IL27735A - Oximecarbamates,their preparation and their use as insecticides and acaricides - Google Patents

Description

27735/2 Λτ+ρ ΉκρκΛ θ' ηπ '^υι Tina οπη Oximecarbamates, their preparation and their uae as insecticidea and acaricidea FARBENPABRIKEN BAYER AKTIENGESELL CflAFT C. 26282 The present Invention relates to new oximecarbamates• which have insecticidal and acaricidal properties, and to processes for their preparation* It is known to use carbamates aa ineecticidal and acaricidal active compounds. Thus* 3-eethyl-4-dimethyl-attinophenyl-N-methylcarbaaate (see U.S. Patent Specifica ion 3»t34,806), B-naphthyl-HHDethylcarbaiJ-ate (see U,3. Patent Specification 2,903,478) and ieopropylmeth lpyrazolyl-K,N-dimethylcarbaaate (see Swiss Patent Specification 282,655) play a considerable part in practice.

The new oximecarbamates according to the invention have the formula C in which R is an alkyl or phenyl radical, ia a lo¾er alkyl radical, and Eg la hydrogen or a lower alkyl radical* It has been found that the compounds according to the invention exhibit strong ineecticidal and acaricidal activities, and have at the same time low toxicity in respect of warm-blooded animals, and low phototoxicity. Their effect sets in rapidly and is long-lasting. The compounds can therefore be used with good success for the control of noxious sucking and biting inseots, Diptera as well as Bites (Acarina).

The invention also consists in processes for the preparation of the oxieecarbamatea of formula I above* By one of thea an oxine of the formula "01"■|>"'p»jf"i" OH is reacted with an isocyanate of the formula Rj H«C m 0 III ae in which formulae R and R^ hare the aame meaningabove.

By another prooeee according to the invention an oxline of formula II is reacted with a carbaaic acid chloride of the formula in which R^ and ^ have the meaning stated above.

In formula I above 6 is preferably an alkyl radical with 1-6 carbon atoms, or a phenyl radical. an alkyl radical with 1-4 carbon atoas and radical with 1-4 carbon atoas.

The first prooeee mentioned above can be Illustrated by the following equation: 0 Cg As examples of ozimee of formula II which can be used, there may b* mentioned α-methylmercapto-, o-ethylmercapto-, a-butylmercapto- and α-dodecylaercapto- as well as a-phenylmercapto-acetaldoxime.

As examples of ieooyanates of formula III there may be mentioned methyl* ethyl and butyl ieocyanate.

The reaction is carried out in the presence of an inert organic solvent* these include, for example, hydrocarbons, such as benain , bensene and toluene, chlorinated hydrocarbons, such as carbon tetrachloride and chlorobeneenes, ethers such as diethyl ether and dioxan, esters such as eth l acetate ketones such as To aocele ate the reaction, there may be added small• amounts of amine, such as triethyl amine, trimethyl amine or dimeth l-aniline.

The reaction temperature may be varied within a wide range* In general, the work ie carried out between 0 and 150°, preferably between 20 and 100°.

In general, approximately equimolecular amounts of the reactants are used. Working up may take place in the usual manner, for example by evaporating the solvent in vacuum or by filtering off the end product with suction, oxime The ege&carbamates are, in general, solid substances which crystallise well* The second process can be illustrated by the following equations 0 O-s— c** —OH + oi — σ —${a&3)2 — > + HC1 The oximes of formula II mentioned above in connection with tht first process are of course also suitable for the second process.

As examples of carbamlc acid chlorides which can be used, there may he mentioned methyl, dimethyl, ethyl and propyl carbamlc acid chloride.

The reaction is preferably effected in the presence of or of the organic solvents mentioned above.

Tor binding the liberated hydrochloric acid, the usual acid-binding agents may he used. Preferred agents include alkali metal hydroxides and alkali metal carbonates, such as sodium The reaction can be effected in the same temperature ranges as stated above.

Approximately equimolecular amounts of the reactants are in general used. The working up of the reaction mixtu e may take place in the usual manner.

As mentioned above, the compounds according to the invention can be used against sucking and biting insects, JJiptera as well as mites (Acarina).

