The Action of Nitrous Acid on Aliphatic Amines

Toxic liver injury and carcinogenesis. Methylation of rat-liver nucleic acids by dimethylnitrosamine in vivo

“…The recent demonstration of the existence of the very unstable monomethylnitros-amine and its decomposition to diazomethane and water (Muller, Haiss & Rundel, 1960) supports the concept of the formation of the diazoalkane. On the other hand, Austin (1960) maintains that breakdown of the monomethylnitrosamine may lead to the formation of a carbonium ion, which may be responsible for methylation. Recent work on the relation of chemical structure to biological activity by Druckrey, Preussmann, Schmahl & Muller (1961) and by D. F. Heath (personal communication) is in agreement with the alkylation hypothesis.…”

The decomposition and toxicity of dialkylnitrosamines in rats

“…Carbonium-ion formation has been postulated to explain the wide variety of products found when primary amines are treated with nitrous acid (see Austin, 1960;and Ridd, 1961). Carbonium ions, however, are only supposed to exist for a few molecular vibrations, and to be formed from monoalkylnitrosamines.…”

Deamination of the Epimeric 3-Aminoandrost-5-en-17-ones and 6-Amino-3α,5α-cycloandrostan-17-ones

“…to include both nitro compounds and nitrite esters. 25 Since the products obtained by deamination ofand 6/3-amino-3a,5a-cycloandrostan-17-one and 3/3aminoandrostan-17-one, prior to basic hydrolysis, all showed absorption at 1543 cm.-1 and 1630 cm.-1 characteristic of nitro compounds and nitrite esters, respectively,15 it seemed desirable to determine the nature of the products formed directly in the deamination medium by isolation of products without basic hydrolysis. 6/3-Amino-3a,5a-cycloandrostan-17-one was deaminated in 1:3 acetic acid-water solution in the usual manner, and the crude product, isolated by ether extraction, was chromatographed on neutral, activity III alumina.…”