1,3-二苯氧基-2-丙醇

反应条件: temp:0.00; pressure:0.00; stir:

反应条件: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: In a 100 mL pear-shaped flask were precisely weighed 0.579 g of tris[tris(dimethylamino)phosphoranylidene-amino]phosphine oxide ([(Me2N)3P=N]3P=O where Me is methyl, same in the following description) as a phosphine oxide represented by formula (1) which was substantially anhydrous by adequate drying over phosphorous pentoxide in a desiccator in vacuo (1.00 mmol) and 9.88 g of phenol (105 mmol). To the mixture warmed to 90° C. was added dropwise 15.0 g of phenyl glycidyl ether (referred to as "PGE"; same in the following description) (100 mmol) over 10 min. After addition, the mixture was stirred at the same temperature for 5 hours, and cooled to room temperature over about 10 min. A small portion of the reaction mixture was quantitatively analyzed by gas chromatography using 1,3,5-trichlorobenzene as an internal standard, indicating that the starting PGE had been almost completely consumed to form desired 1,3-diphenoxy-2-propanol in a yield of 96% based on PGE. In brief, the reaction almost quantitatively proceeded. The reaction mixture was directly subjected to column chromatography to give 22.5 g of 1,3-diphenoxy-2-propanol as a colorless solid in an isolation yield of 92% whose various analyses gave data identical to a reference standard. The catalyst activity (molar amount of a desired product per one mole of catalyst in a unit time; same in the following description) of tris[tris(dimethylamino)phosphoranylidene-amino]phosphine oxide was 20 mol/mol/h, which was surprisingly about 3, 2 or 1.5 times as large as that given by boron trifluoride, N-methylimidazole or triphenylphosphine in Comparative Example 2, 3 or 4, respectively. In a 100 mL pear-shaped flask were precisely weighed After addition cooled to room temperature over about 10 min had been almost completely consumed

反应条件: temp:0.00; pressure:0.00; stir:

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

实验步骤: Using the procedure of Example 51 but replacing 1,5-diphenyl-3-pentanol with the resultant compound of Example 4 gave, after silica gel chromatography using 10% ethyl acetate in hexane, 80 mg (49%) of the desired compound (Rf 0.42, 20% ethyl acetate in hexane). 1H NMR (CDCl3) δ3.44 (s, 3H), 4.18 (dd, J=10, 6 Hz, 2H), 4.22 (dd, J=15, 6 Hz, 2H), 4.33 (pentet, J=6 Hz, 1H), 4.85 (s, 2H), 6.9-7.0 (m, 6H), 7.25-7.35 (m, 4H). Mass spectrum (M +NH4)+ =306. gave

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

实验步骤: A solution of 0.44 ml (6.2 mmol) of dimethylsulfoxide in 25 ml of dichloromethane was cooled under inert atmosphere to -63° C., treated with 2.3 ml (4.6 mmol) of oxalyl chloride (2M in dichloromethane), and stirred for 15 min. A solution of 0.75 g (3.1 mmol) of the resultant compound of Example 4 in 10 ml of dichloromethane was subsequently added, the solution was stirred for 30 min, and 1.73 ml (12.4 mmol) of triethylamine was added. After stirring for an additional 15 min, the solution was quenched with 10% aqueous citric acid, poured into a mixture of 1:1 ether:hexane and 10% citric acid, extracted with ether, washed with aqueous brine, dried over MgSO4, and concentrated to a yellow oil. Purification by flash chromatography using 20% ethyl acetate in hexane gave 0.62 g (83%) of the desired compound as a white, crystalline solid, m.p. 55°-57° C. 1H NMR (CDCl3) δ4.89 (s, 4H), 6.92 (m, 4H), 7.02 (m, 2H), 7.30 (m, 4H). Mass spectrum (M+NH4)+ =260. the solution was stirred for 30 min After stirring for an additional 15 min the solution was quenched with 10% aqueous citric acid poured into a mixture of 1:1 ether hexane and 10% citric acid, extracted with ether washed with aqueous brine dried over MgSO4 concentrated to a yellow oil Purification by flash chromatography

