ChemInform Abstract: THE α- AND β-DEUTERIUM ISOTOPE EFFECTS IN THE HYDROLYSIS OF TETRAHYDRONAPHTHALENE EPOXIDES: RATE-LIMITING HYDROGEN MIGRATION IN THE SPONTANEOUS HYDROLYSIS OF 6-METHOXY-1,2,3,4-TETRAHYDRONAPHTHALENE OXIDE

1982 ◽  
Vol 13 (45) ◽  
Author(s):  
R. E. GILLILAN ◽  
T. M. POHL ◽  
D. L. WHALEN
Keyword(s):  
Isotope Effects ◽  
Hydrogen Migration ◽  
Spontaneous Hydrolysis ◽  
Deuterium Isotope Effects ◽  
Rate Limiting ◽  
Hydrolysis Of

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.

scholarly journals Mixed Solvent Deuterium Isotope Effects on the Hydrolysis of UO22+and Be2+Ions

1972 ◽  
Vol 45 (8) ◽  
pp. 2464-2468 ◽  
Author(s):  
Masunobu Maeda ◽  
Toshihiko Amaya ◽  
Hitoshi Ohtaki ◽  
Hidetake Kakihana
Keyword(s):  
Mixed Solvent ◽  
Isotope Effects ◽  
Deuterium Isotope Effects ◽  
Hydrolysis Of
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