* 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.
2.5 g (8 mmol) 4,4’-dibromo biphenyl was used(utilized) to perform a cyclization reaction to synthesize 2.08g (80percent) of 4,4’-dibromo carbazole. The 4,4’-dibromo carbazole and iodinated phenyl were dissolved in 40 ml of toluene to synthesize Intermediate C through a buchwald reaction.
73.8%
With triphenylphosphine In N,N-dimethyl acetamideInert atmosphere; Reflux
Dibromo-2-nitrobiphenyl (17.85 g, 50 mmol) and triphenylphosphine (32.75 g, 125 mmol) were dissolved in 300 mL of N, N-dimethylacetamide under an argon atmosphere The reaction was refluxed overnight. The reaction was stopped and cooled to room temperature. The mixture was extracted with methylene chloride and washed with water four to five times. After drying, the residue was purified by silica gel column chromatography (petroleum ether / methylene chloride = 2: 1) using 200 to 300 mesh, and recrystallized from ethanol to give white Solid (12 g, 73.8percent).
70%
With triphenylphosphine In 1,2-dichloro-benzeneInert atmosphere; Reflux
4,4’-Dibromo-2-nitro-biphenyl (2.04 g, 5.42 mmol) and PPh3 (3.80g, 14.3 mmol) were refluxing in 1,2-dichlorobenzen (14 mL) under Ar over night. Then the solvent is removed byevaporation under vacuum. The residue was purified with silica chromatography (eluent:dichloromethane/hexanes = 0percent to 44percent). A brown solid (1.29 g, 70percent) was obtained asintermediate 1.
65%
at 160℃;
2,7-dibromo-9-H-carbazole (8): In a 100 mL flame-dried flask, 4,4'-Dibromo-2-nitrobiphenyl (10 g, 28 mmol) was solubilized in 35 mL of triethyl phosphite (P(OEt)3). The reaction was mixed overnight at 160 °C. The reaction mixture was then allowed to cool down at room temperature and P(OEt)3 was distilled off under vacuum, followed by a flash chromatography in cyclohexane to obtain the final product as white crystals (Yield: 65percent). 1H NMR (400 MHz, CD2Cl2): δ (ppm) 8.02 (d, J = 8.3 Hz, 2H); 7.72 (s, 2H); 7.33 (d, J = 8.3 Hz, 2H). 13C NMR (101 MHz, CD2Cl2): δ (ppm) 141.96, 123.26, 122.55, 122.45, 119.94, 114.84.
62%
for 18 h; Inert atmosphere; Reflux
Into the 4,4'-dibromo-2-nitrobiphenyl (compound f-1) to 16.5g 2-neck RBF takes a vacuum. After all caught the Vacuum fill with nitrogen gas. After that, insert the triethyl phosphite (triethyl phospite) 60mL was refluxed for 18 hours. After the reaction was terminated with vacuum distillation to remove the solvent as much as possible The residue was purified by column chromatography: to give the (nucleic acid eluent) to give the 2,7-dibromo-9H-carbazole (compound f-2). (Yield: 62percent)
51%
With triphenylphosphine In chlorobenzene at 120℃; for 16 h;
A solution of (7) (4.0 g, 11.21 mmol) and triphenylphosphine(7.20 g, 27.45 mmol) in 45 mL of chlorobenzene was stirred at120 C for 16 h. The solution was extracted with ethyl acetate andwater, and the organic phasewas dried with anhydrous MgSO4. Thecrude product was concentrated in vacuo and purified by gelchromatography (silica gel, DCM/hexane 1/2 in volume ratio asthe eluant) to give a white solid (1.86 g, 51percent). 1H NMR (CDCl3, ppm):7.35e7.36 (d, J 8.0 Hz, 2H, aromatic protons), 7.58 (s, 2H, aromaticprotons), 7.86e7.88 (d, J 8.0 Hz, 2H, aromatic protons), 8.10 (s, 1H,eNH). 13C NMR (CDCl3, ppm): 113.83, 119.73, 121.45, 121.79, 132.29,140.29. MASS (EI): m/z 325.
51.2%
With triphenylphosphine In 1,2-dichloro-benzene for 18 h; Reflux; Inert atmosphere
Under nitrogen protection,In 250mlA solution of A3 (10 g, 28.0 mmol), triphenylphosphine (18. 4 g, 70 mmol) and 110 ml of o-dichlorobenzene were added successively under reflux to reflux and reacted for 18 hours with stirring. After completion of the reaction, the reaction solution was allowed to cool to room temperature and then poured into an appropriate amount of water and extracted with methylene chloride. The resulting organic phase was dried over anhydrous magnesium sulfate and the organic solvent was removed by rotary evaporator. The initial product was purified by chromatography And the eluent was petroleum ether / ethyl acetate to give 4.7 g of a pale yellow solid (yield: 51.2percent).
48%
at 150℃; for 24 h; Inert atmosphere
7.8 g of Compound 1 was dissolved in 30 mL of triethylphosphite and stirred well. The above will be under the protection of nitrogen The system was heated to 150 ° C for 24 hours. After vacuum distillation to remove excess solvent, the residue was purified by column chromatography. most A white solid was obtained as a pure product in 48percent yield.
Reference:
[1] Macromolecules, 2018, vol. 51, # 18, p. 7407 - 7416
[2] Journal of Materials Chemistry, 2011, vol. 21, # 13, p. 4918 - 4926
[3] Patent: KR2015/144421, 2015, A, . Location in patent: Paragraph 0312; 0313; 0315
[4] Journal of Organic Chemistry, 2005, vol. 70, # 13, p. 5014 - 5019
[5] Journal of Organic Chemistry, 2017, vol. 82, # 19, p. 9931 - 9936
[6] Patent: CN105001233, 2017, B, . Location in patent: Paragraph 0100; 0102; 0104
[7] Journal of Polymer Science, Part A: Polymer Chemistry, 2010, vol. 48, # 23, p. 5479 - 5489
[8] Patent: WO2014/93225, 2014, A2, . Location in patent: Page/Page column 185
[9] Polymer, 2017, vol. 119, p. 274 - 284
[10] Patent: KR101495152, 2015, B1, . Location in patent: Paragraph 0164; 0168-0169
[11] Macromolecules, 2013, vol. 46, # 10, p. 3850 - 3860
[12] Synthesis, 2003, # 16, p. 2470 - 2472
[13] CrystEngComm, 2017, vol. 19, # 19, p. 2632 - 2643
[14] Polymer, 2014, vol. 55, # 23, p. 6058 - 6068
[15] Patent: CN103951705, 2016, B, . Location in patent: Paragraph 0054-0056
[16] Chemical Communications, 2016, vol. 52, # 57, p. 8838 - 8841
[17] Organic and Biomolecular Chemistry, 2011, vol. 9, # 10, p. 3615 - 3618
[18] Patent: CN106632264, 2017, A, . Location in patent: Paragraph 0028; 0029; 0030
[19] Heterocycles, 2010, vol. 81, # 4, p. 977 - 984
[20] Chemistry Letters, 2008, vol. 37, # 3, p. 344 - 345
[21] Tetrahedron, 2010, vol. 66, # 51, p. 9641 - 9649
[22] Polymer, 2010, vol. 51, # 14, p. 3196 - 3202
[23] Tetrahedron, 2011, vol. 67, # 43, p. 8248 - 8254
[24] Bulletin of the Korean Chemical Society, 2011, vol. 32, # 7, p. 2461 - 2464
[25] Journal of Polymer Science, Part A: Polymer Chemistry, 2011, vol. 49, # 20, p. 4458 - 4467
[26] Chemistry - A European Journal, 2012, vol. 18, # 47, p. 15065 - 15072
[27] Science China Chemistry, 2013, vol. 56, # 8, p. 1119 - 1128
[28] Journal of Polymer Science, Part A: Polymer Chemistry, 2016, vol. 54, # 17, p. 2774 - 2784
[29] Zeitschrift fur Anorganische und Allgemeine Chemie, 2017, vol. 643, # 15, p. 999 - 1003
[30] Journal of Materials Chemistry A, 2017, vol. 5, # 38, p. 20263 - 20276
[31] Journal of Materials Chemistry B, 2017, vol. 5, # 24, p. 4725 - 4731
[32] New Journal of Chemistry, 2018, vol. 42, # 4, p. 2830 - 2837
2
[ 86-74-8 ]
[ 136630-39-2 ]
Yield
Reaction Conditions
Operation in experiment
80%
With N-Bromosuccinimide In tetrahydrofuran for 4 h; Cooling with ice; Darkness; Inert atmosphere
In a 100 mL jar, 1.00 g (5.99 mmol) of carbazole was added, dissolved in tetrahydrofuran, and the jar was placed in an ice bath and protected from light.Then, 2.67 g (15 mmol) of NBS was dissolved in tetrahydrofuran and poured into a constant pressure dropping funnel. The solution was slowly dropped into a 100 mL single-mouth flask, and the mixture was stirred in an ice bath under nitrogen for 4 h.The reaction was poured into 100 mL of water and extracted three times with ethyl acetate.The resulting liquid was spin-dried and subjected to column chromatography with ethyl acetate: petroleum ether = 1:200 to give 1.56 g (4.8 mmol) of white.Solid, compound 2, 80percent yield.
