ■,;: -; : i

Glass vessels of approx. 1 liter are used, which are closed with a dough lock. '''""' ^Ji ■ '"' - ' - ^i}; -" ° ~ -

The compound to be investigated is dissolved in acetone at various concentrations / this Lo & uhgr is placed in a glass container and then evaporated under "Laboratory atmosphere sphä :: e. '· ■ ^: ' ^: ■ ^l; - '■' ■ · ■ '"^{:; r>:}'- ^{: z} "' ^: *

The cockroaches are placed in the glass jar.

The percentage mortality according to S Taigen ' ¹ is determined taking into account a comparative experiment without treatment.

The test results obtained, which are expressed as LK ₅₀ (50% lethal concentration) in mg / m, are given in the following table.

130015/076 5

BAD ORfGlNAL

A. ^LK 50 mg Aa2 link B. 0.125 ag / ra2 link C. 0.200 rng / m2 link D. 0.250 mg / m2 link 0.700

Conclusion; The compounds A, B, C and D have an interesting insecticidal *! Activity at the Blatella Germanica.

D. Investigation of the lethal effect in Spodoptera littoralis larvae

The experiments are carried out by topically applying an acetone solution to the dorsal thorax of the larvae using an Arnold micromaniptlator. 10 to 15 larvae are used per dose of the product to be examined. The larvae used are fourth instar larvae, that is, with one
Age of about 10 days during which they are at 24 ° C and one
relative humidity of 65% have been raised, itach
After the treatment, the individuals are placed in an artificial environment (poitoite filieu).

The mortality control is carried out 48 hours after the treatment.

The experimental results, expressed as
given in the following table:

are in

A. ^LD 50 nag / 1 link B. 3.6 rag / 1 link C. '4.0 . • ng / 1 link D. 0.9 mg / 1 link 1.5

130015/0765
BATH ORIGINAL

Conclusion: Compounds A, B, C and D are endowed with strong insecticidal activity with regard to the Spodoptera littoralis larvae.

E. Examination of the insecticidal activity of the compound A, B _T and C D on Epilachna varivestris larvae

The experiments are carried out by topical application analogous to the procedure for the Spodoptera larvae. Larvae in the penultimate instar are used, and after the treatment, the larvae are fed on bean plants. The mortality control is carried out 12 hours after the treatment.

The test results, expressed as LD ₁ . , are given in the following table:

^LD 5O Connection A 2 mg / 1 Connection B 1.5 mg / 1 Compound C 0.3 mg / 1 Connection D 0.3 mg / 1

Conclusion: Compounds A, B, C and D are endowed with strong insecticidal activity with regard to Epilachna verivestric.

F · Test on Aphis fabae

It is a plot experiment carried out outdoors on broad bean plants. Every broad bean plot 360 χ 120 cm has four rows of broad beans. Since the natural infestation with Aphis fabae is considered sufficient, atomize the aqueous solution containing the insecticide on each plot. Use two parcels (= two repetitions) per dose of the product. The treatment is carried out on the basis of 2 1 insecticidal slurries per unit plot.

130015/0765

leads. The population controls are 1 hour before treatment and then carried out 2 weeks after the treatment,

The LD ₅ values are determined. The test results are given in the table below:

A. 0 ^LD 5O link B. 0 ₃ 5 mg / 1 link C. 0 , 65 mg / 1 link D. 0 , 75 mg / 1 link , 4 mg / 1

Conclusion: Compounds A, B, C and D are endowed with strong insecticidal activity with respect to the broad bean aphid.

Investigation of the acaricidal activity of compounds A, B, C and D

Experiments on Tetranychus urticae

Bean leaves are used, which are infested in 25 adults Specimens of Tetranychus urticae per leaf and coated with bait on their surface. The ones from mites Affected bean leaves are divided into two groups:

a) A first group is treated with the compound under investigation. An atomization of the aqueous solution is taken of the compound to be tested on the leaves, using different concentrations.

b) A second group of leaves or comparison group is not dealt with.

The dead adult specimens are counted for 48 hours the treatment.

130015/0765

The experimental results obtained, expressed as LD, -, are indicated in the table below:

A. 3 3 ^LD 50 link B. 2 , 2 g / hl link C. g / hl link D. 5 g / hl link g / hl

Conclusion: Compounds A, B, C and D are endowed with good acaricidal activity with regard to Tetranychus urticae.

Study of the activity against mites, parasites of animals, of compounds A and B.

a) Investigation of the activity of the Boophilus microplus larva

The substance to be examined is in a mixture consisting of dimethylformamide, emulsifiers and Arcopal in this way solved that a 10% emulsifier concentrate is obtained. Man dilute this concentrate with water to get solutions at the desired concentration of 100, 10 and 1 ppm.

The various above solutions are sprayed onto tick larvae of tropical cattle with the aid of a spray tower of the Boophilus microplus type and determines the percentage mortality after 24 hours by counting the dead and living larvae.

The results are as follows:

130015 / 076B

Dose of product
in ppm Connection A
# Mortality Connection B
i> mortality 100
10
: 100
100
68 100
100
88

Conclusion; Compounds A and B have remarkable activity.

Inhibition of the propagation of Ticks Boophilus raicroglus

One dives female specimens of Boophilus ready to be deposited microplus in the solutions prepared above for 5 minutes and then transfer them to a heated one for storage Space.

Determine a) the percentage of ticks that have not laid, b) the amount of eggs laid in relation to a comparison and c) the percentage of hatched Larvae.

