RESEARCH
Azidotriazoles Lose N2 Without Cyclization The first monocoordinate nitrogen derivative from the thermolysis of organic azides is isolated 1,4 - Diphenyl-5-azido-l,2,3-triazole and substituted derivatives lose nitro gen at the exceptionally low (for azides) temperature of 50° C. to form deep red, monomelic compounds. These compounds are easily reduced to the corresponding 5-aminotriazoles [/. Am. Chem. Soc, 86, 2025 (1964)]. Using isotopically labeled compounds, Dr. Peter A. S. Smith, Dr. Leroy Ο. Krbechek, and Dr. Wolfgang Resemann (University of Michigan) find that nitrogen is lost only from the azido group, not from the ring. Furthermore, no rearrange ment takes place and no insertion re actions occur, they find. For the decomposition fragments, the Michigan chemists propose struc tures having a monocoordinate exocyclic nitrogen in equilibrium with a noncyclic isomer. For instance, for
the diphenyl compound, the isomers are: C
I
«H5
\ "Ν
*ISl' I
ΝC = M I
*****
These compounds provide a practi cal route for the synthesis of acetals of α-keto amidines and diarylmaleic acid derivatives. An example is the forma tion of maleimidines and, through them, diarylmaleic anhydrides.
+ CéH5CH2CN. X
H5C4 . C•«"5 6H V ^ l H
•N 2 +
