TBAC/TBHP体系下6-氨基甲酰基取代的啡啶类化合物的合成

doi:10.7503/cjcu20180663

摘要/Abstract

摘要：

采用2-异氰基联苯与N,N-二甲基甲酰胺(DMF)作为反应原料, 在四丁基氯化铵(TBAC)、磷酸氢二钾(K₂HPO₄)和叔丁基过氧化氢(TBHP)组成的催化氧化体系作用下, 通过一步构建2个C—C键, 以较高的产率合成了一系列6-氨基甲酰基取代的啡啶类化合物(产率高达86%). 同时利用该方法研究了一系列含有推电子和吸电子取代基的2-异氰基联苯衍生物的普适性, 为具有药物活性的该类分子的合成提供了一种新的方法.

关键词: 串联环化, 6-酰胺基啡啶, 2-异氰基联苯衍生物

Abstract:

In the presence of simple K₂HPO₄, under catalytic oxidation of tetrabutylammonium chloride(TBAC) and tert-butyl hydroperoxide(TBHP), the couple reaction of 2-isocyanobiphenyl derivatives with N,N-dimethylformamide(DMF) was realized, and 6-aminoformyl-substituted phenanthridine compounds were obtained by formation of two C—C bonds in one pot reaction. A series of 2-isocyanobiphenyl derivatives containg electron-donating and withdrawing substituents was investigated. Corresponding 6-aminoformyl substituted phenanthridines were constructed in moderate to high yields(up to 86% yield), which would provide promising candidates for chemical biology and drug discover.

Key words: Cascade cyclization, Phenanthridine-6-carboxamide, 2-Isocyanobiphenyl derivative

中图分类号:

O626

TrendMD:

代佳男, 杨子祺, 魏忠林, 曹军刚, 梁大鹏, 段海峰, 林英杰. TBAC/TBHP体系下6-氨基甲酰基取代的啡啶类化合物的合成. 高等学校化学学报, 2019, 40(4): 712.

DAI Jianan,YANG Ziqi,WEI Zhonglin,CAO Jungang,LIANG Dapeng,DUAN Haifeng,LIN Yingjie. Synthesis of 6-Aminoformyl-substituted Phenanthridines Promoted by TBAC/TBHP System^†. Chem. J. Chinese Universities, 2019, 40(4): 712.

图/表 9

参考文献 46

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Compd.	Appearance	Yield(%)	Melting point/℃	HRMS, m/z[M+H]⁺(calcd.)
3a	Yellow oil	75		251.1176(251.1179)
3b	White solid	61	150—152	265.1336(265.1335)
3c	White solid	69	123—125	265.1332(265.1335)
3d	White solid	74	146—148	265.1335(265.1335)
3e	White solid	81	129—131	279.1490(279.1492)
3f	White solid	59	227—229	281.1282(281.1285)
3g	White solid	56	153—155	285.0786(285.0789)
3h	White solid	65	163—165	319.1053(319.1053)
3i	Green oil	62		327.1490(327.1492)
3j	White solid	65	204—206	285.0786(285.0789)
3k	Yellow solid	78	129—131	279.1492(279.1492)
3l	Yellow oil	59		295.1440(295.1441)
3m	White solid	86	228—230	287.0993(287.0990)
3n	White solid	53	234—236	319.0400(319.0400)
3o	White solid	60	196—198	351.1490(351.1492)

Compd.	Appearance	Yield(%)	Melting point/℃	HRMS, m/z[M+H]⁺(calcd.)
3a	Yellow oil	75		251.1176(251.1179)
3b	White solid	61	150—152	265.1336(265.1335)
3c	White solid	69	123—125	265.1332(265.1335)
3d	White solid	74	146—148	265.1335(265.1335)
3e	White solid	81	129—131	279.1490(279.1492)
3f	White solid	59	227—229	281.1282(281.1285)
3g	White solid	56	153—155	285.0786(285.0789)
3h	White solid	65	163—165	319.1053(319.1053)
3i	Green oil	62		327.1490(327.1492)
3j	White solid	65	204—206	285.0786(285.0789)
3k	Yellow solid	78	129—131	279.1492(279.1492)
3l	Yellow oil	59		295.1440(295.1441)
3m	White solid	86	228—230	287.0993(287.0990)
3n	White solid	53	234—236	319.0400(319.0400)
3o	White solid	60	196—198	351.1490(351.1492)

