ethyl N-(2-hydroxyethyl)carbamate

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 solution of 32.4 g of 2-bromopropionyl bromide in 70 ml of diethyl ether is added dropwise within one hour while cooling with ice to a solution, cooled to 0° C., of ethyl 2-hyroxyethylcarbamate and 13.1 g of pyridine in 80 ml of diethyl ether. The reaction mixture is then stirred at room temperature for 45 minutes. For the working-up, the mxture is filtered under suction through Celite and the filtrate is poured into water. The aqeuous phase is extracted twice with diethyl ether, and the combined organic phases are washed twice with water and once with saturated sodium chloride solution, dried over anhydrous sodium sulphate and evaporated to dryness. There is obtained ethyl 2-(2-bromopropionyloxy)-ethylcarbamate as a colourless oil which either can be used in the reaction without further purification or can be purified further by chromatography on silica gel with n-hexane/diethyl ether (1:1); nD20 1.4770. while cooling with ice to a solution the mxture is filtered under suction through Celite the filtrate is poured into water The aqeuous phase is extracted twice with diethyl ether the combined organic phases are washed twice with water and once with saturated sodium chloride solution dried over anhydrous sodium sulphate evaporated to dryness

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

実験手順: To a stirred solution of ethyl chloroformate (4 g, 0.037 mol.) and N-hydroxysuccinimide (6.3 g, 0.055 mol.) in 10 mL of DCM at 0° C. under nitrogen atmosphere was added N,N-Diisopropylethylamine (9.5 g, 0.055 mol) in 10 mL of DCM. The progress of the reaction was monitored by thin layer chromatography (TLC). After stirring for 3 hrs at room temperature, the reaction mixture was filtered and the precipitate was washed with 2×10 mL of dichloromethane. The combined filtrate was evaporated and dissolved in 20 mL of acetonitrile, cooled in an ice-bath and then added dropwise a solution of Ethanolamine 23 (3.3 mL, 2.5 eq). The resulting mixture was stirred at ice-bath temperature for 1 h and then overnight at room temperature. The progress of the reaction was monitored by thin layer chromatography (TLC). The reaction mixture was filtered, and the precipitate was washed with 2×10 mL DCM and dried over sodium sulfate. After removing the solvent under reduced pressure, the residue was purified by silica gel column chromatography to give ethyl (2-hydroxyethyl)carbamate. the reaction mixture was filtered the precipitate was washed with 2×10 mL of dichloromethane The combined filtrate was evaporated dissolved in 20 mL of acetonitrile cooled in an ice-bath The resulting mixture was stirred at ice-bath temperature for 1 h overnight at room temperature The reaction mixture was filtered the precipitate was washed with 2×10 mL DCM dried over sodium sulfate After removing the solvent under reduced pressure the residue was purified by silica gel column chromatography

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

実験手順: To a stirred solution of ethyl chloroformate (4 g, 0.037 mol.) and N-hydroxysuccinimide (6.3 g, 0.055 mol.) in 10 mL of DCM at 0° C. under nitrogen atmosphere was added N,N-Diisopropylethylamine (9.5 g, 0.055 mol) in 10 mL of DCM. The progress of the reaction was monitored by thin layer chromatography (TLC). After stirring for 3 hrs at room temperature, the reaction mixture was filtered and the precipitate was washed with 2×10 mL of dichloromethane. The combined filtrate was evaporated and dissolved in 20 mL of acetonitrile, cooled in an ice-bath and then added dropwise a solution of Ethanolamine 23 (3.3 mL, 2.5 eq). The resulting mixture was stirred at ice-bath temperature for 1 h and then overnight at room temperature. The progress of the reaction was monitored by thin layer chromatography (TLC). The reaction mixture was filtered, and the precipitate was washed with 2×10 mL DCM and dried over sodium sulfate. After removing the solvent under reduced pressure, the residue was purified by silica gel column chromatography to give ethyl (2-hydroxyethyl)carbamate. the reaction mixture was filtered the precipitate was washed with 2×10 mL of dichloromethane The combined filtrate was evaporated dissolved in 20 mL of acetonitrile cooled in an ice-bath The resulting mixture was stirred at ice-bath temperature for 1 h overnight at room temperature The reaction mixture was filtered the precipitate was washed with 2×10 mL DCM dried over sodium sulfate After removing the solvent under reduced pressure the residue was purified by silica gel column chromatography

