2,6-dichlorobenzenethiol

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

実験手順: 2,6-dichlorothiophenol, 50.0 gm, was added to 50 ml of ethanol. 63.8 ml of a 25% solution of sodium methoxide (2 equivalents) in methanol was then added to the system. The system was stirred at room temperature for approximately 3 hours. Afterwards, 20 ml of bromoacetic acid was added and the system then heated to reflux. The system was continued at reflux for 16 hours. The reaction was then stopped and the solvent removed by stripping. The resulting material was dissolved with basic aqueous solution water and then washed with methylene chloride. Concentrated HCl was next added to the aqueous solution to acidify it. The product was extracted with methylene chloride. The methylene chloride solution was stripped and triturated with hexane. The product was then filtered, washed with water and air dried to yield 55.3 gm of the 2,6-dichlorothiophenoxyacetic acid. the system then heated to reflux at reflux for 16 hours the solvent removed by stripping The resulting material was dissolved with basic aqueous solution water washed with methylene chloride Concentrated HCl was next added to the aqueous solution The product was extracted with methylene chloride triturated with hexane The product was then filtered washed with water and air dried

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

実験手順: 2,6-dichlorothiophenol, 50 gm, was added to 250 ml of ethanol. 63.8 ml of a 25% solution of sodium methoxide (2 equivalents) in methanol was then added to the system. The system was stirred at room temperature for approximately 3 hours. Afterwards, 20 ml of bromoacetic acid was added and the system then heated to reflux. The system was continued at reflux for 16 hours. The reaction was then stopped and the solvent removed by stripping. The resulting material was dissolved with basic aqueous solution and then washed with methylene chloride. Concentrated HCl was next added to the aqueous solution to acidify it. The product was extracted with methylene chloride. The methylene chloride solution was stripped and triturated with hexane. The product was then filtered, washed with water and air dried to yield 55.3 gm of the title compound. the system then heated to reflux at reflux for 16 hours the solvent removed by stripping The resulting material was dissolved with basic aqueous solution washed with methylene chloride Concentrated HCl was next added to the aqueous solution The product was extracted with methylene chloride triturated with hexane The product was then filtered washed with water and air dried

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

実験手順: 2,6-dichlorothiophenol, 50 gm, was added to 250 ml of ethanol. 63.8 ml of a 25% solution of sodium methoxide (2 equivalents) in methanol was then added to the system. The system was stirred at room temperature for approximately 3 hours. Afterwards, 20 ml of bromoacetic acid was added and the system then heated to reflux. The system was continued at reflux for 16 hours. The reaction was then stopped and the solvent removed by stripping. The resulting material was dissolved with basic aqueous solution and then washed with methylene chloride. Concentrated HCl was next added to the aqueous solution to acidify it. The product was extracted with methylene chloride. The methylene chloride solution was stripped and triturated with hexane. The product was then filtered, washed with water and air dried to yield 55.3 gm of the title compound. the system then heated to reflux at reflux for 16 hours the solvent removed by stripping The resulting material was dissolved with basic aqueous solution washed with methylene chloride Concentrated HCl was next added to the aqueous solution The product was extracted with methylene chloride triturated with hexane The product was then filtered washed with water and air dried

反応条件: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 2,6-Dichlorothiophenol (53 mg, 0.297 mmol, Aldrich) was dissolved in dry MeCN (0.60 mL,) and treated with 2-(E-2-carboxymethylethenyl)-3-[4-(4-methoxyphenyl)butyloxy]-6-chloromethylpyridine hydrochloride (115 mg, 0.270 mmol) and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU, 0.142 mL, 0.949 mmol). The reaction was stirred under an atmosphere of argon at 50° C. for 3 h. The reaction solution was diluted with EtOAc and washed with H2O and brine and dried (MgSO4). Purification by flash column chromatography (silica, EtOAc: CH2Cl2 : hexane, 10:15:75) gave a colorless waxy solid: 1H NMR (250 MHz, CDCl3) δ7.94 (d, J=15.7 Hz, 1H, vinyl), 7.31 (d, J=7.6 Hz, 2H, aryl), 7.13 (m, 4H, aryl, pyridyl), 7.11 (d, J=8.4 Hz, 1H, pyridyl), 6.86 (d, J=8.7 Hz, 2H, phenyl), 6.69 (d, J=15.7 Hz, 1H, vinyl), 4.14 (s, 2H, CH2 -S), 3.97 (t, J=6.1 Hz, 2H, CH2 -O), 3.80 (s, 3H, OMe), 3.78 (s, 3H, methyl ester), 2.63 (t, J=7.2 Hz, 2H, benzylic), 1.81 (m, 4H, CH2CH2); analysis calcd. for C27H27Cl2NO4S: C, 60.90; H, 5.11; N, 2.63; found: C, 60.61; H, 5.01; N, 2.57; MS (ES+): 532.0 (M+H). washed with H2O and brine dried (MgSO4) Purification by flash column chromatography (silica, EtOAc: CH2Cl2 : hexane, 10:15:75) gave a colorless waxy solid

