* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
With copper; potassium carbonate In di-iso-propylbenzene, 1,3- for 30 h; Heating / reflux
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 68.6percent).
64.2%
With 18-crown-6 ether; copper; potassium carbonate In 1,2-dichloro-benzene at 180℃; Inert atmosphere
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 <n="54"/>impurity. Purification was accomplished by dissolving the precipitate in hot boiling THF followed by filtration to obtain a green insoluble impurity. The product began to precipitate on standing and cooling. The filtrate/product mixture was dried under vacuum until the product started crashing out of solution and methanol was added to promote full precipitation. The product was isolated by vacuum filtration and air dried (24 hours). A cream colored flaky product was obtained (7.66Og, 64.2percent).1H (300MHz, DMSO): δ8.27 (d, J= 7.7 Hz, 4H), 8.04-8.16 (m, 4H), 7.74-7.83 (m, 4H), 7.33 (d, J= 2.0 Hz, IH), 7.31 (t, J= 1.7 Hz, 2H), 7.29 (d, J= 1.8 Hz IH) .
60%
With potassium <i>tert</i>-butylate In toluene at 130 - 140℃; for 48 h; Inert atmosphere; Autoclave
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.
50%
With 18-crown-6 ether; copper; potassium carbonate In 1,2-dichloro-benzene for 72 h; Inert atmosphere; Reflux
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.
50%
With 18-crown-6 ether; copper; potassium carbonate In 1,2-dichloro-benzene for 72 h; Inert atmosphere; Reflux
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.
Reference:
[1] Patent: US6337404, 2002, B1, . Location in patent: Example 3
[2] Patent: US6342637, 2002, B1, . Location in patent: Example 3
[3] Bulletin of the Korean Chemical Society, 2011, vol. 32, # 7, p. 2461 - 2464
[4] Journal of Materials Chemistry, 2005, vol. 15, # 23, p. 2304 - 2315
[5] Green Chemistry, 2017, vol. 19, # 9, p. 2111 - 2117
[6] Patent: US2005/118521, 2005, A1, . Location in patent: Page/Page column 7-8
[7] Patent: WO2009/80799, 2009, A2, . Location in patent: Page/Page column 51-53
[8] Russian Chemical Bulletin, 2015, vol. 64, # 8, p. 1978 - 1981[9] Izv. Akad. Nauk, Ser. Khim., 2015, # 8, p. 1978 - 1981,4
[10] Journal of Chemistry, 2016, vol. 2016,
[11] Russian Journal of General Chemistry, 2017, vol. 87, # 8, p. 1800 - 1812[12] Zh. Obshch. Khim., 2017, vol. 87, # 8, p. 13
2
[ 2050-68-2 ]
[ 86-74-8 ]
[ 342638-54-4 ]
[ 1325751-60-7 ]
[ 58328-31-7 ]
Yield
Reaction Conditions
Operation in experiment
90%
With potassium <i>tert</i>-butylate In toluene at 130 - 140℃; for 48 h; Inert atmosphere; Autoclave
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).
Reference:
[1] Russian Chemical Bulletin, 2015, vol. 64, # 8, p. 1978 - 1981[2] Izv. Akad. Nauk, Ser. Khim., 2015, # 8, p. 1978 - 1981,4
3
[ 92-86-4 ]
[ 86-74-8 ]
[ 342638-54-4 ]
[ 1325751-60-7 ]
[ 58328-31-7 ]
Yield
Reaction Conditions
Operation in experiment
77%
With potassium <i>tert</i>-butylate In toluene at 130 - 140℃; for 48 h; Inert atmosphere; Autoclave
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.
