GB583442A - New nitronitriles - Google Patents

Abstract

Nitronitriles of the formula CN-CHR3-CRR1-CHR2NO2, where R and R1 may be hydrogen or a substituted or unsubstituted hydrocarbon radical, R2 may be hydrogen or a substituted or unsubstituted aliphatic radical, either R or R1 with R2 may together form part of a cycloaliphatic ring and R3 may be a substituted or unsubstituted aromatic radical, are prepared by reacting, in the presence of a basic substance, a nitrile of formula R3CH2CN with a D a -nitroolefine of formula CRR1 = CR2NO2 or substances which under alkaline conditions readily gives rise to a D a -nitro-olefine, namely, the esters of alcohols of the formu'a HOCRR1-CHR2NO2 in which R, R1 and R2 are as above which may be derived from organic acids such as acetic acid or from mineral acids such as nitric or hydrochloric acids. In the examples: (1) and (3) 2-nitro-2-butene which may be made by heating 3-nitro-2-butylacetate with sodium acetate and 1-phenyl-2-nitropropene-1 dissolved in dioxane are respectively added to a cooled mixture of sodium in methyl alcohol and benzyl cyanide; (2), (4) and (5) a -nitro-isobutene, 1-nitro-2-acetoxypropane and nitro-tertiarybutylnitrate, which may be made by the action of liquid nitrogen tetroxide on isobutane, dissolved in tertiary-amyl alcohol are respectively added to a cooled mixture of potassium in tertiary amyl alcohol and benzylcyanide; (6) and (8) a -nitro-isobutene and 1-nitrocyclohexene are respectively added to a cooled mixture of potassium in tertiary amyl alcohol and p-bromobenzylcyanide; and (7) a -nitroisobutene is added to a cooled mixture of potassium in tertiary amyl alcohol and a -naphthylacetonitrile. In all the examples, reaction is effected by warming. Other nitro-olefines which may be used are stated to be 1-nitro-1-propene and 2-nitro-1-propene. Other nitriles are p-methoxybenzylcyanide and m-nitrobenzylcyanide. The basic substance used may be an alkali metal hydroxide or alkoxide or a quaternary ammonium hydroxide such as benzyltrimethylammonium hydroxide. The products may be reduced to diamines and are useful as intermediates in the manufacture of dyestuffs, textile assistants and pharmaceuticals. According to the Provisional Specification, the group R2 in the general formula above may be a substituted or unsubstituted hydrocarbon radical.