Reference:
[1] Patent: CN107915753, 2018, A, . Location in patent: Paragraph 0029; 0030; 0031
[2] Bulletin of the Korean Chemical Society, 2011, vol. 32, # 7, p. 2461 - 2464
3
[ 301-13-3 ]
[ 439797-69-0 ]
[ 136630-39-2 ]
[ 544436-46-6 ]
Yield
Reaction Conditions
Operation in experiment
70%
at 160℃; for 5 h; Inert atmosphere
General procedure: The 4,4'-dihalo-2-nitrobiphenyl (0.004 mol) and 4-nitrotoluene (0.006 mol) were heated at 160 °C with an excess of trialkyl phosphite (0.05 mol) under argon for 5 h (a-h, j, k) or 17 h (i, m). After cooling the excess of trialkyl phosphite and the trialkyl phosphate were removed under vacuum. The reaction mixture was chromatographed (column 3.x.60 cm) on silica gel in toluene/heptane (1:1 by vol). The main product 7 (Rf=0.8-0.9) was easy separated from the side product 8 (Rf=0.5-0.6). The prepared new materials (7a-m) were characterized by TLC, elemental analysis, melting point, 1H and 13C NMR and FTIR. The chromatographic pure materials 7 were for melting point determination recrystallized from methanol. The non-alkylated carbazoles 8 were identified by means of separately prepared 2,7-diiodocarbazole10 (8a-c), 2,7-dibromocarbazole8 (8d-f), 2,7-dichlorocarbazole7 (8g-i), and with commercial carbazole11 (8j-m).
Reference:
[1] European Journal of Medicinal Chemistry, 1997, vol. 32, # 10, p. 781 - 793
[2] Molecular Crystals and Liquid Crystals, 2006, vol. 459, # 1, p. 85/[365]-94/[374]
[3] Journal of Organic Chemistry, 1991, vol. 56, # 21, p. 6248 - 6250
5
[ 136630-36-9 ]
[ 136630-39-2 ]
Reference:
[1] Patent: US2005/225235, 2005, A1,
6
[ 568592-14-3 ]
[ 136630-39-2 ]
Reference:
[1] Journal of Organic Chemistry, 2003, vol. 68, # 13, p. 5091 - 5103
7
[ 92-86-4 ]
[ 136630-39-2 ]
Reference:
[1] Journal of Organic Chemistry, 2005, vol. 70, # 13, p. 5014 - 5019
[2] Synthesis, 2003, # 16, p. 2470 - 2472
[3] Organic and Biomolecular Chemistry, 2011, vol. 9, # 10, p. 3615 - 3618
[4] Journal of Polymer Science, Part A: Polymer Chemistry, 2010, vol. 48, # 23, p. 5479 - 5489
[5] Journal of Materials Chemistry, 2011, vol. 21, # 13, p. 4918 - 4926
[6] Polymer, 2010, vol. 51, # 14, p. 3196 - 3202
[7] Tetrahedron, 2011, vol. 67, # 43, p. 8248 - 8254
[8] Bulletin of the Korean Chemical Society, 2011, vol. 32, # 7, p. 2461 - 2464
[9] Journal of Polymer Science, Part A: Polymer Chemistry, 2011, vol. 49, # 20, p. 4458 - 4467
[10] Chemistry - A European Journal, 2012, vol. 18, # 47, p. 15065 - 15072
[11] Science China Chemistry, 2013, vol. 56, # 8, p. 1119 - 1128
[12] Macromolecules, 2013, vol. 46, # 10, p. 3850 - 3860
[13] Polymer, 2014, vol. 55, # 23, p. 6058 - 6068
[14] Journal of Polymer Science, Part A: Polymer Chemistry, 2016, vol. 54, # 17, p. 2774 - 2784
[15] Patent: KR101495152, 2015, B1,
[16] Chemical Communications, 2016, vol. 52, # 57, p. 8838 - 8841
[17] Patent: KR2015/144421, 2015, A,
[18] Patent: CN103951705, 2016, B,
[19] Zeitschrift fur Anorganische und Allgemeine Chemie, 2017, vol. 643, # 15, p. 999 - 1003
[20] Journal of Materials Chemistry A, 2017, vol. 5, # 38, p. 20263 - 20276
[21] Patent: CN106632264, 2017, A,
[22] Polymer, 2017, vol. 119, p. 274 - 284
[23] Journal of Materials Chemistry B, 2017, vol. 5, # 24, p. 4725 - 4731
[24] Patent: CN105001233, 2017, B,
[25] CrystEngComm, 2017, vol. 19, # 19, p. 2632 - 2643
[26] New Journal of Chemistry, 2018, vol. 42, # 4, p. 2830 - 2837
[27] Macromolecules, 2018, vol. 51, # 18, p. 7407 - 7416
8
[ 568592-11-0 ]
[ 136630-39-2 ]
Reference:
[1] Journal of Organic Chemistry, 2003, vol. 68, # 13, p. 5091 - 5103
9
[ 568592-12-1 ]
[ 136630-39-2 ]
Reference:
[1] Journal of Organic Chemistry, 2003, vol. 68, # 13, p. 5091 - 5103
10
[ 568592-10-9 ]
[ 136630-39-2 ]
Reference:
[1] Journal of Organic Chemistry, 2003, vol. 68, # 13, p. 5091 - 5103
11
[ 568592-13-2 ]
[ 136630-39-2 ]
Reference:
[1] Journal of Organic Chemistry, 2003, vol. 68, # 13, p. 5091 - 5103
12
[ 91371-12-9 ]
[ 136630-39-2 ]
Reference:
[1] Molecular Crystals and Liquid Crystals, 2006, vol. 459, # 1, p. 85/[365]-94/[374]
[2] European Journal of Medicinal Chemistry, 1997, vol. 32, # 10, p. 781 - 793
[3] Journal of Organic Chemistry, 1991, vol. 56, # 21, p. 6248 - 6250
13
[ 136630-39-2 ]
[ 406726-92-9 ]
Reference:
[1] Journal of Organic Chemistry, 2004, vol. 69, # 17, p. 5705 - 5711
[2] Patent: CN107266354, 2017, A,
[3] Patent: CN107445885, 2017, A,
14
[ 136630-39-2 ]
[ 958261-51-3 ]
Reference:
[1] Patent: KR101495152, 2015, B1,
15
[ 111-25-1 ]
[ 136630-39-2 ]
[ 654676-12-7 ]
Yield
Reaction Conditions
Operation in experiment
99%
With N-benzyl-N,N,N-triethylammonium chloride; sodium hydroxide In water; toluene at 80℃; for 14 h;
General procedure: A mixture of the corresponding 2,7-disubstituted 9H-carbazole (for the synthesis see Supplementary data) (10mmol), alkylbromide (10.5mmol), BnEt3NCl (0.227g, 1mmol), toluene (20mL) and NaOH solution (0.42g, 10.5mol, in water 50percentw/v) was stirred at 80°C for 14h. Then the reaction mixture was cooled to rt., poured into 50mL of water and acidified with 10percent hydrochloric acid to pH∼2. Organic layer was separated and water phase additionally was extracted with toluene (2×10mL). Combined extracts were washed with water (2×25mL), dried over Na2SO4, filtered and evaporated to dryness. The obtained crude products of the alkylation reaction were purified by column chromatography to give N-alkylcarbazoles 1a–f.
99.8%
With sodium hydride In dimethyl sulfoxide at 20 - 30℃; Inert atmosphere
Under the protection of argon, in 100 ml of the three-port are sequentially added in the bottle 2,7-dibromo diphenylenimine 4.88g (15mmol), hydrogenated sodium 0.72g, DMSO solvent 30 ml, controlling the reaction temperature 20-30°C, dropwise 1-bromo-hexane, HPLC detection reaction is ended. 100 ml water quenching, with 100 ml dichloromethane extraction, layered, for water 50 ml dichloromethane extraction, combined with the phase, drying by anhydrous magnesium sulphate, pressure reducing and recovering the solvent, the crude solid obtained, using dichloromethane-methanol of performing recrystallization, get white product 2,7-di-bromo-N-hexyl carbazole 5.87g, purity 99.8percent (HPLC), the yield of 95.6percent, melting point 70.6-72.5 °C. 1 HNMR (400MHz, CDCl 3), δ: 0.858-0.906 (3H, t), 1.295-1.351 (6H, m), 1.786-1.885 (2H, m), 4.168-4.217 (2H, t), 7.320-7.354 (2H, dd), 7.525-7.530 (2H, d), 7.875-7.903 (2H, d).
