CN103804273B - 氧化吲哚与茚三酮双季碳拼接衍生物及其制备方法 - Google Patents

氧化吲哚与茚三酮双季碳拼接衍生物及其制备方法 Download PDF

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CN103804273B
CN103804273B CN201410039572.0A CN201410039572A CN103804273B CN 103804273 B CN103804273 B CN 103804273B CN 201410039572 A CN201410039572 A CN 201410039572A CN 103804273 B CN103804273 B CN 103804273B
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刘雄利
潘博文
石洋
余章彪
周英
刘雄伟
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Juancheng Tiantuo Biotechnology Co ltd
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Guizhou University
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Abstract

本发明公开了一种氧化吲哚与茚三酮双季碳拼接衍生物，本发明通过3位不同取代的氧化吲哚与水合茚三酮经直接催化Aldol反应，所合成的双季碳拼接衍生物为3-(<i>α</i>-羟基-<i>β</i>-羰基)氧化吲哚类化合物，该类骨架包含在许多医药候选药物分子中，例如药物分子surugatoxin就包含该类骨架；氧化吲哚与茚三酮双季碳拼接衍生物的合成也是潜在的药物分子中间体或和药物类似物，具有极其重要的研究意义。本发明操作简单易行，原料合成便宜易得，可以在水相中进行，也具有较好的空气稳定性，适用性广，对于各种取代基都有很好的兼容性。

Description

氧化吲哚与茚三酮双季碳拼接衍生物及其制备方法
技术领域
本发明涉及化学技术领域，尤其是一种氧化吲哚与茚三酮双季碳拼接衍生物及其制备方法。
背景技术
把两个具有生物活性的分子骨架杂合成一个分子骨架在有机化学和医药化学中是极其重要的研究领域。3,3'-双取代氧化吲哚由于它们广泛存在于复杂的生物活性分子中，吸引了许多化学工作者及医药化学团队的极大兴趣，引起了人们广泛关注，例如，SpirotryprostatinsA、B均是从肉汤发酵液里的曲霉素真菌里提取出来的，被发现是潜在的治疗癌症的药物；Gelsebanine是从GelsemiumElegans(俗称“断肠草”)植物中分离出来的一种成分，具有抗肿瘤细胞活性；Strychnofoline对于黑素瘤以及Ehrlich肿瘤细胞具有抗有丝分裂的活性；长春碱是从天然植物中分离的生物碱，可用于治疗绒毛膜上皮癌、淋巴肉瘤、网状细胞肉瘤、急性白血病、乳腺癌、圣母细胞瘤、卵巢癌、睾丸癌、神经母细胞瘤和恶性黑色素瘤。同时，茚酮骨架也普遍存在于天然产物和药物分子中，例如，tripartin是在放线菌在细菌中发现的一种新的二氯代茚酮，活性测试表明有明显的和特定的组蛋白脱甲基酶抑制效果。pterosinC和paucifloralF分别是从Acrostichumaureum的地上部分与青梅pauciflora的干树皮分离得到的。尤其是，最近发现1,3-茚二酮杂合衍生化分子能够降低白血病细胞中Bcl-2蛋白的细胞内含量，使它们有望发展为新的抗癌药物。鉴于茚酮骨架和3,3'-双取代氧化吲哚骨架化合物具有潜在的生物活性，因此，把茚酮骨架和3,3'-双取代氧化吲哚骨架拼接成杂合衍生物可能会产生一系列结构和活性上有意义的新化合物分子，它们的合成可以为生物活性筛选提供化合物源。
在复杂分子的合成中，双季碳中心的构建，一直是有机合成中的一个重大挑战。
发明内容
本发明的目的是：提供一种氧化吲哚与茚三酮双季碳拼接衍生物及其制备方法，它是一类重要的医药中间体和药物类似物，对药物筛选和制药行业具有重要的应用价值，且其合成方法非常经济简便。
本发明是这样实现的：氧化吲哚与茚三酮双季碳拼接衍生物，该化合物具有如下通式（Ⅰ）的结构：
式中，R1为烷基、不同取代的芳基或苯环上不同取代的苄基；R2为烷基、不同取代的芳基、苯环上不同取代的苄基或杂芳环，R3为氢、卤素或烷基。
所述的杂芳环为含N、O或S中的一种或几种的五到十元环杂芳环基。
氧化吲哚与茚三酮双季碳拼接衍生物的制备方法，将氧化吲哚与水合茚三酮在碱性催化剂条件下，按摩尔比为4:3的比例在水中或有机溶剂中进行羟醛缩合反应，获得氧化吲哚与茚三酮双季碳拼接衍生物。
在水中进行反应时，加入表面活性剂，表面活性剂的加入量是氧化吲哚摩尔量的1-100%。
所述的表面活性剂为季铵盐或磺酸盐。
所述的季铵盐为四丁基溴化铵、十六烷基三甲基溴化胺或四丁基硫酸氢铵；所述的磺酸盐为十二烷基磺酸钠。
所述的碱性催化剂为有机碱或无机碱，碱性催化剂的加入量为氧化吲哚摩尔量的1-100%。
所述的有机碱为DBU、DMAP、DABCO或Et3N；所述的无机碱为Na2CO3。
所述的有机溶剂为乙腈、甲醇、乙醇、丙醇、异丙醇、乙醚、四氢呋喃、苯、甲苯、二甲苯、三甲苯、二氧六环、乙二醇二甲醚、异丙醚、氯仿、二氯甲烷或硝基苯。
氧化吲哚与水合茚三酮的反应温度为25-100oC，反应时间为3-10小时。
本发明的反应原理如下：
其中，R1，R2，R3如上所述。Cat.为碱性催化剂，Additive为添加剂。
由于采用了上述技术方案，与现有技术相比，本发明通过3位不同取代的氧化吲哚与水合茚三酮经直接催化Aldol反应，所合成的双季碳拼接衍生物为3-(α-羟基-β-羰基)氧化吲哚类化合物，该类骨架包含在许多医药候选药物分子中，例如药物分子surugatoxin就包含该类骨架；氧化吲哚与茚三酮双季碳拼接衍生物的合成也是潜在的药物分子中间体或和药物类似物，具有极其重要的研究意义。本发明发明操作简单易行，原料合成便宜易得，可以在水相中进行，也具有较好的空气稳定性，适用性广，对于各种取代基都有很好的兼容性。
附图说明
附图1为本发明的实施例1化合物1的X衍生晶体结构数据；
附图2为本发明的实施例1化合物34的X衍生晶体结构数据。
具体实施方式
本发明的实施例1：氧化吲哚与茚三酮双季碳拼接衍生物的制备，在圆底烧瓶中，依次加入茚三酮0.3mmol(53.4mg)，N-苄基-3-苄基取代氧化吲哚0.4mmol(125.2mg)，DABCO3.4mg（10mmol%），十六烷基三甲基溴化铵11.0mg（10mmol%），再加入6.0mL水，充分搅拌，放入油浴中，温度为60oC反应6小时。
