DE3047219A1 - Cyclopropyl-phenylacetic acid 3-benzyl-benzyl ester derivs. - prepd. by reaction of para-chlorophenyl-cyclopropyl-acetyl halide with 3-benzyl-benzyl alcohol - Google Patents

Abstract

New cyclopropyl-phenyl-acetic acid 3-benzyl-benzyl ester derivs. are of formula (I): (where R1 is H, CN or ethynyl and X1 is F, or R1 is 1-propynyl and X1 is H or F). (I) are pesticides useful particularly as insecticides and acaricides. They are especially useful against insects which are injurious to plants, against flies such as Musca domestica, midge larvae, and keratin-eating insects, (e.g. keratin-eating Lepidoptera larvae). (I) are accordingly suitable for use in plant protection and for protecting wool-contg. textiles against insect attack.

Description

Phenylacetates, process for their preparation and their

Use in pest control The present invention relates to phenyl acetates, processes for their preparation and their use in pest control. The phenyl acetate have the formula in which R1 is hydrogen, cyano- or ethynyl and X1 is fluorine or R, propynyl and X1 is hydrogen or fluorine.

The compounds of the formula I are prepared by methods known per se, for example as follows: 1) C1- -CH - COOH + X - CH-Iv A -CH2- II, R. L. (II) (III? (III) acid binding agent T T 2) C1- - £ K-CO EG-CE cm « CN 1 R1 <I 1 0 \\ 0 / 0X1 CA2 <R2 (IV) (V) acid binding middle 3) Cl 0 = 0H - COOH HO-CHoH 3) C1 ^ - CH - COOH I i 11 2 il 1 - X R, -il CC2NH2 -C (II) (V) water-binding middle 4) C1- / \ @ - CH - COOR HO-CS --CH - \ 4) C1-.IH - COOR HO-1 r + R1 R1 x CH2 CVI) (V) \\ / - RAW In formulas II to VI, R1 and X1 have the meanings given for formula I.

In the formulas III and IV, X stands for a halogen atom, in particular for chlorine or bromine and in the formula VI, R stands for C1-C4-alkyl, in particular for Methyl or ethyl. Acid-binding agents for processes 1 and 2 are particularly useful tertiary amines, such as trialkylamine and pyridine, and also hydroxides, oxides, carbonates and bicarbonates of alkali and alkaline earth metals as well as alkali metal alcoholates such as E.g. potassium t-butoxide and sodium methylate can be considered. As a water-binding agent for method 3, for example, dicyclohexylcarbodiimide can be used. The proceedings 1 to 4 are at a reaction temperature between -10 and 1200C, usually between 20 and 800C, at normal or elevated pressure and preferably in an inert one Solvent or diluent carried out. As a solvent or diluent e.g. ethers and ethereal compounds such as diethyl ether, dipropyl ether, Dioxane, dimethoxyethane and tetrahydrofuran; Amides such as N, N-dialkylated carboxamides; aliphatic, aromatic and halogenated hydrocarbons, especially benzene, Toluene, xylene, chloroform and chlorobenzene; Nitriles such as acetonitrile; Dimethyl sulfoxide and ketones such as acetone and methyl ethyl ketone.

The starting materials of the formulas II to VI are known or can be prepared analogously to known methods.

The compounds of formula I are available as a mixture of different optically active isomers are present if not uniformly optically during manufacture active starting materials are used. The different isomer mixtures can be separated into the individual isomers by known methods. Under the compound of formula I is understood to mean both the individual isomers and their mixtures.

The compounds of the formula I are suitable for combating various types of disease animal and vegetable pests.

The compounds of the formula I are particularly suitable for combating of insects, phytopathogenic mites and ticks, e.g. of the order Lepidoptera, Coleoptera, Homoptera, Heteroptera, Diptera, Acarina, Thysanoptera, Orthoptera, Anoplura, Siphonaptera, Mallophaga, Thysanura, Isoptera, Psocoptera and Hymenoptera.

In particular, compounds of the formula I are suitable for combating plant-damaging insects, especially plant-damaging feeding insects, in ornamental and useful plants, especially in BaurmJoll cultures (e.g. against Spodoptera littoralis and Heliothis virescens) and vegetable crops (e.g. against Leptinotarsa decemlineata and Myzus persicae).

Active ingredients of the formula I also show a very beneficial effect against Flies such as Musca domestica and mosquito larvae.

