phenylthiourea

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: The phenylthiourea (6.00 g, 32.16 mmol) was dissolved in CHCl3 (150 mL) and cooled to 0° C. with an ice bath. To this mixture was added a solution of Br2 (1.6 mL, 32.2 mmol) in CHCl3 (100 mL) dropwise over 30 min. After the addition, the mixture was stirred at 0° C. for 1 h, then allowed to warm to rt. the reaction was refluxed for 3 h to 4 h than allowed to cool to room temperature. The organic solvent was removed and the residue was washed with sulfurous acid. The residue was then neutralized with liquid ammonia. The solid was filtered off, washed with watyer and recrystallized from EtOH. After the addition to warm to rt the reaction was refluxed for 3 h to 4 h to cool to room temperature The organic solvent was removed the residue was washed with sulfurous acid The solid was filtered off washed with watyer recrystallized from EtOH

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

実験手順: 3.8 g of 5-(bromoacetyl)-2,3-dihydroxybenzonitrile dissolved in 25 ml of N,N-dimethylformamide are treated with N-phenylthiourea and stirred at 100° for 5 hours. Thereafter, the solvent is removed by evaporation. The residue is treated with 200 ml of 1N sodium carbonate solution and extracted three times with 100 ml of methylene chloride each time. The combined organic phases are washed with water, dried over sodium sulfate and evaporated. The residue is chromatographed on 30 g of silica gel with ethyl acetate. The thus-obtained crude product is treated with 40 ml of 1N hydrochloric acid, evaporated and crystallized from acetone. There is obtained 5-(2-anilino-4-thiazolyl)-2,3-dihydroxybenzo- nitrile hydrochloride of m.p. 245°-247°. Thereafter, the solvent is removed by evaporation The residue is treated with 200 ml of 1N sodium carbonate solution extracted three times with 100 ml of methylene chloride each time The combined organic phases are washed with water dried over sodium sulfate evaporated The residue is chromatographed on 30 g of silica gel with ethyl acetate The thus-obtained crude product evaporated crystallized from acetone

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

実験手順: 3.8 g of 5-(bromoacetyl)-2,3-dihydroxybenzonitrile dissolved in 25 ml of N,N-dimethylformamide are treated with N-phenylthiourea and stirred at 100° for 5 hours. Thereafter, the solvent is removed by evaporation. The residue is treated with 200 ml of 1N sodium carbonate solution and extracted three times with 100 ml of methylene chloride each time. The combined organic phases are washed with water, dried over sodium sulfate and evaporated. The residue is chromatographed on 30 g of silica gel with ethyl acetate. The thus-obtained crude product is treated with 40 ml of 1N hydrochloric acid, evaporated and crystallized from acetone. There is obtained 5-(2-anilino-4-thiazolyl)-2,3-dihydroxybenzo- nitrile hydrochloride of m.p. 245°-247°. Thereafter, the solvent is removed by evaporation The residue is treated with 200 ml of 1N sodium carbonate solution extracted three times with 100 ml of methylene chloride each time The combined organic phases are washed with water dried over sodium sulfate evaporated The residue is chromatographed on 30 g of silica gel with ethyl acetate The thus-obtained crude product evaporated crystallized from acetone

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

実験手順: 6.1 G. PHENYLTHIOUREA AND 4.3 G. DIMETHYL FORMAMIDE DIMETHYLACETAL WERE SUSPENDED IN 100 ML. OF BENZENE WITH ~ 100 MG OF P-TOLUENE SULFURIC ACID AND THE MIXTURE DISTILLED THROUGH A 6 PLATE DISTILLING COLUMN. The methanol-benzene azeotrope, bp 57°C, came off rapidly. After the bp rose to 80°C, the mixture was cooled and the product crystallized from the benzene. The yield was 6.3 g of solid m.p. 131°-138°C which was triturated with ether to give 6 g m.p. 139°-143°C. OF BENZENE WITH ~ 100 MG OF P-TOLUENE SULFURIC ACID AND THE MIXTURE DISTILLED THROUGH A 6 PLATE DISTILLING COLUMN rose to 80°C the mixture was cooled the product crystallized from the benzene The yield was 6.3 g of solid m.p. 131°-138°C which was triturated with ether to give 6 g m.p. 139°-143°C.

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

実験手順: 6.1 G. PHENYLTHIOUREA AND 4.3 G. DIMETHYL FORMAMIDE DIMETHYLACETAL WERE SUSPENDED IN 100 ML. OF BENZENE WITH ~ 100 MG OF P-TOLUENE SULFURIC ACID AND THE MIXTURE DISTILLED THROUGH A 6 PLATE DISTILLING COLUMN. The methanol-benzene azeotrope, bp 57°C, came off rapidly. After the bp rose to 80°C, the mixture was cooled and the product crystallized from the benzene. The yield was 6.3 g of solid m.p. 131°-138°C which was triturated with ether to give 6 g m.p. 139°-143°C. OF BENZENE WITH ~ 100 MG OF P-TOLUENE SULFURIC ACID AND THE MIXTURE DISTILLED THROUGH A 6 PLATE DISTILLING COLUMN rose to 80°C the mixture was cooled the product crystallized from the benzene The yield was 6.3 g of solid m.p. 131°-138°C which was triturated with ether to give 6 g m.p. 139°-143°C.

