11,20-cyclic carbonate-azithromycin 4-phenproester derivative, its production and medicinal composition
A technology for medicines and compounds, applied in the field of azithromycin derivatives and their preparation, can solve problems such as no description
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Embodiment 1
[0053] Embodiment 1: the preparation of the first intermediate
[0054] a) Preparation of 2′-O-acetyl-azithromycin
[0055] Dissolve azithromycin (2.0 g, 2.67 mmol) in anhydrous dichloromethane (20 mL), add acetic anhydride (0.75 mL, 7.96 mmol) and triethylamine (3.00 mL, 21.6 mmol), and stir at room temperature for 24 h. After the reaction was completed, an equal volume of 5% sodium bicarbonate solution was added, the layers were separated, extracted with dichloromethane (10 mL×2), the organic layers were combined, and dried over anhydrous sodium sulfate. It was filtered and evaporated to dryness under reduced pressure to obtain a white foamy solid, which was recrystallized from acetone-water (2:1) to obtain the white target product (1.84 g), with a yield of 92%. Melting point 167~170℃, R f It was 0.522 (the developing solvent was dichloromethane:methanol=10:1). Molecular formula is C 40 h 74 N 2 o 13 , molecular weight is 791.0, MS is 792.0 (M+H + ).
[0056] b) Pre...
Embodiment 2
[0058] Example 2: Preparation of the second intermediate 4″-O-(1-H-imidazole-1-carbonyl)-2′-O-acetyl-azithromycin 11,12-cyclocarbonate
[0059] Dissolve 2′-O-acetyl-azithromycin (1.5g, 1.90mmol) in anhydrous toluene (20mL), add triethylamine (0.60mL, 4.33mmol) and CDI (N, N′-dicarbonylimidazole) ( 1.23g, 7.6mmol), heated and stirred at 110°C for 2h. After the reaction is complete, add saturated sodium bicarbonate solution (40 mL), separate the layers, extract with toluene (6 mL×2), combine the organic layers, and dry over anhydrous sodium sulfate. Filter and evaporate to dryness under reduced pressure to obtain 1.65 g of white foamy solid with a yield of 95.5%. Melting point 117~120℃, R f It was 0.610 (the developing solvent was dichloromethane:methanol=10:1). Molecular formula is C 45 h 74 N 4 o 15 , molecular weight is 911.1, MS is 912.1 (M+H + ).
Embodiment 3
[0060] Embodiment 3: Preparation of target product 11,12-cyclocarbonate-azithromycin 4 "-carbamate derivative
[0061] a) Preparation of 4″-O-propyl-carbamoyl-2′-O-acetyl-azithromycin 11,12-cyclocarbonate (target product)
[0062] 4″-O-(1-H-imidazole-1-carbonyl)-2′-O-acetyl-azithromycin 11,2-cyclocarbonate (1.5 g, 1.65 mmol) was dissolved in N,N-dimethyl In formamide (DMF) (15mL), add DBU (0.33mL, 2.25mmol) and n-propylamine (0.25mL, 2.25mmol), and stir at room temperature for 12h. After the reaction is complete, add water (30mL), ethyl acetate (15mL×3 ) extraction, combined organic layers, washed with saturated brine (15mL × 3), dried over anhydrous sodium sulfate, and evaporated to dryness under reduced pressure to obtain 1.35g of white foamy solid, yield 91.0%. Rf is 0.621 (developing agent is dichloromethane: Methanol=10:1), the molecular formula is C 45 h 79 N 3 o 15 , molecular weight is 902.0, MS 903.1 (M+H + ).
[0063] b) Preparation of 4″-O-benzyl-carbamoyl-2′...
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