744 Letters in Organic Chemistry, 2018, Vol. 15, No. 9
Nakhaei et al.
3.2.2. 1-Cyclopropyl-6-fluoro-7-(4-methylpiperazin-1-yl)-4-
oxo-1,4-dihydroquinoline-3-carboxylic acid (3ax)
117.6 (C5), 134.9 (C4a), 137.1 (C8), 140.6 (C8a), 150.8
(C7), 151.7 (C2), 154.0 (C6), 166.3 (COOH), 176.4 (C4);
HPLC Purity: 91.89%; Anal. Calc. for C21H24FN3O4 (%): C,
62.83; H, 6.03; N, 10.47; Found: C, 62.78; H, 5.94; N, 10.41.
HPLC Purity: 96.22%; m.p: 245-247°C; FT-IR (ν, cm-1
KBr disc): 3428, 3093, 2935, 1626, 1469, 1299, 1142, 885;
1H NMR (300 MHz, DMSO-d6): δ 1.17 (s, 2H, CH2), 1.32
(d, J = 9.0 Hz, 2H, CH2), 2.23 (s, 3H, CH3), 2.20-2.35 (m,
4H, CH2 ×2), 3.00-3.10 (m, 4H, CH2 ×2), 3.75-3.85 (m, 1H,
CH), 7.47 (d, JHF = 6.0 Hz, 1H, H-8), 7.75 (d, JHF = 12.0 Hz,
1H, H-5), 8.62 (s, 1H, H-2); 13C NMR (75 MHz, DMSO-d6):
8.0 (CH2 ×2), 31.2 (CH3), 36.3 (CH), 45.9 (CH2 ×2), 49.4
(CH2 ×2), 106.0 (C3), 107.1 (C8), 111.0 (C5), 118.0 (C4a),
139.6 (C8a), 146.1 (C7), 148.3 (C2), 151.0 (C6), 166.3
(COOH), 176.7 (C4); Anal. Calc. for C18H20FN3O3 (%): C,
62.60; H, 5.84; N, 12.17; Found: C, 62.53; H, 5.78; N, 12.11.
3.2.6. 9-Fluoro-3-methyl-7-oxo-10-(piperazin-1-yl)-3,7-
dihydro-2H-[1,4]oxazino[2,3,4-ij]quinoline-6-carboxylic
acid (3cw)
M.p: 258-260°C; FT-IR (ν, cm-1 KBr disc): 3255, 3092,
1
2968, 1723, 1454, 1254, 1023, 805; H NMR (300 MHz,
DMSO-d6): δ 1.44 (d, J = 6.0 Hz, 3H, CH3), 2.80-2.85 (m,
4H, CH2 ×2), 3.18-3.25 (m, 4H, CH2 ×2, overlapped with
solvent), 4.37 (d, J = 12.0 Hz, 1H, CH2, diastereotopic pro-
ton), 4.58 (d, J = 12.0 Hz, 1H, CH2, diastereotopic proton),
4.85-4.95 (m, 1H, CH), 7.51 (dd, JHF = 12.0, 6.0 Hz, 1H, H-
5), 8.91 (s, 1H, H-2); 13C NMR (75 MHz, DMSO-d6): 18.4
(CH3), 46.6 (CH2 ×2), 52.0 (CH2 ×2), 55.2 (CH), 68.4 (CH2),
103.6 (C5), 107.1 (C3), 120.0 (C4a), 125.2 (C8a), 132.3 (C7),
140.5 (C8), 146.5 (C2), 154.0 (C6), 166.5 (COOH), 176.7
(C4); HPLC Purity: 96.91%; Anal. Calc. for C17H18FN3O4
(%): C, 58.78; H, 5.22; N, 12.10; Found: C, 58.72; H, 5.17;
N, 10.36.
3.2.3. 1-Cyclopropyl-7-(4-ethylpiperazin-1-yl)-6-fluoro-4-
oxo-1,4-dihydroquinoline-3-carboxylic acid (3ay)
M.p: 218-220°C; FT-IR (ν, cm-1 KBr disc): 3335, 3033,
1
2912, 1627, 1470, 1254, 1154, 803; H NMR (300 MHz,
DMSO-d6): δ 1.05 (t, J = 7.0 Hz, 3H, CH3), 1.10-1.35 (m,
4H, CH2 ×2), 2.42 (q, J = 6.0 Hz, 2H, CH2), 2.50-2.60 (m,
8H, CH2 ×4, overlapped with solvent), 3.75-3.85 (m, 1H,
CH), 7.55 (d, JHF = 6.0 Hz, 1H, H-8), 7.88 (d, JHF = 15.0 Hz,
3.2.7. 9-Fluoro-3-methyl-10-(4-methylpiperazin-1-yl)-7-
oxo-3,7-dihydro-2H-[1,4]oxazino[2,3,4-ij]quinoline-6-
carboxylic acid (3cx)
1H, H-5), 8.65 (s, 1H, H-2), 15.23 (s br., 1H, COOH); 13
C
NMR (75 MHz, DMSO-d6): 8.0 (CH2 ×2), 12.4 (CH3), 36.2
(CH), 40.7 (CH2), 49.8-52.4 (CH2 ×4), 106.5 (C3), 107.1
(C8), 111.3 (C5), 118.8 (C4a), 139.5 (C8a), 145.5 (C7),
148.1 (C2), 155.0 (C6), 166.3 (COOH), 176.5 (C4); HPLC
Purity: 97.65%; Anal. Calc. for C19H22FN3O3 (%): C, 63.50;
H, 6.17; N, 11.69; Found: C, 63.41; H, 6.09; N, 11.62.
