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[ CAS No. 1150-62-5 ]

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Chemical Structure| 1150-62-5
Chemical Structure| 1150-62-5
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CAS No. :1150-62-5 MDL No. :MFCD00004965
Formula : C18H13N Boiling Point : -
Linear Structure Formula :- InChI Key :N/A
M.W :243.30 g/mol Pubchem ID :70851
Synonyms :

Safety of [ 1150-62-5 ]

Signal Word:Warning Class:N/A
Precautionary Statements:P261-P305+P351+P338 UN#:N/A
Hazard Statements:H315-H319-H335 Packing Group:N/A
GHS Pictogram:

Application In Synthesis of [ 1150-62-5 ]

  • Downstream synthetic route of [ 1150-62-5 ]

[ 1150-62-5 ] Synthesis Path-Downstream   1~17

  • 1
  • [ 1150-62-5 ]
  • [ 73087-83-9 ]
YieldReaction ConditionsOperation in experiment
With N-Bromosuccinimide; In N,N-dimethyl-formamide; 2 g of 9-phenyl-carbazole as the intermediate of preparation example 1, and 5.12 g of N-bromosuccinimide were dissolved in N.N-dimethylformamide, and the resulting solution was brominated, thus synthesizing 3,6-dibromo-9-(4-bromophenyl) carbazole compound as an intermediate.
  • 2
  • [ 1150-62-5 ]
  • [ 57103-20-5 ]
YieldReaction ConditionsOperation in experiment
100% With N-Bromosuccinimide; at 20℃; for 12h;Inert atmosphere; To a solution of 9-phenyl-9H-carbazole (2.04 g, 8.05 mmol) in CCl3(15 mL) keeping in dark place, NBS (3.29 g, 18.49 mmol) was added three times.The mixture was stirred for 12 h at room temperature. Then, water was added tothe mixture to give a white precipitate. After filtration and drying, theobtained white solid was recrystallized from petroleum. Yield: 100%.
92% With N-Bromosuccinimide; In ethyl acetate; at 20℃; for 52h; First, into a 200-mL Mayer flask were put 3.7 g (15 mmol) of 9-phenyl-9H-carbazole, 5.4 g (30 mmol) of N-bromosuccinimide (abbreviation: NBS), and75 mL of ethyl acetate. At room temperature, this solution was stirred in the air for 52 hours. Then, water was added thereto and this mixture was furtherstirred. An aqueous layer of the mixture was subjected to extraction with ethyl acetate three times. The extracted solution and an organic layer werecombined, the mixture was washed with water and saturated saline, and then magnesium sulfate was added thereto. The obtained mixture was gravityfilteredand the filtrate was concentrated, so that 5.5 g of the target white powder was obtained in a yield of 92%.
90.3% With N-Bromosuccinimide; In N,N-dimethyl-formamide; at 20 - 25℃; for 24.5h;Inert atmosphere; Under nitrogen protection,N-phenylcarbazole (48.6 g, 0.2 mol) was dissolved in 500 mL DMF (N, N-dimethylformamide) in a 1 L three-necked flask,NBS (N-bromosuccinimide, 78.3 g, 0.44 mol) was slowly added to the reaction system at a temperature of 20 to 25 C,0.5h plus completed.The reaction system was stirred at 20-25 C for 24 hours.After completion of the reaction to the reaction systemAn aqueous solution of sodium sulfite (500 mL, 0.05 mol / L) was added,Quenching reaction,Filter cake,After washing with deionized water,Crystallization is carried out with toluene or absolute ethanol,To give a white solid,Namely the intermediate C01-a,The yield was 90.3%.
90% With N-Bromosuccinimide; In N,N-dimethyl-formamide; at 20 - 25℃; for 24.5h;Inert atmosphere; Under nitrogen protection,N-phenylcarbazole (48.6 g, 0.2 mol) was dissolved in 500 mL of DMF (N, N-dimethylformamide) in a 1 L three-necked flask,To the reaction system was slowly added NBS (N-bromosuccinimide, 78.3 g, 0.44 mol) as a solid at a controlled temperature of 20-25 C,0.5h plus completed.The reaction system was incubated at 20-25 C for 24 hours with stirring.After completion of the reaction, an aqueous solution of sodium sulfite (500 mL, 0.05 mol / L) was added to the reaction system,The reaction mixture was quenched and the filter cake was suction filtered to obtain a cake. The residue was washed with deionized water and then crystallized from toluene or absolute ethanol to give a white solid, which was 3,6-dibromo-N-phenylcarbazole in 90% yield.
87% With N-Bromosuccinimide; In chloroform; at 20℃; for 3h; Preparation of Structural Formula 1B; The Structural Formula 1A (13.2 g, 54.3 mmol) was dissolved in chloroform (300 ml), and N-bromo succinimide (20.3 g, 114.0 mmol)) was added thereto, and agitated for 3 hours at normal temperature. Distilled water was put into the reaction solution, the termination of the reaction was carried out, and the organic material layer was extracted. The reaction solution was concentrated, and recrystallized with EtOH to obtain the Structural Formula 1B (18.9 g, yield 87 %). MS: [M+H]+ = 402
87.8% With bromine; acetic acid; In dichloromethane; at 20℃;Cooling with ice; 0.1640 mol of N-phenyl-9H-carbazole was charged into a 2000 ml three-necked flask, washed with 320 ml of acetic acid and 960 ml of dichlorMethane dissolved, placed in ice water bath; slowly dropping 0.3280mol liquid bromine, room temperature reaction overnight,The reaction solution was neutralized with 1.5 L of 1 mol / L aqueous sodium hydroxide solution to the remaining liquid bromine, and the organic phase was separated to obtain an organic phase,Respectively, washed three times with water, liquid to take organic phase, spin dry,Washed with 300 ml PE (60-90), suction filtered, vacuum dried at 55 C,To give the product 3,6-dibromo-9-phenylcarbazole 0.1440 mol, 87.8% yield.
