2-溴-2-苯基乙醛

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Using N-[3-(dimethylamino)propyl]-N′-phenylthiourea (650 mg) obtained in Reference Example 3 as described below, 2-bromo-2-phenylacetoaldehyde (600 mg) and N,N-dimethylformamide (11 ml), the title compound (497 mg) was obtained in a similar manner to in Example 1. obtained in Reference Example 3

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Using N-[3-(dimethylamino)propyl]-N′-phenylthiourea (650 mg) obtained in Reference Example 3 as described below, 2-bromo-2-phenylacetoaldehyde (600 mg) and N,N-dimethylformamide (11 ml), the title compound (497 mg) was obtained in a similar manner to in Example 1. obtained in Reference Example 3

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: One proceeds according to Example 14 but bromomethyl-p-nitro-phenyl-ketone is used as starting material in the place of α-bromo-α-phenyl-acetaldehyde. The reaction mixture is not worked up by the extraction method according to Example 14 but by precipitating the product with 50 ml of water, filtering off the same and washing it three times with 20 ml of water each. Thus 16.1 g of the desired compound are obtained, yield 98%. The reaction mixture is not worked up by the extraction method by precipitating the product with 50 ml of water filtering off the same and washing it three times with 20 ml of water each

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: One proceeds according to Example 14 but bromomethyl-p-nitro-phenyl-ketone is used as starting material in the place of α-bromo-α-phenyl-acetaldehyde. The reaction mixture is not worked up by the extraction method according to Example 14 but by precipitating the product with 50 ml of water, filtering off the same and washing it three times with 20 ml of water each. Thus 16.1 g of the desired compound are obtained, yield 98%. The reaction mixture is not worked up by the extraction method by precipitating the product with 50 ml of water filtering off the same and washing it three times with 20 ml of water each

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A mixture of 212 mg (0.640 mmole) of 3-amino-5-butyl-4-[(2'-cyanobiphenyl-4-yl)methyl]-4H-1,2,4-triazole (from Example 1, Step D), 151 mg (0.757 mmol) of α-bromophenylacetaldehyde [T. L. Jacobs and W. R. Scott, Jr., J. Am. Chem. Soc., 75, 5500 (1953)], and 2.0 ml of absolute ethanol was stirred at reflux under N2 for 6 hours. The mixture was cooled and concentrated in vacuo. The residue was chromatographed on a column of silica gel (27×2.5 cm) packed in CH2Cl2 (elution with 1% and then 4% MeOH in CH2Cl2). Concentration of the appropriate pooled product fractions afforded 65.3 mg (24%) of the title compound as a yellow oil; homogeneous by TLC in 19:1 CH2Cl2 -MeOH. at reflux under N2 for 6 hours The mixture was cooled concentrated in vacuo The residue was chromatographed on a column of silica gel (27×2.5 cm) elution with 1%

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A mixture of 4.4 g (26 mmole) of 3-(acetoxymethyl)-2-pyridinamine and 6.0 g (30 mmole) of 2-bromo-2-phenylacetaldehyde was heated at 65°. The mixture was dissolved in water, made basic with aqueous potassium carbonate, and extracted with dichloromethane. The organic layer was washed with water, dried over magnesium sulfate, filtered, and concentrated in vacuo. The residue was triturated with diethyl ether to yield 4.1 g of 8-(acetoxymethyl)-3-phenylimidazo[1,2-a]pyridine as confirmed by the nmr and infrared spectra and by elemental analysis. [Calcd. for C16H14N2O2 : C, 72.17; H, 5.30; N, 10.52. Found: C, 71.90; H, 5.25; N, 10.43.] The title compound (1.5 g) was prepared by the method described in Example 26 using 1.3 g (5 mmole) of 8-(acetoxymethyl)-3-phenylimidazo[1,2-a]pyridine instead of 8-hydroxymethyl-2-phenylimidazo[1,2-a]pyridine. Structure assignment was supported by the nmr and infrared spectra and by elemental analysis. was heated at 65° extracted with dichloromethane The organic layer was washed with water dried over magnesium sulfate filtered concentrated in vacuo The residue was triturated with diethyl ether

