氯甲基丙基醚

反应条件: temp:0.00; pressure:0.00; stir:

反应条件: temp:0.00; pressure:0.00; stir:

反应条件: temp:0.00; pressure:0.00; stir:

反应条件: temp:0.00; pressure:0.00; stir:

反应条件: temp:0.00; pressure:0.00; stir:

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

实验步骤: 1.12 g (8.1 mmol) of potassium carbonate were added at 60° C. to a solution of 1.5 g (5.06 mmol) of 7-benzyl-3-cyclopropylmethylxanthine from stage a) in 60 ml of dimethylformamide and the mixture was stirred at this temperature for one hour. 722 μl (6.58 mmol) of propoxymethyl chloride were then added dropwise and the mixture was stirred at 80° C. for 4 hours. 12 ml of water and 5 ml of methanol were added and the mixture was stirred at 50° C. for 2 hours. 60 ml of water were then added again, the mixture was extracted three times using methyl tert-butyl ether, and the combined organic phases were washed twice with water, dried using magnesium sulfate and concentrated under reduced pressure. The crude product was purified by flash chromatography on a silica gel column, dichloromethane/methanol (19.8/0.2). the mixture was stirred at 80° C. for 4 hours the mixture was stirred at 50° C. for 2 hours the mixture was extracted three times the combined organic phases were washed twice with water dried concentrated under reduced pressure The crude product was purified by flash chromatography on a silica gel column, dichloromethane/methanol (19.8/0.2)

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

实验步骤: 0.45 g (3.26 mmol) of potassium carbonate was added at 60° C. to a suspension of 0.65 g (2.04 mmol) of 7-benzyl-3-phenylxanthine from stage a) in 20 ml of dimethylformamide and the mixture was stirred at this temperature for one hour. 0.29 ml (2.65 mmol) of propoxymethyl chloride was then added dropwise and the mixture was stirred at 80° C. for 1.5 hours. 20 ml of water were then added, the mixture was extracted three times using 24 ml of methyl tert-butyl ether each time, and the combined organic phases were washed twice with 12 ml of water each time, dried using magnesium sulfate and concentrated under reduced pressure. The crude product was purified by flash chromatography on a silica gel column heptane/ethyl acetate (5/7). the mixture was stirred at 80° C. for 1.5 hours the mixture was extracted three times the combined organic phases were washed twice with 12 ml of water each time dried concentrated under reduced pressure The crude product was purified by flash chromatography on a silica gel column heptane/ethyl acetate (5/7)

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

实验步骤: 0.86 g (6.2 mmol) of potassium carbonate was added at 60° C. to a suspension of 1.16 g (3.9 mmol) of 7-benzyl-3-isobutylxanthine from stage c) in 60 ml of dimethylformamide and the mixture was stirred at this temperature for 1 hour. 0.56 ml (5.1 mmol) of propoxymethyl chloride was then added dropwise and the mixture was stirred at 80° C. for 5.5 hours. 12 ml of water and 5 ml of methanol were then added, the mixture was allowed to stand overnight, 60 ml of water were again added and the mixture was extracted four times using 150 ml of methyl tert-butyl ether each time. The combined organic phases were washed with 200 ml of water, dried using magnesium sulfate and concentrated under reduced pressure. The crude product was purified by flash chromatography on a silica gel column, dichloromethane. the mixture was stirred at 80° C. for 5.5 hours to stand overnight the mixture was extracted four times The combined organic phases were washed with 200 ml of water dried concentrated under reduced pressure The crude product was purified by flash chromatography on a silica gel column, dichloromethane

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

实验步骤: To a solution of methyl salicylate (0.637 g, 4.19 mmol) in N,N-dimethylformamide (8 ml) were added chloromethyl propyl ether (0.50 ml, 4.54 mmol) and potassium carbonate (0.755 g, 5.46 mmol), and the mixture was stirred at room temperature for 20 hr. Ethyl acetate was added to the reaction mixture, the mixture was washed with water, and the organic layer was dried over sodium sulfate. The solvent was evaporated under reduced pressure, and the obtained residue was purified by silica gel column chromatography (hexane:ethyl acetate) to give methyl 2-propoxymethoxybenzoate (0.414 g, 1.85 mmol, yield 44%). This was dissolved in methanol (5 ml), 1N-aqueous sodium hydroxide solution (5 ml) was added at room temperature, and the mixture was stirred at room temperature for 20 hr. The reaction mixture was concentrated under reduced pressure and neutralized with 5% aqueous citric acid solution, and the mixture was extracted with ethyl acetate. The extract was dried over sodium sulfate, and the solvent was evaporated under reduced pressure to give a carboxylic acid compound 2-propoxymethoxybenzoic acid (0.374 g, 1.78 mmol, yield 96%). the mixture was washed with water the organic layer was dried over sodium sulfate The solvent was evaporated under reduced pressure the obtained residue was purified by silica gel column chromatography (hexane:ethyl acetate)

