[ CAS No. 3652-90-2 ] {[proInfo.proName]}

Name: 3652-90-2|2-Bromo-9H-carbazole|98%
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SKU: A112061
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3d Animation Molecule Structure of 3652-90-2

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Quality Control of [ 3652-90-2 ]

COA NMR CNMR HPLC LC-MS

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SDS Specification

Alternatived Products of [ 3652-90-2 ]

Product Details of [ 3652-90-2 ]

CAS No. :	3652-90-2	MDL No. :	MFCD09750430
Formula :	C₁₂H₈BrN	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	PJRGCJBBXGNEGD-UHFFFAOYSA-N
M.W :	246.10	Pubchem ID :	12717089
Synonyms :

Calculated chemistry of [ 3652-90-2 ]

Physicochemical Properties

Num. heavy atoms :	14
Num. arom. heavy atoms :	13
Fraction Csp3 :	0.0
Num. rotatable bonds :	0
Num. H-bond acceptors :	0.0
Num. H-bond donors :	1.0
Molar Refractivity :	63.5
TPSA :	15.79 Å²

Pharmacokinetics

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

Lipophilicity

Log Po/w (iLOGP) :	2.23
Log Po/w (XLOGP3) :	4.08
Log Po/w (WLOGP) :	4.08
Log Po/w (MLOGP) :	3.5
Log Po/w (SILICOS-IT) :	4.25
Consensus Log Po/w :	3.63

Druglikeness

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

Water Solubility

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

Medicinal Chemistry

PAINS :	0.0 alert
Brenk :	0.0 alert
Leadlikeness :	2.0
Synthetic accessibility :	1.61

Safety of [ 3652-90-2 ]

Signal Word:	Warning	Class:	N/A
Precautionary Statements:	P261-P305+P351+P338	UN#:	N/A
Hazard Statements:	H302-H315-H319-H335	Packing Group:	N/A
GHS Pictogram:

Application In Synthesis of [ 3652-90-2 ]

* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

Upstream synthesis route of [ 3652-90-2 ]
Downstream synthetic route of [ 3652-90-2 ]

[ 3652-90-2 ] Synthesis Path-Upstream 1~7

1
[ 3652-90-2 ]
[ 591-50-4 ]
[ 94994-62-4 ]

Yield	Reaction Conditions	Operation in experiment
92.4%	With copper(l) iodide; caesium carbonate; ethylenediamine In toluene for 12 h; Reflux	After mixing compound C-7-2 (23 g, 0.093 mmol), iodobenzene (20.9 mL, 0.186 mol), CuI (14.2 g, 0.074 mol), Cs₂CO₃ (91.2 g, 0.28 mol), toluene (300 mL), and ethylenediamine (9.46 mL, 0.140 mol), the mixture was stirred under reflux. After 12 hours, the mixture was cooled to room temperature, and CuI and Cs₂CO₃ were removed. Then, the remaining liquid was distilled under reduced pressure, and then separated with a column to obtain compound C-7-3 (28 g, 92.4 percent).
91.65%	for 12 h; Reflux	[165] After mixing compound 1-3 (10 g, 40.63 mmol), CuI (3.8 g, 20.3 mmol), K₃PO₄ (21.56 g, 101.58 mmol), toluene 300 mL, iodobenzene 9.09 mL, and ethylenediamine (2.7 mL, 40.63 mmol), the mixture was stirred under reflux for 12 hours. Then, the mixture was cooled to room temperature and filtered under reduced pressure. The remaining solution was washed with distilled water and extracted with methylene chloride (MC). Then, the resulting product was dried with magnesium sulfate, distilled under reduced pressure, and separated through a column to obtain compound 1-4 (12 g, 37.24 mmol, 91.65 percent).
90%	With copper(l) iodide; caesium carbonate; ethylenediamine In toluene for 3 h; Reflux	After introducing 2-bromocarbazole 100 g (0.406 mol), iodobenzene 166 g (0.813mol), copper iodide 38.7 g (0.203 mol), ethylenediamine 27 mL (0.406 mol), cesiumcarbonate 265 g (0.813 mol), and toluene 1.3 L in a reaction container, the mixture wasstirred under reflux for 3 hours. After the reaction, the mixture was washed withdistilled water, and an organic layer was extracted with ethyl acetate. The extractedorganic layer was dried with magnesium sulfate, and the solvent was removed using arotary evaporator. The remaining substance was then purified with column chromatographyto obtain compound 2-1 (116 g, 90percent).

