间接电氧化2-丁酮制备α-羟基缩酮的研究  

Preparation of α-Hydroxylated Acetal from 2-Butanone by Indirect Electrooxidation

作　　者：黄海清 繆烨 张新胜[1] HUANG Hai-qing;MIAO Ye;ZHANG Xin-sheng(State Key Laboratory of Chemical Engineering,East China University of Science and Technology,Shanghai 200237,China)

机构地区：[1]华东理工大学化学工程国家重点实验室,上海200237

出　　处：《电化学》2020年第3期389-396,共8页Journal of Electrochemistry

基　　金：国家重点研发计划项目(No.2017YFB0307502)资助。

摘　　要：在板框式循环电解槽中,以KOH为电解质,KI为催化剂,石墨电极分别为阳极和阴极,研究电化学间接氧化2-丁酮合成乙偶姻中间体α-羟基缩酮,讨论电流密度、极板间电解液流速、电解液中2-丁酮浓度、电解温度以及通电量等电解条件对中间体收率和电流效率的影响,经优选工艺条件为:电流密度40 m A·cm^-2,流速6.4 cm·s^-1,2-丁酮浓度1.75 mol·L^-1,电解温度30℃,通电量为1.5 F·mol^-1时,中间体收率可达78.9%,电流效率40.1%.循环伏安测试结果表明,电解时碘离子在阳极氧化生成碘单质,甲醇在阴极还原生成甲氧基负离子,原料2-丁酮与电解产物反应,并最终生成乙偶姻中间体.Acetoin(3-hydroxy-2-butanone) is an important food spice. As a platform compound, it is widely used in medicine,tobacco, cosmetics, chemical material and other industries. In this paper, α-hydroxylated acetal, an intermediate of acetoin, was prepared from 2-butanone by indirect electrooxidation in the plate and frame electrolytic cell, in which graphite plates were used as both an anode and a cathode, while KOH as an electrolyte and KI as a catalyst. Acetoin could be prepared by hydrolysis in acidic aqueous solution from acetoin intermediate. The effects of current density, electrolyte flow rate between the plates, 2-butanone concentration and electrolysis temperature on the yield and efficiency of acetoin intermediate were investigated. Under the optimized conditions, namely, the current density of 40 m A·cm^-2, the flow rate of 6.4 cm·s^-1, the 2-butanone concentration of 1.75 mol·L^-1, the electrolysis temperature of 30 ℃, and the passed charge of 1.5 F·mol^-1, the yield and current efficiency of the acetoin intermediate could reach 78.9% and 40.1%, respectively. The cyclic voltammetric tests showed that during electrolysis, iodine ions were oxidized to iodine on the anode, while methanol was reduced to methoxy anion on the cathode. 2-butanone reacted with the electrolytic products, and eventually, the acetoin intermediate was formed.

关 键 词：2-丁酮 乙偶姻中间体 间接电氧化 碘化钾 甲醇 

分 类 号：O646[理学—物理化学]