纳米氧化铜催化一锅法合成β-咔啉类化合物

doi:10.7503/cjcu20180326

高等学校化学学报 ›› 2018, Vol. 39 ›› Issue (11): 2411.doi: 10.7503/cjcu20180326

纳米氧化铜催化一锅法合成β-咔啉类化合物

张金^1,²(), 史天彩¹, 罗力文¹, 刘佳¹, 刘荣¹, 刘乐¹, 梁明¹, 马养民^1,²()

1. 陕西科技大学化学与化工学院, 西安710021
2. 陕西省轻化工助剂重点实验室, 西安710021

收稿日期:2018-04-26 出版日期:2018-11-10 发布日期:2018-08-23
作者简介:联系人简介: 张金, 男, 博士, 副教授, 主要从事功能小分子合成方面的研究. E-mail: zhangjin@sust.edu.cn; 马养民, 男, 博士, 教授, 博士生导师, 主要从事天然产物提取、合成及鉴定方面的研究. E-mail: mym63@sina.com
基金资助:
陕西省教育厅专项科研计划项目(批准号: 17JK0107)、陕西科技大学博士科研启动基金(批准号: BJ12-26)和陕西科技大学大学生创新创业训练计划项目(批准号: 2016102)资助.

One-pot Synthesis of β-Carboline Derivatives Catalyzed by CuO Nanoparticles^†

ZHANG Jin^1,^2,^*(), SHI Tiancai¹, LUO Liwen¹, LIU Jia¹, LIU Rong¹, LIU Le¹, LIANG Ming¹, MA Yangmin^1,^2,^*()

1. College of Chemistry & Chemical Engineering, Shaanxi University of Science and Technology, Xi’an 710021, China
2. Shaanxi Key Laboratory of Chemical Additives for Industry, Shaanxi University of Science and Technology, Xi’an 710021, China

Received:2018-04-26 Online:2018-11-10 Published:2018-08-23
Contact: ZHANG Jin,MA Yangmin E-mail:zhangjin@sust.edu.cn;mym63@sina.com
Supported by:
† Supported by the Scientific Research Project of Shaanxi Province Education Department, China(No.17JK0107), the Foundation for Young Scholars of Shaanxi University of Science & Technology, China(No.BJ12-26) and the Training Programs of Innovation and Entrepreneurship for Undergraduates of Shaanxi University of Science and Technology, China(No.2016102).

摘要/Abstract

摘要：

通过纳米氧化铜催化色氨酸酯与醛的环化-氧化串联反应, 发展了一种快速有效合成1,3-二取代-β-咔啉衍生物的一步合成法. 在温和的条件下, 目标产物可以达到中等到优良的产率. 该反应的特点是纳米氧化铜既作为催化剂促进成环, 又作为氧化剂将四氢-β-咔啉氧化成β-咔啉, 从而提高了反应效率.

关键词: 纳米氧化铜, β-咔啉;, Pictet-Spengler反应, 一锅法合成

Abstract:

Compounds containing β-carboline moiety have a variety of special biochemical and pharmacological activities. In order to explore the method for efficient synthesize β-carbolines, a novel method applied Pictet-Spengler cyclization and coupling oxidation in one-step was studied. Tryptophan esters and aromatic aldehydes were heated in N,N-Dimethylformamide via the promotion of nano CuO. Twenty-five compounds of 1,3-disubstituted-β-carbolines were obtained in moderate to excellent yield with subsequent isolation and purification. Attractive features of this method included simple operation, high efficiency and mild condition. Especially, nano CuO as catalyst and oxidant promoted cyclization and oxidation processes in creating β-carbolines motif.

Key words: Nano CuO, β-Carboline derivative;, Pictet-Spengler reaction, One-pot synthesis

中图分类号:

O626

TrendMD:

张金, 史天彩, 罗力文, 刘佳, 刘荣, 刘乐, 梁明, 马养民. 纳米氧化铜催化一锅法合成β-咔啉类化合物. 高等学校化学学报, 2018, 39(11): 2411.

ZHANG Jin, SHI Tiancai, LUO Liwen, LIU Jia, LIU Rong, LIU Le, LIANG Ming, MA Yangmin. One-pot Synthesis of β-Carboline Derivatives Catalyzed by CuO Nanoparticles^†. Chem. J. Chinese Universities, 2018, 39(11): 2411.

图/表 5

参考文献 33

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Compd.	Appearance	Yield(%)	m. p./℃	HRMS, m/z[M+H]⁺(calcd.)
3a	White solid	87	243—244(242—245^[26])	348.0948(348.0979)
3b	Yellow solid	82	294—295(>260^[26])	348.0954(348.0979)
3c	Yellow solid	76	280—281	348.0962(348.0979)
3d	White solid	60	233—235(229—230^[26])	333.1248(333.1234)
3e	Yellow solid	78	235—237	304.1102(304.1081)
3f	Yellow solid	75	176—177(172—174^[27])	304.1095(304.1081)
3g	White solid	80	228—230	329.1276(329.1285)
3h	White solid	82	268—271	337.0735(337.0738)
Compd.	Appearance	Yield(%)	m. p./℃	HRMS, m/z[M+H]⁺(calcd.)
3i	White solid	83	262—265	381.0229(381.0233)
3j	White solid	62	229—230	345.1587(345.1598)
3k	White solid	57	231—218	331.1072(331.1077)
3l	Yellow solid	72	279—280	362.1128(362.1135)
3m	Yellow solid	79	275—278	376.1295(376.1292)
3n	Yellow solid	74	225—230	390.1441(390.1448)
3o	Yellow solid	76	225—226	404.1614(404.1605)
3p	Yellow solid	85	313—315	362.1129(362.1135)
3q	White solid	86	249—250	376.1286(376.1292)
3r	White solid	82	193—195	390.1443(390.1448)
3s	White solid	84	184—185	404.1601(404.1605)
3t	White solid	64	279—280	402.1448(402.1448)
3u	Yellow solid	77	272—273	362.1133(362.1135)
3v	Yellow solid	70	260—262	376.1288(376.1292)
3w	Yellow solid	63	220—221	390.1445(390.1448)
3x	Yellow solid	70	200—201	404.1601(404.1605)
3y	Yellow solid	60	261—262	402.1443(402.1448)

