Synthesis of 1,3-Di(2-quinolyl)propane Derivatives from Aromatic Aldehyde and 2-Methyl Quinolines Catalyzed by Brönsted Acid Ionic Liquids†

doi:10.7503/cjcu20150190

Abstract

Abstract:

An efficient synthesis of 1,3-bis(2-quinolyl) propanes from aromatic aldehydes and 2-methyl quinolines using Brönsted acid ionic liquid 1-ethyl-3-butyl imidazol p-toluenesulfonate as catalyst was described. The reaction was heated at 120 ℃ in toluene or solvent-free for 48 h to give the desired products in yields of 56%—92%. The structures of the products were characterized by nuclear magnetic resonance spectrometry(NMR) and high-resolution mass spectrometry(HRMS). The method offers several advantages including simple work up procedure, good yields and so on.

Key words: Brönsted acid ionic liquid, 1, 3-Di(2-quinolyl)propane, Aromatic aldehyde, 2-Methyl quinoline

CLC Number:

O621.25

TrendMD:

LIU Qiang, LI He, ZHANG Yonghong, WANG Bin, SUN Yadong, ABDUKADERA Ablimit, LIU Chenjiang. Synthesis of 1,3-Di(2-quinolyl)propane Derivatives from Aromatic Aldehyde and 2-Methyl Quinolines Catalyzed by Brönsted Acid Ionic Liquids^†[J]. Chem. J. Chinese Universities, 2015, 36(9): 1702.

Figures/Tables 5

References 23

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Compd.	Appearance	m. p./℃	ESI-MS(calcd.), m/z
3a	Orange liquid		375.1849(375.1856)[M+H]⁺
3b	Yellow liquid		389.2008(389.2012)[M+H]⁺
3c	Yellow liquid		405.1957(405.1961)[M+H]⁺
3d	Yellow liquid		409.1453(409.1463)[M+H]⁺
3e	Dark yellow liquid		409.1460(409.1463)[M+H]⁺
3f	Yellow liquid		409.1456(409.1463)[M+H]⁺
3g	Yellow liquid		420.1702(420.1707)[M+H]⁺
3h	Gray solid	159—161	420.1703(420.1707)[M+H]⁺
3i	Yellow liquid		453.0955(453.0961)[M+H]⁺
3j	Yellow liquid		393.1757(393.1762)[M+H]⁺
3k	Yellow solid	175—176	499.1155(499.1167)[M+H]⁺
3l	Dark yellow solid	164—166	499.1155(499.1167)[M+H]⁺
3m	Yellow liquid		469.1677(469.1682)[M+H]⁺
3n	Dark yellow liquid		477.0686(477.0686)[M+H]⁺
3o	Dark yellow solid	155—157	465.1563(465.1557)[M+H]⁺
3p	Gray solid	147—149	465.1562(465.1557)[M+H]⁺
3q	Yellow liquid		435.2069(435.2067)[M+H]⁺
3r	Dark yellow liquid		403.2173(403.2169)[M+H]⁺
3s	Yellow liquid		465.0898(465.0896)[M+H]⁺

Compd.	Appearance	m. p./℃	ESI-MS(calcd.), m/z
3a	Orange liquid		375.1849(375.1856)[M+H]⁺
3b	Yellow liquid		389.2008(389.2012)[M+H]⁺
3c	Yellow liquid		405.1957(405.1961)[M+H]⁺
3d	Yellow liquid		409.1453(409.1463)[M+H]⁺
3e	Dark yellow liquid		409.1460(409.1463)[M+H]⁺
3f	Yellow liquid		409.1456(409.1463)[M+H]⁺
3g	Yellow liquid		420.1702(420.1707)[M+H]⁺
3h	Gray solid	159—161	420.1703(420.1707)[M+H]⁺
3i	Yellow liquid		453.0955(453.0961)[M+H]⁺
3j	Yellow liquid		393.1757(393.1762)[M+H]⁺
3k	Yellow solid	175—176	499.1155(499.1167)[M+H]⁺
3l	Dark yellow solid	164—166	499.1155(499.1167)[M+H]⁺
3m	Yellow liquid		469.1677(469.1682)[M+H]⁺
3n	Dark yellow liquid		477.0686(477.0686)[M+H]⁺
3o	Dark yellow solid	155—157	465.1563(465.1557)[M+H]⁺
3p	Gray solid	147—149	465.1562(465.1557)[M+H]⁺
3q	Yellow liquid		435.2069(435.2067)[M+H]⁺
3r	Dark yellow liquid		403.2173(403.2169)[M+H]⁺
3s	Yellow liquid		465.0898(465.0896)[M+H]⁺