79.04% With N-Bromosuccinimide; In N,N-dimethyl-formamide; at 25℃; for 5h; N-bromosuccinimide (15.00 g, 84 mmol, 2.05 eq) is dissolved in 30 ml of dimethylformamide and then slowly added to a flask in which 30 ml of 9-phenyl-9Hcarbazole (10 g, 41 mmol, 1.0 eq) is dissolved in 30 ml of dimethylformamide. After 5 hours of reaction, the reaction product was precipitated with 200 ml of distilled water, filtered and dried to obtain 13.03 g (yield: 79.04%) of the target compound.
64% With N-Bromosuccinimide; In N,N-dimethyl-formamide; at 20℃; Example 3 Synthesis of Carbozole-Based (2-Arm) Fluorescent Molecular Rotor (0310) RRN 38Preparation of 3,6-dibromo-9-phenyl-9H-carbazole (0311) 9-phenyl-9H-carbazole (0.3 g, 1.23 mmol, 1 eq.) was dissolved in DMF. N-Bromosuccinimide (0.44 g, 2.47 mmol, 2 eq.) was then added slowly and the resultant mixture was allowed to stir at room temperature overnight. The reaction mixture was then poured into brine and extracted with DCM. The organic extracts were then dried with Na2SO4 and concentrated. Crude product was then re-precipitated with methanol and THF gave white solids as 3,6-dibromo-9-phenyl-9H-carbazole (0.32 g, 64%). (0312) 1H NMR (CDCl3, 400 MHz) delta 7.24 (s, 1H), 7.48-7.52 (m, 5H), 7.59-7.64 (m, 2H), 8.20 (d, 2H, J=2.0 Hz). 13C NMR (100 MHz, CDCl3) delta 140.1, 137.0, 130.3, 129.5, 128.3, 127.2, 124.1, 123.4, 113.2, 111.7.
56.9% With bromine; In dichloromethane; acetic acid; Example 11 3,6-Dibromo-9-phenylcarbazole 9-Phenylcarbazole (2.000 g, 8.220 mmol) was suspended in 15 mL glacial acetic acid in a 125 ml 3-neck round bottom flask equipped with an addition funnel and a condenser. The reaction was under N2 blanket. Bromine (0.880 ml, 17.262 mmol) mixed with 15 mL glacial acetic acid was added dropwise and stirred at 0 C. Upon completion of the addition the reaction was allowed to warm to room temperature and stirred for about 5 hours. Dichloromethane (100 mL) was added, and stirred vigorously until all the solids dissolved. Two phases were separated in the separation funnel. The acid layer was extracted twice with 50 mL dichloromethane. The organic layers were combined and washed with brine until the pH=7. The organic layers were dried over MgSO4 and filtered. Solvent was removed under vacuum. The crude product was then recrystallized from dichloromethane. Yield: 56.9%. M.P.: 162.7-163.6 C.

  • 5
  • [ 1150-62-5 ]
  • [ 1153-85-1 ]
  • [ 57103-20-5 ]
  • 6
  • [ 1150-62-5 ]
  • [ 25603-67-2 ]
  • 9-phenyl-3,6-bis(9-phenyl-9H-fluoren-9-yl)carbazole [ No CAS ]
  • 7
  • [ 1150-62-5 ]
  • [ 25603-67-2 ]
  • 9-phenyl-3,6-bis(9-phenyl-9H-fluoren-9-yl)carbazole [ No CAS ]
  • 9-phenyl-3-(9-phenyl-9H-fluoren-9-yl)carbazole [ No CAS ]
  • 8
  • [ 1150-62-5 ]
  • [ 57103-21-6 ]
YieldReaction ConditionsOperation in experiment
95% With N-iodo-succinimide; In acetic acid; at 20℃; Firstly, 24.3 g (100 mmol) of 9-phenylcarbazole was dissolved in 700 ml of glacial acetic acid, and 44.9 g (200 mmol) of iV-iodosuccinimide was slowly added thereto. The mixture was stirred overnight at a room temperature. The generated precipitation was filtered and the residue was washed by a saturated sodium hydrogencarbonate water solution, water, and methanol, then was dried. 47.Og (yield 95percent) of 3,6-diiodo-9-phenyl carbazole which was white powder, was obtained.
95% With N-iodo-succinimide; In acetic acid; at 20℃; 24.3g (100 mmol) of N-phenylcarbazole was dissolved in 700 ml of glacial acetic acid, 44.9 g (200 mmol) of N-iodinesuccinimide was gradually added thereto, and then stirring was carried out at a room temperature overnight. The solution became clouded at 2.5 hours from the reaction started, and precipitation started at 3.5 hours from the reaction started. The obtained precipitate was filtered and was suspended in the aqueous solution of sodium hydro gencarbonate to be neutralized. The solution was filtered. And the obtained material was washed with water and dried to obtain 47 g of off-white powder in a yield of 95 percent.
