水相铜/十二烷基取代酰肼-吡啶-N-氧化物催化咪唑的N-芳基化

doi:10.7503/cjcu20170157

摘要/Abstract

摘要：

设计合成了5种新型烷基取代酰肼-吡啶-N-氧化物, 并将其作为水相铜催化含氮杂环与芳香碘代物偶联反应的配体. 实验结果表明, 十二烷基取代酰肼-吡啶-N-氧化物的催化效果最佳. 对影响反应的其它条件, 如铜源、碱、反应时间和温度等条件进行了优化, 建立了最佳反应条件: CuO(10%, 摩尔分数), NaOH(1 mmol), TBAB(5%, 摩尔分数), L5(20%, 摩尔分数), 于120 ℃反应12 h, 无需惰性气体保护. 在此条件下, 芳香碘代物与咪唑偶联反应的产率为60%~92%. 该方法的特点是以水作为反应溶剂, 长链烷基取代酰肼-吡啶-N-氧化物同时起到了铜催化剂配体和相转移催化剂的作用.

关键词: 十二烷基取代酰肼-吡啶-N-氧化物, C—N偶联, 芳基卤化物, 铜催化

Abstract:

Abstract In this paper, five novel dodecyl-substituted hydrazide-pyridine-N-oxide ligands were designed and synthesized as the ligands and phase-transfer catalyst for the N-arylation reaction of nitrogen-containing heterocycles and aromatic iodides. The catalytic activities of substituted hydrazide-pyridine-N-oxides, copper source, alkali, reaction time and temperature were optimized and the optimum reaction conditions were established. Under these conditions, the imidazole could be arylated smoothly with various aryl iodides to provide the corresponding products in the yields of 60%—92%. In the reaction, water was used as the reaction solvent and the long chain alkyl-substituted hydrazide-pyridine-N-oxide acts as a copper catalyst ligand and phase-transfer catalyst.

Key words: Dodecyl substituted hydrazide-pyridine-N-oxide, C—N coupling, Aryl halide, Copper catalyst

中图分类号:

O626

TrendMD:

汪小创, 张洁, 谢建伟. 水相铜/十二烷基取代酰肼-吡啶-N-氧化物催化咪唑的N-芳基化. 高等学校化学学报, 2017, 38(7): 1178.

WANG Xiaochuang, ZHANG Jie, XIE Jianwei. Copper/Dodecyl Substituted Hydrazide-pyridine-N-oxide Catalyzed N-Arylation of Imidazoles with Aryliodides in Water^†. Chem. J. Chinese Universities, 2017, 38(7): 1178.

图/表 8

参考文献 23

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Compd.	Appearance	Yield(%)	m. p./℃	HRMS(calcd.), m/z[M+H]⁺
L1	Dark green oil	60		210.1237(210.1235)
L2	Dark green oil	68		238.1550(238.1550)
L3	Dark green oil	70		266.1863(266.1863)
L4	Light green solid	70	49.0—51.0	294.2176(294.2174)
L5	Light green solid	74	59.0—60.0	322.2489(322.2489)

Compd.	Appearance	Yield(%)	m. p./℃	HRMS(calcd.), m/z[M+H]⁺
L1	Dark green oil	60		210.1237(210.1235)
L2	Dark green oil	68		238.1550(238.1550)
L3	Dark green oil	70		266.1863(266.1863)
L4	Light green solid	70	49.0—51.0	294.2176(294.2174)
L5	Light green solid	74	59.0—60.0	322.2489(322.2489)

Compd.	¹H NMR(400 MHz, CDCl₃), δ	¹³C NMR(100 MHz, CDCl₃), δ
L1	8.40(dd, J=8.4, 2.0 Hz, 1H), 8.26(ddd, J=6.4, 1.2, 0.4 Hz, 1H), 7.48(td, J=7.6, 1.2 Hz, 1H), 7.39(ddd, J=7.6, 6.4, 2.4 Hz, 1H), 3.00(t, J=7.2 Hz, 2H), 1.62—1.55(m, 2H), 1.46—1.37(m, 2H), 0.94(t, J=7.6 Hz, 3H)	158.1, 140.6, 140.0, 128.7, 127.4, 127.2, 52.0, 30.2, 20.3, 14.1
L2	12.32(s, 1H), 8.34(dd,J=8.0, 2.0 Hz, 1H), 8.20(dd, J=6.4, 0.8 Hz, 1H), 7.41(td, J=7.6, 1.2 Hz, 1H), 7.35—7.31(m, 1H), 2.90(t, J=7.6 Hz, 2H), 1.55—1.48(m, 2H), 1.33—1.24(m, 6H), 0.82(t, J=6.8 Hz, 3H)	158.1, 140.5, 134.0, 128.6, 127.3, 127.1, 52.2, 31.7, 28.1, 26.8, 22.6, 14.1
L3	12.33(s, 1H), 8.33(dd,J=8.0, 2.0 Hz, 1H), 8.22(d, J=6.0 Hz, 1H), 7.42(t, J=7.6 Hz, 1H), 7.34(td, J=7.2, 2.0 Hz, 1H), 4.97(s, 1H), 2.90(t, J=7.2 Hz, 2H), 1.56—1.48(m, 2H), 1.33—1.20(m, 10H), 0.81(t, J=7.2 Hz, 3H)	158.0, 140.4, 139.8, 128.5, 127.1, 127.0, 52.1, 31.7, 29.4, 29.2, 28.0, 27.0, 22.6, 14.0
L4	12.30(s, 1H), 8.31(dd,J=8.0, 2.0 Hz, 1H), 8.20(dd, J=6.4, 0.8 Hz, 1H), 7.40(td, J=8.0, 1.2 Hz, 1H), 7.34—7.30(m, 1H), 4.98(s, 1H), 2.88(t, J=7.2 Hz, 2H), 1.53—1.46(m, 2H), 1.29—1.17(m, 14H), 0.79(t, J=7.2 Hz, 3H)	158.0, 140.4, 139.8, 128.5, 127.1, 127.0, 52.1, 31.8, 29.6, 29.5, 29.4, 29.2, 28.0, 27.0, 22.6, 14.1
L5	12.38(s, 1H), 8.39(dd,J=8.0, 2.0 Hz, 1H), 8.26—8.24(m, 1H), 7.46(td, J=8.0, 1.2 Hz, 1H), 7.40—7.35(m, 1H), 2.95(t, J=7.2 Hz, 2H), 1.60—1.53(m, 2H), 1.34—1.24(m, 18H), 0.86(t, J=6.8 Hz, 3H)	158.1, 140.5, 140.0, 128.7, 127.3, 127.1, 52.3, 32.0, 29.9, 29.8, 29.7, 29.6, 29.5, 29.4, 28.2, 27.1, 22.8, 14.2