Compd.	¹H NMR(400 MHz, DMSO-d₆), δ	¹³C NMR(100 MHz, DMSO-d₆), δ
3e	8.00(d, J=8.4 Hz, 2H, NCCCH), 7.89(d, J=8.4 Hz, 2H, ArH), 7.67(m, 4H, ArH), 7.45(t, 2H, ArH), 7.26(s, 1H, ArH), 7.10(d, J=8.4 Hz, 2H, NCCH), 7.21(m, 2H, ArH), 4.06(m, 1H), 3.42(m, 4H)	160.19, 147.84, 146.00, 135.88, 133.97, 129.46, 129.27, 128.85, 126.49, 126.25, 121.99, 77.34, 77.23, 77.02, 76.70, 45.70, 45.41
3k	7.93(d, J=8.4 Hz, 2H, NCCCH), 7.86(q, 2H, ArH), 7.77(q, 2H, ArH), 7.37(m, 5H), 7.28(m, 1H, ArH), 7.15(m, 1H, ArH), 7.07(m, 1H, ArH), 4.76(m, 1H), 3.44(m, 4H)	163.23, 147.87, 140.95, 138.56, 135.51, 133.87, 131.28, 129.58, 128.52, 127.52, 127.34, 126.82, 124.14, 124.03, 122.87, 77.32, 77.00, 76.68, 43.16, 40.07
3l	8.63(d, J=2.8 Hz, 2H, ArH), 8.38(q, 2H, NCCCH), 8.07(q, 4H) 7.39(d, J=2.8 Hz, 1H, ArH), 7.30(d, J=4.0 Hz,	164.18, 149.75, 144.98, 140.18, 137.44, 134.06, 130.61, 129.66, 127.81, 127.05,
3l	2H, ArH), 7.19(m, 2H, ArH), 7.05(m, 1H, ArH), 4.70(m, 1H), 3.52(d, 4H)	125.34, 123.59, 123.59, 122.76, 77.32, 77.00, 76.68, 44.32, 76.68, 44.32
3m	7.82(d, J=8.8 Hz, 2H, NCCCH), 7.40(d, J=7.2 Hz, 1H, ArH), 7.33(t, J=7.6 Hz, 2H, ArH), 7.23(m, 3H, ArH), 7.17(d, J=8.4 Hz, 2H, NCCH), 7.10(t, J=7.2 Hz, 1H, ArH), 4.55(m, 1H), 4.07(d, J=7.6 Hz, 6H), 3.53	159.17, 155.04, 140.98, 139.63, 135.62, 134.15, 129.31, 128.66, 127.73, 127.24, 126.83, 125.63, 119.28, 107.70, 77.32, 77.00, 76.68, 56.05, 44.04
3n	7.87(d, J=8.4 Hz, 2H, NCCCH), 7.74(q, 2H, ArH), 7.54(q, 2H, ArH), 7.41(q, 1H, ArH), 7.31(m, 5H), 7.14(m, 1H, ArH), 7.07(m, 1H, ArH), 4.82(m, 1H), 3.54(m, 4H)	161.33, 143.74, 141.31, 135.92, 134.01, 133.09, 129.50, 129.13, 128.67, 127.86, 127.36, 126.76, 126.46, 125.43, 122.95, 77.32, 77.00, 76.68, 43.37, 40.86

