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Chemical Structure| 1592-95-6
Chemical Structure| 1592-95-6
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Product Details of [ 1592-95-6 ]

CAS No. :1592-95-6 MDL No. :MFCD00222621
Formula : C12H8BrN Boiling Point : -
Linear Structure Formula :- InChI Key :LTBWKAYPXIIVPC-UHFFFAOYSA-N
M.W : 246.10 Pubchem ID :252446
Synonyms :

Calculated chemistry of [ 1592-95-6 ]

Physicochemical Properties

Num. heavy atoms : 14
Num. arom. heavy atoms : 13
Fraction Csp3 : 0.0
Num. rotatable bonds : 0
Num. H-bond acceptors : 0.0
Num. H-bond donors : 1.0
Molar Refractivity : 63.5
TPSA : 15.79 Ų

Pharmacokinetics

GI absorption : High
BBB permeant : Yes
P-gp substrate : Yes
CYP1A2 inhibitor : Yes
CYP2C19 inhibitor : Yes
CYP2C9 inhibitor : No
CYP2D6 inhibitor : No
CYP3A4 inhibitor : Yes
Log Kp (skin permeation) : -4.9 cm/s

Lipophilicity

Log Po/w (iLOGP) : 2.22
Log Po/w (XLOGP3) : 4.08
Log Po/w (WLOGP) : 4.08
Log Po/w (MLOGP) : 3.5
Log Po/w (SILICOS-IT) : 4.25
Consensus Log Po/w : 3.63

Druglikeness

Lipinski : 0.0
Ghose : None
Veber : 0.0
Egan : 0.0
Muegge : 1.0
Bioavailability Score : 0.55

Water Solubility

Log S (ESOL) : -4.62
Solubility : 0.00586 mg/ml ; 0.0000238 mol/l
Class : Moderately soluble
Log S (Ali) : -4.12
Solubility : 0.0188 mg/ml ; 0.0000765 mol/l
Class : Moderately soluble
Log S (SILICOS-IT) : -5.82
Solubility : 0.000375 mg/ml ; 0.00000152 mol/l
Class : Moderately soluble

Medicinal Chemistry

PAINS : 0.0 alert
Brenk : 0.0 alert
Leadlikeness : 2.0
Synthetic accessibility : 1.42

Safety of [ 1592-95-6 ]

Signal Word:Warning Class:N/A
Precautionary Statements:P264-P280-P302+P352-P337+P313-P305+P351+P338-P362+P364-P332+P313 UN#:N/A
Hazard Statements:H315-H319 Packing Group:N/A
GHS Pictogram:

Application In Synthesis of [ 1592-95-6 ]

* 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.

  • Upstream synthesis route of [ 1592-95-6 ]
  • Downstream synthetic route of [ 1592-95-6 ]

[ 1592-95-6 ] Synthesis Path-Upstream   1~44

  • 1
  • [ 86-74-8 ]
  • [ 1592-95-6 ]
YieldReaction ConditionsOperation in experiment
95% With N-Bromosuccinimide In tetrahydrofuran at 25℃; The intermediate F was synthesized through Reaction Scheme 3A below as follows: 8.708 g (50.00 mmol) of carbazole, 8.899 g (50.00 mmol) of NBS and 100 ml of THF were stirred at room temperature (about 25° C.) to obtain 11.70 g of Intermediate F with a yield of 95percent. (0152) 1H-NMR (300 MHz, CDCl3): δ=11.701 (br, 1H), 8.205 (d, 1H), 8.015 (s, 1H), 7.504-7.201 (m, 5H) (0153) 13C-NMR (75 MHz, CDCl3): δ=135.4, 131.4, 124.0, 122.2, 121.1, 121.0, 120.1, 118.9, 113.3, 111.1 (0154)
95% With N-Bromosuccinimide In N,N-dimethyl-formamide at -10℃; Inert atmosphere First, carbazole (16.7 g, 100.0 mmol)Placed in 250mL external constant pressure dropping funnel single-ported bottle A,Vacuum, nitrogen cycle three times,After adding 50mLDMF dissolved,The single-necked flask A was placed in ice-salt bath (ice volume ratio:Saline saturated solution = 10: 1,Temperature is about -10 ° C)After full cooling,NBS (17.7 g, 100.0 mmol)DMF solution was slowly added dropwise to the carbazole solution through a constant pressure dropping funnel.Drip and add ice salt bath,Keep cold.Device does not move,Reaction 18-24h.After the reaction is completed,Pour into a large amount of water sedimentation,After filtration take the solid,Ethanol recrystallized.(The solid and a small amount of ethanol was heated to boiling,If there is still a lot of solid,Then continue to add ethanol,Until completely dissolved - at this time directly placed cooling recrystallization or only a small amount of solid - at this time filtered hot cooling recrystallization,Recrystallization can be added 2/3 amount of water) Yield: 95percent.
91% With N-Bromosuccinimide In tetrahydrofuran at 0 - 20℃; for 12 h; The 16.7g (0.1mol) carbazole was dissolved in tetrahydrofuran (THF, 500mL) in, and then the resulting solution was stirred at 0 10 minutes. Thereto was added N- bromosuccinimide (NBS, 18.68g, 0.105mol), the resulting mixture was stirred at normal temperature for 12 hours, then extracted with ethyl acetate and distilled water. The organic layer was dried over anhydrous magnesium sulfate (MgSO4) was dried, then the solvent was removed, and subjected to silica gel column chromatography to give 22.4g (91percent) Compound A-1.
87% at 50℃; for 2 h; General procedure: In a round-bottomed flask, the substrate (1 mmol) and aqueous HBr(48percent) (1 mL) were mixed in DMSO (1 mL). The mixture was stirredat corresponding temperature for 1–4 h. After cooling to roomtemperature, the reaction was adjusted to pH 7–8 with aqueous NaOHsolution (4 M). Then the mixture was washed twice with EtOAc, andthe combined organic extracts were dried, filtered and concentratedunder reduced pressure to give bromination products.
86.1% With N-Bromosuccinimide In tetrahydrofuran at 20℃; for 5 h; A mixture of carbazole (1, 52.6 mmol) and N-bromosuccinimide (50.0 mmol) in tetrahydrofuran (100 mL) was stirred at room temperature for 5 h. The reaction mixture was evaporated under reduced pressure and the resulting residue was purified by crystallization from hexane-acetone mixture to obtain 3-bromo-9H-carbazole (5).Yield 86.1 percent; White solid, mp: 194.4 , Rf = 0.34 (5:1 n-hexane-ethyl acetate); 1H NMR (400 MHz, DMSO-d6): δH 7.14-7.18 (m, 1H), 7.38-7.49 (m, 4H), 8.15 (d, J = 8.0 Hz, 1H), 8.34 (s, 1H), 11.41 (s, 1H)
85% With N-Bromosuccinimide In N,N-dimethyl-formamide at 20℃; for 2 h; Carbazole (8.25 g, 0.05 mol) was added into 50 ml of DMF anddissolved in stirring. Then the mixed solution of N-bromosuccinimide(NBS) (8.90 g, 0.05 mol) and 50 ml of DMF was added dropwiseinto reaction flask in ice-water bath. The mixture wasstirred at room temperature for 2 h. The solution was poured into500 ml of ice water and the white precipitate was filtered, washedby distilled water, recrystallized by ethanol and dried under vacuum. white powder (10.45 g, 85percent) was obtained. 1H NMR(CDCl3, d, ppm): 8.13 (s, 2H), 7.52-7.54 (d, 2H), 7.31-7.35 (d, 3H).
85% With N-Bromosuccinimide In N,N-dimethyl-formamideCooling with ice Carbazole (1.002 g, 5.997 mmol) was added into DMF solution (50 mL). Then the mixture of N-bromosuccinimide (NBS) (1.068 g, 6.000 mmol) and DMF (20 mL) was added dropwise into reaction flask in ice-water bath. After filtration and washed by water, white powder was obtained [29] (1.254 g, 85.0percent). Mp: 199 °C. 1H NMR (CDCl3, 400 MHz, TMS) δ: 11.40 (s, 1H), 8.33 (d, J = 8.4 Hz, 1H), 8.12 (d, J = 8.4 Hz, 1H), 7.43 (m, 4H), 7.15 (t, J = 7.6 Hz, 1H).
72% With N-Bromosuccinimide In N,N-dimethyl-formamide at 0 - 20℃; for 2 h; 3-Bromocarbazole (1 ). To DMF (67 ml) was added carbazole (10 g, 59.80 mmol) and mixture was stirred at room temperature for 15 minutes. N-bromosuccinimide (10.6 g, 59.56 mmol) in DMF (100 ml) was added dropwise at 0°C. The mixture was allowed to warm to room temperature and stirred for two hours. White precipitates were formed after the mixture was poured into water. The precipitates were filtered and dissolved in dichloromethane. The organic layer was washed with water to remove water soluble impurities. The organic fraction was dried over anhydrous sodium sulfate and the solvent was removed under reduced pressure. The resulting white solid was purified by recrystallization from ethanol to give colorless crystals (10.65 g, 72 percent yield). 1H-NMR (CDCIs, 400 MHz): δ 8.34(bs, 1 H), 8.15(d, J=7.8Hz, 1 H), 7.48(d, J=8.2, 1 H), 7.45(m, 1H), 11.42(s, 1H). (MS, ESI) m/z 246 (M+).
71% With N-Bromosuccinimide; silica gel In dichloromethane at 10 - 20℃; for 42 h; Carbazole (52.26 g, 0.30 mol) was dissolved in dichloromethane (3 L) and silicagel (60 mesh, 600 g) was added to the mixture and the mixture was cooled to 10 0C. A mixture of Λ/-bromosuccinimide (NBS, 55 g, 0.30 mol) in dichloromethane (400 ml_) was added at 10 0C. After addition, the mixture was allowed to reach room temperature. After standing for 42 hours, the mixture was filtered, and the solid was washed with dichloromethane (4 x 200 ml_), the combined filtrates were washed with water (300 ml_) and dried over Na2SO4 . Evaporation in vacuo to dryness afforded 77 g of crude product. Recrystallization from 2-propanol (800 ml_) afforded 71 percent 3-bromocarbazole.
68% With N-Bromosuccinimide In acetonitrile at 20℃; for 1 h; In the procedures shown in Scheme 1, the preparation of 3-bromocarbazole 1 using N-bromosuccinimide was contaminated by some starting material and 3,6-dibromocarbazole, both of which could be removed by fractional recrystallization from toluene. The preparation of 3 was accomplished in good yield by dropwise introduction of the lithiated TBDMS-protected 3-bromocarbazole 2 intermediate to excess 1,4-diiodobutane.
67% With N-Bromosuccinimide In acetic acid monohydrate at 20℃; for 15 h; [Step 1: Synthesis of 3-bromo-9H-carbazole]
32 g (0.19 mmol) of 9H-carbazole was put into a 2 L Erlenmeyer flask, and then ether acetate (1.2 L) was added thereto so that the 9H-carbazole was dissolved in the ether acetate.
To this solution was added 34 g (0.19 mol) of N-bromosuccinimide (NBS), and the mixture was stirred for about 15 hours in the air at room temperature.
After the stirring, water was added to the mixture so that the precipitate was dissolved in the mixture.
The organic layer of this mixture was washed with water three times and then with a saturated saline solution once.
Magnesium sulfate was added so that the organic layer was dried.
After the drying, the mixture was subjected to gravity filtration.
The obtained filtrate was condensed to give a white solid.
The obtained solid was recrystallized with ether acetate/hexane to give 36 g of a white powdered solid, which was the object of the synthesis, at a yield of 67 percent.
A synthesis scheme of Step 1 is shown in (c-1) given below.
67.6% With N-Bromosuccinimide In N,N-dimethyl-formamide at -10 - -5℃; (1) Carbazole (16.7 g, 100 mmol) was dissolved in 100 mL of DMF,In a 500 mL four-necked flask was mechanically stirred,The temperature was controlled with an ice-salt bath-5 ° C to -10 ° C,Further, 100 mL of a DMF solution of NBS (18.7 g, 105 mmol) was added,Stirring was continued and the reaction was continued overnight.The reaction was poured vigorously into water, stirred, filtered and the filter cake was allowed to dry. Ethyl acetate,To give 16.6 g of 3-bromocarbazole in 67.6percent yield.
59% With N-Bromosuccinimide In acetonitrile at 0 - 20℃; Inert atmosphere To a suspension of 9.153 g (54.7 mmol) of carbazole in 100 ml of HPLC grade acetonitrile at O0C was slowly added 10.433 g (58.6 mmol) of N- bromosuccinimide (NBS) under vigorous stirring. After the NBS was added, the contents of the flask's were slowly brought to room temperature and stirred overnight. A bulky white precipitate was filtered, washed with cold acetonitrile (2x30 ml) and hexane (2x50 ml), and dried under vacuum to constant weight to yield 7.95 g (59percent yield) of 3-bromocarbazole 4 as a fluffy white solid. Additional product can be isolated from the filtrate (Rf = 0.26 for carbazole and Rf = 0.16 for 3-bromocarbazole 4 in EtOAc/hexane = 85:15).
58.04% With N-Bromosuccinimide In N,N-dimethyl-formamide at 0℃; for 12 h; [169] Carbazole (20 g, 119.6 mmol) was dissolved in dimethylformamide (DMF) 200 mL, and N-bromosuccinimide (NBS) (21.2 g, 119.6 mmol) was added at 0°C. After stirring for 12 hours, distilled water was added, and the obtained solid was filtered under reduced pressure. The obtained solid was added to methanol, and after stirring, the solution was filtered under reduced pressure. The re-obtained solid was added to ethyl acetate (EA) and methanol, and stirred. Then, the mixture was filtered under reduced pressure to obtain compound 1-6 (17 g, 69.07 mmol, 58.04 percent).
58.04% With N-Bromosuccinimide In N,N-dimethyl-formamide at 0℃; for 12 h; After dissolving carbazole 20 g (119.6 mmol) in dimethylfomiamide (DMF) 200 mL, N-bromosuccineimide (NBS) 21.2 g (119.6 mmol) was added to the mixture at 0°C. After stirring the mixture for 12 hours, distilled water was added to the mixture, and the produced solid was filtered under reduced pressure. The obtained solid was added to methanol, and the mixture was stuffed, and filtered under reduced pressure. Then, the obtained solid was added to a mixture of EA, and methanol, the mixture was stilTed, and filtered under reduced pressure to obtain compound C-3-2 17 g (58.04 percent).
53% With N-Bromosuccinimide In acetonitrile at 20℃; for 16 h; N-Bromosuccinimide (21 .63 g, 121 .53 mmol) was added portionwise to a stirred solution of 9 - -carbazole (19.00 g, 1 13.6 mmol) in acetonitrile (420 ml_) at room temperature. The reaction mixture was stirred at room temperature for 16 hours. After complete consumption of the starting material, as indicated by TLC, the reaction mixture was precipitated and filtered. The precipitate was washed with n-pentane to afford 3- bromo-9 - -carbazole as an off-white solid (14.7 g, 53percent). 1 H NMR (400 MHz, CDCI3): δ 8.19 (br s, 1 H), 8.05-7.97 (m, 2H), 7.54-7.40 (m, 3H), 7.32-7.25 (m, 2H). LCMS: m/z 244.03, 246.03 [M-H]".
51% With N-Bromosuccinimide In N,N-dimethyl-formamide at 0℃; Synthesis of 3-bromocarbazole. NBS (12.77 g, 71.8 mmol) in DMF was added to 9H-carbazole (12 g, 71.8 mmol) in 200 mL at 0 °C dropwise. The reaction was monitored by HPLC. After 2 h, HPLC indicated 76percent of desired product and 6percent of dibrominated compound. The reaction was quenched by adding 500 mL of ice water. The internal temperature was controlled to be lower than 10 °C. The precipitate formed was collected by filtration. The solid was stirred in 400 mL of warm methanol. (-40 °C). The solid was collected by filtration. The solid was dissolved in 150 mL of DCM. 200 mL of methanol was added. The DCM was boiled off. The solvent level was down to 150 mL. The slurry was stirred at room temperature overnight. The solid was collected by filtration. 9 g (51percent yield) of solid was collected.
47% With N-Bromosuccinimide In N,N-dimethyl-formamide at 20℃; A solution of N-bromosuccinimide (10.64 g, 59.8 mol) dissolved in NN-dimethylformamide (DMF) (20 ml) was treated with a constant pressure dropping solution The funnel was added dropwise to a solution of carbazole (10 g, 59.8 mol) in DMF (20 ml)in. After completion of the drop, the ice bath was removed and the reaction was conducted overnight at room temperature. The reaction solution was then washed with deionized water, the solid was precipitated, and the solid was filtered off and the product was recrystallized from ethanol (2). Yield: 47percent.
20 g With N-Bromosuccinimide In N,N-dimethyl-formamide at 20℃; 16 g (grams) of carbazole was dissolved in 80 mL ) n, n ′-dimethylformamide, to this was added 18 g n-bromosuccinimide, and the reaction was stirred at room temperature overnight. The reaction mixture was poured into water and the precipitate filtered. a white solid, washed with methanol and dried under vacuum to obtain 20 g of 3-bromocarbazole.