In particular, the compounds of the formula (I) also have an excellent one Effect against keratin-eating insects, such as against keratin-eating larvae from Leptidoptera, e.g., Tineola spec. and Tinea spec. as well as against those who eat keratin Coleopteran larvae, e.g.

Anthrenus spec. and Attagenus spec. on. The active ingredients of the formula (I) are particularly suitable for protecting keratinic or keratin-containing material against insect caused damage, especially for washable and lightfast protection against insects, especially for moth and beetle retrofitting of such materials. It can use keratin or keratin-containing material in both raw and processed State, e.g. raw or processed sheep wool, products from other animal hair, hides, furs and feathers.

In practice, the effectiveness of the in the invention is particularly important Process used compounds of formula (I) against the larvae of the clothes moth (Tineola bisselliela) and fur moth (Cnea pellionella) as well as against the larvae the fur and carpet beetle (Attagenus spec. or Anthrenus spec.). Is preferred the method according to the invention therefore on the one hand for protecting textiles Wool, e.g. from woolen blankets, wool carpets, woolen linen, woolen clothes and knitted goods or from textiles containing wool, such as blended fabrics, one component of which is wool, E.g. blended fabrics made of wool and other natural fibers, preferably cotton or made of Wool and synthetic fibers, on the other hand also for protecting fur and hides used against infestation by the pests mentioned.

The acaricidal or insecticidal effect can be achieved by adding other insecticides and / or acaricides widen significantly and given Adjust circumstances. Suitable additives are, for example, 3. organic phosphorus compounds; Nitrophenols and their derivatives; Formula amidine; Ureas; other pyrethrin-like Compounds as well as carbamates and chlorinated hydrocarbons.

Compounds of the formula I are also particularly advantageous with substances combined, which have a synergistic or potentiating effect on pyrethroids exercise. Examples of such compounds include: Piperonyl butoxide, propynyl ether, Propynyloximes, propynyl carbamates and propynyl phosphonates, 2- (3, 4-methylenedioxyphenoxy) -3,6,9-trioxaundecane (Sesamex or Sesoxane), S, S, S-tributylphosphorotrithioate, 1,2-methylenedioxy-4-C2- (octylsulfonyl) propyl) benzene.

Compounds of the formula I can be used alone or together with suitable carriers and / or additives are used. Suitable aggregates can be solid or liquid and correspond to those commonly used in formulation technology Substances such as natural or regenerated substances, solvents, dispersants, Wetting, adhesive, thickening, binding and / or fertilizers.

The agents according to the invention are prepared in a manner known per se Way by intimately mixing and / or grinding the active ingredients of the formula I with the suitable carriers, optionally with the addition of the active ingredients inert dispersants or solvents. The active ingredients can be in the following Forms of processing are available and used: Fixed forms of processing: Dusts, grit, granules, (coating granules, impregnation granules and homogeneous granules); Liquid forms of work-up: a) dispersible in water Active ingredient concentrates: wettable powders, pastes, emulsions; b) Solutions.

The content of active ingredient in the agents described above is between 0.1 to 95%, it should be mentioned that when applying from an airplane or by means of other suitable application devices Concentrations up to 99.5% or even pure active ingredient can be used. The active ingredients of Formula I can be formulated, for example, as follows (parts mean parts by weight): Dust: To produce a) 5% and b) 22% dust the following substances are used: a) 5 parts of active ingredient 95 parts of talc; b) 2 parts Active ingredient 1 part of highly dispersed silica 97 parts of talc.

The active ingredient is mixed with the carrier substances and ground.

Granules: The following are used to produce 5% granules Substances used: 5 parts active ingredient 0.25 parts epoxidized vegetable oil 0.25 parts Cetyl polyglycol ether 3.50 parts polyethylene glycol 91 parts kaolin (grain size 0.3-0.8 mm).

The active ingredient is mixed with epoxidized vegetable oil and with 6 parts of acetone dissolved, then polyethylene glycol and cetyl polyglycol ether added. The solution obtained in this way is sprayed onto kaolin and then the acetone evaporates in vacuo.

