脱氧果糖嗪规模化合成工艺研究

Study on Industrial Synthesis of Deoxyfructosazine

为丰富我国烟用香原料种类,对以葡糖胺盐酸盐为反应原料,硼酸类化合物为催化剂,在碱性条件下规模化合成2,5-脱氧果糖嗪(2,5-DOF)的反应过程、反应条件、分离手段、工艺控制等进行了研究,采用元素分析、质谱、红外、核磁共振对合成产物的结构进行了表征,并测定了合成产物的溶解度和熔点。结果表明:①用硼酸作催化剂比较适宜;②葡糖胺盐酸盐、硼酸和氢氧化钠的适宜摩尔比为1∶2.5∶2.5;③用M150型纳滤膜对反应液进行脱无机盐处理,用手持电导率仪监测膜分离过程中无机盐脱除情况比较适宜;④2,5-DOF在乙醇/水混合溶液中的溶解度随着水含量的增大而增大,不溶于丙二醇,在甲醇、丙酮、异丙醇等常用有机溶剂中的溶解度较低,一般不超过3mg/mL;⑤合成产物为目标物,纯度≥97%,产率58.6%。

In order to launch a new tobacco flavor, the industrial synthesis of 2, 5 - deoxyfructosazine（2, 5 - DOF）, [ 2 - （tetrahydroxybutyl） - 5 - （2, 3, 4 - trihydroxybutyl） - pyrazine ], under a basic condition with glycosamine hydrochloride as an initial material and boric acid compounds as catalyst, was studied including reaction process and conditions, separation means and technical control. The synthesis product was characte rized by element analysis, mass spectrometry, IR, ^1 H NMR, and ^13C NMR, and its solubility and melt point were tested as well. The results showed that： 1 ） boric acid was a preferable catalyst; 2） the preferable mole ratio of glucosamine hydrochloride to boric acid and sodium hydroxide was 1：2.5：2.5; 3） it was preferable to separete inorganic salts from reaction solution with nanofihration membrane M150, and monitor the membrane separation with a hand- held conductivity meter; 4） 2, 5 -DOF was slightly soluble in methanol, acetone, and isopropyl alcohol, with a solubility of below 3 mg/mL generally, insoluble in propylene glycol, and its solubility in mixture of alcohol/water increased with the increase of the water proportion, and 5 ） the synthesis product was the target product, 2, 5 -DOF, synthesis yield was 58.6% with purity of 97% and higher.