Reference: [1] Bioorganic and Medicinal Chemistry Letters, 2012, vol. 22, # 1, p. 363 - 366
[2] Organic and Biomolecular Chemistry, 2016, vol. 14, # 39, p. 9406 - 9415
[3] Journal of Materials Chemistry C, 2016, vol. 4, # 24, p. 5795 - 5805
[4] Patent: US8558007, 2013, B2, . Location in patent: Page/Page column 32; 33
[5] Patent: CN104650153, 2017, B, . Location in patent: Paragraph 0032; 0033; 0034; 0035
[6] Journal of the Brazilian Chemical Society, 2010, vol. 21, # 3, p. 496 - 501
[7] Journal of Materials Chemistry C, 2016, vol. 4, # 38, p. 8973 - 8979
[8] Patent: CN105601621, 2016, A, . Location in patent: Paragraph 0288; 0289; 0290
[9] RSC Advances, 2016, vol. 6, # 116, p. 115298 - 115302
[10] Journal of Chemical Research, 2014, vol. 38, # 10, p. 593 - 596
[11] Journal of Polymer Science, Part A: Polymer Chemistry, 2010, vol. 48, # 7, p. 1607 - 1616
[12] Bioorganic and Medicinal Chemistry Letters, 2015, vol. 25, # 19, p. 4304 - 4307
[13] Journal of Molecular Structure, 2014, vol. 1058, # 1, p. 14 - 21
[14] Dyes and Pigments, 2016, vol. 124, p. 268 - 276
[15] Journal of the American Chemical Society, 2013, vol. 135, # 12, p. 4805 - 4814
[16] MedChemComm, 2017, vol. 8, # 1, p. 202 - 210
[17] Chemical Communications, 2010, vol. 46, # 12, p. 2091 - 2093
[18] European Journal of Inorganic Chemistry, 2018, vol. 2018, # 3, p. 531 - 543
[19] RSC Advances, 2013, vol. 3, # 30, p. 12091 - 12095
[20] Patent: WO2016/112027, 2016, A1, . Location in patent: Paragraph 0100
[21] Patent: WO2006/82245, 2006, A1, . Location in patent: Page/Page column 304-305
[22] Organic Letters, 2002, vol. 4, # 14, p. 2321 - 2323
[23] Chemistry of Materials, 2015, vol. 27, # 19, p. 6535 - 6542
[24] Patent: US2017/352818, 2017, A1, . Location in patent: Paragraph 0133; 0134
[25] Patent: EP1972619, 2008, A1, . Location in patent: Page/Page column 265
[26] Patent: CN105566199, 2016, A, . Location in patent: Paragraph 0019
[27] Journal of Fluorescence, 2011, vol. 21, # 2, p. 497 - 506
[28] Patent: WO2010/43693, 2010, A1, . Location in patent: Page/Page column 19
[29] Patent: WO2013/162284, 2013, A1, . Location in patent: Paragraph 168; 169
[30] Patent: WO2014/3440, 2014, A1, . Location in patent: Paragraph 140; 141; 144; 145
[31] Chemical Communications, 2017, vol. 53, # 97, p. 13039 - 13042
[32] Patent: WO2016/8010, 2016, A1, . Location in patent: Page/Page column 40; 41
[33] Patent: WO2011/137072, 2011, A1, . Location in patent: Page/Page column 43; 44
[34] Patent: CN106046054, 2016, A, . Location in patent: Paragraph 0065; 0066; 0067
[35] Advanced Synthesis and Catalysis, 2002, vol. 344, # 2, p. 192 - 199
[36] Synthesis, 2005, # 10, p. 1619 - 1624
[37] Z. Ang., 1901, vol. 14, p. 784
[38] Helvetica Chimica Acta, 1946, vol. 29, p. 573,580
[39] European Journal of Pharmacology, Molecular Pharmacology Section, 1995, vol. 288, # 3, p. 285 - 294
[40] Organic and Biomolecular Chemistry, 2011, vol. 9, # 20, p. 6913 - 6916
[41] Journal of Materials Chemistry, 2011, vol. 21, # 14, p. 5422 - 5429
[42] Journal of Materials Chemistry, 2011, vol. 21, # 21, p. 7811 - 7819
[43] Chemistry - A European Journal, 2012, vol. 18, # 48, p. 15512 - 15522
[44] Dyes and Pigments, 2013, vol. 99, # 1, p. 41 - 51
[45] Arkivoc, 2014, vol. 2014, # 5, p. 123 - 131
[46] Dyes and Pigments, 2017, vol. 141, p. 148 - 160
[47] Dyes and Pigments, 2015, vol. 114, # C, p. 239 - 252
[48] Patent: CN103159745, 2016, B, . Location in patent: Paragraph 0184-0185
[49] Patent: KR2016/51210, 2016, A, . Location in patent: Paragraph 0157; 0158; 0159
[50] Physical Chemistry Chemical Physics, 2016, vol. 18, # 43, p. 30105 - 30116
[51] ChemCatChem, 2018, vol. 10, # 18, p. 3960 - 3963
  • 2
  • [ 105971-15-1 ]
  • [ 1592-95-6 ]
YieldReaction ConditionsOperation in experiment
79% With triphenylphosphine In 1,2-dichloro-benzeneInert atmosphere; Reflux Under nitrogen atmosphere, intermediate F 2.78g (10 mmol) was dissolved in o- dichlorobenzene 20ml and triphenylphosphine 6.56g (25mmol) was added and reflux. After completion of the reaction, MC 200ml, H2O 200ml was added and then the the MC layer was extracted, concentrated and separated by column chromatography using Hex : EA =5 : 1 and dried over anhydrous MgSO4 to give the intermediate G 1.94g (79percent).
79% With triphenylphosphine In 1,2-dichloro-benzeneInert atmosphere; Reflux Intermediate E 2.78g (10mmol) was dissolved in o-dichlorobenzene 40ml under nitrogen, triphenylphosphine 6.56g (25mmol) was added and the mixture was refluxed. After completion of the reaction, 200ml MC and 200ml H2O was added, the MC layer was extracted and dried over anhydrous MgSO4 and concentrated by column with Hex: EA = 5: 1 to give the intermediate F 1.94 g(79percent).
79% With triphenylphosphine In 1,2-dichloro-benzeneInert atmosphere; Reflux Then dissolved under nitrogen the intermediates B 2.78g (10mmol) in 20ml o-dichlorobenzene triphenylphosphine 6.56g (25mmol) and the mixture was refluxed.To 1: After completion of the reaction, 200ml MC, the MC layer then was extracted by the addition of 200ml H2O and dried over anhydrous MgSO4 and concentrated to Hex: MC = 5Column with intermediate CTo give a 1.94g (79percent).
79% With triphenylphosphine In 1,2-dichloro-benzeneInert atmosphere; Reflux Synthesis of Intermediate 27 (0166) (0167) Under a nitrogen atmosphere, Intermediate 26 (2.78 g, 10 mmol) was dissolved in o-DCB (40 mL), and then triphenylphosphine (6.56 g, 25 mmol) was added dropwise and refluxed. (0168) After the reaction was terminated, MC (200 mL) and H2O (200 mL) were added. The MC layer was extracted, dried over anhydrous magnesium sulfate, concentrated, and purified by column chromatography eluting with Hex:MC=5:1, to obtain Intermediate 27 (1.94 g, 79percent). (0169) Intermediate 27 MS(FAB): 246(M+)
79% With triphenylphosphine In 1,2-dichloro-benzeneInert atmosphere; Reflux Under a nitrogen atmosphere, Intermediate 22 (2.78 g, 10 mmol) was dissolved in o-DCB (40 mL), and then triphenylphosphine (6.56 g, 25 mmol) was added and refluxed. After the reaction was terminated, MC (200 mL) and H2O (200 mL) were added. The MC layer was extracted, dried over anhydrous magnesium sulfate, concentrated, and purified by column chromatography eluting with Hex:MC=5:1, to obtain Intermediate 23 (1.94 g, 79percent).
77% With triphenylphosphine In 1,2-dichloro-benzene at 200℃; The intermediate F 1mol Was dissolved in o-dichlorobenzene was added to 2.5mol and triphenylphosphine at 200°C It was stirred. After completion of reaction, after the removal o-dichlorobenzene by distillation and extracted with water and CH2Cl2 and the organic layer no It is dried with MgSO4, and concentrated by column chromatography and recrystallization to the resulting product and then to obtain the desired intermediate G (Yield: 77percent).
74% With triphenylphosphine In 1,2-dichloro-benzene at 200℃; Said Sub 1-I-1 obtained in the synthesis (168.52g, 606mmol) senses a rotation velocity of the disk to in round bottom flasko- dichlorobenzene in a, triphenylphosphine (397.35g, 1514.9mmol) adding an 200 °C stirring section. When reaction is completed the via fractional distillation to remove the dichlorobenzene- o CH 2 Cl 2 extracted and water. Organic layer MgSO 4 to dry a silicagel column with a compound formed after the products and recrystallization 110.36g (yield: 74percent)is obtained.
60% With triphenylphosphine In 1,2-dichloro-benzene at 200℃; Wherein the Sub 1-I-1 (66.39 g, 238.7mmol) after a round bottom flask was dissolved in o-dichlorobenzene (1194ml),it was added triphenylphosphine (156.54 g, 596.8 mmol) and stirred at 200 . After completion ofreaction was removed by distillation and the o-dichlorobenzene and water,extracted CH2Cl2. The resulting compound and the organic layer was dried overMgSO4 and concentrated to silicagel column and the product was recrystallizedfrom 35.25 g (yield: 60percent) was obtained.

