A process for the manufacture of 3-phytyl-2,5,6-trimethylhydroquinone-1-acetate, and optionally therefrom tocopheryl acetate, comprises either C-alkylating 2,3,6-trimethylhydroquinone-1-acetate with isophytol or phytol in the presence of a sulphur(VI) containing catalyst of the formula R1SO2OH, wherein R1 signifies hydroxy, halogen, lower alkyl, halogenated lower alkyl or aryl, in an aprotic organic solvent, or O-alkylating 2,3,6-trimethylhydroquinone-1-acetate with a phytyl halide in a polar aprotic organic solvent in the presence of a base, and subjecting the so-obtained 4-O-phytyl-2,3,6-trimethylhydro-quinone-1-acetate to a rearrangement reaction, and in each case optionally submitting the so-obtained 3-phytyl-2,5,6-trimethylhydroquinone-1-acetate to a ring closure reaction to produce tocopheryl acetate. The invention also includes the novel compound 3-phytyl-2,5,6-trimethylhydroquinone-1-acetate and certain stereoisomers thereof, and also the further novel compound 4-hydroxy-2,3,6-trimethyl-5-[3-(4,8,12-trimethyltridecyl)-but-3-enyl]phenyl acetate which itself is one of several isomers of 3-phytyl-2,5,6-trimethylhydroquinone-1-acetate formed by isomerization under the influence of heating, e.g. during its distillation as part of the isolation and purification procedure following its manufacture as indicated above. (All-rac)-α-tocopherol, which may be derived from its acetate, is known to be the most active industrially important member of the vitamin E group.