Safer Conditions for the Curtius Rearrangement of 1,3,5‐Benzenetricarboxylic Acid

Abstract

A rapid method to prepare 1,3,5‐triaminobenzene and its derivatives is the tris‐Curtius rearrangment of 1,3,5‐benzenetricarboxylic acid. The hazards associated with the acyl azide route are minimized by using 1,2‐dichloroethane as solvent. A second method that avoids acyl azide preparation uses diphenylphosphoryl azide to yield the tricarbamate in one step.

Keywords:

• Curtius rearrangement
• 1,2‐dichloroethane
• diphenylphosphoryl azide
• 1,3,5‐triaminobenzene
• 1,3,5‐triisocyanatobenzene
• trimesic acid

Acknowledgments

The generous financial support of this research by the Office of Naval Research is gratefully acknowledged. Support from Barbara Lupei, Cynthia Kitchens, and the librarians of the Technical Library (NAWCWD) for collecting references 1 and 11 is appreciated. Thanks go to Brian Zentner (NAWCWD) for supplying the trimesic acid, Andrew P. Chafin (NAWCWD) for suggestions and corrections in preparation of this manuscript, and Ms. Chrissy Everett (NAWCWD) for help collecting the combustion analyses.