The position of galloyl groups in acertannin, as 3, 6-digalloylpolygalito, has been established by well-defined processes. In the courses of the processes eight new compounds, octamethoxyacertannin, 2, 4-dimethoxy-1, 5-anhydro-D-sorbitol, 6-tosylpolygalito, 2, 3, 4-tri-benzoyl-6-tosylpolygalitol, 3, 6-anhydro-1, 5-anhydro-D-sorbitol, and 2, 4-ditosyl-3, 6-anhydro-1, 5-anhydro-D-sorbitol, have been characterized.