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The Journal of Organic Chemistry
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Isolated from flash chromatography (50% EtOAc/n-hexane). H
NMR (600 MHz, CDCl3, δ): 8.36 (d, J = 6.0 Hz, 1H), 8.15 (d, J =
8.4 Hz, 1H), 7.93 (d, J = 7.8 Hz, 2H), 7.82 (d, J = 8.4 Hz, 1H), 7.56
(d, J = 9.0 Hz, 1H), 7.47-7.50 (m, 1H), 7.41-7.43 (m, 2H), 7.34-
7.37 (m, 1H). 13C {1H} NMR (150 MHz, CDCl3, δ): 139.6, 137.7,
133.13, 133.10, 132.2, 130.2, 129.6, 129.2, 127.5, 125.9, 125.5,
121.8, 117.9. IR (ZnSe): νmax (cm–1) 3302, 3088, 2922, 1575, 1444,
1346, 1251, 1166, 1089, 862, 731. HRMS (ESI-TOF) (m/z):
[M+H]+ calcd for C15H12ClN2O3S, 335.0252; found, 335.0268.
3-Methyl-8-(phenylsulfonamido)quinoline N-oxide (Table 4,
entry 4c). Pale yellow solid, Yield = 20.4 mg (65%). mp 165-168
°C. Isolated from flash chromatography (70% EtOAc/n-hexane).
1H NMR (600 MHz, CDCl3, δ): 14.45 (br, s, 1H, NH), 8.17 (s, 1H),
7.92-7.94 (m, 2H), 7.76 (d, J = 7.8 Hz, 1H), 7.48 (s, 1H), 7.44-7.47
(m, 1H), 7.38-7.41 (m, 3H), 7.31 (d, J = 8.4 Hz, 1H), 2.39 (s, 3H).
13C{1H} NMR (150 MHz, CDCl3, δ): 139.8, 138.5, 133.6, 132.9,
132.2, 131.5, 129.5, 129.3, 129.1, 128.7, 127.4, 121.9, 117.2, 18.5.
IR (ZnSe): νmax (cm–1) 3088, 2922, 1587, 1446, 1367, 1276, 1149,
1066, 985, 854, 756, 684. HRMS (ESI-TOF) (m/z): [M+H]+ calcd
for C16H15N2O3S, 315.0798; found, 315.0811.
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4-(Acetoxymethyl)-8-(phenylsulfonamido)quinoline N-oxide
(Table 4, entry 4i). Brown solid, Yield = 24.9 mg (67%). mp 180-
182 °C. Isolated from flash chromatography (70% EtOAc/n-hex-
ane). 1H NMR (300 MHz, CDCl3, δ): 8.29 (d, J = 6.3 Hz, 1H), 7.93-
7.96 (m, 2H), 7.90 (dd, J = 7.5, 1.5 Hz, 1H), 7.49-7.56 (m, 2H),
7.39-7.48 (m, 1H), 7.32 (d, J = 6.3 Hz, 1H), 5.39 (s, 1H), 2.14 (s,
1H). 13C{1H} NMR (75 MHz, CDCl3, δ): 170.4, 139.9, 136.4,
134.7, 133.9, 132.9, 130.9, 130.2, 129.9, 129.2, 127.5, 120.7,
118.2, 117.7, 62.3, 20.9. IR (ZnSe): νmax (cm–1) 3095, 2922, 2852,
1735, 1581, 1487, 1309, 1240, 1157, 1043, 937, 846, 756. HRMS
(ESI-TOF) (m/z): [M+H]+ calcd for C18H17N2O5S, 373.0853;
found, 373.0859.
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4-Methyl-8-(phenylsulfonamido)quinoline N-oxide (Table 4,
entry 4d). Pale yellow solid, Yield = 22.6 mg (72%). mp 149-152
°C. Isolated from flash chromatography (70% EtOAc/n-hexane).
