10.1002/ejoc.201800501
European Journal of Organic Chemistry
FULL PAPER
6-chloro-2-(thiophen-2-yl) quinoline-4-carboxamide (3v): According to
(dd, J = 8.2, 2.8 Hz, 1H), 7.46 (d, J = 8.5 Hz, 2H); 13C NMR (75 MHz,
CDCl3+DMSO) δ 168.1,160.1(d, J=245 Hz), 153.9(d, J=2.4 Hz), 146.3,
141.3(d, J=5.6 Hz), 136.7,134.9, 132.0(d, J=9.4 Hz), 128.6, 128.5, 124.2
(d, J=10.7 Hz), 119.8 (d, J=26.0 Hz), 117.3, 109.1(d, J=24.0 Hz); IR:
3361, 3172, 2930, 1641, 1545, 1412, 1228, 1092, 831, 670; HRMS (ESI)
m/z: [M+H]+calcd for C16H11N2OClF: 301.0544; found: 301.0546.
the general procedure (B), 2d (181 mg, 1 mmol) gave 3v (207 mg, 72%)
as a dark brown solid. Rf = 0.3 (EtOAc/hexanes, 4/6); mp 281-283 °C; 1
H
NMR (300 MHz, DMSO) δ 8.39 (s, 1H), 8.24 (s, 2H), 8.11 (d, J = 3.3 Hz,
1H), 8.03 (d, J = 9.0 Hz, 2H), 7.81 (d, J = 3.5 Hz, 1H), 7.79 (s, 1H), 7.29
– 7.22 (m, 1H); 13C NMR (75 MHz, DMSO) δ 167.8, 152.1, 146.2, 143.8,
141.7, 131.2, 130.9, 130.7, 130.5, 128.7, 128.1, 124.3, 123.9, 116.6; IR:
3363, 3169, 2930, 1642, 1583, 1424, 1318, 1063, 871, 663; HRMS (ESI)
m/z: [M+H]+calcd for C14H10N2OSCl: 289.0202; found: 289.0217.
2-(2-methoxyphenyl)-6-nitroquinoline-4-carboxamide(3ab):
According to the general procedure (B), 2f (192 mg, 1 mmol) gave 3ab
(129 mg, 40%) as a yellowsolid. Rf = 0.3 (EtOAc/hexanes, 4/6);mp 247-
249 °C;1H NMR (300 MHz, DMSO) δ 9.24 (d, J = 2.3 Hz, 1H), 8.51 (d, J
= 9.3 Hz, 1H), 8.43 (s, 1H), 8.30 (d, J = 9.1 Hz, 1H), 8.22 (s, 1H), 8.10 (s,
1H), 7.88 (d, J = 7.6 Hz, 1H), 7.56 (t, J = 7.8 Hz, 1H), 7.26 (d, J = 8.3 Hz,
1H), 7.17 (t, J = 7.4 Hz, 1H), 3.91 (s, 3H); 13C NMR (75 MHz, DMSO) δ
167.8, 159.7, 157.3, 150.1, 145.2, 142.4, 131.9, 131.3, 131.2, 127.2,
123.1, 122.6, 122.4, 122.0, 120.9, 112.2, 55.8; IR: 3453, 3174, 2978,
1659, 1588, 1490, 1328, 1233, 1024, 751; HRMS (ESI) m/z: [M+H]+calcd
for C17H14N3O4 : 324.0984; found: 324.0989.
6-chloro-2-(furan-2-yl) quinoline-4-carboxamide (3w): According to
the general procedure (B), 2d (181 mg, 1 mmol) gave 3w (190 mg, 70%)
as a dark brownsolid. Rf = 0.3 (EtOAc/hexanes, 4/6); mp 298-300 °C; 1
H
NMR (300 MHz, CDCl3+DMSO) δ 8.28 (d, J = 2.0 Hz, 1H), 8.18 (s, 1H),
7.96 (d, J = 7.5 Hz, 2H), 7.66 (s, 1H), 7.60 (dd, J = 9.1, 2.2 Hz, 2H), 7.26
(d, J = 3.3 Hz, 1H), 6.59 (s, 1H); 13C NMR (75 MHz, CDCl3+DMSO) δ
167.8, 152.3, 148.3, 146.4, 145.4, 141.6, 131.3, 131.0, 130.6, 124.3,
123.8, 116.2, 112.6, 111.6; IR: 3354, 3169, 1662, 1590, 1364, 1069, 876,
742, 670; HRMS (ESI) m/z: [M+H]+calcd for C14H10N2O2Cl: 273.0431;
found: 273.0430.
