DE2719561A1 - Insecticidal chrysanthemumic acid esters - esp. effective against Spodoptera littoralis and Leptinotarsa decemlineata - Google Patents

Abstract

Chrysanthemumic acid esters of formula (I) are new (where R1 is H or Me; R2 is H, CN or -C CH; R3 is F, Cl, Br, or Me; and R4 is F, Cl or Br). (I) can be used to control various animal and plant pests. (I) are effective against phytopathogenic mites and against ticks of the Dermanyssidae and Ixodidae families, but are esp. effective against insects e.g. Tethigoniidae, Blattidae and Pyrrhocoridae. (I) are esp. effective against plant-eating insects, in partic. those in cotton plants (e.g. against Spodoptera littoralis and Heliottris virescens) and vegetables (e.g. against Leptinotarsa decemlineata and mycus persicae). (I) may also be used against flies e.g. Musca domestica and midges. (I) are more effective against Spodoptera littoralis and Leptinotarsa decemlineata than (I; R1 = Me, R2 = H, R3 = Me and R4 = Me) (see JA 4720339) Specifically claimed is (I; R1 = Me, R2 = H, R3 and R4 = Cl). (I) can be prepd. by conventional esterification e.g. between a substd. cyclopropane carboxylic acid and a halide of the thiazole component.

Description

Chrysanthemum acid esters, process for their preparation and

The pesticide used in Japanese Patent Application No. 4720339 is the compound of the formula described as an insecticide.

In contrast, the present invention relates to chrysanthemum acid esters of the formula Where R1 signifies hydrogen or methyl, R2 signifies hydrogen, cyano or -C # CH, R3 signifies fluorine, chlorine, bromine or methyl and R4 signifies fluorine, chlorine or bromine, processes for their production and their use for controlling pests.

The compounds of the formula I are prepared according to methods known per se, for example as follows: In formulas II to VI, R1 to R4 have the meaning given for formula I.

In the formulas III and IV, X fUt eiii is, in particular, chlorine or Bromine and in the formula VI R is C1-C4-alkyl, in particular methyl or Ethyl.

Acid-binding agents for processes 1 and 2 are particularly useful tertiary amines, such as trialkylalnines and pyridine, and also hydroxides, oxides, carbonates and bicarbonates of alkali and alkaline earth metals and alkali metal alcoholates such as e.g.

Potassium t-butylate and sodium methylate can be considered. As a water-binding Agent for method 3, for example, dicyclohexylcarbodiimide can be used. the Process 1 to 4 are usually at a reaction temperature between -10 and 100 ° C between 20 and 800C, at normal or increased pressure and preferably in one inert solution :: - or diluent carried out.

Suitable solvents or diluents are, for example, ethers and ethereal ones Compounds such as didthyl 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 acutonitrile; Dimethyl sulfoxide and ketones such as acetone and methyl ethyl ketone. Process 2 can also be carried out in aqueous solution.

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

One method of preparing the compound of formula I is in the example 1 described.

The compound of the formula I is optically as a mixture of different active isomers before, if not uniformly optically active during manufacture Ausgarjgsstoffe were used. The various stable mixtures of isomers can be separated into the individual isomers by known methods. inks the compound of the formula I is understood to mean both the individual isomers and mixtures thereof, The compounds of the formula I are suitable for combating various types animal and vegetable pests.

Surprisingly, compounds of the formula I are better suited to control insects such as Spodoptera littoralis and Leptinotarsa decemlineata, than the analogous compound known from Japanese Patent Publication No. 4720339.

So they can be used to combat representatives of phytopathogenic mites for example from the genus Tetranychus and Panonychus as well as ticks of the family Dermanyssidae and Ixodidae are used. However, they are particularly suitable to control insects e.g. of the families Tettigoniidae, Gryllidae, Gryllotalpidae, Blattidae, Reduviidae, Pyrrhocotidae, Cimicidae, belphacidae, Aphididae, Diaspididae, Pseudococcidae, Scarabaeidae, Dermestidae, Coccinellidae, Tenebrionidae, Chrysomelidae, bruchidae, Tineidae, Noctuidae, Lymantriidae, Pyralidae, Culicidae, Tipulidae, Stomoxyde, Trypetidae, Muscidae, Calliphoridae and Pulicidae.

in particular, compounds of the formula I are suitable for combating of plant-damaging insects, especially plant-damaging feeding insects, in ornamental and useful plants, especially in cotton kuittirs (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 Musda 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.

Organic phosphorus compounds, for example, are suitable as additives; Nitrophenols and their Deriavte; Formamidine; Ureas; other pyrethrin-like compounds; oWi carbamates and chlorinated hydrocarbons.

