Preparation of isocyanates from primary amines and carbon dioxide using Mitsunobu chemistry

Dilek Saylik, Michael J. Horvath, Patricia S. Elmes, W. Roy Jackson, Craig G. Lovel, Keith Moody

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Primary alkylamines 1 and hindered arylamines 1 give high yields of isocyanates 5 when reacted with carbon dioxide and the Mitsunobu zwitterions 4 generated from dialkyl azodicarboxylates and Bu3P in dichloromethane at - 78°C. Use of Ph3P still gave high yields of isocyanates from reactions of primary alkylamines, but only low yields were obtained from reactions of aromatic amines. Reactions which failed to give high yields of isocyanates gave either carbamoylhydrazines 6 and/or dicarbamoylhydrazines 10 and/or triazolinones 7. The triazolinones were shown to arise from reactions of reactive aryl isocyanates with the Mitsunobu zwitterion. The carbamoylhydrazines were shown not to arise from reaction of isocyanate with reduced dialkyl azodicarboxylates, and a mechanism for their formation is proposed. Single-crystal X-ray analyses confirmed the structures of 6, 7, and 10.

Original languageEnglish
Pages (from-to)3940-3946
Number of pages7
JournalThe Journal of Organic Chemistry
Issue number11
Publication statusPublished - 28 May 1999

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