ethyl 2-(2-aminophenyl)acetate

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: A solution of ethyl 2-aminophenylacetate (5.60 g, 0.031 mole) and diisopropylethylamine (7.08ml, 0.042 mole) in dry THF (75ml) was treated with 5 chlorovaleryl chloride (4.00 ml, 0.031 mole) and left to stir for 1 h. The reaction mixture was concentrated in vacuo and the residue dissolved in ethyl acetate (200 ml) and washed with 1M HCl (100 ml), dried (Na2SO4) and concentrated in vacuo to afford a beige solid. This was washed with n-pentane/ether (1:1) and dried to afford the title compound as a light beige solid (8.1 g, 91%). left The reaction mixture was concentrated in vacuo the residue dissolved in ethyl acetate (200 ml) washed with 1M HCl (100 ml) dried (Na2SO4) concentrated in vacuo to afford a beige solid This was washed with n-pentane/ether (1:1) dried

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

実験手順: A solution of ethyl 2-aminophenylacetate (5.60 g, 0.031 mole) and diisopropylethylamine (7.08ml, 0.042 mole) in dry THF (75ml) was treated with 5 chlorovaleryl chloride (4.00 ml, 0.031 mole) and left to stir for 1 h. The reaction mixture was concentrated in vacuo and the residue dissolved in ethyl acetate (200 ml) and washed with 1M HCl (100 ml), dried (Na2SO4) and concentrated in vacuo to afford a beige solid. This was washed with n-pentane/ether (1:1) and dried to afford the title compound as a light beige solid (8.1 g, 91%). left The reaction mixture was concentrated in vacuo the residue dissolved in ethyl acetate (200 ml) washed with 1M HCl (100 ml) dried (Na2SO4) concentrated in vacuo to afford a beige solid This was washed with n-pentane/ether (1:1) dried

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

実験手順: A solution of ethyl 2-nitrophenylacetate (13.6 g, 0.065 mole) in ethanol (150 ml) was hydrogenated over 10% Pd/C catalyst (1 g) at room temperature and pressure for 18 hours. The reaction mixture was filtered through keiselguhr and concentrated in vacuo to afford the title compound as a clear oil, which solidified on standing (10.8 g, 93%). The reaction mixture was filtered through keiselguhr concentrated in vacuo

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: In 15% hydrogen chloride-ethanol, m- or o-nitrophenylacetic acid was ethyl-esterified and the resulting ethyl ester was hydrogenated with palladium catalyst in ethanol to give m- or o-aminophenylacetic acid ethyl ester.

