Mechanism of solvolysis of substituted benzyl chlorides in aqueous ethanol

被引：4
|
作者：
Denegri, Bernard [1 ]
Matic, Mirela [1 ]
Vasko, Monika [1 ]
机构：
[1] Univ Zagreb, Fac Pharm & Biochem, Ante Kovacica 1, Zagreb 10000, Croatia
来源：
TETRAHEDRON | 2022年 / 103卷
关键词：
Benzyl chloride; Solvolysis; S(N)1 mechanism; S(N)2 mechanism; Hammett-Brown correlation; DFT; SATURATED CARBON-ATOM; NUCLEOPHILIC-SUBSTITUTION; MENSCHUTKIN REACTION; S(N)2 REACTIONS; LEAVING GROUPS; WATER; SOLVATION; HALIDES; HYDROLYSIS; KINETICS;
D O I：
10.1016/j.tet.2021.132548
中图分类号：
O62 [有机化学];
学科分类号：
070303 ; 081704 ;
摘要：
The mechanism of solvolyses of activated ortho-, meta- and para-substituted benzyl chlorides in aqueous ethanol has been studied by using the Hammett-Brown and Yukawa-Tsuno treatments as well as by correlating logarithms of solvolysis rate constants with relative stabilities of corresponding benzyl carbocations in water calculated at the IEFPCM-M06-2X/6-311+G(3df,3pd) level of theory. Benzyl chlorides containing strong conjugative electron-donors in the para-position solvolyze by the S(N)1 mechanism, whereas other activated benzyl chlorides solvolyze by the S(N)2 mechanism via loose transition states. (C) 2021 Elsevier Ltd. All rights reserved.
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页数：8
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