Polymerization of benzoxazine resins is indicated by the disappearance of a 960-900. cm(-1) band in infrared spectroscopy (IR). Historically, this band was assigned to the C-H out-of-plane bending of the benzene to Which the oxazine ring is attached. This study shows that this band is a mixture of the O-C-2. stretching of the oxazine ring and the phenolic ring vibrational modes. Vibrational frequencies of 3-phenyl-3,4-dihydro-2,H-benzo[e] [1,3] oxazine (PH-a) and 3-(tert-butyl)-3,4-dihydro-2H-benzo[e] [1,3]oxazine (PH-t) are compared with isotope-exchanged and all-substituted compounds. Deuterated berizoxazine monomers, N-15-isotope exchanged benzoxazine monomers, and all-substituted benzoxazine monomers without aromatic C-H groups are synthesized and studied meticulously. The various isotopic-exchanges invoked deuteration around the benzene ring of phenol, selective deuteration of each CH2 in the O-CH2-N (2) and N-CH2-Ar (4) positions on the oxazine ring, or simultaneous deuteration of both positions. The chemical structures Were confirmed by H-1 nuclear magnetic resonance spectroscopy (H-1 NMR). The IR and Raman spectra of each compound are compared. Further analysis of N-15 isotope-exchanged PH-a indicates the influence of the nitrogen isotope on the band position, both experimentally and theoretically. This finding is important for polymerization studies of benzoxazines that utilize vibrational spectroscopy.