Synthesis of quinolines
Russ. Chem. Bull., Int. Ed., Vol. 68, No. 5, May, 2019
1023
a mixture of AcOH (50 mL) and water (0.1 mL, 5.5 mmol) was
refluxed for 24 h and poured into water (150 mL). After 24 h, the
precipitate formed was collected by filtration, washed with water,
dried, and washed with ethanol.
cf. Ref. 27: 81—82 C). Found (%): C, 87.53; H, 5.48; N, 6.57.
C H N. Calculated (%): C, 87.77; H, 5.40; N, 6.82. IR,
15
11
–
1
1
ν/cm : 1596, 1491 (C=C, C=N). H NMR, : 7.53 (dd, 1 H,
H(4´), J = 7.5 Hz, J = 7.5 Hz); 7.57 (dd, 2 H, H(3´) and H(5´),
J = 7.6 Hz, J = 7.5 Hz); 7.63, 7.83 (both ddd, 1 H each, H(6)
and H(7), J = 7.7 Hz, J = 7.7 Hz, J = 1.1 Hz); 8.03, 8.11 (both d,
1 H each, H(5) and H(8), J = 7.6 Hz); 8.14, 8.53 (both d, 1 H
each, H(3) and H(4), J = 8.6 Hz); 8.22 (dd, 2 H, H(2´) and
3
-Hydroxy-2-methylquinolin-4(1H)-one (4a). Yield 0.18 g
(
52%). M.p. 293—294 C (cf. Ref. 11: 298—306 C). Found (%):
C, 68.71; H, 5.23; N, 8.31. C H NO . Calculated (%): C, 68.56;
1
0
9
2
H, 5.18; N, 8.00. IR, ν/cm– : 3255, 2919, 2836 (NH, OH), 1639
1
1
13
1
(
C=O), 1551, 1488 (C=C). H NMR, : 2.40 (s, 3 H, Me); 7.22,
H(6´), J = 7.7 Hz, J = 1.1 Hz). C{ H} NMR, : 156.2 (C(2)),
147.3 (C(8a)), 138.7 (C(1´)), 137.4 (C(4)), 130.1 (C(7)), 129.7
(C(4´)), 129.1 (C(8)), 129.0 (C(3´), C(5´)), 127.9 (C(5)), 127.3
(C(2´), C(6´)), 127.1 (C(4a)), 126.6 (C(6)), 119.9 (C(3)). 15N NMR,
: 301.2. Product 2b (0.46 g (69%)) was isolated along with
compound 5b.
7
.56 (both dd, 1 H each, H(6) and H(7), J = 7.5 Hz, J = 7.4 Hz);
.55, 8.10 (both d, 1 H each, H(8) and H(5), J = 7.5 Hz,
J = 7.4 Hz); 11.86 (br.s, NH).
-Hydroxy-2-phenylquinolin-4(1H)-one (4b). Yield 0.25 g
53%). M.p. 270—271 C (cf. Ref. 3: 265—275 C; cf. Ref. 8:
60—262 C; cf. Refs 10, 12: 278—281 C; cf. Ref. 13: 275—278
7
3
(
2
2-(4-Tolyl)quinoline (5c). Yield 0.12 g (19%). M.p. 85 C
(cf. Ref. 14: 83—84 C; cf. Ref. 15: 80—82 C; cf. Ref. 19: 80—81 C;
cf. Ref. 27: 82—83 C). Found (%): C, 87.33; H, 6.08; N, 6.63.
C). Found (%): C, 76.07; H, 4.32; N, 5.74. C H NO .
15 11 2
–
1
Calculated (%): C, 75.94; H, 4.67; N, 5.90. IR, ν/cm : 3240,
2
J = 7.4 Hz); 7.45—7.59 (m, 5 H, Ph); 7.84, 8.25 (both d, 1 H each,
H(8) and H(5), J = 7.8 Hz, J = 7.4 Hz); 11.59 (br.s, NH).