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

実験手順: To a stirred solution of ethyl chloroformate (4 g, 0.037 mol.) and N-hydroxysuccinimide (6.3 g, 0.055 mol.) in 10 mL of DCM at 0° C. under nitrogen atmosphere was added N,N-Diisopropylethylamine (9.5 g, 0.055 mol) in 10 mL of DCM. The progress of the reaction was monitored by thin layer chromatography (TLC). After stirring for 3 hrs at room temperature, the reaction mixture was filtered and the precipitate was washed with 2×10 mL of dichloromethane. The combined filtrate was evaporated and dissolved in 20 mL of acetonitrile, cooled in an ice-bath and then added dropwise a solution of Ethanolamine 23 (3.3 mL, 2.5 eq). The resulting mixture was stirred at ice-bath temperature for 1 h and then overnight at room temperature. The progress of the reaction was monitored by thin layer chromatography (TLC). The reaction mixture was filtered, and the precipitate was washed with 2×10 mL DCM and dried over sodium sulfate. After removing the solvent under reduced pressure, the residue was purified by silica gel column chromatography to give ethyl (2-hydroxyethyl)carbamate. the reaction mixture was filtered the precipitate was washed with 2×10 mL of dichloromethane The combined filtrate was evaporated dissolved in 20 mL of acetonitrile cooled in an ice-bath The resulting mixture was stirred at ice-bath temperature for 1 h overnight at room temperature The reaction mixture was filtered the precipitate was washed with 2×10 mL DCM dried over sodium sulfate After removing the solvent under reduced pressure the residue was purified by silica gel column chromatography

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

実験手順: To a stirred solution of ethyl chloroformate (4 g, 0.037 mol.) and N-hydroxysuccinimide (6.3 g, 0.055 mol.) in 10 mL of DCM at 0° C. under nitrogen atmosphere was added N,N-Diisopropylethylamine (9.5 g, 0.055 mol) in 10 mL of DCM. The progress of the reaction was monitored by thin layer chromatography (TLC). After stirring for 3 hrs at room temperature, the reaction mixture was filtered and the precipitate was washed with 2×10 mL of dichloromethane. The combined filtrate was evaporated and dissolved in 20 mL of acetonitrile, cooled in an ice-bath and then added dropwise a solution of Ethanolamine 23 (3.3 mL, 2.5 eq). The resulting mixture was stirred at ice-bath temperature for 1 h and then overnight at room temperature. The progress of the reaction was monitored by thin layer chromatography (TLC). The reaction mixture was filtered, and the precipitate was washed with 2×10 mL DCM and dried over sodium sulfate. After removing the solvent under reduced pressure, the residue was purified by silica gel column chromatography to give ethyl (2-hydroxyethyl)carbamate. the reaction mixture was filtered the precipitate was washed with 2×10 mL of dichloromethane The combined filtrate was evaporated dissolved in 20 mL of acetonitrile cooled in an ice-bath The resulting mixture was stirred at ice-bath temperature for 1 h overnight at room temperature The reaction mixture was filtered the precipitate was washed with 2×10 mL DCM dried over sodium sulfate After removing the solvent under reduced pressure the residue was purified by silica gel column chromatography