Reference:
[1] Russian Chemical Bulletin, 2015, vol. 64, # 8, p. 1978 - 1981[2] Izv. Akad. Nauk, Ser. Khim., 2015, # 8, p. 1978 - 1981,4
4
[ 92-86-4 ]
[ 74367-40-1 ]
[ 58328-31-7 ]
Reference:
[1] Organic and Biomolecular Chemistry, 2005, vol. 3, # 20, p. 3767 - 3781
5
[ 92-86-4 ]
[ 86-74-8 ]
[ 58328-31-7 ]
Reference:
[1] Advanced Synthesis and Catalysis, 2015, vol. 357, # 10, p. 2322 - 2330
[2] Chemistry--A European Journal, 1995, vol. 1, # 3, p. 183 - 192
[3] Journal of Organic Chemistry, 1957, vol. 22, p. 226
[4] Journal of Organic Chemistry, 2009, vol. 74, # 9, p. 3341 - 3349
Reference:
[1] Journal of Chemistry, 2016, vol. 2016,
[2] Russian Journal of General Chemistry, 2017, vol. 87, # 8, p. 1800 - 1812[3] Zh. Obshch. Khim., 2017, vol. 87, # 8, p. 13
11
[ 90-41-5 ]
[ 58328-31-7 ]
Reference:
[1] Green Chemistry, 2017, vol. 19, # 9, p. 2111 - 2117
12
[ 92-87-5 ]
[ 342638-54-4 ]
[ 1325751-60-7 ]
[ 58328-31-7 ]
Reference:
[1] Russian Chemical Bulletin, 2015, vol. 64, # 8, p. 1978 - 1981[2] Izv. Akad. Nauk, Ser. Khim., 2015, # 8, p. 1978 - 1981,4
13
[ 2050-68-2 ]
[ 86-74-8 ]
[ 342638-54-4 ]
[ 1325751-60-7 ]
[ 58328-31-7 ]
Yield
Reaction Conditions
Operation in experiment
90%
With potassium <i>tert</i>-butylate In toluene at 130 - 140℃; for 48 h; Inert atmosphere; Autoclave
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).
Reference:
[1] Russian Chemical Bulletin, 2015, vol. 64, # 8, p. 1978 - 1981[2] Izv. Akad. Nauk, Ser. Khim., 2015, # 8, p. 1978 - 1981,4
14
[ 92-86-4 ]
[ 86-74-8 ]
[ 342638-54-4 ]
[ 1325751-60-7 ]
[ 58328-31-7 ]
Yield
Reaction Conditions
Operation in experiment
77%
With potassium <i>tert</i>-butylate In toluene at 130 - 140℃; for 48 h; Inert atmosphere; Autoclave
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.
Reference:
[1] Russian Chemical Bulletin, 2015, vol. 64, # 8, p. 1978 - 1981[2] Izv. Akad. Nauk, Ser. Khim., 2015, # 8, p. 1978 - 1981,4
15
[ 92-87-5 ]
[ 342638-54-4 ]
[ 1325751-60-7 ]
[ 58328-31-7 ]
Reference:
[1] Russian Chemical Bulletin, 2015, vol. 64, # 8, p. 1978 - 1981[2] Izv. Akad. Nauk, Ser. Khim., 2015, # 8, p. 1978 - 1981,4
With copper; potassium carbonate; In di-iso-propylbenzene, 1,3-; for 30h;Heating / reflux;
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%).
64.2%
With 18-crown-6 ether; copper; potassium carbonate; In 1,2-dichloro-benzene; at 180℃;Inert atmosphere;
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 <n="54"/>impurity. Purification was accomplished by dissolving the precipitate in hot boiling THF followed by filtration to obtain a green insoluble impurity. The product began to precipitate on standing and cooling. The filtrate/product mixture was dried under vacuum until the product started crashing out of solution and methanol was added to promote full precipitation. The product was isolated by vacuum filtration and air dried (24 hours). A cream colored flaky product was obtained (7.66Og, 64.2%).1H (300MHz, DMSO): delta8.27 (d, J= 7.7 Hz, 4H), 8.04-8.16 (m, 4H), 7.74-7.83 (m, 4H), 7.33 (d, J= 2.0 Hz, IH), 7.31 (t, J= 1.7 Hz, 2H), 7.29 (d, J= 1.8 Hz IH) .
60%
With potassium tert-butylate; In toluene; at 130 - 140℃; for 48h;Inert atmosphere; Autoclave;
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.
50%
With 18-crown-6 ether; copper; potassium carbonate; In 1,2-dichloro-benzene; for 72h;Inert atmosphere; Reflux;
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.
50%
With 18-crown-6 ether; copper; potassium carbonate; In 1,2-dichloro-benzene; for 72h;Inert atmosphere; Reflux;
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.
With trichlorophosphate; In chloroform; at 60℃; for 8h;
A 200-ml Kolben equipped with a stirrer and a condenser was charged under a nitrogen stream with 60 g (123.8 mmol) of CBP prepared above, 337 g (2475 mmol) of N,N-dimethylformamide, and 750 ml of chloroform. The mixture was heated on a warm water bath to 60 C., and 190 g (1239.4 mmol) of phosphorus oxychloride was added dropwise to the above mixture. After the dropwise addition, the mixture was heated with stirring for 8 hr. This reaction solution was poured into an aqueous sodium carbonate solution. The organic layer was washed with water, and the solvent was distilled off. The residue was subjected to fractionation by column chromatography on silica gel (eluent: toluene) to give 4-(carbazol-9-yl)-4'-(3-formylcarbazol-9-yl)-biphenyl (23 g, yield 36.2%).
