dodecylbenzene

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

Conditions: temp:16.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a mixture of 492 grams of aluminum chloride and 988 mL of 1,2-dichloroethane was added 192 grams of benzene-1,2,4,5-tetracarboxylic acid dianhydride (pyromellitic dianhydride). The resulting mixture was cooled to 16° C. and a solution of 434 grams of 1-dodecylbenzene, 123 grams of diisopropylethylamine and 480 mL of 1,2-dichloroethane was added over a period of 3.5 hours, keeping the temperature between 15° C. and 20° C. during the addition. The mixture was stirred overnight at room temperature and poured into a beaker of 1000 grams of ice and 1000 grams concentrated hydrochloric acid. The mixture was stirred for one hour and the liquid was poured from the coagulate. The mixture was divided into 800 mL portions and each portion was worked up as follows. To 800 mL of the mixture was added 800 mL of tetrahydrofuran, 800 mL of ethyl acetate, and 800 mL of water. The mixture was stirred and phase split. The organic phase was filtered and the filtrate was concentrated in vacuo. The residues were combined. To 127 grams of the combined residue was added 800 mL of ethyl acetate and the mixture was stirred until a suspension of a fine solid resulted. The solid was collected by filtration and washed with 50 mL of ethyl acetate. The solid was dried to give 2,5-bis(4-dodecylbenzoyl)terephthalic acid. the temperature between 15° C. and 20° C. during the addition The mixture was stirred for one hour the liquid was poured from the coagulate The mixture was stirred phase split The organic phase was filtered the filtrate was concentrated in vacuo To 127 grams of the combined residue was added 800 mL of ethyl acetate the mixture was stirred until a suspension of a fine solid resulted The solid was collected by filtration washed with 50 mL of ethyl acetate The solid was dried

Conditions: temp:180.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 12,12-Dimethyl-10,12-dihydroindeno[2,1-b]carbazole synthesized in Example 1 (5.5 g), 2-bromo-9,9-dimethyl-9H-fluorene (6.4 g), sodium bisulfite (0.3 g), a copper powder (0.1 g), 3,5-di(tert-butyl)salicylic acid (0.5 g), potassium carbonate (4.0 g), and dodecylbenzene (5 ml) were added to a nitrogen-substituted reaction vessel, heated, and stirred at 180° C. for 29 hours. The mixture was cooled to 100° C., and insoluble matter was removed by filtration after adding toluene (80 ml), and a filtrate was concentrated. Crystallization using n-hexane (20 ml) was performed to obtain an ocher powder of 12,12-dimethyl-10-(9,9-dimethyl-9H-fluorene-2-yl)-10,12-dihydroindeno[2,1-b]carbazole (7.4 g; yield 80.0%) heated The mixture was cooled to 100° C. insoluble matter was removed by filtration after adding toluene (80 ml) a filtrate was concentrated Crystallization

Conditions: temp:180.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 12,12-Dimethyl-10,12-dihydroindeno[2,1-b]carbazole synthesized in Example 1 (5.5 g), 2-bromo-9,9-dimethyl-9H-fluorene (6.4 g), sodium bisulfite (0.3 g), a copper powder (0.1 g), 3,5-di(tert-butyl)salicylic acid (0.5 g), potassium carbonate (4.0 g), and dodecylbenzene (5 ml) were added to a nitrogen-substituted reaction vessel, heated, and stirred at 180° C. for 29 hours. The mixture was cooled to 100° C., and insoluble matter was removed by filtration after adding toluene (80 ml), and a filtrate was concentrated. Crystallization using n-hexane (20 ml) was performed to obtain an ocher powder of 12,12-dimethyl-10-(9,9-dimethyl-9H-fluorene-2-yl)-10,12-dihydroindeno[2,1-b]carbazole (7.4 g; yield 80.0%) heated The mixture was cooled to 100° C. insoluble matter was removed by filtration after adding toluene (80 ml) a filtrate was concentrated Crystallization

Conditions: temp:190.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 12,12-dimethyl-10,12-dihydroindeno[2,1-b]carbazole synthesized in Example 1 (35.5 g), 4-bromobiphenyl (35.0 g), sodium bisulfite (6.0 g), a copper powder (2.4 g), 3,5-di(tert-butyl)salicylic acid (9.4 g), potassium carbonate (31.2 g), and dodecylbenzene (52 ml) were added to a nitrogen-substituted reaction vessel, heated, and stirred at 190° C. for 26 hours. After cooled to 120° C., the mixture was stirred after adding toluene (35 ml), and a crude product was collected by filtration. After adding toluene (1.6 L) to the crude product, the crude product was heated and extracted at 110° C. After cooled to a room temperature, the crude product was concentrated under reduced pressure. The product was crystallized with methanol (120 ml) to obtain a white powder of 10-(biphenyl-4-yl)-12,12-dimethyl-10,12-dihydroindeno[2,1-b]carbazole (48.5 g; yield 88.1%). heated After cooled to 120° C. the mixture was stirred a crude product was collected by filtration After adding toluene (1.6 L) to the crude product the crude product was heated extracted at 110° C After cooled to a room temperature the crude product was concentrated under reduced pressure The product was crystallized with methanol (120 ml)