2-(p-tolyl) quinoline-4-carboxamide (3ac): According to the general
procedure (B), 4a (147 mg, 1 mmol) gave 3ac (188 mg, 70%) as an off
white solid. Rf = 0.3 (EtOAc/hexanes, 4/6); mp 215-217 °C; 1H NMR
(400 MHz, DMSO) δ 8.32 (s, 1H), 8.25 (d, J = 8.6 Hz, 1H), 8.22 (d, J =
8.2 Hz, 1H), 8.13 (s, 1H), 8.10 (d, J = 8.2 Hz, 1H), 7.93 (s, 1H), 7.83 –
7.77 (m, 1H), 7.66 – 7.59 (m, 1H), 7.38 (d, J = 8.1 Hz, 1H), 2.40 (s,
1H);13C NMR (100 MHz, CDCl3+DMSO) δ 169.4, 156.0, 148.0, 142.1,
139.4, 135.4, 129.5, 129.2, 126.9, 126.5, 125.0, 122.9, 116.4,
20.9;IR:3349, 3173, 2926, 1684, 1588, 1385, 1322, 1054; HRMS (ESI)
m/z: [M+H]+calcd for C17H15N2O: 263.1184 ; found: 263.1187.
6-fluoro-2-phenylquinoline-4-carboxamide (3x): According to the
general procedure (B), 2e (165 mg, 1 mmol) gave 3x (220 mg, 83%) as
an off white solid. Rf = 0.3 (EtOAc/hexanes, 4/6);mp 238-240 °C; 1H NMR
(400 MHz, DMSO) δ 8.40 (s, 1H), 8.31 (d, J = 7.1 Hz, 2H), 8.26 (s, 1H),
8.20 (dd, J = 9.2, 5.7 Hz, 1H), 8.05 (dd, J = 10.5, 2.7 Hz, 1H), 7.98 (s,
1H), 7.76 (td, J = 8.9, 2.8 Hz, 1H), 7.56 (dq, J = 14.2, 7.0 Hz, 3H); 13C
NMR (75 MHz, DMSO) δ 168.2,160.0(d, J=245 Hz), 155.4(d, J=2.6 Hz),
145.4, 141.7(d, J=5.6 Hz), 138.0, 132.4(d, J=9.4 Hz), 129.9, 128.9, 127.3,
124.1 (d, J=10.6 Hz), 120.2, (d, J=25.5 Hz), 117.7, 109.2(d, J=23.8 Hz);
IR; 3361, 3173, 1644, 1550, 1379, 1231, 1133, 768, 682; HRMS (ESI)
m/z: [M+H]+calcd for C16H12N2OF: 267.0934; found: 267.0936.
2-(4-methoxyphenyl) quinoline-4-carboxamide (3ad): According to the
general procedure (B), 4a (147 mg, 1 mmol) gave 3ad (205 mg, 74%) as
a light brown solid. Rf = 0.2 (EtOAc/hexanes, 4/6);mp 213-215 °C; 1H
NMR (300 MHz, DMSO) δ 8.33 (s, 1H), 8.28 (d, J = 8.8 Hz, 2H), 8.22 (d,
J = 7.9 Hz, 1H), 8.11 (s, 1H), 8.08 (d, J = 8.4 Hz, 1H), 7.93 (s, 1H), 7.84
– 7.72 (m, 1H), 7.65 – 7.56 (m, 1H), 7.12 (d, J = 8.9 Hz, 2H), 3.85 (s,
3H); 13C NMR (75 MHz, DMSO) δ 168.8, 160.9, 155.5, 148.0, 143.0,
130.7, 130.1, 129.3, 128.8, 126.6, 125.5, 123.0, 116.1, 114.3, 55.4; IR:
3700, 2930, 2867, 1578, 1479, 1379, 1058, 1006, 820, 709; HRMS (ESI)
m/z: [M+H]+calcd for C17H15N2O2: 279.1134 ; found:279.1136.
6-fluoro-2-(4-methoxyphenyl)quinoline-4-carboxamide(3y):
According to the general procedure (B), 2e (165 mg, 1 mmol) gave 3y
(251 mg, 85%) as a light brown solid. Rf = 0.3 (EtOAc/hexanes, 4/6);mp
245-247 °C; 1H NMR (300 MHz, CDCl3+DMSO) δ 8.26 (s, 1H), 8.18 (d, J
= 8.8 Hz, 2H), 8.08 (s, 1H), 8.06 – 7.99 (m, 2H), 7.67 (s, 1H), 7.50 (td, J
= 9.0, 2.8 Hz, 1H), 7.00 (d, J = 8.8 Hz, 2H), 3.83 (s, 3H); 13C NMR (75
MHz, CDCl3+DMSO) δ 168.5,160.6(d, J=246 Hz), 154.8(d, J=2.5 Hz),
146.3, 140.9 (d, J=5.7 Hz), 131.6(d, J=9.0 Hz), 130.5, 128.4, 123.6 (d,
J=10.4 Hz), 119.2 (d, J=25.7 Hz), 117.1,113.8, 108.9(d, J=23.8 Hz), 54.9;
IR: 3205, 3158, 2928, 2858, 1739, 1660, 1509, 1411, 1237, 1179, 1090,
828; HRMS (ESI) m/z: [M+H]+calcd for C17H14N2O2F: 297.1039; found:
297.1042.