Compd.	Appearance	Yield(%)	m. p./℃	HRMS, m/z[M+H]⁺(calcd.)
3a	White solid	87	243—244(242—245^[26])	348.0948(348.0979)
3b	Yellow solid	82	294—295(>260^[26])	348.0954(348.0979)
3c	Yellow solid	76	280—281	348.0962(348.0979)
3d	White solid	60	233—235(229—230^[26])	333.1248(333.1234)
3e	Yellow solid	78	235—237	304.1102(304.1081)
3f	Yellow solid	75	176—177(172—174^[27])	304.1095(304.1081)
3g	White solid	80	228—230	329.1276(329.1285)
3h	White solid	82	268—271	337.0735(337.0738)
Compd.	Appearance	Yield(%)	m. p./℃	HRMS, m/z[M+H]⁺(calcd.)
3i	White solid	83	262—265	381.0229(381.0233)
3j	White solid	62	229—230	345.1587(345.1598)
3k	White solid	57	231—218	331.1072(331.1077)
3l	Yellow solid	72	279—280	362.1128(362.1135)
3m	Yellow solid	79	275—278	376.1295(376.1292)
3n	Yellow solid	74	225—230	390.1441(390.1448)
3o	Yellow solid	76	225—226	404.1614(404.1605)
3p	Yellow solid	85	313—315	362.1129(362.1135)
3q	White solid	86	249—250	376.1286(376.1292)
3r	White solid	82	193—195	390.1443(390.1448)
3s	White solid	84	184—185	404.1601(404.1605)
3t	White solid	64	279—280	402.1448(402.1448)
3u	Yellow solid	77	272—273	362.1133(362.1135)
3v	Yellow solid	70	260—262	376.1288(376.1292)
3w	Yellow solid	63	220—221	390.1445(390.1448)
3x	Yellow solid	70	200—201	404.1601(404.1605)
3y	Yellow solid	60	261—262	402.1443(402.1448)

