Hydroxylation and amination of azulenes by vicarious nucleophilic substitution of hydrogen

Hydroxylation of azulenes with tert-butylhydroperoxide proceeds efficiently at the 6-position when the former contain electron-withdrawing substituent s in the five-membered ring. Similarly, VNS amination of azulenes proceeds with 4-amino-1,2,4-triazole; its anion, being an active nucleophile, also r eacts with unsubstituted azulene. A variety of transformations of 6-hydroxy azulenes, such as substitution of the corresponding sulfonates with nitroge n, oxygen, sulfur, carbon nucleophiles and halogens, and the Claisen rearra ngement of allylic ethers, is reported.