Synthesis of vinyl ethers of alcohols using calcium carbide under superbasic catalytic conditions (KOH/DMSO)

Matake, Ryosuke; Adachi, Yusuke; Matsubara, Hiroshi

doi:10.1039/c5gc02977e

Cited by 75 publications

(29 citation statements)

References 27 publications

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“…37 Industrially (BASF, GAF, Union Carbide), MVE is synthesized by vinylation of methanol with acetylene under elevated pressure (10-18 atm) at 120-160 ∘ C in the presence of alkali metal hydroxides or their alcoholates. [6][7][8] Furthermore, in acetylene chemistry a trend to replace free acetylene by CaC 2 , 17 particularly in the www.soci.org LN Parshina et al synthesis of vinyl ethers, [16][17][18][19][20][21][22] is gaining strength. It should be emphasized that the successful vinylation is ensured only by application of superbasic catalytic system such as KOH/DMSO, 18,20 KOH/DMSO/KF, 20,22 DMSO/alkali metal (Li, Na, K, Cs) fluorides, 400 mol% relative to methanol with 50 mol% additives of potassium carbonate (K 2 CO 3 ), 21 caesium hydroxide (CsOH) or caesium carbonate/dimethylsulphoxide (Cs 2 CO 3 /DMSO).…”

Section: Introductionmentioning

confidence: 99%

Towards C1 chemistry: methanol vinylation by CaC₂ in water in the presence of potassium or sodium carbonates

Паршина

Опарина

Гусарова

et al. 2019

J of Chemical Tech & Biotech

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BACKGROUND Methyl vinyl ether (MVE), which polymers and copolymers are widely used in industry and medical chemistry, is produced mainly through base‐catalysed vinylation of methanol with acetylene under pressure. The most well‐known and sustainable acetylene source is calcium carbide. Significant economic benefits can be achieved by using calcium carbide as the source of acetylene directly in the industrial production of MVE. RESULTS Eco‐friendly and operationally simple method for vinylation of methanol, one of a major objects of C1 chemistry, using calcium carbide in water in the presence of potassium or sodium carbonates (140–150 °C, 1‐L steel rotating autoclave, maximum autogenic pressure 18–30 atm) has been developed and realized on 10‐g scale. The major co‐product of this reaction is a mixture of calcium hydroxide and calcium carbonate with minor content of potassium or sodium carbonates, which can be safely used for improving acidic soils. CONCLUSION Novel efficient method for vinylation of methanol with calcium carbide in water in the presence of alkali metal carbonates has been developed. The method allows avoiding acetylene gas under pressure that demands special equipment and safety measures. The major advantages of this technology are also availability and low cost of the catalysts. © 2019 Society of Chemical Industry

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Section: Introductionmentioning

confidence: 99%

Towards C1 chemistry: methanol vinylation by CaC₂ in water in the presence of potassium or sodium carbonates

Паршина

Опарина

Гусарова

et al. 2019

J of Chemical Tech & Biotech

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“…Combining the method presented here with recently promising results towards the synthesis of vinyl ethers through environmentally viable routes [27][28][29] and new photoinitiators for polymerizing vinyl ethers, as reviewed by Sangermano et al, 2 adds for a new benign way to reach a wide range of vinyl ether functional building blocks.…”

Section: Introductionmentioning

confidence: 95%

Novel sustainable synthesis of vinyl ether ester building blocks, directly from carboxylic acids and the corresponding hydroxyl vinyl ether, and their photopolymerization