Compd.	¹H NMR(400 MHz), δ	¹³C NMR(100 MHz), δ
3a	12.14(s, 1H), 9.00(s, 1H), 8.77(s, 1H), 8.44(dd, J=19.4, 7.5 Hz, 3H), 7.94(t, J=7.9 Hz, 1H), 7.70(d, J=8.0 Hz, 1H), 7.64(t, J=7.4 Hz, 1H), 7.36(t, J=7.3 Hz, 1H), 3.95(s, 3H)	165.79, 148.11, 141.52, 139.47, 138.87, 136.77, 135.03, 134.68, 130.43, 129.75, 129.02, 123.58, 123.32, 122.21, 121.04, 120.63, 117.48, 112.65, 52.14
3b	12.13(s, 1H), 9.01(s, 1H), 8.47(d, J=8.2 Hz, 3H), 8.30(d, J=8.3 Hz, 2H), 7.67(d, J=20.4 Hz, 2H), 7.36(s, 1H), 3.95(s, 3H)	165.77, 143.62, 141.56, 139.40, 136.85, 134.80, 129.91, 129.07, 123.87, 122.21, 120.97, 120.68, 117.64, 112.70, 52.15
3c	12.02(s, 1H), 12.02(s, 1H), 9.00(s, 1H), 8.47(d, J=7.9 Hz, 1H), 8.24(dd, J=31.2, 15.7 Hz, 1H), 8.07—7.79(m, 3H), 7.73—7.50(m, 2H), 7.50—7.24(m, 1H), 3.90(s, 3H)	165.72, 148.60, 141.32, 139.83, 136.20, 135.29, 133.78, 132.04, 132.03, 130.34, 128.91, 128.64, 124.86, 122.29, 121.07, 120.54, 117.44, 112.50, 52.05
3d	8.99(s, 1H), 8.85(s, 1H), 8.23(d, J=7.9 Hz, 1H), 7.87(d, J=8.6 Hz, 2H), 7.61(t, J=11.8 Hz, 2H), 7.43—7.33(m, 1H), 7.01(d, J=8.6 Hz, 2H), 4.07(s, 3H), 3.85(s, 3H)	166.50, 159.83, 142.34, 140.11, 137.51, 134.54, 129.71, 129.12, 128.36, 121.68, 121.44, 120.55, 116.01, 114.09, 113.98, 111.46, 54.89, 52.18
3e	9.74(s, 1H), 8.95(d, J=10.5 Hz, 1H), 8.72(d, J=5.5 Hz, 2H), 8.26(d, J=7.9 Hz, 1H), 7.87(d, J=5.8 Hz, 2H), 7.74—7.58(m, 2H), 7.47—7.39(m, 1H), 4.08(s, 3H)	166.04, 149.85, 145.12, 140.54, 139.19, 137.86, 134.81, 130.21, 129.02, 122.65, 121.60, 121.36, 121.01, 117.55, 111.68, 52.37
3f	11.67(s, 1H), 8.96—8.91(m, 2H), 8.83(d, J=4.8 Hz, 1H), 8.25(d, J=7.8 Hz, 1H), 8.00—7.95(m, 1H), 7.71(d, J=8.2 Hz, 1H), 7.65(t, J=7.3 Hz, 1H), 7.44—7.38(m, 2H), 4.12(s, 3H)	166.24, 156.53, 147.72, 140.50, 137.07, 136.69, 136.15, 135.66, 130.18, 128.51, 123.10, 121.62, 121.40, 120.98, 120.33, 117.81, 111.83, 52.18
3g	8.88(s, 1H), 8.81(s, 1H), 8.22(d, J=7.9 Hz, 1H), 7.94(d, J=7.1 Hz, 2H), 7.61(d, J=8.0 Hz, 1H), 7.55(dd, J=14.7, 7.6 Hz, 4H), 7.47(t, J=7.3 Hz, 1H), 7.38(t, J=7.9 Hz, 2H), 4.05(s, 3H)	166.92, 142.98, 140.58, 138.31, 137.79, 136.48, 135.15, 129.83, 129.26, 129.23, 129.02, 128.72, 128.38, 122.17, 122.04, 121.18, 116.95, 111.90, 52.70
3h	12.06(s, 1H), 8.97(s, 1H), 8.46(d, J=7.9 Hz, 1H), 8.06—7.94(m, 2H), 7.68(dt, J=13.4, 8.0 Hz, 4H), 7.35(t, J=7.5 Hz, 1H), 3.95(s, 3H)	165.89, 141.50, 140.34, 139.48, 136.63, 134.54, 133.51, 130.68, 129.51, 128.87, 128.26, 127.28, 122.11, 121.05, 120.53, 117.15, 112.73, 52.10
Compd.	¹H NMR(400 MHz), δ	¹³C NMR(100 MHz), δ
3i	11.99(s, 1H), 8.95(s, 1H), 8.44(d, J=7.9 Hz, 1H), 7.98(d, J=8.3 Hz, 2H), 7.84(d, J=8.3 Hz, 2H), 7.69(d, J=8.2 Hz, 1H), 7.62(t, J=7.5 Hz, 1H), 7.34(t, J=7.4 Hz, 1H), 3.94(s, 3H)	165.93, 141.46, 140.79, 136.66, 136.60, 134.50, 131.71, 130.67, 129.38, 128.81, 122.44, 122.09, 121.05, 120.50, 116.98, 112.69, 52.08
3j	8.96(s, 1H), 8.87(s, 1H), 8.24(d, J=7.9 Hz, 1H), 7.84(d, J=8.1 Hz, 2H), 7.71—7.49(m, 2H), 7.43—7.32(m, 3H), 4.07(s, 3H), 2.98(dt, J=13.8, 6.9 Hz, 1H), 1.30(s, 3H), 1.28(s, 3H)	166.50, 149.62, 142.66, 140.09, 137.59, 134.72, 134.62, 129.08, 128.38, 127.81, 126.72, 121.65, 121.47, 120.54, 116.21, 111.42, 52.16, 33.55, 23.42
3k	12.09(s, 1H), 12.09(s, 1H), 10.19(s, 1H), 10.19(s, 1H), 9.01(s, 1H), 9.01(s, 1H), 8.48(d, J=7.9 Hz, 1H), 8.27(d, J=8.2 Hz, 2H), 8.19(d, J=8.3 Hz, 2H), 7.72(d, J=8.2 Hz, 1H), 7.67—7.60(m, 1H), 7.41—7.33(m, 1H), 3.96(s, 3H)	193.01, 165.89, 142.95, 141.54, 140.52, 136.83, 136.14, 134.78, 129.89, 129.69, 129.34, 128.96, 122.15, 121.02, 120.61, 117.36, 112.75, 52.12
3l	12.13(s, 1H), 9.00(s, 1H), 8.48(d, J=8.5 Hz, 3H), 8.30(d, J=8.6 Hz, 2H), 7.79—7.58(m, 2H), 7.37(t, J=7.3 Hz, 1H), 4.43(d, J=7.1 Hz, 2H), 1.63—1.20(m, 3H)	165.24, 147.44, 143.67, 141.57, 139.43, 137.12, 134.78, 129.92, 129.87, 129.05, 123.88, 122.20, 120.98, 120.66, 117.57, 112.70, 60.77, 14.37
3m	11.97(s, 1H), 8.94(s, 1H), 8.46(d, J=7.9 Hz, 1H), 8.26(d, J=8.1 Hz, 1H), 8.01—7.80(m, 3H), 7.62(d, J=5.6 Hz, 2H), 7.36(ddd, J=7.9, 5.6, 2.3 Hz, 1H), 5.25—5.15(m, 1H), 1.37(d, J=6.2 Hz, 6H)	192.33, 164.69, 147.47, 143.72, 141.59, 139.46, 137.47, 134.76, 130.62, 129.92, 129.04, 124.26, 123.91, 122.19, 120.99, 120.65, 117.46, 112.72, 68.20, 21.80
