benzenesulfonylbenzene

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:150.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of bis(3,4-diaminophenyl)ether (22.00 g, 0.096 mol), phenyl-4-hydroxybenzoate (41.00 g, 0.194 mol), diphenylsulfone (110.17 g), and toluene (135 ml) was heated under a nitrogen atmosphere for 3.5 hours at 150° C. The toluene was removed and the temperature increased to 250° C. and maintained for 1.5 hours. A vacuum was subsequently applied and the temperature increased to 280° C. and maintained for 1.25 hours. The cooled dark reaction mixture was washed in hot toluene and dried at 110° C. to afford 20.59 g (50% crude yield) of a dark purple powder. The dark solid was extracted with acetone to afford 12.39 g (30% yield) of a tan solid. The endothermic peak as determined by DTA was 317° C. (broad). Analysis calcd. for C26H18N4O3 : C, 71.88%; H, 4.18%; N, 12.90%. Found: C, 71.91%; H, 4.22%; N, 13.06%. The resulting monomer had the following structural formula: ##STR11## The toluene was removed the temperature increased to 250° C. maintained for 1.5 hours the temperature increased to 280° C. maintained for 1.25 hours The cooled dark reaction mixture was washed in hot toluene dried at 110° C. to afford 20.59 g (50% crude yield) of a dark purple powder The dark solid was extracted with acetone

反応条件: temp:150.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of bis(3,4-diaminophenyl)ether (22.00 g, 0.096 mol), phenyl-4-hydroxybenzoate (41.00 g, 0.194 mol), diphenylsulfone (110.17 g), and toluene (135 ml) was heated under a nitrogen atmosphere for 3.5 hours at 150° C. The toluene was removed and the temperature increased to 250° C. and maintained for 1.5 hours. A vacuum was subsequently applied and the temperature increased to 280° C. and maintained for 1.25 hours. The cooled dark reaction mixture was washed in hot toluene and dried at 110° C. to afford 20.59 g (50% crude yield) of a dark purple powder. The dark solid was extracted with acetone to afford 12.39 g (30% yield) of a tan solid. The endothermic peak as determined by DTA was 317° C. (broad). Analysis calcd. for C26H18N4O3 : C, 71.88%; H, 4.18%; N, 12.90%. Found: C, 71.91%; H, 4.22%; N, 13.06%. The resulting monomer had the following structural formula: ##STR11## The toluene was removed the temperature increased to 250° C. maintained for 1.5 hours the temperature increased to 280° C. maintained for 1.25 hours The cooled dark reaction mixture was washed in hot toluene dried at 110° C. to afford 20.59 g (50% crude yield) of a dark purple powder The dark solid was extracted with acetone

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A 158 g (1.0 mole) quantity of benzenesulfonic acid, 94 g (1.2 moles) of benzene and 5 g of 12-tungstophosphoric acid (H3PW12O40.29H2O) were refluxed with heating and stirring to undergo reaction for 30 minutes. The reaction mixture was analyzed by highperformance liquid chromatography, which showed that the conversion of benzenesulfonic acid was 30%. To the reaction mixture was added the same amount (10 g) of polyphosphoric acid as in Example 15. The mixture was refluxed for 5.5 hours. The same treatment as in Example 15 was followed, giving 87 g of diphenylsulfone in a yield of 40%. with heating reaction for 30 minutes The mixture was refluxed for 5.5 hours

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A 158 g (1.0 mole) quantity of benzenesulfonic acid, 94 g (1.2 moles) of benzene and 5 g of 12-tungstophosphoric acid (H3PW12O40.29H2O) were refluxed with heating and stirring. The reaction system was kept at the reflux temperature for 10 hours, while refluxing the benzene and removing the produced water by subjecting the azeotropic mixture with the benzene to phase separation. The reaction mixture was diluted with 150 g of benzene and the catalyst was separated by filtration. The mother liquor was washed with water and the benzene was distilled off under reduced pressure, giving 210 g of diphenylsulfone (96% yield, m.p. 124° to 128° C.). with heating removing the produced water to phase separation The reaction mixture was diluted with 150 g of benzene the catalyst was separated by filtration The mother liquor was washed with water the benzene was distilled off under reduced pressure