Reference: [1] Patent: KR2015/102733, 2015, A, . Location in patent: Paragraph 0145-0149
[2] Patent: KR2015/102734, 2015, A, . Location in patent: Paragraph 0174-0177
[3] Patent: KR2015/112880, 2015, A, . Location in patent: Paragraph 0113; 0114; 0115; 0116; 0117
[4] Patent: US2017/125677, 2017, A1, . Location in patent: Paragraph 0166-0169
[5] Patent: US2017/125678, 2017, A1, . Location in patent: Paragraph 0139; 0140; 0141; 0142
[6] Patent: KR101565039, 2015, B1, . Location in patent: Paragraph 0119-0122
[7] Patent: KR2015/98062, 2015, A, . Location in patent: Paragraph 0135-0139; 0147; 0148
[8] Patent: KR101535606, 2015, B1, . Location in patent: Paragraph 0129; 0130; 0133; 0134
  • 3
  • [ 21865-50-9 ]
  • [ 1592-95-6 ]
YieldReaction ConditionsOperation in experiment
91% With copper(II) choride dihydrate In dimethyl sulfoxide at 100℃; for 7 h; General procedure: A mixture of starting compound (2.69 mmol), CuCl2.2H2O (10 mol percent) in DMSO (5 mL) stirred at 100 °C. The reaction progress was monitored by thin layer chromatography (PMA was used for stain solution). The reaction mixture was poured into ice cold water. The crude product was purified by column chromatography using ethyl acetate and petroleum ether as eluent to afford carbazoles.
Reference: [1] Tetrahedron Letters, 2018, vol. 59, # 22, p. 2145 - 2149
[2] Organic and Biomolecular Chemistry, 2014, vol. 12, # 27, p. 4832 - 4836
[3] Journal of the Chemical Society, 1945, p. 530,532
  • 4
  • [ 1153-85-1 ]
  • [ 73183-34-3 ]
  • [ 1592-95-6 ]
Reference: [1] Patent: US2011/260138, 2011, A1,
  • 5
  • [ 622-88-8 ]
  • [ 108-94-1 ]
  • [ 1592-95-6 ]
Reference: [1] Green Chemistry, 2012, vol. 14, # 12, p. 3277 - 3280
[2] Tetrahedron Letters, 2018, vol. 59, # 22, p. 2145 - 2149
  • 6
  • [ 86-74-8 ]
  • [ 1592-95-6 ]
  • [ 177775-86-9 ]
Reference: [1] Patent: US2011/309345, 2011, A1,
  • 7
  • [ 3623-23-2 ]
  • [ 88284-48-4 ]
  • [ 1592-95-6 ]
Reference: [1] Angewandte Chemie - International Edition, 2013, vol. 52, # 10, p. 2968 - 2971[2] Angew. Chem., 2013, vol. 125, # 10, p. 3041 - 3044
  • 8
  • [ 91330-91-5 ]
  • [ 1592-95-6 ]
Reference: [1] Green Chemistry, 2018, vol. 20, # 6, p. 1362 - 1366
[2] Journal of the American Chemical Society, 1951, vol. 73, p. 2435
[3] Journal of the American Chemical Society, 1962, vol. 84, p. 480 - 485
  • 9
  • [ 98-80-6 ]
  • [ 1592-95-6 ]
Reference: [1] Patent: KR2015/98062, 2015, A,
[2] Patent: KR101535606, 2015, B1,
[3] Patent: KR101565039, 2015, B1,
[4] Patent: KR2015/102733, 2015, A,
[5] Patent: KR2015/102734, 2015, A,
[6] Patent: US2017/125678, 2017, A1,
[7] Patent: US2017/125677, 2017, A1,
[8] Patent: KR2015/112880, 2015, A,
[9] Green Chemistry, 2018, vol. 20, # 6, p. 1362 - 1366
  • 10
  • [ 343864-78-8 ]
  • [ 1592-95-6 ]
Reference: [1] Patent: KR2015/98062, 2015, A,
[2] Patent: KR101535606, 2015, B1,
[3] Patent: KR101565039, 2015, B1,
[4] Patent: KR2015/102733, 2015, A,
[5] Patent: KR2015/102734, 2015, A,
[6] Patent: US2017/125678, 2017, A1,
[7] Patent: US2017/125677, 2017, A1,
[8] Patent: KR2015/112880, 2015, A,
  • 11
  • [ 5455-13-0 ]
  • [ 1592-95-6 ]
Reference: [1] Journal of the American Chemical Society, 1951, vol. 73, p. 2435
[2] Green Chemistry, 2018, vol. 20, # 6, p. 1362 - 1366
  • 12
  • [ 90-41-5 ]
  • [ 1592-95-6 ]
Reference: [1] Journal of the American Chemical Society, 1951, vol. 73, p. 2435
[2] Green Chemistry, 2018, vol. 20, # 6, p. 1362 - 1366
  • 13
  • [ 7599-23-7 ]
  • [ 1592-95-6 ]
Reference: [1] Journal of the American Chemical Society, 1951, vol. 73, p. 2435
  • 14
  • [ 86-74-8 ]
  • [ 1592-95-6 ]
  • [ 6825-20-3 ]
Reference: [1] Tetrahedron, 1992, vol. 48, # 36, p. 7479 - 7488
[2] Canadian Journal of Chemistry, 1992, vol. 70, # 3, p. 870 - 876
[3] Canadian Journal of Chemistry, 1992, vol. 70, # 3, p. 870 - 876
[4] Tetrahedron, 1992, vol. 48, # 36, p. 7479 - 7488
[5] Canadian Journal of Chemistry, 1992, vol. 70, # 3, p. 870 - 876
[6] Synthesis, 2005, # 10, p. 1619 - 1624
  • 15
  • [ 108-94-1 ]
  • [ 589-21-9 ]
  • [ 1592-95-6 ]
Reference: [1] Organic and Biomolecular Chemistry, 2014, vol. 12, # 27, p. 4832 - 4836
  • 16
  • [ 615-36-1 ]
  • [ 1592-95-6 ]
Reference: [1] Green Chemistry, 2018, vol. 20, # 6, p. 1362 - 1366
  • 17
  • [ 177775-86-9 ]
  • [ 1592-95-6 ]
Reference: [1] Gazzetta Chimica Italiana, 1882, vol. 12, p. 272
  • 18
  • [ 19402-87-0 ]
  • [ 1592-95-6 ]
Reference: [1] Kogyo Kagaku Zasshi, 1957, vol. 60, p. 1146,1147[2] Chem.Abstr., 1959, p. 14979
  • 19
  • [ 177775-87-0 ]
  • [ 1592-95-6 ]
Reference: [1] Gazzetta Chimica Italiana, 1892, vol. 22 II, p. 570,572[2] Gazzetta Chimica Italiana, 1895, vol. 25 II, p. 395,398,399
  • 20
  • [ 574-39-0 ]
  • [ 1592-95-6 ]
Reference: [1] Gazzetta Chimica Italiana, 1882, vol. 12, p. 272
  • 21
  • [ 77-48-5 ]
  • [ 86-74-8 ]
  • [ 1592-95-6 ]
Reference: [1] Anales de la Asociacion Quimica Argentina (1921-2001), 1951, vol. 39, p. 184,186
  • 22
  • [ 86-74-8 ]
  • [ 16807-11-7 ]
  • [ 1592-95-6 ]
Reference: [1] Journal of the Chemical Society. Perkin Transactions 2, 2000, # 7, p. 1583 - 1595
  • 23
  • [ 90408-20-1 ]
  • [ 1592-95-6 ]
Reference: [1] Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999), 1984, # 3, p. 429 - 434
  • 24
  • [ 75-15-0 ]
  • [ 2788-23-0 ]
  • [ 7726-95-6 ]
  • [ 1592-95-6 ]
Reference: [1] Diss.<Braunschweig 1926> S.21,
  • 25
  • [ 1592-95-6 ]
  • [ 124-38-9 ]
  • [ 51035-17-7 ]
YieldReaction ConditionsOperation in experiment
62%
Stage #1: With tert.-butyl lithium In tetrahydrofuran at -78℃; for 1.5 h;
i-Butyllithium (25.0 mL, 36.57 mmol) was added slowly to dry THF (30 mL), at -78 °C. A solution of 3-bromo-9/-/-carbazole (3.00 g, 12.19 mmol) in THF (30 mL) was added over 30 minutes with the temperature maintained at -78 °C. The reaction mixture was maintained at this temperature for one hour while being slowly purged with dry C02 gas. After complete consumption of the starting material, as indicated by TLC, the reaction mixture was quenched with saturated ammonium chloride solution and 1 N HCI. The reaction mixture was warmed to room temperature and extracted with ethyl acetate. The organic layer was dried over anhydrous Na2S04, filtered and concentrated under reduced pressure to get 9 - -carbazole-3-carboxylic acid as an off-white solid (1 .6 g, 62percent). LCMS: m/z 210.1 [M-H]".
Reference: [1] Patent: WO2016/8010, 2016, A1, . Location in patent: Page/Page column 41
  • 26
  • [ 1592-95-6 ]
  • [ 51035-17-7 ]
Reference: [1] Journal of the American Chemical Society, 1941, vol. 63, p. 1553,1554
  • 27
  • [ 86-74-8 ]
  • [ 1592-95-6 ]
  • [ 6825-20-3 ]
Reference: [1] Tetrahedron, 1992, vol. 48, # 36, p. 7479 - 7488
[2] Canadian Journal of Chemistry, 1992, vol. 70, # 3, p. 870 - 876
[3] Canadian Journal of Chemistry, 1992, vol. 70, # 3, p. 870 - 876
[4] Tetrahedron, 1992, vol. 48, # 36, p. 7479 - 7488
[5] Canadian Journal of Chemistry, 1992, vol. 70, # 3, p. 870 - 876
[6] Synthesis, 2005, # 10, p. 1619 - 1624
  • 28
  • [ 1592-95-6 ]
  • [ 100-44-7 ]
  • [ 57103-02-3 ]
Reference: [1] Patent: US2011/309345, 2011, A1,
  • 29
  • [ 1592-95-6 ]
  • [ 7570-45-8 ]
Reference: [1] European Journal of Inorganic Chemistry, 2018, vol. 2018, # 3, p. 531 - 543
  • 30
  • [ 1592-95-6 ]
  • [ 1126522-69-7 ]
  • [ 1984-49-2 ]
YieldReaction ConditionsOperation in experiment
59% With tris-(dibenzylideneacetone)dipalladium(0) In water; toluene A mixture solution of 3-bromo-9H-carbazole (6.75 g, 27.4 mmol), 9-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole (12.15 g, 32.9 mmol), Pd2(dba)3 (0.251 g, 0.274 mmol), SPhos (0.450 g, 1.097 mmol) and K3PO4 (25.3 g, 110 mmol) in toluene (500 mL) and water (50 mL) was refluxed under nitrogen for 10 h.
After cooling to room temperature, the reaction mixture was extracted with dichloromethane and washed with brine.
The combined organic solutions were dried over Na2SO4, filtered, and the solvent was evaporated to yield a crude product, which was recrystallized from DCM/hexane (1/1, v/v, 1200 mL) to yield 9H,9'H-3,3'-bicarbazole (6.66 g, 59percent) as a yellow solid.
Reference: [1] Patent: US2013/26909, 2013, A1, . Location in patent: Page/Page column
  • 31
  • [ 1592-95-6 ]
  • [ 591-50-4 ]
  • [ 1153-85-1 ]
YieldReaction ConditionsOperation in experiment
87.22% With tris-(dibenzylideneacetone)dipalladium(0); tributylphosphine In toluene for 12 h; Heating To a flask including 3-bromo-9H-carbazole and iodobenzene, 0.03 eq. of tris(dibenzilideneacetone)dipalladium(0) (Pd2(dba)3), 0.06 eq. of tributylphosphine, and toluene (0.1 M) were added and stirred for about 12 hours. After that, the reaction product was cooled to ambient temperature, extracted with methylene chloride, and washed with distilled water. The product thus obtained was dried with magnesium sulfate (MgSO4) and distilled under a reduced pressure, and the residue was separated by column chromatography to produce a 3-bromo-9-phenyl-9H-carbazole intermediate (Yield 87.22percent). The mass of the compound identified using a high resolution mass spectrometer (HRMS) was 321, and the molecular formula was identified as C18H12BrN.
86% With tris-(dibenzylideneacetone)dipalladium(0); triphenylphosphine; sodium t-butanolate In toluene at 100℃; To a round bottom flask 3-bromo-9H-carbazole (4.9g, 20mmol), iodobenzene (4.1g, 20mmol), Pd2 (dba) 3 (0.9g, 1mmol), PPh3 (0.5g, 2mmol), NaOt-Bu ( 5.8g, 60mmol), and the reaction allowed to proceed at 100 after the into toluene (210mL). After completion of reaction, the organic layer was dried over MgSO4, and extracted with water and ether and recrystallized silicagel column and the resulting organics concentrated and the product was 5.5g: (yield: 86percent).
86% With copper(l) iodide; 1,10-Phenanthroline; potassium carbonate In 5,5-dimethyl-1,3-cyclohexadiene for 6 h; Reflux 2-neck flask (Two neck flask) the material 1-a '(Cas No. 1592-95-6, 20g, 81.3mmol, 1eq) and iodo benzene (Iodobenzene) (18.23g, 89.4mmol, 1.1eq) was added to . Here, copper iodide (CuI) (3.1g, 16.3mmol, 0.2eq), 1,10- phenanthroline (1,10-phenanthroline) (3.0g, 16.3mmol, 0.2eq), and xylene (xylene) to 150ml then added and stirred under reflux for 6 hours. After the reaction cooled to room temperature, then the solvent was distilled off under reduced pressure and purified by column chromatography to give a 1-b '(22.4g, yield 86percent).
81% With copper; potassium carbonate In nitrobenzene for 16 h; Inert atmosphere; Reflux Under nitrogen atmosphere, intermediate G 2.46g (10mmol) and iodobenzene 3.06g (15mmol) were dissolved in 25ml nitrobenzene, K2CO3 4.15g (30mmol) and Cu 0.19g (3mmol) was added and refluxed for 16 hours. After completion of the reaction, MC 200ml, H2O 200ml was added and then the the MC layer was extracted, concentrated and separated by column chromatography using Hex : EA =5 : 1 and dried over anhydrous MgSO4 to give the intermediate H 2.61g (81percent).
81% With copper; potassium carbonate In nitrobenzene for 16 h; Inert atmosphere; Reflux Under nitrogen intermediates C 2.46g (10mmol) and iodo-benzene 3.06g (15mmol) dissolved in 25ml of nitrobenzene and then, 4.15g K2CO3 (30mmol) and 0.19g Cu (3mmol) were added andIt was refluxed for 16 hours When the reaction is complete, remove the nitrobenzene via distillation, and 200ml MC, was added 200ml of H2O, extract the MC layer was dried over anhydrous MgSO4 and concentrated to Hex: MC = 5: 1 column with an intermediate D 2.61g (81percent to ) to give
79% With copper; potassium carbonate; sodium sulfate In nitrobenzene at 200℃; intermediate G and 1mol iodobenzene nitrobenzene in the 1.5mol It was dissolved, Na2SO4, K2CO3, and the addition of Cu, which was stirred at 200 °. After the reaction is complete when the nitrobenzene removed by distillation and extracted with water and CH2Cl2 and the organic layer over anhydrous MgSO4 In dry, concentrated, and then the desired product was produced by column chromatography and recrystallization To give the intermediate H (Yield: 79percent).
78% With tris-(dibenzylideneacetone)dipalladium(0); triphenylphosphine; sodium t-butanolate In toluene at 100℃; for 24 h; To a round bottom flask Sub 2-1-1 (4.9g, 20mmol), Sub 2-1-2-1 (4.1g, 20mmol),Pd2 (dba) 3 (0.9g, 1mmol), PPh3 (0.5g, 2mmol ), NaOt-Bu (5.8g, 60mmol), were addedto toluene (210mL), respectively, and refluxed under stirring for 24 hours at 100 ° C.ether and with water, dried over MgSO4 and the organic layer was extracted andconcentrated and to the resulting organic silicagel column and recrystallized Sub the 2-1-3-1 5.0g (yield: 78percent) was obtained.
75% With tris-(dibenzylideneacetone)dipalladium(0); triphenylphosphine; sodium t-butanolate In toluene at 100℃; To a round bottom flask Sub 1-1-1 (4.9g, 20mmol), Sub 1-2-1 (4.1g, 20mmol), Pd2 (dba) 3 (0.9g, 1mmol), PPh3 (0.5g, 2mmol), NaOt-Bu (5.8g, 60mmol), and the reaction proceeds at 100°C after the into toluene (210mL). After the reaction was completed with water and extracted with ether. The organic layer was dried over MgSO4, concentrated and the resulting organic matter by silicagel column and recrystallized 4.8g of Sub 1 (1) (yield: 75percent) was obtained.
75% With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate In toluene at 100℃; In round bottom flask SM-1 (4.9g, 20mmol), SM-2-1 (4.48g, 22mmol), Pd2(dba)3(0.3g, 0.6mmol), P(t-Bu)3(0.2g, 2mmol), t-BuONa (5.8g, 60mmol), toluene (300 ml) added, the reaction proceeds at 100 °C after loading. After completion of reaction was obtained with CH2Cl2 and the organic layer was extracted with water, dried over MgSO4, silicagel column and re-crystallization and the resulting organics concentrated to the 4.8g SM-3-1. (Yield: 75percent)
73% With copper; potassium carbonate; sodium sulfate In nitrobenzene at 200℃; The Sub 1-II-1 (35.25 g, 143.2 mmol) toa round bottom flask in nitrobenzene (1790ml) to dissolve and then, iodobenzene(43.83 g, 214.9 mmol), Na2SO4 (20.35 g, 143.2 mmol), K2CO3 (19.80 g, 143.2mmol), was added Cu (2.73g, 43.0 mmol) and stirred at 200 . After completion ofreaction was removed by distillation to nitrobenzene and extracted with waterand CH2Cl2. The resulting compound and the organic layer was dried over MgSO4and concentrated to silicagel column and the product was recrystallized from 33.69 g (yield: 73percent) was obtained.
72% With copper; potassium carbonate; sodium sulfate In nitrobenzene at 200℃; Said Sub 1-II-1 obtained in the synthesis (110.36g, 448.4mmol) senses a rotation velocity of the disk in nitrobenzene for in round bottom flask , iodobenzene (137.23g, 672.7mmol), Na2SO 4 (63.7g, 448.4mmol), K2CO3 (61.98g, 448.4mmol), cu (8.55g, 134.5mmol) added 200 °C stirring section. When reaction is completed the via fractional distillation to remove the nitrobenzene CH 2 Cl 2 extracted and water. Organic layer MgSO 4 to dry a silicagel column with a compound formed after the products and recrystallization 104.03g (yield 72percent)is obtained
57% With 18-crown-6 ether; copper; sodium t-butanolate In toluene at 100℃; for 24 h; bromo-9H-carbazole (50.0 g, 203 mmol) and iodobenzene (49g, 240 mmol), 800 mL of toluene to the mixture after the Cu (764mg, 12 mmol) ,18-Crown-6 (6.3 g, 24 mmol), NaOt- Bu (57.6 g, 600mmol) each added one after, 100°C in 24 hours stirring under reflux causes. ether and water and the organic layer was extracted and then dried with MgSO4 and then concentrated to produce an organic silicagel column and recrystallized Sub 1-1(1) to give 36.6g). (Yield: 57percent)
1.9 g
Stage #1: With tri-tert-butyl phosphine; palladium diacetate In toluene at 20℃; for 1 h; Inert atmosphere
Stage #2: With potassium carbonate In toluene at 80℃; for 6 h; Inert atmosphere
250ml 3 neck round bottom flask the compound 1-3 (5g), Palladium (II) diacetate (0.1g), Tri-tert-butylphosphine (0.3g), toluene(100ml) was stirred into the atmosphere of argon at room temperature for 1 hour. A mixture of potassium carbonate (7.2g), 3-bromo carbazole (6.3g) it was stirred for 6 hours at 80°C. After the addition of water extracted with ethyl acetate and the title through a separation column using hexane and the resulting material water was removed to give a substituent 1-4 1.9g