Reference:
[1] Dyes and Pigments, 2016, vol. 124, p. 133 - 144
[2] Patent: CN105384679, 2016, A, . Location in patent: Paragraph 0009; 0025; 0026; 0027
[3] Journal of Materials Chemistry C, 2016, vol. 4, # 26, p. 6270 - 6279
[4] Heterocycles, 2010, vol. 81, # 4, p. 977 - 984
[5] Journal of Organic Chemistry, 2008, vol. 73, # 23, p. 9207 - 9213
[6] Tetrahedron, 2011, vol. 67, # 43, p. 8248 - 8254
[7] Chemistry - A European Journal, 2012, vol. 18, # 47, p. 15065 - 15072
[8] Journal of Polymer Science, Part A: Polymer Chemistry, 2016, vol. 54, # 17, p. 2774 - 2784
Stage #1: With potassium hydroxide In dimethyl sulfoxide at 80℃; for 1 h; Stage #2: Heating
9-Heptadecanyl-2,7-dibromocarbazole (9): 2,7-dibromo-9-H-carbazole (4 g, 12 mmol) and potassium hydroxide (0.84 g, 17.8 mmol) were solubilized in dry DMSO (40 mL). The reaction mixture was heated at 80 °C for 1 h before adding dropwise a solution of 9-Heptadecane p-toluenesulfonate (6.4 g, 15.6 mmol) in 60 mL of dry DMSO. After cooling down at room temperature, the reaction mixture was poured into 300 mL of water and extracted three times with 100 mL of diethylether, dried over magnesium sulfate and the solvent was removed under vacuum. The white powder was purified by flash chromatography in cyclohexane to afford white crystals (yield: 90percent). 1H NMR (400 MHz, CDCl3): δ (ppm) 7.5 (s, 2H); 7.27 (s, 2H); 7.12 (m, 2H), 4.48 (tt, J = 10.1, 5.1 Hz, 1H); 2.20 (m, 2H); 1.83 (m, 2H) 1.32-1.02 (m, 28H); 0.83 (t, J = 7.0 Hz, 6H). 13C NMR (100 MHz, CDCl3): δ (ppm) 125.61; 125.23; 120.43; 118.54; 111.70, 108.87, 56.43; 33.85; 31.89; 29.53; 29.43; 29.30; 26.94; 22.73; 14.20. HRMS (EI+, m/z) [M]+ calculated (percent) for C29H41Br2N: 561.16057, found 561.16261.
78%
With potassium hydroxide In dimethyl sulfoxide for 24 h;
After loading the compound f-2 (1g) To a round flask, place the compound 4-f (1.9g, 1.5eq). And after inserting the KOH (1g, 5eq) above, it is injected DMSO as a solvent. And then stirred for 24 hours, the organic layer was extracted with MC and the salt water to remove the remaining water over anhydrous magnesium sulfate and, after evaporation of the solvent was recrystallized from a MC and MeOH as a white solid 2,7-dibromo-9- (heptadecane and the -9-yl) -9H-carbazole (compound f-5) obtained. (Yield: 78percent)
Reference:
[1] Polymer, 2017, vol. 119, p. 274 - 284
[2] Macromolecules, 2010, vol. 43, # 22, p. 9376 - 9383
[3] Patent: KR101495152, 2015, B1, . Location in patent: Paragraph 0164; 0177-0178
[4] Journal of the American Chemical Society, 2012, vol. 134, # 46, p. 19035 - 19042
[5] Journal of Polymer Science, Part A: Polymer Chemistry, 2015, vol. 53, # 17, p. 2059 - 2068
[6] Macromolecules, 2012, vol. 45, # 21, p. 8658 - 8664
18
[ 591-50-4 ]
[ 136630-39-2 ]
[ 444796-09-2 ]
Yield
Reaction Conditions
Operation in experiment
80%
With palladium diacetate; tris-(o-tolyl)phosphine; sodium t-butanolate In toluene
2.5 g (8 mmol) 4,4’-dibromo biphenyl was used(utilized) to perform a cyclization reaction to synthesize 2.08g (80percent) of 4,4’-dibromo carbazole. The 4,4’-dibromo carbazole and iodinated phenyl were dissolved in 40 ml of toluene to synthesize Intermediate C through a buchwald reaction.
78%
With copper; potassium carbonate In N,N-dimethyl-formamide at 130℃; Inert atmosphere
Synthesis of 2,7-dibromo-9-phenyl-9H-carbazole A mixture of 32.5 g (100 mmole) 2,7-dibromo-9H-carbazole, 20.4 g (100 mmole) iodobenzene, 9.5 g (150 mmole) of copper powder, 27.6 g (200 mmole) of potassium carbonate, and 600 ml dimethylformamide were heated at 130° C. under nitrogen overnight, then cooled to room temperature, the solution was filtered. The filtrate was extracted three times with dichloromethane and water, dried with anhydrous magnesium sulfate, the solvent was evaporated in vacuum. The residue was purified by column chromatography on silica(hexane-dichloromethane) afforded a white solid (31.3 g, 78 mmol, 78percent).
70%
With copper; potassium carbonate In 1,2-dichloro-benzene at 140℃; for 12 h;
2,7-dibromo-9H-carbazole (3.0 g, 9.32 mmol), iodobenzene (2.1 g, 10.25 mmol), copper powder (1.8 g,27.95 mmol) and potassium carbonate (4.1 g, 29.81 mmol) were added to stirred 60 mL o-dichlorobenzene, the system at 140 °C Reflow for 12 hours. At the end of the reaction, 20 mL of distilled water was added thereto, followed by extraction with ethyl acetate, and the organic phases were combined. After drying over anhydrous magnesium sulfate, it was concentrated and column chromatography afforded 2,7-dibromo-9-phenyl-carbazole (2.4 g, 70percent yield).
Reference:
[1] Patent: KR2015/144421, 2015, A, . Location in patent: Paragraph 0312; 0313; 0315
[2] Journal of Materials Chemistry, 2011, vol. 21, # 13, p. 4918 - 4926
[3] Patent: US2016/204345, 2016, A1, . Location in patent: Paragraph 0034-035
[4] Patent: CN107827808, 2018, A, . Location in patent: Paragraph 0080; 0081; 0082; 0083; 0094; 0095; 0096; 0097
[5] Journal of Materials Chemistry, 2011, vol. 21, # 15, p. 5638 - 5644
[6] RSC Advances, 2015, vol. 5, # 64, p. 51512 - 51523
[7] Patent: US9166177, 2015, B2,
19
[ 108-86-1 ]
[ 136630-39-2 ]
[ 444796-09-2 ]
Reference:
[1] Patent: CN108203427, 2018, A, . Location in patent: Paragraph 0119; 0120
With potassium carbonate In N,N-dimethyl-formamide at 60℃;
88%
With potassium carbonate In N,N-dimethyl-formamide Heating;
78%
Stage #1: 2,7-dibromo-9H-carbazole With potassium carbonate In N,N-dimethyl-formamide at 70℃; for 0.166667h;
Stage #2: 4-Fluoronitrobenzene In N,N-dimethyl-formamide for 48h; Reflux; Inert atmosphere;
2.3.1 Syntheses of 2,7-dibromo-9-(4-nitrophenyl)-9-carbazole (1)
Freshly calcined K2CO3 (13.06 g, 194.6 mmol) and dry dimethylformamide (DMF) (100 mL) were loaded into a flask. The suspension was stirred at 70 ° for 15 min, then 2,7-dibromocarbazole (6.15 g, 18.9 mmol) was added, and in 10 min, 4-fluoronitrobenzene (10.62 g, 75.5 mmol) was also placed into the reaction vessel. The solution was boiled for 48 h in argon atmosphere, then poured into water. The precipitate was filtered off, washed with hot water and ethanol. Pure 2,7-dibromo-9-(4-nitrophenyl)-9H-carbazole was obtained by chromatographic purification on a silica gel column (eluent: toluene/petroleum ether, 2/3). Yield: 78%. 1H NMR (CDCl3, 400 Hz): δH 8.56 (2H, d), 7.98 (2H, d), 7.78 (2H, d), 7.59 (2H, s), 7.49 (2H, d). Anal. calcd for CHNOBr: C, 48.45; H, 2.29; N, 6.28. Found: C, 48.24; H, 2.39; N, 6.15.
