* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Stage #1: With pyridine; boron trifluoride diethyl etherate In N,N-dimethyl-formamide at 75℃; for 1.5 h; Stage #2: With phosphorus pentachloride In N,N-dimethyl-formamide at 55℃; for 0.5 h;
In the first reaction flask, resorcinol (0.72 g, 6.5 mmol), p-nitrophenylacetic acid (1.0 g, 6.0 mmol), BF 3 / Et 2 O (10 mL) was added and stirred at 75 ° C Reaction for 90 min. The reaction was completed, cooled to below 10 ° C, and DMF (10 mL) was added slowly with stirring. (0.72g6.5mmol)(1.0g6.0mmol)BF 3 /Et 2 O(10mL)75°C90min 10°CDMF(10mL) In a second reaction flask, DMF (20 mL) was added, cooled to below 10 ° C, and PCl 5 (2.0 g, 9 mmol) was added portionwise and stirred at 55 ° C for 30 min. The reaction was completed, cooled to below 10 ° C, slowly added to the first reaction flask, room temperature reaction 1h. After completion of the reaction, the reaction solution was poured into hot dilute hydrochloric acid (0.1 N) with stirring, and the solid was precipitated, suction filtered, washed with water and dried. The crude product was recrystallized from methanol to give 0.36 g of product, yield 16.4percent. MS (ESI): m / z = 284 [M + H] & lt; + & gt ;.
Stage #1: at 85℃; for 1.5 h; Stage #2: at 10 - 25℃; for 2 h;
4.1.2 7-Hydroxy-3-(4-nitrophenyl)-4H-benzopyran-4-one (9) A mixture of 4-nitrophenylacetic acid (7; 1.0 g, 6.0 mmol), resorcinol (8; 0.72 g, 6.5 mmol) and BF3/Et2O (10 ml) was heated at 85 °C for 1.5 h with stirring, then cooled down to 10 °C and 10 ml DMF was added slowly. In another flask, 10 ml DMF was added and cooled to 10 °C, PCl5 (2.0 g, 9 mmol) was added in batches, afterwards the mixture was heated to 55 °C and stirred for 0.5 h, after that cooled to 10 °C. Then the mixture was added by droplet into the first flask and stirred at 25 °C for 2 h. Then the reaction mixture was poured into heated dilute hydrochloric acid (0.5 mol/L). The product was filtered, and purified by recrystallization from methanol to yield 9 (0.36 g, 1.26 mmol, 21percent) as a white solid. 1H NMR (DMSO, 300 MHz): δ 8.48 (s, 1H, H-2), 8.28 (2H, J = 8.8 Hz, H-3', H-5'), 8.07 (d, 1H, J = 8.8 Hz, H-5), 7.96 (d, 2H, J = 8. 8 Hz, H-2', H-6'), 7.05 (dd, 1H, J = 8.8, 2.4 Hz, H-6), 6.97 (d, 1H, J = 2.4 Hz, H-8); MS (ESI): m/z = 282 [M-H]-.
