Solvent effects in deamination reactions
- 1 January 1986
- journal article
- research article
- Published by Wiley in Recueil des Travaux Chimiques des Pays-Bas
- Vol. 105 (9) , 272-278
- https://doi.org/10.1002/recl.19861050908
Abstract
Nitrous acid deaminations of (S)‐2‐butanamine, (2R,3S)‐3‐methyl‐2‐pentanamine (8), cyclopropananmine (17) and 4,4‐dimethyl‐2‐adamantanamine (30) have been studied in water and in a series of carboxylic acids of decreasing polarity (acetic, 3,3‐dimethylbutyric, 2‐ethylhexanoic acid). The stereochemistry of aqueous deaminations varies from predominant inversion to predominant retention, depending upon the structure of the substrate (steric hindrance, neighbouring‐group participation, etc.). In carboxylic acid media, alcohols arise with predominant retention, i.e. by front‐side attack of the “internal” nucleophile (water). Inverting displacement of nitrogen by the “external” nucleophile (carboxylic acid/carboxylate) increases with decreasing polarity of the solvent. Even cyclopropanamine yields cyclopropyl esters (2‐10%) of inverted configuration, as shown with the aid of deuterium labels. Current mechanistic concepts are modified to account for these results.Keywords
This publication has 46 references indexed in Scilit:
- Reaktionen von Cyclopropylsulfonaten mit Nucleophilen: S N 2‐Reaktionen an Cyclopropanen unter InversionEuropean Journal of Inorganic Chemistry, 1985
- Solvent effects on the relative energies of carbonium ions. Solvation and internal rotation for the allyl cation in liquid hydrogen fluorideJournal of the American Chemical Society, 1984
- Reactions of alkanediazotic acids at near neutral and basic pH in [18O] H2OJournal of the American Chemical Society, 1984
- The SN2 displacements at 2-norbornyl brosylatesJournal of the American Chemical Society, 1982
- Phase-transfer catalysis. Nucleophilicity of anions in aqueous organic two-phase reactions catalyzed by onium salts. A comparison with homogeneous organic systemsJournal of the American Chemical Society, 1978
- Chemical consequences of orbital interactions. 6. The similarity of solvent effects on carbocationsJournal of the American Chemical Society, 1977
- Nitrogen as Leaving Group: Aliphatic Diazonium IonsAngewandte Chemie International Edition in English, 1976
- Solvolysis of alkyl diazotates. II. Stereochemistry and internal return in the 2-octyl systemJournal of the American Chemical Society, 1967
- Stereochemistry of the Primary Carbon. VI. The Reaction of Optically Active 1-Aminobutane-1-d with Nitrous Acid. Mechanism of the Amine-Nitrous Acid Reaction1Journal of the American Chemical Society, 1957
- Peroxytrifluoroacetic Acid. V. The Oxidation of Ketones to Esters1Journal of the American Chemical Society, 1955