Aminolysis of 3,4-Dinitrophenyl Cinnamate and Benzoate 2: Activation Parameters and Transition-State Structures
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DOI: 10.5012/BKCS.2008.29.3.575
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摘要: The apparent second-order rate constants (k N ) have been dissected into the microscopic (i.e., k 1 and 2 /k -1 associated with reactions of Y-substituted phenyl cinnamates (5a-g) piperidine morpholine on assumption that proceed through a stepwise mechanism change in rate-determining step (RDS). value is larger for more basic piperidine, increases decreasing basicity leaving aryloxides. However, ratio almost same reaction 3,4-dinitrophenyl cinnamate (5a) morpholine, which not possible if mechanism. Thus, aminolysis 5a-g has proposed to concerted activation parameters (ΔH‡ ΔS‡) measured benzoate (la) from kinetic study performed at 5 different temperatures 80 mol % H O/20 DMSO. 5a results lager enthalpy (ΔH‡) but less negative entropy (ΔS‡) than la.
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