sodium;phenoxide

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

実験手順: The procedure of Example 35 was followed except that 1,2-dicyano-4-nitrobenzene (1.0 part) was used in place of the 1,2-dicyano-3-nitrobenzene, 1.0 parts instead of 2.79 parts of sodium phenoxide and 20 parts instead of 50 parts of dimethylformamide were used. 1,2-Dicyano-4-phenoxybenzene (0.6 parts, 49%) was obtained as a white solid, m.pt.98°-100° C.

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

実験手順: A solution of 1,2-dicyano-3-nitrobenzene (2.77 parts) and sodium phenoxide (2.79 parts) in dimethylformamide (50 parts) was stirred at 120° C. for 2 hours. The reaction mixture was poured into water and extracted with diethyl ether (100 parts). The diethyl ether extract was washed with 5% aqueous potassium hydroxide solution (2×200 parts) and water (2×200 parts) and the diethyl ether was removed under reduced pressure to leave a solid. Recrystallisation of the solid from a 1:1 diethyl ether:petroleum spirit (b.pt.60°-80° C.) gave 1,2-dicyano-3-phenoxybenzene (2.1 parts, 60%) as a pale green solid, m.pt.110°-112° C. extracted with diethyl ether (100 parts) The diethyl ether extract was washed with 5% aqueous potassium hydroxide solution (2×200 parts) and water (2×200 parts) the diethyl ether was removed under reduced pressure to leave a solid Recrystallisation of the solid from a 1:1 diethyl ether

反応条件: temp:75.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A 1 liter, 3 neck round bottom flask fitted with an overhead stirrer is charged with 100 mL of dimethylsulfoxide and 6.0 g of 60% sodium hydride, washed free of mineral oil with toluene (3.6 g contained; 150 mmol), then a solution of 34.2 g 150 mmol) of 2,5-dimethyl-4-(phenylmethoxy)-phenol (Example K) in 200 mL of toluene is added at 20°-25° C. When hydrogen evolution is complete, 40.1 g (1.2×150 mmol) of 5 bromo-2,2 dimethylvaleric acid, methyl ester (U.S. Pat. No. 4,665,226) is added and the temperature is raised to 75° C. When the temperature reaches 55° C., a solid separates (sodium phenolate). After 18 hours overnight the mixture is heated to reflux for 4 hours; then the mixture is cooled and 200 mL of water is added. The aqueous layer is extracted with diethyl ether and the organic layers are combined and the solution is washed with water, dried (magnesium sulfate) and evaporated leaving 65.7 g of a dark brown oil which crystallizes on standing. Recrystallization from hexane in the presence of charcoal affords 39.5 g of the title compound; mp 75.5°-76.5° C. A 1 liter, 3 neck round bottom flask fitted with an overhead stirrer 4,665,226) is added reaches 55° C. After 18 hours overnight the mixture is heated to reflux for 4 hours then the mixture is cooled The aqueous layer is extracted with diethyl ether the solution is washed with water dried (magnesium sulfate) evaporated

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

実験手順: In contrast to published information, it has been found that the degree of conversion of sodium phenolate to sodium salicylate is practically independent of the reaction temperature. At 165° C. and at 200° C., 85-88% conversion is easily obtained, but by-product formation is reduced as the temperature is increased. For instance, reaction at 140°-150° C. gives about 9% non-salicylic acids mostly 4-HBA in the crude product mixture whereas reaction at 190°-195° C. (at 5 bar co-pressure) gives less than 0.5% non-salicylic acids in the reaction product mixture. At 165° C. and at 200° C., 85-88% conversion is easily obtained is increased For instance, reaction at 140°-150° C.

反応条件: temp:110.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Sodium phenoxide trihydrate (7.50 g, 44.1 mmol) was dried under vacuum at 65° C. for 18 h at 0.6 mm Hg to yield 5.08 g of sodium phenoxide. Under a nitrogen atmosphere, 3,5-dibromopyridine (4.00 g, 16.9 mmol) and anhydrous N,N-dimethylformamide (40 mL) were added to the sodium phenoxide (5.08 g, 43.8 mmol). The resulting mixture was stirred at 110° C. for 44 h. After cooling to ambient temperature, water (75 mL) was added, and the pH was adjusted to 13.0 using 30% NaOH solution. The solution was extracted with diethyl ether (4×60 mL). The combined ether extracts were washed with saturated NaCl solution (50 mL), dried (NaSO4), filtered and concentrated by rotary evaporation to a brown oil (4.0 g). The oil was vacuum distilled, collecting a forerun (317 mg), bp 48°-65° C. at 0.05 mm Hg. Further distillation afforded 3.35 g (79.8%) of 3-bromo-5-phenoxypyridine as a pale-yellow oil, bp 75°-112° C. at 0.05 mm Hg (lit. bp 110°-115° C. at 1.7 mm Hg, see K. Fujikawa, et al. Agr. Biol. Chem. 34: 68 (1970). After cooling to ambient temperature The solution was extracted with diethyl ether (4×60 mL) The combined ether extracts were washed with saturated NaCl solution (50 mL) dried (NaSO4) filtered concentrated by rotary evaporation to a brown oil (4.0 g) distilled collecting a forerun (317 mg), bp 48°-65° C. at 0.05 mm Hg Further distillation

