Preparation of 1-Ethynylcyclohexano by Ball Milling CaC2 and Cyclohexanone
CHU Haojie, LI Chunxi
State Key Laboratory of Chemical Resource Engineering, School of Chemical Engineering, Beijing University of Chemical Technology, Beijing 100029, China
Abstract：Calcium carbide (CaC2) is an important coal chemical product, and expanding its chemical reactions and applications is of great significance for the sustainable development of the calcium carbide industry. Compared with acetylene, the alkynyl anion of calcium carbide has stronger nucleophilicity and reacts more readily with carbonyl compounds to form alkynyl alcohols. This work investigated the effects of additive type and dosage, reaction mode, ball milling time, and solvent on the reaction of CaC2 with cyclohexanone. The results showed that CsF and trace water could promote this reaction. In dimethyl sulfoxide (DMSO) solvent (1% H2O), with CaC2 6 mmol, CsF 2.5 mmol, cyclohexanone 5 mmol, ball milling for 2 h at a rotation speed of 150 r/min, the conversion of cyclohexanone and the yield of 1-ethynylcyclohexanol could reach 95.1% and 64.4%, respectively. In acetylene-saturated DMSO solvent, the yield of 1-ethynylcyclohexanol could be increased to 80.2%. Partial hydrolysis of CaC2 to calcium acetylene and hydroxide(HC2CaOH) promoted its activation. CsF had a dual role in both disrupting the CaC2 lattice and complexing with the carbonyl group of cyclohexanone to enhance the electrophilicity of the carbonyl carbon, thereby synergistically promoting the reaction of CaC2 with cyclohexanone. This study established a new method for the synthesis of 1-ethynylcyclohexanol from calcium carbide and cyclohexanone, which was instructive for the reaction of calcium carbide with carbonyl compounds.
CHU Haojie,LI Chunxi. Preparation of 1-Ethynylcyclohexano by Ball Milling CaC2 and Cyclohexanone[J]. Chemical Reaction Engineering and Technology, 2025, 41(6): 694-701.
