ACCEPTED MANUSCRIPT
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J = 8.8 Hz, 2H), 7.41-7.39(m, 1H), 7.30(s, 1H, pyrazole-H), 4.18-4.13(m, 1H), 1.19(d, J = 6.4 Hz, 6H);
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C NMR(400 MHz, DMSO-d ) δ: 160.3, 149.1, 146.7, 145.3, 144.7, 132.2, 131.9, 130.2, 129.9, 129.4,
129.0, 128.5, 127.7, 127.6, 126.6, 127.2, 126.7, 126.5 (2C), 125.0 (2C), 124.0, 123.4, 110.0, 40.9, 22.7
+
(2C); HRMS (m/z) [M + Na] calcd. for C H N O 473.1589, found 473.1571.
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5.1.3.4 N-methyl-5-(phenanthren-3-yl)-1-(4-sulfamoylphenyl)-1H-pyrazole-3-carboxamide (6a)
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Yield = 98%; white solid; mp: 274-276 ˚C; H NMR(400 MHz, DMSO-d ) δ: 8.86(s, 1H), 8.68-8.66(m,
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1H), 8.34(q, J = 4.8 Hz, NHMe), 8.00-7.97(m, 1H), 7.93(d, J = 8.4 Hz, 1H), 7.89(d, J = 8.8 Hz, 1H),
7.84(d, J = 8.8 Hz, 2H), 7.82(d, J = 8.8 Hz, 1H), 7.67-7.65(m, 2H), 7.59(d, J = 8.8 Hz, 2H), 7.44(s, 2H),
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7.40-7.38(m, 1H), 7.27(s, 1H), 2.80(d, J = 4.8 Hz, 3H); C NMR(400 MHz, DMSO-d6) δ: 161.9, 148.4,
145.1, 143.9, 142.2, 132.2, 131.9, 130.1, 129.9, 129.3, 129.0, 128.5, 127.8, 127.7, 127.2 (4C), 126.7,
+
126.4 (2C), 123.8, 123.4, 109.2, 26.2; HRMS (m/z) [M + H] calcd. for C H N O S 457.1329, found
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5 20 4 3
457.1315.
5.1.3.5 1-(4-cyanophenyl)-N-methyl-5-(phenanthren-3-yl)-1H-pyrazole-3-carboxamide (7a)
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Yield = 98%; white solid; mp: 215-217 ˚C; H NMR(400 MHz, DMSO-d ) δ: 8.83(s, 1H), 8.67-8.65(m,
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1H), 8.40(q, J = 4.8 Hz, NHMe), 8.04-7.98(m, 1H), 7.95(d, J = 8.4 Hz, 1H), 7.90(d, J = 8.4 Hz, 2H),
7.89(d, J = 8.4 Hz, 1H), 7.83(d, J = 8.4 Hz, 1H), 7.67-7.65(m, 2H), 7.59(d, J = 8.8 Hz, 2H), 7.39-7.36(m,
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1H), 7.26(s, 1H), 2.80(d, J = 4.8 Hz, 3H); C NMR(400 MHz, DMSO-d6) δ: 161.8, 148.6, 145.2, 143.2,
133.9 (2C), 132.2, 131.9, 130.1, 129.9, 129.3, 129.0, 128.5, 127.8, 127.6, 127.5, 127.2, 126.8, 126.5
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(2C), 123.9, 123.4, 118.6, 111.1, 109.5, 26.2; HRMS (m/z) [M + H] calcd. for C H N O 403.1553,
26 18 4
found 403.1553.
5.1.4 General procedure for preparation of amino-derivatives (5): The nitro derivatives 4 (5.7
mmol), hydrazine hydrate (50.5 mmol), and 10% Pd/C (0.25 g) was stirred in 100 mL of MeOH at
reflux for 4 h. The mixture was cooled, filtered through Celite, and concentrated to give the
corresponding amino derivatives in nearly quantitative yield as a white solid.
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5.1.4.1 1-(4-aminophenyl)-N-methyl-5-(phenanthren-3-yl)-1H-pyrazole-3-carboxamide (5a)
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Yield = 98%; white solid; mp: 248-250 ˚C; H NMR(400 MHz, DMSO-d )
δ
:
8.70(s, 1H), 8.58-8.55(m,
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1H), 8.22(q, J = 4.8 Hz, 1H, NHMe), 7.97-7.95(m, 1H), 7.90(d, J = 8.4 Hz, 1H), 7.86(d, J = 8.8 Hz, 1H),
7.82(d, J = 8.8 Hz, 1H), 7.65-7.62(m, 2H), 7.47-7.44(m, 1H), 7.19(s, 1H), 7.04(d, J = 8.4 Hz, 2H), 6.55(d,
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J = 8.4 Hz, 2H), 5.40(s, 2H, NH2), 2.77(d, J = 4.8 Hz, 3H); HRMS (m/z) [M + H] calcd. for C25
20 4
H N O
393.1710, found 393.1707.
5.1.4.2 1-(4-aminophenyl)-N-ethyl-5-(phenanthren-3-yl)-1H-pyrazole-3-carboxamide (5b)
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Yield = 98%; white solid; mp: 228-230 ˚C; H NMR (400 MHz, DMSO-d ) δ: 8.70(s, 1H), 8.58-
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8.56(m, 1H), 8.26(t, J = 6.0 Hz, 1H, NHEt), 7.97-7.95(m, 1H), 7.90(d, J = 8.4 Hz, 1H), 7.84(d, J = 8.8
Hz, 1H), 7.78(d, J = 8.8 Hz, 1H), 7.65-7.62(m, 2H), 7.47-7.44(m, 1H), 7.19(s, 1H), 7.05(d, J = 8.8 Hz,
2H), 6.56(d, J = 8.8 Hz, 2H), 5.40(s, 2H, NH2), 3.28(q, J = 7.2 Hz, 2H), 1.10(t, J = 7.2 Hz, 3H); HRMS
+
(m/z) [M + Na] calcd. for C26
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H N
4
O 429.1686, found 429.1690.
5.1.4.3 1-(4-aminophenyl)-N-isopropyl-5-( phenanthren-3-yl)-1H-pyrazole-3-carboxamide (5c)
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Yield = 95%; white solid; mp: 232-234 ˚C; H NMR (400 MHz, DMSO-d )
δ
:
8.70(s, 1H), 8.57-
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8.55(m, 1H), 7.97-7.76(m, 5H), 7.65-7.62(m, 2H), 7.47-7.44(m, 1H), 7.21(s, 1H), 7.05(d, J = 8.4 Hz, 2H),
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6.56(d, J = 8.8 Hz, 2H), 5.41(s, 2H), 4.16-4.09(m, 1H), 1,16(d, J = 6.8 Hz, 6H); C NMR(400 MHz,