2868
MIRZAIE et al.
[19]). FT-IR spectrum, ν, cm–1: 3255, 3092, 2968,
1723, 1573, 1454, 1392, 1254, 1023, 1011, 805. H
(J = 12.0, 3.0 Hz, 1H, CH2, diastereotopic proton), 4.85–
4.95 m (1H, CH), 7.48 d (J = 12.0 Hz, 1H, C5H), 8.94
s (1H, C2H), 15.15 br.s (1H, COOH). 13C NMR spec-
trum, δ, ppm: 18.4, 46.5, 50.5, 55.2, 55.7, 68.4, 103.8,
107, 120, 125.2, 132.3, 140.4, 146.5, 154.2, 166.5, 176.7.
1
NMR spectrum, δ, ppm: 1.44 d (J = 6.0 Hz, 3H, CH3),
2.80–2.85 m (4H, 2CH2), 3.18–3.25 m (4H, 2CH2,
overlapped with solvent), 4.37 d (J = 12.0 Hz, 1H,
CH2, diastereotopic proton), 4.58 d (J = 12.0 Hz, 1H,
CH2, diastereotopic proton), 4.85–4.95 m (1H, CH),
7.51 d.d (J = 12.0, 6.0 Hz, 1H, C5H), 8.91 s (1H, C2H).
13C NMR spectrum, δ, ppm: 18.4, 46.6, 52.0, 55.2,
68.4, 103.6, 107.1, 120.0, 125.2, 132.3, 140.5, 146.5,
154.0, 166.5, 176.7.
(S)-10-(4-Ethylpiperazin-1-yl)-9-fluoro-3-methyl-
7-oxo-3,7-dihydro-2H-[1,4]oxazino[2,3,4-ij]quino-
line-6-carboxylic acid (3j). Yield 91%, mp 225–228°C
(229–230°C [18]). FT-IR spectrum, ν, cm–1: 3432,
3042, 2975, 1714, 1623, 1529, 1478, 1306, 1243,
1
1200, 1010, 743. H NMR spectrum, δ, ppm: 1.05 t
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 (3g). Yield 83%, mp 248–252°C
(250–257°C [19]). FT-IR spectrum, ν, cm–1: 3419,
3335, 3043, 2968, 1714, 1622, 1523, 1469, 1371,
(J = 6.0 Hz, 3H, CH3), 1.45 d (J = 9.0 Hz, 3H, CH3),
2.35–2.40 m (2H, CH2, overlapped with solvent), 2.40–
2.60 m (4H, 2CH2), 3.15–3.20 m (4H, 2CH2), 4.37 d
(J = 12.0 Hz, 1H, CH2, diastereotopic proton), 4.57 d
(J = 9.0 Hz, 1H, CH2, diastereotopic proton), 4.91 d
(1H, J = 6.0 Hz, CH), 7.56 d (J = 12.0 Hz, 1H, C5H),
8.94 s (1H, C2H). 13C NMR spectrum, δ, ppm: 12.2,
18.4, 46.5, 50.5, 53.4, 55.3, 68.5, 103.0, 107.0, 125.2,
126.8, 132.3, 140.0, 146.7, 154.0, 166.5, 176.6.
1
1255, 1146, 1056, 804. H NMR spectrum, δ, ppm:
1.44 d (J = 9.0 Hz, 3H, CH3), 2.22 s (3H, NCH3), 2.35–
2.50 m (4H, 2CH2), 3.20–3.40 m (4H, 2CH2), 4.35 d.d
(J = 12.0, 3.0 Hz, 1H, CH2, diastereotopic proton), 4.59
d.d (J = 12.0, 3.0, 1H, CH2, diastereotopic proton), 4.85–
4.98 m (1H, CH), 7.52 d (J = 12.0 Hz, 1H, C5H), 8.95
s (1H, C2H), 15.17 br.s (1H, COOH). 13C NMR
spectrum, δ, ppm: 18.4, 46.5, 50.5, 55.2, 55.7, 68.4,
103.5, 107.0, 119.8, 125.2, 132.5, 140.5, 146.5, 154.2,
166.5, 176.7.
(3S)-9-Fluoro-10-{hexahydro-1H-pyrrolo[3,4-b]-
pyridin-6(2H)-yl}-3-methyl-7-oxo-3,7-dihydro-2H-
[1,4]oxazino[2,3,4-ij]quinoline-6-carboxylic acid
(3k). Yield 89%, mp 264–268°C (265–268°C [16]).
FT-IR spectrum, ν, cm–1: 3319, 3044, 2932, 1719,
1
1622, 1527, 1472, 1357, 1191, 1087, 1045, 862. H
(S)-9-Fluoro-3-methyl-7-oxo-10-(piperazin-1-yl)-
3,7dihydro-2H-[1,4]oxazino[2,3,4-ij]quinoline-6-
carboxylic acid (3h). Yield 87%, mp 257–260°C (263–
265°C [21]). FT-IR spectrum, ν, cm–1: 3255, 3092,
2968, 1723, 1573, 1454, 1392, 1254, 1023, 1011, 805.
1H NMR spectrum, δ, ppm: 1.45 d (J = 6.0 Hz, 3H,
CH3), 2.75–2.85 m (4H, 2CH2), 3.15–3.25 m (4H,
2CH2, 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, CH), 7.51 d
(J = 12.0 Hz, 1H, C5H), 8.92 s (1H, C2H). 13C NMR
spectrum, δ, ppm: 18.4, 45.8, 51.0, 55.2, 68.5, 103.6,
107.2, 120.2, 125.2, 132.3, 140.5, 146.5, 154.2, 166.5,
176.7.
NMR spectrum, δ, ppm: 1.30–1.70 m (4H, 2CH2), 1.45
d (J = 6.0 Hz, 3H, CH3), 2.10–2.20 m (1H, CH), 2.80–
2.90 m (1H, CH), 3.15–3.40 m (4H, 2CH2), 4.00–4.15
m (2H, CH2), 4.23 d (J = 12.0 Hz, 1H, CH2, dia-
stereotopic proton), 4.59 d (J = 12.0 Hz, 1H, CH2,
diastereotopic proton), 4.80–4.92 m (1H, CH), 7.47 d
(J = 15 Hz, 1H, C5H), 8.85 s (1H, C2H).
CONCLUSIONS
A facile high yield synthesis of fluoroquinolone
antibacterial agents by direct amination of 7-halo-6-
fluoroquinolone-3-carboxylic acids with amines under
microwave irradiation is developed. Presence of a
solvent is essential for oil bath heating but under
microwave irradiation it shows the adverse effect.
(S)-9-Fluoro-3-methyl-10-(4-methylpiperazin-1-
yl)-7-oxo-3,7-dihydro-2H-[1,4]oxazino[2,3,4-ij]quino-
line-6-carboxylic acid (3i). Yield 89%, mp 223–225°C
(225–226°C [17]). FT-IR spectrum, ν, cm–1: 3251,
3079, 2973, 1721, 1539, 1517, 1439, 1394, 1289, 1087,
ACKNOWLEDGMENTS
1
We acknowledge the financial support from
Payame noor University of Mashhad, and TEMAD
Pharmaceutical Ingredients Company in Iran for their
support.
1004, 801. H NMR spectrum, δ, ppm: 1.44 d (J =
6.0 Hz, 3H, CH3), 2.22 s (3H, NCH3), 2.35–2.50 m
(4H, 2CH2), 3.20–3.30 m (4H, 2CH2), 4.36 d.d (J =
12.0, 3.0 Hz, 1H, CH2, diastereotopic proton), 4.59 d.d
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 12 2016