Tegafur derivatives and their preparation methods and uses
A derivative, tegafur technology, applied in the field of tegafur derivatives and its preparation, can solve the problems of high toxicity and low bioavailability of derivatives, achieve good tumor cell apoptosis induction effect, alleviate toxicity, improve selective effect
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Embodiment 1
[0051] Embodiment 1: the preparation of compound 5a
[0052]
[0053] Take 3 (1.00mmol, 258.00mg, 1.00eq), 1-hydroxybenzotriazole (1.11mmol, 150.00mg, 1.11eq), EDC·HCl (1.11mmol, 213.00mg, 1.11eq), DIPEA (3.05mmol, 532.00mg, 3.05eq), DMF (7.5mL), glycine methyl ester hydrochloride (1.00mmol, 125.55mg, 1.00eq), stirred at room temperature for 16h. After the reaction, add a small amount of water and saturated NaHCO 3 solution, extracted 3 times with ethyl acetate, and the ester layer was washed 2 times with saturated NaCl solution. Anhydrous sodium sulfate was added to dry for 0.5 h, and spin-dried to obtain a white solid 5n.
[0054] 1 H NMR (400MHz, DMSO) δ8.64 (t, J = 5.8Hz, 1H), 8.02 (d, J = 6.7Hz, 1H), 5.99–5.90 (m, 1H), 4.46 (s, 2H), 4.32 –4.24(m,1H),3.88(d,J=5.8Hz,2H),3.83(dd,J=15.0,7.3Hz,1H)3.64(s,3H),2.31–2.21(m,1H),2.06 – 1.89(m,3H). 13 C NMR(101MHz,DMSO)δ170.6,167.1,156.8(d,J=26.1Hz),149.1,139.8(d,J=228.3Hz), 124.5(d,J=33.8Hz),87.8,70.1,52.23,43.4 ,41.3,32.1...
Embodiment 2
[0056] Embodiment 2: the preparation of compound 5b
[0057]
[0058] Take 3 (1.00mmol, 258.00mg, 1.00eq), 1-hydroxybenzotriazole (1.11mmol, 150.00mg, 1.11eq), EDC·HCl (1.11mmol, 213.00mg, 1.11eq), DIPEA (3.05mmol, 532.00mg, 3.05eq), DMF (7.5mL), L-alanine methyl ester hydrochloride (1.00mmol, 139.60mg, 1.00eq). The reaction was stirred at room temperature for 16h. After the reaction, add a small amount of water and saturated NaHCO 3 solution, extracted three times with ethyl acetate, and the ester layer was washed twice with saturated NaCl solution. Anhydrous sodium sulfate was added to dry for 0.5 h, and spin-dried to obtain light yellow solid 5a.
[0059] 1 H NMR (400MHz, DMSO) δ8.64 (d, J = 7.0Hz, 1H), 8.02 (d, J = 6.7Hz, 1H), 5.99–5.92 (m, 1H), 4.44 (q, J = 16.0Hz ,2H),4.33–4.23(m,2H),3.82(q,J=7.4Hz,1H),3.63(s,3H),2.33–2.18(m,1H),2.05–1.88(m, 3H), 1.28(d,J=7.2Hz,3H). 13 C NMR (100MHz, DMSO) δ173.3, 166.3, 156.8(d, J=26.1Hz), 149.1, 139.8(d, J=228.2Hz), 124.5(d, ...
Embodiment 3
[0061] Embodiment 3: the preparation of compound 5c
[0062]
[0063] Take 3 (1.00mmol, 258.00mg, 1.00eq), 1-hydroxybenzotriazole (1.11mmol, 150.00mg, 1.11eq), EDC·HCl (1.11mmol, 213.00mg, 1.11eq), DIPEA (3.05mmol, 532.00mg, 3.05eq), DMF (7.50mL), L-valine methyl ester hydrochloride (1.00mmol, 167.63mg, 1.00eq). The reaction was stirred at room temperature for 16h. After the reaction, add a small amount of water and saturated NaHCO 3 solution, extracted 3 times with ethyl acetate, and the ester layer was washed 2 times with saturated NaCl solution. Anhydrous sodium sulfate was added to dry for 0.5 h, and spin-dried to obtain light yellow solid 5e.
[0064] 1 H NMR (400MHz, DMSO) δ8.56 (d, J = 8.3Hz, 1H), 8.02 (d, J = 6.6Hz, 1H), 5.96 (m, 1H), 4.56-4.42 (m, 2H), 4.27 (dd, J=13.0, 6.3Hz, 1H), 4.21(dd, J=11.9, 7.0Hz, 1H), 3.82(q, J=7.3Hz, 1H), 3.65(s, 3H), 2.32– 2.20(m ,1H),2.12–1.84(m,4H),0.92–0.84(m,6H). 13 C NMR (101MHz, DMSO) δ172.3, 166.7, 156.7 (d, J = 26.2Hz), 14...
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