tert-butyl N-(3-bromophenyl)carbamate

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:

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

実験手順: To a solution of 128 g (470 mmol) of tert-butyl 3-bromophenylcarbamate in 800 mL of dimethylformamide, 19 g (475 mmol) of sodium hydride (60% in oil) are added portionwise and the reaction medium is stirred until the evolution of gas has ceased. 29.3 mL (470 mmol) of methyl iodide are added dropwise and stirring is continued for 18 hours. The reaction medium is poured into ice-cold water and extracted with ethyl acetate. The organic phase is separated out after settling of the phases, dried over magnesium sulfate and evaporated. 152.5 g (92%) of tert-butyl 3-bromophenyl-N-methylcarbamate are obtained. stirring The reaction medium is poured into ice-cold water extracted with ethyl acetate The organic phase is separated out dried over magnesium sulfate evaporated

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

実験手順: To a solution of 129 g (475 mmol) of tert-butyl (3-bromophenyl)carbamate in 800 mL of dimethylformamide are added portionwise 19 g (475 mmol) of sodium hydride (60% in oil) and the reaction medium is stirred until the evolution of gas has ceased. 29 mL (470 mmol) of methyl iodide are added dropwise and stirring is continued for 18 hours. The reaction medium is poured into ice-cold water and extracted with ethyl acetate. The organic phase is separated out after settling of the phases, dried over magnesium sulfate, filtered and evaporated. 115 g (95%) of tert-butyl (3-bromophenyl)-N-methylcarbamate are obtained. stirring The reaction medium is poured into ice-cold water extracted with ethyl acetate The organic phase is separated out dried over magnesium sulfate filtered evaporated

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

実験手順: A tetrahydrofuran (30 ml) solution of N-methyl-N-methyloxy-2-amino-5-chlorobenzamide (4.3 g) and N-tert-butoxycarbonyl-3-bromoaniline (3.79 g) was cooled to −78° C. To the solution was gradually added dropwise a hexane solution of n-butyl lithium (1.6 mol/L) (42 ml). To the mixture were added water (100 ml) and acetic acid ethyl ester (300 ml). The organic layer was washed with water and dried over anhydrous MgSO4. The _solvent was then distilled off, and the residue was purified by means of a silica gel column chromatography to give 2-amino-3′-tert-butoxycarbonylamino-5-chlorobenzophenone (0.7 g) as a yellow oily product. The organic layer was washed with water dried over anhydrous MgSO4 The _solvent was then distilled off the residue was purified by means of a silica gel column chromatography

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

実験手順: A tetrahydrofuran (30 ml) solution of N-methyl-N-methyloxy-2-amino-5-chlorobenzamide (4.3 g) and N-tert-butoxycarbonyl-3-bromoaniline (3.79 g) was cooled to −78° C. To the solution was gradually added dropwise a hexane solution of n-butyl lithium (1.6 mol/L) (42 ml). To the mixture were added water (100 ml) and acetic acid ethyl ester (300 ml). The organic layer was washed with water and dried over anhydrous MgSO4. The _solvent was then distilled off, and the residue was purified by means of a silica gel column chromatography to give 2-amino-3′-tert-butoxycarbonylamino-5-chlorobenzophenone (0.7 g) as a yellow oily product. The organic layer was washed with water dried over anhydrous MgSO4 The _solvent was then distilled off the residue was purified by means of a silica gel column chromatography

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

実験手順: To a solution of 114 g (447 mmol) of tert-butyl (3-bromophenyl)carbamate in 800 ml of DMF are added portionwise 19 g (475 mmol) of sodium hydride (60% in oil) and the reaction medium is stirred until the evolution of gas has ceased. 29.3 ml (470 mmol) of methyl iodide are added dropwise and stirring is continued for 18 hours. The reaction medium is poured into ice-cold water and extracted with ethyl acetate. The organic phase is separated out after settling of the phases, dried over magnesium sulfate and evaporated. 115 g of tert-butyl (3-bromophenyl)-N-methylcarbamate are obtained in a yield of 95%. stirring The reaction medium is poured into ice-cold water extracted with ethyl acetate The organic phase is separated out dried over magnesium sulfate evaporated

