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Thermally-Induced Reactions of Aromatic Crystalline Nitroso Compounds

Three types of organic solid-state reactions, dimerizations, dissociations, and Z-E isomerizations were investigated by using the transformations of aromatic C-nitroso compounds in crystalline solids as a convenient molecular model. Here we propose a conceptual frame for solid-state organic reaction mechanisms by examining activation parameters obtained from kinetic measurements under specific experimental conditions. The possibility of the appearance of a sort of short-lived intermediate liquid phase that constitutes a critical condition for initiating chemical reaction in crystalline solids, similarly to the mechanism for the thermal solid-state reactions proposed by Paul and Curtin is discussed. The analogy of the proposed concept with the recent hypothesis about the variable rigidity/softness of the reaction cavity in the enzyme reactions, and with the newest molecular dynamic simulation studies of solid phase transformations was considered.

Aromatic C-nitroso compunds ; Dimerization ; Kinetics ; Reaction mechanisms ; Solid-state reactions

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