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

Abstract

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

Phosphine-Catalyzed Vinylation at Low Acetylene Pressure

“…Catalysis was performed according to the general procedure. Analytical data are in accordance with those previously reported . Yield: 27%.…”

“…Analytical data are in accordance with those previously reported. 73 Yield: 27%. 1 H NMR (300 MHz, 300 K, C 6 D 6 ): δ 6.34 (dd, 3 J HH = 14.3 Hz, 3 J HH = 6.8 Hz, 1H, OCH), 3.95 (dd, 2 J HH = 2.0 Hz, 3 J HH = 14.3 Hz, 1H, OCHCH 2 ), 3.75 (dd, 2 J HH = 2.0 Hz, 3 J HH = 6.8 Hz, 1H, OCHCH 2 ), 3.28 (s, 3H, OCH 3 ).…”

Nature of the Nucleophilic Oxygenation Reagent Is Key to Acid-Free Gold-Catalyzed Conversion of Terminal and Internal Alkynes to 1,2-Dicarbonyls

“…The use of compressed acetylene requires special facilities and techniques as well as strict safety precautions . To overcome these restrictions, calcium carbide was suggested as a convenient and rather safe source of acetylene, , and we decided to explore this CaC 2 -based method in our experiments.…”

Atom-economical synthesis of 1,2-bis(phosphine oxide)ethanes from calcium carbide with straightforward access to deuterium- and13C-labeled bidentate phosphorus ligands and metal complexes

“…The conditions were selected using previous examples of acetylene gas transformations under superbasic conditions. 114–121…”

“…The chemistry of calcium carbide is a well-developed area 98,99 with a number of representative studies, 100–113 including triple bond transformations under superbasic conditions. 114–121…”