89%	With copper(l) iodide; caesium carbonate; ethylenediamine In toluene for 4 h; Reflux	After mixing compound C-62-2 17 g (69.07 mmol), iodobenzene 15.4 mL (138.15 mmol), CuT 10.5 g (55.26 mmol), ethylenediamine (EDA) 6.9 mL (103.6 mmol), Cs2 CO3 56.26 g (172.6 mmol), and toluene 350 mL, the mixture was stuffed under reflux. After 4 hours, the mixture was cooled to room temperature, and filtered under reduced pressure. The remaining solution was filtered under reduced pressure, and separated with a column to obtain compound C-62-3 20 g (89 percent).
85%	With copper(l) iodide; potassium carbonate; <i>L</i>-proline In dimethyl sulfoxide at 90℃; for 72 h; Inert atmosphere; Sealed tube	A pressure vessel was charged with -bromo-9H-carbazole (10 mmol), iodobenzene (20 mmol), potassium carbonate (20 mmol), L-proline (2 mmol), copper(I) iodide (1 mmol), and dimethyl sulfoxide (25 mL). After three cycles of evacuation and backfilling with nitrogen, the vessel was sealed and stirred at 90° C. for three days. After cooling, the reaction mixture was diluted with dichloromethane (200 mL), washed four times with water (200 mL), and dried over magnesium sulfate. After removing the solvent under reduced pressure, the crude product was chromatographed over silica with hexane as the eluent, giving 2-bromo-9-phenyl-9H-carbazole in 85percent yield.
84.86%	Stage #1: With caesium carbonate In toluene at 50℃; Stage #2: With ethylenediamine In toluene for 14 h; Reflux	Compound 1-2 (30g, 101.29mmol), iodobenzene (41.3g, 202.59mmol), CuI (9.6g, 50.64mmol), Cs₂CO₃ (82.5g, 253.2mmol), and toluene 600mL were mixed and heated at 50°C, and ethylenediamine (6.8mL, 101.29mmol) was added. The mixture was stirred under reflux. 14 hours later, the mixture was cooled to room temperature and distilled water was added. The mixture was extracted with EA, dried with anhydrous MgSO₄, distilled under reduced pressure and column separated, yielding Compound 1-3 (32g, 85.96mmol, 84.86percent).
84.46%	Stage #1: With caesium carbonate In toluene at 50℃; Stage #2: With ethylenediamine In toluene for 14 h; Reflux	Preparation of compound 1-3 [100] After mixing compound 1-2 (30 g, 101.29 mmol), iodobenzene (41.3 g, 202.59 mmol), CuI (9.6 g, 50.64 mmol) and Cs₂CO₃ (82.5 g, 253.2 mmol) with toluene (600 mL), the reaction mixture heated at 50°C. Ethylenediamine (EDA) (6.8 mL, 101.29 mmol) was added to the reaction mixture and was stirred under reflux. After 14 hours, the reaction mixture was cooled to room temperature, and distilled water was added. The reaction mixture was extracted with ethyl acetate, was dried with MgSO₄, was distillated under reduced pressure, and was filtered through column to obtain compound 1-3 (32 g, 85.96 mmol, 84.86 percent).
84%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; triphenylphosphine; sodium t-butanolate In toluene at 100℃;	To a round bottom flask Sub 1-1-1 (4.9g, 20mmol), Sub 1-2-1 (4.1g, 20mmol), Pd2(dba)3 (0.9g, 1mmol), PPh3 (0.5g, 2mmol), NaOt-Bu (5.8g, 60mmol), toluene (210mL) added and allowed to react at 100 °C. When the reaction is complete, the ether and water are added to the resulting solution. The organic layer was dried over MgSO4, concentrated and recrystallized silicagel column and extracted Sub 1-3-1, 5.4g (yield: 84percent) was obtained.
81%	With copper(l) iodide; 1,10-Phenanthroline; potassium carbonate In N,N-dimethyl-formamide at 80℃; for 24 h; Inert atmosphere	[271] In a 100 ml round-bottom three-neck flask under a nitrogen atmosphere, 4.2 g of Intermediate 20, 5.2 g of iodobenzene, 0.3 g of copper iodide, 0.3 g of1, 10-phenanthroline, 7.1 g of potassium carbonate and 50 ml of dimethylfomiamide were placed, and reacted at 80°C for 24 hrs. The reaction solution was cooled and then extracted with dichloromethane and water. The extracted solution was concentrated, subjected to column chromatography using a solvent mixture of dichloromethane and n-hexane and then concentrated, thus obtaining 4.8 g of Intermediate 21 (yield 8 1percent).[272] MS (ESI): [M+H]+ 322
79%	With copper; potassium carbonate; sodium sulfate In nitrobenzene at 200℃;	The obtained Sub 1-II-B1 (37.19g, 151.1mmol) was dissolved in nitrobenzene in a round bottom flask, and iodobenzene (46.24g, 226.7mmol), Na₂SO₄ (21.46g, 151.1mmol), K₂CO₃ (20.89g, 151.1mmol), and Cu (2.88g, 45.3mmol) were added to the reaction solution, followed by stirring at 200°C. Upon completion of the reaction, nitrobenzene was removed by distillation, and the reaction product was extracted with CH₂Cl₂ and water. The extracted organic layer was dried with MgSO₄ and concentrated, and then the produced organic material was separated by a silica gel column and recrystallized to obtain 38.47g of product (yield: 79percent).
79%	With copper; potassium carbonate; sodium sulfate In nitrobenzene at 200℃;	Intermediate B 1mol and iodobenzene 1.5mol After dissolved in nitrobenzene, Na2SO4, K2CO3, the Cu It was added and the resulting mixture was stirred at 200°C . After the reaction is complete when the nitrobenzene removed by distillation and extracted with water and CH2Cl2 and the organic layer over anhydrous MgSO4 Dried and concentrated to give the desired intermediate C and the resulting product was purified by column chromatography and recrystallization after (yield: 79percent).
77%	With copper; potassium carbonate In nitrobenzene for 16 h; Inert atmosphere; Reflux	Under nitrogen atmosphere, intermediate Compound B 2.45g (10mmol), iodobenzene and 3.06g (15mmol) was dissolved in 25ml nitrobenzene, K2CO3 4.15g (30mmol) and Cu 0.19g (3mmol) was added and the mixture was refluxed for 16 hours. After completion of the reaction, MC 100ml, H2O 100ml was added and then the the MC layer was extracted, concentrated and separated by column chromatography using Hex : EA =5 : 1 and dried over anhydrous MgSO4 to give the intermediate C 2.48g (77percent).
73%	With copper; potassium carbonate; sodium sulfate In nitrobenzene at 200℃;	Sub 1-II-1 (80.34g, 326.5mmol) nitrobenzene (653 ml) for in round bottom flask senses a rotation velocity of the disk in, iodobenzene (99.9g, 489.7mmol), Na ₂ SO ₄ (46.37g, 326.5mmol), K ₂ CO ₃ (45.12g, 326.5mmol), cu (6.22g, 97.9mmol) added 200 °C stirring section. When reaction is completed the via fractional distillation to remove the nitrobenzene CH ₂ Cl ₂ extracted and water. Organic layer MgSO ₄ to dry a silicagel column with a compound formed after the products and recrystallization 76.78g (yield: 73percent)is obtained.
73%	With copper; potassium carbonate; sodium sulfate In nitrobenzene at 200℃;	It was dissolved Sub 1-II-1 (80.34g, 326.5mmol) obtained in the above synthesis in nitrobenzene (653ml) in a round bottom flask, iodobenzene (99.9g, 489.7mmol), Na2SO4 (46.37g, 326.5mmol), K2CO3 ( 45.12g, 326.5mmol), was added Cu (6.22g, 97.9mmol) and stirred at 200 . After completion of reaction was removed by distillation to nitrobenzene and extracted with CH2Cl2 wamul. The resulting compound and the organic layer was dried over MgSO4 and concentrated to silicagel column and the product was recrystallized 76.78g: (yield: 73percent).
73%	With copper; potassium carbonate; sodium sulfate In nitrobenzene at 200℃;	Sub 1-II-1 (80.34g , 326.5mmol) was dissolved in nitrobenzene (653ml) in a round bottom flask, iodobenzene (99.9g, 489.7mmol), Na 2 SO 4 (46.37g,326.5mmol), K 2 CO 3 was added (45.12g, 326.5mmol), Cu ( 6.22g, 97.9mmol) and the resulting mixture was stirred at 200 . After completion ofreaction by distillation to remove nitrobenzene and the CH 2 Cl 2 and extracted with water. The organic layer is MgSO 4 and the resulting compoundwas dried and concentrated to a silicagel column and the product was recrystallized 76.78g: (yield: 73percent).
73%	With copper; potassium carbonate; sodium sulfate In nitrobenzene at 200℃;	Sub 1-II-1 (113.37g, 460.7mmol) obtained in the above synthesis was dissolved with nitrobenzene in a round bottom flask, iodobenzene (140.97g, 691mmol), Na2SO4 (65.43g, 460.7mmol), K2CO3 (63.67g, 460.7 mmol), was added Cu (8.78g, 138.2mmol) and stirred at 200° C. After completion of reaction was removed by distillation to nitrobenzene and extracted with CH2Cl2 wamul. The resulting compound and the organic layer was dried over MgSO4 and concentrated to silicagel column and recrystallized to give the product 108.35g (73percent yield).
73%	With copper; potassium carbonate; sodium sulfate In nitrobenzene at 200℃;	Sub-1-II-1 (80.34g, 326.5 mmol) obtained in the above Synthesis was added to a round bottom flask and dissolved in nitrobenzene 653 mL, iodobenzene (99.9 g, 489.7 mmol), Na2SO4 (46.37 g, 326.5 mmol), K2CO3 (45.12 g, 326.5 mmol), and Cu (6.22 g, 97.9 mmol) were added and the resulting mixture was stirred at 200 ° C. After completion of reaction, nitrobenzene was removed by distillation, extracted with water and CH2Cl2, the resulting material was purified by silicagel column, and the organic layer was dried over MgSO4, and concentrated to obtain product 76.78 g (yield: 73percent).
70%	With potassium phosphate; copper(l) iodide; (-)-(1R,2R)-diaminocyclohexane In 1,4-dioxane at 80℃; for 8 h; Inert atmosphere	In argon stream, a mixture obtained by successively mixingthe intermediate 2 (20 g 81 mmol) iodobenzene (18.1 g 89mmol), copper iodide (1.5 g, 8 mmol), tripotassium phoshtermediatephate (34.5 g, 163 mmol), dry dioxane (100 mE), and cycloxylene hexanediamine (1.8 g, 16 mmol) was stirred at 80° C. for 8 h.After cooling the reaction liquid to room temperature, theorganic layer was separated and the organic solvent wasremoved from the organic layer by distillation under reducedpressure. The obtained residue was purified by a silica gelcolunm chromatography to obtain the intermediate 14 (18.3 g, yield: 70percent). The identification of the intermediate 14 wasmade by FD-MS (field desorption mass spectrometry) analy50 sis.
69%	With tri-tert-butyl phosphine; palladium diacetate; sodium t-butanolate In toluene at 20℃; for 15 h; Inert atmosphere	In a 0.5 L reaction flask, 10.0 g (40.6 mmol) of the compound [119-1], 10.7 g (44.7 mmol) of the compound [119-2] 5.9 g (60.9 mmol) of sodium butoxide, and 150 ml of toluene were placed, and the mixture was stirred at room temperature. 0.1 g (0.4 mmol) of palladium acetate, 0.3 g (0.8 mmol) of tri-tert-butylphosphine (50percent) And the mixture was stirred under reflux for 15 hours under a stream of nitrogen. After completion of the reaction, the mixture was slowly cooled to room temperature, and then the reaction solution was poured into a saturated ammonium chloride aqueous solution and extracted with ethyl acetate. The organic layer was separated, dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure and purified by column chromatography to obtain 9.0 g (69percent) of intermediate compound [119-3].
54%	With potassium phosphate; copper(l) iodide; cis-cyclohexane-1,2-diamine In 1,4-dioxane for 48 h; Inert atmosphere; Reflux	A mixture solution of 2-bromo-9H-carbazole (10.0 g, 40.6 mmol), iodobenzene (12.43 g, 61.0 mmol), CuI (0.774 g, 4.06 mmol), (1R,2S)-cyclohexane-1,2-diamine (0.987 ml, 8.13 mmol), and K₃PO₄(17.25 g, 81 mmol) in dioxane (150 ml) was refluxed under nitrogen for 48 h. (0125) (0126) After cooling to room temperature, the mixture was filtered through a plug of Celite® and the solid was washed with DCM. The combined filtrate was evaporated and purified by column chromatography on silica gel with hexane/DCM (9/1, v/v) as eluent to yield 2-bromo-9-phenyl-9H-carbazole (7.4 g, 54percent) as a white solid.
50.4%	With potassium carbonate; copper(l) chloride In dimethyl sulfoxide for 24 h; Reflux	A 500ml reactor 2-bromo mocha carbazole (30g, 121.9mmol), iodobenzene (38.3g, 243.8mmol), copper chloride (I) (0.24g, 2.4mmol), potassium carbonate (20.2g, 146.3mmol), dimethyl Insert the sulfoxide 240 mL was refluxed for 24 hours.After completion of reaction, after cooling to room temperature, into a 200mL ethyl acetate was filtered through a Buchner.Extract the filtrate with water 500 mL, under reduced pressure and then dry the organic layer was treated to remove the organic solvent.Hexane: ethyl acetate (10: 1) the column was isolated using as a developing solvent.19.8g of a white solid to give the 2-bromo-phenyl -N- carbazole.(50.4percent).
37%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tri-tert-butyl phosphine; sodium t-butanolate In toluene for 12 h; Reflux	30.51 g (149.56 mmol) of iodobenzene, 18.32 g (74.78 mmol) of 2-bromo-9H-carbazole, 14.37 g (149.56 mmol) of sodium t-butoxide, and 1.81 ml (7.48 mmol) of tritertbutylphosphine were dissolved in 300 ml of toluene, and 0.68 g (0.75 mmol) of Pd₂(dba)₃ was added thereto, and refluxed and agitated for 12 hours. After the reaction was finished, extraction was performed by dichloromethane, filtering was performed by silica gel, and the column was used at a ratio of hexane:MC=9:1 (v/v) to obtain 8.99 g of 2-bromo-9-phenylcarbazole (yield 37percent). ¹H NMR: 7.24 (t, 1H), 7.36 (m, 3H), 7.50 (dd, 2H), 7.58 (t, 2H), 7.65 (t, 2H), 8.06 (d, 1H), 8.13 (d, 1H). GC-Mass (theoretical value: 321.02 g/mol, measured value: 321 g/mol).