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To the solution of 2-amino-4,4′-bipyridine (0.482 g, 2.815 mmol, 1 equiv) in dioxane (14 mL) was added bromophenylacetaldehyde (0.897 g, 4.50 mmol, 1.6 equiv) and NaHCO3 (0.473 g, 5.63 mmol, 2 equiv). The suspension was stirred at rt for 30 min and then heated to 80° C. for 6 h. The reaction mixture was poured into water and extracted with EtOAc. The combined organic layer was dried, concentrated and purified by flash column chromatography (5% MeOH in CH2Cl2 ) to give 3-phenyl-7-(4-pyridyl)imidazo[1,2-a]pyridine as a solid. 1H NMR (CDCl3) δ 8.72 (d, 2H, J=6.1), 8.45 (d, 1H, J=7.3), 8.00 (s, 1H), 7.80 (s, 1H), 7.61–7.55 (m, 6H), 7.48–7.44 (m, 1H), 7.14 (d, 1H, J=7.3); LRMS m/z (M+H) Calcd: 272.3, found: 272.2. heated to 80° C. for 6 h extracted with EtOAc The combined organic layer was dried concentrated purified by flash column chromatography (5% MeOH in CH2Cl2 )

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Using N-[3-(dimethylamino)propyl]-N′-phenylthiourea (650 mg) obtained in Reference Example 3 as described below, 2-bromo-2-phenylacetoaldehyde (600 mg) and N,N-dimethylformamide (11 ml), the title compound (497 mg) was obtained in a similar manner to in Example 1. obtained in Reference Example 3

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A mixture of bromo-phenyl-acetaldehyde (1 g, 5 mmol), thiourea (0.64 g, 10 mmol) and ethanol (3.5 mL) was heated to reflux overnight. The mixture was then cooled to rt and the resulting yellow precipitate filtered. The precipitate was then washed with aqueous NaHCO3 solution (10 mL) and dried. Recrystallization from 30% methanol gave 5-phenylthiazol-2-amine (500 mg, 2.84 mmol, 56.5%) as a yellow solid. Anal. Calcd. for C9H8N2S m/z 176.2, found: 177.2 (M+H)+; 1H NMR (400 MHz, DMSO-d6) δ ppm 7.41 (m, 3H), 7.33 (m, 2H), 7.18 (m, 1H), 7.13 (m, 2H). was heated to reflux overnight the resulting yellow precipitate filtered The precipitate was then washed with aqueous NaHCO3 solution (10 mL) dried Recrystallization from 30% methanol

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A mixture of bromo-phenyl-acetaldehyde (1 g, 5 mmol), thiourea (0.64 g, 10 mmol) and ethanol (3.5 mL) was heated to reflux overnight. The mixture was then cooled to rt and the resulting yellow precipitate filtered. The precipitate was then washed with aqueous NaHCO3 solution (10 mL) and dried. Recrystallization from 30% methanol gave 5-phenylthiazol-2-amine (500 mg, 2.84 mmol, 56.5%) as a yellow solid. Anal. Calcd. for C9H8N2S m/z 176.2, found: 177.2 (M+H)+; 1H NMR (400 MHz, DMSO-d6) δ ppm 7.41 (m, 3H), 7.33 (m, 2H), 7.18 (m, 1H), 7.13 (m, 2H). was heated to reflux overnight the resulting yellow precipitate filtered The precipitate was then washed with aqueous NaHCO3 solution (10 mL) dried Recrystallization from 30% methanol

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of phenyl-acetaldehyde (1 g, 8.3 mmol) in CH2Cl2 (3 mL) was added dropwise a solution of Br2 (1.3 g, 8.3 mmol) in CH2Cl2 (3 mL) at −10° C. over 30 min. The resulting solution was allowed to warm to rt and then heated to reflux overnight. Aqueous NaHCO3 was added to the cooled mixture and the solution was extracted with CH2Cl2. The organic layer was dried over anhydrous Na2SO4, filtered and concentrated to afford crude bromo-phenyl-acetaldehyde (1 g, 5.05 mmol, 61%) as a green liquid which was taken to the next step directly. Anal. Calcd. for C8H7BrO m/z 198.0, found: 198.0 GC-MS (M)+. heated to reflux overnight the solution was extracted with CH2Cl2 The organic layer was dried over anhydrous Na2SO4 filtered concentrated

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of phenyl-acetaldehyde (1 g, 8.3 mmol) in CH2Cl2 (3 mL) was added dropwise a solution of Br2 (1.3 g, 8.3 mmol) in CH2Cl2 (3 mL) at −10° C. over 30 min. The resulting solution was allowed to warm to rt and then heated to reflux overnight. Aqueous NaHCO3 was added to the cooled mixture and the solution was extracted with CH2Cl2. The organic layer was dried over anhydrous Na2SO4, filtered and concentrated to afford crude bromo-phenyl-acetaldehyde (1 g, 5.05 mmol, 61%) as a green liquid which was taken to the next step directly. Anal. Calcd. for C8H7BrO m/z 198.0, found: 198.0 GC-MS (M)+. heated to reflux overnight the solution was extracted with CH2Cl2 The organic layer was dried over anhydrous Na2SO4 filtered concentrated