Reference: [1] Patent: US2017/162796, 2017, A1, . Location in patent: Paragraph 0126; 0127
[2] Patent: KR2015/58973, 2015, A, . Location in patent: Paragraph 0106; 0107; 0108
[3] Patent: KR2016/51654, 2016, A, . Location in patent: Paragraph 0244-0246
[4] Patent: KR2015/102733, 2015, A, . Location in patent: Paragraph 0151-0155
[5] Patent: KR2015/112880, 2015, A, . Location in patent: Paragraph 0119; 0120; 0121; 0122; 0123
[6] Patent: KR101565039, 2015, B1, . Location in patent: Paragraph 0124-0127
[7] Patent: KR2015/93995, 2015, A, . Location in patent: Paragraph 0149; 0153; 0164-0166
[8] Patent: KR2016/10878, 2016, A, . Location in patent: Paragraph 0123-0125
[9] Patent: KR2015/133998, 2015, A, . Location in patent: Paragraph 0106-0109
[10] Patent: KR101535606, 2015, B1, . Location in patent: Paragraph 0129; 0130; 0135; 0136
[11] Patent: KR2015/98062, 2015, A, . Location in patent: Paragraph 0135-0139; 0149; 0150
[12] Patent: KR2016/18105, 2016, A, . Location in patent: Paragraph 0125; 0126; 0127; 0128
[13] RSC Advances, 2015, vol. 5, # 64, p. 51512 - 51523
[14] Angewandte Chemie - International Edition, 2016, vol. 55, # 9, p. 3017 - 3021[15] Angew. Chem., 2016, vol. 128, # 9, p. 3069 - 3073,5
[16] Patent: KR101507423, 2015, B1, . Location in patent: Paragraph 0167-0173
[17] Patent: KR2015/136712, 2015, A, . Location in patent: Paragraph 0086; 0087; 0088; 0089
[18] Journal of Materials Chemistry C, 2017, vol. 5, # 6, p. 1452 - 1462
  • 32
  • [ 108-86-1 ]
  • [ 1592-95-6 ]
  • [ 1153-85-1 ]
YieldReaction ConditionsOperation in experiment
71% With dibenzo-18-crown-6; potassium acetate; copper In N,N-dimethyl-formamide at 120℃; for 4 h; 3-bromo-9H-carbazole (2.5 g, 0.010 mol) in bromobenzene (1.6 g, 0.010 mol), dibenzo-18-crown-6 (1.1 g, 0.0030 mol), copper (2) (1.2 g, 0.020 mol) , into a 100 mL DMF to potassium acetate (2.8 g, 0.020 mol) it was reacted with stirring for 4 hours at 120 degree . After the reaction cooled to H20: After layer separation the MC column purification (n-Hexane: MC) to give to 2.3 g (yield 71percent).
Reference: [1] Patent: KR2016/56521, 2016, A, . Location in patent: Paragraph 0159-0161
[2] Patent: KR101876777, 2018, B1, . Location in patent: Paragraph 0109-0112; 0114
  • 33
  • [ 1592-95-6 ]
  • [ 73183-34-3 ]
  • [ 855738-89-5 ]
YieldReaction ConditionsOperation in experiment
99% With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; potassium acetate In 1,4-dioxane at 80℃; for 24 h; Inert atmosphere Monobromocarbazole (1 g, 5.98 mmol) was weighed out,Bis pinacolato boronate (1.52g, 5.98mmol)In a 100mL dual-mouth bottle,1,1'-bis (diphenylphosphino) ferrocenepalladium dichloride dichloromethane complex (0.2 g, 0.25 mmol) was added,1.5 g of potassium acetate,1,4-dioxane 40 mL,Join the magnet,Connected to the return pipe,Vacuum,Nitrogen cycle three times,80 , reaction 24h,The reaction was completed with dichloromethane and water twice,Take the organic phase,Dried organic phase,With petroleum ether:Dichloromethane:Ethyl acetate = 20: 2: purified by chromatography, column 1 Yield: 99percent.
85% With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate In toluene for 5 h; Reflux 3-bromo-9H-carbazole (27.0 g, 106.3 mmol), KOAc (26.0 g, 264.9 mmol) and Pd (dppf) Cl 2 (3.6 g, 4.4 mmol) were added to a solution of 3-bromo-9H-carbazole (21.7 g, 88.17 mmol), Bis (pinacolato) diboron Dissolved in 1 L of toluene, and then the mixture was refluxed with stirring for 5 hours. After confirming that the reaction was terminated by TLC, it was cooled to room temperature. After completion of the reaction, distilled water was added thereto, and the mixture was extracted with ethyl acetate. The obtained organic layer was dried over Na2SO4, distilled under reduced pressure, and then purified by column chromatography to obtain 22.0 g of 3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) , Yield: 85percent).
67% With bis-triphenylphosphine-palladium(II) chloride; potassium acetate In 1,4-dioxane for 2 h; Reflux; Inert atmosphere Under an argon stream,3-bromocarbazole (4.92 g), Bispinacolato diboron (10.2 g),Potassium acetate (7.85 g),Dichlorobistriphenylphosphine palladium (281 mg) was suspended in 1,4-dioxane (100 mL)And heated under reflux for 2 hours.After cooling to room temperature,Insolubles were removed by filtration.Next, the filtrate was purified by silica gel chromatography (developing solvent: chloroform)A white solid (yield 3.94 g, yield 67percent) of 3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)carbazole was obtained.
64% With 1,1'-bis-(diphenylphosphino)ferrocene; potassium acetate; palladium diacetate In dimethyl sulfoxide at 90℃; for 24 h; A mixture of compound 2 (4.92 g, 20 mmo 1), pinacolate (6.6 g, 26 mmo 1), acetic acidPalladium (0.134g, 0.6πππο1), dppf (0.66g, 1.2mmol), potassium acetate (5.88g, 60mmol), maintaining the anaerobic environment, Anaerobic DMS0 (50 ml) was added and the mixture was refluxed at 90 ° C for 24 h. After the end of the reaction, the reaction mixture was washed with deionized water (3 x 50 ml) and DCM(100ml). The organic phase was dried over anhydrous magnesium sulphate and evaporated to DCM to give the product 3 by column chromatography. Yield: 64percent.

