Skip to content

Research at St Andrews

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

Research output: Research - peer-reviewArticle

DOI

Open Access permissions

Open

Author(s)

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

School/Research organisations

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.
Close

Details

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

Discover related content
Find related publications, people, projects and more using interactive charts.

View graph of relations

Related by author

  1. Octahydro-1H,5H,7H-dipyrrolo[1,2-c:1',2'-f][1,3,6]oxadiazocine-5-thione

    Aitken, R. A. & Ali, K. 27 Apr 2018 In : Molbank. 2018, 5 p., M993

    Research output: Research - peer-reviewArticle

  2. Structure and thermal reactivity of some 2-substituted 1,3-oxathiolane S-oxides

    Aitken, R. A., Henderson, S. & Slawin, A. M. Z. 20 Mar 2018 In : Journal of Sulfur Chemistry. 39, 13 p.

    Research output: Research - peer-reviewArticle

  3. 5-Amino-3-methyl-1,2,4-thiadiazole

    Aitken, R. A. & Slawin, A. M. Z. 21 Jan 2018 In : Molbank. 2018, 1, 5 p., M977

    Research output: Research - peer-reviewArticle

  4. Gas-phase domino cyclisation of phosphonium ylides leading to the total synthesis of Eustifoline D

    Aitken, R. A. & Murray, L. 15 Nov 2017 In : Tetrahedron Letters. 58, 46, p. 4328-4332 5 p.

    Research output: Research - peer-reviewArticle

  5. The value of 2JP–CO as a diagnostic parameter for the structure and thermal reactivity of carbonyl-stablised phosphonium ylides

    Aitken, R. A., Boubalouta, Y., Chang, D., Cleghorn, L. P., Gray, I. P., Karodia, N., Reid, E. J. & Slawin, A. M. Z. 2 Nov 2017 In : Tetrahedron. 73, 44, p. 6275-6285 11 p.

    Research output: Research - peer-reviewArticle

Related by journal

  1. Improved synthesis and characterisation of 1,3,4-oxadiazole

    Aitken, K. M. & Aitken, R. A. 2012 In : ARKIVOC. 13, v, p. 75-79 5 p.

    Research output: Research - peer-reviewArticle

  2. Pyrolytic Decomposition of Simple Acetylenic Esters

    Aitken, R. A. & Morrison, J. J. 2008 In : ARKIVOC. 9, x, p. 103-112 10 p.

    Research output: Research - peer-reviewArticle

  3. Synthetic applications of chiral 1,3-dioxolan-4-ones and 3-acyloxazolidin-5-ones

    Aitken, R. A., McGill, S. D. & Power, L. A. 2006 In : ARKIVOC. 7, vii, p. 293-300 8 p.

    Research output: Research - peer-reviewArticle

Related by journal

  1. ARKIVOC (Journal)

    Walton, J. C. (Member of editorial board)
    2003 → …

    Activity: Publication peer-review and editorial workEditor of research journal

ID: 250439696