向反应液中加10mL无水乙醇，减压蒸馏除掉溶剂，残留油状物硅胶柱层析（300-400目）分离（石油醚：乙酸乙酯=3：1），得到淡黄色固体，核磁共振和高分辨质谱测试结果如下：1HNMR(CDCl3,400MHz)δ:3.65(d,J=13.3Hz,1H),3.97(d,J=13.3Hz,1H),4.34(d,J=16.0Hz,1H),4.99(d,J=16.0Hz,1H),5.97(s,1H),6.19(d,J=7.5Hz,1H),6.47(d,J=7.2Hz,2H),6.55-6.59(m,1H),6.70-6.72(m,3H),6.80-6.84(m,1H),6.91-6.95(m,2H),7.03-7.11(m,3H),7.19(s,1H),7.55(d,J=7.6Hz,1H),7.66-7.70(m,1H),7.78-7.82(m,1H),8.04(d,J=8.0Hz,1H);13CNMR(CDCl3,100MHz)δ:36.0,43.8,55.6,110.1,122.2,123.5,123.6,124.6,125.3,126.5,126.7,127.2,127.9,128.6,129.1,130.4,134.5,134.6,136.5,136.6,140.6,141.4,143.4,177.1,196.3,198.1;HRMS(ESI)Calcd.forC31H23NNaO4[M+Na]+:496.1525;Found:496.1527。
化合物1的X衍生晶体结构数据如图1所示，其结构式如下：
化合物2～34的制备方法同化合物1，投料比与化合物1相同，可得到化合物2～34，反应产率和熔点见表1，但需强调的是本发明的化合物不限于表1所表示的内容。
本实施例制备化合物2:淡黄色固体，核磁共振和高分辨质谱测试结果如下：1HNMR(CDCl3,400MHz)δ:2.92(s,3H),3.65(d,J=13.2Hz,1H),3.93(d,J=13.2Hz,1H),6.08(s,1H),6.46(d,J=8.0Hz,1H),6.62-6.66(m,1H),6.71(d,J=6.8Hz,3H),6.91-7.02(m,4H),7.59(d,J=7.6Hz,1H),7.71-7.75(m,1H),7.84-7.87(m,1H),8.09(d,J=7.6Hz,1H);13CNMR(CDCl3,100MHz)δ:25.9,36.3,55.5,108.7,122.2,123.5,123.6,124.6,125.3,126.5,127.5,127.8,129.1,129.9,130.3,134.5,136.5,136.6,140.6,141.4,144.0,177.3,196.4,198.2;HRMS(ESI)Calcd.forC25H19NNaO4[M+Na]+:420.1212;Found:420.1212。
采用本实施例制备化合物3:淡黄色固体，核磁共振和高分辨质谱测试结果如下：1HNMR(CDCl3,400MHz)δ:3.77(d,J=13.2Hz,1H),4.02(d,J=13.2Hz,1H),6.10(s,1H),6.31(d,J=8.0Hz,1H),6.67-6.71(m,1H),6.79-6.82(m,3H),6.91-7.03(m,5H),7.07-7.11(m,1H),7.35-7.45(m,3H),7.68(d,J=7.6Hz,1H),7.75-7.79(m,1H),7.86-7.90(m,1H),8.14(d,J=8.0Hz,1H);13CNMR(CDCl3,100MHz)δ:36.7,55.3,109.8,122.6,123.7,123.8,124.7,125.2,126.7,126.9,127.7,128.7,129.0,129.7,130.3,133.3,134.6,136.6,136.7,140.7,141.5,144.5,176.9,196.4,198.3;HRMS(ESI)Calcd.forC30H21NNaO4[M+Na]+:482.1368;Found:482.1369。
采用本实施例制备化合物4:白色固体，核磁共振和高分辨质谱测试结果如下：1HNMR(CDCl3,400MHz)δ:3.67(d,J=13.2Hz,1H),3.94(d,J=13.2Hz,1H),5.83(s,1H),6..55(d,J=8.0Hz,1H),6.62-6.66(m,1H),6.73-6.80(m,3H),6.94-7.02(m,4H),7.63(d,J=7.6Hz,1H),7.73-7.77(m,2H),7.84-7.88(m,1H),8.10(d,J=7.6Hz,1H);13CNMR(CDCl3,100MHz)δ:36.2,56.0,110.5,122.2,123.6,123.7,125.0,125.7,126.6,127.7,129.1,130.2,134.5,136.6,136.7,140.6,140.9,141.4,178.7,196.2,198.1;HRMS(ESI)Calcd.forC24H17NNaO4[M+Na]+:406.1055;Found:406.1055。
采用本实施例制备化合物5:黄色固体，核磁共振和高分辨质谱测试结果如下：1HNMR(CDCl3,400MHz)δ:2.97(s,3H),3.64(d,J=13.6Hz,1H),3.91(d,J=13.6Hz,1H),5.99(s,1H),6.51(d,J=7.6Hz,1H),6.64-6.67(m,3H),6.71(d,J=6.4Hz,1H),6.92(d,J=8.4Hz,2H),7.01-7.04(m,1H),7.60(d,J=7.6Hz,1H),7.73-7.77(m,1H),7.85-7.88(m,1H),8.09(d,J=7.6Hz,1H);13CNMR(CDCl3,100MHz)δ:25.9,35.5,55.4,108.9,122.3,123.5,123.6,124.5,127.7,129.2,131.3,132.5,133.2,136.5,136.6,140.6,141.4,144.0,177.0,196.2,198.0.HRMS(ESI)Calcd.forC25H18ClNNaO4[M+Na]+:454.0822;Found:454.0823。
