Novel 1 alpha-hydroxy Vitamin D4 and novel analogues, 1,25 dihydroxy Vitamin D4 and 1,24 dihydroxy Vitamin D4 which are useful for the treatment of disorders of calcium metabolism. Preparation of the novel 1 alpha-hydroxy Vitamin D4 starts from ergosterol which is converted in six steps to 22,23-dihydroergosterol. 22,23-dihydroergosterol was irradiated to yield Vitamin D4 which was converted in four steps to 1 alpha-hydroxy Vitamin D4 using a cyclovitamin procedure which produced the novel intermediates, Vitamin D4 tosylate, 3,5 cyclovitamin D4 and 1 alpha-hydroxy cyclovitamin D4. 1,25 dihydroxy Vitamin D4 and 1,24-dihydroxy Vitamin D4 are isolated as biological products of the metabolism of novel 1 alpha-hydroxy Vitamin D4 using cultured human liver cells.