Name: 1150-62-5|9-Phenylcarbazole|98%
Brand: Ambeed
SKU: A147872
Price: 5.0 USD
Availability: InStock
Rating: 92 (25 reviews)

1
[ 591-50-4 ]
[ 86-74-8 ]
[ 1150-62-5 ]

Yield	Reaction Conditions	Operation in experiment
98%	With copper (I) iodide; dimethylaminoacetic acid; tetrabutylphosphonium malonate In dimethyl sulfoxide at 120℃; for 24h; Inert atmosphere; Glovebox; Sealed tube;
96%	With copper (I) iodide; Cs₂CO₃ In N,N-dimethyl-formamide at 220℃; for 0.333333h; Microwave irradiation;	4.2. General experimental procedure for microwave-assisted N-arylation of carbazoles 9H-Carbazole (1.0 mmol), Cs2CO3 (1.0 mmol), iodobenzene (1.1 mmol), CuI (0.1 mmol), and DMF (2 mL) were added to a 5-mL vial. The vial was sealed with a crimp cap and placed in a Biotage initiator microwave cavity. After irradiation at 220 °C for the appropriate time and subsequent cooling, the reaction mixture was diluted with saturated aqueous ammonium chloride. Products were isolated by extraction into ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated. Products were purified by silica gel column chromatography using a hexane/ethyl acetate solvent. N-Phenyl-carbazole (2a)22 was obtained (96% yield) as a white solid. Mp 86-87 °C; 1H NMR (400 MHz, CDCl3) δ 8.18 (d, 2H, J=7.6 Hz), 7.61 (m, 4H), 7.50 (t, 1H), 7.44 (d, 4H, J=7.6 Hz), 7.32 (m, 2H); 13C NMR (100 MHz, CDCl3) δ 107.6, 104.5, 96.6, 94.2, 93.9, 92.7, 90.1, 87.0, 86.6, 76.5; MS (m/z, relative intensity): 243 (M+, 100), 140 (11), 120 (16); Anal. Calcd for C18H13N1: C, 88.89; H, 5.35; N, 5.76. Found: C, 88.73; H, 5.29, N, 5.98.
96%	With potassium carbonate In toluene for 8h; Reflux; Inert atmosphere;	2.3.6. General procedure for the synthesis of N-aryl amides and N-arylheterocycles through C-N cross-coupling of amides and N-H heterocycleswith aryl halides General procedure: In order to prepare N-aryl amides and N-aryl heterocycles by meansof C-N coupling reactions (N-arylation reactions), a solution of arylhalide (1 mmol), amide or N-H heterocycle substrate (2 mmol) andK2CO3 (2 mmol) in toluene (5 mL) was poured into a 25 mL roundbottomed flask equipped with a condenser and a mechanical stirrer.Subsequently, CNF-phen-Cu(I) (0.01 mmol, 0.02 g for N-H heterocyclesand 0.005 mmol, 0.01 g for amides) was added to the above solution andthe resulted mixture was stirred under reflux condition and argon atmospherewithin a definite requisite time for each reaction. Screeningthe progress of the reaction was performed via TLC (pure n-hexane).After completion, the reaction mixture was allowed to cool to roomtemperature which was followed by addition of ethyl acetate (15 mL)and keeping on stirring the mixture for a further 15 min. Afterwards, theobtained mixture was filtered and the resulted solid was washed withwater and hot ethyl acetate (40 mL). Then, the solvent was evaporatedunder reduced pressure and the residue was purified by column chromatography(n-hexane: ethyl acetate). The synthesized products werecharacterized by use of 1H NMR (Supplementary Information, Figs. S2-S13) and melting points.

95%	With Pd catalyst Alkaline conditions;
95%	With copper (I) iodide; 1,10-Phenanthroline; potassium hydroxide In 1,2-dimethoxyethane; water monomer at 95℃; for 20h; Schlenk technique; Inert atmosphere; Sealed tube;
94%	With potassium carbonate In N,N-dimethyl-formamide at 120℃; for 6h; Inert atmosphere;	4.2 General procedure for Buchwald-Hartwig C-N cross coupling reaction using PNP-SSS catalyst General procedure: Aryl halide (1.0mmol), amine (1.5-2.0mmol), PNP-SSS (0.6mol%; 0.023g), K2CO3 (2mmol), and DMF (3.0mL) was placed in a 25mL flask equipped with a magnetic stirring bar and heated at 120°C under nitrogen gas. The reaction was then monitored by TLC until the consumption of aryl halide was detected. After completion of the reaction 5mL of water and 5mL of ethyl acetate were added to the reaction mixture. The organic solution was extracted and dried over anhydrous Na2SO4. After removing of organic solvent the crude product was obtained. For further purification the chromatography technique was used.
92%	With potassium carbonate In N,N-dimethyl-formamide at 90℃; for 24h;
92%	With copper (I) iodide; potassium carbonate; <i>L</i>-proline In dimethyl sulfoxide at 110℃; for 36h; Inert atmosphere;
92%	With potassium-t-butoxide; copper 8-hydroxyquinoline In dimethyl sulfoxide at 50 - 110℃; for 10.5h;	1.1; 1.2; 2.1; 2.2; 3.1; 3.2; 4.1; 4.2 Example 4 (1) Coupling reaction process:Under the protection of nitrogen, a stirrer, thermometer, reflux condenser,Carbazole (1.0mol, 167.2g) and copper 8-quinolinolate (0.05mol, 17.6g) were sequentially added to a dry 1000mL four-necked round bottom flask,Potassium tert-butoxide (1.0mol, 112.2g), iodobenzene (1.1mol, 123.0mL) and dimethyl sulfoxide (500mL), then heat to 50-60°C and stir for 30 minutes;After the mixture is uniform, the reaction is continued for 10 hours at a heating rate of 3°C/min to 110°C, during which the conversion rate of the carbazole is measured by the liquid phase.After the reaction is complete (the conversion rate of the carbazole detected by the liquid phase is ≥99%), stop the reaction,After the temperature of the reaction system is reduced to 60°C, DMSO is removed by distillation under reduced pressure,Add ethyl acetate to the solid residue to dissolve and filter under reduced pressure.The filter cake A is retained, the filtrate is washed and extracted with water,The organic layer extract was distilled under reduced pressure to remove ethyl acetate to obtain a crude product.The crude product was recrystallized from ethanol to obtain 223.9 g of light yellow solid N-phenylcarbazole (HPLC detection content ≥99%), and the yield was 92.0%.
91%	With sodium tertiary butoxide In xylene for 1h; Heating; Inert atmosphere;	1 Preparation of Structural Formula 1A; Carbazole (10 g, 59.8 mmol), and iodobenzene (13.4 g, 65.8 mmol) were dissolved in 200 ml of xylene, sodium-tertiary-botoxide (5.5 g, 71.7 mmol), and Pd[P(t-Bu)3]2 (153 mg, 0.299 mmol) were added thereto, and heated and agitated for 1 hour under the nitrogen atmosphere. After 200 ml of distilled water was added to the reaction solution, the manufactured solid was filtered, washed with 100 ml of water and 50 ml of ethanol, and dried under the vacuum to obtain the Structural Formula 1A (13.2 g, yield 91%). MS: [M+ H]+ = 244
91%	With potassium carbonate In toluene at 110℃; for 10h;	4.1.6 General Procedure for N-Arylation of N-H Heterocycle with Aryle Halides To a solution of N-H heterocycle (1 mmol) and aryl halide (2 mmol) in toluene were added catalyst (0.07 g, 0.016 mmol) and K2CO3 (276 g, 2 mmol) and the mixture stirred at 110 °C for the specified time. The progress of the reaction was monitored by TLC. The reaction mixture allowed cooling to room temperature and ethyl acetate (25 mL) was added and the mixture stirred for 15 min to ensure product removal from catalyst. Then the catalyst was filtered, washed with ethyl acetate (2 9 25 mL). The organic layer was evaporated under vacuum on a rotary evaporator and the crude product was obtained. Further purification was achieved by column chromatography using ethyl acetate/n-hexane gradient. Structural assignments of the products are based on their 1H NMR and melting point.
91%	With Cu(HOC₆H₃(O)CHNCH₂CH₂NCHC₆H₃(O)OH); sodium hydroxide at 120℃; for 7h;
91%	With copper (I) iodide; tripotassium phosphate monohydrate In toluene at 110℃; for 7h; Sonication; Inert atmosphere;	2.2. General procedure for C-N coupling reactions General procedure: MGOAPhen (0.04 gr) was dispersed in dry toluene (5 mL) by ultrasonication for 15 min. Then, benzamide (0.121 gr, 1 mmol), iodobenzene (0.408 gr, 2 mmol), copper (I) iodide (0.003 gr, 0.013 mmol) and K 3 PO 4 .H 2 O (0.461 gr, 2 mmol) were added to the dis- persed solution. The reaction mixture was stirred under argon at 110 °C for appropriate time. The reaction progress was monitored by TLC. After completion of the reaction, the mixture was cooled to RT. Then, MGOAPhen was separated by a supermagnet and washed with ethyl acetate (2 ×25 mL). The organic layer was evaporated under vacuum and the related product was purified by column chromatography using n-hexane-ethyl acetate (3:1) as the eluent. The structures of all products were confirmed using their melting points and 1 H NMR spectra and comparison with previously reported data by our research group (Fig. S1 to Fig. S8)
90%	With 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone; potassium carbonate at 170℃; for 8h;	2 Carbazole (16.7 g, 100 mmol), iodobenzene (26.5 g, 130 mmol), CuI (1.9 g, 10 mmol), K2CO3 (138 g, 1 mol), and 18-crown-6 (530 mg, 2 mmol) were dissolved in 1,3-dimethyl-3,4,5,6-tetrahydro-(1H)-pyrimidinone (DMPU) (500 mL), and then heated at 170°C for 8 hrs. After the reaction was completed, the reaction mixture was cooled to room temperature and solid materials were filtered. A small amount of aqueous ammonia was added to the filtrate, and the resultant was three times washed with diethyl ether (300 mL). The washed diethyl ether layer was dried on MgSO4 and dried under reduced pressure to obtain a crude product. The crude product was purified with a silica gel column chromatography to obtain 22 g of the intermediate compound A as a white solid (yield: 90%). 1H NMR (CDCl3, 400MHz) δ (ppm) 8.12 (d, 2H), 7.58-7.53 (m, 4H), 7.46-7.42 (m, 1H), 7.38 (d, 4H), 7.30-7.26 (m, 2H); 13C NMR (CDCl3, 100MHz) δ (ppm) 141.0, 137.9, 130.0, 127.5, 127.3, 126.0, 123.5, 120.4, 120.0, 109.9.
90%	With copper (I) iodide; potassium carbonate In 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone at 170℃; for 8h;	2 Synthesis of Intermediate E; Carbazole (16.7 g, 100 mmol), iodobenzene (26.5 g, 130 mmol), CuI (1.9 g, 10 mmol), K2CO3 (138 g, 1 mol), and 18-Crown-6 (530 mg, 2 mmol) were dissolved in DMPU (500 ml), and the reaction mixture was heated at 170° C. for eight hours. The reaction solution was cooled to room temperature and a solid material was filtered out. A trace amount of an ammonia solution was added to the filtrate, and the resultant solution was extracted three times with diethylether (300 ml). The obtained diethylether layer was dried over magnesium sulfate and then dried under a reduced pressure to obtain a crude product. The crude product was purified by silica gel column chromatography to give intermediate E as a white solid (22 g, yield: 90%). The structure of intermediate E was determined by 1H NMR. 1H NMR (CDCl3, 300 MHz) δ (ppm) 8.12 (d, 2H), 7.58-7.53 (m, 4H), 7.46-7.42 (m, 1H), 7.38 (d, 4H), 7.30-7.26 (m, 2H); 13C NMR (CDCl3, 100 MHz) δ (ppm) 141.0, 137.9, 130.0, 127.5, 127.3, 126.0, 123.5, 120.4, 120.0, 109.9.
90%	With copper (I) iodide; 1,10-Phenanthroline; potassium fluoride on basic alumina In toluene at 110℃; for 7h; Inert atmosphere;
90%	With copper (I) iodide; potassium carbonate; <i>L</i>-proline In dimethyl sulfoxide at 110℃; for 36h; Inert atmosphere;
90%	With 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone; copper (I) iodide; 18-crown-6 ether; potassium carbonate at 170℃; for 8h;	1.1 (1) Synthesis of Intermediate A Carbazole (16.7 g, 100 mmol), iodobenzene (26.5 g, 130 mmol), CuI (1.9 g, 10 mmol), K2CO3 (138 g, 1 mol), and 18-crown-6 (18-C-6) (530 mg, 2 mmol) were dissolved in 1,3-dimethyl-3,4,5,6-tetrahydro-(1H)-pyrimidinone (DMPU) (500 mL) and heated at a temperature of 170°C. for 8 hours. After the reaction was completed, the reaction mixture was cooled to room temperature. A solid material was filtered, and a small amount of ammonia water was added to the resultant filtrate. Washing was performed thereon three times by using diethyl ether (300 mL). The washed diethyl ether layer was dried by using MgSO4 and dried under reduced pressure to obtain a crude product. The crude product was separated and purified by silica gel column chromatography to obtain 22 g (yield of 90%) of Intermediate A as a white solid. 1H NMR (CDCl3, 400 MHz) δ (ppm) 8.12 (d, 2H), 7.58-7.53 (m, 4H), 7.46-7.42 (m, 1H), 7.38 (d, 4H), 7.30-7.26 (m, 2H) 13C NMR (CDCl3, 100 MHz) δ (ppm) 141.0, 137.9, 130.0, 127.5, 127.3, 126.0, 123.5, 120.4, 120.0, 109.9
89%	With copper oxide (I); 2,2,6,6-tetramethylheptane-3,5-dione; potassium hydroxide In N,N-dimethyl-formamide at 110℃; for 24h; Inert atmosphere; Schlenk technique;
87%	With copper (I) iodide; 1,10-Phenanthroline; potassium carbonate In para-xylene at 180℃;
87%	With copper (I) iodide; potassium carbonate; <i>L</i>-proline In dimethyl sulfoxide at 180℃; Inert atmosphere;
87%	With copper (I) iodide; lithium tert-butylate In acetonitrile at 20℃; for 24h; Inert atmosphere; Irradiation;
87.63%	With copper (I) iodide; 1,10-Phenanthroline; Cs₂CO₃ In N,N-dimethyl-formamide at 150℃; Inert atmosphere;	1 0.3100 mol of iodobenzene, 0.2400 mol of carbazole, 0.0218 mol of phenanthroline, 0.0218 mol of cuprous iodide,Cesium carbonate0.3600mol into 1000ml three-necked flask, add 300ml DMF dissolved,Vacuum - nitrogen three times, the temperature to 150 ° C, the reaction overnight, the reaction solution through the silicone funnel,Rinse with methylene chloride to no product dissolution,Spin to about 400ml with 500ml water, liquid, take dichloromethane phase, washed with water three times, spin dry,Add 100ml dissolved,Add 500ml of ethanol to a large amount of solid precipitation, filtration, vacuum drying at 55 ,To give 0.2096 mol of N-phenyl-9H-carbazole in 87.63% yield.
86%	With palladium diacetate; copper (I) iodide; cetyltriammonium bromide; potassium carbonate In water monomer; butan-1-ol for 24h; Heating;
84%	With copper (I) iodide; 18-crown-6 ether; potassium carbonate In N,N-dimethyl-formamide at 140℃; for 24h; Inert atmosphere;
82.2%	With 18-crown-6 ether; copper atom; potassium carbonate In N,N-dimethyl-formamide at 20℃; Inert atmosphere; Reflux;
82%	With copper (I) iodide; 1,10-Phenanthroline; potassium carbonate In o-dimethylbenzene at 142℃; for 48h; Inert atmosphere;	3 Synthesis of 2-(9-phenyl-9H-carbazol-3-yl)-5-(pyridin-2-yl)-1,3,4-oxadiazole (L3) In order to join in the reaction bottleCarbazole (3.34 g, 20 mmol), potassium carbonate (8.28 g, 60 mmol),Phenanthroline (0.56 g, 3 mmol), cuprous iodide (0.58 g, 3 mmol),Plus condensation pipe, nitrogen protection system. Inject iodobenzene (2.8 mL, 25 mmol) andOrtho-xylene (50 ml). It was refluxed in a 142°C oil bath for 48 h.After cooling, 50 mL of distilled water was added and stirred overnight. After filtration, the filtrate was extracted with ethyl acetate.A black organic solution was obtained and dried over anhydrous sodium sulfate. After drying, the organic liquid is concentrated,Column chromatography using ethyl acetate and petroleum ether as eluents gives the product as a white solid.9-Phenyl-9H-carbazole (4.00 g, 16.4 mmol), yield 82%.
81%	With copper atom; Cs₂CO₃ In propyl cyanide for 20h; Reflux; Inert atmosphere;
80%	With copper (I) iodide; 1,10-Phenanthroline; potassium carbonate In N,N-dimethyl-formamide for 24h; Inert atmosphere; Reflux;
80%	With copper (I) iodide; Cs₂CO₃; lithium chloride In N,N-dimethyl-formamide at 150℃; for 48h;
79%	With tris(2-phenylpyridinato-N,C2′)iridium(III); copper (I) iodide; lithium tert-butylate In dimethyl sulfoxide at 32℃; for 18h; Inert atmosphere; Irradiation;
76%	With copper (I) iodide; 1,10-Phenanthroline; potassium carbonate In N,N-dimethyl-formamide for 24h; Inert atmosphere; Reflux;	2.1 Synthesis of 9-PCz Three-necked flask were successively added to the carbazole (8.35g, 0.05mol), iodobenzene (11.22g, 0.055mol), potassium carbonate (7.6g, 0.055mol), 100ml DMF; under nitrogen with stirring was added cuprous iodide ( 0.76g, 4mmol), phenanthroline monohydrate (0.79g, 4mmol), after the replacement with nitrogen, the reaction was refluxed for 24 hours; after completion of the reaction, cooled to room temperature, most of the salt was removed by suction, and saturated sodium chloride aqueous dichloro methane extraction separation, the organic phase washed with water until neutral, dried over anhydrous sodium sulfate and filtered to give a red brown liquid; the solvent was removed by rotary evaporation, silica gel column, eluent petroleum ether pURIFICATION give white crystals, yield 76 %.
76%	With tripotassium phosphate tribasic; copper (I) iodide In toluene for 12h; Reflux;	4 50 g (299 mmol) of carbazole (6), 61 g (299 mmol) of iodobenzene, 84.3 g (897.1 mmol) of potassium phosphate, 68.2 g (358.3 mmmol) of Cooper iodide, Ethylene diamine (40 ml, 598.1 mmol) was suspended in 1500 ml of toluene, and the mixture was refluxed for 12 hours.Extracted with dichloromethane and distilled water, and the organic layer is subjected to silica gel filtration.The organic solution was removed and the product was subjected to silica gel column chromatography to obtain 55 g (yield: 76%) of intermediate product (7).
76%	With potassium carbonate In ethanol; water monomer at 20℃; UV-irradiation; Green chemistry;
76%	With potassium carbonate In 1,2-dichloro-benzene at 180℃; for 6h; Inert atmosphere;
76%	With potassium-t-butoxide; C₃₆H₃₂Cu₂Fe₂I₂Se₄ In acetonitrile at 20℃; for 12h; Schlenk technique; Inert atmosphere; Irradiation;	2.4. Evaluation of photocatalytic activity General procedure: Carbazole (0.034 g, 0.2 mmol), t-BuOK (0.049 g, 0.4 mmol), C1 were placed in a 25 mL Schlenk tube and it was evacuated andpurged with nitrogen three times. MeCN (2 mL) and aryl iodides were added in nitrogen atmosphere. Xenon Lamp with the powerdensity of 290 mW/cm2 was employed as the light source. Afterirradiation with a Xenon Lamp (290 mW/cm2) for 12 h at ambient temperature, the reaction mixture was concentrated in vacuumfollowed by addition of water (5 mL). The resulting mixture wasextracted with EtOAc (3 5 mL). The combined organic layerwas dried over MgSO4 and filtered, then the filtrate was concentratedin vacuum. The crude mixture was purified by silica gel flashcolumn chromatography (petroleum ether/EtOAc, v:v = 20:1) toafford the desired product.
75.6%	With 18-crown-6 ether; copper atom; potassium carbonate In 1,2-dichloro-benzene at 190℃; for 12h;	preparation of the compound (G-1) Carbazole (20g, 119.6mmol), iodobenzene (20 ml, 179 . 41mmol), copper (11.4g, 179 . 41mmol), K 2 CO 3 (49g, 358.8mmol), 18-crown -6 (2.5g, 9 . 56mmol) and 1,2-dichlorobenzene (100 ml) the mixture of 190 °C stirring 12 hours. After cooling to room temperature, the reaction mixture is distilled under reduced pressure. Adding distilled water, and the resulting mixture is extracted with ethyl acetate. Extract of magnesium sulfate drying, and the reduced pressure distillation. Through the column purification to obtain compound (G-1) (22g, 90.42mmol, 75.60%).
75.6%	With 18-crown-6 ether; copper atom; potassium carbonate In 1,2-dichloro-benzene at 190℃; for 12h;	6 Preparation of Compound G-1 20 g (119.6 mmol) of carbazole, 20 ml (179.41 mmol) of iodobenzene, 11.4 g (179.41 mmol) of copper, 49 g (358.8 mmol)18-crown-6, And 600 mL of 1,2-dichlorobenzene were placed, and the mixture was stirred at 190 for 12 hours.The mixture was cooled to room temperature and distilled under reduced pressure.Distilled water was added and extracted with EA. Dried over magnesium sulfate and distilled under reduced pressure.The column was separated to obtain 22 g (90.42 mmol, 75.60%) of the compound G-1
75.6%	With 18-crown-6 ether; copper atom; potassium carbonate In 1,2-dichloro-benzene at 190℃; for 12h;	6 Preparation of Compound G-1 20 g (119.6 mmol) of carbazole, 20 mL (179.41 mmol) of iodobenzene,11.4 g (179.41 mmol) of copper, 49 g (358.8 mmol) of K 2 CO 3, 2.5 g (9.56 mmol) of 18-crown-6 and 600 mL of 1,2-dichlorobenzene were added thereto, and the mixture was stirred at 190 ° C. for 12 hours.Cooled to room temperature and distilled under reduced pressure. Distilled water was added and extracted with EA. Dried over magnesium sulfate and distilled under reduced pressure. Compound G-1 22g (90.42mmol, 75.60%) was obtained by column separation.
75.6%	With 18-crown-6 ether; potassium carbonate In 1,2-dichloro-benzene at 190℃; for 12h;	6 Preparation of compound G-1 Carbazole 20g (119.6mmol), iodobenzene 20mL (179.41mmol), copper 11.4g (179.41mmol),K2CO3 49g (358.8mmol), 18-crown-6 2.5g (9.56mmol), 1,2-dichlorobenzene 600mL was added and stirred at 190°C for 12 hours.It was cooled to room temperature and distilled under reduced pressure. Distilled water was added and extracted with EA. It was dried over magnesium sulfate and distilled under reduced pressure. Column separation was performed to obtain 22g (90.42mmol, 75.60%) of compound G-1
73%	With C₂₄H₂₂N₆Ni; sodium tertiary butoxide In N,N-dimethyl-formamide; acetonitrile at 30℃; for 36h; Inert atmosphere; Schlenk technique;
70%	With copper (I) iodide; potassium carbonate; lithium chloride In N,N-dimethyl-formamide at 140℃; for 48h; Inert atmosphere;	9-Phenyl-9-carbazole (4e). A solution of carbazole4 (0.50 g, 2.99 mmol) in DMF (25 ml) was treated by theaddition of K2CO3 (1.24 g, 8.98 mmol), CuI (0.57 g,0.29 mmol), LiCl * Eu3+ concentration of 10-6 (λexcit 340 ± 2, λemiss 615 ± 2 nm). (0.13 g, 2.99 mmol), and iodobenzene (0.67 g, 3.29 mmol). The mixture was stirred under argonatmosphere at 140° for 48 h. After cooling to roomtemperature, the mixture was poured into 10% NH4Clsolution (50 ml), extracted with EtOAc (3×20 ml), the organicphase was washed with 10% NH4Cl solution (2×10 ml) andH2O (2×10 ml), and dried over anhydrous Na2SO4. Thesolvent was evaporated at reduced pressure, and the residuewas recrystallized from MeOH. Yield 0.51 g (70%), whiteneedles, mp 87-88° (mp 86-87°C19)
62%	With copper atom; potassium carbonate In 1,2-dichloro-benzene for 12h; Reflux;	9- 9H-carbazole 70 g(0.42 mmol), Iodobenzene 46 mL, Cu 40 g, potassium carbonate 174 g, 18-crown-6 9 g, and 1,2-dichlorobenzene 2 L all are input, and then stirred under reflex for 12 hours. Upon completion of the reaction, extraction with EA, drying over MgSO4, distillation under reduced pressure, and column separation were sequentially performed, thereby obtaining Compound 9-4 63.4 g(260.58 mmol, 62%).
60%	With (2-furyl)methyl alcohol; tripotassium phosphate tribasic; copper (I) iodide In water monomer at 150℃; for 12h; Sealed tube; Green chemistry;
60%	Stage #1: 9H-carbazole With copper (I) iodide; Cs₂CO₃ In toluene at 80℃; Inert atmosphere; Stage #2: iodobenzene With Ethane-1,2-diamine In toluene at 110℃; for 15h; Inert atmosphere;	Compound (5) 9-phenyl-9H-carbazole 9H-carbazole (10 g,60 mmol), copper(Ι) iodide (9.1 g, 48 mmol), cesium carbonate (58.4 g,180 mmol) were added to 90 mL of anhydrous toluene solution in 3-neck round bottom flask under N2 atmosphere. After the mixture washeated at 80 °C, iodobenzene (13.3 mL, 120 mmol), ethylenediamine(6 mL, 18 mmol) was added to mixture. Then the mixture was refluxedat 110 °C for 15 h (8.8 g, Yield 60%) 1H NMR (300 MHz, DMSO):δ(ppm) 8.27-8.24 (d, 2H), 7.72-7.66 (t, 2H), 7.64-7.61 (d, 2H),7.57-7.52 (t, 1H), 7.47-7.41 (t, 2H), 7.39-7.36 (d, 2H), 7.32-7.30 (t,2H).
58%	With Cu(OAc)₂*H₂O; Cs₂CO₃ In N,N-dimethyl-formamide at 110℃; for 24h; Inert atmosphere;	4.6. General catalytic procedure for the N-arylation of nitrogen-containing heterocycles with aryl iodides General procedure: To a solution of Cu(OAc)2·H2O (0.01 mmol) in DMF (2 mL) were added aryl iodide (1.2 mmol), nitrogen-containing heterocycle (1.0 mmol), and Cs2CO3 (2 mmol) under nitrogen atmosphere. The mixture was stirred at 110 °C for 24 h. After cooling to ambient temperature, the mixture was partitioned between water and ethyl acetate. The organic layer was separated, and the aqueous layer was extracted with ethyl acetate. The combined organic layers were washed with brine, dried over Na2SO4, and concentrated in vacuo. The residue was purified by flash chromatography on silica gel.
56%	With copper atom; potassium carbonate In N,N-dimethyl-formamide at 140℃; Inert atmosphere;
55%	With [Fe₂-((phenylazo)-1,10-phenanthroline)Cl₂]; potassium-t-butoxide In dimethyl sulfoxide at 120℃; for 40h; Schlenk technique; Inert atmosphere; Sealed tube;
53%	With copper atom; potassium carbonate In 1,2-dichloro-benzene at 178℃; for 18h; Inert atmosphere;	Synthesis of non substituted N-phenyl triscarbazoleN-phenyl carbazole - CzPA mixture of 30 g (0.179 mol, 1.0 eq) of carbazole, 47.58 g (0.233 mol, 1.3 eq) of iodobenzene, 173.5 g (1.25 mol, 7.0 eq) of K2C03, 159.6 g (2.51 mol, 14 eq) of Cu powder and 2.371 g (0.00897 mol, 5 mol%) of 18-crown-6 are stirred in 900 mL of 1,2-dichlorobenzene at 178°C under N2 atmosphere for 18 h. The reaction is cooled down at room temperature and the mixture is filtered through a path of Celite and silica which is rinsed by toluene. The filtrate is evaporated under vacuum to give a yellow-brown solid further recrystallized from ethanol. Collected weight = 23.17 g (0.0950 mol, 53 %) of CzP as pale yellow needles.
53%	With 18-crown-6 ether; copper atom; potassium carbonate In 1,2-dichloro-benzene at 178℃; for 18h; Inert atmosphere;	N-phenyl carbazole - CzP A mixture of 30 g (0.179 mol, 1.0 eq) of carbazole, 47.58 g (0.233 mol, 1.3 eq) of iodobenzene, 173.5 g (1.25 mol, 7.0 eq) of K2CO3, 159.6 g (2.51 mol, 14 eq) of Cu powder and 2.371 g (0.00897 mol, 5 mol%) of 18-crown-6 are stirred in 900 mL of 1,2-dichlorobenzene at 178°C under N2 atmosphere for 18 h. The reaction is cooled down at room temperature and the mixture is filtered through a path of Celite and silica which is rinsed by toluene. The filtrate is evaporated under vacuum to give a yellow-brown solid further recrystallized from ethanol. Collected weight = 23.17 g (0.0950 mol, 53 %) of CzP as pale yellow needles.
52%	With copper atom; potassium carbonate at 200℃; for 5h;
25%	With tripotassium phosphate monohydrate; copper(II) oxide; N,N`-dimethylethylenediamine In toluene at 135℃; for 24h; Inert atmosphere;
	With copper atom; potassium carbonate at 200℃;
	With copper (I) iodide; 1,10-Phenanthroline; potassium carbonate In para-xylene at 180℃;
	With potassium hydroxide In para-xylene Heating;
	With tripotassium phosphate tribasic; copper (I) iodide; <i>L</i>-proline In dimethyl sulfoxide
	With tripotassium phosphate tribasic; copper (I) iodide; trans-1,2-Diaminocyclohexane In 1,4-dioxane at 110℃; for 24h; Inert atmosphere;
	With copper atom; potassium carbonate In 1,3,5-trimethyl-benzene for 3h; Reflux; Inert atmosphere;	1 Bis (4-(N-phenyl-N-(9-phenyl-3-carbazolyl)amino)phenyl)-p-methylphenylamine (A) was synthesised according to the following scheme. 37.0g of iodobenzene, 25.0 g of carbazole, 50.5g of potassium carbonate and 15 g of copper powder were added to mesitylene, and were reacted under reflux for three hours under a nitrogen atmosphere. After completion of the reaction, the resulting reaction mixture was extracted with toluene, and fractionated by silica gel column chromatography using a mixed solvent composed of toluene/hexane (volume ratio of 1/1) to separate the desired compound. The obtained solid was recrystallized from hexane to provide 31.5 g of 9-phenylcarbazole.
	With copper (I) iodide; 1,10-Phenanthroline; potassium hydroxide In para-xylene at 140℃;
	With sodium tertiary butoxide In xylene for 8h; Reflux; Inert atmosphere;	14 Synthesis Example 14 (synthesis of Intermediate 14); Under an argon stream, 670 g of carbazole, 850 kg of iodobenzene, 20 L of xylene, 460 g of t-BuONa, and palladium acetate (Pd(OAc)) were charged, and the mixture was refluxed for 8 hours. Impurities were filtered and the filtrate was concentrated under reduced pressure, followed by washing with hexane and drying, whereby phenylcarbazole was obtained as 820 g of white powder. The same reaction as in the synthesis of Intermediate 1 was carried out except that phenylcarbazole was used instead of 4-bromobiphenyl, whereby 650 g of white powder was obtained. By an FD-MS analysis, the white powder was identified as Intermediate 14.
	With copper atom; potassium carbonate In nitrobenzene for 24h; Reflux;
	With sodium tertiary butoxide In xylene for 8h; Inert atmosphere; Reflux;	1-11 In a stream of argon, 670 g of carbazole, 850 kg of iodobenzene, 20 L of xylene, 460 g of t-BuONa, and palladium acetate (Pd(OAc)2) were loaded, and then the mixture was refluxed for 8 hours. Impurities were filtrated, and then the filtrate was concentrated under reduced pressure and washed with hexane. After that, the washed product was dried. As a result, 820 g of phenylcarbazole were obtained as a white powder. A reaction was performed in the same manner as in the synthesis of Intermediate 1-1 except that phenylcarbazole was used instead of 4-bromobiphenyl. As a result, 650 g of a white powder were obtained. The powder was identified as Intermediate 1-11 by FD-MS analysis
	With sodium tertiary butoxide In xylene for 8h; Inert atmosphere; Reflux;	11 ; In a stream of argon, 670 g of carbazole, 850 kg of iodobenzene, 20 L of xylene, 460 g of t-BuONa, and palladium acetate (Pd(OAc)2) were added, and then the mixture was refluxed for 8 hours. Impurities were filtrated, and then the filtrate was concentrated under reduced pressure and washed with hexane. After that, the washed product was dried. As a result, 820 g of phenylcarbazole were obtained as a white powder. In a stream of argon, 24 g of phenylcarbazole, 8.3 g of potassium iodide, 10.7 g of potassium iodate, 500 mL of ethanol, and 8 mL of sulfuric acid were added into a 1,000-mL three-necked flask, and then the mixture was stirred at 75°C for 2 hours. After that, the reaction product was injected into ice water, and then the mixture was extracted with ethyl acetate and water. After having been washed with water, the extract was subjected to column chromatography with silica gel. As a result, 67 g of a white powder were obtained. A reaction was performed in the same manner as in the synthesis of Intermediate 1 except that was used instead of 4 -bromobiphenyl. As a result, 22.3 g of a white powder were obtained. FD-MS analysis identified the powder as Intermediate 11.
	With 18-crown-6 ether; copper atom; potassium carbonate In 1,2-dichloro-benzene at 190℃; for 20h;
	With 18-crown-6 ether; copper atom; potassium carbonate In N,N-dimethyl-formamide
	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tri-tert-butyl phosphine; sodium tertiary butoxide In toluene Reflux;
	With copper atom; potassium carbonate In Triethylene glycol dimethyl ether
71 %Chromat.	With potassium hydroxide In dimethyl sulfoxide at 80℃; for 24h; Inert atmosphere;
	With copper (I) iodide; 1,10-Phenanthroline; potassium carbonate In N,N-dimethyl-formamide
	With copper (I) iodide Reflux;
	With copper (I) iodide; 1,10-Phenanthroline; sodium hydroxide In para-xylene at 140℃; for 48h;	4.2. Synthesis of L2 9-Phenyl-9H-carbazole was prepared through Ullmanncoupling of carbazole (2.0 g, 0.012 mol) and iodobenzene (2.0 ml,0.018 mol) with a catalytic amount of copper iodide (1.59 g,8.372 mmol) and 1,10-phenanthroline (1.66 g, 8.372 mmol). 9-Phenyl-9H-carbazole (2.04 g, 8.372 mmol) reacted with NBS (1.56 g, 8.791 mmol) to give 3-bromo-9-phenyl-9H-carbazole (2.67 g, 8.287 mmol) which was then converted into its boronic acid derivative (0.95 g, 3.315 mmol) and that subsequently reacted with 2-bromothiazole (0.24 ml, 2.652 mmol). The 2-(9-phenyl-9H-carbazol-3-yl)thiazole ligand L2 was formed as a pale yellow powder (56%). Spectral data: MS (MALDI-TOF): m/z 326.41 (M+). 1H NMR (CDCl3): δ (ppm) 8.78 (d, J=1.4 Hz, 1H, Ar), 8.22 (d,J=6.9 Hz, 1H, Ar), 8.03-8.01 (m, 1H, Ar), 7.88 (d, J=3.2 Hz, 1H, Ar),7.65-7.61 (m, 2H, Ar), 7.59-7.56 (m, 2H, Ar), 7.52-7.48 (m, 1H, Ar),7.45-7.40 (m, 3H, Ar), 7.35-7.32 (m, 1H, Ar), 7.30 (d, J=3.2 Hz, 1H,Ar).
	With copper (I) iodide; potassium carbonate In N,N-dimethyl-formamide at 155℃;