反応条件: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of ethyl 2-bromo-3-(3-cyanophenyl)-3-oxopropionate (0.60 g, 2.03 mmol) in 20 mL of absolute ethanol was added N-phenylthiourea (0.31 g, 2.03 mmol). The resulting mixture was stirred at 80° C. for 3 h. The reaction was allowed to cool and the solvent was evaporated in vacuo. The residue was taken up in ethyl acetate, washed with saturated aq NaHCO3 and brine, dried (MgSO4) and concentrated in vacuo to yield a solid. Trituration with hexanes/ethyl ether left the title compound as an off-white solid (0.35 g, 49%). MS(NH3—CI) 350 (M+H)+. to cool the solvent was evaporated in vacuo washed with saturated aq NaHCO3 and brine dried (MgSO4) concentrated in vacuo to yield a solid

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

実験手順: To 70 ml of ethanol, 10.7 g (70 mmol) of phenylthiourea and 11.6 g (70 mmol) of ethyl 2-chloro-3-oxobutanate were dissolved, followed by heating under refluxing for 8 hours. The reaction liquid was concentrated and dissolved in ethyl acetate and the organic layer was washed with an aqueous solution of sodium carbonate, water and a saturated saline solution in this order, followed by drying over anhydrous magnesium sulfate and concentrating under reduced pressure. Solid obtained was washed with diisopropyl ether to obtain 16.8 g (yield: 91%) of ethyl 4-methyl-2-(N-phenylamino)thiazole-5-carboxylate. (2) To 50 ml of ethanol, 12.8 g (49 mmol) of ethyl-4-methyl-2-(N-phenylamino)thiazole-5-carboxylate was dissolved, followed by adding 24 g (150 mmol) of 25% sodium hydroxide aqueous solution, and stirring at 80° C. for 15 hours. The reaction liquid was poured into ice water, and acetic acid was added to make acidic. Crystal precipitated was filtered, washed with water and a mixed solvent of hexane/ethyl acetate and dried to obtain 5.50 g (yield: 48%) of 4-methyl-2-(N-phenylamino)thiazole-5-carboxylic acid. by heating under refluxing for 8 hours The reaction liquid was concentrated dissolved in ethyl acetate the organic layer was washed with an aqueous solution of sodium carbonate, water by drying over anhydrous magnesium sulfate concentrating under reduced pressure Solid obtained was washed with diisopropyl ether

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

実験手順: Synthesis was performed from N-phenylthiourea and ethyl 2-bromo-3-methylbutanoate according to Method C. Synthesis

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

実験手順: Synthesis was performed from N-phenylthiourea and ethyl 2-bromo-3-methylbutanoate according to Method C. Synthesis

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

実験手順: 3.8 g of 5-(bromoacetyl)-2,3-dihydroxybenzonitrile dissolved in 25 ml of N,N-dimethylformamide are treated with N-phenylthiourea and stirred at 100° for 5 hours. Thereafter, the solvent is removed by evaporation. The residue is treated with 200 ml of 1N sodium carbonate solution and extracted three times with 100 ml of methylene chloride each time. The combined organic phases are washed with water, dried over sodium sulfate and evaporated. The residue is chromatographed on 30 g of silica gel with ethyl acetate. The thus-obtained crude product is treated with 40 ml of 1N hydrochloric acid, evaporated and crystallized from acetone. There is obtained 5-(2-anilino-4-thiazolyl)-2,3-dihydroxybenzo- nitrile hydrochloride of m.p. 245°-247°. Thereafter, the solvent is removed by evaporation The residue is treated with 200 ml of 1N sodium carbonate solution extracted three times with 100 ml of methylene chloride each time The combined organic phases are washed with water dried over sodium sulfate evaporated The residue is chromatographed on 30 g of silica gel with ethyl acetate The thus-obtained crude product evaporated crystallized from acetone

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

実験手順: 3.8 g of 5-(bromoacetyl)-2,3-dihydroxybenzonitrile dissolved in 25 ml of N,N-dimethylformamide are treated with N-phenylthiourea and stirred at 100° for 5 hours. Thereafter, the solvent is removed by evaporation. The residue is treated with 200 ml of 1N sodium carbonate solution and extracted three times with 100 ml of methylene chloride each time. The combined organic phases are washed with water, dried over sodium sulfate and evaporated. The residue is chromatographed on 30 g of silica gel with ethyl acetate. The thus-obtained crude product is treated with 40 ml of 1N hydrochloric acid, evaporated and crystallized from acetone. There is obtained 5-(2-anilino-4-thiazolyl)-2,3-dihydroxybenzo- nitrile hydrochloride of m.p. 245°-247°. Thereafter, the solvent is removed by evaporation The residue is treated with 200 ml of 1N sodium carbonate solution extracted three times with 100 ml of methylene chloride each time The combined organic phases are washed with water dried over sodium sulfate evaporated The residue is chromatographed on 30 g of silica gel with ethyl acetate The thus-obtained crude product evaporated crystallized from acetone