2-bromoethanamine;hydrobromide

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

実験手順: To a solution of 2-bromoethylamine hydrobromide (20.5 g, 0.1 mol) and acetonylacetone (12.5 ml, 0.1 mol) in acetic acid (10 ml) was added potassium acetate (10 g, 0.1 mol), and the mixture was stirred for 1 h at 20° C. and for 2 h at 80° C. The reaction mixture was diluted with water (150 ml) and extracted with diethyl ether (150 ml). The extract was washed with brine and concentrated in vacuo to afford an oily residue. The residue was distilled at 60-64° C./0.5 mm of mercury to afford the title compound as a colourless oil (9.45 g, 47%). extracted with diethyl ether (150 ml) The extract was washed with brine concentrated in vacuo to afford an oily residue The residue was distilled at 60-64° C./0.5 mm of mercury

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

実験手順: 2,6-Difluorobenzoyl chloride (100 g, 566 mmol) was added dropwise over 2 h to a vigorously stirred and ice water cooled mixture of 2-bromoethyl amine hydrobromide (116.05 g, 566 mmol), benzyltriethylammonium chloride (5 g, 22.0 mmol), 10% aq NaOH (680 mL, 1.7 mol), and CH2Cl2 (1.5 L). The resulting mixture was stirred at RT overnight, than was washed with water (3×200 mL), dried (MgSO4), concentrated, and kugelrohr distilled to afford 51.8 g of 2-(2,6-difluorophenyl)-2-oxazoline as a colorless oil, a 50% yield. The resulting mixture was stirred at RT overnight than was washed with water (3×200 mL) dried (MgSO4) concentrated kugelrohr distilled

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

実験手順: 2,6-Difluorobenzoyl chloride (100 g, 566 mmol) was added dropwise over 2 h to a vigorously stirred and ice water cooled mixture of 2-bromoethyl amine hydrobromide (116.05 g, 566 mmol), benzyltriethylammonium chloride (5 g, 22.0 mmol), 10% aq NaOH (680 mL, 1.7 mol), and CH2Cl2 (1.5 L). The resulting mixture was stirred at RT overnight, than was washed with water (3×200 mL), dried-(MgSO4), concentrated, and kugelrohr distilled to afford 51.8 g of 2-(2,6-difluorophenyl)-2-oxazoline as a colorless oil, a 50% yield. The resulting mixture was stirred at RT overnight than was washed with water (3×200 mL), dried-(MgSO4), concentrated kugelrohr distilled

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

実験手順: 272.1 g (976 mmol) of triphenylchloromethane, 800 ml of dichloromethane and 200 g (976 mmol) of 2-bromoethanamine hydrobromide are introduced into a 2-1 round bottom flask placed under nitrogen. The mixture is stirred and 300 ml of triethylamine are added dropwise and stirring is continued for 48 h. The triethylamine hydrochloride which precipitates is separated off, water is added to the filtrate, the organic phase is separated off and is washed with water and dried over sodium sulphate, and the solvent is evaporated off. An oil is obtained, which is purified by chromatography on a column of silica gel. After recrystallisation from a mixture of dichloromethane and cyclohexane 273.17 g of white solid are obtained. Melting point: 108°-109° C. stirring The triethylamine hydrochloride which precipitates is separated off water is added to the filtrate the organic phase is separated off is washed with water dried over sodium sulphate the solvent is evaporated off An oil is obtained which is purified by chromatography on a column of silica gel After recrystallisation from a mixture of dichloromethane and cyclohexane 273.17 g of white solid are obtained

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

実験手順: A mixture of t-butyl azidoformate (15.81 g) and triethylamine (30 ml) was added dropwise to a stirred suspension of 2-bromoethylamine hydrobromide (20.5 g.), in methylene chloride (100 ml.). The mixture was stirred for 3 hr., then filtered. The filtrate was concentrated to a small volume, and the residue was distributed between ether and water. The ether layer was dried, then distilled under reduced pressure, collecting the fraction b.p. 92°-94°/0.9 nm as N-carbo-t-butoxy-2-bromoethylamine (1.756 g.) , then filtered The filtrate was concentrated to a small volume The ether layer was dried distilled under reduced pressure collecting the fraction b.p. 92°-94°/0.9 nm as N-carbo-t-butoxy-2-bromoethylamine (1.756 g.)