94% With potassium metaperiodate; acetic acid; potassium iodide; at 80℃; for 12h;Inert atmosphere; 9-phenyl-9H-carbazole (4.0 g, 16.4 mmol) under a nitrogen atmosphere,KI (3.57g, 21.5mmol),KIO3 (4.6g, 21.5mmol) is mixed with AcOH (80ml).It was then stirred at about 80 ° C for about 12 hours.After the reaction was completed, the solid thus obtained was filtered, washed with water (200 ml), washed with 1M NaHCO3 (100 ml) and washed with 1M Na2S2O3 (100ml).The solid thus formed was dissolved in EA and washed with water.The organic layer was separated, dried over MgSO 4 to remove water and separated by column chromatography (hexane).The intermediate compound (9) (7.62 g, yield 94percent) was obtained.
91% With potassium iodate; acetic acid; potassium iodide; at 100℃; for 1h; N-phenyl-3,6-diiodocarbazo23.17 g (0.0952 mol, 1.0 eq) of CzP are dissolved in 200 mL of refluxing acetic acid. This solution is then cooled down at 100°C before the subsequent addition of 20.9 g (0.126 mol, 1.32 eq) of KI and 15.9 g (0.074 mol, 0.78 eq) of KIO3. After one hour, the purple iodine disappears what indicates that the reaction is complete. The white solid is filtered, rinsed by 2x100 ml of 5percent Na2S203 aqueous solution, 200 mL of water and then dried to give 42.9 g (0.0867 mol, 91 percent) of ICzP as a white solid.
91% N phenyl-3, 6-diiodocanbazole - ICzP; [Show Image] 23.17 g (0.0952 mol, 1.0 eq) of CzP are dissolved in 200 mL of refluxing acetic acid. This solution is then cooled down at 100°C before the subsequent addition of 20.9 g (0.126 mol, 1.32 eq) of KI and 15.9 g (0.074 mol, 0.78 eq) of KI03. After one hour, the purple iodine disappears what indicates that the reaction is complete. The white solid is filtered, rinsed by 2x100 ml of 5percent Na2S2O3 aqueous solution, 200 mL of water and then dried to give 42.9 g (0.0867 mol, 91 percent) of ICzP as a white solid.
74.8% With potassium iodate; acetic acid; potassium iodide; at 135℃; for 18h; A mixture of 9-phenylcarbazole (0.2433 g, 0.1 mmol), potassiumiodide (0.6640 g, 4.0 mmol) and potassium iodate (0.4277 g, 2.0mmol) was refluxed for 18 h in glacial acetic acid (50 mL). The colourof the solution changed from purple to chocolate brown. After thereaction was completed, the mixture was left to cool naturally. Theprecipitate was separated and washed with 10percent sodium hyposulfitesolution (50 mL) and distilled water (30 mL) successively. The whiteneedles obtained were further dried and recrystallised from alcohol togive compound 1 as white crystals: m.p. 185?186 °C; yield 0.3703 g(74.8percent); 1H NMR (400 MHz, Chloroform-d1): delta 8.40 (s, 2H), 7.71?7.58(m, 4H), 7.50 (t, J = 9.4 Hz, 3H), 7.16 (d, J = 8.6 Hz, 2H); FTIR (KBr)(cm?1): 3134(s), 1595(m), 1500(w), 1463(s), 1427(s), 1400(s), 1278(m),1228(s), 1014(m), 867(w), 798(m), 756(m), 696(w), 630(w), 565(w),563(w). Anal. calcd for C18H11I2N: C, 43.67; H, 2.24; N, 2.83; found: C,43.54; H, 2.23; N, 2.84percent
With potassium iodate; sulfuric acid; iodine; acetic acid; In water; at 80℃; for 8h; Example 3; 9-Phenylcarbazole (1.22 g), potassium iodate (0.43 g), iodine (1.40 g), and acetic acid (50 mL) are put into a 100 mL three-necked flask, and the flask is heated to 80° C. Furthermore, sulfuric acid (5 mL) is added 20percent thereto, and the solution is stirred at 80° C. for 8 hours.After the system is cooled, 50 mL of pure water is added to the solution and then powder of sodium carbonate is added thereto little by little to neutralize the solution. The resultant is subjected to extraction with toluene, and washed with a saturated aqueous solution of sodium thiosulfate, and then dried with anhydrous sodium sulfate. The solvent is distilled off therefrom. The resultant white powder is recrystallized from hexane and ethyl acetate to yield 0.93 g of 3,6-diiodo-9-phenylcarbazole (a white needle crystal).
With potassium orthoperiodate dihydrate; potassium iodide; In acetic acid; at 80℃; Bis (6-(3-diphenylamino)-9-phenylcarbazolyl)phenylamine (D) was synthesised according to the following scheme. 30.0 g of 9-phenylcarbazole was dissolved in 50mL of acetic acid at a temperature of 80°C. 81.5 g of potassium iodide and 53.5 g of potassium orthoperiodate dihydrate were added to the resultant in several portions. After addition of the whole quantity, the resultant mixture was reacted with stirring for one hour. After completion of the reaction, the resulting reaction mixture was cooled to room temperature. The reaction mixture was extracted with a mixture of ethyl acetate and 10percent aqueous solution of sodium thiosulfate, and the obtained organic phase was concentrated to provide viscous liquid. The viscous liquid was purified using a mixed solvent of toluene/hexane by alumina column chromatography, thereby 32.7 g of 3,6-diiodo-9-phenylcarbazole (6) was obtained.
