473. Volatile products of pyrolysis of nicotine

Abstract

Jarboe ajzd Roserte.

Chemical composition of tobacco and tobacco smoke

“…The qualitative and quantitative data in are based on several studies (31,256,(289)(290)(291) and give some insight into the mechanism of fragmentation. The arbitrary values in the table are for use only in comparing relative yields of a given product from a given alkaloid at the indicated temperatures and do not reflect the absolute yields of products at one temperature.…”

“…From this over-all pattern, it is evident that dehydrogenation, demethylation, and scission of the pyrrolidine ring are initial steps in the pyrolysis of nicotine. In a Ci-C2 fragmentation of this ring, dehydrogenation of the resulting N-methylaminoalkyl chain would give metanicotine (256) which, on further elimination, would form the observed 3-(l,3-butadienyl) pyridine and subsequently 3-vinylpyridine by appropriate cleavage. Fragmentation of the pyrrolidine ring in the 2,3 or 1,5 positions might ultimately give 3-cyanopyridine after dealkylation of the side chain.…”

“…Many of the pyrolytic reactions of the alkaloids at high temperatures are undoubtedly free radical although ion-controlled mechanisms may be operative to some extent (256). The appearance of such compounds as benzonitrile, naphthalene, and 1,7-diazaindene at these temperatures indicates that a high degree of molecular destruction and combination of fragments is occurring.…”

Vapor pressure data of nicotine, anabasine and cotinine using differential scanning calorimetry

“…According to literature the nicotine is thermally stable in an inert atmosphere up to 600 C [12,13]. No thermal stability information was found for the other two tobacco alkaloids; however, the DSC measurements performed did not indicate thermal instabilities in the measured temperature regions.…”

Studies on bladder carcinogens in the human environment I. Naphthylamines produced by pyrolysis of amino acids

“…However, experimental studies have, as yet, not revealed the presence of specific urinary bladder carcinogens, such as naphthylamines, in cigarette smoke. Pyrolyses performed with many nitrogen compounds, tobacco alkaloids (Van Duuren et al, 1960;Jarboe and Rosene, 1961;Kobashi et al, 1963a, b, c) and amino acids (Heyns and Pavel, 1957;Ma1 et al, 1962), and analyses of the resultant pyrolyzates did not indicate the presence of naphthylamines. A different experimental approach seemed to be necessary to determine if bladder carcinogens can indeed be pyrosynthesized from nitrogen compounds.…”