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

実験手順: To a solution of 114 g (447 mmol) of tert-butyl (3-bromophenyl)carbamate in 800 ml of DMF are added portionwise 19 g (475 mmol) of sodium hydride (60% in oil) and the reaction medium is stirred until the evolution of gas has ceased. 29.3 ml (470 mmol) of methyl iodide are added dropwise and stirring is continued for 18 hours. The reaction medium is poured into ice-cold water and extracted with ethyl acetate. The organic phase is separated out after settling of the phases, dried over magnesium sulfate and evaporated. 115 g of tert-butyl (3-bromophenyl)-N-methylcarbamate are obtained in a yield of 95%. stirring The reaction medium is poured into ice-cold water extracted with ethyl acetate The organic phase is separated out dried over magnesium sulfate evaporated

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

実験手順: To a solution of 114 g (447 mmol) of tert-butyl (3-bromophenyl)carbamate in 800 ml of DMF are added portionwise 19 g (475 mmol) of sodium hydride (60% in oil) and the reaction medium is stirred until the evolution of gas has ceased. 29.3 ml (470 mmol) of methyl iodide are added dropwise and stirring is continued for 18 hours. The reaction medium is poured into ice-water and extracted with ethyl acetate. The organic phase is separated out by settling of the phases, dried over magnesium sulfate and evaporated. 115 g of tert-butyl (3-bromophenyl)-N-methylcarbamate are obtained in a yield of 95%. stirring extracted with ethyl acetate The organic phase is separated out dried over magnesium sulfate evaporated

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

実験手順: To a solution of 114 g (447 mmol) of tert-butyl (3-bromophenyl)carbamate in 800 ml of DMF are added portionwise 19 g (475 mmol) of sodium hydride (60% in oil) and the reaction medium is stirred until the evolution of gas has ceased. 29.3 ml (470 mmol) of methyl iodide are added dropwise and stirring is continued for 18 hours. The reaction medium is poured into ice-water and extracted with ethyl acetate. The organic phase is separated out by settling of the phases, dried over magnesium sulfate and evaporated. 115 g of tert-butyl (3-bromophenyl)-N-methylcarbamate are obtained in a yield of 95%. stirring extracted with ethyl acetate The organic phase is separated out dried over magnesium sulfate evaporated

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

実験手順: A mixture of 4-cyanobenzeneboronic acid (14.7 g, 0.10 mol), 3-bromo-phenyl-carbamic acid tert-butyl ester (27.2 g, 0.10 mol), Pd(Ph3P)4 (11.6 g, 0.01 mol) and K2CO3 (21 g, 0.15 mol) in DMF/H2O (1:1, 350 mL) was stirred under argon at 80° C. overnight. The DMF was evaporated under reduced pressure, and the residue was dissolved in EtOAc (200 mL). The mixture was washed with water and brine, dried over Na2SO4, and concentrated to dryness. The residue was purified by column chromatography (petroleum ether/EtOAc 50:1) on silica gel to give (4′-cyano-biphenyl-3-yl)-carbamic acid tert-butyl ester (17 g, 59%). 1H NMR (300 MHz, DMSO-d6) δ 9.48 (s, 1H), 7.91 (d, J=8.4 Hz, 2H), 7.85 (s, 1H), 7.76 (d, J=8.4 Hz, 2H), 7.32-7.48 (m, 3H), 1.47 (s, 9H). The DMF was evaporated under reduced pressure the residue was dissolved in EtOAc (200 mL) The mixture was washed with water and brine dried over Na2SO4 concentrated to dryness The residue was purified by column chromatography (petroleum ether/EtOAc 50:1) on silica gel