2-amino-1-(3-bromophenyl)ethanol

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:

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: With 7.5 ml of ethanol were mixed 4.5 g of 1-{2-[[5-(dimethylamino)methyl-4-methyl-2-thienyl]methylthio]ethylamino}-1-methylthio-2-nitroethene and 3.5 g of DL-[2-(3-bromophenyl)-2-hydroxyethyl]amine, and the resulting mixture was subjected to reaction at room temperature for 30 hours. Thereto were added 5 ml of isopropanol and 30 ml of diethyl ether, and the mixture thus obtained was stirred, after which the crystals formed were collected by filtration. The crystals were recrystallized from 40 ml of isopropanol to obtain 4.3 g (yield 65%) of N-[2-(3-bromophenyl)-2-hydroxyethyl]-N'-{2-[[5-(dimethylamino)methyl-4-methyl-2-thienyl]methylthio]ethyl}-2-nitro-1,1-ethenediamine having a melting point of 104°-106° C. the resulting mixture was subjected to reaction at room temperature for 30 hours the mixture thus obtained after which the crystals formed were collected by filtration The crystals were recrystallized from 40 ml of isopropanol

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

実験手順: This was prepared in an identical manner to the compound described in Example 1 using 2-hydroxy-2-(3-bromophenyl) ethanamine (2.16 g) and 4-{(E)-2-carbomethoxyethenyl}phenylpropan-2-one (2.18 g). Elution with 1% methanolchloroform on Kieselgel 60 gave the title compound as a solid 1.6 g (benzene-petrol 80-100) m.p. 105°-111° C. as a 42:58 mixture of diastereoisomers. τ(CDCl3) 8.95 (3H, d, J=6 Hz), 6.9-7.7 (7H, m, 2H disappears with D2O), 6.2 (3H, s), 5.5 (1H, m), 3.6 (aH, d, J=16 Hz) 2.55 (8H, m), 2.35 (1H, d, J=16 Hz). This was prepared in an identical manner to the compound Elution with 1% methanolchloroform on Kieselgel 60

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

実験手順: This was prepared in an identical manner to the compound described in Example 1 using 2-hydroxy-2-(3-bromophenyl) ethanamine (2.16 g) and 4-{(E)-2-carbomethoxyethenyl}phenylpropan-2-one (2.18 g). Elution with 1% methanolchloroform on Kieselgel 60 gave the title compound as a solid 1.6 g (benzene-petrol 80-100) m.p. 105°-111° C. as a 42:58 mixture of diastereoisomers. τ(CDCl3) 8.95 (3H, d, J=6 Hz), 6.9-7.7 (7H, m, 2H disappears with D2O), 6.2 (3H, s), 5.5 (1H, m), 3.6 (aH, d, J=16 Hz) 2.55 (8H, m), 2.35 (1H, d, J=16 Hz). This was prepared in an identical manner to the compound Elution with 1% methanolchloroform on Kieselgel 60

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-amino-1-(3-bromo-phenyl)-ethanol (example 33, step 1, 1.34 g) and crude 2-chloro-N-phenyl-acetamide (example 33, step 2, 1.0 g) in acetonitrile (15 mL) was added potassium carbonate (1.03 g). The mixture was heated to 80° C. overnight. A 1M solution of KH2PO4 was added, followed by ethyl acetate. The phases were separated, and the inorganic one was extracted with ethyl acetate (x2). The combined organic layers were washed with brine, dried (Na2SO4) and concentrated in vacuo. Column chromatography (SiO2, CH2Cl2/MeOH 95:5) followed by precipitation from a mixture of diethylether/n-heptane (1:4) gave 2-[2-(3-bromo-phenyl)-2-hydroxy-ethylamino]-N-phenyl-acetamide (0.87 g, 42%) as a white solid, MS: 349.1 (M+H, 1Br)+. The phases were separated the inorganic one was extracted with ethyl acetate (x2) The combined organic layers were washed with brine dried (Na2SO4) concentrated in vacuo Column chromatography (SiO2, CH2Cl2/MeOH 95:5) followed by precipitation from a mixture of diethylether/n-heptane (1:4)

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

実験手順: To a cooled solution of 3-bromobenzaldehyde (1.58 mL) in THF (15 mL) were added trimethylsilyl cyanide (1.7 mL) and N,N-diisopropylethylamine (0.23 mL). The mixture was stirred at room temperature for 2d and at reflux for 2 h. The solution was allowed to cool to room temperature and then was slowly added to a cooled suspension of lithium aluminium hydride (769 mg) in THF (10 mL). The mixture was stirred at 0° C. for 10 min, the cooling bath was removed, and the mixture was heated at reflux for 3 h. After cooling to room temperature, ethylacetate was added slowly, followed by a mixture of Na2SO4/silicagel/H2O. After stirring the suspension for 30 min, the mixture was filtered, the filtrate was dried (Na2SO4), and concentrated in vacuo. The residue was purified by chromatography (SiO2, CH2Cl2/MeOH/ammonia 90:10:2) to give (1.59 g) 2-amino-1-(3-bromo-phenyl)-ethanol as a yellow oil. at reflux for 2 h the cooling bath was removed the mixture was heated at reflux for 3 h After cooling to room temperature ethylacetate was added slowly followed by a mixture of Na2SO4/silicagel/H2O After stirring the suspension for 30 min the mixture was filtered the filtrate was dried (Na2SO4) concentrated in vacuo The residue was purified by chromatography (SiO2, CH2Cl2/MeOH/ammonia 90:10:2)