.beta.-Secondary and Solvent Deuterium Kinetic Isotope Effects and the Mechanisms of Base- and Acid-Catalyzed Hydrolysis of Penicillanic Acid

1995 ◽  
Vol 60 (6) ◽  
pp. 1619-1625 ◽  
Author(s):  
S. A. Deraniyagala ◽  
S. A. Adediran ◽  
R. F. Pratt
Keyword(s):  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Kinetic Isotope ◽  
Penicillanic Acid ◽  
Acid Catalyzed ◽  
Hydrolysis Of

ChemInform Abstract: BENZIDINE REARRANGEMENTS. 18. MECHANISM OF THE ACID-CATALYZED DISPROPORTIONATION OF 4,4′-DIIODOHYDRAZOBENZENE. APPLICATION OF HEAVY-ATOM KINETIC ISOTOPE EFFECTS

1983 ◽  
Vol 14 (32) ◽  
Author(s):  
H. J. SHINE ◽  
J. HABDAS ◽  
H. KWART ◽  
M. BRECHBIEL ◽  
A. G. HORGAN ◽  
...  
Keyword(s):  
Isotope Effects ◽  
Heavy Atom ◽  
Kinetic Isotope Effects ◽  
Kinetic Isotope ◽  
Acid Catalyzed

Vinyl ether hydrolysis. XIII. The failure of I-strain to produce a change in rate-determining step

1980 ◽  
Vol 58 (2) ◽  
pp. 124-129 ◽  
Author(s):  
Y. Chiang ◽  
W. K. Chwang ◽  
A. J. Kresge ◽  
S. Szilagyi
Keyword(s):  
Vinyl Ether ◽  
Acid Catalysis ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Mineral Acid ◽  
Buffer Solutions ◽  
Rate Determining Step ◽  
Kinetic Isotope ◽  
Acetic Acid Buffer ◽  
Hydrolysis Of

Rates of hydrolysis of 1-ethoxy-3,3,5,5-tetramethylcyclopentene and 1-methoxy-2,3,3,5,5-pentamethylcyclopentene measured in mineral acid and formic and acetic acid buffer solutions show general acid catalysis and give large kinetic isotope effects in the normal direction (kH/kD > 1). This indicates that these reactions proceed by the conventional mechanism for vinyl ether hydrolysis in which proton transfer from the catalyzing acid to the substrate is rate-determining, and that the I-strain in these substrates is insufficiently great to shift the reaction mechanism to rapidly reversible substrate protonation followed by rate-determining hydration of the ensuing cationic intermediate.

Carbon Kinetic Isotope Effects and the Mechanisms of Acid-Catalyzed Decarboxylation of 2,4-Dimethoxybenzoic Acid and CO2 Incorporation into 1,3-Dimethoxybenzene

2017 ◽  
Vol 139 (42) ◽  
pp. 15049-15053 ◽  
Author(s):  
Adelle A. Vandersteen ◽  
Graeme W. Howe ◽  
Barbara Sherwood Lollar ◽  
Ronald Kluger
Keyword(s):  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Kinetic Isotope ◽  
Acid Catalyzed

ALPHA-SECONDARY DEUTERIUM KINETIC ISOTOPE EFFECTS FOR HYDROLYSIS OF TREHALOSE BY TREHALASE

2002 ◽  
Author(s):  
Jin-Ha Lee ◽  
Mamoru Nishimoto ◽  
Masayuki Okuyama ◽  
Haruhide Mori ◽  
Atsuo Kimura ◽  
...  
Keyword(s):  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Kinetic Isotope ◽  
Hydrolysis Of

Transition-state structure for the hydronium-ion-promoted hydrolysis of α-d-glucopyranosyl fluoride

2015 ◽  
Vol 93 (4) ◽  
pp. 463-467 ◽  
Author(s):  
Jefferson Chan ◽  
Ariel Tang ◽  
Andrew J. Bennet
Keyword(s):  
Transition State ◽  
Kinetic Isotope Effect ◽  
Bond Cleavage ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Theoretical Modelling ◽  
Kinetic Isotope ◽  
Hydronium Ion ◽  
Anomeric Carbon ◽  
Hydrolysis Of

The transition state for the hydronium-ion-promoted hydrolysis of α-d-glucopyranosyl fluoride in water has been characterized by combining multiple kinetic isotope effect measurements with theoretical modelling. The measured kinetic isotope effects for the C1-deuterium, C2-deuterium, C5-deuterium, anomeric carbon-13, and ring oxygen-18 are 1.219 ± 0.021, 1.099 ± 0.024, 0.976 ± 0.014, 1.014 ± 0.005, and 0.991 ± 0.013, respectively. The transition state for the hydronium ion reaction is late with respect to both C–F bond cleavage and proton transfer.

Hydrolysis of 2-(p-nitrophenoxy)tetrahydropyran: solvent andα-deuterium secondary kinetic isotope effects and relationships with the solvolysis of simple secondary alkyl arenesulfonates and the enzyme-catalyzed hydrolysis of glycosides

2004 ◽  
Vol 17 (67) ◽  
pp. 560-566 ◽  
Author(s):  
Imran A. Ahmad ◽  
Sara L. Birkby ◽  
Claire A. Bullen ◽  
Patrick D. Groves ◽  
Timm Lankau ◽  
...  
Keyword(s):  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Kinetic Isotope ◽  
Hydrolysis Of

Carbon kinetic isotope effects on the hydrolysis of aryl carbonates

1990 ◽  
Vol 112 (16) ◽  
pp. 5996-5998 ◽  
Author(s):  
John F. Marlier ◽  
Marion H. O'Leary
Keyword(s):  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Kinetic Isotope ◽  
Hydrolysis Of
Sign in / Sign up

Export Citation Format

Share Document