Direct hydroxymethylation of β-(I) and γ-tocopherol (III) and their model compounds are established with boric acid catalyst. The yields of 7-hydroxymethyl-β-tocopherol (V), 5-hydroxymethyl-γ-tocopherol (VII), 6-hydroxy-7-hydroxymethyl-2, 2, 5, 8-tetramethylchroman (VI), and 6-hydroxy-5-hydroxymethyl-2, 2, 7, 8-tetramethylchroman (VIII) are 83%, 86%, 75%, and 78%, respectively. 5-Methyl-¹⁴C-d-α-tocopheryl acetate (XIV) is synthesized by the procedure. 1, 1-Bis (β-tocopherol-7'-yl)-methane (XVII), 1, 1-bis (γ-tocopherol-5'-yl)-methane (XV), and their acetates (XVIII) and (XVI) are synthesized from corresponding hydroxymethyl tocopherols and tocopherols.