DE2528345A1 - Alkynyl diphenyl (thio) ethers and amines - with insecticidal and acaricidal activity - Google Patents

Abstract

Alkynyl diphenyl cpds. of formula (I) are new (where n = 0 or 2; R1 is H or Me; R2 is H, Me or halogen; Y is O, SO, S, SO2, SO3 or CH2S; Z is O, S r NH; with the proviso that T2 is Me or halogen when Y-S, Z=O, R1=H and n = 0). and have insecticidal and acaricidal activity e.g. against Dysdercus fasciatus larvae, Aedes aegypti larvae, Tenebrio molitor pupae, Ephestia kuhniella larvae and Tetranychus urticae (eggs, larvae and adults).

Description

"Phenylalkynyl ethers, process for their preparation and.

Pesticides "The present invention relates to phenylalkynyl ethers, Processes for their production and their use in pest control, The phenyl alkynyl ethers have the.

formula where n is the number 0 or 2, R1 is hydrogen or methyl, R2 is hydrogen, methyl or halogen, Y -O-, -S-, or -CIiS-Z -O-, -S- or -NH- are, where, when Y = S, Z = O, R1 = hydrogen and n = O, R2 is methyl or halogen.

The compounds of the formula I are prepared by methods known per se, for example as follows: ZM R1 Base XCHCH2) CH base> 1 (11) (III) In the formulas II and III, n, R1, R2, Y and Z have the meaning given for the formula I and X stands for a halogen, in particular for chlorine or bromine and M for a metal of the 1st or 2nd main group of the periodic table, especially for sodium, potassium or calcium.

A.B. in question: tertiary amines, such as trialkylamines, Pyridine, dialkylanilines; also inorganic bases such as hydrides, hydroxides, alkoxides and carbonates of alkali and alkaline earth metals.

The process is preferred at a reaction temperature of 0-1500C at 0-80 ° C, at normal pressure and in the presence of inert solvents or diluents carried out.

Suitable solvents or diluents are e.g.

Ethers, such as diethyl ether, diisopropyl ether, 1,2-dimethoxyethane, dioxane, Tetrahydrofuran; N, N-dialkylated carboxamides such as dimethylformamide; Ketones such as acetone, methyl ethyl ketone or cyclohexanone and hexamethylphosphoric acid triamide, Dimethyl sulfoxide or C2-C5-A1 alcohols such as isopropanol. . The starting materials the Formulas II and III are known compounds or can be analogous known methods described in the literature are prepared.

Compounds of formula 1 are suitable for combating various types animal and vegetable pests.

In particular, they are suitable for combating insects of the families: Acrididae, Blattidae, Gryllidae, Gryllotalpidae, Tettigoniidae, Cimicidae, Pyrrhocoridae, Reduviidae, Aphididae, Delphacidae, Diaspididae, Pseudococcidae, Chrysomelidae, Coccinellidae, Bruchidae, Scarabaeidae, Dermestidae, Tenebrionidae, Curculionidae, Tineidae, Noctuidae, Lymantriidae, Pyralidae, Galleridae, Culicidae, Ti.pulidae Stomoxydae, Muscidae, Calliphoridae, Trypetidae, Pulicidae as well as acarids of the families: Ixodidae, Argasidae, Tetranychidae, Dermanyssidae.

The insecticidal effect can be increased by adding other insecticides and / or widen acaricides significantly - and adapt to given circumstances.

Examples of suitable additives are: organic phosphorus compounds, nitrophenols and derivatives, Formamidine, ureas> carbamates or chlorinated Hydrocarbons, pyrethroids.

bit compounds of the formula I are known individually or together can be used with suitable carriers and / or additives. Suitable carriers and aggregates can be solid or liquid and correspond to those used in formulation technology Usual substances such as natural or regenerated substances, solution, dispersing Wetting agents, adhesives, thickeners, binders and / or fertilizers.

