黄酮、异黄酮类化合物的制备方法及其应用
阅读说明：本技术 黄酮、异黄酮类化合物的制备方法及其应用 (Preparation method and application of flavone and isoflavone compounds ) 是由 周强辉 马园园 于 2021-09-18 设计创作，主要内容包括：本发明提供一种黄酮类、异黄酮类化合物的制备方法,反应式如下所示：所述制备方法具体包括如下步骤：在惰性气体氛围下,以式A所示化合物、B和C为起始原料,在钯催化剂D、膦配体E、降冰片烯F和碱G的作用下,在溶剂H中搅拌反应,分离,即可得到所述黄酮类、异黄酮类化合物M、J、K或L。该方法涉及的主要原料均为商品化试剂,价格低廉,催化剂为降冰片烯衍生物,相比于现有技术中的类似反应使用的催化剂降冰片烯,其用量大大减少,降低了制备成本,适于工业化生产。本发明还提供制备得到的黄酮类、异黄酮类化合物在制备umbralisib核心骨架中的应用。(The invention provides a preparation method of flavonoid and isoflavone compounds, which has the following reaction formula:)
技术领域
本发明专利涉及有机合成领域，尤其是指一种黄酮、异黄酮类化合物的制备方法及其应用。
背景技术
黄酮和异黄酮是一类非常重要的结构单元，广泛存在于具有生物活性的天然产物和药物分子(Eur J Med Chem,2014,84,206-239)。目前，合成黄酮类和异黄酮类化合物的方法大致分为两类(Chem Rev,2014,114,4960-4992；Chin Chem Lett,2020,31,3073-3082；Mini-Rev Org Chem,2016,13,31-48；Tetrahedron,2012,68,8523-8538)。一类是通过芳香化合物发生Claisen condensation反应(Med Chem Lett,2012,22,5455-5459)、Baker-Venkataraman重排反应(J Chem Soc,1934,10,1767-1969)和Vilsmeier-Haack([8]Org Prep Proced Int,2009,41,69-75)等反应得到，但这些策略大部分只能构建C2或C3单取代的色酮化合物。另一类是通过色酮结构的进一步衍生化得到。然而，这些方法通常是单一任务，得到的黄酮类和异黄酮类化合物的结构多样性有限，限制了它们的使用范围。
因此发展高效、简洁的合成新方法，利用简单易得的原料合成黄酮类和异黄酮类化合物尤为重要。
发明内容
针对现有技术中存在的问题，本发明以简单易得的碘代色酮类化合物为起始原料，在钯催化剂、降冰片烯衍生物、膦配体和碱的作用下，在80℃到140℃下于有机溶剂中搅拌反应，即可得黄酮类和异黄酮类化合物。该方法原料易得、操作简单、化学选择性好、底物适用范围广，为合成含有色酮结构单元的重要药物分子和天然产物提供了一种非常高效、汇聚的方法。
本发明旨在至少在一定程度上解决现有技术中存在的技术问题之一，由此，在本发明的第一方面，本发明提供一种黄酮类、异黄酮类化合物的制备方法，反应式如下所示：
其中，黄酮类、异黄酮类化合物的结构式选自式M所示化合物、式J所示化合物、式K所示化合物和式L所示化合物中的一种；B为芳基卤化物；C为烯烃或炔烃；R1选自芳基、烷基、烷氧基和卤素中的一种，m取自0、1、2，X选自O或S；R2为烷基、酯基、硝基、酰胺基、磺酰基、烷氧基和卤素中的一种；n取自1、2；p取自0、1、2、3；R3和R4分别独立地选自芳基、杂环芳基、烷基、酯基、硅基、酰胺基、磺酰基、膦氧基、烷氧基和氢中的一种；R5为硅基；R6为烷基、巯基、烷氧基、对甲基苯磺酰氧基和卤素中的一种；r取自0、1、2；R7选自氢、杂环芳基、烷基、酯基、羟基、氰基、烷氧基和卤素中的一种；
优选地，R2为甲基、甲氧基、酯基、硝基、酰胺基、磺酰基和卤素中的一种；R3和R4分别独立地选自萘基、杂环芳基、烷基、酯基、硅基、酰胺基、磺酰基、膦氧基、烷氧基和氢中的一种；R6为烷基、巯基、烷氧基、对甲基苯磺酰氧基和卤素中的一种；R7选自氢、烷基、酯基、羟基、氰基、烷氧基、2-甲氧基吡啶、噻吩、二苯并噻吩和卤素中的一种；
所述制备方法具体包括如下步骤：在惰性气体氛围下，以式A所示化合物、B和C为起始原料，在钯催化剂D、膦配体E、降冰片烯F和碱G的作用下，在溶剂H中搅拌反应，分离，即可得到所述黄酮类、异黄酮类化合物M、J、K或L。
在本发明的一个或多个实施例中，B结构式为
其中，Y为碘、溴或对甲苯磺酰氧基。
在本发明的一个或多个实施例中，C结构式为：
在本发明的一个或多个实施例中，黄酮类、异黄酮类化合物的制备方法，反应式如下所示：
黄酮类、异黄酮类化合物的制备方法，包括如下步骤：在保护气体氛围下，式A所示化合物、B1(结构式如上所示)和C1(结构式如上所示)为起始原料，在钯催化剂D、膦配体E、降冰片烯衍生物F和碱G的作用下，在溶剂H中搅拌反应，分离，即可得到黄酮类化合物M或者J。
在本发明的一个或多个实施例中，黄酮类、异黄酮类化合物的制备方法，反应式如下所示：
黄酮类、异黄酮类化合物的制备方法，包括如下步骤：在保护气体氛围下，以式A所示化合物、B1(结构式如上所示)和C2(结构式如上所示)为起始原料，在钯催化剂D、膦配体E、降冰片烯衍生物F和碱G的作用下，在溶剂H中搅拌反应，分离，即可得2,3-双芳基取代色酮类化合物K，即为所述黄酮类、异黄酮类化合物。
在本发明的一个或多个实施例中，黄酮类、异黄酮类化合物的制备方法，反应式如下所示：
黄酮类、异黄酮类化合物的制备方法，包括如下步骤：在保护气体氛围下，以式A所示化合物、B2(结构式如上所示)和C2(结构式如上所示)为起始原料，在钯催化剂D、膦配体E、降冰片烯衍生物F和碱G的作用下，在溶剂H中搅拌反应，分离，即可得到异黄酮类化合物L。
在本发明的一个或多个实施例中，所述膦配体E选自三芳基膦、二环己基(2',4',6'-三异丙基-[1,1'-二苯基]-2-基)膦、二环己基(2',6'-二甲氧基-[1,1'-二苯基]-2-基)膦、2'-(二环己基膦基)-N,N-二甲基-[1,1'-二苯基]-2-胺、三(2-呋喃基)膦、2-(二叔丁基膦)联苯中的任意一种或几种。
在本发明的一个或多个实施例中，所述降冰片烯衍生物F的结构式如下所示：
其中，R8、R9分别独立地为酯基、羰基、氰基、酰胺基或烷基；q为整数，且0≤q≤8；s取自0、1、2。
在本发明的一个或多个实施例中，所述碱G选自碳酸钠、碳酸钾、碳酸铯、醋酸钾、醋酸铯、磷酸三钾、碳酸氢钾、氢氧化钾中的任意一种或几种。
在本发明的一个或多个实施例中，所述溶剂H选自1,4-环氧六烷、四氢呋喃、乙二醇二甲醚、甲苯、乙腈、N,N-二甲基甲酰胺和N-甲基吡咯烷酮中的任意一种或几种。
在本发明的一个或多个实施例中，控制反应温度为80～140℃。
在本发明的一个或多个实施例中，控制反应时间为18～60h。
在本发明的第二方面，本发明提供一种黄酮类、异黄酮类化合物在制备umbralisib核心骨架中的应用，将所述的黄酮类、异黄酮类化合物与卤素反应，得到所述umbralisib核心骨架；所述umbralisib核心骨架的化学式如下式N所示：
所述黄酮类、异黄酮类化合物选自如下式M所示化合物、式J所示化合物、式K所示化合物和式L所示化合物中的一种，
优选地，所述黄酮类、异黄酮类化合物为式L所示化合物；
其中，R1选自芳基、烷基、烷氧基和卤素中的一种，m取自0、1、2，X选自O或S；R2为烷基、酯基、硝基、酰胺基、磺酰基、烷氧基和卤素中的一种；n取自1、2；p取自0、1、2、3；R3和R4分别独立地选自芳基、杂环芳基、烷基、酯基、硅基、酰胺基、磺酰基、膦氧基、烷氧基和氢中的一种；R5为硅基；R6为烷基、巯基、烷氧基、对甲基苯磺酰氧基和卤素中的一种；r取自0、1、2；R7选自氢、杂环芳基、烷基、酯基、羟基、氰基、烷氧基和卤素中的一种；Y为碘、溴或对甲苯磺酰氧基；
优选地，R2为甲基、甲氧基、酯基、硝基、酰胺基、磺酰基和卤素中的一种；R3和R4分别独立地选自萘基、杂环芳基、烷基、酯基、硅基、酰胺基、磺酰基、膦氧基、烷氧基和氢中的一种；R6为烷基、巯基、烷氧基、对甲基苯磺酰氧基和卤素中的一种；R7选自氢、烷基、酯基、羟基、氰基、烷氧基、2-甲氧基吡啶、噻吩、二苯并噻吩和卤素中的一种；
优选地，所述黄酮类、异黄酮类化合物在制备umbralisib核心骨架的化学式如下所示：
与现有技术相比，本发明具有以下优点和有益效果：
1、本发明提供一种黄酮类、异黄酮类化合物的制备方法，该方法涉及的主要原料为碘代色酮类化合物、芳基或烷基卤化物、烯烃类化合物以及芳基三氟硼酸钾盐，这些原料均为商品化试剂，且无需特殊处理，价格低廉或用简单的方法大量制备。
