1-bromo-3-(dimethoxymethyl)benzene

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

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

Procedure: Commercial 2-(3-Bromo-phenyl)-[1,3]dioxolane (1.3 mL, 8.64 mmol) was dissolved in anhydrous MeOH (40 mL) and catalytic amount of H2SO4 was added. The resulting reaction mixture was stirred 4 h at rt and finally extracted with petroleum ether (3×50 mL). The combined organic phases were washed with NaHCO3 (40 mL), dried (MgSO4), filtered and concentrated under vacuum to give 22b as a colourless oil (1.76 g, 88%), whose spectroscopic data were in close agreement with literature (29). The resulting reaction mixture finally extracted with petroleum ether (3×50 mL) The combined organic phases were washed with NaHCO3 (40 mL) dried (MgSO4) filtered concentrated under vacuum

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

Procedure: Commercial 2-(3-Bromo-phenyl)-[1,3]dioxolane (1.3 mL, 8.64 mmol) was dissolved in anhydrous MeOH (40 mL) and catalytic amount of H2SO4 was added. The resulting reaction mixture was stirred 4 h at rt and finally extracted with petroleum ether (3×50 mL). The combined organic phases were washed with NaHCO3 (40 mL), dried (MgSO4), filtered and concentrated under vacuum to give 22b as a colourless oil (1.76 g, 88%), whose spectroscopic data were in close agreement with literature (29). The resulting reaction mixture finally extracted with petroleum ether (3×50 mL) The combined organic phases were washed with NaHCO3 (40 mL) dried (MgSO4) filtered concentrated under vacuum

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

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

Procedure: 534 mg of 3-(tetrahydro-3-hydroxy-3-thiopyranyl)benzaldehyde dimethyl acetal obtained by performing the same reaction as in Referential Example 35 using 3-bromobenzaldehyde dimethyl acetal and tetrahydrothiopyran-3-one as starting materials was dissolved in 5 ml of ethyl acetate, and with stirring under ice cooling, 187 microliters of methanesulfonyl chloride and 553 microliters of triethylamine were added. The mixture was stirred for 30 minutes. The triethylamine hydrochloride was separated by filtration and the solvent was evaporated. The residue was dissolved in 20 ml of benzene, and 373 mg of 90% potassium tert-butoxide was added, and the mixture was stirred at room temperature for 15 hours. Ethyl ether and water were added to the reaction mixture, and the mixture was worked up in a customary manner. The resulting 3-dihydrothiopyranylbenzaldehyde dimethyl acetal was dissolved in a mixture of 3 ml of 1 N HCl and 6 ml of tetrahydrofuran. The solution was stirred at room temperature for 3 hours. The reaction mixture was concentrated under reduced pressure, and the residue was distributed between ethyl ether and water, and worked up in a customary manner. The resulting formyl compound was dissolved in 20 ml of tetrahydrofuran, and 380 mg of lithium aluminium hydride was added. The mixture was stirred for one hour under ice cooling. The reaction mixture was poured into ice water, worked up in a customary manner and purified by silica gel column chromatography [Wakogel C-200, 20 g; eluting solvent: hexane/ethyl acetate=2/1] to give 7 mg (yield 2%) of the captioned 3-(3,4-dihydro-2H-thiopyran-5-yl)benzyl alcohol and 4 mg (yield 1%) of 3-(5,6-dihydro-2H-thiopyran-3-yl)benzyl alcohol. The mixture was stirred for 30 minutes The triethylamine hydrochloride was separated by filtration the solvent was evaporated The residue was dissolved in 20 ml of benzene 373 mg of 90% potassium tert-butoxide was added the mixture was stirred at room temperature for 15 hours Ethyl ether and water were added to the reaction mixture The resulting 3-dihydrothiopyranylbenzaldehyde dimethyl acetal was dissolved in a mixture of 3 ml of 1 N HCl and 6 ml of tetrahydrofuran The solution was stirred at room temperature for 3 hours The reaction mixture was concentrated under reduced pressure The resulting formyl compound was dissolved in 20 ml of tetrahydrofuran 380 mg of lithium aluminium hydride was added The mixture was stirred for one hour under ice cooling The reaction mixture was poured into ice water purified by silica gel column chromatography [Wakogel C-200, 20 g; eluting solvent: hexane/ethyl acetate=2/1]