Reference： [1]Lo, Quintin A.; Sale, David; Braddock, D. Christopher; Davies, Robert P. [European Journal of Organic Chemistry, 2019, vol. 2019, # 9, p. 1944 - 1951]
[2]Location in patent: experimental part Kwon, Jae Kwan; Cho, Joong Hyun; Ryu, Young-Sil; Oh, Se Hwan; Yum, Eul Kgun [Tetrahedron, 2011, vol. 67, # 26, p. 4820 - 4825]
[3]Aghili, Nora; Hosseinzadeh, Rahman; Mavvaji, Mohammad [Polyhedron, 2022, vol. 213]
[4]Current Patent Assignee: TOHOKU UNIVERSITY; KONICA MINOLTA, INC. - JP2017/137258, 2017, A Location in patent: Paragraph 0053; 0054
[5]Malavade, Vrunda; Patil, Manish; Patil, Mahendra [European Journal of Organic Chemistry, 2020, vol. 2020, # 5, p. 561 - 569]
[6]Panahi, Farhad; Daneshgar, Fatemeh; Haghighi, Fatemeh; Khalafi-Nezhad, Ali [Journal of Organometallic Chemistry, 2017, vol. 851, p. 210 - 217]
[7]Xi, Zhenxing; Liu, Fenghui; Zhou, Yongbo; Chen, Wanzhi [Tetrahedron, 2008, vol. 64, # 19, p. 4254 - 4259]
[8]Location in patent: experimental part Zheng, Cai-Jun; Ye, Jun; Lo, Ming-Fai; Fung, Man-Keung; Ou, Xue-Mei; Zhang, Xiao-Hong; Lee, Chun-Sing [Chemistry of Materials, 2012, vol. 24, # 4, p. 643 - 650]
[9]Current Patent Assignee: SINOSTEEL GROUP NANJING NEW MATERIAL RES INSTITUTE; SINOSTEEL NEW MATERIALS - CN112079768, 2020, A Location in patent: Paragraph 0035-0048
[10]Current Patent Assignee: LG CHEM CO.,LTD. - EP2343277, 2011, A2 Location in patent: Page/Page column 32
[11]Hosseinzadeh, Rahman; Aghili, Nora; Tajbakhsh, Mahmood [Catalysis Letters, 2016, vol. 146, # 1, p. 193 - 203]
[12]Sharghi, Hashem; Aberi, Mahdi; Shiri, Pezhman [Applied Organometallic Chemistry, 2017, vol. 31, # 11]
[13]Abaszadeh, Maryam; Ghasemi, Shahram; Hosseinzadeh, Rahman; Tajbakhsh, Mahmood [Journal of Molecular Structure, 2022, vol. 1261]
[14]Current Patent Assignee: Samsung Display (in: Samsung); SAMSUNG ELECTRONICS CO.,LTD. - EP1661888, 2006, A1 Location in patent: Page/Page column 11
[15]Current Patent Assignee: Samsung Display (in: Samsung); SAMSUNG ELECTRONICS CO.,LTD. - US2008/174237, 2008, A1 Location in patent: Page/Page column 13
[16]Location in patent: experimental part Hosseinzadeh, Rahman; Tajbakhsh, Mahmood; Alikarami, Mohammad; Mohadjerani, Maryam [Journal of Heterocyclic Chemistry, 2008, vol. 45, # 6, p. 1815 - 1818]
[17]Zhang, Kai; Sun, Qikun; Zhang, Zhenzhen; Tang, Linagliang; Xie, Zongliang; Chi, Zhenguo; Xue, Shanfeng; Zhang, Haichang; Yang, Wenjun [Chemical Communications, 2018, vol. 54, # 41, p. 5225 - 5228] Sun, Qikun; Zhang, Kai; Zhang, Zhenzhen; Tang, Linagliang; Xie, Zongliang; Chi, Zhenguo; Xue, Shanfeng; Zhang, Haichang; Yang, Wenjun [Chemical Communications, 2018, vol. 54, # 59, p. 8206 - 8209]
[18]Current Patent Assignee: SAMSUNG ELECTRONICS CO.,LTD.; Samsung Display (in: Samsung) - US2020/266354, 2020, A1 Location in patent: Paragraph 0436-0440
[19]Chen, Fei; Liu, Ning; Ji, Enhui; Dai, Bin [RSC Advances, 2015, vol. 5, # 64, p. 51512 - 51523]
[20]Feng, Guo-Liang; Ji, Shun-Jun; Lai, Wen-Yong; Huang, Wei [Synlett, 2006, # 17, p. 2841 - 2845]
[21]Location in patent: scheme or table Liu, Yu; Wang, Hai-Ying; Chen, Gang; Xu, Xiao-Ping; Ji, Shun-Jun [Australian Journal of Chemistry, 2009, vol. 62, # 8, p. 934 - 940]
[22]Ziegler, Daniel T.; Choi, Junwon; Munoz-Molina, Jose Maria; Bissember, Alex C.; Peters, Jonas C.; Fu, Gregory C. [Journal of the American Chemical Society, 2013, vol. 135, # 35, p. 13107 - 13112]
[23]Current Patent Assignee: JILIN OLED OPTICAL AND ELECTRONIC MATERIALS CO LTD - CN104650044, 2017, B Location in patent: Paragraph 0035; 0037
[24]Davydov, D. V.; Beletskaya, I. P. [Russian Chemical Bulletin, 1995, vol. 44, # 6, p. 1141][Izvestiya Akademi Nauk, Seriya Khimicheskaya, 1995, # 6, p. 1181 - 1182]
[25]Guo, Runda; Huang, Zhi; Liu, Wei; Wang, Lei; Wang, Yaxiong; Xiang, Songpo; Ye, Shaofeng; Zhang, Qing [Journal of Materials Chemistry C, 2020, vol. 8, # 11, p. 3705 - 3714]
[26]Location in patent: experimental part Park, Jung Hwan; Kim, Eun Kyung; El-Deeb, Ibrahim M.; Jung, Su Jin; Choi, Dae Hyuk; Kim, Dong-Ha; Yoo, Kyung Ho; Kwon, Jang Hyuk; Lee, So Ha [Bulletin of the Korean Chemical Society, 2011, vol. 32, # 3, p. 841 - 846]
[27]Current Patent Assignee: NANJING UNIVERSITY OF POSTS AND TELECOMMUNICATIONS - CN104163835, 2017, B Location in patent: Paragraph 0047; 0048
[28]Zhu, Rui; Xing, Lixin; Wang, Xinyan; Cheng, Chuanjie; Su, Deyong; Hu, Yuefei [Advanced Synthesis and Catalysis, 2008, vol. 350, # 9, p. 1253 - 1257]
[29]Location in patent: experimental part Jiang, Wei; Duan, Lian; Qiao, Juan; Dong, Guifang; Zhang, Deqiang; Wang, Liduo; Qiu, Yong [Journal of Materials Chemistry, 2011, vol. 21, # 13, p. 4918 - 4926]
[30]Location in patent: experimental part Cho, Joong Hyun; Ryu, Young-Sil; Oh, Se Hwan; Kwon, Jae Kwan; Yum, Eul Kgun [Bulletin of the Korean Chemical Society, 2011, vol. 32, # 7, p. 2461 - 2464]
[31]Yoo, Woo-Jin; Tsukamoto, Tatsuhiro; Kobayashi, Shu [Organic Letters, 2015, vol. 17, # 14, p. 3640 - 3642]
[32]Current Patent Assignee: VALIANT CO., LTD. - CN104370904, 2016, B Location in patent: Paragraph 0062-0064
[33]Current Patent Assignee: SOULBRAIN CO.,LTD. - KR2017/58874, 2017, A Location in patent: Paragraph 0077; 0094; 0095
[34]Singh, Gurpreet; Kumar, Manoj; Bhalla, Vandana [Green Chemistry, 2018, vol. 20, # 23, p. 5346 - 5357]
[35]Kundu, Anu; Kumar, Vadivel Vinod; Anthony, Savarimuthu Philip [Inorganic Chemistry Communications, 2021, vol. 123]
[36]Ji, Wei; Jing, Su; Li, Ai-Min; Qi, Zheng-Hang; Qiu, Wen-Jie; Zha, Guo-Jin; Zhu, Dun-Ru [Journal of Catalysis, 2022, vol. 405, p. 313 - 321]
[37]Current Patent Assignee: DOW INC - CN103524510, 2016, B Location in patent: Paragraph 0124; 0125; 0126
[38]Current Patent Assignee: DOW INC - KR101650294, 2016, B1 Location in patent: Paragraph 0107-0110
[39]Current Patent Assignee: DOW INC - KR101605340, 2016, B1 Location in patent: Paragraph 0107-0110
[40]Current Patent Assignee: DOW INC - KR101552477, 2015, B1 Location in patent: Paragraph 0107-0110
[41]Sikari, Rina; Sinha, Suman; Chakraborty, Gargi; Das, Siuli; van Leest, Nicolaas Petrus; Paul, Nanda D. [Advanced Synthesis and Catalysis, 2019, vol. 361, # 18, p. 4342 - 4353]
[42]Pugachov, Dmitriy E.; Kostryukova, Tatiana S.; Zatonsky, Georgy V.; Vatsadze, Sergey Z.; Vasil’ev, Nikolai V. [Chemistry of Heterocyclic Compounds, 2018, vol. 54, # 5, p. 528 - 534][Khim. Geterotsikl. Soedin., 2018, vol. 54, # 5, p. 528 - 534,7]
[43]Current Patent Assignee: DOW INC - EP2857395, 2015, A1 Location in patent: Paragraph 0079
[44]Ferlin, Francesco; Trombettoni, Valeria; Luciani, Lorenzo; Fusi, Soliver; Piermatti, Oriana; Santoro, Stefano; Vaccaro, Luigi [Green Chemistry, 2018, vol. 20, # 7, p. 1634 - 1639]
[45]Kang, Seokwoo; Jung, Hyocheol; Lee, Hayoon; Lee, Suji; Jung, Mina; Lee, Jaehyun; Chul Kim, Young; Park, Jongwook [Dyes and Pigments, 2018, vol. 156, p. 369 - 378]
[46]Xu, Zhong-Lin; Li, Hong-Xi; Ren, Zhi-Gang; Du, Wei-Yuan; Xu, Wei-Chang; Lang, Jian-Ping [Tetrahedron, 2011, vol. 67, # 29, p. 5282 - 5288]
[47]Kim, Se Hun; Cho, Illhun; Sim, Mun Ki; Park, Sanghyuk; Park, Soo Young [Journal of Materials Chemistry, 2011, vol. 21, # 25, p. 9139 - 9148]
[48]Sinha, Suman; Sikari, Rina; Sinha, Vivek; Jash, Upasona; Das, Siuli; Brandão, Paula; Demeshko, Serhiy; Meyer, Franc; De Bruin, Bas; Paul, Nanda D. [Inorganic Chemistry, 2019, vol. 58, # 3, p. 1935 - 1948]
[49]Current Patent Assignee: NISSAN CHEMICAL CORPORATION - WO2012/25510, 2012, A1 Location in patent: Page/Page column 22-23
[50]Current Patent Assignee: NISSAN CHEMICAL CORPORATION - EP2433928, 2012, A1 Location in patent: Page/Page column 16
[51]Avendano, Carmen; Espada, Modesta; Ocana, Blanca; Garcia-Granda, Santiago; Diaz, Maria del Rosario; et al. [Journal of the Chemical Society. Perkin transactions II, 1993, # 8, p. 1547 - 1555]
[52]Location in patent: scheme or table Larsson, Per-Fredrik; Correa, Arkaitz; Carril, Monica; Norrby, Per-Ola; Bolm, Carsten [Angewandte Chemie - International Edition, 2009, vol. 48, p. 5691 - 5693][Angew. Chem., Int. Ed., 2009, vol. 121, p. 5801 - 5803]
[53]Dunlop; Tucker [Journal of the Chemical Society, 1939, p. 1945,1954]
[54]Feng, Guo-Liang; Lai, Wen-Yong; Ji, Shun-Jun; Huang, Wei [Tetrahedron Letters, 2006, vol. 47, # 39, p. 7089 - 7092]
[55]Wong, Wai-Yeung; Ho, Cheuk-Lam; Gao, Zhi-Qiang; Mi, Bao-Xiu; Chen, Chin-Hsin; Cheah, Kok-Wai; Lin, Zhenyang [Angewandte Chemie - International Edition, 2006, vol. 45, # 46, p. 7800 - 7803]
[56]Location in patent: scheme or table Feng, Guo-Liang; Ji, Shun-Jun; Geng, Li-Jun; Bian, Bing; Liu, Yu [Journal of Chemical Research, 2008, # 3, p. 137 - 140]
[57]Location in patent: scheme or table Albrecht, Ken; Yamamoto, Kimihisa [Journal of the American Chemical Society, 2009, vol. 131, p. 2244 - 2251]
[58]Current Patent Assignee: BANDO CHEMICAL INDUSTRIES LTD - EP2100880, 2009, A1 Location in patent: Page/Page column 14-15
[59]Location in patent: scheme or table Ho, Cheuk-Lam; Wong, Wai-Yeung; Yao, Bing; Xie, Zhiyuen; Wang, Lixiang; Lin, Zhenyang [Journal of Organometallic Chemistry, 2009, vol. 694, # 17, p. 2735 - 2749]
[60]Current Patent Assignee: IDEMITSU KOSAN CO LTD - EP2177516, 2010, A1 Location in patent: Page/Page column 49
[61]Location in patent: scheme or table Koyuncu, Fatma Baycan; Koyuncu, Sermet; Ozdemir, Eyup [Electrochimica Acta, 2010, vol. 55, # 17, p. 4935 - 4941]
[62]Current Patent Assignee: IDEMITSU KOSAN CO LTD - EP2364980, 2011, A1 Location in patent: Page/Page column 72
[63]Current Patent Assignee: IDEMITSU KOSAN CO LTD - EP2399906, 2011, A1 Location in patent: Page/Page column 27; 37
[64]Location in patent: scheme or table Chiu, Ssu-Kai; Chung, Yi-Chun; Liou, Guey-Sheng; Su, Yuhlong Oliver [Journal of the Chinese Chemical Society, 2012, vol. 59, # 3, p. 331 - 337]
[65]Location in patent: scheme or table Zhao, Zujin; Chan, Carrie Y. K.; Chen, Shuming; Deng, Chunmei; Lam, Jacky W. Y.; Jim, Cathy K. W.; Hong, Yuning; Lu, Ping; Chang, Zhengfeng; Chen, Xiaopeng; Kwok, Hoi Sing; Qiu, Huayu; Tang, Ben Zhong [Journal of Materials Chemistry, 2012, vol. 22, # 10, p. 4527 - 4534]
[66]Hsu, Chung-Yi; Hsieh, Mu-Tao; Chen, Yen-Fu; Hsu, Chun-Chia; Hung, Tzu-Lin; Chen, Chun-Shuo; Whang, Thou-Jen [Journal of the Chinese Chemical Society, 2013, vol. 60, # 6, p. 579 - 589]
[67]Wang, Hui-Min; Hsiao, Sheng-Huei [Journal of Polymer Science, Part A: Polymer Chemistry, 2014, vol. 52, # 8, p. 1172 - 1184]
[68]Bhosale, Manohar A.; Bhanage, Bhalchandra M. [RSC Advances, 2014, vol. 4, # 29, p. 15122 - 15130]
[69]Huang, Bin; Yin, Zhihui; Ban, Xinxin; Jiang, Wei; Dai, Yu; Zhang, Junya; Liu, Yuanyuan; Yang, Yaping; Sun, Yueming [Dyes and Pigments, 2015, vol. 117, p. 141 - 148]
[70]Telore, Rahul D.; Sekar, Nagaiyan [Dyes and Pigments, 2016, vol. 129, p. 1 - 8]
[71]Chau, Nga-Yuen; Ho, Po-Yu; Ho, Cheuk-Lam; Ma, Dongge; Wong, Wai-Yeung [Journal of Organometallic Chemistry, 2017, vol. 829, p. 92 - 100]
[72]Lade, Jatin; Lee, Nian-Yun; Patil, Bhausaheb; Deshpande, Yogita Y.; Pownthurai; Hsieh, Chung-An; Pingale, Subhash S.; Chen, Li-Yin; Chaskar, Atul [Organic electronics, 2021, vol. 92]

2
[ 1150-62-5 ]
[ 73087-83-9 ]

Yield	Reaction Conditions	Operation 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.

Reference： [1]Chemische Berichte,1980,vol. 113,p. 577 - 585
[2]Patent: JP5663566,2015,B2 .Location in patent: Paragraph 0162

3
[ 603-34-9 ]
[ 1150-62-5 ]

Yield	Reaction Conditions	Operation in experiment
100%	With oxygen In acetonitrile UV-irradiation;
91%	With tris(1,10-phenanthroline)iron(II) bis(bis(trifluoromethane)sulfonimide); oxygen In tetrahydrofuran at 20℃; for 4h; Irradiation; Inert atmosphere;
90%	With tris(1,10-phenanthroline)iron(II) bis(bis(trifluoromethane)sulfonimide); oxygen In tetrahydrofuran at 20℃; for 3.05h; Irradiation; Inert atmosphere;

76%	With water at 250℃; for 12h;
75%	With tetrakis(acetonitrile)copper(I)tetrafluoroborate; 2.9-dimethyl-1,10-phenanthroline; iodine; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene; methyloxirane In tetrahydrofuran at 20℃; for 10h; Flow reactor; Inert atmosphere; Irradiation;
71%	With iodine; methyloxirane In tetrahydrofuran at 29℃; for 3h; Photolysis; Flow reactor;
60%	With oxygen In acetonitrile for 4h; Irradiation;	Irradiation of triphenylaminein oxygen saturated MeCN 50 mL of a 5×10-3M nitrogen purged solution of Ph3N (61 mg, 0.25 mmol)were irradiated at 310 nm for 4 hours, then evaporated. Purification by column chromatography afforded 30 mg of 9-phenylcarbazole (1, 49% yield, colorless solid). Spectroscopic data of 1 were in accord with the literature.S1 MS (m/z): 243 (M+, 100), 121 (15). Anal. Calcd for C18H13N: C, 88.86; H, 5.39; N, 5.76. Found: C, 88.9; H, 5.4; N, 5.7.Moreover,UV-monitoring of an oxygen-saturated solution of Ph3N (5×10-5 M) in MeCN irradiated at 313nm (optical bench) was carried out, and the yield of 1 quantified in 60% (see figure S1).
45%	With palladium diacetate In acetic acid for 3h; Heating;
	With oxygen In acetonitrile Irradiation;
	In methanol Flash photolysis;

Reference： [1]Protti, Stefano; Mella, Mariella; Bonesi, Sergio M. [New Journal of Chemistry, 2021, vol. 45, # 36, p. 16581 - 16593]
[2]Parisien-Collette, Shawn; Hernandez-Perez, Augusto C.; Collins, Shawn K. [Organic Letters, 2016, vol. 18, # 19, p. 4994 - 4997]
[3]Parisien-Collette, Shawn; Hernandez-Perez, Augusto C.; Collins, Shawn K. [Organic Letters, 2016, vol. 18, # 19, p. 4994 - 4997]
[4]Yamamoto, Mitsuru; Matsubara, Seijiro [Chemistry Letters, 2007, vol. 36, # 1, p. 172 - 173]
[5]Hernandez-Perez, Augusto C.; Collins, Shawn K. [Angewandte Chemie - International Edition, 2013, vol. 52, # 48, p. 12696 - 12700][Angew. Chem., 2013, vol. 125, # 48, p. 12928 - 12932]
[6]Caron, Antoine; Hernandez-Perez, Augusto C.; Collins, Shawn K. [Organic Process Research and Development, 2014, vol. 18, # 11, p. 1571 - 1574]
[7]Bonesi, Sergio Mauricio; Dondi, Daniele; Protti, Stefano; Fagnoni, Maurizio; Albini, Angelo [Tetrahedron Letters, 2014, vol. 55, # 18, p. 2932 - 2935]
[8]Hellwinkel, Dieter; Kistenmacher, Thomas [Liebigs Annalen der Chemie, 1989, p. 945 - 950]
[9]Fox, Marye Anne; Dulay, Maria T.; Krosley, Kevin [Journal of the American Chemical Society, 1994, vol. 116, # 24, p. 10992 - 10999]
[10]Chattopadhyay; Serpa; Arnaut; Formosinho [Physical Chemistry Chemical Physics, 2001, vol. 3, # 17, p. 3690 - 3695]

4
[ 1150-62-5 ]
[ 57103-20-5 ]

Yield	Reaction Conditions	Operation 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.