Compd.		¹³C NMR(101 MHz, CDCl₃), δ
3a	8.68(d, J=8.2 Hz, 1H), 8.62(d, J=8.4 Hz, 1H), 8.21(d, J=8.1 Hz, 1H), 8.09(d, J=8.1 Hz, 1H), 7.91(t, J=7.7 Hz, 1H), 7.82—7.69(m, 3H), 3.33(s, 3H), 2.95(s, 3H)	168.3, 156.4, 143.2, 133.4, 131.5, 130.4, 129.2, 128.1, 127.9, 127.2, 124.2, 123.3, 122.5, 122.3, 38.5, 35.0
3b	8.64(d, J=8.3 Hz, 1H), 8.37(s, 1H), 8.07(t, J=8.8 Hz, 2H), 7.86(t, J=7.6 Hz, 1H), 7.68(t, J=7.6 Hz, 1H), 7.59(d, J=8.3 Hz, 1H), 3.31(s, 3H), 2.93(s, 3H), 2.64(s, 3H).	168.4, 155.4, 141.5, 137.9, 133.0, 131.2, 130.9, 130.0, 127.8, 127.1, 124.0, 123.3, 122.4, 121.8, 38.4, 34.9, 22.1
3c	8.85(d, J=8.4 Hz, 1H), 8.24(d, J=9.3 Hz, 1H), 7.96(d, J=7.9 Hz, 1H), 7.80—7.67(m, 3H), 7.61(t, J=7.7 Hz, 1H), 3.31(s, 3H), 3.15(s, 3H), 2.90(s, 3H)	168.7, 157.2, 144.4, 135.8, 135.7, 132.7, 130.6, 128.3, 127.5, 127.0, 126.7, 125.8, 125.7, 124.6, 38.3, 34.9, 26.9
3d	8.58—8.51(m, 2H), 8.20—8.14(m, 1H), 7.83(s, 1H), 7.76—7.66(m, 3H), 3.32(s, 3H), 2.93(s, 3H), 2.58(s, 3H)	168.4, 156.1, 142.8, 138.2, 133.3, 131.2, 130.2, 128.6, 127.7, 126.4, 124.3, 123.4, 122.3, 122.0, 38.4, 34.9, 21.8
3e	8.63(d, J=8.4 Hz, 1H), 8.22(s, 1H), 8.08(d, J=8.1 Hz, 1H), 7.82(t, J=7.7 Hz, 1H), 7.66(t, J=7.6 Hz, 1H), 7.45(s, 1H), 3.32(s, 3H), 2.93(s, 3H), 2.81(s, 3H), 2.59(s, 3H)	168.8, 153.6, 140.2, 138.1, 137.3, 133.3, 131.6, 130.8, 127.5, 127.0, 123.9, 123.2, 122.6, 119.6, 38.6, 35.0, 22.1, 18.5
3f	8.57(d, J=9.1 Hz, 1H), 8.51(dd, J=6.2, 3.2 Hz, 1H), 8.17(dd, J=6.2, 3.1 Hz, 1H), 7.75—7.65(m, 2H), 7.51(dd, J=9.1, 2.6 Hz, 1H), 7.41(d, J=2.5 Hz, 1H), 3.97(s, 3H), 3.32(s, 3H), 2.95(s, 3H)	168.3, 159.2, 155.3, 142.3, 130.2, 128.1, 127.9, 127.9, 124.6, 124.4, 124.1, 122.4, 121.7, 106.8, 55.8, 38.5, 35.1
3g	8.55(dd, J=19.7, 8.4 Hz, 2H), 8.18(d, J=8.7 Hz, 1H), 8.07(d, J=2.0 Hz, 1H), 7.84—7.69(m, 3H), 3.32(s, 3H), 2.96(s, 3H)	167.7, 155.1, 143.0, 134.0, 132.1, 131.7, 130.5, 129.5, 128.3, 126.4, 124.2, 124.2, 123.6, 122.1, 38.5, 35.1
3h	8.77(t, J=9.8 Hz, 1H), 8.65—8.56(m, 1H), 8.39(s, 1H), 8.22(t, J=8.0 Hz, 1H), 8.11—8.02(m, 1H), 7.88—7.73(m, 2H), 3.40—3.30(m, 3H), 3.04—2.93(m, 3H)	167.5, 155.9, 143.7, 135.5, 130.5(d, J=20.4 Hz), 128.5, 127.3, 124.9, 123.6, 123.3, 122.8, 122.6, 38.6, 35.2
