4-Bromobenzyl(tetrahydro-2H-pyran-2-yl) ether

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

实验步骤: A mixture of magnesium turnings (1.07 g, 0.044 mol) activated with iodine, 1,2-dibromoethane and tetrahydrofuran (40 ml) was kept under a nitrogen atmosphere, and a solution of 4-bromophenylmethyl tetrahydro-2-pyranyl ether (11.20 g, 0.041 mol) in tetrahydrofuran (40 ml) was added dropwise under stirring. The mixture was gently heated to reflux temperature, and heating was continued for 3 h. The mixture was cooled to room temperature, and a solution of 10,11-dihydro-5H-dibenzo[a,d]cyclohepten-5-one (6.86 g, 0.033 mol) in tetrahydrofuran (40 ml) was added dropwise. The mixture was heated at reflux temperature for 1 h, cooled and then poured into an ice-cold saturated solution of ammonium chloride (85 ml). The mixture was extracted with ether (120 ml and 2×70 ml), and the combined organic layers were washed with water (2×40 ml), brine (40 ml) and dried (MgSO4). The solvent was removed in vacuo and the oily residue (14.7 g) was purified by column chromatography on silica gel (200 g) using first benzene and then a mixture of dichloromethane and ethanol (9:1) as eluents. The dichloromethane/ethanol fraction afforded 5.5 g (41%) of 5-(4-(2-tetrahydropyranyloxymethyl)phenyl)-10,11-dihydro-5H-dibenzo[a,d]-cyclohepten-5-ol. The mixture was gently heated to reflux temperature heating The mixture was heated at reflux temperature for 1 h cooled The mixture was extracted with ether (120 ml and 2×70 ml) the combined organic layers were washed with water (2×40 ml), brine (40 ml) dried (MgSO4) The solvent was removed in vacuo the oily residue (14.7 g) was purified by column chromatography on silica gel (200 g) a mixture of dichloromethane and ethanol (9:1) as eluents

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

实验步骤: To a stirred and refluxing Grignard-complex, previously prepared starting from 7.2 parts of magnesium and 81.4 parts of 2-(p-bromobenzyloxy)tetrahydropyran in 200 parts of dry tetrahydrofuran, is added dropwise a solution of 32.7 parts of 2-thiophenecarbonitrile in 70 parts of dry tetrahydrofuran (exothermic reaction: reflux temperature is maintained). Upon completion, stirring at reflux is continued for 4 hours. The reaction mixture is cooled and decomposed with 150 parts of a saturated ammonium chloride solution at about 15° C. The whole is poured onto water and the product is extracted with ether. The organic layer is washed four times with water, dried, filtered and acidified with gaseous hydrogen chloride; an oil is separated. The ether is decanted and the oily product is dissolved in 300 parts of water and 150 parts of concentrated hydrochloric acid solution. The solution is stirred with activated charcoal, filtered and the filtrate is stirred and refluxed for 10 minutes. The product is extracted with chloroform. The latter is washed with water, dried, filtered and evaporated. The residue is distilled, yielding α-hydroxy-p-tolyl 2-thienyl ketone; bp. 180°-190° C at 0.2 mm. pressure. refluxing Grignard-complex previously prepared Upon completion, stirring at reflux The reaction mixture is cooled The whole is poured onto water the product is extracted with ether The organic layer is washed four times with water dried filtered an oil is separated The ether is decanted the oily product is dissolved in 300 parts of water and 150 parts of concentrated hydrochloric acid solution The solution is stirred with activated charcoal filtered the filtrate is stirred refluxed for 10 minutes The product is extracted with chloroform The latter is washed with water dried filtered evaporated The residue is distilled

