his-gly-lys modified methotrexate, its synthesis, anti-metastatic activity and application
A technology of his-gly-lys and -gly-lys is applied in the preparation of anti-tumor metastases, anti-tumor metastases, and the field of methotrexate, and can solve problems such as limiting the application and curative effect of methotrexate.
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Embodiment 1
[0016] Embodiment 1 prepares Boc-Gly-Lys(Cbz)-OBzl(1)
[0017] Dissolve 1.02g (5.81mmol) Boc-Gly with 60mL of anhydrous tetrahydrofuran to obtain No. 1 solution. 0 ℃ and stirring, 1.43g (6.98mmol) dicyclohexyl carbodiimide and 0.79g (5.85mmol) N-hydroxybenzotriazole anhydrous tetrahydrofuran solution was added to the No. 1 solution and stirred for 30 minutes. Then add 2.35g (5.78mmol) HCl Lys(Cbz)-OBzl, adjust the pH of the reaction solution to 9 with N-methylmorpholine, remove the ice bath, and stir well at room temperature for 17 hours after TLC (dichloromethane / Methanol=30 / 1) shows that the reaction is complete, and the reaction is terminated. Filtered and concentrated, the residue was dissolved in 100mL ethyl acetate, and the solution was washed successively with saturated aqueous sodium bicarbonate (30mL×3), saturated aqueous sodium chloride (30mL×3), and 5% aqueous potassium hydrogensulfate (30mL ×3), washed with saturated sodium chloride aqueous solution (30mL×3), wa...
Embodiment 2
[0018] Embodiment 2 prepares Gly-Lys(Cbz)-OBzl(2)
[0019] 1.75 g (3.32 mmol) of compound (1) was dissolved in anhydrous ethyl acetate. Under stirring at 0°C, 20 mL of hydrogen chloride in ethyl acetate (4M) was added, and after stirring for 9 hours, TLC (dichloromethane / methanol=30 / 1) spotting showed that the reaction was complete. Under the condition of warm water bath, the reaction solution was repeatedly concentrated under reduced pressure, then the concentrate was dissolved with anhydrous ethyl acetate, the reaction solution was repeatedly concentrated under reduced pressure (3 times), and then the reactant was washed repeatedly with anhydrous ether to obtain 1.40 g (98 %) the target compound as a yellow viscous oil. ESI-MS(m / e):428[M+H] + .
Embodiment 3
[0020] Example 3 Preparation of Fmoc-His(Trt)-Gly-Lys(Cbz)-OBzl(3)
[0021] Using the method of Example 1, 2.02g (65%) of the target compound was obtained as a colorless powder from 1.87g (3.02mmol) of Fmoc-His (Trt) and 1.40g (3.02mmol) of compound (2). ESI+MS(m / e):1029[M+H] + , 1H NMR (300MHz, DMSO-d 6 ):δ / ppm=8.20(t,J=5.4Hz,1H),7.90(s,1H),7.88(s,1H),7.68-7.64(m,2H),7.43-7.20(m,27H), 7.06-7.03(m,6H),6.73(s,1H),5.12(s,1H),5.07(s,2H),5.00-4.99(m,2H),4.30-4.12(m,4H),3.75- 3.67 (m, 2H), 2.97-2.89 (m, 3H), 2.83-2.74 (m, 1H), 1.68-1.55 (m, 2H), 1.38-1.24 (m, 4H).
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