15507-13-8Relevant articles and documents
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Trinh
, p. 897 (1946)
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The decomposition of aliphatic N-nitro amines in aqueous sulfuric acid. Bisulfate as a nucleophile
Cox, Robin A.
, p. 1774 - 1778 (2007/10/03)
In aqueous sulfuric acid, aliphatic N-nitro amines decompose to N2O and alcohols. An excess acidity analysis of the observed rate constants for the reaction shows that free carbocations are not formed. The reaction is an acid-catalyzed SN2 displacement from the protonated aci-nitro tautomer, the nucleophile being a water molecule at acidities below 82-85% H2SO4, and a bisulfate ion at higher acidities. Bisulfate is the poorer nucleophile by a factor of about 1000. Twelve compounds were studied, of which results obtained for nine at several different temperatures enabled calculation of activation parameters for both nucleophiles. The reaction appears to be mainly enthalpy controlled. The intercept standard-state rate constants are well correlated by the σ* values for the alkyl groups; the slopes are negative, with a more negative value for the slower bisulfate reaction. Interestingly the m?m* slopes also correlate with σ*, although the scatter is bad.
KINETICS OF THE REACTION OF n-BUTANOL WITH CONCENTRATED SULFURIC ACID.
Savel'yanov,Yakushin
, p. 1523 - 1527 (2007/10/02)
The kinetics of the reaction of n-butanol with concentrated sulfuric acid of various intrinsic concentrations was studied over a wide range of strictly controlled conditions, and it was shown that the reaction is satisfactorily described by a kinetic equation for a reversible second-order reaction. An exponential relationship was found between the rate constants of the forward and reverse reactions and the sulfuric acid concentration in the original mixture, due to the similar dependence of the Hammett acidity function of the reaction mixture, which does not alter significantly in the course of the reaction.
