CN114380730A - 硝基芳烃脱硝偶联合成n-芳基吡咯和n-芳基吲哚的方法 - Google Patents
硝基芳烃脱硝偶联合成n-芳基吡咯和n-芳基吲哚的方法 Download PDFInfo
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- CN114380730A CN114380730A CN202111541136.XA CN202111541136A CN114380730A CN 114380730 A CN114380730 A CN 114380730A CN 202111541136 A CN202111541136 A CN 202111541136A CN 114380730 A CN114380730 A CN 114380730A
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- pyrrole
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- xylene
- aryl
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- WDVGNXKCFBOKDF-UHFFFAOYSA-N dicyclohexyl-[3,6-dimethoxy-2-[2,4,6-tri(propan-2-yl)phenyl]phenyl]phosphane Chemical compound COC1=CC=C(OC)C(C=2C(=CC(=CC=2C(C)C)C(C)C)C(C)C)=C1P(C1CCCCC1)C1CCCCC1 WDVGNXKCFBOKDF-UHFFFAOYSA-N 0.000 claims description 43
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- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 claims description 43
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- 229910021585 Nickel(II) bromide Inorganic materials 0.000 claims description 2
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- NFHFRUOZVGFOOS-UHFFFAOYSA-N Pd(PPh3)4 Substances [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 2
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- C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
- C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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Abstract
本发明公开了一种硝基芳烃脱硝偶联合成N‑芳基吡咯和N‑芳基吲哚的方法,以吡咯、吲哚类含氮芳香杂环化合物与硝基芳烃为原料,在过渡金属催化下,通过硝基芳烃与吡咯、吲哚类含氮芳杂环的碳‑氮键脱硝偶联的方式直接生成N‑芳基化吡咯、N‑芳基化吲哚类化合物。与传统方法相比,本发明在合成条件和实用性方面有明显的优势,它具有合成步骤简单、操作简便、原料价廉易得、对官能团兼容性好、化学选择性以及原子经济性高等优点,也更加符合绿色和可持续化学的理念,为此类具有广泛应用价值的化合物的高效合成提供了参考和可靠的技术支持。
Description
技术领域
本发明属于化合物合成方法,尤其涉及一种硝基芳烃脱硝偶联合成N-芳基吡咯和N-芳基吲哚的方法。
背景技术
N-芳基化吡咯、N-芳基化吲哚类化合物,是一种重要的有机小分子中间体,在医药、农药、含氮杂环化学、有机电致发光和太阳能电池光电转化材料等领域被广泛应用。此外,N-芳基化吡咯、N-芳基化吲哚类化合物广泛存在于具有生理活性的天然产物中。研究发现,其在抗肿瘤、抗HIV-1、抗菌、消炎止痛、免疫调节、抗结核和抗精神分裂等方面具有广泛的生物效应。近年来,N-芳基化吡咯、N-芳基化吲哚类化合物的合成引起了广泛的关注,因此,发展新的、高效的此类化合物的合成方法在医药化学和有机合成中具有重要的研究意义。
传统N-芳基化吡咯、N-芳基化吲哚类化合物的合成方法主要有以下三种:(1)芳胺成环法:以1,4-二酮类化合物和芳胺为原料,在酸的作用下发生缩合反应得到目标物。但该方法原料制备困难,反应条件苛刻,需在酸性溶液中长时间回流,限制了部分对酸敏感的官能团的应用,且在反应过程中产生大量的副产物。另外也可以用芳胺重氮化然后再环化制得目标物,但此方法底物普适性有限;(2)含氮杂环化合物与卤代芳烃发生Ullmann类型的C-N偶联反应。传统Ullmann反应须在高温,强碱,以及催化剂过量的条件下反应,且产物收率不高,这些缺陷也导致了它无法实现工业化;(3)含氮杂环化合物与卤代芳烃发生Buchwald-Hartwig类型的C-N偶联反应,该方法常常需要用到卤代芳烃,单一取代的卤代芳烃的往往以相应芳烃为原料,经硝化、还原、重氮化、Sandmeyer取代等多步反应制备,步骤繁杂且污染危害较大,原子经济性不高。
寻找卤代芳烃的代替物是当下的研究热点之一。硝基芳烃是非常有用的合成中间体,是化学工业的基本原料,简便易得,官能团易于转化。因此,硝基芳烃是理想的偶联试剂,若能直接利用硝基芳烃代替卤代芳烃这类合成中间体直接参与反应,不仅大大提高转化效率,同时也满足绿色化学原子经济性的要求。
