1-chloro-4-(2,2-dimethoxyethylsulfanyl)benzene

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

Procedure: A mixture of polyphosphoric acid (11.2 g) in chlorobenzene (290 mL) was heated to reflux and added, under nitrogen, dropwise in about one hour 1-chloro-4-(2,2-dimethoxy-ethylsulfanyl)-benzene (compound PRE9; 9.12 g, 39.2 mmol). The reaction mixture was then heated for one night until reaction is complete, cooled, quenched with water (150 mL) and extracted into methylene chloride (200 mL). Combined organic layer was dried over Na2SO4 and concentrated to give a crude residue that was purified by flash chromatography (silica, eluting solvent: petroleum ether) to give 2.1 g of 5-chloro-benzo[b]thiophene (limpid oil) (Yield=32%). was heated to reflux The reaction mixture was then heated for one night until reaction cooled quenched with water (150 mL) extracted into methylene chloride (200 mL) Combined organic layer was dried over Na2SO4 concentrated to give a crude residue that was purified by flash chromatography (silica, eluting solvent: petroleum ether)

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

Procedure: A mixture of polyphosphoric acid (11.2 g) in chlorobenzene (290 mL) was heated to reflux and added, under nitrogen, dropwise in about one hour 1-chloro-4-(2,2-dimethoxy-ethylsulfanyl)-benzene (compound PRE9; 9.12 g, 39.2 mmol). The reaction mixture was then heated for one night until reaction is complete, cooled, quenched with water (150 mL) and extracted into methylene chloride (200 mL). Combined organic layer was dried over Na2SO4 and concentrated to give a crude residue that was purified by flash chromatography (silica, eluting solvent: petroleum ether) to give 2.1 g of 5-chloro-benzo[b]thiophene (limpid oil) (Yield=32%). was heated to reflux The reaction mixture was then heated for one night until reaction cooled quenched with water (150 mL) extracted into methylene chloride (200 mL) Combined organic layer was dried over Na2SO4 concentrated to give a crude residue that was purified by flash chromatography (silica, eluting solvent: petroleum ether)

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

Procedure: To a solution of 4-chlorobenzenethiol (5.78 g; 40 mmol) in anhydrous acetone (50 mL) was added potassium carbonate (5.52 g, 40 mmol) and dropwise at room temperature 2-bromo-1,1-dimethoxy-ethane (4.7 mL, 40 mmol). After 24 h of stirring, the precipitate was filtered, the filtrate concentrated, the residue diluted with water and diethyl ether (150 mL), the organic layer washed successively with water (60 mL), NaOH 4N (30 mL) and water (60 mL), dried over Na2SO4 and concentrated to give 1-chloro-4-(2,2-dimethoxy-ethylsulfanyl)-benzene (compound PRE9) (9.12 g; orange oil) (Yield=98%). dropwise at room temperature the precipitate was filtered the filtrate concentrated the residue diluted with water and diethyl ether (150 mL) the organic layer washed successively with water (60 mL), NaOH 4N (30 mL) and water (60 mL) dried over Na2SO4 concentrated

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

Procedure: To a solution of 4-chlorobenzenethiol (5.78 g; 40 mmol) in anhydrous acetone (50 mL) was added potassium carbonate (5.52 g, 40 mmol) and dropwise at room temperature 2-bromo-1,1-dimethoxy-ethane (4.7 mL, 40 mmol). After 24 h of stirring, the precipitate was filtered, the filtrate concentrated, the residue diluted with water and diethyl ether (150 mL), the organic layer washed successively with water (60 mL), NaOH 4N (30 mL) and water (60 mL), dried over Na2SO4 and concentrated to give 1-chloro-4-(2,2-dimethoxy-ethylsulfanyl)-benzene (compound PRE9) (9.12 g; orange oil) (Yield=98%). dropwise at room temperature the precipitate was filtered the filtrate concentrated the residue diluted with water and diethyl ether (150 mL) the organic layer washed successively with water (60 mL), NaOH 4N (30 mL) and water (60 mL) dried over Na2SO4 concentrated

