1-chloro-3-phenoxypropan-2-one

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: The synthesis of 2,4-diamino-4-phenoxymethylfuro[2,3-d]pyrimidin-4-one12 is shown in FIG. 20. Phenoxyacetyl chloride 10 was reacted with CH2N2 in the presence of gaseous hydrogen chloride and ether to produce 1-chloro-3-phenoxy-2-propanone 11. 1-chloro-3-phenoxy-2-propanone 11 was reacted with 2,6-diamino-3H-pyrimidin-4-one 1 to produce 2,4-diamino-4-phenoxymethylfuro[2,3-d]pyrimidin-4-one 12 at a 39% yield.

反応条件: temp:20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 8N Jones reagent (100 ml.) was added dropwise to a stirred solution of 1-chloro-2-hydroxy-3-phenoxypropane (28.3 g.) in acetone (100 ml.) during 1 hour while maintaining the reaction temperature at 20° C. The mixture was then stirred for 4 hours, and then sufficient water was added to dissolve the precipitated chromium salts. The mixture was extracted three times with diethyl ether and the combined ethereal extracts were dried over sodium sulphate, concentrated under reduced pressure, dried again over sodium sulphate, and concentrated further and distilled, to give 1-chloro-3-phenoxyacetone (13.9 g.), b.p. 150°-155° C./20 mm.Hg. The mixture was extracted three times with diethyl ether the combined ethereal extracts were dried over sodium sulphate concentrated under reduced pressure dried again over sodium sulphate concentrated further distilled

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

実験手順: A solution of 1-chloro-3-phenoxyacetone (6.8 g.) and triphenylphosphine (12 g.) in chloroform (16 ml.) was saturated with nitrogen and heated at reflux under nitrogen overnight. An excess of dry diethyl ether was added, and then the solvents were decanted from the gum that separated. The remaining solvent was removed in vacuo to give crude 2-oxo-3-phenoxypropyltriphenylphosphonium chloride (10.35 g.). This was stirred vigorously with a solution of sodium carbonate (18 g.) in water (180 ml.) for 24 hours. The solution was extracted with diethyl ether and the ethereal extracts dried over sodium sulphate. The solvent was removed by evaporation to give phenoxyacetylmethylenetriphenylphosphorane (5.3 g.), a sticky solid. heated at reflux under nitrogen overnight the solvents were decanted from the gum that separated The remaining solvent was removed in vacuo

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: The above identified compound, m.p. 110°-112° C. was prepared in substantially the same manner as described in Example XX from 1 chloro-3-phenoxy-propan-2-one and 1-benzyl-3-methyl-imidazolium-2-thione. was prepared in substantially the same manner

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

実験手順: The above identified compound, m.p. 110°-112° C. was prepared in substantially the same manner as described in Example XX from 1 chloro-3-phenoxy-propan-2-one and 1-benzyl-3-methyl-imidazolium-2-thione. was prepared in substantially the same manner

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

実験手順: 1-Chloro-3-phenoxyacetone (13 g, 0.07 mole) dissolved in 20 ml chloroform was mixed with a solution of triphenylphosphine (19.7 g, 1 eq) in 30 ml chloroform at room temperature. The mixture was swirled for 5 minutes and benzene (20 ml) was added. A white crystalline compound appeared when most of the solvents had been evaporated. The product was collected by suction and washed with benzene. Second and third crops were collected by evaporation of the washings. The total yield was 23 g (73%); sublimation without melting at 90°; ir (KBr, cm-1), 3450-3280, 2770, 1720, 1595, 1585, 1485, 1435, 1220, 1110, 1030; nmr (DCCl3, ppm) 8.20-6.80 (m, 22H), 5.30 (br, 2H). had been evaporated The product was collected by suction washed with benzene Second and third crops were collected by evaporation of the washings

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

実験手順: 1-Chloro-3-phenoxyacetone (13 g, 0.07 mole) dissolved in 20 ml chloroform was mixed with a solution of triphenylphosphine (19.7 g, 1 eq) in 30 ml chloroform at room temperature. The mixture was swirled for 5 minutes and benzene (20 ml) was added. A white crystalline compound appeared when most of the solvents had been evaporated. The product was collected by suction and washed with benzene. Second and third crops were collected by evaporation of the washings. The total yield was 23 g (73%); sublimation without melting at 90°; ir (KBr, cm-1), 3450-3280, 2770, 1720, 1595, 1585, 1485, 1435, 1220, 1110, 1030; nmr (DCCl3, ppm) 8.20-6.80 (m, 22H), 5.30 (br, 2H). had been evaporated The product was collected by suction washed with benzene Second and third crops were collected by evaporation of the washings

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

実験手順: To a stirred solution of diazomethane (ca 6 g=0.141 mmol) in ethyl ether (400 ml) was added over 2 hours at 1°-3° phenoxyacetyl chloride (11.95 g=0.07 mole) dissolved in ethyl ether (50 ml). The mixture was stirred at the same temperature for two more hours and was allowed to stand overnight at room temperature. Then 5.5 N hydrochloric acid (25 ml, 0.137 moles) was added with stirring over 110 min. at 16°-20°. After the mixture was stirred for an additional 4 hours, the layers were separated and the ether layer was washed with three 80 ml portions of water and dried over anhydrous sodium sulfate. Removal of the solvent gave the crude product as a yellow oil, 13 g (100%); ir (film, cm-1) 1740, 1595, 1495, 1240; nmr (DCCl3, ppm) 7.40-6.70 (m, 5H), 4.60 (s, 2H), 4.25 (s, 2H). This product was used without purification to prepare phenoxyacetylmethyltriphenylphosphonium chloride. with stirring over 110 min. at 16°-20° After the mixture was stirred for an additional 4 hours the layers were separated the ether layer was washed with three 80 ml portions of water dried over anhydrous sodium sulfate Removal of the solvent

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

実験手順: 1-Chloro-3-phenoxyacetone (13 g, 0.07 mole) dissolved in 20 ml chloroform was mixed with a solution of triphenylphosphine (19.7 g, 1 eq) in 30 ml chloroform at room temperature. The mixture was swirled for 5 minutes and benzene (20 ml) was added. A white crystalline compound appeared when most of the solvents had been evaporated. The product was collected by suction and washed with benzene. Second and third crops were collected by evaporation of the washings. The total yield was 23 g (73%); sublimation without melting at 90°; ir (KBr, cm-1) 3450-3280, 2770, 1720, 1595, 1585, 1485, 1435, 1220, 1110, 1030; nmr (DCCl3, ppm) 8.20-6.80 (m, 22H), 5.30 (br, 2H). had been evaporated The product was collected by suction washed with benzene Second and third crops were collected by evaporation of the washings