10.1002/adsc.201900212
Advanced Synthesis & Catalysis
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solid; m.p = 189-191 C; H NMR (CDCl3, 400 MHz) δ
(ppm) 8.12 (d, 2H, J = 6.8 Hz), 7.85 (d, 2H, J = 7.6 Hz),
7.62 (t, 1H, J = 6.4 Hz), 7.51 (t, 2H, J = 6.8 Hz), 7.35 (d,
2H, J = 7.2 Hz), 4.98 (t, 1H, J = 10.6 Hz), 4.60 (d, 2H, J =
7.2 Hz), 4.39 (s, 2H), 4.00 (s, 5H), 3.27 (d, 2H, J = 10.8
Hz), 2.40 (s, 3H). 13C NMR (CDCl3, 100 MHz) δ (ppm)
(4-methoxyphenyl)(3-phenyl-1-tosyl-4,5-dihydro-1H-
pyrazol-5-yl)methanone (4d): Yield: 86%; 74.4 mg,
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white solid; m.p = 164-166 C; H NMR (CDCl3, 400
MHz) δ (ppm) 8.07 (d, 2H, J = 9.2 Hz), 7.87 (d, 2H, J =
8.4 Hz), 7.66 (d, 2H, J = 6.8 Hz), 7.40 (m, 3H), 7.32 (d, 2H,
J = 8.0 Hz), 6.98 (d, 2H, J = 9.2 Hz), 5.19 (t, 1H, J = 11.0
194.8, 159.2, 144.6, 133.8, 129.5, 129.3, 128.9, 128.8, 70.8, Hz), 3.89 (s, 3H), 3.50 (dd, 1H, J1 = 17.0 Hz, J2 = 12.2 Hz),
69., 68.2, 67.9, 64.9, 40.1, 21.6. HRMS (ES+-TOF) calcd
for C27H25FeN2O3S+ (M+H+): 513.0930, found: 513.0936.
3.33 (dd, 1H, J1 = 16.8 Hz, J2 = 10.4 Hz), 2.42 (s, 3H). 13
C
NMR (CDCl3, 100 MHz) δ (ppm) 193.0, 164.1, 155.9,
144.5, 132.6, 131.6, 130.7, 130.3, 129.6, 128.7, 128.6,
127.2, 126.9, 114.1, 64.7, 55.6, 39.2, 21.6. HRMS (ES+-
TOF) calcd for C24H23N2O4S+ (M+H+): 435.1373, found:
435.1381.
phenyl(2-tosyl-3,3a,4,5-tetrahydro-2H-
benzo[g]indazol-3-yl)methanone (3r): Yield: 61%; 60.1
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mg, white solid; m.p = 182-184 C; H NMR (CDCl3, 400
MHz) δ (ppm) 8.16 (d, 2H, J = 7.6 Hz), 8.04 (d, 1H, J =
7.6 Hz), 7.82 (d, 2H, J = 8.0 Hz), 7.62 (t, 1H, J = 7.4 Hz),
7.51 (t, 2H, J = 7.6 Hz), 7.32 (m, 4H), 7.13 (d, 1H, J = 7.6
Hz), 4.52 (d, 1H, J = 12.4 Hz), 3.57 (dt, 1H, J1 = 12.8 Hz,
J2 = 2.4 Hz), 2.85 (m, 2H), 2.16 (m, 1H), 1.61 (m, 1H). 13C
NMR (CDCl3, 100 MHz) δ (ppm) 194.8, 157.3, 144.7,
134.7, 133.7, 131.2, 131.1, 130.1, 129.6, 129.4, 129.1,
128.9, 128.7, 128.4, 126.9, 126.2, 125.8, 72.9, 51.2, 28.8,
27.5, 21.6. HRMS (ES+-TOF) calcd for C25H23N2O3S+
(M+H+): 431.1424, found: 431.1423.
