DE3040439A1 - N-Methyl-N-amino:sulphinyl-carbamate derivs. - prepd. from thio-substd. oxime n-chloride sulphinyl-carbamate and (alkoxy)amine - Google Patents

Abstract

Oxime N-methyl-N-(aminosulphinyl)carbamate derivs. are cpds. of formula (R1)(R2)N-SO-N(Me)-CO-O-R3 (I) (where R1 is H or 1-6C alkyl; R2 is 1-6C alkyl or 1-6C alkoxy; R3 is -N:CH-C(Me)2-S-Me or -N:C(R5)-SR4; R4 is 1-3C alkyl or allyl; and R5 is 1-4C alkyl, -CONH2 or -CON(Me)2). (I) are pesticides useful esp. as insecticides and acaricides against phytopathogenic organisms as well as against flies, e.g. Musca domestica and mosquito larvae. (I) are also active against phytopathogenic nematodes.

Description

New sulfinylamides

The present invention relates to sulfinylamides, processes for their Manufacture and its use in pest control.

The sulfinylamides have the formula where R1 is hydrogen or C1-C6-alkyl, R2 C1-C6-alkyl or C 1-C6-alkoxy, R4 is C1-C3-alkyl or allyl and R5 is C1-C4-alkyl, -CONH2 or -CON (CH3) 2.

The alkyl and alkoxy groups which come into question for R1, R2, R4 and R5 can be straight-chain or branched. Examples of such groups include methyl, methoxy, ethyl, ethoxy, isopropyl, n-propy; n-, i-, sec-, tert-butyl, n-pentyl, n-hexyl and their isomers. Because of their action, preference is given to compounds of the formula I in which R1 is C1-C6-alkyl, R2 is C1-C6-alkyl, methoxy or ethoxy, R4 is methyl, ethyl or allyl and R5 is methyl, -CONH2 or -CON (CH3) 2.

Of particular importance, however, are compounds of the formula I in which R1 is methyl, R2 is methyl, methoxy or ethoxy, R4 and R5 each represent methyl.

The compounds of the formula I can be prepared by methods known per se, for example as follows: 0 0 R 11 CH3 1) to + ClS - N - C - OR3 base RH 2 0 R. I 2) l) -SOC1 + HN - C - OR R 1 CH3 <1V) 3 (V) In the formulas II-to V, R1 to R3 have the meaning given for the formula I. Suitable bases for processes 1 and 2 are pyridine, alkylpyridines such as picolines and lutidines; tertiary amines and alcoholates such as potassium tert-butoxide are suitable.

The procedures 1 and 2 are carried out at normal pressure, a temperature between -20 to 100 ° C, preferably between -10 to 50 ° C and optionally in an inert Solvent carried out. Suitable solvents are, for example, ether and ethereal Compounds such as diethyl ether, di-isopropyl ether, dioxane, tetrahydrofuran; aliphatic and aromatic hydrocarbons such as chloroform, 1,2-dichloroethane, carbon tetrachloride, Benzene, toluene, xylenes; and ketones such as acetone, methyl ethyl ketone and cyclohexanone.

The starting materials of formulas II, IV and V are known while some of the starting materials of formula III are new. All raw materials can but can be prepared by known methods. The compounds of formula I are suitable to combat various animal and vegetable pests, e.g. against phytopathogenic nematodes.

In particular, however, the compounds of formula 1 are suitable for inoculation from insects, phytopathogenic mites and from ticks e.g. of the order Lepidontera, Coleoptera, Homoptera, Reteroptera, Diptera, Akarina, Thysanoptera, Orthoptera, Anoplura, Siphonaptera, Mallophaga, Thysanura, Isoptera, Psocoptera and Hymenoptera In particular, compounds of the formula 1 are suitable for combating plants which are harmful to plants Insects, in particular plant-damaging feeding insects, in ornamental and useful plants, especially in cotton crops (e.g. against Spodoptera littoralis and Heliothis virescens) and vegetable cultures (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 bn. 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; pyrethrin-like compounds as well as carbamates and chlorinated hydrocarbons.

