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

Опарина, Л. А.; Tlegenov, R. T.; Ермакова, Т. Г.; Кузнецова, Н. П.; Kanitskaya, L. V.; Танцырев, А. П.; Трофимов, Б. А.

doi:10.1023/b:rucb.0000024856.57354.85

Cited by 9 publications

(3 citation statements)

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“…It is indeed unexpected because sodium-tailored bases, alkoxides or hydroxides are much inferior catalysts in vinylation of alcohols with acetylene compared with the corresponding potassium-derived bases. 40,44 Although under the same conditions the yield of MVE obtained with Na 2 CO 3 is 15% less compared to that with K 2 CO 3 (43 and 58%, correspondingly), the use of the former in real technological processes might be more preferential owing to economic reasons (Na 2 CO 3 is about 3-5 times cheaper than K 2 CO 3 ). The optimum K 2 CO 3 catalyst content is 12.5% (that secures 58% yield of MVE), while with the lower (5%) or higher (25%) catalyst loading, yields of the target product considerably drop (30 and 43%, correspondingly, Table 2, entries 4 and 13).…”

Section: Resultsmentioning

confidence: 96%

“…However, a surprising result was the high catalytic activity of Na 2 CO 3 which allowed a conversion/yield value of 43% with 12.5% loading (Table , entry 15) to be obtained. It is indeed unexpected because sodium‐tailored bases, alkoxides or hydroxides are much inferior catalysts in vinylation of alcohols with acetylene compared with the corresponding potassium‐derived bases . Although under the same conditions the yield of MVE obtained with Na 2 CO 3 is 15% less compared to that with K 2 CO 3 (43 and 58%, correspondingly), the use of the former in real technological processes might be more preferential owing to economic reasons (Na 2 CO 3 is about 3–5 times cheaper than K 2 CO 3 ).…”

Section: Resultsmentioning

confidence: 99%

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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: Resultsmentioning

confidence: 96%

Section: Resultsmentioning

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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“…5-8 A great advance in the development of vinylation reaction of alcohols with acetylenes took place due to the superbasic catalytic systems. 9-13 Vinyl ethers of available natural compounds such as steroids, 14 alkaloids, 15 carbohydrates have been synthesized using this methodology. 16 These compounds are of undoubted interest from the point of view of their stereochemical structure.…”

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Synthesis and conformational analysis of furfuryl vinyl ethers

et al. 2008

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Five furfuryl vinyl ethers were synthesized from the corresponding furfuryl alcohols and acetylene at high and atmospheric pressures in superbasic medium KOH-DMSO. On the example of 2 vinyloxymethylfuran and 2 vinyloxymethyltetrahydrofuran, their conformational structures have been studied by quantum chemistry methods, NMR and IR spectroscopy. In particular, from the results of the quantum chemical calculations, as well as on the basis of experimental measurement and nonempirical calculations of the high level spin spin coupling constants 13 C-13 C and 13 C-1 H, a conclusion has been drawn on the s cis orientation of the vinyl groups with respect to the C α -O bond in the predominant conformers of 2 vinyloxy methylfuran and 2 vinyloxymethyltetrahydrofuran.Vinyl ethers are of wide practical use in organic synthesis 1-4 and in chemistry of polymers. 5-8 A great advance in the development of vinylation reaction of alcohols with acetylenes took place due to the superbasic catalytic systems. 9-13 Vinyl ethers of available natural compounds such as steroids, 14 alkaloids, 15 carbohydrates have been synthesized using this methodology. 16 These compounds are of undoubted interest from the point of view of their stereochemical structure. Recently, we have performed a highly selective synthesis of tetravinyl ether of methyl α D glucoside 16 using superbasic catalysts and studied its structure in details. 17 Development of technologically acceptable methods for the synthesis of vinyl ethers on the basis of furfuryl alcohols is no less important task. The latter are compo nents of biomasses enriched with pentoses (including waste of agriculture and wood industry). 18 Furan and hydrofuran rings are important structural fragments in various bio logically active natural and synthetic compounds. 19,20 Introduction of highly reactive double bond into the side chain allows one to considerably broaden synthetic poten tial of these compounds.By the time of the present study, it has been be lieved 21,22 that lowering the temperature of the reaction of 2 hydroxymethylfuran with acetylene to 125-135 °C at high pressure provides an increase in the yield of the vinyl ether to 68%, however, the vinyl ether is not formed below this range of temperatures. 2 Hydroxymethyltetra hydrofuran, on the contrary, reacts with acetylene under more drastic conditions: for successful realization of the reaction, raising the temperature to 180 °C (catalyst, KOH) 23 or the use of metal potassium 24 and sodium 25 for the generation of corresponding alkoxide is required.Recently, 26 starting from alcohol 1a and acetylene we have developed an efficient method for the synthesis of the corresponding 2 vinyloxymethylfuran (3a) at high pressure in the system MOH-DMSO (M = Na, K) (Scheme 1). Processing at 75-85 °C (by 50 °C lower in comparison with the optimum data reported in the litera ture 22 ) allowed us to largely suppress resinification and reach the 80% yield of product 3a.Scheme 1 X = CH 2 (a), CH 2 OCH 2 CH 2 (b), CH-Pr (c) The present work is aimed a...

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vinylation

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2020

Catalysis From a to Z

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

Cited by 9 publications

References 1 publication

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

Synthesis and conformational analysis of furfuryl vinyl ethers

vinylation

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

Cited by 9 publications

References 1 publication

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

Synthesis and conformational analysis of furfuryl vinyl ethers

vinylation

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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