To the sucking insects there belong, mainly, aphids, such as the peach aphid (M eus persicae), the bean aphid (Doralis fabae); scales, such as Aspidiotus hederae, Lecanium hesperidum, Pseudococcus maritimus} Thysanopter , such as hercinothrips femora-lie; and bugs, such as the beet bug (Hesma quadra a) and the bed bug (Cimex lectularius)· The biting insects comprise mainly butterfly caterpillars, such as Plutella maculipennis, Lymantria disparj beetles, such as granary weevils (Sitophilue granarlua), the Colarado beetle (Leptinotarsa -decemlineata) | and also species which live in the soil, such as wlrevorms (Agriotea sp.) and larvae of the cockchafer (Melolontha) ; cockroaches, such as the German cockroach (Blattella germanica)t Orthoptera, such as the house cricket (Gryllus domesti-cus)j termites, such as Setioulltermes; and Hymenoptera, such as ants* The Diptera comprise in particular the flies, such as the vinegar fly (Droeophila melanogaster) , the Mediterranean fruit fly (Ceratitis capitate), the house fly (Musca domestics) and gnats, such ae the mosquito (Aedee aegypti).

In the case of the mites, particularly important are the spider mites (Tetranychidae) , such as the common spider mite (Tetra- nychus urticae), the European red mite (Paratetranychus pilos e);^ blister mites, such as the currant blister mite (Erlophyes rlbls) and tarsonemlds, such as Tarsonemus pal idua; and ticks.

The active compounds according to the invention show, in particular, a strong systemic action and can therefore also be used via, for example, the soil.

The active compounds according to the invention may be converted into the customary formulations, such as solutions, emulsions suspensions, powders, pastes and granulates. These may be prepared in known manner, for example by mixing the active compounds with extenders, i.e. liquid or solid diluents or carriers, optionally with the use of surface-active agents, i.e. emulsifying agents and/or dispersing agents. In the case of the use of water as extender, organic solvents may, for example, also be used as auxiliary solvents.

As liquid diluents or carriers, there are preferably used aromatic hydrocarbons, such as xylenes or benzene, chlorinated aromatic hydrocarbons, such as chlorobenzenes, paraffins, such as mineral oil. fractions, alcohols, such as methanol or butanol, and strongly polar solvents , such as dimethylformamlde or dimethyl- sulphoxide, or water.

As solid diluents or carriers, there are preferably used ground natural minerals , such as kaolins, clays, talcum or chalk, or ground synthetic minerals, such as highly dispersed silicic acid or silicates.

Preferred examples of emulsifying agents include non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alk laryl poly- glycol ethers, alkyl sulphonates and aryl sulphonates. Preferred examples of dispersing agents include lignln, sulphite waste liquors and methyl cellulose.

The active compounds according to the invention may be pre- sent in the formulations in admixture with other active compo nder The formulations contain, in general, from 0.1 to 95, preferably from 0.5 to 90, per cent by weight of active compound.

The active compounds can be used as such, in the form of their formulations or of ready to use preparations made therefrom. Application may take place in customary manner, for example by watering, scattering, dusting or spraying.

The concentrations of active compound can, in use, be varied within a wide range. In general, active compound concentrations of 0.00001-20^, preferably of 0.01-5 , are used for actual application.

The invention therefore also provides an insecticidal or acarlcidal composition containing as active ingredient one of the new oximecarbamates in admixture with a solid diluent or carrier or in admixture with a liquid diluent or carrier containing a surface-active agent.

The invention also provides a method of combating insects and acarids which comprises applying to the insects or acarids or a habitat thereof one of the new oximecarbamates alone or In the form of a composition as above.

The insecticidal and acarlcidal activity of the new oximecarbamates is illustrated by the following Examples A-E.

Example A Plutella test Solvent: 3 parts by weight dimethylformamide Emulsifier: 1 part by weight alkylarylpolyglycol ether To produce a suitable preparation of active compound, 1 part by weight of the active compound is mixed with the stated amount of solvent containing the stated amount of emulsifier and the concentrate is diluted with water to the desired concentration.

