BUFFERED POTASSIUM PEROXYMONOSULFATE ACETONE EPOXIDATION OF ALPHA,BETA-UNSATURATED ACIDS
BUFFERED POTASSIUM PEROXYMONOSULFATE ACETONE EPOXIDATION OF ALPHA,BETA-UNSATURATED ACIDS
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DOI：
10.1021/jo00360a059
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发表时间：
1986-05-16
影响因子：
3.6
通讯作者：
WARD, FE
中科院分区：
文献类型：
--
作者：
COREY, PF;WARD, FE
环氧化程序。一般方法通过从铁-肉桂酸制备反式-β-苯基缩水甘油酸（分离为钾盐）来说明。将反式肉桂酸（111.0 g; 0.75 mol）在丙酮（515 mL）中的搅拌浆液首先用NaHCO 3（274 g; 3.26 mol）处理，然后小心地用水（515 mL）处理。用过硫酸氢钾化合物5（421 g;含有1.825当量KHS 05）在4 X 10 - 4 M EDTA 6二钠水溶液（1610 mL）中的溶液逐滴处理所得粘稠混合物1.5 h。在此加入过程中，通过使用水浴将反应温度保持在24-27 ℃，并将反应pH保持在约1.5。7.4.添加完成后，将混合物再搅拌0.5小时，然后冷却至约100 ° C。10 ℃。将反应用浓HCl（约10 mL）酸化。140 mL）至pH 2，同时将温度保持在10 ℃，然后用EtOAc（1.0 L）处理，随后快速搅拌。过滤混合物以除去不溶性盐，并除去有机层。水层用EtOAc（500 mL）萃取，合并的有机层用饱和NaCl水溶液（200 mL）洗涤一次，经MgSO 4干燥，并在40 ℃浴中真空浓缩。在浓缩结束时，加入无水乙醇（以防止酸结晶析出），并继续浓缩直至除去大部分溶剂。将淡黄色油状残余物溶于无水EtOH（500 mL）中，在冰上冷却，并用KOH（56 g; 1.0 mol）在无水EtOH（250 mL）中的溶液处理。过滤所得粘稠浆液，并用EtOH洗涤固体。将滤饼再悬浮于新鲜的无水EtOH（750 mL）中，过滤，用EtOH洗涤，并在50 ℃烘箱中干燥，得到标题化合物（139 g; 92%），为白色粉末，与Harada 789由3-苯基缩水甘油酸乙酯制备的相同。Anal.对C9 H7 O3 K计算：C，53.44; H，3.49。实测值：C，53.36; H，3.74。
Epoxidation Procedure. The general method is illustrated by the preparation of trans-ß-phenylglycidic acid (isolated as the potassium salt) from irons-cinnamic acid. A stirred slurry of trons-cinnamic acid (111.0 g; 0.75 mol) in acetone (515 mL) was treated first with NaHC03 (274 g; 3.26 mol) and then carefullywith water (515 mL). The resulting thick mixture was treated dropwise, over 1.5 h, with a solution of Oxone monopersulfate compound5 (421 g; contains 1.825 equiv of KHS05) in 4 X 10~ 4 M aqueous disodium EDTA6 (1610 mL). During this addition, the reaction temperature was maintained at 24-27 C by using a water bath and the reaction pH at ca. 7.4. After the addition was complete the mixture was stirred an additional 0.5 h and then cooled to ca. 10 C. The reaction was acidified with concentrated HC1 (ca. 140 mL) to pH 2 while the temperature was maintained at 10 C and then treatedwith EtOAc (1.0 L) followed by rapid stirring. The mixture was filtered to remove insoluble salts, and the organic layer was removed. The aqueous layer was extracted with EtOAc (500 mL), and the combined organic layers were washed once with saturated aqueous NaCl (200 mL), dried over MgS04, and concentrated in vacuo from a 40 C bath. Toward the end of the concentration, absolute EtOH was added (to keep the acid from crystallizing out), and con-centration was continued until most of the solvent was removed. The yellowish oily residue was dissolved in absolute EtOH (500 mL), cooled on ice, and treated with a solution of KOH (56 g; 1.0 mol) in absolute EtOH (250 mL). The resulting thick slurry was filtered, and the solids were washed with EtOH. The filter cake was resuspended in fresh absolute EtOH (750 mL), filtered, washed with EtOH, and dried in a 50 C oven to give the title compound (139 g; 92%) as a white powder, identical with that prepared by Harada7 89from ethyl/3-phenylglycidate. Anal. Caled for C9H703K: C, 53.44; H, 3.49. Found: C, 53.36; H, 3.74.