0.1 g With potassium iodate; acetic acid; potassium iodide; at 135℃; for 18h; A mixture of 9-phenylcarbazole (0.2433 g, 0.1 mmol), potassium iodide (0.6640 g, 4.0 mmol) and potassium iodate (0.4277 g, 2.0 mmol) was mixed with 50 ml of glacial acetic acid at room temperature. Heated to 135 ° C and refluxed for 18 hours. The reaction solution was allowed to cool to room temperature. The precipitate was washed with 50 ml of 10percent sodium thiosulfate solution and 30 ml of distilled water. Weigh 0.1 g of 3,6-diiodo-phenylcarbazole, dissolved in 5 ml of chloroform, filtered and allowed to stand for 3 days to give a colorless block crystal.

  • 9
  • [ 1150-62-5 ]
  • [ 502161-03-7 ]
YieldReaction ConditionsOperation in experiment
87% With iodine; acetic acid; periodic acid; In water; at 80℃; for 2h; 2.433 g (10 mmol) of the intermediate compound A was added to 100 mL of 80% acetic acid, and then 1.357 g (5.35 mmol) of iodine (I2) and 0.333 g (1.46 mmol) of ortho-periodinic acid (H5IO6) were added thereto. The resultant was stirred under nitrogen atmosphere at 80C for 2 hrs. After the reaction was completed, the reaction mixture was three times extracted with ethyl ether (50 mL). The collected organic layer was dried on magnesium sulfate and the solvent was evaporated. The residue was purified with a silica gel column chromatography to obtain 3.23 g of the intermediate compound B as a white solid (yield: 87%). 1H NMR (CDCl3, 300MHz) delta (ppm) 8.43 (d, 1H), 8.05 (d, 1H), 7.62 (dd, 1H), 7.61-7.75 (m, 2H), 7.51-7.43 (m, 3H), 7.41-7.35 (m, 2H), 7.27 (dd, 1H), 7.14 (d, 1H)
87% With iodine; acetic acid; periodic acid; In water; at 80℃; for 2h; Synthesis of Intermediate F; Intermediate E (2.433 g, 10 mmol) was added to an 80% acetic acid (100 ml), and iodine (I2) (1.357 g, 5.35 mmol) and ortho-periodinic acid (H5lO6) (0.333 g, 1.46 mmol) in a solid phase were added thereto. The reaction mixture was stirred at 80 C. under a nitrogen atmosphere for two hours. After the reaction was terminated, the reaction solution was extracted three times with ethylether (50 ml). The collected organic layer was dried over magnesium sulfate to evaporate a solvent. The resultant residue was purified by silica gel column chromatography to give intermediate F as a white solid (3.23 g, yield: 87%). The structure of intermediate F was determined by 1H NMR. 1H NMR (CDCl3, 300 MHz) delta (ppm) 8.43 (d, 1H), 8.05 (d, 1H), 7.62 (dd, 1H), 7.61-7.75 (m, 2H), 7.51-7.43 (m, 3H), 7.41-7.35 (m, 2H), 7.27 (dd, 1H), 7.14 (d, 1H)
87% With iodine; acetic acid; periodic acid; at 80℃; for 2h;Inert atmosphere; 2.433 g of phenylcarbazole (10 mmol) was added into 100 ml of 80% acetic acid, and 1.357 g of Iodine (I2) (5.35 mmol) and 0.333 g of ortho-periodic acid (H5IO6) (1.46 mmol) in a solid state were added thereto to form a mixture. The mixture was stirred at 80C for 2 hours in a nitrogen atmosphere. A reaction was allowed to take place and terminated. After the reaction was terminated, the mixture was extracted with 50 ml of ethylether three times. An organic layer was collected and dried using magnesium sulfate to evaporate the solvent. The residue was separately purified by silica gel column chromatography to obtain 3.23 g (yield 87%) of white solid of Intermediate 1. Intermediate 1 was evaluated by NMR, and the result thereof is shown below. 1H NMR (CDCl3, 300MHz) delta (ppm) 8.43 (d, 1H), 8.05 (d, 1H), 7.62 (dd, 1H), 7.61-7.75 (m, 2H), 7.51-7.43 (m, 3H), 7.41-7.35 (m, 2H), 7.27 (dd, 1H), 7.14 (d, 1H)
85% With iodine; acetic acid; periodic acid; at 80℃; for 2h; 78.9 g (0.324 mol) of the compound represented by the formula 1-a obtained in the above reaction formula 1, 44.4 g (0.175 mol) of iodine, 11.1 g (0.0486 mol) of periodic acid,Acetic acid (500 mL) was added thereto, followed by stirring at 80 C for 2 hours.The reaction was cooled to room temperature and extracted with diethyl ether and water. The organic layer was dehydrated with magnesium sulfate, concentrated under reduced pressure, and subjected to column chromatography using hexane as a developing solvent to obtain 88.0 g (85%) of the compound represented by the formula (1-b).
