NOVEL N-4-PIPERAZINYL CIPROFLOXACIN-ESTER HYBRIDS
1563
1725 (C=O, carboxylic acid), 1626 (C=O, quinolone).
1H NMR spectrum, δ, ppm: 1.18–1.21 m (2H, CH2,
cyclopropyl), 1.35–1.41 m (2H, CH2, cyclopropyl), 2.94 t
(4H, 2CH2, piperazine), 3.43 t (4H, 2CH2, piperazine),
3.56 m (1H, CH, cyclopropyl), 3.60 s (2H, N–CH2–CO),
7.08–7.15 m (2H, C6H5), 7.22–7.29 m (1H, C6H5), 7.35–
7.43 m (3H, C6H5 + CH8 cipro), 7.95 d (J = 13 Hz, 1H,
CH5 cipro), 8.72 s (1H, CH2 cipro), 15.02 s (1H, COOH).
13C NMR spectrum, δC, ppm: 7.1, 34.2, 48.6 d (J =
4.8 Hz), 51.3, 57.8, 103.8 d (J = 2.6 Hz), 106.9, 111.2 d
(J = 23 Hz), 118.7 d (J = 8 Hz), 120.2, 124.9, 128.3, 137.9,
144.7 d (J = 10.5 Hz), 146.2, 149.1, 152.5 d (J = 251 Hz),
165.8, 167.4, 175.9. Found, %: C 64.32, H 5.29, N 8.91.
C25H24FN3O5. Calculated, %: C 64.51, H 5.2, F 4.08, N
9.03, O 17.19. M 465.
(CH3)2CCH], 7.37 d (J = 7.1 Hz, 1H, CH8 cipro), 7.98 d
(J = 13 Hz, 1H, CH5 cipro), 8.73 s (1H, CH2 cipro), 15.02 s
(1H, COOH). 13C NMR spectrum, δC, ppm: 7.1, 16.6,
18.3, 24.3, 24.6, 28.4, 34.2, 34.4, 35.8, 48.6 d (J = 4.8),
51.4, 58, 62.3, 103.8, 107, 111.3 d (J = 24 Hz), 118.8 d
(J = 7.7 Hz), 123.4, 130.3, 138, 144.7 d (J = 10.4 Hz),
146.3, 152.5 d (J = 251 Hz), 165.9, 169.1, 176. Found,
%: C 65.89, H 7.41, N 7.68. C29H38FN3O5. Calculated,
%: C 66.01, H 7.26, F 3.6, N 7.96, O 15.16. M 527.
1-Cyclopropyl-6-fluoro-7-[4-(2-{[(1R,2S,5R)-
2-isopropyl-5-methylcyclohexyl]oxy}-2-oxoethyl)-
piperazin-1-yl]-4-oxo-1,4-dihydroquinoline-3-
carboxylic acid (3h). White solid, yield 77%, mp 218–
219°C. IR spectrum, ν, cm–1: 1737 (C=O, ester), 1628
(C=O, Quinolone). 1H NMR spectrum, δ, ppm: 0.78 d [3H,
J = 6.9 Hz, (CH3)2CH)], 0.81–0.88 m [1H, CH3CH(CH2)
CH2CH2], 0.88–0.94 m [6H, CH3CH + (CH3)2CH],
0.96–1.13 m (2H, CH–CH2–CH + CH–CH–CH2–CH2),
1.17–1.26 m (2H, CH2, cyclopropyl), 1.36–1.43 m
(3H, CH2, cyclopropyl, + O–CH–CH), 1.43–1.56 m
(1H, CH2–CH–CH2), 1.65–1.73 m (2H, CH–CH2–
CH2–CH), 1.79–1.90 m [1H, (CH3)2CH], 1.95–2.05 m
(1H, O–CH–CH2), 2.83 br. d (4H, 2CH2, piperazine),
3.30 d. d (J = 23 Hz, 16.5, 2H, N–CH2–CO) 3.41 br. s
(4H, 2CH2, piperazine), 3.57 br. s (1H, CH, cyclopropyl),
4.73–4.82 m (1H, O–CH–CH), 7.37 d (J = 7.1 Hz, 1H,
CH8 cipro), 7.97 d (J = 13 Hz, 1H, CH5 cipro), 8.74 s (1H,
CH2 cipro), 15.03 s (1H, COOH). 13C NMR spectrum, δC,
ppm: 7.1, 15.3, 19.6, 20.9, 22.4, 25.3, 30.3, 33.1, 34.2,
39.9, 45.9, 48.6 d (J = 4.7 Hz), 51.4, 58.2, 73.7, 103.8 d
(J = 3.2 Hz), 107, 111.3 d (J = 23.4 Hz), 118.8 d (J =
8.04 Hz), 138, 144.5 d (J = 10.3 Hz), 146.3, 152.5 d (J =
251 Hz), 165.9, 168.6, 176. Found, %: C 65.92, H 7.39,
N 7.92. C29H38FN3O5. Calculated, %: C 66.01, H 7.26,
F 3.6, N 7.96, O15.16. M 527.