采用本实施例制备化合物6:淡黄色固体，核磁共振和高分辨质谱测试结果如下：1HNMR(CDCl3,400MHz)δ:3.10(s,3H),3.92(d,J=14.0Hz,1H),4.33(d,J=14.0Hz,1H),5.98(s,1H),6.49-6.54(m,2H),6.77(d,J=7.2Hz,1H),6.91-6.97(m,3H),7.00-7.02(m,2H),7.57(d,J=7.6Hz,1H),7.70-7.74(m,1H),7.83-7.87(m,1H),8.10(d,J=7.6Hz,1H);13CNMR(CDCl3,100MHz)δ:26.2,31.9,55.3,108.3,121.9,123.4,123.6,124.3,125.8,126.0,128.0,129.1,129.3,130.9,133.4,134.8,136.5,140.5,141.4,143.6,177.6,196.1,198.0;HRMS(ESI)Calcd.forC25H18ClNNaO4[M+Na]+:454.0822;Found:454.0825。
采用本实施例制备化合物7:淡黄色固体，核磁共振和高分辨质谱测试结果如下：1HNMR(CDCl3,400MHz)δ:2.96(s,3H),3.63(d,J=13.6Hz,1H),3.92(d,J=13.6Hz,1H),6.03(s,1H),6.50(d,J=7.6Hz,1H),6.64-6.70(m,6H),7.02-7.05(m,1H),7.61(d,J=7.6Hz,1H),7.73-7.77(m,1H),7.85-7.89(m,1H),8.10(d,J=7.6Hz,1H);13CNMR(CDCl3,100MHz)δ:25.9,35.5,55.5,108.8,114.2,114.4,122.2,123.5,124.5,129.2,131.4,131.4,136.4,136.5,140.6,144.0,161.7(d,JCF=194.6Hz),177.1,196.2,198.0.HRMS(ESI)Calcd.forC25H18FNNaO4[M+Na]+:438.1118;Found:438.1118。
采用本实施例制备化合物8:淡黄色固体，核磁共振和高分辨质谱测试结果如下：1HNMR(CDCl3,400MHz)δ:2.97(s,3H),3.67(d,J=13.6Hz,1H),3.93(d,J=13.6Hz,1H),6.00(brs,1H),6.40(d,J=10.0Hz,1H),6.50-6.56(m,2H),6.66-6.72(m,3H),6.89-6.93(m,1H),7.01-7.05(m,1H),7.60(d,J=7.6Hz,1H),7.72-7.76(m,1H),7.85-7.88(m,1H),8.10(d,J=7.6Hz,1H);13CNMR(CDCl3,100MHz)δ:26.0,35.8,55,3,108.8,113.4,116.5,116.7,122.4,123.5,123.6,124.5,125.7,129.3,136.6,136.7,140.5,141.3,143.8,161.9(d,JCF=243.7Hz),177.0,196.2,198.0;HRMS(ESI)Calcd.forC25H18FNNaO4[M+Na]+:438.1118;Found:438.1119。
采用本实施例制备化合物9:淡黄色固体，核磁共振和高分辨质谱测试结果如下：1HNMR(CDCl3,400MHz)δ:3.11(s,3H),3.99(d,J=14.2Hz,1H),4.34(d,J=14.2Hz,1H),5.96(brs,1H),6.50-6.54(m,2H),6.81-6.84(m,2H),6.96-6.98(m,3H),7.23-7.26(m,1H),7.57(d,J=7.6Hz,1H),7.70-7.74(m,1H),7.84(d,J=7.1Hz,1H),8.10(d,J=7.5Hz,1H);13CNMR(CDCl3,100MHz)δ:26.2,34.4,55.3,108.4,121.9,123.4,123.6,124.3,125.8,126.0,126.6,128.2,129.1,130.7,132.8,135.3,136.5,140.5,141.5,143.7,177.6,196.1,198.0;HRMS(ESI)Calcd.forC25H18BrNNaO4[M+Na]+:498.0317;Found:498.0319。
采用本实施例制备化合物10:淡黄色固体，核磁共振和高分辨质谱测试结果如下：1HNMR(CDCl3,400MHz)δ:2.97(s,3H),3.65(d,J=13.6Hz,1H),3.89(d,J=13.6Hz,1H),6.00(s,1H),6.51(d,J=8.0Hz,1H),6.68-6.72(m,3H),6.81-6.85(m,2H),7.02-7.06(m,1H),7.12(d,J=8.0Hz,1H),7.61(d,J=7.6Hz,1H),7.73-7.77(m,1H),7.85-7.89(m,1H),8.10(d,J=7.6Hz,1H);13CNMR(CDCl3,100MHz)δ:25.9,35.9,55.3,108.9,121.4,122.4,123.5,123.6,124.5,124.8,128.67,129.0,129.3,129.6,132.7,136.6,136.7,136.9,140.5,141.3,143.8,177.0,196.2,198.0;HRMS(ESI)Calcd.forC25H18BrNNaO4[M+Na]+:498.0317;Found:498.0317。
采用本实施例制备化合物11:淡黄色固体，核磁共振和高分辨质谱测试结果如下：1HNMR(CDCl3,400MHz)δ:2.98(s,3H),3.62(d,J=13.2Hz,1H),3.89(d,J=13.2Hz,1H),5.97(s,1H),6.52(d,J=7.6Hz,1H),6.60(d,J=8.4Hz,2H),6.66-6.72(m,2H),7.02-7.08(m,3H),7.60(d,J=7.6Hz,1H),7.73-7.77(m,1H),7.85-7.89(m,1H),8.09(d,J=7.6Hz,1H);13CNMR(CDCl3,100MHz)δ:26.0,35.6,55.3,108.9,120.7,122.3,123.5,123.6,124.5,125.1,129.3,130.6,131.7,133.7,136.5,136.6,140.6,141.4,144.0,177.0,196.1,197.9;HRMS(ESI)Calcd.forC25H18BrNNaO4[M+Na]+:498.0317;Found:498.0318。