81% With potassium iodate; sulfuric acid; potassium iodide; In ethanol; at 75℃; for 2h; Into a mixture of 17.7 g (72.7 mmol) of 9-phenylcarbazole, 6.03 g (36.3 mmol) of potassium iodide and 7.78 g (36.4 mmol) of potassium iodate, 5.9 ml of sulfuric acid and 70 ml of ethanol were added, and the resultant mixture was stirred at 75 C for 2 h. After cooling, the reaction production was added with water and ethyl acetate and liquid-liquid extracted. The organic layer was washed with an aqueous solution of sodium hydrogencarbonate and water and then concentrated. The obtained crude product was purified by silica gel column chromatography, to obtain 21.8 g of a white solid, which was identified as the following intermediate 1-7 by FD-MS analysis (yield: 81%).
78% With iodine; acetic acid; periodic acid; at 80℃; for 4h; 400 mL of 85% acetic acid was added to a mixture including 24.3 g (100.0 mmol) of phenyl carbazole, 13.4 g (50.3 mmol) of iodine, and 2.2 g (10.0 mmol) of periodic acid, and the mixture was heated at 80 C. for 4 hours. 500 mL of cold water was added to the reaction mixture, and the reaction mixture was stirred and filtered. A solid phase obtained by the filtration was cleaned with cold water several times. Then, the solid phase was dissolved in 400 mL of ethyl ether, dried, filtered, concentrated, and then separated using column chromatography to obtain 28.7 g of compound 4 in white solid form with a yield of 78%. The structure of compound 4 was identified using HR-MS. (calc.: 369.0014, found: 369.0001)
77% With sulfuric acid; iodine; In methanol; water; for 20h; 500 g of methanol and 65.19 g (0.2568 mol) of iodine were added to 125 g (0.5137 mol) of Intermediate G, and the mixture was cooled to 5 or lower. 10 g (0.1 mol) of sulfuric acid was added to 500 g of water and diluted. While the cooled reactor was maintained at 5 C or lower, the diluted sulfuric acid aqueous solution was slowly added dropwise and stirred for 20 hours while maintaining the same temperature condition. The reaction mixture was concentrated under reduced pressure to remove methanol, 450 g of toluene was added thereto, and the organic layer was separated. The toluene was removed by concentration under reduced pressure, and 400 g of methanol was added thereto, followed by refluxing, cooling, filtration and drying to obtain 146 g (yield: 77%) of intermediate H having a purity of 98.3% .
77% With sulfuric acid; iodine; In methanol; water; at 5℃; for 20h;Cooling; To 125 g (0.5137 mol) of Intermediate G, 500 g of methanol,65.19 g (0.2568 mol) of iodine was added and cooled to 5C or lower.10 g (0.1 mol) of sulfuric acid was added to 500 g of water, diluted, and the cooled reactor was slowly added dropwise while keeping the temperature at 5C or lower. After completing the drop, The reaction was completed by stirring for 20 hours while maintaining the same temperature conditions.The methanol was removed by concentration under reduced pressure, 450 g of toluene was added, the organic layer was separated, toluene was removed under reduced pressure,Methanol (400 g) was added,Cooling, filtration and drying were conducted to obtain 146 g (yield: 77%) of Intermediate H having a purity of 98.3%.
67% With N-iodo-succinimide; In acetic acid; at 20℃;Product distribution / selectivity; 24.3 g (100 mmol) of 9-phenylcarbazole was dissolved in 600 ml of glacial acetic acid, 22.5 g (100 mmol) of N-iodosuccinimide was slowly added thereto, and then stirring was carried out at a room temperature fro overnight. The generated precipitation was filtered and the residue was washed by a saturated sodium hydrogencarbonate water solution, water, and methanol, then was dried. 24.7g (yield 67%) of 3-iodo-9-phenylcarbazole which was white powder, was obtained.1Og (lO.Ommol) of 9-phenyl carbazole, 838mg (5.0mmol) of potassium iodide, l.lg (5.0mmol) of potassium iodate, and 3OmL of glacial acetic acid were put in a three-neck flask and refluxed for 1 hour at 120 0C. After the reaction, the reaction EPO <DP n="56"/>solution was cooled sufficiently and added into water, extracted with toluene, an organic layer was washed with saturated sodium chloride solution once, was dried with magnesium sulfate. This solution was filtered naturally, and the obtained filtrate was concentrated. Then, it was recrystallized with acetone and methanol. 8.0 g (the yield: 50%) of a white solid, which was an objective substance, was obtained.
