9,10-Dibromoanthracene

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

Procedure: To a mixed solution of 286.6 g (0.85 mol) of 9,10-dibromoanthracene, 29.9 g (0.0255 mol) of Pd(PPh3)4 and 3L of benzene was added 1.5L of 2M Na2CO3aq and 1.2 L of ethanol solution of 228.6 g (1.87 mol) of phenyl boric acid, followed by refluxing for 6 hours. To the reaction solution was added 200 mL of 30% H2O2 to terminate the reaction, and an organic layer was recovered. The organic layer was washed with water and dehydrated by anhydrous magnesium sulfate, followed by filtration and concentration of the filtrate to 750 mL in total. The precipitated crystal was filtered and dried to give 212.0 g of 9,10-diphenylanthracene (Yield 75.5%, HPLC purity 97.6%). by refluxing for 6 hours to terminate the reaction an organic layer was recovered The organic layer was washed with water followed by filtration and concentration of the filtrate to 750 mL in total The precipitated crystal was filtered dried

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

Procedure: 1,4-Dibromonaphthalene (M-16), 2,5-dibromothiophene (M-11), and 9,10-dibromoanthracene (M-18) are available commercially from Acros Organics, a division of Fisher Scientific Co. or Aldrich Chemicals. 5,5′-dibromo-2,2′-bithiophene (M-12) is prepared by bromination of 2,2′-bithiophene, as reported by R. M. Kellogg, A. P. Schaap, and H. Wynberg in Journal of Organic Chemistry, Vol. 34, pp. 343-346 (1969). 4,7-dibromo-2,1,3-benzothiadiazole (M-15) is prepared by bromination of 2,1,3-benzothiadiazole as reported by K. Pilgram, M. Zupan, and R. Skiles in Journal of Heterocyclic Chemistry, Vol. 7, pp. 629-633 (1970). 3,6-Dibromo-1,2-phenylenediamine is synthesized from 4,7-dibromo-2,1,3-benzothiadiazole as reported for the selenium analog reported by C. W. Bird, G. W. H. Cheeseman, and A. A. Sarsfield in Journal of Chemical Society, pp. 4767-4670 (1963) and was converted to 5,8-dibromo-2,3-diphenylquinoxaline (M-17) as reported in the same reference.

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

Procedure: 1,4-Dibromonaphthalene (M-16), 2,5-dibromothiophene (M-11), and 9,10-dibromoanthracene (M-18) are available commercially from Acros Organics, a division of Fisher Scientific Co. or Aldrich Chemicals. 5,5′-dibromo-2,2′-bithiophene (M-12) is prepared by bromination of 2,2′-bithiophene, as reported by R. M. Kellogg, A. P. Schaap, and H. Wynberg in Journal of Organic Chemistry, Vol. 34, pp. 343-346 (1969). 4,7-dibromo-2,1,3-benzothiadiazole (M-15) is prepared by bromination of 2,1,3-benzothiadiazole as reported by K. Pilgram, M. Zupan, and R. Skiles in Journal of Heterocyclic Chemistry, Vol. 7, pp. 629-633 (1970). 3,6-Dibromo-1,2-phenylenediamine is synthesized from 4,7-dibromo-2,1,3-benzothiadiazole as reported for the selenium analog reported by C. W. Bird, G. W. H. Cheeseman, and A. A. Sarsfield in Journal of Chemical Society, pp. 4767-4670 (1963) and was converted to 5,8-dibromo-2,3-diphenylquinoxaline (M-17) as reported in the same reference.