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

Procedure: 534 mg of 3-(tetrahydro-3-hydroxy-3-thiopyranyl)benzaldehyde dimethyl acetal obtained by performing the same reaction as in Referential Example 35 using 3-bromobenzaldehyde dimethyl acetal and tetrahydrothiopyran-3-one as starting materials was dissolved in 5 ml of ethyl acetate, and with stirring under ice cooling, 187 microliters of methanesulfonyl chloride and 553 microliters of triethylamine were added. The mixture was stirred for 30 minutes. The triethylamine hydrochloride was separated by filtration and the solvent was evaporated. The residue was dissolved in 20 ml of benzene, and 373 mg of 90% potassium tert-butoxide was added, and the mixture was stirred at room temperature for 15 hours. Ethyl ether and water were added to the reaction mixture, and the mixture was worked up in a customary manner. The resulting 3-dihydrothiopyranylbenzaldehyde dimethyl acetal was dissolved in a mixture of 3 ml of 1 N HCl and 6 ml of tetrahydrofuran. The solution was stirred at room temperature for 3 hours. The reaction mixture was concentrated under reduced pressure, and the residue was distributed between ethyl ether and water, and worked up in a customary manner. The resulting formyl compound was dissolved in 20 ml of tetrahydrofuran, and 380 mg of lithium aluminium hydride was added. The mixture was stirred for one hour under ice cooling. The reaction mixture was poured into ice water, worked up in a customary manner and purified by silica gel column chromatography [Wakogel C-200, 20 g; eluting solvent: hexane/ethyl acetate=2/1] to give 7 mg (yield 2%) of the captioned 3-(3,4-dihydro-2H-thiopyran-5-yl)benzyl alcohol and 4 mg (yield 1%) of 3-(5,6-dihydro-2H-thiopyran-3-yl)benzyl alcohol. The mixture was stirred for 30 minutes The triethylamine hydrochloride was separated by filtration the solvent was evaporated The residue was dissolved in 20 ml of benzene 373 mg of 90% potassium tert-butoxide was added the mixture was stirred at room temperature for 15 hours Ethyl ether and water were added to the reaction mixture The resulting 3-dihydrothiopyranylbenzaldehyde dimethyl acetal was dissolved in a mixture of 3 ml of 1 N HCl and 6 ml of tetrahydrofuran The solution was stirred at room temperature for 3 hours The reaction mixture was concentrated under reduced pressure The resulting formyl compound was dissolved in 20 ml of tetrahydrofuran 380 mg of lithium aluminium hydride was added The mixture was stirred for one hour under ice cooling The reaction mixture was poured into ice water purified by silica gel column chromatography [Wakogel C-200, 20 g; eluting solvent: hexane/ethyl acetate=2/1]

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

Procedure: 534 mg of 3-(tetrahydro-3-hydroxy-3-thiopyranyl)benzaldehyde dimethyl acetal obtained by performing the same reaction as in Referential Example 35 using 3-bromobenzaldehyde dimethyl acetal and tetrahydrothiopyran-3-one as starting materials was dissolved in 5 ml of ethyl acetate, and with stirring under ice cooling, 187 microliters of methanesulfonyl chloride and 553 microliters of triethylamine were added. The mixture was stirred for 30 minutes. The triethylamine hydrochloride was separated by filtration and the solvent was evaporated. The residue was dissolved in 20 ml of benzene, and 373 mg of 90% potassium tert-butoxide was added, and the mixture was stirred at room temperature for 15 hours. Ethyl ether and water were added to the reaction mixture, and the mixture was worked up in a customary manner. The resulting 3-dihydrothiopyranylbenzaldehyde dimethyl acetal was dissolved in a mixture of 3 ml of 1 N HCl and 6 ml of tetrahydrofuran. The solution was stirred at room temperature for 3 hours. The reaction mixture was concentrated under reduced pressure, and the residue was distributed between ethyl ether and water, and worked up in a customary manner. The resulting formyl compound was dissolved in 20 ml of tetrahydrofuran, and 380 mg of lithium aluminium hydride was added. The mixture was stirred for one hour under ice cooling. The reaction mixture was poured into ice water, worked up in a customary manner and purified by silica gel column chromatography [Wakogel C-200, 20 g; eluting solvent: hexane/ethyl acetate=2/1] to give 7 mg (yield 2%) of the captioned 3-(3,4-dihydro-2H-thiopyran-5-yl)benzyl alcohol and 4 mg (yield 1%) of 3-(5,6-dihydro-2H-thiopyran-3-yl)benzyl alcohol. The mixture was stirred for 30 minutes The triethylamine hydrochloride was separated by filtration the solvent was evaporated The residue was dissolved in 20 ml of benzene 373 mg of 90% potassium tert-butoxide was added the mixture was stirred at room temperature for 15 hours Ethyl ether and water were added to the reaction mixture The resulting 3-dihydrothiopyranylbenzaldehyde dimethyl acetal was dissolved in a mixture of 3 ml of 1 N HCl and 6 ml of tetrahydrofuran The solution was stirred at room temperature for 3 hours The reaction mixture was concentrated under reduced pressure The resulting formyl compound was dissolved in 20 ml of tetrahydrofuran 380 mg of lithium aluminium hydride was added The mixture was stirred for one hour under ice cooling The reaction mixture was poured into ice water purified by silica gel column chromatography [Wakogel C-200, 20 g; eluting solvent: hexane/ethyl acetate=2/1]