Reference：
[1] Bioorganic and Medicinal Chemistry, 2015, vol. 23, # 15, p. 4428 - 4433
3
[ 15485-63-9 ]
[ 68-12-2 ]
[ 15485-80-0 ]
Reference：
[1] Chemistry and Biodiversity, 2015, vol. 12, # 4, p. 685 - 696
[2] Chemical Biology and Drug Design, 2013, vol. 82, # 3, p. 317 - 325
[3] Chemical Biology and Drug Design, 2015, vol. 86, # 1, p. 894 - 901
4
[ 15485-63-9 ]
[ 122-51-0 ]
[ 15485-80-0 ]
Reference：
[1] Journal of Scientific and Industrial Research, 1952, vol. 11 B, p. 413
[2] Bioorganic and Medicinal Chemistry, 2003, vol. 11, # 18, p. 4069 - 4081
5
[ 137522-88-4 ]
[ 15485-80-0 ]
Reference：
[1] Journal of Heterocyclic Chemistry, 1991, vol. 28, # 6, p. 1641 - 1642
[2] Chemistry of Heterocyclic Compounds (New York, NY, United States), 1992, vol. 28, # 5, p. 497 - 502[3] Khimiya Geterotsiklicheskikh Soedinenii, Sbornik, 1992, # 5, p. 595 - 600
6
[ 555-21-5 ]
[ 15485-80-0 ]
Reference：
[1] Journal of Scientific and Industrial Research, 1952, vol. 11 B, p. 413
[2] Chemical Biology and Drug Design, 2013, vol. 82, # 3, p. 317 - 325
[3] Chemistry and Biodiversity, 2015, vol. 12, # 4, p. 685 - 696
[4] Chemical Biology and Drug Design, 2015, vol. 86, # 1, p. 894 - 901
7
[ 108-46-3 ]
[ 15485-80-0 ]
Reference：
[1] Journal of Scientific and Industrial Research, 1952, vol. 11 B, p. 413
[2] Chemical Biology and Drug Design, 2013, vol. 82, # 3, p. 317 - 325
[3] Chemistry and Biodiversity, 2015, vol. 12, # 4, p. 685 - 696
[4] Chemical Biology and Drug Design, 2015, vol. 86, # 1, p. 894 - 901
8
[ 15485-63-9 ]
[ 15485-80-0 ]
Reference：
[1] Chemistry of Heterocyclic Compounds (New York, NY, United States), 1992, vol. 28, # 5, p. 497 - 502[2] Khimiya Geterotsiklicheskikh Soedinenii, Sbornik, 1992, # 5, p. 595 - 600
[3] Journal of Heterocyclic Chemistry, 1991, vol. 28, # 6, p. 1641 - 1642
[4] Journal of the Chemical Society, 1953, p. 1852,1856
9
[ 137522-86-2 ]
[ 15485-80-0 ]
Reference：
[1] Journal of the Chemical Society, 1953, p. 1852,1856
10
[ 15485-74-2 ]
[ 15485-80-0 ]
Reference：
[1] Journal of the Chemical Society, 1953, p. 1852,1856
With iron; ammonium chloride; In ethanol; water; for 4h;Reflux;
4.1.3 7-Hydroxy-3-(4-aminophenyl)-4H-benzopyran-4-one (10) To a solution of 9 (3 g, 10 mmol) in 30 ml ethanol, iron powder (6 g, 100 mmol) and NH4Cl (1 g in 3 ml water) solution were added. Then the mixture was refluxed for 4 h. The hot solution was filtered, and the filtrate was concentrated under reduced pressure to give 10 (2 g, 0.75 mmol, 75%) as a white solid. 1H NMR (DMSO, 300 MHz): delta 8.14 (s, 1H, H-2), 8.05 (d, 1H, J = 8.8 Hz, H-5), 7.46 (d, 2H, J = 8. 8 Hz, H-2', H-6'), 6.99 (dd, 1H, J = 8.8, 2.4 Hz, H-6), 6.90 (d, 1H, J = 2.4 Hz, H-8), 6.88 (2H, J = 8.8 Hz, H-3', H-5'); MS (ESI): m/z = 254 [M+H]+.