67 - 68% With N-iodo-succinimide; In acetic acid; at 20℃;Product distribution / selectivity; 4.9 g (20 mmol) of N-phenylcarbazole was dissolved in 100 ml of glacial acetic acid, 4.48 g (20 mmol) of N-iodinesuccinimide was gradually added thereto, and then stirring was carried out at a room temperature overnight. The solution became clouded at 2.5 hours from the reaction started, and was suspended by a light orange precipitate at 3.5 hours from the reaction started. This suspension was dropped to 300 ml of the saturated aqueous solution of sodium chloride to obtain a light salmon pink block object. After washing this block object three times with water, 200 ml of ethyl acetate was added to dissolve the block object, and washing was carried out with sodium hydrogen carbonate and then with water. After magnesium sulfate was added to remove moisture, magnesium sulfate was removed by filtration. Recrystallization was carried out to obtain 5 g of white powder in a yield of 68 % by heating this solution to which hexane was added.Alternatively, 3-iodine-9-phenylcarbazole also can be synthesized by the following method. 24.3 g (100 mmol) of N-phenylcarbazole was dissolved in 600 ml of glacial acetic acid, 22.5 g (100 mmol) of N-iodinesuccinimide was gradually added thereto, and stirring was carried out at a room temperature overnight. The solution EPO <DP n="59"/>became clouded at 2.5 hours from the reaction started, and was suspended by a light orange precipitate at 3.5 hours from the reaction started. This suspension was filtered. The filtrated object was washed with sodium hydrogen carbonate, then with water. Finally, the filtrated was washed with methanol to obtain 24.7 g of white powder in a yield of 67 %. [Step 4]
50% With potassium iodate; potassium iodide; In acetic acid; at 120℃; for 1h;Heating / reflux;Product distribution / selectivity; 24.3 g (100 mmol) of 9-phenylcarbazole was dissolved in 600 ml of glacial acetic acid, 22.5 g (100 mmol) of N-iodosuccinimide was slowly added thereto, and then stirring was carried out at a room temperature fro overnight. The generated precipitation was filtered and the residue was washed by a saturated sodium hydrogencarbonate water solution, water, and methanol, then was dried. 24.7g (yield 67%) of 3-iodo-9-phenylcarbazole which was white powder, was obtained.1Og (lO.Ommol) of 9-phenyl carbazole, 838mg (5.0mmol) of potassium iodide, l.lg (5.0mmol) of potassium iodate, and 3OmL of glacial acetic acid were put in a three-neck flask and refluxed for 1 hour at 120 0C. After the reaction, the reaction EPO <DP n="56"/>solution was cooled sufficiently and added into water, extracted with toluene, an organic layer was washed with saturated sodium chloride solution once, was dried with magnesium sulfate. This solution was filtered naturally, and the obtained filtrate was concentrated. Then, it was recrystallized with acetone and methanol. 8.0 g (the yield: 50%) of a white solid, which was an objective substance, was obtained.
With N-iodo-succinimide; In acetic acid; [Step 1] A synthesis method of 3-iodo-9-phenylcarbazole will be explained. A synthesis scheme of 3-iodo-9-phenylcarbazole is shown in (j-1). 24.3 g (100 mmol) of 9-phenylcarbazole was dissolved in 600 mL of glacial acetic acid, 22.5g (100 mmol) of N-iodosuccinimide was slowly added thereto, and the mixture was stirred at a room temperature for about 20 hours. The generated precipitate was filtered, and the residue was washed with a saturated sodium hydrogen carbonate solution, water, and methanol, and then dried. 24.7 g (yield: 67%) of 3-iodo-9-phenylcarbazole, which was white powder, was obtained. It is to be noted that 3-iodo-9-phenylcarbazole can be synthesised by the following method. 10 g (10.0 mmol) of N-phenylcarbazole, 838 mg (5.0 mmol) of potassium iodide, 1.1 g (5.0 mmol) of potassium iodate, and 30 mL of glacial acetic acid were put in a three-neck flask and refluxed at 120 C. for 1 hour.
With potassium iodate; sulfuric acid; potassium iodide; In ethanol; at 75℃; for 2h; Blending 17.7 g of 9-phenyl carbazole, 6.03 g of potassium iodide, 7.78 g of potassium iodate, 5.90 ml of sulfuric acid and ethanol, the reaction was allowed to proceed at 75 C for 2 h. The resultant solution was cooled, and adding tap water and ethyl acetate, it was separated and extracted. Subsequently, an organic layer was washed with sodium bicarbonate water and tap water and then, it was condensed. Purifying the resultant crude product by means of a silicagel chromatography (toluene), vacuum dried the resultant solid to obtain 21.8 g of white solid, which was analyzed by FD-MS (Field Desorption Mass Spectrum) and identified as Intermediate 1.
With potassium iodate; potassium iodide; In acetic acid; at 80℃; for 2h; The 9-phenylcarbazole was dissolved in 300mL of acetic acid, and then 7 g of potassium iodide and 18 g of potassium iodate were added to the resultant. The resulting solution was reacted at a temperature of 80C for two hours. After completion of the reaction, unreacted iodine in the resulting reaction mixture was reduced with aqueous solution of sodium thiosulfate, and then the reaction mixture was concentrated, followed by purifying the resulting concentrate by silica gel column chromatography. The resulting viscous liquid was subjected to crystallization from hexane to provide 20.5 g of 3-iodo-9-phenylcarbazole (1) as white solid.
With potassium iodate; sulfuric acid; potassium iodide; In ethanol; at 75℃; for 2h;Product distribution / selectivity; 17.7 Grams of 9-phenylcarbazole, 6.03 g of potassium iodide, 7.78 g of potassium iodate, 5.9 ml of sulfuric acid, and ethanol were loaded into a 200-ml three-necked flask, and then the mixture was subjected to a reaction at 75C for 2 hours. After the resultant had been cooled, water and ethyl acetate were added to perform separation and extraction. After that, the organic layer was washed with baking soda water and water, and was then concentrated. The resultant coarse product was purified by silica gel chromatography (toluene), and then the resultant solid was dried under reduced pressure. Thus, 21.8 g of a white solid were obtained. The solid was identified as the intermediate-5 by FD-MS analysis.