Wettable powder: For the production of a) 40%, b) and c) 25%, d) The following ingredients are used: a) 40 parts of active ingredient 5 parts of lignin sulfonic acid, sodium salt, 1 part of dibutylnaphthalenesulfonic acid, sodium salt 54 parts of silica; b) 25 parts of active ingredient 4.5 parts of calcium lignosulfonate 1.9 parts of champagne chalk / hydroxyethyl cellulose (mixture (1: 1) 1.5 parts of sodium dibutyl naphthalene sulfonate 19.5 parts silica 19.5 parts Champagne chalk 28.1 parts kaolin; c) 25 parts Active ingredient 2.5 parts of isooctylphenoxy-polyethylene-ethanol 1.7 parts of champagne chalk / hydroxyethyl cellulose mixture (1: 1) 8.3 parts of sodium aluminum silicate 16.5 parts of kieselguhr 46 parts of kaolin; d) 10 parts of active ingredient 3 parts of a mixture of the sodium salts of saturated fatty alcohol sulfates 5 parts of naphthalenesulfonic acid / formaldehyde condensate 82 parts of kaolin.

The active ingredient is intimately mixed with the additive in suitable mixers mixed and ground on appropriate mills and rollers.

You get wettable powders, which can be mixed with water to form suspensions Allow to dilute the desired concentration.

Emulsifiable concentrates: For the production of a) 10%, b) 25% and c) 50% emulsifiable concentrate, the following substances are used: a) 10 Parts active ingredient 3.4 parts epoxidized vegetable oil 3.4 parts of a combination emulsifier, consisting of fatty alcohol polyglycol ether and alkylarylsulfonate calcium salt 40 Parts of dimethylformamide, 43.2 parts of yylene; b) 25 parts of active ingredient 2.5 parts of epoxidized Vegetable oil 10 parts of an alkylarylsulfonate / fatty alcohol polyglycol ether mixture 5 parts of dimethylformamide, 57.5 parts of xylene; c) 50 parts of active ingredient 4.2 parts of tributylphenol polyglycol ether 5.8 parts of calcium dodecylbenzenesulfonate, 20 parts of cyclohexanone, 20 parts of xylene.

Such concentrates can be diluted with water to produce emulsions any desired concentration can be produced.

Spray: For the production of a) 5% and b) 95% spray the following ingredients are used: a) 5 parts of active ingredient 1 part of epoxidized Vegetable oil 94 parts gasoline (boiling point 160-190 ° C); b) 95 parts of active ingredient 5 parts epoxidized vegetable oil.

Example 1: Preparation of α-cyclopropyl (4-chlorophenyl) acetic acid - «- cyano-3- (4-fluorobenzyl) benzyl ester 3.63 g of α-cyano-3- (4-fluorobenzyl) benzyl alcohol, 3.43 g of α-cyclopropyl (4-chlorophenyl) acetic acid chloride and 50 ml abs. Toluene are at 5-10 ° C within one hour with 1.27 g of pyridine in 10 ml abs. Toluene Yes offset. After two hours at 200C it is another two hours long at 500C. The reaction mixture is 3 times with each 20 ml of water, washed once with 20 ml of 2N hydrochloric acid and again with 20 ml of water and dried with sodium sulfate. After the solvents have evaporated, the Purified crude product on silica gel using dichloromethane.

The compound of the formula is obtained 21 ° with a refraction of nD = 1.5687.

The following connections are also established in the same way: Example 2 Insecticidal Food Poison Effect Cotton plants were sprayed with a 0.05% aqueous active substance emulsion (obtained from a 10% emulsifiable concentrate).

After the covering had dried on, the cotton plants were each with Spodoptera littoralis and Heliothis virescens larvae L3 occupied.

The experiment was carried out at 240 ° C. and 60% relative humidity.

Compounds according to Example 1 showed good insecticidal properties in the above test Food poison effect against Spodoptera and Heliothis larvae.

Example 3: acaricidal effect Phaseolus vulgaris plants were 12 Hours before the test for acaricidal activity with an infected piece of leaf a mass breeding of Tetranychus urticae. The defected movable Stages were made from a chromatography nebulizer with the emulsified test preparations sprayed in such a way that the spray liquid did not run off. After two and seven days larvae, adults and eggs were examined under the dissecting microscope for living and dead individuals evaluated and the result expressed as a percentage. Stood during the "hold time" the treated plants in greenhouse cabins at 250C.

Compounds according to Example 1 were effective in the above test against adults, Larvae and eggs of Tetranychus urticae.

