CN109232585A - 一种多取代嘧啶并二吲哚酮衍生物的制备方法 - Google Patents

一种多取代嘧啶并二吲哚酮衍生物的制备方法 Download PDF

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CN109232585A
CN109232585A CN201811441040.4A CN201811441040A CN109232585A CN 109232585 A CN109232585 A CN 109232585A CN 201811441040 A CN201811441040 A CN 201811441040A CN 109232585 A CN109232585 A CN 109232585A
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indolone derivatives
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CN109232585B (zh
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李明
张林宝
朱明辉
文丽荣
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Shoujian Technology Co ltd
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    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains three hetero rings
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Abstract

本发明公开了属于有机合成技术领域的一种多取代嘧啶并二吲哚酮衍生物的制备方法。所述方法为：向反应容器中，先后加入取代N‑甲氧基吲哚甲酰胺，取代3‑甲基吲哚，叔戊酸银和甲酸钠，加入溶剂六氟异丙醇，油浴100℃搅拌至反应1小时完毕后，使用旋转蒸发仪浓缩滤液得到粗产物，粗产物用硅胶柱层析分离得到目标化合物。本发明提供的多取代嘧啶并二吲哚酮衍生物的合成方法具有科学合理，方法简单，目标化合物产率较高，产物易于纯化等特点。其反应方程式如下：

