IL46199A - O-(m-dialkoxy(alkylenedioxy)methyl)phenyl n-phenylthio-n-methylcarbamates their preparation and pesticidal compositions containing them - Google Patents

Description

46199/2 o »n»»am nnJ3nfe»n»itanpV*na-N -n*nV»j»-lf - oniK o» *3on o*p*f& »*T»tt»B 0-/jn-dialkoxy(allylenediox Jmethyj/ phenyl K-phenylthio—H-methylcarbematee, their preparation and pestlcidal compoBtiona containing them CIBA-GEIQT A.G. 0. 44183 The present invention relates to phenyl carbamates, to processes for their production, and to their use in "pest control.

The phenyl carbamates concerned have the formula wherein each of R^ and R^, which may be the same or different, represents a hydrogen, chlorine or bromine atom or a C^-C^ alkyl group and and both- represent methyl groups, or R-j and R^ together represent a group of the formula : - CH2-CH2 - , -CH2-CH2-CH2- , -CH-CH2- , -CH — CH- , .

CH3 CH3 CH3 - C-CH - , -CH-CH9 -CH0 - , -C C- , /\ 1 I 2 2 / \ /X CH3 CH3 CH3 CH3 CH3 CH3 CK3 . CH¾ or Compounds of formula I preferred on account of their action are those wherein represents hydrogen, R2 represents hydrogen, chlorine, methyl or tert. -butyl, R3 and R, together represent -CH -CH - , ,-CH-CH - or CH2-CH2-CH2.

The compounds of formula I can be produced by the following methods known per se: I CH CH3 0 0 (II) 1 I R5 R4 B (III) In the formulae II to IV, the symbols to R^ have the meanings given for formula I, and X stands for halogen, especially for chlorine, and Me stands for a metal, particular an alkali metal.

Suitable acid-binding agents are: tertiary amines, e.g., trialkylamines, pyridine or dialkylanilines; inorganic bases such as hydrides or hydroxides^ aad- carbonates and bicarbonate of alkali metals and alkaline-earth metals. It is sometimes necessary to use catalysts in the reactions, such as, e.g., copper or copper chloride .

The reactions A and B are performed under normal pressure at a temperature of between -20 and 50°C, preferably between . 0 and 30°C, and in solvents or diluents. These are, in particular, lower aliphatic ketones such as acetone or methyl 46199/2 ethyl ketone; alkanols such as methanol, ethanol or isopropanol; esters such as acetic acid ethyl ester; nitriles such as acetonitrile; N-alkylated acid amides; aromatic and halogenated hydrocarbons, such as benzene, toluene, chloroform or methylene chloride; ethers and ethereal compounds, such as diethyl ether, dioxane or tetrahydrofuran; and also water and, in addition, mixtures of such solvents with each other and with water .

Starting materials of formulae II, III and IV are known and can be produced by methods analogous to known methods .

A process for the production of the starting products II and IV is described, for example, in the English Patent Specification No. 1,122,633.

The compounds of formula I have a broad biocidal action, and are therefore suitable for the control of various vegetable and animal pests. They possess however, above all, insecticidal and acaricidal properties.

The compounds of formula I exhibit a particularly good { action against insects of the families. Blattidae and Chrysomelidae; especially, for instance, against Phyllodromia germanica, Periplaneta americana and Blatta orientalis or Leptinotarsa decemlineata .

The insecticidal or acaricidal action can be broadened and adapted to suit the given circumstances by the addition of other insecticides and/or acaricides .

Suitable additives are, for example: organic phosphorus compounds, derivatives of nitrophenols , formamidines , ureas, carbamates, and/or chlorinated hydrocarbons.

The toxicity towards warm-blooded animals of compounds of formula I is surprisingly substantially lower than that of similar compounds known from the English Patent Spec.

No. 1,122,633.

The compounds of formula I can be used on their own or together with suitable carriers and/or additives .

Suitable carriers and additives may be solid or liquid, and they correspond to the substances common in formulation practice, such as, for example, natural or regenerated substances, solvents, dispersing agents, wetting agents, adhesives, thickeners, binders and/or fertilisers.

For application, the compounds of formula I can be processed into the form of dusts, emulsion concentrates, granulates, dispersions, sprays or solutions, the formulation of these preparations being effected in a manner commonly known in practice .

