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Hydrolyse acide du p ‐nitrophényl‐diazométhane dans les mélanges H 2 OD 2 O: analyse des effets isotopiques
Author(s) -
Diderich G.,
Dahn H.
Publication year - 1972
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.19720550102
Subject(s) - chemistry , kinetic isotope effect , deuterium , hydrolysis , kinetic energy , catalysis , medicinal chemistry , isotope , organic chemistry , physics , quantum mechanics
The velocity of the hydrogen ion catalysed hydrolysis of p ‐nitrophenyl‐diazo‐methane (I) has been measured in H 2 OD 2 O mixtures, giving an isotopic α i = 0.49. The product isotope effect r = 5.1, determined from product analyses, combined with the (overall) solvent isotope effect k H / k D = 2.81, yields the primary kinetic isotope effect ( k H / k D ) I = 3.8, and the secondary kinetic isotope effect ( k H / k D ) II = 0.75. The CICH 2 COOH‐catalysed hydrolysis of I in H 2 OD 2 O mixtures gave a straight‐line plot of k n / k H versus the atomic fraction n of deuterium. With four carboxylic acids, as catalysts, values of about 4.3 for the kinetic (overall) isotope effects were observed.