With particular advantage, compounds of the formula I are also with Combined substances that exert a synergistic or intensifying effect. Examples of such compounds include piperonyl butoxide, propynyl ether, propinyloxime, Propynyl carbamates and propynyl phosphonates, 2- (3,4-methylenedioxyphenoxy) -3,6,9-trioxaundecane (Sesamex or Sesoxane), S, S, S-tributylphosphorotrithioate, 1,2-methylenedioxy-4- (2-octylsulfinyl) propyl benzene.

Compounds of the formula I can be used alone or together with suitable carriers and / or additives are used.

Suitable carriers and additives can be solid or liquid and correspond to the substances customary in formulation technology, such as

natural or regenerated substances, solvents, dispersants, wetting agents, Adhesives, thickeners, binders 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, granulates (coating granulates, impregnation granulates and Romogen granules); Liquid working-up forms: a) in water dispersible 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 of up to 99.5% or even pure active ingredients can be used. The active ingredients of formula I can be formulated as follows (parts mean parts by weight): Dust: The following are used to produce a) 5% and b) 2% dust Substances used: a) 5 parts of active ingredient 95 parts of talc; b) 2 parts of active ingredient 1 part 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 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 mmß The active ingredient is mixed with epoxidized vegetable oil and dissolved with 6 parts of acetone, then polyethylene glycol and cetyl polyglycol ether added. The solution obtained in this way is sprayed onto kaolin and then the acetone evaporated in vacuo.

Wettable powder: For the production of a) 40%, b) and c) 25%, d) The following constituents 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 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 is intimately mixed with the additive in suitable mixers mixed and milled 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 of a combination emulsifier, Consists 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) 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 limits 160-1900C); b) 95 parts of active ingredient 5 parts epoxidized vegetable oil.

Example 1: Preparation of the carbamate of the formula To 9.5 g of the compound of the formula 4.8 g of pydridine dissolved in 50 ml of tetrahydrofuran are added dropwise at 0-5 "C. 6.5 g of thionyl chloride are added dropwise after stirring for four hours at 200.degree. C., first 4.8 g of pyridine and finally at 0-50 C. 3; 1 g of methoxymethylamine are slowly added After stirring for a further four hours at 200 ° C., the mixture is diluted with 400 ml of ether and extracted twice with 75 ml of water 200 and a refraction of nD = 1.5064.

The following connections are also established in the same way: Example 2: Insecticidal feeding poison effect: Spodoptera littoralis, Dysdercus fasciatus and Heliothis virescens A) wool plants were sprayed with an aqueous emulsion containing 0.05% of the compound to be tested.

After the covering had dried on, the plants each had larvae of the species Spodoptera littoralis (L3 stage), Dysdercus fasciatus (L4) or. Heliothis virescens (L3) occupied. One used per test compound and per test species two plants and an evaluation of the mortality rate achieved was carried out after 2, 4, 24 and 48 hours. The experiment was carried out at 240C and at 60Z relative humidity carried out.

The compounds according to Example 1 showed a in the above experiment good activity against larvae of the species Spodoptera littoralis, Dysdercus fasciatus and Heliothis virescens.

B) Systemic insecticidal effect: To determine the systemic Effect were rooted bean plants (Vicia faba) in an 0.1% aqueous solution Active ingredient solution set. After 24 hours they were on the aboveground Po man zenteile aphids (Aphis fabae) set. Through a special facility were the animals are protected from contact and gas effects.

The experiment was carried out at 240 ° C. and 70% relative humidity.

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

Example 3: Insecticidal food poison effect: Leptinotarsa decemlineata With the same procedure using larvae of the species Leptinotarsa decemlineata (L3) and potato plants instead of cotton plants was the one in Example 2 described experimental method repeated.

The compounds according to Example I had a good effect against Larvae of the species Leptinotarsa decemlineata.

Example 4: Action against acarids which are harmful to plants: Tetranychus urticae (OP-sensitive) and Tetranychus cinnabarinus (OP-tolerant) The primary leaves of Phaseolus vulgaris plants were acaricidal 16 hours before the test Effect with an infected piece of leaf from a mass cultivation of Tetranychus urticae (OP-sens.) or Tetranychus cinnabarinus (OP-tol.). (The tolerance refers to the tolerance of Diazinon).

The infected plants treated in this way were tested with one solution containing 400 or 200 ppm of the compound to be tested up to dripping wet sprayed.

