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首页> 外文期刊>Journal of Physical Organic Chemistry >Kinetics and mechanism of gas-phase pyrolysis of ylides. Part 3. 1 Thermal reactivity of α-carbonyl- and thiocarbonyl-stabilized methylenetriphenylphosphoranes
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Kinetics and mechanism of gas-phase pyrolysis of ylides. Part 3. 1 Thermal reactivity of α-carbonyl- and thiocarbonyl-stabilized methylenetriphenylphosphoranes

机译：气相气相裂解的动力学和机理。第3部分。1α-羰基和硫代羰基稳定的亚甲基三苯基膦的热反应性

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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 360-653K temperature range. The values of the Arrhenius logA and energy of activation of these ylides averaged 11.52±0.34s ~(-1) and 133.20±3.14kJmol~(-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 500K were calculated and used to substantiate the proposed mechanism of pyrolysis, and to rationalize the thermal gas-phase reactivities of the ylides under study.
机译：对十四种酮/硫酮稳定的三苯基phosph甲基化物进行了常规的气相和闪蒸热解（FVP）。在360-653K的温度范围内研究了所有这些化合物的一级热气相反应动力学。这些阿里氏菌的Arrhenius logA值和活化能分别平均为11.52±0.34s〜（-1）和133.20±3.14kJmol〜（-1）。分析并比较了密封管（静态）和FVP的产品。提出了一种机制来解释反应产物。计算了在500K时底物的速率常数[k（s-1）]，并用于证实拟议的热解机理，并使所研究的酰化物的热气相反应性合理化。

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