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

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

doi:10.24820/ark.5550190.p010.208

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

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

Research output: Contribution to journal › Article › peer-review

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.

Original language	English
Pages (from-to)	293-301
Number of pages	9
Journal	ARKIVOC
Volume	2017
Issue number	iii
DOIs	https://doi.org/10.24820/ark.5550190.p010.208
Publication status	Published - 31 Aug 2017

Keywords

Cyclic ylides
Pyrolysis
Phosphoranes
Reactive intermediates

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© ARKAT USA, Inc. 2017. This is an open access article published under a Creative Commons Attribution-NonCommercial 4.0 International licence (CC BY-NC 4.0) - https://creativecommons.org/licenses/by-nc/4.0/
Final published version, 201 KBLicence: CC BY-NC

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title = "New reactions and reactive intermediates in the pyrolysis of cyclic phosphonium ylides",

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.",

keywords = "Cyclic ylides, Pyrolysis, Phosphoranes, Reactive intermediates ",

author = "Aitken, {R Alan} and Vidar Bjornstad and Tracy Massil and Jan Skramstad and Young, {Robert J.}",

note = "The authors are grateful to EPSRC and Glaxo-Wellcome (now GSK) for their support of this work through a CASE Studentship to TM. ",

year = "2017",

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doi = "10.24820/ark.5550190.p010.208",

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T1 - New reactions and reactive intermediates in the pyrolysis of cyclic phosphonium ylides

AU - Aitken, R Alan

AU - Bjornstad, Vidar

AU - Massil, Tracy

AU - Skramstad, Jan

AU - Young, Robert J.

N1 - The authors are grateful to EPSRC and Glaxo-Wellcome (now GSK) for their support of this work through a CASE Studentship to TM.

PY - 2017/8/31

Y1 - 2017/8/31

N2 - 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.

AB - 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.

KW - Cyclic ylides

KW - Pyrolysis

KW - Phosphoranes

KW - Reactive intermediates

U2 - 10.24820/ark.5550190.p010.208

DO - 10.24820/ark.5550190.p010.208

M3 - Article

SN - 1551-7004

VL - 2017

SP - 293

EP - 301

JO - ARKIVOC

JF - ARKIVOC

IS - iii

ER -

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

Abstract

Keywords

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