采用本实施例制备化合物12:淡黄色固体，核磁共振和高分辨质谱测试结果如下：1HNMR(CDCl3,400MHz)δ:2.95(s,3H),3.73(d,J=13.2Hz,1H),3.99(d,J=13.2Hz,1H),5.96(s,1H),6.51(d,J=7.6Hz,1H),6.66-6.69(m,1H),6.75(d,J=6.8Hz,1H),6.85(d,J=8.0Hz,2H),7.03-7.06(m,1H),7.21(d,J=8.0Hz,2H),7.61(d,J=7.6Hz,1H),7.74-7.77(m,1H),7.86-7.89(m,1H),8.10(d,J=7.6Hz,1H);13CNMR(CDCl3,100MHz)δ:25.9,36.0,55.3,108.9,122.4,123.6,123.7,124.4,124.5,124.8,129.4,130.3,136.6,136.7,138.9,140.5,141.3,143.9,176.8,196.2,197.9;HRMS(ESI)Calcd.forC26H18F3NNaO4[M+Na]+:488.1086;Found:488.1085。
采用本实施例制备化合物13:淡黄色固体，核磁共振和高分辨质谱测试结果如下：1HNMR(CDCl3,400MHz)δ:2.25(s,3H),2.97(s,3H),3.74(d,J=14.0Hz,1H),4.10(d,J=14.0Hz,1H),6.14-6.15(brs,1H),6.45(d,J=7.6Hz,1H),6.54(d,J=8.0Hz,1H),6.60-6.64(m,1H),6.69-6.71(m,2H),6.91(d,J=6.4Hz,2H),7.02-7.04(m,1H),7.59(d,J=7.6Hz,1H),7.72-7.76(m,1H),7.85-7.89(m,1H),8.11(d,J=7.6Hz,1H);13CNMR(CDCl3,100MHz)δ:20.1,26.0,32.0,55.4,108.7,122.0,123.4,123.6,124.8,125.8,126.6,129.1,129.5,130.2,133.4,136.4,136.5,137.3,140.7,141.4,144.2,177.6,196.4,198.2;HRMS(ESI)Calcd.forC26H21NNaO4[M+Na]+:434.1368;Found:434.1368。
采用本实施例制备化合物14:淡黄色固体，核磁共振和高分辨质谱测试结果如下：1HNMR(CDCl3,400MHz)δ:2.06(s,3H),2.94(s,3H),3.62(d,J=13.2Hz,1H),3.89(d,J=13.2Hz,1H),6.11-6.12(brs,1H),6.46-6.52(m,3H),6.62-6.71(m,2H),6.78-6.82(m,2H),6.98-7.02(m,1H),7.60(d,J=7.6Hz,1H),7.72-7.76(m,1H),7.84-7.88(m,1H),8.10(d,J=7.6Hz,1H);13CNMR(CDCl3,100MHz)δ:21.0,25.9,36.2,55.5,108.6,122.1,123.5,123.6,124.6,126.9,127.2,127.3,129.0,130.7,134.3,136.5,136.6,136.9,140.5,141.3,143.9,177.3,196.4,198.3;HRMS(ESI)Calcd.forC26H21NNaO4[M+Na]+:434.1368;Found:434.1369。
采用本实施例制备化合物15:淡黄色固体，核磁共振和高分辨质谱测试结果如下：1HNMR(CDCl3,400MHz)δ:2.13(s,3H),2.95(s,3H),3.60(d,J=13.6Hz,1H),3.90(d,J=13.6Hz,1H),6.10(brs,1H),6.48(d,J=8.0Hz,1H),6.58-6.65(m,3H),6.69-6.75(m,3H),6.99-7.01(m,1H),7.58(d,J=7.6Hz,1H),7.71-7.75(m,1H),7.84-7.88(m,1H),8.09(d,J=7.6Hz,1H);13CNMR(CDCl3,100MHz)δ:20.9,25.9,35.8,55.6,108.6,122.1,123.4,123.5,124.6,125.5,128.2,128.9,129.8,131.4,135.9,136.4,136.5,140.6,141.4,144.0,177.3,196.3,198.2;HRMS(ESI)Calcd.forC26H21NNaO4[M+Na]+:434.1368;Found:434.1367。
采用本实施例制备化合物16:淡黄色固体，核磁共振和高分辨质谱测试结果如下：1HNMR(CDCl3,400MHz)δ:2.95(s,3H),3.58(d,J=13.6Hz,1H),3.64(s,3H),3.88(d,J=13.6Hz,1H),6.09(brs,1H),6.47-6.53(m,3H),6.62-6.70(m,4H),6.99-7.03(m,1H),7.59(d,J=7.6Hz,1H),7.72-7.75(m,1H),7.84-7.88(m,1H),8.09(d,J=7.6Hz,1H);13CNMR(CDCl3,100MHz)δ:25.9,35.4,55.0,55.6,108.7,112.9,122.2,123.5,123.6,124.5,125.4,126.4,129.0,130.9,136.5,136.6,140.5,141.3,143.9,158.1,177.3,196.4,198.2.HRMS(ESI)Calcd.forC26H21NNaO5[M+Na]+:450.1317;Found:450.1318。
采用本实施例制备化合物17:淡黄色固体，核磁共振和高分辨质谱测试结果如下：1HNMR(CDCl3,400MHz)δ:3.05(s,3H),3.38(s,3H),3.66(d,J=13.6Hz,1H),4.21(d,J=13.6Hz,1H),6.09(brs,1H),6.39-6.48(m,3H),6.61-6.65(m,2H),6.91-6.95(m,2H),7.00-7.03(m,1H),7.55(d,J=7.6Hz,1H),7.69-7.72(m,1H),7.82-7.86(m,1H),8.09(d,J=8.0Hz,1H);13CNMR(CDCl3,100MHz)δ:26.0,28.8,30.9,54.4,108.0,109.5,119.6,121.2,123.3,125.0,125.9,127.8,128.5,131.0,136.4,136.4,140.5,141.4,143.7,157.3,178.0,196.3,198.3;HRMS(ESI)Calcd.forC26H21NNaO5[M+Na]+:450.1317;Found:450.4318。
