IL31032A - Carbamates and pesticidal preparations containing them - Google Patents

Description

31032¾ New carbamates and pesticidal preparations containing them CIBA-GEIGY A.O, C: -29222 The prosont Invention provides new carbamates of the genera formula* wherein Y is oxygen or suphur.

The present Invention also provides a pesticldal preparation which comprises, as active ingredient, one. or, more compounds, of the general formula (I) given above, together with a suitable carrier.

U.S. Paten Ho.. 3,304,225 discloses, inter alia, insecticidal iMnethyl phenyl carbamates substituted at the meta-posltion with a lower alkyl hioalkoxy group. The lower alkylthioalkoxy groups specifically described are only methylthlomethoxy, isopropylthio-methoxy, meth lt ioethoxy and ethylthiomethoxy.

In Belgian atent Ho. 699, 344 there are disclosed, inter allcoxy alia, insecticidal M-methyl phenyl carbamates having a (C^-C^) -methoxy or -ethoxy side chain linked to the 2-position of the phenyl ring. Of these known compounds, the closest in structure to the compounds of the present invention is 2-(isopropoxymothoxy)«* phenyl*H-methyl*carbamate.. On comparative tests, Compound No..1 (in Example 1) of the present Invention, proved to be a markedly more effective insecticide than that known compound.

The new carbamates of formula (i) above can be obtained b using the methods usually employed for the manufacture of this class of substances,, for example, by the reaction of correspondin phenols with methylisooyanate,, methylcarbamlc acid chloride, or by the reaction of corresponding phenylcarbonates or phenyl-ohlOrocarbonates with methylamine 31032/2 j The new carbamates act as insecticides and acaricides against' all stages of development of these pests, and are especially powerful, against house flies, aphids, caterpillars, ticks, bugs and beetles, for example, corn beetles and Colo ado beetles. With regard to contact action, they are greatly superior to the known active substance "Carbaryl" (N-methyl-c-naphthyl-carbamate).

• Their action is especially powerful against Phyllodromia . germanica, Periplaneta americana, Blatta orientalis, . Acheta domestica and Rhodnius prolixus.

The advantage of these carbamates of formula (I) is that they have a pronounced long-term action, which does not allow any impairment to be detected in the dry coating, even after months. After the application, complete protection against,, for example, household pests is thus ensured for this period of time.

The new carbamates are therefore very euitable for combating pests in the field of hygiene and in storage, also in 31032/2 plant protection.' As compounds that are especially active, there may be mentioned: o-[l-methoxy-2-propoxy ]-phenyl-N-methylcarbamate and o-il-methylthio-2-pr0poxy ]-phenyl-N-methylcarbamate.

When used in larger amounts, the compounds of formula (I) possess a growth-suppressing or growth-retarding action against various representatives of monocotyledon or dicotyledon genera of plants.

When used at a concentration which does not allow any phytotoxic phenomena to arise they show an excellent action, . in plant protection, against harmful micro-organisms, for example, against fungi, for example, Alteraaria solani, Phytophthora infestans and Septoria apii, as well as against harmful nematodes and their eggs or larvae.

Furthermore the new compounds and preparations can generally be used as microbicides, for example against varieties of Aspergillus. They are furthermore also active against molluscs.

The new preparations can be used in many different ways and in various forms, for example, in the form of sprays, dusting powders, so-called fly dishes or strips - impregnated with a solution of the active substances - as is well known to every expert. In this context, compare also U.S. Patent Specification No. 3, 329, 702 or British Patent Specification No. 1 , 047, 644 or Swiss Patent Specification No. 424, 359.

. The preparations according to the inventio may be used by themselves or together with conentional pesticides, for example, herbicides, insecticides, acaricides, nematocides, bactericides, fungicides, or molluscicides.

The following Examples illustrate the invention, the parts being by weight.

