A new catalytic system CsFNaOH 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, 140160°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.
* For communication XII see [1].Nucleophilic mono-and diaddition of diols to acetylene occurs under effect of strong bases (alkali metal hydroxides and alcoholates, superbasic system KOH DMSO etc.) at enhanced or atmospheric pressure of acetylene [210] and is accompanied as a rule by further transformations of the target mono-and divinyl ethers (acetalization, the rupture of CO bonds, elimination of a vinyl alcohol etc.) [213]. Therefore the search for new catalysts for the efficient and selective synthesis of mono-and divinyl ethers from diols remains an urgent problem. With this goal we have for the first time studied a reaction of acetylene with diols in the presence of a new catalytic system CsFNaOH [1, 14] whose efficiency is due apparently mainly to the formation in situ of anhydrous cesium hydroxide nanoparticles. The an-hydrous cesium hydroxide is known to be more active [15] but less available than KOH vinylation catalyst.By an example of a series of primary and secondary diols IaIg containing from 2 to 7 carbon atoms between the hydroxy groups we demonstrated that the main R = (CH 2 ) 2 (a), CH(CH 3 )CH(CH 3 ) (b), (CH 2 ) 3 (c), CH(CH 3 )(CH 2 ) 2 (d), (CH 2 ) 4 (e), CH(CH 3 )(CH 2 ) 2 CH(CH 3 ) (f), (CH 2 ) 7 (g).
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Ethers P 0150Nucleophilic Addition to Acetylenes in Superbasic Catalytic Systems. Part 14. Vinylation of Diols in a System CsF-NaOH. -Reactions of acetylene with diols (I) in the presence of the new catalytic system CsF/NaOH provides access to the synthesis of mono-and divinyl ethers. Appropriate conditions for the selective synthesis of divinyl ethers (III) are established. -(OPARINA*, L. A.; KHIL'KO, M. Y.; CHERNYSHOVA, N. A.; SHAIKHUDINOVA, S. I.; PARSHINA, L. N.; PREISS, T.; HENKELMANN, J.; TROFIMOV, B. A.; Russ.
Addition Reaction of β,γ-Unsaturated Alcohols with Divinyl Sulfoxide.-Divinyl sulfoxide (I) is coupled with the allylic alcohols (II) to give the mono-(III) or bisaddition products (IV) depending on the molar ratio of the educts. Pyrolysis of (IIIa) in the presence of KOH leads to the formation of allyl vinyl ether (V). -(KOZYREV, V. G.; VORONKOV, M. G.; ZHMYKHOVA, I. P.; CHERNYSHOVA, N. A.; Zh.
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