(4-fluorophenyl)(3-phenyl-1-tosyl-4,5-dihydro-1H-
pyrazol-5-yl)methanone (4e): Yield: 82%; 69.1 mg, white
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solid; m.p = 166-168 C; H NMR (CDCl3, 400 MHz) δ
(ppm) 8.12 (m, 2H), 7.84 (d, 2H, J = 8.4 Hz), 7.66 (d, 2H,
J = 6.8 Hz), 7.40 (m, 3H), 7.32 (d, 2H, J = 8.4 Hz), 7.17
(d, 2H, J = 8.6 Hz), 5.16 (dd, 1H, J1 = 11.6 Hz, J2 = 10.8
Hz), 3.51 (dd, 1H, J1 = 17.0 Hz, J2 = 11.8 Hz), 3.33 (dd,
1H, J1 = 16.8 Hz, J2 = 10.4 Hz), 2.41 (s, 3H). 13C NMR
(CDCl3, 100 MHz) δ (ppm) 193.1, 166.1 (d, JC-F = 255.1
Hz), 156.2, 144.7, 132.3, 132.0 (d, JC-F = 9.5 Hz), 130.8,
130.7, 130.1, 129.7, 128.7 (d, JC-F = 2.4 Hz), 127.0, 116.0
(d, JC-F = 21.9 Hz), 65.0, 38.9, 21.6. HRMS (ES+-TOF)
calcd for C23H20FN2O3S+ (M+H+): 423.1173, found:
423.1171.
phenyl(2-tosyl-2,3,3a,4,5,6-
hexahydrobenzo[6,7]cyclohepta[1,2-c]pyrazol-3-
yl)methanone (3s): Yield: 67%; 59.4 mg, white solid; m.p
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= 93-95 C; H NMR (CDCl3, 400 MHz) δ (ppm) 8.10 (d,
2H, J = 7.6 Hz), 7.88 (d, 2H, J = 7.2 Hz), 7.84 (d, 2H, J =
8.4 Hz), 7.62 (t, 1H, J = 7.4 Hz), 7.51 (t, 2H, J = 7.8 Hz),
7.34 (d, 2H, J = 8.0 Hz), 7.31 (t, 1H, J = 7.2 Hz), 7.25 (m,
1H), 7.10 (d, 1H, J = 7.2 Hz), 4.67 (d, 1H, J = 10.4 Hz),
5.51 (dt, 1H, J1 = 11.0 Hz, J2 = 4.0 Hz), 2.86 (m, 1H), 2.60
(m, 1H), 2.44 (s, 3H), 1.99 (m, 1H), 1.79 (m, 1H), 1.28 (m,
2H). 13C NMR (CDCl3, 100 MHz) δ (ppm) 194.9, 161.9,
144.6, 140.9, 134.6, 133.8, 131.9, 130.7, 130.3, 129.5,
129.4, 129.3, 128.9, 128.8, 126.7, 72.5, 52.7, 34.7, 31.1,
24.9, 21.7. HRMS (ES+-TOF) calcd for C26H25N2O3S+
(M+H+): 445.1580, found: 445.1587.
(4-chlorophenyl)(3-phenyl-1-tosyl-4,5-dihydro-1H-
pyrazol-5-yl)methanone (4f): Yield: 80%; 70.1 mg, white
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solid; m.p = 159-161 C; H NMR (CDCl3, 400 MHz) δ
(ppm) 8.03 (d, 2H, J = 8.4 Hz), 7.84 (d, 2H, J = 8.4 Hz),
7.66 (d, 2H, J = 6.8 Hz), 7.48 (d, 2H, J = 8.4 Hz), 7.40 (m,
3H), 7.33 (d, 2H, J = 8.0 Hz), 5.14 (t, 1H, J = 11.2 Hz),
3.51 (dd, 1H, J1 = 17.0 Hz, J2 = 11.8 Hz), 3.34 (dd, 1H, J1
= 16.8 Hz, J2 = 10.4 Hz), 2.42 (s, 3H). 13C NMR (CDCl3,
100 MHz) δ (ppm) 193.6, 166.6, 156.1, 144.7, 140.4, 132.6,
132.3, 130.9, 130.6, 130.1, 129.7, 129.2, 128.8, 128.7,
127.0, 65.1, 61.2, 38.9, 21.6. HRMS (ES+-TOF) calcd for
C23H20ClN2O3S+ (M+H+): 439.0878, found: 439.0880.