The agents according to the invention are prepared in a manner known per se by the intimate mixing and/or grinding of active substances of formula I with suitable carriers, optionally with the addition of dispersing agents or solvents which are inert to the active substances The active substances can be obtained and used in the following forms : solid preparations:- dusts, scattering agents, granulates, coated granulates , impregnated granulates and homogeneous granulates; ) -liquid preparations: - a) water-dispersible active-substance concentrates: vettable powders, pastes or emulsions; b) solutions .

The content of active substance in the above described agents is between 0.1 and 95%; it is to be mentioned in this connection that in the case of application from an aeroplane, or by means of other suitable application devices, it is possible to employ also higher concentrations The active substances of -formula I can be formulated, for example, as follows: Dusts : The following substances are used in the preparation of a) a 5% dust, and b) a 2% dust: a) . 5 parts of active substance, 95 parts of talcum; b) 2 parts of active substance, 1 part of highly dispersed silicic acid, 97 parts of talcum.

The active substances are mixed and ground with the carriers .

Granulate : The following substances are used to prepare a 5% granulate : 5 parts of active substance, 0.25 part of epichlorohydrin, 0.25 part of cetyl polyglycol ether, 3.50 parts of polyethylene glycol, 91 parts of kaolin (particle size 0,3 - 0.8 mm).

The active substance is mixed with epichlorohydrin and dissolved with 6 parts of acetone; the polyethylene glycol and cetyl polyglycol ether are then added. The solution thus obtained is sprayed onto kaolin, and the acetone is subsequently evaporated off in vacuo. lettable powder; . - The following constituents are used for the preparation of a) a 40%, b) and. c) a 25%, and d) a 10% wettable powder a) 40 parts of active substance, 5 parts of sodium lignin sulphonate, 1 part of sodium dibutyl-naphthalene sulphonate, 54 parts of silicic acid; b) 25 parts of active substance, 4.5 , parts of calcium lignin sulphonate, 1.9 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1), 1.5 parts of sodium dibutyl naphthalene sulphonate, 19.5 parts of silicic, acid, 19.5 parts of Champagne chalk, 28.1 parts of kaolin; c) 25 parts of active substance, 2.5 parts of isooctylphenoxy-polyoxyethylene-ethanol • 1.7 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1), 8.3 parts of sodium aluminium silicate, 16.5 parts of kieselguhr, . 46 parts of kaolin; d) 10 parts of active substance, '3 parts of a mixture of the sodium salts of saturated fatty alcohol sulphates, 5 parts of naphthalenesulphonic acid/formaldehyde condensate, 82 parts of kaolin.

The active substances are intimately mixed, in suitable mixers, with the additives, and the mixture is then ground in the appropriate mills and rollers. Wettable powders are obtained which can be diluted with water to give suspensions of any desired concentration.

Emulsifiable concentrates : The ■ following substances are used to prepare a) a 10% and b) a 25% emulsifiable concentrate: a) 10 parts of active substance, 3.4 parts of epoxidised vegetable oil, 3.4 parts of a combination emulsifier consisting of fatty alcohol polyglycol ether and alkylaryl sulphonate calcium salt, 40 parts of dimethylformamide, 43.2 parts of xylene; b) 25 parts of active substance, 2.5 parts of epoxidised vegetable oil, 10 parts of an alkylarylsulphonate/fatty alcohol polyglycol ether mixture, 5 parts of dimethylformamide, 57.5 parts of xylene.

From these concentrates it is possible to prepare, by dilution with water, emulsions of any desired concentration.

Spray; The following constituents are used to prepare a 5% spray: 5 parts of active substance, 1 part of epichlorhydrin, 94 parts of ligroin (boiling limits 160 - 190°C) .

Example 1 φ Production of N-methyl-N-p-chloromercapto-phenyl-O- (1 , 3-dioxan-2-yl) -phenyl carbamate 18 g of p-chlorophenylsulphenyl chloride is added dropwise at 5 - 10°C, with continuous stirring, to a mixture of 23.7 g of N-methyl-O- (l,3-dioxan-2-yl) -phenyl-carbamate and 50 ml of pyridine. After the reaction mixture has been stirred for 30 minutes at room temperature, it is poured into a solution of 150 ml of ice-water and 40 ml of concentrated hydrochloric acid, and the whole is stirred for a further 30 minutes . The reaction product is extracted with methylene chloride, the extract is washed with water, dried over sodium sulphate and concentrated by evaporation.

