GB815537A - Improvements in the production of n-nitroso-n-alkyl- and n-nitroso-n-cycloalkyl-hydroxylamines - Google Patents

Abstract

The invention comprises a process for the production of N-nitroso-N-alkyl- or N-nitroso-N-cyclohexyl-, -cycloheptyl- or -cyclo-octyl-hydroxylamines or their derivatives in which the rings bear alkyl, hydroxyalkyl, or cyano substituents, or their ammonium or amine salts or complex metal compounds, in which a solution of an alkali nitrite is allowed to flow while cooling into an aqueous acid solution of the corresponding hydroxylamine in such a manner that the nitrous acid formed is immediately used in reaction with the hydroxylamine, and used in reaction with the hydroxylamine, and if desired reacting the N-nitroso compound simultaneously or subsequently with an equivalent amount of a water-soluble salt of a metal of Groups IIa-VIIa, Ib-IVb or VIII of the periodic classification, or alternatively reacting the N-nitroso compounds in inert organic solvents with anhydrous ammonia or amines. Specified N-alkyl groups are methyl, ethyl, propyl, isopropyl, butyl, tert-buty-(2), heptyl-(4), dodecyl, octadecyl and tetramethyloctyl. The pH of the acid solution may be 0-6, and the solution is preferably cooled to between - 10 DEG and + 10 DEG C. Suitable amines for the preparation of salts are aliphatic and cycloaliphatic primary, secondary and tertiary amines. Specified metals are Be, Mg, Ca, Sr, Ba, Ce, V, U, Mn, Fe, Co, Ni, Cu, Ag, Zn, Hg, Al and Pb. Preferred salts are chlorides, sulphates, nitrates and acetates; the double decomposition may be carried out at pH 7-10. Examples describe the preparation of (1)-(3) N-nitroso-N-cyclohexylhydroxylamine, and its ammonium and methylamine, cyclohexylamine and dicyclohexylamine salts, and its complexes with various metals; (4) and (5) N-nitroso-N-cyclo-octylhydroxylamine, its ammonium and cyclohexylamine salts and metal complexes; (6) N-nitroso-N-isopropyl-hydroxylamine copper complex and amine salts, and N-butyl-N-nitroso-hydroxylamine copper complex; (7) and (8) N-nitroso-N-cycloheptyl-hydroxylamine copper complex; and its ammonium and amine salts: (9) N-nitroso-N-methyl-hydroxylamine and its amine salts and copper complex; (10) N-nitroso-N-[(1 - methylol) - cyclohexyl] - hydroxylamine copper complex; (11) and (12) N-nitroso-[(1-cyano) - cyclohexyl] - hydroxylamine and its ammonium and amine salts, and copper complex.