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With thionyl chloride In benzene for 3h; Heating; |
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With thionyl chloride; N,N-dimethyl-formamide In chloroform for 3.5h; Heating; |
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With thionyl chloride for 2h; Heating; |
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With oxalyl dichloride In dichloromethane at 25℃; |
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With thionyl chloride In benzene Reflux; |
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With oxalyl dichloride; N,N-dimethyl-formamide In dichloromethane at 20℃; for 2h; |
General procedure for the synthesis of thecinnamamides
General procedure: Asolution of the cinnamic acid (5 mmol) and oxalyl chloride (5.5 mmol) in DCM(50 mL) and 2 drops of DMF was stirred at room temperature for 2h, untilevolution of CO2 had ceased.The DCM was removed by rotary evaporation, the residue dissolved in CHCl3(30 mL) and the CHCl3 removed by rotary evaporation to remove anyexcess oxalyl chloride. The residue wasdissolved in DCM (20 mL) and added to a stirred solution of the benzylamine(6.5 mmol) and triethylamine (7 mmol) in DCM (100 mL) at 0 °C. The reaction was stirred at room temperaturefor 1h, washed with 2M aq. HCl (30 mL), water (30 mL) and 2M aq. K2CO3(30 mL) and dried (MgSO4).Removal of the solvent gave a solid which was recrystallised fromEtOAc/petroleum ether. |
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With oxalyl dichloride; N,N-dimethyl-formamide In dichloromethane at 20℃; for 2h; Cooling with ice; |
General Procedure for the Synthesis of Compounds 2a-m
General procedure: To a solution of cinnamic acid (10 mmol) in dichloromethane(30 mL) in an ice bath was added a mixture of oxalyl chloride (1.5 mL, 17.5 mmol) and dimethylformamide (2drops). After the mixture was stirred for 2 h at room temperature, the solvent was removed under reduced pressure to givecinnamoyl chloride which was mixed with 3,4,5-trimethoxyphenol (1.8 g, 10 mmol) and then dissolved in boron trifluoride etherate (10 mL) and heated to reflux for 10 min. After cooling, the mixture was poured into ice water and then the precipitate was filtered and washed with water until free from acid. The resulting precipitate was washed with hexane and then with ether to obtain the corresponding chalcones 1a-m (89-97%) as orange-yellow powders. A mixture of chalcones 1a-m (10 mmol) and iodine (1.0 eq) in DMSO (25 mL) was heated toreflux for 3 h. After cooling, the mixture was poured into icewater. The precipitate was filtered and washed with saturated sodium thiosulfate solution. The residue was chromatographed on a silica gel column with hexane/EtOAc (2 : 1) as the eluent to give pure 2a-m as pale yellow solids. The preparation of 3a-j (Chart 2) were essentially according to our published procedure. 20) All the physicochemical and spectroscopic characteristics of products 2a-j and 3a-j are in agreement with those reported.20) |
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With thionyl chloride at 60℃; for 3h; |
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With thionyl chloride In dichloromethane at 20℃; for 24h; |
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With thionyl chloride; N,N-dimethyl-formamide In dichloromethane at 20℃; |
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With thionyl chloride at 60℃; for 3h; |
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With oxalyl dichloride In tetrahydrofuran at 60 - 70℃; for 4h; |
General procedure for the synthesis of intermediates 6e-6m
General procedure: In a double necked round bottom flask (RB flask), 1.94 g(10 mmol) of the compounds 2e-2m obtained in step 1 was takenand dissolved in 30 mL of tetrahydrofuran (THF). 2 mL (20 mmol)of oxalyl chloride was subsequently added to the RB flask usingdropper. The refluxing was performed for 4 h at 60-70 C. The solutionwas dried carefully under reduced pressure using rota vapourand the product obtained was used directly in the next step |
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With thionyl chloride at 60℃; for 3h; |
General procedure: An 50 mL anhydrous flask was charged withmagnetic stir bar, cinnamic acid (5 mmol, 0.74 g) and SOCl2 (5 mL).After stirring at 60 C for 3 h, the redundant SOCl2 was evaporatedunder reduced pressure and then the liquid was dropwise addedinto another flask containing N-methylaniline (10 mmol, 1.07 g)dissolved in anhydrous CH2Cl2 (20 mL). The mixture was stirredfor 1 h at room temperature. The organic phase was then washedby aqueous HCl and aqueous K2CO3, then dried by anhydrousNa2SO4. After evaporating the CH2Cl2, the N-methyl-N-phenylcinnamamidewas obtained in 97% yield and used in the next stepdirectly. |
