Acetylated methylnaltrexone bromide and preparation method therefor
A technology for acetylating methylnaltrexone and methylnaltrexone, which is applied in the field of medicinal chemical synthesis and can solve the problems such as the preparation method of Delta-7 bromnaltrexone is not disclosed.
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Embodiment 1
[0158] Embodiment 1: the preparation of acetylated methylnaltrexone bromide
[0159] 10mL of dichloromethane and 150mg of methylnaltrexone bromide (0.39mmol, 1eq) were added to a 50mL round bottom flask, and 100mg of triethylamine (0.99mmol, 3eq) was added with stirring. The system was cooled to -10°C, and 61mg (0.78mmol, 2eq) of acetyl chloride solution was slowly added dropwise, then stirred for 1 hour, then slowly warmed to room temperature, and continued to stir for 1 hour. TLC (Thin Layer Chromatography) monitored the completion of the reaction. Stop the reaction, add 20 mL of dichloromethane, wash with tap water twice (20 mL×2), wash with saturated aqueous sodium chloride solution twice (20 mL×2), and dry over anhydrous sodium sulfate. After the organic layer was concentrated, 160 mg of the product was obtained with a yield of 86%, which was directly used in the next reaction.
[0160] 1 H-NMR (400MHz,D 2 O): δ7.09(d, 1H, J=8.0Hz), 7.01(s, 1H, J=8.0Hz), 5.15(s, 1H), ...
Embodiment 2
[0161] Embodiment 2: Preparation of acetylated Delta-7 bromidenaltrexone
[0162] Add 60mL of acetonitrile, 3.6g (12.85mmol, 3.07eq) of 2-iodanoylbenzoic acid, 1.6g (13.67mmol, 3.2eq) of N-methylmorpholine oxide into a 150mL round bottom flask, nitrogen protection, and stir at room temperature for 1.5 Hour. Add acetylated methylnaltrexone bromide 2g (4.19mmol, 1eq), dimethyl sulfoxide 0.6mL (8.46mmol, 2eq), and continue stirring for 24 hours. The reaction was stopped, the solvent was evaporated under reduced pressure, and the solid was purified by column chromatography (eluent: CH 2 Cl 2 / CH3 OH=6 / 1, volume ratio), 400 mg of crude product was obtained with a yield of 20.1%, which was further prepared and purified by HPLC.
Embodiment 3
[0163] Example 3: Purification of acetylated Delta-7 bromidenaltrexone and preparation of acetylated Delta-7 methylnaltrexone formate
[0164] Column: Gemini5uC18150×21.2mm
[0165] Mobile phase: A phase: 0.1% formic acid aqueous solution, B phase: acetonitrile.
[0166] Flow rate: 20mL / min
[0167] Detection wavelength: 214nm
[0168] According to the linear elution in Table 1, collect the first fraction:
[0169] Table 1
[0170]
[0171] The first component liquid is the component liquid that flows out in the first to three minutes, preferably the component liquid that flows out in the first 1.5 to 3 minutes.
[0172] HPLC spectrum see figure 1 .
[0173] NMR data of purified Delta-7 acetylated methylnaltrexone formate:
[0174] 1 H-NMR (400MHz,D 2 O): δ7.17(d, 1H, J=8.0Hz), 7.01(d, 1H, J=8.0Hz), 6.93(d, 1H, J=8.0Hz), 6.16(d, 1H, J=8.0 Hz), 5.11(s, 1H), 4.30(s, 1H), 4.01(d, 1H, J=12.0Hz), 3.83(d, 2H, J=12.0Hz), 3.72(s, 3H), 3.47( d,1H,J=12.0Hz),3.15(d,2H,J=12....
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