Vinyl substituted fatty acids
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example 1
Preparation of (E)-9-nitro-octadec-9-enoic acid
[0123]Commercially available 9-bromononanol was oxidized using Jones' reagent, chromium trioxide (CrO3) in concentrated sulfuric acid (H2SO4), 67%, to form a carboxylic acid protected as an allyl ester (92% yield) and was nitrated using the Kornblum method, silver nitrate (AgNO2) in diethyl ether (Et2O), to form 9-nitro-nonanoic acid, allyl ester, in an overall yield of 42%. Nitroaldol condensation was then carried out by combining this intermediate with commercially available nonyl aldehyde in the presence of a catalytic amount of (10 mol %) of DBU to produce β-hydroxynitro (81% yield) as a 1:1 mixture of diastereomers. The β-hydroxynitro ester intermediate was acetylated in acetic anhydride with a catalytic amount of β-toluenesulfonic acid to produce a β-acetoxynitro ester intermediate in high yield, and the nitroalkene was generated by from the β-acetoxynitro ester intermediate by base-induced elimination with azeotropic removal of w...
example 2
Production of (Z)-isomers
[0124](Z)-9-nitro-octadec-9-enoic was formed from the (E)-9-nitro-octadec-9-enoic acid using the Ono method as described in Ono, N, et al. J. Chem. Soc., Chem. Commun. 1987, 1551-1551 and Sharpless et al., Am. Chem. Soc. 1973, 95, 2697-2699, both of which are hereby incorporated by reference in their entireties, at about 80% to about 90% yield.
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