- Experimental and quantum chemical studies of 2-phosphinylphenol derivatives
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Carbon-oxygen bonds ortho to a phosphoryl group in triarylphosphine oxides undergo cleavage when the oxides are either fused with potassium hydroxide or treated with potassium tert-butoxide in refluxing toluene, presumably through a nucleophilic addition-elimination mechanism. Thus, bis(2-hydroxyphenyl)phenylphosphine oxide is produced along with the expected 2-phenoxyphenyl(phenyl)phosphinic acid from 10-phenyl-10H-phenoxaphosphine 10-oxide. The latter starting material is also produced, together with bis(2-hydroxyphenyl)phenylphosphine oxide, when bis(2-methoxyphenyl)phenylphosphine oxide is fused with potassium hydroxide. Fusion of bis(2-methoxyphenyl)phenylphosphine oxide with sodium hydroxide, however, yields 2-hydroxyphenyl(phenyl)phosphinic acid. Ab initio quantum chemical studies confirm that the downfield 31P chemical shift that is observed in 2-phosphinylphenols is due to hydrogen bonding to the phosphoryl group.
- Levy, Jack B.,Sutton, Steven B.,Olsen, Ronald E.
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p. 601 - 604
(2007/10/03)
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- ALKALINE HYDROLYSIS OF PHENOXA- AND PHENAZAPHOSPHINE OXIDE DERIVATIVES. STRUCTURE OF THE HYDROLYSIS PRODUCT OF 5,10-DIMETHYL-10λ5-PHENAZAPHOSPHINE 10-OXIDE
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Quaternary phosphonium salts - derivatives of 5,10-phenazaphosphine and 5,10-phenoxaphosphine - undergo alkaline hydrolysis with rupture of the endocyclic P-C bond and opening of the central heteroring, unless they contain an external benzyl substituent.T
- Skvortsov, N. K.,Toldov, S. V.,Bel'skii, V. K.
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p. 550 - 553
(2007/10/02)
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