2、本发明制备方法所涉及的反应使用的催化剂降冰片烯衍生物，相比于现有技术中的类似反应使用的催化剂降冰片烯，其用量大大减少，降低了制备成本。
3、本发明制备方法所涉及的反应使用的催化剂是较为廉价的金属钯和磷配体，相比于其他催化剂或者络合物等是一个重要的补充
4、本发明制备方法具有很好的底物适用范围和官能团兼容性；
5、本发明提供一种黄酮类、异黄酮类化合物的制备方法，该方法可以大量制备黄酮类化合物，适于工业化生产，具有较大的应用潜力。
6、本发明还提供制备得到的黄酮类、异黄酮类化合物在制备umbralisib核心骨架中的应用。
具体实施方式
下面将结合实施例对本发明的方案进行解释。本领域技术人员将会理解，下面的实施例仅用于说明本发明，而不应视为限定本发明的范围。实施例中未注明具体技术或条件的，按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。使用的方法如无特别说明，均为本领域公知的常规方法，使用的耗材和试剂如无特别说明，均为市场购得。除非另有说明，本文中所用的专业与科学术语与本领域熟练人员所熟悉的意义相同。此外，任何与所记载内容相似或均等的方法或材料也可应用于本发明中。
实施例1：
在氩气保护下，向干燥并装有磁力搅拌子的反应管中加入醋酸钯(1.2mg,0.005mmol)、三苯基膦(1.4mg,0.005mmol)、碳酸钾(13.8mg,0.1mmol)和3-碘代色酮(27.2mg,0.1mmol)，然后加入溶有1-甲酸乙酯-2-降冰片烯(8.3mg,0.05mmol)的干燥的1,4-环氧六烷(1mL)。之后向上述溶液中再次加入邻溴苯甲酸甲酯(21.5mg,0.1mmol)、苯乙烯(12.5mg,0.12mmol)。所得混合物于100℃在氩气保护氛围下反应18小时。反应结束后冷却至室温，混合物用硅藻土过滤，乙酸乙酯洗涤，减压蒸馏除去溶剂，柱层析分离纯化得化合物1(黄色油状液体，90％产率)。
实施例2～40如下：
实施例41：
在氩气保护下，向干燥并装有磁力搅拌子的反应管中加入醋酸钯(1.2mg,0.005mmol)、三苯基膦(1.4mg,0.005mmol)、碳酸钾(13.8mg,0.1mmol)、3-碘代色酮(27.2mg,0.1mmol)和苯基三氟硼酸钾(27.6mg,0.15mmol)然后加入溶有1-甲酸乙酯-2-降冰片烯(8.3mg,0.05mmol)的干燥四氢呋喃(1mL)。之后向上述溶液中加入邻溴苯甲酸甲酯(21.5mg,0.1mmol)。所得混合物于120℃在氩气保护氛围下反应36小时。反应结束后冷却至室温，混合物用硅藻土过滤，乙酸乙酯洗涤，减压蒸馏除去溶剂，柱层析分离纯化得化合物41(无色油状液体，64％产率)。
实施例42～54如下：
实施例55：
在氩气保护下，向干燥并装有磁力搅拌子的反应管中加入醋酸钯(1.2mg,0.005mmol)、三苯基膦(1.4mg,0.005mmol)、碳酸钾(13.8mg,0.1mmol)、3-碘代色酮(27.2mg,0.1mmol)和苯基三氟硼酸钾(27.6mg,0.15mmol)，然后加入溶有1-甲酸乙酯-2-降冰片烯(8.3mg,0.05mmol)和碘甲烷(14.2mg,0.1mmol)的干燥四氢呋喃(1mL)。所得混合物于100℃在氩气保护氛围下反应36小时。反应结束后冷却至室温，混合物用硅藻土过滤，乙酸乙酯洗涤，减压蒸馏除去溶剂，柱层析分离纯化得化合物55(无色油状液体，41％产率)。
实施例56-66如下：
实施例67：
在氩气保护下，向干燥并装有磁力搅拌子的反应管中加入化合物66(11.0mg,0.044mmol)，并加入1mL CCl4并升温至80℃，逐渐滴加溶有Br2(6.8μL,0.132mmol)的CCl4(0.5mL)溶液，并在避光条件下反应。GC监测反应，待反应完全后，冷却至室温，用硫代硫酸钠溶液淬灭反应，二氯甲烷(3×5mL)萃取有机物，无水硫酸钠干燥有机相后，减压除去溶剂，粗产品直接柱层析分离纯化得化合物67(无色油状液体，99％产率)。
实施例1所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ8.34(dd,J＝7.9,1.7Hz,1H),8.16(dd,J＝7.4,1.8Hz,1H),7.91(d,J＝16.2Hz,1H),7.71–7.62(m,3H),7.57(dd,J＝7.1,1.8Hz,1H),7.45–7.41(m,1H),7.39(d,J＝8.4Hz,1H),7.29–7.22(m,4H),7.19–7.15(m,1H),6.59(d,J＝16.3Hz,1H),3.69(s,3H)；13C NMR(100MHz,CDCl3):δ177.53,166.37,163.84,155.57,138.21,134.16,133.90,133.61,132.42,131.35,131.08,130.64,130.58,128.57,127.62,126.54,126.40,125.22,123.88,119.83,118.10,117.81,52.70；HRMS(ESI-TOF):calc’d forC25H19O4 +[M+H+]383.1278,found383.1269.
实施例2所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ8.64–8.62(m,1H),8.09(dd,J＝7.8,1.3Hz,1H),7.66(td,J＝7.5,1.5Hz,1H),7.61–7.54(m,4H),7.48(d,J＝16.3Hz,1H),7.46(dd,J＝7.6,1.3Hz,1H),7.25–7.14(m,5H),6.71(d,J＝16.4Hz,1H),3.71(s,3H)；13C NMR(100MHz,CDCl3):δ179.75,166.34,150.13,138.18,137.27,136.69,134.29,132.59,131.72,131.34,131.09,131.04,130.56,129.94,129.86,129.63,128.55,127.67,126.70,125.65,122.23,52.58；HRMS(ESI-TOF):calc’d for C25H18NaO3S+[M+Na+]421.0869,found421.0879.
实施例3所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ8.14(dd,J＝7.4,1.8Hz,1H),7.94(d,J＝16.2Hz,1H),7.69–7.61(m,2H),7.57(d,J＝7.1Hz,1H),7.53(t,J＝8.3Hz,1H),7.26–7.21(m,4H),7.18–7.14(m,1H),6.94(d,J＝8.4Hz,1H),6.84(d,J＝8.3Hz,1H),6.57(d,J＝16.2Hz,1H),4.04(s,3H),3.69(s,3H)；13C NMR(100MHz,CDCl3):δ177.40,166.56,161.71,160.31,157.58,138.49,133.86,133.65,133.60,132.30,131.45,131.04,130.85,130.48,128.54,127.45,126.50,119.77,118.95,114.47,109.83,106.40,56.57,52.70；HRMS(ESI-TOF):calc’dfor C26H20NaO5 +[M+Na+]435.1203,found435.1201.
实施例4所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ8.15(dd,J＝7.7,1.5Hz,1H),8.12(d,J＝1.0Hz,1H),7.88(d,J＝16.3Hz,1H),7.70–7.62(m,2H),7.56(dd,J＝7.4,1.6Hz,1H),7.46(dd,J＝8.5,2.2Hz,1H),7.30–7.22(m,5H),7.19–7.15(m,1H),6.60(d,J＝16.2Hz,1H),3.68(s,3H),2.49(s,3H)；13C NMR(100MHz,CDCl3):δ177.59,166.46,163.68,153.90,138.28,135.14,134.89,134.01,132.37,131.36,131.07,130.72,130.51,128.56,127.57,126.55,125.68,123.55,120.01,117.95,117.58,52.70,21.19；HRMS(ESI-TOF):calc’d for C26H20NaO4 +[M+Na+]419.1254,found419.1244.
