methyl 9H-carbazole-4-carboxylate

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

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

実験手順: 0.49 g of 2-bromo-5-cyanopyridine, 2.2 g of caesium carbonate, 0.12 g of 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene and 0.04 g of palladium acetate are successively added to a solution of 0.40 g of 9H-carbazole-4-carboxylic acid methyl ester, obtained according to stage 2 of Example 1, in 30 ml of dioxane under an inert argon atmosphere. The reaction mixture is refluxed for 2 hours, and then cooled, filtered and concentrated under reduced pressure. The residue is purified by silica gel chromatography (15-40 μm), elution being carried out with a mixture of petroleum ether and dichloromethane (60/40 by volume), so as to give 376 mg of 9-(5-cyanopyridin-2-yl)-9H-carbazole-4-carboxylic acid methyl ester in the form of a yellow powder, the characteristics of which are the following: obtained The reaction mixture is refluxed for 2 hours cooled filtered concentrated under reduced pressure The residue is purified by silica gel chromatography (15-40 μm), elution being carried out with a mixture of petroleum ether and dichloromethane (60/40 by volume)

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

実験手順: 0.43 g of 4-bromo-2-fluorobenzonitrile, 2.2 g of caesium carbonate, 0.12 g of 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene and 0.04 g of palladium acetate are added successively to a solution of 0.40 g of 9H-carbazole-4-carboxylic acid methyl ester, obtained according to stage 2 of Example 1, in 30 ml of dioxane under an inert argon atmosphere. The reaction mixture is refluxed for 3 hours, and then cooled, filtered and concentrated under reduced pressure. The residue is purified by silica gel chromatography, elution being carried out with a mixture of heptane and ethyl acetate (96/4 by volume), so to give 496 mg of 9-(4-cyano-3-fluorophenyl)-9H-carbazole-4-carboxylic acid methyl ester, the characteristics of which are the following: obtained The reaction mixture is refluxed for 3 hours cooled filtered concentrated under reduced pressure The residue is purified by silica gel chromatography, elution being carried out with a mixture of heptane and ethyl acetate (96/4 by volume)

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

実験手順: In a 250 ml round-bottomed flask under argon, 391 mg of a suspension of sodium hydride at 60% in petroleum jelly are added at ambient temperature, in 4 stages, in ½ hour, to a solution of 2.0 g of 9H-carbazole-4-carboxylic acid methyl ester obtained according to the preceding stage and of 1.95 g of 2-bromo-4-fluorobenzonitrile in 50 ml of dimethylformamide. The mixture is stirred at ambient temperature for 3 hours. The reaction medium is evaporated to dryness under vacuum and the residue is chromatographed on silica gel (40-63 μm), elution being carried out with a mixture of dichloromethane and cyclohexane (50:50). 3.2 g of 9-(3-bromo-4-cyanophenyl)-9H-carbazole-4-carboxylic acid methyl ester are obtained in the form of a white solid, the characteristics of which are the following: obtained The reaction medium is evaporated to dryness under vacuum the residue is chromatographed on silica gel (40-63 μm), elution being carried out with a mixture of dichloromethane and cyclohexane (50:50)

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

実験手順: A mixture of 52.56 g of methyl indole-4-carboxylate, 51.55 g of 2,5-dimethoxytetrahydrofuran and 28.53 g of p-toluenesulfonic acid monohydrate in 300 ml of methanol was refluxed for 10 hours. Then, following a treatment similar to that of Example 1(1), there was obtained 9.14 g of methyl carbazole-4-carboxylate. was refluxed for 10 hours