有机合成方法学的不断发展为新化合物的合成与发现提供了强有力的保障,然而,随着资源浪费和环境污染等全球性问题的不断加剧,绿色有机合成得到了越来越多研究者的关注。当前已有关于N-芳基化吡咯、N-芳基化吲哚类化合物的合成方法大多原料制备繁杂且依赖于苛刻的反应条件,从而极大地限制了此类方法的实用性。
发明内容
本发明要解决的技术问题是提供一种简单高效、绿色可靠的硝基芳烃脱硝偶联合成N-芳基吡咯和N-芳基吲哚的方法。
为解决上述技术问题,本发明采用以下技术方案:
一种硝基芳烃脱硝偶联合成N-芳基吡咯和N-芳基吲哚,以吡咯、吲哚类含氮芳香杂环化合物与硝基芳烃为原料,在过渡金属催化下,通过硝基芳烃与吡咯、吲哚类含氮芳杂环的碳-氮键脱硝偶联的方式直接生成N-芳基化吡咯、N-芳基化吲哚类化合物。
硝基芳烃、吡咯、吲哚类含氮芳香杂环化合物分别为具有以下式(1)、式(2)结构的化合物:
其中,Ar(是Aromatic的缩写,)表示不同的芳香基团;R1,R2表示含有一个或多个取代的烷基、烷氧基、苯基、腈基、三氟甲基、酯基、卤素或氢(等)。
该法按以下反应方程式进行:
上述N-芳基化吡咯、N-芳基化吲哚类化合物的合成方法,按以下步骤进行操作:在反应器中,加入硝基芳烃、吡咯、吲哚类含氮芳香杂环化合物、金属催化剂、配体、添加剂和溶剂,在N2保护下150℃下搅拌反应16~24h,反应结束后冷却至室温,抽滤,减压旋蒸除去溶剂即得粗产物,粗产物经柱层析纯化得到N-芳基化吡咯、N-芳基化吲哚类化合物。
硝基芳烃与吡咯、吲哚类含氮芳香杂环化合物的摩尔比为(1~4):1。
金属催化剂为Ni(cod)2,NiBr2,NiF2,Ni(acac)2,NiCl2·DME,Cu(OAc)2,Co(acac)3,Pd(PPh3)4,Pd2(dba)3,PdCl2,PdCl2·DPPF,Pd(OAc)2,Pd(PtBu3)2,[Pd(allyl)Cl]2,Pd(acac)2中的一种或两种以上的混合;
配体为BrettPhos,XPhos,SPhos,RuPhos中的一种或两种以上的混合,其结构式如下:
添加剂为Lewis酸、无机或有机盐中的一种或两种以上的混合;
溶剂为三氟甲苯、甲苯、对二甲苯、1,4-二氧六环、正庚烷、叔丁醇、N,N-二甲基甲酰胺和二甲基亚砜中的一种或两种以上的混合。
Lewis酸为乙酸钠、甲醇钠、叔丁醇钠、叔丁醇钾、分子筛,无机或有机盐为四甲基胍、磷酸钾、碳酸钠、碳酸钾、碳酸铷、氢氧化钠、氢氧化钾等。
柱层析提纯所用的洗脱液为石油醚或体积比为(1~300):1的石油醚和乙酸乙酯的混合溶剂。
反应器为Schlenk管(史兰克管)。
针对传统方法存在的工艺步骤繁杂等问题,发明人建立了一种硝基芳烃脱硝偶联合成N-芳基吡咯和N-芳基吲哚,以吡咯、吲哚类含氮芳香杂环化合物与硝基芳烃为原料,在过渡金属催化下,通过硝基芳烃与吡咯、吲哚类含氮芳杂环的碳-氮键脱硝偶联的方式直接生成N-芳基化吡咯、N-芳基化吲哚类化合物。与传统方法相比,本发明在合成条件和实用性方面有明显的优势,它具有合成步骤简单、操作简便、原料价廉易得、对官能团兼容性好、化学选择性以及原子经济性高等优点,也更加符合绿色和可持续化学的理念,为此类具有广泛应用价值的化合物的高效合成提供了参考和可靠的技术支持。
具体实施方式
实施例1
在Schlenk管中加入0.3~0.4mmol对硝基苯甲醚,0.2mmol吡咯,0.02mmol乙酰丙酮钯或三(二亚苄基丙酮)二钯,0.03mmol BrettPhos,0.6mmol碳酸钾、磷酸钾或碳酸铷,1.0~2.0mL邻二甲苯、二氧六环或间二甲苯。在150℃,N2条件下搅拌反应24小时后,停止加热及搅拌,冷却至室温。抽滤,减压旋蒸除去溶剂,再通过柱层析分离纯化,得到目标产物。所用的柱层析洗脱液的体积比为100:1的石油醚:乙酸乙酯混合溶剂。
所得产物的结构如下式所示:
实施例2
在Schlenk管中加入0.3~0.4mmol硝基苯,0.2mmol吡咯,0.02mmol乙酰丙酮钯或三(二亚苄基丙酮)二钯,0.03mmol BrettPhos,0.4~0.6mmol碳酸钾、磷酸钾或碳酸铷,1.0~2.0mL邻二甲苯、二氧六环或间二甲苯。在150℃,N2条件下搅拌反应22小时后,停止加热及搅拌,冷却至室温。抽滤,减压旋蒸除去溶剂,再通过柱层析分离纯化,得到目标产物。所用的柱层析洗脱液的体积比为200:1的石油醚:乙酸乙酯混合溶剂。
所得产物的结构如下式所示:
实施例3
在Schlenk管中加入0.3~0.4mmol对硝基甲苯,0.2mmol吡咯,0.02mmol乙酰丙酮钯或三(二亚苄基丙酮)二钯,0.03mmol BrettPhos,0.4~0.6mmol碳酸钾、磷酸钾或碳酸铷,1.0~2.0mL邻二甲苯、二氧六环或间二甲苯。在150℃,N2条件下搅拌反应16~24小时后,停止加热及搅拌,冷却至室温。抽滤,减压旋蒸除去溶剂,再通过柱层析分离纯化,得到目标产物。所用的柱层析洗脱液为石油醚。
所得产物的结构如下式所示:
实施例4
在Schlenk管中加入0.3~0.4mmol对硝基三氟甲苯,0.2mmol吡咯,0.02mmol乙酰丙酮钯或三(二亚苄基丙酮)二钯,0.03mmol BrettPhos,0.4~0.6mmol碳酸钾、磷酸钾或碳酸铷,1.0~2.0mL邻二甲苯、二氧六环或间二甲苯。在150℃,N2条件下搅拌反应16~24小时后,停止加热及搅拌,冷却至室温。抽滤,减压旋蒸除去溶剂,再通过柱层析分离纯化,得到目标产物。所用的柱层析洗脱液的体积比为200:1的石油醚:乙酸乙酯混合溶剂。
所得产物的结构如下式所示:
实施例5
在Schlenk管中加入0.3~0.4mmol对氟硝基苯,0.2mmol吡咯,0.02mmol乙酰丙酮钯或三(二亚苄基丙酮)二钯,0.03mmol BrettPhos,0.4~0.6mmol碳酸钾、磷酸钾或碳酸铷,1.0~2.0mL邻二甲苯、二氧六环或间二甲苯。在150℃,N2条件下搅拌反应16~24小时后,停止加热及搅拌,冷却至室温。抽滤,减压旋蒸除去溶剂,再通过柱层析分离纯化,得到目标产物。所用的柱层析洗脱液的体积比为200:1的石油醚:乙酸乙酯混合溶剂。
所得产物的结构如下式所示:
实施例6
