Substituent effects upon rates of deamination and base strengths of substituted N-tritylamines

Abstract

Substituted N-tritylamines undergo deamination in aqueous acidic solution containing organic cosolvents, and follow a pseudo first-order specific acid-catalysis rate law (kobs = k0 + kH[H3O+]); the products are the corresponding trityl alcohols in equilibrium with the trityl carbenium ions, and ammonium ions. The change from 4,4′-dimethoxy- to 4,4′,4″-trimethoxy-tritylamine increases reactivity by a factor of about 30 in both k0 and kH, but N-alkyl and N-aryl groups have much greater effects (ca. 106 for both k0 and kH for 4,4′-dimethoxytritylamine) which are largely independent of the nature of the N-alkyl and N-aryl groups. The anions of the catalytic strong acids (perchlorate, chloride, bromide, and nitrate) have only small effects as also does the concentration of acetonitrile as cosolvent; ethanoic acid as cosolvent is mildly rate-enhancing. Substituents in the aniline residue of N-(4,4′-dimethoxytrityl)anilines have virtually no effect upon either k0 or kH (ρ = 0 for both). The results are interpreted by a mechanism involving a pre-equilibrium heterolysis of the (substituted) tritylammonium ion to give an ion–molecule pair which may undergo diffusional or acid-catalysed dissociation before the (substituted) trityl cation undergoes equilibrium nucleophilic capture by water. Base strengths of some substituted N-tritylamines have been measured; the substituted N-trityl group causes all amines (aliphatic and aromatic) to be comparably strongly basic (pKBH+ca. 9).