Azithromycin derivative as well as intermediate, preparation method and application thereof
A technology of azithromycin and derivatives, applied in the field of new compounds, can solve problems such as poor activity of macrolide-resistant bacteria
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Embodiment 1
[0146] Example 1 4"-(2-acetyl) carbazate azithromycin (compound 1)
[0147] 2'-O-acetyl-4"-carbazate azithromycin (E 1 ) (0.353mmol), acetic acid (1.767mmol) and DCC (1.767mmol) were synthesized according to the general method, then filtered to remove insoluble matter, stirred with water, adjusted to pH=3.0-3.5, separated the water phase, and the water phase was oxidized with 3.0N hydroxide The sodium solution was used to adjust the pH to 9.3-9.7, extracted with dichloromethane, the organic phases were combined, washed with water, dried over anhydrous sodium sulfate, filtered, and drained to obtain a crude product. It was dissolved in methanol, refluxed for 18h, the solvent was evaporated to dryness under reduced pressure, dry column chromatography, the volume ratio of ethyl acetate:petroleum ether:diethylamine was 5:10:0.5 as the eluent, and the product was obtained 0.101g , yield 33.7%.
[0148] MS (ESI + , m / e): 849 [M+H] +
[0149] 1 HNMR (CDCl 3 , 400M) δ (ppm):
...
Embodiment 2
[0153] Example 2 4"-(2-hexadecanoyl) carbazate azithromycin (compound 2)
[0154] 2'-O-acetyl-4"-carbazate azithromycin (E 1 ) (0.353mmol), hexadecanoic acid (1.767mmol) and DCC (1.767mmol) were synthesized according to the general method, then filtered to remove the insoluble matter, stirred with water, adjusted to pH=3.0-3.5, separated the water phase, and used 3.0 Adjust the pH to 9.3-9.7 with N sodium hydroxide solution, extract with dichloromethane, combine the organic phases, wash with water, dry over anhydrous sodium sulfate, filter, and drain to obtain a crude product. It was dissolved in methanol, refluxed for 18h, evaporated to dryness under reduced pressure, dry column chromatography, the volume ratio of ethyl acetate:petroleum ether:diethylamine was 5:13:0.6 as the eluent, and the product was 0.187g , yield 50.7%.
[0155] MS (ESI + , m / e): 1045 [M+H] +
[0156] 1 HNMR (CDCl 3 , 400M) δ (ppm):
[0157] 5.21(d, 1H, 11-CH-), 5.11-5.08(d, 1H, -OH), 4.96-4.95(d...
Embodiment 3
[0160] Example 3 4"-[2-(2-methylpropionyl)]carbazate azithromycin (compound 3)
[0161] 2'-O-acetyl-4"-carbazate azithromycin (E 1 ) (0.353mmol), isobutyric acid (1.767mmol) and DCC (1.767mmol) were synthesized according to the general method, then filtered to remove insoluble matter, stirred with water, adjusted to pH = 3.0 ~ 3.5, separated the water phase, and used 3.0N Adjust the pH to 9.3-9.7 with sodium hydroxide solution, extract with dichloromethane, combine the organic phases, wash with water, dry over anhydrous sodium sulfate, filter, and drain to obtain a crude product. It was dissolved in methanol, refluxed for 24h, evaporated to dryness under reduced pressure, dry column chromatography, ethyl acetate:petroleum ether:diethylamine volume ratio was 5:5:0.3 as eluent, and 0.163g of product was obtained , yield 52.6%.
[0162] MS (ESI + , m / e): 877[M+H] +
[0163] 1 HNMR (CDCl 3 , 400M) δ (ppm):
[0164] 9.45-7.40 (d, 2H, 4”-OCONHNH-), 5.15 (d, 1H, 11-CH-), 4.50...
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