Aromatic protonation. III. Kinetic hydrogen isotope effects on acid-catalyzed aromatic hydrogen exchange in 1,3,5-trimethoxybenzene

1967 ◽  
Vol 89 (17) ◽  
pp. 4411-4417 ◽  
Author(s):  
A. Jerry. Kresge ◽  
Yvonne. Chiang
Keyword(s):  
Hydrogen Isotope ◽  
Hydrogen Exchange ◽  
Isotope Effects ◽  
Acid Catalyzed ◽  
Aromatic Hydrogen

Aromatic hydrogen isotope effects in reactions of benzenediazonium salts

1975 ◽  
Vol 97 (4) ◽  
pp. 791-795 ◽  
Author(s):  
C. Gardner Swain ◽  
John E. Sheats ◽  
David G. Gorenstein ◽  
Kenneth G. Harbison
Keyword(s):  
Hydrogen Isotope ◽  
Isotope Effects ◽  
Aromatic Hydrogen

ChemInform Abstract: AROMATIC HYDROGEN ISOTOPE EFFECTS IN REACTIONS OF BENZENEDIAZONIUM SALTS

1975 ◽  
Vol 6 (18) ◽  
pp. no-no
Author(s):  
C. GARDNER SWAIN ◽  
JOHN E. SHEATS ◽  
DAVID G. GORENSTEIN ◽  
KENNETH G. HARBISON
Keyword(s):  
Hydrogen Isotope ◽  
Isotope Effects ◽  
Aromatic Hydrogen

Secondary isotope effects and aromatic hydrogen exchange

1959 ◽  
Vol 1 (13) ◽  
pp. 20-23 ◽  
Author(s):  
A.J. Kresge ◽  
D.P.N. Satchell
Keyword(s):  
Hydrogen Exchange ◽  
Isotope Effects ◽  
Aromatic Hydrogen

Article

1999 ◽  
Vol 77 (5-6) ◽  
pp. 744-751
Author(s):  
Robert Eliason
Keyword(s):  
Acetic Acid ◽  
Carboxylic Acids ◽  
Hydrogen Isotope ◽  
Isotope Effects ◽  
Water Concentration ◽  
Chloroacetic Acid ◽  
Water Effect ◽  
First Order ◽  
Acid Catalyzed ◽  
Catalyzed Reactions

Acid-catalyzed decomposition of diazodiphenylmethane (DDM) has been studied in DMSO containing varying amounts of water. The reaction was found to be first-order in DDM and first-order in acid. The Brønsted plot for a series of carboxylic acids is curved with the H+ point falling below the curve defined by the carboxylic acids. In near-anhydrous DMSO, kinetic hydrogen isotope effects (KIEs) are 1.7 and 1.6 for acetic acid and chloroacetic acid, respectively. The chloroacetic acid KIE increases with increasing water concentration, rising to 2.9 at 3.6 M water. As a function of [H2O], kHA for chloroacetic acid shows a sharply defined minimum occurring at 1 M water. This behavior and the water effect on KIE suggest that the carboxylic acid-catalyzed reactions in near-anhydrous DMSO do not use the ASE-2 mechanism attributed to the reaction of DDM in hydroxylic solvents. A mechanism, leading to an azoalkane, is suggested. Either directly or indirectly, this may lead to diphenylcarbene, which would account for the observed products: benzophenone, benzhydrol, and benzhydryl esters. For the H+ catalyzed decomposition of DDM in near-anhydrous DMSO, benzophenone is not found among the products, and we suggest that this reaction does not undergo a change in mechanism and continues to use the ASE-2 mechanism.Key words: decomposition mechanism, kinetics, solvent effect, reaction with carboxylic acids.

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