ETHYLPHOSPHONOTHIOIC DICHLORIDE

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: To a mixture of 326 g (2.0 moles) ethylphosphonothioic dichloride in 500 ml acetonitrile, a mixture of 152.3 g (2.0 moles) 2-propanethiol and 158.2 g (2.0 moles) pyridine were added over a period of 20 minutes. The reaction mixture was stirred overnight at room temperature and then heated at reflux for four hours, resulting in the formation of solids. The reaction mixture was cooled to room temperature and then filtered. The filtrate was combined with 500 ml hexane, washed twice with 75 ml water and then stripped to give 373 g of the aboveidentified product as a yellow oil. were added over a period of 20 minutes heated at reflux for four hours resulting in the formation of solids The reaction mixture was cooled to room temperature filtered washed twice with 75 ml water

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: To a stirred mixture of 74.2 g (0.455 moles) ##STR16## ethylphosphonothioic dichloride in 400 ml benzene, 30.1 g (0.5 moles) isopropyl alcohol was added. To that mixture 50.6 g (0.5 moles) triethylamine was added at a dropwise rate overnight. The mixture was then warmed for about 1 hour. The mixture was filtered by gravity. Most of the solvent (benzene) was stripped off under reduced pressure and heat to give ethyl-O-isopropylphosphonothioic chloride: ##STR17## was added The mixture was then warmed for about 1 hour The mixture was filtered by gravity heat

反应条件: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 16.3 g (0.1 mol) of ethanethiophosphonic dichloride in 1 l of toluene are initially introduced, and a mixture of 11 g (0.1 mol) of 3-mercaptobutan-1-ol and 22 g (0.22 mol) of triethylamine in 100 ml of tetrahydrofuran is slowly added dropwise at 20° C. The mixture is heated at 80° C. for 2 days, and 200 ml of toluene and 200 ml of water are then added to the reaction mixture. The organic phase is separated off, washed with water and dried, and the solvent is distilled off, first under a vacuum from a waterpump and then under a high vacuum. 11.5 g (59 % of theory) of 2-ethyl-1,3,2-oxathiaphosphepane 2-sulphide having a refractive index nD20 =1.5761 are obtained. is slowly added dropwise at 20° C The organic phase is separated off washed with water dried the solvent is distilled off, first under a vacuum from a waterpump

反应条件: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 16.3 g (0.1 mol) of ethanethiophosphonic dichloride in 1 l of toluene are initially introduced, and a mixture of 11 g (0.1 mol) of 3-mercaptobutan-1-ol and 22 g (0.22 mol) of triethylamine in 100 ml of tetrahydrofuran is slowly added dropwise at 20° C. The mixture is heated at 80° C. for 2 days, and 200 ml of toluene and 200 ml of water are then added to the reaction mixture. The organic phase is separated off, washed with water and dried, and the solvent is distilled off, first under a vacuum from a waterpump and then under a high vacuum. 11.5 g (59 % of theory) of 2-ethyl-1,3,2-oxathiaphosphepane 2-sulphide having a refractive index nD20 =1.5761 are obtained. is slowly added dropwise at 20° C The organic phase is separated off washed with water dried the solvent is distilled off, first under a vacuum from a waterpump

反应条件: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 16.3 g (0.1 mol) of ethanethiophosphonic dichloride in 1 l of toluene are initially introduced, and a mixture of 11 g (0.1 mol) of 3-mercaptobutan-1-ol and 22 g (0.22 mol) of triethylamine in 100 ml of tetrahydrofuran is slowly added dropwise at 20° C. The mixture is heated at 80° C. for 2 days, and 200 ml of toluene and 200 ml of water are then added to the reaction mixture. The organic phase is separated off, washed with water and dried, and the solvent is distilled off, first under a vacuum from a waterpump and then under a high vacuum. 11.5 g (59 % of theory) of 2-ethyl-1,3,2-oxathiaphosphepane 2-sulphide having a refractive index nD20 =1.5761 are obtained. is slowly added dropwise at 20° C The organic phase is separated off washed with water dried the solvent is distilled off, first under a vacuum from a waterpump

