DE2805274A1 - Halovinyl-cyclopropane-carboxylate ester derivs. - useful as insecticides and acaricides - Google Patents

Abstract

Cyclopropanecarboxylic acid derivs. of formulae (I) and (II) are new: (where X1 and X2 are Me, F, Cl or Br; X3 is Cl or Br; R1 is H or Me; R2 is H, Me, Cn or ethynyl; Y1 and Y2 are H or halogen; Y is OH, halogen or 1-4C alkyl. (I) are insecticides and acaricides, esp. active against Spodoptera littoralis and Heliothis virescens on cotton and Leptinotarsa decemlineata and Myzus persicae on vegetables. Cpds. (II) are intermediates for (I). A typical cpd. (I) is alpha-cyano-3-phenoxybenzyl-3-(1-bromo-2,2-dichlorovinyl)-2,2-dim- ethylcyclopropane-1-carboxylate. In an example, this is prepd. starting from 3-(2,2-dichloro-1,2-dibromoethyl)-2,2-dimethylcyclopropane-1-carb- oxylic acid.

Description

Cyclopropanecarboxylic acid esters, process for their preparation

and their use in pest control. The present invention relates to cyclopropane carboxylic acid esters, processes for their preparation and their use in pest control. The cyclopropane carboxylic acid esters have the formula where X1 and X2 are methyl, fluorine, chlorine or bromine, X3 is chlorine or bromine, R1 is hydrogen or methyl, R2 is hydrogen, methyl, cyano or ethynyl and Y1 and Y2 are each hydrogen or halogen.

Halogen is fluorine, chlorine, bromine or iodine, in particular but fluorine, understand. Because of their action, preference is given to compounds of the formula T, in which X1 and X2 are each chlorine, X3 brown, R1 methyl, R2 hydrogen or cyano and Y1 and Y2 each represent hydrogen.

The compounds of formula 1 are prepared according to methods known to those skilled in the art, for example as follows: 1) .3 1 CHCOOH + XCRH [ÜO (Ä1 acidic 1) c =., J 'H - CH-COOH + X-CH-od denCes I. X2 / CX 2 2 medium CH3 R1 (11) (III) C = C-CH-CH-COX + X1 X3 Y 2) / C = C-CH - CH-COX + HO-CH t ~ O ~ O 1 acid-binding X2 X 2 Y2 mean CH3 R1 (IV) (V) 3) - \ C = C-CH-CH-COOH + HO-CH t O <Y -HO> ! \ R'2 R water-binding X2 zCX 2 Y2 mean CH3 R12 (V) (11) In formulas II to VI, R1, R2, X1 to X3, Y1 and Y2 have the meanings given for formula I.

In the formulas III and 1V, X is in particular a halogen atom 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 trialkylamines 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-butylate and sodium metaylate can be considered. As a water-binding Agent for method 3, for example, dicyclohexylcarbodiimide can be used. the Process 1 to 4 are carried out at a reaction temperature between -10 and 1200 C, usually between 20 and 800 C at normal or elevated pressure and preferably in carried out an inert solvent or diluent.

Suitable solvents or diluents are, for example, ethers and ethereal ones Compounds such as dietary 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; prefer acetone and methyl ethyl ketone.

The starting materials of the formulas III and V are known and can be used analogously known methods are produced.

The starting materials of the formulas II, IV and VI are new and methods known per se can be prepared, for example, as follows II IV or VI depending on the meaning of Y.

In formula VII, X1-X3 and R1 have those given for formula I. Meaning and Y stands for hydroxyl, halogen or C1-C4-alkyl. The reaction will at a temperature of -10 to 1200 C, especially at 50-1000 C at normal or increased pressure.

The compound of formula 1 is optically as a mixture of different active isomers if not uniformly optically active during manufacture Starting materials were used. The various isomer mixtures can can be separated into the individual isomers by known methods. Under the Compound of the 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 z.3. of the orders of 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 cotton 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.