Reference： [1] Patent: WO2013/122402, 2013, A1, . Location in patent: Paragraph 196; 201; 202
[2] Patent: WO2013/162284, 2013, A1, . Location in patent: Paragraph 164; 165
[3] Journal of Materials Chemistry, 2012, vol. 22, # 1, p. 215 - 224
[4] Patent: WO2015/99484, 2015, A1, . Location in patent: Paragraph 181-182
[5] Patent: WO2014/3440, 2014, A1, . Location in patent: Paragraph 172; 173; 178; 179
[6] Patent: US9312502, 2016, B2, . Location in patent: Page/Page column 27; 28; 29
[7] Patent: WO2012/39561, 2012, A1, . Location in patent: Page/Page column 20
[8] Patent: WO2012/169821, 2012, A1, . Location in patent: Page/Page column 16
[9] Patent: KR2015/61811, 2015, A, . Location in patent: Paragraph 0109-0111
[10] Patent: WO2017/196081, 2017, A1, . Location in patent: Paragraph 269; 270; 272; 272
[11] Patent: EP2930168, 2015, A1, . Location in patent: Paragraph 0089; 0092; 0290
[12] Patent: KR101565039, 2015, B1, . Location in patent: Paragraph 0098-0101
[13] Patent: KR2015/102733, 2015, A, . Location in patent: Paragraph 0121-0125
[14] Patent: KR101550768, 2015, B1, . Location in patent: Paragraph 0151 - 0154
[15] Patent: KR2015/98171, 2015, A, . Location in patent: Paragraph 0138; 0142; 0151-0154
[16] Patent: KR2015/87787, 2015, A, . Location in patent: Paragraph 0140; 0149-0152
[17] Patent: KR2015/89427, 2015, A, . Location in patent: Paragraph 0136; 0137; 0138; 0143; 0144
[18] Patent: KR101614738, 2016, B1, . Location in patent: Paragraph 0198-0200
[19] Journal of Physical Chemistry B, 2012, vol. 116, # 15, p. 4603 - 4614
[20] Patent: US9306171, 2016, B2, . Location in patent: Page/Page column 154
[21] Patent: KR2015/129282, 2015, A, . Location in patent: Paragraph 0125-0130
[22] Patent: US9773985, 2017, B2, . Location in patent: Page/Page column 121; 122
[23] Patent: KR101649950, 2016, B1, . Location in patent: Paragraph 0085; 0086
[24] Patent: US2013/48975, 2013, A1, . Location in patent: Paragraph 0050; 0051; 0052; 0053
[25] Patent: KR2015/43669, 2015, A, . Location in patent: Paragraph 0127; 0132; 0133
[26] Journal of Organometallic Chemistry, 2017, vol. 829, p. 92 - 100
[27] Patent: KR2017/96767, 2017, A, . Location in patent: Paragraph 0153; 0154
[28] Polyhedron, 2014, vol. 82, p. 71 - 79
[29] Dyes and Pigments, 2018, vol. 156, p. 369 - 378

2
[ 108-86-1 ]
[ 3652-90-2 ]
[ 94994-62-4 ]

Reference： [1] Patent: CN108203428, 2018, A, . Location in patent: Paragraph 0049; 0051
[2] Patent: CN108203427, 2018, A, . Location in patent: Paragraph 0046; 0047

3
[ 3652-90-2 ]
[ 1001911-63-2 ]

Reference： [1] Patent: WO2012/39561, 2012, A1,
[2] Patent: WO2012/169821, 2012, A1,
[3] Patent: WO2013/122402, 2013, A1,
[4] Patent: WO2013/162284, 2013, A1,
[5] Patent: WO2014/3440, 2014, A1,
[6] Patent: KR2015/61811, 2015, A,
[7] Patent: KR101565039, 2015, B1,
[8] Patent: KR2015/102733, 2015, A,
[9] Patent: KR101649950, 2016, B1,
[10] Journal of Organometallic Chemistry, 2017, vol. 829, p. 92 - 100
[11] Polyhedron, 2014, vol. 82, p. 71 - 79

4
[ 3652-90-2 ]
[ 1246669-45-3 ]

Reference： [1] Patent: EP2930168, 2015, A1,
[2] Patent: KR101550768, 2015, B1,
[3] Patent: KR2015/98171, 2015, A,
[4] Patent: KR2015/87787, 2015, A,
[5] Patent: KR2015/43669, 2015, A,
[6] Patent: KR2015/89427, 2015, A,
[7] Patent: KR101614738, 2016, B1,
[8] Patent: WO2017/196081, 2017, A1,
[9] Dyes and Pigments, 2018, vol. 156, p. 369 - 378

5
[ 3652-90-2 ]
[ 591-50-4 ]
[ 1246669-45-3 ]

Reference： [1] Journal of Physical Chemistry B, 2012, vol. 116, # 15, p. 4603 - 4614

6
[ 3652-90-2 ]
[ 1591-31-7 ]
[ 1393835-87-4 ]

Yield	Reaction Conditions	Operation in experiment
70%	With 1,10-Phenanthroline; potassium carbonate; copper(l) chloride In dimethyl sulfoxide at 150℃; for 12 h; Inert atmosphere	22.22 g (90.3 mmol) of a 2-bromocarbazole compound, 37.94 g (135.5 mmol) of 4-iodobiphenyl and 18.72 g (135.5 mmol) of potassium carbonate were dissolved in 400 mL of dimethylsulfoxide, and 3.26 g (135.47 mmol) of 1,10-phenanthroline and 1.79 g (18.06 mmol) of copper chloride (I) were added therein in a dropwise fashion in a 1,000 mL round-bottomed flask having an agitator and a nitrogen atmosphere. The reaction solution was agitated under a nitrogen flow for 12 hours at 150° C. When the reaction was complete, distilled water was poured into the reactant. Then, a solid produced therein was dissolved in chlorobenzene, and activated carbon and anhydrous magnesium sulfate were added thereto. The mixture was agitated. The solution was filtered and recrystallized using chlorobenzene and methanol, obtaining 25 g (yield=70percent) of a compound E.

Reference： [1] Patent: US2013/56720, 2013, A1, . Location in patent: Paragraph 0221-0223
[2] Patent: KR2017/96767, 2017, A, . Location in patent: Paragraph 0151; 0152

7
[ 3652-90-2 ]
[ 92-66-0 ]
[ 1393835-87-4 ]

Reference： [1] Patent: CN108203428, 2018, A, . Location in patent: Paragraph 0135; 0136
[2] Patent: CN108203427, 2018, A, . Location in patent: Paragraph 0129; 0131

[ 3652-90-2 ] Synthesis Path-Downstream 1~88

1
[ 67-56-1 ]
[ 3652-90-2 ]
[ 6933-49-9 ]

Reference： [1]Chemical and pharmaceutical bulletin,1981,vol. 29,p. 1231 - 1236

2
[ 35450-34-1 ]
[ 3652-90-2 ]

Yield	Reaction Conditions	Operation in experiment
75%	With triethyl phosphite; In 1,2-dichloro-benzene; at 80 - 150℃;Inert atmosphere;	Under nitrogen protection, 200 mol of triethyl phosphite and 5 L of 1,2-dichlorobenzene were added to the reactor, and the temperature was raised to 150 C. and microcirculated.At about 80 C, 20 mol of 4'-bromo-2-nitrobiphenyl was dissolved in 18 L of 1,2-dichlorobenzene.Then, a solution of 4'-bromo-2-nitrobiphenyl in 1,2-dichlorobenzene was slowly added dropwise to a mixed system of triethyl phosphite and 1,2-dichlorobenzene under reflux.After the addition was completed, keep the reflux for 4 to 5 hours, detected to 4'-bromo-2-nitrobiphenyl reaction is completed.The ethyl acetate was recrystallized to give 2-bromocarbazole in a yield of 75%.
67.6%		500 g of triethyl phosphite and 202 g of 4-bromo-2'-nitrobiphenyl obtained in the above step 1 were charged into a 2,000-ml reaction flask, and the mixture was heated to 160 C and allowed to react for 2 hours After cooling to 20 C, 300 ml of 35% concentrated hydrochloric acid was added and the mixture was heated to reflux for 1 hour. The mixture was then allowed to cool to about 30 C whereupon a large amount of off-white solid precipitated. After filtration and drying, 136.6 g of 2-bromocarbazole was obtained as an off-white solid. The HPLC spectrum of 2-bromocarbazole as shown in Fig. 2 showed that the 2-bromocarbazole content was 99.91%, the reaction of 2-bromocarbazole
65%	With triethyl phosphite;Inert atmosphere; Reflux;	Under a nitrogen atmosphere, 100 mmol of 4'-bromo-2-nitrobiphenyl was set to reflux overnight in stirring triethylphosphite. After cooling, the triethylphosphite was distilled off and 2-bromo-9H-carbazole was isolated by recrystallization from methanol and further purified by train sublimation, resulting in a 65% yield._

