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AZIZ ET AL.
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1‐Ethyl‐6‐fluoro‐7‐{4‐[3‐((4‐(1‐(hydroxyimino)ethyl)phenyl)amino)‐3‐
oxopropyl]piperazin‐1‐yl}‐4‐oxo‐1,4‐dihydroquinoline‐3‐carboxylic
131.39, 139.60, 140.22, 144.20, 148.60, 153.34 (d, J = 248 Hz),
154.00, 166.19, 168.43, and 176.91; Anal. calcd for C29H32FN5O5: C,
63.38; H, 5.87; N, 12.74. Found: C, 63.51; H, 5.90; N, 13.01.
[21]
acid (3e)
White crystals; yield: (0.535 g, 65.8% yield); mp: 290–292°C as
reported.
1‐Cyclopropyl‐6‐fluoro‐7‐{4‐[1‐(4‐(1‐(methoxyimino)ethyl)‐
phenylamino)‐1‐oxopropan‐2‐yl]piperazin‐1‐yl}‐4‐oxo‐1,4‐
dihydroquinoline‐3‐carboxylic acid (4c)
1‐Ethyl‐6‐fluoro‐7‐{4‐[1‐(4‐(1‐(hydroxyimino)ethyl)phenylamino)‐1‐
oxopropan‐2‐yl]piperazin‐1‐yl}‐4‐oxo‐1,4‐dihydroquinoline‐3‐
carboxylic acid (3f)
White crystals (0.290 g, 55.3% yield); mp: 242–244°C; 1H‐NMR
(400 MHz, DMSO‐d6) δ ppm: 1.18–1.21 (2H, m, cyclopropyl–H),
1.32–1.38 (2H, m, cyclopropyl–H), 1.63 (3H, d, J = 7.6 Hz, CH3CH),
2.17 (3H, s, CH3C=NOCH3), 3.58–3.84 (9H, m, piperazinyl–8H + 1H
of CHCH3), 3.91 (3H, s, C=NOCH3), 4.32–4.36 (1H, m,
cyclopropyl–H), 7.62–7.64 (1H, d, J = 7.6 Hz, H8), 7.64–7.76 (4H, m,
Ar‐H), 7.96 (1H, d, J = 13.6 Hz, H5), 8.69 (1H, s, H2), 10.99 (1H, s,
NHCO), and 15.01 (1H, s, COOH); 13C‐NMR (100 MHz, DMSO‐d6)
δ ppm: 8.08, 12.57, 14.05, 36.39, 47.17, 49.46, 61.99, 63.54, 107.33,
107.54, 111.74 (J = 23 Hz), 119.58, 120.14, 126.89, 132.34, 139.21,
139.61, 144.24, 148.61, 153.59, 153.93, 166.20, 168.43, and 176.86;
Anal. calcd for C29H32FN5O5: C, 63.38; H, 5.87; N, 12.74. Found: C,
63.58; H, 5.94; N, 12.96.
White crystals (0.302 g, 56.2% yield); mp: 294–296°C; IR (KBr)
ύ (cm−1): 3,266 (NH), 1,718 (carboxylic C=O), 1,678, (amidic), and
1,621 (4‐keto C=O); 1H‐NMR (400 MHz, DMSO‐d6) δ ppm: 1.27 (3H,
d, J = 7.6 Hz, CHCH3), 1.43 (3H, t, J = 7.6 Hz, NCH2CH3), 2.14 (3H, s,
CH3C=NOH), 2.75–2.85 (4H, m, piperazinyl–H), 3.35–3.45 (4H, m,
piperazinyl–H), 4.58 (2H, q, J = 7.6, NCH2CH3), 7.18 (1H, d, JH–F
=
7.6 Hz H8), 7.61–7.72 (4H, m, Ar‐H), 7.91 (1H, d, JH–F = 13.6 Hz, H5),
8.92 (1H, s, H2), 9.86 (1H, s, NHCO), 10.96 (1H, s, C=NOH), and
15.27 (1H, s, COOH); 13C‐NMR (100 MHz, DMSO‐d6) δ ppm: 11.82,
13.00, 14.77, 49.28, 49.50, 50.29, 63.72, 106.19, 107.66, 111.68
(d, J = 23 Hz), 119.68, 126.39, 129.77, 132.54, 137.74, 139.51,
145.97, 148.86, 152.91, 153.3 (d, J = 248 Hz), 166.50, 171.63, and
176.66; HRMS (ESI) calcd for C27H30FN5O5 [M–H]−: 522.2158,
found: 522.2161.
