Kinetics of the azidization of 2,4-dinitrohalogenobenzenes with tetraethylammonium azide in acetonitrile and mixed acetonitrile-dioxane solvent
The kinetics of the reaction of 2,4-dinitrohalogenobenzenes (chlorine, bromine, and iodine derivatives) with tetraethylammonium azide in acetonitrile and in a mixed acetonitrile-dioxane solvent (80 vol. % dioxane) were studied. It was established that there is a marked increase (by more than three orders of magnitude) in the azidization rate constant in the transition from protic solvents to aprotic media, due to the decrease in the activation energy barrier of the reaction. The nucleophilicity parameters N/sup +/ for the azide ion in the investigated solvents were determined in terms of Ritchie's relationship. It was established that the effect of the nature of the leaving group on the rate constant of the reactions is complex in character, and it was shown that treatment of the relative reactivity series for the investigated substrates must be based on an analysis of the activation parameters and not restricted to data obtained at only one temperature.
- Research Organization:
- Lensovet Leningrad Technological Institute, USSR
- OSTI ID:
- 6136553
- Journal Information:
- J. Org. Chem. USSR (Engl. Transl.); (United States), Journal Name: J. Org. Chem. USSR (Engl. Transl.); (United States) Vol. 21:10; ISSN JOCYA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400201* -- Chemical & Physicochemical Properties
ACETONITRILE
ACTIVATION ENERGY
AMINES
AMMONIUM COMPOUNDS
AROMATICS
AZIDO COMPOUNDS
BENZENE
BROMINATED AROMATIC HYDROCARBONS
CHEMICAL REACTION KINETICS
CHLORINATED AROMATIC HYDROCARBONS
COMPARATIVE EVALUATIONS
DIOXANE
DISPERSIONS
ENERGY
HALOGENATED AROMATIC HYDROCARBONS
HETEROCYCLIC COMPOUNDS
HYDROCARBONS
IODINATED AROMATIC HYDROCARBONS
KINETICS
MIXED SOLVENTS
MIXTURES
NITRILES
NITRO COMPOUNDS
NITROGEN COMPOUNDS
ORGANIC BROMINE COMPOUNDS
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANIC IODINE COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
ORGANIC SOLVENTS
QUANTITY RATIO
QUATERNARY COMPOUNDS
REACTION KINETICS
SOLVENT PROPERTIES
SOLVENTS
SPECTROPHOTOMETRY