30.6%
With acetic acid; zinc; In ethanol; at 50℃; for 0.5h;
This compound was prepared by the reduction of analog 27. To a suspension of 500 mg of analog 27 and 50 ml of ethanol was added 1.0 g of zinc powder. The mixture was stirred at 50 C while 10 ml of glacial acetic acid was added slowly through a span of 30 min. After analog 27 was completely reduced, reaction mixture was filtered and filtrate was concentrated. The concentrate was suspended in 20 ml of water and extracted with ethyl acetate. The organic layer was evaporated to dryness and residue was recrystallized from methanol: chloroform : petroleum ether (30-60 C) (1: 5: 20) to give 153 mg of yellow amorphous powder of analog 32, a yield of 30.6% (w/w): mp 250 C (decomposes). lH NMR (DMSO-d6) 8 6.59 (d, 2H, J= 8.62 Hz, 3', 5'-H), 6.81 (d, 1H, J= 2.63 Hz, 8-H), 6.89 (dd, 1H, J= 8. 93,2. 56 Hz, 6-H), 7.24 (d, 2H, J= 8.08 Hz, 2', 6'-H), 7.94 (d, 1H, J= 8. 78 Hz, 5-H), 8.21 (s, 1H, 2-H). 13C NMR (DMSO-d6) 8 102.1 (C-8), 113.4 (C-3', 5'), 115.2 (C-6), 117.5 (C-10), 119.0 (C-1'), 123.9 (C-3), 127.2 (C-5), 129.5 (C-2', 6'), 148.5 (C-4'), 152.3 (C- 2), 157.4 (C-9), 162.9 (C-7), 174.9 (C-4). MS (m/z) 254.3 (M + H) +, 276.2 (M + Na) +, 252.6 (M-H)-, Anal. (C15H1o43N) for C, H, N. Cacld : 71.14, 4. 38, 5.53 ; found: 70.89, 4.40, 5.49.
30%
With iron; In ethanol; water; for 4h;Reflux;
7-Hydroxy-3-(4-nitrophenyl)-4H-benzopyran-4-one (3 g, 10 mmol) was added to the reaction flask, and (6 g, 100 mmol) of iron powder, 30 ml of ethanol, 3 ml of water and 1 g of NH4Cl were added and heated to reflux. The reaction was refluxed for 4 hours and filtered while hot To give the product 2 g, yield 30% JS (ESI):
General procedure: 1-(2,4-dihydroxyphenyl)-2-(4-fluorophenyl)ethanone(5.14g, 19.9mmol)Soluble in DMF (11.1 ml, 59.7 mmol),Add boron trifluoride diethyl ether solution (8.7 ml, 99.5 mmol) under ice bath.The temperature was raised to 60 degrees with stirring.DMF solution of uniformly mixed methanesulfonyl chloride is added dropwise to the raw material.After stirring for 5 minutes,The temperature was raised to 95 C and the reaction was carried out for 2 hours under nitrogen atmosphere.After the reaction is completed, the reaction solution is poured into a cold saturated sodium carbonate solution.a yellow solid precipitated, suction filtered,Drying in the infrared.Silica gel column chromatography,A white solid of 3.2 g was obtained in a yield of 60.0%.
With pyridine; In dichloromethane; at 0 - 20℃; for 1h;
EXAMPLE 1 Preparation of a Compound of Formula (2) A. (2) To a suspension of <strong>[15485-80-0]7-hydroxy-3-(4-nitrophenyl)-4H-chromen-4-one</strong> (commercially available, (10 g, 48.3 mmol) in dichloromethane (100 niL), pyridine (15.6 mL, 193.2 mmol) was added and the mixture was then cooled in an ice-bath. To this solution at 0 C, triflic anhydride (16.3 mL, 96.6 mmol) was added slowly and then the solution was warmed up to room temperature and stirred for 1 hour until the reaction was completed. The reaction mixture was partitioned between ethyl acetate and water. The organic phase was dried with magnesium sulfate and solvent removed under reduced pressure. The residue was heated in acetonitrile and the solids filtered off, to give 3-(4-nitrophenyl)-4- oxo-4H-chromen-7-yl trifluoromethanesulfonate.
