Question

How can alkyl isocyanates be prepared from primary amine?

Answer 1

Primary alkylamines 1 and hindered arylamines 1 give high yields of isocyanates 5when 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 triazolinones7. 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.