(4-Bromophenyl)(2,2-diethoxyethyl)sulfane

Conditions: temp:130.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 5-Bromobenzo[b]thiophene (Chemical Abstracts number 4923-87-9) was prepared as described in Banfield et al.; J. Chem. Soc.; 1956; 2603-2607, and in Seed, Alexander J.; et al. J. Mater. Chem.; vol10; 2000; 2069-2080. A mixture of phosphoric acid (218 g) and chlorobenzene (2 L) was heated at 130° C. and then treated with the product from Example 165A (107.0 g) over 2 hours using a syringe pump. The mixture was heated at 130° C. for 15 hours. Dean-Stark trap was used at the beginning of the reflux to remove water from the mixture. The mixture was allowed to cool to room temperature and quenched with 400 mL of water. The bottom aqueous layer was extracted with 200 mL of methylene chloride. The combined organic layer was washed with 200 mL of 10% Na2CO3, and concentrated to brown oil (129.4 g). The crude oil was dissolved in 1L of 10:90 EtOAC:hexane, filtered through a short pad of silica gel and concentrated to a yellow oil (85.54 g, 95.8% yield). Further purification was done by column chromatography (silica gel, 5:95 EtOAc:hexane). The mixture was heated at 130° C. for 15 hours reflux to remove water from the mixture to cool to room temperature quenched with 400 mL of water The bottom aqueous layer was extracted with 200 mL of methylene chloride The combined organic layer was washed with 200 mL of 10% Na2CO3 concentrated to brown oil (129.4 g) The crude oil was dissolved in 1L of 10:90 EtOAC hexane, filtered through a short pad of silica gel

Conditions: temp:55.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 1-Bromo-4-[(2,2-diethoxyethyl)thio]benzene (Chemical Abstracts number 96804-05-6) was prepared as described in Banfield et al.; J. Chem. Soc.; 1956; 2603-2607, and in Amin, et al.; J. Chem. Soc. Perkin Trans. 2; 1982; 1489-1492. 4-Bromothiophenol (20 g, 95%) in ethanol (80 mL) was treated with 21 wt % of sodium ethoxide in ethanol (36 g, 1.05 eq). The solution was heated at 55° C. for 30 minutes and bromoacetaldehyde diethylacetal (22.56 g, 1.05 eq) was added. The mixture was heated at reflux for 10 hours, ethanol was removed and the residue was diluted with 80 mL of water. The product was extracted with 2×120 mL of ethyl acetate. The combined ethyl acetate layer was washed with 2×40 mL of 15% NaCl and concentrated under vacuum to a brown oil (32.0 g, 92.5% potency, 96.5% yield). The product can be further purified by column chromatography (silica gel, 5:95 EtOAc:hexane). The mixture was heated at reflux for 10 hours ethanol was removed the residue was diluted with 80 mL of water The product was extracted with 2×120 mL of ethyl acetate The combined ethyl acetate layer was washed with 2×40 mL of 15% NaCl concentrated under vacuum to a brown oil (32.0 g, 92.5% potency, 96.5% yield) The product can be further purified by column chromatography (silica gel, 5:95 EtOAc:hexane)

Conditions: temp:55.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 1-Bromo-4-[(2,2-diethoxyethyl)thio]benzene (Chemical Abstracts number 96804-05-6) was prepared as described in Banfield et al.; J. Chem. Soc.; 1956; 2603-2607, and in Amin, et al.; J. Chem. Soc. Perkin Trans. 2; 1982; 1489-1492. 4-Bromothiophenol (20 g, 95%) in ethanol (80 mL) was treated with 21 wt % of sodium ethoxide in ethanol (36 g, 1.05 eq). The solution was heated at 55° C. for 30 minutes and bromoacetaldehyde diethylacetal (22.56 g, 1.05 eq) was added. The mixture was heated at reflux for 10 hours, ethanol was removed and the residue was diluted with 80 mL of water. The product was extracted with 2×120 mL of ethyl acetate. The combined ethyl acetate layer was washed with 2×40 mL of 15% NaCl and concentrated under vacuum to a brown oil (32.0 g, 92.5% potency, 96.5% yield). The product can be further purified by column chromatography (silica gel, 5:95 EtOAc:hexane). The mixture was heated at reflux for 10 hours ethanol was removed the residue was diluted with 80 mL of water The product was extracted with 2×120 mL of ethyl acetate The combined ethyl acetate layer was washed with 2×40 mL of 15% NaCl concentrated under vacuum to a brown oil (32.0 g, 92.5% potency, 96.5% yield) The product can be further purified by column chromatography (silica gel, 5:95 EtOAc:hexane)

