PAPER
One-Pot Synthesis of New Pyrazolo[1,5-a]quinoline Systems
1715
2-Methyl-9-phenyl-9H-indolo[3,2-c]pyrazolo[1,5-a]quinoline
(2c)
Yield: 165 mg (95%); pale yellow powder; mp 143–145 °C.
1H NMR (400 MHz, CDCl3): d = 2.637 (s, 3 H, CH3), 6.787 (s, 1 H),
7.058 (t, J = 8 Hz, 1 H), 7.139 (d, J = 7.2 Hz, 1 H), 7.322–7.393 (m,
3 H), 7.487–7.510 (m, 3 H), 7.637–7.644 (m, 3 H), 8.089 (t, J = 7.6
Hz, 1 H), 8.676 (d, J = 8.2 Hz, 1 H).
13C NMR (75 MHz, CDCl3): d = 13.14 (CH3), 14.21 (CH3), 97.18
(CH), 113.02 (C), 116.85 (CH), 122.98 (CH), 123.67 (CH), 127.13
(CH), 129.11 (CH), 129.43 (CH), 129.72 (CH), 133.98 (C), 134.16
(C), 134.51 (C), 140.86 (C), 143.87 (C), 151.51 (C).
ESI-HRMS: m/z [M + H]+ calcd for C20H17N4: 313.1448; found:
313.1452.
3-Methyl-1,5-diphenyl-1H-dipyrazolo[1,5-a:4¢,3¢-c]quinoline
(4d)
Yield: 134 mg (72%); colorless needles; mp 197–198 °C.
13C NMR (100 MHz, CDCl3): d = 14.5 (CH3), 29.85 (CH), 96.75
(CH), 107.71 (C), 110.90 (CH), 114.79 (C), 116.80 (CH), 120.31
(CH), 121.52 (CH), 122.38 (C), 123.10 (CH), 123.44 (CH), 124.69
(CH), 128.09 (CH), 129.19 (CH), 130.40 (CH), 131.54 (C), 134.27
(C), 135.98 (C), 139.06 (C), 141.62 (C), 151.79 (C).
ESI-HRMS: m/z [M + H]+ calcd for C24H18N3: 348.1495; found:
348.1497.
1H NMR (400 MHz, CDCl3): d = 2.735 (d, J = 1.2 Hz, 3 H, CH3),
6.984 (s, 1 H), 7.108 (t, J = 3.8 Hz, 1 H), 7.318–7.412 (m, 3 H), 7.49
(q, J = 7.6 Hz, 2 H), 7.544–7.582 (m, 5 H), 8.090 (d, J = 8 Hz, 2 H),
8.725 (d, J = 8.2 Hz, 1 H).
13C NMR (100 MHz, CDCl3): d = 13.33 (CH3), 94.42 (CH), 94.48
(C), 110.71 (C), 113.49 (CH), 117.38 (CH), 123.02 (CH), 124.20
(C), 126.47 (CH), 127.25 (CH), 128.47 (CH), 128.83 (CH), 129.23
(CH), 129.57 (CH), 133.40 (CH), 134.31 (C), 135.04 (C), 140.91
(CH), 144.03 (C), 153.28 (C).
2,9-Diphenyl-9H-indolo[3,2-c]pyrazolo[1,5-a]quinoline (2d)
Yield: 197 mg (96%); pale yellow powder; mp 174–176 °C.
1H NMR (400 MHz, CDCl3): d = 7.123 (t, J = 8 Hz, 1 H), 7.178 (d,
J = 8 Hz, 1 H), 7.233 (d, J = 8.2 Hz, 1 H), 7.316 (s, 1 H), 7.371–
7.456 (m, 3 H), 7.513–7.595 (m, 5 H), 7.675 (d, J = 2.4 Hz, 3 H),
8.204 (t, J = 7.2 Hz, 3 H), 8.872 (d, J = 8.2 Hz, 1 H).
ESI-HRMS: m/z [M + H]+ calcd for C25H19N4: 375.1604; found:
375.1613.
13C NMR (100 MHz, CDCl3): d = 94.05 (CH), 107.91 (C), 111.06
(CH), 115.31 (CH), 117.35 (CH), 120.44 (CH), 121.70 (C), 122.45
(CH), 123.16 (CH), 123.98 (CH), 124.89 (CH), 126.72 (CH),
128.24 (CH), 128.47 (CH), 128.93 (CH), 129.18 (CH), 129.59
(CH), 130.51 (CH), 131.64 (C), 133.90 (C), 134.49 (C), 136.52 (C),
139.08 (C), 141.74 (C), 153.58 (C).
2-Butyl-5-methyl-1H-imidazo[4,5-c]pyrazolo[1,5-a]quinoline
(6a)
Yield: 111 mg (80%); yellow dense oil.
1H NMR (400 MHz, CDCl3): d = 0.794 (t, J = 4.8 Hz, 3 H, CH3),
1.127–1.280 (m, 2 H, CH2), 1.679–1.755 (m, 2 H, CH2), 2.467 (s, 3
H, CH3), 2.925 (t, J = 7.6 Hz, 2 H, CH2), 6.504 (s, 1 H), 7.286 (t,
J = 8 Hz, 1 H), 7.457–7.499 (m, 1 H), 8.210 (d, J = 8 Hz, 1 H),
8.572 (d, J = 8.2 Hz, 1 H).