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

Procedure: 9,10-Dibromoanthracene (23.63 g, 70.3 mmol), 300 mL of THF and a catalytic amount of dichlorobis(triphenylphosphine)palladium (II) were all placed under nitrogen in a round bottomed flask. The Grignard reagent prepared above was then added via a double-end needle transfer while still warm. After the addition, the reaction mixture was allowed to reflux overnight. After cooling to room temperature, the precipitated solid was collected by vacuum filtration and washed with ether, THF, and water. The collected solid was placed into a beaker and HCl (6M) was added followed by ethanol. This mixture is stirred for 60 minutes and the solid is again collected by vacuum filtration. The product was washed until the washings are neutral. After drying, the solid is refluxed gently in CH2Cl2 for 60 minutes. The pure product was filtered and dried to give 85.2 g solid (82% yield) (AA8790-34). 1H NMR (CDCl3) δ(ppm): 3.97 (s, 6H), 7.29 (dd, J1=8.9 Hz, J2=2.4 Hz, 2H), 7.40 (d, J=6.9 Hz 2H), 7.41 (d, J=6.9 Hz, 2H), 7.53 (d, J=2.2 Hz, 2H), 7.57 (d, J=8.0 Hz, 2H), 7.64 (d, J=6.8 Hz, 2H), 7.65 (d, J=6.8 Hz, 2H), 7.94 (d, J=9 Hz, 2H), 7.97 (s, 2H), 8.10 (d, J=8.4 Hz, 2H);. FD-MS: m/z 490 (M+). all placed under nitrogen in a round bottomed flask was then added via a double-end needle transfer while still warm After the addition to reflux overnight the precipitated solid was collected by vacuum filtration washed with ether, THF, and water was added the solid is again collected by vacuum filtration The product was washed until the washings After drying the solid is refluxed gently in CH2Cl2 for 60 minutes The pure product was filtered dried

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

Procedure: 9,10-Dibromoanthracene (23.63 g, 70.3 mmol), 300 mL of THF and a catalytic amount of dichlorobis(triphenylphosphine)palladium (II) were all placed under nitrogen in a round bottomed flask. The Grignard reagent prepared above was then added via a double-end needle transfer while still warm. After the addition, the reaction mixture was allowed to reflux overnight. After cooling to room temperature, the precipitated solid was collected by vacuum filtration and washed with ether, THF, and water. The collected solid was placed into a beaker and HCl (6M) was added followed by ethanol. This mixture is stirred for 60 minutes and the solid is again collected by vacuum filtration. The product was washed until the washings are neutral. After drying, the solid is refluxed gently in CH2Cl2 for 60 minutes. The pure product was filtered and dried to give 85.2 g solid (82% yield) (AA8790-34). 1H NMR (CDCl3) δ(ppm): 3.97 (s, 6H), 7.29 (dd, J1=8.9 Hz, J2=2.4 Hz, 2H), 7.40 (d, J=6.9 Hz 2H), 7.41 (d, J=6.9 Hz, 2H), 7.53 (d, J=2.2 Hz, 2H), 7.57 (d, J=8.0 Hz, 2H), 7.64 (d, J=6.8 Hz, 2H), 7.65 (d, J=6.8 Hz, 2H), 7.94 (d, J=9 Hz, 2H), 7.97 (s, 2H), 8.10 (d, J=8.4 Hz, 2H);. FD-MS: m/z 490 (M+). all placed under nitrogen in a round bottomed flask was then added via a double-end needle transfer while still warm After the addition to reflux overnight the precipitated solid was collected by vacuum filtration washed with ether, THF, and water was added the solid is again collected by vacuum filtration The product was washed until the washings After drying the solid is refluxed gently in CH2Cl2 for 60 minutes The pure product was filtered dried

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

Procedure: In a nitrogen atmosphere, 12 g (35.7 mmol) of 9,10-dibromoanthracene, and 300 ml of tetrahydrofuran (THF) were added to a round-bottom flask. Next, 14.4 ml (35.7 mmol, 2.5M) of n-butyl lithium was added dropwise slowly into the round-bottom flask at −78° C. After mixing and reacting for 30 min, 12 g (40.7 mmol) triphenylsilyl chloride with 50 ml THF were added dropwise slowly into the round-bottom flask at −78° C. After reacting at room temperature for 24 hours, the resulting mixture was subjected to extraction with a mixed solvent (ethyl acetate:H2O), dried over anhydrous MgSO4, filtered, and condensed, then the crude product was purified by column chromatography (n-hexane/acetyl acetate=15/1), A 9.0 g of pure 9-bromo-10-triphenysilyl anthracene was collected. After mixing After reacting at room temperature for 24 hours the resulting mixture was subjected to extraction with a mixed solvent (ethyl acetate:H2O) dried over anhydrous MgSO4 filtered condensed the crude product was purified by column chromatography (n-hexane/acetyl acetate=15/1) A 9.0 g of pure 9-bromo-10-triphenysilyl anthracene was collected

