Dabigatran etexilate levulinic acid salt, preparation method and application thereof
A technology of dabigatran etexilate and fructonate, applied in the field of acid addition salts of dabigatran etexilate, can solve the problems of poor stability, low bioavailability and the like
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Embodiment 1
[0048] This example is used to illustrate the preparation of dabigatran etexilate fructonate of the present invention.
[0049] Add 1.6 mmol of dabigatran etexilate and 1.6 mmol of fructose to 20 ml of absolute ethanol at 20°C, mix and stir for 6 hours to form a salt, then crystallize at 20°C, filter, and use ethyl acetate After washing and drying, diethyl ether was added for recrystallization to obtain 0.310 g of diethyl ether solvate of dabigatran etexilate fructonate. Measured ESI-MS (electrospray ionization-mass spectrometry) (m / z): 781[M+H] + .
[0050] The above ether solvate was dried to obtain 0.296 g of dabigatran etexilate fructose as a white solid. According to calculation, in the above ether solvate, the content of dabigatran etexilate fructose was 95.4wt%. The ether solvate contained 0.5 molecule of ether per molecule.
[0051] Determination of above-mentioned dabigatran etexilate fructoate:
[0052] ESI-MS(m / z): 744 [M+H] +
[0053] 1 H NMR (DMAO- d 6 ,4...
Embodiment 2
[0061] This example is used to illustrate the preparation of dabigatran etexilate fructonate of the present invention.
[0062] Add 3.2 mmol of dabigatran etexilate and 1.6 mmol of fructoic acid to 20 ml of water at 30°C, mix and stir for 6 hours to form a salt, then crystallize at 30°C, filter, wash with ethyl acetate, and dry Afterwards, add water and carry out recrystallization, obtain the hydrate of the dabigatran etexilate fructose salt of 0.450 g. Measured ESI-MS(m / z): 714[M+H] + .
[0063] The above-mentioned hydrate was dried to obtain 0.439 g of dabigatran etexilate fructonate as a white solid. According to calculation, the content of dabigatran etexilate fructose in the above-mentioned hydrate was 97.5wt%. Each molecule of the hydrate contains 1 molecule of water, that is, monohydrate.
[0064] Determination of above-mentioned dabigatran etexilate fructoate:
[0065] ESI-MS(m / z): 696[M+H] +
[0066] 1 H NMR (DMAO- d 6 ,400 MHz)δ: 0.84(t, J =9.0Hz, 3H,CH 3 ...
Embodiment 3
[0074] This example is used to illustrate the preparation of dabigatran etexilate fructonate of the present invention.
[0075] Add 4.8 mmol of dabigatran etexilate and 1.6 mmol of fructose to 20 ml of absolute ethanol at 0°C, mix and stir for 6 hours to form a salt, then crystallize at 0°C, filter, and wash with ethyl acetate , after drying, ethylene glycol dimethyl ether was added for recrystallization, and 0.420 g of dabigatran etexilate fructose salt was obtained as a white solid.
[0076] Determination of above-mentioned dabigatran etexilate fructoate:
[0077] ESI-MS(m / z): 668[M+H] +
[0078] 1 H NMR (DMAO- d 6 ,400 MHz)δ: 0.84(t, J =9.0Hz, 3H,CH 3 ), 1.09(t, J =8.4Hz, 3H,CH 3 ), 1.28-1.32(m, 6H,CH 2 CH 2 CH 2 ), 1.55-1.60(m, 2H, CH 2 ), 2.88-2.92(m, 2H,CH 2 ),3.76(s, 3H,CH 3 ), 3.94-4.04(m, 4H,2CH 2 ), 4.20(t, J =14.4 Hz, 2H, CH 2 ),4.60(d, J =5.6 Hz, 2H,CH 2 ), 6.76(d, J =8.8 Hz, 2H,ArH), 6.87(d, J =7.6 Hz, 1H,ArH), 7.01-7.16(m, 3H,ArH), 7.38(d, ...
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