65%	With triethyl phosphite;Inert atmosphere; Reflux;	Under a nitrogen atmosphere, 100 mmol of 4?-bromo-2-nitrobiphenyl was set to reflux overnight in stirring tirethylphosphite. After cooling, the triethylphosphite was distilled off and 2-bromo-9H-carbazole was isolated by recrystallization from methanol and further purified by train sublimation, resulting in a 65% yield.
65%		A round bottom flask was charged with 4?-bromo-2-nitro-1,1?-biphenyl (14.5 g, 52.1 mmol), triethyl phosphite (50 g, 301 mmol) and heated to reflux under nitrogen overnight. The reaction mixture was allowed to cool to room temperature and 60 mL of 6 N HCl was added dropwise. The reaction mixture was then heated to 80 C. for 3 hours. The reaction mixture was then cooled and neutralized with 50% NaOH, diluted with water and extracted with 3×150 mL EtOAc. The combined organic extracts were washed with 150 mL water and 150 mL brine, dried over MgSO4 and evaporated to dryness. The lower boiling impurities were removed by Kugelrohr distillation and the residue was chromatographed (SiO2, 9/1 hexane/EtOAc) to yield 8.4 g (65%) of 2-bromo-9H-carbazole as an off-white solid. The product was confirmed by GC/MS and NMR.
65%		Synthesis of 2-Bromo-9H-carbazole (0204) A round bottom flask was charged with 4?-bromo-2-nitro-1,1?-biphenyl (14.5 g, 52.1 mmol), triethyl phosphite (50 g, 301 mmol) and heated to reflux under nitrogen overnight. The reaction mixture was allowed to cool to room temperature (20-25 C.) and 60 mL of 6 N HCl was added dropwise. The reaction mixture was then heated to 80 C. for 3 hours. The reaction mixture was then cooled to 5 C. and neutralized with 50% NaOH, diluted with deionized water and extracted with 3×150 mL EtOAc. The combined extracts were washed with 150 mL deionized water and 150 mL brine, dried over MgSO4 and evaporated to dryness. The lower boiling impurities were removed by Kugelrohr distillation and the residue was subjected to a column chromatography (SiO2 gel, 9/1 hexane/EtOAc) to yield 8.4 g (65%) of 2-Bromo-9H-carbazole as an off-white solid. The product was confirmed by GC/MS and NMR.
56%	With triphenylphosphine; In 1,2-dichloro-benzene; at 180℃; for 10h;Inert atmosphere;	4?-bromo-2-nitro-biphenyl(5.9 g, 21.3 mmol), triphenylphosphine (13.96 g, 53 mmol) were added to 70 mL of anhydrous 1,2-diclorobenzene solution in 3-neck roundbottom flask under N2 atmosphere. The mixture was refluxed at 180 Cfor 10 h (3.27 g, Yield 56%) 1H NMR (300 MHz, THF): delta(ppm) 10.45 (s,1H), 8.04-8.01 (d, 1H), 7.96-7.94 (d, 1H), 7.57 (s, 1H), 7.42-7.32 (m,2H), 7.27-7.24 (d, 1H), 7.17-7.11 (t, 1H).
52%	With triethyl phosphite; at 150 - 160℃; for 30h;Inert atmosphere;	Synthesis of 2-bromo-9H-c 4'-bromo-2-nitrobiphenyl (22.40 g, 80.55 mmol) and P(OEt)3 (150 mL) were added under nitrogen to a three-necked round bottom flask equipped with a magnetic stir bar and a condenser. The mixture was heated to 150-160 C in an oil bath for 30 hours, cooled to ambient temperature, and the excess P(OEt)3 was removed by distillation under high vacuum. The residue was recrystallized in toluene to afford the desired product, 2-bromo-9H-carbazole, (8.30 g) as a white crystal. The filtrate was concentrated and the residue was purified through column chromatography on silica gel using hexane and ethyl acetate (10: 1-5: 1) as eluent to obtain the desired product, 2-bromo-9H-carbazole 1 (2.00 g in 52% yield). ^ NMR (DMSO-d6, 400 MHz): delta 7.17 (t, J= 7.6 Hz, IH), 7.28 (dd, J= 8.0, 1.6 Hz, IH), 7.41 (t, J= 7.6 Hz, IH), 7.49 (d, J = 8.4 Hz, IH), 7.65 (d, J= 1.6 Hz, IH), 8.06 (d, J= 8.4 Hz, IH), 8.11 (d, J = 7.6 Hz, IH), 1 1.38 (s, IH). 13C NMR (DMSO-J6, 100 MHz): delta 111.22, 113.50, 118.11, 119.09, 120.36, 121.29, 121.58, 121.79, 121.90, 126.09, 139.89, 140.62. The spectroscopic data is consistent with that previously reported (Pan, j.; Wang, X.; Zhang, Y.; Buchwald, S. L. Org. Lett. 2011, 13, 4974-4976).
52%	With triethyl phosphite; at 150 - 160℃; for 30h;Inert atmosphere;	4?-Bromo-2-nitrobiphenyl (22.40 g, 80.55 mmol) and P(OEt)3 (150 mL) were added to a three-necked flask equipped with a magnetic stir bar and a condenser under the protection of nitrogen. The mixture was then stirred in an oil bath at a temperature of 150-160 C. for 30 hours, cooled to ambient temperature and the excess P(OEt)3 was removed by distillation under high vacuum. The residue was recrystallized in toluene to get the desired product 2-bromo-9H-carbazole 8.30 g as a white crystal. The filtrate was concentrated and the residue was purified through column chromatography on silica gel using hexane and ethyl acetate (10:1-5:1) as eluent to obtain the desired product 2-bromo-9H-carbazole 2.00 g in 52% total yield. 1H NMR (DMSO-d6, 400 MHz): delta 7.17 (t, J=7.6 Hz, 1H), 7.28 (dd, J=8.0, 1.6 Hz, 1H), 7.41 (t, J=7.6 Hz, 1H), 7.49 (d, J=8.4 Hz, 1H), 7.65 (d, J=1.6 Hz, 1H), 8.06 (d, J=8.4 Hz, 1H), 8.11 (d, J=7.6 Hz, 1H), 11.38 (s, 1H). 13C NMR (DMSO-d6, 100 MHz): delta 111.22, 113.50, 118.11, 119.09, 120.36, 121.29, 121.58, 121.79, 121.90, 126.09, 139.89, 140.62.
45%	With triphenylphosphine; In 1,2-dichloro-benzene; at 180℃; for 18h;Inert atmosphere;	[267] In a 250 ml round-bottom three-neck flask under a nitrogen atmosphere, 10.5 g of Intermediate 19, 24.8 g of triphenylphosphine and 230 ml of o-dichlorobenzene were placed, and stirred at 180C for 18 hrs. The reaction solution was concentrated and then subjected to column chromatography using a solvent mixture of dichloromethane and n-hexane, thus obtaining 4.2 g of Intemiediate 20 (yield 45%).[268] MS (ESI): [M+H]+ 246
44.38%	With triethyl phosphite; at 150℃; for 6h;	Compound 1-1 (28g, 100.68mmol) was mixed with triethylphosphite 300mL and stirred at 150C for 6 hours. The mixture was cooled to room temperature, distilled under reduced pressure, extracted with EA, and then washed with distilled water. Subsequently, drying with anhydrous MgSO4, distillation under reduced pressure and then column separation were conducted, yielding Compound 1-2 (11g, 44.69mmol, 44.38%).
44.38%	With triethyl phosphite; at 150℃; for 6h;	Preparation of compound 1-2 [98] After mixing compound 1-1 (28 g, 100.68 mmol) with triethylphosphite 300 mL, the reaction mixture was stirred for 6 hours at 150C. The reaction mixture was cooled to room temperature, was distillated under reduced pressure, was extracted with ethyl acetate, and was washed with distilled water. The reaction mixture was dried with MgSO4, was distillated under reduced pressure, and was filtered through column to obtain compound 1-2 (11 g, 44.69 mmol, 44.38 %).
44.38%	With triethyl phosphite; at 150℃; for 6h;	Compound 6-1 28g (100.68mmol) was mixed with triethylphosphite 300ml, and then the mixture was stirred at 150 . After 6 hours, the resultant material was cooled to room temperature, and then distilled under reduced pressure, followed by extraction with EA and wash with distilled water. Then, drying over magnesium sulfate, distillation under reduced pressure, and then column separation were performed, thereby obtaining Compound 6-2 11g(44.69mmol, 44.38%).
40.38%	With triethyl phosphate; at 150℃; for 7h;	[163] After dissolving compound 1-2 (28 g, 100.6 mmol) in triethyl phosphate 300 mL, the mixture was reacted at 150C for 7 hours. After terminating the reaction, the mixture was cooled to room temperature, and distilled under reduced pressure. The mixture was extracted with methylene chloride (MC), and washed with distilled water. The remaining moisture was removed with magnesium sulfate. After drying, the resulting product was distilled under reduced pressure, and separated through a column to obtain compound 1-3 (10 g, 40.63 mmol, 40.38 %).
40%	With triethyl phosphite; for 24h;Reflux; Inert atmosphere;	Around bottom flask was charged with 4'-bromo-2-nitrobiphenyl (100 mmol) and triethyl phosphite (100 mL) and set to reflux under a nitrogen atmosphere for 24 hours. Upon cooling, the solvent was distilled off under vacuum, and the crude product was recrystallized from hot toluene to give 2-bromo-9H-carbazole in 40% yield.
	With nitrogen; triphenylphosphine; In methanol; ethyl acetate; 1,2-dichloro-benzene;	H. Synthesis of 2-Bromo-9H-carbazole Triphenylphosphine (156.3 g, 596 mmol, 2.5 equiv) was added over 5 minutes to a solution 4'-bromo-2-nitro-1,1'-biphenyl (66.25 g, 238 mmol, 1.0 equiv) in 1,2-dichlorobenzene (460 mL). The reaction was sparged with nitrogen 5 minutes, then refluxed for 16 hours. The reaction was cooled to room temperature and vacuum distilled to remove most of the 1,2-dichlorobenzene (450 mL). This dark residue was dissolved in ethyl acetate (1.5 L) and treated with decolorizing carbon (50 g) at 50 C. for 30 minutes. After cooling, the mixture was filtered through Celite (200 g), then washed with ethyl acetate washes (2650 mL). The combined filtrates were concentrated under reduced pressure to a volume of ?500 mL. The solution was cooled to room temperature and after 1.5 hours, the resulting pale tan solid (triphenylphosphine oxide) was removed by filtration and discarded. The filtrate was concentrated under reduced pressure. The residue was dissolved in methanol (600 m L) and stored at room temperature for 16 hours. The resulting tan solid was filtered, washed with methanol (2100 mL) and dried under vacuum at 40 C. to give 2-bromo-9H-carbazole as a pale tan solid (33.5 g, 57.2% yield).