After recrystallisation of the solid residue from methanol, there is obtained the compound of the formula in the form of white crystalline powder having a melting point of 108.6 - 109.8°C.

; The following further compounds of formula I are produced in an analogous manne : 46199/2 Example 2 In order to test the action of the compounds against various pests of the families Blattidae and Chrysomelidae, an amount in each case of 2 g of the compounds according to Example 1 was mixed with 38 g of talcum, and the whole was ground as fine as possible. The result was a very effective dusting powder, with which the areas infested by the pests were treated. Dusting powders containing any one of the compounds according to Example 1 exhibited a good action against Phyllo'dromia germanica, Periplaneta americana and Blatta orientalis or Leptinotarsa decemlineata.

Example 3 Insecticldal stomach poison action Cotton and potato plants were sprayed with a 0.05% aqueous active-substance emulsion (obtained from a 10% emulsifiable concentrate) .

After the drying of the" resulting coating, Colorado beetle larvae iLeptinotarsa decemlineata) were placed onto the plants. The test was carried out at 24°C with 60% relative humidity.

The compounds according to Example 1 exhibited in the above test a good insectacidal stomach poison action against Leptinotarsa decemlineata larvae.

Example $ Comparison of toxicity towards warm-blooded animals The toxicity towards warm-blooded animals in the case of the following compound according to the invention is substantially lower than that of the compound known from the English Patent Specification No. 1,122,633, as is shown by the following results.

(DL 50 rat p.o. acute): e invention Specification 18 - "2Ό -

Claims (1)

1. WHAT WE CLAIM IS: A compound of the formula wherein each of 1 and R2> which may be the same or different, represents a hydrogen, chlorine or bromine atom or a Cj-C^ alkyl group and R-j and R^ hot!) represent methyl g ou s, or Rj ahd jj together represent a group of the formula. -CH2-CH2-,-CH2-CK2-CH2- , -CH-CH2- , -CH—CH- , CH3 CH3 CH3 CH -CH C- , -CH -C-CH - , -CH-r1—CH CH- or I I V \ 2 I I I CH¾ CH- CR3 CH3 CH3 CH3 CH3 2. A compound according to claim 1 wherein each of R^ and 12, which may be the same or different, represents a hydrogen, chlorine or bromine atom or a methyl grou . 3. A compound according to claim 1, wherein R^ represents a hydrogen atom, 1¾2 represents a hydrogen or chlorine atom or a methyl or tert.-butyl group, and and ^together represent a group of the formula -CH2-CH2- , -CH CH- , -CH CH2~ or -CH2-CH2-CH2- 4. A compound according to, claim 3 wherein R2 represents a hydrogen, chlorine or bromine atom or a methyl group . 5. A compound of the formula 46199/2 compound of the formula * A compound of the formula A compound of the formula. 46199/2 9. A compound of the formula. A compound of the formula 11. A compound of the formula 46199/2 A compound of the formula A compound of the formula A compound of the formula 46199/2 A compound of the formula A compound of the formula 17. A compound of the formula 46199/2 18. A compound of the formula 19. A pesticidal composition which comprises (i) a compound according to any one of claims 2 or 4 to 17 together with either (ii) a solid diluent or (iii) a liquid diluent and a surfactant . 20. A pesticidal composition which comprises (i) a compound according to claim 1 or claim 3 together with either (ii) a solid diluent or (iii) a liquid diluent and a surfactant. 21. A pesticidal composition containing a compound as claimed in any one of claims 2 or 4 to 17 in the form of a dust, granulate, wettable powder, emulsifiable concentrate or spray. 46199/2 22. A pesticidal composition containing a compound as claimed in claim 1 or claim 3 in the form of a dust, granulate, wettable powder, emulsifiable concentrate or spray. 23. A method of combating pests at a locus, which method comprises applying to the locus a compound as claimed in any one of claims 2 or 4 to 17. 24. A method according to claim 23 wherein the pests comprise insects, or members of the forder Acarina. 25. A method of combating pests at a locus, which method comprises applying to the locus a compound as claimed in claim 1 or claim 3. 26. A method according to claim 25 wherein the pests comprise insects, or members of the order Acarina. For Λβ ; jpfleairif DR. EINf COHN ND PARIBUS i By :