Conditions: temp:190.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 12,12-dimethyl-10,12-dihydroindeno[2,1-b]carbazole synthesized in Example 1 (35.5 g), 4-bromobiphenyl (35.0 g), sodium bisulfite (6.0 g), a copper powder (2.4 g), 3,5-di(tert-butyl)salicylic acid (9.4 g), potassium carbonate (31.2 g), and dodecylbenzene (52 ml) were added to a nitrogen-substituted reaction vessel, heated, and stirred at 190° C. for 26 hours. After cooled to 120° C., the mixture was stirred after adding toluene (35 ml), and a crude product was collected by filtration. After adding toluene (1.6 L) to the crude product, the crude product was heated and extracted at 110° C. After cooled to a room temperature, the crude product was concentrated under reduced pressure. The product was crystallized with methanol (120 ml) to obtain a white powder of 10-(biphenyl-4-yl)-12,12-dimethyl-10,12-dihydroindeno[2,1-b]carbazole (48.5 g; yield 88.1%). heated After cooled to 120° C. the mixture was stirred a crude product was collected by filtration After adding toluene (1.6 L) to the crude product the crude product was heated extracted at 110° C After cooled to a room temperature the crude product was concentrated under reduced pressure The product was crystallized with methanol (120 ml)

Conditions: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 1-phenyldodecane (7.5 g, 30.5 mmol) and concentrated H2SO4 (8.4 mL) was stirred vigorously at 90° C. for 1 h, cooled to room temperature, and then gradually poured with stirring into 10% aqueous KOH solution (175 mL). The resulting white precipitate was collected by filtration, washed with cold water (40 mL) and dried to give potassium 4-dodecylbenzene sulfonate (10.6 g, 29.1 mmol, 84%). This salt (10.0 g, 27.5 mmol) and POCl3 (4.2 g, 27.4 mmol) were stirred at room temperature and gradually heated to 170° C. The hot reaction mixture was poured into cold water and extracted with CHCl2. The organic layer was washed with water, dried over anhydrous Na2SO4, and filtered. Evaporation of the volatiles yielded p-dodecylbenzenesulfonyl chloride as a pale yellow liquid (9.2 g, 97%) which eventually became crystalline, mp 33° C.; 1H NMR (300 MHz, CDCl3) δ 0.88 (t, 3H, J=6.5), 1.20-1.38 (m, 18H), 1.60-1.68 (m, 2H), 2.72 (t, 2H, J=7.5 Hz), 7.40 (d, 2H, J=8.4 Hz), 7.79 (d, 2H, J=8.4 Hz); 13C NMR (75 MHz, CDCl3) δ 14.1, 22.6, 29.1, 29.3, 29.3, 29.5, 29.6, 30.9, 31.9, 36.0, 127.0, 129.6, 141.7, 151.6. cooled to room temperature gradually poured The resulting white precipitate was collected by filtration washed with cold water (40 mL) dried

Conditions: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 1-phenyldodecane (7.5 g, 30.5 mmol) and concentrated H2SO4 (8.4 mL) was stirred vigorously at 90° C. for 1 h, cooled to room temperature, and then gradually poured with stirring into 10% aqueous KOH solution (175 mL). The resulting white precipitate was collected by filtration, washed with cold water (40 mL) and dried to give potassium 4-dodecylbenzene sulfonate (10.6 g, 29.1 mmol, 84%). This salt (10.0 g, 27.5 mmol) and POCl3 (4.2 g, 27.4 mmol) were stirred at room temperature and gradually heated to 170° C. The hot reaction mixture was poured into cold water and extracted with CHCl2. The organic layer was washed with water, dried over anhydrous Na2SO4, and filtered. Evaporation of the volatiles yielded p-dodecylbenzenesulfonyl chloride as a pale yellow liquid (9.2 g, 97%) which eventually became crystalline, mp 33° C.; 1H NMR (300 MHz, CDCl3) δ 0.88 (t, 3H, J=6.5), 1.20-1.38 (m, 18H), 1.60-1.68 (m, 2H), 2.72 (t, 2H, J=7.5 Hz), 7.40 (d, 2H, J=8.4 Hz), 7.79 (d, 2H, J=8.4 Hz); 13C NMR (75 MHz, CDCl3) δ 14.1, 22.6, 29.1, 29.3, 29.3, 29.5, 29.6, 30.9, 31.9, 36.0, 127.0, 129.6, 141.7, 151.6. cooled to room temperature gradually poured The resulting white precipitate was collected by filtration washed with cold water (40 mL) dried