(3-phenyl-1-tosyl-4,5-dihydro-1H-pyrazol-5-yl)(p-
tolyl)methanone (4a): Yield: 85%; 71.5 mg, white solid;
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m.p = 152-154 C; H NMR (CDCl3, 400 MHz) δ (ppm)
7.96 (d, 2H, J = 8.4 Hz), 7.86 (d, 2H, J = 8.0 Hz), 7.65 (m,
2H), 7.40 (m, 3H), 7.31 (t, 4H, J = 7.8 Hz), 5.24 (dd, 1H,
J1 = 11.6 Hz, J2 = 10.4 Hz), 3.51 (dd, 1H, J1 = 17.0 Hz, J2
= 11.8 Hz), 3.31 (dd, 1H, J1 = 17.2 Hz, J2 = 10.4 Hz), 2.43
(s, 3H), 2.41 (s, 3H). 13C NMR (CDCl3, 100 MHz) δ (ppm)
194.7, 175.9, 155.6, 144.5, 138.8, 134.7, 134.4, 132.8,
130.7, 130.3, 129.6, 128.8, 128.6, 126.9, 126.2, 64.6, 39.1,
21.6, 21.4. HRMS (ES+-TOF) calcd for C24H23N2O3S+
(M+H+): 419.1424, found: 419.1430.
(4-bromophenyl)(3-phenyl-1-tosyl-4,5-dihydro-1H-
pyrazol-5-yl)methanone (4g): Yield: 72%; 69.2 mg,
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white solid; m.p = 175-177 C; H NMR (CDCl3, 400
MHz) δ (ppm) 7.94 (d, 2H, J = 8.4 Hz), 7.84 (d, 2H, J =
8.0 Hz), 7.65 (t, 4H, J = 6.8 Hz), 7.40 (m, 3H), 7.32 (d, 2H,
J = 8.0 Hz), 5.14 (t, 1H, J = 11.2 Hz), 3.51 (dd, 1H, J1 =
17.0 Hz, J2 = 12.2 Hz), 3.33 (dd, 1H, J1 = 16.8 Hz, J2 =
10.4 Hz), 2.41 (s, 3H). 13C NMR (CDCl3, 100 MHz) δ
(ppm) 193.8, 156.2, 144.7, 133.0, 132.3, 132.2, 130.9,
130.7, 130.1, 130.0, 129.2, 128.7, 128.7, 127.0, 65.0, 38.9,
21.6. HRMS (ES+-TOF) calcd for C23H19BrN2O3S
(M+H+): 483.0373, found: 483.0374.
(3-phenyl-1-tosyl-4,5-dihydro-1H-pyrazol-5-yl)(o-
tolyl)methanone (4b): Yield: 53%; 44.6 mg, white solid;
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m.p = 126-128 C; H NMR (CDCl3, 400 MHz) δ (ppm)
7.80 (d, 2H, J = 8.4 Hz), 7.70 (d, 1H, J = 7.6 Hz), 7.65 (d,
2H, J = 8.0 Hz), 7.41 (m, 4H), 7.31 (m, 4H), 5.24 (dd, 1H,
J1 = 11.6 Hz, J2 = 10.0 Hz), 3.49 (dd, 1H, J1 = 16.8 Hz, J2
= 12.0 Hz), 3.32 (dd, 1H, J1 = 17.0 Hz, J2 = 9.8 Hz), 2.54
(s, 3H), 2.40 (s, 3H). 13C NMR (CDCl3, 100 MHz) δ (ppm)
198.1, 155.7, 144.5, 139.5, 135.5, 132.9, 132.1, 131.9,
130.7, 130.2, 129.6, 128.6, 128.4, 126.9, 125.6, 65.7, 38.7,
21.6, 21.1. HRMS (ES+-TOF) calcd for C24H23N2O3S+
(M+H+): 419.1424, found: 419.1428.