The percentage inhibition of growth is calculated as a function of the figures obtained, 100% indicating that the inhibition is complete and 0 % indicating that the growth is identical to that obtained in the comparative experiments. You get:

130015/0765

BATH ORIGINAL

$> Inhibition $> Inhibition Dose in ppm (Connection A) (Connection B) 100 iOO 100 50 92 100 25th 58 93 12.5 35 87 6.2 31 76 3.1 25th 48 t, 5 24 53 0.75 16 Zk 0.38 11 33 0.19 34 17th

Conclusion: Compounds A and B have remarkable activity.

130015/0765

Claims (11)

Dr. F. Zumstein Sr. - Dr.i.'Assmwn: Dr. "R Kbenigsberger Dipl.-Phys R. Holzbauer - Dipi.-Vng. F. KHngseisen -Dr. F. Zumstein jun. Munich 2 · BräuhausstraQe 4 · Telephone collection no. 22 53 41 · Ti'jgramme Zumpat · Telex 528079 14 / 90 / N Cas 1899 D- claims 1. Cyclopropanecarboxylic acid ester of the general formula I: CH _ 0 - C in which X. and X ₂ , which can be identical or different, denote a fluorine, chlorine or bromine ion, v / whether the acidic coupling component lR-cis or IR-trans structure and the alcoholic coupling component (R) - , (S) or. (RS) configuration. 2. Compounds of formula I according to claim 1, wherein X. ur. <; X _{2 are} identical and represent a fluorine, chlorine or bromine atom. 3. Process for the preparation of cyclopropanecarboxylic acid ester: -. of the general formula I as defined in claim 1, characterized in that 6-phenoxy-2-picolinaldehyde with a compound which forms CN ions and with an IR-cis- or IR-trans-2,2-dimethyl- 3- (2, 2-dihalovinyl J-cyclopropane-l-carL'onic acid, in which halo means a fluorine, chlorine or bromine atom, or reacts with a functional derivative of this acid to form a (I \ S) -a- cyano-6-pheno: cy-2-pyridylmethyl-2 to obtain 2-dimethyl 3- (2,2-dihalovinylJ-cyclopropane-l-carboxylate. 130015/0765 BADORLGiNAL whose acidic coupling component has the same structure as that of the starting acid, and then if desired Using a physical method, the two diastereomers of the ester of the alcohol with tkS) configuration separates to a (R) -a-cyano-6-phenoxy-2-pyridylmethyl-2, 2-dimethyl-3- (2, 2-dihalovinyl J-cyclopropar.-1-carboxylate and an (S) -a-cyano-6-phenoxy-2-pyridylmethyl-2,2-dimethyl-3- (2,2-dihalovinyl) -cyclopropane-1-carboxylate to obtain whose acidic linking component has the same structure as that of the starting acid. 4. The method according to claim 3, characterized in that the reaction of the aldehyde, the compound forming CN ~ ions and the acid or its functional derivative using the method known as phase transfer catalysis in aqueous Milieu is carried out in the presence of a basic agent and a water-immiscible solvent. 5. The method according to claim 4, characterized in that the basic agent Tetradecyltrirr.ethylammoniumbromid and the water-immiscible solvent is toluene. 6. The method according to claim 3, characterized in that the separation of the two diastereomers of a (RS) -oc-cyano-6-phenoxy-2 pyridylmethyl 2,2-dimethyl-3- (2,2-dihalovinyl) cyclopropane-1-carboxylate is effected by chromatography. ; 7. The method according to claim 3, characterized in that the separation of one of the two diastereomers of an (RS) -a-cyano-6-phenoxy-2-pyridylmethyl-2,2-dimethyl-3- (2,2-dihalovinyD-cyclopropane -l-carboxylate caused by crystallization. 8. The method according to claim 7, characterized in that the ester of the racemic alcohol is the (RS) -Ct-cyano-6-phenoxy-2-pyridylmethyl-IR-trans-2,2-dimethyl-3- (2,2- dichlorovinyD-cyclopropane-1-carboxylate and that this is caused by 130015/0765 Stain sation 'isolated diastereomers the (R) -a ~ cyano-6-phenoxy-2-pyridylmethyl-IR-trans-2,2-dimethyl-3- (2,2-dichlorovinyl / cyclopropane-1-carboxylate is. 9. The method according to claim 7, characterized in that the ester of the racemic alkenol the (R, S) -a-cyano-6-phenoxy-. 2-pyridylmethyl-IR ~ trans-2,2-dimethyl-3- (2,2-dibromovinyl) ~ cyclopropane-'J-carboxylate or the (R, S) -oc-cyano-6-phenoxy-2-pyridylmethyl- lR-trans-2,2-dimethyl-3- (2,2-difluorovinyl) -cyclopropane-1-carboxylate and that the diastereomer isolated by crystallization is the (R) ~ a-cyano-b-phenoxy ~ 2- pyridylmethyl-IR-trans-2,2-dimethyl-3- (2,2-dibromonyl) -cyclopropane-1-carboxylate or the (R) -a-cyano-6-phenoxy ~ 2-pyridylmethyl-IR-trans- Is 2,2-dimethyl-3- (2,2-difluorovinyl) -cyclopropane-1-carboxylate. 10. ■ In particular, insecticidal and acaricidal pesticidal compositions, characterized in that it is used as an active ingredient at least one of the compounds of general formula I. as defined in claim 1 included. 11. Acaricidal compositions for veterinary use, characterized in that they are used as active ingredients .sumidest one of the compounds of general formula I. as defined in claim 1 included. 130015/0765