Hochaktive Katalysatorsysteme für die Vinylethersynthese aus Acetylen und Alkoholen—Kaliumalkoholat/Kronenether in Kohlenwasserstoffen

Steinborn, Dirk; Mosinski, Holger; Rosenstock, Thomas

doi:10.1016/0022-328x(91)86108-3

Cited by 10 publications

(10 citation statements)

References 8 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Due to their low toxicity [58] and efficient manufacturing, vinyl ethers have been extensively used in research and industry without any significant amendments to the concept of their synthesis [59,60]. A number of modifications have been introduced, including variation of eliminating agents [61], upgrade of the catalysts and conditions for trans-vinylation processes [62][63][64][65], adjustment of the solvents and expansion of the substrate scope for the addition technique [66,67]. The increasing demand for vinyl monomers requires a sustainable and scalable manufacturing methodology, preferably based on renewables.…”

Section: Advanced Green Syntheses Of Vinyl Ether Monomersmentioning

confidence: 99%

Recent advances in applications of vinyl ether monomers for precise synthesis of custom-tailored polymers

Kirillov

Rodygin

Ananikov

2020

European Polymer Journal

View full text Add to dashboard Cite

This review highlights recent progress in the synthesis and application of vinyl ethers (VEs) as monomers for modern homo-and co-polymerization processes. VEs can be easily prepared using a number of traditional synthetic protocols including a more sustainable and straightforward manner by reacting gaseous acetylene or calcium carbide with alcohols. The remarkably tunable chemistry of VEs allows designing and obtaining polymers with well-defined structures and controllable properties. Both VE homopolymerization and copolymerization systems are considered, and specific emphasis is given to the novel initiating systems and to the methods of stereocontrol.

show abstract

Section: Advanced Green Syntheses Of Vinyl Ether Monomersmentioning

confidence: 99%

Recent advances in applications of vinyl ether monomers for precise synthesis of custom-tailored polymers

Kirillov

Rodygin

Ananikov

2020

European Polymer Journal

View full text Add to dashboard Cite

show abstract

“…The systematic investigation of alcohols vinylation with acetylenes discovered by A.E. Faworsky [2] and further developed by W. Reppe [3] and M.F.Shostakovskii [4] provide deeper theoretical insight into the nucleophilic additions to the triple bond [5] and constant refining of the synthesis of vinyl ethers of versatile structures [3 12].Here the main trend in stimulating vinilation reaction is the application of superbasic systems, like alkali metal hydroxidepolar solvent lacking hydroxy groups (DMSO, N-methylpyrrolidone, HMPA) [5, 712], or alkali metal alcoholateLewis base (Crown ether)solvent lacking hydroxy groups (hydrocarbon) [13,14].We report here on the application of highly basic systems CsFMOH and CsFMOHDMS (M = Li, Na) as efficient catalysts to alcohols vinylation.In [15,16] it was shown by an example of 1-heptanol vinylation under enhanced and atmospheric acetylene pressure in the presence of alkali metal hydroxides that the catalysts under investigation fit to the following series according to the decreasing efficiency:The comparison of the catalytic activity of KOH hydrates (2KOH·H 2 O and KOH·H 2 O) confirmed the known [4,7] negative effect of water on the vinylation process. Consequently, the use of anhydrous alkali metal hydroxides, first of all of CsOH would considerably accelerate the vinylation of the hydroxy compounds.…”

mentioning

confidence: 99%

“…Here the main trend in stimulating vinilation reaction is the application of superbasic systems, like alkali metal hydroxidepolar solvent lacking hydroxy groups (DMSO, N-methylpyrrolidone, HMPA) [5, 712], or alkali metal alcoholateLewis base (Crown ether)solvent lacking hydroxy groups (hydrocarbon) [13,14].…”

mentioning

confidence: 99%

“…Faworsky [2] and further developed by W. Reppe [3] and M.F.Shostakovskii [4] provide deeper theoretical insight into the nucleophilic additions to the triple bond [5] and constant refining of the synthesis of vinyl ethers of versatile structures [3 12]. Here the main trend in stimulating vinilation reaction is the application of superbasic systems, like alkali metal hydroxidepolar solvent lacking hydroxy groups (DMSO, N-methylpyrrolidone, HMPA) [5,712], or alkali metal alcoholateLewis base (Crown ether)solvent lacking hydroxy groups (hydrocarbon) [13,14].…”

mentioning

confidence: 99%

“…7, 1012, 14,15,17). The conversion of alcohol suggests that the reactivity tends to grow in the series C 4 < C 6 » C 7 < C 9 » C 12 , whereas the selectivity of the reaction is virtually unchanged.…”

