Revisiting the condensation reaction of lignin in alkaline pulping with quantitativity part III: predominant formation of α-β-type over α-5-type condensation product in soda cooking treatments of apocynol and creosol

Abstract Progress in the condensation of lignin is believed to interfere with delignification in alkaline pulping processes without any clear evidence, which motivated us to revisit it quantitatively. This study is the 3rd in the series which evaluates the condensation reactions of lignin in model systems of soda cooking processes using 4-(1-hydroxyethyl)-2-methoxyphenol (apocynol, Ap) and 2-methoxy-4-methylphenol (creosol, Cr). Ap was primarily converted to 2-methoxy-4-vinylphenol (vinylguaiacol, Vg) via the quinone methide intermediate to establish equilibrium before condensation reactions proceeded. Only the α-5-type condensation product between Ap and Cr (ApCr, 1-(4-hydroxy-3-methoxyphenyl)-1-(2-hydroxy-3-methoxy-5-methylphenyl)ethane) and the α-β-type condensation product between Ap and Vg or two molecules of Vg (ApVg, trans-1,3-bis(4-hydroxy-3-methoxyphenyl)but-1-ene) were identified without detecting any self-condensation products of Ap. The α-β-type condensation has not been well known and is an important finding of this study. The formation of ApVg was over 10 times faster than that of ApCr, which demonstrates that the α-β-type condensation is a major mode in soda cooking. However, because origins of α-β-type condensation substructures, such as C6-C2-type enol ethers, do not exist in native lignin, the results support our previous conclusion that the condensation reactions of lignin progress less frequently than previously believed.