1-(benzenesulfonyl)-4-chlorobenzene

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

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

Procedure: To a solution of benzimidazole (11.8 g, 0.10 mol) in DMF (500 ml), is added, at room temperature under nitrogen, sodium hydride (60% in mineral oil, 4.4 g, 0.11 mol), and the mixture is stirred for 10 min. The mixture is admixed with 4-chlorophenyl phenyl sulfone (26.1 g, 0.10 mol) and stirred at 100° C. for 16 h. After again adding sodium hydride (60% in mineral oil, 2.0 g, 0.05 mol) at room temperature, the mixture is stirred at 130° C. for 16 h. After cooling to room temperature, the mixture is added to ice-water. Precipitated product is filtered off and washed with water. Yield: 91%. After cooling to room temperature Precipitated product is filtered off washed with water

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

Procedure: A mixture of 4-chlorophenyl phenyl sulfone (10.1 g, 40.0 mmol), hydrazine mono-hydrate (30 mL), and triethylamine (4 drops) in ethylene glycol (20 mL) is heated at 150° for 15 hr. Upon cooling, the mixture is diluted with H2O and filtered. The residual solid is washed with H2O until the washings are neural (pH=6). This material is then triturated with methylene chloride and dried under reduced pressure at 50° to give the title compound, IR (drift) 3282, 1586, 1514, 1306, 1291, 1158, 1145, 1104, 996, 813, 756, 730, 717, 688 and 678 cm−1; NMR (300 MHz, CDCl3) 7.70-7.85, 7.45-7.65, 6.79 and 4.22 δ; MS (EI) m/z 248 (M+), 125, 123, 108, 107, 90, 80, 77, 63 and 51. is heated at 150° for 15 hr Upon cooling filtered The residual solid is washed with H2O until the washings This material is then triturated with methylene chloride dried under reduced pressure at 50°

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

Procedure: A mixture of 4-chlorophenyl phenyl sulfone (10.1 g, 40.0 mmol), hydrazine mono-hydrate (30 mL), and triethylamine (4 drops) in ethylene glycol (20 mL) is heated at 150° for 15 hr. Upon cooling, the mixture is diluted with H2O and filtered. The residual solid is washed with H2O until the washings are neural (pH=6). This material is then triturated with methylene chloride and dried under reduced pressure at 50° to give the title compound, IR (drift) 3282, 1586, 1514, 1306, 1291, 1158, 1145, 1104, 996, 813, 756, 730, 717, 688 and 678 cm−1; NMR (300 MHz, CDCl3) 7.70-7.85, 7.45-7.65, 6.79 and 4.22 δ; MS (EI) m/z 248 (M+), 125, 123, 108, 107, 90, 80, 77, 63 and 51. is heated at 150° for 15 hr Upon cooling filtered The residual solid is washed with H2O until the washings This material is then triturated with methylene chloride dried under reduced pressure at 50°

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

Procedure: A mixture of 4-chlorophenyl phenyl sulfone (10.1 g, 40.0 mmol), hydrazine mono-hydrate (30 mL), and triethylamine (4 drops) in ethylene glycol (20 mL) is heated at 150° for 15 hr. Upon cooling, the mixture is diluted with H2O and filtered. The residual solid is washed with H2O until the washings are neural (pH=6). This material is then triturated with methylene chloride and dried under reduced pressure at 50° to give the title compound, IR (drift) 3282, 1586, 1514, 1306, 1291, 1158, 1145, 1104, 996, 813, 756, 730, 717, 688 and 678 cm−1; NMR (300 MHz, CDCl3) 7.70-7.85, 7.45-7.65, 6.79 and 4.22 δ; MS (EI) m/z 248 (M+), 125, 123, 108, 107, 90, 80, 77, 63 and 51. is heated at 150° for 15 hr Upon cooling filtered The residual solid is washed with H2O until the washings This material is then triturated with methylene chloride dried under reduced pressure at 50°

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

Procedure: FIGS. 1 and 2 illustrate the behavior of the new phase transfer catalysts in the formation of 1,1′-(1-methylethylidene)bis[4-[4-(phenylsulfonyl)phenoxy]benzene (CAS No. 90139-53-0). When the P2-EthylMethyl mesylate was used as a PTC at 1.0 mole % in the model reaction in refluxing o-DCB at 180° C. (See 4 (FIG. 1)), the reaction exhibited pseudo-first order kinetics. This indicates that no catalyst decomposition nor diminution in rate was occurring during the reaction. In order to further test the stability of the phosphazenium salt, similar reactions were carried out at higher temperatures, in 3,4-dichlorotoluene (bp=200° C.) (See 6 (FIG. 1)) and in 1,2,4-trichlorobenzene (bp=214° C.) (See 2 (FIG. 1)). As shown in FIG. 1, even at 200° C., essentially linear reaction kinetics were observed, indicating no decomposition of the P2-EthylMethyl mesylate phase transfer catalyst. In trichlorobenzene, only a small amount of decomposition was observed, after 60 minutes (See 2 (FIG. 1)). In this instance only 0.5 mole % catalyst was used, since after initial range-finding experiments it was determined that reaction using 1.0 mole % would be too fast to follow accurately at 214° C. was occurring during the reaction As shown in FIG. 1, even at 200° C. essentially linear reaction kinetics since after initial range-finding experiments it was determined that reaction to follow accurately at 214° C.