3n	12.13(s, 1H), 8.99(s, 1H), 8.82(s, 1H), 8.49(d, J=7.8 Hz, 2H), 8.42(d, J=7.9 Hz, 1H), 7.95(t, J=8.0 Hz, 1H), 7.71(d, J=8.1 Hz, 1H), 7.65(t, J=7.5 Hz, 1H), 7.37(t, J=7.4 Hz, 1H), 4.39(t, J=6.6 Hz, 2H), 1.84—1.72(m, 2H), 1.56—1.44(m, 2H), 0.99(t, J=7.4 Hz, 3H)	148.18, 141.55, 139.41, 138.96, 137.08, 134.94, 134.66, 130.45, 129.82, 129.02, 123.56, 123.33, 122.21, 121.06, 120.62, 117.31, 112.67, 64.46, 30.42, 18.78, 13.66
3o	12.03(s, 1H), 8.96(s, 1H), 8.48(d, J=7.9 Hz, 1H), 8.26(dd, J=8.1, 0.9 Hz, 1H), 8.01—7.90(m, 2H), 7.86(s, 1H), 7.66—7.58(m, 2H), 7.36(s, 1H), 4.31(t, J=6.7 Hz, 2H), 1.80—1.69(m, 2H), 1.46—1.32(m, 4H), 0.91(t, J=7.1 Hz, 3H)	147.47, 143.69, 141.58, 139.44, 137.13, 134.80, 129.91, 129.08, 123.90, 122.24, 120.98, 120.67, 117.55, 112.72, 64.61, 28.03, 27.66, 21.83, 13.90
3p	12.15(s, 1H), 9.01(s, 1H), 8.79(s, 1H), 8.57—8.31(m, 3H), 7.95(s, 1H), 7.67(d, J=18.2 Hz, 2H), 7.38(d, J=7.2 Hz, 1H), 4.43(d, J=7.0 Hz, 2H), 1.40(t, J=6.9 Hz, 3H)	165.25, 148.15, 141.54, 139.51, 138.94, 137.09, 135.04, 134.68, 130.47, 129.75, 129.02, 123.58, 123.34, 122.21, 121.06, 120.63, 117.39, 112.66, 60.76, 14.37
3q	12.12(s, 1H), 8.97(s, 1H), 8.80(s, 1H), 8.46(dd, J=20.0, 8.1 Hz, 3H), 7.96(t, J=8.0 Hz, 1H), 7.74—7.61(m, 2H), 7.37(t, J=7. Hz, 1H), 5.26(s, 1H), 1.41(d, J=6.2 Hz, 6H)	164.68, 148.12, 141.53, 139.47, 138.95, 137.33, 135.02, 134.62, 130.45, 129.70, 128.99, 123.56, 123.34, 122.19, 121.05, 120.59, 117.30, 114.88, 112.65, 68.18, 21.80
3r	12.03(s, 1H), 8.97(s, 1H), 8.48(d, J=7.9 Hz, 1H), 8.26(d, J=7.4 Hz, 1H), 8.00—7.89(m, 2H), 7.86(t, J=7.6 Hz, 1H), 7.62(s, 2H), 7.39—7.30(m, 1H), 4.32(t, J=6.6 Hz, 2H), 1.78—1.64(m, 2H), 1.45(dd, J=15.0, 7.4 Hz, 2H), 0.95(t, J=7.4 Hz, 3H)	165.24, 155.49, 148.81, 141.34, 139.56, 136.49, 135.19, 133.61, 131.96, 131.89, 130.29, 128.90, 128.73, 124.84, 122.28, 121.06, 120.51, 117.29, 112.51, 64.38, 30.38, 18.69, 13.65
3s	12.15(s, 1H), 8.99(s, 1H), 8.82(s, 1H), 8.55—8.37(m, 3H), 7.96(t, J=8.0 Hz, 1H), 7.75—7.60(m, 2H), 7.37(t, J=7.5 Hz, 1H), 4.38(t, J=6.7 Hz, 2H), 1.80(s, 2H), 1.54—1.31(m, 4H), 0.92(t, J = 7.1 Hz, 3H)	165.28, 148.14, 141.53, 139.36, 138.93, 137.02, 134.93, 134.63, 130.43, 129.79, 129.02, 123.56, 123.33, 122.21, 121.04, 120.61, 117.33, 112.66, 64.74, 28.03, 27.71, 21.85, 13.88
Compd.	¹H NMR(400 MHz), δ	¹³C NMR(100 MHz), δ
3t	12.11(s, 1H), 8.94(s, 1H), 8.47(d, J=8.6 Hz, 3H), 8.30(d, J=8.6 Hz, 2H), 7.70(d, J=8.2 Hz, 1H), 7.64(t, J=7.6 Hz, 1H), 7.36(t, J=7.4 Hz, 1H), 5.40(s, 1H), 1.99(s, 2H), 1.83(s, 4H), 1.65(s, 2H)	164.89, 147.40, 143.69, 141.56, 137.38, 134.70, 129.85, 129.01, 123.86, 122.20, 120.97, 120.59, 117.44, 112.70, 77.30, 32.34, 23.47
3u	12.01(s, 1H), 8.98(s, 1H), 8.47(d, J=7.9 Hz, 1H), 8.28(dd, J=8.1, 0.8 Hz, 1H), 8.00—7.84(m, 3H), 7.62(d, J=5.4 Hz, 2H), 7.36(ddd, J=8.0, 5.8, 2.3 Hz, 1H), 4.37(q, J=7.1 Hz, 2H), 1.36(t, J=7.1 Hz, 3H)	165.21, 148.66, 141.32, 139.74, 136.48, 135.24, 133.74, 132.04, 132.01, 130.32, 128.89, 128.64, 124.85, 122.26, 121.07, 120.52, 117.34, 112.50, 60.68, 14.31
3v	12.00(s, 1H), 8.95(s, 1H), 8.47(d, J=7.9 Hz, 1H), 8.27(d, J=8.1 Hz, 1H), 7.91(ddd, J=24.5, 15.1, 7.4 Hz, 3H), 7.62(d, J=5.4 Hz, 2H), 7.42—7.29(m, 1H), 5.20(dt, J=12.4, 6.2 Hz, 1H), 1.36(d, J=6.2 Hz, 6H)	164.66, 148.74, 141.33, 139.62, 136.80, 135.17, 133.67, 132.02, 131.97, 130.30, 128.86, 128.63, 124.95, 124.84, 122.24, 121.07, 120.49, 117.23, 112.50, 68.07, 21.77
3w	12.13(s, 1H), 8.98(s, 1H), 8.48(d, J=8.7 Hz, 3H), 8.31(d, J=8.8 Hz, 2H), 7.71(d, J=8.2 Hz, 1H), 7.64(t, J=7.6 Hz, 1H), 7.36(t, J=7.4 Hz, 1H), 4.38(t, J=6.7 Hz, 2H), 1.82—1.72(m, 2H), 1.54—1.42(m, 2H), 0.97(t, J=7.4 Hz, 3H)	165.25, 147.44, 143.67, 141.57, 139.40, 137.11, 134.77, 129.88, 129.05, 123.88, 122.21, 120.97, 120.65, 117.52, 112.71, 64.47, 30.42, 18.76, 13.67
3x	12.15(s, 1H), 9.00(s, 1H), 8.54-8.44(m, 3H), 8.36—8.29(m, 2H), 7.76—7.60(m, 2H), 7.42—7.33(m, 1H), 4.38(s, 2H), 1.84—1.74(m, 2H), 1.48—1.35(m, 4H), 0.92(t, J=7.1 Hz, 3H)	165.26, 147.45, 143.68, 141.57, 139.41, 137.12, 134.78, 129.99, 129.07, 123.89, 122.21, 120.97, 120.65, 117.54, 112.71, 64.76, 55.98, 28.03, 27.66, 21.84, 18.53
3y	12.12(s, 1H), 7.93(td, J=7.9, 3.2 Hz, 1H), 7.70(d, J=8.1 Hz, 1H), 7.64(t, J=7.6 Hz, 1H), 7.36(t, J=7.4 Hz, 1H), 5.44—5.36(m, 1H), 2.07—1.95(m, 2H), 1.84(t, J=11.9 Hz, 4H), 1.72—1.59(m, 2H)	164.89, 148.11, 141.52, 139.31, 138.94, 137.28, 134.90, 134.55, 130.42, 129.75, 128.97, 123.52, 123.31, 122.20, 121.04, 120.55, 117.25, 115.44, 112.64, 77.29, 32.35, 23.44

