methyl N-[amino(methylsulfanyl)methylidene]carbamate

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

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

Procedure: To 13 parts of methyl N-(1-amino-1-methoxymethylene)carbamate, m.p. 36°-39.5°, prepared similar to the procedure in Example 3 for methyl N-(1-amino-1-methylthiomethylene)carbamate in 140 parts of methylene chloride is added 15 parts of p-chlorophenyl isocyanate. The reaction mixture is stirred overnight and the solution filtered to give 10 parts of methyl 4-(p-chlorophenyl)-N-methoxycarbonylallophanimidate melting at 170° dec. the solution filtered

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

Procedure: To 69.5 parts 2-methyl-2-thiopseudourea sulfate and 47 parts of methyl chloroformate in 1,000 parts water at 0°C is added dropwise 56.9 parts of potassium hydroxide in 200 parts of water. The reaction mixture is stirred at room temperature for 3 hours and then extracted with methylene chloride. The methylene chloride extract is dried and the solvent evaporated on a rotary evaporator to give 45 parts of methyl N-(1-amino-1-methylthiomethylene)carbamate melting at 72°-77°C. extracted with methylene chloride The methylene chloride extract is dried the solvent evaporated on a rotary evaporator

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

Procedure: To 13 parts of methyl N-(1-amino-1-methoxymethylene)-carbamate, m.p. 36°-39.5°, prepared similar to the procedure in Example 3 for methyl N-(1-amino-1-methylthiomethylene)-carbamate in 140 parts of methylene chloride is added 15 parts of p-chlorophenyl isocyanate. The reaction mixture is stirred overnight and the solution filtered to give 10 parts of methyl 4-(p-chlorophenyl)-N-methoxycarbonylallophanimidate melting at 170° dec. the solution filtered

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

Procedure: To 69.5 parts 2-methyl-2-thiopseudourea sulfate and 47 parts of methyl chloroformate in 1000 parts water at 0° C is added dropwise 56.9 parts of potassium hydroxide in 200 parts of water. The reaction mixture is stirred at room temperature for 3 hours and then extracted with methylene chloride. The methylene chloride extract is dried and the solvent evaporated on a rotary evaporator to give 45 parts of methyl N-(1-amino-1-methylthiomethylene)carbamate melting at 72°-77° C. extracted with methylene chloride The methylene chloride extract is dried the solvent evaporated on a rotary evaporator

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

Procedure: To 69.5 parts 2-methyl-2-thiopseudourea sulfate and 47 parts of methyl chloroformate in 1000 parts water at 0° C is added dropwise 56.9 parts of potassium hydroxide in 200 parts of water. The reaction mixture is stirred at room temperature for 3 hours and then extracted with methylene chloride. The methylene chloride extract is dried and the solvent evaporated on a rotary evaporator to give 45 parts of methyl N-(1-amino-1-methylthiomethylene)carbamate melting at 72°-77° C. extracted with methylene chloride The methylene chloride extract is dried the solvent evaporated on a rotary evaporator

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

Procedure: 4-Methylphenylisocyanate (19.0 g.) was added during 10 minutes to a solution of methyl N-[1-amino-1-(methylthio)methylene]carbamate (21.2 g.) in methylene chloride (200 ml.). After 2 hours of stirring, sodium methoxide [obtained by dissolving sodium (3.5 g.) in methanol (30 ml.)] was added at 15°-20° C. The subsequent mixture was stirred at that temperature for 18 hours and the resultant solid collected by filtration and dissolved in water (200 ml.). The solution obtained was acidified with concentrated hydrochloric acid and the solid which formed was collected by filtration, washed well with water and dried to give 3-(4-methylphenyl)-6-methylthiotetrahydro-1,3,5-triazine-2,4-dione (29 g., 81%), m.p. 276°-278° C. The subsequent mixture was stirred at that temperature for 18 hours the resultant solid collected by filtration dissolved in water (200 ml.) The solution obtained the solid which formed was collected by filtration washed well with water dried

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

Procedure: Methyl N-[1-(amino)-1-(methylthio)methylene]carbamate (14.8 g.) was dissolved in methylene chloride (150 ml.). 3-Trifluoromethylphenyl isocyanate (18.7 g.) was added to the solution during 5 minutes and the mixture was stirred at room temperature for 2.5 hours. A freshly prepared solution of sodium (2.3 g.) in methanol (20 ml.) was then added during 5 minutes and the subsequent mixture was stirred at room temperature for 16 hours. The mixture was then evaporated and the residue was dissolved in water (400 ml.). The aqueous solution obtained, was extracted with ethyl acetate (2×400 ml.) to remove neutral byproducts, and then acidified with concentrated hydrochloric acid to pH1. The solid which precipitated was separated by filtration, washed with water (3×500 ml.), and dried (over phosphorus pentoxide) to give 3-(3-trifluoromethylphenyl)-6-methylthio-tetrahydro-1,3,5-triazine-2,4-dione (25.9 g., 86%) as a white solid, m.p. 225°-228° C. the subsequent mixture was stirred at room temperature for 16 hours The mixture was then evaporated the residue was dissolved in water (400 ml.) The aqueous solution obtained was extracted with ethyl acetate (2×400 ml.) to remove neutral byproducts The solid which precipitated was separated by filtration washed with water (3×500 ml.) dried (over phosphorus pentoxide)

