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

Robert Alan Aitken; NA Al-Awadi; Graham Dawson; O El-Dusouqi; DMM Farrell; K Kaul; A Kumar

doi:10.1016/j.tet.2004.10.058

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

Robert Alan Aitken, NA Al-Awadi, Graham Dawson, O El-Dusouqi, DMM Farrell, K Kaul, A Kumar

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

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. (C) 2004 Elsevier Ltd. All rights reserved.

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

Keywords

ylides
pyrolysis
kinetics
substituent effects
STABILIZED PHOSPHORUS YLIDES
PHASE PYROLYTIC REACTIONS
FLASH VACUUM PYROLYSIS
WITTIG REAGENTS
ISOTHIOCYANATES
ISOCYANATES
BEHAVIOR

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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. (C) 2004 Elsevier Ltd. All rights reserved.",

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author = "Aitken, {Robert Alan} and NA Al-Awadi and Graham Dawson and O El-Dusouqi and DMM Farrell and K Kaul and A Kumar",

year = "2005",

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

language = "English",

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

AU - Aitken, Robert Alan

AU - Al-Awadi, NA

AU - Dawson, Graham

AU - El-Dusouqi, O

AU - Farrell, DMM

AU - Kaul, K

AU - Kumar, A

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. (C) 2004 Elsevier Ltd. All rights reserved.

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. (C) 2004 Elsevier Ltd. All rights reserved.

KW - ylides

KW - pyrolysis

KW - kinetics

KW - substituent effects

KW - STABILIZED PHOSPHORUS YLIDES

KW - PHASE PYROLYTIC REACTIONS

KW - FLASH VACUUM PYROLYSIS

KW - WITTIG REAGENTS

KW - ISOTHIOCYANATES

KW - ISOCYANATES

KW - BEHAVIOR

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U2 - 10.1016/j.tet.2004.10.058

DO - 10.1016/j.tet.2004.10.058

M3 - Article

SN - 0040-4020

VL - 61

SP - 129

EP - 135

JO - Tetrahedron

JF - Tetrahedron

ER -

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

Abstract

Keywords

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