在Schlenk管中加入0.3~0.4mmol对硝基苯甲酸乙酯,0.2mmol吡咯,0.02mmol乙酰丙酮钯或三(二亚苄基丙酮)二钯,0.03mmol BrettPhos,0.4~0.6mmol碳酸钾、磷酸钾或碳酸铷,1.0~2.0mL邻二甲苯、二氧六环或间二甲苯。在150℃,N2条件下搅拌反应16~24小时后,停止加热及搅拌,冷却至室温。抽滤,减压旋蒸除去溶剂,再通过柱层析分离纯化,得到目标产物。所用的柱层析洗脱液的体积比为60:1的石油醚:乙酸乙酯混合溶剂。
所得产物的结构如下式所示:
实施例7
在Schlenk管中加入0.3~0.4mmol对硝基苯乙酮,0.2mmol吡咯,0.02mmol乙酰丙酮钯或三(二亚苄基丙酮)二钯,0.03mmol BrettPhos,0.4~0.6mmol碳酸钾、磷酸钾或碳酸铷,1.0~2.0mL邻二甲苯、二氧六环或间二甲苯。在150℃,N2条件下搅拌反应16~24小时后,停止加热及搅拌,冷却至室温。抽滤,减压旋蒸除去溶剂,再通过柱层析分离纯化,得到目标产物。所用的柱层析洗脱液的体积比为20:1的石油醚:乙酸乙酯混合溶剂。
所得产物的结构如下式所示:
实施例8
在Schlenk管中加入0.3~0.4mmol间硝基苯甲酸甲酯,0.2mmol吡咯,0.02mmol乙酰丙酮钯或三(二亚苄基丙酮)二钯,0.03mmol BrettPhos,0.4~0.6mmol碳酸钾、磷酸钾或碳酸铷,1.0~2.0mL邻二甲苯、二氧六环或间二甲苯。在150℃,N2条件下搅拌反应16~24小时后,停止加热及搅拌,冷却至室温。抽滤,减压旋蒸除去溶剂,再通过柱层析分离纯化,得到目标产物。所用的柱层析洗脱液的体积比为100:1的石油醚:乙酸乙酯混合溶剂。
所得产物的结构如下式所示:
实施例9
在Schlenk管中加入0.3~0.4mmol间硝基甲苯,0.2mmol吡咯,0.02mmol乙酰丙酮钯或三(二亚苄基丙酮)二钯,0.03mmol BrettPhos,0.4~0.6mmol碳酸钾、磷酸钾或碳酸铷,1.0~2.0mL邻二甲苯、二氧六环或间二甲苯。在150℃,N2条件下搅拌反应16~24小时后,停止加热及搅拌,冷却至室温。抽滤,减压旋蒸除去溶剂,再通过柱层析分离纯化,得到目标产物。所用的柱层析洗脱液为石油醚。
所得产物的结构如下式所示:
实施例10
在Schlenk管中加入0.3~0.4mmol间硝基三氟甲氧基苯,0.2mmol吡咯,0.02mmol乙酰丙酮钯或三(二亚苄基丙酮)二钯,0.03mmol BrettPhos,0.4~0.6mmol碳酸钾、磷酸钾或碳酸铷,1.0~2.0mL邻二甲苯、二氧六环或间二甲苯。在150℃,N2条件下搅拌反应16~24小时后,停止加热及搅拌,冷却至室温。抽滤,减压旋蒸除去溶剂,再通过柱层析分离纯化,得到目标产物。所用的柱层析洗脱液的体积比为40:1的石油醚:乙酸乙酯混合溶剂。
所得产物的结构表征数据如下:
1H NMR(500MHz,CDCl3)δ7.45(t,J=8.2Hz,1H),7.38-7.32(m,1H),7.26(d,J=3.7Hz,1H),7.15-7.08(m,3H),6.39(t,J=2.2Hz,2H).
13C NMR(126MHz,CDCl3)δ150.0(q,JC-F=1.8Hz),142.0,130.7,123.5,121.4,119.4,119.2,118.4,117.5,117.3(q,JC-F=256.3Hz),113.1,111.2.
HRMS(APCI)calcd for C11H8F3NO[M+H+],228.0631;found:228.0621.
根据以上数据推断所得产物的结构如下式所示:
实施例11
在Schlenk管中加入0.3~0.4mmol邻硝基苯甲醚,0.2mmol吡咯,0.02mmol乙酰丙酮钯或三(二亚苄基丙酮)二钯,0.03mmol BrettPhos,0.4~0.6mmol碳酸钾、磷酸钾或碳酸铷,1.0~2.0mL邻二甲苯、二氧六环或间二甲苯。在150℃,N2条件下搅拌反应16~24小时后,停止加热及搅拌,冷却至室温。抽滤,减压旋蒸除去溶剂,再通过柱层析分离纯化,得到目标产物。所用的柱层析洗脱液的体积比为300:1的石油醚:乙酸乙酯混合溶剂。
所得产物的结构结构如下式所示:
实施例12
在Schlenk管中加入0.3~0.4mmol邻硝基甲苯,0.2mmol吡咯,0.02mmol乙酰丙酮钯或三(二亚苄基丙酮)二钯,0.03mmol BrettPhos,0.4~0.6mmol碳酸钾、磷酸钾或碳酸铷,1.0~2.0mL邻二甲苯、二氧六环或间二甲苯。在150℃,N2条件下搅拌反应16~24小时后,停止加热及搅拌,冷却至室温。抽滤,减压旋蒸除去溶剂,再通过柱层析分离纯化,得到目标产物。所用的柱层析洗脱液为石油醚。
所得产物的结构如下式所示:
实施例13
在Schlenk管中加入0.3~0.4mmol 3,5-二甲基硝基苯,0.2mmol吡咯,0.02mmol乙酰丙酮钯或三(二亚苄基丙酮)二钯,0.03mmol BrettPhos,0.4~0.6mmol碳酸钾、磷酸钾或碳酸铷,1.0~2.0mL邻二甲苯、二氧六环或间二甲苯。在150℃,N2条件下搅拌反应16~24小时后,停止加热及搅拌,冷却至室温。抽滤,减压旋蒸除去溶剂,再通过柱层析分离纯化,得到目标产物。所用的柱层析洗脱液为石油醚。
所得产物的结构如下式所示:
实施例14
在Schlenk管中加入0.3~0.4mmol 1-硝基萘,0.2mmol吡咯,0.02mmol乙酰丙酮钯或三(二亚苄基丙酮)二钯,0.03mmol BrettPhos,0.4~0.6mmol碳酸钾、磷酸钾或碳酸铷,1.0~2.0mL邻二甲苯、二氧六环或间二甲苯。在150℃,N2条件下搅拌反应16~24小时后,停止加热及搅拌,冷却至室温。抽滤,减压旋蒸除去溶剂,再通过柱层析分离纯化,得到目标产物。所用的柱层析洗脱液为石油醚。
所得产物的结构如下式所示:
实施例15
在Schlenk管中加入0.3~0.4mmol 1-硝基芘,0.2mmol吡咯,0.02mmol乙酰丙酮钯或三(二亚苄基丙酮)二钯,0.03mmol BrettPhos,0.4~0.6mmol碳酸钾、磷酸钾或碳酸铷,1.0~2.0mL邻二甲苯、二氧六环或间二甲苯。在150℃,N2条件下搅拌反应16~24小时后,停止加热及搅拌,冷却至室温。抽滤,减压旋蒸除去溶剂,再通过柱层析分离纯化,得到目标产物。所用的柱层析洗脱液为石油醚。
