1-tanshinone ester derivatives with cardioprotective effect and their application
A technology for tanshinone ester and myocardial protection, which is applied in the field of 1-tanshinone ester derivatives, can solve the problems of poor polarity, low bioavailability and weak efficacy of tanshinone, and achieves the effect of good myocardial protection.
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Embodiment 1
[0056] In a round bottom flask I, add 276 mg of 1-hydroxy-tanshinone and anhydrous CCl 4 (solvent), add 24.2 mg of benzoyl peroxide, add 142.4 mg of N-bromosuccinimide (NBS) in batches, control the temperature at about 60 ° C, stop the reaction after reflux for 1.0 h, and purify on silica gel to obtain 1-Br - Tanshinone IIA;
[0057] In the round bottom flask II, add 180.15 mg of ferulic acid, dimethylformamide (DMF) as solvent, use K 2 CO 3 Adjust the pH to 7.5, stir well, add 298.6 mg of 1-Br-tanshinone IIA, keep the temperature at 50°C, react for 1 hour to end the reaction, remove DMF after cooling, purify by silica gel column or crystallization method, and obtain the target derivative as shown below.
[0058] The target derivative is a brown-red needle-like solid, and its NMR data is:
[0059] 1 H-NMR (400MHz, CDCl 3 , TMS) δ 7.75 (2H, s, H-6, 7), 7.63(1H, d, J=1.6Hz, H-24), 7.59-7.63 (1H, dd, J=1.6, 8.2 Hz, H- 28), 7.52-7.54 (1H, d, J=8.2Hz,H-27), 7.24 (1H, s, H-15)...
Embodiment 2
[0071] In a round bottom flask I, add 276 mg of 1-hydroxy-tanshinone and anhydrous CCl 4 (solvent), add 24.2 mg benzoyl peroxide, add 355.96 mg N-bromosuccinimide (NBS) in batches, control the temperature at about 80 ° C, stop the reaction after reflux for 4.0 h, and purify on silica gel to obtain 1- Br-tanshinone Ⅱ A;
[0072] In the round bottom flask II, add 397.4 mg Danshensu, dimethylformamide (DMF) as solvent, use K 2 CO 3 Adjust the pH to 9.0, stir well, add 373.23mg 1-Br-tanshinone IIA, keep the temperature at 70°C, react for 4h to end the reaction, remove DMF after cooling, use silica gel column or crystallization method to purify, the target derivative obtained is as follows .
[0073] The target derivative is a red solid, and its NMR data are:
[0074] 1 H-NMR (400MHz, CDCl 3, TMS) δ 7.70 (1H, s, H-6), 7.68 (1H, s, H-7),7.62-7.66 (2H, m, H-24, 28),7.48-7.50(1H, d, J =8.38 Hz, H-27),7.26-7.28(1H,m, H-1), 7.18(1H, s, H-15),4.22-4.25(1H, t, H-21), 2.83-2.86 ( 2...
Embodiment 3
[0081] In round bottom flask Ⅰ, add 278mg 1-hydroxy-cryptanshinone and anhydrous CCl 4 (solvent), add 12.1 mg of benzoyl peroxide, add 249.2 mg of N-bromosuccinimide (NBS) in batches, control the temperature at about 70 ° C, stop the reaction after reflux for 2.5 h, and purify on silica gel to obtain 1 - Br-cryptanshinone;
[0082] In the round bottom flask II, add 198.7mg of ferulic acid, dimethylformamide (DMF) as solvent, use K 2 CO 3 Adjust the pH to 8.5, stir well, add 298.6mg 1-Br-cryptanshinone, keep the temperature at 60°C, react for 3h to end the reaction, remove DMF after cooling, purify by silica gel column or crystallization method, and obtain the target derivative as follows.
[0083] The target derivative is a red solid, and its NMR data are:
[0084] 1 H-NMR (400MHz, CDCl 3 , TMS) δ 7.75 (2H, s, H-6, 7), 7.63(1H, d, J=1.6Hz, H-24), 7.59-7.63 (1H, dd, J=1.6, 8.2 Hz, H- 28), 7.52-7.54 (1H, d, J=8.2Hz, H-27), 6.98-6.99 (1H, m, H-1), 6.85 (1H, d, J=16 Hz, H-22...
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