Reference： [1]Organic electronics,2014,vol. 15,p. 2667 - 2676
[2]Tetrahedron,1998,vol. 54,p. 12707 - 12714
[3]Journal of Materials Chemistry,2011,vol. 21,p. 9139 - 9148
[4]Patent: JP2015/63518,2015,A .Location in patent: Paragraph 0253; 0254
[5]Patent: CN105906612,2016,A .Location in patent: Paragraph 0051; 0052
[6]Patent: CN105175405,2017,B .Location in patent: Paragraph 0039-0041
[7]Patent: EP2343277,2011,A2 .Location in patent: Page/Page column 32
[8]Patent: CN104650044,2017,B .Location in patent: Paragraph 0035; 0038
[9]Synlett,2006,p. 2841 - 2845
[10]Macromolecules,2005,vol. 38,p. 4970 - 4976
[11]Patent: KR101638767,2016,B1 .Location in patent: Paragraph 0109-0112
[12]Patent: US2016/195519,2016,A1 .Location in patent: Paragraph 0310; 0311; 0312
[13]Patent: US2006/83945,2006,A1
[14]Journal of Materials Chemistry,2011,vol. 21,p. 4918 - 4926
[15]Journal of Chemical Research,2008,p. 137 - 140
[16]Chemistry - A European Journal,2008,vol. 14,p. 4731 - 4740
[17]Journal of Nanoscience and Nanotechnology,2010,vol. 10,p. 6811 - 6814
[18]Journal of the Chinese Chemical Society,2012,vol. 59,p. 331 - 337
[19]Journal of Materials Chemistry,2012,vol. 22,p. 4527 - 4534
[20]Journal of the Chinese Chemical Society,2013,vol. 60,p. 579 - 589
[21]Chemistry - A European Journal,2016,vol. 22,p. 7468 - 7478

5
[ 108-86-1 ]
[ 86-74-8 ]
[ 1150-62-5 ]

Yield	Reaction Conditions	Operation in experiment
99%	With tri-tert-butyl phosphine; potassium carbonate In o-dimethylbenzene at 20 - 120℃; for 2h;	1 EXAMPLE 1 Into a 10 mL Schrenk tube, a stirrer was put, and the tube was flushed with nitrogen. Then, 45 mg (0.049 mmol) of dipalladium(0) tris(dibenzylideneacetone), 66 mg (0.32 mmol) of tri-tert-butylphosphine and 1 mL of o-xylene were added, and this solution was stirred for 20 minutes at 60° C. in a nitrogen atmosphere to obtain a catalyst solution. A 100 mL three necked round bottomed flask was flushed with nitrogen, 0.79 g (5.0 mmol) of bromobenzene, 1.66 g (9.9 mmol) of carbazole, 1.37 g (9.9 mmol) of potassium carbonate, 39 mg (0.15 mmol) of 18-crown-6 and 30 mL of o-xylene were added. At room temperature, to this solution, the previous catalyst solution was added by a syringe, and the reaction solution was heated to 120° C. Two hours later, the heating was terminated, and the reaction solution was left to cool to room temperature. This reaction solution was extracted with 100 g of toluene, and the obtained organic layer was dried over anhydrous magnesium sulfate. This organic layer was subjected to a gas chromatography quantitative analysis using triphenylamine as an internal standard substance, whereby N-phenyl carbazole was 1.21 g (yield: 99%).
99%	Stage #1: 9H-carbazole With methylmagnesium chloride In tetrahydrofuran; 5,5-dimethyl-1,3-cyclohexadiene at 5 - 20℃; for 0.166667h; Inert atmosphere; Stage #2: phenyl bromide With PdCl(π-allyl)(cyclohexyl-(1-methyl-2,2-diphenylcyclopropylphophine)) In tetrahydrofuran; 5,5-dimethyl-1,3-cyclohexadiene at 108 - 112℃; for 0.5h; Inert atmosphere;
98%	With di-tert-butyl(2,2-diphenyl-1-methyl-1-cyclopropyl)phosphine; ϖ-allylpalladium (II) chloride dimer; sodium tertiary butoxide In 5,5-dimethyl-1,3-cyclohexadiene at 120℃; for 3h; Inert atmosphere;

98%	With sodium tertiary butoxide In xylene at 120℃; for 3h;	7 To a solution of carbazole (0.34g, 2.0mmol) in xylene (4ml) were added sodium tert-butoxide (0.23g, 2.4mmol), bromobenzene (0.23ml, 2.2mmol), palladium acetate (4.5mg, 0.02mmol) and 2,2-diphenyl-1-(di-tert-butylphosphino)-1-methylcyclopropane (14.1mg, 0.04mmol) obtained in Example 4 under a nitrogen atmosphere and the mixture was stirred for 3 hours at 120°C. The reaction mixture was cooled, washed with water, and dried over anhydrous magnesium sulfate. Then, the solvent was removed under reduced pressure, and the concentrate was purified by column chromatography to give N-phenylcarbazole (0.479g, 98%, purity: >99%) as white crystal. 1H-NMR (CDCl3) δ 7.23-7.67 (m, 11H), 8.15 (br-d, J=7.6Hz, 2H).
97%	With 18-crown-6 ether; tri-tert-butyl phosphine; potassium carbonate In toluene; xylene for 18h; Inert atmosphere; Reflux;	1 Example 1. Synthesis of Compound 1[0125] Synthesis of 9-phenylcarbazole. Pd2(dba)3 (1.095 g, 1.196 mmol) and tri-tert- butylphosphine (4.78 ml, 4.78 mmol, 1.0 M in toluene) were mixed in 400 mL of xylene. The mixture was stirred under N2 for 20 min. 9H-carbazole (20 g, 120 mmol), bromobenzene (28.2 g, 179 mmol), 18-Crown-6 (3.16 g, 11.96 mmol), and potassium carbonate (24.80 g, 179 mmol) were then added in sequence, and the mixture was heated to reflux under N2 for 18 h. The xylene solution was decanted. The solvent was evaporated and residue was purified by vacuum distillation. 22.3 g (97% yield) of product was obtained after purification.
97%	With copper (I) iodide; trans-1,2-Diaminocyclohexane; Cs₂CO₃ In sulfolane at 110℃; for 5h; Inert atmosphere;	1.1; 3.1 The first step is the synthesis of N-phenylcarbazole: Under nitrogen protection, In the reaction flask, add carbazole (16.7g, 0.1mol), bromobenzene (17.3g, 0.11mol), cesium carbonate (35.8g, 0.11mol) and 140mL of sulfolane. After the addition is complete, stir well, and then add iodine After stirring uniformly, cuprous chloride (1.9 g, 0.01 mol) and trans-cyclohexanediamine (1.14 g, 0.01 mol) were heated to 110° C., reacted for 5 hours, and the reaction was completed as detected by HPLC. After filtering through Celite and evaporating the solvent under reduced pressure, 110 mL of ethyl acetate was added for extraction twice, washed with 1N hydrochloric acid, and the ethyl acetate layers were combined and spin-dried to obtain 23.6 g of a light yellow solid with a yield of 97%.
95.2%	With potassium hydroxide; all racemic-α-tocopherol; epicatechin at 115 - 125℃; for 6h;
95%	With copper (I) iodide; potassium carbonate In N,N-dimethyl acetamide at 180℃; for 24h; Inert atmosphere;
95%	With sodium tertiary butoxide In toluene at 110℃; for 12h;
95%	With copper atom; potassium carbonate; nitrobenzene at 120 - 160℃; Inert atmosphere;	1 Example 1 First, 1 times the equivalent of carbazole,1 to 1.5 equivalents of halogenated benzene, such as bromobenzene,Fluorobenzene and the like,0.44 times the equivalent of Cu (electrolytic refined copper),4.04 times the equivalent of K2CO3 into the reaction vessel,Nitrobenzene as the reaction solvent,Nitrogen protection under 120 ~ 160 reaction 12 ~ 48h,The reaction solution was distilled under reduced pressure to give crude 9-phenylcarbazole,The pure product was obtained by column chromatography in a yield of 85-95%.
94.8%	With tetraphenyl phosphonium chloride; anhydrous sodium carbonate at 115 - 125℃; for 2h;	11 Synthesis of 9-Phenylcarbazole (exemplified compound I-27) Example 11 Synthesis of 9-Phenylcarbazole (exemplified compound I-27) Carbazole was mixed in an amount of 16.47 g (98.52 mmol) with 31.0 g (197.04 mmol) of bromobenzene, 10.44 g (98.52 mmol) of sodium carbonate, 0.4 g (8.0 mmol) of copper (I) chloride, and 3.0 g (8.0 mmol) of tetraphenylphosphonium chloride. This mixture was reacted at 115-125° C. for 2 hours in a nitrogen stream. After the reaction, 50 mL of toluene and 100 mL of water were added and the resultant mixture was subjected to liquid separation. Thereafter, the organic layer was washed with water and dried with anhydrous sodium sulfate. After the drying agent was removed by filtration, 15.6 g of activated clay was added. The resultant mixture was stirred at 50-55° C. for 1 hour and the clay was removed by filtration. The toluene was concentrated under reduced pressure and 352 mL of methanol was added to the residue. The resultant solution was subjected to crystallization. Thus, the target compound (1-27) was obtained as white crude crystals in an amount of 22.7 g (yield, 94.8%). The target compound obtained had a melting point of 96-97° C. and a content as determined by HPLC of 99.8% (HPLC conditions: column, ODS-80TM; eluent, acetonitrile/water (V/V=65/35); buffer, triethylamine and acetic acid each in an amount of 0.1%; detection UV, 254 nm; flow rate, 1.0 mL/min)
94%	With potassium hydroxide; N-hydroxy-N-phenyl-carbamic acid ethyl ester; isoascorbic acid at 115 - 125℃; for 6h;
94.2%	With potassium hydroxide; isoascorbic acid; 4-hydroxy-4-methyl-1-phenylsemicarbazide at 115 - 125℃; for 6h;
94%	With potassium hydroxide; all racemic-α-tocopherol; 2,2,6,6-tetramethyl-piperidinol at 115 - 125℃; for 6h;
94.6%	With potassium hydroxide; all racemic-α-tocopherol; 1-phenyl-1H-pyrazolidin-3-one at 115 - 125℃; for 6h;
94.5%	With potassium hydroxide; all racemic-α-tocopherol; N-phenylbenzohydroxamic acid at 115 - 125℃; for 6h;
94.8%	With potassium hydroxide; 2,3-dihydroxyfumaric acid; 6,6’,7,7’-tetrahydroxy-4,4,4’,4’-tetramethyl-2,2’-spirobichroman at 115 - 125℃; for 6h;
94.6%	With potassium hydroxide; 6,6’,7,7’-tetrahydroxy-4,4,4’,4’-tetramethyl-2,2’-spirobichroman; 2-(N-methyl-N-phenylamino)-5-methylthiophene at 115 - 125℃; for 6h;
94.1%	With copper (I) iodide; potassium carbonate In ethylene glycol; N,N-dimethyl-formamide at 110℃; for 24h; Inert atmosphere;	1-6; 1-5 Example 2 Under nitrogen protection, add 71.4g bromobenzene (99%, 0.45mol), 50.6g carbazole (99%, 0.3mol), 5.7g cuprous iodide (99.9%, 0.03mol) into a 1L reaction flask, 62.7g potassium carbonate (99%, 0.45mol), ethylene glycol 230mL, N,N-dimethylformamide 230mL, after the feeding is completed, the temperature is raised to 110°C, the stirring speed is 600rpm, and the temperature is kept for 24hr. After the reaction, water and ethyl acetate were added for extraction, and the organic layer was desolventized to obtain a crude product which was crystallized with ethanol to obtain 68.9 g of N-phenylcarbazole with a content of 99.6% and a yield of 94.1%.
93.1%	With potassium hydroxide; all racemic-α-tocopherol; ascorbic acid at 115 - 125℃; for 6h;
93.9%	With potassium hydroxide; N'-methyl-N-methyl-N-phenylhydrazine; isoascorbic acid at 115 - 125℃; for 6h;
93.7%	With potassium hydroxide; C₉H₁₂N₂O₃; isoascorbic acid at 115 - 125℃; for 6h;
93.9%	With potassium hydroxide; ascorbic acid at 115 - 125℃; for 6h;
93.2%	With potassium hydroxide; all racemic-α-tocopherol at 115 - 125℃; for 6h;
93.5%	With potassium hydroxide; all racemic-α-tocopherol; Propionic acid N,N'-dimethyl-N'-propionyl-hydrazide at 115 - 125℃; for 6h;
93.7%	With potassium hydroxide; all racemic-α-tocopherol; N,N-didecylaniline at 115 - 125℃; for 6h;
91.4%	With potassium hydroxide at 115 - 125℃; for 6h;
90%	With potassium carbonate In toluene for 10h; Reflux; Inert atmosphere;	2.3.6. General procedure for the synthesis of N-aryl amides and N-arylheterocycles through C-N cross-coupling of amides and N-H heterocycleswith aryl halides General procedure: In order to prepare N-aryl amides and N-aryl heterocycles by meansof C-N coupling reactions (N-arylation reactions), a solution of arylhalide (1 mmol), amide or N-H heterocycle substrate (2 mmol) andK2CO3 (2 mmol) in toluene (5 mL) was poured into a 25 mL roundbottomed flask equipped with a condenser and a mechanical stirrer.Subsequently, CNF-phen-Cu(I) (0.01 mmol, 0.02 g for N-H heterocyclesand 0.005 mmol, 0.01 g for amides) was added to the above solution andthe resulted mixture was stirred under reflux condition and argon atmospherewithin a definite requisite time for each reaction. Screeningthe progress of the reaction was performed via TLC (pure n-hexane).After completion, the reaction mixture was allowed to cool to roomtemperature which was followed by addition of ethyl acetate (15 mL)and keeping on stirring the mixture for a further 15 min. Afterwards, theobtained mixture was filtered and the resulted solid was washed withwater and hot ethyl acetate (40 mL). Then, the solvent was evaporatedunder reduced pressure and the residue was purified by column chromatography(n-hexane: ethyl acetate). The synthesized products werecharacterized by use of 1H NMR (Supplementary Information, Figs. S2-S13) and melting points.
88%	With potassium carbonate In N,N-dimethyl-formamide at 120℃; for 10h; Inert atmosphere;	4.2 General procedure for Buchwald-Hartwig C-N cross coupling reaction using PNP-SSS catalyst General procedure: Aryl halide (1.0mmol), amine (1.5-2.0mmol), PNP-SSS (0.6mol%; 0.023g), K2CO3 (2mmol), and DMF (3.0mL) was placed in a 25mL flask equipped with a magnetic stirring bar and heated at 120°C under nitrogen gas. The reaction was then monitored by TLC until the consumption of aryl halide was detected. After completion of the reaction 5mL of water and 5mL of ethyl acetate were added to the reaction mixture. The organic solution was extracted and dried over anhydrous Na2SO4. After removing of organic solvent the crude product was obtained. For further purification the chromatography technique was used.
88%	Stage #1: 9H-carbazole With [1,1'-bis(diphenylphosphino)ferrocene]nickel(II) chloride; isopropylmagnesium chloride lithium chloride In 2-methyltetrahydrofuran; toluene at 20℃; for 0.166667h; Inert atmosphere; Stage #2: phenyl bromide In 2-methyltetrahydrofuran; toluene at 110℃; for 8h; Inert atmosphere;
86%	With copper (I) iodide; 1-Hydroxymethyl-1H-benzotriazole; potassium-t-butoxide In dimethyl sulfoxide at 120℃; for 18h; Inert atmosphere;
86%	With copper (I) iodide; potassium carbonate In N,N-dimethyl-formamide at 140℃; for 24h;	1-2.1 Intermediate H Synthesis 100 g (0.598 mol) of 9H-carbazole,400 g of DMF, 11.3 g (0.059 mol) of CuI,112.6 g (0.429 mol) of bromobenzene,165.3 g (1.196 mol) of potassium carbonate was added and the mixture was refluxed at 140 ° C for 24 hours, and the reaction was terminated.DMF was removed under reduced pressure, and 500 g of toluene and 200 g of water were added. The organic layer was separated and concentrated under reduced pressure to remove toluene. 250 g of ethyl acetate was added, and the mixture was refluxed, cooled,Intermediate G 125g (yield 86%) was obtained
86%	With copper (I) iodide; potassium carbonate In N,N-dimethyl-formamide at 140℃; for 24h;	1-2.1 Synthesis of intermediate G 100 g (0.598 mol) of 9H-carbazole, DMF 400 g, 11.3 g (0.059 mol) of CuI, 112.6 g (0.429 mol) of bromobenzene, 165.3 g (1.196 mol) of potassium carbonate was added and the mixture was refluxed at 140 ° C for 24 hours to complete the reaction.The DMF was removed by concentration under reduced pressure, and 500 g of toluene, After 200 g of water was added and the organic layer was separated,After the toluene was removed by concentration under reduced pressure,After adding 250 g of ethyl acetate,Cooled and dried to obtain 125 g (yield: 86%) of intermediate G having a purity of 98.7%.
85%	With copper (I) iodide; Cs₂CO₃ In N,N-dimethyl-formamide at 220℃; for 1h; Microwave irradiation;	4.2. General experimental procedure for microwave-assisted N-arylation of carbazoles General procedure: 9H-Carbazole (1.0 mmol), Cs2CO3 (1.0 mmol), iodobenzene (1.1 mmol), CuI (0.1 mmol), and DMF (2 mL) were added to a 5-mL vial. The vial was sealed with a crimp cap and placed in a Biotage initiator microwave cavity. After irradiation at 220 °C for the appropriate time and subsequent cooling, the reaction mixture was diluted with saturated aqueous ammonium chloride. Products were isolated by extraction into ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated. Products were purified by silica gel column chromatography using a hexane/ethyl acetate solvent. N-Phenyl-carbazole (2a)22 was obtained (96% yield) as a white solid.
84%	With copper (I) iodide; 1,10-Phenanthroline; potassium fluoride on basic alumina In toluene at 110℃; for 8h; Inert atmosphere;
82%	With copper(II) ferrite; potassium-t-butoxide In N,N-dimethyl-formamide at 155℃; for 24h; Inert atmosphere;	General procedure: To a solution of N-heterocycle (1 equiv), bromobenzene (1.02 equiv) and tBuOK (2 equiv) in dry DMF, CuFe2O4 (10 mol %) was added and heated at reflux for 24 h under N2 atmosphere. After cooling to room temperature, the mixture was diluted with ethyl acetate and the catalyst was separated by a magnetic separator. The catalyst was washed with ethyl acetate. The combined ethyl acetate layer was washed with water (twice), dried over anhydrous Na2SO4, and concentrated to yield the crude product, which was further purified by silica gel column chromatography using petroleum ether/ethyl acetate to yield N-arylated product.
82%	With potassium carbonate In toluene at 110℃; for 12h;	4.1.6 General Procedure for N-Arylation of N-H Heterocycle with Aryle Halides To a solution of N-H heterocycle (1 mmol) and aryl halide (2 mmol) in toluene were added catalyst (0.07 g, 0.016 mmol) and K2CO3 (276 g, 2 mmol) and the mixture stirred at 110 °C for the specified time. The progress of the reaction was monitored by TLC. The reaction mixture allowed cooling to room temperature and ethyl acetate (25 mL) was added and the mixture stirred for 15 min to ensure product removal from catalyst. Then the catalyst was filtered, washed with ethyl acetate (2 9 25 mL). The organic layer was evaporated under vacuum on a rotary evaporator and the crude product was obtained. Further purification was achieved by column chromatography using ethyl acetate/n-hexane gradient. Structural assignments of the products are based on their 1H NMR and melting point.
82%	With potassium-t-butoxide In N,N-dimethyl-formamide at 100℃; for 12h;
80%	With copper (I) iodide; 1,10-Phenanthroline; potassium carbonate at 130℃; for 48h; Inert atmosphere;
75%	With copper atom; potassium carbonate In 1,2-dichloro-benzene at 180℃; for 24h;	3 Synthesis of intermediate I-4 9H-carbazole 5.02 g (30 mmol), bromobenzene, 4.71 g (30 mmol), copper powder 1.14 g (18 mmol), and K2CO3 6.22 g (45 mmol) of o-dichlorobenzene (o-dichlorobenzene) 80 mL in It was dissolved and stirred for 24 hours at 180°C. After cooling to room temperature the reaction solution was added to 60 mL water and extracted three times with ethyl acetate 50 mL. Drying the obtained organic layer with magnesium sulfate, and separation of the residue obtained by evaporating the solvent was subjected to silica gel column chromatography to yield intermediate I-4 5.47 g (75% yield). The resulting compound was confirmed by LC-MS.
75%	With copper atom; potassium carbonate In 1,2-dichloro-benzene at 180℃; for 24h;	1 1) Synthesis of intermediate I-1 9H-carbazole 5.02 g (30 mmol), bromobenzene, 4.71 g (30 mmol), copper powder (copper power) 1.14 g (18 mmol), and K2CO3 6.22 g (45 mmol) of o-dichlorobenzene 80 was dissolved in mL was stirred for 24 hours at 180oC. After cooling to room temperature the reaction solution was added to 60 mL water and extracted three times with ethyl acetate 50 mL. The combined organic layers were dried over magnesium sulfate, and separation of the residue obtained by evaporation of the solvent in jelgwan silica chromatography to yield the intermediate I-1 5.47 g (75% yield).
75%	With copper atom; potassium carbonate In 1,2-dichloro-benzene at 180℃; for 24h;	1.1 Synthesis of intermediate I-1 9H-carbazole 5.02 g (30 mmol), bromobenzene, 4.71 g (30 mmol), copper powder 1.14 g (18 mol), and 6.22g K2CO3 (45 mmol) of o-dichlorobenzene dissolved in 80 mL then 180 ° C in was stirred for 24 hours. After cooling to room temperature the reaction solution was added to 60 mL water and extracted three times with ethyl acetate 50 mL. The combined organic layers were dried over magnesium sulfate, and separation of the residue obtained by evaporation of the solvent in silica gel chromatography to yield the intermediate I-1 5.47 g (75% yield). The resulting compound was confirmed by LC-MS. I-1 5.47 g ( 75 %) . LC-MS . C18H13N : M+243.10
75%	With copper atom; potassium carbonate In 1,2-dichloro-benzene at 180℃; for 24h;	1 Synthesis of intermediate I-1 9H- carbazole 5.02 g (30 mmol),Bromo benzene 4.71 g (30 mmol),1.14 g copper power (18 mmol)And 6.22 g K2CO3 (45 mmol) was dissolved in o-dichlorobenzene 80 mL was stirred at 180 for 24 hours. After cooling to room temperature the reaction solution was added to 60 mL water and extracted three times with ethyl acetate 50 mL. Dry the organic layer obtained therefrom with magnesium sulfate and remove the solvent is evaporated to give a residue was subjected to silica gel column chromatography to give the intermediate I-1 5.47 g (75% yield).
75%	With copper atom; potassium carbonate In 1,2-dichloro-benzene at 180℃; for 24h;	1 1) Synthesis of intermediate I-1 9H-carbazole 5.02 g (30 mmol), bromobenzene, 4.71 g (30 mmol), copper power 1.14 g (18 mmol) and K2CO36.22 g (45 mmol) of o-dichlorobenzene was dissolved in 80 mL then 180 oC in It was stirred for 24 hours. After cooling to room temperature the reaction solution was added to 60 mL water and extracted three times with ethyl acetate 50 mL. The combined organic layers were dried over magnesium sulfate and silica jelgwan the residue obtained by evaporation of the solventSeparated by chromatography To give intermediate I-1To give the 5.47 g (75% yield).
75%	With copper atom; potassium carbonate In 1,2-dichloro-benzene at 180℃; for 24h;	1.1 Synthesis of Intermediate I-1 After dissolving 5.02 g (30 mmol) of 9H-carbazole, 4.71 g (30 mmol) of bromobenzene, 1.14 g (18 mmol) of copper power and 6.22 g (45 mmol) of K2CO3 in 80 mL of o-dichlorobenzene Followed by stirring at 180 DEG C for 24 hours.After the reaction solution was cooled to room temperature, 60 mL of water was added and extracted three times with 50 mL of ethyl acetate. The resulting organic layer was dried over magnesium sulfate and the solvent was evaporated. The obtained residue was purified by silica gel column chromatography to obtain 5.47 g (yield 75%) of Intermediate I-1. The resulting compound was identified via LC-MS.
75%	With copper atom; potassium carbonate In 1,2-dichloro-benzene at 180℃; for 24h;	2 Synthesis of intermediate I-3 5.02 g (30 mmol) of 9H-carbazole,4.71 g (30 mmol) of bromobenzene,1.14 g (18 mmol) of copper powder and6.22 g (45 mmol) of K2CO3 was dissolved in 80 mL of o-dichlorobenzene,The reaction solution was stirred at a temperature of 180 ° C for 24 hours.The resulting reaction solution was cooled to room temperature,The organic layer was extracted three times by using 60 mL of water and 50 mL of ethyl acetate.The organic layer thus collected was dried with magnesium sulfate,The residue obtained after the solvent was evaporated from the silica gel column chromatography was used to separate and purify the residue,To obtain 5.47 g of intermediate I-3 (yield: 75%).The compounds thus produced were determined by using LC-MS.
75%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; triphenylphosphine; sodium tertiary butoxide In toluene at 100℃; for 24h;	Synthesis of 9-phenyl-9H-carbazole Pd 2 (dba) 3 (8.24 g, 9 mmol) and PPh 3 (7.87 g, 30 mmol) were added to a solution of the compound of Example 1 (50.2 g, 300 mmol) andbromobenzene (56.5 g , NaO t- Bu (86.5 g, 900 mmol) was added thereto, and the mixture was refluxed at 100 ° C for 24 hours. The organic layerwas extracted with ether and water. The organic layer was dried over MgSO 4 and concentrated. The resulting organic material was purified andrecrystallized from a silica gel column to obtain 52.5 g (75%) of the product.
75%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; triphenylphosphine; sodium tertiary butoxide In toluene at 100℃; for 24h;	1 Sub 1-1 Synthesis: 9-phenyl-9H-carbazole Carbazole (50.2 g, 300 mmol)And bromobenzene (56.5 g, 360 mmol)And 2,800 mL of tolueneAfter mixing inPd2 (dba) 3 (8.24 g, 9 mmol),PPh3 (7.87 g, 30 mmol), NaOt-Bu (86.5 g, 900 mmol)Respectively,At 100 is stirred for 24 hours reflux time.ether and water. The organic layer was dried over MgSO4 and concentrated. The resulting organic material was purified by silicagel columnAnd recrystallized to obtain 52.5 g (75%) of the product.
73%	With copper atom; potassium carbonate In 1,2-dichloro-benzene at 180℃; for 24h;	1.1 Synthesis of Intermediate A-1 6.69 g (40 mmol) of 9H-carbazole, 6.28 g (40 mmol) of bromobenzene, 1.52 g (24 mmol) of copper powder, and 8.29 g (60 mmol) of K2CO3 were dissolved in 100 mL of o-dichlorobenzene, and then, the resultant solution was stirred at a temperature of 180 °C. for 24 hours. The reaction solution was cooled to room (e.g., ambient) temperature, 60 mL of water was added thereto, and the result was extracted three times by using 50 mL of ethyl acetate. An organic layer obtained therefrom was dried by using magnesium sulfate, and then residues obtained by evaporation of a solvent therefore were separation-purified by using silica gel column chromatography to obtain 7.10 g of Intermediate A-1 (yield: 73%).
72%	With potassium carbonate; copper chloride (II) In dimethyl sulfoxide at 160℃; for 24h;	1.1 1) Synthesis of a compound represented by the formula 1-a 100.0 g (0.598 mol) of carbazole, 122.1 g (0.777 mol) of bromobenzene, 248 g (1.794 mol) of potassium carbonate, 14.8 g (0.149 mol) of copper chloride and 600 mL of dimethylsulfoxide were placed in a 1 L round bottom flask, And the mixture was refluxed and stirred at 160 ° C for 24 hours. The reaction mixture was cooled to room temperature, extracted with ethyl acetate and water, and the organic layer was concentrated under reduced pressure. The residue was purified by column chromatography using hexane as a developing solvent to obtain 118.0 g (72%) of a compound represented by the formula (1-a).
70%	With copper atom; potassium carbonate In N,N-dimethyl-formamide at 140℃; Inert atmosphere;	2 2.2. Synthesis of 9-Phenyl Carbazole Carbazole (0.33 g, 2 mmol), bromobenzene (0.61 g, 2.6 mmol), Cupowder (0.51 g, 8 mmol) and potassium carbonate (0.691 g, 5 mmol)were dissolved in 20 mL dimethylformamide (DMF) and stirred overnightat 140 °C under nitrogen atmosphere. The progress of reactionwas monitored by TLC using ethyl acetate-hexane (1:9) solvent system.After ensuring the completion of reaction itwas poured into the ice coldsolution. The precipitated solid of 9-phenyl carbazolewas extracted intodichloromethane and finally dried over anhydrous magnesium sulphate.The crude product obtained after removal of solventwas purifiedby column chromatography. The synthesis route is shown in Scheme 1.9-Phenyl carbazole was obtained as brown solid, 70% yield, m. p 94 °C(literature 95-97 °C), 1H NMR (300 MHz, DMSO-d6, δ ppm): (SupplementaryFig. S1) 8.05 (3H, d, J = 7.8 Hz), 7.46(3H, d, J = 8.1 Hz), 7.35(4H, t, J = 8.1 Hz), 7.13 (3H, t, J = 7.5 Hz). MS (EI): m/z = 243 (M+)(Supplementary Fig. S2).
70%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tri-tert-butyl phosphine; sodium tertiary butoxide In toluene for 18h; Reflux; Inert atmosphere;	2.1 Step 1: Suspend 9H-Carbazole 1eq (41.2g), Bromobenzene 1eq (50.3.g), sodium-t-butoxide 2eq (47.4g), Pd2(dba)3 0.05eq (7.1g) in toluene (800ml) After that, tri-tertiary butylphosphine 0.15eq (7.48g) was stirred under reflux for 18 hours under a nitrogen stream. After completion of the reaction, extraction was performed with toluene and distilled water, and the organic layer was dried over magnesium sulfate (MgSO4), filtered, and the filtrate was concentrated under reduced pressure. The organic solution was removed, followed by silica gel column with hexane:dichloromethane=7:3 (v/v), and the product solid was recrystallized from dichloromethane and acetone to obtain intermediate b-1 (42.0g, Y=70%).
67%	With copper; potassium carbonate In dimethyl sulfoxide at 130℃; for 9h;	2.3. Typical procedure for the N-arylation of heterocycles General procedure: Cu-clay nanohybrid (N1, 5 wt.%) was added to a mixture of bromobenzene (1.2 mmol), imidazole (1 mmol) and K2CO3 (2 mmol) in DMSO and stirred at 130 °C. The reaction was monitored by thin layer chromatography. After the reaction, the catalyst was separated from the reaction mixture by centrifugation and washed with distilled ethyl acetate. The recovered catalyst was used for further reaction. The product was extracted with ethyl acetate and purified using column chromatography on silica gel (ethyl acetate/hexane: 30/70). The purified products were characterized by NMR and IR spectroscopies and ESI-MS technique.
60%	With tri-tert-butyl phosphine; palladium diacetate; potassium carbonate In 5,5-dimethyl-1,3-cyclohexadiene at 120℃; for 6h;
55%	With 1,1'-bis(diphenylphosphanyl)ferrocene; palladium 10% on activated carbon; sodium tertiary butoxide In 1,3,5-trimethyl-benzene at 180℃; for 24h; Inert atmosphere;
51%	With potassium-t-butoxide; C₃₆H₃₂Cu₂Fe₂I₂Se₄ In acetonitrile at 20℃; for 12h; Schlenk technique; Inert atmosphere; Irradiation;	2.4. Evaluation of photocatalytic activity General procedure: Carbazole (0.034 g, 0.2 mmol), t-BuOK (0.049 g, 0.4 mmol), C1 were placed in a 25 mL Schlenk tube and it was evacuated andpurged with nitrogen three times. MeCN (2 mL) and aryl iodides were added in nitrogen atmosphere. Xenon Lamp with the powerdensity of 290 mW/cm2 was employed as the light source. Afterirradiation with a Xenon Lamp (290 mW/cm2) for 12 h at ambienttemperature, the reaction mixture was concentrated in vacuumfollowed by addition of water (5 mL). The resulting mixture wasextracted with EtOAc (3 5 mL). The combined organic layerwas dried over MgSO4 and filtered, then the filtrate was concentratedin vacuum. The crude mixture was purified by silica gel flashcolumn chromatography (petroleum ether/EtOAc, v:v = 20:1) toafford the desired product.
44%	With copper (I) iodide; 18-crown-6 ether; potassium carbonate In 1,2-dichloro-benzene for 48h; Inert atmosphere; Reflux;	Synthesis of 9-phenyl-9H-carbazole (5): Carbazole (10 g, 59.88 mmol), bromobenzene (18.40 g, 59.88 mmol), K2CO3 (12.42 g, 89.82 mmol), 18-crown-6 (1.11 g, 4.19 mmol), CuI (654.48 mg, 3.59 mmol) were added to 1,2-dichlorobenzene (10 mL), then refluxed under nitrogen for 48 h. After cooling, the reaction mixture was quenched with (NH4)2CO3 solution and extracted with CH2Cl2, then dried over anhydrous MgSO4. After removal of the solvent, the residue was purified by column chromatography on silica gel using CH2Cl2/petroleum (1:5, v/v) as eluent followed by recrystallization from mixture of CH2Cl2 and ethanol to give white crystals. Yield: 44%. 1H NMR (500 MHz,DMSO, δ): 8.26 (d, J = 7.72 Hz, 2H),7.68 (t, J = 31.43 Hz, 39.04 Hz, 5H),7.43 (d, J = 22.77 Hz, 4H), 7.31 (d, J = 7.37 Hz, 7.31 Hz, 2H).
44%	With copper (I) iodide; potassium carbonate In 1,2-dichloro-benzene at 180℃; for 48h;
43.58%	With copper (I) iodide; 18-crown-6 ether; potassium carbonate In 1,2-dichloro-benzene at 180℃; for 48h; Inert atmosphere;
28%	With tri-tert-butyl phosphine; potassium carbonate In o-dimethylbenzene at 20 - 120℃; for 2 - 31h;	1; 2 COMPARATIVE EXAMPLE 1 The same operation as in Example 1 was carried out except that no 18-crown-6 was added, whereby 0.34 g (yield: 28%) of N-phenylcarbazole was obtained.COMPARATIVE EXAMPLE 2 The same operation as in Example 1 was carried out except that no 18-crown-6 was added, and the reaction time was changed to 31 hours, whereby 0.90 g (yield: 74%) of N-phenylcarbazole was obtained.
12%	Stage #1: 9H-carbazole With sodium hydride; magnesium(II) bromide In 1,2-dichloro-benzene at 135℃; for 2h; Inert atmosphere; Stage #2: phenyl bromide With iron(II) stearate In 1,2-dichloro-benzene at 150℃; for 14h; Inert atmosphere;	10 Examples 2 to 11 and Comparative Example 1 General procedure: In a 100 ml flask purged with a nitrogen atmosphere,30 g of o-dichlorobenzene, 2.54 g (15 mmol) of diphenylamine,0.48 g (19 mmol) of sodium hydride,3.68 g (20 mmol) of magnesium bromide was charged,The reaction solution was heated to 135 ° C. while stirring.After aging for 2 hours at the same temperature,0.035 g (0.1 mmol) of iron (III) acetylacetonate,1.87 g (10 mmol) of bromoanisole was added,Further aging was carried out for 14 hours at the same temperature. After completion of the reaction,After cooling, water was added to dissolve the salt and liquid separation was carried out. After separating the organic layer,As a result of analysis by GC using the internal standard method,4- (N, N-diphenylamino) anisole as a target product was produced in a yield of 88%.Diphenylamine of Example 1,Bromoanisole, iron (III) acetylacetonate,And the temperature condition after addition of bromoanisole were changed to the conditions described in the appended table 1,The reaction was carried out according to the method described in Example 1.The result is shown in table 1.
	With Rb<SUB>2</SUB>CO<SUB>3</SUB>; tri-tert-butyl phosphine In xylene at 120℃; for 3h;
	With potassium n-butoxide In N,N-dimethyl-formamide
	With copper (I) iodide; 18-crown-6 ether; potassium carbonate
	With copper (I) iodide; 1,10-Phenanthroline; potassium carbonate
	With copper (I) iodide In para-xylene
	With tri-tert-butyl phosphine; palladium diacetate; sodium n-butanolate In toluene Reflux;	1 Preparation Example 1: Synthesis of intermediate 2.5 g of carbazole, 2 g of bromobenzene, and 0.064 g of palladium acetate catalyst were dissolved in 40 mL of toluene, and the resulting solution was heated to 60 degrees C. Subsequently, a solution of 1.5 g of sodium butoxide and 0.385 g of tri-tert-butylphosphine dissolved in toluene was slowly added dropwise. The mixture was refluxed at a steady of 100 degrees C. After completion of the reaction, the reaction mixture was extracted with dichloromethane and distilled water, and the solvent was dried. The resulting solid was filtered and purified, yielding 9-phenyl carbazole compound as an intermediate.
	With tri-tert-butyl phosphine; palladium diacetate; sodium tertiary butoxide In toluene for 48h; Reflux; Inert atmosphere;	Synthesis of 9-phenyl-9H-carbazole (Compound 1a) Carbazole (3.42 g, 20.5 mmol), bromobenzene (4.65 g, 29.6 mmol), sodium-tert-butoxide (4.50 g, 46.8 mmol), tri-tert-butylphosphine (180 mg, 0.89 mmol) and palladium (II )acetate (97mg, 0.43 mmol) was dehydrated toluene (30 mL) added, 48 hours under nitrogen atmosphere to reflux. After the solution cooled, and the toluene was removed under reduced pressure. The resulting mixture was extracted with chloroform. The crude product was purified by column chromatography (silica gel, hexane / chloroform = 4: 1)
	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; triphenylphosphine; sodium tertiary butoxide In toluene at 100℃; for 24h;	General procedure: Carbazole (1 eq.) and Sub 1-1 (1.1 eq.) were addedtoluene, and then, Pd2(dba)3 (0.05 eq.), PPh3 (0.1 eq.), and NaOt-Bu (3 eq.) were added thereto, and then, the mixturewas refluxed at a temperature of 1000 C. for 24 hours whilestirring, and then, extracted with ether and watet An organiclayer was dried by using Mg504, and the obtained organicmaterial was re-crystallized by silicagel colunm chromatography to produce Sub 1-2.
	With tris(dibenzylideneacetone)dipalladium⁽⁰⁾ chloroform complex; tri-tert-butyl phosphine; sodium tertiary butoxide In toluene at 110℃; Inert atmosphere;
60 g	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tri-tert-butyl phosphine; sodium tertiary butoxide In 5,5-dimethyl-1,3-cyclohexadiene for 12h; Reflux;	3.1 Carbazole 50g (299 mmol),Bromophenyl(359 mmol), sodium tertiary butoxide (86 g, 897 mmol), Pd 2 (dba) 3 14 g (359 mmol), tri- tertiary-butylphosphine 15 ml (30 mmol)XyleneAnd the mixture was refluxed for 12 hours.Extraction is carried out with dichloromethane and distilled water, and the organic layer is subjected to silica gel filtration.The organic solution was removed and the residue was subjected to silica gel column chromatography 9-phenyl-9H-carbazole,60 g.
	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; triphenylphosphine; sodium tertiary butoxide In toluene at 100℃; for 24h;	Synthesis of Sub 1-2 General procedure: Carbazole (1 equivalent) and Sub 1-1 (1.1 equivalent) were added to toluene and Pd2(dba)3 (0.05 equivalent),After adding PPh3 (0.1 equivalent) and NaOt-Bu (3 equivalent), respectively,After stirring at 100°C for 24 hours and refluxing,After extraction with ether and water, the organic layer was dried over MgSO 4, concentrated, and the resulting organic material was subjected to silica gel column chromatography and recrystallized to obtain Sub1-2.