Reference: [1] Patent: CN104650153, 2017, B, . Location in patent: Paragraph 0036; 0037; 0038; 0039
[2] Patent: KR2015/68182, 2015, A, . Location in patent: Paragraph 0097-0099; 0107-0109
[3] Patent: JP2015/6995, 2015, A, . Location in patent: Paragraph 0132
[4] Patent: CN106046054, 2016, A, . Location in patent: Paragraph 0068; 0069
  • 34
  • [ 1592-95-6 ]
  • [ 1591-31-7 ]
  • [ 894791-46-9 ]
YieldReaction ConditionsOperation in experiment
87.6% With tris-(dibenzylideneacetone)dipalladium(0); tributylphosphine In toluene for 12 h; Heating To a flask including 3-bromo-9H-carbazole and 4-iodo-1,1′-biphenyl, 0.03 eq. of tris(dibenzilideneacetone)dipalladium(0) (Pd2(dba)3), 0.06 eq. of tributylphosphine, and toluene (0.1 M) were added and stirred for about 12 hours. After that, the reaction product was cooled to ambient temperature, extracted with methylene chloride, and washed with distilled water. The product thus obtained was dried with magnesium sulfate (MgSO4) and distilled under a reduced pressure, and the residue was separated by column chromatography to produce a 3-bromo-9-(naphthalen-4-yl)-9H-carbazole intermediate (Yield 87.6percent). The mass of the compound identified using a high resolution mass spectrometer (HRMS) was 371, and the molecular formula was identified as C22H14BrN.
78% With copper(l) iodide; potassium carbonate; o-phenanthroline In N,N-dimethyl-formamide at 155℃; Inert atmosphere B aniline (10mmol, 1 . 69g), 3,6-dibromo-9-phenyl carbazole (11mmol, 4 . 41g) by adding 100 ml three-neck bottle, cuprous iodide is added under nitrogen (3mmol, 0 . 57g), potassium carbonate (30mmol, 4 . 15g), O-phenan throline (3mmol, 0 . 54g), 50mLN, N dimethyl formamide solution, 155 °C sleepovers reaction. After the reaction, water washing, extraction, drying of the organic layer, the solvent after evaporation to dryness, to obtain the product C-1 silica gel chromatography (2.44g, y = 50percent),
Reference: [1] Patent: US2017/162796, 2017, A1, . Location in patent: Paragraph 0146; 0147
[2] Patent: CN105418485, 2016, A, . Location in patent: Paragraph 0033; 0034; 0035
  • 35
  • [ 1592-95-6 ]
  • [ 352-34-1 ]
  • [ 894791-46-9 ]
Reference: [1] RSC Advances, 2016, vol. 6, # 49, p. 43250 - 43260
  • 36
  • [ 854952-58-2 ]
  • [ 1592-95-6 ]
  • [ 1060735-14-9 ]
YieldReaction ConditionsOperation in experiment
97%
Stage #1: With potassium carbonate In ethanol; water; toluene for 0.5 h; Inert atmosphere
Stage #2: With tris-(dibenzylideneacetone)dipalladium(0); triphenylphosphine In ethanol; water; toluene for 2 h; Reflux
(1)3-Boronic acid-9-phenylcarbazole12.92 g (0.053 mol) of 3-bromocarbazole, 17.28 g (0.125 mol) of potassium carbonate and 100 mL of a solvent (toluene: EtOH: H 2 O = 10: 2: 1) The mixture was purged with nitrogen for 30 min, 0.046 g of Pd2 (dba) 3 and 0.026 g of triphenylphosphine were added and the mixture was heated to reflux. After 2 h, no starting material was detected by TLC. The reaction was terminated by adding water to the aqueous layer and the organic layer was filtered through silica gel to remove the catalyst Toluene was distilled off under reduced pressure, cooled to 13 ° C, suction filtered and dried in vacuo to give 19.80 g of 9-phenyl-3,3'-bicarbazole as a solid in 97percent yield.
86% With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; sodium carbonate In 1,4-dioxane; water for 4 h; Inert atmosphere; Reflux In argon atmosphere, intermediate B (2.41g, 8.4 mmol), intermediate F (1.71g, 7.0 mmol), dichloro(diphenylphosphinoferrocene)palladium-methylene chloride complex (0.057g, 0.07 mmol), 1,4-dioxane (21 mL) and an aqueous solution of 2M sodium carbonate (10.5 mL) were sequentially added. The resulting mixture was heated under reflux for 4 hours. The reaction mixture was cooled to room temperature, and the precipitated solids were filtered off and washed with 1,4-dioxane and water, followed by drying under reduced pressure. The residue obtained was purified by means of silica-gel chromatography to obtain intermediate G (2.49g, yield: 86percent).
82% With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In ethanol; toluene at 100℃; for 12 h; Inert atmosphere A mixture of (9-phenyl-9H-carbazol-3-yl)boronic acid (14.2 g,49.5 mmol), 3-bromo-9H-carbazole (11.1 g, 45.0 mmol), Pd(PPh3)4(1.05 g, 0.9 mmol), K2CO3 (2.0 M aqueous solution, 80 mL), toluene(160 mL) and ethanol (80 mL) were stirred under nitrogen at 100 Cfor 12 h. Until the reaction cooled to room temperature, the greypowder was filtered from the solution and was recrystallized byethanol to afford the product (15.1 g, yield: 82percent). 1H NMR (CDCl3,400 MHz) δ [ppm]: 8.44 (s, 1H), 8.39 (s, 1H), 8.24-8.22 (d,J=7.76 Hz, 1H), 8.18-8.16 (d, J=7.76 Hz, 1H), 7.80-7.75 (m, 2H),7.63-7.62 (t, J=5.76 Hz, 4H), 7.52-7.43 (m, 8H), 7.33-7.27 (m, 2H).MS (APCI):calcd for C30H20N2: 408.1626; found: 408.1636 [M+H]+.
80% With potassium carbonate In 1,2-dimethoxyethane; water at 80℃; for 3 h; [Step 1: Synthesis of 9-phenyl-3,3'-bi(9H-carbazole)] (PCC)]
2.5 g of (10 mmol) 3-bromo-9H-carbazole, 2.9 g of (10 mmol) N-phenylcarbazol-3-boronic acid, and 152 mg of (0.50 mmol) tri(ortho-tolyl)phosphine were put into a 200 mL three-neck flask.
The air in the flask was replaced with nitrogen.
To the mixture were added 50 mL of dimethoxyethanol and 10 mL of an aqueous solution of potassium carbonate (2 mol/L).
This mixture was stirred to be degassed while the pressure was reduced.
After the degassing, 50 mg (0.2 mmol) of palladium acetate was added to the mixture.
This mixture was stirred at 80 °C for 3 hours under a stream of nitrogen.
After the stirring, about 50 mL of toluene was added to this mixture.
The mixture was stirred for about 30 minutes and then washed with water and a saturated saline solution in this order.
After the washing, an organic layer was dried with magnesium sulfate.
This mixture was subjected to gravity filtration.
The obtained filtrate was condensed to give an oily substance.
The obtained oily substance was dissolved in toluene.
This solution was subjected to suction filtration through Florisil (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 540-00135), alumina, and celite (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 531-16855).
The obtained filtrate was concentrated to give 3.3 g of a white solid, which was the object of the synthesis, at a yield of 80 percent.
A synthesis scheme of Step 1 is shown in (b-1) given below.
The solid obtained in the above Step 1 was analyzed by nuclear magnetic resonance measurement (1H NMR).
The measurement result is described below, and the 1H NMR chart is shown in
.
They show that the organic compound PCC of the present invention represented by the structural formula (501), which is used in any of the anthracene derivatives of the present invention, was obtained in this synthesis example.
1H NMR (DMSO-d6, 300 MHz): δ = 7.16-7.21 (m, 1H), 7.29-7.60 (m, 8H), 7.67-7.74 (m, 4H), 7.81-7.87 (m, 2H), 8.24 (d, J = 7.8 Hz, 1 H), 8.83 (d, J = 7.8 Hz, 1H), 8.54 (d, J = 1.5 Hz, 1H), 8.65 (d, J = 1.5 Hz, 1H), 11.30(s, 1H).
80% With potassium carbonate; tris-(o-tolyl)phosphine In water; dimethoxyethanol; toluene at 80℃; for 3.5 h; Inert atmosphere In a 200 mL three-necked flask were put 2.5 g (10 mmol) of 3-bromocarbazole, 2.9 g (10 mmol) of N-phenylcarbazole-3-boronic acid, and 152 mg (0.50 mmol) of tri(ortho-tolyl)phosphine.
The atmosphere in the flask was replaced with nitrogen.
To this mixture were added 50 mL of dimethoxyethanol (DME) and 10 mL of an aqueous potassium carbonate solution (2 mol/l).
This mixture was degassed by being stirred while the pressure was reduced.
After the mixture was degassed, to this mixture was added 50 mg (0.2 mmol) of palladium(II) acetate.
The mixture was stirred under nitrogen stream at 80° C. for 3 hours.
After the mixture was stirred, to this mixture was added about 50 mL of toluene, followed by stirring for about 30 minutes.
This mixture was washed with water and a saturated saline solution in that order.
After the mixture was washed, the organic layer was dried with magnesium sulfate.
This mixture was gravity filtered, and the obtained filtrate was concentrated to give an oily substance.
The obtained oily substance was dissolved in toluene, and this solution was filtered through Florisil (a product of Wako Pure Chemical Industries, Ltd., Catalog No. 540-00135), alumina, and Celite (a product of Wako Pure Chemical Industries, Ltd., Catalog No. 531-16855).
The obtained filtrate was concentrated to give the object of the synthesis as 3.3 g of a white solid at a yield of 80percent.
The synthesis scheme of Step 1 is illustrated in (c-1) below.
80% With tetrakis(triphenylphosphine) palladium(0) In tetrahydrofuran; water at 80 - 90℃; Alkaline conditions Insert the SM-1 (4.9g, 20mmol) in a round bottom flask, Sub 1-1 (a) (6.9g, 24mmol), Pd(PPh3)4 (0.7g, 0.6mmol), NaOH (2.4g, 60ml), placed a THF (60mL), water added (30mL). Then heated to reflux 80 °C~90°C. After completion of reaction, diluted with distilled water at room temperature and extracted with water and CH2Cl2. The Ministry of Health and Welfare compound was concentrated by drying the organic layer with MgSO4 silicagel column and recrystallized to obtain 6.5g of Sub 3-1 (a). (Yield: 80percent)
78% With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In ethanol; water; toluene for 5 h; Inert atmosphere; Reflux 3-Bromocarbazole (0.1219 mol) was dissolved in 300 ml of toluene,And N-phenylcarbazole-3-boronic acid (0.1209 mol) was added under nitrogen,30 ml of ethanol,Potassium carbonate (0.2418 mol),30ml water,Tetrakis (triphenylphosphine) palladium (0.00122 mol)And then heated to reflux reaction 5h,HPLC reaction is completed, the reaction solution spin and add dichloromethane and water extraction, take the organic phase of silica gel funnel,The organic phase was dried under reduced pressure to give compound 180-1 (yield 78percent) by column chromatography.
73% With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In ethanol; toluene at 120℃; for 5 h; After dissolving 3-bromo-9H-carbazole (60 g, 243.80 mmol), (9-phenyl-9H-carbazol-3-yl)boronic acid (84 g, 292.S6mmol), and tetrakis(triphenylphosphine)palladium (Pd(PPh3)4) (14 g, 12.19 mmol) in 2M Na2CO3 (500 mL), toluene (1000 mL), and ethanol (500 mL) of a flask, the mixture was under reflux at 120°C for 5 hours. After completion of the reaction, the mixture was extracted with ethyl acetate. The remaining moisture was removed from the obtained organic layer with magnesium sulfate. The product was then dried, and purified by column chromatography to obtain compound 1-1 (73 g, yield: 73percent).
73% With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In ethanol; toluene at 120℃; for 5 h; To the flask was added 3-bromo-9H-carbazole(O) (Pd (PPh3) 4) (60 g, 243.80 mmol), (9-phenyl-9H-carbazol-3-yl) boronic acid (84 g, 292.56 mmol), tetrakis (triphenylphosphine) palladium 14 g, 12.19 mmol), 500 mL of 2M Na 2 CO 3, 1000 mL of toluene and 500 mL of ethanol, and the mixture was refluxed at 120 ° C for 5 hours. After the reaction was completed, the organic layer was extracted with ethyl acetate, and the residue was dried with magnesium sulfate. The organic layer was dried and separated by column to obtain Compound 1-1 (73 g, yield: 73percent).
72% With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In ethanol; water; toluene at 90 - 100℃; for 3 h; 9-phenyl-9H-carbazol-3-yl boronic acid (14 g, 48.76 mmol), 3-bromo-9H-carbazole (10 g, 40.63 mmol), K2CO3 (13.5 g, 97.52 mmol) and Pd(PPh3)4 (2.35 g, 2.03 mmol) were added to toluene 200 mL, EtOH 50 mL and purified water 50 mL. After stirring the reaction mixture for 3 hours at 90 to 100°C, the mixture was cooled to room temperature. An aqueous layer was removed from the mixture by a gravity separation. The obtained organic layer was concentrated, was triturated with MC, and then was filtered to obtain compound C-2-1 (12 g, 72percent).