1H NMR (600 MHz, CDCl3, δ): 15.04 (br, s, 1H, NH), 8.18 (d, J =
6.0 Hz, 1H), 7.92 (d, J = 7.8 Hz, 2H), 7.85 (d, J = 5.4 Hz, 1H), 7.45-
7.48 (m, 2H), 7.43 (d, J = 7.2 Hz, 1H), 7.36-7.39 (m, 2H), 7.08 (d,
J = 6.0 Hz, 1H), 2.56 (s, 3H). 13C{1H} NMR (150 MHz, CDCl3, δ):
139.9, 137.9, 136.4, 134.4, 132.8, 131.7, 129.13, 129.05, 127.4,
125.5, 121.7, 118.9, 118.1, 19.4. IR (ZnSe): νmax (cm–1) 3093, 2920,
1575, 1446, 1313, 1280, 1149, 1043, 804, 715. HRMS (ESI-TOF)
(m/z): [M+H]+ calcd
315.0815.
for C16H15N2O3S, 315.0798; found,
5-(Phenylsulfonamido)benzo[h]quinoline N-oxide (Table 4,
entry, 4j). Yellow solid, Yield = 19.3 mg (55%). mp 210-212 °C.
Isolated from flash chromatography (70% EtOAc/n-hexane). 1H
NMR (600 MHz, CDCl3, δ): 8.60 (d, J = 8.4 Hz, 1H), 8.45 (d, J =
6.0 Hz, 1H), 8.38 (d, J = 7.8 Hz, 1H), 8.13 (s, 1H), 7.93 (d, J = 7.8
Hz, 2H), 7.83 (d, J = 8.4 Hz, 1H), 7.66-7.68 (m, 1H), 7.60-7.62 (m,
1H), 7.46-7.49 (m, 1H), 7.41 (t, J = 7.2 Hz, 1H), 7.34-7.36 (m, 2H).
13C{1H} NMR (150 MHz, CDCl3, δ): 139.8, 138.4, 132.9, 132.1,
130.7, 129.9, 129.6, 129.2, 129.1, 128.6, 127.8, 127.5, 127.3,
125.3, 123.1, 121.7, 119.3. IR (ZnSe): νmax (cm–1) 3101, 2920,
1616, 1598, 1446, 1332, 1280, 1157, 1076, 950, 885, 750. HRMS
(ESI-TOF) (m/z): [M+H]+ calcd for C19H15N2O3S, 351.0798;
found, 351.0809.
6-Methyl-8-(phenylsulfonamido)quinoline N-oxide (Table 4,
entry 4e). Pale yellow solid, Yield = 22.9 mg (73%). mp 168-170
°C. Isolated from flash chromatography (70% EtOAc/n-hexane).
1H NMR (600 MHz, CDCl3, δ): 14.43 (br, s, 1H, NH), 8.21 (dd, J
= 6.0 Hz, 0.6 Hz, 1H), 7.93-7.94 (m, 2H), 7.70 (d, J = 1.2 Hz, 1H),
7.60 (d, J = 8.4 Hz, 1H), 7.45-7.47 (m, 1H), 7.40 (t, J = 7.8 Hz,
2H), 7.17-7.19 (m, 2H), 2.42 (s, 3H). 13C {1H} NMR (150 MHz,
CDCl3, δ): 139.9, 139.8, 136.4, 133.4, 132.9, 132.5, 129.8, 129.1,
128.6, 127.4, 121.8, 121.0, 120.2, 21.8. IR (ZnSe): νmax (cm–1)
3061, 1583, 1444, 1394, 1284, 1153, 1091, 918, 858, 721. HRMS
(ESI-TOF) (m/z): [M+H]+ calcd for C16H15N2O3S, 315.0798;
found, 315.0819.
General Procedure for Synthesis of 8-Acetamidoquinoline N-
oxide from p-Tosyl azide. To a solution of quinoline N-oxide 1a
(0.1mmol) in TFE (0.5 mL per mmol) in a reaction vial equipped
with magnetic stir bar, p-tosyl azide (2k) (1.1 equiv.), Rh catalyst
(5 mol%), silver salt (20 mol%) and NaOAc (20 mol%) were
added. Reaction mixture was allowed to stir at 110 °C for 24 h on
heating block, filtered through a pad of celite and then celite was
washed with ethyl acetate (10 mL x 3) to extract the traces of reac-
tion mixture. After that organic solvents were removed under re-
duced pressure. The residue was purified by flash chromatography
on silica gel (mesh 230-400) to give the desired product. Eluting
solvents for chromatography are indicated under the specific com-
pound headings.
6-Methyoxy-8-(phenylsulfonamido)quinoline N-oxide (Table
4, entry 4f). Pale yellow solid, Yield = 19.8 mg (60%). mp 185-188
°C. Isolated from flash chromatography (80% EtOAc/n-hexane).
