APROTIC DIAZOTIZATION OF ALIPHATIC AMINES . HYDROCARBON PRODUCTS AND REACTION PARAMETERS

From reaction of isobutylamine with isoamyl nitrite in aprotic media only moderate amounts of gaseous products are obtained consisting mainly of nitrous oxide and small amounts of hydrocarbons and nitrogen. However, in protic media the amount of hydrocarbons and nitrogen increase with a concomitant decrease in nitrous oxide. In the presence of 1 equiv of acetic acid, the reaction in aprotic media is highly efficient in that hydrocarbons and counterion-derived products are obtained in high yield and nitrous oxide formation is negligible. The hydrocarbon mixtures obtained from diazotization of isobutylamine with alkyl nitrite-acetic acid in “aprotic media,” e.g., diethyl Carbitol, chloroform, and n-amyl alcohol, contain appreciable amounts of methylcyclopropane (10-15%). In “protic media,” such as ethylene glycol and water, the amount of skeletal rearranged olefins (1-and 2-butenes) increase at the expense of methylcyclopropane. The results are similar to those obtained from decomposition of diazoisobutane and N-nitroso- and N-nitroacetamides and -urethans in aprotic and protic media, respectively. It is proposed that all products arise via cationic processes. © 1969, American Chemical Society. All rights reserved.