3i	8.75—8.70(m, 1H), 8.60(d, J=8.2 Hz, 1H), 8.26—8.14(m, 3H), 8.01(s, 1H), 7.74—7.71(m, 3H), 7.52(t, J=8.0 Hz, 3H), 3.32(s, 3H), 2.88(s, 3H)	168.3, 162.6, 156.5, 143.1, 140.9, 140.0, 132.3, 130.8, 129.1, 128.1, 127.9, 127.6, 127.4, 125.1, 124.0, 123.7, 123.0, 122.2, 38.5, 35.0
3j	8.63—8.51(m, 2H), 8.18—8.05(m, 2H), 7.95—7.86(m, 1H), 7.79—7.66(m, 2H), 3.32(d, J=1.0 Hz, 3H), 2.93(d, J=1.3 Hz, 3H)	168.0, 156.6, 141.6, 133.9, 132.3, 131.8, 131.8, 129.7, 128.7, 127.3, 125.3, 123.4, 122.5, 121.9, 38.4, 35.0
3k	8.52(d, J=8.5 Hz, 1H), 8.32(s, 1H), 8.05(d, J=8.3 Hz, 1H), 7.82(s, 1H), 7.67(d, J=8.3 Hz, 1H), 7.54(t, J=7.6 Hz, 1H), 3.31(s, 3H), 2.92(s, 3H), 2.63(s, 3H), 2.57(s, 3H)	168.6, 155.1, 141.2, 137.9, 137.7, 133.0, 130.9, 130.4, 129.9, 126.3, 124.1, 123.5, 122.2, 121.6, 38.4, 34.9, 22.1, 21.7
3l	8.52(t, J=8.9 Hz, 1H), 8.26(s, 1H), 8.04(d, J=8.3 Hz, 1H), 7.57—7.42(m, 2H), 7.38(d, J=2.4 Hz, 1H), 3.95(s, 3H), 3.30(s, 3H), 2.93(s, 3H), 2.61(s, 3H)	168.5, 162.5, 159.1, 154.3, 140.6, 137.9, 129.9, 129.9, 127.5, 124.7, 124.2, 124.0, 122.1, 121.3, 106.6, 55.7, 38.5, 35.0, 25.9
3m	8.52(dd, J=9.1, 5.0 Hz, 1H), 8.21—8.08(m, 2H), 7.75(dd, J=9.0, 2.4 Hz, 1H), 7.68—7.58(m, 1H), 7.53—7.44(m, 1H), 3.31(s, 3H), 2.96(s, 3H)	167.6, 139.6, 132.7, 125.3, 124.7, 124.7, 121.0, 120.8, 118.2, 118.0, 112.1, 111.8, 107.2, 107.0, 38.5, 35.1.
3n	8.49(d, J=8.9 Hz, 2H), 8.08(dd, J=12.8, 5.3 Hz, 2H), 7.83(dd, J=8.8, 1.9 Hz, 1H), 7.70(dd, J=8.7, 2.0 Hz, 1H), 3.32(s, 3H), 2.95(s, 3H)	167.3, 155.3, 141.4, 134.8, 134.4, 132.4, 131.9, 130.7, 130.1, 126.6, 124.7, 124.4, 124.2, 121.8, 38.5, 35.1
3o	8.84(d, J=8.2 Hz, 1H), 8.76(d, J=8.4 Hz, 1H), 8.70(t, 2H), 8.52(d, J=8.1 Hz, 1H), 8.30(d, J=8.2 Hz, 1H), 7.79(t, J=7.3 Hz, 2H), 7.76—7.60(m, 4H), 3.31(s, 3H), 2.82(s, 3H)	170.8, 152.7, 145.6, 135.1, 132.7, 130.6, 130.1, 129.4, 129.2, 129.1, 128.2, 128.1, 127.9, 127.8, 127.7, 127.3, 127.0, 125.8, 123.9, 123.7, 123.5, 120.4, 38.4, 35.4