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

実験手順: A solution of 32.4 g of 2-bromopropionyl bromide in 70 ml of diethyl ether is added dropwise within one hour while cooling with ice to a solution, cooled to 0° C., of ethyl 2-hyroxyethylcarbamate and 13.1 g of pyridine in 80 ml of diethyl ether. The reaction mixture is then stirred at room temperature for 45 minutes. For the working-up, the mxture is filtered under suction through Celite and the filtrate is poured into water. The aqeuous phase is extracted twice with diethyl ether, and the combined organic phases are washed twice with water and once with saturated sodium chloride solution, dried over anhydrous sodium sulphate and evaporated to dryness. There is obtained ethyl 2-(2-bromopropionyloxy)-ethylcarbamate as a colourless oil which either can be used in the reaction without further purification or can be purified further by chromatography on silica gel with n-hexane/diethyl ether (1:1); nD20 1.4770. while cooling with ice to a solution the mxture is filtered under suction through Celite the filtrate is poured into water The aqeuous phase is extracted twice with diethyl ether the combined organic phases are washed twice with water and once with saturated sodium chloride solution dried over anhydrous sodium sulphate evaporated to dryness

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

実験手順: A solution of 32.4 g of 2-bromopropionyl bromide in 70 ml of diethyl ether is added dropwise within one hour while cooling with ice to a solution, cooled to 0° C., of ethyl 2-hyroxyethylcarbamate and 13.1 g of pyridine in 80 ml of diethyl ether. The reaction mixture is then stirred at room temperature for 45 minutes. For the working-up, the mxture is filtered under suction through Celite and the filtrate is poured into water. The aqeuous phase is extracted twice with diethyl ether, and the combined organic phases are washed twice with water and once with saturated sodium chloride solution, dried over anhydrous sodium sulphate and evaporated to dryness. There is obtained ethyl 2-(2-bromopropionyloxy)-ethylcarbamate as a colourless oil which either can be used in the reaction without further purification or can be purified further by chromatography on silica gel with n-hexane/diethyl ether (1:1); nD20 1.4770. while cooling with ice to a solution the mxture is filtered under suction through Celite the filtrate is poured into water The aqeuous phase is extracted twice with diethyl ether the combined organic phases are washed twice with water and once with saturated sodium chloride solution dried over anhydrous sodium sulphate evaporated to dryness

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

実験手順: 40.6 grams of ethanolamine were charged to a standard neck reaction vessel fitted with an agitator, packed column and a thermometer. 70.3 grams of ethylene carbonate was added, and the temperature was allowed to rise to 100° C. The mixture was then held at 100° C. for 2 hours. The crude 2-hydroxyethyl urethane of ethanol formed had a viscosity of 4.5 poise at 30° C. (as measured by an ICI cone and plate viscometer) and a base number of 3.0. The residual base number corresponded to a conversion of amine to urethane of 99.4%. The mixture was heated to 150° C. and 689.1 grams of dodecanedioic acid were added. The solution was heated slowly to 220° C., with water being removed continuously, over a 1.5 hour period. The reaction product was then cooled and poured out. The final product had a melting point of 81° C. to 84° C. fitted with an agitator to rise to 100° C

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: 40.6 grams of ethanolamine were charged to a standard neck reaction vessel fitted with an agitator, packed column and a thermometer. 70.3 grams of ethylene carbonate was added, and the temperature was allowed to rise to 100° C. The mixture was then held at 100° C. for 2 hours. The crude 2-hydroxyethyl urethane of ethanol formed had a viscosity of 4.5 poise at 30° C. (as measured by an ICI cone and plate viscometer) and a base number of 3.0. The residual base number corresponded to a conversion of amine to urethane of 99.4%. The mixture was heated to 150° C. and 689.1 grams of dodecanedioic acid were added. The solution was heated slowly to 220° C., with water being removed continuously, over a 1.5 hour period. The reaction product was then cooled and poured out. The final product had a melting point of 81° C. to 84° C. fitted with an agitator to rise to 100° C

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

実験手順: starting from 5,7-dihydro-6H-dibenz[c,e]azepine-6-carbonitrile and ethyl 2-hydroxy-ethylcarbamate, there is obtained 2-ethoxycarbonylamino-ethyl 5,7-dihydro-6H-dibenz[c,e]azepine-6-carboximidate as a resinous product, mass spectrum m/e: M+ 353 (2), 308 (4), 237 (32), 194 (78), 116 (100), 88 (61);