Trifluoromethylpyrimidine derivatives containing Schiff base structural unit and preparation method and use thereof
A technology of trifluoromethylpyrimidine and structural unit, which is applied in the field of medicinal chemistry and can solve problems such as the inability of drugs to satisfy patients
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Embodiment 1
[0031] Example 1 (E) Preparation of 4-(2-phenylenedihydrazine)-2-(prop-2-yn-1-ylthio)-6-(trifluoromethyl)pyrimidine (5a)
[0032] 2-Mercapto-6-(trifluoromethyl)pyrimidin-4-ol (1.95 g, 10 mmol) was dissolved in potassium hydroxide (0.67 g, 12.05 mmol) in N,N-dimethylformyl at room temperature (20ml) in the amine solution, slowly add bromopropyne (940ul, 12.05mmol) dropwise, be warming up to 80 ℃ to take place substitution reaction, TLC detects that the reaction is completed, the reaction solution is cooled to room temperature, added in the ice-water mixture and stirred, there is a large amount of light A yellow solid was precipitated, filtered with suction, washed with water 3-4 times, and dried to obtain the compound 3-(prop-2-yn-1-ylsulfanyl)-5-(trifluoromethyl)phenol.
[0033] Light yellow solid, yield 83.5%; 1 H NMR (400MHz, DMSO-d 6 )δ7.29(s, 1H), 5.19(d, J=2.3Hz, 2H), 4.82(d, J=2.3Hz, 1H). 13 C NMR (101MHz, DMSO-d 6 )δ170.89,168.65,163.40,159.39,155.72,155.37,155.02,1...
Embodiment 2
[0040] Example 2(E)-4-(2-(3-Fluorobenzylidene)hydrazino)-2-(prop-2-yn-1-ylthio)-6-(trifluoromethyl)pyrimidine Preparation of (5b)
[0041] At room temperature, (3-(prop-2-yn-1-ylsulfanyl)-5-(trifluoromethyl)phenyl) (0.15 g, 0.609 mmol) hydrazine was added to 6 ml of absolute ethanol, and the temperature was raised to 80 ° C, slowly add 3-fluorobenzaldehyde (60.97ul, 0.609mmol), TLC detection reaction is completed, the reaction solution is cooled to room temperature, and column chromatography (V 石油醚 : V 乙酸乙酯 =6:1), concentrate the eluent to obtain the product.
[0042] White solid, yield 74.0%; 1 H NMR (400MHz, DMSO-d 6 )δ 1 H NMR(400MHz,DMSO)δ12.26(s,1H),8.21(s,1H),7.67(d,J=9.8Hz,1H),7.59(d,J=7.8Hz,1H),7.49(dt , J=13.8, 6.9Hz, 1H), 7.34(s, 1H), 7.30–7.23(m, 1H), 3.99(d, J=2.6Hz, 2H), 3.18(t, J=2.6Hz, 1H) . 13 C NMR (101MHz, DMSO-d 6 )δ169.92,163.66,162.15,161.23,144.41,136.43,130.88,130.79,123.59,116.89,116.68,113.10,112.88,96.17,79.88,73.44,18.57.HR-MS(ESI)Calcd for ...
Embodiment 3
[0043] Example 3(E)-4-(2-(4-Fluorobenzylidene)hydrazino)-2-(prop-2-yn-1-ylthio)-6-(trifluoromethyl)pyrimidine Preparation of (5c)
[0044] Substitute 3-fluorobenzaldehyde with 4-fluorobenzaldehyde, and the preparation method is the same as that in Example 2.
[0045] White solid powder, yield 62.4%; 1 H NMR (400MHz, DMSO-d 6 )δ12.19(s, 1H), 8.22(s, 1H), 8.05–8.00(m, 4H), 7.33(s, 1H), 4.00(d, J=2.5Hz, 2H), 3.19(t, J = 2.6Hz, 1H). 13 C NMR (101MHz, DMSO-d 6 )δ170.09,161.97,152.63,147.84,141.66,127.28,124.40,122.01,119.16,117.08,114.31,95.70,79.91,73.40,61.18,55.75,18.57.HR-MS(ESI):Calcd for CSI 15 H 11 F 4 N 4 S[M+H] + : 355.0641, found: 355.0642.
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