Compd.	¹H NMR(400 MHz, DMSO-d₆), δ	¹³C NMR(100 MHz, DMSO-d₆), δ
3e	8.00(d, J=8.4 Hz, 2H, NCCCH), 7.89(d, J=8.4 Hz, 2H, ArH), 7.67(m, 4H, ArH), 7.45(t, 2H, ArH), 7.26(s, 1H, ArH), 7.10(d, J=8.4 Hz, 2H, NCCH), 7.21(m, 2H, ArH), 4.06(m, 1H), 3.42(m, 4H)	160.19, 147.84, 146.00, 135.88, 133.97, 129.46, 129.27, 128.85, 126.49, 126.25, 121.99, 77.34, 77.23, 77.02, 76.70, 45.70, 45.41
3k	7.93(d, J=8.4 Hz, 2H, NCCCH), 7.86(q, 2H, ArH), 7.77(q, 2H, ArH), 7.37(m, 5H), 7.28(m, 1H, ArH), 7.15(m, 1H, ArH), 7.07(m, 1H, ArH), 4.76(m, 1H), 3.44(m, 4H)	163.23, 147.87, 140.95, 138.56, 135.51, 133.87, 131.28, 129.58, 128.52, 127.52, 127.34, 126.82, 124.14, 124.03, 122.87, 77.32, 77.00, 76.68, 43.16, 40.07
3l	8.63(d, J=2.8 Hz, 2H, ArH), 8.38(q, 2H, NCCCH), 8.07(q, 4H) 7.39(d, J=2.8 Hz, 1H, ArH), 7.30(d, J=4.0 Hz,	164.18, 149.75, 144.98, 140.18, 137.44, 134.06, 130.61, 129.66, 127.81, 127.05,
3l	2H, ArH), 7.19(m, 2H, ArH), 7.05(m, 1H, ArH), 4.70(m, 1H), 3.52(d, 4H)	125.34, 123.59, 123.59, 122.76, 77.32, 77.00, 76.68, 44.32, 76.68, 44.32
3m	7.82(d, J=8.8 Hz, 2H, NCCCH), 7.40(d, J=7.2 Hz, 1H, ArH), 7.33(t, J=7.6 Hz, 2H, ArH), 7.23(m, 3H, ArH), 7.17(d, J=8.4 Hz, 2H, NCCH), 7.10(t, J=7.2 Hz, 1H, ArH), 4.55(m, 1H), 4.07(d, J=7.6 Hz, 6H), 3.53	159.17, 155.04, 140.98, 139.63, 135.62, 134.15, 129.31, 128.66, 127.73, 127.24, 126.83, 125.63, 119.28, 107.70, 77.32, 77.00, 76.68, 56.05, 44.04
3n	7.87(d, J=8.4 Hz, 2H, NCCCH), 7.74(q, 2H, ArH), 7.54(q, 2H, ArH), 7.41(q, 1H, ArH), 7.31(m, 5H), 7.14(m, 1H, ArH), 7.07(m, 1H, ArH), 4.82(m, 1H), 3.54(m, 4H)	161.33, 143.74, 141.31, 135.92, 134.01, 133.09, 129.50, 129.13, 128.67, 127.86, 127.36, 126.76, 126.46, 125.43, 122.95, 77.32, 77.00, 76.68, 43.37, 40.86

Compd.	R₁	R₂	Yield^b(%)	Compd.	R₁	R₂	Yield^b(%)
3a	H	H	84	3k	8-NO₂	2-Cl	92
3b	H	4-CH₃	70	3l	6-NO₂	2-Cl	76
3c	H	4-OCH₃	56	3m	8-OCH₃	2-Cl	88
3d	H	2-Cl	90	3n	8-Cl	2-Cl	75
3e	H	3-Cl	85	3o	8-NO₂	H	90
3f	H	4-Cl	64	3p	6-NO₂	H	67
3g	H	3-NO₂	86	3q	8-OCH₃	H	75
3h	H	4-NO₂	78	3r	6-CH₃	H	80
3i	H	2-Br	81	3s	8-Cl	H	67
3j	H	4-F	62