2-methyl-1,3-diphenylpropane-1,3-dione

反応条件: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Dibenzoylethane (1.50 g, 6.30 mmol) and ammonium acetate (2.00 g, 25.2 mmol) were mixed together and the mixture was heated to 100° C. for 4 hours. The reaction mixture was cooled down to room temperature, diluted with 30 ml of water and basified with 1N NaOH until pH 14. The reaction mixture was extracted several times with chloroform. The combined organic phases were washed with 1N NaOH, water, brine and dried over MgSO4. Filtration and concentration afforded a crude product which was purified on silica gel column with hexanes/ethyl acetate (10/1) as eluant, the product was collected to yield after evaporation to dryness 0.90 g (65.2%). A light yellow solid; 1H-NMR (CDCl3): 67 ppm 7.20-7.60 (m, ArH, 10H), 6.6 (d, ArH, 2H). The reaction mixture was cooled down to room temperature The reaction mixture was extracted several times with chloroform The combined organic phases were washed with 1N NaOH, water, brine dried over MgSO4 Filtration and concentration

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 21.2 g (0.2 mol) of benzaldehyde and 100 ml of absolute dimethylformamide is added dropwise in the course of 1/2 hour to a mixture of 9.8 g (0.2 mol) of NaCN and 100 ml of absolute dimethylformamide in a manner analogous to Example 3. Stirring is continued for 21/2 hours at 35° C. A solution of 26.6 g (0.15 mol) of dimethyl-β-benzoyl-ethylamine and 100 ml of absolute dimethylformamide is then slowly added dropwise in the course of 2 hours. Stirring is continued for 2 hours at the same temperature and water is then added to the reaction mixture in three times its quantity. The reaction product precipitates immediately. After cooling in an ice bath, the precipitated product is suction filtered and thoroughly washed with water. 34.3 g of crude product are isolated. 21.6 g (60.5% of the theory) of dibenzoyl ethane are isolated by recrystallisation from ethanol; m.p. 143° C. 2 hours at 35° C Stirring is then added to the reaction mixture in three times its quantity The reaction product precipitates immediately After cooling in an ice bath the precipitated product is suction filtered thoroughly washed with water 34.3 g of crude product are isolated

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 21.2 g (0.2 mol) of benzaldehyde and 100 ml of absolute dimethylformamide is added dropwise in the course of 1/2 hour to a mixture of 9.8 g (0.2 mol) of NaCN and 100 ml of absolute dimethylformamide in a manner analogous to Example 3. Stirring is continued for 21/2 hours at 35° C. A solution of 26.6 g (0.15 mol) of dimethyl-β-benzoyl-ethylamine and 100 ml of absolute dimethylformamide is then slowly added dropwise in the course of 2 hours. Stirring is continued for 2 hours at the same temperature and water is then added to the reaction mixture in three times its quantity. The reaction product precipitates immediately. After cooling in an ice bath, the precipitated product is suction filtered and thoroughly washed with water. 34.3 g of crude product are isolated. 21.6 g (60.5% of the theory) of dibenzoyl ethane are isolated by recrystallisation from ethanol; m.p. 143° C. 2 hours at 35° C Stirring is then added to the reaction mixture in three times its quantity The reaction product precipitates immediately After cooling in an ice bath the precipitated product is suction filtered thoroughly washed with water 34.3 g of crude product are isolated

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a three-neck flask in N2 atmosphere free of water and oxygen were successively added 0.066 mol potassium tert-butoxide and 150 mlTHF. Then to the resulting mixture was slowly added dropwise 0.06 mol dibenzoylmethane with stirring while cooling the mixture with ice-bath. The reaction was allowed to continue at room temperature for 1 hour, then 0.07 mol iodomethane was added dropwise at room temperature. Next, the reaction was allowed to continue at room temperature for further 48 hours. After the reaction was finished, the solvent was removed by distillation. To the solid mixture was added saturated saline until the solid mixture was just completely dissolved. The solution was extracted with suitable amount of anhydrous ethyl ether for three times. The organic phase was combined and dried over anhydrous sodium sulfate. The solvent was removed to give 12 g product. while cooling the mixture with ice-bath to continue at room temperature for further 48 hours the solvent was removed by distillation To the solid mixture was added saturated saline until the solid mixture was just completely dissolved The solution was extracted with suitable amount of anhydrous ethyl ether for three times dried over anhydrous sodium sulfate The solvent was removed

反応条件: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Dibenzoylethane (1.50 g, 6.30 mmol) and ammonium acetate (2.00 g, 25.2 mmol) were mixed together and the mixture was heated to 100° C. for 4 hours. The reaction mixture was cooled down to room temperature, diluted with 30 ml of water and basified with 1N NaOH until pH 14. The reaction mixture was extracted several times with chloroform. The combined organic phases were washed with 1N NaOH, water, brine and dried over MgSO4. Filtration and concentration afforded a crude product which was purified on silica gel column with hexanes/ethyl acetate (10/1) as eluant, the product was collected to yield after evaporation to dryness 0.90 g (65.2%). A light yellow solid; 1H-NMR (CDCl3): 67 ppm 7.20-7.60 (m, ArH, 10H), 6.6 (d, ArH, 2H). The reaction mixture was cooled down to room temperature The reaction mixture was extracted several times with chloroform The combined organic phases were washed with 1N NaOH, water, brine dried over MgSO4 Filtration and concentration

