F
W.-j. Wang et al.
Paper
Synthesis
13C NMR (100 MHz, DMSO-d6): δ = 165.4, 151.2, 149.3, 147.3, 139.0,
132.1, 129.2, 123.6, 119.3, 112.8.
HRMS (ESI): m/z [M + H]+ calcd for C12H11ClN3O: 248.0585; found:
248.0577.
1H NMR (400 MHz, DMSO-d6): δ = 11.17 (br s, 1 H), 7.75 (d, J = 8.0 Hz,
1 H), 7.70 (d, J = 8.6 Hz, 1 H), 7.55 (d, J = 8.4 Hz, 2 H), 7.45–7.41 (m, 1
H), 7.31 (d, J = 8.2 Hz, 2 H), 7.14 (t, J = 7.4 Hz, 1 H), 2.35 (s, 3 H).
13C NMR (100 MHz, DMSO-d6): δ = 156.0, 139.2, 137.8, 134.1, 129.8,
128.1, 120.7, 120.4, 120.0, 114.5, 110.2, 20.4.
HRMS (ESI): m/z [M + H]+ calcd for C14H13N2O: 225.1022; found:
2-Iodo-3-methyl-N′-phenylbenzohydrazide (6b)
225.1024.
White solid; yield: 1.58 g (90%); mp 194.8–195.6 °C.
IR (KBr): 3242, 2970, 1651, 1493, 1313, 1014, 947, 762 cm–1
.
1-(o-Tolyl)-1H-indazol-3(2H)-one (2c)
1H NMR (400 MHz, DMSO-d6): δ = 10.12 (d, J = 2.7 Hz, 1 H), 7.96 (d, J =
2.7 Hz, 1 H), 7.43–7.37 (m, 2 H), 7.20–7.15 (m, 3 H), 6.90 (d, J = 8.1 Hz,
2 H), 6.73 (t, J = 7.2 Hz, 1 H), 2.45 (s, 3 H).
White solid; yield: 42.6 mg (95%); mp 180.8–184.0 °C.
IR (KBr): 2924, 2582, 1618, 1544, 1313, 750 cm–1
.
13C NMR (100 MHz, DMSO-d6): δ = 169.9, 149.7, 143.3, 142.5, 130.9,
129.2, 128.6, 126.1, 119.0, 112.9, 100.7, 29.1.
HRMS (ESI): m/z [M + H]+ calcd for C14H14IN2O: 353.0145; found:
353.0143.
1H NMR (400 MHz, DMSO-d6): δ = 10.96 (s, 1 H), 7.74 (d, J = 8.0 Hz, 1
H), 7.45–7.41 (m, 1 H), 7.39–7.32 (m, 4 H), 7.09 (dd, J = 7.9, 7.1 Hz, 1
H), 7.05 (d, J = 8.5 Hz, 1 H), 2.13 (s, 3 H).
13C NMR (100 MHz, DMSO-d6): δ = 155.6, 141.2, 138.2, 134.6, 131.4,
127.9, 127.7, 126.8, 126.7, 120.2, 119.5, 113.2, 109.6, 17.7.
HRMS (ESI): m/z [M + H]+ calcd for C14H13N2O: 225.1022; found:
2-Iodo-N′-(4-methoxyphenyl)benzohydrazide (6c)
225.1025.
White solid; yield: 1.75 g (95%); mp 141.2–143.4 °C.
IR (KBr): 3278, 2999, 2833, 1651, 1510, 1246, 1032, 829, 744 cm–1
.
1-(m-Tolyl)-1H-indazol-3(2H)-one (2d)
1H NMR (400 MHz, DMSO-d6): δ = 10.12 (s, 1 H), 7.92 (d, J = 7.8 Hz, 1
H), 7.66 (s, 1 H), 7.49 (t, J = 7.4 Hz, 1 H), 7.43 (dd, J = 7.5, 1.5 Hz, 1 H),
7.22 (td, J = 7.7, 1.7 Hz, 1 H), 6.87 (d, J = 8.9 Hz, 2 H), 6.79 (d, J = 9.0 Hz,
2 H), 3.67 (s, 3 H).
13C NMR (100 MHz, DMSO-d6): δ = 169.1, 153.2, 143.4, 141.7, 139.8,
131.7, 129.0, 128.6, 114.6, 114.4, 94.3, 55.7.
White solid; yield: 44.4 mg (99%); mp 178.3–179.3 °C.
IR (KBr): 2921, 2588, 1610, 1547, 1309, 1238, 789, 742 cm–1
1H NMR (400 MHz, DMSO-d6): δ = 11.20 (br s, 1 H), 7.78–7.74 (m, 2
H), 7.50–7.43 (m, 3 H), 7.39 (t, J = 7.7 Hz, 1 H), 7.15 (dd, J = 11.3, 4.2
Hz, 1 H), 7.07 (d, J = 7.4 Hz, 1 H), 2.40 (s, 3 H).
.
HRMS (ESI): m/z [M + H]+ calcd for C14H14IN2O2: 369.0095; found:
13C NMR (100 MHz, DMSO-d6): δ = 156.2, 140.2, 139.2, 139.0, 129.2,
369.0102.
