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参考文献:A Switchable Oxidation Process Leading To Two Various Versatile Pharmaceutical Intermediates
标题:A Switchable Oxidation Process Leading To Two Various Versatile Pharmaceutical Intermediates
摘要:An Efficient High-Yielding And Environmentally Benign Switchable Oxidation Process That Can Selectively Produce Two Different Versatile Synthetic Intermediates Is Disclosed. One Of The Two Intermediates,2,3-Dimethoxy-5-Methylcyclohexa-2,5-Diene-1,4-Dione (Coenzyme Q(0)),Is Obtained By Menu Of A Telescoped Two-Step Synthetic Protocol That In The First Step Involves Treatment Of The Substrate (1,2,3-Trimethoxy-5-Methylbenzene) With Hydrogen Peroxide In Acetic Acid With P-Toluene Sulphonic Acid Present As A Bronsted Acid Catalyst,Succeeded By A Telescoped Second Step That Entails Treatment With Fuming Nitric Acid To Achieve The Target Molecule In An Excellent Isolated Yield (88%). If The Substrate Is Treated Directly With Nitric Acid (659) In Glacial Acetic Acid Two Different Products Can Be Obtained,Namely Acetic Acid 3,4,5-Trimethoxybenzyl Ester In A Superb Isolated Yield (93%) Or,Under Slightly Altered Reaction Conditions,1,2,3-Trimethoxy-5-(Nitromethyl)Benzene In A Moderate To Low Yield (35%) And Low Selectivity. The Two Pathways Leading To The Two Different Products In The Nitric Acid Oxidation Protocol Were Investigated By Means Of Dft Calculations As An Aid To Elaborate A Proposal For The Reaction Mechanism.
DOI:10.1021/op100185X