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

实验步骤: To a stirred and refluxing Grignard-complex, previously prepared starting from 7.2 parts of magnesium and 81.4 parts of 2-(p-bromobenzyloxy)tetrahydropyran in 200 parts of dry tetrahydrofuran, is added dropwise a solution of 32.7 parts of 2-thiophenecarbonitrile in 70 parts of dry tetrahydrofuran (exothermic reaction: reflux temperature is maintained). Upon completion, stirring at reflux is continued for 4 hours. The reaction mixture is cooled and decomposed with 150 parts of a saturated ammonium chloride solution at about 15° C. The whole is poured onto water and the product is extracted with ether. The organic layer is washed four times with water, dried, filtered and acidified with gaseous hydrogen chloride; an oil is separated. The ether is decanted and the oily product is dissolved in 300 parts of water and 150 parts of concentrated hydrochloric acid solution. The solution is stirred with activated charcoal, filtered and the filtrate is stirred and refluxed for 10 minutes. The product is extracted with chloroform. The latter is washed with water, dried, filtered and evaporated. The residue is distilled, yielding α-hydroxy-p-tolyl 2-thienyl ketone; bp. 180°-190° C at 0.2 mm. pressure. refluxing Grignard-complex previously prepared Upon completion, stirring at reflux The reaction mixture is cooled The whole is poured onto water the product is extracted with ether The organic layer is washed four times with water dried filtered an oil is separated The ether is decanted the oily product is dissolved in 300 parts of water and 150 parts of concentrated hydrochloric acid solution The solution is stirred with activated charcoal filtered the filtrate is stirred refluxed for 10 minutes The product is extracted with chloroform The latter is washed with water dried filtered evaporated The residue is distilled

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

实验步骤: To a stirred and refluxing Grignard-complex, previously prepared starting from 7.2 parts of magnesium and 81.4 parts of 2-(p-bromobenzyloxy)tetrahydropyran in 200 parts of dry tetrahydrofuran, is added dropwise a solution of 32.7 parts of 2-thiophenecarbonitrile in 70 parts of dry tetrahydrofuran (exothermic reaction: reflux temperature is maintained). Upon completion, stirring at reflux is continued for 4 hours. The reaction mixture is cooled and decomposed with 150 parts of a saturated ammonium chloride solution at about 15° C. The whole is poured onto water and the product is extracted with ether. The organic layer is washed four times with water, dried, filtered and acidified with gaseous hydrogen chloride: an oil is separated. The ether is decanted and the oily product is dissolved in 300 parts of water and 150 parts of concentrated hydrochloric acid solution. The solution is stirred with activated charcoal, filtered and the filtrate is stirred and refluxed for 10 minutes. The product is extracted with chloroform. The latter is washed with water, dried, filtered and evaporated. The residue is distilled, yielding α-hydroxy-p-tolyl 2-thienyl ketone; b.p. 180°-190° C at 0.2 mm. pressure. refluxing Grignard-complex previously prepared Upon completion, stirring at reflux The reaction mixture is cooled The whole is poured onto water the product is extracted with ether The organic layer is washed four times with water dried filtered an oil is separated The ether is decanted the oily product is dissolved in 300 parts of water and 150 parts of concentrated hydrochloric acid solution The solution is stirred with activated charcoal filtered the filtrate is stirred refluxed for 10 minutes The product is extracted with chloroform The latter is washed with water dried filtered evaporated The residue is distilled

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

实验步骤: To a stirred and refluxing Grignard-complex, previously prepared starting from 7.2 parts of magnesium and 81.4 parts of 2-(p-bromobenzyloxy)tetrahydropyran in 200 parts of dry tetrahydrofuran, is added dropwise a solution of 32.7 parts of 2-thiophenecarbonitrile in 70 parts of dry tetrahydrofuran (exothermic reaction: reflux temperature is maintained). Upon completion, stirring at reflux is continued for 4 hours. The reaction mixture is cooled and decomposed with 150 parts of a saturated ammonium chloride solution at about 15° C. The whole is poured onto water and the product is extracted with ether. The organic layer is washed four times with water, dried, filtered and acidified with gaseous hydrogen chloride: an oil is separated. The ether is decanted and the oily product is dissolved in 300 parts of water and 150 parts of concentrated hydrochloric acid solution. The solution is stirred with activated charcoal, filtered and the filtrate is stirred and refluxed for 10 minutes. The product is extracted with chloroform. The latter is washed with water, dried, filtered and evaporated. The residue is distilled, yielding α-hydroxy-p-tolyl 2-thienyl ketone; b.p. 180°-190° C at 0.2 mm. pressure. refluxing Grignard-complex previously prepared Upon completion, stirring at reflux The reaction mixture is cooled The whole is poured onto water the product is extracted with ether The organic layer is washed four times with water dried filtered an oil is separated The ether is decanted the oily product is dissolved in 300 parts of water and 150 parts of concentrated hydrochloric acid solution The solution is stirred with activated charcoal filtered the filtrate is stirred refluxed for 10 minutes The product is extracted with chloroform The latter is washed with water dried filtered evaporated The residue is distilled