27.44%
A round bottom flask was set -up in an ice bath under nitrogen flow. DMF (7.2 niL, 93.39 mmol) was added to the flask while stirring. POCl 3 (8.5 niL, 92.86 mmol) was slowly added to the flask to give the white Vilsmeier -Haack reagent as a solid that was set aside on ice. CZ-I-83 (7.6Og, 15.68 mmol) was weighed into a separate flask set -up for reflux and under nitrogen flow. To this second flask dichloroethane (~180 mL) was added and the flask was heated (80 0C) to give a brownish -yellow solution. The Vilsmeier -Haack reagent was added to the second flask and the reaction was allowed to proceed under reflux. The reaction was monitored by TLC. A small sample of the mixture was removed and added to vial. Deionized water and Ethyl Acetate were added to the vial and shaken vigorously. The organic layer was spotted against starting material and eluted (toluene: dichloromethane = 1 : 1). After several days the reaction still had a minor amount of starting material but was stopped. The reaction mixture was slowly added into a beaker half filled with ice to give a precipitate in a dark greenish liquid. Flask washed with ice water and subsequently dichloromethane to fully extract organic components and added to beaker. After melting, solution from the beaker was dried with a rotary evaporator to remove organic solvents (water remains). Vacuum filtration of solids was attempted but filtering was not possible due to filter clogging. Instead, the reaction mixture was extracted with dichloromethane (3x) using a separatory funnel and all fractions were combin ed. Organic solvents were then removed under high vacuum with heating until a small amount of solution was present. This solution was purified by column chromatography (silica gel, dichloromethane: toluene = 3:2) but solubility issues resulted inadequate s eparation <n="55"/>of starting material from monosubstituted product. A second column was required to purify the product. The isolated crude product from the first column was dissolved in hot dichloromethane and toluene and processed with a rotary evaporator to minimal solvents while heating to ensure good solubility. The product fractions were dried on a rotary evaporator. The product (mono -substituted) was isolated by vacuum filtration with deionized water for washing and air dried (24 hours) to give a yellow powder (2.078g, 27.44%).1H (300MHz, CDCl3): deltaltheta.15 (s, IH), 8.71 (d, J= 1.1 Hz, IH), 8.12 -8.29 (m, 3H), 7.86-8.05 (m, 5H), 7.72 (t, J= 8.8 Hz, 4H), 7.11 -7.60 (m, 1 IH). 13C (1Hj (75MHz, CDCl3): deltal92.03, 144.69, 142.05, 141.00, 140.52, 139.20, 136.40, 129.29, 128.83, 127.78, 127.35, 124.18, 123.97, 12 3.76, 123.59, 121.61, 121.01, 120.66, 120.39, 110.72, 110.44, 110.04.
With di-tert-butyl(2,2-diphenyl-1-methyl-1-cyclopropyl)phosphine; bis(eta3-allyl-mu-chloropalladium(II)); methylmagnesium chloride; In tetrahydrofuran; 5,5-dimethyl-1,3-cyclohexadiene; at 5℃;Inert atmosphere; Reflux;
General procedure: [PdCl(pi-allyl)]2 (1 1.6 mg, 0.1 mol %) and cBRIDP (44.4 mg, 0.4 mol %) were placed into a 50 mL, two-necked, round bottomed flask equipped a gas inlet, and the flask was evacuated and filled with nitrogen. Subsequently, to the mixture was added dehydrated THF (8.2 mL, 101.0 mmol, 3.2 equivalents) to prepare a catalyst solution. A 200 mL, four-necked, round-bottomed flask equipped with a Teflon coated magnetic stirring bar, condenser, dropping funnel, thermometer, and a gas inlet was evacuated and filled with nitrogen. Carbazole (10.9 g, 65.0 mmol, 2.06 equivalents) and dehydrated xylenes (66 mL) were charged into the flask, and the mixture was cooled to 5C using an ice bath. Subsequently, to the mixture was added a THF solution of MeMgCl (3.22 mol/L, 20.0 mL, 64.4 mmol, 2.04 equivalents) dropwise via the dropping