2-(3-Cyano-4-alkoxy)phenyl-4-substituted thiazole-5-carboxylic acid compounds, composition, preparation method and use thereof
A technology of phenylthiazole and compound, which is applied in the field of treatment and/or prevention of hyperuricemia and gout, and can solve the problems of undiscovered thiazole-5-carboxylic acid compound composition and preparation method, etc.
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[0100] Preparation of intermediate 13-bromo-4-hydroxybenzonitrile
[0101] Add 50g (0.420mol) of p-hydroxybenzonitrile, 1.5g (0.006mol) of iodine, and 200mL of dichloromethane into a 1000mL three-necked flask, and stir mechanically at -5°C for 10min. Slowly drop 43.4mL (0.840mol) bromine and 200mL dichloromethane mixed solution into the above reaction solution, and react at room temperature for 24h. After the reaction was completed, the above reaction solution was slowly poured into 550mL (16%) sodium bisulfite aqueous solution, stirred for 30min, filtered with suction, washed with water, and dried to obtain 74.1g of white solid, yield: 89.1%, mp: 154.8-155.7 ℃. MS(ESI): m / z197.1[M-H] -
[0102] Preparation of intermediate 23-bromo-4-isobutoxybenzonitrile (general method 1)
[0103]Add 5.0g (0.025mol) of 3-bromo-4-hydroxybenzonitrile (intermediate 1), 6.8g (0.05mol) of bromoisobutane, 6.9g (0.05mol) of anhydrous potassium carbonate in a 100mL single-necked bottle React wi...
Embodiment 1
[0450] Preparation of Example 12-(3-cyano-4-isobutoxy)phenyl-4-phenylthiazole-5-carboxylic acid (general method eight)
[0451] Add 6.1g (0.015mol) ethyl 2-(3-cyano-4-isobutoxyphenyl)-4-phenylthiazole-5-carboxylate (intermediate 85) to a 250mL single-necked bottle, 1.9g ( 0.045mol) lithium hydroxide, 12mL water, 120mL DMF, react at 50°C for 8h, after the reaction is complete, pour the above reaction liquid into 500mL water, adjust the pH value to 1 with concentrated hydrochloric acid, let stand at room temperature for 4h, suction filter, collect and filter Cake to get a crude product, recrystallized (absolute ethanol: acetone = 1:1) to obtain 4.1g of white powder, yield: 72.2%, mp: 199.4-199.9°C.
[0452] MS(ESI):m / z377.1[M-H] - ;IR(KBr)3429.7,2963.0,2230.3,1724.8,1652.8,1603.3,1573.6,1512.1,1485.5,1441.4,1386.5,1358.3,1327.4,1297.4,1255.9,1201.6,1179.0,1133.7,1078.8,1023.6,1002.5cm -1 ; 1 H-MNR (300MHz, DMSO-d 6 )δ(ppm):8.37(d,1H,J=2.1Hz,Ar-H),8.28(dd,1H,J=2.1Hz,J=9.0Hz,A...
Embodiment 2
[0453] Preparation of Example 22-(3-cyano-4-methoxy)phenyl-4-phenylthiazole-5-carboxylic acid
[0454] According to General Method 8, using (Intermediate 86) as raw material, the crude product was recrystallized (absolute ethanol: acetone = 1:1) to obtain 3.5 g of white powder, yield: 69.4%, mp: 254.8-255.4 °C.
[0455] MS(ESI):m / z337.1[M+H] + ;IR(KBr):3442.3, 2937.9, 2361.4, 2229.7, 1678.0, 1648.4, 1603.2, 1511.1, 1484.4, 1443.9, 1427.6, 1329.3, 1285.0, 1183.8, 1167.8, 1144.2, 11033.1.1, -1 ; 1 H-MNR (300MHz, DMSO-d 6 )δ(ppm):13.47(s,1H,COOH),8.37(d,1H,J=2.1Hz,Ar-H),8.31(dd,1H,J=2.4Hz,J=9.0Hz,Ar-H ),7.81(m,2H,Ar-H),7.46(m,3H,Ar-H),7.40(d,1H,J=9.0Hz,Ar-H),4.00(s,3H,CH 3 ).
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