Mechanism of selective formation of 2-amino-substituted 1,4-benzodiazepin-4-oxides and 2-aminomethyl substituted quinazolin-3-oxides from chloromethyl quinazolin-N-oxides indications from perturbation theory

Article abstract of DOI:10.1002/ardp.19943270204

The o-amino-acetophenone and -benzophenone oximes 1a-c react with chloroacetyl chloride giving the 2-chloromethyl-quinazoline-3-oxides 6a-c. The mechanism is explained using the perturbation theory. With ammonia and N-prim. aliphatic amines, compounds 6a-c yield 1,4-benzodiazepines 16 and 17 as ring-enlarged products, with aromatic and with N-sec. aliphatic amines, quinazoline derivatives 10-13 are formed. The constitution of the heterocycles is proved by nmr spectroscopic methods. Selective formation of the heterocyclic products is explained with the relative thermodynamic stability of the corresponding 2-adducts 14.