funnel at such a rate that the temperature of the reaction solution was kept at 20C or lower, and then the dropping funnel was washed with dehydrated xylenes (1 1 mL). Subsequently, to the solution were added 1,3-dichlorobenzene (3.6 mL, 31.6 mmol, 1.0 equivalent) and the catalyst solution (8.2 mL) successively, and the solution was stirred for 10 minutes under reflux. After cooling the reaction mixture to room temperature, to the mixture were added water (25 mL) and ammonium chloride (1.7 g). The aqueous layer was separated off, and the organic layer was concentrated under reduced pressure to give solid residue. The residue was dissolved in toluene, and the solution was decolorized by silica gel (1 g) and filtered through a Celite pad. The filtrate was concentrated under reduced pressure to give the solid, which was recrystallized from toluene/methanol to afford 12.5 g of mCP as a white powder. Isolated yield: 96.8%. 1H NMR (300 MHz, CDC13): 7.31 (ddd, J = 1.2, 6.6, 7.8 Hz, 4H), 7.44 (ddd, J = 1.2, 6.9, 8.1 Hz, 4H), 7.54 (d, J = 8.1 Hz, 4H), 7.70 (dd, J = 2.1, 7.5 Hz, 2H), 7.80-7.88 (m, 2H), 8.15 (d, J = 7.8 Hz, 4H).13C NMR (75 MHz, CDC13): 109.7, 120.3, 120.4, 123.6, 125.3, 125.8, 126.1, 131.2, 139.4, 140.6.
Illustrative of useful substituted carbazoles are the following: 4-(9H-carbazol-9-yl)-N,N-bis[4-(9H-carbazol-9-yl)phenyl]-benzenamine (TCTA); 4-(3-phenyl-9H-carbazol-9-yl)-N,N-bis[4(3-phenyl-9H-carbazol-9-yl)phenyl]-benzenamine; 9,9'-[5'-[4-(9H-carbazol-9-yl)phenyl][1,1':3',1"-terphenyl]-4,4"-diyl]bis-9H-carbazole. 9,9'-(2,2'-dimethyl[1,1'-biphenyl]-4,4'-diyl)bis-9H-carbazole (CDBP); 9,9'-[1,1'-biphenyl]-4,4'-diylbis-9H-carbazole (CBP); 9,9'-(1,3-phenylene)bis-9H-carbazole (mCP); 9,9'-(1,4-phenylene)bis-9H-carbazole; 9,9',9"-(1,3,5-benzenetriyl)tris-9H-carbazole; 9-[4-(9H-carbazol-9-yl)phenyl]-N,N-diphenyl-9H-carbazol-3-amine; ...
Illustrative of useful substituted carbazoles are the following: 4-(9H-carbazol-9-yl)-N,N-bis[4-(9H-carbazol-9-yl)phenyl]-benzenamine (TCTA); 4-(3-phenyl-9H-carbazol-9-yl)-N,N-bis[4(3-phenyl-9H-carbazol-9-yl)phenyl]-benzenamine; 9,9'-[5-[4-(9H-carbazol-9-yl)phenyl][1,1':3',1"-terphenyl]-4,4"-diyl]bis-9H-carbazole. 9,9'-(2,2'-dimethyl[1,1'-biphenyl]-4,4'-diyl)bis-9H-carbazole (CDBP); 9,9'-[1,1'-biphenyl]-4,4'-diylbis-9H-carbazole (CBP); 9,9'-(1,3-phenylene)bis-9H-carbazole (mCP); 9,9'-(1,4-phenylene)bis-9H-carbazole; 9,9',9"-(1,3,5-benzenetriyl)tris-9H-carbazole; 9-[4-(9H-carbazol-9-yl)phenyl]-N,N-diphenyl-9H-carbazol-3-amine; ...
Step 1: 4,4'-di(9H-carbazol-9-yl)biphenyl (CZ-I-83) 4,4'-Diiodobiphenyl (10.001 g, 24.63 mmol), carbazole (9.078 g, 54.29 mmol), K2CO3 (20.087 g, 145.34 mmol), 18-crown-6 (0.100 g, 0.34 mmol), and copper powder (10.051 g, 158.16 mmol) were combined in reaction flask. To the flask, o-dichlorobenzene (50 mL) was added. The reaction was heated under inert N2 atmosphere at 180 C. overnight. TLC showed evidence of limited di-substitution product which necessitated the addition of K2CO3 (4.994 g, 36.13 mmol) and Cu powder (5.223 g, 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 promoted 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 impurity. Purification was accomplished by dissolving the precipitate in hot boiling THF followed by filtration to obtain a green insoluble impurity. The product began to precipitate on standing and cooling. The filtrate/product mixture was dried under vacuum until the product started crashing out of solution and methanol was added to promote full precipitation. The product was isolated by vacuum filtration and air dried (24 hours). A cream colored flaky product was obtained (7.660 g, 64.2%). 1H (300 MHz, DMSO): delta8.27 (d, J=7.7 Hz, 4H), 8.04-8.16 (m, 4H), 7.74-7.83 (m, 4H), 7.33 (d, J=2.0 Hz, 1H), 7.31 (t, J=1.7 Hz, 2H), 7.29 (d, J=1.8 Hz 1H).