所得产物的结构如下式所示:
实施例16
在Schlenk管中加入0.3~0.4mmol对硝基联苯,0.2mmol吡咯,0.02mmol乙酰丙酮钯或三(二亚苄基丙酮)二钯,0.03mmol BrettPhos,0.4~0.6mmol碳酸钾、磷酸钾或碳酸铷,1.0~2.0mL邻二甲苯、二氧六环或间二甲苯。在150℃,N2条件下搅拌反应16~24小时后,停止加热及搅拌,冷却至室温。抽滤,减压旋蒸除去溶剂,再通过柱层析分离纯化,得到目标产物。所用的柱层析洗脱液的体积比为100:1的石油醚:乙酸乙酯混合溶剂。
所得产物的结构如下式所示:
实施例17
在Schlenk管中加入0.3~0.4mmol对二甲氨基硝基苯,0.2mmol吡咯,0.02mmol乙酰丙酮钯或三(二亚苄基丙酮)二钯,0.03mmol BrettPhos,0.4~0.6mmol碳酸钾、磷酸钾或碳酸铷,1.0~2.0mL邻二甲苯、二氧六环或间二甲苯。在150℃,N2条件下搅拌反应16~24小时后,停止加热及搅拌,冷却至室温。抽滤,减压旋蒸除去溶剂,再通过柱层析分离纯化,得到目标产物。所用的柱层析洗脱液的体积比为40:1的石油醚:乙酸乙酯混合溶剂。
所得产物的结构如下式所示:
实施例18
在Schlenk管中加入0.3~0.4mmol对吗啉基硝基苯,0.2mmol吡咯,0.02mmol乙酰丙酮钯或三(二亚苄基丙酮)二钯,0.03mmol BrettPhos,0.4~0.6mmol碳酸钾、磷酸钾或碳酸铷,1.0~2.0mL邻二甲苯、二氧六环或间二甲苯。在150℃,N2条件下搅拌反应16~24小时后,停止加热及搅拌,冷却至室温。抽滤,减压旋蒸除去溶剂,再通过柱层析分离纯化,得到目标产物。所用的柱层析洗脱液的体积比为10:1的石油醚:乙酸乙酯混合溶剂。
所得产物的结构如下式所示:
实施例19
在Schlenk管中加入0.3~0.4mmol对二氧戊环基硝基苯,0.2mmol吡咯,0.02mmol乙酰丙酮钯或三(二亚苄基丙酮)二钯,0.03mmol BrettPhos,0.4~0.6mmol碳酸钾、磷酸钾或碳酸铷,1.0~2.0mL邻二甲苯、二氧六环或间二甲苯。在150℃,N2条件下搅拌反应16~24小时后,停止加热及搅拌,冷却至室温。抽滤,减压旋蒸除去溶剂,再通过柱层析分离纯化,得到目标产物。所用的柱层析洗脱液的体积比为20:1的石油醚:乙酸乙酯混合溶剂。
所得产物的结构表征数据如下:
1H NMR(500MHz,CDCl3)δ7.59-7.52(m,2H),7.46-7.38(m,2H),7.12(t,J=2.2Hz,2H),6.40-6.35(m,2H),5.85(s,1H),4.20-4.11(m,2H),4.11-4.02(m,2H).
13C NMR(126MHz,CDCl3)δ141.3,135.1,127.8,120.2,119.2,110.5,103.2,65.3.
HRMS(APCI)calcd for C13H13NO2[M+H+],216.1019;found:216.1018.
根据以上数据推断所得产物的结构如下式所示:
实施例20
在Schlenk管中加入0.3~0.4mmol 2-甲氧基-3-硝基吡啶,0.2mmol吡咯,0.02mmol乙酰丙酮钯或三(二亚苄基丙酮)二钯,0.03mmol BrettPhos,0.4~0.6mmol碳酸钾、磷酸钾或碳酸铷,1.0~2.0mL邻二甲苯、二氧六环或间二甲苯。在150℃,N2条件下搅拌反应16~24小时后,停止加热及搅拌,冷却至室温。抽滤,减压旋蒸除去溶剂,再通过柱层析分离纯化,得到目标产物。所用的柱层析洗脱液的体积比为60:1的石油醚:乙酸乙酯混合溶剂。
所得产物的结构如下式所示:
实施例21
在Schlenk管中加入0.3~0.4mmol 5-硝基喹啉,0.2mmol吡咯,0.02mmol乙酰丙酮钯或三(二亚苄基丙酮)二钯,0.03mmol BrettPhos,0.4~0.6mmol碳酸钾、磷酸钾或碳酸铷,1.0~2.0mL邻二甲苯、二氧六环或间二甲苯。在150℃,N2条件下搅拌反应16~24小时后,停止加热及搅拌,冷却至室温。抽滤,减压旋蒸除去溶剂,再通过柱层析分离纯化,得到目标产物。所用的柱层析洗脱液的体积比为20:1的石油醚:乙酸乙酯混合溶剂。
所得产物的结构表征数据如下:
1H NMR(500MHz,CDCl3)δ8.93(dd,J=4.2,1.6Hz,1H),8.11(dd,J=22.7,8.5Hz,2H),7.75-7.68(m,1H),7.53-7.47(m,1H),7.38(dd,J=8.6,4.2Hz,1H),6.95(t,J=2.1Hz,2H),6.41(t,J=2.1Hz,2H).
13C NMR(126MHz,CDCl3)δ150.8,148.5,137.8,131.8,129.1,128.7,124.9,123.4,123.0,121.7,109.5.
HRMS(APCI)calcd for C13H10N2[M+H+],195.0917;found:195.0916.
根据以上数据推断所得产物的结构如下式所示:
实施例22
在Schlenk管中加入0.3~0.4mmol 5-硝基-N-甲基吲哚,0.2mmol吡咯,0.02mmol乙酰丙酮钯或三(二亚苄基丙酮)二钯,0.03mmol BrettPhos,0.4~0.6mmol碳酸钾、磷酸钾或碳酸铷,1.0~2.0mL邻二甲苯、二氧六环或间二甲苯。在150℃,N2条件下搅拌反应16~24小时后,停止加热及搅拌,冷却至室温。抽滤,减压旋蒸除去溶剂,再通过柱层析分离纯化,得到目标产物。所用的柱层析洗脱液的体积比为200:1的石油醚:乙酸乙酯混合溶剂。
所得产物的结构表征数据如下:
1H NMR(500MHz,CDCl3)δ7.75-7.67(m,1H),7.37(tdd,J=6.6,6.0,1.8Hz,2H),7.22-7.13(m,3H),6.58(dd,J=2.3,1.4Hz,1H),6.49-6.40(m,2H),3.84(s,3H).
