Synthesis, thermal reactivity and kinetics of substituted [(benzoyl)(phenylcarbamoyl)methylene]triphenylphosphoranes and their thiocarbamoyl analogues

R. Alan Aitken; Nouria A. Al-Awadi; Graham Dawson; Osman M.E. El-Dusouqi; Dorcas M.M. Farrell; Kamini Kaul; Ajith Kumar

doi:10.1016/j.tet.2004.10.058

Synthesis, thermal reactivity and kinetics of substituted [(benzoyl)(phenylcarbamoyl)methylene]triphenylphosphoranes and their thiocarbamoyl analogues

R. Alan Aitken, Nouria A. Al-Awadi, Graham Dawson, Osman M.E. El-Dusouqi, Dorcas M.M. Farrell, Kamini Kaul, Ajith Kumar

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

15 Citations (Scopus)

Abstract

A range of 16 substituted benzoyl/arylcarbamoyl and benzoyl/ arylthiocarbamoyl stabilised ylides have been prepared. They are found under conditions of flash vacuum pyrolysis to fragment giving a benzoyl ylide and aryl isocyanate or isothiocyanate accompanied in some cases by secondary pyrolysis products. Kinetic studies show the thiocarbamoyl ylides to react consistently faster than their carbamoyl analogues and substituent effects suggest a polar cyclic transition state, which involves attack by the benzoyl oxygen on the carbamoyl/thiocarbamoyl NH. Graphical Abstract.

Original language	English
Pages (from-to)	129-135
Number of pages	7
Journal	Tetrahedron
Volume	61
Issue number	1
DOIs	https://doi.org/10.1016/j.tet.2004.10.058
Publication status	Published - 3 Jan 2005
Externally published	Yes

Keywords

Kinetics
Pyrolysis
Substituent effects
Ylides

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10.1016/j.tet.2004.10.058

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title = "Synthesis, thermal reactivity and kinetics of substituted [(benzoyl)(phenylcarbamoyl)methylene]triphenylphosphoranes and their thiocarbamoyl analogues",

abstract = "A range of 16 substituted benzoyl/arylcarbamoyl and benzoyl/ arylthiocarbamoyl stabilised ylides have been prepared. They are found under conditions of flash vacuum pyrolysis to fragment giving a benzoyl ylide and aryl isocyanate or isothiocyanate accompanied in some cases by secondary pyrolysis products. Kinetic studies show the thiocarbamoyl ylides to react consistently faster than their carbamoyl analogues and substituent effects suggest a polar cyclic transition state, which involves attack by the benzoyl oxygen on the carbamoyl/thiocarbamoyl NH. Graphical Abstract.",

keywords = "Kinetics, Pyrolysis, Substituent effects, Ylides",

author = "Aitken, {R. Alan} and Al-Awadi, {Nouria A.} and Graham Dawson and El-Dusouqi, {Osman M.E.} and Farrell, {Dorcas M.M.} and Kamini Kaul and Ajith Kumar",

note = "Funding Information: We thank Kuwait University for support (Research Grant SC 03/99) and provision of facilities through ANALAB and SAF.",

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doi = "10.1016/j.tet.2004.10.058",

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T1 - Synthesis, thermal reactivity and kinetics of substituted [(benzoyl)(phenylcarbamoyl)methylene]triphenylphosphoranes and their thiocarbamoyl analogues

AU - Aitken, R. Alan

AU - Al-Awadi, Nouria A.

AU - Dawson, Graham

AU - El-Dusouqi, Osman M.E.

AU - Farrell, Dorcas M.M.

AU - Kaul, Kamini

AU - Kumar, Ajith

N1 - Funding Information: We thank Kuwait University for support (Research Grant SC 03/99) and provision of facilities through ANALAB and SAF.

PY - 2005/1/3

Y1 - 2005/1/3

N2 - A range of 16 substituted benzoyl/arylcarbamoyl and benzoyl/ arylthiocarbamoyl stabilised ylides have been prepared. They are found under conditions of flash vacuum pyrolysis to fragment giving a benzoyl ylide and aryl isocyanate or isothiocyanate accompanied in some cases by secondary pyrolysis products. Kinetic studies show the thiocarbamoyl ylides to react consistently faster than their carbamoyl analogues and substituent effects suggest a polar cyclic transition state, which involves attack by the benzoyl oxygen on the carbamoyl/thiocarbamoyl NH. Graphical Abstract.

AB - A range of 16 substituted benzoyl/arylcarbamoyl and benzoyl/ arylthiocarbamoyl stabilised ylides have been prepared. They are found under conditions of flash vacuum pyrolysis to fragment giving a benzoyl ylide and aryl isocyanate or isothiocyanate accompanied in some cases by secondary pyrolysis products. Kinetic studies show the thiocarbamoyl ylides to react consistently faster than their carbamoyl analogues and substituent effects suggest a polar cyclic transition state, which involves attack by the benzoyl oxygen on the carbamoyl/thiocarbamoyl NH. Graphical Abstract.

KW - Kinetics

KW - Pyrolysis

KW - Substituent effects

KW - Ylides

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U2 - 10.1016/j.tet.2004.10.058

DO - 10.1016/j.tet.2004.10.058

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SN - 0040-4020

VL - 61

SP - 129

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JO - Tetrahedron

JF - Tetrahedron

IS - 1

ER -

Synthesis, thermal reactivity and kinetics of substituted [(benzoyl)(phenylcarbamoyl)methylene]triphenylphosphoranes and their thiocarbamoyl analogues

Abstract

Keywords

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