Preparation method of everolimus and intermediate of everolimus
An intermediate and system technology, applied in the field of pharmaceutical synthesis, can solve the problems of difficult column chromatography of crude products, unfavorable industrial production, and many deprotection by-products, etc., and achieves the effects of high yield, convenient operation and simple purification.
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Embodiment 1
[0028] Dissolve 17.5g of rapamycin and 0.8g of sodium hydroxide in acetonitrile (150ml), heat to 80°C, and add 28.27g of 2-(tert-butyldimethylsilyloxy)ethyl trifluoromethanesulfonate with stirring , reacted for 3 hours, concentrated under reduced pressure, and the crude product was purified by column chromatography to obtain intermediate compound II with a yield of 89.3%.
Embodiment 2
[0030] Dissolve 18.3g of rapamycin and 0.8g of sodium hydroxide in N,N-dimethylformamide (150ml), heat to 80°C, stir and add 2-(tert-butyldimethyl 29.56 g of silyloxy)ethyl ester was reacted for 3 hours, concentrated under reduced pressure, and the crude product was purified by column chromatography to obtain intermediate compound II with a yield of 81.2%.
Embodiment 3
[0032]
[0033] Add compound II (5.36g, 5mmol) into acetonitrile (100ml), keep the temperature at -10-5°C, add triethylamine trihydrogen trifluoride (11ml) to react for 7-8h, TLC detects that the reaction is basically complete, add bicarbonate Adjust the pH to 7-8 with sodium solution, extract with dichloromethane (100ml×3), combine the organic layers, wash with sodium chloride solution (300ml×2), dry the organic layer with anhydrous sodium sulfate, filter and concentrate, and concentrate the solid through Purified by preparative liquid chromatography to obtain compound I (white solid, 4.43 g), with a molar yield of 92.5%. HPLC: 99.56%. LC / MS(m / c)980.68(M+Na + ), after NMR structure analysis, it is determined that the product is compound I, and its collection of spectra is as follows figure 1 , figure 2 shown.
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