Reference： [1]Current Patent Assignee: TOSOH CORPORATION - US2007/282111, 2007, A1 Location in patent: Page/Page column 3; 4
[2]Nakayama, Yuji; Yokoyama, Naota; Nara, Hideki; Kobayashi, Tohru; Fujiwhara, Mitsuhiko [Advanced Synthesis and Catalysis, 2015, vol. 357, # 10, p. 2322 - 2330]
[3]Suzuki, Ken; Hori, Yoji; Kobayashi, Tohru [Advanced Synthesis and Catalysis, 2008, vol. 350, # 5, p. 652 - 656]
[4]Current Patent Assignee: TAKASAGO INTERNATIONAL CORPORATION - WO2004/72088, 2004, A2 Location in patent: Page/Page column 48
[5]Current Patent Assignee: UNIVERSAL DISPLAY CORP - WO2011/137072, 2011, A1 Location in patent: Page/Page column 42
[6]Current Patent Assignee: CANGZHOU PURUIDONGFANG TECH; CANGZHOU ECOLOGICAL ENV MONITORING CENTER - CN112321622, 2021, A Location in patent: Paragraph 0026-0028; 0040-0042
[7]Current Patent Assignee: SANKYO KASEI CO.,LTD. - JP2005/350416, 2005, A Location in patent: Page/Page column 43-44
[8]Mao, Mao; Ren, Ming-Guang; Song, Qin-Hua [Chemistry - A European Journal, 2012, vol. 18, # 48, p. 15512 - 15522]
[9]Fareghi-Alamdari, Reza; Haqiqi, Mohsen G.; Zekri, Negar [New Journal of Chemistry, 2016, vol. 40, # 2, p. 1287 - 1296]
[10]Current Patent Assignee: NANJING UNIVERSITY OF POSTS AND TELECOMMUNICATIONS - CN106883163, 2017, A Location in patent: Paragraph 0024; 0025; 0026
[11]Current Patent Assignee: FUJIFILM HOLDINGS CORP. - US2006/69287, 2006, A1 Location in patent: Page/Page column 17
[12]Current Patent Assignee: SANKYO KASEI CO.,LTD. - JP2005/350416, 2005, A Location in patent: Page/Page column 43-44
[13]Current Patent Assignee: SANKYO KASEI CO.,LTD. - JP2005/350416, 2005, A Location in patent: Page/Page column 43-44
[14]Current Patent Assignee: SANKYO KASEI CO.,LTD. - JP2005/350416, 2005, A Location in patent: Page/Page column 43-44
[15]Current Patent Assignee: SANKYO KASEI CO.,LTD. - JP2005/350416, 2005, A Location in patent: Page/Page column 43-44
[16]Current Patent Assignee: SANKYO KASEI CO.,LTD. - JP2005/350416, 2005, A Location in patent: Page/Page column 43-44
[17]Current Patent Assignee: SANKYO KASEI CO.,LTD. - JP2005/350416, 2005, A Location in patent: Page/Page column 43-44
[18]Current Patent Assignee: SANKYO KASEI CO.,LTD. - JP2005/350416, 2005, A Location in patent: Page/Page column 43-44
[19]Current Patent Assignee: SINOSTEEL NEW MATERIALS; SINOSTEEL GROUP NANJING NEW MATERIAL RES INSTITUTE - CN111777543, 2020, A Location in patent: Paragraph 0026; 0030-0051
[20]Current Patent Assignee: SANKYO KASEI CO.,LTD. - JP2005/350416, 2005, A Location in patent: Page/Page column 42-43
[21]Current Patent Assignee: SANKYO KASEI CO.,LTD. - JP2005/350416, 2005, A Location in patent: Page/Page column 43-44
[22]Current Patent Assignee: SANKYO KASEI CO.,LTD. - JP2005/350416, 2005, A Location in patent: Page/Page column 43-44
[23]Current Patent Assignee: SANKYO KASEI CO.,LTD. - JP2005/350416, 2005, A Location in patent: Page/Page column 43
[24]Current Patent Assignee: SANKYO KASEI CO.,LTD. - JP2005/350416, 2005, A Location in patent: Page/Page column 43
[25]Current Patent Assignee: SANKYO KASEI CO.,LTD. - JP2005/350416, 2005, A Location in patent: Page/Page column 43-44
[26]Current Patent Assignee: SANKYO KASEI CO.,LTD. - JP2005/350416, 2005, A Location in patent: Page/Page column 43-44
[27]Current Patent Assignee: SANKYO KASEI CO.,LTD. - JP2005/350416, 2005, A Location in patent: Page/Page column 43
[28]Aghili, Nora; Hosseinzadeh, Rahman; Mavvaji, Mohammad [Polyhedron, 2022, vol. 213]
[29]Panahi, Farhad; Daneshgar, Fatemeh; Haghighi, Fatemeh; Khalafi-Nezhad, Ali [Journal of Organometallic Chemistry, 2017, vol. 851, p. 210 - 217]
[30]Hu, Kunjun; Gao, Yunlong; Jin, Jian [Organometallics, 2022, vol. 41, # 5, p. 509 - 513]
[31]Jha, Rajeev R.; Singh, Jaspal; Tiwari, Rakesh K.; Verma, Akhilesh K. [ARKIVOC, 2012, vol. 2013, # 2, p. 228 - 248]
[32]Current Patent Assignee: ICB CO LTD ULSAN - KR2016/19744, 2016, A Location in patent: Paragraph 0057-0060; 0079-0081
[33]Current Patent Assignee: ICB CO LTD ULSAN - KR2016/19745, 2016, A Location in patent: Paragraph 0047; 0049-0050
[34]Location in patent: experimental part Kwon, Jae Kwan; Cho, Joong Hyun; Ryu, Young-Sil; Oh, Se Hwan; Yum, Eul Kgun [Tetrahedron, 2011, vol. 67, # 26, p. 4820 - 4825]
[35]Location in patent: experimental part Hosseinzadeh, Rahman; Tajbakhsh, Mahmood; Alikarami, Mohammad; Mohadjerani, Maryam [Journal of Heterocyclic Chemistry, 2008, vol. 45, # 6, p. 1815 - 1818]
[36]Panda, Niranjan; Jena, Ashis Kumar; Mohapatra, Sasmita; Rout, Smruti Ranjan [Tetrahedron Letters, 2011, vol. 52, # 16, p. 1924 - 1927]
[37]Hosseinzadeh, Rahman; Aghili, Nora; Tajbakhsh, Mahmood [Catalysis Letters, 2016, vol. 146, # 1, p. 193 - 203]
[38]Sarvestani, Mosayeb; Azadi, Roya [Applied Organometallic Chemistry, 2018, vol. 32, # 1]
[39]Sun, Mingzhi; Zhu, Liping; Kan, Wenjing; Wei, Ying; Ma, Dongge; Fan, Xuefeng; Huang, Wei; Xu, Hui [Journal of Materials Chemistry C, 2015, vol. 3, # 36, p. 9469 - 9478]
[40]Current Patent Assignee: SAMSUNG ELECTRONICS CO.,LTD.; Samsung Display (in: Samsung) - KR2016/30003, 2016, A Location in patent: Paragraph 0353; 0354; 0355; 0356
[41]Current Patent Assignee: SAMSUNG ELECTRONICS CO.,LTD.; Samsung Display (in: Samsung) - KR2015/18229, 2015, A Location in patent: Paragraph 0320-0321
[42]Current Patent Assignee: SAMSUNG ELECTRONICS CO.,LTD.; Samsung Display (in: Samsung) - KR2015/69346, 2015, A Location in patent: Paragraph 0401-0404
[43]Current Patent Assignee: SAMSUNG ELECTRONICS CO.,LTD.; Samsung Display (in: Samsung) - KR2015/27897, 2015, A Location in patent: Paragraph 0371; 0373; 0374
[44]Current Patent Assignee: SAMSUNG ELECTRONICS CO.,LTD.; Samsung Display (in: Samsung) - KR2015/25259, 2015, A Location in patent: Paragraph 0226-0228
[45]Current Patent Assignee: Samsung Display (in: Samsung); SAMSUNG ELECTRONICS CO.,LTD. - KR2015/28860, 2015, A Location in patent: Paragraph 0346-0350
[46]Current Patent Assignee: Samsung Display (in: Samsung); SAMSUNG ELECTRONICS CO.,LTD. - CN106565689, 2017, A Location in patent: Paragraph 0317; 0318; 0319; 0320; 0321
[47]Current Patent Assignee: DUKSAN HI METAL CO LTD; DUK SAN NEOLUX CO., LTD. - TWI580673, 2017, B Location in patent: Page/Page column 38
[48]Current Patent Assignee: DUK SAN NEOLUX CO., LTD. - KR2019/40150, 2019, A Location in patent: Paragraph 0065-0069
[49]Current Patent Assignee: Samsung Display (in: Samsung); SAMSUNG ELECTRONICS CO.,LTD. - KR2015/28935, 2015, A Location in patent: Paragraph 0330-0332
[50]Current Patent Assignee: HODOGAYA CHEMICAL CO LTD - KR101791161, 2017, B1 Location in patent: Paragraph 0116-0122
[51]Suryawanshi, Sonali B.; Mahajan, Prasad G.; Bodake, Anita J.; Kolekar, Govind B.; Patil, Shivajirao R. [Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2017, vol. 183, p. 232 - 238]
[52]Current Patent Assignee: SAMSUNG SDI CO.,LTD. - KR102129510, 2020, B1 Location in patent: Paragraph 0270-0272
[53]Talukdar, Dhrubajyoti; Das, Gautam; Thakur, Suman; Karak, Niranjan; Thakur, Ashim J. [Catalysis Communications, 2015, vol. 59, p. 238 - 243]
[54]Ganesh; Nguyen, Hong-Minh; Mane, Rajaram S.; Kim, Nakjoong; Shinde, Dipak V.; Bhande, Sambhaji S.; Naushad, Mu.; Hui; Han, Sung Hwan [Dalton Transactions, 2014, vol. 43, # 29, p. 11305 - 11308]
[55]Monguchi, Yasunari; Marumoto, Takahisa; Takamatsu, Haruki; Sawama, Yoshinari; Sajiki, Hironao [Advanced Synthesis and Catalysis, 2014, vol. 356, # 8, p. 1866 - 1872]
[56]Ji, Wei; Jing, Su; Li, Ai-Min; Qi, Zheng-Hang; Qiu, Wen-Jie; Zha, Guo-Jin; Zhu, Dun-Ru [Journal of Catalysis, 2022, vol. 405, p. 313 - 321]
[57]Gao, Zhao; Wang, Zhiming; Shan, Tong; Liu, Yulong; Shen, Fangzhong; Pan, Yuyu; Zhang, Huanhuan; He, Xin; Lu, Ping; Yang, Bing; Ma, Yuguang [Organic electronics, 2014, vol. 15, # 11, p. 2667 - 2676]
[58]Gao, Zhao; Wang, Zhiming; Shan, Tong; Liu, Yulong; Shen, Fangzhong; Pan, Yuyu; Zhang, Huanhuan; He, Xin; Lu, Ping; Yang, Bing; Ma, Yuguang [Organic electronics, 2014, vol. 15, # 11, p. 2667 - 2676]
[59]Gao, Zhao; Liu, Yulong; Wang, Zhiming; Shen, Fangzhong; Liu, He; Sun, Guannan; Yao, Liang; Lv, Ying; Lu, Ping; Ma, Yuguang [Chemistry - A European Journal, 2013, vol. 19, # 8, p. 2602 - 2605]
[60]Current Patent Assignee: TOSOH CORPORATION - US2007/282111, 2007, A1 Location in patent: Page/Page column 4
[61]Current Patent Assignee: KYOTO UNIVERSITY; TOSOH CORPORATION - JP5777106, 2015, B2 Location in patent: Paragraph 0034-0036
[62]Watanabe, Makoto; Nishiyama, Masakazu; Yamamoto, Toshihide; Koie, Yasuyuki [Tetrahedron Letters, 2000, vol. 41, # 4, p. 481 - 483]
[63]Wei, Kai-Ju; Ni, Jia; Gao, Jian; Liu, Yangzhong; Liu, Qing-Liang [European Journal of Inorganic Chemistry, 2007, # 24, p. 3868 - 3880]
[64]Location in patent: scheme or table Song, Yabin; Di, Chong-An; Wei, Zhongming; Zhao, Tianyue; Xu, Wei; Liu, Yunqi; Zhang, Deqing; Zhu, Daoben [Chemistry - A European Journal, 2008, vol. 14, # 15, p. 4731 - 4740]
[65]Location in patent: scheme or table Yu, Fang-Fang; Fan, He-Liang; Huang, Hai-Fang; Cao, Qian-Yong; Dai, Yan-Feng; Gao, Xi-Cun; Shang, Yu-Zhu; Zhang, Min-Yan; Long, Li; Xu, Hong; Li, Xi-Feng; Wei, Bin [Inorganica Chimica Acta, 2012, vol. 390, p. 119 - 122]
[66]Li, Jiuyan; Wang, Renjie; Yang, Ruixia; Zhou, Wei; Wang, Xin [Journal of Materials Chemistry C, 2013, vol. 1, # 26, p. 4171 - 4179]
[67]Current Patent Assignee: SK CHEMICALS CO LTD - JP5663566, 2015, B2 Location in patent: Paragraph 0158
[68]Current Patent Assignee: SAMSUNG ELECTRONICS CO.,LTD.; CHIBA UNIVERSITY - JP2015/218136, 2015, A Location in patent: Paragraph 0064; 0065
[69]Current Patent Assignee: SAMSUNG ELECTRONICS CO.,LTD.; Samsung Display (in: Samsung) - US9515265, 2016, B2 Location in patent: Page/Page column 104; 107; 108
[70]Karimata, Ayumu; Suzuki, Shuichi; Kozaki, Masatoshi; Okada, Keiji [RSC Advances, 2017, vol. 7, # 88, p. 56144 - 56152]
[71]Current Patent Assignee: LG DISPLAY CO.,LTD. - KR2019/12678, 2019, A Location in patent: Paragraph 0162-0166
[72]Current Patent Assignee: Samsung Display (in: Samsung); SAMSUNG ELECTRONICS CO.,LTD. - KR102223682, 2021, B1 Location in patent: Paragraph 0223; 0227-0228

6
[ 1150-62-5 ]
[ 57103-21-6 ]
[ 502161-03-7 ]

Reference： [1]Journal of Heterocyclic Chemistry,2002,vol. 39,p. 933 - 941
[2]Journal of Heterocyclic Chemistry,2002,vol. 39,p. 933 - 941
[3]Tetrahedron Letters,2006,vol. 47,p. 6957 - 6960

7
[ 1150-62-5 ]
[ 33513-42-7 ]
[ 87220-68-6 ]

Yield	Reaction Conditions	Operation in experiment
81%	With trichlorophosphate; at 0 - 90℃; for 8h;Inert atmosphere;	After dissolving 1eq (42.0g) of intermediate b-1 in 10eq (126g) of DMF and anhydrous, the temperature of the reactor is lowered to 0C, and 1.2eq (31.7g) of phosphoric chloride is slowly added. When the addition is complete, the reaction is completed by heating at 90C for 8 hours under reflux of nitrogen. When the reaction was completed, dichloromethane and distilled water were added for extraction, and the organic layer was dried over magnesium sulfate (MgSO4), filtered, and the filtrate was concentrated under reduced pressure. The organic solution was removed, and the product solid was recrystallized from dichloromethane and nucleic acid by silica gel column with hexane:dichloromethane=7:3 (v/v) to obtain intermediate b-2 (37.9g, Y=81%).
80%	With trichlorophosphate; at 0 - 20℃; for 12h;Inert atmosphere;	To a mixture of DMF (6.36 mL, 82.02 mmol) and 9-phenyl-9H-carbazole (2g, 8.22 mmol) was added drop wisely POCl3 (9.58 mL, 102.75 mmol) at0 C for over 30 min, then the reaction mixture was stirred at room temperaturefor 12 h and then poured into 100 mL ice water mixture. After filtration, thereaction mixture was extracted with CH2Cl2 then driedover anhydrous MgSO4. After removal of the solvent, the residue waspurified by column chromatography on silica gel using CH2Cl2/petroleum(1:2, v/v) to afford white powder. Yield: 80%. 1H NMR (500 MHz,DMSO, δ): 10.11 (s, 1H), 8.88 (s, 1H), 8.42 (d, J = 7.95 Hz, 1H), 7.99 (d, J= 8.56 Hz, 1H), 7.74 (t, J = 7.86 Hz,7.57 Hz, 2H), 7.68 (d, J = 7.27 Hz,2H), 7.63 (t, J = 7.31 Hz, 7.35 Hz,1H), 7.54 (t, J = 7.81 Hz, 7.50 Hz,1H), 7.49 (d, J = 8.55 Hz, 1H), 7.41(t, J = 7.22 Hz, 8.18 Hz, 2H).
79%		POCl3 (2.30 mL, 24.7 mmol) was added dropwise to DMF (14.6 mL,189.0 mmol) under stirring at 0 C. The resulting mixture was stirred at0 C for 4 h and then warmed to room temperature. To this mixture 9-phenyl-9H-carbazole 1 (5.0 g, 20.5 mmol) was added. The reactionmixture was heated to 90 C and stirred for 7 h. The solution was pouredinto an ice-bath, neutralized with sodium bicarbonate and extractedwith DCM (3 × 40 mL). The combined organic layer was dried withanhydrous Na2SO4 and concentrated under reduced pressure. The residueobtained was purified with column chromatography on 100: 200mesh silica gel by using 20% ethyl acetate in n-hexane as the eluent toafford compound 2 as a white solid (4.40 g, 79%).mp 108-110 C; 1H NMR (500 MHz, CDCl3): δ = 7.36-7.41 (distortedq, J = 8.0, 7.0 Hz, 2H), 7.43-7.49 (m, 2H), 7.52-7.56 (m, 3H), 7.65 (t, J= 8.0, 7.5 Hz, 2H), 7.94-7.96 (dd, J = 9.0, 1.5 Hz, 1H), 8.21 (d, J = 8.0Hz, 1H), 8.68 (s, 1H), 10.12 (s, 1H); 13C NMR (125 MHz, CDCl3): δ =110.09, 110.40, 120.65, 121.18, 123.22, 123.58, 123.82, 126.98,127.18, 127.44, 128.32, 129.45, 130.11, 136.71, 141.87, 144.50,191.71; ESI-MS: m/z 272.02 [M + H]+.