Example 1 1-Methoxy-2-propyl-p-toluenesulphonate 420 Parts of p-toluenesulphonyl chloride are . added, in portions, at a temperature of 0°C, to 216 parts of 1-methoxy~2- propanol. Thereafter, 324 parts of pyridine are added drop by drop to the mixture whilst stirring at 0°C, and the mixture is kept for a further 16 hours at this temperature. After dilution with 1000 parts of ice water, the product is extracted with 1000 parts by volume of ether. The ether solution is repeatedly washed with 2 N hydrochloric acid, saturated sodium bicarbonate solution and water, dried over anhydrous sodium sulphate and evaporated. The remaining product is an oil. ■^•'(1 -Methoxy-2-propyloxy)-phenol 90 parts of 44.5 strength sodium hydroxide solution are added drop by drop under nitrogen to a solution of 110 parts of pyrocatechol and 244 parts of 1-methoxy-2-propyl-p-toluene- sulphonate in 500 parts by volume of dimethylsulphoxide . During the addition, the temperature rises to 42°C. The mixture is stirred for 14 hours at room temperature, poured into 2000 parts of water, and extracted three times each time with 250 parts by volume of toluene. The toluene solution is washed twice each time with 200 parts of water, and evaporated. The residue is distilled in a high vacuum. Boiling point 70-82°C/0.04 mm Hg. or Jfr- ( 1 -Methoxy-2-propoxy)~phenyl-N-methyl-carbamate (Compound 1 ) 38 Parts of 0-( 1 -methoxy-2-propoxy)-phenol are dissolved in 250 parts by volume of dry toluene, and mixed with 0.3 parts of triethylene diamine and with 13 parts of methylisocyanate added in portions. The solution is kept for 14 hours at 35°C, and is then evaporated. The product crystallises gradually; - 6 - '= ■'· · 31032/2 melting point 57°C. It can be recrystallised' from carbon tetrachloride-cyclohexahe .

Example 2 o-( l-Methylthio-2-propoxy )-phenyl-N-methyl-carbamate ( Compound 2 ) This compound m.p. 57-59°C is manufactured in an analogous manner.

. Examples of Formulations.

Dusting Agents · .

Equal parts of an active substance according to the invention and precipitated silica are finely ground together.

Dusting agents, preferably containing 1-6 °/e of an aotive substance, can be manufactured therefrom by mixing with kaolin , or talc. . · Spraying; Powders · ' . '· In order to. manufacture a spraying powder, the "following components are, for example, mixed and finely ground: 50 parts of active substance according to the present invention, 20 parts of Hisil (highly adsorptive silica), 25 parts' of Bolus alba (kaolin), 3.5 parts of a reaction product of p-tert. octylphenol thereafter heated to "boiling point and 268 parts of 1 -methoxy-2-propyl-p-toluenesulphonate are added drop by drop. The mixture is boiled under reflux for 24 hours, filtered and evaporated.

The residue is taken up in 750 parts by volume of toluene, and washed once with water, and then twice each time with 250 parts by volume of 15 f° strength sodium hydroxide solution. The alkaline extract is immediately neutralised with hydrochloric acid and extracted with toluene. The toluene solution is dried over anhydrous sodium sulphate, filtered and evaporated. The residue is distilled in a high vacuum. o-( 1 -Methxy-2-propylthio)-phenyl-N-methylcarbamate (Compound No.3) 45 Parts of o-( 1 -methoxy-2-propylthio)-phenol are dissolved in 250 parts by volume of dry toluene and mixed with 0.2 parts of diethylene triamine and with 17 parts of methyliscyanate added drop by drop. The solution is kept for 14 hours at -35°C. The oily product is obtained by evaporating the solution in vacuo.t Example 4 o-( 1-Methoxy-2-propylthio)-phenyl- .N-dimethylcarbamate (Compound No. 4) 45 Parts of o-( 1 -methoxy-2-propylthio)-phenol are mixed with 1 0 parts by volume of dry dioxane, 30 parts of triethyl-amine and 32 parts of dimethylcarbamic acid chloridethe^latter"added in portions. The mixture is stirred for 14 hours at 90°C.

The precipitated triethylamine hydrochloride is filtered off.

The filtrate is evaporated, dissolved in 250 parts by volume of toluene and washed twice, each time with 200 parts by volume of 10 o strength sodium hydroxide solution in the presence of ice. The solution is dried over anhydrous sodium sulphate, filtered and evaporated. The residue obtained is oily o-(1- methoxy-2-propylthio)-phenyl- ,N-dimethylcarbamate .