实施例5所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ8.18(dd,J＝7.4,1.8Hz,1H),7.97(dd,J＝8.3,2.7Hz,1H),7.90(d,J＝16.2Hz,1H),7.72–7.64(m,2H),7.56(dd,J＝7.1,1.8Hz,1H),7.42–7.35(m,2H),7.28–7.22(m,4H),7.20–7.16(m,1H),6.55(d,J＝16.2Hz,1H),3.71(s,3H)；13C NMR(100MHz,CDCl3):δ176.74(d,J＝2.4Hz),165.18(d,J＝209.7Hz),159.73(d,J＝246.0Hz),151.83,138.08,134.44,133.76,132.52,131.31,131.15,130.72,130.54,128.60,127.74,126.58,125.01(d,J＝7.3Hz),121.88(d,J＝25.9Hz),119.97(d,J＝8.0Hz),119.51,117.56,111.16(d,J＝23.9Hz),52.73；19F NMR(376MHz,CDCl3):δ-115.40；HRMS(ESI-TOF):calc’d for C25H17FNaO4 +[M+Na+]423.1003,found423.0997.
实施例6所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ8.29(d,J＝2.6Hz,1H),8.19–8.17(m,1H),7.88(d,J＝16.3Hz,1H),7.70–7.66(m,2H),7.60–7.55(m,2H),7.35(d,J＝8.9Hz,1H),7.28–7.22(m,4H),7.20–7.16(m,1H),6.55(d,J＝16.3Hz,1H),3.71(s,3H)；13C NMR(100MHz,CDCl3):δ176.31,166.15,164.04,153.88,138.00,134.55,133.80,133.65,132.53,131.28,131.15,131.10,130.74,130.50,128.58,127.76,126.58,125.77,124.79,119.60,119.42,118.19,52.72；HRMS(ESI-TOF):calc’d for C25H17ClNaO4 +[M+Na+]439.0708,found439.0706.
实施例7所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ8.45(d,J＝2.4Hz,1H),8.17(dd,J＝7.6,1.6Hz,1H),7.87(d,J＝16.2Hz,1H),7.72(dd,J＝8.8,2.5Hz,1H),7.66(qd,J＝7.4,1.7Hz,2H),7.56(dd,J＝7.3,1.6Hz,1H),7.29(d,J＝8.9Hz,1H),7.25–7.21(m,4H),7.20–7.16(m,1H),6.54(d,J＝16.3Hz,1H),3.71(s,3H)；13C NMR(100MHz,CDCl3):δ176.16,166.15,164.02,154.31,137.99,136.53,134.58,133.64,132.53,131.28,131.16,130.75,130.49,128.99,128.59,127.77,126.59,125.17,119.83,119.41,118.58,118.30,52.73；HRMS(ESI-TOF):calc’d for C25H17BrNaO4 +[M+Na+]483.0202,found483.0198.
实施例8所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ8.15(dd,J＝7.7,1.5Hz,1H),7.92(d,J＝16.3Hz,1H),7.71(d,J＝3.1Hz,1H),7.69–7.62(m,2H),7.56(dd,J＝7.3,1.6Hz,1H),7.34(d,J＝9.1Hz,1H),7.29–7.22(m,5H),7.19–7.15(m,1H),6.59(d,J＝16.2Hz,1H),3.93(s,3H),3.69(s,3H)；13C NMR(100MHz,CDCl3):δ177.34,166.42,163.70,157.11,150.51,138.30,134.03,133.98,132.39,131.37,131.09,130.72,130.55,128.60,127.60,126.55,124.46,123.79,120.00,119.29,117.37,105.41,56.07,52.72；HRMS(ESI-TOF):calc’d for C26H20NaO5 +[M+Na+]435.1203,found435.1196.
实施例9所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ8.22(d,J＝8.1Hz,1H),8.16(dd,J＝7.4,1.7Hz,1H),7.91(d,J＝16.3Hz,1H),7.70–7.62(m,2H),7.56(dd,J＝7.2,1.8Hz,1H),7.29–7.22(m,5H),7.19–7.15(m,2H),6.59(d,J＝16.3Hz,1H),3.70(s,3H),2.48(s,3H)；13C NMR(100MHz,CDCl3):δ177.44,166.40,163.54,155.69,144.91,138.27,133.99,132.37,131.36,131.04,130.65,130.48,128.54,127.54,126.78,126.51,126.14,121.64,119.97,117.94,117.48,52.68,21.92；HRMS(ESI-TOF):calc’d for C26H20NaO4 +[M+Na+]419.1254,found419.1249.
实施例10所得产物的表征如下：
1HNMR(400MHz,CDCl3):δ8.36(dd,J＝8.9,6.3Hz,1H),8.18(dd,J＝7.7,1.4Hz,1H),7.88(dd,J＝16.2,1.0Hz,1H),7.72–7.64(m,2H),7.56(dd,J＝7.4,1.5Hz,1H),7.28–7.22(m,4H),7.20–7.14(m,2H),7.07(dd,J＝8.9,2.4Hz,1H),6.56(dd,J＝16.3,0.9Hz,1H),3.73(s,3H)；13CNMR(100MHz,CDCl3):δ176.64,166.15,165.65(d,J＝254.7Hz),163.99,156.45(d,J＝13.2Hz),138.05,134.51,133.63,132.53,131.32,131.14,130.70,130.47,128.99(d,J＝10.5Hz),128.57,127.72,126.55,120.75(d,J＝2.2Hz),119.46,118.20,114.05(d,J＝22.6Hz),104.37(d,J＝25.3Hz),52.71；19F NMR(376MHz,CDCl3):δ-103.29；HRMS(ESI-TOF):calc’d for C25H17FNaO4 +[M+Na+]423.1003,found423.1001.
实施例11所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ8.28(d,J＝8.4Hz,1H),8.18(dd,J＝7.6,1.6Hz,1H),7.88(d,J＝16.3Hz,1H),7.72–7.66(m,2H),7.56(dd,J＝7.4,1.6Hz,1H),7.42(d,J＝1.7Hz,1H),7.40(dd,J＝8.4,1.9Hz,1H),7.28–7.22(m,4H),7.20–7.16(m,1H),6.55(d,J＝16.3Hz,1H),3.74(s,3H)；13C NMR(100MHz,CDCl3):δ176.74,166.12,163.92,155.62,139.59,138.03,134.57,133.63,132.55,131.32,131.17,130.74,130.45,128.59,127.85,127.76,126.58,126.08,122.41,119.44,118.41,117.86,52.75；HRMS(ESI-TOF):calc’dfor C25H17ClNaO4 +[M+Na+]439.0708,found439.0707.
实施例12所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ8.19(d,J＝8.4Hz,1H),8.21–8.14(m,1H),7.88(d,J＝16.2Hz,1H),7.71–7.63(m,2H),7.59(d,J＝1.8Hz,1H),7.56(t,J＝2.0Hz,1H),7.54–7.53(m,1H),7.27–7.22(m,4H),7.20–7.15(m,1H),6.54(d,J＝16.2Hz,1H),3.73(s,3H)；13C NMR(100MHz,CDCl3):δ176.85,166.12,163.88,155.58,138.03,134.58,133.64,132.57,131.32,131.18,130.75,130.45,128.85,128.60,127.89,127.81,127.77,126.59,122.77,120.93,119.45,118.45,52.77；HRMS(ESI-TOF):calc’d for C25H17BrNaO4 +[M+Na+]483.0202,found483.0199.
实施例13所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ8.24(d,J＝8.9Hz,1H),8.16(dd,J＝7.6,1.7Hz,1H),7.89(d,J＝16.3Hz,1H),7.71–7.62(m,2H),7.56(dd,J＝7.2,1.7Hz,1H),7.28–7.22(m,4H),7.19–7.15(m,1H),7.01(dd,J＝8.9,2.3Hz,1H),6.79(d,J＝2.3Hz,1H),6.58(d,J＝16.2Hz,1H),3.88(s,3H),3.71(s,3H)；13C NMR(100MHz,CDCl3):δ176.99,166.48,164.15,163.32,157.29,138.31,134.10,133.98,132.43,131.41,131.10,130.68,130.51,128.57,127.85,127.57,126.55,119.95,117.94,117.84,114.79,99.81,55.93,52.73；HRMS(ESI-TOF):calc’d for C26H20NaO5 +[M+Na+]435.1203,found435.1195.
实施例14所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ8.18(dd,J＝7.3,1.8Hz,1H),7.88(d,J＝16.3Hz,1H),7.77(ddd,J＝8.2,3.0,1.8Hz,1H),7.69(td,J＝7.3,1.7Hz,2H),7.57(dd,J＝6.9,1.9Hz,1H),7.28–7.24(m,4H),7.24–7.17(m,2H),6.54(d,J＝16.3Hz,1H),3.76(s,3H)；13C NMR(100MHz,CDCl3):δ175.68,166.04,163.82,158.42(dd,J＝248.6,9.5Hz),151.41(dd,J＝257.4,11.7Hz),141.26(d,J＝10.8Hz),137.88,135.01,133.29,132.57,131.45,131.20,130.93,130.59,128.63,127.91,126.63,126.06(d,J＝8.1Hz),119.13,118.09,108.92(dd,J＝28.8,20.1Hz),106.44(dd,J＝23.4,4.4Hz),53.14(d,J＝84.3Hz)；19F NMR(376MHz,CDCl3):δ-112.27,-128.79；HRMS(ESI-TOF):calc’d for C25H16F2NaO4 +[M+Na+]441.0909,found441.0906.
