(2,4-dichlorophenyl)methanethiol

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

Procedure: The title compound (cis/trans=16:84) was prepared as pale brown crystals in 63.2% yield in a similar procedure to that described in Example 1 by using 1-(2-butenyl)-7-chloro-2,3-dimethylpyrrolo[2,3-d]pyridazine (cis/trans=22/78) and 2,4-dichlorophenylmethanethiol.

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

Procedure: The title compound (cis/trans=16:84) was prepared as pale brown crystals in 63.2% yield in a similar procedure to that described in Example 1 by using 1-(2-butenyl)-7-chloro-2,3-dimethylpyrrolo[2,3-d]pyridazine (cis/trans=22/78) and 2,4-dichlorophenylmethanethiol.

Conditions: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a mixture of methyl 6-chloro-3-(2-ethoxy-2-oxoethoxy)thieno[2,3-b]pyridine-2-carboxylate (126.4 mg) and DMSO (3.8 mL) were added K2CO3 (63.6 mg) and 2,4-dichlorobenzyl mercaptan (0.065 mL). The mixture was stirred at 80° C. for 3 h. The mixture was quenched with saturated aqueous NaHCO3 and extracted with EtOAc. The combined organic layer was washed successively with water and brine, dried over MgSO4, and concentrated in vacuo. The residue was purified by silica gel column chromatography (EtOAc/hexane) to give the title compound (73.9 mg). The mixture was quenched with saturated aqueous NaHCO3 extracted with EtOAc The combined organic layer was washed successively with water and brine dried over MgSO4 concentrated in vacuo The residue was purified by silica gel column chromatography (EtOAc/hexane)

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

Procedure: To a solution of 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (15.71 mg), DIPEA (0.187 ml), 2,4-dichlorobenzyl mercaptan (0.085 mL) and ethyl(6-(((trifluoromethyl)sulfonyl)oxy)-1-benzothiophen-3-yl)acetate (200 mg) in toluene (6 mL) was added tris(dibenzylideneacetone)dipalladium(0) (24.86 mg) at room temperature. The mixture was refluxed 1.5 h. After cooling, water was poured into mixture, and the mixture was extracted with EtOAc. The organic layer was washed with brine, dried over Na2SO4 and concentrated in vacuo. The residue was purified by silica gel column chromatography (EtOAc/hexane) to give the title compound (238 mg). The mixture was refluxed 1.5 h After cooling the mixture was extracted with EtOAc The organic layer was washed with brine dried over Na2SO4 concentrated in vacuo The residue was purified by silica gel column chromatography (EtOAc/hexane)

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

Procedure: A solution of 3-methoxy-4-acetoxyphenylacetylene (0.02 mol), 2,4-dichlorobenzyl mercaptan (0.02 mol) and metallic sodium (0.02 g atom) is subjected to the General Procedure to form (Z)-3-methoxy-4-acetoxystyryl-2,4-dichlorobenzylsulfide. The title compound is obtained following oxidation of the sulfide, according to the General Procedure.

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

Procedure: A solution of 3-methoxy-4-acetoxyphenylacetylene (0.02 mol), 2,4-dichlorobenzyl mercaptan (0.02 mol) and metallic sodium (0.02 g atom) is subjected to the General Procedure to form (Z)-3-methoxy-4-acetoxystyryl-2,4-dichlorobenzylsulfide. The title compound is obtained following oxidation of the sulfide, according to the General Procedure.

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

Procedure: A solution of 2,4-difluorophenylacetylene (0.02 mol), 2,4-dichlorobenzyl mercaptan (0.02 mol) and metallic sodium (0.02 g atom) is subjected to the General Procedure to form (Z)-2,4-difluorostyryl-2,4-dichlorobenzylsulfide. The title compound is obtained following oxidation of the sulfide, according to the General Procedure.

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

Procedure: To 1.04 gm. of sodium metal dissolved in 80 ml. of ethanol is added 5.55 ml. of 2,4-dichlorobenzylmercaptan followed by 1.5 gm. of 17β-methanesulfonyloxy-1,4-androstadiene-3,11-dione. Heat at reflux for 76 hours under an atmosphere of nitrogen. In a manner similar to that described in Example 1E, isolate the title compound. Heat at reflux for 76 hours under an atmosphere of nitrogen

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

Procedure: The title compound (cis/trans=16:84) was prepared as pale brown crystals in 63.2% yield in a similar procedure to that described in Example 1 by using 1-(2-butenyl)-7-chloro-2,3-dimethylpyrrolo[2,3-d]pyridazine (cis/trans=22/78) and 2,4-dichlorophenylmethanethiol.

Conditions: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a mixture of methyl 6-chloro-3-(2-ethoxy-2-oxoethoxy)thieno[2,3-b]pyridine-2-carboxylate (126.4 mg) and DMSO (3.8 mL) were added K2CO3 (63.6 mg) and 2,4-dichlorobenzyl mercaptan (0.065 mL). The mixture was stirred at 80° C. for 3 h. The mixture was quenched with saturated aqueous NaHCO3 and extracted with EtOAc. The combined organic layer was washed successively with water and brine, dried over MgSO4, and concentrated in vacuo. The residue was purified by silica gel column chromatography (EtOAc/hexane) to give the title compound (73.9 mg). The mixture was quenched with saturated aqueous NaHCO3 extracted with EtOAc The combined organic layer was washed successively with water and brine dried over MgSO4 concentrated in vacuo The residue was purified by silica gel column chromatography (EtOAc/hexane)

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

Procedure: To a solution of 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (15.71 mg), DIPEA (0.187 ml), 2,4-dichlorobenzyl mercaptan (0.085 mL) and ethyl(6-(((trifluoromethyl)sulfonyl)oxy)-1-benzothiophen-3-yl)acetate (200 mg) in toluene (6 mL) was added tris(dibenzylideneacetone)dipalladium(0) (24.86 mg) at room temperature. The mixture was refluxed 1.5 h. After cooling, water was poured into mixture, and the mixture was extracted with EtOAc. The organic layer was washed with brine, dried over Na2SO4 and concentrated in vacuo. The residue was purified by silica gel column chromatography (EtOAc/hexane) to give the title compound (238 mg). The mixture was refluxed 1.5 h After cooling the mixture was extracted with EtOAc The organic layer was washed with brine dried over Na2SO4 concentrated in vacuo The residue was purified by silica gel column chromatography (EtOAc/hexane)