Stage #1: 2,7-dibromo-9H-carbazole With potassium <i>tert</i>-butylate In tetrahydrofuran at 20℃; for 0.333333h; Inert atmosphere; Schlenk technique;
Stage #2: 3-bromomethylheptane In tetrahydrofuran Reflux; Inert atmosphere; Schlenk technique;
96%
Stage #1: 2,7-dibromo-9H-carbazole With sodium hydride In N,N-dimethyl-formamide for 0.5h;
Stage #2: 3-bromomethylheptane In N,N-dimethyl-formamide for 18h;
93.6%
Stage #1: 2,7-dibromo-9H-carbazole With sodium hydride In N,N-dimethyl-formamide; mineral oil at 20℃; for 0.5h; Inert atmosphere;
Stage #2: 3-bromomethylheptane In N,N-dimethyl-formamide; mineral oil at 90℃; Inert atmosphere;
82%
With sodium hydride In N,N-dimethyl-formamide; mineral oil at 20℃; for 24h; Inert atmosphere;
Synthesis of 2,7-dibromo-9-(2-ethylhexyl)carbazole
Analogously to the description in [S2], a solution of 2,7-dibromocarbazole (1.00 g, 3.10 mmol) and NaH (0.2 g, 4.5 mmol) in DMF (5 mL) was degassed with nitrogen for 15 min. 2-Ethylhexyl bromide (0.90 g, 4.5 mmol) was added by a syringe. The mixture was stirred at room temperature for 24 h. Water was added, and the organic layer was extracted with CH2Cl2 (30 mL × 3). After the combined organic layers were dried over MgSO4, the solvent was removed under reduced pressure. Column chromatography (SiO2, hexane) gave the desired product as colorless liquid (1.1 g, 82%). 1H NMR (300 MHz, CDCl3): δ 7.85 (d, J = 8.3 Hz, 2H), 7.48 (d, J = 1.1 Hz, 2H), 7.33 (dd, J = 1.4, 8.3 Hz, 2H), 4.00 (dd, J = 2.7, 7.5 Hz, 2H), 2.33-1.70 (m, 1H), 1.45-1.15 (m, 8H), 1.02-0.82 ppm (m, 6H). 13C NMR (75 MHz, CDCl3): δ 142.70, 123.35, 122.26, 122.07, 120.49, 113.12, 48.39, 39.84, 31.46, 29.23, 25.00, 23.72, 14.70, 11.56 ppm. IR (neat): ν = 2958, 2925, 2859, 1859, 1682, 1620, 1584, 1482, 1451, 1327, 1310, 1225, 1247, 1131, 1054, 997, 967, 946, 910, 876, 843, 820, 796, 767, 743, 701, 685, 666, 651, 638 cm-1
80%
Stage #1: 2,7-dibromo-9H-carbazole With potassium carbonate In N,N-dimethyl-formamide at 80℃; for 2h; Inert atmosphere; Enzymatic reaction;
Stage #2: 3-bromomethylheptane In N,N-dimethyl-formamide at 80℃; for 24h;
78%
With potassium carbonate In N,N-dimethyl-formamide at 80℃; for 24h;
65%
With potassium hydroxide In water; dimethyl sulfoxide at 50℃; for 24h; Inert atmosphere;
58%
With potassium carbonate In N,N-dimethyl-formamide at 70℃; for 24h;
With tetrabutylammomium bromide; sodium hydroxide In dimethyl sulfoxide at 20℃; for 8h;
2.4.2. Synthesis of compound 5
General procedure: According to the literature [58], to a mixture of 2,7-dibromo-9Hfluorene(3.24 g, 10 mmol), bromooctane (4 mL, 23 mmol) andtetrabutylammonium bromide (TBAB, catalytic amount) in DMSO(100 mL) was added sodium hydroxide solution (25 mL, 50 wt%).The resulting mixture was stirred at room temperature for 8 h. Theprogress of the reactionwas monitored by TLC using hexane:CH2Cl2as the eluent. After completion of the reaction, the reaction mixturewas poured into water and extracted with CH2Cl2. The organiclayers were separated, dried over anhydrous MgSO4, and filtered.Solvents were removed under reduced pressure and the cruderesiduewas further purified by column chromatography (hexane aseluent) to afford the compound 5 as a white solid (4.95 g, yield:91%).
91%
With tetrabutylammomium bromide; sodium hydroxide In dimethyl sulfoxide at 20℃; for 10h;
5
General procedure: Into a 250mL single-necked flask, added the compound 2, 7-dibromofluorene (3.24 g, 10mmol), DMSO (100mL), the amount of TBAB and sodium hydroxide solution (25mL, 50wt %), after stirring at room temperature for a few minutes, added the drops of bromo-n-octane (4mL, 23mmol) with a syringe, and carry on reaction at room temperature for 10h. Stop the reaction, by using hydrochloric acid adjust the pH-= 7, extracted with ethyl acetate, washed with saturated brine, and dried over anhydrous magnesium sulfate. Filter, the filtrate is evaporated to remove the solvent, the crude product is purified by silica gel (200-300 mesh) column chromatography [eluent, petroleum ether] and obtained 4.91 g white solid 2,7-dibromo-9,9-dioctylfluorene, yield 90%.
89%
With potassium carbonate In N,N-dimethyl-formamide for 10h; Inert atmosphere; Reflux;
1.1; 2.1 (1) Synthesis of compound a:
under the protection of nitrogen, add 2,7-dibromo-9H-carbazole (10mmol), 1-bromo-octane (11mmol), potassium carbonate (0.1mmol), 70mL into a three-necked flask DMF solvent. After refluxing and stirring the reaction for 10 hours, it was cooled to room temperature. Extract with dichloromethane, dry the organic phase with magnesium sulfate, spin-dry the solvent to obtain a crude product. Purified by a silica gel chromatographic column, the target compound a is obtained with a yield of 89%.
88%
With sodium hydroxide In N,N-dimethyl-formamide at 20℃;
84%
With potassium carbonate In N,N-dimethyl-formamide at 80℃; for 16h;
82%
With potassium carbonate In N,N-dimethyl-formamide at 80℃; for 12h;
81.3%
With sodium hydroxide In dimethyl sulfoxide at 20℃; for 4h;
2.1.7. 2,7-Dibromo-N-octylcarbazole (7)
To a solution of 2,7-dibromocarbazole (1.63 g, 50.0 mmol) in10 mL DMSO were added 1-bromooctane (1.45 g, 75.0 mmol) and5 mL of a 50% NaOH solution. The mixture was stirred at room temperature for 4 h. The reaction mixture was extracted withdiethyl ether and then dried over MgSO4. After evaporation of thesolvent, the resulting crude solid was purified by silica gel columnchromatography (hexane) to obtain a white solid (1.77 g, 81.3%). 1HNMR (CDCl3), δ (ppm): 7.83 (s, 2H), 7.46 (d, J = 2.0 Hz, 2H), 7.31 (d,J = 8.0 Hz, 2H), 4.28 (t, J = 7.0 Hz, 2H), 1.83 (m, 2H), 1.50-1.20 (m,8H), 0.86 (m, 2H), 0.82 (t, J = 7.0 Hz, 3H).
80%
Stage #1: 2,7-dibromo-9H-carbazole With sodium hydride In N,N-dimethyl-formamide at 0 - 23℃; for 0.5h;
Stage #2: 1-bromo-octane In N,N-dimethyl-formamide at 23℃; for 12h;
2,7-Dibromo-9-octyl-9H-carbazole (14b).
2,7-Dibromocarbazole (13) (300 mg, 0.923 mmol) and NaH (48.0 mg, 1.20 mmol) was dissolved in DMF (5.0 mL) at 0 . After stirring at room temperature for 30 min, 1-bromooctane (340 μL, 1.93 mmol) was added to the mixture and stirred at room temperature for 12 h. The reaction was quenched with addition of H2O and diluted with EtOAc. The organic layer was washed with brine, dried over MgSO4, and concentrated in vacuo. The residue was purified by flash column chromatography (n-hexane/EtOAc = 50:1) to give compound 14b (324 mg, 80%, white solid). 1H NMR (400 MHz, CDCl3): δ 0.87 (t, J = 6.9 Hz, 3H), 1.24-1.33 (m, 10H), 1.76-1.83 (m, 2H), 4.12 (t, J = 7.4 Hz, 2H), 7.31 (dd, J = 1.6, 8.3 Hz, 2H), 7.49 (d, J = 1.5 Hz, 2H), 7.83 (d, J = 8.2 Hz, 2H); 13C NMR (100 MHz, CDCl3): δ 14.09, 22.63, 27.18, 28.77, 29.17, 29.29, 31.79, 43.33, 112.00, 119.70, 121.29, 121.45, 122.52, 141.36.
77.4%
Stage #1: 2,7-dibromo-9H-carbazole With sodium hydride In dimethyl sulfoxide at 0℃; for 0.5h; Inert atmosphere;
Stage #2: 1-bromo-octane In dimethyl sulfoxide at 20℃; Inert atmosphere;
1.5 Preparation of 2,7-dibromo-9-octylcarbazole (A5)
Under nitrogen protection,A4 (2 g, 6.2 mmol) was added sequentially to a 50 ml round bottom flask,30 ml of anhydrous dimethylsulfoxide was reduced to 0 ° C, and sodium cyanide (0. 3 g, 12.3 mmol) was added under stirring. After stirring for 30 minutes, 1-bromooctane (1. 19 g, 6 .15_01), raise the temperature of the system to room temperature, continue to react overnight. After completion of the reaction, the reaction solution was poured into an appropriate amount of water and extracted with methylene chloride. The resulting organic phase was dried over anhydrous magnesium sulfate and the organic solvent was removed by rotary evaporator. The initial product was purified by chromatography on a column of eluent Ether / dichloromethane to give 2. 08 g of a pale yellow solid (yield: 77.4%).
