ethyl 3-ethoxypropanoate

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

Procedure: In order to prepare the test coating, 100 grams of the above oligomer were mixed with 0.1 gram of T-12 tin catalyst, and 20 grams of EEP solvent. A second component was prepared from 126.4 grams of isocyanate multifunctional oligomer biurets formed by the reaction product between hexamethylene diisocyanate and water and 20 g of EEP solvent. Three mil wet films were cast from the mixed components which dried hard in two hours and had a Sward hardness of 10 in 24 hours.

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

Procedure: 3-Ethoxy-propionic acid ethyl ester (12.31 g, 84.2 mmol) was dissolved in tetrahydrofuran (40 mL) to which LiHMDS (89 mL, 88.9 mmol, 1.0 M in THF) was slowly added. 4-Cyclopentylamino-2-methylsulfanyl-pyrimidine-5-carbaldehyde (10.0 g, 42.2 mmol) was then added neat and the reaction mixture was stirred at ambient temperature for 17 hours then brought to reflux for 7 hours. The reaction mixture was diluted with ethyl acetate and water, the layers separated, the organic layer dried over MgSO4 and the solvent evaporated to give a crude oil. The crude product was dissolved in ethyl acetate and diluted with hexanes to give a precipitate, which was collected by filtration to give 8-cyclopentyl-6-ethoxymethyl-2-methylsulfanyl-8H-pyrido[2,3-d]pyrimidin-7-one as an off-white solid (4.70 g, 34.9%).1H NMR δ(400 MHz, CDCl3) 8.47 (s, 1H), 7.52 (t, J=1.5 Hz, 1H), 5.82 (m, 1H), 4.32 (d, J=1.7 Hz, 1H), 3.53 (q, J=7.1 Hz, 2H), 2.47 (s, 3H), 2.17 (m, 2H), 1.93 (m, 2H), 1.73 (m, 2H), 1.54 (m, 2H), 1.15 (t, J=7.1 Hz, 3H). was slowly added to reflux for 7 hours the layers separated the organic layer dried over MgSO4 the solvent evaporated to give a crude oil to give a precipitate, which was collected by filtration

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

Procedure: 3-Ethoxy-propionic acid ethyl ester (12.31 g, 84.2 mmol) was dissolved in tetrahydrofuran (40 mL) to which LiHMDS (89 mL, 88.9 mmol, 1.0 M in THF) was slowly added. 4-Cyclopentylamino-2-methylsulfanyl-pyrimidine-5-carbaldehyde (10.0 g, 42.2 mmol) was then added neat and the reaction mixture was stirred at ambient temperature for 17 hours then brought to reflux for 7 hours. The reaction mixture was diluted with ethyl acetate and water, the layers separated, the organic layer dried over MgSO4 and the solvent evaporated to give a crude oil. The crude product was dissolved in ethyl acetate and diluted with hexanes to give a precipitate, which was collected by filtration to give 8-cyclopentyl-6-ethoxymethyl-2-methylsulfanyl-8H-pyrido[2,3-d]pyrimidin-7-one as an off-white solid (4.70 g, 34.9%).1H NMR δ(400 MHz, CDCl3) 8.47 (s, 1H), 7.52 (t, J=1.5 Hz, 1H), 5.82 (m, 1H), 4.32 (d, J=1.7 Hz, 1H), 3.53 (q, J=7.1 Hz, 2H), 2.47 (s, 3H), 2.17 (m, 2H), 1.93 (m, 2H), 1.73 (m, 2H), 1.54 (m, 2H), 1.15 (t, J=7.1 Hz, 3H). was slowly added to reflux for 7 hours the layers separated the organic layer dried over MgSO4 the solvent evaporated to give a crude oil to give a precipitate, which was collected by filtration

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

Procedure: 3-Ethoxy-propionic acid ethyl ester (12.31 g, 84.2 mmol) was dissolved in tetrahydrofuran (40 mL) to which LiHMDS (89 mL, 88.9 mmol, 1.0 M in THF) was slowly added. 4-Cyclopentylamino-2-methylsulfanyl-pyrimidine-5-carbaldehyde (10.0 g, 42.2 mmol) was then added neat and the reaction mixture was stirred at ambient temperature for 17 hours then brought to reflux for 7 hours. The reaction mixture was diluted with ethyl acetate and water, the layers separated, the organic layer dried over MgSO4 and the solvent evaporated to give a crude oil. The crude product was dissolved in ethyl acetate and diluted with hexanes to give a precipitate, which was collected by filtration to give 8-cyclopentyl-6-ethoxymethyl-2-methylsulfanyl-8H-pyrido[2,3-d]pyrimidin-7-one as an off-white solid (4.70 g, 34.9%). 1H NMR δ (400 MHz, CDCl3) 8.47 (s, 1H), 7.52 (t, J=1.5 Hz, 1H), 5.82 (m, 1H), 4.32 (d, J=1.7 Hz, 1H), 3.53 (q, J=7.1 Hz, 2H), 2.47 (s, 3H), 2.17 (m, 2H), 1.93 (m, 2H), 1.73 (m, 2H), 1.54 (m, 2H), 1.15 (t, J=7.1 Hz, 3H). was slowly added to reflux for 7 hours the layers separated the organic layer dried over MgSO4 the solvent evaporated to give a crude oil to give a precipitate, which was collected by filtration

