sodium;benzenethiolate

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

Procedure: An amount of 21.4 g (0.08 mole) of the thus obtained 4-nitrophenylphenyl sulfone was dissolved in a two phase solvent composed of a mixture of 80 g of nitrobenzene and 80 g of water, and was reacted with sodium thiophenolate in the same manner as in Example 1.

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

Procedure: A mixture of 103.5 gm of 2,3-dichloro-6-nitroaniline (0.5 mol) and 72.5 gm of sodium thiophenolate (0.55 mol) was dissolved in 800 ml of acetonitrile, and the solution was refluxed for 5 hours. The mixture was then processed according to the procedure set forth in Example 22 (b)(i). The yield was 108 gm of ochre-coloured, crystalline product (77% of theory), m.p. 144°-146° C. the solution was refluxed for 5 hours

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

Procedure: A mixture of 103.5 gm of 2,3-dichloro-6-nitroaniline (0.5 mol) and 72.5 gm of sodium thiophenolate (0.55 mol) was dissolved in 800 ml of acetonitrile, and the solution was refluxed for 5 hours. The mixture was then processed according to the procedure set forth in Example 22 (b)(i). The yield was 108 gm of ochre-coloured, crystalline product (77% of theory), m.p. 144°-146° C. the solution was refluxed for 5 hours

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

Procedure: An amount of 2.9 gm of sodium thiophenolate was added to a solution of 4.4 gm (0.02 mol) of 2,3-dichloro-6-nitro-N-methylaniline dissolved in 50 ml of acetonitrile. The mixture was refluxed for half an hour and subsequently evaporated, and the residue was taken up with chloroform and water. The chloroform layer was separated, dried, and evaporated. Six grams of brown oil, which crystallized with isopropanol, were obtained. The yield from the crystallization was 4 gm of product (67.5% of theory) in the form of yellow crystals, m.p. 79° C. The mixture was refluxed for half an hour subsequently evaporated The chloroform layer was separated dried evaporated Six grams of brown oil, which crystallized with isopropanol were obtained The yield from the crystallization

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

Procedure: An amount of 2.9 gm of sodium thiophenolate was added to a solution of 4.4 gm (0.02 mol) of 2,3-dichloro-6-nitro-N-methylaniline dissolved in 50 ml of acetonitrile. The mixture was refluxed for half an hour and subsequently evaporated, and the residue was taken up with chloroform and water. The chloroform layer was separated, dried, and evaporated. Six grams of brown oil, which crystallized with isopropanol, were obtained. The yield from the crystallization was 4 gm of product (67.5% of theory) in the form of yellow crystals, m.p. 79° C. The mixture was refluxed for half an hour subsequently evaporated The chloroform layer was separated dried evaporated Six grams of brown oil, which crystallized with isopropanol were obtained The yield from the crystallization

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

Procedure: A solution of (Z)-1,2-dichloroethene (0.49 g, 5.04 mmol) and compound 43 (2.0 g, 15.15 mmol) in HMPA (10 mL) was stirred under nitrogen for 1 h. The solvent was removed under reduced pressure to give the crude product that was then purified by column chromatography using 100% hexane as a solvent to give control (1.04 g, 85%). 1H NMR (400 MHz, CDCl3) δ 6.55 (s, 2H), 7.29 (m, 2H), 7.35 (t, J=7.7 Hz, 4H), 7.43 (s, 2H), 7.44 (m, 2H). HRMS ESI (m/z): Calculated for C14H12S2 [M]+: 244.0380. found: 244.0377. The solvent was removed under reduced pressure

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

Procedure: A solution of (Z)-1,2-dichloroethene (0.49 g, 5.04 mmol) and compound 43 (2.0 g, 15.15 mmol) in HMPA (10 mL) was stirred under nitrogen for 1 h. The solvent was removed under reduced pressure to give the crude product that was then purified by column chromatography using 100% hexane as a solvent to give control (1.04 g, 85%). 1H NMR (400 MHz, CDCl3) δ 6.55 (s, 2H), 7.29 (m, 2H), 7.35 (t, J=7.7 Hz, 4H), 7.43 (s, 2H), 7.44 (m, 2H). HRMS ESI (m/z): Calculated for C14H12S2 [M]+: 244.0380. found: 244.0377. The solvent was removed under reduced pressure

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

Procedure: A mixture of 1-bromo-2-methoxy-6-methoxyphenylnaphthalene (850 mg, 2.47 mmol, 1 eq), sodium benzenthiolate (391 mg, 2.96 mmol, 1.2 eq) and anhydrous DMF (10 ml) was refluxed under nitrogen for 11 hours. After cooling to room temperature, the mixture was poured onto ice. The precipitate was filtered off, washed with water and dried. Yield: 385 mg, 42%. was refluxed under nitrogen for 11 hours the mixture was poured onto ice The precipitate was filtered off washed with water dried

