TiCl4-Catalyzed Addition of HN3 to Aldehydes and Ketones. Thermolysis and Photolysis of α-Azido Ethers

Article abstract of DOI:10.1021/jo00236a006

Aldehydes react with hydrazoic acid and alcohols in the presence of catalytic amounts of TiCl4 to produce α-azido ethers.The conversion of simple ketones to methyl α-azido alkyl ethers can be accomplished by means of hydrazoic acid and methyl orthoformate.Both gas-phase thermolysis and photolysis of representative α-azido ethers were studied and shown to produce mainly imino ethers.In the thermolysis, migratory preference decreases in the series H >> CH3 > Ph >> OR.