Dihydroartemisinin carbamate and its preparation method and application
A technology of dihydroartemisinin ester of aminodithiocarboxylate and methylaminodithiocarboxylate is applied in the directions of pharmaceutical formulations, medical preparations containing active ingredients, organic active ingredients, etc., and can solve the problem of poor water solubility and fat solubility. , poor oral availability, short half-life and other problems
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Embodiment 1
[0018] (3R, 5aS, 6R, 8aS, 9R, 12S, 12aR)-octahydro-3-( N , N -diethylaminodithiocarboxy)methylene-6,9-dimethyl-3,12-oxo-12H-pyrano[4,3-j]-1,2-benzodithia Preparation of Ping-10(3H)alcohol (1)
[0019] The structure of compound (1) is shown below:
[0020]
[0021] Add 3.62 g (0.01 mol) of (3R, 5aS, 6R, 8aS, 9R, 12S, 12aR)-octahydro-3-bromomethylene-6,9-dimethyl-3,12 to the dry reactor -Oxo-12H-pyrano[4,3-j]-1,2-benzodithiapine-10(3H)alcohol and 25mL DMF, stirring, adding 2.05g (0.012mol) of N , N -Sodium diethylaminodithioformate, reacted for 12 hours, and evaporated the solvent under reduced pressure. Add 20mL ethyl acetate and 20mL water to the residue, stir, separate layers, extract the aqueous layer with ethyl acetate 15mLX2, combine the organic phases, dry, filter, concentrate, and purify by column chromatography to obtain the target compound (1), with a yield of 76% .
Embodiment 2
[0023] (3R, 5aS, 6R, 8aS, 9R, 12S, 12aR)-octahydro-3-( N -methylaminodithiocarboxy)methylene-6,9-dimethyl-3,12-oxo-12H-pyrano[4,3-j]-1,2-benzodithiapine Preparation of -10(3H)alcohol (2)
[0024] The structure of compound (2) is shown below:
[0025]
[0026] Add 3.18 g (0.01 mol) of (3R, 5aS, 6R, 8aS, 9R, 12S, 12aR)-octahydro-3-chloromethylene-6,9-dimethyl-3,12 to the dry reactor -Oxo-12H-pyrano[4,3-j]-1,2-benzodithiapine-10(3H)alcohol and 25mL isopropanol, stirred, added 1.55g (0.012mol) N -sodium methylcarbamate and 0.82 g (0.0005mol) KI, reacted for 12 hours, and evaporated the solvent under reduced pressure. Add 20mL ethyl acetate and 20mL water to the residue, stir, separate layers, extract the aqueous layer with ethyl acetate 15mLX2, combine the organic phases, dry, filter, concentrate, and purify by column chromatography to obtain the target compound (2), with a yield of 67% .
Embodiment 3
[0028] (3R, 5aS, 6R, 8aS, 9R, 12S, 12aR)-octahydro-3-[ N –(α-Methoxycarbonyl)methylaminodithiocarboxy]methylene-6,9-dimethyl-3,12-oxo-12H-pyrano[4,3-j]-1, Preparation of 2-benzodithiapine-10(3H)alcohol (3)
[0029] The structure of compound (3) is shown below:
[0030]
[0031] With 2.24g (0.012mol) N -Sodium (α-methoxycarbonyl)methylcarbamate instead N , N -Sodium diethylaminodithioformate, other operations are the same as in Example 1, to obtain compound (3), yield 79%.
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