13C NMR(126MHz,CDCl3)δ135.0,134.0,130.2,128.7,120.3,116.2,113.2,109.7,109.4,101.1,32.9.
HRMS(APCI)calcd for C13H12N2[M+H+],197.1073;found:197.1072.
根据以上数据推断所得产物的结构如下式所示:
实施例23
在Schlenk管中加入0.3~0.4mmol 5-硝基苯并噻吩,0.2mmol吡咯,0.02mmol乙酰丙酮钯或三(二亚苄基丙酮)二钯,0.03mmol BrettPhos,0.4~0.6mmol碳酸钾、磷酸钾或碳酸铷,1.0~2.0mL邻二甲苯、二氧六环或间二甲苯。在150℃,N2条件下搅拌反应16~24小时后,停止加热及搅拌,冷却至室温。抽滤,减压旋蒸除去溶剂,再通过柱层析分离纯化,得到目标产物。所用的柱层析洗脱液的体积比为100:1的石油醚:乙酸乙酯混合溶剂。
所得产物的结构表征数据如下:
1H NMR(500MHz,CDCl3)δ7.92(d,J=8.6Hz,1H),7.84(d,J=2.1Hz,1H),7.55(d,J=5.4Hz,1H),7.45(dd,J=8.6,2.1Hz,1H),7.38(d,J=5.4Hz,1H),7.18(d,J=1.0Hz,2H),6.44(d,J=2.0Hz,2H).
13C NMR(126MHz,CDCl3)δ140.4,138.0,137.0,128.3,123.7,123.3,119.8,118.2,115.1,110.3.
HRMS(APCI)calcd for C21H17F[M+H+],200.0528;found:200.0527.
根据以上数据推断所得产物的结构如下式所示:
实施例24
在Schlenk管中加入0.3~0.4mmol 2-甲酸乙酯基-5-硝基苯并呋喃,0.2mmol吡咯,0.02mmol乙酰丙酮钯或三(二亚苄基丙酮)二钯,0.03mmol BrettPhos,0.4~0.6mmol碳酸钾、磷酸钾或碳酸铷,1.0~2.0mL邻二甲苯、二氧六环或间二甲苯。在150℃,N2条件下搅拌反应16~24小时后,停止加热及搅拌,冷却至室温。抽滤,减压旋蒸除去溶剂,再通过柱层析分离纯化,得到目标产物。所用的柱层析洗脱液的体积比为100:1的石油醚:乙酸乙酯混合溶剂。
所得产物的结构表征数据如下:
1H NMR(500MHz,CDCl3)δ7.66-7.58(m,2H),7.53(s,1H),7.51-7.46(m,1H),7.07(t,J=1.9Hz,2H),6.37(t,J=2.1Hz,2H),4.46(q,J=7.1Hz,2H),1.44(t,J=7.1Hz,3H).
13C NMR(126MHz,CDCl3)δ159.2,153.5,147.0,137.4,127.7,121.5,119.9,114.3,113.6,113.0,110.4,61.6,14.2.
HRMS(APCI)calcd for C15H13NO3[M+H+],256.0968;found:256.0964.
根据以上数据推断所得产物的结构如下式所示:
实施例25
在Schlenk管中加入0.3~0.4mmol对硝基苯甲醚,0.2mmol吲哚,0.02mmol乙酰丙酮钯或三(二亚苄基丙酮)二钯,0.03mmol BrettPhos,0.4~0.6mmol碳酸钾、磷酸钾或碳酸铷,1.0~2.0mL邻二甲苯、二氧六环或间二甲苯。在150℃,N2条件下搅拌反应16~24小时后,停止加热及搅拌,冷却至室温。抽滤,减压旋蒸除去溶剂,再通过柱层析分离纯化,得到目标产物。所用的柱层析洗脱液的体积比为200:1的石油醚:乙酸乙酯混合溶剂。
所得产物的结构如下式所示:
实施例26
在Schlenk管中加入0.3~0.4mmol对硝基苯甲醚,0.2mmol 5-甲氧基吲哚,0.02mmol乙酰丙酮钯或三(二亚苄基丙酮)二钯,0.03mmol BrettPhos,0.4~0.6mmol碳酸钾、磷酸钾或碳酸铷,1.0~2.0mL邻二甲苯、二氧六环或间二甲苯。在150℃,N2条件下搅拌反应16~24小时后,停止加热及搅拌,冷却至室温。抽滤,减压旋蒸除去溶剂,再通过柱层析分离纯化,得到目标产物。所用的柱层析洗脱液的体积比为200:1的石油醚:乙酸乙酯混合溶剂。
所得产物的结构如下式所示:
实施例27
在Schlenk管中加入0.3~0.4mmol对硝基苯甲醚,0.2mmol 5-甲酸甲酯基吲哚,0.02mmol乙酰丙酮钯或三(二亚苄基丙酮)二钯,0.03mmol BrettPhos,0.4~0.6mmol碳酸钾、磷酸钾或碳酸铷,1.0~2.0mL邻二甲苯、二氧六环或间二甲苯。在150℃,N2条件下搅拌反应16~24小时后,停止加热及搅拌,冷却至室温。抽滤,减压旋蒸除去溶剂,再通过柱层析分离纯化,得到目标产物。所用的柱层析洗脱液的体积比为20:1的石油醚:乙酸乙酯混合溶剂。
所得产物的结构表征数据如下:
1H NMR(500MHz,CDCl3)δ8.47(d,J=1.5Hz,1H),7.92(dd,J=8.7,1.6Hz,1H),7.44(d,J=8.7Hz,1H),7.40-7.34(m,2H),7.32(d,J=3.2Hz,1H),7.09-6.99(m,2H),6.74(d,J=3.2Hz,1H),3.95(s,3H),3.87(s,3H).
13C NMR(126MHz,CDCl3)δ167.9,158.5,138.6,132.0,129.7,128.4,125.9,123.9,123.4,122.0,114.7,109.9,104.1,55.5,51.7.
HRMS(APCI)calcd for C17H15NO3[M+H+],282.1125;found:282.1123.
根据以上数据推断所得产物的结构如下式所示:
实施例28
在Schlenk管中加入0.3~0.4mmol对硝基苯甲醚,0.2mmol 4-甲酸甲酯基吲哚,0.02mmol乙酰丙酮钯或三(二亚苄基丙酮)二钯,0.03mmol BrettPhos,0.4~0.6mmol碳酸钾、磷酸钾或碳酸铷,1.0~2.0mL邻二甲苯、二氧六环或间二甲苯。在150℃,N2条件下搅拌反应16~24小时后,停止加热及搅拌,冷却至室温。抽滤,减压旋蒸除去溶剂,再通过柱层析分离纯化,得到目标产物。所用的柱层析洗脱液的体积比为40:1的石油醚:乙酸乙酯混合溶剂。
所得产物的结构表征数据如下:
1H NMR(500MHz,CDCl3)δ7.97(dd,J=7.5,0.7Hz,1H),7.62(d,J=8.2Hz,1H),7.41(d,J=3.2Hz,1H),7.39-7.34(m,2H),7.34-7.31(m,1H),7.24(t,J=7.8Hz,1H),7.07-6.99(m,2H),4.02(s,3H),3.87(s,3H).