实施例15所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ10.17(d,J＝8.6Hz,1H),8.16(d,J＝6.9Hz,1H),8.04(d,J＝9.0Hz,1H),7.90(d,J＝8.0Hz,1H),7.82(d,J＝16.4Hz,1H),7.77(d,J＝8.0Hz,1H),7.69–7.60(m,4H),7.42(d,J＝9.0Hz,1H),7.31(d,J＝7.6Hz,2H),7.26(t,J＝7.2Hz,2H),7.19(d,J＝7.1Hz,1H),6.76(d,J＝16.3Hz,1H),3.67(s,3H)；13C NMR(100MHz,CDCl3):δ179.26,166.53,161.20,156.69,138.20,135.52,134.48,133.61,132.40,131.55,131.08,130.93,130.87,130.84,130.53,129.35,128.58,128.43,127.65,127.27,126.61,120.41,119.99,117.44,116.86,52.69；HRMS(ESI-TOF):calc’d for C29H20NaO4 +[M+Na+]455.1254,found455.1247.
实施例16所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ8.23(dd,J＝5.5,2.2Hz,1H),8.21(dd,J＝4.3,1.9Hz,1H),7.86(d,J＝16.2Hz,1H),7.70–7.62(m,2H),7.58(ddd,J＝8.6,7.1,1.7Hz,1H),7.53(dd,J＝6.9,1.9Hz,1H),7.38(t,J＝7.5Hz,1H),7.28–7.22(m,5H),7.20–7.14(m,2H),7.10(t,J＝7.3Hz,2H),7.07–7.03(m,2H),6.57(d,J＝16.2Hz,1H),5.11(s,2H)；13C NMR(100MHz,CDCl3):δ177.30,165.83,163.64,155.39,138.22,134.68,134.13,133.91,133.43,132.54,131.32,130.57,128.58,128.49,128.46,127.63,126.57,126.39,125.00,123.79,119.81,118.12,117.75,67.77；HRMS(ESI-TOF):calc’d for C31H22NaO4 +[M+Na+]481.1410,found481.1402.
实施例17所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ8.30(dd,J＝8.0,1.6Hz,1H),8.01(d,J＝16.2Hz,1H),7.66–7.63(m,2H),7.60–7.50(m,3H),7.42(t,J＝7.4Hz,1H),7.38–7.34(m,3H),7.27(t,J＝7.5Hz,2H),7.20(t,J＝7.1Hz,1H),6.75(d,J＝16.2Hz,1H),2.94(s,3H),2.90(s,3H)；13CNMR(100MHz,CDCl3):δ177.41,169.83,162.13,155.41,138.16,137.42,134.79,133.69,131.54,131.10,130.65,129.02,128.62,127.79,127.70,126.63,126.42,125.31,123.75,119.65,118.50,117.66,39.24,35.10；HRMS(ESI-TOF):calc’d for C26H21NNaO3 +[M+Na+]418.1414,found481.1409.
实施例18所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ8.31(d,J＝7.1Hz,1H),8.01(d,J＝16.3Hz,1H),7.69–7.62(m,3H),7.61–7.54(m,2H),7.44–7.41(m,2H),7.36–7.35(m,2H),7.30–7.26(m,2H),7.22–7.18(m,1H),6.76(d,J＝16.3Hz,1H),3.46(s,3H),3.15(s,3H)；13C NMR(150MHz,CDCl3):δ177.58,169.70,162.50,155.39,138.27,135.65,134.66,133.67,131.62,131.31,130.44,129.61,128.63,128.57,127.67,126.65,126.43,125.32,123.75,119.96,118.25,117.73,61.39,32.86；HRMS(ESI-TOF):calc’d for C26H21NNaO4 +[M+Na+]434.1363,found434.1357.
实施例19所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ8.35(dd,J＝8.0,1.7Hz,1H),8.29–8.27(m,1H),7.86(d,J＝16.3Hz,1H),7.82–7.78(m,2H),7.69(ddd,J＝8.6,7.2,1.7Hz,1H),7.65–7.63(m,1H),7.46(t,J＝7.8Hz,1H),7.39(d,J＝8.4Hz,1H),7.25–7.22(m,4H),7.21–7.18(m,1H),6.50(d,J＝16.3Hz,1H),3.16(s,3H)；13C NMR(100MHz,CDCl3):δ177.29,160.93,155.37,139.98,137.81,135.22,134.08,133.98,132.61,132.57,131.55,130.68,128.68,127.98,126.70,126.59,125.60,123.99,119.28,117.52,45.07；HRMS(ESI-TOF):calc’d forC24H18NaO4S+[M+Na+]425.0818,found425.0814.
实施例20所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ8.33(dd,J＝8.0,1.7Hz,1H),8.29(dd,J＝8.0,1.5Hz,1H),7.83–7.73(m,3H),7.67(td,J＝7.1,1.7Hz,2H),7.45(t,J＝7.5Hz,1H),7.37(d,J＝8.4Hz,1H),7.30–7.24(m,4H),7.22–7.18(m,1H),6.61(d,J＝16.2Hz,1H)；13C NMR(100MHz,CDCl3):δ177.31,159.87,155.61,148.02,137.78,135.46,133.90,133.83,132.67,131.65,128.64,128.39,127.97,126.65,126.39,125.53,125.42,123.76,118.90,118.87,117.89；HRMS(ESI-TOF):calc’d for C23H15NNaO4 +[M+Na+]392.0893,found392.0887.
实施例21所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ8.32(dd,J＝8.0,1.6Hz,1H),7.87(d,J＝16.1Hz,1H),7.76(d,J＝2.6Hz,1H),7.66(ddd,J＝8.5,7.1,1.7Hz,1H),7.56(d,J＝8.4Hz,1H),7.44(t,J＝7.6Hz,1H),7.35(d,J＝8.5Hz,1H),7.33–7.26(m,5H),7.23–7.19(m,1H),6.63(d,J＝16.1Hz,1H),3.99(s,3H)；13C NMR(100MHz,CDCl3):δ177.44,161.64,160.13,155.60,149.13,137.96,135.14,133.80,133.77,128.64,127.89,126.67,126.37,125.42,123.78,120.36,119.50,119.25,118.82,117.87,110.60,56.36；HRMS(ESI-TOF):calc’d forC24H17NNaO5 +[M+Na+]422.0999,found422.0994.
实施例22所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ8.32(dd,J＝8.0,1.7Hz,1H),8.09(d,J＝8.4Hz,1H),7.89(d,J＝16.2Hz,1H),7.64(ddd,J＝8.6,7.1,1.7Hz,1H),7.60(dd,J＝8.5,2.2Hz,1H),7.55(d,J＝2.2Hz,1H),7.42(t,J＝7.6Hz,1H),7.37(d,J＝8.4Hz,1H),7.28–7.22(m,4H),7.20–7.16(m,1H),6.50(d,J＝16.2Hz,1H),3.67(s,3H)；13C NMR(100MHz,CDCl3):δ177.32,165.43,161.97,155.54,138.90,138.01,135.54,134.83,133.77,132.51,131.21,130.73,128.98,128.64,127.83,126.63,126.46,125.38,123.85,119.20,118.39,117.82,52.86；HRMS(ESI-TOF):calc’d for C25H17ClNaO4 +[M+Na+]439.0708,found439.0701.
实施例23所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ8.34(dd,J＝8.0,1.7Hz,1H),7.97(d,J＝4.2Hz,1H),7.95(d,J＝10.5Hz,1H),7.64(ddd,J＝8.6,7.0,1.7Hz,1H),7.49–7.47(m,1H),7.46–7.40(m,2H),7.38(d,J＝8.4Hz,1H),7.31–7.23(m,4H),7.20–7.15(m,1H),6.61(d,J＝16.3Hz,1H),3.67(s,3H),2.51(s,3H)；13C NMR(100MHz,CDCl3):δ177.56,166.65,164.09,155.56,141.03,138.32,133.99,133.53,132.98,131.64,131.32,131.05,130.59,128.56,127.56,126.57,126.39,125.16,123.89,120.07,118.07,117.79,52.65,21.49；HRMS(ESI-TOF):calc’d for C26H20NaO4 +[M+Na+]419.1254,found419.1250.
实施例24所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ8.33(dd,J＝8.0,1.6Hz,1H),7.96(d,J＝16.3Hz,1H),7.67–7.63(m,2H),7.49(d,J＝8.5Hz,1H),7.43(t,J＝7.6Hz,1H),7.39(d,J＝8.4Hz,1H),7.32–7.30(m,2H),7.28–7.24(m,2H),7.21–7.16(m,2H),6.63(d,J＝16.3Hz,1H),3.95(s,3H),3.68(s,3H)；13C NMR(100MHz,CDCl3):δ177.62,166.47,163.89,161.01,155.56,138.35,133.96,133.53,132.94,132.38,128.59,127.57,126.58,126.40,126.03,125.15,123.89,120.17,118.13,117.99,117.77,116.00,55.90,52.80；HRMS(ESI-TOF):calc’dfor C26H21O5 +[M+Na+]413.1384,found413.1378.
