A convenient synthesis of arylbenzenes

Hey, D. H.; Liang, Katherine S. Y.; Perkins, M. J.; Williams, Gareth

doi:10.1039/j39670001153

Cited by 1 publication

(3 citation statements)

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“…The alkaline hydrolysis of phosphonium salts is one of the prototypical reactions in phosphorus chemistry, having been reported on for the first time (to our knowledge) as early as 1857 . The reaction has been the subject of numerous mechanistic investigations over the course of many years . Phosphorane (P V ) species are the only observable intermediates in phosphonium salt and ylide hydrolysis and alcoholysis reactions (vide infra) .…”

Section: Introductionmentioning

confidence: 99%

“… Phosphonium salt and ylide alcoholysis reactions of: a) Schmidbaur, b) Hey and Ingold and Eyles and Trippett, c) Grayson and Keough …”

Section: Introductionmentioning

confidence: 99%

“…The nature of the products of these reactions seems to depend on the conditions. Heating of the alkoxytetralkylphosphoranes generated from ylide 3 (Scheme a) or of tetraalkylphosphonium alkoxide salts ( 5 – 7 , generated by treatment of phosphonium halides with NaOEt in dry ethanol, Scheme b) in the absence of solvent gave phosphine oxide and alkane. In both the alcoholysis of 3 and that of 5 – 7 , the alkane formed was the product of C−C bond formation between the oxygen‐bearing carbon of the alkoxy group and the phosphorus‐bearing group of the phosphonium ylide or salt that is, between groups initially attached to P and C, respectively .…”

Section: Introductionmentioning

confidence: 99%

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The Mechanism of Phosphonium Ylide Alcoholysis and Hydrolysis: Concerted Addition of the O−H Bond Across the P=C Bond

Byrne

Gilheany

2016

Chemistry A European J

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The previous work on the hydrolysis and alcoholysis reactions of phosphonium ylides is summarized and reviewed in the context of their currently accepted mechanisms. Several experimental facts relating to ylide hydrolysis and to salt and ylide alcoholysis are shown to conflict with those mechanisms. In particular, we demonstrate that the pKa values of water and alcohols are too high in organic media to bring about protonation of ylide. Therefore, we propose concerted addition of the water or alcohol O-H bond across the ylide P=C bond. In support of this, we provide NMR spectroscopic evidence for equilibrium between ylide and aclohol that does not require the involvement of phosphonium hydroxide. We report the first P-alkoxyphosphorane to be characterised by NMR spectroscopy that does not undergo exchange on an NMR timescale. Two-dimensional NMR spectroscopic techniques have been applied to the characterisation to P-alkoxyphosphoranes for the first time.

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Section: Introductionmentioning

confidence: 99%

“… Phosphonium salt and ylide alcoholysis reactions of: a) Schmidbaur, b) Hey and Ingold and Eyles and Trippett, c) Grayson and Keough …”

Section: Introductionmentioning

confidence: 99%