13C NMR(126MHz,CDCl3)δ167.8,158.5,137.2,132.1,130.3,128.3,126.2,123.6,121.6,121.2,115.1,114.7,103.9,55.5,51.7.
HRMS(APCI)calcd for C17H15NO3[M+H+],282.1125;found:282.1122.
根据以上数据推断所得产物的结构如下式所示:
实施例29
在Schlenk管中加入0.3~0.4mmol对硝基苯甲醚,0.2mmol 4-氰基吲哚,0.02mmol乙酰丙酮钯或三(二亚苄基丙酮)二钯,0.03mmol BrettPhos,0.4~0.6mmol碳酸钾、磷酸钾或碳酸铷,1.0~2.0mL邻二甲苯、二氧六环或间二甲苯。在150℃,N2条件下搅拌反应16~24小时后,停止加热及搅拌,冷却至室温。抽滤,减压旋蒸除去溶剂,再通过柱层析分离纯化,得到目标产物。所用的柱层析洗脱液的体积比为40:1的石油醚:乙酸乙酯混合溶剂。
所得产物的结构表征数据如下:
1H NMR(500MHz,CDCl3)δ7.62(d,J=8.4Hz,1H),7.51(dd,J=7.4,0.7Hz,1H),7.44(d,J=3.2Hz,1H),7.40-7.34(m,2H),7.23(dd,J=8.3,7.5Hz,1H),7.09-7.02(m,2H),6.87(dd,J=3.2,0.7Hz,1H),3.89(s,3H).
13C NMR(126MHz,CDCl3)δ158.9,136.2,131.5,131.0,130.1,126.3,125.5,121.7,118.6,115.2,114.9,103.3,101.7,55.6.
HRMS(APCI)calcd for C16H12N2O[M+H+],249.1022;found:249.1022.
根据以上数据推断所得产物的结构如下式所示:
实施例30
在Schlenk管中加入0.3~0.4mmol对硝基苯甲醚,0.2mmol 4-氟吲哚,0.02mmol乙酰丙酮钯或三(二亚苄基丙酮)二钯,0.03mmol BrettPhos,0.4~0.6mmol碳酸钾、磷酸钾或碳酸铷,1.0~2.0mL邻二甲苯、二氧六环或间二甲苯。在150℃,N2条件下搅拌反应16~24小时后,停止加热及搅拌,冷却至室温。抽滤,减压旋蒸除去溶剂,再通过柱层析分离纯化,得到目标产物。所用的柱层析洗脱液的体积比为40:1的石油醚:乙酸乙酯混合溶剂。
所得产物的结构表征数据如下:
1H NMR(500MHz,CDCl3)δ7.45-7.36(m,2H),7.28-7.21(m,2H),7.13(td,J=8.0,5.2Hz,1H),7.09-7.01(m,2H),6.86(ddd,J=10.2,7.8,0.6Hz,1H),6.77(dd,J=3.2,0.8Hz,1H),3.90(s,3H).
13C NMR(126MHz,CDCl3)δ158.5,157.3,155.4(d,JC-F=245.6Hz),139.0,138.9(d,JC-F=11.0Hz),132.4,128.2,126.0,122.6,122.5(d,JC-F=7.8Hz),118.0,117.9(d,JC-F=7.8Hz),114.7,106.5,106.5(d,JC-F=3.6Hz),104.8,104.7(d,JC-F=18.9Hz),98.8,55.5.
HRMS(APCI)calcd for C15H12FNO[M+H+],242.0976;found:242.0973.
根据以上数据推断所得产物的结构如下式所示:
实施例31
在Schlenk管中加入0.3~0.4mmol对硝基苯甲醚,0.2mmol 4-甲氧基吲哚,0.02mmol乙酰丙酮钯或三(二亚苄基丙酮)二钯,0.03mmol BrettPhos,0.4~0.6mmol碳酸钾、磷酸钾或碳酸铷,1.0~2.0mL邻二甲苯、二氧六环或间二甲苯。在150℃,N2条件下搅拌反应16~24小时后,停止加热及搅拌,冷却至室温。抽滤,减压旋蒸除去溶剂,再通过柱层析分离纯化,得到目标产物。所用的柱层析洗脱液的体积比为200:1的石油醚:乙酸乙酯混合溶剂。
所得产物的结构表征数据如下:
1H NMR(500MHz,CDCl3)δ7.53-7.44(m,2H),7.31-7.18(m,3H),7.12-7.04(m,2H),6.90(dd,J=5.0,2.4Hz,1H),6.68(dd,J=7.0,3.8Hz,1H),4.07(s,3H),3.92(s,3H).
13C NMR(126MHz,CDCl3)δ158.1,153.3,137.6,132.8,126.7,125.8,122.9,119.4,114.5,103.7,100.1,99.8,55.4,55.2.
HRMS(APCI)calcd for C16H15NO2[M+H+],254.1176;found:254.1172.
根据以上数据推断所得产物的结构如下式所示:
实施例32
在Schlenk管中加入0.3~0.4mmol对硝基苯甲醚,0.2mmol 4-苄氧基吲哚,0.02mmol乙酰丙酮钯或三(二亚苄基丙酮)二钯,0.03mmol BrettPhos,0.4~0.6mmol碳酸钾、磷酸钾或碳酸铷,1.0~2.0mL邻二甲苯、二氧六环或间二甲苯。在150℃,N2条件下搅拌反应16~24小时后,停止加热及搅拌,冷却至室温。抽滤,减压旋蒸除去溶剂,再通过柱层析分离纯化,得到目标产物。所用的柱层析洗脱液的体积比为200:1的石油醚:乙酸乙酯混合溶剂。
所得产物的结构表征数据如下:
1H NMR(500MHz,CDCl3)δ7.61(d,J=7.7Hz,2H),7.54-7.38(m,5H),7.26(dd,J=3.1,1.6Hz,1H),7.19(dd,J=7.5,5.7Hz,2H),7.13-7.05(m,2H),6.93(d,J=3.1Hz,1H),6.71(dd,J=4.9,3.3Hz,1H),5.34(s,2H),3.91(s,3H).