With sodium hydride In N,N-dimethyl-formamide at 20℃;
With tetra-n-propylammonium perruthenate.; sodium hydroxide In butanone at 70℃;
With sodium hydride In N,N-dimethyl-formamide at 20℃;
Stage #1: 2,7-dibromo-9H-carbazole With sodium hydride In N,N-dimethyl-formamide at 0℃; for 0.5h;
Stage #2: 1-bromo-octane In N,N-dimethyl-formamide at 20℃;
1.1
(1) One gram of 2,7-dibromocarbazole was dissolved in 30 mlN, N-dimethyl-formamide (DMF) solution,The above solution was placed in a 0 ° C ice bath,1.2 equivalents of 74 mg sodium hydride was added slowly,After stirring for half an hour,1.5 equivalents of 1-bromooctane were slowly added,After overnight reaction at room temperature, the product was obtained by column chromatography.
Stage #1: 2,7-dibromo-9H-carbazole With sodium hydride In N,N-dimethyl-formamide at 0℃; for 0.5h;
Stage #2: 1-bromo-octane In N,N-dimethyl-formamide at 20℃;
1.1
(1) Dissolving 1 gram of 2,7-dibromocarbazole in 30 ml of N,N-dimethylformamide (DMF) solution,The above solution was placed in an ice bath at 0 ° C, and 1.2 equivalent of 74 mg of sodium hydride solid was slowly added.After stirring for half an hour, 1.5 equivalents of 1-bromooctane were slowly added, and after reacting at room temperature overnight,The product was obtained by column chromatography.
2,7-dibromo-9-(2-decyltetradecyl)-9H-carbazole[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
91%
With potassium hydroxide; In N,N-dimethyl-formamide; at 60℃; for 8h;Inert atmosphere;
2,7-dibromocarbazole (32.5 g,100mmol) and potassium hydroxide (28g, 500mmol) are dissolved in 200mL DMF,Heated to 60 C under nitrogen,At this point, 2-decylromotetradecane (62.55 g, 150 mmol) was slowly added.Reaction for 8 hours. Stop the reaction and cool to room temperature,The reaction solution was poured into water and extracted with dichloromethane. Purified by column chromatography,Using 200-300 mesh silica gel as the stationary phase and petroleum ether as the eluent, a white waxy solid (60 g, 91%) was obtained.
<strong>[136630-36-9]4,4'-dibromo-2,2'-diaminobiphenyl</strong> (3.5 g, 10.23 mmol) was dissolved in phosphoric acid and heated at 190 C. for 24 hours. The reaction mixture was cooled to room temperature and then NaHCO3 (aq) was gradually added thereto to form a solid. Then, the solid was filtered to obtain 2,7-dibromocarbazole (2.2 g, 66%), the compound represented by formula e. MS [M+] 323.
With N-benzyl-N,N,N-triethylammonium chloride; sodium hydroxide; In water; toluene; at 80℃; for 14h;
General procedure: A mixture of the corresponding 2,7-disubstituted 9H-carbazole (for the synthesis see Supplementary data) (10mmol), alkylbromide (10.5mmol), BnEt3NCl (0.227g, 1mmol), toluene (20mL) and NaOH solution (0.42g, 10.5mol, in water 50%w/v) was stirred at 80C for 14h. Then the reaction mixture was cooled to rt., poured into 50mL of water and acidified with 10% hydrochloric acid to pH∼2. Organic layer was separated and water phase additionally was extracted with toluene (2×10mL). Combined extracts were washed with water (2×25mL), dried over Na2SO4, filtered and evaporated to dryness. The obtained crude products of the alkylation reaction were purified by column chromatography to give N-alkylcarbazoles 1a-f.
99.8%
With sodium hydride; In dimethyl sulfoxide; at 20 - 30℃;Inert atmosphere;
Under the protection of argon, in 100 ml of the three-port are sequentially added in the bottle 2,7-dibromo diphenylenimine 4.88g (15mmol), hydrogenated sodium 0.72g, DMSO solvent 30 ml, controlling the reaction temperature 20-30C, dropwise 1-bromo-hexane, HPLC detection reaction is ended. 100 ml water quenching, with 100 ml dichloromethane extraction, layered, for water 50 ml dichloromethane extraction, combined with the phase, drying by anhydrous magnesium sulphate, pressure reducing and recovering the solvent, the crude solid obtained, using dichloromethane-methanol of performing recrystallization, get white product 2,7-di-bromo-N-hexyl carbazole 5.87g, purity 99.8% (HPLC), the yield of 95.6%, melting point 70.6-72.5 C. 1 HNMR (400MHz, CDCl 3), δ: 0.858-0.906 (3H, t), 1.295-1.351 (6H, m), 1.786-1.885 (2H, m), 4.168-4.217 (2H, t), 7.320-7.354 (2H, dd), 7.525-7.530 (2H, d), 7.875-7.903 (2H, d).
87.3%
To a mixture of compound 11 (18.09g, 0.053mol) in THF (74mL) was added KI (0.094g, 0.53mmol), sodium tert-butoxide (21.37g, 0.221mol) and 1-bromohexane (10.2mL, 0.074mol). The resulting solution was stirred at 80C for 9h. Then pyridine (7.4mL) was added and the whole system was refluxed for 30min. The above solution was quenched with 1N HCl to neutral and then extracted with ethyl acetate (50mL×3). The organic layer was collected and dried over MgSO4(S). After filtration and removal of the solvent, the crude product was purified with column chromatography on silica gel using hexane as eluent to afford the white solid with yield of 87.3% (19.85g). 1H NMR (300MHz, CDCl3) δ: 7.81-7.78 (d, J=8.4Hz, 2H, H5), 7.467-7.462 (d, J=1.5Hz, 2H, H2), 7.30-7.27 (dd, J1=8.1Hz, J2=1.5Hz, 2H, H4), 4.10-4.05 (m, 2H, Hf), 1.79-1.74 (m, 2H, He), 1.29 (m, 6H, Hb, Hc, Hd), 0.88-0.83 (m, 3H, Ha); 13C NMR (75MHz, CDCl3) δ: 141.24 (C1), 122.43 (C4), 121.37 (C5), 121.18 (C6), 119.62 (C3), 111.89 (C2), 43.24 (Cf), 31.44 (Ce), 28.69 (Cd), 26.79 (Cc), 22.50 (Cb), 13.96 (Ca); MALDI-TOF (m/z): [M]+ calcd for C18H19Br2N, 409.1639; found, 409.1652.
With copper(l) iodide; caesium carbonate In N,N-dimethyl-formamide at 220℃; for 0.5h; Microwave irradiation;
4.2. General experimental procedure for microwave-assisted N-arylation of carbazoles
General procedure: 9H-Carbazole (1.0 mmol), Cs2CO3 (1.0 mmol), iodobenzene (1.1 mmol), CuI (0.1 mmol), and DMF (2 mL) were added to a 5-mL vial. The vial was sealed with a crimp cap and placed in a Biotage initiator microwave cavity. After irradiation at 220 °C for the appropriate time and subsequent cooling, the reaction mixture was diluted with saturated aqueous ammonium chloride. Products were isolated by extraction into ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated. Products were purified by silica gel column chromatography using a hexane/ethyl acetate solvent. N-Phenyl-carbazole (2a)22 was obtained (96% yield) as a white solid.
70%
With copper(l) iodide; caesium carbonate; lithium chloride In N,N-dimethyl-formamide at 150℃; for 48h;
47%
With copper(I) oxide; 2,2,6,6-tetramethylheptane-3,5-dione; potassium hydroxide In N,N-dimethyl-formamide at 130℃; for 24h; Inert atmosphere; Schlenk technique;
With sodium hydride In N,N-dimethyl-formamide at 20℃; Inert atmosphere;
96%
With tetrabutylammomium bromide; potassium carbonate In N,N-dimethyl-formamide at 145℃; for 24h; Inert atmosphere;
84%
With sodium hydroxide In N,N-dimethyl-formamide Inert atmosphere;
76%
With sodium hydride In N,N-dimethyl-formamide at 20℃; for 24h; Inert atmosphere;
69%
Stage #1: 2,7-dibromo-9H-carbazole With sodium hydride In N,N-dimethyl-formamide at 0 - 23℃; for 0.5h;
Stage #2: 1-dodecylbromide In N,N-dimethyl-formamide at 23℃; for 12h;
2,7-Dibromo-9-dodecyl-9H-carbazole (14d).
