Kinetic and equilibrium studies of σ-adduct formation and nucleophilic substitution in the reactions of 2-phenoxy-3,5-dinitropyridine and 2-ethoxy-3,5-dinitropyridine with aliphatic amines in dipolar aprotic solvents

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Crampton, M.R.
Emokpae, T.A.
Howard, Judith A. K.
Isanbor, C.
Mondala, Raju
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Royal Society of Chemistry
The reactions of aliphatic amines with 2-phenoxy-3,5-dinitropyridine, 4, and 2-ethoxy-3,5-dinitropyridine, 5, in DMSO result in the rapid reversible formation of anionic σ-adducts at the 6-position. Kinetic studies show that proton transfer from the initially formed zwitterions to base may be rate-limiting. Slower reactions result, except in the case of 5 and piperidine, in displacement of the 2-substitutent via intermediates which have lower thermodynamic stabilities than their 6-isomers. Base catalysis of the substitution process is attributed in the case of 4 to rate-limiting proton transfer from zwitterionic intermediates, but in 5 to acid catalysis of ethoxide departure (SB-GA mechanism). X-Ray crystallography of 5 shows a planar non-strained structure although the structure of 2-piperidino-3,5-dinitropyridine, 10c, shows distortion resulting from steric interactions of the 2- and 3-substituents. Kinetic and equilibrium results are compared with those for related reactions of the more sterically strained 2,4,6-trinitrobenzene derivatives. Results for the reactions of 4 and 5 with pyrrolidine in three dipolar aprotic solvents are compared. Values of equilibrium constants for σ-adduct formation decrease in the order DMSO > DMF ≫ Acetonitrile, while values of rate constants for proton transfer are in the reverse order.
Research Subject Categories::NATURAL SCIENCES::Chemistry::Physical chemistry::Kinetics , Base catalysis , Nucleophilic substitution
Crampton, M. R., Emokpae, T. A., Howard, J. A., Isanbor, C., & Mondal, R. (2003). Kinetic and equilibrium studies of σ-adduct formation and nucleophilic substitution in the reactions of 2-phenoxy-3, 5-dinitropyridine and 2-ethoxy-3, 5-dinitropyridine with aliphatic amines in dipolar aprotic solvents. Organic & biomolecular chemistry, 1(6), 1004-1011.