75%		DMF (43.4 mL) is added to a round-bottomed flask and nitrogen is added and the reaction temperature is adjusted to 0 & lt; 0 & gt; C. Thenphosphoryl chloride (32 g, 200 mmol) is slowly added dropwise and the temperature is raised to room temperature and then stirred for 1 hour. The reaction temperature is adjusted again to 0 C and a solution of 9-phenyl carbazole (2.92 g, 120 mmol) in 1,2-dichloroethane (52 mL) is addeddropwise over 1 hour. After the reaction was completed, the reaction mixture was extracted with ice water and CH 2 Cl 2 , and the obtained organic layer was separatedwith water and subjected to column chromatography using MgSO 4, and recrystallized from ethanol and hexane to obtain 31.4 g 75%) of 3-aldehyde-9-phenyl carbazole (intermediate A).
45%	With trichlorophosphate; In 1,2-dichloro-ethane; for 12h;Reflux;	Add in dry reaction flaskPOCl3 (0.91 mL, 10 mmol) andDMF (1.5 mL, 20 mmol), stirred at room temperature for 1 h,10 mL of 1,2-dichloroethane was added to obtain reaction solution A.Reaction A was transferred to a constant pressure dropping funnel and added dropwise to 80 mL containing9-Phenyl-9H-carbazole (2.43 g, 10 mmol) in 1,2-dichloroethane.After the addition was complete, the reaction was heated at reflux and stirred for 12 h. Cool to room temperatureThe reaction was slowly poured into 1 L of vigorously stirred deionized water and extracted with DCM.Several layers were combined and washed three times with deionized water. The resulting organic phase was dried over anhydrous MgSO4.After drying, the solid was filtered off, and the resulting filtrate was concentrated using ethyl acetate and petroleum ether as eluents.Column chromatography yields the product as a white solid9-Phenyl-9H-carbazole-3-carbaldehyde (1.22 g, 4.5 mmol), yield 45%.
		Phosphorus oxychloride (9.18 mL) was added dropwise to distilled DMF (10 mL) and the mixture of 9-phenyl-9H-carbazole (11.03 g, 45.4 mmol) and DMF (25 mL) were also added dropwise to phosphorus oxychloride/DMF mixture at room temperature. The mixture constant stirring continuously for 2 h at 80C and left at room temperature, after pouring ice water and then neutralized with NaOH up to 7-8 pH, after slowly forming brown precipitate. It has been filtered using methanol and purified by column chromatography (ethyl acetate/hexane). In addition, 9-phenyl-9H-carbazole-2-carbaldehyde (11.53 g) and ethanol (125 mL) were incorporated into a 250 mL flask and then 10 g BrCl was progressively added to the mixture at 75 C (0.5 drop/s) until the reaction was completed. A brown solid (6-bromo-9-phenyl-9H-carbazole-2-carbaldyde) formed and recrystallized by anhydrous ethanol.

Reference： [1]Patent: KR102129510,2020,B1 .Location in patent: Paragraph 0270-0271; 0273
[2]Organic electronics,2014,vol. 15,p. 2667 - 2676
[3]Journal of Materials Chemistry C,2015,vol. 3,p. 9469 - 9478
[4]Journal of Materials Chemistry C,2019,vol. 7,p. 9671 - 9677
[5]Organic electronics,2021,vol. 92
[6]Organic electronics,2014,vol. 15,p. 2667 - 2676
[7]Patent: TWI580673,2017,B .Location in patent: Page/Page column 44
[8]Macromolecules,2003,vol. 36,p. 3457 - 3464
[9]Molecular Crystals and Liquid Crystals,2011,vol. 536,p. 182 - 191
[10]Journal of Materials Chemistry,2002,vol. 12,p. 3469 - 3474
[11]Patent: CN104163835,2017,B .Location in patent: Paragraph 0049
[12]Journal of Materials Chemistry C,2013,vol. 1,p. 4171 - 4179
[13]Dyes and Pigments,2016,vol. 129,p. 1 - 8
[14]Organic electronics,2021,vol. 92
[15]Asian Journal of Chemistry,2021,vol. 33,p. 1541 - 1550

8
[ 13029-09-9 ]
[ 62-53-3 ]
[ 1150-62-5 ]

Reference： [1]Dalton Transactions,2019,vol. 48,p. 3447 - 3452
[2]Advanced Synthesis and Catalysis,2010,vol. 352,p. 616 - 620
[3]Angewandte Chemie - International Edition,2003,vol. 42,p. 2051 - 2053
[4]Tetrahedron,2006,vol. 62,p. 6792 - 6801

9
[ 1150-62-5 ]
9,9′-diphenyl-9H,9′H-3,3′-bicarbazole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
97%	Stage #1: N-phenylcarbazole With methanesulfonic acid In dichloromethane at 0℃; Inert atmosphere; Stage #2: With 2,3-dicyano-5,6-dichloro-p-benzoquinone In dichloromethane at 20℃; for 0.0166667h; Inert atmosphere; regioselective reaction;
82%	With iron(III) chloride In dichloromethane at 20℃; for 5h; Inert atmosphere;
70.4%	With iron(III) chloride In dichloromethane at 20℃; for 6h;	1 1mmol N-phenylcarbazole Was reacted with 4 mmol of anhydrous ferric chloridein the presence of 1mmol of N-phenylcarbazole as a raw material and reacted in 10 ml of dichloromethane as a solvent at 20 ° Cfor 6 hours.Each time the board once to observe the reaction of the situation, two hours can be completely responsive.And then treated with 10 ml of anhydrous methanol.Standing 43 hours after the filter, directly get high-quality crystal, and then a small amount of methanol washing.Dryafter drying to give 0.171 g product, i.e. the title compound N- phenyl carbazole dimer.The reaction starting material was N-phenylcarbazole (1 mmol,0.243 g) and the product was N-phenylcarbazole dimer (0.171 g) in a yield of 70.4%.

67%	With 5% rhodium-on-charcoal; trifluoroacetic acid at 50℃; for 42h; Green chemistry; regioselective reaction;
52%	With nitrogen; iron(III) chloride In chloroform at 20℃; for 4h;
46%	With Eaton’s reagent In neat (no solvent) at 110℃; for 12h; Inert atmosphere; Schlenk technique;
	With iron(III) chloride In chloroform

Reference： [1]Mallick, Sudesh; Maddala, Sudhakar; Kollimalayan, Kalidass; Venkatakrishnan, Parthasarathy [Journal of Organic Chemistry, 2019, vol. 84, # 1, p. 73 - 93]
[2]Zhang, Qijian; Zhuang, Hao; He, Jinghui; Xia, Shugang; Li, Hua; Li, Najun; Xu, Qingfeng; Lu, Jianmei [Journal of Materials Chemistry C, 2015, vol. 3, # 26, p. 6778 - 6785]
[3]Current Patent Assignee: QILU UNIVERSITY OF TECHNOLOGY (SHANDONG ACADEMY OF SCIENCES) - CN105820105, 2016, A Location in patent: Page/Page column 4
[4]Matsumoto, Kenji; Toubaru, Yasunori; Tachikawa, Shohei; Miki, Ayaka; Sakai, Kentaro; Koroki, Syota; Hirokane, Tsukasa; Shindo, Mitsuru; Yoshida, Masahiro [Journal of Organic Chemistry, 2020, vol. 85, # 23, p. 15154 - 15166]
[5]Kim, Yeong Eun; Kwon, Young Soon; Lee, Kwang Soon; Park, Jong Wook; Seo, Hyeon Jin; Kim, Tae Wan [Molecular Crystals and Liquid Crystals, 2004, vol. 424, p. 153 - 158]
[6]Yuan, Jie; Jin, Lu; Chen, Runfeng; Tang, Xingxing; Xie, Xiang; Tang, Yuting; Huang, Wei [New Journal of Chemistry, 2018, vol. 42, # 18, p. 14704 - 14708]
[7]Location in patent: scheme or table Chiu, Ssu-Kai; Chung, Yi-Chun; Liou, Guey-Sheng; Su, Yuhlong Oliver [Journal of the Chinese Chemical Society, 2012, vol. 59, # 3, p. 331 - 337]

10
[ 1150-62-5 ]
[ 1153-85-1 ]

Yield	Reaction Conditions	Operation in experiment
99%	With N-Bromosuccinimide In ethyl acetate; toluene	S.1.3 [Step 3: Synthesis of 3-bromo-9-phenyl-9H-carbazole] [Step 3: Synthesis of 3-bromo-9-phenyl-9H-carbazole] Into a 1000 mL three-neck flask were put 24 g (100 mmol) of 9-phenylcarbazole, 18 g (100 mmol) of N-bromosuccinimide, 450 mL of toluene, and 200 mL of ethyl acetate, and the mixture was stirred for 45 hours at room temperature. This suspending solution was washed with water, and magnesium sulfate was added therein, so that moisture was removed. Then, the suspending solution was filtered to provide a filtrate was obtained. The obtained filtrate was concentrated and dried, whereby 32 g of a caramel-like solid of 3-bromo-9-phenyl-9H-carbazole, which was the object of the synthesis, was obtained in a yield of 99% (synthesis scheme (a-6)).
99%	With N-Bromosuccinimide In ethyl acetate; toluene at 20℃; for 45h;	2-1 [Step 2-1: Synthesis of 3-bromo-9-phenyl-9H-carbazole][0274]A synthetic scheme of 3-bromo-9-phenyl-9H-carbazole in Step 2-1 is shown in the following (D-2-1). [0275][0276]In a 1000 mL conical flask, 24 g (100 mmol) of 9-phenyl-9H-carbazole, 18 g(100 mmol) of JV-bromo succinimide, 450 mL of toluene, and 200 mL of ethyl acetate were added, and the mixture was stirred at room temperature for 45 hours. This suspension was washed with water and then magnesium sulfate was added thereto to remove moisture. This suspension was filtrated, and the obtained filtrate was concentrated and dried. Accordingly, 32 g of a caramel-like object,3-bromo-9-phenyl-9H-carbazole, was obtained at a yield of 99 %.
99%	With N-Bromosuccinimide In ethyl acetate; toluene at 20℃; for 45h;	1.3 [Step 3: Synthesis of 3-bromo-9-phenyl-9H-carbazole]Into a 1000 mL three-neck flask were put 24 g (100 mmol) of 9-phenylcarbazole, 18 g (100 mmol) of N-bromosuccinimide, 450 mL of toluene, and 200 mL of ethyl acetate, and the mixture was stirred for 45 hours at room temperature. This suspending solution was washed with water, and magnesium sulfate was added therein, so that moisture was removed. Then, the suspending solution was filtered to provide a filtrate was obtained. The obtained filtrate was concentrated and dried, whereby 32 g of a caramel-like solid of 3-bromo-9-phenyl-9H-carbazole, which was the object of the synthesis, was obtained in a yield of 99 % (synthesis scheme (a-6)).