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

Procedure: To a solution of 24.6 grams (0.1 mole) of n-dodecylbenzene in 150 ml of carbon tetrachloride was added with stirring 34.8 grams (0.3 mole) of chlorosulfonic acid over a 1-hour period. The reaction was exothermic with the temperature rising to 27° C. Stirring was continued for 4 hours after which the reaction mixture was carefully poured onto 1 liter of cracked ice with vigorous stirring. Chloroform (200 ml) was added and the aqueous layer was saturated with sodium chloride. The chloroform layer was separated, washed two times with 500 ml of saturated aqueous sodium chloride solution, dried over Molecular Sieves 4A and filtered. The solvent was removed in vacuo, and the resulting residue was recrystallized from 100 ml of hexane. The dried product weighed 22.6 grams and melted at 33°-35° C. rising to 27° C The chloroform layer was separated washed two times with 500 ml of saturated aqueous sodium chloride solution dried over Molecular Sieves 4A filtered The solvent was removed in vacuo the resulting residue was recrystallized from 100 ml of hexane

Conditions: temp:16.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a mixture of 492 grams of aluminum chloride and 988 mL of 1,2-dichloroethane was added 192 grams of benzene-1,2,4,5-tetracarboxylic acid dianhydride (pyromellitic dianhydride). The resulting mixture was cooled to 16° C. and a solution of 434 grams of 1-dodecylbenzene, 123 grams of diisopropylethylamine and 480 mL of 1,2-dichloroethane was added over a period of 3.5 hours, keeping the temperature between 15° C. and 20° C. during the addition. The mixture was stirred overnight at room temperature and poured into a beaker of 1000 grams of ice and 1000 grams concentrated hydrochloric acid. The mixture was stirred for one hour and the liquid was poured from the coagulate. The mixture was divided into 800 mL portions and each portion was worked up as follows. To 800 mL of the mixture was added 800 mL of tetrahydrofuran, 800 mL of ethyl acetate and 800 mL of water. The mixture was stirred and phase split. The organic phase was filtered and the filtrate was concentrated in vacuo. The resulting residues were combined. To 127 grams of the combined residue was added 800 mL of ethyl acetate and the resulting mixture was stirred until a suspension of a fine solid resulted. The solid was collected by filtration and washed with 50 mL of ethyl acetate. The solid was dried to give 2,5-bis(4-dodecylbenzoyl)terephthalic acid. the temperature between 15° C. and 20° C. during the addition The mixture was stirred for one hour the liquid was poured from the coagulate The mixture was stirred phase split The organic phase was filtered the filtrate was concentrated in vacuo To 127 grams of the combined residue was added 800 mL of ethyl acetate the resulting mixture was stirred until a suspension of a fine solid resulted The solid was collected by filtration washed with 50 mL of ethyl acetate The solid was dried

Conditions: temp:180.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 12,12-Dimethyl-10,12-dihydroindeno[2,1-b]carbazole synthesized in Example 1 (5.5 g), 2-bromo-9,9-dimethyl-9H-fluorene (6.4 g), sodium bisulfite (0.3 g), a copper powder (0.1 g), 3,5-di(tert-butyl)salicylic acid (0.5 g), potassium carbonate (4.0 g), and dodecylbenzene (5 ml) were added to a nitrogen-substituted reaction vessel, heated, and stirred at 180° C. for 29 hours. The mixture was cooled to 100° C., and insoluble matter was removed by filtration after adding toluene (80 ml), and a filtrate was concentrated. Crystallization using n-hexane (20 ml) was performed to obtain an ocher powder of 12,12-dimethyl-10-(9,9-dimethyl-9H-fluorene-2-yl)-10,12-dihydroindeno[2,1-b]carbazole (7.4 g; yield 80.0%) heated The mixture was cooled to 100° C. insoluble matter was removed by filtration after adding toluene (80 ml) a filtrate was concentrated Crystallization

Conditions: temp:190.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 12,12-dimethyl-10,12-dihydroindeno[2,1-b]carbazole synthesized in Example 1 (35.5 g), 4-bromobiphenyl (35.0 g), sodium bisulfite (6.0 g), a copper powder (2.4 g), 3,5-di(tert-butyl)salicylic acid (9.4 g), potassium carbonate (31.2 g), and dodecylbenzene (52 ml) were added to a nitrogen-substituted reaction vessel, heated, and stirred at 190° C. for 26 hours. After cooled to 120° C., the mixture was stirred after adding toluene (35 ml), and a crude product was collected by filtration. After adding toluene (1.6 L) to the crude product, the crude product was heated and extracted at 110° C. After cooled to a room temperature, the crude product was concentrated under reduced pressure. The product was crystallized with methanol (120 ml) to obtain a white powder of 10-(biphenyl-4-yl)-12,12-dimethyl-10,12-dihydroindeno[2,1-b]carbazole (48.5 g; yield 88.1%). heated After cooled to 120° C. the mixture was stirred a crude product was collected by filtration After adding toluene (1.6 L) to the crude product the crude product was heated extracted at 110° C After cooled to a room temperature the crude product was concentrated under reduced pressure The product was crystallized with methanol (120 ml)