2182-55-0Relevant academic research and scientific papers
PROCESS TO PRODUCE A MONO VINYL ETHER
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Page/Page column 8-9, (2020/03/23)
A process to produce a mono vinylether of formula (I) R-O-CH=CH2 wherein R represents an organic group with at least three carbon atoms comprising a) reacting a mono hydroxy compound of formula (II) R-OH wherein R has the above meaning with acetylene in presence of a catalyst to get a product mixture comprising the mono vinyl ether, unconverted mono hydroxy compound and the catalyst b) adding an ester comprising at least one ester group of formula (III) X-O2 C- wherein X is a hydrocarbon group comprising less carbon atoms than R to the product mixture obtained in process step a) and reacting the remaining mono hydroxy compound R-OH with the ester in the presence of the catalyst to get a transesterification product comprising at least one ester group of formula (IV) R-O2C- and an alcohol of formula (V) X-OH wherein R and X have the above meaning and c) isolating the mono vinyl ether from the product mixture obtained after process step b), optionally followed by purification of the mono vinyl ether by distillation.
A solid acetylene reagent with enhanced reactivity: Fluoride-mediated functionalization of alcohols and phenols
Werner, Georg,Rodygin, Konstantin S.,Kostin, Anton A.,Gordeev, Evgeniy G.,Kashin, Alexey S.,Ananikov, Valentine P.
supporting information, p. 3032 - 3041 (2017/07/24)
The direct vinylation of an OH group in alcohols and phenols was carried out utilizing a novel CaC2/KF solid acetylene reagent in a simple K2CO3/KOH/DMSO system. The functionalization of a series of hydroxyl-group-containing substrates and the post-modification of biologically active molecules were successfully performed using standard laboratory equipment, providing straightforward access to the corresponding vinyl ethers. The overall process developed involves an atom-economical addition reaction employing only inorganic reagents, which significantly simplifies the reaction set-up and the isolation of products. A mechanistic study revealed a dual role of the F- additive, which both mediates the surface etching/renewal of the calcium carbide particles and activates the CC bond towards the addition reaction. The development of the fluoride-mediated nucleophilic addition of alcohols eliminates the need for strong bases and may substantially extend the areas of application of this attractive synthetic methodology due to increasing functional group tolerance. As a replacement for dangerous and difficult to handle high-pressure acetylene, we propose the solid reagent CaC2/KF, which is easy to handle, does not require dedicated laboratory equipment and demonstrates enhanced reactivity of the acetylenic triple bond. Theoretical calculations have shown that fluoride-mediated activation of the hydroxyl group towards nucleophilic addition significantly reduces the activation barrier and facilitates the reaction.
PROCESS FOR PRODUCTION OF HIGH-PURITY VINYL ETHER
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Page/Page column 6, (2010/10/19)
A process for producing a high-purity vinyl ether, which comprises: a step of subjecting an alcohol represented by the general formula (1) [in-line-formulae]R—O—H??(1)[/in-line-formulae] to a vinyl ether formation reaction in the presence of a catalyst to synthesize a vinyl ether represented by the general formula (2), [in-line-formulae]R—O—CH═CH2??(2)[/in-line-formulae]a step of removing the catalyst from the reaction mixture obtained in the above step to obtain a crude vinyl ether containing the vinyl ether and the unreacted raw material alcohol,a step of reacting the unreacted raw material alcohol in the crude vinyl ether, with the vinyl ether in the presence of an acid catalyst, to convert the alcohol into an acetal represented by the general formula (3), and a step of subjecting a crude vinyl ether containing the acetal (III) to distillation to obtain a high-purity vinyl ether.
Au(I) complexes-catalyzed transfer vinylation of alcohols and carboxylic acids
Nakamura, Aki,Tokunaga, Makoto
, p. 3729 - 3732 (2008/09/20)
Au(I) complexes-catalyzed transfer vinylation of alcohols and carboxylic acids has been achieved. The catalyst system consists of 2 mol % AuClPPh3 and 2 mol % AgOAc. Primary alcohols and secondary alcohols were converted into corresponding vinyl ethers in good yield (64-93%); however, tertiary alcohols showed poor reactivities. Carboxylic acids were also transformed into corresponding vinyl esters in good yield (78-96%).
Nucleophilic addition to acetylenes in superbasic catalytic systems: XIII. Fluoride cesium containing systems, efficient catalysts for alkanols vinylation
Oparina,Shaikhudinova,Parshina,Vysotskaya,Preiss,Henkelmann,Trofimov
, p. 656 - 660 (2007/10/03)
New catalytic systems CsF-MOH (M = Li, Na) were developed for the synthesis of alkyl vinyl ethers comparable in efficiency to cesium alcoholates. The addition of primary and secondary alcohols to acetylene occurs in the presence of these systems at the atmospheric (DMSO, 100°C) or at enhanced (without solvent, 135-140°C) acetylene pressure and affords alkyl vinyl ethers in up to 93% yield. 2005 Pleiades Publishing, Inc.
Synthesis of allyl and alkyl vinyl ethers using an in situ prepared air-stable palladium catalyst. Efficient transfer vinylation of primary, secondary, and tertiary alcohols
Bosch, Martin,Schlaf, Marcel
, p. 5225 - 5227 (2007/10/03)
An air-stable palladium catalyst formed in situ from commercially available components efficiently catalyzed the transfer vinylation between butyl vinyl ether and various allyl and alkyl alcohols to give the corresponding allyl and alkyl vinyl ethers in 61-98% yield in a single step.
A facile one-pot synthesis of symmetrical and unsymmetrical acetaldehyde acetals from primary alcohols
Guy,DiPietro
, p. 687 - 692 (2007/10/02)
Initial formation of a vinyl ether 2 by treatment of a primary alcohol 1 with ethyl vinyl ether in the presence of mercury (II) acetate followed by treatment with the same or a different alcohol in the presence of p-toluenesulfonic acid affords the symmetrical and unsymmetrical acetaldehyde acetals 3 in good overall yield. The method is easily scaled up and represents a significant improvement over currently available procedures.
