Studies on electro-oxidation of lignin and lignin model compounds. Part 2: N-Hydroxyphthalimide (NHPI)-mediated indirect electro-oxidation of non-phenolic lignin model compounds

Abstract

Abstract The N-hydroxyphthalimide (NHPI)-mediated indirect electro-oxidation of non-phenolic lignin model compounds has been investigated for selective Cα-carbonylation of lignin. A cyclic voltammogram of NHPI in 0.1 M LiClO4/CH3CN with 2,6-lutidine interpreted that NHPI can act as a mediator in the indicated process in the range 0.5–0.8 V vs. Ag/Ag+. The corresponding Cα-carbonyl compounds was obtained in high yields (85–97%) in the case of the monomer 1-(4-ethoxy-3-methoxyphenyl) ethanol in 0.1 M LiClO4/CH3CN or 0.1 M LiClO4/(CH3CN/H2O=7/3) with a small amount of 2,6-lutidine at 0.7 V vs. Ag/Ag+. The processing of the dimeric lignin model compound (4-ethoxy-3-methoxyphenylglycerol-β-guaiacyl ether) also gave the corresponding Cα-carbonyl compound in high yield (88–92%). The reaction proceeds through hydrogen atom transfer in the NHPI-mediated electro-oxidation. On the other hand, the direct electro-oxidation and indirect electro-oxidation mediated by ABTS [2,2′-azinobis(3-ethylbenzothiazoline-6-sulfonate)] of the dimeric compound preferentially gave the corresponding Cα-Cβ cleavage product in low or moderate yields (5–40%). The conclusion is that NHPI is an excellent mediator for selective Cα-carbonylation of non-phenolic β-O-4 structures in lignin in electronic mediator system.