Vinylation of Pentaerythritol

Abstract

VINYLATION OF PENTAERYTHRITOL 47 1 monia waa evaporated. The residue was treated with 100 removed. The residue was distilled to give 28.9 g. (89%) of ml. of water and 110 ml. of concentrated hydrochloric 1-dimethylamino-1-phenylpropane (IVb), b.p. 58-58.5' acid, and most of the t-butyl alcohol was distilled. After at 2.5 mm., ny 1.5016. The picrate, m.p. and mixed m.p cooling, the acid solution was made alkaline with sodium 167-168', was recrystallized from ethanol. hydroxide solution, and the resulting mixture was extracted with ether. The ether extract was dried, and the solvent DURHAM, N. C.The catalytic vinylation of pentaerythritol in aqueous base afforded a mixture of products from which the pure divinyl ether I1 was isolated in 22% yield. The total mixture of compounds obtained from the aqueous vinylation was treated further with acetylene under non-aqueow basic conditions to give a mixture of the tetravinyl ether of pentaerythritol (V) (60-?0%) and 5,5-di(vinyloxymethyl)-2-methyl-l,3-dioxane (VII) (3040%). There appears t o be a relationship between the acidity of an alcohol and its tendency to undergo vinylation in an aqueous solution. Sixiiple monohydric aliphatic alcohols do not undergo base-catalyzed vinylation in water, whereas, polyhydroxy compounds capable of forming intramolecular hydrogen bonds react with acetylene in aqueous base to give products of vinylation.

Living/controlled cationic cyclopolymerization of divinyl ether with a cyclic acetal moiety: Synthesis of poly(vinyl ether)s with high glass transition temperature based on incorporation of cyclized main chain and cyclic side chains

“…[10][11][12][13][14][15][16][17][18][19][20] In contrast, much smaller rings (8menbered rings through head-to-tail intramolecular addition) will be formed in the polymer backbones from divinyl ether 1. Synthesis of divinyl ether 1 was reported, 21 but the details of cationic polymerization remain unknown. It should be noted that to measure the cyclopolymerization tendency precisely, the use of living/controlled propagating species is important, because it becomes possible to easily detect the postpolymer-polymer side reactions like crosslinking and/or branching by monitoring the broadening of the otherwise narrow polymer molecular weight distributions (MWDs).…”