mentioning

confidence: 99%

See 2 more Smart Citations

Nucleophilic Addition to Acetylenes in Superbasic Catalytic Systems: XIII. Fluoride Cesium Containing Systems, Efficient Catalysts for Alkanols Vinylation

et al. 2005

View full text Add to dashboard Cite

New catalytic systems CsFMOH (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. * For communication XII see [1]. The systematic investigation of alcohols vinylation with acetylenes discovered by A.E. Faworsky [2] and further developed by W. Reppe [3] and M.F.Shostakovskii [4] provide deeper theoretical insight into the nucleophilic additions to the triple bond [5] and constant refining of the synthesis of vinyl ethers of versatile structures [3 12].Here the main trend in stimulating vinilation reaction is the application of superbasic systems, like alkali metal hydroxidepolar solvent lacking hydroxy groups (DMSO, N-methylpyrrolidone, HMPA) [5, 712], or alkali metal alcoholateLewis base (Crown ether)solvent lacking hydroxy groups (hydrocarbon) [13,14].We report here on the application of highly basic systems CsFMOH and CsFMOHDMS (M = Li, Na) as efficient catalysts to alcohols vinylation.In [15,16] it was shown by an example of 1-heptanol vinylation under enhanced and atmospheric acetylene pressure in the presence of alkali metal hydroxides that the catalysts under investigation fit to the following series according to the decreasing efficiency:The comparison of the catalytic activity of KOH hydrates (2KOH·H 2 O and KOH·H 2 O) confirmed the known [4,7] negative effect of water on the vinylation process. Consequently, the use of anhydrous alkali metal hydroxides, first of all of CsOH would considerably accelerate the vinylation of the hydroxy compounds. However the preparation of anhydrous cesium and rubidium is a laborious process. Usually azeotropic removal of water is used with an appropriate high-boiling solvent (octane, toluene). The present article contains findings evidencing the possibility of a successful application to the vinyl ethers synthesis of a catalytic system CsFMOH (M = Li, Na) where the anhydrous CsOH is formed directly in the course of vinylation. This system possesses significant advantages compared to traditional vinylation catalysts like sodium and potassium hydroxides.The high catalytic efficiency of the system developed is apparently due predominantly to the exchange between the lithium or sodium hydroxides and cesium fluoride resulting in cesium hydroxide and sparingly soluble lithium or sodium fluorides.The nature of the alkali metal cation in the MOH (where M = Li, Na) used in the catalytic couple CsF MOH did not virtually affect the rate of vinylation in keeping with the preliminary occurrence of the exchange reaction and with the actual catalysis of alcohol vinylation by the arising cesium hydroxide. The formation of sparingly soluble lithium and sodium fluorides shifts the exchange equilibrium to the right. Therewith the better solubility in alcohols of NaOH compared to...

show abstract

Use of Iridium‐Catalyzed Transfer Vinylation for the Synthesis of Bio‐Based (bis)‐Vinyl Ethers

Spiegelberg

Jiao²,

Grauke

et al. 2022

Adv Synth Catal

View full text Add to dashboard Cite

The iridium catalyzed transfer vinylation of bio‐based polyols and of other alcohols and phenols with interesting structural motifs was accomplished with vinyl acetate in 2‐MeTHF as a green solvent. The optimized synthetic procedure has as main advantages the use of catalytic instead of stoichiometric amounts of base and high selectivities towards the formation of bis‐vinyl ethers as a result of the suppression of the acetal formation reaction that typically occurs in the vinylation of diols. In addition, the thermodynamically preferred transesterification reaction leading to the acetate esters and bis‐esters was completely suppressed. DFT calculations revealed an iridium‐acetate complex as the active catalytic species and they disclosed the importance of the carbonyl group of vinyl acetate for the formation of a six‐membered cyclic intermediate.

show abstract

Hochaktive Katalysatorsysteme für die Vinylethersynthese aus Acetylen und Alkoholen—Kaliumalkoholat/Kronenether in Kohlenwasserstoffen

Cited by 10 publications

References 8 publications

Recent advances in applications of vinyl ether monomers for precise synthesis of custom-tailored polymers

Recent advances in applications of vinyl ether monomers for precise synthesis of custom-tailored polymers

Nucleophilic Addition to Acetylenes in Superbasic Catalytic Systems: XIII. Fluoride Cesium Containing Systems, Efficient Catalysts for Alkanols Vinylation

Use of Iridium‐Catalyzed Transfer Vinylation for the Synthesis of Bio‐Based (bis)‐Vinyl Ethers

Contact Info

Product

Resources

About