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

实验步骤: Using the procedure of Example 51 but replacing 1,5-diphenyl-3-pentanol with the resultant compound of Example 4 gave, after silica gel chromatography using 10% ethyl acetate in hexane, 80 mg (49%) of the desired compound (Rf 0.42, 20% ethyl acetate in hexane). 1H NMR (CDCl3) δ 3 44 (s, 3H), 4.18 (dd, J=10, 6 Hz, 2H), 4.22 (dd, J=15, 6 Hz, 2H), 4.33 (pentet, J=6 Hz, 1H), 4.85 (s, 2H), 6.9-7.0 (m, 6H), 7.25-7.35 (m, 4H). Mass spectrum (M+NH4)+ =306. gave

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

实验步骤: Using the procedure of Example 51 but replacing 1,5-diphenyl-3-pentanol with the resultant compound of Example 4 gave, after silica gel chromatography using 10% ethyl acetate in hexane, 80 mg (49%) of the desired compound (Rf 0.42, 20% ethyl acetate in hexane). 1H NMR (CDCl3) δ 3 44 (s, 3H), 4.18 (dd, J=10, 6 Hz, 2H), 4.22 (dd, J=15, 6 Hz, 2H), 4.33 (pentet, J=6 Hz, 1H), 4.85 (s, 2H), 6.9-7.0 (m, 6H), 7.25-7.35 (m, 4H). Mass spectrum (M+NH4)+ =306. gave

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

实验步骤: A solution of 0.44 ml (6.2 mmol) of dimethylsulfoxide in 25 ml of dichloromethane was cooled under inert atmosphere to -63° C., treated with 2.3 ml (4.6 mmol) of oxalyl chloride (2M in dichloromethane), and stirred for 15 min. A solution of 0.75 g (3.1 mmol) of the resultant compound of Example 4 in 10 ml of dichloromethane was subsequently added, the solution was stirred for 30 min, and 173 ml (12.4 mmol) of triethylamine was added. After stirring for an additional 15 min, the solution was quenched with 10% aqueous citric acid, poured into a mixture of 1:1 ether:hexane and 10% citric acid, extracted with ether, washed with aqueous brine, dried over MgSO4, and concentrated to a yellow oil. Purification by flash chromatography using 20% ethyl acetate in hexane gave 0.62 g (83%) of the desired compound as a white, crystalline solid, m.p. 55°-57° C. 1H NMR (CDCl3) δ 4.89 (s, 4H), 6.92 (m, 4H), 7.02 (m, 2H), 7.30 (m, 4H). Mass spectrum (M+NH4)+= 260. the solution was stirred for 30 min After stirring for an additional 15 min the solution was quenched with 10% aqueous citric acid poured into a mixture of 1:1 ether hexane and 10% citric acid, extracted with ether washed with aqueous brine dried over MgSO4 concentrated to a yellow oil Purification by flash chromatography

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

实验步骤: A solution of 0.44 ml (6.2 mmol) of dimethylsulfoxide in 25 ml of dichloromethane was cooled under inert atmosphere to -63° C., treated with 2.3 ml (4.6 mmol) of oxalyl chloride (2M in dichloromethane), and stirred for 15 min. A solution of 0.75 g (3.1 mmol) of the resultant compound of Example 4 in 10 ml of dichloromethane was subsequently added, the solution was stirred for 30 min, and 173 ml (12.4 mmol) of triethylamine was added. After stirring for an additional 15 min, the solution was quenched with 10% aqueous citric acid, poured into a mixture of 1:1 ether:hexane and 10% citric acid, extracted with ether, washed with aqueous brine, dried over MgSO4, and concentrated to a yellow oil. Purification by flash chromatography using 20% ethyl acetate in hexane gave 0.62 g (83%) of the desired compound as a white, crystalline solid, m.p. 55°-57° C. 1H NMR (CDCl3) δ 4.89 (s, 4H), 6.92 (m, 4H), 7.02 (m, 2H), 7.30 (m, 4H). Mass spectrum (M+NH4)+= 260. the solution was stirred for 30 min After stirring for an additional 15 min the solution was quenched with 10% aqueous citric acid poured into a mixture of 1:1 ether hexane and 10% citric acid, extracted with ether washed with aqueous brine dried over MgSO4 concentrated to a yellow oil Purification by flash chromatography

