Abstract
12-Aminododecanoic acid and 11-aminoundecanoic acid, monomer precursors for nylon-12 and nylon-11, respectively, have been synthesized from vernolic (cis-12,13-epoxy-cis-9-octadecenoic) acid via a reaction sequence that includes the formation of 12-oxododecanoic acid oxime. Saponification of vernonia oil, followed by a low-temperature recrystallization at −20°C, gave 51% vernolic acid (97% purity, m.p. 23–25°C). Hydrogenation afforded cis-12,13-epoxystearic acid (m.p. 52–54°C, lit. m.p. 52–54°C), which upon oxidation with periodic acid in tertiary butyl alcohol gave 12-oxododecanoic acid with an isolated yield of 71.0%. Reaction of the oxoacid with hydroxylamine hydrochloride gave 12-oxododecanoic acid oxime, which was catalytically reduced to give 12-aminododecanoic acid with a yield greater than 85% and a melting point of 184–186°C (lit. m.p. 185–187°C). 11-Aminoundecanoic acid was prepared from the 12-oxododecanoic acid oxime via a three-step reaction sequence that involved a Beckmann rearrangement, Hofmann degradation, and hydrolysis. Thus, the aldoxime acid was hydrolyzed in the presence of nickel acetate tetrahydrate to give 11-carbamoylundecanoic acid (48% yield, m.p. 129–131°C, lit. m.p. 129–130°C). The amide was then treated with a solution of sodium methoxide and bromine at 70–80°C to give 11-(methoxycarbonylamino)undecanoic acid at 75% yield (m.p. 84–86°C; elemental analysis, calculated for C13H25NO4: C, 60.19; H, 9.73; N, 5.40; O, 24.68%; found C, 60.02; H, 9.81; N, 5.26; O, 24.91%), which upon alkaline hydrolysis and subsequent neutralization gave 11-aminoundecanoic acid at 34% yield (m.p. 189–192°C, lit. m.p. 190°C). Mass spectrometric and 13C nuclear magnetic resonance data of the previously unreported 11-(methoxycarbonylamino)undecanoic acid is provided.
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Ayorinde, F.O., Nana, E.Y., Nicely, P.D. et al. Syntheses of 12-aminododecanoic and 11-aminoundecanoic acids from vernolic acid. J Amer Oil Chem Soc 74, 531–538 (1997). https://doi.org/10.1007/s11746-997-0176-z
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DOI: https://doi.org/10.1007/s11746-997-0176-z