1
925, 2854 (NH, OH), 1633 (C=O), 1547, 1485 (C=C). H NMR,
C H N. Calculated (%): C, 87.64; H, 5.98; N, 6.39. IR,
16 13
–
1
1
: 7.36, 7.72 (both dd, 1 H each, H(6) and H(7), J = 7.7 Hz,
ν/cm : 1596, 1498 (C=C, C=N). H NMR, : 2.38 (s, 3 H, Me);
7.35, 8.17 (both d, 2 H each, Ar, J = 7.8 Hz); 7.58, 7.77 (both dd,
1 H each, H(6) and H(7), J = 7.9 Hz, J = 7.9 Hz); 7.97, 8.41
(both d, 1 H each, H(5) and H(8), J = 8.2 Hz); 8.06, 8.09 (both d,
1 H each, H(3) and H(4), J = 8.0 Hz). Product 2c (0.49 g (69%))
was isolated along with compound 5c.
3
-Hydroxy-2-(4-methylphenyl)quinolin-4(1H)-one (4c). Yield
0
.26 g (51%). M.p. 269—272 C. Found (%): C, 76.23; H, 5.42;
N, 5.31. C H NO . Calculated: C, 76.47; H, 5.22; N, 5.57. IR,
16
13
2
–
1
ν/cm : 3300, 2922, 2854 (NH, OH), 1634 (C=O), 1547, 1485
2-(4-Methoxyphenyl)quinoline (5d). Yield 0.14 g (20%). M.p.
123—124 C (cf. Ref. 14: 123—124 C; cf. Ref. 15: 117—120 C;
cf. Ref. 27: 123—124 C). Found (%): C, 81.39; H, 5.38; N, 6.03.
1
(
C=C). H NMR, : 2.39 (s, 3 H, Me); 7.26, 7.58 (both dd,
1
H each, H(6) and H(7), J = 8.0 Hz, J = 7.9 Hz); 7.38, 7.71
both d, 2 H each, Ar, J = 8.7 Hz); 8.14 (d, 2 H, H(8) and H(5),
J = 7.9 Hz); 11.50 (br.s, NH).
-Hydroxy-2-(4-methoxyphenyl)quinolin-4(1H)-one (4d).
Yield 0.29 g (55%). M.p. 273—274 C. Found (%): C, 71.77;
(
C H NO. Calculated (%): C, 81.68; H, 5.57; N, 5.95. IR,
16 13
–
1
1
ν/cm : 1596, 1497 (C=C, C=N). H NMR, : 3.81 (s, 3 H, OMe),
7.09, 8.16 (both d, 2 H each, Ar, J = 8.5 Hz); 7.56, 7.76 (both dd,
1 H each, H(6) and H(7), J = 7.9 Hz, J = 7.9 Hz); 7.94 (d, 1 H,
H(5), J = 8.0 Hz), 8.04 (d, 2 H, H(3) and H(8), J = 8.0 Hz);
8.39 (d, 1 H, H(4), J = 8.0 Hz). Product 2d (0.52 g (70%)) was
isolated along with compound 5d.
3
H, 4.77; N, 5.21. C H NO . Calculated (%): C, 71.89; H, 4.91;
1
6
13
3
–
1
N, 5.24. IR, ν/cm : 3266, 2955 (NH, OH), 1634 (C=O), 1547,
1
1
487 (C=C). H NMR, : 3.85 (s, 3 H, OMe); 7.13, 7.78 (both d,
2
H each, Ar, J = 8.7 Hz); 7.28, 7.58 (both dd, 1 H each, H(6)
2-(4-Chlorophenyl)quinoline (5e). Yield 0.16 g (23%). M.p.
113 C (cf. Ref. 14: 112—113 C; cf. Ref. 15: 110—113 C; cf. Ref. 27:
111—112 C). Found (%): C, 75.35; H, 4.39; Cl, 15.00; N, 5.99.
and H(7), J = 7.4 Hz, J = 7.2 Hz); 7.72, 8.14 (both d, 1 H each,
13
1
H(8) and H(5), J = 7.4 Hz, J = 7.2 Hz); 11.51 (br.s, NH). C{ H}
NMR, : 169.3 (C(4)), 160.0 (C(4´)), 137.8 (C(8a)), 137.4 (C(3)),
C H ClN. Calculated (%): C, 75.16; H, 4.21; Cl, 14.79; N, 5.84.