2,7-Dibromocarbazole (13) (300 mg, 0.923 mmol) and NaH (48.0 mg, 1.20 mmol) was dissolved in DMF (5.0 mL) at 0 . After stirring at room temperature for 30 min, 1-bromododecane (470 μL, 1.93 mmol) was added to the mixture and stirred at room temperature for 12 h. The reaction was quenched with addition of H2O and diluted with EtOAc. The organic layer was washed with brine, dried over MgSO4, and concentrated in vacuo. The residue was purified by flash column chromatography (n-hexane/EtOAc = 50:1) to give compound 14d (312 mg, 69%, white solid). 1H NMR (400 MHz, CDCl3): 0.87 (t, J = 6.9 Hz, 3H), 1.24-1.35 (m, 18H), 1.78-1.86 (m, 2H), 4.16 (t, J = 7.4 Hz, 2H), 7.33 (dd, J = 1.6, 8.3 Hz, 2H), 7.51 (d, J = 1.6 Hz, 2H), 7.87 (d, J = 8.3 Hz, 2H); 13C NMR (100 MHz, CDCl3): δ 14.16, 22.72, 27.19, 28.79, 29.35, 29.52, 29.59, 29.63, 31.94, 43.86, 112.02, 119.70, 121.28, 121.49, 122.52, 141.36.
47%
With potassium carbonate In N,N-dimethyl-formamide at 80℃; for 16h; Inert atmosphere;
With copper(l) iodide; 1,10-Phenanthroline; potassium carbonate; In water; N,N-dimethyl-formamide;
2,7-dibromo-9H-carbazole (3.25 g, 10.0 mmol), 1-iodobenzene(2.45 g, 12.0 mmol), K2CO3 (4.17 g, 30 mmol), CuI (0.38 g, 2.0 mmol), 1,10-Phenanthroline hydrate (0.40 g, 2.0 mmol) andDMF (30.0 mL) were added to a 100 mL flask. The mixture washeated to 160 C under nitrogen for 24 h. After cooling to roomtemperature, the reaction mixture was extracted with dichloromethaneand water. The combined organic layers were dried overNa2SO4, filtered, and evaporated under reduced pressure. The cruderesidue was purified by column chromatography with dichloromethaneand petroleum ether as eluent to afford 3.80 g of whitesolid, in 92.9% yield. 1H NMR (500 MHz, CDCl3, d): 7.94 (d, J 8.2 Hz,2H), 7.65 (t, J 7.6 Hz, 2H), 7.54-7.47 (m, 5H), 7.40 (t, J 8.2 Hz, 2H).
80%
With palladium diacetate; tris-(o-tolyl)phosphine; sodium t-butanolate; In toluene;
2.5 g (8 mmol) 4,4?-dibromo biphenyl was used(utilized) to perform a cyclization reaction to synthesize 2.08g (80%) of 4,4?-dibromo carbazole. The 4,4?-dibromo carbazole and iodinated phenyl were dissolved in 40 ml of toluene to synthesize Intermediate C through a buchwald reaction.
78%
With copper; potassium carbonate; In N,N-dimethyl-formamide; at 130℃;Inert atmosphere;
Synthesis of 2,7-dibromo-9-phenyl-9H-carbazole A mixture of 32.5 g (100 mmole) 2,7-dibromo-9H-carbazole, 20.4 g (100 mmole) iodobenzene, 9.5 g (150 mmole) of copper powder, 27.6 g (200 mmole) of potassium carbonate, and 600 ml dimethylformamide were heated at 130 C. under nitrogen overnight, then cooled to room temperature, the solution was filtered. The filtrate was extracted three times with dichloromethane and water, dried with anhydrous magnesium sulfate, the solvent was evaporated in vacuum. The residue was purified by column chromatography on silica(hexane-dichloromethane) afforded a white solid (31.3 g, 78 mmol, 78%).
70%
With copper; potassium carbonate; In 1,2-dichloro-benzene; at 140℃; for 12h;
2,7-dibromo-9H-carbazole (3.0 g, 9.32 mmol), iodobenzene (2.1 g, 10.25 mmol), copper powder (1.8 g,27.95 mmol) and potassium carbonate (4.1 g, 29.81 mmol) were added to stirred 60 mL o-dichlorobenzene, the system at 140 C Reflow for 12 hours. At the end of the reaction, 20 mL of distilled water was added thereto, followed by extraction with ethyl acetate, and the organic phases were combined. After drying over anhydrous magnesium sulfate, it was concentrated and column chromatography afforded 2,7-dibromo-9-phenyl-carbazole (2.4 g, 70% yield).
With potassium carbonate;
Synthesis of 2,7-dibromo-9-phenyl-9H-carbazole A mixture of 32.5 g (100 mmole) 2,7-dibromo-9H-carbazole, 20.4 g (100 mmole) iodobenzene, 9.5 g (150 mmole) of copper powder, 27.6 g (200 mmole) of potassium carbonate, and 600 ml dimethylformamide were heated at 130 C. under nitrogen overnight, then cooled to room temperature, the solution was filtered. The filtrate was extracted three times with dichloromethane and water, dried with anhydrous magnesium sulfate, the solvent was evaporated in vacuum. The residue was purified by column chromatography on silica(hexane-dichloromethane) afforded a white solid (31.3 g, 78 mmol, 78%).
toluene-4-sulfonic acid 1-octyl-nonyl ester[ No CAS ]
[ 136630-39-2 ]
[ 955964-73-5 ]
Yield
Reaction Conditions
Operation in experiment
90%
9-Heptadecanyl-2,7-dibromocarbazole (9): 2,7-dibromo-9-H-carbazole (4 g, 12 mmol) and potassium hydroxide (0.84 g, 17.8 mmol) were solubilized in dry DMSO (40 mL). The reaction mixture was heated at 80 C for 1 h before adding dropwise a solution of 9-Heptadecane p-toluenesulfonate (6.4 g, 15.6 mmol) in 60 mL of dry DMSO. After cooling down at room temperature, the reaction mixture was poured into 300 mL of water and extracted three times with 100 mL of diethylether, dried over magnesium sulfate and the solvent was removed under vacuum. The white powder was purified by flash chromatography in cyclohexane to afford white crystals (yield: 90%). 1H NMR (400 MHz, CDCl3): delta (ppm) 7.5 (s, 2H); 7.27 (s, 2H); 7.12 (m, 2H), 4.48 (tt, J = 10.1, 5.1 Hz, 1H); 2.20 (m, 2H); 1.83 (m, 2H) 1.32-1.02 (m, 28H); 0.83 (t, J = 7.0 Hz, 6H). 13C NMR (100 MHz, CDCl3): delta (ppm) 125.61; 125.23; 120.43; 118.54; 111.70, 108.87, 56.43; 33.85; 31.89; 29.53; 29.43; 29.30; 26.94; 22.73; 14.20. HRMS (EI+, m/z) [M]+ calculated (%) for C29H41Br2N: 561.16057, found 561.16261.
78%
With potassium hydroxide; In dimethyl sulfoxide; for 24h;
After loading the compound f-2 (1g) To a round flask, place the compound 4-f (1.9g, 1.5eq). And after inserting the KOH (1g, 5eq) above, it is injected DMSO as a solvent. And then stirred for 24 hours, the organic layer was extracted with MC and the salt water to remove the remaining water over anhydrous magnesium sulfate and, after evaporation of the solvent was recrystallized from a MC and MeOH as a white solid 2,7-dibromo-9- (heptadecane and the -9-yl) -9H-carbazole (compound f-5) obtained. (Yield: 78%)
With tetrakis(triphenylphosphine)palladium (0); In ethanol; toluene;
Example 6 Synthesis of Carbazole Derivative 6 Toluene (80 mL), ethanol (20 mL) and 2M sodium carbonate aqueous solution (40 g) were added to a mixture of 2,7-dibromocarbazole (6.50 g), phenylboronic acid (7.32 g) and tetrakistriphenylphosphine palladium (0.734 g), followed by refluxing under nitrogen flow for 3 hours. The resultant mixture was left to cool to room temperature. Then, the insoluble matter was filtrated and the solvent was evaporated, to thereby obtain 4.15 g of 2,7-diphenylcarbazole as pale brown powder.
With caesium carbonate In N,N-dimethyl-formamide at 150℃; for 24h;
Metal-Free N-Arylation of Carbazoles; General Procedure
General procedure: A mixture of a fluorinated aryl halide (2.0 mmol), a carbazole (0.5 mmol), and a base (2.0 mmol) in solvent (2 mL) was allowed to react under air atmosphere. The reaction mixture was heated to the specified temperature for 24 h. After reaction completion, the mixture was added to brine (15 mL) and extracted with CH2Cl2 (3 × 15 mL). The combined extract was concentrated under reduced pressure and the product was isolated by short chromatography on a silica gel (200-300 mesh) column.
