4,4'-Bis(N-carbazolyl)-1,1'-biphenyl

White to brown powder

A 2-L Kolben equipped with a stirrer and a drain device was charged under a nitrogen stream with 150 g (369.5 mmol) of 4, 4'-diiodobiphenyl, 123.5 g (738.6 mmol) of carbazole, 23 g of copper powder, 100 g of potassium carbonate, and 500 ml of 1, 3-diisopropylbenzene. 4, 4'-Diiodobiphenyl (lO.OOlg, 24.63 mmol), carbazole (9.078g, 54.29 mmol), KGeneral procedure: Potassium tertbutoxide (1.12 g, 10 mmol) and carbazole (1.67 g, 10 mmol) were added to appropriate dihalobiphenyl 1 (1 mmol) in dry toluene (20 mL). The mixture was heated in a glass autoclave under argon at 130—140 C for 48 h.The resulting suspension was diluted with water to remove inorganic impurities. The organic layer was separated, concentrated to dryness, and chromatographed on silica gel using a 0—10percent acetone solution in hexane.General procedure: General procedure of Ullmann coupling procedure for preparation of carbazole-thiophene is as follows. A mixture of carbazole 1, 3-(thiophen-2-yl)carbazole 7 or 3, 6-(dithiophene-2-yl)9Hcarbazole 9 (2 eq) and 4, 4-diiodobiphenyl 2, 4, 4-diiodo-2'2-dimethyl-1, 1-biphenyl 3 or 1, 4-diiodobenzene 4 (1 eq) in 1, 2-dichlorobenzene (10 mL) was purged with nitrogen for 30 minutes. K2CO3 (1 eq), copper powder (2 eq), and 18-crown-6 (20 molpercent) were added to the mixture and the resulting mixture was refluxed under nitrogen atmosphere for 3 days. The organic phase was filtered and the solvent removed under vacuo and purified with column chromatography (silica, ethyl acetate-hexane) to afford desired products.General procedure: A mixture of 2 equiv of carbazole1 or thienyl-substituted carbazole 8–10 and 1 equiv of 4, 4′-diiodobiphenyl (2) or 4, 4′-diiodo-2, 2′-dimethyl-1, 1′-biphenyl (3) in 10 mL of 1, 2-dichlorobenzene was purged with nitrogen for 30 min, 1 equiv of K2CO3, 2 eq of copper powder, and 20 mol percent of 18-crown-6 were added, and the mixture was refluxed in a nitrogen atmosphere for 3 days. The mixture was filtered, the solvent was removed under reduced pressure, and the residue was purified by silica gel column chromatography using ethyl acetate–hexane as eluent.Potassium tertbutoxide (1.12 g, 10 mmol) and carbazole (1.67 g, 10 mmol) were added to appropriate dihalobiphenyl 1 (1 mmol) in dry toluene (20 mL). The mixture was heated in a glass autoclave under argon at 130—140 C for 48 h.The resulting suspension was diluted with water to remove inorganic impurities. The organic layer was separated, concentrated to dryness, and chromatographed on silica gel using a 0—10percent acetone solution in hexane. 4, 4'-Bis(9Hcarbozol-9-yl)-1, 1'biphenyl (2a), the yield was 0.43 g (90percent), m.p. >250 C. Found (percent): C, 89.08; H, 4.84.C36H24N2. Calculated (percent): C, 89.23; H, 4.99. 1H NMR (DMSOd6), : 8.28 (m, 4 H); 8.09 (m, 4 H); 7.80 (m, 4 H);7.47—7.50 (m, 8 H); 7.26—7.28 (m, 4 H). ESIMS, m/z (Irel (percent)):485.20 [M + H]+ (100).General procedure: Potassium tertbutoxide (1.12 g, 10 mmol) and carbazole (1.67 g, 10 mmol) were added to appropriate dihalobiphenyl 1 (1 mmol) in dry toluene (20 mL). The mixture was heated in a glass autoclave under argon at 130—140 C for 48 h.The resulting suspension was diluted with water to remove inorganic impurities. The organic layer was separated, concentrated to dryness, and chromatographed on silica gel using a 0—10percent acetone solution in hexane.A 2-L Kolben equipped with a stirrer and a drain device was charged under a nitrogen stream with 150 g (369.5 mmol) of 4, 