For application, the compounds of the formula I can be converted into dusts, Emulsion concentrates, granules, dispersions, sprays, to solutions or slurries in the usual formulation, which is part of general knowledge in application technology, are processed.

The agents according to the invention are prepared in a manner known per se Way by intimately mixing and / or grinding 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 are available in the following working-up forms and are used: Fixed forms of processing: dust, Litter, granules, coating granules, impregnation granules and homogeneous granules Liquid processing s forms a) Active ingredient concentrates dispersible in water: Wettable powders, pastes, emulsions; b) Solutions The content of active ingredient in the means described above is between 0.1 and 95%.

The active ingredients of the formula I can, for example, be formulated as follows : Dusts: For the production of a) 5% 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 of talc The active ingredients are mixed with the carrier materials 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 polyethylene glycol 91 parts kaolin (grain size 0.3-0.8 mm).

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

Slaritz powder: For the production of a) 40%, b) and c) 25% and d) 10% wettable powder, the following ingredients are used: a) 40 parts Active ingredient 5 parts of sodium lignin sulfonic acid, 1 part of sodium dibutylnaphthalene sulfonic acid, 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 silica, 19.5 parts of champagne chalk,, 28.1 parts Kaolin; c) 25 parts of active ingredient 2.5 parts of isooctylphenoxt-polyethylene sthanol, 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 mixture of Sodium salts of saturated fatty alcohol sulfates, 5 parts of naphthalene sulfonic acid 1-formaldehyde condensate, 82 parts kaolin The active ingredients are mixed with the additives in suitable mixers intimately 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: The following substances are used to produce a) 10% b) 2570 and c) 50% emulsifiable concentrate: a) 10 parts of active ingredient, 3.4 parts of epoxidized vegetable oil, 3.4 parts of a combination emulsifier from fatty alcohol polyoxyethylene 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 alkyarylsulfonate / 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 calcium dodecylbenzenesulfonate 20 parts cyclohexanone 20 parts xylene from such Concentrates can be diluted with water to create emulsions of any desired concentration getting produced.

Spray: To produce a) 5% 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 - 1900) b) 95 parts of active ingredient 5 parts of epichlorohydrin Example 1 Production of 5- (4-phenylmercapto-phenylthio) -pentine-1 In a solution of 24g (O.IIIM) 4-mercaptodiphenyl sulfide, 12.6g (O.IIIM) solid potassium tert. butoxide was added and the mixture was stirred at room temperature for 20 minutes. 10.2 g of (O.lOM) 5-chloropentin-1 are added dropwise over the course of 10 minutes and the mixture is stirred for 18 hours at room temperature. For working up, the reaction mixture is poured into water and extracted with ether. The separated ether phase is washed three times with 10% potassium hydroxide solution and then four times with saturated sodium chloride solution. After the ether extract has been dried over sodium sulfate, the solvent is distilled off in vacuo. The oily residue is chromatographed on silica gel with ether: hexane = 1: 3 as the eluent. The compound of the formula is obtained 200 as a colorless oil with a refractive index of nD = 1.6432 Example 2 Preparation of 5- (4-phenylmercapto-phenoxy) -pentine-1 To a solution of 22.2 g (0; 11M) 4-hydroxydiphenyl sulfide in 80 ml of anhydrous dimethyl sulfoxide 12.6 g (0.11M) of solid potassium tert. butoxide was added and the mixture was stirred at room temperature for 20 minutes. 10.2 g (0.10M) of 5-chloropentine-1 are added dropwise over the course of 10 minutes and the mixture is stirred at room temperature for 18 hours. For working up, the reaction mixture is poured into water and extracted with ether. The separated ether phase is washed three times with 1070 potassium hydroxide solution and then four times with saturated sodium chloride solution. After the ether extract has been dried over sodium sulfate, the solvent is distilled off in vacuo. The oily residue is chromatographed on silica gel with ether: hexane = 1: 3 as the eluent. The compound of the formula is obtained after crystallization from petroleum ether, melting point 35 - 36oC.

