Fabrication et application de carbamyloximes de cétones monocycliques et de cétones bicycliques.

摘要

The invention comprises a compound of the general formula wherein R1 is a methyl or ethyl radical; R2 is a hydrogen atom, a methyl or ethyl radical, and Z is a divalent radical represented by wherein the free valences of ring carbons are satisfied by hydrogen atoms, halogen atoms, alkyl, haloalkyl, alkenyl, cycloalkyl, aryl, substituted aryl, aralkyl, cyano, acyloxy, alkoxy, alkylthio, arylthio, N-alkylthiocarbamylmercapto, thiocyanato, or N,N-dialkylthiocarbamylmercapto radicals, or combinations thereof. The novel compounds in which R2 is hydrogen may be made by contacting an oxime Z= N-OH with from 0.25 to 2 moles per mole of oxime of an isocyanate R1NCO at a temperature of from 10 DEG C. to 130 DEG C. and a pressure of from 1 atm. to 10 atm. Inert solvents may be used and preferably a tertiary amine or organotin catalyst is employed. The carbamyloximes having two alkyl substituents R1 and R2 are made by reacting the oxime Z=N-OH with a dialkylcarbamyl chloride at a temperature from 10 DEG C. to 130 DEG C. in the presence of a tertiary amine. The initial oximes Z=N-OH may be made by the addition of excess of hydroxylamine hydrochloride and sodium acetate in aqueous solution to the corresponding ketone Z=O in an inert, water miscible solvent and heating to 50 DEG to 100 DEG C. Alternatively a substituted bicyclo[2.2.1]-2-heptene is made by Diels Alder reaction from a cyclopentadiene and a substituted ethylene, is converted by addition of nitrosyl chloride to the corresponding nitrosochloride which is rearranged to the 3-chlorobicyclo[2.2.1]-heptan-2-one oxime. The bicyclo[2.2.1]-5-hepten-2-one oximes are similarly made from the corresponding bicyclo[2.2.1]-2,5-heptadiene made from an acetylene and a cyclopentadiene. The 3-chloro-compounds may be treated with sodium alkoxides, sodium cyanide or sodium methyl mercaptides to give the corresponding alkoxy, cyano or methyl mercapto compounds. The bicyclo[2.2.1]-2-heptanone oxime is made by catalytic hydrogenation of the bicyclo[2.2.1]-heptenes or heptadienes to the heptane and reacting this with nitrosyl chloride under the catalytic influence of light. Detailed examples are given.ALSO:Pesticidal compositions comprise compounds of the formula wherein R1 is a methyl or ethyl radical; R2 is a hydrogen atom, a methyl or ethyl radical, and Z is a divalent radical represented by one of the formul p wherein the free valencies of ring carbon are satisfied by hydrogen atoms, halogen atoms, alkyl, haloalkyl, alkenyl, cycloalkyl, aryl, substituted aryl, aralkyl, cyano, acyloxy, alkoxy, alkylthio, arylthio, N-alkylthiocarbamyl-mercapto, thiocyanate or N,N-dialkylthiocarbamylmercapto radicals, in admixture with an inert carrier. The carrier may be a liquid, to form sprays, or a solid, to form dusts. The compositions are evaluated as insecticides, nematocides and acaricides against bean aphid, armyworm, Mexican bean beetle, housefly, two-spotted mite and root-knot nematode.