ethyl 2-(N-methylanilino)acetate

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

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

Procedure: A solution of 15.5 g (80 mmol) of ethyl N-methyl-N-phenylglycinate in 80 g of ice and 40 mL of conc.HCl was stirred at 0-5° while a solution of 6 g (87 mmol) of NaNO2 in 40 mL of water was added dropwise over 30 min. After stirring at this temp. for 1 hr, a solution of 27 g (250 mmol) of Na2CO3 in 150 mL of water was added dropwise with cooling. The green solid was collected, washed with cold water, extracted into CH2Cl2, passed thorugh silica with CH2Cl2 to remove an impurity, and the product eluded with 10% ethyl acetate/CH2Cl2 to give 14.7 g (66 mmol, 83%) mp 55-56° after washing with 10% ethyl acetate/hexane. Anal. C11H14N2O3 (222): Calcd.: C,59.45; H,6,35; N,12.60. Found: C,59.46; H,6.14; N,12.49. MS(FD) m/z 222. 1H NMR(CDCl3)δ: 7.8,broad s,2H,ArH; 6.69,d,2H,ArH; 4.22,q,2H,CH2—O; 4.20,s,2H,CH2—N; 3.23,s,3H,CH3—N; 1.27,t,3H,CH3—C. was added dropwise over 30 min with cooling The green solid was collected washed with cold water extracted into CH2Cl2 to remove an impurity to give 14.7 g (66 mmol, 83%) mp 55-56° after washing with 10% ethyl acetate/hexane

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

Procedure: A solution of 16.7 g (100 mmol) of ethyl bromoacetate, 10.7 g (100 mmol) of N-methylaniline, and 12.9 g (100 mmol) of N,N-diisopropylethylamine in 100 mL of acetonitrile was allowed to stand for 24hr. and then diluted with 200 ml of ether. The amine salt was filtered and the filtrate concentrated, dissolved in 150 ml of CH2Cl2, washed with water, filtered through a plug of sodium sulfate/silica and distilled: 15.5 g (80%), b.p. 132°/12 mm. The amine salt was filtered the filtrate concentrated dissolved in 150 ml of CH2Cl2 washed with water filtered through a plug of sodium sulfate/silica distilled

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

Procedure: To a solution of bromoethylacetate, 3.3 mL (30.0 mmol) in 100 mL of tetrahydrofuran was added 4.14 g (30.0 mmol) of potassium carbonate and 3.25 mL of N-methylaniline. The reaction mixture stirred overnight at rt. and was concentrated to dryness. The residue was partitioned between 20% isopropanol/chloroform and saturated aqueous NaHCO3. The mixture was washed with saturated NaHCO3, washed with brine, dried over Na2SO4, filtered and concentrated to dryness. The residue was purified by column chromatography using EtOAc/hexanes as eluent and concentrated to dryness to give 4.74 g (82%) of the desired product as a tan oil. MS (ion spray) 194.1 (M+1). and was concentrated to dryness The residue was partitioned between 20% isopropanol/chloroform and saturated aqueous NaHCO3 The mixture was washed with saturated NaHCO3 washed with brine dried over Na2SO4 filtered concentrated to dryness The residue was purified by column chromatography concentrated to dryness

Conditions: temp:150.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Into a 100 ml. flask fitted with a condenser and a Dean-Stark trap there were placed 49.5 gms. ethylene glycol, 17 gms. of ethyl N-methyl-N-phenylglycinate and 0.7 gm. sodium methoxide. The flask and contents were heated to 150° C. in an oil bath and stirred for 13 hours. The reaction mixture was allowed to cool to room temperature and 1.25 ml. of concentrated HCl in 3.5 ml. water were added and the mixture was stirred for 10 minutes. After the ethylene glycol was distilled off at atmospheric pressure, 11.5 gms. of product was obtained by vacuum distillation, b.p. (0.3 mm.) 139°-149° C. flask fitted with a condenser to cool to room temperature the mixture was stirred for 10 minutes After the ethylene glycol was distilled off at atmospheric pressure, 11.5 gms of product was obtained by vacuum distillation, b.p (0.3 mm.) 139°-149° C.

Conditions: temp:150.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Into a 100 ml. flask fitted with a condenser and a Dean-Stark trap there were placed 49.5 gms. ethylene glycol, 17 gms. of ethyl N-methyl-N-phenylglycinate and 0.7 gm. sodium methoxide. The flask and contents were heated to 150° C. in an oil bath and stirred for 13 hours. The reaction mixture was allowed to cool to room temperature and 1.25 ml. of concentrated HCl in 3.5 ml. water were added and the mixture was stirred for 10 minutes. After the ethylene glycol was distilled off at atmospheric pressure, 11.5 gms. of product was obtained by vacuum distillation, b.p. (0.3 mm.) 139°-149° C. flask fitted with a condenser to cool to room temperature the mixture was stirred for 10 minutes After the ethylene glycol was distilled off at atmospheric pressure, 11.5 gms of product was obtained by vacuum distillation, b.p (0.3 mm.) 139°-149° C.

