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Effects of ortho ‐substituents in S E 1 protonolysis of phenylmercuric chloride
Author(s) -
Wang Yulan,
Zhang Jinli,
Wu Yangjie
Publication year - 2007
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.1137
Subject(s) - chemistry , protonolysis , substituent , reaction rate constant , medicinal chemistry , intramolecular force , chloride , hydrochloric acid , resonance (particle physics) , kinetics , stereochemistry , inorganic chemistry , catalysis , organic chemistry , physics , particle physics , quantum mechanics
Abstract The kinetics of the reactions of o ‐substituted phenylmercuric chlorides, o ‐RC 6 H 4 HgCl (R = CH 3 , H, C 2 H 5 O, CH 3 O, C 6 H 5 , F, COOC 2 H 5 , Cl, Br, CF 3 , NO 2 ), with hydrochloric acid in 80% aqueous dioxane in the presence of NaI were studied. The reactions are of the first order. The rate constant at 40°C decreases in the order of R: CH 3 > H > C 2 H 5 O > CH 3 O > C 6 H 5 > F > COOC 2 H 5 > Cl > Br > CF 3 > NO 2 . The analysis of effects of those o ‐substitutes is carried out through multiple regression of log k / k H with the corresponding inductive substituent constants σ I and the various resonance substituent constants σ R 0 , σ R (BA), σ R + , σ R −and σ x , and the corresponding Swain–Lupton field effect constant $\Im $ and resonance effect constant $\Re $ . The results showed that o ‐substituent intramolecular coordination with the neighbor mercury (field effect) is the main effect in effects of o ‐substituents on rate of the S E 1 protonolysis. Copyright © 2007 John Wiley & Sons, Ltd.