chloro-dimethoxy-sulfanylidene-lambda5-phosphane

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:

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

実験手順: 7 g of potassium carbonate and 8 g of O,O-dimethyl chlorothiophosphate were added to a solution of 9.8 g of 2-cyano-3-hydroxy-5-n-butoxy-thiophene in 150 ml of acetonitrile and the mixture was stirred for 24 hours at 20° C. and was then filtered. The filtrate was evaporated to dryness and the residue was chromatographed over silica gel. Elution with benzene yielded 11 g of 2-cyano-3-(dimethoxythiophosphoryloxy)-5-n-butoxy-thiophene with a refractive index of nD20 =1.5375. was then filtered The filtrate was evaporated to dryness the residue was chromatographed over silica gel Elution with benzene

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

実験手順: 7 g of potassium carbonate and 8 g of O,O-dimethyl chlorothiophosphate were added to a solution of 9.8 g of 2-cyano-3-hydroxy-5-n-butoxy-thiophene in 150 ml of acetonitrile and the mixture was stirred for 24 hours at 20° C. and was then filtered. The filtrate was evaporated to dryness and the residue was chromatographed over silica gel. Elution with benzene yielded 11 g of 2-cyano-3-(dimethoxythiophosphoryloxy)-5-n-butoxy-thiophene with a refractive index of nD20 =1.5375. was then filtered The filtrate was evaporated to dryness the residue was chromatographed over silica gel Elution with benzene

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

実験手順: 7 g of potassium carbonate and 8 g of O,O-dimethyl chlorothiophosphate were added to a solution of 10.5 g of 2-cyano-3-hydroxy-5-phenyl-thiophene in 120 ml of acetone and the mixture was stirred at 20° C. for 15 hours and was then filtered. The filtrate was evaporated to dryness and the crystal residue was empasted with petroleum ether. The crystals were then crystallized from isopropyl ether to obtain 12.8 g of 2-cyano-3-(dimethoxythiophosphoryloxy)-5-phenylthiophene melting at 95° C. was then filtered The filtrate was evaporated to dryness The crystals were then crystallized from isopropyl ether

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

実験手順: 7 g of potassium carbonate and 8 g of O,O-dimethyl chlorothiophosphate were added to a solution of 10.5 g of 2-cyano-3-hydroxy-5-phenyl-thiophene in 120 ml of acetone and the mixture was stirred at 20° C. for 15 hours and was then filtered. The filtrate was evaporated to dryness and the crystal residue was empasted with petroleum ether. The crystals were then crystallized from isopropyl ether to obtain 12.8 g of 2-cyano-3-(dimethoxythiophosphoryloxy)-5-phenylthiophene melting at 95° C. was then filtered The filtrate was evaporated to dryness The crystals were then crystallized from isopropyl ether

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

実験手順: 11.2 g of potassium carbonate and 12.8 g of O,O-dimethyl chlorothiophosphate were added to a solution of 11.2 g of 2-cyano-3-hydroxy-5-methyl-thiophene in 200 ml of acetone and the mixture was stirred for 15 hours at 20° C. and was then filtered. The filtrate was evaporated to dryness and the residue was chromatographed over silica gel. Elution with a 7-3 cyclohexane-ethyl acetate mixture yielded 18.7 g of 2-cyano-3-(dimethoxythiophosphoryloxy)-5-methyl-thiophene with a refractive index of nD20 =1.539. was then filtered The filtrate was evaporated to dryness the residue was chromatographed over silica gel Elution with a 7-3 cyclohexane-ethyl acetate mixture

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

実験手順: 11.2 g of potassium carbonate and 12.8 g of O,O-dimethyl chlorothiophosphate were added to a solution of 11.2 g of 2-cyano-3-hydroxy-5-methyl-thiophene in 200 ml of acetone and the mixture was stirred for 15 hours at 20° C. and was then filtered. The filtrate was evaporated to dryness and the residue was chromatographed over silica gel. Elution with a 7-3 cyclohexane-ethyl acetate mixture yielded 18.7 g of 2-cyano-3-(dimethoxythiophosphoryloxy)-5-methyl-thiophene with a refractive index of nD20 =1.539. was then filtered The filtrate was evaporated to dryness the residue was chromatographed over silica gel Elution with a 7-3 cyclohexane-ethyl acetate mixture

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

実験手順: A solution of diethylamine (7.31 g, 100 mmol) in dichloromethane (250 ml) at 5° C. was treated with O,O-dimethyl phosphorochloridothioate (8.03 g, 50 mmol) in dichloromethane (50 ml) in a dropwise fashion. The resulting mixture was stirred 1 h and then washed with 1N HCl (2X 100 ml) and water (100 ml). The dichloromethane solution was dried over magnesium sulfate and filtered, and the filtrate was concentrated under reduced pressure to give an oil. Distillation employing a Kugelrohr apparatus at 45°-50° C. and less than 1 mm Hg pressure gave 5.27 g (53 percent of theory) of the desired product; nD25 1.4735. washed with 1N HCl (2X 100 ml) and water (100 ml) The dichloromethane solution was dried over magnesium sulfate filtered the filtrate was concentrated under reduced pressure to give an oil Distillation at 45°-50° C.

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

実験手順: A solution of diethylamine (7.31 g, 100 mmol) in dichloromethane (250 ml) at 5° C. was treated with O,O-dimethyl phosphorochloridothioate (8.03 g, 50 mmol) in dichloromethane (50 ml) in a dropwise fashion. The resulting mixture was stirred 1 h and then washed with 1N HCl (2X 100 ml) and water (100 ml). The dichloromethane solution was dried over magnesium sulfate and filtered, and the filtrate was concentrated under reduced pressure to give an oil. Distillation employing a Kugelrohr apparatus at 45°-50° C. and less than 1 mm Hg pressure gave 5.27 g (53 percent of theory) of the desired product; nD25 1.4735. washed with 1N HCl (2X 100 ml) and water (100 ml) The dichloromethane solution was dried over magnesium sulfate filtered the filtrate was concentrated under reduced pressure to give an oil Distillation at 45°-50° C.

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

実験手順: To a stirred mixture of 6 grams of 2-(1,1-dimethylethyl)-5-pyrimidinol, 6 grams of finely powdered potassium carbonate and 40 ml of acetonitrile was added 6.33 grams of O,O-dimethyl phosphorochloridothioate. The mixture was stirred without external heating until all O,O-dimethyl phosphorochloridothioate was consumed as shown by GLC. The solids present were removed by filtration, the filtrate concentrated under vacuum, the residue taken up in diethyl ether, the ether solution washed twice with 2% aqueous sodium hydroxide, once with saturated sodium chloride solution and dried over anhydrous sodium sulfate. The solvent was removed under vacuum, while leaving a pale amber colored oil having a refractive index at 25° of 1.5027. Elemental analysis showed the product to contain 43.82% carbon; 6.09% hydrogen and 10.10% nitrogen. Theoretical composition is 43.47% carbon; 6.20% hydrogen and 10.14% nitrogen. was consumed The solids present were removed by filtration the filtrate concentrated under vacuum the ether solution washed twice with 2% aqueous sodium hydroxide, once with saturated sodium chloride solution dried over anhydrous sodium sulfate The solvent was removed under vacuum while leaving a pale amber at 25°