ethyl N-hydroxycarbamate

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

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

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

Procedure: 50 ml of a methanolic solution of 12.3 g (0.22 mole) of potassium hydroxide was added to 50 ml of an ice-cooled methanolic solution of 23.1 g (0.22 mole) of N-carboethoxyhydroxylamine to prepare a solution containing a potassium salt of N-carboethoxyhydroxylamine, and 50 ml of a methanolic solution of 33.7 g (0.2 mole) of 2,4,6-trimethylbenzyl chloride was added to the resulting solution at room temperature. The resulting mixture was heated under refluxing for 1 hour, and the solvent was distilled off. 150 ml of diethyl ether and 50 ml of water were then added to the residue and the organic layer was separated, dried over anhydrous sodium sulfate and concentrated under a reduced pressure. The residue thus obtained was distilled under a reduced pressure to obtain 25.5 g (53.8% yield) of substantially pure N-carboethoxy-O-(2,4,6-trimethylbenzyl)hydroxylamine having a boiling point of 148°-153° C/0.9 mmHg. to prepare a solution was added to the resulting solution at room temperature The resulting mixture was heated under refluxing for 1 hour the solvent was distilled off 150 ml of diethyl ether and 50 ml of water were then added to the residue the organic layer was separated dried over anhydrous sodium sulfate concentrated under a reduced pressure The residue thus obtained was distilled under a reduced pressure

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

Procedure: 0.9 g of carbonyldiimidazole was added to a solution of 1.8 g of 3-(3-hydroxymethyl-4-chloro-6-fluorophenyl)-1-amino-6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione in 100 ml of tetrahydrofuran. After the reaction mixture had been stirred for 1 hour, 0.58 g of N-ethoxycarbonylhydroxylamine was added. The mixture was subsequently stirred for a further 14 hours at 20° C. whereupon the solvent was removed by distillation. The residue was taken up in 100 ml of methylene chloride. The resulting organic phase was washed with water, dried over sodium sulfate and finally concentrated. The crude product was purified by means of chromatography on silica gel (eluent: methylene chloride). Yield: 0.2 g. The mixture was subsequently stirred for a further 14 hours at 20° C. whereupon the solvent was removed by distillation The resulting organic phase was washed with water dried over sodium sulfate finally concentrated The crude product was purified by means of chromatography on silica gel (eluent: methylene chloride)

Conditions: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 100 g of N-hydroxyurethane and 80.3 g of allyl chloride were added, at 20° C., to a solution of 53.8 g of potassium hydroxide in 750 ml of ethanol. The mixture was stirred and refluxed (80° C.) for 4 hours, then was cooled to 25° C. and filtered. The solvent was evaporated from the filtrate and the residue, an oil, was distilled, 51°-55° C., 0.2 Torr., to give ethyl (2-propenyloxy)carbamate, 3A, as a colorless oil. was cooled to 25° C. filtered The solvent was evaporated from the filtrate the residue, an oil, was distilled, 51°-55° C.

Conditions: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 100 g of N-hydroxyurethane and 80.3 g of allyl chloride were added, at 20° C., to a solution of 53.8 g of potassium hydroxide in 750 ml of ethanol. The mixture was stirred and refluxed (80° C.) for 4 hours, then was cooled to 25° C. and filtered. The solvent was evaporated from the filtrate and the residue, an oil, was distilled, 51°-55° C., 0.2 Torr., to give ethyl (2-propenyloxy)carbamate, 3A, as a colorless oil. was cooled to 25° C. filtered The solvent was evaporated from the filtrate the residue, an oil, was distilled, 51°-55° C.

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

Procedure: 4-Chlorobenzoyl chloride (1.10 mL, 8.57 mmol) is added slowly to a solution of ethyl hydroxycarbamate 6 (1.00 g, 9.52 mmol) and triethylamine (1.19 mL, 8.57 mmol) in diethyl ether (30 mL) at 0° C. then stirred at room temperature for 30 min. The reaction is quenched with HCl (1 M; 10 mL) then water (100 mL) is added and extracted with diethyl ether (100 mL). The organic layer is washed with sat. NaHCO3 (50 mL), water (50 mL), dried with MgSO4 and concentrated. The residue is purified by flash column chromatography (silica gel, petroleum ether/ethyl acetate 9:1 then 8:2) to yield 7 (1.54 g) as an off-white solid. M.p. 79° C. (determined by differential scanning calorimetry, sharp onset); FTIR (neat, cm−1) 3210, 3094, 2990, 1765, 1708, 1588, 1495, 1487, 1473, 1443, 1401, 1368, 1298, 1283, 1249, 1235, 1177, 1121, 1107, 1090, 1054, 1016, 996, 876, 852, 771, 747, 728, 681; 1H NMR (500 MHz, CDCl3) δ 8.34 (s, 1H), 8.02 (dt, J=2.1, 8.7 Hz, 2H), 7.46 (dt, J=2.1, 8.7 Hz, 2H), 4.28 (q, J=7.1 Hz, 2H), 1.31 (t, J=7.1 Hz, 3H); 13C NMR (125 MHz, CDCl3) δ 165.1, 156.6, 140.9, 131.3, 129.1, 125.2, 63.0, 14.3; HRMS (ES+) m/z calcd for C10H10ClNO4 (M+Na)+ 266.0191, found 266.0199. The reaction is quenched with HCl (1 M; 10 mL) water (100 mL) is added extracted with diethyl ether (100 mL) The organic layer is washed with sat. NaHCO3 (50 mL), water (50 mL) dried with MgSO4 concentrated The residue is purified by flash column chromatography (silica gel, petroleum ether/ethyl acetate 9:1