1H NMR (600 MHz, CDCl3, δ): 14.62 (br, s, 1H, NH), 8.13 (d, J =
6.0 Hz, 1H), 7.94-7.96 (m, 2H), 7.58 (d, J = 8.4 Hz, 1H), 7.47 (t, J
= 7.2 Hz, 1H), 7.44 (d, J = 2.4 Hz, 1H), 7.40-7.43 (m, 2H), 7.16
(dd, J = 8.4, 6.0 Hz, 1H), 6.68 (d, J = 2.4 Hz, 1H), 3.84 (s, 3H).
13C{1H} NMR (150 MHz, CDCl3, δ): 159.3, 139.7, 135.2, 135.0,
133.8, 132.9, 129.1, 128.4, 127.5, 127.1, 121.4, 109.1, 101.1, 55.8.
IR (ZnSe): νmax (cm–1) 3307, 2922, 1587, 1448, 1276, 1165, 1080,
794, 684. HRMS (ESI-TOF) (m/z): [M+H]+ calcd for
C16H15N2O4S, 331.0747; found, 331.0765.
Characterization
Sata.
8-((4-Methylphenyl)sulfon-
6-Bromo-8-(phenylsulfonamido)quinoline N-oxide (Table 4,
entry, 4g). Pale yellow solid, Yield = 29.6 mg (78%). mp 200-202
°C. Isolated from flash chromatography (60% EtOAc/n-hexane).
1H NMR (600 MHz, CDCl3, δ): 14.55 (br, s, 1H, NH), 8.28-8.29
(m, 1H), 7.96-7.98 (m, 2H), 7.95 (d, J = 1.8 Hz, 1H), 7.60 (d, J =
8.4 Hz, 1H), 7.55 (d, J = 1.8 Hz, 1H), 7.50-7.53 (m, 1H), 7.45-7.47
(m, 2H), 7.25-7.27 (m, 1H). 13C {1H} NMR (150 MHz, CDCl3, δ):
139.5, 137.2, 135.1, 133.26, 133.25, 130.1, 129.3, 127.9, 127.5,
124.0, 123.7, 122.1, 120.4. IR (ZnSe): νmax (cm–1) 3103, 3064,
1649, 1587, 1446, 1319, 1276, 1153, 1089, 869, 788. HRMS (ESI-
TOF) (m/z): [M+H]+ calcd for C15H12BrN2O3S, 378.9747; found,
378.9767.
amido)quinoline N-oxide7c (Table 4, 4k ). Black solid, Yield = 28.9
mg (92%). Isolated from flash chromatography (80% EtOAc/n-
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hexane). H NMR (300 MHz, CDCl3, δ): 14.37 (br, s, 1H, NH),
8.31 (dd, J = 6.0, 0.9 Hz, 1H), 7.81-7.86 (m, 3H), 7.70 (d, J = 7.8
Hz, 1H), 7.43-7.49 (m, 1H), 7.40 (dd, J = 8.4, 1.5 Hz, 1H), 7.23-
7.26 (m, 1H), 7.19 (d, J = 8.4 Hz, 2H), 2.32 (s, 3H). 13C{1H} NMR
(150 MHz, CDCl3, δ): 143.8, 137.2, 136.9, 133.9, 132.6, 131.3,
129.7, 129.4, 129.1, 127.5, 122.3, 121.0, 118.1, 21.6.
8-((Phenylmethyl)sulfonamido)quinoline N-oxide7c (Table 4,
4l ). Brown viscous, Yield = 25.1 mg (80%). Isolated from flash
chromatography (80% EtOAc/n-hexane). 1H NMR (300 MHz,
CDCl3, δ): 14.12 (br, s, 1H, NH), 8.34 (dd, J = 6.0, 0.9 Hz, 1H),
7.79-7.82 (m, 1H), 7.69 (dd, J = 6.9, 2.4 Hz, 1H), 7.47-7.51 (m,
1H), 7.41-7.46 (m, 1H), 7.30-7.35 (m, 1H), 7.26-7.29 (m, 2H),
6-Chloro-8-(phenylsulfonamido)quinoline N-oxide (Table 4,
entry, 4h). Yellow solid, Yield = 19.4 mg (58%). mp 180-182 °C.
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