Naphtho[1,8-bc]thiophens. II. Mass spectrometry

Abstract

II.* MASS SPECTROMETRY By D. G. HAWTHORN,E~$ and Q. N. PORTER^ [Manzlscript received March 6, 19671 The high-resolution mass spectra of some derivatives of naphtho[l,S-be]- thiophen have been analysed. The base peak in the spectra is usually the naphtho- [1,8-bclthienylium cation (mle 171) or one of its substitution products; this emphasizes the stability of this species. Structures are suggested for most of the other ions observed in the spectra. INTRODUUTION In Part I, which dealt with the synthesis of naphtho[l,8-bclthiophen derivatives, the mass spectra of the 2-methyl-2H- (I; R = CH,) and 2-phenyl-2H- (I; R = Ph) compounds were briefly described. It was suggested that in each case the cleavage shown gave the ion of mle 171, for which the naphthothienylium cation structure ac was proposed. (1) ac; m/e 171 In this paper we present a complete analysis of the spectra of these compounds, and of some related naphtho[l,8-bclthiophen derivatives. For reasons outlined in Part I of this series, it is not possible to write structures for fragment ions from aromatic and heteroaromatic molecules with the confidence with which this can be done for many less-aromatic systems. In writing ionic structures to formalize the observed spectra, the following principles have been used: (i) Where the formation of an odd-electron system is involved, the ion is, if possible, written as a radical cation derivable from an aromatic system. There is * Part I, Aust. J. Chem., 1966, 19, 1909. t Department of Organic Chemistry, University of Melbourne, Vic. 3052. $ Present Address: Division of Applied Mineralogy, CSIRO Chemical Research Labora- tories, Melbourne, Vic. 3001. Aust. J. Chem., 1968, 21, 171-83