Preparation method and applications of isoflavone type compounds with selective estrogen receptor modulating activity
A compound, isoflavone technology, applied in the field of medicinal chemistry, can solve the problems of few literature reports
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Embodiment 1
[0083] Daidzein (1a)
[0084] Add 1.1g (10mmol) of resorcinol and 1.52g (10mmol) of p-hydroxyphenylacetic acid to the freshly steamed BF 3 In 6ml of diethyl ether, heat to an internal temperature of 70°C, react for 3h, cool down, add 8ml of dry DMF in an ice bath, heat up to 55°C, add dropwise a mixture of 4ml of methanesulfonyl chloride and 6ml of DMF, dropwise after 0.5h, gradually Raise the temperature to 70°C for 3 hours, cool, pour into 50ml of ice water, filter with suction, wash with water, dry, recrystallize with ethanol to obtain 2.2g of light white solid, yield 86.6%, mp316-319°C.
Embodiment 2
[0086] Genistein (1b)
[0087] 3.8 grams (0.03mol) of phloroglucinol, 4.0 grams (0.03mol) of p-hydroxyphenylacetonitrile, anhydrous ZnCl 2 Put 2.5 g (0.018 mol) and 50 ml of diethyl ether in a reaction bottle, and inject HCl gas at about 0°C under stirring, gradually an orange solid is produced, and seal it overnight. The next day, diethyl ether was poured off, 50ml of water was added to reflux for 3 hours, and suction filtration and drying gave 7.3 grams of powdery yellow solid (2,4,6,4′-tetrahydroxydeoxybenzoin), yield 93.6%, mp 250°C (decomposition) .
[0088] 1.3 g (5 mmol) of 2,4,6,4′-tetrahydroxydeoxybenzoin was dissolved in 20 ml of DMF, and BF was added below 10°C 3 ·Et 2 O 6ml, stirred at room temperature for 30min, heated, and added CH dropwise at about 60oC 3 SO 2 Cl solution (10mlCH 3 SO 2 Dissolve Cl in 20ml DMF), drop it in 30 minutes, heat up to 90-100°C, react for 4 hours to obtain a light brown-black reaction solution, pour the reaction solution into 2...
Embodiment 3
[0090] 7-(3-Bromopropoxy)-4'-hydroxyisoflavone (3a)
[0091] 1.3g (5.1mmol) of daidzein, 30ml of N,N-dimethylformamide, 0.7g (5.1mmol) of potassium carbonate, a small amount of potassium iodide, 1.1g (5.4mmol) of 1,3-dibromopropane, stirred at room temperature for 24h , filtered into 100ml of cold water, neutralized to pH3-4 with 10% HCl, extracted with ethyl acetate (50mL, 30mL×3), washed with water (15mL×2), anhydrous MgSO 4 After drying, the ethyl acetate was distilled off to obtain the crude product, which was separated by column layer (ethyl acetate:petroleum ether=2.5:1) to obtain 350 mg of light yellow solid, yield 18.7%, mp: 175-177°C. 1 H-NMR (300MHz, acetone): δ2.28-2.36 (m, 2H, CH 2 ), 3.82-3.86 (t, 2H, J=6.5Hz, CH 2 Br), 4.31-4.35(t, 2H, J=6.0Hz, CH 2 O), 6.88-6.91 (dd, 2H, J=6.6, 2.0Hz, 3', 5'-H), 7.06-7.10 (dd, 1H, J=8.8, 2.4Hz, 6-H), 7.09-7.10 (d, 2H, J=2.4Hz, 8-H), 7.47-7.50 (dd, 2H, J=6.6, 2.0Hz, 2', 6'-H), 8.09-8.12 (d, 1H, J=8.8 Hz, 5-H), 8.18(s, 1H, 2-...
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