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

Procedure: 41.9 parts by weight of hexane-1,6-diol are melted together in powder form at about 85° C and then treated at 130° C with 583 parts by weight of a hydroxyurethane with a hydroxyl content of 6% by weight obtained from 1 mol of hexane-1,6-diol, 0.7 mol of 1,1,1-trimethylolpropane, 1.8% by weight of caprolactam and 1.3 mol of tolylene diisocyanate (mixture of isomers 2,4 : 2,6 = 80 : 20) to form a highly fluid melt which can easily be stirred. Its viscosity is about 320 cP at 105° C. are melted together in powder form at about 85° C

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

Procedure: 41.9 parts by weight of hexane-1,6-diol are melted together in powder form at about 85° C and then treated at 130° C with 583 parts by weight of a hydroxyurethane with a hydroxyl content of 6% by weight obtained from 1 mol of hexane-1,6-diol, 0.7 mol of 1,1,1-trimethylolpropane, 1.8% by weight of caprolactam and 1.3 mol of tolylene diisocyanate (mixture of isomers 2,4 : 2,6 = 80 : 20) to form a highly fluid melt which can easily be stirred. Its viscosity is about 320 cP at 105° C. are melted together in powder form at about 85° C

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

Procedure: 50 ml of a methanolic solution of 12.3 g (0.22 mole) of potassium hydroxide was added to 50 ml of an ice-cooled methanolic solution of 23.1 g (0.22 mole) of N-carboethoxyhydroxylamine to prepare a solution containing a potassium salt of N-carboethoxyhydroxylamine, and 50 ml of a methanolic solution of 33.7 g (0.2 mole) of 2,4,6-trimethylbenzyl chloride was added to the resulting solution at room temperature. The resulting mixture was heated under refluxing for 1 hour, and the solvent was distilled off. 150 ml of diethyl ether and 50 ml of water were then added to the residue and the organic layer was separated, dried over anhydrous sodium sulfate and concentrated under a reduced pressure. The residue thus obtained was distilled under a reduced pressure to obtain 25.5 g (53.8% yield) of substantially pure N-carboethoxy-O-(2,4,6-trimethylbenzyl)hydroxylamine having a boiling point of 148°-153° C/0.9 mmHg. to prepare a solution was added to the resulting solution at room temperature The resulting mixture was heated under refluxing for 1 hour the solvent was distilled off 150 ml of diethyl ether and 50 ml of water were then added to the residue the organic layer was separated dried over anhydrous sodium sulfate concentrated under a reduced pressure The residue thus obtained was distilled under a reduced pressure

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

Procedure: 50 ml of a methanolic solution of 12.3 g (0.22 mole) of potassium hydroxide was added to 50 ml of an ice-cooled methanolic solution of 23.1 g (0.22 mole) of N-carboethoxyhydroxylamine to prepare a solution containing a potassium salt of N-carboethoxyhydroxylamine, and 50 ml of a methanolic solution of 33.7 g (0.2 mole) of 2,4,6-trimethylbenzyl chloride was added to the resulting solution at room temperature. The resulting mixture was heated under refluxing for 1 hour, and the solvent was distilled off. 150 ml of diethyl ether and 50 ml of water were then added to the residue and the organic layer was separated, dried over anhydrous sodium sulfate and concentrated under a reduced pressure. The residue thus obtained was distilled under a reduced pressure to obtain 25.5 g (53.8% yield) of substantially pure N-carboethoxy-O-(2,4,6-trimethylbenzyl)hydroxylamine having a boiling point of 148°-153° C/0.9 mmHg. to prepare a solution was added to the resulting solution at room temperature The resulting mixture was heated under refluxing for 1 hour the solvent was distilled off 150 ml of diethyl ether and 50 ml of water were then added to the residue the organic layer was separated dried over anhydrous sodium sulfate concentrated under a reduced pressure The residue thus obtained was distilled under a reduced pressure

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