2-prop-2-enoxyethanol

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

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

Procedure: Combine allyl hydroxyethyl ether (1.02 g, 10 mmol), and diisopropylethylamine (4.0 mL, 23 mmol), and dichloromethane (20 mL). Cool in an ice-bath. Add dropwise, methanesulfonyl chloride (1.0 mL, 13 mmol). After 1.5 hours, extract the reaction mixture with 1M aqueous hydrochloric acid solution, saturated aqueous sodium bicarbonate solution, and saturated aqueous sodium chloride solution. Dry the organic layer over Na2SO4, filter, and evaporate in vacuo to obtain allyl methanesulfonylethyl ether: Rf=0.80 (silica gel, 20% ethyl acetate/dichloromethane). Cool in an ice-bath Add dropwise extract the reaction mixture with 1M aqueous hydrochloric acid solution, saturated aqueous sodium bicarbonate solution, and saturated aqueous sodium chloride solution Dry the organic layer over Na2SO4 filter evaporate in vacuo

Conditions: temp:190.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In a 300 mL autoclave equipped with a thermal couple and a mechanical stirrer, a mixture of 2-allyloxyethanol (109.5 g, 1.07 mol) and dicyclopentadiene (35.4 g, 0.27 mol) was stirred and heated to 190° C. The reaction was cooled after 3 h. Three such reactions were run and the reaction mixtures were combined. The mixture was distilled using a short-path distillation column under vacuum at 70° C. at 500 mTorr. The distillate (170 g) was dissolved in a mixture of 250 mL of CH3OH and 150 mL of H2O. Hexane (3×125 mL) was added to the mixture in order to extract out cyclopentadiene impurities. To the remaining methanol/water solution NaCl was added to force the product to oil out from solution. Ethyl acetate (200 mL) was added to extract the oil from water. After the solvents were removed by rotovaporation the product was dried under vacuum. Yield 157 g (58%). 1H NMR (500 MHz, CDCl3): Endo isomer: 6.13 (m, 1H); 5.93 (m, 1H); 3.72 (t, 2H); 3.52 (m, 2H); 3.22 (t, 1H); 3.10 (t, 1H); 2.90 (s, 1H); 2.80 (s, 1H); 2.37 (m, 1H); 2.09 (br s, 1H); 1.82 (m, 1H); 1.43 (d, 1H), 1.26 (d, 1H), 0.50 (d of t, 1H). Exo isomer: 6.10 (m, 1H); 6.07 (m, 1H); 3.75 (t, 2H); 3.36 (m, 2H); 3.50 (t, 1H); 3.40 (t, 1H); 2.80 (s, 1H); 2.74 (s, 1H); 2.09 (br s, 1H); 1.71 (m, 1H); 1.33 (d, 1H), 1.30 (d, 1H); 1.24 (m, partially obscured by endo isomer, 1H); 1.11 (d of t, 1H). Endo/exo ratio by 1H NMR was determined to be 82/18. In a 300 mL autoclave equipped with a thermal couple and a mechanical stirrer The reaction was cooled after 3 h the reaction mixtures The mixture was distilled a short-path distillation column under vacuum at 70° C. at 500 mTorr The distillate (170 g) was dissolved in a mixture of 250 mL of CH3OH and 150 mL of H2O Hexane (3×125 mL) was added to the mixture in order to extract out cyclopentadiene impurities To the remaining methanol/water solution NaCl was added Ethyl acetate (200 mL) was added to extract the oil from water After the solvents were removed by rotovaporation the product was dried under vacuum

