Patent GB-998360-A (GB)
Title: Carbamyloximes of cyclic ketones, their preparation and pesticidal compositions containing them
IPC: A01N47/24
Filed: 1962-09-21
Abstract: The invention comprises a compound of the general formula <FORM:0998360/C2/1> 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 <PICT:0998360/C2/1> 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 <FORM:0998360/C2/2> 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 <FORM:0998360/A5-A6/1> 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  <FORM:0998360/A5-A6/2> <FORM:0998360/A5-A6/3> <FORM:0998360/A5-A6/4> <FORM:0998360/A5-A6/5> 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.