(4-nitrophenyl)(3-phenyl-1-tosyl-4,5-dihydro-1H-
pyrazol-5-yl)methanone (4h): Yield: 51%; 46.2 mg,
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yellow solid; m.p = 135-137 C; H NMR (DMSO, 400
MHz) δ (ppm) 8.45 (d, 2H, J = 8.8 Hz), 8.36 (d, 2H, J =
8.8 Hz), 7.83 (d, 2H, J = 8.0 Hz), 7.69 (d, 2H, J = 6.8 Hz),
7.48 (m, 5H), 5.62 (t, 1H, J = 10.8 Hz), 3.85 (dd, 1H, J1 =
17.6 Hz, J2 = 12.0 Hz), 3.49 (dd, 1H, J1 = 17.6 Hz, J2 = 9.6
Hz), 2.41 (s, 3H). 13C NMR (DMSO, 100 MHz) δ (ppm)
194.6, 157.5, 150.9, 145.1, 139.4, 132.6, 131.4, 130.8,
130.4, 130.3, 129.3, 128.8, 127.4, 124.5, 64.9, 39.0, 21.6.
HRMS (ES+-TOF) calcd for C23H20N3O5S+ (M+H+):
450.1118, found: 450.1129.
(3-phenyl-1-tosyl-4,5-dihydro-1H-pyrazol-5-yl)(m-
tolyl)methanone (4c): Yield: 78%; 65.2 mg, white solid;
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m.p = 120-121 C; H NMR (CDCl3, 400 MHz) δ (ppm)
7.86 (m, 4H), 7.66 (d, 2H, J = 6.8 Hz), 7.39 (m, 5H), 7.30
(d, 2H, J = 8.4 Hz), 5.35 (t, 1H, J = 11.2 Hz), 3.53 (dd, 1H,
J1 = 17.0 Hz, J2 = 11.8 Hz), 3.31 (dd, 1H, J1 = 17.2 Hz, J2
= 10.4 Hz), 2.43 (s, 3H), 2.42 (s, 3H). 13C NMR (CDCl3,
(3,4-dichlorophenyl)(3-phenyl-1-tosyl-4,5-dihydro-
1H-pyrazol-5-yl)methanone (4i): Yield: 70%; 66.0 mg,
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white solid; m.p = 171-173 C; H NMR (CDCl3, 400
MHz) δ (ppm) 8.15 (s, 1H), 7.92 (d, 1H, J = 8.8 Hz), 7.83
(d, 2H, J = 8.4 Hz), 7.66 (d, 2H, J = 6.8 Hz), 7.58 (d, 1H, J
100 MHz) δ (ppm) 194.1, 155.8, 144.9, 144.5, 132.7, 131.8, = 8.4 Hz), 7.40 (m, 3H), 7.33 (d, 2H, J = 8.0 Hz), 5.11 (t,
130.7, 130.3, 129.6, 129.5, 129.2, 128.7, 128.6, 126.9, 64.7,
39.1, 21.7, 21.6. HRMS (ES+-TOF) calcd for
C24H23N2O3S+ (M+H+): 419.1424, found: 419.1429.
1H, J = 11.0 Hz), 3.51 (dd, 1H, J1 = 17.0 Hz, J2 = 11.8 Hz),
3.33 (dd, 1H, J1 = 17.0 Hz, J2 = 10.6 Hz), 2.42 (s, 3H). 13
C
NMR (CDCl3, 100 MHz) δ (ppm) 192.7, 156.3, 144.9,
138.5, 133.8, 133.6, 132.1, 131.1, 131.0, 130.9, 129.9,
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