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

Procedure: A mixture of polyphosphoric acid (11.2 g) in chlorobenzene (290 mL) was heated to reflux and added, under nitrogen, dropwise in about one hour 1-chloro-4-(2,2-dimethoxy-ethylsulfanyl)-benzene (compound PRE9; 9.12 g, 39.2 mmol). The reaction mixture was then heated for one night until reaction is complete, cooled, quenched with water (150 mL) and extracted into methylene chloride (200 mL). Combined organic layer was dried over Na2SO4 and concentrated to give a crude residue that was purified by flash chromatography (silica, eluting solvent: petroleum ether) to give 2.1 g of 5-chloro-benzo[b]thiophene (limpid oil) (Yield=32%). was heated to reflux The reaction mixture was then heated for one night until reaction cooled quenched with water (150 mL) extracted into methylene chloride (200 mL) Combined organic layer was dried over Na2SO4 concentrated to give a crude residue that was purified by flash chromatography (silica, eluting solvent: petroleum ether)

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

Procedure: To a solution of 4-chlorobenzenethiol (5.78 g; 40 mmol) in anhydrous acetone (50 mL) was added potassium carbonate (5.52 g, 40 mmol) and dropwise at room temperature 2-bromo-1,1-dimethoxy-ethane (4.7 mL, 40 mmol). After 24 h of stirring, the precipitate was filtered, the filtrate concentrated, the residue diluted with water and diethyl ether (150 mL), the organic layer washed successively with water (60 mL), NaOH 4N (30 mL) and water (60 mL), dried over Na2SO4 and concentrated to give 1-chloro-4-(2,2-dimethoxy-ethylsulfanyl)-benzene (compound PRE9) (9.12 g; orange oil) (Yield=98%). dropwise at room temperature the precipitate was filtered the filtrate concentrated the residue diluted with water and diethyl ether (150 mL) the organic layer washed successively with water (60 mL), NaOH 4N (30 mL) and water (60 mL) dried over Na2SO4 concentrated

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

Procedure: To a solution of 4-chlorobenzenethiol (5.78 g; 40 mmol) in anhydrous acetone (50 mL) was added potassium carbonate (5.52 g, 40 mmol) and dropwise at room temperature 2-bromo-1,1-dimethoxy-ethane (4.7 mL, 40 mmol). After 24 h of stirring, the precipitate was filtered, the filtrate concentrated, the residue diluted with water and diethyl ether (150 mL), the organic layer washed successively with water (60 mL), NaOH 4N (30 mL) and water (60 mL), dried over Na2SO4 and concentrated to give 1-chloro-4-(2,2-dimethoxy-ethylsulfanyl)-benzene (compound PRE9) (9.12 g; orange oil) (Yield=98%). dropwise at room temperature the precipitate was filtered the filtrate concentrated the residue diluted with water and diethyl ether (150 mL) the organic layer washed successively with water (60 mL), NaOH 4N (30 mL) and water (60 mL) dried over Na2SO4 concentrated

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

Procedure: A mixture of polyphosphoric acid (11.2 g) in chlorobenzene (290 mL) was heated to reflux and added, under nitrogen, dropwise in about one hour 1-chloro-4-(2,2-dimethoxy-ethylsulfanyl)-benzene (compound PRE9; 9.12 g, 39.2 mmol). The reaction mixture was then heated for one night until reaction is complete, cooled, quenched with water (150 mL) and extracted into methylene chloride (200 mL). Combined organic layer was dried over Na2SO4 and concentrated to give a crude residue that was purified by flash chromatography (silica, eluting solvent: petroleum ether) to give 2.1 g of 5-chloro-benzo[b]thiophene (limpid oil) (Yield=32%). was heated to reflux The reaction mixture was then heated for one night until reaction cooled quenched with water (150 mL) extracted into methylene chloride (200 mL) Combined organic layer was dried over Na2SO4 concentrated to give a crude residue that was purified by flash chromatography (silica, eluting solvent: petroleum ether)