Compd.	¹H NMR(400 MHz), δ	¹³C NMR(100 MHz), δ
3a	12.14(s, 1H), 9.00(s, 1H), 8.77(s, 1H), 8.44(dd, J=19.4, 7.5 Hz, 3H), 7.94(t, J=7.9 Hz, 1H), 7.70(d, J=8.0 Hz, 1H), 7.64(t, J=7.4 Hz, 1H), 7.36(t, J=7.3 Hz, 1H), 3.95(s, 3H)	165.79, 148.11, 141.52, 139.47, 138.87, 136.77, 135.03, 134.68, 130.43, 129.75, 129.02, 123.58, 123.32, 122.21, 121.04, 120.63, 117.48, 112.65, 52.14
3b	12.13(s, 1H), 9.01(s, 1H), 8.47(d, J=8.2 Hz, 3H), 8.30(d, J=8.3 Hz, 2H), 7.67(d, J=20.4 Hz, 2H), 7.36(s, 1H), 3.95(s, 3H)	165.77, 143.62, 141.56, 139.40, 136.85, 134.80, 129.91, 129.07, 123.87, 122.21, 120.97, 120.68, 117.64, 112.70, 52.15
3c	12.02(s, 1H), 12.02(s, 1H), 9.00(s, 1H), 8.47(d, J=7.9 Hz, 1H), 8.24(dd, J=31.2, 15.7 Hz, 1H), 8.07—7.79(m, 3H), 7.73—7.50(m, 2H), 7.50—7.24(m, 1H), 3.90(s, 3H)	165.72, 148.60, 141.32, 139.83, 136.20, 135.29, 133.78, 132.04, 132.03, 130.34, 128.91, 128.64, 124.86, 122.29, 121.07, 120.54, 117.44, 112.50, 52.05
3d	8.99(s, 1H), 8.85(s, 1H), 8.23(d, J=7.9 Hz, 1H), 7.87(d, J=8.6 Hz, 2H), 7.61(t, J=11.8 Hz, 2H), 7.43—7.33(m, 1H), 7.01(d, J=8.6 Hz, 2H), 4.07(s, 3H), 3.85(s, 3H)	166.50, 159.83, 142.34, 140.11, 137.51, 134.54, 129.71, 129.12, 128.36, 121.68, 121.44, 120.55, 116.01, 114.09, 113.98, 111.46, 54.89, 52.18
3e	9.74(s, 1H), 8.95(d, J=10.5 Hz, 1H), 8.72(d, J=5.5 Hz, 2H), 8.26(d, J=7.9 Hz, 1H), 7.87(d, J=5.8 Hz, 2H), 7.74—7.58(m, 2H), 7.47—7.39(m, 1H), 4.08(s, 3H)	166.04, 149.85, 145.12, 140.54, 139.19, 137.86, 134.81, 130.21, 129.02, 122.65, 121.60, 121.36, 121.01, 117.55, 111.68, 52.37
3f	11.67(s, 1H), 8.96—8.91(m, 2H), 8.83(d, J=4.8 Hz, 1H), 8.25(d, J=7.8 Hz, 1H), 8.00—7.95(m, 1H), 7.71(d, J=8.2 Hz, 1H), 7.65(t, J=7.3 Hz, 1H), 7.44—7.38(m, 2H), 4.12(s, 3H)	166.24, 156.53, 147.72, 140.50, 137.07, 136.69, 136.15, 135.66, 130.18, 128.51, 123.10, 121.62, 121.40, 120.98, 120.33, 117.81, 111.83, 52.18
3g	8.88(s, 1H), 8.81(s, 1H), 8.22(d, J=7.9 Hz, 1H), 7.94(d, J=7.1 Hz, 2H), 7.61(d, J=8.0 Hz, 1H), 7.55(dd, J=14.7, 7.6 Hz, 4H), 7.47(t, J=7.3 Hz, 1H), 7.38(t, J=7.9 Hz, 2H), 4.05(s, 3H)	166.92, 142.98, 140.58, 138.31, 137.79, 136.48, 135.15, 129.83, 129.26, 129.23, 129.02, 128.72, 128.38, 122.17, 122.04, 121.18, 116.95, 111.90, 52.70
3h	12.06(s, 1H), 8.97(s, 1H), 8.46(d, J=7.9 Hz, 1H), 8.06—7.94(m, 2H), 7.68(dt, J=13.4, 8.0 Hz, 4H), 7.35(t, J=7.5 Hz, 1H), 3.95(s, 3H)	165.89, 141.50, 140.34, 139.48, 136.63, 134.54, 133.51, 130.68, 129.51, 128.87, 128.26, 127.28, 122.11, 121.05, 120.53, 117.15, 112.73, 52.10
Compd.	¹H NMR(400 MHz), δ	¹³C NMR(100 MHz), δ
3i	11.99(s, 1H), 8.95(s, 1H), 8.44(d, J=7.9 Hz, 1H), 7.98(d, J=8.3 Hz, 2H), 7.84(d, J=8.3 Hz, 2H), 7.69(d, J=8.2 Hz, 1H), 7.62(t, J=7.5 Hz, 1H), 7.34(t, J=7.4 Hz, 1H), 3.94(s, 3H)	165.93, 141.46, 140.79, 136.66, 136.60, 134.50, 131.71, 130.67, 129.38, 128.81, 122.44, 122.09, 121.05, 120.50, 116.98, 112.69, 52.08