With caesium carbonate In N,N-dimethyl acetamide at 150℃; for 24h;
With caesium carbonate In N,N-dimethyl-formamide at 150℃; for 24h;
With caesium carbonate In N,N-dimethyl-formamide at 150℃; for 24h;
Metal-Free N-Arylation of Carbazoles; General Procedure
General procedure: A mixture of a fluorinated aryl halide (2.0 mmol), a carbazole (0.5 mmol), and a base (2.0 mmol) in solvent (2 mL) was allowed to react under air atmosphere. The reaction mixture was heated to the specified temperature for 24 h. After reaction completion, the mixture was added to brine (15 mL) and extracted with CH2Cl2 (3 × 15 mL). The combined extract was concentrated under reduced pressure and the product was isolated by short chromatography on a silica gel (200-300 mesh) column.
9-([1,1'-biphenyl]-3-yl)-2,7-dibromo-9H-carbazole[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
4.2 g
With caesium carbonate; In dimethyl sulfoxide; at 170℃; for 22h;Inert atmosphere;
2,7-dibromo-9H-carbazole (26.9g), <strong>[2367-22-8]3-fluoro-1,1'-biphenyl</strong> (21.4g), a flask containing cesium carbonate (40.5g) and dimethyl sulfoxide (400ml), under a nitrogen atmosphere, this mixture was stirred for 22 hours at 170 C.Thereafter, the reaction solution was cooled to room temperature and water and liquid separation added ethyl acetate. Ethyl acetate was dissolved in chloroform by heating distilled off under reduced pressure to give solid was subjected to hot filtration. After adsorbed resulting filtrate onto silica gel and dried, separately prepared in advance silica gel chromatography was charged to (eluent heptane / toluene mixed solvent). Gradually increase the proportion of toluene in the developing solution was eluted the desired product. And further recrystallized from heptane, was obtained 9-([1,1'-biphenyl]-3-yl)-2,7-dibromo-9H-carbazole (4.2 g)
4.2 g
With caesium carbonate; In dimethyl sulfoxide; at 170℃; for 22h;Inert atmosphere;
2,7-dibromo-9H-carbazole (26.9g), <strong>[2367-22-8]3-fluoro-1,1'-biphenyl</strong> (21.4g), the flask containing cesium carbonate (40.5g) and dimethyl sulfoxide (400ml), under a nitrogen atmosphere, the mixture was stirred for 22 hours at 170C. Thereafter, the reaction solution was cooled to room temperature and water and liquid separation added ethyl acetate. The ethyl acetate was dissolved in chloroform, which was heated distilled off under reduced pressure to give solid, it was subjected to hot filtration. The obtained filtrate was adsorbed on silica gel, dried, separately prepared in advance silica gel chromatography was charged in (developing solution heptane / toluene mixed solvent). Gradually increase the proportion of toluene in the developing solution was eluted the desired product. And further recrystallized from heptane, 9-([1,1'-biphenyl]-3-yl)-2,7-dibromo-9H-carbazole (4.2 g) was obtained.
2,7-dibromo-9-(2-ethoxyethyl)-9H-carbazole[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
81%
Add 3 g of potassium hydroxide solid to a 250 mL flask, then add 30 mL of DMF and stir well. After the above system was stirred for 10 minutes, 2 g of compound 2 was added thereto, and then the system was stirred for 30 minutes. Subsequently, 1.38 mL of was added2-bromoethyl ether, the reaction 18 hours at room temperature. After the reaction was completed, the above system was poured into 400 mL of water and extracted with 400 mL of dichloromethane. The organic layer was dried with 4 g of anhydrous magnesium sulfate and the solvent was evaporated to give a white product in a yield of 81%.
Stage #1: 2,7-dibromo-9H-carbazole With sodium hydride In N,N-dimethyl-formamide for 1h;
Stage #2: benzyl bromide In N,N-dimethyl-formamide for 6h; Inert atmosphere;
2,7-dibromo-9-(pyrimidin-2-yl)-9H-carbazole[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
99%
With 1-methyl-1H-imidazole; copper(l) iodide; In toluene; at 130℃; for 24h;Inert atmosphere;
Add to dry three-necked flask with reflux condenser and magnetic rotor 2,7-dibromo-carbazole (1.66g, 5.10mmol, 1.0 eq), <strong>[4595-60-2]2-<strong>[4595-60-2]bromopyrimidine</strong></strong> (0.97 g, 6.10 mmol, 1.2 equiv.), Copper (I) iodide (19.4 mg, 0.10 mmol, 0.02 eq) Lithium tert-butoxide (0.82 g, 10.2 mmol, 2.0 equiv.), Nitrogen replacing three times an d then 1-methylimidazole (16.0 uL, 0.20 mmol, 0.04 equiv) and toluene (20 mL) were added. The reaction mixture was refluxed with stirring at 130 C for 1 day. The TLC was monitored by TLC to obtain the starting 2,7-dibromocarbazole. Saturated sodium sulfite solution was quenched, filtered, washed thoroughly with ethyl acetate, separated from the organic phase in the mother liquor, dried over anhydrous sodium sulfate, filtered and evaporated under reduced pressure to remove the solvent. The resulting crude product was purified by silica gel column chromatography eluting with petroleum ether / methylene chloride = 5: 1 to 3: 2 to give 2.03 g of A-2Br as a white solid in a yield of 99%.
99%
With 1-methyl-1H-imidazole; copper(l) iodide; lithium tert-butoxide; In toluene; at 130℃; for 24h;Inert atmosphere;
Into a dry three-necked flask which is equipped with a reflux condenser and a magnetic rotor are successively added with 2, 7-dibromocarbazole (1.66 g, 5.01mmol, 1.0 equivalent), Bromopyrimidine (0.97 g, 6.11mmol, 1.2 equiv), cuprous iodide (19.4 mg, 0.100mmol, 0.02 equiv), lithium t-butoxide (0.828, 10.2mmol, 2.0 equiv), Nitrogen exchange three times, and then 1-methylimidazole (16.OuL, 0.20mmo 1, 0.04 equivalent) and toluene (20mL). The reaction mixture is refluxed with stirring at 130 C for 1 day, TLC thin layer chromatography to the raw material 2, 7-dibromocarbazole reaction is completed. Saturated sodium sulfite solution is quenched, filtered, washed thoroughly with ethyl acetate; the organic phase is separated mother liquor, dried over anhydrous sodium sulfate, filtered and evaporated under reduced pressure to remove the solvent. The resulting crude product is purified by silica gel column chromatography, Eluent (petroleum ether / methylene chloride = 5: 1 to 3: 2), obtained A-2Br white solid 2.03g, yield 99%.
99%
With 1-methyl-1H-imidazole; copper(l) iodide; lithium tert-butoxide; In toluene; at 130℃; for 24h;Inert atmosphere;
Add to a dry three-necked bottle with a reflux condenser and a magnetic rotor2,7-dibromocarbazole (1.66 g, 5.10 mmol, 1.0 equiv),<strong>[4595-60-2]2-<strong>[4595-60-2]bromopyrimidine</strong></strong> (0.97 g, 6.10 mmol, 1.2 equiv),Cuprous iodide (19.4 mg, 0.10 mmol, 0.02 eq),Lithium tert-butoxide (0.82 g, 10.2 mmol, 2.0 equiv),Remove nitrogen three times,Then 1-methylimidazole (16.0 uL, 0.20 mmol, 0.04 equiv) was addedAnd toluene (20 mL).The reaction mixture was stirred and refluxed at 130 C for 1 day.TLC thin layer chromatography was monitored until the 2,7-dibromocarbazole reaction was complete.Saturated sodium sulfite solution quenched and filteredWash the insolubles thoroughly with ethyl acetate,Divide the organic phase in the mother liquor,Drying over anhydrous sodium sulfate, filtration,The solvent was distilled off under reduced pressure.The crude product was isolated and purified by silica gel column chromatography.Eluent (petroleum ether/dichloromethane=5:1-3:2),Obtained white solid 2.03g, yield 99%
99%
With 1-methyl-1H-imidazole; copper(l) iodide; lithium tert-butoxide; In toluene; at 130℃; for 24h;
To a dry three-necked flask with a reflux condenser and a magnetic rotor were sequentially added 2,7-dibromocarbazole (1.66 g, 5.10 mmol, 1.0 eq), <strong>[4595-60-2]2-<strong>[4595-60-2]bromopyrimidine</strong></strong> (0.97 g, 6.10 mmol, 1.2 eq). Cuprous iodide (19.4 mg, 0.10 mmol, 0.02 equiv), lithium tert-butoxide (0.82 g, 10.2 mmol, 2.0 equiv), nitrogen purged three times, then 1-methylimidazole (16.0 uL, 0.20 mmol, 0.04) Equivalent) and toluene (20 mL). The reaction mixture was stirred and refluxed at 130oC for 1 day.TLC thin layer chromatography was monitored until the 2,7-dibromocarbazole reaction was complete.The saturated sodium sulfite solution was quenched, filtered, and the insolubles were thoroughly washed with ethyl acetate. The organic phase in the mother liquor was separated, dried over anhydrous sodium sulfate, filtered, and the solvent was distilled off under reduced pressure. The resulting crude product was separated and purified by silica gel column chromatography eluting solvent (petroleum ether/dichloromethane=5:1-3:2) to obtain 2.03 g of A-2Br as a white solid with a yield of 99%.