9
[ 58328-31-7 ]
[ 68-12-2 ]
[ 597570-65-5 ]
Yield
Reaction Conditions
Operation in experiment
48%
Step 2: Add DMF (1.7 mL, 22 mmol) to a 250 ml two-necked flask.Phosphorus oxychloride (1.9 ml, 21 mmol) was added dropwise to the flask at 0 C under an inert atmosphere and stirred for one hour.A solution of 4,4'-bis(9-carbazolyl)biphenyl(0.50 g, 1.0 mmol) in 10 mL of dichloroethane was added to the flask and reacted at 90 C for 20 hours.Monitor the end of the reaction, pour into ice water, add sodium hydroxide to neutral,Extract with dichloromethane and remove the solvent by evaporation under reduced pressure.Separation by column chromatography (dichloromethane) gave a white solid yellow solid (yield: 48%).
With N-Bromosuccinimide; In tetrahydrofuran; at 40℃; for 16h;
a) 4,4'-Bis(4,4'-bisbromocarbazolyl)biphenyl 74.8 g (420 mmol) of N-bromosuccinimide are added in portions to a solution of 48.5 g (100 mmol) of biscarbazolylbiphenyl in 1000 ml of THF at 40 C. with vigorous stirring, and the mixture is then stirred for 16 h. The mixture is subsequently transferred onto 2000 g of ice, and the resultant precipitate is filtered off with suction, washed three times with 300 ml of water and twice with 200 ml of ethanol and recrystallised from DMF. Yield: 74.3 g (93 mmol), 92.8% of theory; purity 98% according to 1H-NMR.
With potassium tert-butylate; In toluene; at 130 - 140℃; for 48h;Inert atmosphere; Autoclave;
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.
With potassium tert-butylate; In toluene; at 130 - 140℃; for 48h;Inert atmosphere; Autoclave;
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. 4,4'-Bis(9Hcarbozol-9-yl)-1,1'biphenyl (2a), the yield was 0.43 g (90%), m.p. >250 C. Found (%): C, 89.08; H, 4.84.C36H24N2. Calculated (%): 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 (%)):485.20 [M + H]+ (100).
With N-Bromosuccinimide; silica gel; In dichloromethane; at 20℃; for 24h;
N-methyl-4,4'-biphenyl (CBP) (1.0 mmol), N-bromosuccinimide (NBS) (1.05 mmol) and silica gel (100 g) were dissolved in dichloromethane (150 ml) was stirred at room temperature for 24 hours at room temperature and filtered directly with a sandcore funnel. The organic solvent was evaporated to dryness to give a white solid powder in 80% yield.
With silver nitrate; In water; chlorobenzene; at 100℃; for 24h;
4,4'-bis (9H-carbazol-9-yl) biphenyl (484.6 mg)Was dissolved in chlorobenzene (30 mL)Silver nitrate (169.9 mg)And sodium tetrakis (pentafluorophenyl) borate (702.0 mg)Was dissolved in water (15 mL) and stirred in a three-necked flask.After reacting for 24 hours while heating at 100 C. with an oil bath, it was cooled to room temperature and left to stand at room temperature for 12 hours.The organic phase was filtered off with a PTFE filter having a pore size of 0.2 mum and washed with a separatory funnel.The organic phase was dried to give electron accepting compound 7 (348 mg).
Stage #1: 9H-carbazole With methylmagnesium chloride In tetrahydrofuran; 5,5-dimethyl-1,3-cyclohexadiene at 5℃; for 0.5h; Inert atmosphere; Schlenk technique; Glovebox;
Stage #2: 4,4'-dichlorobiphenyl With (2,6-bis(2,4,6-triisopropylphenyl)phenyl)-dicyclohexylphosphine In tetrahydrofuran; 5,5-dimethyl-1,3-cyclohexadiene; dodecane at 145℃; for 3h; Inert atmosphere; Schlenk technique; Glovebox; Sealed tube;
1-4 Example 1.