反応条件: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 2,6-Dichlorothiophenol (53 mg, 0.297 mmol, Aldrich) was dissolved in dry MeCN (0.60 mL,) and treated with 2-(E-2-carboxymethylethenyl)-3-[4-(4-methoxyphenyl)butyloxy]-6-chloromethylpyridine hydrochloride (115 mg, 0.270 mmol) and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU, 0.142 mL, 0.949 mmol). The reaction was stirred under an atmosphere of argon at 50° C. for 3 h. The reaction solution was diluted with EtOAc and washed with H2O and brine and dried (MgSO4). Purification by flash column chromatography (silica, EtOAc: CH2Cl2 : hexane, 10:15:75) gave a colorless waxy solid: 1H NMR (250 MHz, CDCl3) δ7.94 (d, J=15.7 Hz, 1H, vinyl), 7.31 (d, J=7.6 Hz, 2H, aryl), 7.13 (m, 4H, aryl, pyridyl), 7.11 (d, J=8.4 Hz, 1H, pyridyl), 6.86 (d, J=8.7 Hz, 2H, phenyl), 6.69 (d, J=15.7 Hz, 1H, vinyl), 4.14 (s, 2H, CH2 -S), 3.97 (t, J=6.1 Hz, 2H, CH2 -O), 3.80 (s, 3H, OMe), 3.78 (s, 3H, methyl ester), 2.63 (t, J=7.2 Hz, 2H, benzylic), 1.81 (m, 4H, CH2CH2); analysis calcd. for C27H27Cl2NO4S: C, 60.90; H, 5.11; N, 2.63; found: C, 60.61; H, 5.01; N, 2.57; MS (ES+): 532.0 (M+H). washed with H2O and brine dried (MgSO4) Purification by flash column chromatography (silica, EtOAc: CH2Cl2 : hexane, 10:15:75) gave a colorless waxy solid

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

実験手順: In a manner similar to Step A of Example 1, the reaction of 26.0 g (0.25 mole) 2,6-dichlorothiophenol, 20.0 g (0.15 mole) potassium carbonate and 75.4 g (0.30 mole) 1,2-dibromotetrafluoroethane in 200 ml of N,N-dimethylformamide produced 31.5 g of 2-(2-bromo-1,1,2,2-tetrafluoroethylthio)-1,3-dichlorobenzene as an oil. The nmr and ir spectra were consistent with the proposed structure.

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

実験手順: In a manner similar to Step A of Example 1, the reaction of 26.0 g (0.25 mole) 2,6-dichlorothiophenol, 20.0 g (0.15 mole) potassium carbonate and 75.4 g (0.30 mole) 1,2-dibromotetrafluoroethane in 200 ml of N,N-dimethylformamide produced 31.5 g of 2-(2-bromo-1,1,2,2-tetrafluoroethylthio)-1,3-dichlorobenzene as an oil. The nmr and ir spectra were consistent with the proposed structure.

