Salt of pomalidomide prodrug
A technology for drugs and maleates, applied in the field of medicine, can solve problems such as poor structural stability
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Embodiment 1
[0026] The preparation of embodiment 1 salt
[0027] The inventor has selected a variety of acids (comprising sulfuric acid, phosphoric acid, hydrochloric acid, formic acid, acetic acid, oxalic acid, oleic acid, lactic acid, nicotinic acid, pamoic acid, methanesulfonic acid, maleic acid, citric acid, fumaric acid, benzenesulfonic acid) Acid, malic acid, lactobionic acid, hippuric acid, benzoic acid, cinnamic acid, adipic acid, stearic acid, orotic acid, glycolic acid, salicylic acid, citric acid, L-tartaric acid, p-toluenesulfonic acid, 4 - chlorobenzenesulfonic acid, D-glutamic acid, 2-naphthalenesulfonic acid, 1,5-naphthalene disulfonic acid), various solvent systems (including ethyl acetate, isopropanol, acetonitrile, methylene chloride, n-propane One or more of alcohol, 2-butanone, tetrahydrofuran, isopropyl acetate, ethanol, n-butanol and n-heptane) for preliminary tests.
[0028] After extensive testing, only hydrochloric acid, sulfuric acid, phosphoric acid, maleic aci...
Embodiment 11
[0030] Preparation of Compound 1
[0031]
[0032] Step1: Under nitrogen protection, add S.M.B (20g, 73.2mmol, 1.00eq) and DMF (400ml) into a 1000mL three-neck reaction flask, and stir electromagnetically. Then sodium hydride (3.5g, 87.5mmol, 1.2eq) was added slowly, and after stirring for 30min, potassium iodide (12g, 72.2mmol, 0.99eq) and TBAB (tetrabutylammonium bromide) (3.52g, 10.9mmol, 0.15 eq), after stirring for 15min, S.M.1 (23.8g, 72.8mmol, 0.99eq) was added and stirred for 12h. Stop the reaction, pour the reaction system into 2L of water, stir for 1h, solids are precipitated, filter to obtain a yellow solid filter cake, the filter cake is washed with 500ml DCM (dichloromethane), separate the liquids, take the organic phase and concentrate it under reduced pressure. Analysis (PE:EA=1.5:1), 13.20g yellow solid product, yield 35.8%.
[0033] Step2: Under nitrogen protection, add Int 1-01 (500mg, 1mmol, 1.00eq) and DCM 5ml into a 100ml three-neck reaction flask, stir...
Embodiment 12
[0038] The preparation of embodiment 1.2 hydrochloride
[0039] 7.0 g of tert-butoxycarbonyl-L-valine (3-(4-(amino)-1,3-dioxoisoindoline-2-yl)-2,6-dioxopiperidine -1-yl)methyl ester (Int 1-01) was suspended in 139 mL of dichloromethane and stirred at 0°C. Add 139mL of hydrochloric acid ethyl acetate solution, naturally rise to room temperature and react for 1 hour. Filter and dry the filter cake in vacuum. The dried solid was slurried with 100 mL of dichloromethane for 2 hours at room temperature. Filter and dry the filter cake in vacuum. 4.58 g of the target product was obtained.
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