乙二醇单己醚

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Into a reaction vessel, 3.29 g (22.5 mmol) of 2-hexyloxyethanol and 5.33 g (67.5 mmol) of pyridine were charged, and 4.72 g (24.7 mmol) of p-toluenesulfonic acid chloride was added thereto in an ice bath, which were then stirred for 1 hour and thereafter further stirred at room temperature for 3 hours. After the reaction was completed, 3N HCl was added to make the reaction mixture acidic, followed by extraction with toluene twice. The extract obtained was washed with water, and thereafter sodium sulfuric anhydride was added to effect drying. After the solvent was evaporated off, the resultant mixture was purified by silica gel chromatography (eluting solvent: toluene/ethyl acetate=10/1) to obtain 6.45 g (21.5 mmol) of 2-hexyloxyethyl p-toluenesulfonate. Yield: 95%. further stirred at room temperature for 3 hours followed by extraction with toluene twice The extract obtained was washed with water sodium sulfuric anhydride was added to effect drying After the solvent was evaporated off the resultant mixture was purified by silica gel chromatography (eluting solvent: toluene/ethyl acetate=10/1)

反应条件: temp:85.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: In a reactor consisting of a 300-cc four-necked flask, a stirrer, a thermometer, a nitrogen inlet tube, a nitrogen line, a Dean-Stark tube, a condenser, a three-way cock, and a vacuum apparatus were placed 36.54 g (0.25 mole) of adipic acid, 87.74 g (0.60 mole) of ethylene glycol mono-n-hexyl ether, 2.38 g (0.0125 mole) of para-toluenesulfonic acid monohydrate, and 86 g of toluene and the mixture was allowed to react with stirring at 85° C. for 30 hours in a nitrogen atmosphere. An aqueous solution of sodium hydroxide was added to the reaction mixture to neutralize the para-toluenesulfonic acid and the oily layer was separated from the aqueous layer. The oily layer was washed with alkali and then with water and the oily layer was separated and dried over anhydrous sodium sulfate. The oil was stripped of water, ethylbenzene, and the unchanged ethylene glycol mono-n-hexyl ether by distillation to yield di(hexyloxyethyl) adipate. In a reactor consisting of a 300-cc four-necked flask, a stirrer to react the oily layer was separated from the aqueous layer The oily layer was washed with alkali with water and the oily layer was separated dried over anhydrous sodium sulfate the unchanged ethylene glycol mono-n-hexyl ether by distillation

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A mixture of ethylene glycol mono-n-hexyl ether (15.0 g, 0.1 mol) and sodium hydride (0.1 mol) was dissolved in dry DMF (150 mL). After the mixture was stirred for 1-2 hours, N-(2-bromoethyl)phthalimide (25.4 g, 0.1 mol) was added with continued stirring and the mixture was warmed on a steam bath for 8 h. The DMF was then removed by evaporation and the residue dissolved in hot toluene, and the solution was concentrated to remove solvent. The residue was purified using silica gel chromatography using ethyl acetate to give 25 g (78%). 1H NMR (CDCl3, TMS): δ 0.87 (t, 3H, J=6.8Hz), 1.24˜1.30 (m, 8H), 1.56˜1.60 (m, 2H), 3.47 (t, 3H, J=6.8 Hz), 3.72 (dd, 2H, J1=4.4 Hz, J2=5.6 Hz), 4.06 (t, 3H, J=9.6 Hz), 4.41˜4.46 (m, 4H) 7.50˜7.52 (m, 2H), 7.72˜7.76 (m, 2H). A solution of the thus-derived isoindoledione and hydrazine hydrate (5.5 g, 0.11 mol) in EtOH (200 mL) was heated at reflux for 8 hours. The precipitate (phthalhydrazide) was removed by filtration, and the filtrate was concentrated to low volume and refiltered. The filtrate was then concentrated to dryness, treated with water (20 mL) and sodium hydroxide (11 g), and extracted with methylene chloride (4×100 mL). The combined organic layers are dried over MgSO4, concentrated, and purified by silica gel to provide 7 g of the amine product (50%). 1H-NMR (CDCl3, TMS): δ 0.89 (t, 3H, J=6.8 Hz), 1.29˜1.36 (m, 6H), 1.55˜1.60 (m, 2H), 2.03 (m, 2H), 3.45˜3.49 (m, 4H), 3.53˜3.55 (m, 2H), 3.71˜3.74 (m, 2H). with continued stirring the mixture was warmed on a steam bath for 8 h The DMF was then removed by evaporation the residue dissolved in hot toluene the solution was concentrated to remove solvent The residue was purified to give 25 g (78%) at reflux for 8 hours The precipitate (phthalhydrazide) was removed by filtration the filtrate was concentrated to low volume The filtrate was then concentrated to dryness treated with water (20 mL) and sodium hydroxide (11 g) extracted with methylene chloride (4×100 mL) The combined organic layers are dried over MgSO4 concentrated purified by silica gel