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

实验步骤: A mixture of magnesium turnings (1.07 g, 0.044 mol) activated with iodine, 1,2-dibromoethane and tetrahydrofuran (40 ml) was kept under a nitrogen atmosphere, and a solution of 4-bromophenylmethyl tetrahydro-2-pyranyl ether (11.20 g, 0.041 mol) in tetrahydrofuran (40 ml) was added dropwise under stirring. The mixture was gently heated to reflux temperature, and heating was continued for 3 h. The mixture was cooled to room temperature, and a solution of 10,11-dihydro-5H-dibenzo[a,d]cyclohepten-5-one (6.86 g, 0.033 mol) in tetrahydrofuran (40 ml) was added dropwise. The mixture was heated at reflux temperature for 1 h, cooled and then poured into an ice-cold saturated solution of ammonium chloride (85 ml). The mixture was extracted with ether (120 ml and 2×70 ml), and the combined organic layers were washed with water (2×40 ml), brine (40 ml) and dried (MgSO4). The solvent was removed in vacuo and the oily residue (14.7 g) was purified by column chromatography on silica gel (200 g) using first benzene and then a mixture of dichloromethane and ethanol (9:1) as eluents. The dichloromethane/ethanol fraction afforded 5.5 g (41%) of 5-(4-(2-tetrahydropyranyloxymethyl)phenyl)-10,11-dihydro-5H-dibenzo[a,d]-cyclohepten-5-ol. The mixture was gently heated to reflux temperature heating The mixture was heated at reflux temperature for 1 h cooled The mixture was extracted with ether (120 ml and 2×70 ml) the combined organic layers were washed with water (2×40 ml), brine (40 ml) dried (MgSO4) The solvent was removed in vacuo the oily residue (14.7 g) was purified by column chromatography on silica gel (200 g) a mixture of dichloromethane and ethanol (9:1) as eluents

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

实验步骤: A mixture of magnesium turnings (1.07 g, 0.044 mol) activated with iodine, 1,2-dibromoethane and tetrahydrofuran (40 ml) was kept under a nitrogen atmosphere, and a solution of 4-bromophenylmethyl tetrahydro-2-pyranyl ether (11.20 g, 0.041 mol) in tetrahydrofuran (40 ml) was added dropwise under stirring. The mixture was gently heated to reflux temperature, and heating was continued for 3 h. The mixture was cooled to room temperature, and a solution of 10,11-dihydro-5H-dibenzo[a,d]cyclohepten-5-one (6.86 g, 0.033 mol) in tetrahydrofuran (40 ml) was added dropwise. The mixture was heated at reflux temperature for 1 h, cooled and then poured into an ice-cold saturated solution of ammonium chloride (85 ml). The mixture was extracted with ether (120 ml and 2×70 ml), and the combined organic layers were washed with water (2×40 ml), brine (40 ml) and dried (MgSO4). The solvent was removed in vacuo and the oily residue (14.7 g) was purified by column chromatography on silica gel (200 g) using first benzene and then a mixture of dichloromethane and ethanol (9:1) as eluents. The dichloromethane/ethanol fraction afforded 5.5 g (41%) of 5-(4-(2-tetrahydropyranyloxymethyl)phenyl)-10,11-dihydro-5H-dibenzo[a,d]-cyclohepten-5-ol. The mixture was gently heated to reflux temperature heating The mixture was heated at reflux temperature for 1 h cooled The mixture was extracted with ether (120 ml and 2×70 ml) the combined organic layers were washed with water (2×40 ml), brine (40 ml) dried (MgSO4) The solvent was removed in vacuo the oily residue (14.7 g) was purified by column chromatography on silica gel (200 g) a mixture of dichloromethane and ethanol (9:1) as eluents