Conditions: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A round bottom flask was charged with a magnetic stir bar, N,N-dibenzyl-1-(4-chlorobutyl)-1H-imidazo[4,5-c]quinolin-4-amine (7.0 g, 15.38 mmol), sodium benzenethiolate (3.46 g, 26.15 mmol), and anhydrous dimethyl formamide (77 mL) under a nitrogen atmosphere. The reaction mixture was heated to 60° C. to give a heterogeneous mixture that was maintained at 60° C. for 4 hours at which time the starting material was completely consumed. The cooled solution was partitioned between ethyl acetate and water. The layers were separated. The organic layer was washed with saturated aqueous sodium bicarbonate and brine, dried over anhydrous sodium sulfate, filtered and then concentrated under reduced pressure to afford a colorless oil. The material was purified by chromatography over silica gel (80/20 hexanes/ethyl acetate) to provide N,N-dibenzyl-1-[4-(phenylthio)butyl]-1H-imidazo[4,5-c]quinolin-4-amine (7.5 g, 14.19 mmol) as a colorless oil. MS (CI) for C34H32N4S m/z 529 (MH+), 439, 349 A round bottom flask was charged with a magnetic stir bar to give a heterogeneous mixture that was maintained at 60° C. for 4 hours at which time the starting material was completely consumed The cooled solution was partitioned between ethyl acetate and water The layers were separated The organic layer was washed with saturated aqueous sodium bicarbonate and brine dried over anhydrous sodium sulfate filtered concentrated under reduced pressure to afford a colorless oil The material was purified by chromatography over silica gel (80/20 hexanes/ethyl acetate)

Conditions: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A round bottom flask was charged with a magnetic stir bar, N,N-dibenzyl-1-(4-chlorobutyl)-1H-imidazo[4,5-c]quinolin-4-amine (7.0 g, 15.38 mmol), sodium benzenethiolate (3.46 g, 26.15 mmol), and anhydrous dimethyl formamide (77 mL) under a nitrogen atmosphere. The reaction mixture was heated to 60° C. to give a heterogeneous mixture that was maintained at 60° C. for 4 hours at which time the starting material was completely consumed. The cooled solution was partitioned between ethyl acetate and water. The layers were separated. The organic layer was washed with saturated aqueous sodium bicarbonate and brine, dried over anhydrous sodium sulfate, filtered and then concentrated under reduced pressure to afford a colorless oil. The material was purified by chromatography over silica gel (80/20 hexanes/ethyl acetate) to provide N,N-dibenzyl-1-[4-(phenylthio)butyl]-1H-imidazo[4,5-c]quinolin-4-amine (7.5 g, 14.19 mmol) as a colorless oil. MS (CI) for C34H32N4S m/z 529 (MH+), 439, 349 A round bottom flask was charged with a magnetic stir bar to give a heterogeneous mixture that was maintained at 60° C. for 4 hours at which time the starting material was completely consumed The cooled solution was partitioned between ethyl acetate and water The layers were separated The organic layer was washed with saturated aqueous sodium bicarbonate and brine dried over anhydrous sodium sulfate filtered concentrated under reduced pressure to afford a colorless oil The material was purified by chromatography over silica gel (80/20 hexanes/ethyl acetate)

Conditions: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A round bottom flask was charged with a magnetic stir bar, 1-(2-chloroethyl)-1H-imidazo[4,5-c]quinolin-4-amine (2.0 g, 8.11 mmol), sodium benzenethiolate (1.79 g, 12.16 mmol), and anhydrous dimethyl sulfoxide (40 mL) under a nitrogen atmosphere. The reaction mixture was heated to 100° C. to give a homogeneous solution that was maintained at 100° C. for 30 minutes at which time the starting material was completely consumed. The hot solution was poured into rapidly stirred water (300 mL) which caused a solid to precipitate out of solution. The solid was collected by filtration to afford an off-white solid. The material was triturated with acetonitrile and collected by filtration to give 1-[2-(phenylthio)ethyl]-1H-imidazo[4,5-c]quinolin-4-amine (2.08 g, 6.49 mmol) as an off-white powder, m. p. 233-235° C. A round bottom flask was charged with a magnetic stir bar to give a homogeneous solution that was maintained at 100° C. for 30 minutes at which time the starting material was completely consumed The hot solution was poured into rapidly stirred water (300 mL) which to precipitate out of solution The solid was collected by filtration to afford an off-white solid The material was triturated with acetonitrile collected by filtration

Conditions: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A round bottom flask was charged with a magnetic stir bar, 1-(2-chloroethyl)-1H-imidazo[4,5-c]quinolin-4-amine (2.0 g, 8.11 mmol), sodium benzenethiolate (1.79 g, 12.16 mmol), and anhydrous dimethyl sulfoxide (40 mL) under a nitrogen atmosphere. The reaction mixture was heated to 100° C. to give a homogeneous solution that was maintained at 100° C. for 30 minutes at which time the starting material was completely consumed. The hot solution was poured into rapidly stirred water (300 mL) which caused a solid to precipitate out of solution. The solid was collected by filtration to afford an off-white solid. The material was triturated with acetonitrile and collected by filtration to give 1-[2-(phenylthio)ethyl]-1H-imidazo[4,5-c]quinolin-4-amine (2.08 g, 6.49 mmol) as an off-white powder, m. p. 233-235° C. A round bottom flask was charged with a magnetic stir bar to give a homogeneous solution that was maintained at 100° C. for 30 minutes at which time the starting material was completely consumed The hot solution was poured into rapidly stirred water (300 mL) which to precipitate out of solution The solid was collected by filtration to afford an off-white solid The material was triturated with acetonitrile collected by filtration