5-aminobenzene-1,3-diol

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: To a 200-mL, 2-necked flask was added 31.5 g (250 mmol) of 1,3,5-trihydroxybenzene. After replaced with argon, 25 mL of 28% ammonia and water were added thereto, and the resulting mixture was stirred in a water bath for 18 hours. Water was removed away in vacuo and 50 mL of isopropanol was added. The obtained mixture was ice-cooled for 2 hours to precipitate a solid and the precipitated solid was obtained by filtration. The solid was washed with isopropanol and then vacuum-dried, whereby a desired product was obtained (Quantity: 11.4 g, 91.3 mmol, Yield: 37%). were added Water was removed away in vacuo and 50 mL of isopropanol was added cooled for 2 hours to precipitate a solid the precipitated solid was obtained by filtration The solid was washed with isopropanol vacuum-dried

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

実験手順: To a mixture of 5-aminobenzene-1,3-diol (0.60 g, 3.7 mmole) and sodium hydrogencarbonate (1.4 g, 16 mmole) in THF/water (15 mL, 1:1 v/v) was added dropwise benzyl chloroformate 1.6 mL, 11 mmole). After 3 h at rt, THF was removed under vacuum and the remaining aqueous layer was extracted with ethyl acetate. Purification by column chromatography over silica gel provided benzyl N-(3,5-dihydroxyphenyl)carbamate. 1H NMR (CD3OD): δ 7.42-7.25 (m, 5H), 6.46 (d, 2H, J=2.4 Hz), 5.97-5.94 (m, 1H), 5.14 (s, 2H). THF was removed under vacuum the remaining aqueous layer was extracted with ethyl acetate Purification by column chromatography over silica gel

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

実験手順: To a mixture of 5-aminobenzene-1,3-diol (0.60 g, 3.7 mmole) and sodium hydrogencarbonate (1.4 g, 16 mmole) in THF/water (15 mL, 1:1 v/v) was added dropwise benzyl chloroformate 1.6 mL, 11 mmole). After 3 h at rt, THF was removed under vacuum and the remaining aqueous layer was extracted with ethyl acetate. Purification by column chromatograpy over silica gel provided benzyl N-(3,5-dihydroxyphenyl)carbamate. 1H NMR (CD3OD): δ 7.42–7.25 (m, 5H), 6.46 (d, 2H, J=2.4 Hz), 5.97–5.94 (m, 1H), 5.14 (s, 2H). THF was removed under vacuum the remaining aqueous layer was extracted with ethyl acetate Purification by column chromatograpy over silica gel

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

実験手順: To a mixture of 5-aminobenzene-1,3-diol (0.60 g, 3.7 mmole) and sodium hydrogencarbonate (1.4 g, 16 mmole) in THF/water (15 mL, 1:1 v/v) was added dropwise benzyl chloroformate 1.6 mL, 11 mmole). After 3 h at rt, THF was removed under vacuum and the remaining aqueous layer was extracted with ethyl acetate. Purification by column chromatograpy over silica gel provided benzyl N-(3,5-dihydroxyphenyl)carbamate. 1H NMR (CD3OD): δ 7.42–7.25 (m, 5H), 6.46 (d, 2H, J=2.4 Hz), 5.97–5.94 (m, 1H), 5.14 (s, 2H). THF was removed under vacuum the remaining aqueous layer was extracted with ethyl acetate Purification by column chromatograpy over silica gel

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

実験手順: To a mixture of 5-aminobenzene-1,3-diol (0.60 g, 3.7 mmole) and sodium hydrogencarbonate (1.4 g, 16 mmole) in THF/water (15 mL, 1:1 v/v) was added dropwise benzyl chloroformate 1.6 mL, 11 mmole). After 3 h at rt, THF was removed under vacuum and the remaining aqueous layer was extracted with ethyl acetate. Purification by column chromatography over silica gel provided benzyl N-(3,5-dihydroxyphenyl)carbamate. 1H NMR (CD3OD): δ 7.42-7.25 (m, 5H), 6.46 (d, 2H, J=2.4 Hz), 5.97-5.94 (m, 1H), 5.14 (s, 2H). THF was removed under vacuum the remaining aqueous layer was extracted with ethyl acetate Purification by column chromatography over silica gel

