The mass spectra of some simple phenylhydrazides and a re-examination of the fragmentations of phenylhydrazine

✍ Scribed by Peder Wolkoff; Steen Hammerum

• Publisher: John Wiley and Sons
• Year: 1976
• Tongue: English
• Weight: 479 KB
• Volume: 11
• Category: Article
• ISSN: 1076-5174
• DOI: 10.1002/oms.1210110407

✦ Synopsis

Abstract

The elimination of small neutral fragments from acetyl‐, formyl‐ and ethoxycarbonyl‐ phenylhydrazines with formation of [C6H8N2]^+^⋅ ions has been studied. Evidence is obtained from deuterium labelling and from metastable peak intensity ratios, to show that ketene loss from both acetylphenylhydrazines is accompanied (or preceded) by hydrogen transfer to the acylated nitrogen atom to give ions structurally analogous to the phenylhydrazine molecular ion. The decomposing [C6H8N2]^+^⋅ ions formed from formyl‐ and ethoxycarbonylphenylhydrazines are also suggested to have a phenylhydrazine‐like structure. In the molecular ion of phenylhydrazine interchange occurs between the two ortho hydrogen atoms and two of the three hydrazine hydrogens prior to decomposition; labelling data suggest that the N‐1 hydrogen does not participate in the interchange process.