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With oxalyl dichloride; N,N-dimethyl-formamide In dichloromethane at 20℃; |
5.11 General procedure for the preparation of compounds 9a-n
General procedure: Oxalyl chloride (2.0mmol) was added drop-wise to a stirred mixture of compounds 8a-n (1.0mmol) and DMF (0.02mmol) in dichloromethane (16mL) in room temperature for 10min, and the mixture was distilled and dissolved in dichloromethane (16mL) immediately. The solution was used for the next step without further purification. |
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With thionyl chloride at 75℃; for 2h; |
General procedure: Compounds A11-A15, A17, A18, A20-A22, B1-B12, C7-C10 and C13-C20 were preparedaccording to method B in Fig 1 by reaction of the corresponding acyl chloride and thecorresponding alcohol. The general procedure was as follows. The mixture of cinnamic acid orcinnamic acids with substituents on the phenyl ring (0.10 mol) and 30 mL thionyl chloridewas refluxed at 75°C for 2 h. The excess thionyl chloride was removed under reduced pressure.After the residue was dissolved in 10 mL DCM, the corresponding alcohol (10 mmol) wasadded at 0°C. The solution was stirred at 0°C for 1 h, and then washed with water (3 × 30 mL)followed by 5% Na2CO3 aqueous solution, and dried over anhydrous sodium sulfate. After filtration,the solvent was removed under reduced pressure. The residue was purified by silica gelcolumn chromatography ( 40 mm × L 40 cm) to afford the desired product. |
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With thionyl chloride for 1h; Reflux; Inert atmosphere; Schlenk technique; |
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With phosphorus pentachloride at 20℃; for 0.5h; |
3.1
In the first step, 0.05 mol of 4-bromobenzene acrylate and 0.075 mol of phosphorus pentachloride are added to the reaction vessel.Stir the reaction at room temperature for 30 min; |
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With oxalyl dichloride In tetrahydrofuran for 6h; Inert atmosphere; Cooling with ice; |
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With thionyl chloride Reflux; Schlenk technique; |
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With oxalyl dichloride; N,N-dimethyl-formamide at 0 - 20℃; for 1.5h; |
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With oxalyl dichloride In N,N-dimethyl-formamide at 0 - 5℃; for 1h; |
8.2
In a fume hood, add 81.82g (0.008mol) of VI81.82g (0.008mol) to a pear-shaped bottle, dropwise add 0.25mL of N, N-dimethylformamide (DMF), and cool to 0-5 ° C in an ice bath. Slowly add 2.00 mL (0.021 mol) of oxalyl chloride, and the addition is completed within 10 minutes. After dripping, the ice bath was removed, and the reaction was continued for 1 h until the solution was clear, and no gas was generated in the system. Use a rotary evaporator to evaporate the excess solvent and oxalyl chloride to obtain VII8. Add 16 mL of dichloromethane to dissolve it and seal it for later use. |
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With thionyl chloride; N,N-dimethyl-formamide In dichloromethane at 0 - 20℃; for 5h; |
5; 8
The synthesis process is as follows: at 0 ° C, SOCl2 (2.4 mmol) and DMF (2 drops) are added to p-bromocinnamic acid (2.0 mmol) in anhydrous DCM (5 mL), and the reaction mixture is stirred at room temperature 5h. After the reaction is completed, the substituted cinnamoyl chloride is obtained by concentration. At 0 ° C, 4-hydroxycoumarin (1.6 mmol) and DIEA (3.2 mmol) were added to dry DCM (5 mL), then p-bromocinnamoyl chloride dissolved in dry DCM (5 mL) was slowly added Into the reaction system. After 30 minutes, the reaction was moved to room temperature and proceeded. Follow the reaction by TLC until the reaction is complete. The reaction was quenched with saturated sodium bicarbonate, then extracted with ethyl acetate, washed with water and saturated sodium chloride, dried over anhydrous Na2SO4, and finally purified by column chromatography. The yield was 61.7%. |
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With oxalyl dichloride; N,N-dimethyl-formamide In dichloromethane at 20℃; for 0.2h; |
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