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

实验步骤: To a stirred and refluxing Grignard-complex, previously prepared starting from 7.2 parts of magnesium and 81.4 parts of 2-(p-bromobenzyloxy)tetrahydropyran in 200 parts of dry tetrahydrofuran, is added dropwise a solution of 32.7 parts of 2-thiophenecarbonitrile in 70 parts of dry tetrahydrofuran (exothermic reaction: reflux temperature is maintained). Upon completion, stirring at reflux is continued for 4 hours. The reaction mixture is cooled and decomposed with 150 parts of a saturated ammonium chloride solution at about 15° C. The whole is poured onto water and the product is extracted with ether. The organic layer is washed four times with water, dried, filtered and acidified with gaseous hydrogen chloride; an oil is separated. The ether is decanted and the oily product is dissolved in 300 parts of water and 150 parts of concentrated hydrochloric acid solution. The solution is stirred with activated charcoal, filtered and the filtrate is stirred and refluxed for 10 minutes. The product is extracted with chloroform. The latter is washed with water, dried, filtered and evaporated. The residue is distilled, yielding α-hydroxy-p-tolyl 2-thienyl ketone; bp. 180°-190° C at 0.2 mm. pressure. refluxing Grignard-complex previously prepared Upon completion, stirring at reflux The reaction mixture is cooled The whole is poured onto water the product is extracted with ether The organic layer is washed four times with water dried filtered an oil is separated The ether is decanted the oily product is dissolved in 300 parts of water and 150 parts of concentrated hydrochloric acid solution The solution is stirred with activated charcoal filtered the filtrate is stirred refluxed for 10 minutes The product is extracted with chloroform The latter is washed with water dried filtered evaporated The residue is distilled

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

实验步骤: To a stirred and refluxing Grignard-complex, previously prepared starting from 7.2 parts of magnesium and 81.4 parts of 2-(p-bromobenzyloxy)tetrahydropyran in 200 parts of dry tetrahydrofuran, is added dropwise a solution of 32.7 parts of 2-thiophenecarbonitrile in 70 parts of dry tetrahydrofuran (exothermic reaction: reflux temperature is maintained). Upon completion, stirring at reflux is continued for 4 hours. The reaction mixture is cooled and decomposed with 150 parts of a saturated ammonium chloride solution at about 15° C. The whole is poured onto water and the product is extracted with ether. The organic layer is washed four times with water, dried, filtered and acidifed with gaseous hydrogen chloride: an oil is separated. The ether is decanted and the oily product is dissolved in 300 parts of water and 150 parts of concentrated hydrochloric acid solution. The solution is stirred with activated charcoal, filtered and the filtrate is stirred and refluxed for 10 minutes. The product is extracted with chloroform. The latter is washed with water, dried, filtered and evaporated. The residue is distilled, yielding α-hydroxy-p-tolyl 2-thienyl ketone; bp. 180°-190° C at 0.2 mm. pressure. refluxing Grignard-complex previously prepared Upon completion, stirring at reflux The reaction mixture is cooled The whole is poured onto water the product is extracted with ether The organic layer is washed four times with water dried filtered an oil is separated The ether is decanted the oily product is dissolved in 300 parts of water and 150 parts of concentrated hydrochloric acid solution The solution is stirred with activated charcoal filtered the filtrate is stirred refluxed for 10 minutes The product is extracted with chloroform The latter is washed with water dried filtered evaporated The residue is distilled

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

实验步骤: To a stirred and refluxing Grignard-complex, previously prepared starting from 7.2 parts of magnesium and 81.4 parts of 2-(p-bromobenzyloxy)tetrahydropyran in 200 parts of dry tetrahydrofuran, is added dropwise a solution of 32.7 parts of 2-thiophenecarbonitrile in 70 parts of dry tetrahydrofuran (exothermic reaction: reflux temperature is maintained). Upon completion, stirring at reflux is continued for 4 hours. The reaction mixture is cooled and decomposed with 150 parts of a saturated ammonium chloride solution at about 15° C. The whole is poured onto water and the product is extracted with ether. The organic layer is washed four times with water, dried, filtered and acidified with gaseous hydrogen chloride: an oil is separated. The ether is decanted and the oily product is dissolved in 300 parts of water and 150 parts of concentrated hydrochloric acid solution. The solution is stirred with activated charcoal, filtered and the filtrate is stirred and refluxed for 10 minutes. The product is extracted with chloroform. The latter is washed with water, dried, filtered and evaporated. The residue is distilled, yielding α-hydroxy-p-tolyl 2-thienyl ketone; b.p. 180°-190° C at 0.2 mm. pressure. refluxing Grignard-complex previously prepared Upon completion, stirring at reflux The reaction mixture is cooled The whole is poured onto water the product is extracted with ether The organic layer is washed four times with water dried filtered an oil is separated The ether is decanted the oily product is dissolved in 300 parts of water and 150 parts of concentrated hydrochloric acid solution The solution is stirred with activated charcoal filtered the filtrate is stirred refluxed for 10 minutes The product is extracted with chloroform The latter is washed with water dried filtered evaporated The residue is distilled

