Oxazine Ring-Related Vibrational Modes of Benzoxazine Monomers Using Fully Aromatically Substituted, Deuterated,15N Isotope Exchanged, and Oxazine-Ring-Substituted Compounds and Theoretical Calculations

Han, L; Iguchi, D; Gil, P; Heyl, TR; Sedwick, VM; Arza, CR; Ohashi, S; Lacks, DJ; Ishida, H

HERO ID

4272809

Reference Type

Journal Article

Year

2017

Language

English

PMID

28747051

HERO ID 4272809
In Press No
Year 2017
Title Oxazine Ring-Related Vibrational Modes of Benzoxazine Monomers Using Fully Aromatically Substituted, Deuterated,15N Isotope Exchanged, and Oxazine-Ring-Substituted Compounds and Theoretical Calculations
Authors Han, L; Iguchi, D; Gil, P; Heyl, TR; Sedwick, VM; Arza, CR; Ohashi, S; Lacks, DJ; Ishida, H
Journal Journal of Physical Chemistry A
Volume 121
Issue 33
Page Numbers 6269-6282
Abstract Polymerization of benzoxazine resins is indicated by the disappearance of a 960-900 cm-1band 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-C2stretching of the oxazine ring and the phenolic ring vibrational modes. Vibrational frequencies of 3-phenyl-3,4-dihydro-2H-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 benzoxazine monomers,15N-isotope exchanged benzoxazine monomers, and all-substituted benzoxazine monomers without aromatic C-H groups are synthesized and studied meticulously. The various isotopic-exchanges involved deuteration around the benzene ring of phenol, selective deuteration of each CH2in 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 by1H nuclear magnetic resonance spectroscopy (1H NMR). The IR and Raman spectra of each compound are compared. Further analysis of15N 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.
Doi 10.1021/acs.jpca.7b05249
Pmid 28747051
Wosid WOS:000408598100009
Url https://www.scopus.com/inward/record.uri?eid=2-s2.0-85028329836&doi=10.1021%2facs.jpca.7b05249&partnerID=40&md5=71da71b714c2293b05c63acacd9036fb
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Dupe Override No
Is Public Yes
Language Text English