BASE-CATALYZED TRIOSE CONDENSATIONS
BASE-CATALYZED TRIOSE CONDENSATIONS
复制标题
碱催化的三糖缩合反应
DOI：
10.1021/ja00981a033
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发表时间：
1967-01-01
影响因子：
15
通讯作者：
ARMBRUSTER, CW
中科院分区：
文献类型：
--
作者：
GUTSCHE, CD;REDMORE, D;ARMBRUSTER, CW
在无机碱或有机碱的催化下，D-甘油醛和二羟基丙酮的缩醛反应已被证明是D-果糖、D-山梨糖和DL-树形酮糖的混合物。利用化学分析、酶分析和旋光测量，先前报道的甘油醛缩醛反应动力学已被证实为对三个离子和碱基的一级反应。用膨胀法测定了二羟基丙酮缩醛反应动力学，反应动力学对三者和碱体为一级反应。通过使用不同取代吡啶的稀水溶液，从化学意义上说明了这两个反应的一般碱催化，并在每种情况下论证了空间位阻对一般碱催化的现象。这些数据被用来比较两个三聚体，比较三聚体与相关体系，重新解释某些文献推论，并提出一个三聚体缩醛体系的总体反应方案。
The aldolization reactions of D-glyceraldehyde and of dihydroxyacetone, catalyzed by inorganic or organic bases, have been shown to yield mixtures of D-fructose, D-sorbose, and DL-dendroketose. Using chemical assays, enzymatic assays, and polarimetric measurements, the previously reported kinetics of the glyceraldehyde aldolization have been substantiated as being first order with respect to the trióse and the base. Using dilatometric measurements, the reaction kinetics of the dihydroxyacetone aldolization have been shown to be first order with respect to the trióse and the base. The general base catalysis of both reactions hasbeen illustrated in the chemical sense through the use of dilute aqueous solutions of variously substituted pyridines, and in each case the phe-nomenon of steric hindrance to general base catalysis has been demonstrated. These data are used to compare the two trioses with each other, to compare the trioses with related systems, to reinterpret certain literature inferences, and to set forth an over-all reaction scheme for the trióse aldolization system.