13C NMR(126MHz,CDCl3)δ158.1,152.5,137.7,137.5,132.8,128.4,127.7,127.2,126.8,125.8,122.9,119.8,114.6,104.0,101.4,100.3,69.9,55.5.
HRMS(APCI)calcd for C22H19NO2[M+H+],330.1489;found:330.1485.
根据以上数据推断所得产物的结构如下式所示:
实施例33
在Schlenk管中加入0.3~0.4mmol对硝基苯甲醚,0.2mmol 2,3-二甲基吲哚,0.02mmol乙酰丙酮钯或三(二亚苄基丙酮)二钯,0.03mmol BrettPhos,0.4~0.6mmol碳酸钾、磷酸钾或碳酸铷,1.0~2.0mL邻二甲苯、二氧六环或间二甲苯。在150℃,N2条件下搅拌反应16~24小时后,停止加热及搅拌,冷却至室温。抽滤,减压旋蒸除去溶剂,再通过柱层析分离纯化,得到目标产物。所用的柱层析洗脱液的体积比为40:1的石油醚:乙酸乙酯混合溶剂。
所得产物的结构如下式所示:
实施例34
在Schlenk管中加入0.3~0.4mmol对硝基苯甲醚,0.2mmol 3-甲基吲哚,0.02mmol乙酰丙酮钯或三(二亚苄基丙酮)二钯,0.03mmol BrettPhos,0.4~0.6mmol碳酸钾、磷酸钾或碳酸铷,1.0~2.0mL邻二甲苯、二氧六环或间二甲苯。在150℃,N2条件下搅拌反应16~24小时后,停止加热及搅拌,冷却至室温。抽滤,减压旋蒸除去溶剂,再通过柱层析分离纯化,得到目标产物。所用的柱层析洗脱液的体积比为200:1的石油醚:乙酸乙酯混合溶剂。
所得产物的结构如下式所示:
实施例35
在Schlenk管中加入0.3~0.4mmol对硝基苯甲醚,0.2mmol 2-甲基吲哚,0.02mmol乙酰丙酮钯或三(二亚苄基丙酮)二钯,0.03mmol BrettPhos,0.4~0.6mmol碳酸钾、磷酸钾或碳酸铷,1.0~2.0mL邻二甲苯、二氧六环或间二甲苯。在150℃,N2条件下搅拌反应16~24小时后,停止加热及搅拌,冷却至室温。抽滤,减压旋蒸除去溶剂,再通过柱层析分离纯化,得到目标产物。所用的柱层析洗脱液的体积比为40:1的石油醚:乙酸乙酯混合溶剂。
所得产物的结构如下式所示:
实施例36
在Schlenk管中加入0.3~0.4mmol对硝基苯甲醚,0.2mmol 2-甲基吡咯,0.02mmol乙酰丙酮钯或三(二亚苄基丙酮)二钯,0.03mmol BrettPhos,0.4~0.6mmol碳酸钾、磷酸钾或碳酸铷,1.0~2.0mL邻二甲苯、二氧六环或间二甲苯。在150℃,N2条件下搅拌反应16~24小时后,停止加热及搅拌,冷却至室温。抽滤,减压旋蒸除去溶剂,再通过柱层析分离纯化,得到目标产物。所用的柱层析洗脱液的体积比为200:1的石油醚:乙酸乙酯混合溶剂。
所得产物的结构表征数据如下:
1H NMR(500MHz,CDCl3)δ7.26–7.21(m,2H),7.00-6.95(m,2H),6.77-6.71(m,1H),6.20(t,J=2.9Hz,1H),6.09-5.98(m,1H),3.87(s,3H),2.20(s,3H).
13C NMR(126MHz,CDCl3)δ158.4,133.4,129.2,127.0,121.5,114.1,107.5,107.5,55.4,12.7.
HRMS(APCI)calcd for C12H13NO[M+H+],188.1070;found:188.1069.
根据以上数据推断所得产物的结构如下式所示:
实施例37
在Schlenk管中加入0.3~0.4mmol对硝基苯甲醚,0.2mmol咔唑,0.02mmol乙酰丙酮钯或三(二亚苄基丙酮)二钯,0.03mmol BrettPhos,0.4~0.6mmol碳酸钾、磷酸钾或碳酸铷,1.0~2.0mL邻二甲苯、二氧六环或间二甲苯。在150℃,N2条件下搅拌反应16~24小时后,停止加热及搅拌,冷却至室温。抽滤,减压旋蒸除去溶剂,再通过柱层析分离纯化,得到目标产物。所用的柱层析洗脱液的体积比为200:1的石油醚:乙酸乙酯混合溶剂。
所得产物的结构如下式所示:
实施例38
在Schlenk管中加入0.3~0.4mmol对硝基苯甲醚,0.2mmol吩恶嗪,0.02mmol乙酰丙酮钯或三(二亚苄基丙酮)二钯,0.03mmol BrettPhos,0.4~0.6mmol碳酸钾、磷酸钾或碳酸铷,1.0~2.0mL邻二甲苯、二氧六环或间二甲苯。在150℃,N2条件下搅拌反应16~24小时后,停止加热及搅拌,冷却至室温。抽滤,减压旋蒸除去溶剂,再通过柱层析分离纯化,得到目标产物。所用的柱层析洗脱液的体积比为40:1的石油醚:乙酸乙酯混合溶剂。
所得产物的结构如下式所示:
实施例39
在Schlenk管中加入0.3~0.4mmol 1-(4-硝基苯基)-3-(三氟甲基)-1H-吡唑-4-羧酸乙酯,0.2mmol吡咯,0.02mmol乙酰丙酮钯或三(二亚苄基丙酮)二钯,0.03mmolBrettPhos,0.4~0.6mmol碳酸钾、磷酸钾或碳酸铷,1.0~2.0mL邻二甲苯、二氧六环或间二甲苯。在150℃,N2条件下搅拌反应16~24小时后,停止加热及搅拌,冷却至室温。抽滤,减压旋蒸除去溶剂,再通过柱层析分离纯化,得到目标产物。所用的柱层析洗脱液的体积比为40:1的石油醚:乙酸乙酯混合溶剂。
所得产物的结构表征数据如下:
1H NMR(500MHz,CDCl3)δ8.13(s,1H),7.57-7.43(m,4H),7.14(t,J=2.2Hz,2H),6.39(t,J=2.2Hz,2H),4.39(q,J=7.1Hz,2H),1.39(t,J=7.1Hz,3H).