et al. 2018

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Increased environmental awareness has led to a demand for sustainable, bio-based materials.Consequently, the development of new benign synthesis pathways utilizing a minimum of reaction steps and available bio-based building blocks is needed. In the present study, vinyl ether alcohols and functional carboxylic acids were used to synthesize bifunctional vinyl ether esters using the immobilized enzyme Candida antarctica lipase B as a catalyst. Vinyl ethers are attractive alternatives to (meth) acrylates due to low allergenic hazards, low toxicity, and fast polymerization; however, difficult synthesis limits the monomer availability. The synthesis was performed in one-pot and the described method was successful within a broad temperature range (22-90 C) and in various organic solvents as well as in the bulk. The synthesis of different vinyl ether esters reached high conversions (above 90%) after less than 1 h and products were purified by removing the enzyme by filtration using only small amounts of acetone. This approach is a straightforward route to reach monomers with multiple types of functionalities that can be used as different photo-curable thermoset resins. In this work, this was demonstrated by polymerizing the monomers with cationic and radical UV-polymerization. By changing the functional carboxylic acids, the architecture of the final polymer can be tailored, herein demonstrated by two examples. In the developed versatile method, carboxylic acids can be used directly as acyl donors, constituting a more sustainable alternative to the carboxylic acid derivatives used today.

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“…It could be useful for the late‐stage vinylation of complex functionalized molecules, such as estradiol, cholesterol, metoprolol, and hydroxyzine (Scheme ). Aliphatic and aromatic alcohols, ferrocenol, and terpenols are also prone to vinylation under similar conditions in excellent yields.…”

Section: Sustainable Access Usage and Recycling Of Calcium Carbidementioning

confidence: 99%

Calcium‐Based Sustainable Chemical Technologies for Total Carbon Recycling

2019

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Calcium carbide, a stable solid compound composed of two atoms of carbon and one of calcium, has proven its effectiveness in chemical synthesis, due to the safety and convenience of handling the C≡C acetylenic units. The areas of CaC2 application are very diverse, and the development of calcium‐mediated approaches resolves several important challenges. This Review aims to discuss the laboratory chemistry of calcium carbide, and to go beyond its frontiers to organic synthesis, life sciences, materials and construction, carbon dioxide capturing, alloy manufacturing, and agriculture. The recyclability of calcium carbide and the availability of large‐scale industrial production facilities, as well as the future possibility of fossil‐resource‐independent manufacturing, position this compound as a key chemical platform for sustainable development. Easy regeneration and reuse of the carbide highlight calcium‐based sustainable chemical technologies as promising instruments for total carbon recycling.

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Synthesis of vinyl ethers of alcohols using calcium carbide under superbasic catalytic conditions (KOH/DMSO)

Abstract: A convenient preparation of vinyl ethers from alcohols with calcium carbide was developed. This protocol is an alternative to the Favorskii-Reppe reaction without any high pressure device.

Cited by 75 publications

References 27 publications

Towards C1 chemistry: methanol vinylation by CaC₂ in water in the presence of potassium or sodium carbonates

Towards C1 chemistry: methanol vinylation by CaC₂ in water in the presence of potassium or sodium carbonates

Novel sustainable synthesis of vinyl ether ester building blocks, directly from carboxylic acids and the corresponding hydroxyl vinyl ether, and their photopolymerization

Calcium‐Based Sustainable Chemical Technologies for Total Carbon Recycling

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Synthesis of vinyl ethers of alcohols using calcium carbide under superbasic catalytic conditions (KOH/DMSO)

Abstract: A convenient preparation of vinyl ethers from alcohols with calcium carbide was developed. This protocol is an alternative to the Favorskii-Reppe reaction without any high pressure device.

Cited by 75 publications

References 27 publications

Towards C1 chemistry: methanol vinylation by CaC2 in water in the presence of potassium or sodium carbonates

Towards C1 chemistry: methanol vinylation by CaC2 in water in the presence of potassium or sodium carbonates

Novel sustainable synthesis of vinyl ether ester building blocks, directly from carboxylic acids and the corresponding hydroxyl vinyl ether, and their photopolymerization

Calcium‐Based Sustainable Chemical Technologies for Total Carbon Recycling

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Product

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Towards C1 chemistry: methanol vinylation by CaC₂ in water in the presence of potassium or sodium carbonates

Towards C1 chemistry: methanol vinylation by CaC₂ in water in the presence of potassium or sodium carbonates