Description

一种多取代嘧啶并二吲哚酮衍生物的制备方法
技术领域
本发明属于有机合成技术领域，具体涉及一种多取代嘧啶并二吲哚酮衍生物的制备方法。
背景技术
吲哚及其衍生物作为重要的杂环生物碱，大多具有显著的生理活性。目前，已上市的含吲哚结构的药物如：吲哚心安为受体阻断剂药，用于治疗心率失常、心绞痛和高血压。吲哚布芬为抗凝血药，具有显著的抗凝血性能。吲哚美辛为治疗风湿性疾病和多种关节炎的非甾体消炎药(J Nat Prod，1998，57(8):1053-1071.)。此外吲哚乙酸、吲哚-3-丁酸等是重要的植物生长调节剂(有机化学,2006,26:563-567)，能促进植物根和茎生长。3-二甲胺基吲哚是一类植物源农药，除对繁缕属杂草具有很强的抑制作用外(农药,2004,13:76)，还能使昆虫产生拒食性，具有开发为杀虫剂的潜力。
嘧啶酮类化合物也是一类重要的杂环化合物在很多领域都具有很好的应有前景，例如，抗癌和抗菌活性(J.Med.Chem.1987,30,1256-1261)。
作为嘧啶酮和吲哚两种含氮杂环的结合，嘧啶并二吲哚酮衍生物很可能具有这两种化合物的优势。鉴于嘧啶并二吲哚酮衍生物的广泛的生物活性和应用价值，发展一种实用有效地合成多取代嘧啶并二吲哚酮衍生物的新方法具有重要意义。
发明内容
本发明提供了一种多取代嘧啶并二吲哚酮衍生物的制备方法。
一种多取代嘧啶并二吲哚酮衍生物的制备方法，所述嘧啶并二吲哚酮衍生物具有式Ⅰ所示的结构：
R1取代基团选自氟、氯、溴、碘、甲氧基、甲基；R2选自甲基、乙基、异丙基、苄基；其特征在于，向反应器中，加入取代N-甲氧基吲哚甲酰胺，取代3-甲基吲哚，叔戊酸银和甲酸钠。在溶剂中搅拌反应完毕后，使用旋转蒸发仪浓缩得到粗产物，粗产物使用硅胶柱层析分离得到目标产物，其化学过程见反应式Ⅱ：
所述的取代N-甲氧基吲哚甲酰胺、取代3-甲基吲哚、叔戊酸银、和甲酸钠的摩尔比值为1：2：2：4。所述溶剂为六氟异丙醇,反应温度为100℃，反应时间为1h。
本发明的有益效果为：本发明提供的嘧啶并二吲哚酮衍生物的合成方法科学合理，提供了一种合成多取代嘧啶并二吲哚酮的新途径，通过本方法得到了具有多种取代基的嘧啶并二吲哚酮衍生物，其特点为：方法简单，目标化合物收率较高，产品易于纯化。
附图说明
图1为实施例1制备的化合物3aa的NMR图谱；
图2为实施例3制备的化合物3ca的NMR图谱；
图3为实施例7制备的化合物3ab的NMR图谱。
具体实施方式
下面结合附图和具体的实施例对本发明进一步详细的说明：
下述实施例中所述试验方法，如无特殊说明，均为常规方法；所述试剂和材料，如无特殊说明，均可从商业途径获得。
实施例1
1)嘧啶并二吲哚酮衍生物3aa的制备
向15mL厚壁耐压管中加入N-甲氧基吲哚甲酰胺1a(0.1mmol,38.0mg)、2a(0.2mmol,29.0mg)，叔戊酸银(0.2mmol,41.2mg)和甲酸钠(0.4mmol，27.2mg)加入六氟异丙醇(4mL)，在100℃的油浴中搅拌，反应1小时。反应完毕后，使用旋转蒸发仪除去溶剂得到粗产物，粗产物经柱层析分离(200-300目硅胶)(石油醚/乙酸乙酯＝15/1)，使用旋转蒸发仪除去溶剂，得到目标产物无取代嘧啶并二吲哚酮3aa，其收率为97％。
谱图解析数据3aa:
1H NMR(500MHz,CDCl3):δ8.48(d,J＝8.3Hz,1H),7.61(d,J＝7.8Hz,1H),7.46(d,J＝7.3Hz,1H),7.41–7.24(m,3H),6.94(t,J＝7.4Hz,1H),6.73(d,J＝7.9Hz,1H),6.70(s,1H),4.13(s,1H),3.34(s,3H),2.83(s,3H),1.73(s,3H).13C NMR(125MHz,CDCl3):δ152.2,150.2,136.0,130.2,129.0,128.7,128.3,125.1,124.9,123.1,120.5,119.5,115.9,109.3,69.5,69.1,64.2,33.5,18.4.HRMS(ESI-TOF,[M+Na]+):For C20H19N3O2,356.1375,Found:356.1374.
实施例2
用1b代替实例1中的1a,其他条件同实例1,实验结果见表1。
谱图解析数据3ba:
1H NMR(400MHz,CDCl3):δ8.42(dd,J＝9.1,4.7Hz,1H),7.47–7.43(m,1H),7.37–7.31(m,1H),7.27–7.22(m,1H),7.10(td,J＝9.2,2.6Hz,1H),6.94(td,J＝7.5,0.8Hz,1H),6.73(d,J＝7.9Hz,1H),6.65(s,1H),4.11(s,1H),3.33(s,3H),2.83(s,3H),1.73(s,3H).13CNMR(125MHz,CDCl3):δ160.4,158.5,152.1,150.0,132.3,130.4,130.3,129.8,129.7,128.2,124.9,119.6,116.9,116.8,113.1,112.9,109.3,108.8,106.0,105.9,69.3,64.3,33.6,18.4.HRMS(ESI-TOF,[M+H]+):For C20H18FN3O2,352.1461,Found:352,1462.