In an inert atmosphere, add a stir bar to a dry 50 mL Schlenk bottle,Add carbazole (0.368 g, 2.2 mmol) and xylene (3 mL), cool to 5 ,Methylmagnesium chloride (3.0 M in THF, 2.3 mmol, 0.77 mL) (about 1.5 min) was added dropwise via syringe. After the addition, the reaction was stirred for 15 min and transferred to a glove box for use. In a glove box, add 4, 4’-dichlorobiphenyl (0.223 g, 1.0 mmol),Complex [2,6-bis (2,4,6-triisopropylphenyl) phenyl-dicyclohexylphosphine] (allyl) palladium (II) chloride (0.86 mg, 0.001 mmol),2,6-bis (2,4,6-triisopropylphenyl) phenyl-dicyclohexylphosphine (0.68 mg, 0.001 mmol) and 0.13 mL of dodecane (as an internal standard for GC analysis) were dissolved in 1 mL xylene.The Schlenk bottle reaction solution was transferred to a pressure-resistant tube at room temperature, sealed, and reacted at an oil bath at 145 ° C for 3 h.The reaction solution was filtered through silica gel and diatomaceous earth, the filtrate was concentrated under reduced pressure, and the residue was separated and purified by silica gel column chromatography(Petroleum ether: ethyl acetate = 10: 1), to obtain a white solid 0.47 g, a yield of 98%.
Stage #1: 4,4'-bis(9H-carbazol-9-yl)biphenyl With N-Bromosuccinimide In dichloromethane for 12h; Darkness;
Stage #2: With copper(l) iodide; sodium methylate In N,N-dimethyl-formamide at 100℃; for 24h;
Stage #3: With boron tribromide In dichloromethane for 24h; Cooling with ice;
Synthesis of G1:
Add the reaction material (5mmol) into a 100mL two-neck flask, then add 50mL of dichloromethane solvent to dissolve it,Gradually add NBS (N-bromosuccinimide (12mmol)) in batches,React for 12h under dark conditions. After the reaction is over, cool to room temperature,The reaction was stopped by adding water. After extraction and separation with dichloromethane, washing and drying with water, the intermediate product is obtained by concentration. Add 50mL solvent DMF to dissolve the obtained intermediate product, then add sodium methoxide CH3ONa (7.5mmol) and cuprous iodide (7.5mmol) into the solution, and make the mixed solution reflux and react at 100 for 24h. After the reaction is over, it is cooled to room temperature, and water is added to terminate the reaction. After extraction and separation with dichloromethane, washing and drying with water, the intermediate product is obtained. At this time, the intermediate product is re-dissolved in dichloromethane, and an appropriate amount of BBr3 is added under ice bath conditions. After reacting for 24 hours, the reaction was terminated with methanol. Use n-hexane/dichloromethane as eluent, separate and purify with silica gel chromatographic column, remove the solvent by rotary evaporation, collect the product, and finally vacuum dry at room temperature for 12h, and weigh. The monomer G1 was obtained with a yield of 43%.
With 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone; copper(II) choride dihydrate; 18-crown-6 ether; potassium <i>tert</i>-butylate; silver carbonate at 140℃; for 48h;
1 Example 1
The one-step synthesis of 4,4'-bis(9H-carbazol-9-yl)biphenyl compounds includes the following steps:In this embodiment, in the carbazole compound represented by formula II, R1 and R2 are both hydrogen and are carbazole;In the 1,4-diiodobenzene compound represented by formula III, R3 is hydrogen, which is 1,4-diiodobenzene;In an air atmosphere, carbazole 167mg (1mmol), 1,4-diiodobenzene 329mg (1mmol), potassium tert-butoxide 224mg (2mmol),CuCl2·2H2O 171mg (1mmol), Ag2CO3 331mg (1.2mmol), 18-crown ether-6 8mg (0.03mmol) and DMPU 2.5mL were added to the reactor, heated to 140 for 48h,After the reaction is over, cool, spin off the solvent DMPU, add 50 mL of dichloromethane for extraction, wash with saturated sodium carbonate solution, and then with saturated sodium chloride solution.Dry with anhydrous sodium sulfate, filter, spin off the solvent DMPU,Subsequent column chromatography separation (eluent petroleum ether: DCM, v/v=10/1) to obtain 181 mg of 4,4'-bis(9H-carbazol-9-yl)biphenyl, the structure is as follows:The yield was 75% by weight