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

実験手順: 4-Methoxyphenol (1.95 g, 15.7 mmol) was allowed to react with 28% sodium methoxide (15.7 mmol) in methanol (30 ml), at room temperature for 30 minutes. After the reaction was completed, the solvent was distilled off to obtain sodium phenoxide. The obtained sodium phenoxide and 5-acetamidophthalide obtained in Reference Example 8 (3.0 g, 15.7 mmol) were heated under reflux in xylene (30 ml) for 14 hours. The reaction mixture was poured into water and washed twice with ether (30 ml). The aqueous layer was adjusted to pH 3 with 1 mol/l hydrochloric acid and the precipitated solid was separated by filtration to give 3-acetamido-6-(4-methoxyphenoxymethyl)benzoic acid (2.49 g, 51%). were heated washed twice with ether (30 ml) the precipitated solid was separated by filtration

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

実験手順: A solution of 47.5 g (0.3 mol) of chloromethyl phenyl sulphide in 50 ml of dimethylformamide was added dropwise to a solution of 40 g (0.34 mol) of sodium phenolate in 200 ml of dimethylformamide at room temperature in the course of 30 minutes, while stirring. The temperature of the reaction mixture thereby rose from 24° C. to 35° C. The mixture was subsequently stirred at room temperature for 14 hours and then concentrated by stripping off the solvent under reduced pressure. The oil which remained was washed successively with water, 0.1N aqueous sodium hydroxide solution and water and, after drying sodium sulphate, subjected to fractional vacuum distillation. 50 g (77.2% of theory) of phenoxy-phenylthiomethane were obtained in this manner in the form of a colourless liquid of boiling point 112°-117° C./0.16 mm Hg. thereby rose from 24° C. to 35° C The mixture was subsequently stirred at room temperature for 14 hours concentrated The oil which remained was washed successively with water, 0.1N aqueous sodium hydroxide solution and water after drying sodium sulphate subjected to fractional vacuum distillation

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

実験手順: A solution of 47.5 g (0.3 mol) of chloromethyl phenyl sulphide in 50 ml of dimethylformamide was added dropwise to a solution of 40 g (0.34 mol) of sodium phenolate in 200 ml of dimethylformamide at room temperature in the course of 30 minutes, while stirring. The temperature of the reaction mixture thereby rose from 24° C. to 35° C. The mixture was subsequently stirred at room temperature for 14 hours and then concentrated by stripping off the solvent under reduced pressure. The oil which remained was washed successively with water, 0.1N aqueous sodium hydroxide solution and water and, after drying sodium sulphate, subjected to fractional vacuum distillation. 50 g (77.2% of theory) of phenoxy-phenylthiomethane were obtained in this manner in the form of a colourless liquid of boiling point 112°-117° C./0.16 mm Hg. thereby rose from 24° C. to 35° C The mixture was subsequently stirred at room temperature for 14 hours concentrated The oil which remained was washed successively with water, 0.1N aqueous sodium hydroxide solution and water after drying sodium sulphate subjected to fractional vacuum distillation

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

実験手順: A suspension of 0.1 mole of sodium phenoxide and 0.1 mole of 2-amino-3-morpholino-5-bromopyrazine is refluxed 10-20 hours. The cooled mixture is extracted with diethyl ether, washed with cold 2N sodium hydroxide solution, dried and evaporated to give 2-amino-3-morpholino-5-phenoxypyrazine. is refluxed 10-20 hours The cooled mixture is extracted with diethyl ether washed with cold 2N sodium hydroxide solution dried evaporated

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

実験手順: A suspension of 0.1 mole of sodium phenoxide and 0.1 mole of 2-amino-3-morpholino-5-bromopyrazine is refluxed 10-20 hours. The cooled mixture is extracted with diethyl ether, washed with cold 2N sodium hydroxide solution, dried and evaporated to give 2-amino-3-morpholino-5-phenoxypyrazine. is refluxed 10-20 hours The cooled mixture is extracted with diethyl ether washed with cold 2N sodium hydroxide solution dried evaporated

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

実験手順: A suspension of 0.1 mole of sodium phenoxide and 0.1 mole 2,3-dichloropyrazine is refluxed 10-20 hours. The cooled mixture is extracted with diethyl ether, washed with cold 2N sodium hydroxide solution, dried, and evaporated to give 2-chloro-3-phenoxypyrazine. is refluxed 10-20 hours The cooled mixture is extracted with diethyl ether washed with cold 2N sodium hydroxide solution dried evaporated

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

実験手順: A suspension of 0.1 mole of sodium phenoxide and 0.1 mole 2,3-dichloropyrazine is refluxed 10-20 hours. The cooled mixture is extracted with diethyl ether, washed with cold 2N sodium hydroxide solution, dried, and evaporated to give 2-chloro-3-phenoxypyrazine. is refluxed 10-20 hours The cooled mixture is extracted with diethyl ether washed with cold 2N sodium hydroxide solution dried evaporated