Substituent and H/D randomization in the mass spectra of substituted diphenylacetylenic compounds

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The mass spectra of several substituted diphenylacetylenes are reported and the [metastable ion]/[daughter ion] ratios for the isomeric chloro‐ and bromodiphenylacetylenes suggested substituent scrambling in their respective molecular ions. The metastable ion data also indicated equilibration of the chloro substituents in a series of isomeric dichlorodiphenylacetylenes. In addition, the fragmentation patterns for the amino‐ and nitrodiphenylacetylenes differed somewhat from most other aromatic amino and nitro compounds. The aminodiphenylacetylenes fragment with expulsion of H2CN from the molecular ion and the expulsion of HCN from the [M – 1]+ ion was only a relatively minor reaction. 4‐Nitrodiphenylacetylene loses NO from the molecular ion and OH from the [M – NO]+˙, whereas the more familiar loss of OH from the molecular ion was not observed. The mass spectra of several deuterated substituted diphenylacetylenes clearly showed extensive (but not complete) H/D equilibration in the molecular ion or some subsequent decomposition ion. Comparative studies between 4‐chloro and 4‐bromo substituted biphenyl, diphenylacetylene and diphenyldiacetylene indicated similar degrees of H/D randomization, and the results showed that the CC group did not inhibit the proton equilibration between the two phenyl groups.

Original languageEnglish (US)
Pages (from-to)1329-1336
Number of pages8
JournalOrganic Mass Spectrometry
Issue number12
StatePublished - Dec 1973

ASJC Scopus subject areas

  • Biochemistry
  • Molecular Medicine
  • Instrumentation


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