Conditions: temp:190.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In a 300 mL autoclave equipped with a thermal couple and a mechanical stirrer, a mixture of 2-allyloxyethanol (109.5 g, 1.07 mol) and dicyclopentadiene (35.4 g, 0.27 mol) was stirred and heated to 190° C. The reaction was cooled after 3 h. Three such reactions were run and the reaction mixtures were combined. The mixture was distilled using a short-path distillation column under vacuum at 70° C. at 500 mTorr. The distillate (170 g) was dissolved in a mixture of 250 mL of CH3OH and 150 mL of H2O. Hexane (3×125 mL) was added to the mixture in order to extract out cyclopentadiene impurities. To the remaining methanol/water solution NaCl was added to force the product to oil out from solution. Ethyl acetate (200 mL) was added to extract the oil from water. After the solvents were removed by rotovaporation the product was dried under vacuum. Yield 157 g (58%). 1H NMR (500 MHz, CDCl3): Endo isomer: 6.13 (m, 1H); 5.93 (m, 1H); 3.72 (t, 2H); 3.52 (m, 2H); 3.22 (t, 1H); 3.10 (t, 1H); 2.90 (s, 1H); 2.80 (s, 1H); 2.37 (m, 1H); 2.09 (br s, 1H); 1.82 (m, 1H); 1.43 (d, 1H), 1.26 (d, 1H), 0.50 (d of t, 1H). Exo isomer: 6.10 (m, 1H); 6.07 (m, 1H); 3.75 (t, 2H); 3.36 (m, 2H); 3.50 (t, 1H); 3.40 (t, 1H); 2.80 (s, 1H); 2.74 (s, 1H); 2.09 (br s, 1H); 1.71 (m, 1H); 1.33 (d, 1H), 1.30 (d, 1H); 1.24 (m, partially obscured by endo isomer, 1H); 1.11 (d of t, 1H). Endo/exo ratio by 1H NMR was determined to be 82/18. In a 300 mL autoclave equipped with a thermal couple and a mechanical stirrer The reaction was cooled after 3 h the reaction mixtures The mixture was distilled a short-path distillation column under vacuum at 70° C. at 500 mTorr The distillate (170 g) was dissolved in a mixture of 250 mL of CH3OH and 150 mL of H2O Hexane (3×125 mL) was added to the mixture in order to extract out cyclopentadiene impurities To the remaining methanol/water solution NaCl was added Ethyl acetate (200 mL) was added to extract the oil from water After the solvents were removed by rotovaporation the product was dried under vacuum

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 50-mL two-necked flask is purged with nitrogen and then charged with 2-allyloxyethanol (2.5 mL, 23.4 mmol), pyridine (3 mL) and THF (10 mL). The solution is cooled to 0° C., and 2-bromopropionyl chloride (2 mL, 19.52 mmol) is added dropwise slowly. The resulting mixture is stirred at that temperature for an hour, then ethyl acetate (10 mL) is added, and the resulting pyridine hydrochloride is filtered off. The filtrate is washed with dilute hydrochloric acid (10 mL), then with an aqueous solution of NaHCO3 (10 mL) and further with brine (10 mL). The organic layer is dried over Na2SO4 and the volatile matter is distilled off under reduced pressure. The crude product thus obtained is distilled under reduced pressure to give allyloxyethyl 2-bromopropionate (78.5-81 (1.3 mmHg), 2.986 g) of the formula shown below. A 50-mL two-necked flask is purged with nitrogen the resulting pyridine hydrochloride is filtered off The filtrate is washed with dilute hydrochloric acid (10 mL) The organic layer is dried over Na2SO4 the volatile matter is distilled off under reduced pressure The crude product thus obtained is distilled under reduced pressure

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

Procedure: A three-necked flask equipped with stirrer, thermometer, reflux condenser and Dean-Stark trap is charged with methacrylic acid (137.7 g, 1.6 mol), ethylene glycol monoallyl ether (80.7 g, 0.8 mol), p-toluenesulfonic acid (0.76 g, 4.0 mmol) and toluene (650 mL). After allowing the reaction to proceed at 120° C. for 5 hours, 0.12 g of p-toluenesulfonic acid is added, and the reaction is further allowed to proceed at the same temperature for 6 hours. Then, 0.1 g of p-toluenesulfonic acid is added, and the reaction is further allowed to proceed at the same temperature for 9 hours, whereupon the reaction is completed. During the whole reaction period, methacrylic acid and ethylene glycol monoallyl ether are monitored with liquid chromatography. The final conversion amounted to 98%. The reaction mixture is neutralized by adding an aqueous solution of NaHCO3 and allowed to separate into two layers. The aqueous layer is extracted once with toluene. The combined organic layer is dried over CaCl2 and the volatile matter is distilled off under reduced pressure. The crude product is distilled under reduced pressure (60, 2 mmHg) to give 98.7 g (73% yield) of 2-allyloxyethyl methacrylate shown below. A three-necked flask equipped with stirrer thermometer, reflux condenser the reaction to proceed at the same temperature for 6 hours to proceed at the same temperature for 9 hours, whereupon the reaction to separate into two layers The aqueous layer is extracted once with toluene The combined organic layer is dried over CaCl2 the volatile matter is distilled off under reduced pressure The crude product is distilled under reduced pressure (60, 2 mmHg)