反応条件: temp:11.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A suspension of NaH (60%, 8.0 g, 0.2 mole) in dry THF (40 ml) was prepared, and a mixture of diethyl malonate (32.0 g, 0.2 mole) and THF (50 ml) was slowly added into the suspension to provide a mixture. The mixture was cooled to 10 to 12° C., and a solution of ClCH2COCl (11.3 g, 0.1 mole) in THF (100 ml) was added dropwise thereinto. Then, the reaction solution was kept at 10 to 12° C. for 1 hour, warmed by warm water (40 to 45° C.) for about 1 hour, and then cooled to 10 to 12° C. A solution of the ethyl 2-(2′-aminophenyl)acetate (0.1 mole) prepared in step (a) in THF (50 ml) was added dropwise into the above reaction solution, and then stirred at room temperature for 1 hour and heated on a water bath for several hours. The obtained reaction solution was examined by TLC to determine whether the reaction was complete. Then, the reaction solution was vacuum concentrated to remove most of the THF. Ice water (600 ml) was poured into the vacuum concentration flask. Then, the reaction solution in the vacuum concentration flask was extracted by CHCl3 several times. The obtained extract was washed by water and dried by dry MgSO4, and vacuum concentrated to remove CHCl3. The concentrated liquid was placed at room temperature for crystallization. The crystal was collected and recrystallized by ethanol to obtain 13.66 g of a white acicular crystal. The productivity was 41% and the melting point of the crystal was 91.2° C. The data of the optical spectrum was as follows: MS (m/z, %): 332.8 (M+, 35.85), 333.8 (M++1, 7.73); IR (KBr disc) cm−1: 3121.86 (—NH—), 1737.28 (C8′═O), 1698.3 (C4=O), 1664.19 (C3-CO-OEt); UVλmax nm (MeOH) (log ε): 291.0 (3.825); 1H-NMR (200 MHz, DMSO-d6) δ: 1.176 (3H, t, J=7 Hz, H-10′), 1.23 (3H, t, 166J=7 Hz, H-2″), 3.763 (2H, s, H-7′), 4.049 (2H, q, J=7 Hz, H-9′), 4.192 (2H, q, J=7 Hz, H-2″), 4.573 (2H, s, H-5), 7.321˜7.453 (4H, m, H-3′, H-4′, H-5′, H-6′), 10.115 (1H, s, NH); 13C-NMR (200 MHz, DMSO-d6) δ: 14.09 (C-10′), 14.65 (C-2″), 37.29 (C-7′), 56.30 (C-1″), 60.96 (C-9′), 75.17 (C-5′), 86.93 (C-3), 126.79 (C-6′), 127.64 (C-4′), 128.17 (C-2′), 130.33 (C-3′), 131.44 (C-5′), 134.03 (C-1′), 164.09 (C-2), 170.88 (C-8′), 177.90 (C-3″), 188.98 (C-4). was prepared was slowly added into the suspension to provide a mixture warmed cooled to 10 to 12° C heated on a water bath for several hours The obtained reaction solution concentrated to remove most of the THF Ice water (600 ml) was poured into the vacuum concentration flask Then, the reaction solution in the vacuum concentration flask was extracted by CHCl3 several times The obtained extract was washed by water dried by dry MgSO4, and vacuum concentrated to remove CHCl3 The concentrated liquid was placed at room temperature for crystallization The crystal was collected recrystallized by ethanol to obtain 13.66 g of a white acicular crystal was 91.2° C

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

実験手順: A solution of ethyl 2-aminophenylacetate (5.60 g, 0.031 mole) and diisopropylethylamine (7.08 ml, 0.042 mole) in dry THF (75 ml) was treated with 5 chlorovaleryl chloride (4.00 ml, 0.031 mole) and left to stir for 1 h. The reaction mixture was concentrated in vacuo and the residue dissolved in ethyl acetate (200 ml) and washed with 1M HCl (100 ml), dried (Na2SO4) and concentrated in vacuo to afford a beige solid. This was washed with n-pentane/ether (1:1) and dried to afford the title compound as a light beige solid (8.1 g, 91%). left The reaction mixture was concentrated in vacuo the residue dissolved in ethyl acetate (200 ml) washed with 1M HCl (100 ml) dried (Na2SO4) concentrated in vacuo to afford a beige solid This was washed with n-pentane/ether (1:1) dried

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

実験手順: A solution of ethyl 2-nitrophenylacetate (13.6 g, 0.065 mole) in ethanol (150 ml) was hydrogenated over 10% Pd/C catalyst (1 g) at room temperature and pressure for 18 hours. The reaction mixture was filtered through keiselguhr and concentrated in vacuo to afford the title compound as a clear oil, which solidified on standing (10.8 g, 93%). The reaction mixture was filtered through keiselguhr concentrated 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 ethyl 2-aminophenylacetate (5.60 g, 0.031 mole) and diisopropylethylamine (7.08ml, 0.042 mole) in dry THF (75ml) was treated with 5 chlorovaleryl chloride (4.00 ml, 0.031 mole) and left to stir for 1 h. The reaction mixture was concentrated in vacuo and the residue dissolved in ethyl acetate (200 ml) and washed with 1M HCl (100 ml), dried (Na2SO4) and concentrated in vacuo to afford a beige solid. This was washed with n-pentane/ether (1:1) and dried to afford the title compound as a light beige solid (8.1 g, 91%). left The reaction mixture was concentrated in vacuo the residue dissolved in ethyl acetate (200 ml) washed with 1M HCl (100 ml) dried (Na2SO4) concentrated in vacuo to afford a beige solid This was washed with n-pentane/ether (1:1) dried