Premium
Nucleophilic participation in the solvolyses of 2‐aryl‐2‐halopropanes and the previously claimed advantage of using Y BnX scales
Author(s) -
Kevill Dennis N.,
D'Souza Malcolm J.
Publication year - 1993
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.610061109
Subject(s) - chemistry , solvolysis , nucleophile , aryl , medicinal chemistry , solvation , confidence interval , propane , computational chemistry , hydrolysis , organic chemistry , medicine , molecule , catalysis , alkyl
Contrary to a recent report, the specific rates of solvolyses of five 2‐aryl‐2‐chloropropanes give only marginally (not significantly) better correlations with use of the Y BnCl scale rather than the Y Cl scale. With the use of the extended (two‐term) Grunwald–Winstein equation, some evidence for a weak nucleophilic solvation is obtained, but at a low confidence level. The specific rates of 2‐bromo‐2( p ‐trifluoromethylphenyl)propane solvolysis are significantly better correlated using Y Br (rather than Y BnBr ) values and, indeed, the use of N T values in conjunction with Y Br values leads to an l value of 0·17 ± 0·06 and evidence for a weak nucleophilic participation at a 98·7% confidence level.