Reference： [1]ACS Chemical Neuroscience,2019,vol. 10,p. 396 - 411
[2]Patent: CN105061296,2018,B .Location in patent: Paragraph 0033; 0034
[3]Patent: CN105315194,2016,A .Location in patent: Paragraph 0022; 0024; 0027
[4]Patent: US2012/302753,2012,A1 .Location in patent: Page/Page column 28
[5]Patent: US2015/274762,2015,A1 .Location in patent: Paragraph 0158; 0159
[6]Patent: US9461254,2016,B2 .Location in patent: Page/Page column 185-186
[7]Patent: US9450195,2016,B2 .Location in patent: Page/Page column 141
[8]Dyes and Pigments,2018,vol. 156,p. 369 - 378
[9]Patent: WO2015/27060,2015,A1 .Location in patent: Paragraph 00112
[10]Patent: US10020455,2018,B2 .Location in patent: Paragraph 681; 684
[11]Patent: WO2017/196081,2017,A1 .Location in patent: Paragraph 265; 266; 267; 268
[12]Patent: WO2012/39561,2012,A1 .Location in patent: Page/Page column 20
[13]Patent: WO2012/169821,2012,A1 .Location in patent: Page/Page column 16
[14]Patent: EP2857395,2015,A1 .Location in patent: Paragraph 0061
[15]Patent: WO2013/162284,2013,A1 .Location in patent: Paragraph 162; 163
[16]Patent: US9312502,2016,B2 .Location in patent: Page/Page column 27; 28
[17]Journal of Heterocyclic Chemistry,2001,vol. 38,p. 11 - 23
[18]Macromolecules,2010,vol. 43,p. 1379 - 1386
[19]Journal of Materials Chemistry C,2013,vol. 1,p. 4171 - 4179
[20]Patent: US2016/72082,2016,A1

3
[ 3460-18-2 ]
[ 98-80-6 ]
[ 3652-90-2 ]
[ 88590-00-5 ]

Reference： [1]Synthesis,2005,p. 1619 - 1624

4
[ 110-87-2 ]
[ 3652-90-2 ]
[ 183012-41-1 ]

Yield	Reaction Conditions	Operation in experiment
99%	With pyridinium p-toluenesulfonate In dichloromethane Reflux;
90%	In dichloromethane at 20 - 50℃; for 4h;	1 10 mmol of 2-bromo-9H-carbazole, 0.1 mmol of pyridinium toluene-4-sulphonate, and 50 mmol of 3,4-dihydro-2H-pyran was added to dichloromethane at room temperature and let stir for 2 hours before the temperature was raised to 50° C. for 2 hours further. The solution was cooled, concentrated under reduced pressure, and subjected to column chromatography of silica with dichloromethane as the eluent. After concentrating under reduced pressure, 2-bromo-9-(tetrahydro-2H-pyran-2-yl)-9H-carbazole was isolated in 90% yield. 2-(1H-pyrazol-1-yl)-9-(tetrahydro-2H-pyran-2-yl)-9H-carbazole:
	With camphor-10-sulfonic acid In dichloromethane	R.3 2-Bromo-9-tetrahydropyranyl-9H-carbazole Reference Example 3 2-Bromo-9-tetrahydropyranyl-9H-carbazole A mixture of 24.61 g (100 mmol) of 2-bromo-9H-carbazole, 250 ml of methylene chloride, 11.4 ml (125 mmol) of 3,4-dihydro-2H-pyran and 1.16 g (5.0 mmol) of camphorsulfonic acid was stirred at room temperature for 30 minutes. The reaction solution was poured into 1 N aqueous sodium hydroxide and partitioned. The resulting organic layer was washed with water and brine and dried over sodium sulfate. Then, the solvent was evaporated under reduced pressure to give a yellow and oily crude product. The crude product was crystallized from methanol to give 23.80 g of the title compound as white crystals. Nuclear magnetic resonance spectrum (DMSO-d6, TMS internal standard) δ: 1.62 (1H, d, J=13Hz), 1.72-1.89 (3H, m), 1.96-1.98 (1H, m), 2.26-2.34 (1H, m), 3.78-3.83 (1H, m), 4.14-4.16 (1H, m), 6.00 (1H, dd, J=2Hz, 11Hz), 7.24 (1H, t, J=7Hz), 7.36 (1H, dd, J=2Hz, 9Hz), 7.45-7.48 (1H, m), 7.80 (1H, d, J=8Hz), 8.00 (1H, d, J=1Hz), 8.10 (1H, d, J=8Hz), 8.16 (1H, d, J=7Hz).

Reference： [1]Current Patent Assignee: ARIZONA BOARD OF REGENTS - US2016/359120, 2016, A1 Location in patent: Paragraph 0146
[2]Current Patent Assignee: ARIZONA BOARD OF REGENTS - US2012/302753, 2012, A1 Location in patent: Page/Page column 29
[3]Current Patent Assignee: ASTELLAS PHARMA INC - EP820989, 1998, A1

5
[ 86-79-3 ]
[ 3652-90-2 ]

Yield	Reaction Conditions	Operation in experiment
	With N-Bromosuccinimide; 2,2'-azobis(isobutyronitrile); In tetrachloromethane; for 2h;	The title compound was prepared according to the following method. First in a similar manner to Preparative Example 11, 1 M NBS and AIBN were added to a carbon tetrachloride solution containing 0.5 mM of <strong>[86-79-3]2-hydroxycarbazole</strong>; and the mixture was stirred for two hours and filtered under reduced pressure, to give 2-bromocarbazole. Subsequently in a similar manner to Preparative Example 8, 0.3 mole of metal magnesium and 30 ml of THF were placed in a flask under a nitrogen environment, 2-bromocarbazole above was added thereto; and the mixture was allowed to react at 60 C. for two hours, to give a Grignard reagent. The Grignard reagent was then added to a THF solution containing 0.5 mole of tetrachlorosilane, and the mixture was allowed to react at 20 C. for one hour. After reaction, the reaction solution was filtered under reduced pressure for removal of magnesium chloride, and THF and unreacted compound were removed from the filtrate, to give the title compound at a yield of 60%.Infrared absorption spectrum measurement of the compound obtained showed an absorbance derived from SiC bond at 1080 cm-1, indicating that the compound had a SiC bond.Further, nuclear magnetic resonance (NMR) measurement of the compound was performed. Since the direct NMR measurement of the compound obtained was not possible because of the high reactivity of the compound, the compound was allowed to react with ethanol (with accompanied generation of hydrogen chloride), converting the terminal chlorine into an ethoxy group, before measurement.8.5 ppm (m) (1H, hydrogen bound directly to nitrogen atom)7.6 ppm to 7.5 ppm (m) (4H, aromatic)7.2 ppm (m) (3H, aromatic)3.5 ppm (m) (6H, ethoxy group methylene group)1.4 ppm (m) (9H, ethoxy group methyl group)These results indicated that the compound obtained was the compound represented by General Formula (alphaII-3).

Reference： [1]Patent: US2009/5557,2009,A1 .Location in patent: Page/Page column 25

6
[ 18908-66-2 ]
[ 3652-90-2 ]
[ 856422-39-4 ]

Yield	Reaction Conditions	Operation in experiment
91%	Stage #1: 2-bromo-9H-carbazole With potassium <i>tert</i>-butylate In tetrahydrofuran at 20℃; for 2h; Stage #2: 3-bromomethylheptane In tetrahydrofuran Reflux;	2-bromo-9-octyl-9H-carbazole (3) A mixture of 2-bromo-9H-carbazole (5.0 g, 20.4 mmol), t-BuOK (2.5 g, 22.3 mmol) were dissolved in 100 mL THF and stirred 2 h under room temperature. Then, 1-bromo-iso-octane (7.8 g, 40.6 mmol) was added and the mixture was allowed to reflux overnight. The cooled reaction mixture was extracted by CH2Cl2 in water, dried with MgSO4. The organic solvent was removed under reduced pressure and the product was purified by silica gel chromography using petroleum ether: CH2Cl2 = 7:1 as white oil product (6.6 g, 91%).1H NMR (CDCl3, 500 MHz, ppm): 8.06 (d, 1H), 7.90 (d, 1H), 7.49 (s, 1H), 7.45 (t,1H), 7.36 (d, 1H), 7.29 (d, 1H), 7.23 (t, 1H),4.06 (t, 2H), 2.06 (m, 1H), 1.49-1.13 (m, 8H), 0.9-0.71 m, 6H. 13C NMR (CDCl3, 500 MHz) 141.78, 141.06, 126.03, 122.32, 121.90,121.77, 121.42, 120.29, 119.31, 119.21, 112.05, 109.22, 47.54, 39.42, 30.93, 28.72, 24.40, 23.08, 14.06, 10.93. (GC/Q-TOF, m/z). Calcd for C20H24BrN (M +): 357.1. Found: 357.1.
88%	With tetra(n-butyl)ammonium hydrogensulfate; potassium hydroxide In acetone for 12h; Reflux;	3 Example 3 Synthesis of 2-bromo-N-9- (2-ethylhexyl) carbazole 492.2 mg (2.00 mmol) of 2-bromocarbazole was dissolved in a three-necked reaction flask containing 12 ml of acetone and then224.4 mg (4.00 mmol) powdered potassium hydroxide (KOH), 772.48 mg (4.00 mmol) 2-ethylhexyl bromide,33.33 mg phase transfer catalyst tetrabutylammonium hydrogen sulfate. The reaction mixture was slowly heated to reflux for 12 hours. Will be reversedAfter allowing to cool to room temperature, it is extracted with methylene chloride, dried over anhydrous sodium sulfate overnight, and the solvent is evaporated in vacuo to give the crude product. CrudeThe product was purified by silica gel column chromatography using a mixed solvent of n-hexane and ethyl acetate (10: 1, v / v) as eluent to giveTo a colorless, oily liquid, 628.51 mg (yield: 88%).
85%	With tetra(n-butyl)ammonium hydrogensulfate; potassium hydroxide In acetone Reflux;	2.2.1. Synthesis of M1 Potassium hydroxide powder (1.35 g, 24 mmol), 2-ethylhexyl bromide(4.26 mL, 24 mmol), and tetrabutylammonium hydrogen sulfate(0.2 g, 0.59 mmol) were added to Cz-Br in acetone (30 mL,0.4 mol L-1). The reaction mixture was heated slowly to reflux forovernight, and then poured into water and extracted with dichloromethane.The organic layer was washed with water and driedover anhydrous magnesium sulfate. Further purification was performedby column chromatography on silica gel with hexane: ethyl acetate (10:1, v/v) as eluent, yielding 3.86 g (85%) of 2-bromo-9-(2-ethylhexyl)carbazole (M1) as colorless oil. 1H-NMR (400 MHz, CDCl3, δ): 8.02 (d,1H), 7.87 (d, 1H), 7.45 (m, 2H), 7.32 (d, 1H), 7.29 (d, 1H), 7.20 (t, 1H),4.00 (m, 2H), 2.00 (m, 1H), 1.40-1.15 (m, 8H), 0.95-0.78 (m, 6H).

