1-bromo-2-ethylsulfanylbenzene

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

Conditions: temp:-70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 14.1 g of 1-bromo-2-ethylsulfanylbenzene and 65 mL of THF was cooled to −70° C., and 44.7 mL of n-butyllithium (1.63 M hexane solvent) was added to the mixture at a rate so as to maintain an internal temperature of −60° C. or lower, and the mixture was stirred at −50° C. for 30 minutes. A mixture of 14 g of isopropoxyboronic acid pinacol ester and 5 mL of THF was added to the mixture at a rate so as to maintain an internal temperature of −60° C. or lower, and the mixture was heated to room temperature. Water was poured to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with water, then dried over anhydrous sodium sulfate and concentrated under reduced pressure. The resulting residue was applied to a silica gel column chromatography to obtain 7.9 g of 2-ethylsulfanylphenylboronic acid pinacol ester. to maintain an internal temperature of −60° C. was added to the mixture at a rate so as to maintain an internal temperature of −60° C. lower, and the mixture was heated to room temperature the mixture was extracted with ethyl acetate The organic layer was washed with water dried over anhydrous sodium sulfate concentrated under reduced pressure

Conditions: temp:-70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 14.1 g of 1-bromo-2-ethylsulfanylbenzene and 65 mL of THF was cooled to −70° C., and 44.7 ml of n-butyl lithium (1.63M hexane solvent) was added at a rate such that the internal temperature of the mixture was kept at −60° C. or less, and the mixture was stirred at −50° C. for 30 minutes. A mixture of 14 g of isopropoxyboronic acid pinacol ester and 5 mL of THF was added at a rate such that the internal temperature of the mixture was kept at −60° C. or less, and the mixture was heated to the room temperature. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with water, then dried over anhydrous sodium sulfate and concentrated under reduced pressure. The resulting residue was applied to a silica gel column chromatography to obtain 7.9 g of 2-ethylsulfanylphenylboronic acid pinacol ester. was kept at −60° C. or less was added at a rate such that the internal temperature of the mixture was kept at −60° C. or less the mixture was heated to the room temperature the mixture was extracted with ethyl acetate The organic layer was washed with water dried over anhydrous sodium sulfate concentrated under reduced pressure

Conditions: temp:-70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 9.5 g (50 mmol) of triisopropyl borate are added to a solution of 10.9 g (50.0 mmol) of 1-bromo-2-ethylsulfanylbenzene kept at −70° C. 33.3 ml of a 15% solution of BuLi in hexane (55 mmol) are then added. The mixture is stirred at −70° C. for a further 30 minutes, then 1 N hydrochloric acid and ethyl acetate are added. The organic phase is separated off, dried and evaporated. The residue is taken up in diethyl ether and filtered. A colourless solid is obtained; FAB 182 kept at −70° C The organic phase is separated off dried evaporated filtered A colourless solid is obtained

Conditions: temp:-70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 9.5 g (50 mmol) of triisopropyl borate are added to a solution of 10.9 g (50.0 mmol) of 1-bromo-2-ethylsulfanylbenzene kept at −70° C. 33.3 ml of a 15% solution of BuLi in hexane (55 mmol) are then added. The mixture is stirred at −70° C. for a further 30 minutes, then 1 N hydrochloric acid and ethyl acetate are added. The organic phase is separated off, dried and evaporated. The residue is taken up in diethyl ether and filtered. A colourless solid is obtained; FAB 182 kept at −70° C The organic phase is separated off dried evaporated filtered A colourless solid is obtained

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

Conditions: temp:-70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 14.1 g of 1-bromo-2-ethylsulfanylbenzene and 65 mL of THF was cooled to −70° C., and 44.7 mL of n-butyllithium (1.63 M hexane solvent) was added to the mixture at a rate so as to maintain an internal temperature of −60° C. or lower, and the mixture was stirred at −50° C. for 30 minutes. A mixture of 14 g of isopropoxyboronic acid pinacol ester and 5 mL of THF was added to the mixture at a rate so as to maintain an internal temperature of −60° C. or lower, and the mixture was heated to room temperature. Water was poured to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with water, then dried over anhydrous sodium sulfate and concentrated under reduced pressure. The resulting residue was applied to a silica gel column chromatography to obtain 7.9 g of 2-ethylsulfanylphenylboronic acid pinacol ester. to maintain an internal temperature of −60° C. was added to the mixture at a rate so as to maintain an internal temperature of −60° C. lower, and the mixture was heated to room temperature the mixture was extracted with ethyl acetate The organic layer was washed with water dried over anhydrous sodium sulfate concentrated under reduced pressure