With potassium iodate; sulfuric acid; potassium iodide; In ethanol; at 75℃; for 2h; 17.7 g of 9-phenylcarbazole, 6.03 g of potassium iodide, 7.78 g of potassium iodate, 5.9 mL of sulfuric acid, and ethanol were loaded, and then the mixture was subjected to a reaction at 75C for 2 hours. After the resultant had been cooled, clean water and ethyl acetate were added to perform separation and extraction. After that, the organic layer was washed with baking soda water and clean water, and was then concentrated. The resultant coarseproduct was purified by silica gel chromatography (toluene), and then the resultant solid was dried under reduced pressure. Thus, 21.8 g of a white solid were obtained. The solid was identified as the Intermediate 3 by FD-MS analysis.
With potassium iodate; sulfuric acid; potassium iodide; In ethanol; at 75℃; for 2h; 5.90 mL of sulfuric acid, and ethanol were added to 17.7 g of 9-phenylcarbazole, 6.03 g of potassium iodide, and 7.78 g of potassium iodate, and then the mixture was subjected to a reaction at 75C for 2 hours. After the resultant had been cooled, water and ethyl acetate were added to perform separation and extraction. After that, the organic layer was washed with baking soda water and water, and was then concentrated. The resultant coarse product was purified by silica gel chromatography (developing solvent: toluene), and then the resultant solid was dried under reduced pressure. Thus, 21.8 g of a white solid were obtained. The white solid was identified as the intermediate 7 by FD-MS analysis.
With potassium iodate; sulfuric acid; In ethanol; water; at 75℃; for 2h; 17.7 g of 9-phenylcarbazole, 6.03 g of potassium iodide, 7.78 g of potassium iodate, 5.90 mL of sulfuric acid and ethanol were placed and reacted at 75 C. for 2 hours.After cooling, water and ethyl acetate was added thereto. After the resulting mixture was separated and extracted, an organic phase thereof was washed with sodium bicarbonate water and water, and concentrated. The crude product obtained was purified by silica-gel chromatography (toluene), and the solids obtained were dried under reduced pressure to obtain 21.8 g of white solids. The white solids were identified as Intermediate 1 by FD-MS analysis.
With potassium iodate; sulfuric acid; potassium iodide; In ethanol; at 75℃; for 2h; Synthesis Example 9 (synthesis of intermediate 9)> 5.90 mL of sulfuric acid and ethanol were added to 17.7 g of 9-phenylcarbazole, 6.03g of potassium iodide, and 7.78 g of potassium iodate, and then the mixture was reacted at 75C for 2 hours. After the resultant had been cooled, water and ethyl acetate were added and extracted the resultant. After that, the organic layer was washed with baking soda water and water, and was then concentrated. The resultant coarse product was purified by silica gel chromatography (developing solvent: toluene), and then the resultant solid was dried under reduced pressure. Thus, 21.8 g of a white solid were obtained. The white solid was identified as the intermediate 9 by FD-MS analysis.
21.8 g With potassium iodate; sulfuric acid; potassium iodide; In ethanol; at 75℃; for 2h; 17.7 g of 9-phenylcarbazole, 6.03 g of potassium iodide, 7.78 g of potassium iodate, 5.90 mL of sulfuric acid and ethanol were placed and reacted at 75 C. for 2 hours.After cooling, water and ethyl acetate were added thereto to be separated into a water phase and an organic phase. The organic phase was extracted, washed with sodium bicarbonate water and water, and concentrated to obtain a crude product. The crude product was purified with silica gel chromatography (with toluene), and the resultant solids were dried under reduced pressure to obtain 21.8 g of white solids. The solids were identified as Intermediate 1 by FD-MS analysis.
21.8 g With potassium iodate; sulfuric acid; potassium iodide; In ethanol; at 75℃; for 2h; After adding 5.90 mL of sulfuric acid and 70 mL of ethanol to 17.7 g of 9-phenylcarbazole, 6.03 g of potassiumiodide and 7.78 g of potassium iodate, the resultant mixture was allowed to react at 75 C for 2 h. After cooling, waterand ethyl acetate were added and the resultant mixture was subjected to liquid-liquid extraction. The organic layer waswashed with an aqueous sodium hydrogen carbonate solution and water and then concentrated. The obtained crudeproduct was purified by silica gel column chromatography. The purified solid was vacuum-dried to obtain 21.8 g of whilesolid, which was identified as Intermediate 2 shown below by FD-MS analysis.

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[2]Patent: US2008/174237,2008,A1 .Location in patent: Page/Page column 13-14
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  • 10
  • [ 657408-07-6 ]
  • potassium phosphate [ No CAS ]
  • [ 1592-95-6 ]
  • [ 5408-56-0 ]
  • [ 1060735-14-9 ]
  • [ 1126522-69-7 ]
  • [ 865-48-5 ]
  • [ 1150-62-5 ]
YieldReaction ConditionsOperation in experiment
With N2;tris-(dibenzylideneacetone)dipalladium(0); Pd2(dba)3; In tetrahydrofuran; 5,5-dimethyl-1,3-cyclohexadiene; hexane; dichloromethane; toluene; A mixture of 9-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-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 H2O 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 (87%) of product was obtained. Synthesis of Compound 1. A mixture of <strong>[5408-56-0]2-iododibenzo[b,d]furan</strong> (2.59 g, 8.81 mmol), 9-phenyl-9H,9'H-3,3'-bicarbazole (3 g. 7.34 mmol), and sodium t-butoxide (1.764 g, 18.36 mmol) in 200 mL of xylene was bubbled with N2 for 20 min. Dicyclohexyl(2',6'-dimethoxybiphenyl-2-yl)phosphine (0.121 g, 0.294 mmol) and Pd2(dba)3 (0.067 g, 0.073 mmol) were then added, and the mixture was heated to reflux under N2 for 24 h. The mixture was cooled and filtered through Celite. After solvent evaporation, the residue was coated on Celite and purified by column chromatography 3.7 g of product was obtained after column.