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

実験手順: To a mixture of 5-aminobenzene-1,3-diol (0.60 g, 3.7 mmole) and sodium hydrogencarbonate (1.4 g, 16 mmole) in THF/water (15 mL, 1:1 v/v) was added dropwise benzyl chloroformate 1.6 mL, 11 mmole). After 3 h at rt, THF was removed under vacuum and the remaining aqueous layer was extracted with ethyl acetate. Purification by column chromatograpy over silica gel provided benzyl N-(3,5-dihydroxyphenyl)carbamate. 1H NMR (CD3OD): δ 7.42-7.25 (m, 5H), 6.46 (d, 2H, J=2.4 Hz), 5.97-5.94 (m, 1H), 5.14 (s, 2H). THF was removed under vacuum the remaining aqueous layer was extracted with ethyl acetate Purification by column chromatograpy over silica gel

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

実験手順: A mixture of 3,5-dihydroxyaniline (2.0 g), 2-ethoxy-1,1-bis(ethoxycarbonyl)ethene (3.0 g) and ethanol (10 ml) was left to stand at room temperature for 2 days. The resulting solid was filtered off, dissolved in dimethylsulphoxide (20 ml) and then treated with water (100 ml). The resulting solid was washed with water, to give 1,1-bis(ethoxycarbonyl)-2-(3,5-dihydroxyphenylamino)ethene (3.2 g), m.p. 190°-192° C. was left The resulting solid was filtered off dissolved in dimethylsulphoxide (20 ml) treated with water (100 ml) The resulting solid was washed with water

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

実験手順: A mixture of 3,5-dihydroxyaniline (2.0 g), 2-ethoxy-1,1-bis(ethoxycarbonyl)ethene (3.0 g) and ethanol (10 ml) was left to stand at room temperature for 2 days. The resulting solid was filtered off, dissolved in dimethylsulphoxide (20 ml) and then treated with water (100 ml). The resulting solid was washed with water, to give 1,1-bis(ethoxycarbonyl)-2-(3,5-dihydroxyphenylamino)ethene (3.2 g), m.p. 190°-192° C. was left The resulting solid was filtered off dissolved in dimethylsulphoxide (20 ml) treated with water (100 ml) The resulting solid was washed with water

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

実験手順: To a mixture of 5-aminobenzene-1,3-diol (0.60 g, 3.7 mmole) and sodium hydrogencarbonate (1.4 g, 16 mmole) in THF/water (15 mL, 1:1 v/v) was added dropwise benzyl chloroformate 1.6 mL, 11 mmole). After 3 h at rt, THF was removed under vacuum and the remaining aqueous layer was extracted with ethyl acetate. Purification by column chromatography over silica gel provided benzyl N-(3,5-dihydroxyphenyl)carbamate. 1H NMR (CD3OD): δ 7.42-7.25 (m, 5H), 6.46 (d, 2H, J=2.4 Hz), 5.97-5.94 (m, 1H), 5.14 (s, 2H). THF was removed under vacuum the remaining aqueous layer was extracted with ethyl acetate Purification by column chromatography over silica gel

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

実験手順: To a mixture of 5-aminobenzene-1,3-diol (0.60 g, 3.7 mmole) and sodium hydrogencarbonate (1.4 g, 16 mmole) in THF/water (15 mL, 1:1 v/v) was added dropwise benzyl chloroformate 1.6 mL, 11 mmole). After 3 h at rt, THF was removed under vacuum and the remaining aqueous layer was extracted with ethyl acetate. Purification by column chromatograpy over silica gel provided benzyl N-(3,5-dihydroxyphenyl)carbamate. 1H NMR (CD3OD): δ 7.42-7.25 (m, 5H), 6.46 (d, 2H, J=2.4 Hz), 5.97-5.94 (m, 1H), 5.14 (s, 2H). THF was removed under vacuum the remaining aqueous layer was extracted with ethyl acetate Purification by column chromatograpy over silica gel

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

実験手順: To a 200-mL, 2-necked flask was added 31.5 g (250 mmol) of 1,3,5-trihydroxybenzene. After replaced with argon, 25 mL of 28% ammonia and water were added thereto, and the resulting mixture was stirred in a water bath for 18 hours. Water was removed away in vacuo and 50 mL of isopropanol was added. The obtained mixture was ice-cooled for 2 hours to precipitate a solid and the precipitated solid was obtained by filtration. The solid was washed with isopropanol and then vacuum-dried, whereby a desired product was obtained (Quantity: 11.4 g, 91.3 mmol, Yield: 37%). were added Water was removed away in vacuo and 50 mL of isopropanol was added cooled for 2 hours to precipitate a solid the precipitated solid was obtained by filtration The solid was washed with isopropanol vacuum-dried