Synthesis and some chemical conversions of acetylenic derivatives of 1,4-dioxane

Abstract

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

Synthesis of 2,2-Disubstituted and 2,2,3-Trisubstituted 1,4-Dioxane-Derived Building Blocks

“…for C7H13N3O2: C 49.11;H 7.65;N 24.54. Found: C 49.27;H 7.98;nonane (43) Yield 27.4 g (100% from 41 (46.7 g, 0.150 mol)). Colorless liquid.…”

“…Common approaches for the construction and modification of the 1,4-dioxane core were comprehensively reviewed in a recent monography. 33 Predominating meth- ods rely on intramolecular cyclizations of 1,2-diol derivatives bearing an electrophilic moiety at the appropriate position 28,29,[34][35][36][37][38][39][40][41][42][43][44][45] or Lewis acid-mediated reaction of epoxides with -halohydrins [46][47][48][49] or 1,2-diols, 50 followed by intramolecular cyclization. Among all present methods, oxirane ring-opening with ethylene glycol monosodium salt followed by cyclization of the intermediate diol has been evaluated as a straightforward and efficient approach for the preparation of 1,4-dioxanes.…”

“…Dimethyl-1,4-dioxan-2-yl)methanesulfonyl Chloride(48) NCS (65.0 g, 0.487 mol) was dissolved in MeCN (250 mL) with H 2 O (27.5 mL), and sat. aq HCl (7.5 mL) was added.…”