methyl N-phenylcarbamate

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:190.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 838 g aniline, 676 g methyl carbamate, 1442 g methanol and 30.0 g anhydrous pulverized zinc chloride were introduced into the pressure vessel. The pressure vessel and the column were then purged with nitrogen. The mixture was subsequently heated (with stirring) to 190° C., and the top valve of the column was adjusted so that the pressure in the apparatus was just sufficient for the reactants to reach the reaction temperature. Ammonia which evolved was separated from the evaporating alcohol in the column and then removed from the top of the column. The reaction mixture was stirred for 6.5 hours at 190° C., while the ammonia which evolved was removed. The mixture was then cooled and removed from the pressure vessel after the pressure in the apparatus had been reduced. The mixture was filtered and then distilled at atmospheric pressure to remove the excess methanol. The product was then fractionally distilled at 0.2 m bar. 1120 g N-phenyl-carbamic acid methyl ester (82.3% of the theoretical yield) were collected and crystallized. The product had a melting point of 45° to 46° C. were introduced into the pressure vessel The pressure vessel and the column were then purged with nitrogen The mixture was subsequently heated Ammonia which evolved was separated from the evaporating alcohol in the column removed from the top of the column The reaction mixture was stirred for 6.5 hours at 190° C., while the ammonia which evolved was removed The mixture was then cooled removed from the pressure vessel after the pressure in the apparatus The mixture was filtered distilled at atmospheric pressure to remove the excess methanol The product was then fractionally distilled at 0.2 m bar

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

Procedure: A mixture of 15.1 g. (0.10 mole) of methyl carbanilate, 105 ml. of 2-propanol, and 0.60 g. of 5% Rh on carbon was added to a 300-ml. Magne Drive (tradmark) autoclave. The vessel was sealed, purged first with nitrogen and then with hydrogen, and pressured with hydrogen to 600 psig. The autoclave was heated with agitation at 500-800 psig for 0.3 hr. at 25°-75°, followed by an additional 0.8 hr. at 75° with little or no gas absorption. The autoclave was cooled and depressurized. The reaction product was removed and filtered through Celite (trademark) filter aid to remove the catalyst. The solvent was removed in a rotary evaporator under vacuum. The white solid residue was dried in a vacuum dessicator and consisted of 15.1 g. (96% yield) of methyl cyclohexylcarbamate, m.p. 73°-74°. An authentic sample prepared from cyclohexyl isocyanate and methanol melted at 73.5°-74°. A mixture of 15.1 g The vessel was sealed purged first with nitrogen The autoclave was heated with agitation at 500-800 psig for 0.3 hr at 75° with little or no gas absorption The autoclave was cooled The reaction product was removed filtered through Celite (trademark) filter aid to remove the catalyst The solvent was removed in a rotary evaporator under vacuum The white solid residue was dried in a vacuum dessicator

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

Procedure: In a 200 ml stirring type autoclave were charged 30 mmols of N,N'-diphenylurea, 15 mmols of nitrobenzene, 50 ml of methanol, 1 mmol of potassium tetrabromopalladate, 2 mmols of iodine and 2 mmols of triethylamine. After the air inside the autoclave had been replaced with carbon monoxide, carbon monoxide was pressurized into the autoclave to 120 Kg/cm2, and the reaction was carried out at 180° C. for 6 hours with stirring. As the result of analysis of the reaction solution, the conversions of N,N'-diphenylurea and nitrobenzene were 30% and 38%, respectively, and 15 mmols of methyl N-phenylcarbamate were obtained. with stirring As the result of analysis of the reaction solution

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

Procedure: In a 200 ml stirring type autoclave were charged 30 mmols of N,N'-diphenylurea, 15 mmols of nitrobenzene, 50 ml of methanol, 0.5 mmol of palladium chloride and 5 mmols of cesium iodide. After the air inside the autoclave had been replaced with carbon monoxide, carbon monooxide was pressurized into the autoclave to 120 Kg/cm2, and the reaction was carried out at 180° C. for 4 hours with stirring. As the result of analysis of the reaction solution obtained, the conversions of N,N'-diphenylurea and nitrobenzene were 25% and 30%, respectively, and 14 mmols of methyl N-phenylcarbamate were obtained. with stirring As the result of analysis of the reaction solution obtained

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

Procedure: In a 200 ml stirring type autoclave were charged 30 mmols of N,N'-diphenylurea, 15 mmols of nitrobenzene, 50 ml of methanol, 0.5 mmol of palladium chloride and 5 mmols of tetrabutylammonium iodide. After the air inside the autoclave had been replaced with carbon monoxide, carbon monoxide was pressurized into the autoclave to 140 Kg/cm2, and the reaction was carried out at 180° C. for 5 hours with stirring. As the result of analysis of the reaction solution obtained, the conversions of N,N'-diphenylurea and nitrobenzene were 26% and 33%, respectively, and 15 mmols of methyl N-phenylcarbamate were obtained. with stirring As the result of analysis of the reaction solution obtained

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

Procedure: Following the procedure described in Example 1, 745 g of aniline, 255 g of N,N'-diphenyl urea, 481 g of urea, 1333 g of methanol and 6.0 g of zinc octoate were reacted for 3.5 hours at 200° C. in the pressure apparatus described in Example 1. The mixture was then cooled and, after the apparatus had been vented, another 72 g of urea were added. The mixture was then reheated and reacted for 4 hours at 200° C. After cooling and venting of the apparatus, the mixture was removed, filtered and subjected to fractional distillation. Most of the methanol excess was separated off at atmospheric pressure. The product was then distilled at 0.2 mbar. 1323 g (84.1% of the theoretical yield) of N-phenyl carbamic acid methyl ester melting at from 45° to 47° C. were obtained. were reacted for 3.5 hours at 200° C. in the pressure apparatus The mixture was then cooled reacted for 4 hours at 200° C After cooling the mixture was removed filtered subjected to fractional distillation Most of the methanol excess was separated off at atmospheric pressure The product was then distilled at 0.2 mbar