采用本实施例制备化合物18:淡黄色固体，核磁共振和高分辨质谱测试结果如下：1HNMR(CDCl3,400MHz)δ:1.08(d,J=4.0Hz,6H),2.67-2.72(m,1H),2.90(s,3H),3.59(d,J=13.2Hz,1H),3.91(d,J=13.2Hz,1H),6.14(brs,1H),6.46(d,J=7.6Hz,1H),6.60-6.70(m,4H),6.79(d,J=8.4Hz,2H),7.00-7.02(m,1H),7.60(d,J=7.6Hz,1H),7.72-7.76(m,1H),7.84-7.88(m,1H),8.10(d,J=7.6Hz,1H);13CNMR(CDCl3,100MHz)δ:23.8,23.9,25.8,33.5,36.0,55.5,108.6,122.1,123.5,123.6,124.5,125.4,129.0,129.7,131.6,136.5,136.6,140.5,141.3,144.0,147.0,177.3,196.4,198.3;HRMS(ESI)Calcd.forC28H25NNaO4[M+Na]+:462.1681;Found:462.1680。
采用本实施例制备化合物19:淡黄色固体，核磁共振和高分辨质谱测试结果如下：1HNMR(CDCl3,400MHz)δ:1.15(s,9H),2.89(s,3H),3.59(d,J=13.2Hz,1H),3.91(d,J=13.2Hz,1H),6.14-6.15(brs,1H),6.46(d,J=7.6Hz,1H),6.60-6.67(m,3H),6.70(d,J=6.4Hz,1H),6.95(d,J=8.4Hz,2H),7.00-7.04(m,1H),7.59(d,J=7.6Hz,1H),7.72-7.75(m,1H),7.84-7.88(m,1H),8.10(d,J=7.6Hz,1H);13CNMR(CDCl3,100MHz)δ:25.8,31.2,34.2,36.0,55.5,108.6,122.1,123.5,123.6,124.2,124.6,125.6,129.0,129.5,131.3,136.5,136.6,140.6,141.4,144.0,149.4,177.3,196.3,198.3;HRMS(ESI)Calcd.forC29H27NNaO4[M+Na]+:476.1838;Found:476.1838。
采用本实施例制备化合物20:淡黄色固体，核磁共振和高分辨质谱测试结果如下：1HNMR(CDCl3,400MHz)δ:3.05(s,3H),3.33(s,3H),3.61(d,J=14.0Hz,1H),3.64(s,3H),4.09(d,J=14.0Hz,1H),5.98(d,J=2.4Hz,1H),6.09(brs,1H),6.17-6.20(m,1H),6.45-6.51(m,2H),6.61(d,J=7.2Hz,1H),6.90-6.94(m,2H),7.54(d,J=7.6Hz,1H),7.68-7.72(m,1H),7.81-7.85(m,1H),8.08(d,J=7.6Hz,1H);13CNMR(CDCl3,100MHz)δ:26.0,28.3,30.9,54.4,55.1,97.5,103.3,108.0,115.8,121.1,123.5,125.9,128.5,131.5,136.3,136.4,140.5,141.4,143.7,158.2,159.4,178.0,196.3,198.4;HRMS(ESI)Calcd.forC27H23NNaO6[M+Na]+:480.1423;Found:480.1424。
采用本实施例制备化合物21:淡黄色固体，核磁共振和高分辨质谱测试结果如下：1HNMR(CDCl3,400MHz)δ:3.07(s,3H),3.38(s,3H),3.60(s,3H),3.67(d,J=13.2Hz,1H),4.14(d,J=13.2Hz,1H),6.02(brs,1H),6.35(d,J=8.8Hz,1H),6.46-6.56(m,4H),6.63(d,J=6.8Hz,1H),6.90-6.94(m,1H),7.55(d,J=7.6Hz,1H),7.69-7.72(m,1H),7.81-7.85(m,1H),8.08(d,J=7.6Hz,1H);13CNMR(CDCl3,100MHz)δ:26.0,28.8,30.9,55.1,55.6,108.0,110.6,113.1,116.0,121.3,123.3,123.5,125.8,128.6,136.3,136.4,140.5,141.3,143.7,151.6,152.6,177.8,196.2,198.3;HRMS(ESI)Calcd.forC27H23NNaO6[M+Na]+:480.1423;Found:480.1425。
采用本实施例制备化合物22:白色固体，核磁共振和高分辨质谱测试结果如下：1HNMR(CDCl3,400MHz)δ:2.93(s,3H),3.45(s,3H),3.58(d,J=13.2Hz,1H),3.72(s,3H),3.88(d,J=13.2Hz,1H),6.03(d,J=0.8Hz,2H),6.41-6.44(m,1H),6.48-6.52(m,2H),6.67(d,J=7.6Hz,1H),6.73(d,J=6.8Hz,1H),7.00-7.04(m,1H),7.60(d,J=7.6Hz,1H),7.72-7.76(m,1H),7.84-7.87(m,1H),8.09(d,J=7.6Hz,1H);13CNMR(CDCl3,100MHz)δ:25.9,30.9,35.9,55.3,55.6,108.9,110.1,112.5,122.1,122.3,123.5,123.6,124.5,125.6,126.8,129.0,136.5,136.6,140.5,141.3,144.1,147.4,177.3,196.3,198.2;HRMS(ESI)Calcd.forC27H23NNaO6[M+Na]+:480.1423;Found:480.1424。