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

実験手順: A mixture of t-butyl azidoformate (15.81 g) and triethylamine (30 ml) was added dropwise to a stirred suspension of 2-bromoethylamine hydrobromide (20.5 g.); in methylene chloride (100 ml.). The mixture was stirred for 3 hr., then filtered. The filtrate was concentrated to a small volume, and the residue was distributed between ether and water. The ether layer was dried, then distilled under reduced pressure, collecting the fraction b.p. 92°-94°/0.9 mm as N-carbo-t-butoxy-2-bromoethylamine (1.756 g.) , then filtered The filtrate was concentrated to a small volume The ether layer was dried distilled under reduced pressure collecting the fraction b.p. 92°-94°/0.9 mm as N-carbo-t-butoxy-2-bromoethylamine (1.756 g.)

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

実験手順: 2,6-Difluorobenzoyl chloride (100 g, 566 mmol) was added dropwise over 2 h to a vigorously stirred and ice water cooled mixture of 2-bromoethyl amine hydrobromide (116.05 g, 566 mmol), benzyltriethylammonium chloride (5 g, 22.0 mmol), 10% aq NaOH (680 mL, 1.7 mol), and CH2Cl2 (1.5 L). The resulting mixture was stirred at RT overnight, than was washed with water (3×200 mL), dried(MgSO4), concentrated, and kugelrohr distilled to afford 51.8 g of 2-(2,6-difluorophenyl)-2-oxazoline as a colorless oil, a 50% yield. The resulting mixture was stirred at RT overnight than was washed with water (3×200 mL), dried(MgSO4) concentrated kugelrohr distilled

反応条件: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 3.7 g (0.01 mole) of 5-amino-N,N-diethyl-2H[1]benzoselenino[4,3,2-cd]indazole-2-ethanamine, 5.9 g (0.029 mole) of 2-bromoethylamine, hydrobromide, and 25 ml of ethanol is heated under reflux for ten hours. Additional 2-bromoethylamine, hydrobromide (2.0 g) is added and the solution is heated at reflux for 38 hours, then allowed to cool to 25° C. The solids are collected and washed with cold ethanol to give 3.5 g of the dried product as a salt with 2.8 equivalents of hydrogen bromide; mp 268°-270° C. (dec.). is heated under reflux for ten hours the solution is heated at reflux for 38 hours The solids are collected washed with cold ethanol

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

実験手順: Reaction of a solution of 3.6 g (0.0095 mol) of 5-amino-N,N-diethyl-3,9-dimethoxy-2H[1]benzothiopyrano[4,3,2-cd]indazole-2-ethanamine and 5.8 g (0.0283 mol) of 2-bromoethylamine, hydrobromide, in 30 ml of EtOH as described in Example 38 gave 1.8 g of product.

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

実験手順: Reaction of a solution of 4.5 g (0.0122 mol) of 5-amino-N,N-diethyl-8-methoxy-2H[1]benzothiopyrano-[4,3,2-cd]indazole-2-ethanamine and 7.5 g (0.0366 mol) of 2-bromoethylamine, hydrobromide, in 40 ml of EtOH as described in Example 38 gave 2.4 g of product.

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

実験手順: Reaction of a solution of 3.5 g (0.0095 mol) of 5-amino-N,N-diethyl-7-methoxy-2H[1]benzothiopyrano-[4,3,2-cd]indazole-2-ethanamine and 5.8 g (0.0283 mol) of 2-bromoethylamine, hyrobromide, in 30 ml of EtOH as described in Example 38 gave 1.6 g of product.

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

実験手順: 60% NaH in oil (0.91 g, 22.8 mmol) was added to a suspension of 4,5-diphenyl-2-imidazolethiol (2.5 g, 9.9 mmol) in dry THF (80 ml) at room temperature under stirring. After 15 minutes, 2-bromoethylamine hydrobromide (2.0 g, 9.9 mmol) was added to the mixture. The reaction mixture was refluxed for 1 hour, then poured into water (500 ml) and extracted with ethyl acetate. The extract was dried (MgSO4) and concentrated. The residue was recrystallized (toluene) to give 2-(2-aminoethylthio)-4,5-diphenylimidazole (51.3%): mp 152°-154° C. The reaction mixture was refluxed for 1 hour extracted with ethyl acetate The extract was dried (MgSO4) concentrated The residue was recrystallized (toluene)