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

Procedure: Magnesium metal (1.2 g) was added to 2 ml of tetrahydrofuran. With stirring at room temperature, 20 ml of a solution of 2.0 g of 3-bromobenzaldehyde dimethyl acetal in a 1:1 mixture of tetrahydrofuran and ethyl ether was added dropwise over the course of 1 hour. With stirring under ice cooling, 15 ml of a tetrahydrofuran solution of 2.25 g of 3-methyl-2-butenyl bromide was added to the resulting solution. The temperature of the mixture was returned to room temperature, and then it was stirred for 1 hour. A saturated aqueous solution of ammonium chloride was added to the reaction mixture to terminate the reaction. Ethyl ether was added, and the reaction mixture was treated in a customary manner to give 1.71 g (yield 90%) of 3-(3-methyl-2-butenyl)benzaldehyde dimethyl acetal as a colorless oil. was added dropwise over the course of 1 hour With stirring under ice cooling was returned to room temperature it was stirred for 1 hour to terminate the reaction the reaction mixture was treated in a customary manner

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

Procedure: Magnesium metal (1.2 g) was added to 2 ml of tetrahydrofuran. With stirring at room temperature, 20 ml of a solution of 2.0 g of 3-bromobenzaldehyde dimethyl acetal in a 1:1 mixture of tetrahydrofuran and ethyl ether was added dropwise over the course of 1 hour. With stirring under ice cooling, 15 ml of a tetrahydrofuran solution of 2.25 g of 3-methyl-2-butenyl bromide was added to the resulting solution. The temperature of the mixture was returned to room temperature, and then it was stirred for 1 hour. A saturated aqueous solution of ammonium chloride was added to the reaction mixture to terminate the reaction. Ethyl ether was added, and the reaction mixture was treated in a customary manner to give 1.71 g (yield 90%) of 3-(3-methyl-2-butenyl)benzaldehyde dimethyl acetal as a colorless oil. was added dropwise over the course of 1 hour With stirring under ice cooling was returned to room temperature it was stirred for 1 hour to terminate the reaction the reaction mixture was treated in a customary manner

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

Procedure: Magnesium metal (1.2 g) was added to 2 ml of tetrahydrofuran. With stirring at room temperature, 20 ml of a solution of 2.0 g of 3-bromobenzaldehyde dimethyl acetal in a 1:1 mixture of tetrahydrofuran and ethyl ether was added dropwise over the course of 1 hour. With stirring under ice cooling, 15 ml of a tetrahydrofuran solution of 2.25 g of 3-methyl-2-butenyl bromide was added to the resulting solution. The temperature of the mixture was returned to room temperature, and then it was stirred for 1 hour. A saturated aqueous solution of ammonium chloride was added to the reaction mixture to terminate the reaction. Ethyl ether was added, and the reaction mixture was treated in a customary manner to give 1.71 g (yield 90%) of 3-(3-methyl-2-butenyl)benzaldehyde dimethyl acetal as a colorless oil. was added dropwise over the course of 1 hour With stirring under ice cooling was returned to room temperature it was stirred for 1 hour to terminate the reaction the reaction mixture was treated in a customary manner