采用本实施例制备化合物23:淡黄色固体，核磁共振和高分辨质谱测试结果如下：1HNMR(CDCl3,400MHz)δ:3.10(s,3H),3.62(s,3H),3.67-3.74(m,4H),4.16(d,J=13.6Hz,1H),5.93(s,1H),6.46-6.54(m,4H),6.66-6.70(m,2H),6.87-6.91(m,1H),7.52(d,J=7.6Hz,1H),7.66-7.70(m,1H),7.79-7.83(m,1H),8.05(d,J=7.6Hz,1H);13CNMR(CDCl3,100MHz)δ:26.2,28.2,30.9,55.6,60.5,108.1,111.1,122.0,122.2,123.0,123.2,123.4,125.7,128.7,129.5,136.4,140.4,141.3,143.5,147.7,152.3,177.8,196.3,198.2;HRMS(ESI)Calcd.forC27H23NNaO6[M+Na]+:480.1423;Found:480.1425。
采用本实施例制备化合物24:淡黄色固体，核磁共振和高分辨质谱测试结果如下：1HNMR(CDCl3,400MHz)δ:3.08(s,3H),3.43(s,3H),3.63(d,J=13.6Hz,1H),3.67(s,3H),3.68(s,3H),4.08(d,J=13.6Hz,1H),5.96(brs,1H),6.31(d,J=8.8Hz,1H),6.45-6.50(m,2H),6.59-6.66(m,2H),6.88-6.91(m,1H),7.54(d,J=7.6Hz,1H),7.67-7.71(m,1H),7.80-7.84(m,1H),8.06(d,J=7.6Hz,1H);13CNMR(CDCl3,100MHz)δ:26.1,28.5,55.5,55.8,60.5,60.6,106.2,108.0,121.3,121.6,123.3,123.5,124.6,124.8,126.0,128.5,136.4,136.4,140.4,141.3,143.6,152.1,152.2,178.0,196.3,198.2;HRMS(ESI)Calcd.forC28H25NNaO7[M+Na]+:10.1529;Found:10.1530。
采用本实施例制备化合物25:淡黄色固体，核磁共振和高分辨质谱测试结果如下：1HNMR(CDCl3,400MHz)δ:3.05(s,3H),3.44(s,3H),3.63(s,3H),3.68(s,1H),3.71(d,J=13.6Hz,1H),4.02(d,J=13.6Hz,1H),6.11(s,1H),6.45-6.54(m,3H),6.66(d,J=6.8Hz,1H),6.92-6.96(m,1H),7.56(d,J=7.6Hz,1H),7.69-7.73(m,1H),7.81-7.85(m,1H),8.08(d,J=7.6Hz,1H);13CNMR(CDCl3,100MHz)δ:26.0,28.2,30.9,55.6,55.7,56.1,96.4,108.1,114.0,114.6,121.4,123.3,123.5,125.3,125.6,128.6,136.3,136.4,140.5,141.3,141.9,143.8,147.9,151.6,177.9,196.3,198.3;HRMS(ESI)Calcd.forC28H25NNaO7[M+Na]+:10.1529;Found:10.1529。
采用本实施例制备化合物26:淡黄色固体，核磁共振和高分辨质谱测试结果如下：1HNMR(CDCl3,400MHz)δ:2.95(s,3H),3.53(s,6H),3.59(d,J=13.6Hz,1H),3.68(s,3H),3.86(d,J=13.6Hz,1H),5.91(s,2H),6.01(brs,1H),6.51(d,J=8.0Hz,1H),6.65-6.69(m,1H),6.73(d,J=7.2Hz,1H),7.01-7.05(m,1H),7.62(d,J=7.6Hz,1H),7.73-7.77(m,1H),7.85-7.88(m,1H),8.09(d,J=7.6Hz,1H);13CNMR(CDCl3,100MHz)δ:25.9,30.9,36.6,55.5,55.8,60.7,106.7,108.9,122.0,123.5,123.6,124.4,125.6,129.1,130.0,136.5,136.7,140.5,141.3,144.2,152.1,177.2,196.3,198.1;HRMS(ESI)Calcd.forC28H25NNaO7[M+Na]+:10.1529;Found:10.1529。
采用本实施例制备化合物27:淡黄色固体，核磁共振和高分辨质谱测试结果如下：1HNMR(CDCl3,400MHz)δ:2.10(s,3H),2.20(s,3H),2.98(s,3H),3.68(d,J=14.0Hz,1H),4.06(d,J=14.0Hz,1H),6.16(s,1H),6.34(d,J=8.0Hz,1H),6.51-6.56(m,2H),6.59-6.63(m,1H),6.68-6.73(m,2H),7.02-7.06(m,1H),7.58(d,J=7.6Hz,1H),7.71-7.75(m,1H),7.84-7.87(m,1H),8.10(d,J=7.6Hz,1H);13CNMR(CDCl3,100MHz)δ:20.0,20.8,26.0,31.5,55.4,108.7,122.0,123.4,123.6,124.8,125.6,125.7,129.1,129.4,130.2,131.0,135.9,136.5,136.6,137.0,140.6,141.4,144.1,177.7,196.4,198.3;HRMS(ESI)Calcd.forC27H23NNaO4[M+Na]+:448.1525;Found:448.1526。
采用本实施例制备化合物28:淡黄色固体，核磁共振和高分辨质谱测试结果如下：1HNMR(CDCl3,400MHz)δ:3.12(s,3H),3.90(d,J=14.4Hz,1H),4.28(d,J=14.4Hz,1H),5.88(s,1H),6.54-6.58(m,2H),6.76(d,J=7.6Hz,1H),6.93-7.01(m,3H),7.05(d,J=2.0Hz,1H),7.58(d,J=7.6Hz,1H),7.71-7.75(m,1H),7.84-7.87(m,1H),8.10(d,J=8.0Hz,1H);13CNMR(CDCl3,100MHz)δ:26.2,31.3,55.1,108.6,122.0,123.4,123.6,124.0,125.7,126.3,129.1,129.3,131.8,132.0,133.0,135.5,136.6,136.6,140.4,141.3,143.5,177.3,196.1,197.9;HRMS(ESI)Calcd.forC25H17Cl2NNaO4[M+Na]+:488.0432;Found:488.0431。