反应条件: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of anhydrous diisopropylamine (11.9 g, 0.118 mol) in 100 ml of anhydrous THF was added dropwise under argon atmosphere a solution of n-butyl lithium in hexane (1.59N, 74.2 ml, 0.118 mol) with stirring at -78° C. and further stirred for 30 min. To this solution was addded dropwise a solution of methyl isobutyrate (10.0 g, 0.098 mol) in anhydrous THF (10 ml). The resulting mixture was stirred for 30 min. HMPA (7 g, 0.039 mol) and chloromethyl propyl ether (13.8 g, 0.127 mol) were added, and stirred for 30 min. The reaction mixture was allowed to warm to room temperature. To the mixture was then added an aqueous saturated solution of ammonium chloride (300 ml) cooled in an ice bath. The organic layer was washed with 30 ml of water and with 20 ml of brine, and dried over anhydrous sodium sulfate. The solvent was distilled out successively at normal pressure and then the residue was distilled in vacuo to give a colourless and transparent oil of methyl 2,2-dimethyl-4-oxaheptylate (12.6 g, 0.0724 mol, b.p. 84°-87° C./30 mmHg, yield: 73.9%). The product was assigned the structure by the following data. further stirred for 30 min The resulting mixture was stirred for 30 min stirred for 30 min to warm to room temperature cooled in an ice bath The organic layer was washed with 30 ml of water and with 20 ml of brine dried over anhydrous sodium sulfate The solvent was distilled out successively at normal pressure the residue was distilled in vacuo

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

实验步骤: 4,5-Bis(4-methoxyphenyl)-2-(pyrrol-2-yl)thiazole obtained in the same manner as described in Reference Example 6 (1.81 g, 5 mmole), chloromethyl n-propyl ether (0.65 g, 6 mmole), and tetra-n-butylammonium bromide (0.16 g, 0.5 mmole) are refluxed in two phases of benzene (20 ml) and 50% aqueous sodium hydroxide (20 ml) for 20 minutes. To the mixture are added water and benzene under ice-cooling, and the mixture is shaken. The benzene layer is taken, washed with water, dried over anhydrous magnesium sulfate, and distilled under reduced pressure to remove the solvent. The residue is subjected to silica gel column chromatography (solvent, ethyl acetate:cyclohexane=1:20) to give oily 4,5-bis(4-methoxyphenyl)-2-(1-n-propoxymethylpyrrol-2-yl)thiazole (1.80 g, yield: 83%). cooling washed with water dried over anhydrous magnesium sulfate distilled under reduced pressure to remove the solvent

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

实验步骤: 4,5-Bis(4-methoxyphenyl)-2-(pyrrol-2-yl)thiazole obtained in the same manner as described in Reference Example 6 (1.81 g, 5 mmole), chloromethyl n-propyl ether (0.65 g, 6 mmole), and tetra-n-butylammonium bromide (0.16 g, 0.5 mmole) are refluxed in two phases of benzene (20 ml) and 50% aqueous sodium hydroxide (20 ml) for 20 minutes. To the mixture are added water and benzene under ice-cooling, and the mixture is shaken. The benzene layer is taken, washed with water, dried over anhydrous magnesium sulfate, and distilled under reduced pressure to remove the solvent. The residue is subjected to silica gel column chromatography (solvent, ethyl acetate:cyclohexane=1:20) to give oily 4,5-bis(4-methoxyphenyl)-2-(1-n-propoxymethylpyrrol-2-yl)thiazole (1.80 g, yield: 83%). cooling washed with water dried over anhydrous magnesium sulfate distilled under reduced pressure to remove the solvent