Quasiphosphonium intermediates-IV1 1 Part III. H.R. Hudson, A. Kow and J.C. Roberts, J. Chem. Soc. Perkin II paper 3/066 (1983). Isolation and identification of intermediates in the arbuzov and perkow reactions of neopentyl esters of phosphorus(III) acids with α-halogenoacetophenones

Imre Petneházy, Gyöngyi Szakál, L. Tőke, Harry R. Hudson, Luba Powroznyk, Christopher J. Cooksey

Research output: Contribution to journalArticle

20 Citations (Scopus)

Abstract

Crystalline ketophosphonium bromides have been isolated as intermediates in the reactions of trineopentyl phosphite, dineopentyl phenylphosphonite, and neopentyl diphenylphosphinite with α-bromoacetophenone. Thermal decomposition in solution occurs in each case to yield neopentyl bromide and the corresponding Arbuzov product only. Rearrangement to the Perkow intermediate or product does not occur. An identifiable Perkow intermediate was separated from the reaction of neopentyl diphenylphosphinite with α-chloroacetophenone at O° and was shown to yield neopentyl chloride and the corresponding Perkow product by a first-order process in chloroform (t 1 2 ca 40min at 33°). It is suggested that the betaine formed by initial attack of phosphorus at the carbonyl carbon atom may be a common first intermediate in reactions that yield both Arbuzov and Perkow products.

Original languageEnglish
Pages (from-to)4229-4235
Number of pages7
JournalTetrahedron
Volume39
Issue number24
DOIs
Publication statusPublished - 1983

Fingerprint

omega-Chloroacetophenone
Phosphorus Acids
Phosphites
Betaine
Chloroform
Bromides
Phosphorus
Esters
Pyrolysis
Carbon
Hot Temperature
Crystalline materials
Atoms
Acids
neopentyl chloride
neopentyl bromide
phenacyl bromide

ASJC Scopus subject areas

  • Biochemistry
  • Organic Chemistry
  • Drug Discovery

Cite this

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title = "Quasiphosphonium intermediates-IV1 1 Part III. H.R. Hudson, A. Kow and J.C. Roberts, J. Chem. Soc. Perkin II paper 3/066 (1983). Isolation and identification of intermediates in the arbuzov and perkow reactions of neopentyl esters of phosphorus(III) acids with α-halogenoacetophenones",
abstract = "Crystalline ketophosphonium bromides have been isolated as intermediates in the reactions of trineopentyl phosphite, dineopentyl phenylphosphonite, and neopentyl diphenylphosphinite with α-bromoacetophenone. Thermal decomposition in solution occurs in each case to yield neopentyl bromide and the corresponding Arbuzov product only. Rearrangement to the Perkow intermediate or product does not occur. An identifiable Perkow intermediate was separated from the reaction of neopentyl diphenylphosphinite with α-chloroacetophenone at O° and was shown to yield neopentyl chloride and the corresponding Perkow product by a first-order process in chloroform (t 1 2 ca 40min at 33°). It is suggested that the betaine formed by initial attack of phosphorus at the carbonyl carbon atom may be a common first intermediate in reactions that yield both Arbuzov and Perkow products.",
author = "Imre Petneh{\'a}zy and Gy{\"o}ngyi Szak{\'a}l and L. Tőke and Hudson, {Harry R.} and Luba Powroznyk and Cooksey, {Christopher J.}",
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AU - Petneházy, Imre

AU - Szakál, Gyöngyi

AU - Tőke, L.

AU - Hudson, Harry R.

AU - Powroznyk, Luba

AU - Cooksey, Christopher J.

PY - 1983

Y1 - 1983

N2 - Crystalline ketophosphonium bromides have been isolated as intermediates in the reactions of trineopentyl phosphite, dineopentyl phenylphosphonite, and neopentyl diphenylphosphinite with α-bromoacetophenone. Thermal decomposition in solution occurs in each case to yield neopentyl bromide and the corresponding Arbuzov product only. Rearrangement to the Perkow intermediate or product does not occur. An identifiable Perkow intermediate was separated from the reaction of neopentyl diphenylphosphinite with α-chloroacetophenone at O° and was shown to yield neopentyl chloride and the corresponding Perkow product by a first-order process in chloroform (t 1 2 ca 40min at 33°). It is suggested that the betaine formed by initial attack of phosphorus at the carbonyl carbon atom may be a common first intermediate in reactions that yield both Arbuzov and Perkow products.

AB - Crystalline ketophosphonium bromides have been isolated as intermediates in the reactions of trineopentyl phosphite, dineopentyl phenylphosphonite, and neopentyl diphenylphosphinite with α-bromoacetophenone. Thermal decomposition in solution occurs in each case to yield neopentyl bromide and the corresponding Arbuzov product only. Rearrangement to the Perkow intermediate or product does not occur. An identifiable Perkow intermediate was separated from the reaction of neopentyl diphenylphosphinite with α-chloroacetophenone at O° and was shown to yield neopentyl chloride and the corresponding Perkow product by a first-order process in chloroform (t 1 2 ca 40min at 33°). It is suggested that the betaine formed by initial attack of phosphorus at the carbonyl carbon atom may be a common first intermediate in reactions that yield both Arbuzov and Perkow products.

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