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

Procedure: A solution of 15.5 g (80 mmol) of ethyl N-methyl-N-phenylglycinate in 80 g of ice and 40 mL of conc.HCl was stirred at 0-5° while a solution of 6 g (87 mmol) of NaNO2 in 40 mL of water was added dropwise over 30 min. After stirring at this temp. for 1 hr, a solution of 27 g (250 mmol) of Na2CO3 in 150 mL of water was added dropwise with cooling. The green solid was collected, washed with cold water, extracted into CH2Cl2, passed thorugh silica with CH2Cl2 to remove an impurity, and the product eluded with 10% ethyl acetate/CH2Cl2 to give 14.7 g (66 mmol, 83%) mp 55-56° after washing with 10% ethyl acetate/hexane. Anal. C11H14N2O3 (222): Calcd.: C,59.45; H,6,35; N,12.60. Found: C,59.46; H,6.14; N,12.49. MS(FD) m/z 222. 1H NMR(CDCl3)δ: 7.8,broad s,2H,ArH; 6.69,d,2H,ArH; 4.22,q,2H,CH2 --O; 4.20,s,2H,CH2 --N; 3.23,s,3H,CH3 --N; 1.27,t,3H,CH3 --C. was added dropwise over 30 min with cooling The green solid was collected washed with cold water extracted into CH2Cl2 to remove an impurity to give 14.7 g (66 mmol, 83%) mp 55-56° after washing with 10% ethyl acetate/hexane

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

Procedure: A solution of 16.7 g (100 mmol) of ethyl bromoacetate, 10.7 g (100 mmol) of N-methylaniline, and 12.9 g (100 mmol) of N,N-diisopropylethylamine in 100 mL of acetonitrile was allowed to stand for 24 hr. and then diluted with 200 ml of ether. The amine salt was filtered and the filtrate concentrated, dissolved in 150 ml of CH2Cl2, washed with water, filtered through a plug of sodium sulfate/silica and distilled: 15.5 g (80%), b.p. 132°/12 mm. The amine salt was filtered the filtrate concentrated dissolved in 150 ml of CH2Cl2 washed with water filtered through a plug of sodium sulfate/silica distilled

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

Procedure: A solution of 16.7 g (100 mmol) of ethyl bromoacetate, 10.7 g (100 mmol) of N-methylaniline, and 12.9 g (100 mmol) of N,N-diisopropylethylamine in 100 mL of acetonitrile was allowed to stand for 24 hr. and then diluted with 200 ml of ether. The amine salt was filtered and the filtrate concentrated, dissolved in 150 ml of CH2Cl2, washed with water, filtered through a plug of sodium sulfate/silica and distilled: 15.5 g (80%), b.p. 132°/12 mm. The amine salt was filtered the filtrate concentrated dissolved in 150 ml of CH2Cl2 washed with water filtered through a plug of sodium sulfate/silica distilled

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

Procedure: A solution of 15.5 g (80 mmol) of ethyl N-methyl-N-phenylglycinate in 80 g of ice and 40 mL of conc.HCl was stirred at 0-5° while a solution of 6 g (87 mmol) of NaNO2 in 40 mL of water was added dropwise over 30 min. After stirring at this temp. for 1 hr, a solution of 27 g (250 mmol) of Na2CO3 in 150 mL of water was added dropwise with cooling. The green solid was collected, washed with cold water, extracted into CH2Cl2, passed thorugh silica with CH2Cl2 to remove an impurity, and the product eluded with 10% ethyl acetate/CH2Cl2 to give 14.7 g (66 mmol, 83%) mp 55-56° after washing with 10% ethyl acetate/hexane. Anal. C11H14N2O3 (222): Calcd.: C,59.45; H,6,35; N,12.60. Found: C,59.46; H,6.14; N,12.49. MS(FD) m/z 222. 1H NMR(CDCl3)δ: 7.8,broad s,2H,ArH; 6.69,d,2H,ArH; 4.22,q,2H,CH2—O; 4.20,s,2H,CH2—N; 3.23,s,3H,CH3—N; 1.27,t,3H,CH3—C. was added dropwise over 30 min with cooling The green solid was collected washed with cold water extracted into CH2Cl2 to remove an impurity to give 14.7 g (66 mmol, 83%) mp 55-56° after washing with 10% ethyl acetate/hexane

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

Procedure: A solution of 16.7 g (100 mmol) of ethyl bromoacetate, 10.7 g (100 mmol) of N-methylaniline, and 12.9 g (100 mmol) of N,N-diisopropylethylamine in 100 mL of acetonitrile was allowed to stand for 24hr. and then diluted with 200 ml of ether. The amine salt was filtered and the filtrate concentrated, dissolved in 150 ml of CH2Cl2, washed with water, filtered through a plug of sodium sulfate/silica and distilled: 15.5 g (80%), b.p. 132°/12 mm. The amine salt was filtered the filtrate concentrated dissolved in 150 ml of CH2Cl2 washed with water filtered through a plug of sodium sulfate/silica distilled

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

Procedure: To a solution of bromoethylacetate, 3.3 mL (30.0 mmol) in 100 mL of tetrahydrofuran was added 4.14 g (30.0 mmol) of potassium carbonate and 3.25 mL of N-methylaniline. The reaction mixture stirred overnight at rt. and was concentrated to dryness. The residue was partitioned between 20% isopropanol/chloroform and saturated aqueous NaHCO3. The mixture was washed with saturated NaHCO3, washed with brine, dried over Na2SO4, filtered and concentrated to dryness. The residue was purified by column chromatography using EtOAc/hexanes as eluent and concentrated to dryness to give 4.74 g (82%) of the desired product as a tan oil. MS (ion spray) 194.1 (M+1). and was concentrated to dryness The residue was partitioned between 20% isopropanol/chloroform and saturated aqueous NaHCO3 The mixture was washed with saturated NaHCO3 washed with brine dried over Na2SO4 filtered concentrated to dryness The residue was purified by column chromatography concentrated to dryness