实施例25所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ8.97(d,J＝2.4Hz,1H),8.51(dd,J＝8.4,2.4Hz,1H),8.34(d,J＝7.2Hz,1H),7.86–7.80(m,2H),7.71–7.67(m,1H),7.47(t,J＝7.6Hz,1H),7.39(d,J＝8.4Hz,1H),7.27–7.26(m,4H),7.24–7.19(m,1H),6.51(d,J＝16.2Hz,1H),3.79(s,3H)；13C NMR(100MHz,CDCl3):δ177.11,164.39,160.51,155.57,148.74,139.55,137.58,135.78,134.01,132.95,132.58,128.71,128.14,126.85,126.62,126.52,126.15,125.60,123.77,118.86,118.58,117.77,53.38；HRMS(ESI-TOF):calc’d for C25H17NNaO6 +[M+Na+]450.0948,found450.0946.
实施例26所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ8.32(dd,J＝8.0,1.7Hz,1H),7.89(d,J＝16.3Hz,1H),7.83(dd,J＝8.9,2.7Hz,1H),7.64(ddd,J＝8.6,7.1,1.7Hz,1H),7.55(dd,J＝8.5,5.3Hz,1H),7.42(ddd,J＝8.1,7.1,1.1Hz,1H),7.39–7.34(m,2H),7.28–7.22(m,4H),7.20–7.15(m,1H),6.53(d,J＝16.2Hz,1H),3.69(s,3H)；13C NMR(100MHz,CDCl3):δ177.34,165.11(d,J＝2.8Hz),163.23(d,J＝252.9Hz),162.47,155.46,137.96,134.45,133.61,133.42(d,J＝8.4Hz),132.95(d,J＝7.6Hz),129.96(d,J＝3.7Hz),128.53,127.68,126.46,126.35,125.22,123.75,119.60,119.40(d,J＝3.7Hz),118.36(d,J＝3.2Hz),118.14,117.67,52.91；19F NMR(376MHz,CDCl3):δ-108.10；HRMS(ESI-TOF):calc’d for C25H17FNaO4 +[M+Na+]423.1003,found423.0995.
实施例27所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ8.31(dd,J＝8.0,1.7Hz,1H),8.19(dd,J＝7.4,1.8Hz,1H),7.73–7.65(m,3H),7.49–7.38(m,4H),7.17(d,J＝15.8Hz,1H),3.72(s,3H),3.69(s,3H)；13C NMR(100MHz,CDCl3):δ176.92,168.33,168.11,165.86,155.45,135.94,134.05,133.05,132.71,131.40,131.23,131.11,130.14,126.49,125.73,123.85,122.54,117.87,116.07,52.71,51.61；HRMS(ESI-TOF):calc’d for C21H16NaO6 +[M+Na+]387.0839,found387.0835.
实施例28所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ8.31(dd,J＝8.0,1.6Hz,1H),8.17(dd,J＝7.7,1.5Hz,1H),7.73–7.63(m,3H),7.49(d,J＝8.7Hz,1H),7.45(t,J＝7.5Hz,1H),7.40(d,J＝9.5Hz,1H),7.37(d,J＝2.1Hz,1H),7.07(d,J＝15.7Hz,1H),3.71(s,3H),1.43(s,9H)；13C NMR(100MHz,CDCl3):δ177.02,167.85,167.21,165.88,155.44,134.53,133.97,133.11,132.69,131.35,131.23,131.01,130.14,126.49,125.65,124.92,123.91,117.85,116.18,80.14,52.69,28.25；HRMS(ESI-TOF):calc’d for C24H22NaO6 +[M+Na+]429.1309,found429.1305.
实施例29所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ8.31(dd,J＝8.0,1.7Hz,1H),8.17(dd,J＝7.6,1.5Hz,1H),8.14(d,J＝15.1Hz,1H),7.71–7.62(m,3H),7.50(dd,J＝7.3,1.4Hz,1H),7.45(ddd,J＝8.1,7.2,1.1Hz,1H),7.39(dd,J＝8.4,1.1Hz,1H),7.13(d,J＝15.1Hz,1H),3.70(s,3H),3.17(s,3H),2.98(s,3H)；13C NMR(100MHz,CDCl3):δ177.57,167.93,167.48,165.92,155.46,133.93,133.32,133.27,132.77,131.39,130.94,130.02,126.31,125.61,123.97,122.05,117.94,116.47,52.63,37.47,35.85；HRMS(ESI-TOF):calc’d for C22H19NNaO5 +[M+Na+]400.1155,found400.1151.
实施例30所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ8.29(dd,J＝8.0,1.7Hz,1H),8.17(dd,J＝7.6,1.6Hz,1H),7.71–7.62(m,3H),7.48–7.33(m,4H),6.93(dd,J＝25.0,17.3Hz,1H),4.00(p,J＝7.2Hz,4H),3.71(s,3H),1.24(t,J＝7.0Hz,6H)；13C NMR(100MHz,CDCl3):δ177.16,167.91,165.82,155.46,139.54(d,J＝8.1Hz),134.07,132.98,132.74,131.43,131.20,131.11,130.17,126.38,125.73,124.02,119.67(d,J＝184.4Hz),117.91,116.05(d,J＝21.6Hz),61.77(d,J＝5.3Hz),52.71,16.42(d,J＝6.5Hz)；31P NMR(162MHz,CDCl3)δ19.35；HRMS(ESI-TOF):calc’d for C23H23NaO7P+[M+Na+]465.1074,found465.1070.
实施例31所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ8.23(ddd,J＝9.1,7.6,1.7Hz,2H),8.15(d,J＝15.0Hz,1H),7.84(d,J＝7.2Hz,2H),7.79–7.71(m,2H),7.71–7.65(m,1H),7.57(t,J＝7.3Hz,1H),7.53–7.46(m,3H),7.47–7.43(m,1H),7.40(d,J＝8.4Hz,1H),7.11(d,J＝15.0Hz,1H),3.74(s,3H)；13C NMR(100MHz,CDCl3):δ176.63,169.54,165.77,155.46,140.91,134.40,133.27,133.04,132.87,132.37,131.58,131.51,131.22,130.23,129.30,127.76,126.37,126.08,123.66,117.99,114.61,52.83；HRMS(ESI-TOF):calc’d for C25H18NaO6S+[M+Na+]469.0716,found469.0713.
实施例32所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ8.28(dd,J＝8.0,1.7Hz,1H),8.05–8.03(m,1H),7.70–7.66(m,1H),7.62–7.55(m,2H),7.46–7.39(m,3H),7.27(s,1H),3.75(s,3H),3.71(s,3H),1.59(s,3H)；13C NMR(100MHz,CDCl3):δ176.47,167.95,166.69,163.07,156.19,134.05,133.61,133.37,132.20,130.98,130.77,130.73,130.54,130.39,126.43,125.49,123.25,118.42,117.88,52.72,52.07,14.81；HRMS(ESI-TOF):calc’d for C22H18NaO6 +[M+Na+]401.0996,found401.1002.
实施例33所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ8.29(dd,J＝7.9,1.7Hz,1H),8.10(dd,J＝7.7,1.4Hz,1H),7.66–7.59(m,3H),7.51(dd,J＝7.2,1.6Hz,1H),7.43–7.41(m,1H),7.38(d,J＝8.5Hz,1H),6.76(d,J＝19.4Hz,1H),6.44(d,J＝19.3Hz,1H),3.70(s,3H),-0.04(s,9H)；13C NMR(100MHz,CDCl3):δ177.61,166.51,163.68,155.72,137.96,134.29,134.02,133.56,132.13,131.20,130.86,130.82,130.33,126.37,125.16,124.13,119.57,117.84,52.70,-1.52；HRMS(ESI-TOF):calc’d for C22H22NaO4Si+[M+Na+]401.1180,found401.1179.
实施例34所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ8.31(dd,J＝8.0,1.7Hz,1H),8.13(dd,J＝7.8,1.4Hz,1H),7.69–7.60(m,3H),7.51(dd,J＝7.7,1.2Hz,1H),7.42(ddd,J＝8.1,7.2,1.1Hz,1H),7.38(dd,J＝8.4,1.0Hz,1H),6.29–6.16(m,2H),5.32(dd,J＝10.8,3.2Hz,1H),3.71(s,3H)；13C NMR(100MHz,CDCl3):δ177.58,166.33,163.84,155.69,133.94,133.61,132.46,131.18,131.06,130.46,130.42,127.81,126.40,125.20,124.01,120.86,118.27,117.83,52.71；HRMS(ESI-TOF):calc’d for C19H14NaO4 +[M+Na+]329.0784,found329.0784.
实施例35所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ8.23(dd,J＝8.0,1.7Hz,1H),8.06(dd,J＝7.4,1.7Hz,1H),7.64–7.56(m,3H),7.44(dd,J＝7.2,1.7Hz,1H),7.38–7.34(m,2H),7.30(dd,J＝8.4,1.0Hz,1H),3.61(s,3H)；13C NMR(100MHz,CDCl3):δ177.43,166.27,163.72,155.53,134.15,133.39,132.39,131.49,131.07,130.16,126.46,125.98,124.96,123.88,118.88,117.68,52.53；HRMS(ESI-TOF):calc’d for C17H12NaO4 +[M+Na+]303.0628,found303.0620.