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

Procedure: A three-necked flask equipped with stirrer, thermometer, reflux condenser and Dean-Stark trap is charged with methacrylic acid (137.7 g, 1.6 mol), ethylene glycol monoallyl ether (80.7 g, 0.8 mol), p-toluenesulfonic acid (0.76 g, 4.0 mmol) and toluene (650 mL). After allowing the reaction to proceed at 120° C. for 5 hours, 0.12 g of p-toluenesulfonic acid is added, and the reaction is further allowed to proceed at the same temperature for 6 hours. Then, 0.1 g of p-toluenesulfonic acid is added, and the reaction is further allowed to proceed at the same temperature for 9 hours, whereupon the reaction is completed. During the whole reaction period, methacrylic acid and ethylene glycol monoallyl ether are monitored with liquid chromatography. The final conversion amounted to 98%. The reaction mixture is neutralized by adding an aqueous solution of NaHCO3 and allowed to separate into two layers. The aqueous layer is extracted once with toluene. The combined organic layer is dried over CaCl2 and the volatile matter is distilled off under reduced pressure. The crude product is distilled under reduced pressure (60, 2 mmHg) to give 98.7 g (73% yield) of 2-allyloxyethyl methacrylate shown below. A three-necked flask equipped with stirrer thermometer, reflux condenser the reaction to proceed at the same temperature for 6 hours to proceed at the same temperature for 9 hours, whereupon the reaction to separate into two layers The aqueous layer is extracted once with toluene The combined organic layer is dried over CaCl2 the volatile matter is distilled off under reduced pressure The crude product is distilled under reduced pressure (60, 2 mmHg)

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

Procedure: Combine allyl hydroxyethyl ether (1.02 g, 10 mmol), and diisopropylethylamine (4.0 mL, 23 mmol), and dichloromethane (20 mL). Cool in an ice-bath. Add dropwise, methanesulfonyl chloride (1.0 mL, 13 mmol). After 1.5 hours, extract the reaction mixture with 1 M aqueous hydrochloric acid solution, saturated aqueous sodium bicarbonate solution, and saturated aqueous sodium chloride solution. Dry the organic layer over Na2SO4, filter, and evaporate invacuo to obtain allyl methanesulfonylethyl ether: Rf =0.80 (silica gel, 20% ethyl acetate/dichloromethane). Cool in an ice-bath Add dropwise extract the reaction mixture with 1 M aqueous hydrochloric acid solution, saturated aqueous sodium bicarbonate solution, and saturated aqueous sodium chloride solution Dry the organic layer over Na2SO4 filter evaporate invacuo

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

Procedure: Combine allyl hydroxyethyl ether (1.02 g, 10 mmol), and diisopropylethylamine (4.0 mL, 23 mmol), and dichloromethane (20 mL). Cool in an ice-bath. Add dropwise, methanesulfonyl chloride (1.0 mL, 13 mmol). After 1.5 hours, extract the reaction mixture with 1 M aqueous hydrochloric acid solution, saturated aqueous sodium bicarbonate solution, and saturated aqueous sodium chloride solution. Dry the organic layer over Na2SO4, filter, and evaporate invacuo to obtain allyl methanesulfonylethyl ether: Rf =0.80 (silica gel, 20% ethyl acetate/dichloromethane). Cool in an ice-bath Add dropwise extract the reaction mixture with 1 M aqueous hydrochloric acid solution, saturated aqueous sodium bicarbonate solution, and saturated aqueous sodium chloride solution Dry the organic layer over Na2SO4 filter evaporate invacuo