3j	8.96(s, 1H), 8.87(s, 1H), 8.24(d, J=7.9 Hz, 1H), 7.84(d, J=8.1 Hz, 2H), 7.71—7.49(m, 2H), 7.43—7.32(m, 3H), 4.07(s, 3H), 2.98(dt, J=13.8, 6.9 Hz, 1H), 1.30(s, 3H), 1.28(s, 3H)	166.50, 149.62, 142.66, 140.09, 137.59, 134.72, 134.62, 129.08, 128.38, 127.81, 126.72, 121.65, 121.47, 120.54, 116.21, 111.42, 52.16, 33.55, 23.42
3k	12.09(s, 1H), 12.09(s, 1H), 10.19(s, 1H), 10.19(s, 1H), 9.01(s, 1H), 9.01(s, 1H), 8.48(d, J=7.9 Hz, 1H), 8.27(d, J=8.2 Hz, 2H), 8.19(d, J=8.3 Hz, 2H), 7.72(d, J=8.2 Hz, 1H), 7.67—7.60(m, 1H), 7.41—7.33(m, 1H), 3.96(s, 3H)	193.01, 165.89, 142.95, 141.54, 140.52, 136.83, 136.14, 134.78, 129.89, 129.69, 129.34, 128.96, 122.15, 121.02, 120.61, 117.36, 112.75, 52.12
3l	12.13(s, 1H), 9.00(s, 1H), 8.48(d, J=8.5 Hz, 3H), 8.30(d, J=8.6 Hz, 2H), 7.79—7.58(m, 2H), 7.37(t, J=7.3 Hz, 1H), 4.43(d, J=7.1 Hz, 2H), 1.63—1.20(m, 3H)	165.24, 147.44, 143.67, 141.57, 139.43, 137.12, 134.78, 129.92, 129.87, 129.05, 123.88, 122.20, 120.98, 120.66, 117.57, 112.70, 60.77, 14.37
3m	11.97(s, 1H), 8.94(s, 1H), 8.46(d, J=7.9 Hz, 1H), 8.26(d, J=8.1 Hz, 1H), 8.01—7.80(m, 3H), 7.62(d, J=5.6 Hz, 2H), 7.36(ddd, J=7.9, 5.6, 2.3 Hz, 1H), 5.25—5.15(m, 1H), 1.37(d, J=6.2 Hz, 6H)	192.33, 164.69, 147.47, 143.72, 141.59, 139.46, 137.47, 134.76, 130.62, 129.92, 129.04, 124.26, 123.91, 122.19, 120.99, 120.65, 117.46, 112.72, 68.20, 21.80
3n	12.13(s, 1H), 8.99(s, 1H), 8.82(s, 1H), 8.49(d, J=7.8 Hz, 2H), 8.42(d, J=7.9 Hz, 1H), 7.95(t, J=8.0 Hz, 1H), 7.71(d, J=8.1 Hz, 1H), 7.65(t, J=7.5 Hz, 1H), 7.37(t, J=7.4 Hz, 1H), 4.39(t, J=6.6 Hz, 2H), 1.84—1.72(m, 2H), 1.56—1.44(m, 2H), 0.99(t, J=7.4 Hz, 3H)	148.18, 141.55, 139.41, 138.96, 137.08, 134.94, 134.66, 130.45, 129.82, 129.02, 123.56, 123.33, 122.21, 121.06, 120.62, 117.31, 112.67, 64.46, 30.42, 18.78, 13.66
3o	12.03(s, 1H), 8.96(s, 1H), 8.48(d, J=7.9 Hz, 1H), 8.26(dd, J=8.1, 0.9 Hz, 1H), 8.01—7.90(m, 2H), 7.86(s, 1H), 7.66—7.58(m, 2H), 7.36(s, 1H), 4.31(t, J=6.7 Hz, 2H), 1.80—1.69(m, 2H), 1.46—1.32(m, 4H), 0.91(t, J=7.1 Hz, 3H)	147.47, 143.69, 141.58, 139.44, 137.13, 134.80, 129.91, 129.08, 123.90, 122.24, 120.98, 120.67, 117.55, 112.72, 64.61, 28.03, 27.66, 21.83, 13.90
3p	12.15(s, 1H), 9.01(s, 1H), 8.79(s, 1H), 8.57—8.31(m, 3H), 7.95(s, 1H), 7.67(d, J=18.2 Hz, 2H), 7.38(d, J=7.2 Hz, 1H), 4.43(d, J=7.0 Hz, 2H), 1.40(t, J=6.9 Hz, 3H)	165.25, 148.15, 141.54, 139.51, 138.94, 137.09, 135.04, 134.68, 130.47, 129.75, 129.02, 123.58, 123.34, 122.21, 121.06, 120.63, 117.39, 112.66, 60.76, 14.37
3q	12.12(s, 1H), 8.97(s, 1H), 8.80(s, 1H), 8.46(dd, J=20.0, 8.1 Hz, 3H), 7.96(t, J=8.0 Hz, 1H), 7.74—7.61(m, 2H), 7.37(t, J=7. Hz, 1H), 5.26(s, 1H), 1.41(d, J=6.2 Hz, 6H)	164.68, 148.12, 141.53, 139.47, 138.95, 137.33, 135.02, 134.62, 130.45, 129.70, 128.99, 123.56, 123.34, 122.19, 121.05, 120.59, 117.30, 114.88, 112.65, 68.18, 21.80
