Generation and selected reactions of chlorinated thiocarbonyl S-imides*

Grzegorz Mloston, Paulina Pipiak, Jürgen Voss, Dirk Buddensiek, Alexander Erich Eugen Senning

Research output: Contribution to journalJournal articleResearchpeer-review

Abstract

N-Aryl-1,1,1-trichloromethanesulfenamides ArNH-SCCl3 easily undergo dehydrochlorination upon treatment with potassium hydroxide in ethanolic solution. The intermediate thiocarbonyl S-imides formed thereby behave differently depending on the type of the N-aryl group. The sterically crowded N-(2,6-dimethylphenyl)- and -N-(2,4,6-trimethylphenyl)-1,1,1-trichloromethanesulfenamides yield the corresponding sulfur N,N'-diaryldiimides via a multi-step reaction, whereas the less crowded 2-methylphenyl and 4-methylphenyl derivatives undergo a regioselective 'head-to-head' dimerization leading to 5,5,6,6-tetrachloro-1,4,2,3-dithiadiazinanes in high yields. An identical reaction course is observed in the case of the 4-methoxy- and 4-bromoaniline derivatives. A diradical mechanism is postulated to explain the 'head-to-head' dimerization pathway.
Original languageEnglish
JournalJournal of Sulfur Chemistry
Volume38
Issue number5
Pages (from-to)530-547
ISSN1741-5993
DOIs
Publication statusPublished - 2017

Keywords

  • Chlorinated organic compounds
  • Head-to-head dimerization
  • Reactive intermediates
  • Thiocarbonyl compounds
  • Thiocarbonyl S-imides

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