The possibility has been shown of synthesizing acetylenic derivatives of 1,4-dioxane in high yield by the interaction of glycidyl ethers of acetylenic alcohols with ethylene bromohydrin in the presence of boron trifluoride etherate. Dehydrobromination of the corresponding bromohydrin was then carried out in the presence of metallic sodium in absolute diethyl ether. Acetylenic derivatives of 1,4-dioxane enter into hydrosilylation, aminomethylation, and diene condensation reactions with the formation of new derivatives of 1,4-dioxane.It is known that oxygen-containing heterocyclic compounds with multiple bonds are reactive and may be applied widely in organic synthesis for obtaining polyfunctional compounds with practically useful properties, particularly biologically active compounds [1][2][3][4][5]. The preparation of unsaturated derivatives of 1,4-dioxane from glycidyl ethers of unsaturated alcohols has been insufficiently studied [5][6][7][8][9]. While continuing investigations started previously [10], we have synthesized a series of acetylenic derivatives of 1,4-dioxane from glycidyl ethers of primary and tertiary acetylenic alcohols and have studied some of their chemical conversions. OH Br O O O R R O O R O O H Br R O O R O R O + ( ) n BF 3· · OEt 2 ( ) n ( ) n 1a -d Na ether 1 a, c R = H, b, d R = Me; a, b n = 0, c, d n = 1