1,3-dichloro-2-(1,3-dichloropropan-2-yloxy)propane

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A 3 L 3-neck flask fitted with overhead mechanical stirrer, thermometer, condenser, and N2 line was charged with perylene (Aldrich Chemical Co., Milwaukee, WI, 53201, 25 g, 99 mmol) and o-dichlorobenzene (500 mL). The liquid was warmed until all the large chunks of solid dissolved (80° ) and then cooled quickly to give finely divided crystals. After further cooling with a salt-ice bath to 5°, SnCl4 (Aldrich, 98%, 51.2 g, 0.897 mol, 23 mL), was added in one portion. No temperature change occurred. The pot temperature was kept below 5°, and 1,1-dichloromethylmethylether (Aldrich, 14.9 g, 0.13 mol, 11.7 mL) was added dropwise over 1 h. The resulting suspension was warmed slowly to 40° over 2 h and further stirred for 16 h. Considerable HCl gas evolution occurred during the warming and the early part of the reaction at 40°. The reaction mixture was then cooled to 10° and hydrolysed by careful addition of 1 L of cold H2O. After 4 h the layers were separated and the organic layer filtered, dried with anhydrous Na2SO4 (Mallinckrodt Co., 2nd and Mallinckrodt St., St. Louis, MO, 63147, 100 g) and filtered again. The clear yellow solution was passed through a 500 g plug of SiO2 using PhCH3 as the eluting solvent with 500 mL fractions. This chromatography separated unreacted perylene from the aldehyde and a more polar product. Fractions (5 L) containing the aldehyde were combined and the PhCH3 removed. The resulting oily solid was shaken with CH3OH (200 mL) and the orange-brown crystals which formed were collected by filtration to give after drying 23.2 g (83%) of 3-perylenecarbaldehyde mp 223°-233°, (C,H), (lit. mp 236°(darkens >230 °)), N. P. Buu-Hoi and C. T. Long, Recueil 75 1121 (1956). A 3 L 3-neck flask fitted with overhead mechanical stirrer The liquid was warmed until all the large chunks of solid dissolved (80° ) cooled quickly to give finely divided crystals After further cooling with a salt-ice bath to 5° was kept below 5° The resulting suspension was warmed slowly to 40° over 2 h the early part of the reaction at 40° After 4 h the layers were separated the organic layer filtered dried with anhydrous Na2SO4 (Mallinckrodt Co., 2nd and Mallinckrodt St., St. Louis, MO, 63147, 100 g) filtered again This chromatography separated unreacted perylene from the aldehyde Fractions (5 L) containing the aldehyde the PhCH3 removed The resulting oily solid was shaken with CH3OH (200 mL) the orange-brown crystals which formed were collected by filtration to give after drying 23.2 g (83%) of 3-perylenecarbaldehyde mp 223°-233°, (C,H), (lit. mp 236°(darkens >230 °)), N

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 9.4 ml (83.4 mmol) 2,3-dihydrobenzofuran in 250 ml methylene dichloride was cooled under nitrogen to 0° to -5° C. and 18 ml (167 mmole) titanium tetrachloride was added dropwise at 0° C. The resulting brown mixture was stirred 10 minutes and 8.3 ml (91.6 mmole) 1,1-dichloromethylmethyl ether was then added dropwise at 0° C. During this addition the reaction mixture became dark red in color. The mixture was allowed to warm to room temperature, stirred for 2 hours and poured slowly into a 2 liter beaker containing 700 ml saturated aqueous sodium bicarbonate solution The resulting mixture was filtered through diatomaceous earth and the solids washed with methylene dichloride. The separated organic layer was dried (Na2SO4) and the solvent evaporated to afford a residual oil, 10 g, (81%) which appeared homogeneous on silica gel thin-layer chromatography (TLC), eluting with an ethyl acetate/hexane/5% acetic acid, 1:5:5 by volume. Mass spectrum (m/e): 148 (M+), 147, 119. During this addition the reaction mixture stirred for 2 hours poured slowly into a 2 liter beaker was filtered through diatomaceous earth the solids washed with methylene dichloride The separated organic layer was dried (Na2SO4) the solvent evaporated to afford a residual oil, 10 g, (81%) which eluting with an ethyl acetate/hexane/5% acetic acid, 1:5:5 by volume

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 9.4 ml (83.4 mmol) 2,3-dihydrobenzofuran in 250 ml methylene dichloride was cooled under nitrogen to 0° to -5° C. and 18 ml (167 mmole) titanium tetrachloride was added dropwise at 0° C. The resulting brown mixture was stirred 10 minutes and 8.3 ml (91.6 mmole) 1,1-dichloromethylmethyl ether was then added dropwise at 0° C. During this addition the reaction mixture became dark red in color. The mixture was allowed to warm to room temperature, stirred for 2 hours and poured slowly into a 2 liter beaker containing 700 ml saturated aqueous sodium bicarbonate solution The resulting mixture was filtered through diatomaceous earth and the solids washed with methylene dichloride. The separated organic layer was dried (Na2SO4) and the solvent evaporated to afford a residual oil, 10 g, (81%) which appeared homogeneous on silica gel thin-layer chromatography (TLC), eluting with an ethyl acetate/hexane/5% acetic acid, 1:5:5 by volume. Mass spectrum (m/e): 148 (M+), 147, 119. During this addition the reaction mixture stirred for 2 hours poured slowly into a 2 liter beaker was filtered through diatomaceous earth the solids washed with methylene dichloride The separated organic layer was dried (Na2SO4) the solvent evaporated to afford a residual oil, 10 g, (81%) which eluting with an ethyl acetate/hexane/5% acetic acid, 1:5:5 by volume