Example 4: Action against ticks A) Rhipicephalus bursa 5 adults each Ticks or 50 tick larvae were counted in a glass tube and kept for 1 to 2 minutes in 2 ml of an aqueous emulsion from a dilution series of 100, 10, 1 or 0.1 ppm test substance immersed. The tube was then covered with a standardized cotton ball closed and turned upside down so that the active ingredient emulsion from the cotton wool could be included.

The evaluation was carried out in the adults after 2 weeks and in the Larvae after 2 days. Two repetitions were run for each attempt.

B) Boophilus microplus (larvae) With an analogous dilution series as in test A) were each with 20 sensitive resp. OP-resistant larval trials carried out.

(The resistance relates to the tolerance of Diazinon).

Compounds according to Example 1 were effective against adults in these tests and larvae of Rhipicephalus bursa and sensitive resp. OP-resistant larvae of Boophilus microplus.

Example 5: (extraction method) A 0.4% stock solution was used in each case one of the compounds according to Example 1 is prepared in methyl cellosolve. Then became an aqueous application liquor prepared at room temperature, which in 120 ml distilled water 0.12 ml "Sandozin KB", 0.6 ml formic acid 1:10 and 0.75 ml the respective 0.4% stock solution contained.

Then 3 g of wool flannel fabric were wetted through with hot water and entered at room temperature. Constantly changing the wool pattern the bath temperature is heated to 60 ° C within 20 minutes and at 60 ° C for 30 minutes treated. It was then cooled, and the wool swatch was distilled twice for 3 minutes Rinsed with water, squeezed by hand and air dried. The active ingredient concentration was 1000 ppm calculated on the weight of the wool.

The sample dried in this way was subjected to the moth resistance test (anti-seizure protection against clothes moth Tineola biselliella Hum.), according to the authenticity check against Larvae of the fur beetle Attagenus piceus 01 and carpet beetle (Anthrenus vorax Wat.), subject to SNV 195902.

There were larvae of Anthrenus vorax and 6 to 7 weeks old, respectively Larvae of Attagenus piceus used for testing. From the treated wool flannel samples Pieces of the same size were cut out and kept at constant temperature for 14 days (280C) and constant relative humidity (65%) the attack (frass) of each 15 larvae of the respective pest exposed. The assessment was made on the one hand according to the relative weight loss of the test object and, on the other hand, according to the number still living organisms.

The compounds tested according to Example 1 showed a very good one Effect against the 3 pests used.

Example 6: (padding method) A 0.4 stock solution was used in each case one of the compounds according to Example 1 is prepared in methyl cellosolve. 12.5 ml of the respective stock solution were with Methylcellosolve, which 0.65 g / 1 "Sandozin KB" contains, diluted to 50 ml (= solution no. 1). 25 ml of solution no. 1 are mixed with Metylcellosolve, which contains 0.5 g / l l'Sandozin KB ", diluted to 50 ml (= solution No. 2). 25 ml of solution no. 2 are again with Methylcellosclve, which 0.5 g / l "Sandozin KB" contains, diluted to 50 ml (= solution no. 3).

3 ml each of solutions No. 1, 2 and 3 were placed in crystallizing dishes emptied and moistened each baited rondelle made of wool flannel for 3 seconds. The damp rondelles were then padded between aluminum foils, in such a way that the squeezed rondelles have each taken up 50% of the liquor. The concentrations of active ingredient were then in sequence 500 ppm, 250 ppm and 125 ppm for treated discs from solutions 1, 2 and 3.

The moist rondelles were air dried and the same Subjected to biological tests as described in Example 5.

The compounds tested according to Example 1 showed a very good one Effective against all 3 pests, even at the lowest concentration of 125 ppm.

Claims (8)

Claims 14 A compound of the formula where R1 is hydrogen, cyano or ethynyl and X1 is fluorine or R is prop-l-ynyl and X1 is hydrogen or fluorine. 2. The compound according to claim 1 of the formula 3. The compound according to claim 1 of the formula 4. The compound according to claim 1 of the formula 5. A process for the preparation of compounds according to claim 1, characterized in that a compound of the formula in the presence of an acid-binding agent with a compound of the formula in which R1 and X1 have the meaning given in claim 1 and X stands for a halogen. 6. A pesticide that acts as an active component a compound according to claim 1 and suitable carriers and / or other additives contains. 7. Use of a compound according to claim 1 for combating various animal and vegetable pests. 8. Use according to claim 7 for combating insects .Lid representatives of the order Akarina.