m.p: M.p: 253-255°C; FT-IR (ν, cm-1 KBr disc): 3335,
1
3043, 2968, 1622, 1469, 1255, 1146, 804; H NMR (300
MHz, DMSO-d6): δ 1.44 (d, J = 9.0 Hz, 3H, CH3), 2.22 (s,
3H, CH3), 2.35-2.50 (m, 4H, CH2 ×2), 3.20-3.40 (m, 4H, CH2
×2), 4.35 (dd, J = 12.0, 3.0 Hz, 1H, CH2, diastereotopic pro-
ton), 4.59 (dd, J = 12.0, 3.0, 1H, CH2, diastereotopic proton),
4.85-4.98 (m, 1H, CH), 7.52 (d, JHF = 12.0 Hz, 1H, H-5),
8.95 (s, 1H, H-2), 15.17 (s br., 1H, COOH); 13C NMR (75
MHz, DMSO-d6): 18.4 (CH3), 46.5 (CH3), 50.5 (CH2 ×2),
55.2 (CH2 ×2), 55.7 (CH), 68.4 (CH2), 103.5 (C5), 107.0
(C3), 119.8 (C4a), 125.2 (C8a), 132.5 (C7), 140.5 (C8),
146.5 (C2), 154.2 (C6), 166.5 (COOH), 176.7 (C4); HPLC
Purity: 92.63%; Anal. Calc. for C18H20FN3O4 (%): C, 59.83;
H, 5.58; N, 11.63; Found: C, 59.77; H, 5.08; N, 11.58.
3.2.4. 1-Cyclopropyl-6-fluoro-7-((4aR,7aR)-hexahydro-1H-
pyrrolo[3,4-b]pyridin-6(2H)-yl)-4-oxo-1,4-
dihydroquinoline-3-carboxylic acid (3az)
M.p: 258-260°C; FT-IR (ν, cm-1 KBr disc): 3308, 3076,
1
2938, 1629, 1412, 1336, 1180, 888; H NMR (300 MHz,
DMSO-d6): δ 1.10-1.35 (m, 4H, CH2 ×2), 1.55-1.70 (m, 4H,
CH2 ×2), 1.88 (m, 1H, CH), 2.08 (m, 1H, CH), 2.50-2.60 (m,
1H, CH), 3.33 (t, J = 6.0 Hz, 2H, CH2), 3.30-3.55 (m, 4H,
CH2 ×2), 3.63-3.75 (m, 1H, CH), 6.91 (d, JHF = 6.0 Hz, 1H,
H-8), 7.65 (d, JHF = 15.0 Hz, 1H, H-5), 8.49 (s, 1H, H-2);
HPLC Purity: 95.21%; Anal. Calc. for C20H22FN3O3 (%): C,
64.68; H, 5.97; N, 11.31; Found: C, 64.61; H, 5.59; N, 11.25.
3.2.8. (S)-9-Fluoro-3-methyl-7-oxo-10-(piperazin-1-yl)-3,7-
dihydro-2H-[1,4]oxazino[2,3,4-ij]quinoline-6-carboxylic
acid (3dw)
M.p: 260-262°C; FT-IR (ν, cm-1 KBr disc): 3255, 3092,
3.2.5. 1-Cyclopropyl-6-fluoro-7-((4aR,7aR)-hexahydro-1H-
pyrrolo[3,4-b]pyridin-6(2H)-yl)-8 methoxy-4-oxo-1,4-
dihydroquinoline-3-carboxylic acid (3bz)
1
2968, 1723, 1454, 1254, 1023, 805; H NMR (300 MHz,
DMSO-d6): δ 1.45 (d, J = 6.0 Hz, 3H, CH3), 2.75-2.85 (m,
4H, CH2 ×2), 3.15-3.25 (m, 4H, CH2 ×2, overlapped with
solvent), 4.30-4.40 (m, 1H, CH2, diastereotopic proton), 4.52-
4.62 (m, 1H, CH2, diastereotopic proton), 4.85-4.95 (m, 1H,
M.p: 239-241°C; FT-IR (ν, cm-1 KBr disc): 3470, 3033,
1
2929, 1624, 1457, 1324, 1186, 805; H NMR (300 MHz,
DMSO-d6): δ 0.81-1.25 (m, 4H, CH2 ×2), 1.63-1.85 (m, 4H,
CH2 ×2), 2.60-2.70 (m, 2H, CH2), 3.10-3.20 (m, 1H, CH),
3.37 (s, 3H, CH3), 3.60-3.65 (m, 1H, CH), 3.70-3.80 (m, 1H,
CH), 3.80-3.97 (m, 2H, CH2), 4.04-4.19 (m, 2H, CH2), 7.63
(dd, JHF = 12.0, 3.0 Hz, 1H, H-5), 8.64 (s, 1H, H-2), 15.15 (s
br., COOH); 13C NMR (75 MHz, DMSO-d6): 8.8 (CH2 ×2)
10.0 (CH2), 17.2 (CH2), 20.9 (CH), 34.6 (CH2), 39.1 (CH),
41.1 (CH2), 41.8 (CH), 54.4 (CH2), 62.3 (CH3), 106.8 (C3),
CH), 7.51 (d, JHF = 12.0 Hz, 1H, H-5), 8.92 (s, 1H, H-2); 13
C
NMR (75 MHz, DMSO-d6): 18.4 (CH3), 45.8 (CH2 ×2), 51.0
(CH2 ×2), 55.2 (CH), 68.5 (CH2), 103.6 (C5), 107.2 (C3),
120.2 (C4a), 125.2 (C8a), 132.3 (C7), 140.5 (C8), 146.5
(C2), 154.2 (C6), 166.5 (COOH), 176.7 (C4); HPLC Purity:
94.96%; Anal. Calc. for C17H18FN3O4 (%): C, 58.78; H,
5.22; N, 12.10; Found: C, 58.70; H, 4.93; N, 11.51.