实施例36所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ8.38(d,J＝7.9Hz,1H),8.19(dd,J＝7.2,1.8Hz,1H),8.07(d,J＝16.3Hz,1H),7.79–7.73(m,2H),7.71–7.65(m,5H),7.61(dd,J＝7.1,1.8Hz,1H),7.47–7.38(m,5H),6.74(d,J＝16.2Hz,1H),3.71(s,3H)；13C NMR(100MHz,CDCl3):δ177.55,166.43,163.84,155.60,135.66,134.26,133.94,133.71,133.63,133.09,132.45,131.41,131.12,130.75,130.63,128.18,128.14,127.71,126.95,126.45,126.28,125.93,125.25,123.90,123.32,120.19,118.22,117.83,52.73；HRMS(ESI-TOF):calc’d forC29H20NaO4 +[M+Na+]455.1254,found455.1251.
实施例37所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ8.35(dd,J＝8.0,1.7Hz,1H),8.20(dd,J＝7.4,1.8Hz,1H),7.99–7.93(m,2H),7.74–7.65(m,5H),7.60(dd,J＝7.1,1.7Hz,1H),7.51(s,1H),7.45(t,J＝7.5Hz,1H),7.43–7.36(m,2H),7.27–7.25(m,1H),7.18(d,J＝8.1Hz,2H),7.13(t,J＝7.6Hz,1H),6.65(d,J＝16.4Hz,1H),3.70(s,3H),2.32(s,3H)；13C NMR(100MHz,CDCl3):δ177.59,166.27,163.83,155.60,145.11,135.66,135.11,133.97,133.67,132.59,131.30,131.24,130.70,130.55,130.00,129.16,126.95,126.40,125.29,124.93,124.12,123.90,123.50,121.83,121.12,120.47,118.06,117.88,113.87,52.73,21.67；HRMS(ESI-TOF):calc’d for C34H25NNaO6S+[M+Na+]598.1295,found598.1293.
实施例38所得产物的表征如下：
1H NMR(400MHz,Methanol-d4):δ8.22(dd,J＝8.2,1.7Hz,1H),8.12(dd,J＝7.8,1.3Hz,1H),7.78–7.73(m,2H),7.68(td,J＝7.6,1.4Hz,1H),7.59(dd,J＝7.5,1.4Hz,1H),7.51–7.47(m,2H),6.56(d,J＝16.0Hz,1H),6.16(d,J＝16.1Hz,1H),3.71(s,3H),1.14(s,6H)；13C NMR(100MHz,CDCl3):δ177.51,166.86,162.98,155.73,144.10,133.82,133.59,132.28,131.04,130.94,130.84,130.42,126.28,125.17,123.74,118.22,117.85,116.84,71.23,52.75,29.66；HRMS(ESI-TOF):calc’d for C22H20NaO5 +[M+Na+]387.1203,found387.1205.
实施例39所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ8.29(dd,J＝8.1,1.7Hz,1H),7.70(d,J＝2.6Hz,1H),7.66(ddd,J＝8.6,7.1,1.7Hz,1H),7.53(d,J＝8.5Hz,1H),7.45–7.39(m,1H),7.36(d,J＝8.4Hz,1H),7.26(q,J＝4.3,3.5Hz,4H),7.05(d,J＝8.5Hz,1H),6.98(d,J＝15.9Hz,1H),6.65(dd,J＝8.4,2.7Hz,1H),6.58(d,J＝2.6Hz,1H),6.19(d,J＝15.9Hz,1H),5.91(s,1H),3.91(s,3H),2.82–2.71(m,2H),2.09(dd,J＝12.9,3.4Hz,1H),1.99–1.81(m,4H),1.71–1.65(m,2H),1.46–1.33(m,5H),1.27–1.20(m,1H),1.13(td,J＝12.6,4.1Hz,1H),0.87(s,3H)；13C NMR(100MHz,CDCl3):δ178.00,161.58,159.74,155.84,153.86,149.16,142.79,138.27,133.98,133.47,132.50,126.47,126.29,125.51,123.57,120.54,119.71,119.30,117.97,116.87,115.37,112.74,110.29,84.50,56.32,49.57,47.43,43.41,39.44,37.32,32.52,29.76,27.44,26.30,23.50,14.24；HRMS(ESI-TOF):calc’d for C36H35NNaO7 +[M+Na+]616.2306,found616.2293.
实施例40所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ8.28(dd,J＝8.0,1.7Hz,1H),8.09(dd,J＝7.7,1.5Hz,1H),7.74(dd,J＝7.5,1.5Hz,1H),7.65(qd,J＝8.2,7.7,1.7Hz,2H),7.59(td,J＝7.6,1.5Hz,1H),7.45–7.40(m,2H),3.72(s,3H),0.95(s,21H)；13C NMR(100MHz,CDCl3):δ176.35,168.92,166.32,155.79,134.01,133.88,132.18,130.85,130.79,130.59,130.11,126.32,125.67,122.97,118.06,109.26,100.24,97.73,52.65,18.65,11.24；HRMS(ESI-TOF):calc’d for C28H32NaO4Si+[M+Na+]483.1962,found483.1956.
实施例41所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ8.33(dd,J＝8.3,1.7Hz,1H),7.95(dd,J＝7.6,1.5Hz,1H),7.68(ddd,J＝8.8,7.3,1.7Hz,1H),7.46–7.35(m,4H),7.23–7.16(m,6H),3.76(s,3H)；13C NMR(100MHz,CDCl3):δ177.27,166.93,162.82,156.27,134.45,133.81,132.48,131.86,131.47,131.02,130.83,130.48,129.87,128.04,127.61,126.60,125.23,123.92,123.26,117.91,52.70；HRMS(ESI-TOF):calc’d for C23H16NaO4 +[M+Na+]379.0941,found379.0934.
实施例42所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ8.10(s,1H),7.94(dd,J＝7.6,1.4Hz,1H),7.49(dd,J＝8.5,2.2Hz,1H),7.41(ddd,J＝14.9,7.4,1.5Hz,2H),7.37–7.31(m,2H),7.21–7.16(m,5H),3.75(s,3H),2.49(s,3H)；13C NMR(100MHz,CDCl3):δ177.32,167.01,162.65,154.57,135.16,135.08,134.54,132.66,131.80,131.46,131.07,130.89,130.45,129.80,128.03,127.54,125.85,123.57,123.08,117.67,52.70,21.14；HRMS(ESI-TOF):calc’d forC24H18NaO4 +[M+Na+]393.1097,found393.1109.
实施例43所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ7.97–7.94(m,2H),7.46–7.33(m,4H),7.26–7.16(m,6H),3.77(s,3H)；13C NMR(100MHz,CDCl3):δ176.57(d,J＝2.4Hz),166.77,163.17,159.74(d,J＝246.6Hz),152.52,134.28,132.17,131.95,131.42,130.95,130.70,130.53,130.01,128.10,127.74,125.07(d,J＝7.3Hz),122.67,122.06(d,J＝25.5Hz),120.04(d,J＝8.2Hz),111.36(d,J＝23.6Hz),52.72；19F NMR(376MHz,CDCl3):δ-115.47；HRMS(ESI-TOF):calc’d for C23H15FNaO4 +[M+Na+]397.0847,found397.0849.
实施例44所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ8.28(dd,J＝8.0,1.7Hz,1H),7.66(ddd,J＝8.7,7.2,1.7Hz,1H),7.41(td,J＝7.5,1.1Hz,1H),7.39–7.26(m,6H),7.25–7.18(m,4H),3.01(s,3H),2.80(s,3H)；13C NMR(100MHz,CDCl3):δ177.04,170.12,161.46,156.15,136.88,133.74,132.44,131.70,131.41,129.50,128.74,128.08,127.66,127.03,126.74,125.25,123.96,123.68,117.65,39.15,35.10；HRMS(ESI-TOF):calc’d for C24H19NNaO3 +[M+Na+]392.1257,found392.1260.
实施例45所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ8.32(dd,J＝8.0,1.7Hz,1H),8.08(dd,J＝7.9,1.5Hz,1H),7.70(ddd,J＝8.6,7.2,1.7Hz,1H),7.56–7.47(m,2H),7.47–7.43(m,1H),7.40(d,J＝8.4Hz,1H),7.28(d,J＝1.7Hz,1H),7.23(s,5H)；13C NMR(100MHz,CDCl3):δ177.06,159.40,156.28,148.22,134.11,133.28,132.68,131.83,130.95,130.85,129.00,128.36,128.09,126.59,125.58,124.91,123.90,118.05；HRMS(ESI-TOF):calc’d for C21H13NNaO4 +[M+Na+]366.0737,found366.0728.