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

实验步骤: Into a three liter flask were placed 523 grams (4.6 moles) of 6-fluoro-2-pyridinol, 638 grams (4.6 moles) potassium carbonate, 1.0 grams HgCl2 and two liters of acetonitrile. The mixture was stirred at 50°-55° C. for two hours and allowed to cooled. The mixture was stirred while 269 grams (2.1 moles) of ethylphosphonothioic dichloride was added dropwise. An exotherm from 25° C. to 55° C. was obtained. The mixture was stirred at 50° C. for five hours and allowed to cool. The insolubles were filtered off and the solvent removed under reduced pressure at 45° C. The resulting oil was taken up in 1.5 liters of methylene chloride and washed once with one liter of water, once with one liter of aqueous 2% NaOH and again with one liter of water. The product layer was dried over sodium sulfate, filtered and the solvent removed under reduced pressure at 45° C. The resulting oil was poured into 250 milliliters of cold n-hexane and stirred. The solid product was filtered off and dried to give a 52% yield of the desired O,O-bis(6 -fluoro-2-pyridinyl) ethylphosphonothioate, m.p. 46°-48° C. (compound No. 1). Into a three liter flask were placed to cooled was added dropwise An exotherm from 25° C. to 55° C. was obtained The mixture was stirred at 50° C. for five hours to cool The insolubles were filtered off the solvent removed under reduced pressure at 45° C washed once with one liter of water, once with one liter of aqueous 2% NaOH and again with one liter of water The product layer was dried over sodium sulfate filtered the solvent removed under reduced pressure at 45° C The resulting oil was poured into 250 milliliters of cold n-hexane stirred The solid product was filtered off dried

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

实验步骤: Into a 500 milliliter (ml) flask were placed 22 grams (g) (0.15 mole (m)) of the sodium salt of 6-fluoro-2-pyridinol, 1 gram HgCl2 and 200 milliliters of acetonitrile. The mixture was stirred while 9.5 grams (0.075 mole) of ethylphosphonothioic dichloride was added. An exotherm from 24° C. to 38° C. was obtained. The mixture was stirred at 40°-45° C. for five hours and allowed to cool. The insolubles were filtered off and the liquid phase distilled under reduced pressure until all the solvent was removed. The resulting oil was taken up in 300 milliliters of methylene chloride and washed once with 200 milliliters of water, once with 200 milliliters of aqueous 2% NaOH and twice with 200 milliliters portions of water. The product layer was dried over sodium sulfate, filtered and distilled under reduced pressure at 45° C. until the solvent was removed. The resulting oil was mixed in 150 mls of n-hexane and cooled to dry ice/acetone bath temperatures. The resulting solids were filtered off and dried to give a 60% yield of O,O-bis(6-fluoro-2-pyridinyl) ethylphosphonothioate, a solid, m.p. 47°-49° C. Product was confirmed by N.M.R. and I.R. spectra (compound No. 1). Into a 500 milliliter (ml) flask were placed was added An exotherm from 24° C. to 38° C. was obtained to cool The insolubles were filtered off the liquid phase distilled under reduced pressure until all the solvent was removed washed once with 200 milliliters of water, once with 200 milliliters of aqueous 2% NaOH and twice with 200 milliliters portions of water The product layer was dried over sodium sulfate filtered distilled under reduced pressure at 45° C. until the solvent was removed The resulting oil was mixed in 150 mls of n-hexane cooled to dry ice/acetone bath temperatures The resulting solids were filtered off dried

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

实验步骤: To a stirred mixture of 74.2 g (0.455 mole) ##STR16## ethylphosphonothioic acid dichloride in 400 mls benzene, 30.1 g (0.5 mole) isopropyl alcohol was added. To that mixture 50.6 g (0.5 mole) triethylamine was added at a dropwise rate overnight. The mixture was then warmed for about 1 hour. The mixture was filtered by gravity. Most of the solvent (benzene) was stripped off under reduced pressure and heat to give ethyl-O-isopropylphosphonothioic chloride ##STR17## was added The mixture was then warmed for about 1 hour The mixture was filtered by gravity heat

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

实验步骤: To a mixture of 326 g (2.0 moles) ethylphosphonothioic dichloride in 500 ml acetonitrile, a mixture of 152.3 g (2.0 moles) 2-propanethiol and 158.2 g (2.0 moles) pyridine were added over a period of 20 minutes. The reaction mixture was stirred overnight at room temperature and then heated at reflux for four hours, resulting in the formation of solids. The reaction mixture was cooled to room temperature and then filtered. The filtrate was combined with 500 ml hexane, washed twice with 75 ml water and then stripped to give 373 g of the aboveidentified product as a yellow oil. were added over a period of 20 minutes heated at reflux for four hours resulting in the formation of solids The reaction mixture was cooled to room temperature filtered washed twice with 75 ml water