摘要
通过对不同溶剂存在下甲酸甲酯与甲醇钠非催化合成碳酸二甲酯反应的研究,发现四氢呋喃比质子性溶剂甲醇和极性非质子性溶剂二甲基甲酰胺等更适合该合成反应,它兼有两者的优点,对两者的缺点又有不同程度的克服。本文重点考察了甲醇和一氧化碳对催化合成DMC反应的影响,结果发现当反应体系中有甲醇存在时,甲醇会与甲氧基负离子通过氢键结合,降低甲氧基负离子的亲核活性,影响反应生成DMC的速率。与甲醇不同,一氧化碳能有效抑制甲酸甲酯的分解反应,当使用CO/O2作氧化剂时,得到了较好的DMC收率和选择性。
Effect of different kinds of solvent on the non-catalytic reaction of synthesis of DMC was studied at room temperature, it was found that, as a solvent, tetrahydrofuran（THF） has the advantages of both protic solvent and polar aprotic solvent.Not only can it promote the reaction of synthesis of DMC, but also prohibit the decomposition of methyl formate. Besides, effect of methanol and carbon monoxide on the catalytic reaction was studied especially. Methanol was found to form hydrogen bond with methoxy-anion ,which reduces the nucleophilic activity of methoxy-anion in the reaction of nucleophilic substitution. Different from methanol, carbon monoxide can prohibit the decomposition of methyl formate and improve yield of DMC at the same time. An enhanced selectivity of DMC was observed, when mixed gases of carbon monoxide and oxygen were used as oxidant.
出处
《精细化工原料及中间体》
2006年第2期22-26,共5页
Fine Chemical Industrial Raw Materials & Intermediates
