The Reaction of Ethylamine-1-C^(14) with Nitrous Acid

Abstract

Ethylamine-1-C^(14) on treatment with perchloric acid and sodium nitrite in aqueous solution gave ethylene and a 38% yield of C^(l4)-labeled ethanol which was shown by degradation and C^(14)-analysis to contain 1.5% of the rearrangement product, ethanol-2-C^(l4). The rearrangement product was demonstrated not to be formed in the degradation procedure or by hydration of the ethylene produced in the amine-nitrous acid reaction. It is concluded that the ethyl cation is not converted to ethyleneprotonium ion (II) at a rate which is comparable to that of its reaction with water. The reaction of ethylamine with perchloric acid and sodium nitrite in 99.8% deuterium oxide gave ethanol which contained only 1.1 atom % of deuterium attached to carbon. This result indicates that less than 10% of the ethanol could have been formed via diazoethane as an intermediate.

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