4.1.2 7-Hydroxy-3-(4-nitrophenyl)-4H-benzopyran-4-one (9) A mixture of 4-nitrophenylacetic acid (7; 1.0 g, 6.0 mmol), resorcinol (8; 0.72 g, 6.5 mmol) and BF3/Et2O (10 ml) was heated at 85 C for 1.5 h with stirring, then cooled down to 10 C and 10 ml DMF was added slowly. In another flask, 10 ml DMF was added and cooled to 10 C, PCl5 (2.0 g, 9 mmol) was added in batches, afterwards the mixture was heated to 55 C and stirred for 0.5 h, after that cooled to 10 C. Then the mixture was added by droplet into the first flask and stirred at 25 C for 2 h. Then the reaction mixture was poured into heated dilute hydrochloric acid (0.5 mol/L). The product was filtered, and purified by recrystallization from methanol to yield 9 (0.36 g, 1.26 mmol, 21%) as a white solid. 1H NMR (DMSO, 300 MHz): delta 8.48 (s, 1H, H-2), 8.28 (2H, J = 8.8 Hz, H-3', H-5'), 8.07 (d, 1H, J = 8.8 Hz, H-5), 7.96 (d, 2H, J = 8. 8 Hz, H-2', H-6'), 7.05 (dd, 1H, J = 8.8, 2.4 Hz, H-6), 6.97 (d, 1H, J = 2.4 Hz, H-8); MS (ESI): m/z = 282 [M-H]-.
In the first reaction flask, resorcinol (0.72 g, 6.5 mmol), p-nitrophenylacetic acid (1.0 g, 6.0 mmol), BF 3 / Et 2 O (10 mL) was added and stirred at 75 C Reaction for 90 min. The reaction was completed, cooled to below 10 C, and DMF (10 mL) was added slowly with stirring. (0.72g6.5mmol)(1.0g6.0mmol)BF 3 /Et 2 O(10mL)75C90min 10CDMF(10mL) In a second reaction flask, DMF (20 mL) was added, cooled to below 10 C, and PCl 5 (2.0 g, 9 mmol) was added portionwise and stirred at 55 C for 30 min. The reaction was completed, cooled to below 10 C, slowly added to the first reaction flask, room temperature reaction 1h. After completion of the reaction, the reaction solution was poured into hot dilute hydrochloric acid (0.1 N) with stirring, and the solid was precipitated, suction filtered, washed with water and dried. The crude product was recrystallized from methanol to give 0.36 g of product, yield 16.4%. MS (ESI): m / z = 284 [M + H] & lt; + & gt ;.
With boron trifluoride diethyl etherate; In N,N-dimethyl-formamide; at 60 - 95℃; for 2h;Inert atmosphere;
General procedure: BF3·Et2O (10 mL) was added to a mixture of resorcinol (0.67 g, 6.1 mmol) and substituted phenylacetic acids (7a-7d; 5.5 mmol). The reaction mixture was stirred at 80-90C for 5-7 h under a nitrogen atmosphere, then was poured into ice-cold water and was extracted with ethyl acetate. The combined organic layer was washed with saturated sodium bicarbonate solution and brine, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure to afford 8a-8d as red oil liquid which was used in the next step without further purification. BF3·Et2O (3 mL) was added to a solution of benzylketone (8a-8d ) in dry DMF (10 mL). The solution was warmed to 60C and a solution of methanesulfonyl chloride (5 mL) in dry DMF (5 mL) was added. The resulting mixture was then heated to 95C and stirred for 2 h under a nitrogen atmosphere. After cooling, it was poured into cold saturated sodium carbonate solution and stirred overnight to give a precipitate, filtered. The residue was purified with column chromatography over silica gel to give pure products 9a-9d.
7-(((3-(2,6-dichlorophenyl)-5-(isopropyl)-1,2-oxazol-4-yl)methyl)oxy)-3-(4-nitrophenyl)-4H-benzopyran-4-one[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
88%
With potassium carbonate; potassium iodide; In N,N-dimethyl-formamide; at 60℃; for 8h;Inert atmosphere;
General procedure: A mixture of phenols 9a-9d (0.8 mmol), compound 6 (0.24 g, 0.8 mmol), potassium carbonate (0.22 g, 1.6 mmol) and potassium iodide (0.013 g, 0.08 mmol) in DMF (5 mL) was stirred at 60 C for 8 h under a nitrogen atmosphere. After that, the reaction mixture was partitioned with ethyl acetate and water. The organic layer was washed with brine and dried over anhydrous sodium sulfate. The solvent was removed and the residue was chromatographed over silica gel to give pure compounds 10a-10d.
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