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

Procedure: In a nitrogen atmosphere, 12 g (35.7 mmol) of 9,10-dibromoanthracene, and 300 ml of tetrahydrofuran (THF) were added to a round-bottom flask. Next, 14.4 ml (35.7 mmol, 2.5M) of n-butyl lithium was added dropwise slowly into the round-bottom flask at −78° C. After mixing and reacting for 30 min, 12 g (40.7 mmol) triphenylsilyl chloride with 50 ml THF were added dropwise slowly into the round-bottom flask at −78° C. After reacting at room temperature for 24 hours, the resulting mixture was subjected to extraction with a mixed solvent (ethyl acetate:H2O), dried over anhydrous MgSO4, filtered, and condensed, then the crude product was purified by column chromatography (n-hexane/acetyl acetate=15/1), A 9.0 g of pure 9-bromo-10-triphenysilyl anthracene was collected. After mixing After reacting at room temperature for 24 hours the resulting mixture was subjected to extraction with a mixed solvent (ethyl acetate:H2O) dried over anhydrous MgSO4 filtered condensed the crude product was purified by column chromatography (n-hexane/acetyl acetate=15/1) A 9.0 g of pure 9-bromo-10-triphenysilyl anthracene was collected

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

Procedure: Into a 100 mL three-neck flask were added 835 mg (2.5 mmol) of 9,10-dibromoanthracene, 1.7 g (5.0 mmol) of N,9-diphenyl-9H-carbazol-3-amine (abbreviation: PCA), and 1.0 g (10 mmol) of sodium-tert-butoxide, and the atmosphere in the flask was substituted by nitrogen. Thereafter, 25 mL of toluene and 0.1 mL of tri(tert-butyl)phosphine (10 wt % hexane solution) were added to the mixture. This mixture was stirred under reduced atmosphere to be degassed. After degassing, 72 mg (0.13 mmol) of bis(dibenzylideneacetone)palladium(0) was added. This mixture was stirred at 80° C. for 5 hours under nitrogen. After the reaction, the mixture was added with about 20 mL of toluene and then washed with water. An aqueous layer was extracted with toluene, and the extracted solution was combined with an organic layer and washed with saturated saline. The organic layer was dried with magnesium sulfate, this mixture was naturally filtered, and the filtrate was concentrated. A solid obtained was purified by silica gel column chromatography (developing solvent; hexane:toluene=7:3). Recrystallization of the obtained solid with a mixed solvent of dichloromethane and hexane gave 1.4 g of 9,10-bis[N-phenyl-N-(9-phenylcarbazol-3-yl)amino]anthracene (abbreviation: PCA2A) as orange powder in 67% yield. By a nuclear magnetic resonance measurement, it was confirmed that this compound was 9,10-bis[N-phenyl-N-(9-phenylcarbazol-3-yl)amino]anthracene (abbreviation: PCA2A). to be degassed After degassing This mixture was stirred at 80° C. for 5 hours under nitrogen After the reaction washed with water An aqueous layer was extracted with toluene washed with saturated saline The organic layer was dried with magnesium sulfate this mixture was naturally filtered the filtrate was concentrated A solid obtained was purified by silica gel column chromatography (developing solvent; hexane:toluene=7:3) Recrystallization of the obtained solid with a mixed solvent of dichloromethane and hexane