实施例3
用1c代替实例1中的1a,其他条件同实例1,实验结果见表1。
谱图解析数据3ca:
1H NMR(500MHz,CDCl3):δ8.40(d,J＝8.8Hz,1H),7.57(d,J＝1.8Hz,1H),7.45(d,J＝7.4Hz,1H),7.33(m,2H),6.94(t,J＝7.5Hz,1H),6.73(d,J＝7.9Hz,1H),6.64(s,1H),4.11(s,1H),3.32(s,3H),2.82(s,3H),1.73(s,3H).13C NMR(125MHz,CDCl3):δ152.2,149.9,134.3,130.3,130.2,130.2,128.8,128.2,125.3,125.0,120.1,119.7,116.9,109.4,108.4,69.4,64.3,33.6,18.5.HRMS(ESI-TOF,[M+H]+):For C20H18ClN3O2,368.1166,Found:368.1161.
实施例4
用1d代替实例1中的1a,其他条件同实例1,实验结果见表1。
谱图解析数据3da:
1H NMR(500MHz,CDCl3):δ8.35(d,J＝8.8Hz,1H),7.74(s,1H),7.46(t,J＝7.4Hz,2H),7.34(t,J＝7.6Hz,1H),6.94(t,J＝7.4Hz,1H),6.73(d,J＝7.9Hz,1H),6.63(s,1H),4.11(s,1H),3.32(s,3H),2.82(s,3H),1.73(s,3H).13C NMR(125MHz,CDCl3):δ152.1,149.8,134.6,130.6,130.3,130.0,128.1,127.9,124.9,123.2,119.6,117.2,116.4,109.4,108.2,69.3,64.3,33.6,18.5.HRMS(ESI-TOF,[M+H]+):For C20H18BrN3O2,412.0661,Found:412,0651.
实施例5
用1e代替实例1中的1a,其他条件同实例1,实验结果见表1。
谱图解析数据3ea:
1H NMR(400MHz,CDCl3):δ8.24(d,J＝8.7Hz,1H),7.95(d,J＝1.5Hz,1H),7.64(dd,J＝8.7,1.7Hz,1H),7.48–7.42(m,1H),7.34(td,J＝7.8,1.3Hz,1H),6.94(td,J＝7.5,0.8Hz,1H),6.72(d,J＝7.9Hz,1H),6.61(s,1H),4.11(s,1H),3.32(s,3H),2.81(s,3H),1.73(s,3H).13C NMR(125MHz,CDCl3):δ152.1,149.9,135.2,133.6,131.3,130.4,129.7,129.4,128.1,125.0,119.7,117.7,109.4,108.0,100.0,87.2,69.3,64.3,33.7,18.5.HRMS(ESI-TOF,[M+H]+):For C20H18IN3O2,460.0522,Found:460.0516.
实施例6
用1f代替实例1中的1a,其他条件同实例1,实验结果见表1。
谱图解析数据3fa:
1H NMR(500MHz,CDCl3):δ8.35(d,J＝9.0Hz,1H),7.44(d,J＝7.4Hz,1H),7.33(t,J＝7.7Hz,1H),7.05(s,1H),7.00(d,J＝10.2Hz,1H),6.93(t,J＝7.4Hz,1H),6.72(d,J＝7.9Hz,1H),6.61(s,1H),4.10(s,1H),3.87(s,3H),3.33(s,3H),2.83(s,3H),1.72(s,3H).13C NMR(125MHz,CDCl3):δ156.2,152.2,150.2,130.7,130.2,129.8,129.3,128.4,124.9,119.5,116.5,113.8,109.3,109.0,103.1,69.5,69.2,64.3,55.7,33.5,18.3.HRMS(ESI-TOF,[M+Na]+):For C21H21N3O3,386.1481,Found:386.1483.
实施例7
用1g代替实例1中的1a,其他条件同实例1,实验结果见表1。
谱图解析数据3ga:
1H NMR(400MHz,CDCl3):δ8.33(d,J＝8.5Hz,1H),7.47–7.42(m,1H),7.38(s,1H),7.33(td,J＝7.7,1.3Hz,1H),7.20(dd,J＝8.5,1.3Hz,1H),6.93(td,J＝7.5,0.8Hz,1H),6.72(d,J＝7.9Hz,1H),6.61(s,1H),4.10(s,1H),3.33(s,3H),2.82(s,3H),2.46(s,3H),1.72(s,3H).13C NMR(100MHz,CDCl3):δ152.2,150.4,134.2,132.7,130.2,129.3,128.8,128.5,126.5,124.9,120.4,119.5,115.5,109.3,109.0,69.6,69.2,64.3,33.6,21.4,18.4.HRMS(ESI-TOF,[M+Na]+):For C21H21N3O2,370.1531,Found:370.1531.
实施例8
用2b代替实例1中的2a,其他条件同实例1,实验结果见表1。
谱图解析数据3ab:
1H NMR(500MHz,CDCl3):δ8.47(d,J＝8.3Hz,1H),7.59(d,J＝7.8Hz,1H),7.44(d,J＝8.2Hz,1H),7.37(t,J＝8.4Hz,1H),7.33–7.25(m,2H),6.87(t,J＝7.3Hz,1H),6.67(t,J＝3.9Hz,2H),4.48(s,1H),3.48(dq,J＝14.4,7.1Hz,1H),3.36–3.23(m,4H),1.73(s,3H),1.12(t,J＝7.1Hz,3H).13C NMR(125MHz,CDCl3):δ150.2,135.9,130.1,129.0,128.7,128.2,125.1,125.0,123.0,120.5,118.5,115.9,109.0,108.7,69.2,64.6,64.2,38.2,18.3,8.7.HRMS(ESI-TOF,[M+Na]+):For C21H21N3O2,370.1531Found:370.1530.
实施例9
用2c代替实例1中的2a,其他条件同实例1,实验结果见表1。
谱图解析数据3ac:
1H NMR(500MHz,CDCl3):δ8.48(d,J＝8.3Hz,1H),7.60(d,J＝7.8Hz,1H),7.42(d,J＝7.4Hz,1H),7.38(t,J＝7.8Hz,1H),7.27(td,J＝14.2,13.3,7.7Hz,2H),6.85(dd,J＝7.4,5.3Hz,2H),6.67(s,1H),4.41(s,1H),3.76(p,J＝6.9Hz,1H),3.29(s,3H),1.67(s,3H),1.39(d,J＝7.1Hz,3H),1.20(d,J＝6.8Hz,3H).13C NMR(125MHz,CDCl3):δ150.1,149.6,136.1,129.7,128.9,128.3,125.2,125.0,123.0,120.5,118.2,115.8,110.1,110.0,69.1,65.4,64.1,46.3,21.0,18.2,15.3.HRMS(ESI-TOF,[M+Na]+):For C22H23N3O2,384.1688,Found:384.1687.
实施例10
用2d代替实例1中的2a,其他条件同实例1,实验结果见表1。
谱图解析数据3ad:
1H NMR(400MHz,CDCl3):δ8.48(d,J＝8.3Hz,1H),7.56(d,J＝7.8Hz,1H),7.46(d,J＝7.4Hz,1H),7.41–7.35(m,1H),7.30–7.26(m,2H),7.25–7.17(m,5H),6.89(t,J＝7.4Hz,1H),6.67–6.56(m,2H),4.74(d,J＝16.1Hz,1H),4.53(s,1H),4.18(d,J＝16.1Hz,1H),3.34(s,3H),δ1.73(s,3H).13C NMR(125MHz,CDCl3):δ151.3,150.1,137.3,136.0,130.2,128.9,128.6,128.5,127.7,127.3,127.2,125.1,123.1,120.6,118.8,115.8,109.6,109.1,69.3,66.4,64.2,49.2,18.3.HRMS(ESI-TOF,[M+Na]+):For C26H23N3O2,432.1688,Found:432.1684.
表1

Claims (3)

1.一种多取代嘧啶并二吲哚酮衍生物的制备方法，所述多取代嘧啶并二吲哚酮衍生物具有式Ⅰ所示的结构：
式Ⅰ中，R1取代基团选自氟、氯、溴、碘、甲氧基、甲基；R2取代基团选自甲基、乙基、异丙基、苄基；其特征在于，向反应器中，加入取代N-甲氧基吲哚甲酰胺，取代3-甲基吲哚，叔戊酸银和甲酸钠。在溶剂中搅拌反应完毕后，使用旋转蒸发仪浓缩得到粗产物，粗产物使用硅胶柱层析分离得到目标产物，其化学过程见反应式Ⅱ：
。
2.根据权利要求1所述的制备方法，取代N-甲氧基吲哚甲酰胺、取代3-甲基吲哚、叔戊酸银和甲酸钠的摩尔比值为1：2：2：4。
3.按照权利要求1所述的制备方法，其特征在于：溶剂为六氟异丙醇,反应温度为100℃，反应时间为1小时。
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