采用本实施例制备化合物29:淡黄色固体，核磁共振和高分辨质谱测试结果如下：1HNMR(CDCl3,400MHz)δ:3.12(s,3H),3.97(d,J=14.0Hz,1H),4.41(d,J=14.0Hz,1H),5.89(brs,1H),6.52-6.57(m,2H),6.75(d,J=7.6Hz,1H),6.86-6.90(m,1H),6.97-7.01(m,2H),7.11-7.13(m,1H),7.57(d,J=7.6Hz,1H),7.71-7.73(m,1H),7.84-7.86(m,1H),8.10(d,J=7.6Hz,1H);13CNMR(CDCl3,100MHz)δ:26.2,32,7,55.2,108.5,122.1,123.4,123.6,123.9,125.7,126.3,128.9,129.1,129.3,132.8,135.9,136.6,136.7,140.4,141.4,143.5,177.4,196.1,197.9;HRMS(ESI)Calcd.forC25H17Cl2NNaO4[M+Na]+:488.0432;Found:488.0433。
采用本实施例制备化合物30:淡黄色固体，核磁共振和高分辨质谱测试结果如下：1HNMR(CDCl3,400MHz)δ:0.38(t,J=7.4Hz,3H),2.30-2.35(m,1H),2.58-2.63(m,1H),3.21(s,3H),5.59(s,1H),6.48(d,J=7.2Hz,1H),6.54-6.58(m,1H),6.71(d,J=7.6Hz,1H),7.01-7.06(m,1H),7.48(d,J=7.6Hz,1H),7.61-7.65(m,1H),7.73-7.76(m,1H),7.95(d,J=7.6Hz,1H);13CNMR(CDCl3,100MHz)δ:7.8,23.0,26.3,55.3,78.3,108.8,122.5,123.2,123.4,124.2,125.6,129.0,136.4,136.5,140.4,141.3,144.3,177.9,196.2,198.4;HRMS(ESI)Calcd.forC20H17NNaO4[M+Na]+:358.1055;Found:358.1057。
采用本实施例制备化合物31:淡红色固体，核磁共振和高分辨质谱测试结果如下：1HNMR(DMSO-d6,400MHz)δ:3.61(s,2H),6.41(d,J=8.4Hz,1H),6.75-6.77(m,2H),6.94-7.02(m,3H),7.24-7.27(1H),7.75-7.82(m,2H),7.91-7.93(m,1H),8.01(d,J=4.0Hz,2H),10.3(brs,1H);13CNMR(DMSO-d6,100MHz)δ:36.2,60.5,111.3,113.5,123.4,126.8,128.0,129.8,130.4,131.2,131.3,135.8,136.7,137.5,139.9,141.4,141.9,175.8,197.5,199.5;HRMS(ESI)Calcd.forC24H16BrNNaO4[M+Na]+:484.0160;Found:484.0160。
采用本实施例制备化合物32:淡黄色固体，核磁共振和高分辨质谱测试结果如下：1HNMR(CDCl3,400MHz)δ:1.94(s,3H),2.89(s,3H),3.58(d,J=13.6Hz,1H),3.92(d,J=13.6Hz,1H),6.13(s,1H),6.34(d,J=8.0Hz,1H),6.47(s,1H),6.70-6.73(m,2H),6.77-6.79(m,1H),6.92-6.99(m,3H),7.57(d,J=7.6Hz,1H),7.71-7.75(m,1H),7.84-7.87(m,1H),8.10(d,J=8.0Hz,1H);13CNMR(CDCl3,100MHz)δ:20.7,25.9,36.1,55.5,108.4,123.4,123.5,125.1,125.4,126.5,127.4,129.3,129.9,131.7,134.6,136.3,136.5,140.5,141.4,141.5,177.0,196.4,198.2;HRMS(ESI)Calcd.forC26H21NNaO4[M+Na]+:434.1368;Found:434.1367。
采用本实施例制备化合物33:淡黄色固体，核磁共振和高分辨质谱测试结果如下：1HNMR(CDCl3,400MHz)δ:3.02(s,3H),3.90(d,J=14.4Hz,1H),4.19(d,J=14.4Hz,1H),5.88(s,1H),6.50(d,J=2.8Hz,1H),6.57(d,J=8.0Hz,1H),6.64-6.72(m,3H),6.84-6.86(m,1H),7.05-7.09(m,1H),7.59(d,J=8.0Hz,1H),7.71-7.75(m,1H),7.83-7.87(m,1H),8.07(d,J=7.6Hz,1H);13CNMR(CDCl3,100MHz)δ:26.1,30.7,55.3,108.9,122.5,123.5,123.6,124.4,124.5,125.2,126.1,127.2,129.4,136.1,136.6,136.7,140.5,141.3,144.4,177.0,196.2,197.9;HRMS(ESI)Calcd.forC23H17NNaO4S[M+Na]+:426.0776;Found:426.0776。
采用本实施例制备化合物34:淡黄色固体，核磁共振和高分辨质谱测试结果如下：1HNMR(CDCl3,400MHz)δ:3.28(s,3H),3.65(d,J=13.6Hz,1H),3.92(d,J=13.6Hz,1H),5.96(s,1H),6.56-6.60(m,1H),6.67-6.70(m,3H),6.93-7.04(m,4H),7.67(d,J=7.6Hz,1H),7.75-7.79(m,1H),7.85-7.89(m,1H),8.08(d,J=8.0Hz,1H);13CNMR(CDCl3,100MHz)δ:29.3,36.6,55.4,116.0,122.9,123.0,123.6,123.7,126.8,127.6,128.2,129.8,131.4,134.0,136.7,136.8,140.0,140.4,141.3,177.6,196.1,197.9;HRMS(ESI)Calcd.forC25H18ClNNaO4[M+Na]+:454.0822;Found:454.0823.