实施例46所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ8.32(dd,J＝7.9,1.7Hz,1H),7.97(dd,J＝7.6,1.5Hz,1H),7.69(ddd,J＝8.6,7.2,1.7Hz,1H),7.50–7.37(m,4H),7.22–7.11(m,2H),6.98–6.94(m,2H),6.92–6.84(m,1H),3.77(s,3H)；13C NMR(100MHz,CDCl3):δ176.93,166.78,163.23,162.50(d,J＝245.5Hz),156.26,134.74(d,J＝8.7Hz),134.15,134.00,132.04,131.31,130.75,130.62,130.15,129.50(d,J＝8.6Hz),126.84(d,J＝3.1Hz),126.59,125.41,123.82,122.24,118.16,117.96,114.66(d,J＝21.1Hz),52.76；19F NMR(376MHz,CDCl3):δ-113.72；HRMS(ESI-TOF):calc’d for C23H15FNaO4 +[M+Na+]397.0847,found397.0845.
实施例47所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ8.32(dd,J＝8.2,1.6Hz,1H),7.95(dd,J＝7.3,1.7Hz,1H),7.69(td,J＝7.7,1.7Hz,1H),7.48–7.38(m,4H),7.21(dd,J＝7.2,1.7Hz,1H),7.15–7.06(m,3H),7.00(dt,J＝7.0,1.7Hz,1H),3.77(s,3H),2.30(s,3H)；13C NMR(100MHz,CDCl3):δ177.07,166.86,163.00,156.25,138.01,134.38,133.89,133.20,132.00,131.38,130.79,130.49,129.99,129.21,128.37,127.97,126.59,126.33,125.31,123.88,122.85,117.94,52.74,16.03；HRMS(ESI-TOF):calc’d for C24H18NaO4S+[M+Na+]425.0818,found425.0818.
实施例48所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ8.33–8.30(m,1H),7.95(dd,J＝7.4,1.6Hz,1H),7.69–7.65(m,1H),7.45–7.36(m,4H),7.18(dd,J＝7.5,1.6Hz,1H),7.13(d,J＝8.7Hz,2H),6.75(d,J＝8.7Hz,2H),3.75(s,3H),3.75(s,3H)；13C NMR(100MHz,CDCl3):δ177.55,167.03,162.55,158.97,156.26,134.67,133.73,132.19,131.91,131.50,130.84,130.48,129.76,126.60,125.15,124.62,123.87,122.81,117.88,113.63,55.27,52.69；HRMS(ESI-TOF):calc’d for C24H18NaO5 +[M+Na+]409.1046,found409.1042.
实施例49所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ8.30(dd,J＝7.9,1.7Hz,1H),7.96(dd,J＝7.8,1.4Hz,1H),7.69(ddd,J＝8.7,7.2,1.7Hz,1H),7.62–7.59(m,2H),7.49–7.38(m,4H),7.25(d,J＝8.2Hz,2H),7.12(d,J＝8.7Hz,3H),6.81(d,J＝8.6Hz,2H),3.75(s,3H),2.43(s,3H)；13CNMR(100MHz,CDCl3):δ176.92,166.67,163.14,156.23,148.95,145.35,134.18,134.02,132.34,132.28,131.92,131.59,131.36,130.83,130.52,130.01,129.79,128.64,126.49,125.43,123.74,122.06,122.00,117.96,52.74,21.84；HRMS(ESI-TOF):calc’d forC30H22NaO7S+[M+Na+]549.0978,found549.0985.
实施例50所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ8.33–8.31(m,1H),7.95(dd,J＝7.6,1.6Hz,1H),7.67(ddd,J＝8.8,7.5,1.8Hz,1H),7.47–7.35(m,4H),7.19(dd,J＝7.5,1.5Hz,1H),7.09(d,J＝8.1Hz,2H),7.01(d,J＝7.8Hz,2H),3.75(s,3H),2.26(s,3H)；13C NMR(100MHz,CDCl3):δ177.42,166.99,162.55,156.25,137.25,134.59,133.72,131.87,131.48,130.81,130.45,129.77,129.35,128.83,126.60,125.14,123.89,123.18,117.87,52.68,21.39；HRMS(ESI-TOF):calc’d for C24H18NaO4 +[M+Na+]393.1097,found393.1096.
实施例51所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ8.32(dd,J＝8.4,1.7Hz,1H),7.95–7.93(m,1H),7.66(ddd,J＝8.8,7.2,1.7Hz,1H),7.44–7.37(m,4H),7.21(dd,J＝6.8,2.2Hz,1H),7.01(d,J＝2.2Hz,1H),6.94(dd,J＝8.4,2.3Hz,1H),6.64(d,J＝8.4Hz,1H),3.75(s,6H),2.10(s,3H)；13C NMR(100MHz,CDCl3):δ177.67,167.07,162.39,157.22,156.25,134.74,133.67,133.18,131.85,131.45,130.83,130.39,129.67,129.51,126.61,126.14,125.09,124.09,123.89,123.06,117.88,109.64,55.32,52.67,16.34；HRMS(ESI-TOF):calc’d forC25H20NaO5 +[M+Na+]423.1203,found423.1204.
实施例52所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ8.31(dd,J＝8.0,1.7Hz,1H),8.00(dd,J＝7.5,1.7Hz,1H),7.92(d,J＝2.4Hz,1H),7.69(ddd,J＝8.7,7.2,1.7Hz,1H),7.53(dd,J＝8.5,2.4Hz,1H),7.49–7.41(m,4H),7.20(dd,J＝7.0,1.9Hz,1H),6.65(d,J＝8.5Hz,1H),3.85(s,3H),3.76(s,3H)；13C NMR(100MHz,CDCl3):δ177.32,166.67,163.33,163.27,156.30,148.63,141.20,134.26,134.00,132.26,131.40,130.83,130.75,130.16,126.53,125.39,123.64,121.59,119.88,117.98,110.28,53.54,52.73；HRMS(ESI-TOF):calc’d for C23H17NNaO5 +[M+Na+]410.0999,found410.1001.
实施例53所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ8.34(dd,J＝7.9,1.7Hz,1H),8.06–8.04(m,1H),7.68(ddd,J＝8.6,7.2,1.7Hz,1H),7.53–7.47(m,2H),7.48–7.39(m,2H),7.38–7.34(m,1H),7.28–7.26(m,1H),6.83(dd,J＝5.1,3.6Hz,1H),6.76(dd,J＝3.6,1.2Hz,1H),3.75(s,3H)；13C NMR(100MHz,CDCl3):δ176.59,166.51,163.22,155.97,134.70,133.95,132.53,132.40,130.85,130.75,130.65,130.27,129.29,127.11,126.66,126.24,125.42,123.40,117.92,117.15,52.72；HRMS(ESI-TOF):calc’d for C21H14NaO4S+[M+Na+]385.0505,found385.0497.
实施例54所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ8.36(dd,J＝8.2,1.7Hz,1H),8.10(d,J＝1.7Hz,1H),8.03–7.97(m,1H),7.94(dd,J＝7.7,1.4Hz,1H),7.82–7.78(m,1H),7.71(ddd,J＝8.8,7.2,1.7Hz,1H),7.66(d,J＝8.3Hz,1H),7.49–7.44(m,2H),7.43–7.40(m,2H),7.37(dd,J＝7.6,1.5Hz,1H),7.32(td,J＝7.5,1.4Hz,1H),7.26–7.21(m,2H),3.80(s,3H)；13C NMR(100MHz,CDCl3):δ177.42,166.99,163.10,156.31,139.70,138.88,135.59,135.51,134.41,133.91,132.01,131.49,130.85,130.48,129.96,129.56,128.80,126.77,126.62,125.33,124.43,124.30,123.90,123.02,122.87,122.46,121.73,117.96,52.76；HRMS(ESI-TOF):calc’d for C29H18NaO4S+[M+Na+]485.0818,found485.0828.
实施例55所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ8.24(dd,J＝7.9,1.7Hz,1H),7.66(ddd,J＝8.6,7.1,1.7Hz,1H),7.48–7.41(m,3H),7.41–7.34(m,2H),7.32–7.27(m,2H),2.33(s,3H)；13C NMR(100MHz,CDCl3):δ176.93,163.45,156.06,133.48,133.27,130.57,128.55,127.92,126.45,124.96,123.81,123.66,117.78,19.70；HRMS(ESI-TOF):calc’d for C16H12NaO2 +[M+Na+]259.0730,found259.0727.
实施例56所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ8.24(dd,J＝7.9,1.7Hz,1H),7.67(ddd,J＝8.7,7.1,1.7Hz,1H),7.48–7.35(m,5H),7.29–7.26(m,2H),2.60(q,J＝7.5Hz,2H),1.27(t,J＝7.6Hz,3H)；13C NMR(100MHz,CDCl3):δ177.25,167.54,156.18,133.45,133.24,130.49,128.58,127.91,126.43,124.92,123.64,123.21,117.82,26.31,12.10；HRMS(ESI-TOF):calc’d for C17H14NaO2 +[M+Na+]273.0886,found273.0884.
