轴手性酰基硫脲催化合成吡唑啉酮衍生物  

Synthesis of Pyrazolinone Derivatives Catalyzed by Axisymmetric Acylthioureas

作　　者：杨兰西 秦婷 安雪婕 陈治明 YANG Lan-xi;QIN Ting;AN Xue-jie;CHEN Zhi-ming(Key Laboratory of Functional Materials Chemistry of Guizhou Province,School of Chemistry and Materials Science,Guizhou Normal University,Guiyang 550001,China)

机构地区：[1]贵州师范大学化学与材料科学学院贵州省功能材料化学重点实验室,贵州贵阳550001

出　　处：《化学试剂》2022年第4期623-631,共9页Chemical Reagents

基　　金：国家自然科学基金资助项目(21362006)。

摘　　要：吡唑啉酮环化合物因具有生物药理活性等多种特性和用途,被认为是极具价值的结构基元之一,吡唑环上易形成氢键等特性使得药物分子中的吡唑啉酮结构能够发挥生理活性。合成了多种以3,3′-二羧酸-1,1′-联萘酚为手性骨架、结构上下对称的新型多活性中心C_(2)轴手性氢键型双酰基硫脲催化剂,将其用于催化合成吡唑啉酮衍生物。实验结果表明:在35℃下,以10 mol%(R)-N_(3),N_(3)′-双(4-甲基苯乙基)-2,2′-二羟基-[1,1′-联萘]-3,3′-二甲酰基硫脲为催化剂,底物物质的量比为1∶1.5,于10 mL CH_(2)Cl_(2)溶剂中回流反应24 h后,目标产物吡唑啉酮获得了良好的产率(89%)及e.e.值(91%),并对底物进行了扩展,其范围较广,有较好的普适性。The pyrazolone ring compound has many characteristics and uses such as biopharmacological activity and is considered to be one of the most valuable structural elements.The pyrazolone structure in the drug molecule can exert its physiological activity due to the easy formation of hydrogen bonds on the pyrazolone ring.Therefore,a variety of novel multi-active center C_(2)-axis chiral hydrogen-bonded bisacylthiourea catalysts were synthesized with 3,3′-dicarboxylic acid-1,1′-binaphthylol as the chiral framework and the symmetrical structure,which were used to catalyze the synthesis of pyrazolone derivatives.The results show that the target product pyrazolone derivatives has a good yield of 89% with an e.e.value of 91% at 35 ℃,with 10 mol%(R)-N_(3),N_(3)′-bis(4-methylphenethyl)-2,2′-dihydroxy-[1,1′-binaphthyl]-3,3′-diformylthiourea as the catalyst and the substrate molar ratio 1∶1.5,after the mixture being refluxed in 10 mL CH_(2)Cl_(2) for 24 h.The substrate has been expanded,with a wider range and good universality.

关 键 词：BINOL轴手性 酰基硫脲 5-氧代-1吡唑啉衍生物 硝基乙烯 

分 类 号：O626.21[理学—有机化学]