3,3-diethoxypropan-1-ol

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

Procedure: A reactor was charged with 30 ml of THF, 0.13 g of 3, 3-diethoxypropanol and 2 ml solution of potassium naphthalene dissolved in tetrahydrofuran in a concentration of 0.5 mol/L-tetrahydrofuran, and the resulting mixture was stirred for three minutes in an argon atmosphere, and, thus, there was formed a potassium derivative (potassium 3, 3-diethoxypropanoxide) of 3, 3-diethoxypropanol.

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

Procedure: THF 20 ml, 3, 3-diethoxypropanol 0.15 g, and a potassium naphthalene 0.5 mol/L-tetrahydrofuran solution 2 ml was added to the reaction container and agitated for 3 minutes in an argon atmosphere; a potassium compound of 3, 3-diethoxypropanol (potassium 3, 3-diethoxypropanoxide) was produced.

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

Procedure: THF 20 ml, 3, 3-diethoxypropanol 0.15 g, and a potassium naphthalene 0.5 mol/L-tetrahydrofuran solution 2 ml was added to the reaction container and agitated for 3 minutes in an argon atmosphere; a potassium compound of 3, 3-diethoxypropanol (potassium 3, 3-diethoxypropanoxide) was produced.

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

Procedure: THF 20 ml, 3, 3-diethoxypropanol 01.5 g, and a potassium naphthalene 0.5 mol/L-tetrahydrofuran solution 2 ml was added to the reaction container and agitated for 3 minutes in an argon atmosphere; a potassium compound of 3, 3-diethoxypropanol (potassium 3, 3-diethoxypropanoxide) was produced.

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

Procedure: THF 20 ml, 3, 3-diethoxypropanol 0.15 g, and a potassium naphthalene 0.5 mol/L-tetrahydrofuran solution 2 ml was added to the reaction container and agitated for 3 minutes in an argon atmosphere; a potassium compound of 3, 3-diethoxypropanol (potassium 3, 3-diethoxypropanoxide) was produced.

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

Procedure: THF 20 ml, 3, 3-diethoxypropanol 0.15 g, and a potassium naphthalene 0.5 mol/L-tetrahydrofuran solution 2 ml was added to the reaction container and agitated for 3 minutes in an argon atmosphere; a potassium compound of 3, 3-diethoxypropanol (potassium 3, 3-diethoxypropanoxide) was produced.

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

Procedure: In an argon atmosphere, a reactor was charged with 30 ml of THF, 0.147 g of 3,3-diethoxypropanol and 3.0 ml of 0.34 mol/l solution of potassium naphthalene in THF, which were stirred for 10 minutes at room temperature. A potassium compound of 3,3-diethoxypropanol was thus formed. To the resultant solution, 7.04 g of ethylene oxide was added, and the resultant mixture was stirred at room temperature and at 1 atm. The resultant solution was allowed to react for two days, and then, 26.0 ml of 1.92 mol/l solution of DL-lactide in THF was added, and the resultant mixture was further stirred for two hours. Then, 3.1 g of methacrylic anhydride was added, and the resultant mixture was stirred for two days at room temperature. The resultant solution was poured into cooled 2-propanol, and the thus formed polymer was precipitated. The precipitate which was isolated by centrifugation was purified by freeze drying from benzene, with a yield of 11.48 g (79.4%). According to GPC and 1H-NMR, polyethylene glycol (PEG) segment, polylactide (PLA) and block copolymer had each a molecular weight of 5800, 4000 and 9800.

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

Procedure: 9-Bromo-2,3,4,5-tetrahydrobenzo[b][1,4]oxazepin-3-ol was prepared using a procedure analogous to 9-bromo-2,3,4,5-tetrahydrobenzo[b][1,4]oxazepine except that 3,3-diethoxypropan-1-ol was replaced by 3,3-diethoxypropane-1,2-diol. LCMS, [M+H]+=246.1. 1H NMR (400 MHz, CDCl3) δ 7.11 (dd, J=7.7, 1.8 Hz, 1H), 6.81-6.69 (m, 2H), 4.37 (ddd, J=12.3, 3.7, 1.3 Hz, 1H), 3.99 (br. s., 1H), 3.93 (dd, J=12.3, 2.2 Hz, 1H), 3.57 (br. s., 1H), 3.40 (dd, J=13.0, 4.0 Hz, 1H), 3.22 (dd, J=13.0, 2.4 Hz, 1H), 3.01 (br. s., 1H).