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

Procedure: In order to prepare the test coating, 100 grams of the above oligomer were mixed with 0.1 gram of T-12 tin catalyst, and 20 grams of EEP solvent. A second component was prepared from 126.4 grams of isocyanate multifunctional oligomer biurets formed by the reaction product between hexamethylene diisocyanate and water and 20 g of EEP solvent. Three mil wet films were cast from the mixed components which dried hard in two hours and had a Sward hardness of 10 in 24 hours.

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

Procedure: 3-Ethoxy-propionic acid ethyl ester (12.31 g, 84.2 mmol) was dissolved in tetrahydrofuran (40 mL) to which LiHMDS (89 mL, 88.9 mmol, 1.0 M in THF) was slowly added. 4-Cyclopentylamino-2-methylsulfanyl-pyrimidine-5-carbaldehyde (10.0 g, 42.2 mmol) was then added neat and the reaction mixture was stirred at ambient temperature for 17 hours then brought to reflux for 7 hours. The reaction mixture was diluted with ethyl acetate and water, the layers separated, the organic layer dried over MgSO4 and the solvent evaporated to give a crude oil. The crude product was dissolved in ethyl acetate and diluted with hexanes to give a precipitate, which was collected by filtration to give 8-cyclopentyl-6-ethoxymethyl-2-methylsulfanyl-8H-pyrido[2,3-d]pyrimidin-7-one as an off-white solid (4.70 g, 34.9%).1H NMR δ(400 MHz, CDCl3) 8.47 (s, 1H), 7.52 (t, J=1.5 Hz, 1H), 5.82 (m, 1H), 4.32 (d, J=1.7 Hz, 1H), 3.53 (q, J=7.1 Hz, 2H), 2.47 (s, 3H), 2.17 (m, 2H), 1.93 (m, 2H), 1.73 (m, 2H), 1.54 (m, 2H), 1.15 (t, J=7.1 Hz, 3H). was slowly added to reflux for 7 hours the layers separated the organic layer dried over MgSO4 the solvent evaporated to give a crude oil to give a precipitate, which was collected by filtration

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

Procedure: A 100 ml three-necked round bottom flask equipped with a dry ice condenser, magnetic stirrer, gas inlet and thermometer was charged with 40 ml of diethoxymethane, 5.0 g of ethyl 3-ethoxypropionate and 1.00 g dodecane (an internal standard for gas-liquid chromatography analysis), and the flask was placed in a 30° C. water bath. Ketene gas, produced by cracking diketene in a 550° C. furnace, was added until the solution became saturated. A portion (0.1143 g) of the catalyst prepared as described above and stored for one week at room temperature, was added on the tip of the thermometer. An exothermic reaction ensued, briefly raising the pot temperature to 80° C. The mixture was kept saturated with ketene for 30 minutes. The mixture was then analyzed by gas-liquid chromatography, and it was found that the 0.1143 g of catalyst had produced 17.3 g of ethyl 3-ethoxypropionate, not including the 5 grams added at the start. This catalyst was thus capable of producing 156 g of ethyl 3-ethoxypropionate for each gram of catalyst. A 100 ml three-necked round bottom flask equipped with a dry ice condenser, magnetic stirrer, gas inlet was placed in a 30° C.

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

Procedure: A 100 ml three-necked round bottom flask equipped with a dry ice condenser, magnetic stirrer, gas inlet and thermometer was charged with 40 ml of diethoxymethane, 5.0 g of ethyl 3-ethoxypropionate and 1.00 g dodecane (an internal standard for gas-liquid chromatography analysis), and the flask was placed in a 30° C. water bath. Ketene gas, produced by cracking diketene in a 550° C. furnace, was added until the solution became saturated. A portion (0.1143 g) of the catalyst prepared as described above and stored for one week at room temperature, was added on the tip of the thermometer. An exothermic reaction ensued, briefly raising the pot temperature to 80° C. The mixture was kept saturated with ketene for 30 minutes. The mixture was then analyzed by gas-liquid chromatography, and it was found that the 0.1143 g of catalyst had produced 17.3 g of ethyl 3-ethoxypropionate, not including the 5 grams added at the start. This catalyst was thus capable of producing 156 g of ethyl 3-ethoxypropionate for each gram of catalyst. A 100 ml three-necked round bottom flask equipped with a dry ice condenser, magnetic stirrer, gas inlet was placed in a 30° C.