80%

Stage #1: 2-bromo-9H-carbazole With potassium tert-butylate In N,N-dimethyl-formamide at 20℃; for 1h; Stage #2: 3-bromomethylheptane In N,N-dimethyl-formamide at 130℃; for 65h;

Reference： [1]An, Jincheng; Yang, Xichuan; Tian, Zhifeng; Cai, Bin; Zhang, Li; Yu, Ze; Wang, Xiuna; Hagfeldt, Anders; Sun, Licheng [Tetrahedron, 2021, vol. 88]
[2]Current Patent Assignee: CHANGZHOU UNIVERSITY - CN106674229, 2017, A Location in patent: Paragraph 0029; 0030
[3]Wang, Yanbin; Wang, Teng; Chen, Jinxing; Kim, Hyung Do; Gao, Penghan; Wang, Biaobing; Iriguchi, Ryo; Ohkita, Hideo [Dyes and Pigments, 2018, vol. 158, p. 213 - 218]
[4]Moss, Kathryn C.; Bourdakos, Konstantinos N.; Bhalla, Vandana; Kamtekar, Kiran T.; Bryce, Martin R.; Fox, Mark A.; Vaughan, Helen L.; Dias, Fernando B.; Monkman, Andrew P. [Journal of Organic Chemistry, 2010, vol. 75, # 20, p. 6771 - 6781]

7
[ 70873-41-5 ]
[ 3652-90-2 ]

Yield	Reaction Conditions	Operation in experiment
82.4%	With triethylphosphine; for 12h;Reflux;	71.9 g (0.26 mol) of the compound represented by the formula (6-a) obtained from the scheme [19] was added to a 1 L round bottom flask,And 360 mL of triethylphosphineAnd refluxed for 12 hours. After completion of the reaction, the temperature was lowered to room temperature and the crystals were filtered. The residue was recrystallized from methanol and dried to obtain 52.4 g (82.4%) of a compound represented by the general formula [6-b]
77%	With triphenylphosphine; In 1,2-dichloro-benzene; at 200℃;	The intermediate A 1mol Was dissolved in o-dichlorobenzene was added to 2.5mol triphenylphosphine and the resulting mixture was stirred at 200C . After completion of reaction by distillation to remove the o-dichlorobenzene and dried the organic layer was extracted CH2Cl2 and water with anhydrous MgSO4 and purified by column chromatography and re-crystallization and the resulting product was then concentrated to give the desired intermediate B (yield: 77%).
77%	With triphenylphosphine; In 1,2-dichloro-benzene;Inert atmosphere; Reflux;	Under nitrogen atmosphere, intermediate A 2.78g (10mmol) was dissolved in 20ml o- dichlorobenzene and triphenylphosphine 6.56g (25mmol) was added and the mixture was refluxed. After completion of the reaction, MC 100ml, H2O 100ml was added and then the the MC layer was extracted, concentrated and separated by column chromatography using Hex : EA =5 : 1 and dried over anhydrous MgSO4 to give the intermediate B 1.89g (77%).

74%	With triphenylphosphine; In 1,2-dichloro-benzene; at 200℃;	After the Sub 1-I-1 (122.68g, 441.1mmol) was dissolved in o-dichlorobenzene (1810ml) in a round bottom flask,Was added triphenylphosphine (289.26g, 1102.8mmol) was stirred at 200 . After completion of reaction by distillationRemove the o-dichlorobenzene and extracted with water and CH2Cl2. The resulting compound and the organic layer was dried over MgSO4, and concentratedA silicagel column and the product was recrystallized 80.34g: (yield: 74%).
74%	With triphenylphosphine; In 1,2-dichloro-benzene; at 200℃;	After dissolved Sub 1-I-1 (122.68g, 441.1mmol) obtained in the above synthesis witho-dichlorobenzene (1810ml) in a round bottom flask, was added triphenylphosphine(289.26g, 1102.8mmol) was stirred at 200 C. After completion of reaction wasremoved by distillation and the o-dichlorobenzene and water, extracted CH2Cl2. Theresulting compound and the organic layer was dried over MgSO4 and concentrated to silicagel column and the product was recrystallized 80.34g: (yield: 74%).
74%	With triphenylphosphine; In 1,2-dichloro-benzene; at 200℃;	Sub 1-I-1 (122.68g , 441.1mmol) in a round bottom flask o was dissolved in o-dichlorobenzene (1810ml), was added triphenylphosphine (289.26g,1102.8mmol) was stirred at 200 . When the reaction is complete by distillation o remove -dichlorobenzene and CH 2 Cl 2 and extracted with water.The organic layer is MgSO 4 and the resulting compound was dried and concentrated to a silicagel column and the product was recrystallized 80.34g:(yield: 74%).
74%	With triphenylphosphine; In 1,2-dichloro-benzene; at 200℃;	Sub 1-I-1 (122.68 g, 441.1 mmol) obtained in the synthesis was dissolved in o-dichlorobenzene 1810 mL in a round bottom flask, triphenylphosphine (289.26 g, 1102.8 mmol) was added and the resulting mixture was stirred at 200 C. After completion of the reaction, o-dichlorobenzene and water was removed by distillation, and extracted with CH2Cl2. The organic layer was dried with MgSO4, concentrated using silica gel column and recrystallized to obtain product 80.34 g (yield: 74%) .
72%	With triphenylphosphine; In 1,2-dichloro-benzene; at 200℃;	The obtained Sub 1-I-B1 (705.93g, 2538.4mmol) was dissolved in o-dichlorobenzene in a round bottom flask, and triphenylphosphine (1664.49g, 6346mmol) was added to the reaction solution, followed by stirring at 200C. Upon completion of the reaction, o-dichlorobenzene was removed by distillation, and the reaction product was extracted with CH2Cl2 and water. The extracted organic layer was dried with MgSO4 and concentrated, and then the produced organic material was separated by a silica gel column and recrystallized to obtain 449.78g of product (yield: 72%).
71%	With triphenylphosphine; In 1,2-dichloro-benzene; at 200℃;	M 2-I-32 (128.07 g, 460.5 mmol) obtained in the above synthesis was dissolved in o-dichlorobenzene in a round bottom flask, and then triphenylphosphine (301.97 g, 1151.3 mmol) was added, followed by stirring at 200 C. Upon completion of the reaction, o-dichlorobenzene was removed through distillation, followed by extraction with CH2Cl2 and water. The organic layer was dried over MgSO4 and concentrated, and then the thus generated compound was subjected to a silica gel column and recrystallization to give a product 80.47 g (yield: 71%).
70%	With triphenylphosphine; In 1,2-dichloro-benzene; at 200℃;	The Sub 1-I-1 (183.01g, 658.1mmol) obtained in the above synthesis was dissolved in o-dichlorobenzene in a round bottom flask, was added triphenylphosphine (431.51g, 1645.2mmol) was stirred at 200C . After completion of reaction was removed by distillation and the o-dichlorobenzene and water, extracted CH2Cl2. The resulting compound and the organic layer was dried over MgSO4, concentrated and recrystallized by silicagel column 113.37g product (yield: 70%) was obtained.
68%	With triphenylphosphine; In 1,2-dichloro-benzene; at 180℃; for 8h;Inert atmosphere;	Subsequently, under an argon gas atmosphere, the intermediate body 7-2 (6.6 g, 23.7 mmol), triphenylphosphine (15.6 g, 59.3 mmol), and o-dichlorobenzene (24 mL) were added together in sequential order, and heated to reflux at 180 degrees C for 8 hours. After cooled down to the room temperature, the reaction solution was refined by silica-gel column chromatography, whereby an intermediate body 1-3 (4 g, a yield of 68%) was obtained.
68%	With triphenylphosphine; In 1,2-dichloro-benzene; at 180℃; for 8h;Inert atmosphere;	In argon stream, a mixture obtained by successively mixingthe intermediate 1 (6.6 g, 23.7 mmol), triphenylphosphine(15.6 g, 59.3 mmol), and o-dichlorobenzene (24 mL) washeated at 180 C. for 8 h.After cooling the reaction liquid to room temperature, the reaction product was purified by a silica gel column chromatography to obtain the intermediate 2 (4 g, yield: 68%). The identification of the intermediate 2 was made by FD-MS (field desorption mass spectrometry) analysis.
68%	With triphenylphosphine; In 1,2-dichloro-benzene; at 180℃; for 8h;Inert atmosphere;	Under argon flow, Intermediate 1 (6.6 g, 23.7 mmol) was added sequentially, Triphenylphosphine (15.6 g, 59.3 mmol) O-dichlorobenzene (24 mL), And heated at 180 C for 8 hours. After the reaction solution was allowed to cool to room temperature, Purification by silica gel column chromatography, Intermediate 2 (4 g, yield 68%) was obtained. By FD-MS (field desorption mass spectrometry) analysis, Identified as intermediate 2.
68%	With triphenylphosphine; In 1,2-dichloro-benzene; at 180℃; for 8h;Inert atmosphere;	Subsequently, under an argon gas atmosphere, the intermediate 1-3 (6.6 g, 23.7 mmol), triphenylphosphine (15.6 g, 59.3 mmol), and o-dichlorobenzene (24 mL) were added together in sequential order, and heated to reflux at 180 degrees C. for eight hours. -After cooled down to the room temperature, the reaction solution was refined by silica-gel column chromatography, whereby an intermediate 1-4 (4 g, a yield of 68%) was obtained.
68%	With triphenylphosphine; In 1,2-dichloro-benzene; at 180℃; for 8h;Inert atmosphere;	Subsequently, under an argon gas atmosphere, the intermediate body 7-2 (6.6 g, 23.7 mmol), triphenylphosphine (15.6 g, 59.3 mmol), and o-dichlorobenzene (24 mL) were added together in sequential order, and heated to reflux at 180 degrees C. for 8 hours. After cooled down to the room temperature, the reaction solution was refined by silica-gel column chromatography, whereby an intermediate body 2H-3 (4 g, a yield of 68%) was obtained.
48%	With triethyl phosphite; In 1,2-dichloro-benzene; at 150℃; for 24h;	After adding compound C-7-1 (42 g, 150 mmol) in a mixture solvent of P(OEt)3 (450 mL), and 1,2-dichlorobenzene (300 mL), the mixture was stirred for 1 day at 150C. After completing the reaction, the mixture was concentrated under reduced pressure, and then extracted with EA, and then the organic layer was concentrated. The obtained product was separated with a column with MC/hexane to obtain compound C-7-2 (18 g, 48 %).
48%	With triethyl phosphite; In 1,2-dichloro-benzene; at 150℃; for 24h;	After dissolving compound C-62-1 42 g (150 mmol) in a mixture solvent of P(OEt)3450 mL, and 1,2-dichlorobenzene 300 mL, the mixture was stuffed at 150C for oneday. After completing the reaction, the mixture was concentrated under reducedpressure, extracted with EA, and the organic layer was concentrated. Then, theobtained product was separated with a column using MC/Hex to obtain compound C-62-2 18 g (48 %).
	With triethyl phosphite; at 160 - 165℃; for 14h;	triethylphosphate to 4-bromo-2-nitro-1,1'-biphenyl is heated to reflux in a state 160 ~165 C for 14 hours. When the reaction is complete, remove the remaining triethylphosphite by distillation under reduced pressure, and, MeOH: H 2 solid produced filtered and then diluted with a mixed solvent of 1: O = 1. The resulting solid MeOH: H 2 and wash with 1 mixed solvent and petroleum ether: O = 1. After the solids dissolved in methylene chloride MgSO 4 and concentrated to a dry silicagel column and to obtain a 2-bromo-9H-carbazole ( petroleum ether: methylene chloride = 2: 1).
	With triethyl phosphite;Reflux;	1,4-Dibromo-2-nitrobenzene (4.60 g, 0.016 mol) and phenylboronic acid (2.0 g, 0.016 mol) were refluxed in toluene (40 ml) with a catalytic amount of Pd(PPh3)4 (568 mg, 0.492 mmol). 4-Bromo-2-nitro-1-phenylbenzene (3.17 g, 0.011 mol) was formed and then refluxed in triethylphosphite to yield 2-bromocarbazole.2-Bromocarbazole (1.27 g, 5.162mmol) and iodobenzene (0.87 ml,7.741 mmol) were refluxed to yield 2-bromophenylcarbazole. After consecutive reactions with n-butyllithium and trimethylborate,boronic acid (0.622 g, 2.167 mmol) prepared would react with 2-bromothiazole (0.16 ml, 1.734 mmol). The ligand L3 was obtained as a white powder (60%). Spectral data: MS (MALDITOF):m/z 326.36 (M+). 1H NMR (CDCl3): delta (ppm) 8.17 (t, J=8.8 Hz,2H, Ar), 8.05 (s, 1H, Ar), 7.87-7.85 (m, 2H, Ar), 7.66-7.52 (m, 2H,Ar), 7.52-7.48 (m, 2H, Ar), 7.46-7.38 (m, 2H, Ar), 7.33-7.29 (m, 2H,Ar).

