N-dichlorophosphoryl-N-methylmethanamine

Conditions: temp:105.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Using the procedure described in M. Goehring and K. Niedenzu, Chem. Ber. 89, pp 1768-1771 (1956), 1300-1400 grams of a material containing 53.5% (by weight) of N,N-diethylphosphoric triamide and 46.5% (by weight) of ammonium chloride was prepared by reacting 1035 g of N,N-dimethylphosphoramidic dichloride and ammonia in ether at 0° C. The N,N-dimethylphosphoramidic dichloride was prepared by adding 425 g (9.45 mol) of dimethylamine to 4000 mL (6580 g, 42.7 mol) of phosphorus oxychloride at 0°-10° C., heating the reaction mixture at reflux (105° C.) for 18 h, and distilling the products at reduced pressure (31P NMR (CDCl3): δ 17.7 ppm). Pure N,N-dimethylphosphoric triamide can be obtained by extracting the crude material with chloroform, evaporating the chloroform, and recrystallizing the residue from acetone/chloroform. For example, extraction of 130 g of crude material with 1300 mL of hot chloroform provided 30 g of pure material, mp 128.5°-131° C. (lit. 119° C.), after recrystallization was prepared at 0° C heating the reaction mixture distilling the products at reduced pressure (31P NMR (CDCl3): δ 17.7 ppm)

Conditions: temp:105.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Using the procedure described in M. Goehring and K. Niedenzu, Chem. Ber. 89, pp 1768-1771 (1956), 1300-1400 grams of a material containing 53.5% (by weight) of N,N-diethylphosphoric triamide and 46.5% (by weight) of ammonium chloride was prepared by reacting 1035 g of N,N-dimethylphosphoramidic dichloride and ammonia in ether at 0° C. The N,N-dimethylphosphoramidic dichloride was prepared by adding 425 g (9.45 mol) of dimethylamine to 4000 mL (6580 g, 42.7 mol) of phosphorus oxychloride at 0°-10° C., heating the reaction mixture at reflux (105° C.) for 18 h, and distilling the products at reduced pressure (31P NMR (CDCl3): δ 17.7 ppm). Pure N,N-dimethylphosphoric triamide can be obtained by extracting the crude material with chloroform, evaporating the chloroform, and recrystallizing the residue from acetone/chloroform. For example, extraction of 130 g of crude material with 1300 mL of hot chloroform provided 30 g of pure material, mp 128.5°-131° C. (lit. 119° C.), after recrystallization was prepared at 0° C heating the reaction mixture distilling the products at reduced pressure (31P NMR (CDCl3): δ 17.7 ppm)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: N,N-Dimethylphosphoramidodichloridate (1.8 mL, 15.22 mmol) was added to a solution of 3-methoxy-4-nitrobenzoic acid (300 mg, 1.52 mmol) in anhydrous 1,2-dimethoxyethane (15 mL) and the resulting mixture was heated at reflux for 110 hours ca. The reaction mixture was then cooled and poured into ice-water (50 mL); the resulting mixture was extracted with diethyl ether (50 mL), the organic layer was separated and the aqueous layer was extracted with dichloromethane (50 mL). The combined organic extracts were concentrated under reduced pressure; the residue was dissolved in dichloromethane and washed with water (30 mL), dried over anhydrous sodium sulfate, filtered and evaporated under reduced pressure. The tan liquid residue was purified by flash chromatography (DCM/MeOH, 98/2) to give 185 mg of 3-methoxy-N,N-dimethyl-4-nitro-benzamide as a yellow oil. the resulting mixture was heated at reflux for 110 hours was then cooled the resulting mixture was extracted with diethyl ether (50 mL) the organic layer was separated the aqueous layer was extracted with dichloromethane (50 mL) The combined organic extracts were concentrated under reduced pressure the residue was dissolved in dichloromethane washed with water (30 mL) dried over anhydrous sodium sulfate filtered evaporated under reduced pressure The tan liquid residue was purified by flash chromatography (DCM/MeOH, 98/2)

Conditions: temp:105.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Using the procedure described in M. Goehring and K. Niedenzu, Chem. Ber. 89, pp 1768-1771 (1956), 1300-1400 grams of a material containing 53.5% (by weight) of N,N-diethylphosphoric triamide and 46.5% (by weight) of ammonium chloride was prepared by reacting 1035 g of N,N-dimethylphosphoramidic dichloride and ammonia in ether at 0° C. The N,N-dimethylphosphoramidic dichloride was prepared by adding 425 g (9.45 mol) of dimethylamine to 4000 mL (6580 g, 42.7 mol) of phosphorus oxychloride at 0°-10° C., heating the reaction mixture at reflux (105° C.) for 18 h, and distilling the products at reduced pressure (31P NMR (CDCl3): δ 17.7 ppm). Pure N,N-dimethylphosphoric triamide can be obtained by extracting the crude material with chloroform, evaporating the chloroform, and recrystallizing the residue from acetone/chloroform. For example, extraction of 130 g of crude material with 1300 mL of hot chloroform provided 30 g of pure material, mp 128.5°-131° C. (lit. 119° C.), after recrystallization was prepared at 0° C heating the reaction mixture distilling the products at reduced pressure (31P NMR (CDCl3): δ 17.7 ppm)