The third member of the cumulenethione series, H2CnS, propadienethione, has been produced by pyrolysis of cyclopenteno-I ,2,3-thiadiazole and detected by microwave spectroscopy which provided rotational parameters for the 32s and 3 4 s isotopomers, the dipole moment [2.064(8) Debye], and an indication that propadienethione is a planar molecule of C2" symmetry.

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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 Bu 3 P in dichloromethane at -78 °C. Use of Ph 3 P 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. 3940