The acaricidal or insecticidal effect can be achieved by adding other insecticides and / or acaricides widen significantly and given Adjust circumstances. Org. Phosphorus compounds; Nitrophenols and their derivatives; Formamidine; 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 propynylphosphonates, 2- (3,4-methylenedioxyphenoxy) -3,6, 9-trioxaundecane (Sesamex or Sesoxane), S, S, S.Tributylphosphorotrithioate, 1,2-methylenedioxy-4- (2- (octylsulfonyl) propyl) benzene.

Compounds of the formula I know on their own or together with suitable carriers and / or additives are used. Suitable aggregates can be solid or liquid and correspond to those customary 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 excipients, 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: Solid processing dusts, Litter, form granules: (coating granules, impregnation granules and Homogeneous granules); Liquid processing forms: a) Active substance concentrates dispersible in water: Wettable powders, pastes, emulsions; b) Solutions The content of active substance in the means described above is between 0.1 and 95X, it should be mentioned that that with the application from the aircraft 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 the formula I can be formulated as follows, for example (parts mean parts by weight): Dusting agent: For the production of a) 5% and b) 2% The following substances are used as dust: a) '5 parts Active ingredient 95 parts of talc; b) 2 parts of active ingredient 1 part of highly disperse 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 of active ingredient, 0.25 parts of epichlorohydrin, 0.25 parts of cetyl polyglycol ether 3.50 parts of polyethylene glycol 91 parts of kaolin (grain size 0.3-0.8 mm).

The active ingredient is mixed with epichlorohydrin and added 6 parts Acetone dissolved, then polyethylene glycol and Cctylpolyglykoläther are added. The solution obtained in this way is sprayed onto kaolin and then the acetone evaporated in a vacuum.

Wettable powder: For the production of a) 40%, b) and c) 25%, d) 10% wettable powders are used as follows: a) 40 parts of active ingredient 5 parts of lingin 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 of KieselsSure 19.5 parts of Champagne Chalk 28.1 parts of 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 sodium aluminum silicate 16.5 parts kieselguhr 46 parts 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 becomes intimately with the additive in suitable mixers mixed and ground on appropriate mills and rollers. Spray powder is obtained which can be diluted with water to form suspensions of any 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 of active ingredient 3.4 parts of epoxidized vegetable oil 3.4 parts a combination emulsifier, consisting of fatty alcohol polyglyco1 ether and alkyl aryl sulfonate calcium salt 40 parts of dimethylformamide, 43.2 parts of xylene; 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 tri-butylphenol 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.

Spraying agent: For the production of a) 5th and b) 95% spraying agent the following ingredients are used: a) 5 parts of active ingredient 1 part of epichlorohydrin 94 parts of gasoline (boiling point 160-190 ° C); b) 95 9s parts of active ingredient 5 parts of epichlorohydrin.

Example 1 A. Preparation of 3- (2 ', 2'-dichloro-1'-bromovinyl) -2,2-dimethylcyclopropane carboxylic acid To a solution of 1.34 g of sodium in 80 ml of ethanol, 14.75 g of 3- ( 2 ', 2'-dichloro-1', 2'-dibromo) -2,2-dimethyl-cyclopropanecarboxylic acid was added. The mixture is then stirred under reflux for four hours, cooled and poured into ice water. made alkaline and extracted with ether. The aqueous layer is acidified and extracted with hexane. After drying the hexane layer with sodium sulfate and distilling off the hexane, the compound of the formula is obtained with a boiling point of 1100 C / O, OO1 Torr.

B. Preparation of 3- (1-bromo-2,2-dichlorovinyl) -2,2-dimethylcyclopropane carboxylic acid α-cyano-3'-phenoxybemzyl ester.

11.0 g of 3-bromo-2,2-dichlorovinyl) -2,2-dimethyl-cyclopropanecarboxylic acid chloride in 9 ml of benzene become a solution of 8 g of cyano-3-phenoxybenzyl alcohol, 3 ml Pyridine and 40 ml of benzene were added dropwise at 10-150C. The reaction mixture is under nitrogen stirred at room temperature for ten hours.

Then the mixture is poured into ice water. The organic layer is washed with 3% hydrochloric acid, water, 3% sodium bicarbonate solution and again with water. After drying over sodium sulfate and distilling off the benzene, the compound of the formula is obtained as a viscous liquid with a refraction of nD20 = 1.5738.