3r	12.03(s, 1H), 8.97(s, 1H), 8.48(d, J=7.9 Hz, 1H), 8.26(d, J=7.4 Hz, 1H), 8.00—7.89(m, 2H), 7.86(t, J=7.6 Hz, 1H), 7.62(s, 2H), 7.39—7.30(m, 1H), 4.32(t, J=6.6 Hz, 2H), 1.78—1.64(m, 2H), 1.45(dd, J=15.0, 7.4 Hz, 2H), 0.95(t, J=7.4 Hz, 3H)	165.24, 155.49, 148.81, 141.34, 139.56, 136.49, 135.19, 133.61, 131.96, 131.89, 130.29, 128.90, 128.73, 124.84, 122.28, 121.06, 120.51, 117.29, 112.51, 64.38, 30.38, 18.69, 13.65
3s	12.15(s, 1H), 8.99(s, 1H), 8.82(s, 1H), 8.55—8.37(m, 3H), 7.96(t, J=8.0 Hz, 1H), 7.75—7.60(m, 2H), 7.37(t, J=7.5 Hz, 1H), 4.38(t, J=6.7 Hz, 2H), 1.80(s, 2H), 1.54—1.31(m, 4H), 0.92(t, J = 7.1 Hz, 3H)	165.28, 148.14, 141.53, 139.36, 138.93, 137.02, 134.93, 134.63, 130.43, 129.79, 129.02, 123.56, 123.33, 122.21, 121.04, 120.61, 117.33, 112.66, 64.74, 28.03, 27.71, 21.85, 13.88
Compd.	¹H NMR(400 MHz), δ	¹³C NMR(100 MHz), δ
3t	12.11(s, 1H), 8.94(s, 1H), 8.47(d, J=8.6 Hz, 3H), 8.30(d, J=8.6 Hz, 2H), 7.70(d, J=8.2 Hz, 1H), 7.64(t, J=7.6 Hz, 1H), 7.36(t, J=7.4 Hz, 1H), 5.40(s, 1H), 1.99(s, 2H), 1.83(s, 4H), 1.65(s, 2H)	164.89, 147.40, 143.69, 141.56, 137.38, 134.70, 129.85, 129.01, 123.86, 122.20, 120.97, 120.59, 117.44, 112.70, 77.30, 32.34, 23.47
3u	12.01(s, 1H), 8.98(s, 1H), 8.47(d, J=7.9 Hz, 1H), 8.28(dd, J=8.1, 0.8 Hz, 1H), 8.00—7.84(m, 3H), 7.62(d, J=5.4 Hz, 2H), 7.36(ddd, J=8.0, 5.8, 2.3 Hz, 1H), 4.37(q, J=7.1 Hz, 2H), 1.36(t, J=7.1 Hz, 3H)	165.21, 148.66, 141.32, 139.74, 136.48, 135.24, 133.74, 132.04, 132.01, 130.32, 128.89, 128.64, 124.85, 122.26, 121.07, 120.52, 117.34, 112.50, 60.68, 14.31
3v	12.00(s, 1H), 8.95(s, 1H), 8.47(d, J=7.9 Hz, 1H), 8.27(d, J=8.1 Hz, 1H), 7.91(ddd, J=24.5, 15.1, 7.4 Hz, 3H), 7.62(d, J=5.4 Hz, 2H), 7.42—7.29(m, 1H), 5.20(dt, J=12.4, 6.2 Hz, 1H), 1.36(d, J=6.2 Hz, 6H)	164.66, 148.74, 141.33, 139.62, 136.80, 135.17, 133.67, 132.02, 131.97, 130.30, 128.86, 128.63, 124.95, 124.84, 122.24, 121.07, 120.49, 117.23, 112.50, 68.07, 21.77
3w	12.13(s, 1H), 8.98(s, 1H), 8.48(d, J=8.7 Hz, 3H), 8.31(d, J=8.8 Hz, 2H), 7.71(d, J=8.2 Hz, 1H), 7.64(t, J=7.6 Hz, 1H), 7.36(t, J=7.4 Hz, 1H), 4.38(t, J=6.7 Hz, 2H), 1.82—1.72(m, 2H), 1.54—1.42(m, 2H), 0.97(t, J=7.4 Hz, 3H)	165.25, 147.44, 143.67, 141.57, 139.40, 137.11, 134.77, 129.88, 129.05, 123.88, 122.21, 120.97, 120.65, 117.52, 112.71, 64.47, 30.42, 18.76, 13.67
3x	12.15(s, 1H), 9.00(s, 1H), 8.54-8.44(m, 3H), 8.36—8.29(m, 2H), 7.76—7.60(m, 2H), 7.42—7.33(m, 1H), 4.38(s, 2H), 1.84—1.74(m, 2H), 1.48—1.35(m, 4H), 0.92(t, J=7.1 Hz, 3H)	165.26, 147.45, 143.68, 141.57, 139.41, 137.12, 134.78, 129.99, 129.07, 123.89, 122.21, 120.97, 120.65, 117.54, 112.71, 64.76, 55.98, 28.03, 27.66, 21.84, 18.53
3y	12.12(s, 1H), 7.93(td, J=7.9, 3.2 Hz, 1H), 7.70(d, J=8.1 Hz, 1H), 7.64(t, J=7.6 Hz, 1H), 7.36(t, J=7.4 Hz, 1H), 5.44—5.36(m, 1H), 2.07—1.95(m, 2H), 1.84(t, J=11.9 Hz, 4H), 1.72—1.59(m, 2H)	164.89, 148.11, 141.52, 139.31, 138.94, 137.28, 134.90, 134.55, 130.42, 129.75, 128.97, 123.52, 123.31, 122.20, 121.04, 120.55, 117.25, 115.44, 112.64, 77.29, 32.35, 23.44