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

实验步骤: A mixture of magnesium turnings (1.07 g, 0.044 mol) activated with iodine, 1,2-dibromoethane and tetrahydrofuran (40 ml) was kept under a nitrogen atmosphere, and a solution of 4-bromophenylmethyl tetrahydro-2-pyranyl ether (11.20 g, 0.041 mol) in tetrahydrofuran (40 ml) was added dropwise under stirring. The mixture was gently heated to reflux temperature, and heating was continued for 3 h. The mixture was cooled to room temperature, and a solution of 10,11-dihydro-5H-dibenzo[a,d]cyclohepten-5-one (6.86 g, 0.033 mol) in tetrahydrofuran (40 ml) was added dropwise. The mixture was heated at reflux temperature for 1 h, cooled and then poured into an ice-cold saturated solution of ammonium chloride (85 ml). The mixture was extracted with ether (120 ml and 2×70 ml), and the combined organic layers were washed with water (2×40 ml), brine (40 ml) and dried (MgSO4). The solvent was removed in vacuo and the oily residue (14.7 g) was purified by column chromatography on silica gel (200 g) using first benzene and then a mixture of dichloromethane and ethanol (9:1) as eluents. The dichloromethane/ethanol fraction afforded 5.5 g (41%) of 5-(4-(2-tetrahydropyranyloxymethyl)phenyl)-10,11-dihydro-5H-dibenzo[a,d]-cyclohepten-5-ol. The mixture was gently heated to reflux temperature heating The mixture was heated at reflux temperature for 1 h cooled The mixture was extracted with ether (120 ml and 2×70 ml) the combined organic layers were washed with water (2×40 ml), brine (40 ml) dried (MgSO4) The solvent was removed in vacuo the oily residue (14.7 g) was purified by column chromatography on silica gel (200 g) a mixture of dichloromethane and ethanol (9:1) as eluents

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

实验步骤: To a stirred and refluxing Grignard-complex, previously prepared starting from 7.2 parts of magnesium and 81.4 parts of 2-(p-bromobenzyloxy)tetrahydropyran in 200 parts of dry tetrahydrofuran, is added dropwise a solution of 32.7 parts of 2-thiophenecarbonitrile in 70 parts of dry tetrahydrofuran (exothermic reaction: reflux temperature is maintained). Upon completion, stirring at reflux is continued for 4 hours. The reaction mixture is cooled and decomposed with 150 parts of a saturated ammonium chloride solution at about 15° C. The whole is poured onto water and the product is extracted with ether. The organic layer is washed four times with water, dried, filtered and acidified with gaseous hydrogen chloride; an oil is separated. The ether is decanted and the oily product is dissolved in 300 parts of water and 150 parts of concentrated hydrochloric acid solution. The solution is stirred with activated charcoal, filtered and the filtrate is stirred and refluxed for 10 minutes. The product is extracted with chloroform. The latter is washed with water, dried, filtered and evaporated. The residue is distilled, yielding α-hydroxy-p-tolyl 2-thienyl ketone; bp. 180°-190° C at 0.2 mm. pressure. refluxing Grignard-complex previously prepared Upon completion, stirring at reflux The reaction mixture is cooled The whole is poured onto water the product is extracted with ether The organic layer is washed four times with water dried filtered an oil is separated The ether is decanted the oily product is dissolved in 300 parts of water and 150 parts of concentrated hydrochloric acid solution The solution is stirred with activated charcoal filtered the filtrate is stirred refluxed for 10 minutes The product is extracted with chloroform The latter is washed with water dried filtered evaporated The residue is distilled