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

Procedure: To a solution of 4-chlorobenzenethiol (5.78 g; 40 mmol) in anhydrous acetone (50 mL) was added potassium carbonate (5.52 g, 40 mmol) and dropwise at room temperature 2-bromo-1,1-dimethoxy-ethane (4.7 mL, 40 mmol). After 24 h of stirring, the precipitate was filtered, the filtrate concentrated, the residue diluted with water and diethyl ether (150 mL), the organic layer washed successively with water (60 mL), NaOH 4N (30 mL) and water (60 mL), dried over Na2SO4 and concentrated to give 1-chloro-4-(2,2-dimethoxy-ethylsulfanyl)-benzene (compound PRE9) (9.12 g; orange oil) (Yield=98%). dropwise at room temperature the precipitate was filtered the filtrate concentrated the residue diluted with water and diethyl ether (150 mL) the organic layer washed successively with water (60 mL), NaOH 4N (30 mL) and water (60 mL) dried over Na2SO4 concentrated

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

Procedure: To a solution of 4-chlorobenzenethiol (5.78 g; 40 mmol) in anhydrous acetone (50 mL) was added potassium carbonate (5.52 g, 40 mmol) and dropwise at room temperature 2-bromo-1,1-dimethoxy-ethane (4.7 mL, 40 mmol). After 24 h of stirring, the precipitate was filtered, the filtrate concentrated, the residue diluted with water and diethyl ether (150 mL), the organic layer washed successively with water (60 mL), NaOH 4N (30 mL) and water (60 mL), dried over Na2SO4 and concentrated to give 1-chloro-4-(2,2-dimethoxy-ethylsulfanyl)-benzene (compound PRE9) (9.12 g; orange oil) (Yield=98%). dropwise at room temperature the precipitate was filtered the filtrate concentrated the residue diluted with water and diethyl ether (150 mL) the organic layer washed successively with water (60 mL), NaOH 4N (30 mL) and water (60 mL) dried over Na2SO4 concentrated

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

Procedure: To a solution of 4-chlorobenzenethiol (13 mmol) and Et3N (1.4 g, 13 mmol) in THF (25 mL) at room temperature was added 2-bromo-1,1-dimethoxyethane (2.36 g, 13 mmol) in THF (5 mL). After stirring at room temperature for 30 minutes, the reaction mixture was poured into water (200 mL) and extracted with diethyl ether (3×150 mL). The combined organic layer was dried over Na2SO4. After filtration and concentration, the crude product was purified by column chromatography to give the title compound. extracted with diethyl ether (3×150 mL) The combined organic layer was dried over Na2SO4 After filtration and concentration the crude product was purified by column chromatography

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

Procedure: A mixture of polyphosphoric acid (11.2 g) in chlorobenzene (290 mL) was heated to reflux and added, under nitrogen, dropwise in about one hour 1-chloro-4-(2,2-dimethoxy-ethylsulfanyl)-benzene (compound PRE9; 9.12 g, 39.2 mmol). The reaction mixture was then heated for one night until reaction is complete, cooled, quenched with water (150 mL) and extracted into methylene chloride (200 mL). Combined organic layer was dried over Na2SO4 and concentrated to give a crude residue that was purified by flash chromatography (silica, eluting solvent: petroleum ether) to give 2.1 g of 5-chloro-benzo[b]thiophene (limpid oil) (Yield=32%). was heated to reflux The reaction mixture was then heated for one night until reaction cooled quenched with water (150 mL) extracted into methylene chloride (200 mL) Combined organic layer was dried over Na2SO4 concentrated to give a crude residue that was purified by flash chromatography (silica, eluting solvent: petroleum ether)