Synthesis of Anti-inflammatory Agents by Electrochemical Fixation of Carbon Dioxide

1.抗炎剂及其前体的合成(1)在常压二氧化碳存在下，以铂为阴极，以镁为阳极，在DMF中电解相应的芳基取代的乙烯基溴化物，高产率地合成了卤代乙烯-2-芳基-2-丙烯酸的电化学羧化反应。2-芳基-2-丙烯酸是各种抗炎剂如布洛芬、萘普生和酮洛芬的前体，实际上通过这种电化学羧化反应可以高产率地合成抗炎活性化合物。(2)芳甲酮的电化学羧化反应-类似于芳甲酮的电化学羧化反应，高产率地得到了抗炎剂的前体2-芳基-2-羟基丙酸。该方法对洛索洛芬的合成非常有用。(3)取代卤代苄的电化学羧化反应--Sim…1-芳基-1-卤代乙烷进行更多的电化学羧化反应，以较高的产率得到消旋剂混合物。超临界二氧化碳在抗炎剂合成中的应用当超临界二氧化碳同时作为试剂和反应介质时，二氧化碳与乙烯基溴化物、芳基甲基酮和苯基卤化物的电化学固定有效地进行，得到各种抗炎剂。以芳基取代的三氟乙烯酯、脂肪族的三氟乙烯酯和苯基取代的烯烃为原料，通过电化学羧化合成有用的羧酸，得到相应的α，β-不饱和酸、β-酮基羧酸和2-苯基琥珀酸。微波诱导反应高效、立体选择性地合成卤化乙烯利用微波诱导反应，在较短的反应时间(1-2分钟)内，实现了(E)-和(Z)-卤代乙烯的高效立体选择性合成。较少

1. Synthesis of Anti-inflammatory Agents and Their Precursors(1)Electrochemical carboxylation of vinyl halides -2-Aryl-2-propenoic acids were prepared in high yields by electrolysis of the corresponding aryl-substituted vinyl bromides in DMF in the presence of atmospheric pressure of carbon dioxide with a platinum cathode and a magnesium anode. 2-Aryl-2-propenoic acids, precursors of various anti-inflammatory agents such as ibuprofen, naproxen, and ketoprofen, were actually prepared in high yields by using this electrochemical carboylation and can readily be transformed into anti-inflammatory active compounds by enantioselectiev hydrogenation.(2)Electrochemical carboxylation of aryl methyl ketones -Similar electrochemical carboxylation of aryl methyl ketones gave 2-aryl-2-hydroxypropanoic acids, precursors of anti-inflammatory agents, in high yields. This method was found to be very useful for a synthesis of loxoprofen.(3)Electrochemical carboxylation of substituted benzyl halides -Sim … More ilar electrochemical carboxylation of 1-aryl-1-haloethanes gave a racemic mixture of anti-inflammatory agents in high yields.2. Use of Supercritical Carbon Dioxide in the Synthesis of Anti-inflammatory AgentsElectrochemical fixation of carbon dioxide to vinyl bromides, aryl methyl ketones, and benzylic halides took place efficiently to give various anti-inflammatory agents when supercritical carbon dioxide was used both as a reagent and-a reaction medium.3. Synthesis of Useful Carboxylic Acids by Electrochemical CarboxylationElectrochemical carboxylation of aryl-substituted vinyl triflates, aliphatic vinyl triflates, and phenyl-substituted alkenes gave the corresponding α, β-unsaturated acids, β-keto carboxylic acids, and 2-phenylsuccinic acids in high yields.4. Highly Efficient and Stereoselective Synthesis of Vinyl Halides by Microwave-induced ReactionHighly efficient and stereoselective synthesis of(E)-and(Z)-vinyl halides, which are starting compounds for a synthesis of anti-inflammatory agents, was achieved in a short reaction time(1-2 min)by using microwave-induced reaction. Less