A one-pot synthetic approach to new fused heterocyclic skeleton 12H,14H-quinazolino[3,4-a]-3,1-benzoxazine by Staudinger/aza-Wittig sequence has been developed. The sequential reaction of azides 3 with triphenylphosphine and acyl chlorides or CS 2 produced 12H,14H-quinazolino[3,4-a]-3,1-benzoxazines 5 or 6 in good yields via a consecutive Staudinger/aza-Wittig/ cyclization react...