Conditions: temp:130.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 5-Bromobenzo[b]thiophene (Chemical Abstracts number 4923-87-9) was prepared as described in Banfield et al.; J. Chem. Soc.; 1956; 2603-2607, and in Seed, Alexander J.; et al. J. Mater. Chem.; vol10; 2000; 2069-2080. A mixture of phosphoric acid (218 g) and chlorobenzene (2 L) was heated at 130° C. and then treated with the product from Example 165A (107.0 g) over 2 hours using a syringe pump. The mixture was heated at 130° C. for 15 hours. Dean-Stark trap was used at the beginning of the reflux to remove water from the mixture. The mixture was allowed to cool to room temperature and quenched with 400 mL of water. The bottom aqueous layer was extracted with 200 mL of methylene chloride. The combined organic layer was washed with 200 mL of 10% Na2CO3, and concentrated to brown oil (129.4 g). The crude oil was dissolved in 1 L of 10:90 EtOAC:hexane, filtered through a short pad of silica gel and concentrated to a yellow oil (85.54 g, 95.8% yield). Further purification was done by column chromatography (silica gel, 5:95 EtOAc:hexane). The mixture was heated at 130° C. for 15 hours reflux to remove water from the mixture to cool to room temperature quenched with 400 mL of water The bottom aqueous layer was extracted with 200 mL of methylene chloride The combined organic layer was washed with 200 mL of 10% Na2CO3 concentrated to brown oil (129.4 g) The crude oil was dissolved in 1 L of 10:90 EtOAC hexane, filtered through a short pad of silica gel

Conditions: temp:55.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 1-Bromo-4-[(2,2-diethoxyethyl)thio]benzene (Chemical Abstracts number 96804-05-6) was prepared as described in Banfield et al.; J. Chem. Soc.; 1956; 2603-2607, and in Amin, et al.; J. Chem. Soc. Perkin Trans. 2; 1982; 1489-1492. 4-Bromothiophenol (20 g, 95%) in ethanol (80 mL) was treated with 21 wt % of sodium ethoxide in ethanol (36 g, 1.05 eq). The solution was heated at 55° C. for 30 minutes and bromoacetaldehyde diethylacetal (22.56 g, 1.05 eq) was added. The mixture was heated at reflux for 10 hours, ethanol was removed and the residue was diluted with 80 mL of water. The product was extracted with 2×120 mL of ethyl acetate. The combined ethyl acetate layer was washed with 2×40 mL of 15% NaCl and concentrated under vacuum to a brown oil (32.0 g, 92.5% potency, 96.5% yield). The product can be further purified by column chromatography (silica gel, 5:95 EtOAc:hexane). The mixture was heated at reflux for 10 hours ethanol was removed the residue was diluted with 80 mL of water The product was extracted with 2×120 mL of ethyl acetate The combined ethyl acetate layer was washed with 2×40 mL of 15% NaCl concentrated under vacuum to a brown oil (32.0 g, 92.5% potency, 96.5% yield) The product can be further purified by column chromatography (silica gel, 5:95 EtOAc:hexane)

Conditions: temp:130.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 5-Bromobenzo[b]thiophene (Chemical Abstracts number 4923-87-9) was prepared as described in Banfield et al.; J. Chem. Soc.; 1956; 2603-2607, and in Seed, Alexander J.; et al. J. Mater. Chem.; vol10; 2000; 2069-2080. A mixture of phosphoric acid (218 g) and chlorobenzene (2 L) was heated at 130° C. and then treated with the product from Example 165A (107.0 g) over 2 hours using a syringe pump. The mixture was heated at 130° C. for 15 hours. Dean-Stark trap was used at the beginning of the reflux to remove water from the mixture. The mixture was allowed to cool to room temperature and quenched with 400 mL of water. The bottom aqueous layer was extracted with 200 mL of methylene chloride. The combined organic layer was washed with 200 mL of 10% Na2CO3, and concentrated to brown oil (129.4 g). The crude oil was dissolved in 1L of 10:90 EtOAC:hexane, filtered through a short pad of silica gel and concentrated to a yellow oil (85.54 g, 95.8% yield). Further purification was done by column chromatography (silica gel, 5:95 EtOAc:hexane). The mixture was heated at 130° C. for 15 hours reflux to remove water from the mixture to cool to room temperature quenched with 400 mL of water The bottom aqueous layer was extracted with 200 mL of methylene chloride The combined organic layer was washed with 200 mL of 10% Na2CO3 concentrated to brown oil (129.4 g) The crude oil was dissolved in 1L of 10:90 EtOAC hexane, filtered through a short pad of silica gel