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 6-Bromo-2-naphthol (25.33 g) was suspended in dichloromethane (300 ml) and titanium tetrachloride (25.0 ml) was slowly added dropwise under cooling in an ice bath. 1,1-Dichloromethylmethyl ether (10.5 ml) was added dropwise to the reaction mixture and the mixture was stirred at the same temperature for 1 hr. The reaction mixture was poured into iced water and dichloromethane was added. The organic layer was separated and the aqueous layer was extracted with dichloromethane. The combined organic layers were washed successively with IN hydrochloric acid, water and saturated aqueous sodium hydrogen carbonate, dried over anhydrous magnesium sulfate and concentrated to give the title compound (28.17 g) as brown crystals. under cooling in an ice bath was added The organic layer was separated the aqueous layer was extracted with dichloromethane The combined organic layers were washed successively with IN hydrochloric acid, water and saturated aqueous sodium hydrogen carbonate dried over anhydrous magnesium sulfate concentrated

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 6-Bromo-2-naphthol (25.33 g) was suspended in dichloromethane (300 ml) and titanium tetrachloride (25.0 ml) was slowly added dropwise under cooling in an ice bath. 1,1-Dichloromethylmethyl ether (10.5 ml) was added dropwise to the reaction mixture and the mixture was stirred at the same temperature for 1 hr. The reaction mixture was poured into iced water and dichloromethane was added. The organic layer was separated and the aqueous layer was extracted with dichloromethane. The combined organic layers were washed successively with IN hydrochloric acid, water and saturated aqueous sodium hydrogen carbonate, dried over anhydrous magnesium sulfate and concentrated to give the title compound (28.17 g) as brown crystals. under cooling in an ice bath was added The organic layer was separated the aqueous layer was extracted with dichloromethane The combined organic layers were washed successively with IN hydrochloric acid, water and saturated aqueous sodium hydrogen carbonate dried over anhydrous magnesium sulfate concentrated

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: The compound of Example 29, (2.0 g, 4.197 mmoles) was suspended in chloroform (120 mls) to which was added 1,1-dichloromethylmethyl ether (10 ml). The reaction mixture was heated at 40° for 48 hours, and concentrated in vacuo. The residue was recrystallized to afford the title compound, m.p. 135°-136°. The reaction mixture was heated at 40° for 48 hours concentrated in vacuo The residue was recrystallized

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of 1-(4-methylphenylsulfonyl)-4-phenylpiperidine (1.0 g) and 1,1-dichloromethylmethylether (0.57 ml) in dichloromethane (5 ml) was added at 0° C. a solution of titanium tetrachloride (0.7 ml) in dichloromethane (5 ml), and the mixture was stirred at room temperature for 2 hours. The mixture was added to stirred ice/water to stop the reaction. The mixture was extracted with ethyl acetate. The organic layer was washed with sodium bicarbonate solution and saturated brine and dried with magnesium sulfate. Under reduced pressure, the mixture was concentrated, and the residue was purified with column chromatography (ethyl acetate/hexane=1:4→1:2) to give pale yellow crystals of 4-[1-(4-methylphenylsulfonyl)piperidin-4-yl]benzaldehyde (0.381 g). (469.4 mg of the starting materials were collected) The mixture was added the reaction The mixture was extracted with ethyl acetate The organic layer was washed with sodium bicarbonate solution and saturated brine dried with magnesium sulfate Under reduced pressure, the mixture was concentrated the residue was purified with column chromatography (ethyl acetate/hexane=1:4→1:2)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of 1-(4-methylphenylsulfonyl)-4-phenylpiperidine (1.0 g) and 1,1-dichloromethylmethylether (0.57 ml) in dichloromethane (5 ml) was added at 0° C. a solution of titanium tetrachloride (0.7 ml) in dichloromethane (5 ml), and the mixture was stirred at room temperature for 2 hours. The mixture was added to stirred ice/water to stop the reaction. The mixture was extracted with ethyl acetate. The organic layer was washed with sodium bicarbonate solution and saturated brine and dried with magnesium sulfate. Under reduced pressure, the mixture was concentrated, and the residue was purified with column chromatography (ethyl acetate/hexane=1:4→1:2) to give pale yellow crystals of 4-[1-(4-methylphenylsulfonyl)piperidin-4-yl]benzaldehyde (0.381 g). (469.4 mg of the starting materials were collected) The mixture was added the reaction The mixture was extracted with ethyl acetate The organic layer was washed with sodium bicarbonate solution and saturated brine dried with magnesium sulfate Under reduced pressure, the mixture was concentrated the residue was purified with column chromatography (ethyl acetate/hexane=1:4→1:2)