The following connections are also established in the same way: nD20 = 1.6739 m.p. 43-45 ° C nD20 = 1.5978 m.p. 73-750C m.p .: 55-57 ° C m.p. 150 ° -151 ° C m.p. 127-128 ° C m.p. 80-830C M.p. 61-62 ° C nD20: 1.6101 nD20: 1.5558 m.p. 63-65 ° C nD20: 1.7095 m.p. 34-35 ° C nD20: 1.5980 nD20: 1.6158 nD: 1.6037 20 nD: 1.6100 m.p. 45-460C Example 3 A) Contact effect on Dysdercus fasciatus larvae A certain amount of a 0.1% acetone solution (corresponding to 10 mg AS / m2 ) was pipetted into an aluminum dish and distributed evenly.

After the acetone had evaporated, some Food and moist cotton wool contained 10 larvae of the 5th instar of Dysdercus fasciatus given. The bowl was then covered with a sieve lid. After approx. 10 days, i.e. as soon as the control animals reach the Had completed adult moult, the test animals were examined according to the number of normal adults.

Compounds according to Example 1 and 2 showed a good effect in the above Test.

B) Contact effect on A'edes aegypti larvae Contained in a cup a solution of the active ingredient (concentration 5 ppm) were about 20 2-day Larvae of the yellow fever mosquito of the Egyptian). The mug was then equipped with a Sieve lid covered. After the control animals had completed their adult moulting, were the test animals examined and the percentage of normal adults compared intended for control.

Compounds according to Example 1 and 2 showed a good effect in the above Test.

C) Contact effect on Tenebrio molitor dolls A certain amount a 0.1% acetone active ingredient solution corresponding to 10 mg AS / m² was in a Aluminum dish pipetted and evenly distributed.

After the acetone had evaporated, 10 freshly skinned pupae were produced placed on the treated area. The bowl was covered with a sieve lid.

After the control animals had left the doll casing as adults, the test animals were examined according to the number of normal adults.

Compounds according to Example 1 and 2 showed a good effect in the above Test.

Example 4 Effect against Ephestia kUhniella 50 g of wheat flour were used mixed in two cups with a certain amount of active ingredient formulated as 5% dust, so that the concentration was 0.05%.

10 larvae of Ephestia kUhniella were added per cup (25 g flour). The course of the population and the number were recorded over the course of 8 weeks the moth noted.

Compounds according to Example 1 and 2 showed a good effect in the above Test.

Example 5 Action against spider mites Phasedkis vulgaris (French beans) were tested for acaricidal activity with an infected piece of leaf 12 hours before the test from a mass breed of Tetranychus urticae.

The spilled mobile stages were obtained from a chromatography nebulizer dusted with the emulsified test preparations in a concentration of 0.04% that no drainage of the spray series occurred. After two to 7 days, larvae became adults and eggs under the dissecting microscope on living and dead individuals evaluated and the result expressed as a percentage. During the "holding time" the treated ones stood Plants in greenhouse cabins at 250C.

Compounds according to Example 1 and 2 showed a good effect in the above Test against eggs, larvae and adults of Tetranychus urticae.

Claims (7)

Claims A compound of the formula where n is the number 0 or 2, R1 is hydrogen or methyl, R9 is hydrogen, methyl or halogen, Y -O-, -S-, or -CH2S-Z is -O-, -S- or -NH-, where, when Y = S, Z = O, R1 = hydrogen and n = O, R2 is methyl or halogen. 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) Process for the preparation of compounds according to Claims 1 to 4, characterized in that a compound of the formula in the presence of a base with a compound of the formula lets react, in which n, R1, R2, Y and Z have the meaning given in claim 1 and X is a halogen and M is a metal of the 1st or 2nd main group of the periodic table. 6) Pesticides which, as the active component, have a Compound according to claims 1 to 4 and suitable carriers and / or other additives contain. 7) Use of compounds according to Claims 1 to 4 for combating of insects and representatives of the order Akarina.