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Solvent Effects on the Reactions of Stabilized Carbonium Ions with Nucleophiles.

AD654968

Publication Date	1966
Personal Author	Ritchie, C. D.; Skinner, G. A.; Badding, V. G.
Page Count	11
Abstract	The rates and equilibria of reactions of three derivatives of malachite green (4,4'-bis(dimethylamino)triphenylmethyltetrafluoroborate) with several nucleophiles in water, methanol, dimethyl sulfoxide, and dimethylformamide solvents were studied. In all solvents azide ion reacts much faster with the carbonium ions than does cyanide ion, although the equilibrium constants for formation of the covalent product are greater in the case of cyanide. The rate constants for reactions of the carbonium ions with the nucleophiles are found to be more sensitive to changes in solvent than are the equilibrium constants. Both forward and reverse rate constants are changed in the same direction by a change of solvent. It is argued that this latter observation requires the consideration of solvent reorientation as an essential part of the activation process. (Author)
Keywords	Dyes Chemical indicators Solutions Stabilization Chemical equilibrium Reaction kinetics Solvents Water Methanols Sulfoxides Formamides Cyanides Azides Hydroxides Molecular association Reprints Crystal violet Dimethyl formamide Dimethyl sulfoxide Malachite green Methylates Nitro malachite green
NTIS Subject Category	99F - Physical & Theoretical Chemistry
Corporate Authors	State Univ of New York Buffalo Dept of Chemistry
Document Type	Journal Article
NTIS Issue Number	196717
Contract Number	DA-ARO(D)-31-124-G773

Solvent Effects on the Reactions of Stabilized Carbonium Ions with Nucleophiles.

Solvent Effects on the Reactions of Stabilized Carbonium Ions with Nucleophiles.
AD654968

Publication Date	1966
Personal Author	Ritchie, C. D.; Skinner, G. A.; Badding, V. G.
Page Count	11
Abstract	The rates and equilibria of reactions of three derivatives of malachite green (4,4'-bis(dimethylamino)triphenylmethyltetrafluoroborate) with several nucleophiles in water, methanol, dimethyl sulfoxide, and dimethylformamide solvents were studied. In all solvents azide ion reacts much faster with the carbonium ions than does cyanide ion, although the equilibrium constants for formation of the covalent product are greater in the case of cyanide. The rate constants for reactions of the carbonium ions with the nucleophiles are found to be more sensitive to changes in solvent than are the equilibrium constants. Both forward and reverse rate constants are changed in the same direction by a change of solvent. It is argued that this latter observation requires the consideration of solvent reorientation as an essential part of the activation process. (Author)
Keywords	Dyes Chemical indicators Solutions Stabilization Chemical equilibrium Reaction kinetics Solvents Water Methanols Sulfoxides Formamides Cyanides Azides Hydroxides Molecular association Reprints Crystal violet Dimethyl formamide Dimethyl sulfoxide Malachite green Methylates Nitro malachite green
NTIS Subject Category	99F - Physical & Theoretical Chemistry
Corporate Authors	State Univ of New York Buffalo Dept of Chemistry
Document Type	Journal Article
NTIS Issue Number	196717
Contract Number	DA-ARO(D)-31-124-G773