1‐Ethyl‐6‐fluoro‐7‐{4‐[2‐((4‐(1‐(methoxyimino)ethyl)phenyl)amino)‐
2‐oxoethyl]piperazin‐1‐yl}‐4‐oxo‐1,4‐dihydroquinoline‐3‐carboxylic
acid (4d)
1‐Cyclopropyl‐6‐fluoro‐7‐{4‐[2‐((4‐(1‐(methoxyimino)ethyl)phenyl)‐
amino)‐2‐oxoethyl]piperazin‐1‐yl}‐4‐oxo‐1,4‐dihydroquinoline‐3‐
carboxylic acid (4a)
White crystals (0.165 g, 65.22% yield); mp: 242–244°C; 1H‐NMR
(400 MHz, DMSO‐d6) δ ppm: 1.45 (3H, t, J = 7.6 Hz, NCH2CH3),
2.16 (3H, s, CH3C=NOCH3), 2.77–2.81 (4H, m, piperazinyl–H),
3.27 (2H, s, NHCOCH2N), 3.40–3.46 (4H, m, piperazinyl–H), 3.91
(3H, s, C=NOCH3), 4.59 (2H, q, J = 7.6 Hz, NCH2CH3), 7.20 (1H, d,
White powder, yield (0.378 g, 71% yield); mp: 253–254 °C; 1H‐NMR
(400 MHz, DMSO‐d6) δ ppm: 1.17–1.23 (2H, m, cyclopropyl–H),
1.32–1.38 (2H, m, cyclopropyl–H), 2.17 (3H, s, CH3C–NOCH3),
3.55–3.68 (8H, m, piperazinyl–H), 3.87 (2H, s, NHCOCH2), 3.92 (3H,
s, C=NOCH3), 4.24 (1H, m, cyclopropyl–H), 7.63–7.68 (5H, m, 4
Ar‐H + H8), 7.97 (1H, d, JH–F = 13.6 Hz, H5), 8.70 (1H,s, H2), 9.78 (1H,
s, NHCO), and 15.04 (1H, s, COOH); 13C‐NMR (100 MHz, DMSO‐d6)
δ ppm: 8.09, 12.56, 36.41, 46.94, 51.93, 57.53, 61.97, 107.39, 107.52,
111.73 (d, J = 23 Hz), 119.24, 119.82, 126.95, 132.12, 139.29,
139.61, 144.23, 148.58, 153.33 (d, J = 245 Hz), 153.94, 163.68,
166.22, and 176.90; Anal. calcd for C28H30FN5O5: C, 62.79; H, 5.65;
N, 13.08. Found: C, 62.98; H, 5.63; N, 13.37.
J
H–F = 7.6 Hz, H8), 7.63–7.68 (4H, m, Ar‐H), 7.92 (1H, d, JH–F =
13.6 Hz, H5), 8.92 (1H, s, H2), 9.82 (1H, s, NHCO), and 15.26 (1H,
s, COOH); 13C‐NMR (100 MHz, DMSO‐d6) δ ppm: 12.56, 14.77,
49.50, 49.92, 52.08, 52.82, 61.92, 106.21, 107.70, 111.59
(d, J = 23 Hz), 119.68, 126.76, 131.41, 137.77, 139.93, 145.95,
148.85, 153.60 (d, J = 248 Hz), 154.02, 166.49, 168.75, and
176.68; Anal. calcd for C27H30FN5O5: C, 61.94; H, 5.78; N, 13.38.
Found: C, 62.23; H, 5.85; N, 13.61.
1‐Ethyl‐6‐fluoro‐7‐{4‐[3‐((4‐(1‐methoxyimino)ethyl)phenyl)amino)‐3‐
oxopropyl]piperazin‐1‐yl}‐4‐oxo‐1,4‐dihydroquinoline‐3‐carboxylic
acid (4e)
1‐Cyclopropyl‐6‐fluoro‐7‐{4‐[3‐((4‐(1‐methoxyimino)ethyl)phenyl)‐
amino)‐3‐oxopropyl]piperazin‐1‐yl}‐4‐oxo‐1,4‐dihydroquinoline‐3‐
carboxylic acid (4b)
White crystals (0.404 g, 76% yield); mp: 278–279°C; 1H‐NMR
(400 MHz, DMSO‐d6) δ ppm: 1.45 (3H, t, J = 7.6 Hz, NCH2CH3),
2.14 (3H, s, CH3C=N–OH), 2.68 (2H, t, NHCOCH2CH2N), 2.75–2.84
(4H, m, piperazinyl–4H), 3.28 (2H, t, NHCOCH2CH2), 3.40–3.48 (4H,
m, piperazinyl–4H), 3.91 (3H, s, –C=NOCH3), 4.59 (2H, q, J = 7.6 Hz,
–N–CH2CH3), 7.19 (1H, d, JH–F = 7.6 Hz s, H8), 7.62 (2H, d, J = 8.0 Hz,
Ar‐H), 7.66 (2H, d, J = 8 Hz, Ar‐H), 7.91 (1H, d, JH–F = 13.6 Hz, H5),
8.92 (1H, s, H2), 10.10 (1H, s, NHCO), and 15.25 (1H, s, –COOH);
13C‐NMR (100 MHz, DMSO‐d6) δ ppm: 12.54, 14.77, 34.70, 49.50,
49.92, 52.81, 52.61, 61.90, 106.27, 107.70, 111.70 (d, J = 23 Hz),
119.70, 126.40, 132.63, 137.77, 139.40, 140.56, 145.94, 148.85,
153.36 (d, J = 248 Hz), 154.60, 166.48, 168.62, and 176.68; Anal.
White crystals (0.520 g, 95% yield); mp: 255–256°C; 1H‐NMR
(400 MHz, DMSO‐d6) δ ppm: 1.19–1.23 (2H, m, cyclopropyl–H),
1.32–1.38 (2H, m, cyclopropyl–H), 2.07 (2H, t, J = 7.6 Hz,
NHCOCH2CH2N), 2.16 (3H, s, CH3C=NOH), 3.05 (2H, t, J = 7.6 Hz,
NHCOCH2CH2N), 3.45–3.80 (8H, m, piperazinyl–H), 3.85–3.88 (1H,
m, cyclopropyl–H), 3.91 (3H, s, C=NOCH3), 7.60–7.69 (5H, m, 4Ar‐
H + H8), 7.96 (1H, d, JH–F = 13.6 Hz, H5), 8.69 (1H, s, H2), 10.42
(1H, s, NHCO), and 15.01 (1H, s, COOH); 13C‐NMR (100 MHz,
DMSO‐d6) δ ppm: 8.09, 12.54, 31.01, 36.40, 46.81, 51.28, 52.09,
61.92, 107.34, 107.54, 111.73 (d, J = 22 Hz), 119.48, 120.02, 126.82,