Abstract: 2-Substituted-1,4-benzodioxanes such as Piperoxan (Ⅰ) and Prosympal (Ⅱ) are adrenergic blocking agents. Several related compounds of this series such as ethoxybutamoxane (V) have, besides their typical peripheral sympatholytic action, also depressant effects on the central nervous system. A number of 2-substituted-1, 4-benzodioxanes have been prepared in the present work for screening as potential hypotensive and tranquillizing agents. 2-Chloro or 2-bromomethyl-1, 4-benzodioxane, on treatment with pyrrolidine, cyclohexylamine, hexamethylenimine and heptamethylenimine gave the respective 2-substitutedaminomethyl-1, 4-benzodioxanes (Ⅵa, Ⅵb, Ⅵd and Ⅵe); and with hydrazine gave N, N-bis-(1, 4-benzodioxan-2-ylmethyl) hydrazine (Ⅺ). 2-Hydroxymethyl-1, 4-benzodioxane was treated with acetic anhydride, cinnamoyl chloride and 3,4,5-trimethoxybenzoyl chloride respectively, giving the corresponding esters (Ⅶa, Ⅶb and Ⅶc). The β-dimethylaminoethyl ether (Ⅹ) was formed when the hydroxy compound reacted with β-dimethylaminoethyl chloride in the presence of Sodium. The esters of β-substituted-aminoethanol (Ⅷa, Ⅷb) and amide (Ⅸa, Ⅸb) were formed when 1, 4-benzodioxan-2-carbonyl chloride was treated with β-morpholinoethanol, β-dimethylaminoethanol, phenethylamine and 2-chlorophenothiazine. Reduction of phenethylamide (Ⅸa) by means of lithium aluminium hydride gave 2-β-phenylethylaminomethyl-1, 4-benzodioxane.