Conditions: temp:-70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 14.1 g of 1-bromo-2-ethylsulfanylbenzene and 65 mL of THF was cooled to −70° C., and 44.7 ml of n-butyl lithium (1.63M hexane solvent) was added at a rate such that the internal temperature of the mixture was kept at −60° C. or less, and the mixture was stirred at −50° C. for 30 minutes. A mixture of 14 g of isopropoxyboronic acid pinacol ester and 5 mL of THF was added at a rate such that the internal temperature of the mixture was kept at −60° C. or less, and the mixture was heated to the room temperature. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with water, then dried over anhydrous sodium sulfate and concentrated under reduced pressure. The resulting residue was applied to a silica gel column chromatography to obtain 7.9 g of 2-ethylsulfanylphenylboronic acid pinacol ester. was kept at −60° C. or less was added at a rate such that the internal temperature of the mixture was kept at −60° C. or less the mixture was heated to the room temperature the mixture was extracted with ethyl acetate The organic layer was washed with water dried over anhydrous sodium sulfate concentrated under reduced pressure

Conditions: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of the Grignard reagent of 1-ethylmercapto-2-bromobenzene in tetrahydrofuran was prepared in the following way: 1.50 g (6.9 mmol) of 1-ethylmercapto-2-bromobenzene were added to 218 mg (9.0 mmol) of magnesium in 8 ml of anhydrous tetrahydrofuran at room temperature under N2 and was heated to reflux for 1 h. Meanwhile, a solution of 1.20 g (6.2 mmol) of (2-bromoallyl)trimethylsilane and 358 mg (0.31 mmol) of tetrakis(triphenylphosphine)-palladium in 6 ml of dry benzene was stirred at 80° C. under N2 for 30 min. Then it was cooled to 50° C. and to it was added the Grignard reagent described above. The reaction mixture was stirred at 40° C. for 3 h and was poured into 100 ml of ether. It was washed with water (20 ml×2), dried over MgSO4 and concentrated. The residue was purified by silica gel chromatography with hexane to give [2-(2-ethylmercaptophenyl)allyl trimethylsilane as a colorless oil. was heated to reflux for 1 h It was washed with water (20 ml×2) dried over MgSO4 concentrated The residue was purified by silica gel chromatography with hexane

Conditions: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of the Grignard reagent of 1-ethylmercapto-2-bromobenzene in tetrahydrofuran was prepared in the following way: 1.50 g (6.9 mmol) of 1-ethylmercapto-2-bromobenzene were added to 218 mg (9.0 mmol) of magnesium in 8 ml of anhydrous tetrahydrofuran at room temperature under N2 and was heated to reflux for 1 h. Meanwhile, a solution of 1.20 g (6.2 mmol) of (2-bromoallyl)trimethylsilane and 358 mg (0.31 mmol) of tetrakis(triphenylphosphine)-palladium in 6 ml of dry benzene was stirred at 80° C. under N2 for 30 min. Then it was cooled to 50° C. and to it was added the Grignard reagent described above. The reaction mixture was stirred at 40° C. for 3 h and was poured into 100 ml of ether. It was washed with water (20 ml×2), dried over MgSO4 and concentrated. The residue was purified by silica gel chromatography with hexane to give [2-(2-ethylmercaptophenyl)allyl trimethylsilane as a colorless oil. was heated to reflux for 1 h It was washed with water (20 ml×2) dried over MgSO4 concentrated The residue was purified by silica gel chromatography with hexane

Conditions: temp:57.51; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a suspension of 1.00 g (5.3 mmol) of 2-bromo-benzenethiol and 1.47 g (10.6 mmol) of potassium carbonate in 15 ml of N,N-dimethylformamide was added 1.65 g (10.6 mmol) of iodoethane at 0° C. The reaction mixture was stirred at 55-60° C. for 12 h and was poured into 200 ml of ether. It was washed with water (20 ml×3), dried over MgSO4 and concentrated to afford 1-ethylmercapto-2-bromobenzene as a colorless oil. It was washed with water (20 ml×3) dried over MgSO4 concentrated

Conditions: temp:57.51; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a suspension of 1.00 g (5.3 mmol) of 2-bromo-benzenethiol and 1.47 g (10.6 mmol) of potassium carbonate in 15 ml of N,N-dimethylformamide was added 1.65 g (10.6 mmol) of iodoethane at 0° C. The reaction mixture was stirred at 55-60° C. for 12 h and was poured into 200 ml of ether. It was washed with water (20 ml×3), dried over MgSO4 and concentrated to afford 1-ethylmercapto-2-bromobenzene as a colorless oil. It was washed with water (20 ml×3) dried over MgSO4 concentrated