2-(thiophen-2-yl) quinoline-4-carboxamide (3ae): According to the
general procedure (B), 4a (147 mg, 1 mmol) gave 3ae (157 mg, 62%) as
a pale-yellow solid. Rf = 0.3 (EtOAc/hexanes, 4/6);mp 237-239 °C;1H
NMR (400 MHz, DMSO) δ 8.30 (s, 1H), 8.17 (d, J = 8.4 Hz, 1H), 8.14 (s,
1H), 8.08 (s, 1H), 8.00 (d, J = 8.4 Hz, 1H), 7.96 (s, 1H), 7.76 (d, J = 4.0
Hz, 2H), 7.61 (d, J = 6.9 Hz, 1H), 7.24 (s, 1H); 13C NMR (75 MHz,
DMSO) δ 168.4, 151.6, 147.7, 144.3, 143.2, 130.3, 129.9, 128.8, 128.6,
127.6, 126.7, 125.5, 123.2, 115.3; IR; 3364, 3169, 2923, 1643, 1583,
1381, 1234, 818, 700; HRMS (ESI) m/z: [M+H]+calcd for C14H11N2OS:
255.0592; found:255.0597.
6-fluoro-2-(2-methoxyphenyl)quinoline-4-carboxamide(3z): According
to the general procedure (B), 2e (167 mg, 1 mmol) gave 3z (251 mg,
85%) as an off whitesolid. Rf = 0.3 (EtOAc/hexanes, 4/6); mp 209-
211 °C; 1H NMR (300 MHz, CDCl3+DMSO) δ 8.07 (dd, J = 9.3, 5.6 Hz,
1H), 8.03 (d, J = 8.4 Hz, 2H), 7.95 (dd, J = 10.3, 2.7 Hz, 1H), 7.76 (dd, J
= 7.7, 1.5 Hz, 1H), 7.55 – 7.44 (m, 2H), 7.39 (dd, J = 8.1, 1.5 Hz, 1H),
7.06 (s, 1H), 7.05 – 7.00 (m, 1H), 3.84 (s, 3H); 13C NMR (75 MHz,
CDCl3+DMSO) δ 168.9,160.1(d, J=247 Hz), 156.9, 155.4, 145.3, 140.1(d,
J=5.6 Hz), 131.8(d, J=9.1 Hz), 130.7(d, J=23.2 Hz), 128.0, 123.8,123.7,
121.7, 120.7, 119.3,111.4, 108.9(d, J=23.5 Hz), 55.4; IR : 3352, 3181,
1640, 1457, 1372, 1231, 1080, 1035, 830, 755, 685; HRMS (ESI) m/z:
[M+H]+calcd for C17H14N2O2F: 297.1039; found: 297.1043.
2-(furan-2-yl) quinoline-4-carboxamide (3af): According to the general
procedure (B), 4a (147 mg, 1 mmol) gave 3af (142 mg, 60%) as a dark
brownsolid. Rf = 0.3 (EtOAc/hexanes, 4/6);mp 255-257 °C;1H NMR (300
MHz, CDCl3+DMSO) δ 8.23 (s, 1H), 8.20 (d, J = 8.5Hz, 1H), 8.01 (d, J =
8.4 Hz, 1H), 7.94 (s, 1H), 7.83 (s, 2H), 7.73 (s, 1H), 7.54 (s, 1H), 7.34 (s,
1H), 6.66 (s, 1H); 13C NMR (75 MHz, CDCl3+DMSO) δ 168.4, 152.6,
147.8, 147.7, 144.6, 142.9, 129.9, 128.7, 126.5, 125.4, 123.1, 114.9,
112.3, 110.7; IR: 3349, 3151, 3076, 1660, 1588, 1364, 1236, 1011, 746;
HRMS (ESI) m/z: [M+H]+calcd for C14H11N2O2: 239.0821; found:
239.0830.
2-(4-chlorophenyl)-6-fluoroquinoline-4-carboxamide (3aa): According
to the general procedure (B), 2e (165 mg, 1 mmol) gave 3aa (249 mg,
83%) as a whitesolid. Rf = 0.3 (EtOAc/hexanes, 4/6); mp 262-264 °C;1H
NMR (300 MHz, CDCl3+DMSO) δ 8.23 (s, 1H), 8.20 (d, J = 8.6 Hz, 2H),
8.11 (s, 1H), 8.09 – 8.07 (m, 1H), 8.06 – 8.03 (m, 1H), 7.61 (s, 1H), 7.52
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