Phenol benzoxazine synthesis

The polybenzoxazines (PBZs) provide a new class of phenolic resins that were first described by Ishida in 1998 (Ref. 15). Synthesis of the resins involves three components a phenol, a primary amine and formaldehyde. The first stage involves the formation of a multifunctional benzoxazine monomer Figure 23.30 a)). The monomer can then be ring-opened at elevated temperatures (160-220 C) to yield a polymeric stmcture (Figure 23.30(b)). 

Compounds (412) were formed from the thiophenols (411) with phosgene or thiophosgene (X = O, S) <79GEP(0)2811163> or with BrCN (X = NH) <79GEP(0)28lll3i>. (In a similar [5 + 1 fragment] synthesis, the analogous benzoxazines were obtained from the appropriate phenols see Section 8.25.3.6.4.)... 

Schreiber, for the preparation of phenolic resins with improved thermal, mechanical, and dielectric characteristics. However, no systematic study was reported in Schreiber s patents. Thus, it was of interest to examine in more detail several points such as 1) the synthesis of an homologeous series of benzoxazines, 2) their reaction with phenols, which may be considered as the initiation step of the polymerization by a ring opening mechanism, 3) the pol3nnerization kinetics of benzoxazines, initiated either thermally or with phenols, and 4) the application possibilities of these monomers and polymers. 

Yang P and Gu Y (2012), Synthesis of a novel benzoxazine-containing benzoxazole structure and its high performance thermoset , J Appl Polym Sci, 124, 2415-2422. Yoonessi M, Toghiani H, Wheeler R, Porcar L, Kline S and Pittman Jr C U (2008), Neutron scattering, electron microscopy and dynamic mechanical studies of carbon nanofiber/phenolic resin composites . Carbon, 46, 577-588, and references therein. Yosomiya R (1990), Adhesion and Bonding in Composites, New York, Marcel Dekker, l-A. 

Synthesis of benzoxazines through aziridine ring opening followed by intramolecular C—N bond formation was reported by Sekar and co-workers. " In this approach, a domino ring opening of A -Ts aziridines 332 with o-iodo-phenols 333 followed by copper-catalyzed intramolecular C(aryl)-N(amide) bond formation in the presence of ethyl-enediamine ligand has been established to afford the resultant product 334 in excellent yield (Scheme 40.73). The trans selectivity was confirmed by H NMR spectroscopy and single crystal X-ray analysis. 

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