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

Procedure: A 50 cm long, 5 cm diameter water-jacketted reactor (Reactor C) was charged with 1 liter of Dowex MSA 1 strong base resin. The resin was treated in sequence with 2000 ml of ethanol, 2000 ml of water, 3800 ml of 4 weight percent aqueous sodium hydroxide, and 5000 ml of methanol-ethanol mixture. This reactor was used to react mixtures containing ethyl acrylate and both methanol and ethanol to produce mixtures of ethyl 3-methoxypropanoate, methyl 3-ethoxypropanoate, ethyl 3-ethoxypropanoate and methyl 3-methoxypropanoate. In each run about 7.5 liters of a feed solution containing the components identified in Table IV was used. There was no problem of ethyl acrylate breakthrough at the end of each run. The mixture was recovered by distillation to remove the alcohols. was charged with 1 liter of Dowex MSA 1 strong base resin This reactor was used to react mixtures

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

Procedure: 3-Ethoxy-propionic acid ethyl ester (12.31 g, 84.2 mmol) was dissolved in tetrahydrofuran (40 mL) to which LiHMDS (89 mL, 88.9 mmol, 1.0 M in THF) was slowly added. 4-Cyclopentylamino-2-methylsulfanyl-pyrimidine-5-carbaldehyde (10.0 g, 42.2 mmol) was then added neat and the reaction mixture was stirred at ambient temperature for 17 hours then brought to reflux for 7 hours. The reaction mixture was diluted with ethyl acetate and water, the layers separated, the organic layer dried over MgSO4 and the solvent evaporated to give a crude oil. The crude product was dissolved in ethyl acetate and diluted with hexanes to give a precipitate, which was collected by filtration to give 8-cyclopentyl-6-ethoxymethyl-2-methylsulfanyl-8H-pyrido[2,3-d]pyrimidin-7-one as an off-white solid (4.70 g, 34.9%). 1H NMR δ (400 MHz, CDCl3) 8.47 (s, 1H), 7.52 (t, J=1.5 Hz, 1H), 5.82 (m, 1H), 4.32 (d, J=1.7 Hz, 1H), 3.53 (q, J=7.1 Hz, 2H), 2.47 (s, 3H), 2.17 (m, 2H), 1.93 (m, 2H), 1.73 (m, 2H), 1.54 (m, 2H), 1.15 (t, J=7.1 Hz, 3H). was slowly added to reflux for 7 hours the layers separated the organic layer dried over MgSO4 the solvent evaporated to give a crude oil to give a precipitate, which was collected by filtration

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

Procedure: 3-Ethoxy-propionic acid ethyl ester (12.31 g, 84.2 mmol) was dissolved in tetrahydrofuran (40 mL) to which LiHMDS (89 mL, 88.9 mmol, 1.0 M in THF) was slowly added. 4-Cyclopentylamino-2-methylsulfanyl-pyrimidine-5-carbaldehyde (10.0 g, 42.2 mmol) was then added neat and the reaction mixture was stirred at ambient temperature for 17 hours then brought to reflux for 7 hours. The reaction mixture was diluted with ethyl acetate and water, the layers separated, the organic layer dried over MgSO4 and the solvent evaporated to give a crude oil. The crude product was dissolved in ethyl acetate and diluted with hexanes to give a precipitate, which was collected by filtration to give 8-cyclopentyl-6-ethoxymethyl-2-methylsulfanyl-8H-pyrido[2,3-d]pyrimidin-7-one as an off-white solid (4.70 g, 34.9%). 1H NMR δ (400 MHz, CDCl3) 8.47 (s, 1H), 7.52 (t, J=1.5 Hz, 1H), 5.82 (m, 1H), 4.32 (d, J=1.7 Hz, 1H), 3.53 (q, J=7.1 Hz, 2H), 2.47 (s, 3H), 2.17 (m, 2H), 1.93 (m, 2H), 1.73 (m, 2H), 1.54 (m, 2H), 1.15 (t, J=7.1 Hz, 3H). was slowly added to reflux for 7 hours the layers separated the organic layer dried over MgSO4 the solvent evaporated to give a crude oil to give a precipitate, which was collected by filtration

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

Procedure: In order to prepare the test coating, 100 grams of the above oligomer were mixed with 0.1 gram of T-12 tin catalyst, and 20 grams of EEP solvent. A second component was prepared from 126.4 grams of isocyanate multifunctional oligomer biurets formed by the reaction product between hexamethylene diisocyanate and water and 20 g of EEP solvent. Three mil wet films were cast from the mixed components which dried hard in two hours and had a Sward hardness of 10 in 24 hours.