[(2-ethoxy-2-oxoethyl)amino]methylphosphonic acid

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: A suitable reaction vessel is charged with 3.94 grams (0.02 mole) of ethyl N-phosphonomethylglycinate in 15 ml. of water. While cooling below about 15° C. in an icebath, 50% aqueous sodium hydroxide is added to obtain a pH of about 8. There is then added 2.51 grams (0.022 mole) of methylsuccinic anhydride with stirring and continued cooling. Two further 1.0 gram portions of anhydride are added to complete the reaction, the pH being maintained with additional alkali. The reaction mixture is diluted with water and passed through a column of ion exchange resin in the acid form. The first seven 20 ml. cuts are combined in 20 ml. of water, and a further 1.2 gram portion of anhydride is added. The resultant reaction mixture is passed through the column, and the first four 20 ml. cuts are combined and dried. The product is cooled in dry ice to yield N-carbethoxymethyl-N-(phosphonomethyl)-2-methylsuccinamic acid (in the monohydrate form) as a clear glass-gum. Elemental analysis gives 4.01% nitrogen and 9.13% phosphorus as against calculated values of 4.25% and 9.40% for C10H18NO8P.H2O. ##STR18## is added to obtain a pH of about 8 continued cooling the reaction the pH being maintained with additional alkali The resultant reaction mixture dried The product is cooled in dry ice

反応条件: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To ethyl-N-phosphonomethylglycinate (197 g.; 1.0 mol.) dissolved in 600 ml. of water at 0° C. was added sodium carbonate (159 g.; 1.5 mol.). The resulting mixture was stirred until the gas evolution ceased. The resulting solution was added over a period of one hour to a solution of carbonyl sulfide (66 g.; 1.1 mol.) which previously had been condensed in 600 ml. of methanol at -20° C. in an ice-acetone bath. Following the addition, carbonyl sulfide was sparged through the reaction mixture for seven hours. To the mixture was added benzylchloride (171 g.; 1.0 mol.) and the resulting mixture was allowed to gradually warm to 25° C. over a period of 16 hours. The reaction mixture was then filtered and the methanol removed from the filtrate in vacuo. The residue was acidified to pH2 by the addition of concentrated hydrochloric acid. An oil separated and was extracted into 2 liters of ethylacetate. The extract was dried over sodium sulfate and concentrated in vacuo to yield a viscous oil. The oil was dried over phosphorous pentoxide in a vacuum dessicator for 48 hours to yield ethyl-N-[(benzylthio)carbonyl]-N-(phosphonomethyl)-glycinate, monohydrate (250 g.) as a yellow glass having a melting point of 56°-58° C. and the following analysis: condensed in 600 ml at -20° C. was sparged through the reaction mixture for seven hours The reaction mixture was then filtered the methanol removed from the filtrate in vacuo The residue was acidified to pH2 by the addition of concentrated hydrochloric acid An oil separated was extracted into 2 liters of ethylacetate The extract was dried over sodium sulfate concentrated in vacuo to yield a viscous oil The oil was dried over phosphorous pentoxide in a vacuum dessicator for 48 hours

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

実験手順: A suitable reaction vessel is charged with 3.94 grams (0.02 mole) of ethyl N-phosphonomethylglycinate in 15 ml. of water. While cooling below about 15° C. in an icebath, 50% aqueous sodium hydroxide is added to obtain a pH of about 8. There is then added 2.51 grams (0.022 mole) of methylsuccinic anhydride with stirring and continued cooling. Two further 1.0 gram portions of anhydride are added to complete the reaction, the pH being maintained with additional alkali. The reaction mixture is diluted with water and passed through a column of ion exchange resin in the acid form. The first seven 20 ml. cuts are combined in 20 ml. of water, and a further 1.2 gram portion of anhydride is added. The resultant reaction mixture is passed through the column, and the first four 20 ml. cuts are combined and dried. The product is cooled in dry ice to yield N-carbethoxymethyl-N-(phosphonomethyl)-2-methylsuccinamic acid (in the monohydrate form) as a clear glass-gum. Elemental analysis gives 4.01% nitrogen and 9.13% phosphorus as against calculated values of 4.25% and 9.40% for C10H18NO8P.H2O. ##STR18## is added to obtain a pH of about 8 continued cooling the reaction the pH being maintained with additional alkali The resultant reaction mixture dried The product is cooled in dry ice

反応条件: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To ethyl-N-phosphonomethylglycinate (197 g.; 1.0 mol.) dissolved in 600 ml. of water at 0° C. was added sodium carbonate (159 g.; 1.5 mol). The resulting mixture was stirred until the gas evolution ceased. The resulting solution was added over a period of one hour to a solution of carbonyl sulfide (66 g.; 1.1 mol.) which previously had been condensed in 600 ml. of methanol at -20° C. in an ice-acetone bath. Following the addition, carbonyl sulfide was sparged through the reaction mixture for seven hours. To the mixture was added benzylchloride (171 g.; 1.0 mol.) and the resulting mixture was allowed to gradually warm to 25° C. over a period of 16 hours. The reaction mixture was then filtered and the methanol removed from the filtrate in vacuo. The residue was acidified to pH2 by the addition of concentrated hydrochloric acid. An oil separated and was extracted into 2 liters of ethylacetate. The extract was dried over sodium sulfate and concentrated in vacuo to yield a viscous oil. The oil was dried over phosphorous pentoxide in a vacuum dessicator for 48 hours to yield ethyl-N-[(benzylthio)carbonyl]-N-(phosphonomethyl)-glycinate, monohydrate (250 g.) as a yellow glass having a melting point of 56°-58° C. and the following analysis: condensed in 600 ml at -20° C. was sparged through the reaction mixture for seven hours The reaction mixture was then filtered the methanol removed from the filtrate in vacuo The residue was acidified to pH2 by the addition of concentrated hydrochloric acid An oil separated was extracted into 2 liters of ethylacetate The extract was dried over sodium sulfate concentrated in vacuo to yield a viscous oil The oil was dried over phosphorous pentoxide in a vacuum dessicator for 48 hours