实施例57所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ7.86(dd,J＝8.3,3.1Hz,1H),7.50–7.41(m,3H),7.41–7.34(m,2H),7.28–7.25(m,2H),2.60(q,J＝7.5Hz,2H),1.26(t,J＝7.5Hz,3H)；13C NMR(100MHz,CDCl3):δ176.47(d,J＝2.2Hz),167.86,159.51(d,J＝245.7Hz),152.37,132.87,130.40,128.62,128.03,124.72(d,J＝7.3Hz),122.60,121.65(d,J＝25.5Hz),119.89(d,J＝8.4Hz),111.11(d,J＝23.4Hz),26.27,12.03；19F NMR(376MHz,CDCl3):δ-115.94；HRMS(ESI-TOF):calc’d for C17H13FNaO2 +[M+Na+]291.0792,found291.0795.
实施例58所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ8.23(dd,J＝8.0,1.7Hz,1H),7.66(ddd,J＝8.7,7.1,1.7Hz,1H),7.47–7.35(m,5H),7.28–7.26(m,2H),2.57(t,J＝7.7Hz,2H),1.69(dq,J＝9.1,7.6Hz,2H),1.36–1.25(m,2H),0.85(t,J＝7.3Hz,3H)；13C NMR(100MHz,CDCl3):δ177.23,166.79,156.15,133.44,133.29,130.57,128.54,127.88,126.43,124.91,123.71,123.63,117.81,32.42,29.71,22.43,13.84；HRMS(ESI-TOF):calc’d for C19H18NaO2 +[M+Na+]301.1199,found301.1200.
实施例59所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ8.23(dd,J＝8.0,1.7Hz,1H),7.67(ddd,J＝8.8,7.0,1.7Hz,1H),7.47–7.35(m,5H),7.28–7.26(m,2H),3.35(t,J＝6.2Hz,2H),3.26(s,3H),2.69–2.65(m,2H),2.01–1.94(m,2H)；13C NMR(100MHz,CDCl3):δ177.19,166.10,156.13,133.52,133.11,130.54,128.60,127.97,126.45,124.99,123.91,123.63,117.82,71.65,58.65,29.63,27.53；HRMS(ESI-TOF):calc’d for C19H18NaO3 +[M+Na+]317.1148,found317.1145.
实施例60所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ8.23(dd,J＝7.9,1.7Hz,1H),7.67(ddd,J＝8.7,7.1,1.8Hz,1H),7.47–7.35(m,5H),7.29–7.26(m,2H),3.62(t,J＝6.3Hz,2H),2.71–2.69(t,J＝7.6Hz,2H),1.99–1.92(m,2H),1.59(s,1H)；13C NMR(100MHz,CDCl3):δ177.15,165.99,156.12,133.58,133.08,130.49,128.69,128.06,126.46,125.05,123.95,123.60,117.80,61.90,30.41,29.21；HRMS(ESI-TOF):calc’d for C18H16NaO3 +[M+Na+]303.0992,found303.0987.
实施例61所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ8.24(dd,J＝8.0,1.7Hz,1H),7.69(ddd,J＝8.7,7.1,1.8Hz,1H),7.48–7.38(m,5H),7.27–7.24(m,2H),2.77–2.74(m,2H),2.36(t,J＝7.2Hz,2H),2.07(p,J＝7.3Hz,2H)；13C NMR(100MHz,CDCl3):δ176.97,163.62,156.00,133.83,132.51,130.36,128.87,128.35,126.55,125.32,124.57,123.58,118.78,117.81,31.48,23.45,16.97；HRMS(ESI-TOF):calc’d for C19H15NNaO2 +[M+Na+]312.0995,found312.0992.
实施例62所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ8.23(dd,J＝7.9,1.7Hz,1H),7.67(ddd,J＝8.7,7.1,1.7Hz,1H),7.47–7.35(m,5H),7.27–7.25(m,2H),4.05(q,J＝7.1Hz,2H),2.64(t,J＝7.6Hz,2H),2.31(t,J＝7.4Hz,2H),2.04(p,J＝7.5Hz,2H),1.20(t,J＝7.1Hz,3H)；13C NMR(100MHz,CDCl3):δ177.14,172.83,165.34,156.09,133.59,132.96,130.50,128.65,128.03,126.45,125.06,124.13,123.59,117.86,60.63,33.57,31.91,22.73,14.30；HRMS(ESI-TOF):calc’d for C21H20NaO4 +[M+Na+]359.1254,found359.1246.
实施例63所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ8.24(dd,J＝7.9,1.7Hz,1H),7.67(ddd,J＝8.6,7.1,1.7Hz,1H),7.48–7.36(m,5H),7.27–7.25(m,2H),3.46(t,J＝6.4Hz,2H),2.62(t,J＝7.5Hz,2H),1.92–1.82(m,2H),1.83–1.73(m,2H)；13C NMR(100MHz,CDCl3):δ177.14,165.66,156.11,133.60,133.03,130.51,128.68,128.06,126.47,125.07,124.02,123.62,117.83,44.41,31.89,31.80,24.74；HRMS(ESI-TOF):calc’d for C19H17ClNaO2 +[M+Na+]335.0809,found335.0803.
实施例64所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ8.23(dd,J＝8.0,1.7Hz,1H),7.66(ddd,J＝8.7,7.1,1.7Hz,1H),7.47–7.35(m,5H),7.28–7.26(m,2H),4.87(t,J＝4.3Hz,1H),4.01–3.77(m,4H),2.75–2.71(m,2H),2.11–2.04(m,2H)；13C NMR(100MHz,CDCl3):δ177.18,165.65,156.11,133.53,132.98,130.51,128.59,128.00,126.45,125.00,123.81,123.64,117.82,103.32,65.14,31.23,27.13；HRMS(ESI-TOF):calc’d for C20H18NaO4 +[M+Na+]345.1097,found 345.1092.
实施例65所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ8.23(dd,J＝8.0,1.7Hz,1H),7.68(ddd,J＝8.6,7.1,1.8Hz,1H),7.48(d,J＝8.4Hz,1H),7.42–7.35(m,4H),7.10–7.07(m,2H),6.83(s,1H),6.76(dd,J＝8.1,1.9Hz,1H),6.63(d,J＝8.1Hz,1H),4.52(t,J＝8.6Hz,2H),3.10(t,J＝8.7Hz,2H),2.98–2.90(m,2H),2.87–2.77(m,2H)；13C NMR(100MHz,CDCl3):δ177.19,165.45,158.82,156.10,133.54,132.99,132.08,130.51,128.47,127.97,127.91,127.33,126.47,125.00,124.97,124.26,123.63,117.78,109.24,71.32,35.13,33.06,29.84；HRMS(ESI-TOF):calc’d for C25H20NaO3 +[M+Na+]391.1305,found 391.1301.
实施例66所得产物的表征如下：
1H NMR(400MHz,CDCl3):δ7.85(dd,J＝8.2,3.1Hz,1H),7.48(dd,J＝9.2,4.2Hz,1H),7.44–7.36(m,2H),7.09(td,J＝8.6,2.6Hz,1H),7.04(d,J＝7.6Hz,1H),6.99(dt,J＝9.5,2.1Hz,1H),2.60(q,J＝7.6Hz,2H),1.27(t,J＝7.5Hz,3H)；13C NMR(100MHz,CDCl3):δ176.19,168.04,162.89(d,J＝246.4Hz),159.61(d,J＝246.3Hz),152.38,135.01(d,J＝8.4Hz),130.17(d,J＝8.6Hz),126.24(d,J＝2.9Hz),124.65(d,J＝7.3Hz),121.88(d,J＝25.5Hz),121.64,119.96(d,J＝8.0Hz),117.61(d,J＝21.4Hz),115.12(d,J＝21.0Hz),111.16(d,J＝23.9Hz),26.29,11.99；19F NMR(376MHz,CDCl3):δ-113.01,-115.59；HRMS(ESI-TOF):calc’d for C17H12F2NaO2 +[M+Na+]309.0698,found309.0699.
实施例67所得产物的表征如下：
1H NMR(400MHz,DMSO-d6):δ7.91(dd,J＝9.2,4.2Hz,1H),7.80(td,J＝8.6,3.1Hz,1H),7.74(dd,J＝8.3,3.1Hz,1H),7.55(q,J＝7.9Hz,1H),7.31(td,J＝8.9,2.6Hz,1H),7.24–7.14(m,2H),4.98(q,J＝6.8Hz,1H),1.97(d,J＝6.8Hz,3H)；13C NMR(100MHz,DMSO-d6):δ175.29,162.16,161.95(d,J＝244.1Hz),159.17(d,J＝244.8Hz),151.65,133.55(d,J＝8.2Hz),130.53(d,J＝8.6Hz),126.12,123.80(d,J＝7.4Hz),123.04(d,J＝25.4Hz),121.21(d,J＝8.5Hz),119.74,117.16,115.37(d,J＝20.9Hz),109.96(d,J＝23.7Hz),42.76,22.07；19F NMR(376MHz,DMSO-d6):δ-113.04,-114.86；HRMS(ESI-TOF):calc’d for C17H12BrF2O2 +[M+H+]364.9983,found364.9978.
尽管上面已经示出和描述了本发明的实施例，可以理解的是，上述实施例是示例性的，不能理解为对本发明的限制，本领域的普通技术人员在本发明的范围内可以对上述实施例进行变化、修改、替换和变型，均应包含在本发明保护范围之内。