128.2, 125.5, 121.2, 120.4, 120.2, 117.7, 114.7, 110.4, 21.1.
HRMS (ESI): m/z [M + H]+ calcd for C14H13N2O: 225.1022; found:
225.1024.
N′-(4-Fluorophenyl)-2-iodobenzohydrazide (6d)
White solid; yield: 1.42 g (80%); mp 204.2–205.6 °C.
IR (KBr): 3261, 3001, 1651, 1504, 1209, 910, 829, 721, 687 cm–1
1-(4-Fluorophenyl)-1H-indazol-3(2H)-one (2e)13b
.
White solid; yield: 44.7 mg (98%); mp 220.2–221.7 °C.
1H NMR (400 MHz, DMSO-d6): δ = 10.17 (s, 1 H), 7.93 (dd, J = 7.9, 0.8
Hz, 2 H), 7.48 (dtd, J = 9.3, 7.5, 1.4 Hz, 2 H), 7.23 (ddd, J = 7.9, 7.3, 1.9
Hz, 1 H), 7.00–6.89 (m, 2 H), 6.93–6.89 (m, 2 H).
13C NMR (100 MHz, DMSO-d6): δ = 169.2, 157.6 (J = 232 Hz), 146.1,
141.5, 139.8, 131.7, 129.0, 128.5, 115.7 (J = 22 Hz), 114.2 (J = 8 Hz),
94.1.
1H NMR (400 MHz, DMSO-d6): δ = 11.25 (br s, 1 H), 7.76 (d, J = 7.9 Hz,
1 H), 7.71–7.68 (m, 3 H), 7.45 (t, J = 7.6 Hz, 1 H), 7.35 (t, J = 8.5 Hz, 2
H), 7.15 (t, J = 7.4 Hz, 1 H).
13C NMR (100 MHz, DMSO-d6): δ = 160.9 (J = 241 Hz), 156.8, 139.8,
137.1, 128.9, 123.2 (d, J = 8 Hz), 121.0, 120.8, 116.8 (J = 23 Hz), 115.1,
110.5.
HRMS (ESI): m/z [M + H]+ calcd for C13H11FIN2O: 356.9902; found:
356.9895.
1-(Naphthalen-1-yl)-1H-indazol-3(2H)-one (2f)
1-Phenyl-1H-indazol-3(2H)-one (2a);13b Typical Procedure
White solid; yield: 50.0 mg (96%); mp 237.1–239.7 °C.
To a dried 50-mL Radleys reaction tube were added 1a (49.3 mg, 0.2
mmol), KOt-Bu (67.4 mg, 0.6 mmol), and THF (4 mL). The mixture was
stirred at reflux for 2 h under N2 atmosphere. The mixture was cooled
to r.t., the solvent was removed under reduced pressure, and the resi-
due was purified by column chromatography (petroleum ether/EtOAc,
5:1) to give 2a (41.7 mg, 99%) as a white solid; mp 213.5–214.6 °C.
1H NMR (400 MHz, DMSO-d6): δ = 11.24 (s, 1 H), 7.77 (d, J = 8.9 Hz, 2
H), 7.69 (d, J = 7.6 Hz, 2 H), 7.52 (t, J = 7.9 Hz, 2 H), 7.47–7.43 (m, 1 H),
7.26 (t, J = 7.4 Hz, 1 H), 7.16 (t, J = 7.7 Hz, 1 H).
IR (KBr): 3021, 2588, 1618, 1543, 1444, 1311, 771, 740 cm–1
.
1H NMR (400 MHz, DMSO-d6): δ = 11.18 (s, 1 H), 8.08–8.03 (m, 2 H),
7.81 (d, J = 8.0 Hz, 1 H), 7.73 (d, J = 8.4 Hz, 1 H), 7.67–7.58 (m, 3 H),
7.52 (t, J = 7.1 Hz, 1 H), 7.35 (t, J = 7.3 Hz, 1 H), 7.14 (t, J = 7.4 Hz, 1 H),
7.09 (d, J = 8.5 Hz, 1 H).
13C NMR (100 MHz, DMSO-d6): δ = 156.2, 142.1, 135.7, 134.2, 129.2,
128.3, 128.0, 127.9, 126.7, 126.6, 125.7, 123.8, 123.5, 120.4, 119.9,
113.7, 109.8.
HRMS (ESI): m/z [M + H]+ calcd for C17H13N2O: 261.1022; found:
261.1029.
13C NMR (100 MHz, DMSO-d6): δ = 156.8, 140.7, 139.7, 130.0, 128.8,
125.2, 121.1, 121.0, 120.8, 115.3, 110.8.
7-Methyl-1-phenyl-1H-indazol-3(2H)-one (2h)
1-(p-Tolyl)-1H-indazol-3(2H)-one (2b)
White solid; yield: 40.8 mg (85%); mp 172.3–174.5 °C.
IR (KBr): 3021, 2588, 1618, 1543, 1444, 1311, 771, 740 cm–1
White solid; yield: 44.4 mg (99%); mp 223.4–225.7 °C.
IR (KBr): 2918, 2582, 1546, 1311, 823, 738 cm–1
.
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© Georg Thieme Verlag Stuttgart · New York — Synthesis 2016, 48, A–H