72% With potassium carbonate In ethanol; water; toluene at 90 - 100℃; for 3 h; Preparation of compound C-1-1 [88] 9-phenyl-9H-carbazol-3-yl boronic acid (14 g, 48.76 mmol), 3-bromo-9H-carbazole (10 g, 40.63 mmol), K2CO3 (13.5 g, 97.52 mmol) and Pd(PPh3)4 (2.35 g, 2.03 mmol) were added to a mixture of toluene 200mL, EtOH 50mL and purified water 50mL. After stirring the reaction mixture for 3 hours at 90~100°C, the mixture was cooled to room temperature. An aqueous layer was removed from the mixture by a gravity separation. The obtained organic layer was concentrated, was triturated with methylene chloride (MC), and then was filtered to produce compound C-1-1 (12 g, 72percent).
72% With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In ethanol; water; toluene at 95℃; for 3 h; Preparation of compound 1-7 [101] After putting compound 1-5 (14 g, 48.76 mmol), compound 1-6 (10 g, 40.63 mmol), K2CO3 (13.5 g, 97.52 mmol) and Pd(PPh3)4 (2.35 g, 2.03 mmol) into toluene (200 mL), ethanol (50mL) and purified water (50 mL), the reaction mixture was stirred for 3 hours at 95°C. After terminating the reaction, the reaction mixture was cooled to room temperature. The aqueous layer was removed, and the organic layer was concentrated, was triturated with MC, and was filtered to obtain compound 1-7 (12 g, 72 percent).
72% With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In ethanol; water; toluene at 90 - 100℃; for 3 h; Preparation of compound 42-3 [157] After dissolving compound 42-1 (14 g, 48.76 mmol), compound 42-2 (10 g, 40.63 mmol), K2CO3 (13.5 g, 97.52 mmol), and tetrakis(triphenylphosphine)palladium(O) [Pd(PPh3)4] (2.35 g, 2.03 mmol) in a mixture solvent of toluene (200 mL), EtOH (50 mL), and purified water (50 mL), the mixture was stirred for 3 hours at 90-100°C. Then, the mixture was cooled to room temperature and two phase mixture of organic layer/aqueous layer was obtained. The aqueous layer was removed, and the organic layer was concentrated and then separated with a column to obtain compound 42-3 (12 g, 72 percent).
62% With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In 1,2-dimethoxyethane; water for 24 h; Reflux; Inert atmosphere 49.22 Grams (200 mmol) of No.10 3-bromocarbazole, 63.17 g (220 mmol) of No.11 9-phenylcarbazole-3-boronic acid, a 2-M aqueous solution of sodium carbonate (200 ml), and 400 ml of 1,2-dimethoxyethane were loaded into a three-necked flask. Next, 2.31 g (2 mmol) of Pd(PPh3)4 were added to the mixture and then the whole was refluxed under a nitrogen atmosphere for 24 hours. [0242] After the completion of the reaction, the sample was transferred to a separating funnel and extracted with dichloromethane several times. The resultant was dried with anhydrous magnesium sulfate, and was then filtered and concentrated. The concentrate was purified by silica gel chromatography (dichloromethane:hexane=6:4), and was then washed by being dispersed in methanol. Thus, a white solid (Compound (1-1)) was obtained. [0243] Identification was performed by 1H-NMR and molecular weight measurement based on FD/MS. Product amount: 50.6 g Yield: 62percent
60% With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran at 80℃; for 10 h; Inert atmosphere 100 g (348 mmol) of 9-phenyl-9H-carbazol-3-ylboronic acid was dissolved in 0.93 L of tetrahydrofuran (THF) in a nitrogen environment, 85.6 g (348 mmol) of 3-bromo-9H-carbazole and 4.02 g (3.48 mmol) of tetrakis(triphenylphosphine)palladium were added thereto, and the mixture was agitated. Then, 120 g (870 mmol) of potassium carbonate was added thereto, and the mixture was heated and refluxed at 80° C for 10 hours. When the reaction was terminated, water was added to the reaction solution, and the mixture was extracted with dichloromethane (DCM) and treated with anhydrous MgSO4 to remove moisture and then, filtered and concentrated under a reduced pressure. Then, the obtained residue was separated and purified through flash column chromatography, obtaining 85.3 g of a compound I-30 (a yield: 60 percent). (0218) HRMS (70 eV, EI+): m/z calcd for C30H20N2: 408.1626, found: 408. (0219) Elemental Analysis: C, 88 percent; H, 5 percent
60% With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran at 80℃; for 10 h; Inert atmosphere In a nitrogen atmosphere 9-phenyl-9H-carbazol-3-ylboronic acid (100 g, 348 mmol) and then in a tetrahydrofuran (THF) 0.93 L Enoch, here a 3-bromo-9H-carbazole (85.6 g, 348 mmol) and put the tetrakis (triphenylphosphine) palladium (4.02 g, 3.48 mmol) was stirred. Into the potassuim carbonate (120 g, 870 mmol) in saturated water it was heated to reflux at 80 for 10 hours. After the reaction was completed, the reaction solution into water and extracted with dichloromethane (DCM) and then water was removed with anhydrous MgSO4, filter and was concentrated under reduced pressure. Thus, the obtained residue was purified by flash column chromatography separation to give the compound I-30 (85.3 g, 60percent) as to obtain
60% With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; water at 80℃; for 10 h; Inert atmosphere 9-phenyl-carbazol-3-ylboronic acid (100 g, 348 mmol) purchased from the tokyo chemical industry under nitrogen atmosphere was dissolved in 0.93 L of tetrahydrofuran (THF) and 3-bromo-9H-carbazole (85.6 g, 348 mmol) purchased from the tokyo chemical industry and tetrakis (triphenylphosphine) palladium(4.02 g, 3.48 mmol) and potassium carbonate (120 g, 870 mmol) saturated in water,And the mixture was refluxed by heating at 80 ° C for 10 hours. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM) The water was removed with MgSO4, filtered and concentrated under reduced pressure.The residue thus obtained was purified by flash column chromatographyTo obtain Intermediate I-32 (85.3 g, 60percent).
58.57% With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In ethanol; toluene for 5 h; Reflux After adding compound C-3-1 12 g (41.79 mmol), compound C-3-2 11.3 g (45.97mmol), Pd(PPh3)4 1.4 g (1.25 mmol), and 2 M K2C03 52 mL to a mixture solvent of toluene 150 mL, and ethanol 30 mL, the mixture was stirred under reflux. After 5 hours, the mixture was cooled to room temperature, and distilled water was added to the mixture. Then, the mixture was extracted with EA, dried with magnesium sulfate, distilled under reduced pressure, and recrystallized with EA and methanol to obtain compound C-3-3 10 g (58.57 percent).
57% With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; potassium phosphate; tris-(dibenzylideneacetone)dipalladium(0) In 5,5-dimethyl-1,3-cyclohexadiene; ethanol; waterInert atmosphere; Heating A three-necked flask equipped with a stirrer was charged with 984 mg (4.00 mmol) of 3-bromocarbazole (Compound e), 1.26 g (4.40 mmol) of 9-phenylcarbazole-3-boronic acid (compound f), 20 ml of 2M tripotassium phosphate (K3PO4) aqueous solution (40.0 mmol of tripotassium phosphate), 40 ml of xylene, 20 ml of ethanol was added and nitrogen bubbling was carried out for 1 hour. Thereto, 256 mg (0.28 mmol) of tris(dibenzylidene acetone)dipalladium (0) (Pd2(dba)3), 230 mg (0.56 mmol) of 2-dicyclohexylphosphino-2 ', 6'-dimethoxybiphenyl (SPhos) was added and the mixture was heated and stirred overnight. After removing the solvent, extraction with toluene and saturated brine, washing was carried out. Thereafter, drying was carried out with magnesium sulfate, and the drying agent was filtered off. After concentrating the filtrate, purification was carried out by silica gel column chromatography (dichloromethane: hexane = 1: 1) . 937 mg (2.30 mmol) of the objective compound g was obtained in a yield of 57percent.
45% With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; water at 80℃; for 24 h; 100 g (406 mmol) of 3-bromo-9H-carbazole was dissolved in 1.2 L of tetrahydrofuran (THF) in a nitrogen environment, 128 g (447 mmol) of 9-phenyl-9H-carbazol-3-ylboronic acid and 4.69 g (4.06 mmol) of tetrakis(triphenylphosphine)palladium were added thereto, and the mixture was agitated. 120 g (812 mmol)) of potassium carbonate saturated in water was added thereto, and the mixture was heated and refluxed at 80 °C for 24 hours. When the reaction was terminated, water was added to the reaction solution, and the mixture was extracted with dichloromethane (DCM) and treated with anhydrous MgSO4 to remove moisture and then, filtered and concentrated under a reduced pressure. The obtained residue was separated and purified through flash column chromatography, obtaining a compound I-19 (74.6 g, 45 percent). HRMS (70 eV, EI+): m/z calcd for C30H2ON2: 408.1626, found: 408.2. Elemental Analysis: C, 88 percent; H, 5 percent
45% With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In ethanol; water; toluene at 120℃; for 24 h; After dissolving compound1(3-bromo-9H-carbazole) (20g, 69.70 mmol), compound2[(9-phenyl-9H-carbazol-3-yl)boronic acid] (17.2g, 69.70 mmol), Pd(PPh3)4(2.4g, 2.10 mmol), and Na2CO3(18.5g, 174.30 mmol) in toluene, ethanol, and H2O of a flask, the mixture was under reflux at 120°C for a day. After completion of the reaction, the mixture was extracted with ethyl acetate. The obtained organic layer was dried, and subjected to column chromatography to obtain compound 3(12.8g, yield: 45percent).
45% With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In ethanol; water; toluene at 120℃; for 24 h; Multi function cap chemical compound in at 1 ( 3-bromo -9H-carbazole) (20g, 69.70 mmol), compound 2 [ (9-phenyl -9H-carbazole-3-one) boronic acid] (17.2g, 69.70 mmol), Pd (PPh 3) 4 (2.4g, 2.10 mmol), and Na 2 CO 3 (18.5g, 174.30 mmol) is toluene, ethanol, H 2 O in. recirculating a during day in 120 °C senses a rotation velocity of the disk. Reaction vessel with a great overall height to ethyl acetate to behind and dry extracting organic layer separated by column chromatography the compounds 3 ( 12.8g, yield: 45percent) is obtained.
52 g With sodium carbonate In ethanol; water; toluene for 2 h; Reflux At reflux temperature, there was added (9-phenyl -9H- carbazol-3-yl) boronicacid (50.0g), 3- bromo -9H- carbazole (39.0g), Pd-132 (Johnson Matthey ) (1.2g), sodiumcarbonate (46.1g), toluene (400ml), ethanol (100ml) and water (100 ml) was stirred for 2hours the flask was heated. The reaction mixture was cooled until room temperature,water and toluene were separated. Then, the use of amino-modified silica gel (NHDM1020:Rich Shixi Australasia (Fuji Silysia) Ltd.) column chromatography (eluent: toluene) togive 9-phenyl obtain -9H, 9'H-3,3'- linking carbazole (52.0g).
12 g With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; water for 6 h; Reflux (0.049 mol) of 3-bromo-9H-carbazole and 13.5 g (0.098 mol) of potassium carbonate were dissolved in 200 mL of tetrahydrofuran And water (50 mL). 2.35 g (2.03 mmol) of tetrakis (triphenylphosphine) palladium (0) was added under reflux and stirred for 6 hours. After completion of the reaction,The organic layer is separated by cooling and concentrated under reduced pressure. The concentrated compound was slurry filtered with chloroform and hexane to obtain 12 g of intermediate 17-1.
13.5 g With palladium diacetate; potassium carbonate; tris-(o-tolyl)phosphine In 1,2-dimethoxyethane; water for 6 h; Reflux; Inert atmosphere 3-Bromocarbazole 20.9 g,9-phenylcarbazole-3-boronic acid 15.0 g,Palladium acetate 366 mg,A mixed solution of tris (2-methylphenyl) phosphine 300 mg, 2 M potassium carbonate aqueous solution of 105 mb dimethoxyethane 260 ml was refluxed under nitrogen for 6 hours. After cooling to room temperature, extraction was carried out with 500 ml of tetrahydrofuran. The organic layer was washed with saturated brine100 ml, 2 times, dried by magnesium sulfate, and evaporated. The resulting concentrate was purified by recrystallization from o-xylene and dried in vacuo to give 9-phenyl-9H, 9'H-3,3-carbazole 13.5 g.

