L. A. Oparina

Non-catalytic addition of 1,2,4-triazole to nucleophilic and electrophilic alkenes

Non-catalytic addition of 1,2,4-triazole to vinyl ethers and esters occurs on heating (65-175°C, 4-20 h) to give Markovnikov adducts (yield 30-100%). Electron-deficient alkenes (acrylonitrile, acrylic acid, 4-phenyl-3-buten-2-one) react with 1,2,4-triazole (78-190°C, 4-20 h) to give anti-Markovnikov adducts in yields of 45-83%.

Nucleophilic Addition to Acetylenes in Superbasic Catalytic Systems: XVI*. Vinylation of Alcohols of the Furan Series under Atmospheric Pressure

Abstract2-Hydroxymethylfuran and 2-hydroxymethyltetrahydrofuran reacted with acetylene in the superbasic catalytic system KOH-DMSO at 75-85°C under atmospheric pressure to give in 1.5–3 h the corresponding 2-vinyloxymethyl derivatives in 88 and 91% yield, respectively.

Nucleophilic addition to acetylenes in superbasic catalytic systems: XV. Vinylation of 2-hydroxymethylfuran

Abstract2-Hydroxymethylfuran reacted with acetylene in superbasic catalytic systems MOH-DMSO (M = Na, K) under mild temperature conditions (75–85°C, 1–2 h), yielding 80% of 2-vinyloxymethylfuran. The product, as well as acetaldehyde acetals derived therefrom, turned out to be promising as modifiers for electrolyte in lithium-sulfur rechargeable batteries.

Functional Acetal Methacrylates: III. * Electrophilic Addition of Diols to 2-(Vinyloxy)ethyl Methacrylate

Reactions of 2-(vinyloxy)ethyl methacrylate with diols [ethylene glycol, diethylene glycol, triethylene glycol, oligoethylene glycol-400, Z-2-butene-1,4-diol, 2-butyne-1,4-diol, 1,1,3,3-tetramethyl-1,3-bis(3-hydroxypropyl)disiloxane, 2,2-bis(4-hydroxyphenyl)propane] and polyols (glycerol, pentaerythritol) under electrophilic conditions (1 wt% of CF3COOH, 20-60°C, 1-3 h) result in quantitative formation of functional acetal methacrylates.

Nucleophilic addition to acetylenes in superbasic catalytic systems: XVIII. Vinylation of phenols and naphthols with acetylene

Phenols and naphthols react with acetylene in a superbasic system KOH-DMSO forming the corresponding aryl vinyl ethers in up to 80% yields.

Nucleophilic addition to acetylenes in superbasic catalytic systems: XVII. Vinyl ethers with furyl and cycloacetal fragments: Synthesis and structure

Abstract4-Hydroxymethyl-2-(2-furyl)-1,3-dioxolane and 5-hydroxy-2-(2-furyl)-1,3-dioxane consisting of mixtures of cis- and trans-isomers react with acetylene in the superbasic catalytic system KOHH-DMSO at the atmospheric or higher pressure (80–85°C, 2–3 h) giving the corresponding vinyl ethers in 88–90% yield. The ratio of the structural and configurational isomers in vinyl ethers remains the same as in the initial compounds.

Vinylation of hydroxy-containing cyclic formaldehyde acetals with acetylene

Nucleophilic addition of alcohols having cyclic acetal fragments to acetylene smoothly occurs under relatively mild conditions (KOH, 100–125°C, 1–2 h, initial acetylene pressure 11–12 atm) to give the corresponding vinyl ethers in 80–83% yield.

Nucleophilic Addition to Acetylenes in Superbasic Catalytic Systems: XIV. Vinilation of Diols in a System CsF-NaOH

A new catalytic system CsF-NaOH was developed for the synthesis of mono- and divinyl ethers of alkanediols exceeding in efficiency KOH. The nucleophilic addition of diols to acetylene in the presence of this system occurs both at enhance pressure (without solvent, 140–160°C) and atmospheric pressure (in DMSO medium, 100°C) of acetylene. Conditions were established of a selective preparation in a high yield of divinyl ethers from diols.

Nucleophilic addition to acetylenes in superbasic catalytic systems. 12. Vinylation of lupinine

The addition of a natural alkaloid lupinine to acetylene in the presence of superbasic catalytic systems (KOH—DMSO, KOBut—DMSO, KOH—dioxane) under elevated or atmospheric pressure affords O-vinyllupinine (in up to 88% yield), a promising optically active monomer and intermediate for the preparation of new quinolizidine alkaloids. The same vinyl ether was obtained (in 60% yield) by the reaction of lupinine with vinyl acetate in the presence of Hg(OAc)2.

Nucleophilic addition to acetylenes in superbasic catalytic systems: XI. Transformations of alkali metal hydroxides during vinylation of 1-heptanol with acetylene under elevated pressure

Base-catalyzed addition of 1-heptanol to acetylene under elevated pressure of the latter is accompanied by side processes including formation of carboxylic acid salts (alkali metal heptanoates and acetates) with liberation of hydrogen and acetylene polymerization. The rate of acetylene absorption depends on the alkali metal nature and falls down in the series CsOH·H2O ≥ RbOH·H2O > 2KOH·H2O > NaOH > LiOH. Approximately the same order is observed for variation of the rate of deactivation of the catalyst owing to its transformation into metal carboxylate. Dehydration of the catalyst accelerates both vinylation and acetylene polymerization.