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The kinetic data on the deprotonation of 2-nitroethanol and 2-nitro-1,3-propanediol which concerned the rate of reversible carbon deprotonation by hydroxide ion, water, aminews, and carboxylate ions and pKa values for the ionization at carbon, pK(super CH)(sub a), and oxygen, pK(super OH)(sub a) and ionization of the aci-forms pK(super NOH)(sub a) at 25 degree celsius is reported. The rate constants in the order nitromethane > metroethane > 2-nitropropane is also reported. The rate of proton transfer induced by the substitution of one hydrogen in CH3NO2 by a CH2OH group is also discussed.

Kinetic studies of the reaction of different aliphatic amines with phosphoimidazolide-activated of guanosine and cytidine (ImPN) derivatives reveal that kinetic barrier for the reaction increases with the size of the alkyl group in the aliphatic secondary amines. Kinetic data support the higher reactivity of the primary amino groups than the secondary amino groups toward ImPN. The slow reactivity accounts for the absence of substitution products of the secondary amino groups of the polyamines.

Two kinetic processes, observed in the hydrolysis of benzylideneacetylacetone in a strong basic medium, include fast step in the reversible OH- addition to the substrate to form T(sub OH)(super -) and the rate-determining step in the carbon protonation of T(sub OH)(super -) to form the products. pH jump experiments determine rate constants for all forward and reversible steps and are compared with those of the benzylidenemalondialdehyde and benzylidene Meldrum's acid hydrolysis.

The kinetics of aminolysis of a Fischer metal carbene complex, (methoxy(phenyl)carbene)pentacarbonylchromium(O) in a polar solvent is examined. The transition metal carbene complex composed of five alipathic amines is measured in 20% acetonitrile and 80% water at 25 degrees centigrade. Results indicate a general base catalysis since the second order constants increased as amine and hydroxide ion concentrations increased. The mechanisms involved in the process of aminolysis are discussed.

The deprotonation of arylnitromethanes by alkyl thiolate and aryloxide ions serves as basis for a study of factors affecting proton abstraction from a carbon acid. The kinetic study points to the hydrogen-bonding ability of the central atom and, where the former is negligible, the demand for partial transition state desolvation of the base as the two strongest such factors. The similarityin the transition state imbalances of this reaction with that of amines suggestthat they are not characteristic of the thiolate ions but of the acid-base interactions that affect nucleophilic additions but not proton transfers.