抄録
The syntheses of the metabolites of phylloquinone, α-tocopherol and ubiquinones are described. 1. 2, 3, 5-Trimethyl-6-(3'-carboxybutyl)-1, 4-benzoquinone (VIIa), 2-methyl-3-(3'-carboxybutyl)-1, 4-naphthoquinone (VIIb) and 2, 3-dimethoxy-5-methyl-6-(3'-carboxybutyl)-1, 4-benzoquinone (VIIc) were synthesized by two routes. 2, 3, 5-Trimethylphenol (Ia) and 3-methyl-1-naphthol (Ib) were condensed with methylsuccinic anhydride (II), followed by reduction of the carbonyl groups and oxidation of the phenols to quinones (VIIa, VIIb). 2, 3, 5-Trimethyl-1, 4-benzoquinone (XVIIIa), 2-methyl-1, 4-naphthoquinone (XVIIIb) and 2, 3-dimethoxy-5-methyl-1, 4-benzoquinone (XVIIIc) were treated with γ, γ'-dimethoxy-carbonylvaleryl peroxide (XVII) on one step to give the esters (VIIIa, VIIIb, VIIIc) of these quinones. 2. 2, 3, 5-Trimethyl-6-(5'-carboxy-3'-methyl-2'-pentenyl)-1, 4-benzoquinone (XXVa), 2-methyl-3-(5'-carboxy-3'-methyl-2'-pentenyl)-1, 4-naphthoquinone (XXVb) and 2, 3-dimethoxy-5-methyl-6-(5'-carboxy-3'-methyl-2'-pentenyl)-1, 4-benzoquinone (XXVc) were synthesized by boron trifluoride-catalyzed condensation of 2, 3, 5-trimethyl-1, 4-benzohydroquinone (XXIIIa), 2-methyl-1, 4-naphthohydroquinone derivatives (XXIIIb, XXVII, XXVIII) and 2, 3-dimethoxy-5-methyl-1, 4-benzohydroquinone (XXIIIc) with methyl ε-hydroxy-γ-methyl-γ-hexenoate (XX) or methyl γ-hydroxy-γ-vinylvalerate (XXII), followed by hydrolysis of the esters to carboxylic acids and subsequent oxidation of the hydroquinones to quinones.
