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Substituent and Isotope Effects on the Hydrolysis Rates of 2‐Aryl‐2‐diazocarboxylic Esters
Author(s) -
BuiNguyen MaiHuong,
Dahn Hans,
McGarrity John F.
Publication year - 1980
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19800630108
Subject(s) - chemistry , kinetic isotope effect , hydrolysis , aryl , substituent , solvent , acid catalysis , reactivity (psychology) , catalysis , medicinal chemistry , organic chemistry , deuterium , alkyl , medicine , physics , alternative medicine , quantum mechanics , pathology
Abstract The overall kinetic solvent isotope effects on the acid catalyzed hydrolysis of a series of 2‐aryl‐2‐diazocarboxylic esters ArCN 2 COOCH 3 , and one 2‐aryl‐2‐diazocarboxamide C 6 H 5 CH 2 CON (CH 3 ) 2 vary inversely with the reactivity of the substrate, between limits of 3.14 and 1.46. A linear Hammett plot for the hydrolysis rates of the a ‐diazocarboxylic esters indicates that there is no mechanistic change for the hydronium‐ion‐catalyzed reaction. The relation between hydrolysis rate and buffer acid concentration deviates from linearity for high values of the latter. It is shown on the basis of the solvent isotope effects for the non‐linear region that this deviation does not stem from a mechanistic change caused by the buffer base component. The specific salt effects on the general acid‐catalyzed reaction are discussed.