Compounds of the formula I are also particularly advantageous with substances combined, have a synergistic bath enhancing effect on pyrethroids exercise. Examples of such compounds include piperonyl butoxide, propynyl propynyloxime, Propynyl carbamate ether / and propynyl phosphonate, 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 can be used alone or together with suitable carriers and / or additives are used. Suitable aggregates can be test or liquid and correspond to those commonly used in formulation technology Substances such as natural or regenerated substances, solvents, dispersants, Wetting, adhesive, thickening, dying 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 deh suitable excipients, optionally below the addition of the active ingredients inert dispersing or solvents.

The active ingredients can be in the following working-up forms and are used: Solid processing forms: dusts, grit, granulates (Coated granules, impregnation granules and homogeneous granules): Liquid processing forms: n) Active substance concentrates dispersible in water: wettable powders, Pastes, emulsions; b) Solutions About content of active ingredient in the The means described above is between 0.1 and 95%, it should be mentioned that when applying from the aircraft or using other suitable application devices Wetden can use concentrations up to 99.5% or even pure active ingredient.

The active ingredients of the formula I can, for example, be formulated as follows (parts mean parts by weight): Dust: For the production of a) igen and b) 2% dust, the following substances are used: a) 5 parts of active ingredient, 95 parts of talc; b) 2 parts of active ingredient, 1 part of highly disperse silica, 97 parts Talc.

The active ingredient is mixed with the carrier pods 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 substance is mixed with epichlorohydrin and made up of 6 parts Dissolved acetone, then polyethylene glycol and cetyl polyglycol ether are added. The solution obtained is sprayed onto kaolin and then the acetone evaporated in a vacuum.

Spray powder: To create 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 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 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 aggregate substance in suitable mixers mixed and ground on appropriate moles and rollers. Injection powder is obtained, which can be diluted with water to form suspensions of the desired concentration.

Emulsifiable concentrates: For the production of a) 10% b) 25% and c) 50% emulsifiable concentrate, the following substances are used: n) 10 Parts of active ingredient, 3.4 parts of 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 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 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) gene and b) 95% spray the following ingredients are used: a) 5 parts of active ingredient, 1 part of epichlorohydrin, 94 parts of gasoline (boiling limits 160-1900C); b) 95 parts of active ingredient, 5 parts of epichlorohydrin.

Example 1 Preparation of 2-Benzyl-4-methyl-1,3-thiazol-5-yl-methyl-2,2-dimethyl-3- (2,2-dichlorovinyl) -cyclopropanecarboxylic acid ester.

To a solution of 3.5 g of 2,2-dimethyl-3- (2,2-dichlorovinyl) -cyclopropane carboxylic acid chloride and 3.7 g of 2-benzyl-4-methyl-5-hydroxymethyl-1,3-thiazole in 40 ml Toluene is added dropwise 1.5 g of pyridine at room temperature. The mixture is stirred for 12 hours at room temperature. After washing neutral, drying and distilling off the solvents, the compound of the formula is obtained 210 as a light yellow oil with a refraction of nD = 1.5615.

Example 2 A) Insecticidal food poison effect Tobacco and potato plants were with a 0.05% aqueous active substance emulsion (obtained from a 10% emulsifiable concentrate).

After the topping had dried on, the tobacco and potato plants were grown with caterpillars of spodoptera littoralis in the L3 stage and of Heliothis virescehs in the L3 stage occupied.

The experiment was carried out at 24 ° C. and 60 ° C. relative humidity.

The connection according to Example 1 showed a positive in the above test Food poison effect against Spodoptera littoralis and lleliothis viresecns caterpillars.

B) Insecticidal contact effect in the day before application of the active ingredient broad beans (Vicla faba) with about 200 aphids (Aphis fabae) infected per plant. The application of a spray mixture in one concentration of 1000 ppm (made from a 25% wettable powder) was carried out by means of a l) compressed air syringe on the lice-covered blStttr.

The rating took place 24 hours after the application.

The compound according to Example 1 showed good contact action in the above test new Aphis fabae.

Claims (6)

Patent claims 4) A compound of the formula where R1 is hydrogen or methyl, R2 is hydrogen, cyano or -C = -CH, R3 is fluorine, chlorine, bromine or methyl and R4 is fluorine, chlorine or bromine. 2. The compound according to claim 1 of the formula 3. Process for the preparation of compounds according to claim 1, characterized. that you can get a compound of the formula in the presence of an acid-binding agent with a compound of the formula reacted, in which R1 to R4 have the meaning given in claim 1 and X stands for a halogen atom. 4. Pesticide, which is an active component Compound according to claim 1 and suitable carriers and / or other additives contains. 5. Use of compounds according to claim 1 for combating various animal and vegetable pests. 6. Use according to claim 5 for combating insects.