Compd.	¹H NMR(400 MHz, CDCl₃), δ	¹³C NMR(100 MHz, CDCl₃), δ
L1	8.40(dd, J=8.4, 2.0 Hz, 1H), 8.26(ddd, J=6.4, 1.2, 0.4 Hz, 1H), 7.48(td, J=7.6, 1.2 Hz, 1H), 7.39(ddd, J=7.6, 6.4, 2.4 Hz, 1H), 3.00(t, J=7.2 Hz, 2H), 1.62—1.55(m, 2H), 1.46—1.37(m, 2H), 0.94(t, J=7.6 Hz, 3H)	158.1, 140.6, 140.0, 128.7, 127.4, 127.2, 52.0, 30.2, 20.3, 14.1
L2	12.32(s, 1H), 8.34(dd,J=8.0, 2.0 Hz, 1H), 8.20(dd, J=6.4, 0.8 Hz, 1H), 7.41(td, J=7.6, 1.2 Hz, 1H), 7.35—7.31(m, 1H), 2.90(t, J=7.6 Hz, 2H), 1.55—1.48(m, 2H), 1.33—1.24(m, 6H), 0.82(t, J=6.8 Hz, 3H)	158.1, 140.5, 134.0, 128.6, 127.3, 127.1, 52.2, 31.7, 28.1, 26.8, 22.6, 14.1
L3	12.33(s, 1H), 8.33(dd,J=8.0, 2.0 Hz, 1H), 8.22(d, J=6.0 Hz, 1H), 7.42(t, J=7.6 Hz, 1H), 7.34(td, J=7.2, 2.0 Hz, 1H), 4.97(s, 1H), 2.90(t, J=7.2 Hz, 2H), 1.56—1.48(m, 2H), 1.33—1.20(m, 10H), 0.81(t, J=7.2 Hz, 3H)	158.0, 140.4, 139.8, 128.5, 127.1, 127.0, 52.1, 31.7, 29.4, 29.2, 28.0, 27.0, 22.6, 14.0
L4	12.30(s, 1H), 8.31(dd,J=8.0, 2.0 Hz, 1H), 8.20(dd, J=6.4, 0.8 Hz, 1H), 7.40(td, J=8.0, 1.2 Hz, 1H), 7.34—7.30(m, 1H), 4.98(s, 1H), 2.88(t, J=7.2 Hz, 2H), 1.53—1.46(m, 2H), 1.29—1.17(m, 14H), 0.79(t, J=7.2 Hz, 3H)	158.0, 140.4, 139.8, 128.5, 127.1, 127.0, 52.1, 31.8, 29.6, 29.5, 29.4, 29.2, 28.0, 27.0, 22.6, 14.1
L5	12.38(s, 1H), 8.39(dd,J=8.0, 2.0 Hz, 1H), 8.26—8.24(m, 1H), 7.46(td, J=8.0, 1.2 Hz, 1H), 7.40—7.35(m, 1H), 2.95(t, J=7.2 Hz, 2H), 1.60—1.53(m, 2H), 1.34—1.24(m, 18H), 0.86(t, J=6.8 Hz, 3H)	158.1, 140.5, 140.0, 128.7, 127.3, 127.1, 52.3, 32.0, 29.9, 29.8, 29.7, 29.6, 29.5, 29.4, 28.2, 27.1, 22.8, 14.2

Compd.	Molecular formula	GC-MS(calcd.), m/z(M⁺)	Compd.	Molecular formula	GC-MS(calcd.), m/z(M⁺)
3a	C₁₀H₁₀N₂O	174(174)	3i	C₁₀H₁₀N₂	158(158)
3b	C₉H₈N₂	144(144)	3j	C₁₅H₁₂N₂	220(220)
3c	C₉H₇FN₂	162(162)	3k	C₁₁H₁₀N₂O	186(186)
3d	C₁₁H₁₂N₂O	188(188)	3l	C₁₅H₁₃NO	223(223)
3e	C₁₀H₁₀N₂O	174(174)	3m	C₁₄H₁₀ClN	227(227)
3f	C₁₀H₁₀N₂O		3n	C₁₅H₁₃NO	223(223)
3g	C₉H₈N₂O	160(160)	3o	C₁₆H₁₅NO	237(237)
3h	C₉H₇ClN₂	178(178)	3p	C₁₀H₈N₂O₂	188(188)