Cabbage leaves (Brassica oleracea) are sprayed with the preparation of the active compound until dew moist and are then in- fee ed with caterpillars of the diamond-back moth (Plutella maculipennle) .

A ter the speci ied periods of time, the degree of destruction is determined as a percentage: lOOjS means that all the caterpillars are killed whereas 0£ means that none of the caterpillars are killed.

The active compounds , the concentrations of the active compounds, the evaluation times and the results can be seen from the following Table: TABLE (plant-damaging insects) Concentration Degree of Active compounds of active destruction compound in after in # 3 days Example B Myzus test (contact action) Solvent: 3 parts by weight dimethyl formamide Emulsifier: 1 part by weight alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of the active compound is mixed with the stated amount of solvent containing the stated amount of emulsifier and the concentrate Is diluted with water to the desired concentration.

Cabbage plants (Brassica oleracea) which have been heavily infested with peach aphlds (Myzus persicae) are sprayed with the preparation of the active compound until dripping wet.

After the specified periods of time, the degree of destruction is determined as a percentage: 100 means that all the aphlds are killed whereas 0% means that none of the aphlds are killed.

The active compounds, the concentrations of the active compounds, the evaluation times and the results can be seen from the following Table: TABLE (plant-damaging insects) Concentration of Degree of Active Compounds active compound destruction in i» in # after 24 hours Example C Rhopalosiphum test (systemic action) Solvent: 3 parts by weight dimethyl formamide Biaulsifier: 1 part by weight alkylaryl polyglycol ether by weight of the active compound is mixed with the stated amoturflV of solvent containing the stated amount of emulsifier and the concentrate is diluted with water to the desired concentration.

Oat plants (Arena Sativa) which have been strongly infested with oat aphids (Ehopaloslphum padi) are watered with the preparation of the active compound so that the preparation penetrates into the soil without wetting the leaves of the oat plante. (The active compound is taken up by the oat plants from the soil and thus reaches the infested leaves.

After the specified periods of time, the degree of destruction is determined as a percentage: 100 means that all the aphids are killed whereas 0% means that none of the aphids are killed.

The active compounds, the concentrations of the active compounds, the evaluation times and the results can be seen from the following Table: TABLE (plant-damaging insects) Concentration of Degree of Active compounds active compound destruction in J* in ?£· after 2 days CH, 0.2 100 0.02 100 C I = 3 N-0- NH - Concentration of Degree of Active compound active compound destruction in in 56 after 2 days Example D Tetranychus test Solvent: 3 parts by weight dimethyl formamide Emulsifler: 1 part by weight alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of the active compound is mixed with the stated amount of solvent containing the stated amount of emulsifier and the concentrate is diluted with water to the desired concentration.

Bean plants (Phaseolus vulgaris), which have a height of approximately 10 - 30 cm., are sprayed with the preparation of the active compound until dripping wet. These bean plants are heavily infected with spider mites (Tetranychus telarius) in all stages of development.

After the specified periods of time, the effectiveness of the preparation of active compound is determined by counting the dead mites. The degree of destruction thus obtained is expressed as a percentage: 100 means that all the spider mites are killed whereas 0% means that none of the spider mites are killed.

The active compounds, the concentrations of the active compounds, the evaluation times and the results can be seen from the following Table: TABLE (plant-damaging mites) Concentration of Degree of Active compounds active compound destruction in i» in # after 2 days Example B Laphygma test Solvent: 3 parts by weight acetone Emulslfler: 1 part by weight alkylarylpolyglycol ether To produce a suitable preparation of active compound, 1 part by weight of the active compound is mixed with the stated amount of solvent containing the stated amount of emulslfler and the concentrate is diluted with water to the desired concentration.

Cotton leaves (Grosaypium barbadense) are sprayed dew-moist with the preparation of the active compound and they are infested with caterpillars of the owlet moth (Laphygima exigua).

After the stated periods of time, the degree of destruction is determined as a percentage: 100J6 means that all the caterpillars are killed whereas 0 means that none of the caterillars are killed.

The active compounds, the concentrations of the active compounds, the evaluation times and the results can be seen from the following Table: (plant-damaging insects) Concentration of Degree of Active compounds active compound destruction in in i» after 3 days (known) The process of the invention is illustrated by the following Examples 1-7.