Compd.		¹³C NMR(101 MHz, CDCl₃), δ
3a	8.68(d, J=8.2 Hz, 1H), 8.62(d, J=8.4 Hz, 1H), 8.21(d, J=8.1 Hz, 1H), 8.09(d, J=8.1 Hz, 1H), 7.91(t, J=7.7 Hz, 1H), 7.82—7.69(m, 3H), 3.33(s, 3H), 2.95(s, 3H)	168.3, 156.4, 143.2, 133.4, 131.5, 130.4, 129.2, 128.1, 127.9, 127.2, 124.2, 123.3, 122.5, 122.3, 38.5, 35.0
3b	8.64(d, J=8.3 Hz, 1H), 8.37(s, 1H), 8.07(t, J=8.8 Hz, 2H), 7.86(t, J=7.6 Hz, 1H), 7.68(t, J=7.6 Hz, 1H), 7.59(d, J=8.3 Hz, 1H), 3.31(s, 3H), 2.93(s, 3H), 2.64(s, 3H).	168.4, 155.4, 141.5, 137.9, 133.0, 131.2, 130.9, 130.0, 127.8, 127.1, 124.0, 123.3, 122.4, 121.8, 38.4, 34.9, 22.1
3c	8.85(d, J=8.4 Hz, 1H), 8.24(d, J=9.3 Hz, 1H), 7.96(d, J=7.9 Hz, 1H), 7.80—7.67(m, 3H), 7.61(t, J=7.7 Hz, 1H), 3.31(s, 3H), 3.15(s, 3H), 2.90(s, 3H)	168.7, 157.2, 144.4, 135.8, 135.7, 132.7, 130.6, 128.3, 127.5, 127.0, 126.7, 125.8, 125.7, 124.6, 38.3, 34.9, 26.9
3d	8.58—8.51(m, 2H), 8.20—8.14(m, 1H), 7.83(s, 1H), 7.76—7.66(m, 3H), 3.32(s, 3H), 2.93(s, 3H), 2.58(s, 3H)	168.4, 156.1, 142.8, 138.2, 133.3, 131.2, 130.2, 128.6, 127.7, 126.4, 124.3, 123.4, 122.3, 122.0, 38.4, 34.9, 21.8
3e	8.63(d, J=8.4 Hz, 1H), 8.22(s, 1H), 8.08(d, J=8.1 Hz, 1H), 7.82(t, J=7.7 Hz, 1H), 7.66(t, J=7.6 Hz, 1H), 7.45(s, 1H), 3.32(s, 3H), 2.93(s, 3H), 2.81(s, 3H), 2.59(s, 3H)	168.8, 153.6, 140.2, 138.1, 137.3, 133.3, 131.6, 130.8, 127.5, 127.0, 123.9, 123.2, 122.6, 119.6, 38.6, 35.0, 22.1, 18.5
3f	8.57(d, J=9.1 Hz, 1H), 8.51(dd, J=6.2, 3.2 Hz, 1H), 8.17(dd, J=6.2, 3.1 Hz, 1H), 7.75—7.65(m, 2H), 7.51(dd, J=9.1, 2.6 Hz, 1H), 7.41(d, J=2.5 Hz, 1H), 3.97(s, 3H), 3.32(s, 3H), 2.95(s, 3H)	168.3, 159.2, 155.3, 142.3, 130.2, 128.1, 127.9, 127.9, 124.6, 124.4, 124.1, 122.4, 121.7, 106.8, 55.8, 38.5, 35.1
3g	8.55(dd, J=19.7, 8.4 Hz, 2H), 8.18(d, J=8.7 Hz, 1H), 8.07(d, J=2.0 Hz, 1H), 7.84—7.69(m, 3H), 3.32(s, 3H), 2.96(s, 3H)	167.7, 155.1, 143.0, 134.0, 132.1, 131.7, 130.5, 129.5, 128.3, 126.4, 124.2, 124.2, 123.6, 122.1, 38.5, 35.1
3h	8.77(t, J=9.8 Hz, 1H), 8.65—8.56(m, 1H), 8.39(s, 1H), 8.22(t, J=8.0 Hz, 1H), 8.11—8.02(m, 1H), 7.88—7.73(m, 2H), 3.40—3.30(m, 3H), 3.04—2.93(m, 3H)	167.5, 155.9, 143.7, 135.5, 130.5(d, J=20.4 Hz), 128.5, 127.3, 124.9, 123.6, 123.3, 122.8, 122.6, 38.6, 35.2
