62
F. A. EL-SAMAHY ET AL.
1
3
(Cl_C); H NMR (500 MHz, CDCl3): δ = 5.75 (d, JHH
=
gel to give compounds E,Z-3a–c, E-3d, and 5 along with triph-
enylphosphine oxide (TPPO), which was obtained at 75/25 v/v
(petroleum ether (60–80°C)/acetone as an eluent) as colorless
crystals (80% yield) (comparative mp. mixed mp. with authen-
3
=
12.3 Hz, 1H, CH CH-CO), 7.63 (m, 1H, CH-6), 7.65 (d, JHH
3
=
= 12.2 Hz, 1H, CH CH-CO), 7.81 (m, 1H, CH-7), 7.94 (d, JHH
= 8.4 Hz, 1H, CH-5), 8.02 (d, 3JHH = 8.4 Hz, 1H, CH-8), 8.89 (s,
1H, CH-4). 13C NMR (75 MHz, DMSO): δ = 99.7 (CN), 116.0,
125.9, 127.9, 128.3, 128.5, 132.1, 138.0, 144.0, 146.0 (ethylenic
and quinolinyl carbon atoms); MS (EI, 70 eV) m/z (%) 214 (65)
[M+]; Anal. Calcd. for C12H7ClN2 (214.6): C, 67.15; H, 3.29; N,
13.05, Found: C, 66.97; H, 3.40; N, 12.90%.
(Z)-Ethyl 3-(2-chloroquinolin-3-yl)acrylate (Z-3a)
Eluent: petroleum ether (60–80°C) / acetone (95/5, v/v); Yel-
lowish crystals, mp 80–81°C; IR (KBr), ν (cm−1): 3050 (C_H
aromatic), 2977 (C_H aliphatic), 1724 (CO ester), 1617, 1585
(Z)-Methyl 3-(2-chloroquinolin-3-yl)acrylate (Z-3c)
_
1
=
=
(C N, C C), 1194 (CO stretching), 745 (Cl C); H NMR
(500 MHz, CDCl3): δ = 1.18 (t, 3JHH = 7.7 Hz, 3H, OCH2CH3),
Eluent: petroleum ether (60–80°C)/acetone (95/5, v/v); colorless
crystals, mp 97–98°C. IR (KBr), ν(cm−1): 3050 (C_H aromatic),
4.12 (q, 3JHH = 7.7 Hz, 2H, OCH2CH3), 6.22 (d, 3JHH = 12.2 Hz,
_
3
=
=
2948 (C H aliphatic), 1722 (CO ester), 1634, 1561 (C N, C C),
=
=
1H, CH CH-CO), 7.23 (d, JHH = 11.5 Hz, 1H, CH CH-CO),
7.58 (m, 1H, CH-6), 7.83 (m, 1H, CH-7), 7.85 (d, 3JHH = 7.6 Hz,
1H, CH-5), 8.05 (d, 3JHH = 7.6 Hz, 1H, CH-8), 8.44 (s, 1H, CH-
4); MS (EI, 70 eV) m/z (%) 226 (63) [M+_ Cl]; Anal. Calcd.
for C14H12ClNO2 (261.7): C, 64.25; H, 4.62; N, 5.35, Found: C,
64.37; H, 4.59; N, 5.28%.
1296 (CO stretching), 752 (Cl_C); 1H NMR (500 MHz, CDCl3):
3
δ = 3.74 (s, 3H, COOCH3), 6.22 (d, JHH = 12.3 Hz, 1H,
3
=
=
CH CH-CO), 7.22 (d, JHH = 13.0 Hz, 1H, CH CH-CO), 7.58
3
(m, 1H, CH-6), 7.76 (m, 1H, CH-7), 7.85 (d, JHH = 8.4 Hz,
1H, CH-5), 8.01 (d, 3JHH = 7.7 Hz, 1H, CH-8), 8.45 (s, 1H,
CH-4); MS (EI, 70 eV) m/z (%) 247 (<5) [M+]; Anal. Calcd.
for C13H10ClNO2 (247.6): C, 63.04; H, 4.07; N, 5.66, Found: C,
62.78; H, 4.02; N, 5.60%.