Conditions: temp:10.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In the following, tetrahydrofuran (THF) to be used was dehydrated on molecular sieves of 4 angstrom overnight. Inside of a 5 L four-neck flask was substituted with nitrogen gas and 2.2 kg of THF was placed therein, followed by cooling to 10° C. or lower. Then, 50 g of lithium aluminum hydride was placed therein and 250 g of ethyl 3,3-diethoxypropionate was added dropwise so that inner temperature did not exceed 10° C. After completion of the dropwise addition, temperature was elevated to 20° C. and reaction was carried out for 1 hour. After the reaction, 420 g of distilled water was added and the whole was stirred for 2 hours, then filtration was performed through No. 2 filtration paper, and subsequently a cake was washed with 1.1 kg of THF. The filtrate was concentrated at 40° C. to obtain 213 g of crude 3,3-diethoxy-1-propanol (hereinafter 33DEP). to be used was dehydrated on molecular sieves of 4 angstrom overnight did not exceed 10° C After completion of the dropwise addition, temperature was elevated to 20° C. reaction was added filtration 2 filtration paper subsequently a cake was washed with 1.1 kg of THF The filtrate was concentrated at 40° C.

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

Procedure: In an argon atmosphere, a reactor was charged with 30 ml of THF, 0.147 g of 3,3-diethoxypropanol and 3.0 ml of 0.34 mol/l solution of potassium naphthalene in THF, which were stirred for 10 minutes at room temperature. A potassium compound of 3,3-diethoxypropanol was thus formed. To the resultant solution, 7.04 g of ethylene oxide was added, and the resultant mixture was stirred at room temperature and at 1 atm. The resultant solution was allowed to react for two days, and then, 26.0 ml of 1.92 mol/l solution of DL-lactide in THF was added, and the resultant mixture was further stirred for two hours. Then, 3.1 g of methacrylic anhydride was added, and the resultant mixture was stirred for two days at room temperature. The resultant solution was poured into cooled 2-propanol, and the thus formed polymer was precipitated. The precipitate which was isolated by centrifugation was purified by freeze drying from benzene, with a yield of 11.48 g (79.4%). According to GPC and 1H-NMR, polyethylene glycol (PEG) segment, polylactide (PLA) and block copolymer had each a molecular weight of 5800, 4000 and 9800.

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

Procedure: To a stirred solution of 3,3-diethoxy-1-propanol (3.0 g, 22.2 mmol) in anhydrous THF (50 mL) was added sodium hydride (60% dispersion in mineral oil, 1.07 g, 26.6 mmol). The reaction mixture was stirred for 30 minutes, and 3-bromo-2-methyl-1-propene (3.63 g, 24.5 mmol) then added. The reaction mixture was then stirred for a further 18 hours. The reaction mixture was quenched with saturated sodium hydrogen carbonate and extracted with ethyl acetate (×3). The combined organic extracts were washed with saturated aqueous sodium hydrogen carbonate solution and brine, dried (sodium sulfate), filtered and concentrated under reduced pressure to afford an oil (2.25 g, 50%). The material used in the next step without further purification. The reaction mixture was then stirred for a further 18 hours The reaction mixture was quenched with saturated sodium hydrogen carbonate extracted with ethyl acetate (×3) The combined organic extracts were washed with saturated aqueous sodium hydrogen carbonate solution and brine dried (sodium sulfate) filtered concentrated under reduced pressure

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

Procedure: A reactor was charged with 30 ml of THF, 0.13 g of 3, 3-diethoxypropanol and 2 ml solution of potassium naphthalene dissolved in tetrahydrofuran in a concentration of 0.5 mol/L-tetrahydrofuran, and the resulting mixture was stirred for three minutes in an argon atmosphere, and, thus, there was formed a potassium derivative (potassium 3, 3-diethoxypropanoxide) of 3, 3-diethoxypropanol.