反应条件: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: In a 100 mL pear-shaped flask were precisely weighed 0.579 g of tris[tris(dimethylamino)phosphoranylidene-amino]phosphine oxide ([(Me2N)3P=N]3P=O where Me is methyl, same in the following description) as a phosphine oxide represented by formula (1) which was substantially anhydrous by adequate drying over phosphorous pentoxide in a desiccator in vacuo (1.00 mmol) and 9.88 g of phenol (105 mmol). To the mixture warmed to 90° C. was added dropwise 15.0 g of phenyl glycidyl ether (referred to as "PGE"; same in the following description) (100 mmol) over 10 min. After addition, the mixture was stirred at the same temperature for 5 hours, and cooled to room temperature over about 10 min. A small portion of the reaction mixture was quantitatively analyzed by gas chromatography using 1,3,5-trichlorobenzene as an internal standard, indicating that the starting PGE had been almost completely consumed to form desired 1,3-diphenoxy-2-propanol in a yield of 96% based on PGE. In brief, the reaction almost quantitatively proceeded. The reaction mixture was directly subjected to column chromatography to give 22.5 g of 1,3-diphenoxy-2-propanol as a colorless solid in an isolation yield of 92% whose various analyses gave data identical to a reference standard. The catalyst activity (molar amount of a desired product per one mole of catalyst in a unit time; same in the following description) of tris[tris(dimethylamino)phosphoranylidene-amino]phosphine oxide was 20 mol/mol/h, which was surprisingly about 3, 2 or 1.5 times as large as that given by boron trifluoride, N-methylimidazole or triphenylphosphine in Comparative Example 2, 3 or 4, respectively. In a 100 mL pear-shaped flask were precisely weighed After addition cooled to room temperature over about 10 min had been almost completely consumed

反应条件: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: In a 100 mL pear-shaped flask were precisely weighed 0.579 g of tris[tris(dimethylamino)phosphoranylidene-amino]phosphine oxide ([(Me2N)3P=N]3P=O where Me is methyl, same in the following description) as a phosphine oxide represented by formula (1) which was substantially anhydrous by adequate drying over phosphorous pentoxide in a desiccator in vacuo (1.00 mmol) and 9.88 g of phenol (105 mmol). To the mixture warmed to 90° C. was added dropwise 15.0 g of phenyl glycidyl ether (referred to as "PGE"; same in the following description) (100 mmol) over 10 min. After addition, the mixture was stirred at the same temperature for 5 hours, and cooled to room temperature over about 10 min. A small portion of the reaction mixture was quantitatively analyzed by gas chromatography using 1,3,5-trichlorobenzene as an internal standard, indicating that the starting PGE had been almost completely consumed to form desired 1,3-diphenoxy-2-propanol in a yield of 96% based on PGE. In brief, the reaction almost quantitatively proceeded. The reaction mixture was directly subjected to column chromatography to give 22.5 g of 1,3-diphenoxy-2-propanol as a colorless solid in an isolation yield of 92% whose various analyses gave data identical to a reference standard. The catalyst activity (molar amount of a desired product per one mole of catalyst in a unit time; same in the following description) of tris[tris(dimethylamino)phosphoranylidene-amino]phosphine oxide was 20 mol/mol/h, which was surprisingly about 3, 2 or 1.5 times as large as that given by boron trifluoride, N-methylimidazole or triphenylphosphine in Comparative Example 2, 3 or 4, respectively. In a 100 mL pear-shaped flask were precisely weighed After addition cooled to room temperature over about 10 min had been almost completely consumed

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

实验步骤: 9.6 g (39.3 mmol) of 2-hydroxy-1,3-diphenoxypropane are dissolved in 80 ml of tetrahydrofurane (THF) and cooled by an ice bath. To the solution are added dropwise 6.8 g (86.4 mmol) of acetyl chloride and 6.0 g (59.0 mmol) of triethylamine successively. The reaction mixture is stirred at room temperature overnight, poured into 50 ml of water, and extracted with ethyl acetate. The organic phase is washed with water and brine, dried over MgSO4, and concentrated. The residue is purified by flash chromatography on silica gel with ethyl acetate and hexane (1:9) as eluent, yielding 5.1 g of 2-acetyloxy-1,3-diphenoxypropane as a colorless liquid. cooled by an ice bath extracted with ethyl acetate The organic phase is washed with water and brine dried over MgSO4 concentrated The residue is purified by flash chromatography on silica gel with ethyl acetate and hexane (1:9) as eluent