Reference： [1]Patent: KR101897045,2018,B1 .Location in patent: Paragraph 0269; 0276; 0278-0281
[2]Patent: KR101565039,2015,B1 .Location in patent: Paragraph 0093-0096
[3]Patent: KR2015/102733,2015,A .Location in patent: Paragraph 0115-0119
[4]Patent: KR101550768,2015,B1 .Location in patent: Paragraph 0147 - 0150
[5]Patent: KR2015/98171,2015,A .Location in patent: Paragraph 0138; 0142; 0147-0150
[6]Patent: KR2015/87787,2015,A .Location in patent: Paragraph 0140; 0145-0148
[7]Patent: KR101614738,2016,B1 .Location in patent: Paragraph 0194-0197
[8]Organic and Biomolecular Chemistry,2011,vol. 9,p. 4662 - 4670
[9]Patent: EP2930168,2015,A1 .Location in patent: Paragraph 0089; 0091
[10]Patent: JP2016/508131,2016,A .Location in patent: Paragraph 0051; 0053
[11]Patent: KR2015/89427,2015,A .Location in patent: Paragraph 0136; 0137; 0138; 0141; 0142
[12]Patent: EP2415769,2012,A1 .Location in patent: Page/Page column 114-115
[13]Patent: US9306171,2016,B2 .Location in patent: Page/Page column 136; 137
[14]Patent: TWI554499,2016,B .Location in patent: Page/Page column 83
[15]Patent: US9711732,2017,B2 .Location in patent: Page/Page column 214
[16]Patent: US9966541,2018,B2 .Location in patent: Page/Page column 100-101
[17]Patent: WO2013/122402,2013,A1 .Location in patent: Paragraph 196; 199; 200
[18]Patent: WO2014/3440,2014,A1 .Location in patent: Paragraph 172; 173; 176; 177
[19]Tetrahedron,2011,vol. 67,p. 8248 - 8254
[20]Journal of Materials Chemistry,2011,vol. 21,p. 7811 - 7819
[21]Bulletin of the Korean Chemical Society,2011,vol. 32,p. 2461 - 2464
[22]Journal of Materials Chemistry,2012,vol. 22,p. 215 - 224
[23]Dalton Transactions,2014,vol. 43,p. 13076 - 13086
[24]Patent: KR2015/43669,2015,A .Location in patent: Paragraph 0127; 0130; 0131
[25]Journal of Organometallic Chemistry,2017,vol. 829,p. 92 - 100
[26]Polyhedron,2014,vol. 82,p. 71 - 79

8
[ 112671-42-8 ]
[ 3652-90-2 ]

Reference： [1]Organic and Biomolecular Chemistry,2011,vol. 9,p. 4662 - 4670
[2]Patent: EP2930168,2015,A1
[3]Patent: KR101550768,2015,B1
[4]Patent: KR2015/98171,2015,A
[5]Patent: KR2015/43669,2015,A
[6]Patent: KR2015/89427,2015,A
[7]Patent: KR101565039,2015,B1
[8]Patent: KR2015/102733,2015,A

9
[ 3652-90-2 ]
[ 645-00-1 ]
[ 1313900-06-9 ]

Yield	Reaction Conditions	Operation in experiment
85%	With copper(l) iodide; caesium carbonate In N,N-dimethyl-formamide at 220℃; for 0.5h; Microwave irradiation;	4.2. General experimental procedure for microwave-assisted N-arylation of carbazoles General procedure: 9H-Carbazole (1.0 mmol), Cs2CO3 (1.0 mmol), iodobenzene (1.1 mmol), CuI (0.1 mmol), and DMF (2 mL) were added to a 5-mL vial. The vial was sealed with a crimp cap and placed in a Biotage initiator microwave cavity. After irradiation at 220 °C for the appropriate time and subsequent cooling, the reaction mixture was diluted with saturated aqueous ammonium chloride. Products were isolated by extraction into ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated. Products were purified by silica gel column chromatography using a hexane/ethyl acetate solvent. N-Phenyl-carbazole (2a)22 was obtained (96% yield) as a white solid.

Reference： [1]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]

10
[ 3652-90-2 ]
[ 589-87-7 ]
[ 1313900-03-6 ]

Yield	Reaction Conditions	Operation in experiment
85%	With copper(l) iodide; caesium carbonate; lithium chloride In N,N-dimethyl-formamide at 150℃; for 48h;
82%	With copper(l) iodide; caesium carbonate In N,N-dimethyl-formamide at 220℃; for 0.5h; Microwave irradiation;	4.2. General experimental procedure for microwave-assisted N-arylation of carbazoles General procedure: 9H-Carbazole (1.0 mmol), Cs2CO3 (1.0 mmol), iodobenzene (1.1 mmol), CuI (0.1 mmol), and DMF (2 mL) were added to a 5-mL vial. The vial was sealed with a crimp cap and placed in a Biotage initiator microwave cavity. After irradiation at 220 °C for the appropriate time and subsequent cooling, the reaction mixture was diluted with saturated aqueous ammonium chloride. Products were isolated by extraction into ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated. Products were purified by silica gel column chromatography using a hexane/ethyl acetate solvent. N-Phenyl-carbazole (2a)22 was obtained (96% yield) as a white solid.

