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

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

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

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.

Mechanism of hydration and isomerisation of 4-ethylidene-2,6-di-tert-butyl-2,5-cyclohexadien-1-one. Kinetics, acid-base catalysis and solvent deuterium isotope effects

1979 ◽  
Vol 44 (1) ◽  
pp. 110-122 ◽  
Author(s):  
Jiří Velek ◽  
Bohumír Koutek ◽  
Milan Souček
Keyword(s):  
Aqueous Medium ◽  
Rate Equation ◽  
Kinetic Data ◽  
Isotope Effects ◽  
Base Catalysis ◽  
Quinone Methide ◽  
Reaction Products ◽  
Acid Base ◽  
Deuterium Isotope Effects ◽  
Hydroxybenzyl Alcohol

Competitive hydration and isomerisation of the quinone methide I at 25 °C in an aqueous medium in the region of pH 2.4-13.0 was studied spectrophotometrically. The only reaction products in the studied range of pH are 4-hydroxybenzyl alcohol (II) and 4-hydroxystyrene (III). The form of the overall rate equation corresponds to a general acid-base catalysis. The mechanism of both reactions for three markedly separated pH regions is discussed on the basis of kinetic data and solvent deuterium effect.

Sign in / Sign up

Export Citation Format

Share Document