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首页> 外文期刊>Journal of Physical Organic Chemistry >Theoretical calculations for neighboring group participation in gas-phase elimination kinetics of 2-hydroxyphenethyl chloride and 2-methoxyphenethyl chloride
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Theoretical calculations for neighboring group participation in gas-phase elimination kinetics of 2-hydroxyphenethyl chloride and 2-methoxyphenethyl chloride

机译：邻基参与2-羟基苯乙基氯和2-甲氧基苯乙基氯气相消除动力学的理论计算

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摘要

Theoretical calculation of the kinetics and mechanisms of gas-phase elimination of 2-hydroxyphenethyl chloride and2-methoxyphenethyl chloride has been carried out at the MP2/6-31G(d,p), B3LYP/6-31G(d,p), B3LYP/6-31 + G(d,p),B3PW91/6-31G(d,p) and CCSD(T) levels of the theory. The two substrates undergo parallel elimination reactions. Thefirst process of elimination appears to proceed through a three-membered cyclic transition state by the anchimericassistance of the aromatic ring to produce the corresponding styrene product and HCI. The second process ofelimination occurs through a five-membered cyclic transition state by participation of the oxygen of o-OH or theo-OCH3 to yield in both cases benzohydrofuran. The B3PW91 /6-31 G(d,p) method was found to be in good agreementwith the experimental kinetic and thermodynamic parameters for both substrates in the two reaction channels.However, some differences in the performance of the different methods are observed. NBO analysis of the pyrolysis ofboth phenethyl chlorides implies a C—CI bond polarization, in the sense of e+ CIS–, which is a rate-determining stepfor both parallel reactions. Synchronicity parameters imply polar transition states of these elimination reactions.
机译：在MP2 / 6-31G（d，p），B3LYP / 6-31G（d，p），B3LYP上进行了气相消除2-羟基苯乙基氯和2-甲氧基苯乙基氯的动力学和机理的理论计算/ 6-31 + G（d，p），B3PW91 / 6-31G（d，p）和CCSD（T）的理论水平。两种底物进行平行消除反应。消除的第一个过程似乎是通过三环环状过渡态进行的，该三态环状过渡态是通过芳环的邻氨基苯甲酸酯协助生成相应的苯乙烯产物和HCl的。消除的第二个过程是通过五元环状过渡态发生的，在这两种情况下，邻-OH或氧-OCH3的氧参与生成苯并氢呋喃。发现B3PW91 / 6-31 G（d，p）方法与两个反应通道中两种底物的实验动力学和热力学参数吻合良好，但是观察到了不同方法的性能差异。 NBO分析这两种苯乙基氯的热解，就e + CIS–而言，意味着C-CI键极化，这是两个平行反应的决定速率的步骤。同步性参数暗示了这些消除反应的极性过渡态。

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