The following connection is also established in the same way: Example 2 A) Insecticidal food poison effect Cotton plants were sprayed with a 0.05% aqueous active substance emulsion (obtained from an above emulsifiable concentrate). After the coating had dried on, the cotton plants were each populated with Spodoptera littoralis and Heilothis virescens larvae L3. The soil test was carried out at 240C and 60% relative humidity.

The compounds according to Example 1 showed good results in the above test insecticidal feed poison effect against Spodoptera and Heliothis larvae.

B) Systemic insecticidal effect To determine the systemic In effect, bean plants (Vicia faba) with roots in an 0.1% aqueous solution Active ingredient solution (obtained from a 10% additive concentrate) set. After 24 hours, aphids (Aphis fabae) were found on the above-ground parts of the plant. set. Thanks to a special device, the animals were protected from contact and gas effects protected. The experiment was carried out at 24 ° C and 70% relative humidity.

The compounds according to Example 1 showed systemic in the above test insecticidal effect against Aphis fabae.

Example 3 Action against Chilo supressalis 6 rice plants each of the variety Caloro were placed in plastic pots with a top diameter of 17 cm. transplanted and raised to a height of approx. 60 cm. The infestation with chilo suppressalis larvae (L1: 3-4 mm long) took place 2 days after the addition of the active ingredient in Granulate form (application rate 8 kg of active substance per hectare) into the paddy water. The insecticidal activity was evaluated 10 days after the granules had been added.

The compounds according to Example 1 were effective against chilo in the above test suppressalis.

Example 4 Acaricidal activity 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 250 C.

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

Example 5 Action against soil nematodes To test the action against Soil nematodes became the active ingredients in through root cell nematodes (Meloidogyne arenaria) infected soil and mixed thoroughly. In the earth prepared in this way Tomato seedlings were planted and immediately afterwards in a series of experiments In another series of experiments, tomato seeds were sown after a waiting period of 8 days.

The nematicidal activity was assessed 28 days after planting or after sowing the galls present on the roots are counted. In this test the active ingredients according to Example 1 showed a good action against Meloidogyne arenaria.

Example 6 Effect against ticks A) Rhipicephalus bursa 5 adults each Ticks or 50 tick larvae were counted in a glass tube and counted for 1 to 2 Minutes in 2 ml of an aqueous emulsion from a dilution series of 100 each, 10, 1 or 0.1 ppm test substance immersed. The tube was then standardized with a Cotton ball closed and turned upside down, so that the active ingredient emulsion could be absorbed by the wadding.

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

Example 7 Action against Erysiphe graminis on Hordeum vulgare Ca. Barley plants 8 cm high were prepared with a wettable powder of the active ingredient Spray mixture (0.05% active substance) sprayed. After 48 hours the treated Plants pollinated with conidia of the fungus. The infected barley plants were placed in a greenhouse at about 22 ° C. and assessed the fungal attack after 10 days.

The compounds according to the example were effective against Erysiphe in this test graminis.

Claims (9)

Claims .1. A compound of the formula where X1 and X2 are each methyl, fluorine, chlorine or bromine, -X3 is chlorine or bromine, R1 is hydrogen or methyl, R2 is hydrogen, methyl, cyano or ethynyl and Y1 and Y2 are each hydrogen or halogen. 2. A compound according to claim 1, wherein X1 and Y2 are each chlorine, X3 Bromine, R1 denote methyl, R2 denote hydrogen or cyano and Y1 and Y2 each denote hydrogen. 3. The compound according to claim 2 of the formula 4. The compound according to claim 2 of the formula 5. Process for the preparation of a compound 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 reacted, in which R11 R2 X1 to X3, Y1 and Y2 have the meaning given in claim 1 and X stands for a halogen atom. 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 of various animal and vegetable pests. 8. Use according to claim 7 for combating insects and representatives of the order Acarina 9. A compound of the formula where X1 and X2 are each methyl, fluorine, chlorine or bromine, X3 is chlorine or bromine, R1 is hydrogen or methyl and Y is hydroxyl, halogen or C1-C4-alkyl.