Preparation of dinitroparaffins, nitro alcohols and nitroolefins

摘要

Dinitroparaffins of the formula nitroalcohols of the formula nitroalcohols of the formula or nitroolefins of the formula R-CH=CH-NO2 wherein R represents a C1- 22 normal alkyl radical are prepared by contacting a C3- 24 normal alpha-olefin with an equilibrium mixture of NO2 and N2O4 in the presence of a paraffin solvent at a temperature ranging from 50 DEG to 150 DEG C. for a time ranging from 0.1 second to 10 minutes and subjecting the nitrated product (a mixture of said dinitroparaffins with nitro-nitrites of the formula to controlled hydrolysis or alcoholysis by (a) a catalytic amount of a base and a C1- 6 aliphatic alcohol or a mixture thereof with water to produce a mixture of said nitroalcohols and said nitroolefins, or (b) only said C1- 6 aliphatic alcohol, or water, or a mixture of said C1- 6 aliphatic alcohol and water to produce a mixture of said nitroalcohols and said dinitroparaffins. The nitroalcohols may be separated from the dinitroparaffins or nitroolefins and either dehydrated to nitroolefins by treatment with an alcoholic alkali metal hydroxide solution or hydrogenated to corresponding amino alcohols. The separated dinitroparaffins may be hydrolyzed to nitroolefins by contacting them with an aqueous slurry of a Group II metal oxide. Alternatively, treatment (b) of the second stage of the process may be followed by treatment (a) to give a mixture of said nitroalcohols and said nitroolefins.