Journal
JOURNAL OF ORGANIC CHEMISTRY
Volume 70, Issue 5, Pages 1647-1653Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jo048163j
Keywords
-
Categories
Ask authors/readers for more resources
Product selectivities [S = ([ester product]/[acid product]) x ([water]/[alcohol solvent])] are reported for solvolyses of p-methoxybenzoyl chloride (2) in aqueous methanol, ethanol, 2,2,2-trifluoroethanol, n-propyl alcohol, isopropyl alcohol, and tert-butyl alcohol at 25, 35, and 45 degreesC. S values are small and depend significantly on the alcohol cosolvent, varying from 1.3 in methanol to 0.1 in tert-butyl alcohol, but S depends only slightly on the solvent composition, and on the temperature. As S adjusts the product ratios for changes in bulk solvent compositions, it is suggested that preferential solvation by either alcohol or water at the reaction site is not a major factor influencing rates or products. Logarithms of rates of solvolyses of 2 correlate well with Kosower Z values (based on solvatochromism). In contrast, another solvatochromic polarity index, E-T(30), shows dispersion in correlations with the solvent ionizing power parameter, Y-OTs, probably due to aromatic ring and other solvation effects.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available