纳米氧化铜催化一锅法合成β-咔啉类化合物

One-pot Synthesis of β-Carboline Derivatives Catalyzed by CuO Nanoparticles^†

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Entry	Catalyst	Catalyst amount(%, molar fraction)	Solvent	t/h	Temperature/℃	Yield^b(%)
1	Nano CeO₂	10	DMF	6	60	20
2	Nano Fe₃O₄	10	DMF	6	60	Trace
3	Nano TiO₂	10	DMF	6	60	35
4	Nano CuO	10	DMF	6	60	80
5	CuO powder	10	DMF	6	60	32
6	Nano CuO	50	DMF	6	60	80
7	Nano CuO	100	DMF	6	60	80
8			DMF	6	60	Trace
9	Nano CuO	10	EtOH	6	60	60
10	Nano CuO	10	MeOH	6	60	45
11	Nano CuO	10	H₂O	6	60	10
12	Nano CuO	10	CH₃CN	6	60	69
13	Nano CuO	10	Toluene	6	60	73
14	Nano CuO	10	DMF	2	60	27
15	Nano CuO	10	DMF	4	60	49
16	Nano CuO	10	DMF	8	60	63
17	Nano CuO	10	DMF	12	60	70
18	Nano CuO	10	DMF	24	60	81
19	Nano CuO	10	DMF	12	90	85
20	Nano CuO	10	DMF	12	120	87
21	Nano CuO	10	DMF	12	150	83
22^c	Nano CuO	10	DMF	12	90	13
23^d			DMF	12	90	20

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纳米氧化铜催化一锅法合成β-咔啉类化合物

One-pot Synthesis of β-Carboline Derivatives Catalyzed by CuO Nanoparticles†

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One-pot Synthesis of β-Carboline Derivatives Catalyzed by CuO Nanoparticles^†