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a stirred solution of 2-allyloxy-ethanol 7 (10.9 mL, 100 mmol, 1.0 equiv.) in THF (200 mL) was carefully added NaH (60%, 4.8 g, 120 mmol, 1.2 equiv.) in small portions at room temperature. The reaction was then refluxed for 1 h (until H2 release ceased) then cooled to 0° C. Methyl bromoacetate (11.4 mL, 120 mmol, 1.2 equiv.) was then added dropwise. After 15 min at 0° C., the reaction was submitted to a EtOAc/H2O extraction. The combined organic layers were washed with brine, dried over anhydrous MgSO4, filtered then evaporated under reduced pressure. Purification was achieved by Kugelrohr distillation under reduced pressure and provided 9.77 g (55%) of ester (8) as a colorless oil; bp=130-145° C. (water tap vacuum); 1H NMR (400 MHz, CDCl3) δ 5.91 (m, 1H), 5.28 (m, 1H), 4.99 (m, 1H), 4.19 (s, 2H), 4.02 (m, 2H), 3.76 (s, 3H), 3.75 (m, 2H), 3.64 (m, 2H); 13C NMR (100 MHz, CDCl3) δ 171.1, 134.8, 117.3, 72.4, 71.2, 69.7, 68.9, 51.9; IR (neat) 1755 cm−1; HRMS (ESI, m/z) calcd. for C8H15O4 (MH+) 175.0964. found 175.0960. at room temperature The reaction was then refluxed for 1 h (until H2 release ceased) the reaction was submitted to a EtOAc/H2O extraction The combined organic layers were washed with brine dried over anhydrous MgSO4 filtered then evaporated under reduced pressure Purification was achieved by Kugelrohr distillation under reduced pressure

Conditions: temp:120.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a three-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a Dean-Stark apparatus were added methacrylic acid (137.7 g, 1.6 moles), ethyleneglycol monoallylether (80.7 g, 0.8 moles), p-toluenesulfonic acid (0.76 g, 4.0 mmole) and toluene (650 mL). The mixture was heated to 120° C. for 5 hours with exclusion of water. Another portion of p-toluenesulfonic acid (0.12 g) and the mixture was heated to 120° C. for 6 hours. The other portion of p-toluenesulfonic acid (0.1 g) was added and the mixture was heated to 120° C. for 9 hours. During the reaction, the consumption of methacrylic acid and ethyleneglycol monoallylether were monitored by liquid chromatography and the conversion reached 98%. The mixture was neutralized by addition of aq. NaHCO3 and the layers were separated. The aqueous layer was extracted with toluene and the combined organic layers were dried over CaCl2 and concentrated under reduced pressure. Distillation of the crude material (60° C. at 2 mmng) yielded 2-allyloxyethyl methacrylate (98.7 g, 73%) shown below. To a three-necked flask equipped with a stirrer During the reaction the consumption of methacrylic acid and ethyleneglycol monoallylether The mixture was neutralized by addition of aq. NaHCO3 the layers were separated The aqueous layer was extracted with toluene the combined organic layers were dried over CaCl2 concentrated under reduced pressure Distillation of the crude material (60° C. at 2 mmng)

Conditions: temp:120.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a three-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a Dean-Stark apparatus were added methacrylic acid (137.7 g, 1.6 moles), ethyleneglycol monoallylether (80.7 g, 0.8 moles), p-toluenesulfonic acid (0.76 g, 4.0 mmole) and toluene (650 mL). The mixture was heated to 120° C. for 5 hours with exclusion of water. Another portion of p-toluenesulfonic acid (0.12 g) and the mixture was heated to 120° C. for 6 hours. The other portion of p-toluenesulfonic acid (0.1 g) was added and the mixture was heated to 120° C. for 9 hours. During the reaction, the consumption of methacrylic acid and ethyleneglycol monoallylether were monitored by liquid chromatography and the conversion reached 98%. The mixture was neutralized by addition of aq. NaHCO3 and the layers were separated. The aqueous layer was extracted with toluene and the combined organic layers were dried over CaCl2 and concentrated under reduced pressure. Distillation of the crude material (60° C. at 2 mmng) yielded 2-allyloxyethyl methacrylate (98.7 g, 73%) shown below. To a three-necked flask equipped with a stirrer During the reaction the consumption of methacrylic acid and ethyleneglycol monoallylether The mixture was neutralized by addition of aq. NaHCO3 the layers were separated The aqueous layer was extracted with toluene the combined organic layers were dried over CaCl2 concentrated under reduced pressure Distillation of the crude material (60° C. at 2 mmng)