Phytolaccagenin C-23 site alcoholic hydroxyl oxidation derivative, and preparation method and application thereof
A technology of pokeweed saponin and alcohol hydroxyl, applied in the field of medicine
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[0023] A typical implementation of the present application provides a C-23-position alcohol hydroxyl oxidation derivative of pokeweed saponin, whose chemical structural formula is:
[0024]
[0025] Wherein, R is an aldehyde group or a carboxyl group.
[0026] Preferably, R is carboxyl. The anti-inflammatory experiments confirmed that the cytotoxicity of R being carboxyl is lower than that of R being aldehyde.
[0027] Another embodiment of the present application provides a method for preparing the above-mentioned phykrogenin C-23 alcohol hydroxyl oxidation derivatives. Phylogenin intermediate is obtained through protection of fork, and then the alcoholic hydroxyl group at the C-23 position of the phytogenin intermediate is oxidized by PCC oxidation method or TEMPO oxidation method, and then the acetonide fork protection group is removed to obtain phytoside C-23 Alcohol Oxidation Derivatives.
[0028] In order to obtain a higher yield of pokewegenin intermediates, it is...
Embodiment 1
[0043] Example 1 Compound {2',2'-dimethyl-[2,3-d][1,3]dioxole}-2β,3β,23-dihydroxy-30-methoxy-30-oxoolean-12-en-28- Preparation of oic acid (P-c)
[0044] Phytolaccagenin (532mg, 1mmol) was dissolved in 10ml of dry THF, TsOH (17.2mg, 0.1mmol) was added, then 2,2-dimethoxypropane (DMP, 750μL, 1.5mmol) was added dropwise, stirred at room temperature for 2h, and the reaction After termination, it was concentrated under reduced pressure, separated by silica gel column chromatography (MeOH / DCM), and the crude product was recrystallized to obtain compound P-c (489 mg, 85.6%).
[0045] {2',2'-dimethyl-[2,3-d][1,3]dioxole}-2β,3β,23-dihydroxy-30-methoxy-30-oxoolean-12-en-28-oic acid(P-c ):White solid powder(489mg, 85.6%).M.p.:>250℃. 1 H-NMR (600M, C 5 D. 5 N):5.39(m,1H),4.24(m,1H),4.16(m,1H),3.92(s,2H),3.89(d,J=1.2,1H),3.71(d,J=10.2, 1H), 3.67(s, 3H), 3.02(d, J=10.2, 1H), 2.35(d, J=14.4, 1H), 2.20(d, J=12.6, 1H), 2.14-2.10(m, 3H ),2.07-2.01(m,4H),1.90-1.80(m,3H),1.77(d,J=2.4,2H),1...
Embodiment 2
[0046] Example 2 Preparation of compound 2β,3β-dihydroxy-30-methoxy-23,30-dioxoolean-12-en-28-oic acid (P-d)
[0047] PCC oxidation method: Dissolve compound P-c (57.2mg, 0.1mmol) in 10mL DCM, drop into the DCM solution of PCC (containing PCC45mg, 0.2mmol), add 80mg of silica gel to the reaction solution at the same time, stir at room temperature for 2h, after the reaction is terminated, add 10 times the volume of diethyl ether, filtered, the filtrate was concentrated under reduced pressure, and separated by silica gel column chromatography (MeOH / DCM) to obtain an intermediate. After the structure of the intermediate was confirmed by MS and NMR, it was dissolved in 1N HCl solution / THF (1:1 ), stirred at 20°C for 2h, then concentrated under reduced pressure, and separated by silica gel column chromatography (MeOH / DCM) to obtain compound P-d (22.5mg, 45.8%).
[0048] TEMPO oxidation method: compound P-c (57.2mg, 0.1mmol) was dissolved in 3mL DCM, added 1.5mL PBS solution (0.67M,...
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