99%	With N-Bromosuccinimide In ethyl acetate; toluene at 20℃; for 45h;	1 Step 1: Synthesis of 3-bromo-9-phenyl-9H-carbazole In a 1000 mL Erlenmeyer flask, 24 g (100 mmol) of 9-phenyl-9H-carbazole, 18 g (100 mmol) of N-bromosuccinimide, 450 mL of toluene, and 200 mL of ethyl acetate were added, and the mixture was stirred at room temperature for 45 hours. After the reaction, the resulting mixture was washed with water, and the organic layer is dried with magnesium sulfate. The mixture was filtered, and the resulting filtrate was concentrated to give 32 g of the target substance 3-bromo-9-phenyl-9H-carbazole in 99% yield. The synthetic scheme of 3-bromo-9-phenyl-9H-carbazole is shown in the scheme (C-1).
99%	With N-Bromosuccinimide In ethyl acetate; toluene at 20℃; for 45h;	2.2-1 [Step 2-1: Synthesis of 3-bromo-9-phenyl-9H-carbazole] The synthesis scheme of 3-bromo-9-phenyl-9H-carbazole in Step 2-1 is illustrated in the following (D-2-1). [Show Image] In a 1L conical flask, 24 g (100 mmol) of 9-phenyl-9H-carbazole, 18 g (100 mmol) of N-bromosuccinimide, 450 mL of toluene, and 200 mL of ethyl acetate were stirred at room temperature for 45 hours. This suspension was washed with water, and magnesium sulfate was added thereto, so that moisture was removed. This suspension was filtered, and the obtained filtrate was concentrated and dried. The amount and yield of a solid, which was the substance to be produced, were 32 g and 99%, respectively.
95%	With N-Bromosuccinimide In toluene at 0℃; for 2h; Inert atmosphere; Darkness;	1 Synthesis of Compound P1 Weigh S1 (10 mmol) into a 100 mL two-necked flask.Add 30 mL of nitrogen degassed toluene to dissolve S1.One of the interfaces is connected to a constant pressure dropping funnel.Nitrogen replaces the gas in the reaction system.Weigh NBS (10.5mmol),Add 20 mL of toluene to dissolve it, at 0 ° C and protected from light,The toluene solution of NBS was added dropwise to a toluene solution of S9 through a dropping funnel, and after stirring for 2 hours, the mixture was slowly warmed to room temperature and stirred overnight.After the reaction was over, 50 mL of deionized water was added to quench the reaction.Extract with dichloromethane (100 mL x 3) and collect the organic phase.Drying with anhydrous Na2SO4. filter,The solvent was distilled off under reduced pressure using a rotary evaporator.The crude product was obtained. The crude product was purified by silica gel column chromatography gradient elution.Finally purified to obtain solid powder S2(9.5 mmol, yield 95%).
95%	With N-Bromosuccinimide In toluene at 0 - 20℃; Inert atmosphere; Darkness;	1 Synthesis of Compound P1 Weighed S1 (10.0 mmol) was added to a 100 mL two-necked flask, and 30 mL of nitrogen-deaerated toluene was added to dissolve S1. One of the two flasks was connected to a constant pressure dropping funnel, and the reaction system was replaced with nitrogen. The gas inside.NBS (N-bromosuccinimide) (10.5 mmol) was weighed, dissolved in 20 mL of toluene, and the toluene solution of NBS was added dropwise through a dropping funnel at 0 ° C in the dark. After stirring for 2 hours in a toluene solution of S1, the temperature of the reaction system was slowly raised to room temperature and stirred overnight. After the reaction was completed, the reaction was quenched by adding 50 mL of deionized water and extracted with dichloromethane.(100 mL X 3), the organic phase was collected, and the organic phase was dried over anhydrous Na2SO4. The dried organic phase was filtered, and the solvent was evaporated under reduced pressure using a rotary evaporator to give a crude product. The crude product was purified by silica gel column chromatography eluting to afford solid powder S2 (9.5 mmol, 95%).
95%	With N-Bromosuccinimide In toluene at 0 - 20℃; for 2h;	1 Synthesis of Compound P1 Weigh S1 (10 mmol) into a 100 mL two-necked flask.Add 30 mL of nitrogen degassed toluene to dissolve S1.One of the two flasks is connected to a constant pressure dropping funnel.The gas in the reaction system was replaced with nitrogen.Weigh NBS (N-bromosuccinimide) (10.5 mmol),Add 20 mL of toluene to dissolve it.At 0 ° C and protected from light,The toluene solution of NBS was dropwise added to the toluene solution of S1 through a dropping funnel.After stirring for 2 h, the temperature of the reaction system was slowly raised to room temperature and stirred overnight. After completion of the reaction, the reaction was quenched by the addition of 50 mL of EtOAc (EtOAc). The dried organic phase was filtered, and the solvent was evaporated under reduced pressure using a rotary evaporator to give a crude product. The crude product was purified by silica gel column chromatography gradient elution.Solid powder S2 (9.5 mmol, 95%) was obtained.
95%	With N-Bromosuccinimide In toluene at 0 - 20℃; Inert atmosphere; Darkness;	1 S1 (10 mmol) was weighed into a 100 mL two-necked flask, and 30 mL of nitrogen degassed toluene was added to dissolve S1, one of which was connected to a constant pressure dropping funnel, and the gas in the reaction system was replaced with nitrogen. Weigh NBS (10.5mmol), add 20mL of toluene to dissolve it, at 0 ° C and protected from light,The toluene solution of NBS was added dropwise to the toluene solution of S1 through a dropping funnel, and after stirring for 2 hours,Slowly warm to room temperature and stir overnight. After the reaction was over, 50 mL of deionized water was added to quench the reaction.It was extracted with dichloromethane (100 mL × 3), and the organic phase was collected and dried over anhydrous Na2SO4. After filtration, the solvent was distilled off under reduced pressure using a rotary evaporator.The crude product was obtained. The crude product was purified by silica gel chromatography gradient elution column, to give the final solid powder S2 (9.5mmol, 95% yield).
94%	With N-Bromosuccinimide In N,N-dimethyl-formamide at 0℃;
94%	With N-Bromosuccinimide In N,N-dimethyl-formamide at 0℃; Darkness; Inert atmosphere;
92%	With N-Bromosuccinimide In ethyl acetate; toluene at 20℃; for 45h;	12-1 [Synthesis Example 12-1] Synthesis of [Intermediate 12-a] In a 1-L reactor, 9-phenyl carbazole (50 g, 205 mmol), N-bromosuccinimide (36.5 g, 205 mmol), toluene (700 ml), and ethylacetate (300 ml) were placed and stirred together at room temperature for 45 hours. After completion of the reaction, the organic layer was extracted and concentrated at a reduced pressure. Purification by column chromatography afforded Intermediate 12-a (60.7 g): yield 92%
88%	With N-Bromosuccinimide In acetic acid at 20℃;	1.1 Firstly, 24.3 g (100 mmol) of 9-phenylcarbazole was dissolved in 600 ml of glacial acetic acid, and 17.8 g (100 mmol) of N-bromosuccinimide was slowly added thereto. The mixture was stirred overnight at a room temperature. This glacial acetic acid solution was dropped in 1 L of ice water while stirring it. A precipitated white solid was washed three times with water. This solid was dissolved in 150 ml of diethyl ether, and washed with a saturated sodium hydrogencarbonate solution and water. This organic layer was dried with magnesium sulfate, and filtered. The obtained filtrate was concentrated. About 50 ml of methanol was added into the thus obtained EPO concentrated solution and uniformly dissolved therein. This solution was left still to precipitate a white solid. This solid was collected and dried to obtain 28.4 g (the yield:88%) of 3-bromo-9-phenylcarbazole, which was white powder.
88%	With N-Bromosuccinimide In acetic acid at 20℃;	1.2 Firstly, 24.3 g (100 mmol) of N-phenylcarbazole was dissolved in 600 ml of glacial, acetic acid, and 17.8 g (100 mmol) of N-bromo succinic acid imide was slowly added thereto. The mixture was stirred for overnight at a room temperature. This glacial acetic acid solution was dropped in 1 L of ice water while stirring them. A precipitated white solid was washed three times with water. This white solid was dissolved in 150 ml of diethyl ether, and washed with a saturated sodium hydrogencarbonate solution and water. This organic layer was dried with magnesium sulfate, and filtered. The obtained filtrate was concentrated. The thus obtained EPO residue was added with about 50 ml of methanol and uniformly dissolved therein by being irradiated with supersonic. This solution was left to precipitate a white solid. This solution was filtrated and the filtrate was dried to obtain 28.4 g (the yield: 88%) of 3-bromo-9-phenylcarbazole, which was a white powder. [0134]Further, a synthetic scheme (c - 1) of 3-bromo-9-phenylcarbazole is shown below.
88%	With N-Bromosuccinimide In acetic acid at 20℃; for 24h;	1.1.2.i; b.1 First, 24.3 g (100 mmol) of N-phenylcarbazole was dissolved in 600 mL of gracial acetic acid, and 17.8 g (100 mmol) of N-bromosuccinimide was slowly added thereto. Then, the mixture was stirred for 24 hours at room temperature. This gracial acetic acid solution was dropped into 1 L of ice water while being stirred. The precipitated white solid was washed with water three times. This solid was dissolved in 150 mL of diethylether, and washed with a saturated sodium hydrogen carbonate solution and water in this order. This organic layer was dried with magnesium sulfate and then filtrated to obtain a filtrate. The filtrate was concentrated. The obtained residue was added with about 50 mL of methanol and was irradiated with ultrasonic waves so as to be dissolved uniformly. This solution was left at rest, and a white solid was precipitated. This solution was filtered, and the precipitate was dried to obtain 28.4 g (in a yield of 88%) of a white powder, which was 3-bromo-9-phenylcarbazole.
88%	With N-Bromosuccinimide; acetic acid at 20℃; for 20h;	1.1 EXAMPLE 1; A method for synthesizing N,N',N-triphenyl-N,N',N-tris(9-phenylcarbazol-3-yl)-benzene-1,3,5-triamine (abbr.: PCA3B) represented by Structural Formula (21) as an example of the aromatic amine compound of the present invention is explained.; [Step 1]; First, a method for synthesizing 3-bromo-9-phenylcarbazole is explained. A synthetic scheme of 3-bromo-9-phenylcarbazole is shown in (B-1).; 24.3 g (100 mmol) of 9-phenylcarbazole was dissolved in 600 mL of a glacial acetic acid, 17.8 g (100 mmol) of N-bromosuccinimide was gradually added thereto, and the mixture was stirred for approximately 20 hours at a room temperature. This glacial acetic acid solution was dropped into 1 L of ice water while stirring. The precipitated white solid was washed with water three times. This solid was dissolved in 150 mL of diethyl ether and the solution was washed with a saturated aqueous sodium hydrogen carbonate solution and water. An organic layer thereof was dried with magnesium sulfate. The organic layer was filtered, and the obtained filtrate was concentrated, where about approximately 50 mL of methanol was added and dissolved uniformly. The white solid was precipitated by leaving this solution at rest. This solid was recovered and dried, thereby obtaining 28.4 g (yield: 88%) of 3-bromo-9-phenylcarbazole as a white powder.
88%	With N-Bromosuccinimide; acetic acid at 20℃; for 18h;	2.2.i Step 2: Synthesis of N-phenyl-(9-phenylcarbazol-3-yl)amine (abbreviation: PCA; In Step 2, PCA was synthesized according to (i) and (ii) shown below.; (i) Synthesis of 3-bromo-9-phenylcarbazole First, 24.3 g (100 mmol) of N-phenylcarbazole was dissolved in 600 mL of glacial acetic acid, 17.8 g (100 mmol) of N-bromosuccinimide was slowly added therein, and the mixture was stirred at room temperature for 18 hours. This reaction solution was dripped to 1 L of ice water while being stirred, and a white solid which was precipitated was washed with water three times. The obtained solid was dissolved in 150 mL of diethyl ether and washed with a saturated sodium hydrogen-carbonate aqueous solution and water. After being washed, an organic layer was dried with magnesium sulfate. After filtration, the filtrate was concentrated. Thereafter, approximately 50 mL of methanol was added to an obtained solid, and the solid was irradiated with ultrasonic waves to be uniformly dissolved. This solution was left at rest, and a white precipitate was obtained. This precipitate was collected by filtration and dried; thus, 28.4 g of a white powder of 3-bromo-9-phenylcarbazole that was an object was obtained (yield: 88%).
88%	With N-Bromosuccinimide In methanol; diethyl ether; water; acetic acid	S.5.1 (1) [Step 1: Synthesis Method of N-phenyl-(9-phenylcarbazole-3-yl)amine (Hereinafter, Referred to as PCA)] Synthesis of 3-bromo-9-phenylcarbazole 24.3 g (100 mmol) of N-phenylcarbazole was dissolved in 600 mL of glacial acetic acid, 17.8 g (100 mmol) of N-bromosuccinimide was slowly added, and the mixture was stirred for approximately 12 hours at the room temperature. This glacial acetic acid solution dropped to 1000 mL of iced water while being stirred. After the drop, a precipitated white solid was washed 3 times with water. This solid was dissolved in 150 mL of diethyl ether, and washed with a saturated sodium hydrogen carbonate solution and water to separate an aqueous layer and an organic layer. This organic layer was dried with magnesium sulfate and filtered. The filtrate was concentrated to obtain a solid. Then, about 50 mL of methanol was added to the solid and the solid was uniformly dissolved by irradiation with ultrasonic waves. By leaving this solution at rest, a white solid was extracted. This white solid was filtered and dried, whereby 28.4 g of a white powdered solid of 3-bromo-9-phenylcarbazole was obtained in the yield of 88% (Synthesis Scheme (j-1)).
88%	With N-Bromosuccinimide In acetic acid at 20℃; for 12h;	d.1 First, 24.3 g (100 mmol) of iV-phenylcarbazole was dissolved in 600 mL of EPO glacial acetic acid, 17.8 g (100 mmol) of iV-bromosuccinimide was slowly added, and the mixture was stirred for about 12 hours at room temperature. This glacial acetic acid solution was added dropwise to 1 L of iced water while stirring. The white solid extracted was washed 3 times with water This solid was dissolved in 150 mL of diethyl ether, and washed with a saturated sodium hydrogen carbonate solution and water. This organic layer was dried with magnesium sulfate. This was filtered, and the filtrate obtained was concentrated. To the residue obtained was added about 50 mL of methanol, and by irradiation with ultrasonic waves, the residue was dissolved evenly in the solution. By leaving this solution at rest, a white solid was extracted. This white solid was filtered, and by drying the solid, 28.4 g of 3-bromo-9-phenylcarbazole in a white powdered form was obtained (yield rate: 88%). [0303]Next, a synthesis scheme (d-1) of 3-bromo-9-phenylcarbazole will be shown. [0304],(d- 1)
88%	With N-Bromosuccinimide In methanol; (2S)-N-methyl-1-phenylpropan-2-amine hydrate; diethyl ether; acetic acid	3.1.i (i) (i) Synthesis of 3-bromo-9-phenylcarbazole A synthetic scheme of 3-bromo-9-phenylcarbazole is shown in (E-1). 24.3 g (100 mmol) of 9-phenylcarbazole was dissolved into 600 mL of glacial acetic acid, and 17.8 g (100 mmol) of N-bromosuccinimide was slowly added thereto, which was followed by stirring at room temperature for about 15 hours. This glacial acetic acid solution was dropped to 1 L of ice water while being stirred, and a white solid which was precipitated was collected by suction filtration and washed with water three times. The solid was dissolved into 150 mL of diethyl ether, and the solution washed with a saturated sodium hydrogencarbonate aqueous solution and water. The organic layer was dried with magnesium sulfate. After filtration, the obtained filtrate was concentrated, and about 50 mL of methanol was added thereto to homogeneously dissolve the residue. This solution was left at rest, and a white solid was precipitated. This solid was collected and dried, giving 28.4 g of a white powder of 3-bromo-9-phenylcarbazole in the yield of 88%.
88%	With N-Bromosuccinimide; acetic acid at 20℃; for 12h;	2.1.i (i) Synthesis of 3-bromo-9-phenylcarbazole;. A synthetic scheme of 3-bromo-9-phenylcarbazole is shown in (C-5).[0293](C-5) [0294]24.3 g (100 mmol) of 9-phenylcarbazole was put into a 2L Meyer flask, and dissolved in 600 mL of glacial acetic acid. Then, 17.8 g (100 mmol) ofN-bromosuccinimide was slowly added, and the solution was stirred for about 12 hours at room temperature. This solution was dropped into 1 L of ice water while stirring. A white solid precipitated was collected by suction filtration, and then washed with water three times. This solid was dissolved in 150 mL of diethyl ether, and the solution was washed with a saturated aqueous solution of sodium bicarbonate and then with water.The organic layer was dried over magnesium sulfate, filtered, and concentrated, and then the residue was dissolved in ca. 50 mL of ethanol. The precipitate formed as .a white solid was collected by suction filtration and dried, giving 28.4 g (88% yield) of3-bromo-9-phenylcarbazole as white powder. '*
88%	With N-Bromosuccinimide In methanol; (2S)-N-methyl-1-phenylpropan-2-amine hydrate; diethyl ether; acetic acid	2.1 [Step 1] [Step 1] Synthesis of 3-bromo-9-phenylcarbazole A synthesis method of 3-bromo-9-phenylcarbazole is described. A synthesis scheme of 3-bromo-9-phenylcarbazole is shown in (C-1). 24.3 g (100 mmol) of 9-phenylcarbazole was put into a 2-L Erlenmeyer flask and dissolved by addition of 600 mL of glacial acetic acid. 17.8 g (100 mmol) of N-bromosuccinimide was slowly added into this solution and stirred for about 12 hours at room temperature. By dripping this reaction solution into 1 L of ice water while being stirred, a white solid was separated out. This separated white solid was recovered by suction filtration and washed three times with water. This solid was dissolved in 150 mL of diethyl ether and washed with a saturated sodium acid carbonate solution and water. This organic layer was dried with magnesium sulfate. Suction filtration of the mixture was performed, and the resulting filtrate was enriched. Recrystallization thereof was performed by addition of about 50 mL of methanol into this enriched solution and being left standing, whereby 28.4 g of a white powder solid of 3-bromo-9-phenylcarbazole was obtained at a yield of 88%.
88%	With N-Bromosuccinimide; acetic acid In diethyl ether at 20℃; for 12h;	1.1.i (i) Synthesis of 3-bromo-9-phenylcarbazole A synthetic scheme of 3-bromo-9-phenylcarbazole is shown in (B-1). 24.3 g (100 mmol) of 9-phenylcarbazole was put into a 2 L Meyer flask, and dissolved in 600 mL of glacial acetic acid. Then, 17.8 g (100 mmol) of N-bromosuccinimide was slowly added thereto, and the solution was stirred for about 12 hours at room temperature. This glacial acetic acid solution was dropped into 1 L of ice water while being stirred. A white solid precipitated was collected by suction filtration, and then washed with water three times. This solid was dissolved in 150 mL of diethyl ether, and the solution was washed with a saturated aqueous solution of sodium bicarbonate and then with water. The organic layer was dried with magnesium sulfate, the mixture was filtered, and the filtrate was concentrated. Thus, an oily substance was obtained. The oily substance was dissolved in about 50 mL of methanol. A precipitate of a white solid was produced by keeping this solution still. This solid was collected by suction filtration and dried. Then, 28.4 g (88% yield) of 3-bromo-9-phenylcarbazole was obtained as white powder.
88%	Stage #1: N-phenylcarbazole With N-Bromosuccinimide; acetic acid at 20℃; for 12h; Stage #2: With water; sodium hydrogencarbonate In diethyl ether	1.2.i [Step 2] Synthesis of N,9-diphenyl-9H-carbazol-3-amine (abbreviation: PCA); (i) Synthesis of 3-bromo-9-phenylcarbazole; A synthetic scheme of 3-bromo-9-phenylcarbazole is shown in (C-5). 24.3 g (100 mmol) of 9-phenylcarbazole was put into a 2 L Meyer flask, and dissolved in 600 mL of glacial acetic acid. Then, 17.8 g (100 mmol) of N-bromosuccinimide was slowly added, and the solution was stirred for about 12 hours at room temperature. This solution was dropped into 1 L of ice water while stirring. A white solid precipitated was collected by suction filtration, and then washed with water three times. This solid was dissolved in 150 mL of diethyl ether, and the solution was washed with a saturated aqueous solution of sodium bicarbonate and then with water. The organic layer was dried over magnesium sulfate, filtered, and concentrated, and then the residue was dissolved in ca. 50 mL of ethanol. The precipitate formed as a white solid was collected by suction filtration and dried, giving 28.4 g (88% yield) of 3-bromo-9-phenylcarbazole as white powder.
88%	With N-Bromosuccinimide In methanol; (2S)-N-methyl-1-phenylpropan-2-amine hydrate; diethyl ether; acetic acid	2.i (i) (i) Synthesis of 3-bromo-9-phenylcarbazole A synthesis scheme of 3-bromo-9-phenylcarbazole is shown in (D-1). 24.3 g (100 mmol) of 9-phenylcarbazole was put into a 2 L Meyer flask, and dissolved in 600 mL of glacial acetic acid. Then, 17.8 g (100 mmol) of N-bromosuccinimide was slowly added thereto, and the solution was stirred at room temperature for about 12 hours. This glacial acetic acid solution was dropped into 1 L of ice water while being stirred. A white solid substance precipitated was collected by suction filtration, and then washed with water three times. This solid substance was dissolved in 150 mL of diethyl ether, and the solution was washed with a saturated sodium hydrogen carbonate aqueous solution and then with water. The organic layer was dried with magnesium sulfate, the mixture was filtered by suction filtration, and the filtrate was concentrated. Thus, an oily substance was obtained. The oily substance was dissolved in about 50 mL of methanol. A precipitate of a white solid substance was produced by keeping this solution still. This solid substance was collected by suction filtration and dried. Then, 28.4 g (88% yield) of 3-bromo-9-phenylcarbazole was obtained as white powder.
88%	With N-Bromosuccinimide In acetic acid at 20℃; for 12h;	1.2.1 24.3 g (100 mmol) of jV-phenylcarbazole was dissolved in 600 mL of glacial acetic acid, and 17.8 g (100 mmol) of -V-bromosuccinimide was slowly added thereto. The mixture was stirred for about 12 hours at a room temperature. This glacial acetic acid solution was dropped into 1 L of ice water while stirring it. A precipitated white solid was washed with water three times. This solid was dissolved in 150 mL of diethyl ether, and washed with a saturated sodium hydrogen carbonate solution and water. This organic layer was dried with magnesium sulfate. A mixture is filtered and a filtrate was concentrated. When an obtained residue was recrystallized with methanol, 28.4 g of 3-bromo-9-phenylcarbazole that was a target substance and was white powder was obtained in a yield of 88 % (Synthesis Scheme (c-1)).
88%	With N-Bromosuccinimide; acetic acid at 20℃; for 12h;	2.1 24.3 g (100 mmol) of 9-phenylcarbazole was put into a 2-L Erlenmeyer flask and dissolved by addition of 600 mL of glacial acetic acid. 17.8 g (100 mmol) of N-bromosuccinimide was slowly added into this solution and stirred for about 12 hours at room temperature. By dripping this reaction solution into 1 L of ice water while being stirred, a white solid was separated out. This separated white solid was recovered by suction filtration and washed three times with water. This solid was dissolved in 150 mL of diethyl ether and washed with a saturated sodium acid carbonate solution and water. This organic layer was dried with magnesium sulfate. Suction filtration of the mixture was performed, and the resulting filtrate was enriched. Recrystallization thereof was performed by addition of about 50 mL of methanol into this enriched solution and being left standing, whereby 28.4 g of a white powder solid of 3-bromo-9-phenylcarbazole was obtained at a yield of 88%.
88%	With N-Bromosuccinimide; acetic acid at 20℃; for 12h;	2.1.i 24.3 g (100 mmol) of 9-phenylcarbazole was put into a 2 L Meyer flask, and dissolved in 600 mL of glacial acetic acid. Then, 17.8 g (100 mmol) of N-bromosuccinimide was slowly added thereto, and the solution was stirred at room temperature for about 12 hours. This glacial acetic acid solution was dropped into 1 L of ice water while being stirred. A white solid substance precipitated was collected by suction filtration, and then washed with water three times. This solid substance was dissolved in 150 mL of diethyl ether, and the solution was washed with a saturated sodium hydrogen carbonate aqueous solution and then with water. The organic layer was dried with magnesium sulfate, the mixture was filtered by suction filtration, and the filtrate was concentrated. Thus, an oily substance was obtained. The oily substance was dissolved in about 50 mL of methanol. A precipitate of a white solid substance was produced by keeping this solution still. This solid substance was collected by suction filtration and dried. Then, 28.4 g (88% yield) of 3-bromo-9-phenylcarbazole was obtained as white powder.
87.9%	With hydrogen bromide; dihydrogen peroxide In dichloromethane at -10℃; for 6h;	1-5; 1-5 Example 2 At room temperature, add 243.3g of N-phenylcarbazole (99%, 1.00mol) and 500mL of dichloromethane to a 1000mL four-necked round bottom flask equipped with a stirrer and thermometer. Stir until completely dissolved, and then reduce the reaction. System temperature to -10; 212.4g hydrobromic acid (40%, 1.05mol, 153.9mL) was added dropwise, and 119.0g hydrogen peroxide (30%, 1.05mol, 107.2) was added dropwise after the reaction temperature was constant at -10 mL), where the dropping rate of the brominating agent is 3.0mL/min, and the dropping rate of the oxidizing agent is 0.5mL/min. The dripping process can strictly control the reaction temperature below -10; under the condition of -10 The reaction is 6 hours, during which the conversion rate of N-phenylcarbazole in the liquid phase detection reaches ≥99% to stop the reaction. After the reaction is over, a quantitative saturated aqueous solution of sodium carbonate is added to the reaction system to adjust the pH of the mixed solution to neutral, and the mixture is washed 3 times with a water washing separation method, and the dichloromethane is removed by rotary evaporation to obtain a crude product. The crude product is recrystallized with 500 mL of ethanol three timesA white solid is obtained, and the white solid is transferred to a vacuum drying oven at 60°C and P=0.095MPa for drying for 3 hours283.2 g of white crystal 3-bromo-N-phenylcarbazole was obtained (the content detected by HPLC was ≥99%), and the yield was 87.9%.
86%	With N-Bromosuccinimide In chloroform at 20℃; for 1h;	6 Preparation of Structural Formula 33A; The Structural Formula 1A (15 g, 61.6 mmol) was dissolved in chloroform (300 ml), and N-bromo succinimide (11.0 g, 61.6 mmol) was added thereto, and agitated for 1 hour 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 n-hexane to obtain the Structural Formula 33A (17 g, yield 86%). MS: [M+H]+ = 323
85%	With N-Bromosuccinimide In dichloromethane at 20℃; for 12h;	3 Synthesis of intermediate I-5 Intermediate I-4 5.47 g (22.5 mmol) and 80 mL CH2Cl2 to completely dissolved the solution N-bromosuccinimide (N-bromosuccinimide) 4.00 g (22.5 mmol) gave after the into room temperature in 12 hours dongan stirring. Was added to 60 mL of water to the reaction solution was extracted three times with 50 mL CH2Cl2. The obtained organic layer was dried with magnesium sulfate and evaporation of the solvent was recrystallized from methanol to give the intermediate I-5 6.16 g (yield 85%). The resulting compound was confirmed by LC-MS.
85%	With N-Bromosuccinimide In dichloromethane at 20℃; for 12h;	2 2) Synthesis of intermediate I-2 Intermediate I-1 5.47 g (22.5 mmol) to a CH2Cl2 solution was completely dissolved in 80 mL N- bromosuccinimide 4.00 g (22.5mmol) was stirred for 12 hours at room temperature gave put. 60 mL of water was added to the reaction solution in CH2Cl2 50 mLAnd extracted three times. After the collected organic layer was dried with magnesium sulfate and evaporation of the solvents, recrystallized from methanol andI-2 6.16 g (yield: 85%).
85%	With N-Bromosuccinimide In dichloromethane at 20℃; for 12h;	1.2 Synthesis of intermediate I-2 Intermediate I-1 5.47 g (22.5 mmol) ofCH2Cl2 80 mLCompletely dissolved in the solutionAfter N- bromo-succinimide 4.00 g (22.5mmol) was stirred at room temperature for 12 hours. 60 mL of water was added to the reaction solution was extracted three times with 50 mL CH2Cl2. The combined organic layers were dried over magnesium sulfate, and the solvent was recrystallized in methanol to give after evaporation 6.16 g of intermediate I-2 (yield: 85%). The resulting compound was confirmed by LC-MS. C18H12BrN: M+ 321.0
85%	With N-Bromosuccinimide In dichloromethane at 20℃; for 12h;	1 Synthesis of intermediate I-2 General procedure: Intermediate I-1 5.47 g (22.5 mmol) ofCH2 Cl 2 80 mLthe solution was completely dissolved in N-bromosuccinimide 4.00 g (22.5 mmol) gave after the into room temperature in 12 hours stirring.It was added to 60 mL of water to the reaction mixture CH2Cl2and extracted 3 times with 50 mL.After drying the organic layer obtained therefrom by magnesium sulfate, and evaporation of the solvents, recrystallized from methanol to give intermediate I-2 6.16 g (yield 85%).
85%	With N-Bromosuccinimide In dichloromethane at 20℃; for 12h;	2 2) Synthesis of intermediate I-2 Intermediate I-1 5.47 g (22.5 mmol) N-bromosuccinimide4.00 g put (22.5mmol) in a CH2Cl2 solution was completely dissolved in 80 mL at room temperature gave It was stirred for 12 hours.Was added to 60 mL of water to the reaction solution was extracted three times with 50 mL CH2Cl2.After the collected organic layer was dried with magnesium sulfate and evaporation of the solvent was recrystallized with methanol Intermediate I-2. It was a 6.16 g (85% yield).
85%	With N-Bromosuccinimide In dichloromethane at 20℃; for 12h;	1.2 Synthesis of intermediate I-2 To a solution of 5.47 g (22.5 mmol) of Intermediate I-1 in 80 mL of methylene chloride, 4.00 g (22.5 mmol) of Nbromosuccinimide was added and the mixture was stirred at room temperature for 12 hours. To the reaction solution was added 60 mL of water and extracted three times with 50 mL of methylene chloride. The organic layer thus obtained was dried over magnesium sulfate, the solvent was evaporated, and the residue was recrystallized from methanol to obtain 6.16 g (yield: 85%) of Intermediate I-2. The resulting compound was identified via LC-MS.
85%	With N-Bromosuccinimide In dichloromethane at 20℃; for 12h;	2 Synthesis of Intermediate I-4 4.00 g (22.5 mmol) of N-bromosuccinimide was added to a solution of 5.47 g (22.5 mmol)Of the intermediate I-3 was completely dissolved in 80 mL of CH2Cl2,The reaction solution was stirred at room temperature for 12 hours.The organic layer was extracted three times from the reaction solution by using 60 mL of water and 50 mL of CH2Cl2.The organic layer thus collected was dried with magnesium sulfate,The residue obtained after evaporation of the solvent from it was recrystallized using methanol,To obtain 6.16 g of intermediate I-4 (yield: 85%).The compounds thus produced were determined by using LC-MS.
85%	With N-Bromosuccinimide In chloroform at 20℃; for 0.5h;	Compound (6) 3-bromo-9-phenyl-9H-carbazole 9-phenyl-9Hcarbazole(6 g, 27 mmol), N-Bromosuccinimide (4.3 g, 27 mmol) wereadded to 30 mL of chloroform solution in 3-neck round bottom flaskand stirred for 30 min at room temperature. After vaporizing the solvent,the crude product was recrystallized using hexane. (7.4 g, Yield85%) 1H NMR (300 MHz, CDCl3): δ(ppm) 8.25-8.24 (d, 1H), 8.10-8.07(d, 1H), 7.64-7.58 (t, 2H), 7.54-7.45 (m, 4H), 7.44-7.37 (m, 2H),7.32-7.27 (m, 2H).
84%	With N-Bromosuccinimide In N,N-dimethyl-formamide at 0℃; for 12h;
83%	With N-Bromosuccinimide In 1,2-dichloro-ethane at -5 - 0℃; for 12h;	2.2 Synthesis of 3-BrPCz Three necked flask were successively added to the 9-phenyl-carbazole (6.08g, 0.025mol), 1,2- dichloroethane 80ml; stirred to dissolve, was added NBS (4.45g, 0.025mol), - 5 ~ 0 for 12h after stirring added an aqueous sodium bisulfate, 0.5H; stratification, the organic phase washed with saturated brine until neutral, dried over anhydrous sodium sulfate by filtration, the solvent was removed by rotary evaporation to give a yellow viscous liquid; silica gel column, eluted agent petroleum ether rotary evaporation to give a viscous yellow liquid, yield 83%.
82%	With N-Bromosuccinimide In dichloromethane at 20℃; for 12h;	1.2 Synthesis of Intermediate A-2 7.10 g (29.2 mmol) of Intermediate A-1 was completely dissolved in 100 mL of CH2Cl2 (methylene chloride), 5.20 g (29.2 mmol) of N-bromosuccinimide was added thereto, and the resultant solution was stirred at room temper store for 12 hours. 80 mL of water was added to the reaction solution, and then an extraction was performed thereon three times by using 60 mL of methylene chloride. An organic layer obtained therefrom was dried by using magnesium sulfate, a solvent was evaporated therefrom, and then, the resultant solution was re-crystallized by using methanol to obtain 7.70 g (yield 82%) of Intermediate A-2.
80%	With N-Bromosuccinimide In N,N-dimethyl-formamide at 20℃;
80%	With N-Bromosuccinimide In N,N-dimethyl-formamide at 0 - 20℃;
74%	With N-Bromosuccinimide In dichloromethane at 20℃; for 24h;	Synthesis of 3-bromo-9-phenyl-9H-carbazole Sub-1-1 (48.66 g, 200 mmol) obtained in the above synthesis was dissolved in 600 mL of methylene chloride. NBS (N-bromosuccinimide) (59.4 g,210 mmol) was slowly added thereto and stirred at room temperature for 24 hours. After the reaction was completed, 300 mL of 5% HCl was added, and 300 mL of water was added to remove residual NBS. The organic layer wasextracted with ether and water, dried over MgSO 4 and concentrated. To obtain 47.7 (74%) of the product.
74.3%	With N-Bromosuccinimide In dichloromethane at 20℃; for 24h;	1 Sub 1-2 Synthesis: 3-bromo-9-phenyl-9H-carbazole Sub 1-1 (46 g, 200 mmol) obtained in the above synthesis was dissolved in 600 mL of methylene chloride,NBS (N-bromosuccimide) (38.5 g, 220 mmol) was slowly added,The mixture is stirred at room temperature for 24 hours.After the reaction was completed, 300 mL of 5% HCl was added,300 mL of water was added,After removing the remaining NBS,ether and water. The organic layer was dried over MgSO4 and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 47.7 g (74.3%) of the product.
69.7%	With N-Bromosuccinimide; dibenzoyl peroxide In dichloromethane at 20℃; for 12h; Inert atmosphere;
62.4%	With N-Bromosuccinimide In tetrahydrofuran at 20℃; for 24h; Inert atmosphere;	9 Compound 9-4 63.4 g (260.58 mmol) was put into a 1-neck flask, which is then filled with argon under vacuum ambient. Tetrahydrofurane 500 mL was added thereinto, and then stirred at 0 for 10 minutes. NBS 7.35 g (40.78 mmol) was added thereinto, and stirred at room temperature for 1 day. Upon completion of the reaction, the resultant reaction material was extracted with distilled water and EA. The organic layer was dried over MgSO4 and the solvent was removed by a rotary evaporator, followed by column chromatography using hexane and EA as a developing solvent, thereby obtaining Compound 9-5 52.4 g (162.63 mmol, 62.4%).
62%	With N-Bromosuccinimide In N,N-dimethyl-formamide at 20℃; for 12h;	5 55 g (226.1 mmol) of intermediate product 7, 44.2 g (248.7 mmol) of NBS was suspended in 500 ml of dimethylformamide, followed by stirring at room temperature for 12 hours. Add the reaction mixture to distilled water and stir at room temperature for 6 hours. The filtrate is filtered under reduced pressure, the solid is dissolved in methyl alcohol, and the mixture is stirred at room temperature. After filtration under reduced pressure, 45 g (yield: 62%) of the intermediate product (8) was obtained.
42%	With N-Bromosuccinimide In N,N-dimethyl-formamide at 0 - 20℃;
	With N-Bromosuccinimide In N,N-dimethyl-formamide at 0℃;
	With N-Bromosuccinimide In N,N-dimethyl-formamide
	With N-Bromosuccinimide In chloroform; N,N-dimethyl-formamide at 0℃; Darkness;
	With N-Bromosuccinimide In dichloromethane
	With N-Bromosuccinimide In ethyl acetate
	With N-Bromosuccinimide In N,N-dimethyl-formamide at 0℃;	1 Synthesis of 3-bromo-9-phenylcarbazole. NBS (19.31 g, 109 mmol) in DMF was added to 9-phenyl-9H-carbazole (24 g, 99 mmol) in 200 mL at 0 °C dropwise. The reaction was monitored by HPLC. The reaction was quenched by adding 500 mL of water after 2 h. After stirring at room temperature for 24h, the clear solution was decanted and solid residue was dissolved in dichloromethane and washed with water and LiCl solution. The solution was dried with MgS04 and the solvent was evaporated. The residue was used for the next step without further purification. The product contains starting material, monobromo, and dibromo. 31 g of product was obtained.
	With N-Bromosuccinimide In tetrahydrofuran at 0℃;
	With N-Bromosuccinimide In dichloromethane
	With N-Bromosuccinimide In tetrahydrofuran
	With N-Bromosuccinimide In N,N-dimethyl-formamide	2 Preparation Example 2: Synthesis of Intermediate 2 g of 9-phenylcarbazole and 1.46 g of N-bromosuccinimide were dissolved in N.N-dimethylformamide, and the resulting solution was brominated, yielding 3-bromo-9-phenyl carbazole compound as an intermediate. By the same method, a 3,6-dibromo-9-phenyl carbazole compound was synthesized.
	With N-Bromosuccinimide; acetic acid In chloroform at 0℃; for 18h;	Synthesis of Compound 2a Compound 1a (4.40 g, 18.1 mmol) was dissolved in a mixed solvent of chloroform (120 mL) and acetic acid (30 mL). The solution was cooled to 0 ° C., N-bromosuccinimide (3.21 g, 18.0 mmol) was added in three portions, stirred at 0 ° C. for 18 hours and then extracted with chloroform. The crude product was purified by column chromatography (silica gel, hexane / chloroform = 9: 1)
	With N-Bromosuccinimide In dichloromethane at 20℃; for 24h;	General procedure: Sub 1-2 (1 eq.) was dissolved in methylenechloride, and then, N-bromosuccimide (N135) (1.1 eq.) was slowly added thereto, and then, the mixture was stirred at room temperature for 24 hours. When the reaction stopped, 5% concentration of HC1 was added thereto, and then water was added thereto to remove the residual NBS. Thereafier, the resultantsolution was extracted with ether and water, and an organiclayer was dried and concentrated by using Mg504, and theobtained organic material was purified by silicagel colunmchromatography and re-crystallized to obtain Sub 1-3.
	With N-Bromosuccinimide In chloroform at 20℃;	4.2. Synthesis of L2 9-Phenyl-9H-carbazole was prepared through Ullmanncoupling of carbazole (2.0 g, 0.012 mol) and iodobenzene (2.0 ml,0.018 mol) with a catalytic amount of copper iodide (1.59 g,8.372 mmol) and 1,10-phenanthroline (1.66 g, 8.372 mmol). 9-Phenyl-9H-carbazole (2.04 g, 8.372 mmol) reacted with NBS (1.56 g, 8.791 mmol) to give 3-bromo-9-phenyl-9H-carbazole (2.67 g, 8.287 mmol) which was then converted into its boronic acid derivative (0.95 g, 3.315 mmol) and that subsequently reacted with 2-bromothiazole (0.24 ml, 2.652 mmol). The 2-(9-phenyl-9H-carbazol-3-yl)thiazole ligand L2 was formed as a pale yellow powder (56%). Spectral data: MS (MALDI-TOF): m/z 326.41 (M+). 1H NMR (CDCl3): δ (ppm) 8.78 (d, J=1.4 Hz, 1H, Ar), 8.22 (d,J=6.9 Hz, 1H, Ar), 8.03-8.01 (m, 1H, Ar), 7.88 (d, J=3.2 Hz, 1H, Ar),7.65-7.61 (m, 2H, Ar), 7.59-7.56 (m, 2H, Ar), 7.52-7.48 (m, 1H, Ar),7.45-7.40 (m, 3H, Ar), 7.35-7.32 (m, 1H, Ar), 7.30 (d, J=3.2 Hz, 1H,Ar).
	With N-Bromosuccinimide In chloroform at 20℃; for 5h;	1.1 Preparation of formula A-1 N-Phenylcarbazole (27 g, 111 mmol) was dissolved in chloroform (200 mL), N-bromosuccinimide (19.7 g, 111 mmol) was added and the mixture was stirred at room temperature for 5 hours.Distilled water was added to the reaction solution, and the organic layer was extracted. After concentrating the reaction solution, the following reaction was carried out without purification.
	With N-Bromosuccinimide In N,N-dimethyl-formamide at 80℃; Darkness; Cooling with ice;
40 g	With N-Bromosuccinimide In N,N-dimethyl-formamide at 20℃; for 12h;	3.2 Compound 9-phenyl-9H-carbazole 37 g (114 mmol),22 g (126 mmol) of NBS were dissolved in dimethylformamideAnd the mixture was stirred at room temperature for 12 hours.Add the reaction mixture to distilled water and stir at room temperature for 6 hours.The filtrate is filtered under reduced pressure, the solid is dissolved in methyl alcohol, and the mixture is stirred at room temperature.After filtration under reduced pressure, 40 g of 3-bromo-9-phenyl-9H-carbazole was obtained
	With bromine; acetic acid at 20℃;
	With N-Bromosuccinimide In dichloromethane at 20℃; for 24h;	Synthesis of Sub 1-3 General procedure: After dissolving Sub 1-2 (1 equivalent) in methylene chloride,After slowly adding NBS (N-bromosuccimide) (1.1 equivalent),It was stirred at room temperature for 24 hours.When the reaction was completed, 5% concentration of HCl was added, and then water was added to remove residual NBS.After extraction with ether and water, the organic layer was dried over MgSO 4, concentrated, and the resulting organic material was subjected to silica gel column chromatography and recrystallization to obtain Sub 1-3.
	With N-Bromosuccinimide

