Toward the Synthesis of Tetrazino‐tetrazine 1,3,6,8‐Tetraoxide (TTTO): An Approach to Non‐annulated 1,2,3,4‐Tetrazine 1,3‐Dioxides

Abstract

Abstract A novel approach for the synthesis of 6‐( tert ‐butyl‐ NNO ‐azoxy)‐5‐methylthio‐1,2,3,4‐tetrazine 1,3‐dioxide ( 1 ) was developed. This compound is likely to be a precursor of tetrazino‐tetrazine 1,3,6,8‐tetraoxide. The synthetic strategy consists of four steps: a synthesis of bis( tert ‐butyl‐ NNO ‐azoxy)methane, coupling of the latter with dimethyl nitrodithioimidocarbonate to give N ‐nitroimine 3 , O ‐alkylation of the latter to O ‐alkylated nitroenamine and its reaction with BF 3 · Et 2 O to afford tetrazine 1,3‐dioxide 1 . An X‐ray diffraction study of 1 was accomplished.