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a three-neck flask in N2 atmosphere free of water and oxygen were successively added 0.066 mol potassium tert-butoxide and 150 mlTHF. Then to the resulting mixture was slowly added dropwise 0.06 mol dibenzoylmethane with stirring while cooling the mixture with ice-bath. The reaction was allowed to continue at room temperature for 1 hour, then 0.07 mol iodomethane was added dropwise at room temperature. Next, the reaction was allowed to continue at room temperature for further 48 hours. After the reaction was finished, the solvent was removed by distillation. To the solid mixture was added saturated saline until the solid mixture was just completely dissolved. The solution was extracted with suitable amount of anhydrous ethyl ether for three times. The organic phase was combined and dried over anhydrous sodium sulfate. The solvent was removed to give 12 g product. while cooling the mixture with ice-bath to continue at room temperature for further 48 hours the solvent was removed by distillation To the solid mixture was added saturated saline until the solid mixture was just completely dissolved The solution was extracted with suitable amount of anhydrous ethyl ether for three times dried over anhydrous sodium sulfate The solvent was removed

反応条件: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Dibenzoylethane (1.50 g, 6.30 mmol) and ammonium acetate (2.00 g, 25.2 mmol) were mixed together and the mixture was heated to 100° C. for 4 hours. The reaction mixture was cooled down to room temperature, diluted with 30 ml of water and basified with 1N NaOH until pH 14. The reaction mixture was extracted several times with chloroform. The combined organic phases were washed with 1N NaOH, water, brine and dried over MgSO4. Filtration and concentration afforded a crude product which was purified on silica gel column with hexanes/ethyl acetate (10/1) as eluant, the product was collected to yield after evaporation to dryness 0.90 g (65.2%). A light yellow solid; 1H-NMR (CDCl3): 67 ppm 7.20-7.60 (m, ArH, 10H), 6.6 (d, ArH, 2H). The reaction mixture was cooled down to room temperature The reaction mixture was extracted several times with chloroform The combined organic phases were washed with 1N NaOH, water, brine dried over MgSO4 Filtration and concentration

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of dibenzoylethane (5 g, 21.0 mmol) and t-butyl carbazate (3.98 g, 30.1 mmol) in EtOH (170 mL) and AcOH (21 mL) was heated to reflux under Ar for 4.5 h, cooled to rt and diluted with water (400 mL). The resulting suspension was stirred under Ar at rt for 3 h, and then allowed to settle overnight at rt. The solid was filtered, washed with small portions of water and dried in vacuo to afford (2,5-Diphenyl-pyrrol-1-yl)-carbamic acid tert-butyl ester (6.72 g, 96%) as a white solid: 1H NMR (CDCl3, chemical shifts in ppm relative to TMS): 1.14 (s, 3H), 1.38 (s, 6H), 6.35 (s, 2H), 6.84 (bs, 2H), 7.29-7.53 (m, 10H). to reflux under Ar for 4.5 h to settle overnight at rt The solid was filtered washed with small portions of water dried in vacuo

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 21.2 g (0.2 mol) of benzaldehyde and 100 ml of absolute dimethylformamide is added dropwise in the course of 1/2 hour to a mixture of 9.8 g (0.2 mol) of NaCN and 100 ml of absolute dimethylformamide in a manner analogous to Example 3. Stirring is continued for 21/2 hours at 35° C. A solution of 26.6 g (0.15 mol) of dimethyl-β-benzoyl-ethylamine and 100 ml of absolute dimethylformamide is then slowly added dropwise in the course of 2 hours. Stirring is continued for 2 hours at the same temperature and water is then added to the reaction mixture in three times its quantity. The reaction product precipitates immediately. After cooling in an ice bath, the precipitated product is suction filtered and thoroughly washed with water. 34.3 g of crude product are isolated. 21.6 g (60.5% of the theory) of dibenzoyl ethane are isolated by recrystallisation from ethanol; m.p. 143° C. 2 hours at 35° C Stirring is then added to the reaction mixture in three times its quantity The reaction product precipitates immediately After cooling in an ice bath the precipitated product is suction filtered thoroughly washed with water 34.3 g of crude product are isolated

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a three-neck flask in N2 atmosphere free of water and oxygen were successively added 0.066 mol potassium tert-butoxide and 150 mlTHF. Then to the resulting mixture was slowly added dropwise 0.06 mol dibenzoylmethane with stirring while cooling the mixture with ice-bath. The reaction was allowed to continue at room temperature for 1 hour, then 0.07 mol iodomethane was added dropwise at room temperature. Next, the reaction was allowed to continue at room temperature for further 48 hours. After the reaction was finished, the solvent was removed by distillation. To the solid mixture was added saturated saline until the solid mixture was just completely dissolved. The solution was extracted with suitable amount of anhydrous ethyl ether for three times. The organic phase was combined and dried over anhydrous sodium sulfate. The solvent was removed to give 12 g product. while cooling the mixture with ice-bath to continue at room temperature for further 48 hours the solvent was removed by distillation To the solid mixture was added saturated saline until the solid mixture was just completely dissolved The solution was extracted with suitable amount of anhydrous ethyl ether for three times dried over anhydrous sodium sulfate The solvent was removed