Reference： [1]Current Patent Assignee: SEMICONDUCTOR ENERGY LABORATORY CO.,LTD. - US2009/174321, 2009, A1
[2]Current Patent Assignee: SEMICONDUCTOR ENERGY LABORATORY CO.,LTD. - WO2009/72587, 2009, A1 Location in patent: Page/Page column 142
[3]Current Patent Assignee: SEMICONDUCTOR ENERGY LABORATORY CO.,LTD. - WO2009/81800, 2009, A1 Location in patent: Page/Page column 129
[4]Current Patent Assignee: SEMICONDUCTOR ENERGY LABORATORY CO.,LTD. - US2010/99890, 2010, A1 Location in patent: Page/Page column 42
[5]Current Patent Assignee: SEMICONDUCTOR ENERGY LABORATORY CO.,LTD. - EP2354135, 2011, A1 Location in patent: Page/Page column 75
[6]Current Patent Assignee: TIANMA MICROELECTRONICS CO., LTD. - CN109096246, 2018, A Location in patent: Paragraph 0086; 0087; 0088; 0089
[7]Current Patent Assignee: TIANMA MICROELECTRONICS CO., LTD. - CN109232598, 2019, A Location in patent: Paragraph 0094; 0095; 0096; 0097
[8]Current Patent Assignee: TIANMA MICROELECTRONICS CO., LTD. - CN109293645, 2019, A Location in patent: Paragraph 0094-0099
[9]Current Patent Assignee: TIANMA MICROELECTRONICS CO., LTD. - CN110256415, 2019, A Location in patent: Paragraph 0123-0127
[10]Feng, Guo-Liang; Ji, Shun-Jun; Lai, Wen-Yong; Huang, Wei [Synlett, 2006, # 17, p. 2841 - 2845]
[11]Location in patent: scheme or table Liu, Yu; Wang, Hai-Ying; Chen, Gang; Xu, Xiao-Ping; Ji, Shun-Jun [Australian Journal of Chemistry, 2009, vol. 62, # 8, p. 934 - 940]
[12]Current Patent Assignee: HODOGAYA CHEMICAL CO LTD - US2018/72753, 2018, A1 Location in patent: Paragraph 0247-0248
[13]Current Patent Assignee: SEMICONDUCTOR ENERGY LABORATORY CO.,LTD. - WO2006/70912, 2006, A1 Location in patent: Page/Page column 52; 53
[14]Current Patent Assignee: SEMICONDUCTOR ENERGY LABORATORY CO.,LTD. - WO2006/70907, 2006, A1 Location in patent: Page/Page column 68-69
[15]Current Patent Assignee: SEMICONDUCTOR ENERGY LABORATORY CO.,LTD. - US2007/80630, 2007, A1 Location in patent: Page/Page column 62; 63
[16]Current Patent Assignee: SEMICONDUCTOR ENERGY LABORATORY CO.,LTD. - US2007/96639, 2007, A1 Location in patent: Page/Page column 101-102
[17]Current Patent Assignee: SEMICONDUCTOR ENERGY LABORATORY CO.,LTD. - US2007/149784, 2007, A1 Location in patent: Page/Page column 68
[18]Current Patent Assignee: SEMICONDUCTOR ENERGY LABORATORY CO.,LTD. - US2007/161793, 2007, A1
[19]Current Patent Assignee: SEMICONDUCTOR ENERGY LABORATORY CO.,LTD. - WO2007/43354, 2007, A1 Location in patent: Page/Page column 87-88
[20]Current Patent Assignee: SEMICONDUCTOR ENERGY LABORATORY CO.,LTD. - US2007/222374, 2007, A1
[21]Current Patent Assignee: SEMICONDUCTOR ENERGY LABORATORY CO.,LTD. - WO2007/125934, 2007, A1 Location in patent: Page/Page column 135-136
[22]Current Patent Assignee: SEMICONDUCTOR ENERGY LABORATORY CO.,LTD. - US2008/79354, 2008, A1
[23]Current Patent Assignee: SEMICONDUCTOR ENERGY LABORATORY CO.,LTD. - US2008/86012, 2008, A1 Location in patent: Page/Page column 67
[24]Current Patent Assignee: SEMICONDUCTOR ENERGY LABORATORY CO.,LTD. - US2008/103315, 2008, A1 Location in patent: Page/Page column 82
[25]Current Patent Assignee: SEMICONDUCTOR ENERGY LABORATORY CO.,LTD. - US2009/4506, 2009, A1
[26]Current Patent Assignee: SEMICONDUCTOR ENERGY LABORATORY CO.,LTD. - WO2007/29530, 2007, A1 Location in patent: Page/Page column 62-63
[27]Current Patent Assignee: SEMICONDUCTOR ENERGY LABORATORY CO.,LTD. - US2012/242936, 2012, A1 Location in patent: Page/Page column 48-49
[28]Current Patent Assignee: SEMICONDUCTOR ENERGY LABORATORY CO.,LTD. - US8288012, 2012, B2 Location in patent: Page/Page column 156-157
[29]Current Patent Assignee: SINOSTEEL NEW MATERIALS; SINOSTEEL GROUP NANJING NEW MATERIAL RES INSTITUTE - CN112209869, 2021, A Location in patent: Paragraph 0049-0084
[30]Current Patent Assignee: LG CHEM CO.,LTD. - EP2343277, 2011, A2 Location in patent: Page/Page column 42
[31]Current Patent Assignee: SAMSUNG ELECTRONICS CO.,LTD.; Samsung Display (in: Samsung) - KR2016/30003, 2016, A Location in patent: Paragraph 0353; 0354; 0357; 0358
[32]Current Patent Assignee: SAMSUNG ELECTRONICS CO.,LTD.; Samsung Display (in: Samsung) - KR2015/18229, 2015, A Location in patent: Paragraph 0323-0324
[33]Current Patent Assignee: SAMSUNG ELECTRONICS CO.,LTD.; Samsung Display (in: Samsung) - KR2015/69346, 2015, A Location in patent: Paragraph 0401; 0402; 0405; 0406
[34]Current Patent Assignee: SAMSUNG ELECTRONICS CO.,LTD.; Samsung Display (in: Samsung) - KR2015/27897, 2015, A Location in patent: Paragraph 0371;0375;0376
[35]Current Patent Assignee: SAMSUNG ELECTRONICS CO.,LTD.; Samsung Display (in: Samsung) - KR2015/25259, 2015, A Location in patent: Paragraph 0226; 0229; 0230
[36]Current Patent Assignee: Samsung Display (in: Samsung); SAMSUNG ELECTRONICS CO.,LTD. - KR2015/28860, 2015, A Location in patent: Paragraph 0347; 0351; 0352
[37]Current Patent Assignee: Samsung Display (in: Samsung); SAMSUNG ELECTRONICS CO.,LTD. - CN106565689, 2017, A Location in patent: Paragraph 0317; 0318; 0322; 0323; 0324
[38]Kang, Seokwoo; Jung, Hyocheol; Lee, Hayoon; Lee, Suji; Jung, Mina; Lee, Jaehyun; Chul Kim, Young; Park, Jongwook [Dyes and Pigments, 2018, vol. 156, p. 369 - 378]
[39]Guo, Runda; Huang, Zhi; Liu, Wei; Wang, Lei; Wang, Yaxiong; Xiang, Songpo; Ye, Shaofeng; Zhang, Qing [Journal of Materials Chemistry C, 2020, vol. 8, # 11, p. 3705 - 3714]
[40]Current Patent Assignee: VALIANT CO., LTD. - CN104370904, 2016, B Location in patent: Paragraph 0062; 0065; 0066
[41]Current Patent Assignee: Samsung Display (in: Samsung); SAMSUNG ELECTRONICS CO.,LTD. - KR2015/28935, 2015, A Location in patent: Paragraph 0330; 0333; 0334
[42]Kim, Se Hun; Cho, Illhun; Sim, Mun Ki; Park, Sanghyuk; Park, Soo Young [Journal of Materials Chemistry, 2011, vol. 21, # 25, p. 9139 - 9148]
[43]Location in patent: scheme or table Chen, You-Ming; Hung, Wen-Yi; You, Hong-Wei; Chaskar, Atul; Ting, Hao-Chun; Chen, Hsiao-Fan; Wong, Ken-Tsung; Liu, Yi-Hung [Journal of Materials Chemistry, 2011, vol. 21, # 38, p. 14971 - 14978]
[44]Current Patent Assignee: DUKSAN HI METAL CO LTD; DUK SAN NEOLUX CO., LTD. - TWI580673, 2017, B Location in patent: Page/Page column 38; 39
[45]Current Patent Assignee: DUK SAN NEOLUX CO., LTD. - KR2019/40150, 2019, A Location in patent: Paragraph 0065; 0071-0073
[46]Location in patent: experimental part Park, Jung Hwan; Kim, Eun Kyung; El-Deeb, Ibrahim M.; Jung, Su Jin; Choi, Dae Hyuk; Kim, Dong-Ha; Yoo, Kyung Ho; Kwon, Jang Hyuk; Lee, So Ha [Bulletin of the Korean Chemical Society, 2011, vol. 32, # 3, p. 841 - 846]
[47]Current Patent Assignee: DOW INC - EP2857395, 2015, A1 Location in patent: Paragraph 0080
[48]Current Patent Assignee: SOULBRAIN CO.,LTD. - KR2017/58874, 2017, A Location in patent: Paragraph 0077; 0099; 0100
[49]Grisorio, Roberto; Dell'Aquila, Antonio; Romanazzi, Giuseppe; Suranna, Gian Paolo; Mastrorilli, Piero; Cosma, Pynalisa; Acierno, Domenico; Amendola, Eugenio; Ciccarella, Giuseppe; Nobile, Cosimo Francesco [Tetrahedron, 2006, vol. 62, # 4, p. 627 - 634]
[50]Feng, Guo-Liang; Lai, Wen-Yong; Ji, Shun-Jun; Huang, Wei [Tetrahedron Letters, 2006, vol. 47, # 39, p. 7089 - 7092]
[51]Wong, Wai-Yeung; Ho, Cheuk-Lam; Gao, Zhi-Qiang; Mi, Bao-Xiu; Chen, Chin-Hsin; Cheah, Kok-Wai; Lin, Zhenyang [Angewandte Chemie - International Edition, 2006, vol. 45, # 46, p. 7800 - 7803]
[52]Location in patent: scheme or table Feng, Guo-Liang; Ji, Shun-Jun; Geng, Li-Jun; Bian, Bing; Liu, Yu [Journal of Chemical Research, 2008, # 3, p. 137 - 140]
[53]Location in patent: scheme or table Ho, Cheuk-Lam; Wong, Wai-Yeung; Yao, Bing; Xie, Zhiyuen; Wang, Lixiang; Lin, Zhenyang [Journal of Organometallic Chemistry, 2009, vol. 694, # 17, p. 2735 - 2749]
[54]Current Patent Assignee: SEMICONDUCTOR ENERGY LABORATORY CO.,LTD. - WO2007/29530, 2007, A1 Location in patent: Page/Page column 62-63
[55]Current Patent Assignee: UNIVERSAL DISPLAY CORP - WO2011/137072, 2011, A1 Location in patent: Page/Page column 43
[56]Location in patent: scheme or table Bin, Jong-Kwan; Hong, Jong-In [Organic electronics, 2011, vol. 12, # 5, p. 802 - 808]
[57]Location in patent: scheme or table Yu, Fang-Fang; Fan, He-Liang; Huang, Hai-Fang; Cao, Qian-Yong; Dai, Yan-Feng; Gao, Xi-Cun; Shang, Yu-Zhu; Zhang, Min-Yan; Long, Li; Xu, Hong; Li, Xi-Feng; Wei, Bin [Inorganica Chimica Acta, 2012, vol. 390, p. 119 - 122]
[58]Huang, Bin; Yin, Zhihui; Ban, Xinxin; Jiang, Wei; Dai, Yu; Zhang, Junya; Liu, Yuanyuan; Yang, Yaping; Sun, Yueming [Dyes and Pigments, 2015, vol. 117, p. 141 - 148]
[59]Current Patent Assignee: SK CHEMICALS CO LTD - JP5663566, 2015, B2 Location in patent: Paragraph 0159
[60]Current Patent Assignee: SAMSUNG ELECTRONICS CO.,LTD.; CHIBA UNIVERSITY - JP2015/218136, 2015, A Location in patent: Paragraph 0064; 0066
[61]Current Patent Assignee: SAMSUNG ELECTRONICS CO.,LTD.; Samsung Display (in: Samsung) - US9515265, 2016, B2 Location in patent: Page/Page column 104; 108
[62]Chau, Nga-Yuen; Ho, Po-Yu; Ho, Cheuk-Lam; Ma, Dongge; Wong, Wai-Yeung [Journal of Organometallic Chemistry, 2017, vol. 829, p. 92 - 100]
[63]Current Patent Assignee: LG CHEM CO.,LTD. - KR2017/63363, 2017, A Location in patent: Paragraph 0314-0315; 0321-0323
[64]Zhang, Cheng; Li, Yang; Zhou, Yan; Zhang, Qijian; Li, Hua; Lu, Jianmei [Chemical Communications, 2018, vol. 54, # 75, p. 10610 - 10613]
[65]Current Patent Assignee: LG DISPLAY CO.,LTD. - KR2019/12678, 2019, A Location in patent: Paragraph 0162; 0167-0170
[66]Current Patent Assignee: VALIANT CO., LTD. - CN110551135, 2019, A Location in patent: Paragraph 0058; 0062; 0063
[67]Current Patent Assignee: Samsung Display (in: Samsung); SAMSUNG ELECTRONICS CO.,LTD. - KR102223682, 2021, B1 Location in patent: Paragraph 0223; 0229-0230
[68]Yi, Rong-Huei; Lei, Ya-Chun; Tseng, Yeh-Hsiang; Lin, Yi-Fan; Cheng, Yen-Chia; Fang, Yu-Chuan; Ho, Cheng-Yung; Tsai, Wei-Wen; Chang, Chih-Hao; Lu, Chin-Wei [Chemistry - A European Journal, 2022, vol. 28, # 1]

11
[ 1150-62-5 ]
[ 1153-85-1 ]
[ 57103-20-5 ]

Reference： [1]Helvetica Chimica Acta,2006,vol. 89,p. 1123 - 1139

12
[ 945391-00-4 ]
[ 62-53-3 ]
[ 1150-62-5 ]

Yield	Reaction Conditions	Operation in experiment
86%	With potassium phosphate; di-tert-butyl (2'-methyl-[1,1'-biphenyl]-2-yl)phosphine In toluene at 100℃; for 24h;

Reference： [1]Kawaguchi, Keiko; Nakano, Koji; Nozaki, Kyoko [Journal of Organic Chemistry, 2007, vol. 72, # 14, p. 5119 - 5128]

13
[ 1150-62-5 ]
[ 25603-67-2 ]
9-phenyl-3,6-bis(9-phenyl-9H-fluoren-9-yl)carbazole [ No CAS ]

Reference： [1]Organic Letters,2006,vol. 8,p. 2799 - 2802

14
[ 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 ]

Reference： [1]Organic Letters,2006,vol. 8,p. 2799 - 2802

15
[ 122-39-4 ]
[ 583-53-9 ]
[ 1150-62-5 ]

Yield	Reaction Conditions	Operation in experiment
96%	With sodium t-butanolate; tricyclohexylphosphine In toluene at 105℃; for 18h;
96%	With palladium diacetate; sodium t-butanolate; tricyclohexylphosphine In toluene at 105℃; for 18h; Inert atmosphere; regioselective reaction;

Reference： [1]Ackermann, Lutz; Althammer, Andreas [Angewandte Chemie - International Edition, 2007, vol. 46, # 10, p. 1627 - 1629]
[2]Location in patent: scheme or table Ackermann, Lutz; Althammer, Andreas; Mayer, Peter [Synthesis, 2009, # 20, p. 3493 - 3503]

16
[ 694-80-4 ]
[ 122-39-4 ]
[ 1150-62-5 ]

Yield	Reaction Conditions	Operation in experiment
88%	With sodium t-butanolate; tricyclohexylphosphine In toluene at 105℃; for 18h;
88%	With palladium diacetate; sodium t-butanolate; tricyclohexylphosphine In toluene at 105℃; for 18h; Inert atmosphere; regioselective reaction;

Reference： [1]Ackermann, Lutz; Althammer, Andreas [Angewandte Chemie - International Edition, 2007, vol. 46, # 10, p. 1627 - 1629]
[2]Location in patent: scheme or table Ackermann, Lutz; Althammer, Andreas; Mayer, Peter [Synthesis, 2009, # 20, p. 3493 - 3503]

17
[ 122-39-4 ]
[ 95-50-1 ]
[ 1150-62-5 ]

Yield	Reaction Conditions	Operation in experiment
85%	With sodium t-butanolate; tricyclohexylphosphine In toluene at 105℃; for 18h;
85%	With palladium diacetate; sodium t-butanolate; tricyclohexylphosphine In toluene at 105℃; for 18h; Inert atmosphere; regioselective reaction;

Reference： [1]Ackermann, Lutz; Althammer, Andreas [Angewandte Chemie - International Edition, 2007, vol. 46, # 10, p. 1627 - 1629]
[2]Location in patent: experimental part Ackermann, Lutz; Althammer, Andreas; Mayer, Peter [Synthesis, 2009, # 20, p. 3493 - 3503]

18
[ 1150-62-5 ]
[ 57103-21-6 ]

Yield	Reaction Conditions	Operation 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.

Reference： [1]Patent: WO2006/70912,2006,A1 .Location in patent: Page/Page column 58; 59
[2]Patent: WO2006/43647,2006,A1 .Location in patent: Page/Page column 59-60
[3]Patent: CN109320449,2019,A .Location in patent: Paragraph 0210; 0211; 0212; 0213
[4]Patent: WO2012/25510,2012,A1 .Location in patent: Page/Page column 23
[5]Patent: EP2433928,2012,A1 .Location in patent: Page/Page column 16-17
[6]Journal of Chemical Research,2017,vol. 41,p. 79 - 81
[7]European Journal of Inorganic Chemistry,2007,p. 3868 - 3880
[8]Patent: US2008/312453,2008,A1 .Location in patent: Page/Page column 15
[9]Patent: EP2100880,2009,A1 .Location in patent: Page/Page column 17-18
[10]Dyes and Pigments,2014,vol. 100,p. 66 - 72
[11]Patent: CN106631987,2017,A .Location in patent: Paragraph 0014-0015

19
[ 1150-62-5 ]
[ 502161-03-7 ]

Yield	Reaction Conditions	Operation 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.

Reference： [1]Patent: EP1661888,2006,A1 .Location in patent: Page/Page column 11
[2]Patent: US2008/174237,2008,A1 .Location in patent: Page/Page column 13-14
[3]Patent: EP2149555,2010,A1 .Location in patent: Page/Page column 19
[4]Patent: KR101791161,2017,B1 .Location in patent: Paragraph 0116; 0123-0128
[5]Patent: EP2738166,2014,A1 .Location in patent: Paragraph 0162
[6]Patent: US8865322,2014,B2 .Location in patent: Page/Page column 25; 26; 38; 39
[7]Patent: KR2016/19744,2016,A .Location in patent: Paragraph 0058; 0061; 0062; 0079; 0082; 0083
[8]Patent: KR2016/19745,2016,A .Location in patent: Paragraph 0047; 0051-0052
[9]Patent: WO2006/70912,2006,A1 .Location in patent: Page/Page column 54
[10]Patent: WO2006/43647,2006,A1 .Location in patent: Page/Page column 56
[11]Patent: WO2006/70912,2006,A1 .Location in patent: Page/Page column 54; 55
[12]Patent: US2007/31701,2007,A1
[13]Patent: EP2085382,2009,A1 .Location in patent: Page/Page column 38
[14]Patent: EP2100880,2009,A1 .Location in patent: Page/Page column 14-15
[15]Patent: EP2468725,2012,A1 .Location in patent: Page/Page column 119
[16]Patent: EP2484665,2012,A1 .Location in patent: Page/Page column 62
[17]Patent: EP2502908,2012,A1 .Location in patent: Page/Page column 41
[18]Patent: US2012/273766,2012,A1 .Location in patent: Page/Page column 70
[19]Patent: EP2527334,2012,A1 .Location in patent: Page/Page column 89
[20]Patent: EP2617712,2013,A1 .Location in patent: Paragraph 0157
[21]Patent: EP2690093,2014,A1 .Location in patent: Paragraph 0130

20
[ 1150-62-5 ]
[ 145771-93-3 ]

Yield	Reaction Conditions	Operation in experiment
	With trichlorophosphate In N,N-dimethyl-formamide; toluene	8.1 (1) (1) 3,6-Diformyl-9-phenylcarbazole (2c) 23.0 g (93.1 mmol) of 9-phenylcarbazole (4c) (manufactured by Aldrich Co.), 49.0 g (670.5 mmol) of DMF, 25.4 g (186.2 mmol) of zinc chloride, 85.7 g (558.7 mmol) of phosphorus oxychloride and 230 ml of toluene were allowed to react and after treated in the same manner as with Example 1 (1) to obtain 11.8 g of 3,6-diformyl-9-phenylcarbazole (2c). Yield; 42.2%, m.p.; 193°-194° C. MS; 299(M+), 270, 241, 84 1 H-NMR (δ; ppm in CDCl3); 7.46 (d, J=8.5 Hz, 2H), 7.53-7.62 (m, 3H), 7.66-7.71 (m, 2H), 8.02 (dd, J=8.6 Hz, J=1.6 Hz, 2H), 8.72 (s, 2H), 10.15 (s, 2H)
	Multi-step reaction with 2 steps 1: N-Bromosuccinimide / 12 h / 20 °C / Inert atmosphere 2: n-butyllithium / tetrahydrofuran / 7 h / -78 °C / Inert atmosphere
	Multi-step reaction with 2 steps 1.1: bromine; acetic acid / dichloromethane / 20 °C / Cooling with ice 2.1: n-butyllithium / tetrahydrofuran / 1 h / Inert atmosphere; Cooling with acetone-dry ice 2.2: 20 °C

Reference： [1]Current Patent Assignee: TAKASAGO INTERNATIONAL CORPORATION - US5736284, 1998, A
[2]Gao, Zhao; Wang, Zhiming; Shan, Tong; Liu, Yulong; Shen, Fangzhong; Pan, Yuyu; Zhang, Huanhuan; He, Xin; Lu, Ping; Yang, Bing; Ma, Yuguang [Organic electronics, 2014, vol. 15, # 11, p. 2667 - 2676]
[3]Current Patent Assignee: JILIN OLED OPTICAL AND ELECTRONIC MATERIALS CO LTD - CN104650044, 2017, B

21
[ 85-44-9 ]
[ 1150-62-5 ]
C₂₆H₁₇NO₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: phthalic anhydride; N-phenylcarbazole With aluminum (III) chloride In dichloromethane at 0 - 20℃; Stage #2: With hydrogenchloride In dichloromethane; water Cooling with ice;
10 g	Stage #1: phthalic anhydride With aluminum (III) chloride In 1,2-dichloro-ethane at 0℃; for 0.5h; Stage #2: N-phenylcarbazole With aluminum (III) chloride In 1,2-dichloro-ethane at 0 - 20℃;	25.1 A mixture of 7 g (23.8 mmol) of phthalic anhydride, 6.4 g (23.8 mmol) of anhydrous aluminum chloride was dissolved in 80 ml of dichloroethane, After stirring at 0 ° C for 30 min, 8 g (48 mmol) of 9-phenylcarbazole was added, 6.4 g (23.8 mmol) of anhydrous aluminum chloride. Stirred at 0-2 & lt; 0 & gt; C for 12 h, Then react at room temperature overnight. Then, 100 g of an ice-water mixture was added, 40ml of concentrated hydrochloric acid, continue to stir for 20min after filtration products, The resulting crystals were washed with 100 ml of deionized water to give colorless crystals (60-1) and 10 g

Reference： [1]Location in patent: experimental part Senthil Kumar, Natarajan; Arul Clement; Mohanakrishnan, Arasambattu K. [Tetrahedron, 2009, vol. 65, # 4, p. 822 - 830]
[2]Current Patent Assignee: CHANGCHUN HAIPU RUNSI TECHNOLOGY CO LTD - CN107188873, 2017, A Location in patent: Paragraph 0107; 0108; 0109

22
[ 86-74-8 ]
[ 108-90-7 ]
[ 1150-62-5 ]

Yield	Reaction Conditions	Operation in experiment
99%	Stage #1: 9H-carbazole With methylmagnesium chloride In tetrahydrofuran; 5,5-dimethyl-1,3-cyclohexadiene at 5 - 20℃; for 0.166667h; Inert atmosphere; Stage #2: chlorobenzene With PdCl(π-allyl)(cyclohexyl-(1-methyl-2,2-diphenylcyclopropylphophine)) In tetrahydrofuran; 5,5-dimethyl-1,3-cyclohexadiene at 108 - 112℃; for 0.5h; Inert atmosphere;
94%	With di-tert-butyl(2,2-diphenyl-1-methyl-1-cyclopropyl)phosphine; bis(η3-allyl-μ-chloropalladium(II)); sodium t-butanolate In 5,5-dimethyl-1,3-cyclohexadiene at 120℃; for 3h; Inert atmosphere;
88%	With 5-(di-tert-butylphosphino)-1′, 3′, 5′-triphenyl-1′H-[1,4′]bipyrazole; bis[chloro(1,2,3-trihapto-allylbenzene)palladium(II)]; sodium t-butanolate In toluene at 110℃; for 12h; Inert atmosphere; Glovebox;

86%	With sodium t-butanolate In toluene at 110℃; for 24h;
85%	With bis(1,5-cyclooctadiene)nickel ⁽⁰⁾; sodium t-butanolate at 100 - 110℃; for 12h;
71%	With potassium carbonate In N,N-dimethyl-formamide at 120℃; for 24h; Inert atmosphere;	4.2 General procedure for Buchwald-Hartwig C-N cross coupling reaction using PNP-SSS catalyst General procedure: Aryl halide (1.0mmol), amine (1.5-2.0mmol), PNP-SSS (0.6mol%; 0.023g), K2CO3 (2mmol), and DMF (3.0mL) was placed in a 25mL flask equipped with a magnetic stirring bar and heated at 120°C under nitrogen gas. The reaction was then monitored by TLC until the consumption of aryl halide was detected. After completion of the reaction 5mL of water and 5mL of ethyl acetate were added to the reaction mixture. The organic solution was extracted and dried over anhydrous Na2SO4. After removing of organic solvent the crude product was obtained. For further purification the chromatography technique was used.
57%	With copper 8-hydroxyquinolinate; sodium hydroxide In 5,5-dimethyl-1,3-cyclohexadiene at 50 - 110℃; for 10.5h;	5.1; 5.2 Example 5 (1) Coupling reaction process:Under the protection of nitrogen, a stirrer, thermometer,Carbazole (1.0mol, 167.2g) was added to the reflux condenser and dry 1000mL four-necked round bottom flask in sequence,Copper 8-quinolinolate (0.01mol, 3.52g), sodium hydroxide (0.5mol, 20g),Chlorobenzene (1.05mol, 106.5mL) and xylene (500mL), then heated to 50-60°C and stirred for 30 minutes; after mixing uniformly, the reaction was continued for 10 hours at a heating rate of 3/min to 110°C, during which liquid Phase detection of carbazole conversion rate. After the reaction is complete (liquid phase detection carbazole conversion rate ≥99%), stop the reaction, and wait until the temperature of the reaction system is reduced to 60°C, distill DMSO off under reduced pressure, add ethyl acetate to the solid residue to dissolve, and filter under vacuum , Filter cake A is retained, the filtrate is washed with water and extracted, the organic layer extract is distilled under reduced pressure to remove ethyl acetate to obtain a crude product, and the crude product is recrystallized from ethanol to obtain a light yellow solid N-phenylcarbazole 138.8g (HPLC detection content ≥99%), the yield is 57.0%.
35%	With potassium <i>tert</i>-butylate; C₃₆H₃₂Cu₂Fe₂I₂Se₄ In acetonitrile at 20℃; for 12h; Schlenk technique; Inert atmosphere; Irradiation;	2.4. Evaluation of photocatalytic activity General procedure: Carbazole (0.034 g, 0.2 mmol), t-BuOK (0.049 g, 0.4 mmol), C1 were placed in a 25 mL Schlenk tube and it was evacuated andpurged with nitrogen three times. MeCN (2 mL) and aryl iodides were added in nitrogen atmosphere. Xenon Lamp with the powerdensity of 290 mW/cm2 was employed as the light source. Afterirradiation with a Xenon Lamp (290 mW/cm2) for 12 h at ambienttemperature, the reaction mixture was concentrated in vacuumfollowed by addition of water (5 mL). The resulting mixture wasextracted with EtOAc (3 5 mL). The combined organic layerwas dried over MgSO4 and filtered, then the filtrate was concentratedin vacuum. The crude mixture was purified by silica gel flashcolumn chromatography (petroleum ether/EtOAc, v:v = 20:1) toafford the desired product.
32%	With potassium hydroxide In dimethyl sulfoxide at 135℃; for 48h; Inert atmosphere; Sealed tube;	3.3. Typical Experiment Procedure for the Synthesis of 5a General procedure: To a 50 mL screw-capped thick-walled Pyrex tube equipped with a magnetic stirrer, carbazole (4a,167.2 mg, 1.0 mmol), chlorobenzene (2b, 281.4 mg, 2.5 mmol), KOH (168.2 mg, 3.0 mmol) and DMSO(5.0 mL) were added sequentially under nitrogen atmosphere. The tube was then sealed and stirred at135 °C in an oil bath for 48 h. After removal of the solvent under reduced pressure, purification was performed by flash column chromatography on silica gel with petroleum ether/ethyl acetate (gradient mixture ratio from 100:0 to 85:15) as eluent to afford N-phenylcarbazole (5a, 77.8 mg, 0.32 mmol,32% yield).