Example 1 0 C^ - S - C = N- 0 - $ - NHCRj CH^ 11.9 g a-ethylmercapto-acetaldoxime are dissolved in about 150 ml benzene. 6 g methylisocyanate are then added to the solution and, after the addition of 2-3 drops triethylamine, he l s effected for 1 hours after which the recrystallised from ethyl acetate/white spirit. Colourless crystals, m.p. 58°C; yield 14 g.

Example 2 As described in Example 1, 11.9 g of the said oxime in benzene are heated to the boil for 1¼ hours with 7.1 g ethyliso-cyanate and 2 drops trie hylamine. When the clear solution is evaporated, a crystalline residue is obtained which, after recrystal 1 isation from white spirit, melts at 68°C.

Yield about 85 - 90 of the theory.

Example 5 g methylisocyanate and a few drops of triethylamine are added to 74 g a-butylmercapto-acetaldoxime in about 500 ml benzene. The mixture is heated to the boil for 1 - l£ hours. It is then evaporated in a vacuum, and the solid residue is recryetallised from white spirit. About 80 g colourless crystals are obtained; m.p. 73°C C12¾5 - S - C = N - 0 - l- NHCEj CH, j As described in Exemplee 1-3» 13 g 2-dodecylmercapto-acetaldoxime are reacted in 150 ml benzene with 3 g methylisocyanate and 2 drops triethylamine. Working up is effected as described and 13 g colourless crystals are obtained which, after being dissolved in, and allowed to crystallise (without filtra n , CH^ .8 g dimethylcarbamic acid chloride, dissolved in 50 ml.

L6.7 g of benzene, are added dropwise, with stirring, to a solution of / and' 11-g of trimet ylamine u-pfaenylmercapto-acetaldoxime/in 100 ml benzene. This is followed by stirring at boiling temperature for 2-3 hours, filtering off cold with suction and evaporation of the filtrate in a vacuum.

The initially oily distillation residue becomes solid after standing, m.p. 67°C.

Example 7 8 g powdered sodium hydroxide are added in portions, within 15 minutes and at room temperature, to a solution of 23*8 g. a- ethylmercapto-acetaldoxime and 21.5 g dimethylcarbamic acid chloride in 180 cur xylene. This was followed by filtering φ from sodium chloride, and the filtrate was then concentrated. As residue, 37 g carbamate were obtained. m.p. 75 - 77° (after recrystallisation from cyclohexane) In analogy with Examples 1 - 5, the following carbam te was prepared. m.p. 75 - 76c - -

Claims (1)

1. of the formula tt2 which ie an alkyl or phenyl is a lower alkyl and hydrogen or a lower alkyl according to Claim 1 in which is an alkyl radical with 1 6 atoms or a phenyl according to Claim 1 or 2 in which an alkyl radical with t 4 carbon according to any of Claims 1 to 3 or which alkyl radical with 1 4 carbon The of the formula 6k fhe of the formula 0 of the formula 0 ti of the formula 0 The of the formula 0 The of the formula 0 The of the rmula The of the formula She of the formula A process the production of according to of Claims 1 to 15 which an oxiiae of the II 1B reacted with an of the formula in and have th same meaning as in process for production of according to of Claims 1 to 13 in which an of the formula in Claim 14 la reacted with a acid chloride of the formula ox IT in which and have the same meaning in Claim A process according to Claim 14 or 15 in which the reaction ia carried out at 20 to A process according to any of Claims 14 to 16 in which the reaction carried out in the presence of an inert for the production of according to Claim 1 substantially as described herein with reference to Examples 1 to or acarieidal compositions containing aa active ingredient an according to of Claims 1 to 13 in admixture with a liquid diluent or carrier containing a according to Claim 19 containing from to by weight of the active A method of combating insects or aoarida which comprises applying to or acarlde or an insect or habitat an oximecarbamate according to any of Claims 1 to 33 alone or in the form of a composition according to 19 or A method according to Claim 21 in which a composition is used containing to preferably to by weight of the active A according to any of Claims 21 or 22 in whloh the initially applied to soil for growing PARTNERS insufficientOCRQuality