Conditions: temp:55.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 1-Bromo-4-[(2,2-diethoxyethyl)thio]benzene (Chemical Abstracts number 96804-05-6) was prepared as described in Banfield et al.; J. Chem. Soc.; 1956; 2603-2607, and in Amin, et al.; J. Chem. Soc. Perkin Trans. 2; 1982; 1489-1492. 4-Bromothiophenol (20 g, 95%) in ethanol (80 mL) was treated with 21 wt % of sodium ethoxide in ethanol (36 g, 1.05 eq). The solution was heated at 55° C. for 30 minutes and bromoacetaldehyde diethylacetal (22.56 g, 1.05 eq) was added. The mixture was heated at reflux for 10 hours, ethanol was removed and the residue was diluted with 80 mL of water. The product was extracted with 2×120 mL of ethyl acetate. The combined ethyl acetate layer was washed with 2×40 mL of 15% NaCl and concentrated under vacuum to a brown oil (32.0 g, 92.5% potency, 96.5% yield). The product can be further purified by column chromatography (silica gel, 5:95 EtOAc:hexane). The mixture was heated at reflux for 10 hours ethanol was removed the residue was diluted with 80 mL of water The product was extracted with 2×120 mL of ethyl acetate The combined ethyl acetate layer was washed with 2×40 mL of 15% NaCl concentrated under vacuum to a brown oil (32.0 g, 92.5% potency, 96.5% yield) The product can be further purified by column chromatography (silica gel, 5:95 EtOAc:hexane)

Conditions: temp:130.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 5-Bromobenzo[b]thiophene (Chemical Abstracts number 4923-87-9) was prepared as described in Banfield et al.; J. Chem. Soc.; 1956; 2603-2607, and in Seed, Alexander J.; et al. J. Mater. Chem.; vol10; 2000; 2069-2080. A mixture of phosphoric acid (218 g) and chlorobenzene (2 L) was heated at 130° C. and then treated with the product from Example 165A (107.0 g) over 2 hours using a syringe pump. The mixture was heated at 130° C. for 15 hours. Dean-Stark trap was used at the beginning of the reflux to remove water from the mixture. The mixture was allowed to cool to room temperature and quenched with 400 mL of water. The bottom aqueous layer was extracted with 200 mL of methylene chloride. The combined organic layer was washed with 200 mL of 10% Na2CO3, and concentrated to brown oil (129.4 g). The crude oil was dissolved in 1 L of 10:90 EtOAC:hexane, filtered through a short pad of silica gel and concentrated to a yellow oil (85.54 g, 95.8% yield). Further purification was done by column chromatography (silica gel, 5:95 EtOAc:hexane). The mixture was heated at 130° C. for 15 hours reflux to remove water from the mixture to cool to room temperature quenched with 400 mL of water The bottom aqueous layer was extracted with 200 mL of methylene chloride The combined organic layer was washed with 200 mL of 10% Na2CO3 concentrated to brown oil (129.4 g) The crude oil was dissolved in 1 L of 10:90 EtOAC hexane, filtered through a short pad of silica gel

Conditions: temp:55.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 1-Bromo-4-[(2,2-diethoxyethyl)thio]benzene (Chemical Abstracts number 96804-05-6) was prepared as described in Banfield et al.; J. Chem. Soc.; 1956; 2603-2607, and in Amin, et al.; J. Chem. Soc. Perkin Trans. 2; 1982; 1489-1492. 4-Bromothiophenol (20 g, 95%) in ethanol (80 mL) was treated with 21 wt % of sodium ethoxide in ethanol (36 g, 1.05 eq). The solution was heated at 55° C. for 30 minutes and bromoacetaldehyde diethylacetal (22.56 g, 1.05 eq) was added. The mixture was heated at reflux for 10 hours, ethanol was removed and the residue was diluted with 80 mL of water. The product was extracted with 2×120 mL of ethyl acetate. The combined ethyl acetate layer was washed with 2×40 mL of 15% NaCl and concentrated under vacuum to a brown oil (32.0 g, 92.5% potency, 96.5% yield). The product can be further purified by column chromatography (silica gel, 5:95 EtOAc:hexane). The mixture was heated at reflux for 10 hours ethanol was removed the residue was diluted with 80 mL of water The product was extracted with 2×120 mL of ethyl acetate The combined ethyl acetate layer was washed with 2×40 mL of 15% NaCl concentrated under vacuum to a brown oil (32.0 g, 92.5% potency, 96.5% yield) The product can be further purified by column chromatography (silica gel, 5:95 EtOAc:hexane)