Kinetics and mechanism of gas-phase pyrolysis of ylides. Part 3.1 Thermal reactivity of α-carbonyl- and thiocarbonyl-stabilized methylenetriphenylphosphoranes

被引：5
作者：
Al-Bashir, Rasha F. [2 ]
Al-Awadi, Nouria A. [1 ]
El-Dusouqui, Osman M. E. [1 ]
机构：
[1] Kuwait Univ, Dept Math, Kuwait 13060, Kuwait
[2] Coll Technol Studies, Dept Appl Sci, Publ Author Appl Educ & Training, Kuwait, Kuwait
来源：
JOURNAL OF PHYSICAL ORGANIC CHEMISTRY | 2011年 / 24卷 / 04期
关键词：
gas-phase; kinetics; mechanism; pyrolysis; ylides; FLASH VACUUM PYROLYSIS; PHOSPHORUS YLIDES; PHOSPHINE ALKYLENES; GENERATION; COMPLEXES; SECONDARY; ROUTE; STATE; ACIDS;
D O I：
10.1002/poc.1752
中图分类号：
O62 [有机化学];
学科分类号：
070303 ; 081704 ;
摘要：
Fourteen ketone/thione-stabilized triphenylphosphonium methylides were subjected to conventional gas-phase and flash vacuum pyrolysis (FVP). The kinetics of the first-order thermal gas-phase reactions of all these compounds were investigated over 360-653 K temperature range. The values of the Arrhenius log A and energy of activation of these ylides averaged 11.52+/-0.34 s(-1) and 133.20+/-3.14 kJ mol(-1), respectively. The products of sealed-tube (static) and FVP were analyzed and compared. A mechanism is proposed to account for the products of reaction. The rate constants [k(s(-1))] of the substrates at 500 K were calculated and used to substantiate the proposed mechanism of pyrolysis, and to rationalize the thermal gas-phase reactivities of the ylides under study. Copyright (C) 2010 John Wiley & Sons, Ltd.
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收藏
页码：311 / 319
页数：9
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