Patent GB-1295080-A (GB)
IPC: A01N43/34
Filed: 1969-12-24
Abstract: 1295080 1 - Carbamoyl - N - carbamoyloxy thioformimidates E I DU PONT DE NEMOURS & CO 24 Dec 1969 [27 Dec 1968 (4)] 62894/69 Heading C2C Alkyl 1 - (carbamoyl) - N - hydroxythioformimidates of the formula and their N-carbamoyloxy derivatives of the formula (wherein R<SP>1</SP> is hydrogen, methyl, ethyl or isopropyl ; R 1  is alkyl of 1 to 4 carbon atoms or alkenyl of 3 or 4 carbon atoms; R 2  is hydrogen, alkyl of 1 to 4 carbon atoms, alkenyl of 3 or 4 carbon atoms, methoxy, or cycloalkyl of 3 to 5 carbon atoms; R 3  is hydrogen, alkyl of 1 to 4 carbon atoms or alkenyl of 3 or 4 carbon atoms; or R 2  and R 3  together form an alkylene radical containing 2 to 6 carbon atoms; subject to the proviso that R 2  and R 3  do not contain a total of more than 7 carbon atoms; R 4  is alkyl of 1 to 3 carbon atoms, allyl or propargyl; and R 5  is hydrogen or methyl) are prepared by either: (1) (a) (i) oximating an alkyl acetoacetate with nitrous acid produced in situ, in the presence or absence of an R<SP>1</SP>OH solvent at - 10 to 50 C., and pH >4 and chlorinating the oxime at -10 to 40 C. in an R<SP>1</SP>OH solvent, or (ii) chlorinating an alkyl acetoacetate in the presence or absence of an R<SP>1</SP>OH solvent at 0 to 70 C.; and oximating the chlorinated product with an alkyl nitrite in the presence of hydrogen chloride and an R<SP>1</SP>OH solvent, at from -20 to 50 C., (b) reacting the hydroxamoyl chloride product of step (a) (i) or (ii) with an alkyl mercaptan of the general formula R 1 SH in an R<SP>1</SP>OH solvent and then raising the pH to from 5 to 9 to produce a 1-alkoxycarbonyl-N-hydroxythioformimidate; and (c) aminating the thioformimidate with ammonia, a primary amine or a secondary amine NHR 2 R 3 , in the presence of an R<SP>1</SP>OH solvent; or (2) (a) synthesizing a carbamoyl formhydroxamoyl chloride by aminating diketene with a molar equivalent of ammonia or an amine NHR 2 R 3  in the presence of water, diethyl ether, benzene, or methylene chloride, at from -20 to 80 C. to produce an acetoacetamide; then either (i) oximating the acetoacetamide with nitrous acid produced in situ, in an R<SP>1</SP>OH solvent at -10 to 50 C., and pH >4.0 and chlorinating the oxime at from -10 to 75 C. in an R<SP>1</SP>OH solvent, or (ii) chlorinating the said acetoacetamide in an R<SP>1</SP>OH solvent, at from -10 to 70 C. to produce a 2-chloroacetamide ; and oximating the 2-chloroacetamide in an R<SP>1</SP>OH solvent with nitrous acid produced in situ, at -20 to 50 C. and pH >4.0 ; (b) reacting the resultant carbamoylformhydroxamoyl chloride with an alkyl mercaptan R 1 SH in an R<SP>1</SP>OH solvent and then raising the pH to from 5 to 9 and finally acylating the resultant alkyl 1 - (carbamoyl) - N- hydroxythioformimidate in the presence of water, acetone, methylene chloride, methyl ethyl ketone or methyl isobutyl ketone as solvent with (A) an isocyanate R 4 -NCO in the presence or absence of a basic catalyst; or with (B) a carbamoyl chloride R 4 R 5 NCOCl in the presence of a basic catalyst. The processes are illustrated with detailed examples and over 100 compounds are tabulated. The compounds are pesticides and may be formulated with conventional carriers or diluents (see also Specification 1,181,023).