After 24 hours and again after 7 days, adults and larvae became (all moving stages) evaluated under the binocular for living and dead individuals.

One plant was used per carpal center and per test species. During the course of the experiment, the plants stood in greenhouse cabins at 25 ° C.

The compounds according to Example 1 showed a in this experiment positive effect against individuals of the species Tetranychus urticae and Tetranychus cinnabarinus.

Example 5: Action against Rhipicephalus bursa (adults and larvae), Amblyomma hebraeum (+ adults, nymphs and larvae) and Boophilus microplus (larvae - OP-sensitive and OP-tolerant) The test objects are larvae (approx. 50 each), nymphs (approx. 25 each) or adults (approx. o each) of Rhipicephalus bursa, Amblyomma hebraeum and Boophilus microplus are used. The test animals will be for a short time in an aqueous emulsion or solution containing 0.1; 1.0; 10; 50 or 100 ppm of the connection to be tested immersed.

The emulsion or solutions in test tubes were then taken up with cotton wool and the wetted test animals in the so cotaminated tubes left.

An evaluation of the kill rate achieved at each concentration took place after 3 days for larvae and after 14 days for nymphs and adults.

The compounds according to Example 1 showed a in this experiment good effect against larvae, nymphs and adults of the species Rhipicephalus bursa and Amblyomma hebraeum and against larvae (OP-res. and OP-sens.) of the species Boophilus microplus.

Example 6: Action against Musca dcmestica 50 g of freshly prepared each CSSA nutrient substrate for the was weighed into beakers. From a 1% by weight aqueous Formulation of the active ingredient in question was a certain amount on the in The nutrient substrate located in the cups is pipetted.

Then there were 25 one-day times per active ingredient and concentration of Musca domestica in the beaker containing the thus treated nutrient substrate. After the maggots pupated, the pupae formed were flushed out separated from the substrate with water and placed in vessels closed with sieve lids deposited.

The pupae flushed out per batch were counted (toxic influence of the active ingredient on the maggot development). Then after 10 days the number of the flies hatched from the pupae are determined.

The compounds according to Example 1 showed a good effect in the above Test.

Example 7: Action against Ades aegypti on the surface of 150 ml of water in a container became so much of an 0.15% emulsion preparation of the active ingredient are pipetted into concentrations of 10.5 and 1 ppm each became. Then the container was loaded with 30-40 2-day Aedes larvae. To Mortality was checked for 1, 2 and 5 days.

The compounds according to Example I showed a good effect in this test against Alldes aegypti.

Example 8: Action against soil nematodes To test the action against Soil nematodes were the active ingredients in the specified concentration in soil infected by root cell deaths (Meloidogyne arenaria) and intimately mixed. Immediately afterwards tomato seedlings were placed in the soil prepared in this way in a test series planted and in another series of experiments sown tomatoes after a waiting period of 8 days.

To assess the nematocidal effect, 28 days after Plants or, after sowing, the galls present on the roots are counted.

In this test, active ingredients according to Example 1 showed a good effect against Meloidogyne arenaria.

Claims (9)

Claims A compound of the formula where R1 is hydrogen or C1-C6-alkyl, R2 C1-C6-alkyl or C1-C6-alkoxy, R4 denotes C1-C3-alkyl or allyl and R5 denotes C1-C4-alkyl, -CONH2 or -CON (CH3) 2. 2. A compound according to claim 1, wherein R1 is C1-C5-alkyl, R2 is C1-C6-alkyl, methoxy or ethoxy, R4 is methyl, ethyl or allyl and R5 is methyl, -CONH2 or -CON (CH3) 2. 3. A compound according to claim 2, wherein R1 is methyl, R2 is methyl, kethoxy or ethoxy, R4 and Rs each mean methyl. The compound according to claim 3 of the formula 5. The compound according to claim 3 of the formula 6. Process for the preparation of compounds according to claim 1, characterized in that a compound of the formula in the presence of a base with a compound of the formula lets react, wherein R1, R2 and R3 have the meaning given in claim 1. 7. A pesticide in addition to a suitable one Carrier and / or other aggregate as an active component a compound according to Claim 1 contains. 8. Use of a compound according to claim 1 for combating various animal and vegetable pests. 9. Use according to claim 8 for combating insects and representatives of the order Akarina.