反応条件: temp:150.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 1,2-diaminobenzene (25.17 g, 0.233 mol), phenyl-4-hydroxphenylbenzoate (50.17 g, 0.234 mol), diphenylsulfone (121.15 g), and toluene (100 ml) were heated under a nitrogen atmosphere for 16 hours at 150° C. The toluene was removed and the temperature increased to 260° C. and maintained for two and one-half hours. A vacuum was subsequently applied and the temperature increased to 290° C. and maintained for one and one-half hours. The warm reaction mixture was precipitated in toluene, washed in hot toluene, and subsequently dried at 110° C. to afford 45.00 g (92% crude yield) of a red-tan powder, m.p. (DTA) 279° C. (broad). The solid was recrystallized from 40% aqueous ethanol using charcoal to afford a light tan crystalline product (31.46 g, 64% yield). The compound exhibited a sharp melt by DTA with an endothermic minimum at 280° C. Anal. calcd for C13H10N2O: C, 74.27%; H, 4.79%; N, 13.32%; Found: C, 74.21%; H, 4.75%; N, 13.21%. The toluene was removed the temperature increased to 260° C. maintained for two and one-half hours the temperature increased to 290° C. maintained for one and one-half hours The warm reaction mixture was precipitated in toluene washed in hot toluene subsequently dried at 110° C. to afford 45.00 g (92% crude yield) of a red-tan powder, m.p. (DTA) 279° C. (broad) The solid was recrystallized from 40% aqueous ethanol

反応条件: temp:150.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of bis(3,4-diaminophenyl)ether (22.00 g, 0.096 mol), phenyl-4-hydroxybenzoate (41.00 g, 0.194 mol), diphenylsulfone (110.17 g), and toluene (135 ml) was heated under a nitrogen atmosphere for 3.5 hours at 150° C. The toluene was removed and the temperature increased to 250° C. and maintained for 1.5 hours. A vacuum was subsequently applied and the temperature increased to 280° C. and maintained for 1.25 hours. The cooled dark reaction mixture was washed in hot toluene and dried at 110° C. to afford 20.59 g (50% crude yield) of a dark purple powder. The dark solid was extracted with acetone to afford 12.39 g (30% yield) of a tan solid. The endothermic peak as determined by DTA was 317° C. (broad). Analysis calcd. for C26H18N4O3 : C, 71.88%; H, 4.18%; N, 12.90%. Found: C, 71.91%; H, 4.22%; N, 13.06%. The resulting monomer had the following structural formula: ##STR11## The toluene was removed the temperature increased to 250° C. maintained for 1.5 hours the temperature increased to 280° C. maintained for 1.25 hours The cooled dark reaction mixture was washed in hot toluene dried at 110° C. to afford 20.59 g (50% crude yield) of a dark purple powder The dark solid was extracted with acetone

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:150.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 1,2-diaminobenzene (25.17 g, 0.233 mol), phenyl-4-hydroxphenylbenzoate (50.17 g, 0.234 mol), diphenylsulfone (121.15 g), and toluene (100 ml) were heated under a nitrogen atmosphere for 16 hours at 150° C. The toluene was removed and the temperature increased to 260° C. and maintained for two and one-half hours. A vacuum was subsequently applied and the temperature increased to 290° C. and maintained for one and one-half hours. The warm reaction mixture was precipitated in toluene, washed in hot toluene, and subsequently dried at 110° C. to afford 45.00 g (92% crude yield) of a red-tan powder, m.p. (DTA) 279° C. (broad). The solid was recrystallized from 40% aqueous ethanol using charcoal to afford a light tan crystalline product (31.46 g, 64% yield). The compound exhibited a sharp melt by DTA with an endothermic minimum at 280° C. Anal. calcd for C13H10N2O: C, 74.27%; H, 4.79%; N, 13.32%; Found: C, 74.21%; H, 4.75%; N, 13.21%. The toluene was removed the temperature increased to 260° C. maintained for two and one-half hours the temperature increased to 290° C. maintained for one and one-half hours The warm reaction mixture was precipitated in toluene washed in hot toluene subsequently dried at 110° C. to afford 45.00 g (92% crude yield) of a red-tan powder, m.p. (DTA) 279° C. (broad) The solid was recrystallized from 40% aqueous ethanol

