2-Bromo-3,3-diphenylallyltriphenylphosphonium bromide, upon treatment with 1 equiv of base, yields 3,3-diphenylallenyltriphenylphosphonium bromide, whereas excess base produces, in situ, a cumulative ylide (15). The allenylphosphonium salt is unreactive to methyl alcohol and -butyl mercaptan, but adds aniline. This latter adduct can be dehydrohalogenated to an imino-stabilized phosphorus ylide (12) which reacts with aromatic aldehydes via the Wittig reaction. The cumulative ylide (15) undergoes Wittig reactions with aromatic aldehydes, aromatic isocyanates, and diphenylketene.The reaction of chlorodiphenylacetonitrile with triphenylphosphine has been described.1 The reactive intermediate (1) which is formed has been shown to react with nucleophiles such as alcohols, mercaptans, amines, and carboxylic acids. Because it seemed probable that 1 existed as an a-halovinylphosphinimine (C6H5)2C=C-N=P(C6H5)3 I Cl 1 rather than a ketiminephosphonium salt (2) it was of interest to prepare and study the chemistry of an a-halovinyl ylide (3).(C6H5)2C=C=N-P(C6H5)3 Cl-2 in the ir spectrum and a doublet at 1.3 (/ = 9 cps) for 5 (C6H5)2C=C=CH-P(C6H5)3 Br-6
Stable enol phosphonium salts were isolated from the reaction of certain a-haloacetophenones and triphenylphosphine. Pyrolysis and solvolysis of the enol phosphonium salts were also studied. The stereochemistry of the pyrolysis of lib is discussed. Treatment of chlorodiphenylacetonitrile with triphenylphosphine led to the formation of an intermediate which, upon being treated with methanol, afforded the N-acylphosphinimine XIV.Treatment of chlorodiphenylacetonitrile with triethyl phosphite led to ketene imine XXIV and tetraphenylsuccinonitrile as a by-product. The formation of stable enol phosphonium salts, N-acylphosphinimine, ketenimine, and tetraphenylsuccinonitrile is interpreted mechinteresting since either cisor zrans-dichlorostilbene 5068
Aus Benzophenon (I) kann über die Zwischenstufen (II) bis (IV) das Phosphoniumbromid (V) dargestellt werden (96% Ausbeute), dessen vorsichtige Dehydrohalogenierung zu dem Allenylphosphoniumbromid (VI) führt (81%).
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