Reference： [1]Nakayama, Yuji; Yokoyama, Naota; Nara, Hideki; Kobayashi, Tohru; Fujiwhara, Mitsuhiko [Advanced Synthesis and Catalysis, 2015, vol. 357, # 10, p. 2322 - 2330]
[2]Suzuki, Ken; Hori, Yoji; Kobayashi, Tohru [Advanced Synthesis and Catalysis, 2008, vol. 350, # 5, p. 652 - 656]
[3]Crawford, Sarah M.; Lavery, Christopher B.; Stradiotto, Mark [Chemistry - A European Journal, 2013, vol. 19, # 49, p. 16760 - 16771]
[4]Fareghi-Alamdari, Reza; Haqiqi, Mohsen G.; Zekri, Negar [New Journal of Chemistry, 2016, vol. 40, # 2, p. 1287 - 1296]
[5]Panahi, Farhad; Roozbin, Fatemeh; Rahimi, Sajjad; Moayyed, Mohammadesmaeil; Valaei, Aria; Iranpoor, Nasser [RSC Advances, 2016, vol. 6, # 84, p. 80670 - 80678]
[6]Panahi, Farhad; Daneshgar, Fatemeh; Haghighi, Fatemeh; Khalafi-Nezhad, Ali [Journal of Organometallic Chemistry, 2017, vol. 851, p. 210 - 217]
[7]Current Patent Assignee: SINOSTEEL GROUP NANJING NEW MATERIAL RES INSTITUTE; SINOSTEEL NEW MATERIALS - CN112079768, 2020, A Location in patent: Paragraph 0049-0051
[8]Ji, Wei; Jing, Su; Li, Ai-Min; Qi, Zheng-Hang; Qiu, Wen-Jie; Zha, Guo-Jin; Zhu, Dun-Ru [Journal of Catalysis, 2022, vol. 405, p. 313 - 321]
[9]Iqbal, Muhammad Asif; Mehmood, Hina; Lv, Jiaying; Hua, Ruimao [Molecules, 2019, vol. 24, # 6]

23
[ 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 ]

Yield	Reaction Conditions	Operation 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.

Reference： [1]Patent: US2011/260138,2011,A1

24
[ 1150-62-5 ]
[ 1126522-69-7 ]

Yield	Reaction Conditions	Operation in experiment
	With N-Bromosuccinimide In dichloromethane; water; N,N-dimethyl-formamide	1 Synthesis of Compound 1 NBS (19.31 g, 109 mmol) in DMF was added to 9-phenyl-9H-carbazole (24 g, 99 mmol) in 200 mL at 0° C. dropwise. The reaction was monitored by HPLC. The reaction was quenched by adding 500 mL of water after 2 h. After stirring at room temperature for 24 h, the clear solution was decanted and solid residue was dissolved in dichloromethane and washed with water and LiCl solution. The solution was dried with MgSO4 and the solvent was evaporated. The residue was used for the next step without further purification. The product contains starting material, monobromo, and dibromo. 31 g of product was obtained. Synthesis of 9-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole.
	Multi-step reaction with 2 steps 1: N-Bromosuccinimide / N,N-dimethyl-formamide / 0 °C 2: potassium acetate / (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride / 1,4-dioxane / 6 h / 80 °C / Inert atmosphere
	Multi-step reaction with 2 steps 1.1: N-Bromosuccinimide / N,N-dimethyl-formamide / 20 °C 2.1: n-butyllithium / tetrahydrofuran; hexane / 2 h / -78 °C 2.2: -78 - 20 °C

	Multi-step reaction with 2 steps 1: acetic acid; iodine; periodic acid / 4 h / 80 °C 2: (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium <i>tert</i>-butylate / toluene / 6 h / 90 °C / Inert atmosphere
	Multi-step reaction with 2 steps 1: N-Bromosuccinimide / tetrahydrofuran 2: potassium acetate; (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride / 1,4-dioxane
	Multi-step reaction with 2 steps 1: N-Bromosuccinimide / dichloromethane / 24 h / 20 °C 2: (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate / N,N-dimethyl-formamide / 24 h
	Multi-step reaction with 2 steps 1.1: N-Bromosuccinimide / chloroform / 0.5 h / 20 °C 2.1: n-butyllithium / tetrahydrofuran / 0.5 h / -78 °C 2.2: -78 - 20 °C
	Multi-step reaction with 2 steps 1: N-Bromosuccinimide / N,N-dimethyl-formamide / 12 h / 20 °C 2: (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate / 1,4-dioxane / 12 h / Reflux

Reference： [1]Current Patent Assignee: UNIVERSAL DISPLAY CORP - US2011/260138, 2011, A1
[2]Current Patent Assignee: UNIVERSAL DISPLAY CORP - WO2011/137072, 2011, A1
[3]Kim, Se Hun; Cho, Illhun; Sim, Mun Ki; Park, Sanghyuk; Park, Soo Young [Journal of Materials Chemistry, 2011, vol. 21, # 25, p. 9139 - 9148]
[4]Current Patent Assignee: Samsung Display (in: Samsung); SAMSUNG ELECTRONICS CO.,LTD. - US8865322, 2014, B2
[5]Huang, Bin; Yin, Zhihui; Ban, Xinxin; Jiang, Wei; Dai, Yu; Zhang, Junya; Liu, Yuanyuan; Yang, Yaping; Sun, Yueming [Dyes and Pigments, 2015, vol. 117, p. 141 - 148]
[6]Current Patent Assignee: DUKSAN HI METAL CO LTD; DUK SAN NEOLUX CO., LTD. - TWI580673, 2017, B Current Patent Assignee: DUK SAN NEOLUX CO., LTD. - KR2019/40150, 2019, A
[7]Kang, Seokwoo; Jung, Hyocheol; Lee, Hayoon; Lee, Suji; Jung, Mina; Lee, Jaehyun; Chul Kim, Young; Park, Jongwook [Dyes and Pigments, 2018, vol. 156, p. 369 - 378]
[8]Current Patent Assignee: LG DISPLAY CO.,LTD. - KR2019/12678, 2019, A

25
[ 1150-62-5 ]
[ 14348-75-5 ]
[ 1207299-19-1 ]

Yield	Reaction Conditions	Operation in experiment
72%	With methanesulfonic acid at 140℃; for 10h; Inert atmosphere;	2.1.1 A mixture of 2,7-dibromo-9H-fluoren-9-one (1.02 g), 9-phen ylcarbazole (12.2 g) and methanesulfonic acid (1 mL) was heated at 140 C under a nitrogen atmosphere for 10 h. After cooling to roomtemperature, the mixturewas poured into an excess of sodium carbonate solution for removing the superfluous acid, then extracted with dichloromethane. Evaporation of the solvent, followed by column chromatography on silica gel with petroleum etherdichloromethane gave a white product. Yield: 1.74 g (72%).
63%	With methanesulfonic acid at 140℃; for 10h; Inert atmosphere;
	With methanesulfonic acid at 140℃; for 10h; Inert atmosphere;

Reference： [1]Wu, Chuan; Tao, Silu; Chen, Mingming; Mo, Hin-Wai; Ng, Tsz Wai; Liu, Xiaoke; Zhang, Xiaohong; Zhao, Weiming; Lee, Chun-Sing [Dyes and Pigments, 2013, vol. 97, # 2, p. 273 - 277]
[2]Location in patent: experimental part Tao, Silu; Zhou, Yechun; Lee, Chun-Sing; Zhang, Xiaohong; Lee, Shuit-Tong [Chemistry of Materials, 2010, vol. 22, # 6, p. 2138 - 2141]
[3]Du, Xiaoyang; Huang, Yun; Tao, Silu; Yang, Xiaoxia; Wu, Chuan; Wei, Huaixin; Chan, Mei-Yee; Yam, Vivian Wing-Wah; Lee, Chun-Sing [Chemistry - An Asian Journal, 2014, vol. 9, # 6, p. 1500 - 1505]

26
[ 1150-62-5 ]
[ 618442-57-2 ]

Reference： [1]Journal of Materials Chemistry,2011,vol. 21,p. 9139 - 9148

27
[ 50890-67-0 ]
[ 1150-62-5 ]
[ 1359755-88-6 ]

Yield	Reaction Conditions	Operation in experiment
91%	With eaton’s reagent In dichloromethane at 100℃; for 1h; Inert atmosphere;
50%	With methanesulfonic acid at 100℃; for 1h;	Synthesis of 9,9-bis(9-ethylcarbazol-3-yl)-4,5-diazafluorene (L1) and 9,9-bis(9-phenylcarbazaol-3-yl)-4,5-diazafluorene (L2) General procedure: The description of the synthesis of L1 and L2 is identical to the one described in the literature [18]. L1: A mixture of 9-ethylcarbazole (6.44g, 33.0mmol), 4,5-diazafluoren-9-one (1.0g, 5.50mmol) and methane sulfonic acid (1.57mL, 24.2mmol) was heated at 100°C for 1h with constant stirring. After the completion of the reaction, the reaction mixture was cooled to room temperature and extracted with dichloromethane and dried over Na2SO4. The solvent was removed under reduced pressure. The pure product was obtained through column chromatography on silica gel (dichloromethane/acetone; 9/1) as a white solid. Yield 2.30g, 75%.
	With eaton’s reagent

With methanesulfonic acid at 100℃; for 1h;

Reference： [1]Location in patent: experimental part Zheng, Cai-Jun; Ye, Jun; Lo, Ming-Fai; Fung, Man-Keung; Ou, Xue-Mei; Zhang, Xiao-Hong; Lee, Chun-Sing [Chemistry of Materials, 2012, vol. 24, # 4, p. 643 - 650]
[2]Sivakumar, Radhakrishnan; Manivel, Arumugam; Meléndrez, Manuel; Martínez-Oyanedel, José; Bunster, Marta; Vergara, Carola; Manidurai, Paulraj [Polyhedron, 2015, vol. 87, p. 135 - 140]
[3]Zhang, Fuli; Guan, Yuqiao; Wang, Shimin; Li, Suzhi; Zhang, Fuqiang; Feng, Yafei; Chen, Shufen; Cao, Guangxiu; Zhai, Bin [Dyes and Pigments, 2016, vol. 130, p. 1 - 8]
[4]Sivakumar, Radhakrishnan; Recabarren, Rodrigo; Ramkumar, Sekar; Manivel, Arumugam; Alzate-Morales, Jans; Contreras, David; Manidurai, Paulraj [New Journal of Chemistry, 2017, vol. 41, # 13, p. 5605 - 5612]

28
[ 1150-62-5 ]
[ 1028647-93-9 ]

Reference： [1]Patent: EP2468725,2012,A1
[2]Patent: EP2484665,2012,A1
[3]Patent: EP2502908,2012,A1
[4]Patent: US8865322,2014,B2
[5]Patent: KR2016/19744,2016,A
[6]Patent: KR2016/19745,2016,A
[7]Patent: TWI580673,2017,B

29
[ 1150-62-5 ]
[ 500293-84-5 ]
[ 1352826-88-0 ]

Yield	Reaction Conditions	Operation in experiment
70%	With trifluoroacetic acid In dichloromethane at 20℃; for 14h;	7.4.2. 3-(3,6-Dibromo-9-phenyl-9H-fluoren-9-yl)-9-phenyl-9H-carbazole (2) To 0.8 g 2 and 0.577 g 9-penyl carbazole dissolved in CH2Cl2 was added 0.5 mL CF3COOH, then the mixturewas stirred at room temperature for 14 h. Ice cold NaHCO3 aqueous was added, and the product was extracted with CH2Cl2. Yield: 70%.

Reference： [1]Qian, Yinbo; Cao, Feng; Guo, Wenping [Tetrahedron, 2013, vol. 69, # 21, p. 4169 - 4175]

30
[ 189999-35-7 ]
[ 62-53-3 ]
[ 1150-62-5 ]

Yield	Reaction Conditions	Operation in experiment
100%	With copper diacetate; sodium carbonate In ethylene glycol; isopropyl alcohol at 90℃; for 16h; Inert atmosphere;	4 General procedure for the synthesis of carbazoles General procedure: To a stirred solution of cyclicdiphenyliodonium trifluoromethanesulfonate (100 mg, 234 mmol, 1 eq) in iPrOH (1.8 mL) and ethylene glycol (0.2 mL), was added amine (4 eq), sodium carbonate (3 eq), Cu(OAc)2 (0.2 eq). The reaction proceeded at a reflux for 16 h under argon atmosphere before iPrOH was removed by a rotary evaporation. The remained mixture was partitioned between water and EtOAc, and the aqueous phase was extracted with EtOAc. The combined organic phases were washed with H2O and brine, dried over anhydrous Na2SO4, evaporated in a vacuo. The residue was purified by column chromatography on a silica gel (PE/EtOAc) to provide carbazole derivatives. 5.1.2.4 9-phenyl-9H-carbazole (1) A white solid. HPLC tR = 8.079 min, 100%. 1H NMR (400 MHz, CDCl3) δ 8.15 (d, J = 7.7 Hz, 2H), 7.65-7.54 (m, 4H), 7.47 (t, J = 6.9 Hz, 1H), 7.41 (d, J = 3.7 Hz, 4H), 7.33-7.27 (m, 2H) ppm. 13C NMR (100 MHz, CDCl3) δ 140.9, 137.8, 129.9, 127.5, 127.2, 125.9, 123.4, 120.3, 119.9, 109.8 ppm. IR υ 3047, 2926, 1675, 1589, 1446, 1321, 1226, 1169, 1011, 922, 746 cm-1. LRMS (ESI, m/z): 244.2 [M + H]+.
70%	With copper diacetate; sodium carbonate; ethylene glycol In isopropyl alcohol at 85℃; for 16h; Inert atmosphere;
45%	With palladium diacetate; caesium carbonate; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene In para-xylene at 125℃; for 3h; Inert atmosphere;

With copper diacetate; sodium carbonate In ethylene glycol; isopropyl alcohol for 16h; Inert atmosphere; Reflux; Green chemistry;

Reference： [1]Zhu, Daqian; Chen, Meihui; Li, Min; Luo, Bingling; Zhao, Yang; Huang, Peng; Xue, Fengtian; Rapposelli, Simona; Pi, Rongbiao; Wen, Shijun [European Journal of Medicinal Chemistry, 2013, vol. 68, p. 81 - 88]
[2]Zhu, Daqian; Liu, Qi; Luo, Bingling; Chen, Meihui; Pi, Rongbiao; Huang, Peng; Wen, Shijun [Advanced Synthesis and Catalysis, 2013, vol. 355, # 11-12, p. 2172 - 2178]
[3]Riedmueller, Stefan; Nachtsheim, Boris J. [Beilstein Journal of Organic Chemistry, 2013, vol. 9, p. 1202 - 1209]
[4]You, Xin; Zhu, Daqian; Lu, Wenhua; Sun, Yichen; Qiao, Shuang; Luo, Bingling; Du, Yongliang; Pi, Rongbiao; Hu, Yumin; Huang, Peng; Wen, Shijun [RSC Advances, 2018, vol. 8, # 31, p. 17183 - 17190]

31
[ 1150-62-5 ]
[ 33513-42-7 ]
[ 110677-45-7 ]

Yield	Reaction Conditions	Operation in experiment
55%	With trichlorophosphate; at 0 - 85℃; for 2h;Inert atmosphere;	In an ice-water bath at 0 C, 9-phenyl-9H-carbazole (2.43 g, 10 mmol),Dissolved in 25ml of anhydrous DMF solution, and slowly added 25mL of POCl3.And slowly heated the mixture to 85 C under nitrogen protection for 2h,After cooling to room temperature, the reaction mixture was poured into an ice bath and neutralized with NaOH,It was then extracted with chloroform and dried over anhydrous sodium sulfate.It was separated and purified by silica gel column chromatography, and finally the target product 1b was obtained.1.778 g of a yellow solid with a reaction yield of 55%.

Reference： [1]Dalton Transactions,2014,vol. 43,p. 11305 - 11308
[2]Patent: CN110845489,2020,A .Location in patent: Paragraph 0042-0045; 0056-0059
[3]Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy,2018,vol. 199,p. 441 - 447

32
[ 1150-62-5 ]
[ 4885-02-3 ]
[ 87220-68-6 ]

Reference： [1]Photochemical and Photobiological Sciences,2013,vol. 12,p. 284 - 297

33
[ 419536-33-7 ]
[ 1150-62-5 ]

Yield	Reaction Conditions	Operation in experiment
98%	With silver nitrate; triethylamine In ethanol; water at 80℃; for 0.25h;
95%	With copper(ll) sulfate pentahydrate; oxygen; diisopropylamine In ethanol; water at 80℃; for 1.5h; Green chemistry;

Reference： [1]Liu, Chun; Li, Xinmin; Wu, Yonghua [RSC Advances, 2015, vol. 5, # 20, p. 15354 - 15358]
[2]Liu, Chun; Li, Xinmin; Wu, Yonghua; Qiu, Jieshan [RSC Advances, 2014, vol. 4, # 97, p. 54307 - 54311]

34
[ 38257-52-2 ]
[ 1150-62-5 ]

Reference： [1]Organic Process Research and Development,2014,vol. 18,p. 1571 - 1574

35
[ 1150-62-5 ]
[ 103021-76-7 ]
C₃₇H₂₃Cl₂N [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
49%	With methanesulfonic acid; phosphorus pentoxide In dichloromethane at 20℃; for 2h; Inert atmosphere;	2 Preparation of compound 2-2 Preparation of compound 2-2 After introducing compound 2-1 (15.8 g, 48.3 mmol), 9-phenylcarbazole (17.6 g, 72.5 mmol), and methylenechloride (MC) 250 mL in a reaction container, the mixture was subjected into nitrogen atmosphere. Eaton’s reagent 1.5 mL was then slowly added dropwise thereto, and the mixture was stirred at room temperature for 2 hours. Thereafter, the reaction was completed with distilled water, and the mixture was extracted with methylenechloride. The extracted organic layer was dried with magnesium sulfate, and the solvent was removed using a rotary evaporator. The remaining substance was then purified with column chromatography to obtain compound 2-2 (13.2 g, 49%).

Reference： [1]Current Patent Assignee: DOW INC - WO2015/99485, 2015, A1 Location in patent: Paragraph 174-175

36
[ 1150-62-5 ]
[ 58328-31-7 ]

Reference： [1]Inorganic Chemistry,2016,vol. 55,p. 887 - 893

37
[ 86-74-8 ]
[ 583-53-9 ]
[ 1150-62-5 ]
[ 902518-11-0 ]

Yield	Reaction Conditions	Operation 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.

Reference： [1]Patent: EP2937355,2015,A1 .Location in patent: Paragraph 0054-0058

38
[ 591-50-4 ]
[ 86-74-8 ]
[ 147-85-3 ]
[ 1150-62-5 ]

Yield	Reaction Conditions	Operation in experiment
92%	With potassium carbonate In water; dimethyl sulfoxide	1 9-phenyl-9-carbazole (named as compound 3 in FIG. 6) 9-phenyl-9-carbazole (named as compound 3 in FIG. 6) A mixture of iodobenzene (2.0 g, 10 mmol), carbazole (1.67 g, 10 mmol), CuI (190 mg, 1.0 mmol), L-proline(115 mg, 1.0 mmol), K2CO3 (2.8 g, 20.0 mmol), and DMSO (20 mL) was heated at 110° C. for 36 h under argon. After cooling to room temperature, the reaction was quenched with water. The mixture was extracted with CH2Cl2 and dried over Na2SO4. After the solvent had been removed, the residue was purified by column chromatography on silica gel using petroleum as eluent to give a white solid (2.23 g, 92%). 1HNMR (DMSO-d6, 400 Hz): δ=8.25 (d, J=7.76 Hz, 2H), 7.69 (t, J=8.0 Hz, 2H), 7.64-7.61(m, 2H), 7.55 (t, J=7.30, 1H), 7.44(t, J=7.4 Hz, 2H), 7.38(d, J=8.0, 2H), 7.29(t, J=7.32, 2H). HRMS calcd for 243.3026, found 243.1023.

Reference： [1]Current Patent Assignee: NANO AND ADVANCED MATERIALS INSTITUTE LIMITED - US9269908, 2016, B2

39
[ 1150-62-5 ]
C₂₄H₁₈N₂O [ No CAS ]
C₄₁H₂₇N₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
58%	With Eaton’s reagent In dichloromethane at 20℃; for 2h; Inert atmosphere;	2.4 Step 4: Synthesis of Compound 2 Intermediate product (F) 13.6 g (49.0 mmol), 9 - phenyl carbazole 11.9 g (49.0 mmol) dissolved in 40 mL of dichloromethane.A stream of nitrogen was added the Eaton reagent (Eaton's reagent) 2 mL and stirred for 2 hours at room temperature.Wash the reaction mixture with 20 mL water, 20 mL saturated aqueous sodium bicarbonate solution, saturated brine 20 mL and dried over anhydrous magnesium sulfate and filtered and concentrated.The concentrated residue was purified by a dichloromethane: ethyl acetate = 5: 1 (v / v) and purified by silica gel column in the solvent 16 g compound 2 (yield: 58%) was obtained

Reference： [1]Current Patent Assignee: SAMSUNG C&T CORPORATION - KR2015/31041, 2015, A Location in patent: Paragraph 0147; 0158; 0159

40
[ 1150-62-5 ]
C₂₃H₁₆N₂O [ No CAS ]
C₄₁H₂₇N₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
65%	With Eaton’s reagent; acetic acid at 100℃; for 18h;	3.2 Step 2: synthesis of compound 3 Into the compound (H) 25 g (74.30 mmol), phenyl-carbazol-9- 27.12 g (111.45 mmol) in 250 mL acetic acid, and stirred Eaton mwot reagents into 5 mL up to 100 ° temperatureThe mixture was heated and stirred for 18 hours.The reaction mixture was cooled to ambient temperature and was stirred into the reaction solution to 500 mL ice water to precipitate a solid. The resulting solid is filtered, dried, washed with water, methanol. By collection of the dried solid was purified by silica gel column purification with compound 3, 27.1 g (yield: 65%) was obtained.

Reference： [1]Current Patent Assignee: SAMSUNG C&T CORPORATION - KR2015/31041, 2015, A Location in patent: Paragraph 0163; 0167; 0168

41
[ 1150-62-5 ]
C₁₇H₁₂N₂O [ No CAS ]
C₃₅H₂₃N₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
65%	With Eaton’s reagent In dichloromethane at 20℃; for 2h; Inert atmosphere;	1.4 Step 4: Synthesis of Compound 1 Intermediate product (C) 11 g (41.6 mmol), phenyl-carbazol-9- 10 g (41.6 mmol) of dissolved in dichloromethane 40 mL.A stream of nitrogen was added the Eaton reagent (Eaton's reagent) 2 mL and stirred for 2 hours at room temperature.Wash the reaction mixture with 20 mL water, 20 mL saturated aqueous sodium bicarbonate solution, saturated brine 20 mL and dried over anhydrous magnesium sulfate and filtered and concentrated.The concentrated residue was purified by a dichloromethane: ethyl acetate = 3: to give a: 1 (v / v) and purified by silica gel column in the solvent 13.1 g compound 1 (yield 65%).

Reference： [1]Current Patent Assignee: SAMSUNG C&T CORPORATION - KR2015/31041, 2015, A Location in patent: Paragraph 0130; 0142; 0143

42
[ 624-38-4 ]
[ 86-74-8 ]
[ 1150-62-5 ]
[ 19287-68-4 ]
[ 57103-15-8 ]

Yield	Reaction Conditions	Operation in experiment
1: 41% 2: 15% 3: 9%	With copper(l) iodide; potassium carbonate In 1-methyl-pyrrolidin-2-one at 175℃; for 24h; Schlenk technique; Inert atmosphere;	4.4. Cross coupling of carbazoles 12b-d with dihalobenzenes 13 and 16 General procedure: 4.4.1. Mediated by cuprous salts. Starting material 12b, 12c or 12d (0.75-3.00 mmol) was placed in a flame-dried Schlenk flask together with para-diiodobenzene (13) or para-bromoiodobenzene (16) (1.1-1.2 equiv), cuprous salt (7-20 mol %), base (2 equiv) and an additive (0-7 mol %). The atmosphere in the flask was exchanged for argon (3x) and the solvent (0.9-5.0 ml) was introduced through a rubber septum. The mixture was stirred at the temperature and for the time stated in Table 1. Upon cooling down, the solids were filtered off over a short Celite plug (50-80 ml DCM) and if feasible, the residue was concentrated under vacuum to dryness with a small amount of SiO2. In the case of high-boiling point solvents, the solution was concentrated to a volume of 20-40 ml, extracted excessively with distilled water (4x100-150 ml), organic matter was dried with ample Na2SO4, filtered and concentrated under vacuum to dryness with a small amount of SiO2. The product was isolated after chromatography on a SiO2 column (100% hexanes/10% DCM in hexanes).

Reference： [1]Kerner, Lukáš; Gmucová, Katarína; Kožíšek, Jozef; Petříček, Václav; Putala, Martin [Tetrahedron, 2016, vol. 72, # 44, p. 7081 - 7092]

43
[ 1150-62-5 ]
[ 6630-81-5 ]
C₄₉H₃₂N₂O₂S [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
87%	With boron trifluoride diethyl etherate In dichloromethane at 20℃; for 8h;	Synthesis of 1b General procedure: 9-phenylcarbazole (0.97g, 4mmol) and OPhSOH (0.45g, 1mmol) were dissolved in anhydrous dichloromethane solution (50mL). Then, the BF3·Et2O (0.14g, 1mmol) was added slowly into the reaction mixture. Large amount of water was added to quench reaction after 8h, and extracted with dichloromethane. The combined organic abstract was dried over anhydrous MgSO4 and filtered. The solution was evaporated under vacuum condition and the crude product was purified by silica gel column chromatography to afford light yellow solid (0.61g) with 91.0% yield.