反応条件: temp:150.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of bis(3,4-diaminophenyl)ether (22.00 g, 0.096 mol), phenyl-4-hydroxybenzoate (41.00 g, 0.194 mol), diphenylsulfone (110.17 g), and toluene (135 ml) was heated under a nitrogen atmosphere for 3.5 hours at 150° C. The toluene was removed and the temperature increased to 250° C. and maintained for 1.5 hours. A vacuum was subsequently applied and the temperature increased to 280° C. and maintained for 1.25 hours. The cooled dark reaction mixture was washed in hot toluene and dried at 110° C. to afford 20.59 g (50% crude yield) of a dark purple powder. The dark solid was extracted with acetone to afford 12.39 g (30% yield) of a tan solid. The endothermic peak as determined by DTA was 317° C. (broad). Analysis calcd. for C26H18N4O3 : C, 71.88%; H, 4.18%; N, 12.90%. Found: C, 71.91%; H, 4.22%; N, 13.06%. The resulting monomer had the following structural formula: ##STR11## The toluene was removed the temperature increased to 250° C. maintained for 1.5 hours the temperature increased to 280° C. maintained for 1.25 hours The cooled dark reaction mixture was washed in hot toluene dried at 110° C. to afford 20.59 g (50% crude yield) of a dark purple powder The dark solid was extracted with acetone

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: The product of step A was converted to the phenyl sulfone derivative following the procedure of example 1, step C. The crude material was purified by flash column chromatography (SiO2 98:2 to 65:35 hexane/ethyl acetate) to give tert-butyl 2-phenylsulfonyl-5-[(trimethylsilyl)ethoxy]methyl-5,6,7,8,9,10-hexahydro-7,10-iminocyclohept[b]indole-carboxylate (1.30 g, 58%) as a brown foam: 1H NMR (CDCl3, 300 MHz) δ 8.28 (s, 1H), 8.03-8.09 (m, 2H), 7.75-7.83 (m, 1H), 7.51-7.62 (m, 4H), 5.28-5.49 (m, 3H), 4.66-4.89 (m, 1H), 3.45-3.68 (m, 3H), 2.64 (d, J=16.2 Hz, 1H), 2.45-2.52 (m, 1H), 2.25-2.38 (m, 1H), 2.01-2.11 (m, 1H), 1.64-1.75 (m, 1H), 1.46 (br s, 9H), 0.88-0.95 (m, 2H), −0.11 (s, 9H). The crude material was purified by flash column chromatography (SiO2 98:2 to 65:35 hexane/ethyl acetate)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: The product of step E was converted to the phenylsulfone derivative following the procedure of Example 71, step D. The crude product was purified by flash column chromatography (SiO2, 75:25 hexanes/ethyl acetate) to give tert-butyl 2-phenylsulfonyl-4-chloro-5-methyl-5,6,7,8,9,10-hexahydro-7,10-epiminocyclohepta[b]indole-carboxylate (165 mg, 63%) as an off-white solid: 1H NMR (CDCl3, 300 MHz): δ 8.02-8.07 (m, 1H), 7.91-7.97 (m, 2H), 7.42-7.62 (m, 4H), 5.10-5.32 (m, 1H), 4.55-4.80 (m, 1H), 3.94 (s, 3H), 3.15-3.48 (m, 1H), 2.47 (d, J=16.2 Hz, 1H), 2.10-2.40 (m, 2H), 1.85-1.96 (m, 1H), 1.52-1.65 (m, 1H), 1.38 (br s, 9H). The crude product was purified by flash column chromatography (SiO2, 75:25 hexanes/ethyl acetate)