1
5
10
–
1
1
1
31.8 (C(2)), 130.6 (C(2´), C(6´)), 130.4 (C(7)), 124.3 (C(1´)),
IR, ν/cm : 1595, 1487 (C=C, C=N). H NMR, : 7.61, 8.31
(both d, 2 H each, Ar, J = 8.6 Hz); 7.61, 7.79 (both ddd, 1 H
each, H(6) and H(7), J = 8.4 Hz, J = 7.4 Hz, J = 1.4 Hz); 8.01,
8.07 (both d, 1 H each, H(5) and H(8), J = 7.4 Hz, J = 8.4 Hz);
8.16, 8.47 (both d, 1 H each, H(3) and H(4), J = 8.6 Hz). Product
2e (0.52 g (68%)) was isolated along with compound 5e.
1
24.3 (C(5)), 121.9 (C(6)), 121.5 (C(4a)), 118.4 (C(8)), 113.7
1
5
(
C(3´), C(5´)), 55.3 (OCH ). N NMR, : 125.8.
3
2
-(4-Chlorophenyl)-3-hydroxyquinolin-4(1H)-one (4e). Yield
.32 g (58%). M.p. 289—291 C (cf. Ref. 10: 291.5—294 C).
0
Found (%): C, 66.38; H, 3.52; Cl, 13.22; N, 5.28. C H ClNO .
1
5
10
2
1
–
Calculated (%): C, 66.31; H, 3.71; Cl, 13.05; N, 5.16. IR, ν/cm
:
X-ray diffraction study of compound 5e. A single crystal of
compound 5e was grown by slow evaporation of its acetone solu-
tion at room temperature. The X-ray diffraction data were col-
lected at 293(2) K with a Bruker KAPPA APEX II diffracto-
meter equipped with a four circle CCD detector (graphite mono-
chromator, (Mo-K) = 0.71073 Å, scan mode). APEX3
v2015.9-0 (Bruker AXS) program package was used for data col-
lection and indexing, structure solution and refinement of the
single cell parameters, semi-empirical correction accounting
(using equivalent reflections based on the Laue group), account-
ing for the systematic errors, and determination of the space
group of the crystal. The structure was solved by a direct method
1
3
276, 2958 (NH, OH), 1637 (C=O), 1548, 1492 (C=C). H NMR,
: 7.27, 7.60 (both dd, 1 H each, H(6) and H(7), J = 7.6 Hz,
J = 7.5 Hz); 7.63, 7.84 (both dd, 2 H each, Ar, J = 8.4 Hz);
7
(
.71, 8.14 (both d, 1 H each, H(8) and H(5), J = 7.6 Hz); 11.57
br.s, NH).
Synthesis of 2-arylquinolines 5b—e (general procedure). To
a solution of [2-(2-nitrophenyl)oxiran-1-yl]arylketone 1b—e
(
9
3 mmol) in dioxane (200 mL), a solution of Na S O (5.22 g,
2 2 4
0 mmol) in water (300 mL) was added. The reaction mixture
was refluxed for 12 h and poured into water. After 12 h, the pre-
cipitate formed was collected by filtration, washed with water,
1
33
and dried. According to H NMR data, the obtained solid was
using SHELXT-2018/2 software and refined by a full matrix
2
34
a mixture of compounds 2 and 5 in a ~3 : 1 ratio. Compounds 2
and 5 were separated by silica gel column chromatography (silica
least squares method on F using SHELXL-2018/3 software.
All nonhydrogen atoms were refined anisotropically. Hydrogen
atoms were positioned geometrically and refined using a riding
model. All calculations were performed with WinGX-2018.3
gel 40 A, elution with CHCl ).
3
2
-Phenylquinoline (5b). Yield 0.13 g (21%). M.p. 82 C
cf. Ref. 14: 82—83 C; cf. Ref. 15: 85—87 C; cf. Ref. 19: 80—82 C;
3
5
(
program package.