Deuterium Isotope Effects During Acid Catalyzed Anomerization and C1 Acetoxy Exchange Reactions of Acetylated D-Aldopyranoses1

1961 ◽  
Vol 83 (12) ◽  
pp. 2661-2663
Author(s):  
William A. Bonner
Keyword(s):  
Isotope Effects ◽  
Exchange Reactions ◽  
Acid Catalyzed ◽  
Deuterium Isotope Effects

Deuterium isotope effects in liquid-liquid phase diagrams: Water + phenol and water + 2-methylpropanoic acid systems

1983 ◽  
Vol 36 (2) ◽  
pp. 215 ◽  
Author(s):  
DV Fenby ◽  
JR Khurma ◽  
ZS Kooner ◽  
RF Smith
Keyword(s):  
Liquid Phase ◽  
Phase Diagrams ◽  
Isotope Effects ◽  
Dispersion Interactions ◽  
Exchange Reactions ◽  
Molar Excess ◽  
Deuterium Isotope Effects ◽  
London Dispersion ◽  
Molar Excess Volumes ◽  
System Water

Phase-separation temperatures Tp have been measured for the systems H2O+C6H5OH, H2O+ C6H5OD, H20+ CsD5OD, D20+ C6H50H, D2O+ C6H5OD, D2O+ C6DsOD, H2O+ (CH3)2CHCO2H and D2O+ (CH3)2CHCO2H. For water+ 2-methylpropanoic acid, the differences in the Tp-x curves for the exchange and no-exchange systems are striking. For water + phenol, on the other hand, the effect of deuterium-exchange reactions on the Tp-x curves is very small. The results for all systems are in accord with the qualitative predictions of the Rabinovich theory, which accounts for deuterium isotope effects in liquid-liquid phase diagrams in terms of hydrogen bond and London dispersion interactions. Molar excess enthalpies and molar excess volumes at 300.15 K are reported for the system water + 2-methylpropanoic acid. The results are compared with those for water + acetic acid.

Secondary deuterium isotope effects for acid-catalyzed hydrolysis of inosine adenosine

1978 ◽  
Vol 100 (24) ◽  
pp. 7620-7624 ◽  
Author(s):  
R. Romero ◽  
R. Stein ◽  
H. G. Bull ◽  
E. H. Cordes
Keyword(s):  
Isotope Effects ◽  
Acid Catalyzed ◽  
Deuterium Isotope Effects ◽  
Hydrolysis Of

Calorimetric study of deuterium isotope effects in water-acetone systems

1981 ◽  
Vol 34 (3) ◽  
pp. 635 ◽  
Author(s):  
JR Khurma ◽  
DV Fenby
Keyword(s):  
Isotope Effects ◽  
Exothermic Reaction ◽  
Deuterium Exchange ◽  
Calorimetric Study ◽  
Excess Enthalpies ◽  
Exchange Reactions ◽  
Molar Excess ◽  
Deuterium Isotope Effects

Molar excess enthalpies of H20 + (CH3),CO, H20 + (CD3),C0, D20 + (CH3)2C0 and D20+ (CD3)2CO at 298.15 K are reported and, in the case of the first system, compared with earlier studies. The results are comparable to those reported for deuterium isotope effects in the molar excess enthalpies of other systems containing (CH3)2CO and (CD3)2CO; they do not suggest the occurrence of any deuterium exchange reactions. A calorimetric study of the mixing of (CD3)2CO with H2O containing a small quantity of NaOH indicates the occurrence of slow, exothermic reaction(s).

ChemInform Abstract: SECONDARY DEUTERIUM ISOTOPE EFFECTS FOR ACID-CATALYZED HYDROLYSIS OF INOSINE ADENOSINE

1979 ◽  
Vol 10 (9) ◽  
Author(s):  
R. ROMERO ◽  
R. STEIN ◽  
H. G. BULL ◽  
E. H. CORDES
Keyword(s):  
Isotope Effects ◽  
Acid Catalyzed ◽  
Deuterium Isotope Effects ◽  
Hydrolysis Of

Deuterium isotope effects in the acid-catalyzed hydration of 1-phenyl-1,3-butadiene

1969 ◽  
Vol 91 (25) ◽  
pp. 7154-7158 ◽  
Author(s):  
Yeshayan Pocker ◽  
Martin J. Hill
Keyword(s):  
Isotope Effects ◽  
Acid Catalyzed ◽  
Deuterium Isotope Effects

Deuterium Isotope Effects in Some Acid-catalyzed Cyclizations of 2-Deuterio-2'-carboxybiphenyl

1958 ◽  
Vol 80 (13) ◽  
pp. 3285-3288 ◽  
Author(s):  
Donald B. Denney ◽  
Peter P. Klemchuk
Keyword(s):  
Isotope Effects ◽  
Acid Catalyzed ◽  
Deuterium Isotope Effects

The Meyer Reaction of Phenylnitromethane in Acid. III. The Tautomerization to the aci-Form

1971 ◽  
Vol 49 (21) ◽  
pp. 3493-3501 ◽  
Author(s):  
J. T. Edward ◽  
P. H. Tremaine
Keyword(s):  
Rate Increase ◽  
Isotope Effects ◽  
Dilute Acid ◽  
Rate Limiting Step ◽  
Limiting Step ◽  
Acid Catalyzed ◽  
Deuterium Isotope Effects ◽  
Rate Limiting ◽  
Hydrolysis Of ◽  
Competing Reactions

The rate-acidity profiles for the Meyer rearrangement–hydrolysis of phenylnitromethane in sulfuric, perchloric, and hydrochloric acid show a maximum near 3 M acid. Ring-substituted phenylnitromethanes also show a maximum in their rate profiles, at slightly different acid concentrations. These maxima arise because the slow formation of the aci-form is followed by two competing reactions: fast tautomerization back to the nitro-form, and fast rearrangement–hydrolysis to the Meyer products. The rearrangement is rate-limiting in dilute acid and is acid-catalyzed, causing the rate increase. In more concentrated acid, the rate-limiting step is the nitro to aci tautomerization, which is not acid-catalyzed, and which goes more slowly as the activity of water decreases.The tautomerization was studied by means of primary and solvent deuterium isotope effects, and was found to occur through proton abstraction by water, through a transition state closely resembling the products.

Sign in / Sign up

Export Citation Format

Share Document