Photodiscoloration of western hemlock (Tsuga heterophylla) sapwood III Early stage of photodiscoloration reaction with lignans

Abstract

The reaction during the early stage of photodiscoloration of constituents in western hemlock [Tsuga heterophylla (Raf. Sarg., Pinaceae] sapwood was investigated with chemical methods. The main photodiscoloring constituents, hydroxymatairesinol, allohydroxymatairesinol, α-conidendrin, and oxomatairesinol, were used as substrates for light-irradiation experiments in vitro. The structures of photodiscoloration reaction products were elucidated by isolation and instrumental analyses and/or co-high-performance liquid chromatography analyses with authentic specimens. The experiment was undertaken to distinguish each series of liquid phases using chloroform, water (both including a trace of methanol), and methanol, and the solid phase. The reaction products allohydroxymatairesi (2), oxomatairesinol (3), α-conidendrin (4), allo-7′-methoxymatairesinol (5), 7′-methoxymatairesinol (6), and vanillin (7) were isolated or detected in the reaction mixture of a hydroxymatairesinol system. The reaction products hydroxymatairesinol (1), 3, 4, 5, 6, and 7 were confirmed in the reaction system of allohydroxymatairesinol, which was an epimer of hydroxymatairesinol. Product 3 was confirmed from the α-conidendrin system, and reaction product 7 was confirmed from oxomatairesinol. The photodiscoloration reaction of western hemlock sapwood could be initiated by the formation of phenoxy radicals from the respective constituents. The reaction was then presumed to progress via formation of a quinonemethide intermediate in many of them. It was suggested that the reactive species, such as phenoxy radical or quinonemethide intermediate, formed by lightirradiation might be converted to quinone derivatives and colored oligomers. Products 1, 2, 3, 4, and 7, formed from substrates such as hydroxymatairesinol, allohydroxymatairesinol, α-conidendrin, and oxomatairesinol, were the same as the original metabolic constituents of western hemlock. Therefore it was concluded that the photodiscoloration of western hemlock depends not on the quantitative level of a few respective metabolites but, rather, on the coexistence of many metabolites.