Generation and Characterization of a 4π-Electron Three-Membered Ring 1H-Diazirine: An Elusive Intermediate in Nitrile Imine-Carbodiimide Isomerization

Nunes C. M., Araujo-Andrade C., Fausto R., Reva I.

JOURNAL OF ORGANIC CHEMISTRY, vol.79, no.8, pp.3641-3646, 2014 (SCI-Expanded) identifier identifier identifier

  • Publication Type: Article / Article
  • Volume: 79 Issue: 8
  • Publication Date: 2014
  • Doi Number: 10.1021/jo402744f
  • Journal Name: JOURNAL OF ORGANIC CHEMISTRY
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Page Numbers: pp.3641-3646
  • Istanbul Kültür University Affiliated: Yes

Abstract

The photolysis at 222 nm of 5-methyltetrazole isolated in a cryogenic argon matrix leads to formation of methyl nitrile innine as primary product. Subsequent irradiation at 328 nm induces transformation of the nitrile imine into 4 pi-electron three-membered-ring 3-methyl-1H-diazirine, which photorearranges to give methyl carbodiimide. These products were characterized by IR spectroscopy and theoretical calculations. For the first time, a 1H-diazirine was captured as intermediate in the photoisomerization of nitrile imines into carbodiimides.