The following compounds are manufactured analogously: ) o-[ 1-Ethoxy-2-propoxy] -phenyl-N-methylcarbamate, 6) O-[1-allyloxy-2-propoxy]-phenyl-N-methylcarbamate, 7) o-[ 1-propargyl-oxy-2-propoxy]-phenyl-N-methylcarbamate, 8) o-[ 1-methylthio-2-propoxy]-phenyl- -methylcarbamate, 9 ) o-[l-methylthio-2-propylthio]-phenyl-N-methylcarbamate, 10) o-[ 1-ethoxy-2-propylthio]-phenyl-N-methylcarbamate , 1 1 ) o-[ 1 -ethylthio-2-propoxy] -phenyl-N-methylcarbamate, 1 2 ) o-[ 1 -ethylthio-2-propylthio]-phenyl-N-methylcarbamate, 1 3 ) o-[l-methoxy-2-butoxy]-phenyl-N-methylcarbamate, 14) o-[l-methylthio-2-propoxy]-phenyl-N, -dimethylcarbamate, 1 5) o[l-methylthio-2-propylthio]-phenyl-N,N-dimethylcarbamate, 16) o-[ 1 -ethylthio-2-propylthio]-phenyl-N, -dimethylcarbamate, 17) o-Ll-methoxy-2-propoxy]-4-methylphenyl-N-methylcarbamate, 18) o-[l-methoxy-2-propoxy] -5-chlorophenyl-N-methylcarbamate, 1 9 ) m-[l-ethoxy-2-butoxy] -5-methylphenyl-N-methylcarbamate .

Examples of Formulations Dusting Agents Equal parts of an active substance according to the invention and precipitated silica are finely ground together. Dusting agents, preferably containing 1-6 of an active substance, can be manufactured therefrom by mixing with kaolin or talc.

Spraying Powders ■ In order to manufacture a spraying powder, the following components are, for example, mixed and finely ground: 50 parts of active substance according to the present invention, 20 parts of Hisil (highly adsorptive silica), 25 parts of Bolus alba (kaolin), 3. 5 parts of a reaction product of p-tert. octylphenol aaad ethylene oxide and 1.5 parts of (sodium 1-benzyl-2-stearyl benzimidazole-6.3 ' -disulphonate ) .

Emulsion Concentrate Easily soluble active substances can also be formulated as an emulsion concentrate by the following method: 20 parts of active substance, 70 parts of xylene, 10 parts of a mixture of a reaction product of an alkylphenol with ethylene oxide and calcium dodecylbenzene-sulphonate are mixed. On dilution with water to the desired concentration, a sprayable emulsion is produced.

Example 5 In order to test their action against various storage pest 2 g of compound 1 were mixed with 38 g of talc and the whole was very finely ground . A highly active dusting powder was thus obtained, with which the following results were achieved.

Minimum Concentration for 100 o Mortality in 24 Hours Test Animals Exposure Time 2 m« Active Substance per m German cockroach (Phyllodromia germanica) 3 American cockroach (Periplaneta americana) 3 Russian cockroach (Blatta orientalis) 25 -, Blood sucking bug ~ .(Rhodnius prolixus) 25 Domestic cricket (Acheta domestica) 25

Claims (7)

Case 5-63O7/E - Israel - 1 - 3IO32/2 Claims

1. Compounds of the general formula wherein Y is oxygen or .sulphur.

2. The compound;, of the formula

3. A process for the manufacture of compounds of the formula CH, 3 wherein Y is. oxygen or sulphur by reaction of a phenol of formula with methylisocyanate or methylcarbamic acid chloride.

4. A pesticidal preparation, which comprises as the active Case 5-6307/E - Israel - 2 - 31032/2 in which Y represents oxygen or sulphur together with a suitable carrier.

5. A preparation as claimed in claim 4, which comprises as the active ingredient the compound of the formula

6. A method of treating living plants to combat harmful insects and pest's of the order acarina, which comprises applying to the plants a compound as claimed in claim 1.

7. A method of combating insects and pests of the order acarina, especially combating pests in the field of hygiene and in storage, which comprises treating them with a compound as claimed in claim 1. For the Applicants DR. REIHHOLD COH /AND