1-Cyclopropyl-6-fluoro-7-{4-(2-[(4-methoxybenzyl)-
oxy)-2-oxoethyl]piperazin-1-yl}-4-oxo-1,4-di-
hydroquinoline-3-carboxylic acid (3f). White solid,
yield 67%, mp 179–180°C. IR spectrum, ν, cm–1: 1744
(C=O, ester), 1730 (C=O, carboxylic acid), 1628 (C=O,
quinolone). 1H NMR spectrum, δ, ppm: 1.18–1.22 m (2H,
CH2, cyclopropyl), 1.35–1.43 m (2H, CH2, cyclopropyl),
2.8–2.86 t (4H, 2CH2, piperazine), 3.34 s (2H, N–CH2–
CO), 3.37–3.41 t (4H, 2CH2, piperazine), 3.53–3.61 m
(1H, CH, cyclopropyl), 3.81 s (3H, OCH3), 5.12 s (2H,
COOCH2), 6.87–6.91d(J=8.5Hz, 2H, C6H4), 7.29–7.34d
(J = 8.5 Hz, 2H, C6H4), 7.36 d (J = 7.1 Hz, 1H, CH8
cipro), 7.96 d (J = 13 Hz, 1H, CH5 cipro), 8.73 s (1H,
CH2 cipro), 15.01 s (1H, COOH). 13C NMR spectrum,
δC, ppm: 7.1, 34.2, 48.6 d (J = 4.8 Hz), 51.4, 54.2, 57.9,
65.3, 103.8 d (J = 2.9 Hz), 107, 111.3 d (J = 23 Hz),
112.9, 118.8 d (J = 8.1 Hz), 129.25, 129.29, 138, 144.7 d
(J = 10.5 Hz), 146.3, 152.1 d (J = 251 Hz), 158.7,
165.9, 168.8, 176. Found, %: C 63.89, H 5.48, N 8.12.
C27H28FN3O6. Calculated, %: C 63.65, H 5.54, F 3.73,
N 8.25, O 18.84. M 509.
1-Cyclopropyl-6-fluoro-4-oxo-7-{4-[2-oxo-2-
(pyridin-2-ylmethoxy)ethyl]piperazin-1-yl}-1,4-
dihydroquinoline-3-carboxylic acid (3i). White solid,
yield 76%, mp 190–191°C. IR spectrum, ν, cm–1: 1757
(C=O, ester), 1730 (C=O, carboxylic acid), 1628 (C=O,
1-Cyclopropyl-7-(4-{2-[(3,7-dimethyloct-6-en-1-yl)-
oxy]-2-oxoethyl}piperazin-1-yl)-6-fluoro-4-oxo-1,4-
dihydroquinoline-3-carboxylic acid (3g). Light yellow
solid, yield 74%, mp 97–98°C. IR spectrum, ν, cm–1: 1739
(C=O, ester), 1627 (C=O, quinolone). 1H NMR spectrum,
δ, ppm: 0.93 d (3H, CH3–CH), 1.15–1.22 m (3H, CH2,
cyclopropyl + C=CH2–CH2–CH2), 1.25–1.85 m [12H,
CH2, cyclopropyl + (CH3)2CCHCH2CH2CH(CH3)CH2],
1.90–2.08 m (2H, CCHCH2), 2.81–2.86 t (4H, 2CH2,
piperazine), 3.32 s (2H, N–CH2–CO), 3.37–3.43 t (4H,
2CH2, piperazine), 3.52–3.61 m (1H, CH, cyclopropyl),
4.15–4.22 m (2H, COOCH2), 5.05–5.11 m [1H,
1
quinolone). H NMR spectrum, δ, ppm: 1.18–1.23 m
(2H, CH2, cyclopropyl), 1.36–1.43 m (2H, CH2,
cyclopropyl), 2.87 t (4H, 2CH2, piperazine), 3.40 t (4H,
2CH2, piperazine), 3.45 s (2H, N–CH2–CO), 3.52–3.59 m
(1H, CH, cyclopropyl), 5.30 s (1H, OCH2), 7.26 m (1H,
N–CH=CH), 7.37 d [J = 7.2 Hz, 2H, OCH2C(=N)CH +
CH8 cipro], 7.73 t. d (J = 7.69 Hz, 1.63, 1H, N–CH=CH–
CH), 7.97 d (J = 13 Hz, 1H, CH5 cipro), 8.61 d (J =
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 90 No. 8 2020