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

Procedure: To a solution of benzimidazole (11.8 g, 0.10 mol) in DMF (500 ml), is added, at room temperature under nitrogen, sodium hydride (60% in mineral oil, 4.4 g, 0.11 mol), and the mixture is stirred for 10 min. The mixture is admixed with 4-chlorophenyl phenyl sulfone (26.1 g, 0.10 mol) and stirred at 100° C. for 16 h. After again adding sodium hydride (60% in mineral oil, 2.0 g, 0.05 mol) at room temperature, the mixture is stirred at 130° C. for 16 h. After cooling to room temperature, the mixture is added to ice-water. Precipitated product is filtered off and washed with water. Yield: 91%. After cooling to room temperature Precipitated product is filtered off washed with water

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

Procedure: To a solution of benzimidazole (11.8 g, 0.10 mol) in DMF (500 ml), is added, at room temperature under nitrogen, sodium hydride (60% in mineral oil, 4.4 g, 0.11 mol), and the mixture is stirred for 10 min. The mixture is admixed with 4-chlorophenyl phenyl sulfone (26.1 g, 0.10 mol) and stirred at 100° C. for 16 h. After again adding sodium hydride (60% in mineral oil, 2.0 g, 0.05 mol) at room temperature, the mixture is stirred at 130° C. for 16 h. After cooling to room temperature, the mixture is added to ice-water. Precipitated product is filtered off and washed with water. Yield: 91%. After cooling to room temperature Precipitated product is filtered off washed with water

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

Procedure: 1.25 g of sodium thiomethylate are added under a nitrogen atmosphere to a solution of 15 g (0.0593 mol) of 1-chloro-4-(phenylsulfonyl)benzene in 150 ml of hexamethylphosphoramide. The mixture obtained is heated for 4 hours at 100° C. and then cooled and hydrolyzed in an ice/water mixture. The reaction medium obtained is extracted with ethyl acetate and the aqueous phase obtained is then poured into a 4 N solution of hydrochloric acid at 0° C. The product formed precipitates. After filtration, washing with water until the pH of the washings is neutral, and drying, 13.44 g (yield: 90.5%) of the expected product are obtained. M.p.=117° C. The mixture obtained cooled The reaction medium obtained is extracted with ethyl acetate the aqueous phase obtained The product formed precipitates After filtration washing with water until the pH of the washings drying

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

Procedure: A mixture of 4-chlorophenyl phenyl sulfone (10.1 g, 40.0 mmol), hydrazine mono hydrate (30 mL), and triethylamine (4 drops) in ethylene glycol (20 mL) is heated at 150° for 15 hr. Upon cooling, the mixture is diluted with H2O and filtered. The residual solid is washed with H2O until the washings are neural (pH=6). This material is then triturated with methylene chloride and dried under reduced pressure at 50° to give the title compound, IR (drift) 3282, 1586, 1514, 1306, 1291, 1158, 1145, 1104, 996, 813, 756, 730, 717, 688 and 678 cm−1, NMR (300 MHz, CDCl3) 7.70-7.85, 7.45-7.65, 6.79 and 4.22 δ; MS (EI) m/z 248 (M+), 125, 123, 108, 107, 90, 80, 77, 63 and 51. is heated at 150° for 15 hr Upon cooling filtered The residual solid is washed with H2O until the washings This material is then triturated with methylene chloride dried under reduced pressure at 50°

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

Procedure: A mixture of 4-chlorophenyl phenyl sulfone (10.1 g, 40.0 mmol), hydrazine monohydrate (30 mL), and triethylamine (4 drops) in ethylene glycol (20 mL) is heated at 150° for 15 hr. Upon cooling, the mixture is diluted with H2O and filtered. The residual solid is washed with H2O until the washings are neural (pH=6). This material is then triturated with methylene chloride and dried under reduced pressure at 50° to give the title compound, IR (drift) 3282, 1586, 1514, 1306, 1291, 1158, 1145, 1104, 996, 813, 756, 730, 717, 688 and 678 cm−1; NMR (300 MHz, CDCl3) 7.70–7.85, 7.45–7.65, 6.79 and 4.22 δ; MS (EI) m/z 248 (M+), 125, 123, 108, 107, 90, 80, 77, 63 and 51. is heated at 150° for 15 hr Upon cooling filtered The residual solid is washed with H2O until the washings This material is then triturated with methylene chloride dried under reduced pressure at 50°

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

Procedure: A mixture of 4-chlorophenyl phenyl sulfone (10.1 g, 40.0 mmol), hydrazine mono-hydrate (30 mL), and triethylamine (4 drops) in ethylene glycol (20 mL) is heated at 150° for 15 hr. Upon cooling, the mixture is diluted with H2O and filtered. The residual solid is washed with H2O until the washings are neural (pH=6). This material is then triturated with methylene chloride and dried under reduced pressure at 50° to give the title compound, IR (drift) 3282, 1586, 1514, 1306, 1291, 1158, 1145, 1104, 996, 813, 756, 730, 717, 688 and 678 cm−1; NMR (300 MHz, CDCl3) 7.70-7.85, 7.45-7.65, 6.79 and 4.22 δ; MS (EI) m/z 248 (M+), 125, 123, 108, 107, 90, 80, 77, 63 and 51. is heated at 150° for 15 hr Upon cooling filtered The residual solid is washed with H2O until the washings This material is then triturated with methylene chloride dried under reduced pressure at 50°