ESI-HRMS: m/z [M + H]+ calcd for C29H20N3: 410.1652; found:
410.1648.
3,5-Dimethyl-1H-dipyrazolo[1,5-a:4¢,3¢-c]quinoline (4a)
13C NMR (100 MHz, CDCl3): d = 13.66 (CH3), 14.32 (CH3), 22.49
(CH2), 29.03 (CH2), 30.96 (CH2), 96.25 (CH), 116.45 (CH, C),
122.29 (CH, C), 124.68 (CH, C), 127.52 (C), 132.71 (CH, C),
151.51 (C), 154.05 (C).
Yield: 106 mg (90%); colorless needles; mp 208–211 °C.
1H NMR (400 MHz, CDCl3): d = 2.540 (s, 3 H, CH3), 2.655 (s, 3 H,
CH3), 6.450 (s, 1 H), 7.395 (t, J = 7.2 Hz, 1 H), 7.607 (t, J = 7.2 Hz,
1 H), 8.111 (d, J = 7.6 Hz, 1 H), 8.490 (d, J = 8.2 Hz, 1 H).
ESI-HRMS: m/z [M + H]+ calcd for C17H19N4: 279.1604; found:
279.1606.
13C NMR (100 MHz, CDCl3): d = 13.99 (CH3), 29.63 (CH3), 97.51
(C), 116.08 (CH), 119.23 (C), 122.91 (CH), 123.60 (C), 124.65
(CH), 128.63 (C), 133.13 (C), 134.52 (CH), 150.60 (C).
ESI-HRMS: m/z [M + H]+ calcd for C14H13N4: 237.1135; found:
237.1137.
2-Butyl-5-phenyl-1H-imidazo[4,5-c]pyrazolo[1,5-a]quinoline
(6b)
Yield: 102 mg (60%); yellow dense oil.
1H NMR (400 MHz, CDCl3): d = 0.768 (t, J = 7.2 Hz, 3 H, CH3),
0.848–0.887 (m, 2 H, CH2), 1.734–1.800 (m, 2 H, CH2), 2.922 (t,
J = 8 Hz, 2 H, CH2), 7.011 (s, 1 H), 7.308–7.426 (m, 5 H), 7.550 (t,
J = 8 Hz, 1 H), 7.978 (d, J = 7.6 Hz, 2 H), 8.130 (d, J = 8 Hz, 1 H),
8.747 (d, J = 8.2 Hz, 1 H).
13C NMR (100 MHz, CDCl3): d = 13.79 (CH3), 22.56 (CH2), 29.04
(CH2), 30.98 (CH2), 93.36 (CH), 116.98 (CH, C), 122.00 (C),
124.89 (2 CH, C), 124.95 (C), 126.54 (CH), 127.44 (CH), 128.47
(CH), 128.87 (2 CH), 132.87 (CH, C), 133.50 (C), 153.15 (C),
153.76 (C).
3-Methyl-5-phenyl-1H-dipyrazolo[1,5-a:4¢,3¢-c]quinoline (4b)
Yield: 126 mg (85%); colorless needles; mp 263–264 °C.
1H NMR (400 MHz, DMSO–CDCl3): d = 3.188 (s, 3 H, CH3), 6.906
(s, 1 H), 7.234–7.410 (m, 4 H), 7.535–7.971 (m, 1 H), 7.980 (t,
J = 7.6 Hz, 2 H), 8.222 (d, J = 7.2 Hz, 1 H), 8.529 (d, J = 8.4 Hz, 1
H).
13C NMR (100 MHz, CDCl3): d = 28.93 (CH3), 93.61 (C), 107.71
(C), 115.95 (2 CH), 122.41 (C), 124.12 (C), 125.52 (4 CH), 127.65
(C), 128.09 (3 CH), 129.26 (C), 132.72 (CH), 135.07 (C), 151.93
(C).
ESI-HRMS: m/z [M + H]+ calcd for C22H21N4: 341.1761; found:
341.1763.
ESI-HRMS: m/z [M + H]+ calcd for C19H15N4: 299.1291; found:
299.1289.
Supporting Information for this article is available online at
3,5-Dimethyl-1-phenyl-1H-dipyrazolo[1,5-a:4¢,3¢-c]quinoline
(4c)
Yield: 124 mg (80%); white powder; mp 191–193 °C.
Acknowledgment
1H NMR (300 MHz, CDCl3): d = 2.577 (s, 3 H, CH3), 2.702 (s, 3 H,
CH3), 6.547 (s, 1 H), 7.123 (t, J = 7.5 Hz, 1 H), 7.343 (d, J = 7.8 Hz,
1 H), 7.535–7.598 (m, 6 H), 8.581 (d, J = 8.4 Hz, 1 H).
We are grateful to the National Natural Science Foundation of
China (Grant No. 20872056) for financial support.
Synthesis 2011, No. 11, 1711–1716 © Thieme Stuttgart · New York