With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; for 10h;Inert atmosphere; Reflux;
A 250 mL three-necked flask was charged with 0.02 mol of 2,7-dibromocarbazole, 0.03 mol of bromobenzene, and 0.04 mol of sodium t-butoxide under a nitrogen atmosphere.10-4mol Pd2(dba)3, 10-4mol P(t-Bu)3 and 200mL toluene, heated under reflux for 10 hours, sampling the plate, the raw material reaction is complete;Naturally cooled to room temperature (20 ~ 25 C), filtered, collected filtrate and vacuum distillation (-0.09MPa, 85 C), column chromatography, to obtain the starting material A2;
With palladium dichloride In toluene for 48h; Reflux; Inert atmosphere;
2.2.2. Synthesis of 3,6-Bis-(2,3-dihydro-thieno[3,4-b][1,4]dioxin-5-yl)-9H-carbazole (DTC)
General procedure: Tributyl-(3,4-ethoxylene-dioxythiophen-2-yl)-stannane(5 mmol, 2.2 g), 3,6-Dibromocarbazole (2.5 mmol, 0.8 g) and PdCl2(0.171 mmol, 0.12 g) were dissolved in anhydrous toluene (50 mL)in a 250 mL round bottom flask, then the mixture was degassed and refluxed for 48 h under a nitrogen atmosphere. After being cooled to room temperature, the mixture was washed with saturated salt water and extracted with trichloromethane (TCM). The organic phase was collected and dried with anhydrous MgSO4, solvent was removed under column pressure and the product was processed by column chromatography on silica gel with petroleum: TCM (10 : 1,by volume) to give a light-yellow power (0.65 g, 58% yield).
Stage #1: C22H23BO2; 2,7-dibromo-9H-carbazole With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In ethanol; water; toluene at 85℃; for 12h; Inert atmosphere;
Stage #2: 2-(9,9'-spirobi[fluoren]-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane In ethanol; water; toluene at 85℃; for 12h; Inert atmosphere;
5.1
1) In a 500ml three-neck bottle,Add 2,7-dibromo-9H-indazole (32.50 g, 100 mmol),3-(naphthalen-2-yl)benzene borate (33.02 g, 100 mmol),Potassium carbonate (27.64 g, 200 mmol), 150 g of toluene,75 g of ethanol, 75 g of water, and added tetrakis(triphenylphosphine)palladium under the protection of N2.After reacting at 85 ° C for 12 h, the reaction was completed by TLC and the temperature was lowered.After falling to room temperature,9,9'-spirobiphenyl-3-borate (44.24 g, 100 mmol) was added to a three-necked flask and reacted at 85 ° C for 12 h.The reaction was completed by TLC. After cooling to room temperature,The reaction solution was washed twice with water (200 ml), and the organic layer was separated.Adding activated carbon to decolorize, filtering, and distilling off the solvent under reduced pressure.Recrystallized twice with ethyl acetate,Drying under vacuum gave the intermediate 2-(9,9'-spirobi-3-yl)-7-(3-(naphthalen-2-yl)phenyl)-9H-carbazole.
2-([1,1'-biphenyl]-3-yl)-7-([1,1':4,1"-terphenyl]-4-yl)-9H-carbazole[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
The compound (2) of the present invention can be synthesized by the following method.1) In a 500ml three-neck bottle,Add 2,7-dibromo-9H-carbazole(32.50g, 100mmol),[1,1':4,1"-terphenyl]-4-borate(35.60g, 100mmol),Potassium carbonate (27.64 g, 200 mmol), 150 g of toluene, 75 g of ethanol,75 g of water, adding tetrakis(triphenylphosphine)palladium under N2 protection,After reacting at 85 C for 12 h, the reaction was completed by TLC and the temperature was lowered.After the temperature was lowered to room temperature, [1,1'-biphenyl]-3-borate (29.62 g, 100 mmol) was added to a three-necked flask, and reacted at 85 C for 12 h, and the reaction was confirmed by TLC.After cooling to room temperature, the reaction solution was washed twice with water (200 ml).The organic phase is obtained by liquid separation, and decolorization by adding activated carbon.Filtration, distilling off the solvent under reduced pressure, and then recrystallizing twice with ethyl acetate.Drying under vacuum gave the intermediate 2-([1,1'-biphenyl]-3-yl)-7-([1,1':4,1"-terphenyl]-4-yl)-9H- Carbazole.
bis(4-(2,7-dibromo-9H-carbazol-9yl)phenyl)methanone[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
76.2%
With sodium cyanide In N,N-dimethyl-formamide at 100℃; for 3.5h; Inert atmosphere;
2; 4
S1. In a dry flask, add 2,7-dibromocarbazole and 4,4'-difluorobenzophenone at a ratio of 2.2: 1, and then add an appropriate amount of sodium cyanide, N, N dimethyl Formamide, nitrogen and oxygen, stir well for 0.5h, and then react at 100 ° C for 3h under anhydrous and anaerobic conditions;S2, the system is cooled to room temperature after the reaction, most of the solvent is distilled off under reduced pressure, a large amount of water is added, a small amount of sodium chloride is added at the same time, and the mixture is left to stand for 15 minutes, and then filtered to obtain a crude product. The mixed solvent of ethyl acetate and petroleum ether and the mixed solvent of tetrahydrofuran and petroleum ether with a volume ratio of 1: 8 were thoroughly washed and vacuum filtered, and the obtained solid was dried under vacuum for a period of time to obtain the final product. The final product was bis (4- (2,7-dibromo-9H-carbazol-9yl) phenyl) methanone (DBCz-BP) with a yield of 76.2%.
9,9'-(6-(2,7-dibromo-9H-carbazol-9-yl)-1,3,5-triazine-2,4-diyl)bis(9H-carbazole)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
86%
Stage #1: 2,7-dibromo-9H-carbazole With n-butyllithium In tetrahydrofuran; hexane for 0.5h; Inert atmosphere;
Stage #2: 9,9’-(6-chloro-1,3,5-triazine-2,4-diyl)bis(9H-carbazole) In tetrahydrofuran; hexane at 20℃; for 12.1667h; Inert atmosphere;
2-(3-(2,7-dibromo 9H-carbazol-9-yl)phenyl)-5-phenyl-1,3,4-oxadiazole[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
90%
Stage #1: 2,7-dibromo-9H-carbazole With potassium hydroxide In N,N-dimethyl-formamide at 20℃; for 0.5h;
Stage #2: 2-(3-bromophenyl)-5-phenyl-1,3,4-oxadiazole In N,N-dimethyl-formamide at 85℃; for 10h;
3 Example 3
Dissolve 2,7-dibromocarbazole (6.5g, 20mmol) in 50ml N,N-dimethylformamide (DMF),Add potassium hydroxide (2.7g, 48mmol), stir at room temperature for 30min,Then add 2-(3-bromophenyl)-5-phenyl-1,3,4-oxadiazole (12.94g, 43mmol),After the addition is complete, continue stirring at 85°C for 10 hours.After the reaction was completed, the reaction solution was poured into water, and a light yellow solid precipitated.The solid is filtered under reduced pressure and rinsed with distilled water several times.After vacuuming and drying, 2-(3-(2,7-dibromo 9H-carbazol-9-yl)phenyl)-5-phenyl-1,3,4-oxadiazole(9.8g, yield 90%),
4-(2,7-dibromo-9H-carbazol-9-yl)benzonitrile[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
88%
With potassium carbonate In N,N-dimethyl-formamide at 140℃; for 10h; Inert atmosphere;
3.1; 4.1
(1) Weigh p-fluorobenzonitrile (3.63g, 30mmol), 2,7-dibromocarbazole (8.125g, 25mmol) and potassium carbonate (10.37g, 75mmol) into a 250mL double-necked round-bottomed flask, vacuumize Then pass N2 for protection. After that, 60 mL of ultra-dry DMF was injected into the reaction flask, and the reaction was carried out under reflux at 140° C. for 10 hours. After the reaction was completed, the mixture cooled to room temperature was poured into 200 mL of water, and the crude product was obtained by precipitation and filtration. Then, it was separated and purified by silica gel column chromatography using PE/DCM as eluent to obtain a white intermediate 2Br-CNCz with a yield of 88%.
82%
With potassium carbonate In N,N-dimethyl-formamide at 120℃; for 12h; Inert atmosphere;
With caesium carbonate In 1-methyl-pyrrolidin-2-one at 120℃;
1 Synthetic intermediate (002-a)
Dissolve 2,7-dibromocarbazole (1eq) in N-methylpyrrolidone (NMP) (100mL), then add cesium carbonate (5eq) and fluorobenzene (3eq), stir at 120°C for 24 hours, then add 1L water, the white solid was filtered, washed repeatedly with water, dehydrated and then separated and purified by silica gel chromatography to obtain a white solid intermediate (002-a) with a yield of 94%.