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

実験手順: Using the method of Example 3, Step A, 2,6-dichlorobenzenethiol (1.69 g, 9.46 mmol), 60% sodium hydride in mineral oil (378 mg, 9.46 mmol), and 2-chloro-4-nitropyridine (1.50 g, 9.46 mmol) were reacted to provide 2-chloro-4-(2,6-dichlorophenylthio)pyridine (1.37 g, 50% yield) as a white powder. 1H NMR (CDCl3) δ 8.15 (d, 1H), 7.53 (d, 2H), 7.41 (t, 1H), 6.84 (s, 1H), 6.79 (d, 1H). were reacted

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

実験手順: Using the method of Example 3, Step A, 2,6-dichlorobenzenethiol (1.69 g, 9.46 mmol), 60% sodium hydride in mineral oil (378 mg, 9.46 mmol), and 2-chloro-4-nitropyridine (1.50 g, 9.46 mmol) were reacted to provide 2-chloro-4-(2,6-dichlorophenylthio)pyridine (1.37 g, 50% yield) as a white powder. 1H NMR (CDCl3) δ 8.15 (d, 1H), 7.53 (d, 2H), 7.41 (t, 1H), 6.84 (s, 1H), 6.79 (d, 1H). were reacted

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

実験手順: 2,6-dichlorothiophenol, 50.0 gm, was added to 250 ml of ethanol. 63.8 ml of a 25% solution of sodium methoxide (2 equivalents) in methanol was then added to the system. The system was stirred at room temperature for approximately 3 hours. Afterwards, 20 ml of bromoacetic acid was added and the system was then heated to reflux. The system was continued at reflux for 16 hours. The reaction was then stopped and the solvent removed by stripping. The resulting material was dissolved with a basic aqueous solution and then washed with methylene chloride. Concentrated HCl was next added to the aqueous solution to acidify it. The product was extracted with methylene chloride. The methylene chloride solution was stripped and then triturated with hexane. The product was then filtered, washed with water and air dried to yield 5.3 gm of the 2,6-dichlorothiophenoxyacetic acid. the system was then heated to reflux at reflux for 16 hours the solvent removed by stripping The resulting material was dissolved with a basic aqueous solution washed with methylene chloride Concentrated HCl was next added to the aqueous solution The product was extracted with methylene chloride triturated with hexane The product was then filtered washed with water and air dried

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

実験手順: 2,6-dichlorothiophenol, 50.0 gm, was added to 250 ml of ethanol. 63.8 ml of a 25% solution of sodium methoxide (2 equivalents) in methanol was then added to the system. The system was stirred at room temperature for approximately 3 hours. Afterwards, 20 ml of bromoacetic acid was added and the system was then heated to reflux. The system was continued at reflux for 16 hours. The reaction was then stopped and the solvent removed by stripping. The resulting material was dissolved with a basic aqueous solution and then washed with methylene chloride. Concentrated HCl was next added to the aqueous solution to acidify it. The product was extracted with methylene chloride. The methylene chloride solution was stripped and then triturated with hexane. The product was then filtered, washed with water and air dried to yield 5.3 gm of the 2,6-dichlorothiophenoxyacetic acid. the system was then heated to reflux at reflux for 16 hours the solvent removed by stripping The resulting material was dissolved with a basic aqueous solution washed with methylene chloride Concentrated HCl was next added to the aqueous solution The product was extracted with methylene chloride triturated with hexane The product was then filtered washed with water and air dried

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

実験手順: 2,6-dichlorothiophenol, 50.0 gm, was added to 250 ml of ethanol. 63.8 ml of a 25% solution of sodium methoxide (2 equivalents) in methanol was then added to the system. The system was stirred at room temperature for approximately 3 hours. Afterwards, 20 ml of bromoacetic acid was added and the system was then heated to reflux. The system was continued at reflux for 16 hours. The reaction was then stopped and the solvent removed by stripping. The resulting material was dissolved with a basic aqueous solution and then washed with methylene chloride. Concentrated HCl was next added to the aqueous solution to acidify it. The product was extracted with methylene chloride. The methylene chloride solution was stripped and then triturated with hexane. The product was then filtered, washed with water and air dried to yield 55.3 gm of the 2,6-dichlorothiophenoxyacetic acid. the system was then heated to reflux at reflux for 16 hours the solvent removed by stripping The resulting material was dissolved with a basic aqueous solution washed with methylene chloride Concentrated HCl was next added to the aqueous solution The product was extracted with methylene chloride triturated with hexane The product was then filtered washed with water and air dried