3i	8.75—8.70(m, 1H), 8.60(d, J=8.2 Hz, 1H), 8.26—8.14(m, 3H), 8.01(s, 1H), 7.74—7.71(m, 3H), 7.52(t, J=8.0 Hz, 3H), 3.32(s, 3H), 2.88(s, 3H)	168.3, 162.6, 156.5, 143.1, 140.9, 140.0, 132.3, 130.8, 129.1, 128.1, 127.9, 127.6, 127.4, 125.1, 124.0, 123.7, 123.0, 122.2, 38.5, 35.0
3j	8.63—8.51(m, 2H), 8.18—8.05(m, 2H), 7.95—7.86(m, 1H), 7.79—7.66(m, 2H), 3.32(d, J=1.0 Hz, 3H), 2.93(d, J=1.3 Hz, 3H)	168.0, 156.6, 141.6, 133.9, 132.3, 131.8, 131.8, 129.7, 128.7, 127.3, 125.3, 123.4, 122.5, 121.9, 38.4, 35.0
3k	8.52(d, J=8.5 Hz, 1H), 8.32(s, 1H), 8.05(d, J=8.3 Hz, 1H), 7.82(s, 1H), 7.67(d, J=8.3 Hz, 1H), 7.54(t, J=7.6 Hz, 1H), 3.31(s, 3H), 2.92(s, 3H), 2.63(s, 3H), 2.57(s, 3H)	168.6, 155.1, 141.2, 137.9, 137.7, 133.0, 130.9, 130.4, 129.9, 126.3, 124.1, 123.5, 122.2, 121.6, 38.4, 34.9, 22.1, 21.7
3l	8.52(t, J=8.9 Hz, 1H), 8.26(s, 1H), 8.04(d, J=8.3 Hz, 1H), 7.57—7.42(m, 2H), 7.38(d, J=2.4 Hz, 1H), 3.95(s, 3H), 3.30(s, 3H), 2.93(s, 3H), 2.61(s, 3H)	168.5, 162.5, 159.1, 154.3, 140.6, 137.9, 129.9, 129.9, 127.5, 124.7, 124.2, 124.0, 122.1, 121.3, 106.6, 55.7, 38.5, 35.0, 25.9
3m	8.52(dd, J=9.1, 5.0 Hz, 1H), 8.21—8.08(m, 2H), 7.75(dd, J=9.0, 2.4 Hz, 1H), 7.68—7.58(m, 1H), 7.53—7.44(m, 1H), 3.31(s, 3H), 2.96(s, 3H)	167.6, 139.6, 132.7, 125.3, 124.7, 124.7, 121.0, 120.8, 118.2, 118.0, 112.1, 111.8, 107.2, 107.0, 38.5, 35.1.
3n	8.49(d, J=8.9 Hz, 2H), 8.08(dd, J=12.8, 5.3 Hz, 2H), 7.83(dd, J=8.8, 1.9 Hz, 1H), 7.70(dd, J=8.7, 2.0 Hz, 1H), 3.32(s, 3H), 2.95(s, 3H)	167.3, 155.3, 141.4, 134.8, 134.4, 132.4, 131.9, 130.7, 130.1, 126.6, 124.7, 124.4, 124.2, 121.8, 38.5, 35.1
3o	8.84(d, J=8.2 Hz, 1H), 8.76(d, J=8.4 Hz, 1H), 8.70(t, 2H), 8.52(d, J=8.1 Hz, 1H), 8.30(d, J=8.2 Hz, 1H), 7.79(t, J=7.3 Hz, 2H), 7.76—7.60(m, 4H), 3.31(s, 3H), 2.82(s, 3H)	170.8, 152.7, 145.6, 135.1, 132.7, 130.6, 130.1, 129.4, 129.2, 129.1, 128.2, 128.1, 127.9, 127.8, 127.7, 127.3, 127.0, 125.8, 123.9, 123.7, 123.5, 120.4, 38.4, 35.4

Entry	n(1a)/ mmol	n(2)/ mmol	n(DBU)/ mmol	n(TBAI)/ mmol	n(TBHP)/ mmol	Solvent (5 mL)	Time/h	Yield^b(%)
1	0.5	1	0.5	0.5	3	1,1,2-TCA	6	——
2	0.5	0.25	0.25	0.25	0.75	1,1,2-TCA	6	——
3	0.5		0.5	0.5	3	DMF	6	28
4	0.5		0.5	0.5	3	DMF	12	28
5	0.5		0.5	0.5	3	DMF	24	25
6	0.5		0.5	0.5	3	DMF	48	17