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

Procedure: To the yellow suspension of 9,10-Dibromoanthracene (2 g, 5.95 mmol) in THF (20 mL) at −90° C., n-BuLi (2.88 mL, 7.18 mmol, 2.5 M in hexane) was added dropwise. Orange solution was observed after 45 min additional stirring. Anhydrous DMF (0.92 mL, 11.9 mmol) was added to the orange solution. The reaction mixture was slowly warmed to room temp and stirred overnight. The reaction mixture was quenched with H2O and extracted with CH2Cl2. The organic layer was washed with 10% aq. Na2CO3 solution (3×50 mL). The CH2Cl2 layer was separated, dried over anhydrous Na2SO4, filtered and removed in vacuo to give yellow solid. The crude product was purified by column chromatography using 30% CH2Cl2/hexane to give 6 in 68% yield. R1=0.3 (30% CH2Cl2/hexane; 1H NMR (CDCl3) δ 11.39 (s, 1H), 8.77-8.82 (d, 2H), 8.55-8.60 (d, 2H), 7.56-7.67 (m, 4H). (Ref. de Montigny, Frederic; Argouarch, Gilles; Lapinte, Claude. New route to unsymmetrical 9,10-disubstituted ethynylanthracene derivatives. Synthesis, 2006, 2, 293-298.) The reaction mixture was quenched with H2O extracted with CH2Cl2 The organic layer was washed with 10% aq. Na2CO3 solution (3×50 mL) The CH2Cl2 layer was separated dried over anhydrous Na2SO4 filtered removed in vacuo to give yellow solid The crude product was purified by column chromatography to give 6 in 68% yield

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

Procedure: To the yellow suspension of 9,10-Dibromoanthracene (2 g, 5.95 mmol) in THF (20 mL) at −90° C., n-BuLi (2.88 mL, 7.18 mmol, 2.5 M in hexane) was added dropwise. Orange solution was observed after 45 min additional stirring. Anhydrous DMF (0.92 mL, 11.9 mmol) was added to the orange solution. The reaction mixture was slowly warmed to room temp and stirred overnight. The reaction mixture was quenched with H2O and extracted with CH2Cl2. The organic layer was washed with 10% aq. Na2CO3 solution (3×50 mL). The CH2Cl2 layer was separated, dried over anhydrous Na2SO4, filtered and removed in vacuo to give yellow solid. The crude product was purified by column chromatography using 30% CH2Cl2/hexane to give 6 in 68% yield. R1=0.3 (30% CH2Cl2/hexane; 1H NMR (CDCl3) δ 11.39 (s, 1H), 8.77-8.82 (d, 2H), 8.55-8.60 (d, 2H), 7.56-7.67 (m, 4H). (Ref. de Montigny, Frederic; Argouarch, Gilles; Lapinte, Claude. New route to unsymmetrical 9,10-disubstituted ethynylanthracene derivatives. Synthesis, 2006, 2, 293-298.) The reaction mixture was quenched with H2O extracted with CH2Cl2 The organic layer was washed with 10% aq. Na2CO3 solution (3×50 mL) The CH2Cl2 layer was separated dried over anhydrous Na2SO4 filtered removed in vacuo to give yellow solid The crude product was purified by column chromatography to give 6 in 68% yield

Conditions: temp:-69.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Under an argon atmosphere, the temperature of a solution of 9,10-dibromoanthracene (5 g, 15 mmol) in dry-THF (50 ml) was cooled to −69° C., and t-butyllithium (18 mmol) was dropped to the solution. After the mixture had been stirred for 3 hours, chlorotrimethylsilane (3 ml, 22.5 mmol) was added to the mixture, and the whole was stirred at −69° C. for an additional 3 hours. After the temperature of the resultant had been increased to room temperature, the resultant was quenched with sodium bicarbonate water, extracted with toluene, and dried with sodium sulfate. Then, the solvent was removed by distillation. The residue was dispersed and washed with hexane, the insoluble matter was removed, and the filtrate was condensed. The condensate was washed with ethanol, and was then subjected to silica gel column chromatography, whereby 1 g of 9-bromo-10-trimethylsilylanthracene was obtained. the whole was stirred at −69° C. for an additional 3 hours After the temperature of the resultant had been increased to room temperature the resultant was quenched with sodium bicarbonate water extracted with toluene dried with sodium sulfate Then, the solvent was removed by distillation The residue was dispersed washed with hexane the insoluble matter was removed condensed The condensate was washed with ethanol

Conditions: temp:170.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Potassium hydroxide (19.6 g) and thiophenol (35.5 ml) were heated at 170 degrees C. in dimethylacetamide for two hours. 9,10-dibromoanthracene (37.5 g) was added and the mixture heated at 170 degrees C. an additional two hours. (The corresponding dichloro compound has also been used successfully.) The mixture was quenched with water and the precipitate recrystallized from chloroform/ethanol to give DTPA. an additional two hours ) The mixture was quenched with water the precipitate recrystallized from chloroform/ethanol