单基团保护法[精选].docVIP

单基团保护法制备三氯蔗糖的研究* 郑建仙 高宪枫 袁尔东 （华南理工大学食品与生物工程学院，广州，510640） 摘 要 单基团保护法制备三氯蔗糖，主要包括活泼C-6位羟基的单基团保护、选择性氯化和去保护基等三个步骤，其中C-6位羟基的单基团保护是核心步骤。研究发现，降低温度是对蔗糖C-6位最活泼羟基进行单一选择性保护的有效方法。在-25℃下，蔗糖与乙酸酐（摩尔比为0.95）反应6h即可。选择性氯化的最佳反应条件为：蔗糖-6-乙酸酯（S-6-a）浓度15%（w/v），S-6-a∶Vilsmeier =1∶7（mol/mol），反应温度120℃，反应时间2.5h。对氯化产物进行全乙酰化后以TGSPA的形式结晶出来，再去除保护基，可有效减轻分离纯化的压力，确保产品纯度和得率。单酯化反应和氯化反应还可合二为一，以有效缩短制备路线，提高反应的可操作性。本研究通过大量试验确定了具体制备路线，并优化了各反应参数，三氯蔗糖终产品得率为8.3%。利用单基团保护法，可有效缩短三氯蔗糖的制备路线，简化操作过程，但对反应条件和分离设备的要求较高。 关键词 三氯蔗糖 单基团保护法 选择性氯化 Research on the Monogroup-protected Synthesis of Sucralose Abstract The monogroup-protected synthesis method of sucralose contains monogroup protection of C-6 hydroxy, selective chlorination of particular groups and deshielding of protected hydroxy, in which monogroup protection of C-6 hydroxy is the key step. The temperature reduction was shown to be an effective method for the most active C-6 hydroxy mono-protection. Sucrose reacted with acetic anhydride for 6h at -25℃. The optimized parameters of selective chlorination were 15% (w/v) sucrose-6-acetate (S-6-a), S-6-a:Vilsmeier=1:7, 125℃ and 2.5h. The chlorinated S-6-a could be crystallized in the form of trichloro-pentaacetate (TGSPA) after holo-acetylation. The additional process would release the pressure of separation, which is required in the monogroup-protected method, and finally increase the productivity. The mono-esterification and chlorination can be combined, which can be advantaged to shorten the reaction routes and improve operation. After a lot of experiments, the definite route of preparation and the optimized reaction parameters were determined. And the productivity of sucralose reached 8.3%. With the monogroup-protected method, the synthesis route could be shortened and the operation units simplified, although the reaction conditions and separation equipments are requested strictly. Keywords sucralose monogroup-protected synthesis selective chlorination 三氯蔗糖因其甜度高、甜味特性好、无能量、安全性高、稳定性好等优点，可在很多用途上替