Copper/Dodecyl Substituted Hydrazide-pyridine-N-oxide Catalyzed N-Arylation of Imidazoles with Aryliodides in Water†

doi:10.7503/cjcu20170157

Abstract

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

CLC Number:

O626

TrendMD:

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

Figures/Tables 8

References 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)