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

Procedure: 4-Methylphenylisocyanate (19.0 g.) was added during 10 minutes to a solution of methyl N-[1-amino-1-(methylthio)methylene]carbamate (21.2 g.) in methylene chloride (200 ml.). After 2 hours of stirring, sodium methoxide [obtained by dissolving sodium (3.5 g.) in methanol (30 ml.)] was added at 15°-20° C. The subsequent mixture was stirred at that temperature for 18 hours and the resultant solid collected by filtration and dissolved in water (200 ml.). The solution obtained was acidified with concentrated hydrochloric acid and the solid which formed was collected by filtration, washed well with water and dried to give 3-(4-methylphenyl)-6-methylthiotetrahydro-1,3,5-triazine-2,4-dione (29 g., 81%), m.p. 276°-278° C. The subsequent mixture was stirred at that temperature for 18 hours the resultant solid collected by filtration dissolved in water (200 ml.) The solution obtained the solid which formed was collected by filtration washed well with water dried

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

Procedure: Methyl N-[1-(amino)-1-(methylthio)methylene]carbamate (14.8 g.) was dissolved in methylene chloride (150 ml.). 3-Trifluoromethylphenyl isocyanate (18.7 g.) was added to the solution during 5 minutes and the mixture was stirred at room temperature for 2.5 hours. A freshly prepared solution of sodium (2.3 g.) in methanol (20 ml.) was then added during 5 minutes and the subsequent mixture was stirred at room temperature for 16 hours. The mixture was then evaporated and the residue was dissolved in water (400 ml.). The aqueous solution obtained, was extracted with ethyl acetate (2×400 ml.) to remove neutral byproducts, and then acidified with concentrated hydrochloric acid to pH1. The solid which precipitated was separated by filtration, washed with water (3×500 ml.), and dried (over phosphorus pentoxide) to give 3-(3-trifluoromethylphenyl)-6-methylthio-tetrahydro-1,3,5-triazine-2,4-dione (25.9 g., 86%) as a white solid, m.p. 225°-228° C. the subsequent mixture was stirred at room temperature for 16 hours The mixture was then evaporated the residue was dissolved in water (400 ml.) The aqueous solution obtained was extracted with ethyl acetate (2×400 ml.) to remove neutral byproducts The solid which precipitated was separated by filtration washed with water (3×500 ml.) dried (over phosphorus pentoxide)

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

Procedure: To a solution of 148 parts of said methyl N-(1-amino-1-methylthiomethylene)carbamate in 2,000 parts methylene chloride is added 154 parts of 4-chlorophenyl isocyanate. The reaction is stirred overnight. Then to it is added 54 parts of sodium methoxide in 540 parts of methanol. The reaction mixture is then refluxed for one hour. The reaction mass is cooled, and 2,000 parts of ether are added. The solid collected by filtration is dissolved in water and the solution neutralized with hydrochloric acid. The new solid thus formed is collected, dried, and recrystallized from ethanol/H2O to give 140 parts of 3-(4-chlorophenyl)-6-methylthio-s-triazine-2,4-(1H,3H)-dione melting at 292°-295° C. The reaction mixture is then refluxed for one hour The reaction mass is cooled The solid collected by filtration is dissolved in water The new solid thus formed is collected dried recrystallized from ethanol/H2O

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

Procedure: To a solution of 148 parts of methyl N-(1-amino-1-methylthiomethylene)-carbamate, prepared as in Example 2, in 2,000 parts methylene chloride is added 154 parts of p-chlorophenyl isocyanate. The reaction is stirred for 3 days. Then to it is added 54 parts of sodium methoxide in 540 parts of methanol. The reaction mixture is then refluxed for 1 hour. The reaction mass is cooled, and 2,000 parts of ether are added. The solid collected by filtration is dissolved in water and the solution neutralized with hydrochloric acid. The new solid thus formed is collected, dried, and recrystallized from ethanol/H2O to give 140 parts of 3-(p-chlorophenyl)-6-methylthio-s-triazine-2,4(1H,3H)-dione melting at 292°-295°C. The reaction mixture is then refluxed for 1 hour The reaction mass is cooled The solid collected by filtration is dissolved in water The new solid thus formed is collected dried recrystallized from ethanol/H2O