13C NMR(126MHz,CDCl3)δ160.9,142.5,141.6,136.3,133.0,132.7,132.4,132.1(q,JC-F=40.2Hz),127.1,122.3,120.3,120.1,119.1,118.0,116.8,116.8(d,JC-F=1.1Hz),115.8(q,JC-F=272.0Hz),111.4,61.3,14.0;19F NMR(471MHz,CDCl3)δ-55.30.
HRMS(APCI)calcd for C17H14F3N3O2[M+H+],350.1111;found:350.1108.
根据以上数据推断所得产物的结构如下式所示:
实施例40
在Schlenk管中加入0.3~0.4mmol 2-硝基-3-甲氧基雌酚酮,0.2mmol吡咯,0.02mmol乙酰丙酮钯或三(二亚苄基丙酮)二钯,0.03mmol BrettPhos,0.4~0.6mmol碳酸钾、磷酸钾或碳酸铷,1.0~2.0mL邻二甲苯、二氧六环或间二甲苯。在150℃,N2条件下搅拌反应16~24小时后,停止加热及搅拌,冷却至室温。抽滤,减压旋蒸除去溶剂,再通过柱层析分离纯化,得到目标产物。所用的柱层析洗脱液的体积比为40:1的石油醚:乙酸乙酯混合溶剂。
所得产物的结构表征数据如下:
1H NMR(500MHz,CDCl3)δ7.21(s,1H),6.95(t,J=2.0Hz,2H),6.75(s,1H),6.30(t,J=2.1Hz,2H),3.80(s,3H),2.96(dd,J=8.6,3.7Hz,2H),2.52(dd,J=19.0,8.7Hz,1H),2.41-2.34(m,1H),2.29(d,J=3.7Hz,1H),2.21-2.03(m,3H),1.99-1.93(m,1H),1.66-1.46(m,6H),0.93(s,3H).
13C NMR(126MHz,CDCl3)δ150.7,135.8,132.2,128.1,123.1,122.1,112.6,108.5,55.8,50.3,47.9,43.8,38.2,35.8,31.5,29.4,26.5,25.9,21.5,13.8.
HRMS(APCI)calcd for C23H27NO2[M+H+],350.2115;found:350.2112.
根据以上数据推断所得产物的结构如下式所示:
实施例41
在Schlenk管中加入0.3~0.4mmol对硝基苯甲醚,0.2mmol褪黑素,0.02mmol乙酰丙酮钯或三(二亚苄基丙酮)二钯,0.03mmol BrettPhos,0.4~0.6mmol碳酸钾、磷酸钾或碳酸铷,1.0~2.0mL邻二甲苯、二氧六环或间二甲苯。在150℃,N2条件下搅拌反应16~24小时后,停止加热及搅拌,冷却至室温。抽滤,减压旋蒸除去溶剂,再通过柱层析分离纯化,得到目标产物。所用的柱层析洗脱液的体积比为40:1的石油醚:乙酸乙酯混合溶剂。
所得产物的结构表征数据如下:
1H NMR(500MHz,CDCl3)δ7.37-7.29(m,3H),7.09(d,J=2.5Hz,2H),7.01-6.95(m,2H),6.86(dd,J=8.9,2.4Hz,1H),6.09(s,1H),3.86(s,3H),3.84(s,3H),3.59(q,J=6.8Hz,2H),2.97(t,J=6.9Hz,2H),1.94(s,3H).
13C NMR(126MHz,CDCl3)δ170.1,157.7,154.1,132.6,131.6,128.8,126.3,125.1,114.6,113.0,112.3,111.2,100.6,55.7,55.4,39.7,25.1,23.1.
HRMS(APCI)calcd for C20H22N2O3[M+H+],339.1703;found:339.1699
根据以上数据推断所得产物的结构如下式所示:
Claims (9)
1.一种硝基芳烃脱硝偶联合成N-芳基吡咯和N-芳基吲哚的方法,其特征在于以吡咯、吲哚类含氮芳香杂环化合物与硝基芳烃为原料,在过渡金属催化下,通过硝基芳烃与吡咯、吲哚类含氮芳杂环的碳-氮键脱硝偶联的方式直接生成N-芳基化吡咯、N-芳基化吲哚类化合物。
4.根据权利要求2所述的硝基芳烃脱硝偶联合成N-芳基吡咯和N-芳基吲哚,其特征在于按以下步骤进行操作:在反应器中,加入硝基芳烃、吡咯类含氮芳香杂环化合物、金属催化剂、配体、添加剂和溶剂,在N2保护下150℃下搅拌反应16~24h,反应结束后冷却至室温,抽滤,减压旋蒸除去溶剂即得粗产物,粗产物经柱层析纯化得到N-芳基化吡咯类化合物。
5.根据权利要求4所述的硝基芳烃脱硝偶联合成N-芳基吡咯和N-芳基吲哚,其特征在于:所述硝基芳烃与吡咯类含氮芳香杂环化合物的摩尔比为(1~4):1。
6.根据权利要求4所述的硝基芳烃脱硝偶联合成N-芳基吡咯和N-芳基吲哚,其特征在于:
所述金属催化剂为Ni(cod)2,NiBr2,NiF2,Ni(acac)2,NiCl2·DME,Cu(OAc)2,Co(acac)3,Pd(PPh3)4,Pd2(dba)3,PdCl2,PdCl2·DPPF,Pd(OAc)2,Pd(PtBu3)2,[Pd(allyl)Cl]2,Pd(acac)2中的一种或两种以上的混合;
所述配体为BrettPhos,XPhos,SPhos,RuPhos中的一种或两种以上的混合,其结构式如下:
所述添加剂为Lewis酸、无机或有机盐中的一种或两种以上的混合;
所述溶剂为三氟甲苯、甲苯、对二甲苯、1,4-二氧六环、正庚烷、叔丁醇、N,N-二甲基甲酰胺和二甲基亚砜中的一种或两种以上的混合。
7.根据权利要求6所述的硝基芳烃脱硝偶联合成N-芳基吡咯和N-芳基吲哚,其特征在于:所述Lewis酸为乙酸钠、甲醇钠、叔丁醇钠、叔丁醇钾、分子筛,所述无机或有机盐为四甲基胍、磷酸钾、碳酸钠、碳酸钾、碳酸铷、氢氧化钠、氢氧化钾等。
8.根据权利要求4所述的硝基芳烃脱硝偶联合成N-芳基吡咯和N-芳基吲哚,其特征在于:所述柱层析提纯所用的洗脱液为石油醚或体积比为(1~300):1的石油醚和乙酸乙酯的混合溶剂。
9.根据权利要求1所述的硝基芳烃脱硝偶联合成N-芳基吡咯和N-芳基吲哚,其特征在于:所述反应器为Schlenk管。
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