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New reactions and reactive intermediates in the pyrolysis of cyclic phosphonium ylides

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Author(s)

R Alan Aitken, Vidar Bjornstad, Tracy Massil, Jan Skramstad, Robert J. Young

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Abstract

Pyrolysis, either neat or in diphenyl ether solution, results in the conversion of both 4-triphenylphosphoranylidenetetrahydrofuran-2,3,5-trione and 4-triphenylphosphoranylidenetetrahydrothio-phene-2,3,5-trione into 3,5-bis(triphenylphosphoranylidene)cyclopentane-1,2,4-trione. These reactions involve extrusion of CO2 or COS to give 3-triphenylphosphoranylidenecyclopropane-1,2-dione which further loses CO to give triphenylphosphoranylideneketene. The precise way in which these two reactive phosphorus compounds combine to give the observed product has been examined by chemical and isotopic labelling studies. Cyclotrimerization of triphenylphosphoranylideneketene upon thermolysis in diphenyl ether has also been observed for the first time. The erroneous literature interpretation of the 13C NMR spectrum for triphenylphosphoranylideneketene is corrected.
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Original languageEnglish
Pages (from-to)293-301
Number of pages9
JournalARKIVOC
Volume2017
Issue numberiii
DOIs
StatePublished - 31 Aug 2017

    Research areas

  • Cyclic ylides, Pyrolysis, Phosphoranes, Reactive intermediates

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