化合物34的X衍生晶体结构数据如图2所示，其结构式如下：
本发明的实施例2：化合物1:在圆底烧瓶中，依次加入茚三酮0.3mmol(53.4mg)，N-苄基-3-苄基取代氧化吲哚0.4mmol(125.2mg)，DABCO3.4mg（10mmol%），再加入6.0mL二氯甲烷，充分搅拌，室温反应至原料反应结束（2小时）。
减压蒸馏除掉溶剂，残留油状物硅胶柱层析（300-400目）分离（石油醚：乙酸乙酯=3：1），得到淡黄色固体。产率：97%。
采用本实施例制备，投料比与化合物1相同，可分别得到化合物2（产率91%），化合物3（产率92%），化合物4（产率93%），化合物5（产率94%），化合物6（产率97%），化合物7（产率95%），化合物8（产率97%），化合物9（产率96%），化合物10（产率97%），化合物11（产率96%），化合物12（产率96%），化合物13（产率98%），化合物14（产率96%），化合物15（产率94%），化合物16（产率97%），化合物17（产率95%），化合物18（产率93%），化合物19（产率97%），化合物20（产率90%），化合物21（产率95%），化合物22（产率92%），化合物23（产率96%），化合物24（产率80%），化合物25（产率92%），化合物26（产率93%），化合物27（产率97%），化合物28（产率95%），化合物29（产率94%），化合物30（产率90%），化合物31（产率89%），化合物32（产率85%），化合物33（产率93%）,化合物34（产率93%）。
本发明的实施例3：化合物1:在圆底烧瓶中，依次加入茚三酮0.3mmol(53.4mg)，N-苄基-3-苄基取代氧化吲哚0.4mmol(125.2mg)，Na2CO33.2mg（10mmol%），再加入6.0mL乙醇，充分搅拌，室温反应至原料反应结束（2小时）。
减压蒸馏除掉溶剂，残留油状物硅胶柱层析（300-400目）分离（石油醚：乙酸乙酯=3：1），得到淡黄色固体。产率：95%。
采用本实施例制备，投料比与化合物1相同，可分别得到化合物2（产率92%），化合物3（产率93%），化合物4（产率92%），化合物5（产率95%），化合物6（产率97%），化合物7（产率95%），化合物8（产率97%），化合物9（产率94%），化合物10（产率95%），化合物11（产率94%），化合物12（产率94%），化合物13（产率92%），化合物14（产率94%），化合物15（产率95%），化合物16（产率94%），化合物17（产率95%），化合物18（产率91%），化合物19（产率95%），化合物20（产率91%），化合物21（产率94%），化合物22（产率93%），化合物23（产率94%），化合物24（产率79%），化合物25（产率90%），化合物26（产率93%），化合物27（产率94%），化合物28（产率95%），化合物29（产率92%），化合物30（产率95%），化合物31（产率84%），化合物32（产率87%），化合物33（产率91%）,化合物34（产率91%）。

Claims (2)

1.一种氧化吲哚与茚三酮双季碳拼接衍生物，其特征在于：该化合物具有如下通式（1）-（34）其中之一的所示的结构：
。
2.一种如权利要求1所述的氧化吲哚与茚三酮双季碳拼接衍生物的制备方法，其特征在于：将氧化吲哚与水合茚三酮在碱性催化剂条件下，按摩尔比为4:3的比例在水中或有机溶剂中进行羟醛缩合反应，获得氧化吲哚与茚三酮双季碳拼接衍生物；在水中进行反应时，加入表面活性剂，表面活性剂的加入量是氧化吲哚摩尔量的1-100%；所述的表面活性剂为季铵盐或磺酸盐；所述的季铵盐为四丁基溴化铵、十六烷基三甲基溴化胺或四丁基硫酸氢铵；所述的磺酸盐为十二烷基磺酸钠；所述的碱性催化剂为有机碱或无机碱，碱性催化剂的加入量为氧化吲哚摩尔量的1-100%；所述的有机碱为DBU、DMAP、DABCO或Et3N；所述的无机碱为Na2CO3；所述的有机溶剂为乙腈、甲醇、乙醇、丙醇、异丙醇、乙醚、四氢呋喃、苯、甲苯、二甲苯、三甲苯、二氧六环、乙二醇二甲醚、异丙醚、氯仿、二氯甲烷或硝基苯；氧化吲哚与水合茚三酮的反应温度为25-100℃，反应时间为3-10小时。
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