  • 11
  • [ 1150-62-5 ]
  • [ 618442-57-2 ]
  • 13
  • [ 1150-62-5 ]
  • [ 58328-31-7 ]
  • 14
  • [ 86-74-8 ]
  • [ 583-53-9 ]
  • [ 1150-62-5 ]
  • [ 902518-11-0 ]
YieldReaction ConditionsOperation in experiment
13.8%; 60% With copper(I) oxide; potassium phosphate; N,N`-dimethylethylenediamine; In 5,5-dimethyl-1,3-cyclohexadiene; at 170℃; for 24h;Inert atmosphere; To a 500 mL four-necked round-bottomed flask, a three-way stopcock, a mechanical stirrer, a condenser, and a thermometer were attached, and the inside was purged with nitrogen. To this flask, carbazole (19.4 g, 116. 3 mmol, 1.0 eq.), 1,2-dibromobenzene (54.8 g, 232.6 mmol, 2.0 eq.), xylenes (120 mL), copper (I) oxide (3.3 g, 23.3 mmol, 0.2 eq.), N,N'-dimethylethylenediamine (5.0 mL, 46.5 mmol, 0.4 eq.), and potassium phosphate (54.3 g, 255.9 mmol, 2.2 eq.) were sequentially added, and the obtained suspension was stirred at 170°C for 24 hours. Reaction conversion: 80.2percent. Note that no improvement in conversion was observed, even when the reaction time was extended further. (Post Treatment and Purification) After the reaction mixture had been cooled to room temperature, toluene and a 28percent aqueous ammonia solution were added to the mixture. The mixture was transferred to a separating funnel, shaken and allowed to stand, and the layers were separated. The organic layer was washed five times with a 28percent aqueous ammonia solution (each time the washing was repeated, the blue color of the aqueous layer faded), once with water, and three times with a 1 N aqueous hydrochloric acid solution (hardly soluble black tar was formed in each of the organic layer and the aqueous layer). The organic layer was concentrated, and the obtained residue was purified by conducting silica gel column chromatography (Eluent: n-hexane/toluene=10/1 to 2/1) three times (because column fractions containing by-products were purified repeatedly) to give 22.5 g of title compound (7) as a pale yellow solid. Isolated Yield: 60.0percent. Note that 3.9 g of a by-product, N-phenylcarbazole, was obtained as a colorless solid. Isolated Yield: 13.8percent. 1H NMR (300 MHz, deuterated chloroform (hereinafter, abbreviated as CDCl3)): delta=8.15 (d, J=7.8 Hz, 2H), 7.85 (dd, J=1.5, 8.1 Hz, 1H), 7.56-7.35 (m, 5H), 7.29 (dt, J=0.9, 6.9 Hz, 2H), 7.06 (d, J=8.1 Hz, 2H). 13C NMR (75 MHz, CDCl3): delta=140.8, 136.7, 134.2, 131.1, 130.1, 128.8, 125.9, 123.8, 123.2, 120.3, 120.0, 110.0.
  • 15
  • [ 86-74-8 ]
  • [ 66003-78-9 ]
  • [ 1150-62-5 ]
  • 16
  • [ 76-09-5 ]
  • [ 1150-62-5 ]
  • [ 13517-10-7 ]
  • [ 1126522-69-7 ]
  • [ 1246669-45-3 ]
YieldReaction ConditionsOperation in experiment
Boron triiodide (39.2 mg, 0.10 mmol),9-phenylcarbazole (9 8.4 mg, 0.40 mmol)And 1,2,4-trichlorobenzene (1.0 ml)The mixture was heated and stirred at 180 C. for 6 hours under a nitrogen atmosphere.The reaction solution is cooled to room temperature and evaporated under reduced pressure.9-phenyl-2-diiodoboryl carbazole (Y-12)And 9-phenyl-3-diiodoboryl-carbazole(Y-13) was obtained as a mixture. After that,Triethyl amine (0.170 ml, 1.2 mmol),Add pinacol (35.1 mg, 0.30 mmol),Stir at room temperature. Thereafter, the solvent was distilled off under reduced pressure.The crude product obtained is subjected to gel permeation chromatographyWhen isolated and purified by (eluent: toluene),Compound (Y'-2-13) and Compound as White SolidMixture of (Y'-2-14) in a ratio of 15:85Obtained as (19.2 mg, 52% yield).
  • 17
  • [ 86-74-8 ]
  • [ 583-53-9 ]
  • [ 1150-62-5 ]
  • [ 902518-11-0 ]
  • 9-(2-iodophenyl)-9H-carbazole [ No CAS ]
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