4'-diiodobiphenyl, 123.5 g (738.6 mmol) of carbazole, 23 g of copper powder, 100 g of potassium carbonate, and 500 ml of 1, 3-diisopropylbenzene. The mixture was heated under reflux for 30 hr and was allowed to cool. Toluene was then added, and the mixture was filtered. The solvent in the filtrate was distilled off under reduced pressure. Methanol (500 ml) was added to the residue to precipitate crystals. The crystals were collected by filtration to give CBP (4, 4'-bis(carbazol-9-yl)-biphenyl) (122.8 g, yield 68.6%).4, 4'-Diiodobiphenyl (lO.OOlg, 24.63 mmol), carbazole (9.078g, 54.29 mmol), K2CO3 (20.087g, 145.34 mmol), 18 -crown-6 (0.10Og, 0.34 mmol), and copper powder (10.05 Ig, 158.16 mmol) were combined in reaction flask. To the flask, 0 - dichlorobenzene (50 mL) was added. The reaction was heated under inert N2 atmosphere at 180 0C overnight. TLC showed evide nee of limited di -substitution product which necessitated the addition of K2CO3 (4.994g, 36.13 mmol) and Cu powder (5.223g, 82.19 mmol) to the reaction flask to promote di -substitution. The reaction was allowed to proceed overnight. Additional reagents had no noticeable effect on the reaction so the reaction was stopped. Insoluble material was removed by vacuum filtration and washed with several portions of THF. On standing, a crystalline product crashed out of the filtrate. Further crystallization was prom oted by the addition of a large amount of methanol. The precipitate was vacuum filtered to isolate. TLC (hexanes: DCM = 8:2) confirmed precipitate was product with minor General procedure: Potassium tertbutoxide (1.12 g, 10 mmol) and carbazole (1.67 g, 10 mmol) were added to appropriate dihalobiphenyl 1 (1 mmol) in dry toluene (20 mL). The mixture was heated in a glass autoclave under argon at 130-140 C for 48 h.The resulting suspension was diluted with water to remove inorganic impurities. The organic layer was separated, concentrated to dryness, and chromatographed on silica gel using a 0-10% acetone solution in hexane.General procedure: General procedure of Ullmann coupling procedure for preparation of carbazole-thiophene is as follows. A mixture of carbazole 1, 3-(thiophen-2-yl)carbazole 7 or 3, 6-(dithiophene-2-yl)9Hcarbazole 9 (2 eq) and 4, 4-diiodobiphenyl 2, 4, 4-diiodo-2'2-dimethyl-1, 1-biphenyl 3 or 1, 4-diiodobenzene 4 (1 eq) in 1, 2-dichlorobenzene (10 mL) was purged with nitrogen for 30 minutes. K2CO3 (1 eq), copper powder (2 eq), and 18-crown-6 (20 mol%) were added to the mixture and the resulting mixture was refluxed under nitrogen atmosphere for 3 days. The organic phase was filtered and the solvent removed under vacuo and purified with column chromatography (silica, ethyl acetate-hexane) to afford desired products.General procedure: A mixture of 2 equiv of carbazole1 or thienyl-substituted carbazole 8-10 and 1 equiv of 4, 4?-diiodobiphenyl (2) or 4, 4?-diiodo-2, 2?-dimethyl-1, 1?-biphenyl (3) in 10 mL of 1, 2-dichlorobenzene was purged with nitrogen for 30 min, 1 equiv of K2CO3, 2 eq of copper powder, and 20 mol % of 18-crown-6 were added, and the mixture was refluxed in a nitrogen atmosphere for 3 days. The mixture was filtered, the solvent was removed under reduced pressure, and the residue was purified by silica gel column chromatography using ethyl acetate-hexane as eluent.

Molecular Weight:484.6
XLogP3:9.7
Rotatable Bond Count:3
Exact Mass:484.193948774
Monoisotopic Mass:484.193948774
Topological Polar Surface Area:9.9
Heavy Atom Count:38
Complexity:683
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes