Oleanolic acid-pyrimidine conjugate as well as preparation method and application thereof
A technology of oleanolic acid and conjugates, applied in the field of medicine, can solve problems such as obstruction and weak anti-tumor activity
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Embodiment 1
[0119] Example 1: 3β-Hydroxy-oleanane-12-ene-28-acid-[(uracil-1)-ethyl]ester (I 1 ) and 1,3-bis-(3β-hydroxy-oleanane-12-ene-28-acyloxyethyl)-2,4(1H,3H)-pyrimidinedione (II 1 ) preparation
[0120] a) Dissolve 4.99mmol (2.28g) of oleanolic acid in 10mL of DMF, add 24.95mmol (3.44g) of potassium carbonate and 6.49mmol (0.56mL) of 1,2-dibromoethane, and stir at 60°C for 0.5 hours , spin off the solvent under reduced pressure, the residue was dissolved in 50 mL of ethyl acetate, washed successively with 1N HCl, water, saturated sodium bicarbonate, water and saturated brine, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated to obtain a residue Purified by silica gel column chromatography, eluted with a mixed solvent of petroleum ether: ethyl acetate = 8:1 (volume ratio), and the eluent was evaporated to dryness to obtain 3β-hydroxy-oleanane-12-ene-28 -Acid-(2-bromoethyl)ester 1.60g (white solid, yield 57%); 1 H NMR (500MHz, CDCl 3 )0.74, 0.78, ...
Embodiment 2
[0130] Example 2: 3β-Hydroxy-oleanane-12-ene-28-oic acid-[(thymine-1)-ethyl]ester (I 2 ) and 5-methyl-1,3-bis-(3β-hydroxy-oleanane-12-ene-28-acyloxyethyl)-2,4(1H,3H)-pyrimidinedione (II 2 ) preparation
[0131] a) Dissolve 4.99mmol (2.28g) of oleanolic acid in 10mL of DMF, add 24.95mmol (3.44g) of potassium carbonate and 6.49mmol (0.56mL) of 1,2-dibromoethane, and stir at 60°C for 0.5 hours , spin off the solvent under reduced pressure, the residue was dissolved in 50 mL of ethyl acetate, washed successively with 1N HCl, water, saturated sodium bicarbonate, water and saturated brine, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated to obtain a residue Purified by silica gel column chromatography, eluted with a mixed solvent of petroleum ether: ethyl acetate = 8:1 (volume ratio), and the eluent was evaporated to dryness to obtain 3β-hydroxy-oleanane-12-ene-28 -Acid-(2-bromoethyl)ester 1.60g (white solid, yield 57%); 1 H NMR (500MHz, CDCl 3...
Embodiment 3
[0141] Example 3: 3β-Hydroxy-oleanane-12-ene-28-acid-[(uracil-1)-n-butyl]ester; (I 3 ) and 1,3-bis-(3β-hydroxy-oleanane-12-ene-28-acyloxybutyl)-2,4(1H,3H)-pyrimidinedione (II 3 ) preparation
[0142] a) Dissolve 4.99mmol (2.28g) of oleanolic acid in 10mL of DMF, add 14.97mmol (2.07g) of potassium carbonate and 0.72mL (5.99mmol) of 1,4-dibromobutane, and stir at 0°C for 72 hours , spin off the solvent, the residue was dissolved in 50 mL of ethyl acetate, washed with 1N HCl, water, saturated sodium bicarbonate, water and saturated brine in sequence, dried over anhydrous magnesium sulfate, filtered, the filtrate was concentrated, and the obtained residue was washed with silica gel Purified by column chromatography, eluted with a mixed solvent of petroleum ether: ethyl acetate = 4:1 (volume ratio), and the eluent was evaporated to dryness to obtain 3β-hydroxy-oleanane-12-ene-28 acid- (4-bromobutyl) ester 1.78g (white solid, yield 61%); 1 H NMR (500MHz, CDCl 3 )0.72, 0.77, 0.89...
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