(E)-Ethyl 3-(2-chloroquinolin-3-yl)acrylate (E-3a)
Eluent: petroleum ether (60–80°C) / acetone (93/7, v/v); col-
orless crystals, mp 129–130°C. IR (KBr), ν(cm−1): 3060 (C_H
aromatic), 2989, 2936 (C_H aliphatic), 1712 (CO ester), 1614,
(E)-Methyl 3-(2-chloroquinolin-3-yl)acrylate (E-3c)
Eluent: petroleum ether (60–80°C)/acetone (93/7, v/v); colorless
crystals, mp 147–148°C. IR (KBr), ν(cm−1): 3057, 3035 (C_H
aromatic), 3005, 2948 (C_H aliphatic), 1709 (CO ester), 1613,
_
1
=
=
1580 (C N, C C), 1286 (CO stretching), 746 (Cl C); H NMR
(500 MHz, CDCl3): δ = 1.35 (t, 3JHH = 7.7 Hz, 3H, OCH2CH3),
4.31 (q, 3JHH = 7.7 Hz, 2H, OCH2CH3), 6.56 (d, 3JHH = 15.5 Hz,
_
1
=
=
1584 (C N, C C), 1287 (CO stretching), 746 (Cl C); H NMR
=
1H, CH CH-CO), 7.84 (m, 1H, CH-6), 7.94 (m, 1H, CH-7),
(500 MHz, CDCl3): δ = 3.85 (s, 3H, COOCH3), 6.57 (d, 3JHH
3
3
8.02 (d, JHH = 8.4 Hz, 1H, CH-5), 8.03 (d, JHH = 8.5 Hz,
=
= 16.1 Hz, 1H, CH CH-CO), 7.60 (m, 1H, CH-6), 7.78 (m,
1H, CH-8), 8.11 (d, 3JHH = 16.1 Hz, 1H, CH CH-CO), 8.38 (s,
=
3
3
1H, CH-7), 7.86 (d, JHH = 8.4 Hz, 1H, CH-5), 8.02 (d, JHH
1H, CH-4); 13C NMR (75 MHz, CDCl3): δ = 14.4 (OCH2CH3),
3
=
= 8.4 Hz, 1H, CH-8), 8.13 (d, JHH = 16.1 Hz, 1H, CH CH-
61.1 (OCH2CH3), 123.0, 127.8 128.2, 128.6, 131.7, 136.2, 139.4,
CO), 8.38 (s, 1H, CH-4). 13C NMR (75 MHz, CDCl3): δ = 52.0
148.0, 166.0 (ethylenic and quinolinyl carbon atoms), 188.3
(COOCH3), 122.3, 126.9, 127.4, 127.6, 128.0, 128.4, 131.5, 136.1,
+
=
(C O); MS (EI, 70 eV) m/z (%) 261 (13), [M ]; Anal. Calcd.
139.5, 147.9 (ethylenic and quinolinyl carbon atoms), 180.0
for C14H12ClNO2 (261.7): C, 64.25; H, 4.62; N, 5.35, Found: C,
64.31; H, 4.60; N, 5.26%.
+
=
(C O); MS (EI, 70 eV) m/z (%) 247 (10) [M ]; Anal. Calcd.
for C13H10ClNO2 (247.6): C, 63.04; H, 4.07; N, 5.66, Found: C,
62.97; H, 3.77; N, 5.54%.
(E)-3-(2-Chloroquinolin-3-yl)acrylonitrile (E-3b)
Eluent: n-hexane/acetone (90/10, v/v); colorless crystals, mp
(E)-4-(2-Chloroquinolin-3-yl)but-3-en-2-one (E-3d)
171–173°C. IR (KBr), ν(cm−1): 3056 (C_H aromatic), 2950
_
Eluent: petroleum ether (60–80°C)/acetone (85/15,v/v); color-
less crystals, mp 130–132°C. IR (KBr), ν(cm−1): 3058 (C_H aro-
matic), 2900 (C_H aliphatic), 1677 (α,β-unsaturated ketone),
=
=
(C H aliphatic), 2211 (CN), 1608, 1578 (C N, C C), 747
(Cl_C); H NMR (500 MHz, CDCl3): δ = 6.05 (d, JHH
=
1
3
=
16.8 Hz, 1H, CH CH-CO), 7.63 (m, 1H, CH-6), 7.83 (m, 1H,
_
1
3
3
=
=
1602, 1578 (C N, C C), 1287 (CO stretching), 743 (Cl C); H
CH-7), 7.86 (d, JHH = 7.0 Hz, 1H, CH-5), 7.89 (d, JHH
=
3
NMR (500 MHz, CDCl3): δ = 2.47 (s, 3H, COCH3), 6.75 (d,
=
15.8 Hz, 1H, CH CH-CO), 8.03 (d, JHH = 7.0 Hz, 1H, CH-8),
8.32 (s, 1H, CH-4); 13C NMR (75 MHz, CDCl3): δ = 100.7 (CN),
117.2, 126.3, 126.6, 127.9, 128.1, 128.3, 128.4, 132.2, 135.8, 145.4,
148.1 (ethylenic and quinolinyl carbon atoms); MS (EI, 70 eV)
m/z (%) 214 (44), [M+]; Anal. Calcd. for C12H7ClN2 (214.6): C,
67.15; H, 3.29; N, 13.05, Found: C, 66.89; H,3.33; N, 13.23%.
3
=
JHH = 16.1 Hz, 1H, CH CH-CO), 7. 80 (m, 1H, CH-6), 7.86
(m, 1H, CH-7), 7.88 (d, 3JHH = 16.1 Hz, 1H, CH CH-CO), 7.91
=
(d, 3JHH = 7.7 Hz, 1H, CH-5), 8.00 (d, 3JHH = 8.4 Hz, 1H, CH-
8), 8.40 (s, 1H, CH-4); MS (EI, 70 eV) m/z (%) 231(87) [M+];
Anal. Calcd. for C13H10ClNO (231.6): C, 67.39; H, 4.35; N, 6.05,
Found: C, 67.27; H, 4.37; N, 5.84%.
(Z)-3-(2-Chloroquinolin-3-yl)acrylonitrile (Z-3b)
Acridin-3-ol (5)
Eluent: n-hexane/acetone (88/12, v/v); colorless crystals, mp
133–134°C. IR (KBr), ν(cm−1): 3057 (C_H aromatic), 2969 Eluent: petroleum ether (60–80°C)/acetone (80/20, v/v); color-
_
(C H aliphatic), 2216 (CN), 1607, 1582 (C N, C C), 754 less crystals, mp 150–152°C. IR (KBr), ν(cm−1): 3446 (OH),
=
=