Reference: [1] Patent: CN106631984, 2017, A, . Location in patent: Paragraph 0020; 0021
[2] Patent: EP2662368, 2013, A1, . Location in patent: Paragraph 0155; 0156
[3] Dyes and Pigments, 2017, vol. 136, p. 54 - 62
[4] Patent: EP1972619, 2008, A1, . Location in patent: Page/Page column 262-263
[5] Patent: US2009/247795, 2009, A1, . Location in patent: Page/Page column 10
[6] Patent: KR2015/133998, 2015, A, . Location in patent: Paragraph 0142-0144
[7] Patent: CN106928237, 2017, A, . Location in patent: Paragraph 0199; 0200
[8] RSC Advances, 2016, vol. 6, # 68, p. 64133 - 64139
[9] Patent: WO2015/167300, 2015, A1, . Location in patent: Paragraph 161; 162; 163
[10] Patent: KR2016/11463, 2016, A, . Location in patent: Paragraph 0043-0045
[11] Patent: WO2012/121561, 2012, A1, . Location in patent: Page/Page column 18
[12] Patent: WO2012/141499, 2012, A1, . Location in patent: Page/Page column 14
[13] Patent: WO2013/32278, 2013, A1, . Location in patent: Paragraph 100; 101
[14] Patent: WO2013/154325, 2013, A1, . Location in patent: Paragraph 154-157
[15] Patent: US2013/20565, 2013, A1, . Location in patent: Paragraph 0240-0243
[16] Patent: EP2947071, 2015, A1, . Location in patent: Paragraph 0216-0219
[17] Patent: KR2015/117173, 2015, A, . Location in patent: Paragraph 0446-0448
[18] Patent: KR2017/124412, 2017, A, . Location in patent: Paragraph 0342-0344
[19] Patent: WO2014/3440, 2014, A1, . Location in patent: Paragraph 140; 141; 146; 147
[20] Patent: JP2017/145198, 2017, A, . Location in patent: Paragraph 0049-0050
[21] Patent: EP2889296, 2015, A1, . Location in patent: Paragraph 0228-0231
[22] Patent: WO2016/52962, 2016, A1, . Location in patent: Paragraph 161-162
[23] Patent: KR2016/37788, 2016, A, . Location in patent: Paragraph 0177-0180
[24] Journal of Materials Chemistry C, 2015, vol. 3, # 20, p. 5347 - 5353
[25] Patent: CN105431439, 2016, A, . Location in patent: Paragraph 1127; 1128; 1129
[26] Patent: KR101672074, 2016, B1, . Location in patent: Paragraph 0430-0434
[27] Patent: TWI558693, 2016, B, . Location in patent: Paragraph 0120
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YieldReaction ConditionsOperation in experiment
87% With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; potassium phosphate In water; toluene for 5 h; Inert atmosphere; Reflux Synthesis of 9-phenyl-9H,9'H-3,3'-bicarbazole. A mixture of 9-phenyl-3-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)-9H-carbazole (12 g, 32.5 mmol), 3-bromo-9H-carbazole (6.66 g, 27.1 mmol), and potassium phosphate (34.5 g, 162 mmol) in 500 mL of toluene and 50 mL of H20 was bubbled with N2 for 20 min. Dicyclohexyl(2',6'- dimethoxybiphenyl-2-yl)phosphine (0.445 g, 1.083 mmol) and Pd2(dba)3 (0.248 g, 0.271 mmol) were then added, and the mixture was heated to reflux under N2 for 5 h. TLC indicated the reaction was done. The reaction was extracted with dichloromethane and washed with brine and dried with magnesium sulfate. The solution was heated up to boil. Hexane was added. The dichloromethane was boiled off and hexanes volume reached about 1200 mL. Precipitate formed during boiling off dichloromethane. The solution was cooled to room temperature and stirred overnight. The precipitate was filtered and dissolved in THF and ran a short silica gel plug. After dried under vacuum at 60 °C, 9.6 g (87percent) of product was obtained.
77% With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; water at 80℃; for 24 h; Inert atmosphere Under a nitrogen atmosphere, 26g (104.9mmol) 3- bromo-carbazole was dissolved in 400mL of tetrahydrofuran was added 46.5g (125.9mmol) 9- -9H- carbazol-3-phenyl-3-boronic acid pinacol thereto alcohol esters (Matt Rix Technologies (MatrixScientifeic)) and 6.1g (5.25mmol) of tetrakis (triphenylphosphine) palladium and the mixture was stirred. Subsequently, thereto added 43.5g (314.75mmol) saturated aqueous potassium carbonate, and the mixture was heated at reflux for 80 24 hours. When the reaction was completed, water was added to the reaction solution, and the mixture was extracted with methylene chloride, after removal of water therefrom over anhydrous MgSO4 filtered and concentrated under reduced pressure. Subsequently, the obtained residue was separated therefrom and purified by column chromatography to give 33g (77percent) of intermediate 1-3.
75% With tetrakis(triphenylphosphine) palladium(0); sodium hydroxide In tetrahydrofuran; water at 80℃; for 12 h; Inert atmosphere Nitrogen airflow under 9-phenyl-3-(4, 4, 5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl)-9H-carbazole (2.59 g, 7.03 mmol) and 3-bromo-9H-carbazole (2.07 g, 8.43 mmol), NaOH (0.84 g, 21.08 mmol) and THF/H2O (40 ml/20 ml) after being mixed with, 40? In Pd (PPh3)4(0.48 g, 5 mol percent) for inserting and removing 80? In adaptation stirring time 12.Extracts the completion after methylene chloride MgSO4was filtering for inserting and removing. Evaporating a solvent from an organic layer obtained after removing the column chromatography (Hexane: MC = 3:1 (v/v)) for purifying the IC-3 (2.15 g, yield 75percent)is obtained.
68% With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; water; toluene for 12 h; Inert atmosphere; Reflux 26.96 g (81.4 mmol) of N-phenyl carbazole-3-boronic acid pinacolate, 23.96 g (97.36 mmol) of carbazole-3-boronic acid, 230 mL of tetrahydrofuran, and 100 mL of a 2M potassium carbonate aqueous solution were mixed and then, heated and refluxed under a nitrogen flow for 12 hours in a 500 mL round-bottomed flask having an agitator and a nitrogen atmosphere. When the reaction was complete, methanol was poured into the reactant. Then, a solid produced therein was filtered and dissolved in chlorobenzene, and activated carbon and anhydrous magnesium sulfate were added thereto. The mixture was agitated. The solution was filtered and recrystallized using chlorobenzene and methanol, obtaining 22.6 g (yield of 68percent) of a compound J.
68% With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; water; toluene for 12 h; Reflux It was the N- phenylcarbazole -3- boronic acidpinacol rate 26.96 g (81.4 mmol), and 3- bromo carbazole 23.96 g (97.36 mmol),the tetrahydrofuran 230 mL and 2M- potassium carbonate aqueous solution 100mlthe heating reflow after doing the mixing under the nitrogen air current for 12hours. After the solid material pouring into the reactant into the methanol andis generated after the reaction termination is filtered the solid material isagain melted in the chlorobenzene and the activated charcoal and MagnesiumSulfate Anhydrous are put and it is stirred. The solution was recrystallized byusing *** one next chlorobenzene and methanol and the compound J 22.6 g (yield: 68percent) was obtained
68% With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; water for 12 h; Inert atmosphere; Reflux N-phenyl carbazole -3-boronic acid Pinachol ester g 26.96 (81.4 mmol), 3-bromo-carbazol-23.96g (97.36 mmol) and 230 mL of tetrahydrofuran and 2M-potassium carbonate aqueous solution 100ml the mixture, and then it was heated under reflux for 12 hours under nitrogen flow.Filter the resulting solid was poured into methanol to the reaction After completion of the reaction, which was then agitated again to dissolve the solids chlorobenzene put the active carbon and anhydrous magnesium sulfate.Pilneo a solution and then recrystallized with chlorobenzene and methanol to obtain a compound J 22.6 g (yield: 68percent) was obtained.
68% With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; water; toluene at 120℃; for 12 h; Inert atmosphere In the nitrogen ambient, after compound9-phenyl-3 - (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9H-carbazoles(26.96 g, 81.4 mmol) were melted in the Toluene / THF 0.2 L here3-bromo-9H-carbazoles (23.96 g, 97.36 mmol) and tetrakis (triphenylphosphine)palladiums (0.90 g, 0.8 mmmol) were put and it mixed. Saturated potassuimcarbonates (28 g, 203.49 mmol) were put in water and it heated up in 120 for 12 hours and it refluxed. After water was put in into the reaction solutionafter the reaction completion and it extracted in the dichloromethane(DCM) moisture was removed to the anhydrous MgSO4 it filtered and it wasconcentrated under reduced pressure. The residue obtained in this way wasrefined to the flash column chromatography after dividing and compound Js (22.6g, 68percent) were obtained
68% With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; water; toluene at 120℃; for 12 h; Inert atmosphere First Step: Synthesis of Compound J (0230) The compound, 9-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole (26.96 g, 81.4 mmol) was dissolved in 0.2 L of toluene/THF in a nitrogen environment, 3-bromo-9H-carbazole (23.96 g, 97.36 mmol) and tetrakis(triphenylphosphine)palladium (0.90 g, 0.8 mmmol) were added thereto, and the mixture was stirred. Potassium carbonate saturated in water (28 g, 203.49 mmol) was added thereto, and the resulting mixture was heated and refluxed at 120° C. for 12 hours. When the reaction was complete, water was added to the reaction solution, dichloromethane (DCM) was used for an extraction, and an extract therefrom was filtered after removing moisture with anhydrous MgSO4 and concentrated under a reduced pressure. The obtained residue was separated and purified through flash column chromatography to obtain the compound J (22.6 g, 68percent). (0231) HRMS (70 eV, EI+): m/z calcd for C30H20N2:408.16, found: 408 (0232) Elemental Analysis: C, 88percent; H, 5percent
68%
Stage #1: With tetrakis(triphenylphosphine) palladium(0) In tetrahydrofuran; tolueneInert atmosphere
Stage #2: With potassium carbonate In tetrahydrofuran; water; toluene at 120℃; for 12 h;
In a nitrogen atmosphere, the compound 9-phenyl-3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9H-carbazole 26.96 g, 81.4 mmol) was dissolved in 0.2 liter of toluene / THF, to which was added 3-bromo-9H-carbazole (23.96 g, 97.36 mmol) and tetrakis (triphenylphosphine) palladium (0.90 g, 0.8 And the mixture was stirred. Then, a saturated aqueous solution of potassium carbonate (28 g, 203.49 mmol) was added thereto, and the obtained mixture was heated and refluxed at 120 ° C for 12 hours. When the reaction was complete, water was added to the reaction solution, extracted with dichloromethane (DCM), and the extract was treated with anhydrous MgSO4 to dehumidify, filter and concentrate under reduced pressure. The resulting residue was isolated and purified by flash column chromatography to afford compound J (22.6 g, 68percent).
68% With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; water; toluene for 12 h; Reflux; Inert atmosphere 26.96 g (81.4 mmol) of N-phenyl carbazole-3- boronic acid pinacolate and 23.96 g (97.36 mmol) of 3-bromo carbazole were mixed with 230 mE of tetrahydrothran and 100 ml of 2 molar (M) potassium carbonate aqueous solution, and the mixture was heated under reflux in a nitrogen stream for 12 hours. After the reaction was completed, a solid produced by pouring methanol into the reactant was filtered and then dissolved in chlorobenzene, activated carbon and anhydrous magnesium sulfate were added thereto, and the mixture was agitated. The solution was filtered and recrystallized by using chlorobenzene and methanol to obtain 22.6 g (68percent) of Compound (J). HRMS (70 eV, EI+): mlz calcd for C30H20N2: 408.16, found: 408. Elemental Analysis: C, 88percent; H, 5percent
62% With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In 1,4-dioxane; water at 120℃; for 5 h; Reflux 3-Bromocarbazole 20 g (81.3 mmol) and 9-phenyl-3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9H-carbazole in 33 g (89.4 mmol) dioxane 500 mL of purified water was added and 250 mL.Pd (PPh3) 44.7 g (4.1 mmol), K2CO334 g (244 mmol) was heated under reflux for 5 hours at 120 was added.Allowed to cool to room temperature and quench the reaction with 500 mL aqueous solution of ammonium chloride to the reaction mixture.Extract the mixture with EA 500 mL, and washed with distilled water.The resulting organic layer was dried over anhydrous MgSO4,and was evaporated under reduced pressure to give the objective compound was purified by silica gel column chromatography to obtain 20.6 g (yield 62percent).
32.7% With potassium carbonate In ethanol; toluene at 74 - 80℃; for 5 h; Inert atmosphere 3-Bromo-9H-carbazole (3.6 g), 9-phenyl-3-(4,4,5,5-tetramethyl-[1,3,2]dioxabororan-2-yl)-9H-carbazole (6.0 g), toluene (40 ml), ethanol (10 ml), and a 2M potassium carbonate aqueous solution (11 ml) were added to a nitrogen-substituted reaction vessel, and aerated with nitrogen gas for 30 min under ultrasonic waves. The mixture was heated after adding tetrakis(triphenylphosphine)palladium (0.85 g), and stirred at 74°C for 3.5 hours. After adding toluene (100 ml), the mixture was heated, and further stirred at 80°C for 1 hour. The mixture was then cooled to 50°C, and the insolubles were removed by filtration. The filtrate was then concentrated under reduced pressure to obtain a yellowish white crude product. Toluene (300 ml) was added to dissolve the crude product, and the solution was subjected to adsorptive purification with a NH silica gel (16.11 g), and concentrated under reduced pressure to obtain a white powder. The white powder was then purified by being dispersed and washed in ethyl acetate (35 ml) under heat to obtain a white powder of 9-phenyl-9H,9'H-[3,3']bicarbazolyl (1.96 g; yield 32.7percent).

