Micellar Effects in the Nitrous Acid Deamination Reaction of (R)-2H>-1-Octanamine

Article abstract of DOI:10.1021/jo00057a025

The nitrous acid deamination of 1-octanamine (1) afforded mixtures of isomeric octenes, octanols, and octyl nitrites.The aggregation of 1*HClO4 in micelles induced the formation of dioctyl ethers and of 1-nitrooctane as additional products.In homogeneous solution (submicellar aqueous conditions or HOAc), <1-²H>-1-octanol was obtained from <1-²H>-1 with ca. 95 percent inversion of configuration.Above the critical micelle concentration, the enantiomeric purity of <1-²H>-1-octanol decreased while <1-²H>-1-nitrooctane was formed with ca. 90 percent retention of configuration. 1-Octyl..NO2 radical pairs, rather than ion pairs, are likely to intervene on the retentive route to 1-nitrooctane and 1-octyl nitrite.Equilibration, via NO exchange, of (R)-<1-²H>-1-octyl nitrite with the more abundant (S)-<1-²H>-1-octanol is thought to account for the diminished ee of both products.