Reference: [1] Patent: WO2011/137072, 2011, A1, . Location in patent: Page/Page column 44
[2] Patent: CN105566200, 2016, A, . Location in patent: Paragraph 0210; 0216; 0217
[3] Patent: KR2015/42335, 2015, A, . Location in patent: Paragraph 0105-0108
[4] Patent: US2013/56720, 2013, A1, . Location in patent: Paragraph 0247-0249
[5] Patent: KR2015/28579, 2015, A, . Location in patent: Paragraph 0364-0367
[6] Patent: KR2016/54448, 2016, A, . Location in patent: Paragraph 0363-0367
[7] Patent: KR2015/135070, 2015, A, . Location in patent: Paragraph 0370-0374
[8] Patent: US2017/84845, 2017, A1, . Location in patent: Paragraph 0229-0232
[9] Patent: TW2017/2233, 2017, A, . Location in patent: Paragraph 0184; 0185; 0186
[10] Patent: US2017/346025, 2017, A1, . Location in patent: Paragraph 0622; 0623; 0624; 0625
[11] Patent: KR101571592, 2015, B1, . Location in patent: Paragraph 0126-0129
[12] Patent: EP2471771, 2012, A1, . Location in patent: Page/Page column 42
  • 38
  • [ 854952-58-2 ]
  • [ 1592-95-6 ]
  • [ 6163-58-2 ]
  • [ 1060735-14-9 ]
Reference: [1] Patent: US8231942, 2012, B2,
  • 39
  • [ 1592-95-6 ]
  • [ 1060735-14-9 ]
Reference: [1] Patent: KR2015/133998, 2015, A,
[2] Patent: KR2016/56521, 2016, A,
  • 40
  • [ 1592-95-6 ]
  • [ 1126522-69-7 ]
Reference: [1] Patent: KR2015/98062, 2015, A,
[2] Patent: KR101507423, 2015, B1,
[3] Patent: KR101535606, 2015, B1,
  • 41
  • [ 108-86-1 ]
  • [ 1592-95-6 ]
  • [ 1126522-69-7 ]
Reference: [1] Patent: KR101876777, 2018, B1,
  • 42
  • [ 1592-95-6 ]
  • [ 460-00-4 ]
  • [ 1226860-66-7 ]
YieldReaction ConditionsOperation in experiment
73% With caesium carbonate In N,N-dimethyl-formamide at 150℃; for 24 h; 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.
Reference: [1] Synthesis (Germany), 2016, vol. 48, # 5, p. 737 - 750
  • 43
  • [ 1592-95-6 ]
  • [ 589-87-7 ]
  • [ 1226860-66-7 ]
Reference: [1] RSC Advances, 2015, vol. 5, # 64, p. 51512 - 51523
  • 44
  • [ 1592-95-6 ]
  • [ 612-55-5 ]
  • [ 934545-80-9 ]
YieldReaction ConditionsOperation in experiment
85.1% With tris-(dibenzylideneacetone)dipalladium(0); tributylphosphine In toluene for 12 h; Heating To a flask including 3-bromo-9H-carbazole and 2-iodonaphthalene, 0.03 eq. of tris(dibenzilideneacetone)dipalladium(0) (Pd2(dba)3), 0.06 eq. of tributylphosphine, and toluene (0.1 M) were added and stirred for about 12 hours. After that, the reaction product was cooled to ambient temperature, extracted with methylene chloride, and washed with distilled water. The product thus obtained was dried with magnesium sulfate (MgSO4) and distilled under a reduced pressure, and the residue was separated by column chromatography to produce a 3-bromo-9-(naphthalen-2-yl)-9H-carbazole intermediate (Yield 85.1percent). The mass of the compound identified using a high resolution mass spectrometer (HRMS) was 371, and the molecular formula was identified
Reference: [1] Patent: US2017/162796, 2017, A1, . Location in patent: Paragraph 0134; 0135
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