Reference： [1]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]
[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]

11
[ 3652-90-2 ]
[ 111-25-1 ]
[ 864550-95-8 ]

Yield	Reaction Conditions	Operation in experiment
Ca. 94%		To a 250 mL three-necked flask, 2-bromocarbazole (6.0 g, 24.38 mmol), sodium hydroxide solution (50%) 4 ml, tetrabutylammonium bromide (0.4 g, 1.24 mmol), and the temperature was stirred for 5 min at room temperature. Bromine hexane (8.045 g, 48 mmol) was added dropwise with a syringe.After 12 h of reaction, the eluent was purified by column chromatography to petroleum ether to afford product 1a as an oil, which, after vacuum drying, weighed 7.57 g (yield about 94%).

Reference： [1]Patent: CN108424424,2018,A .Location in patent: Paragraph 0040; 0042; 0043
[2]Tetrahedron,2011,vol. 67,p. 8248 - 8254

12
[ 854952-58-2 ]
[ 3652-90-2 ]
[ 1345202-03-0 ]

Yield	Reaction Conditions	Operation in experiment
81%	With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; sodium carbonate; In 1,4-dioxane; water; for 4h;Inert atmosphere; Reflux;	In argon atmosphere, intermediate B (2.41g, 8.4 mmol), intermediate C (1.71g, 7.0 mmol), dichloro(diphenylphosphinoferrocene)palladium-methylene chloride complex (0.057g, 0.07 mmol), 1,4-dioxane (21 mL) and an aqueous solution of 2M sodium carbonate (10.5 mL) were sequentially added. The resulting mixture was heated under reflux for 4 hours. The reaction mixture was cooled to room temperature, and the precipitated solids were filtered off and washed with 1,4-dioxane and water, followed by drying under reduced pressure. The residue obtained was purified by means of silica-gel chromatography to obtain intermediate D (2.29g, yield: 81%).
80%	With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; water; toluene; at 100℃;	24.6 g (100 mmol, 1.0 eq.) of 2-bromocarbazole and 31.6 g (110 mmol, 1.1 eq.) of N-phenyl-3-carbazoleboronic acid were added to a 2 L three-necked flask, and 1100 ml of toluene and 110 ml of ethanol were added. Dissolve, pass nitrogen for 15 minutes,A further 150 ml of a 2M aqueous solution containing 41.5 g (300 mmol, 3.0 eq.) of K2CO3 and finally 2.3 g of Pd(PPh3)4 (2 mol %) are added.The temperature was raised to 100C and the reaction ended overnight. Activated carbon adsorption was added, suction filtration, solvent removal, drying, recrystallization with toluene and ethanol, 32.7 g of Intermediate-6 was obtained with a yield of 80%.
72%	With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In ethanol; water; toluene; at 95℃; for 3h;	Preparation example 1: Preparation of compound C-14 [94] [95] Preparation of compound C-1-1 [96] 9-phenyl-9H-carbazol-3-yl boronic acid (10.1 g, 40.63 mmol), 2-bromo-9H-carbazole (14 g, 48.76 mmol), K2CO3 (13.5 g, 97.52 mmol) and Pd(PPh3)4 (2.35 g, 2.03 mmol) were added to a mixture of toluene 200mL, EtOH 50mL and purified water 50mL. After stirring the reaction mixture for 3 hours at 95C, the mixture was cooled to room temperature. An aqueous layer was removed from the mixture by a gravity separation. The obtained organic layer was concentrated, was triturated with methylene chloride (MC), and then was filtered to produce compound C-1-1 (11.9 g, 72%).

71%	With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; for 4h;Reflux; Inert atmosphere;	In a nitrogen atmosphere, 2-bromo-9H-carbazole (30.0 g, 122.5 mmol) and (9-phenyl-9H-carbazol-3-yl) boronic acid (35.2 g, 122.5 mmol) were added to 300 ml of tetrahydrofuran and stirred. It was refluxed. Thereafter, potassium carbonate (33.9 g, 244.9 mmol) was dissolved in 100 ml of water, stirred sufficiently, and then tetrakistriphenyl-phosphinopalladium (4.2 g, 3 mol%) was added thereto. After 4 hours the reaction was lowered to room temperature and filtered. The filtrate was dissolved in chloroform and extracted with water, and then the organic layer was dried over magnesium sulfate. Thereafter, the organic layer was dried and compound sub 2 (35.5 g, 71%) was prepared through ethyl acetate recrystallization.
71%	With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; for 4h;Inert atmosphere; Reflux;	In a nitrogen atmosphere, 2-bromo-9H-carbazole (30.0 g, 122.5 mmol) and (9-phenyl-9H-carbazol-3-yl) boronic acid (35.2 g, 122.5 mmol) were added to 300 ml of tetrahydrofuran and stirred. It was refluxed. Thereafter, potassium carbonate (33.9 g, 244.9 mmol) was dissolved in 100 ml of water, stirred sufficiently, and then tetrakistriphenyl-phosphinopalladium (4.2 g, 3 mol%) was added thereto. After the reaction for 4 hours, the temperature was lowered to room temperature and filtered. The filtrate was dissolved in chloroform and extracted with water, and then the organic layer was dried over magnesium sulfate. Thereafter, the organic layer was dried, and then compound sub 2 (35.5 g, yield: 71%) was obtained through ethyl acetate recrystallization.
65%	With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; for 17h;Reflux;	2-Bromocarbazole (2.46 g, 10.0 mmol), 9-phenylcarbazole-3-boronic acid (3.16 g, 11.0 mmol), K2CO3 (4.15 g, 30.0 mmol), Pd (PPh3) 4 (0.53 g, 0.46 mmol) was dissolved in a mixed solvent of THF (90 ml) and water (30 ml), and the mixture was refluxed with stirring for 17 hours. After cooling to room temperature, the mixture was concentrated under reduced pressure and extracted with methylene chloride and water.The extract was subjected to column chromatography using MC: Hx to obtain Compound 10-3 (2.7 g, 65%).
49%	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In water; toluene; for 8h;Inert atmosphere; Reflux;	Under a nitrogen atmosphere, the intermediate body 1-3 (4 g, 16 mmol), N-phenylcarbazolyl-3-boronic acid (5.1 g, 17.8 mmol), tetrakis(triphenylphosphine)palladium (0.56 g, 0.48 mmol), toluene (50 mL) and an aqueous solution of 2M sodium carbonate (24 mL) were added together in sequential order, and heated to reflux for 8 hours. After the reaction solution was cooled down to the room temperature, an organic layer was removed and an organic solvent was distilled away under reduced pressure. The obtained residue was refined by silica-gel column chromatography, whereby an intermediate body 1-4 (3.2 g, a yield of 49%) was obtained.
49%	With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In water; toluene; for 8h;Reflux; Inert atmosphere;	Under a nitrogen atmosphere, the intermediate 1-4 (4 g, 16 mmol), N-phenylcarbazolyl-3-boronic acid (5.1 g, 17.8 mmol), tetrakis(triphenylphosphine)palladium (0.56 g, 0.48 mmol), toluene (50 mL) and an aqueous solution of 2M sodium carbonate (24 mL) were added together in sequential order, and heated to reflux for eight hours. -After the reaction solution was cooled down to the room temperature, an organic phase was removed and an organic solvent was distilled away under reduced pressure. The obtained residue was refined by silica-gel column chromatography, whereby an intermediate 1-5 (3.2 g, a yield of 49%) was obtained.
49%	With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In water; toluene; for 8h;Inert atmosphere; Reflux;	Under a nitrogen atmosphere, the intermediate body 2H-3 (4 g, 16 mmol), N-phenylcarbazolyl-3-boronic acid (5.1 g, 17.8 mmol), tetrakis(triphenylphosphine)palladium (0.56 g, 0.48 mmol), toluene (50 mL) and an aqueous solution of 2M sodium carbonate (24 mL) were added together in sequential order, and heated to reflux for 8 hours. After the reaction solution was cooled down to the room temperature, an organic layer was removed and an organic solvent was distilled away under reduced pressure. The obtained residue was refined by silica-gel column chromatography, whereby an intermediate body 2H-4 (3.2 g, a yield of 49%) was obtained.
45%	With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; water; toluene; at 120℃; for 24h;	After dissolving compound 1 (2-bromo-9H-carbazole) (20 g, 69.70 mmol), compound 2 ((9-phenyl-9H-carbazol-3-yl)boronic acid) (17.2 g, 69.70 mmol), Pd(PPh3 ) (2.4 g, 2.10 mmol), and Na2CO3 (18.5 g, 174.30 mmol) intoluene, ethanol, and H20, the mixture was under reflux at 120C for 1 day. After completion of the reaction, the mixture was extracted with ethyl acetate. The obtained organic layer was dried, and purified by column chromatography to obtain compound 3 (12.8 g, yield: 45 %).

Reference： [1]Patent: EP2662368,2013,A1 .Location in patent: Paragraph 0152; 0153
[2]Patent: CN108101897,2018,A .Location in patent: Paragraph 0094-0098
[3]Patent: WO2012/134124,2012,A1 .Location in patent: Page/Page column 15-16
[4]Patent: KR2020/10117,2020,A .Location in patent: Paragraph 0149; 0155-0158
[5]Patent: KR2020/10137,2020,A .Location in patent: Paragraph 0205-0208
[6]Patent: KR2017/79348,2017,A .Location in patent: Paragraph 0198; 0207-0210
[7]Patent: EP2415769,2012,A1 .Location in patent: Page/Page column 114-115
[8]Patent: US9711732,2017,B2 .Location in patent: Page/Page column 214
[9]Patent: US9966541,2018,B2 .Location in patent: Page/Page column 101
[10]Patent: WO2015/167300,2015,A1 .Location in patent: Paragraph 298; 299; 300

13
[ 3652-90-2 ]
[ 591-50-4 ]
[ 94994-62-4 ]

Yield	Reaction Conditions	Operation in experiment
92.4%	With copper(l) iodide; caesium carbonate; ethylenediamine; In toluene; for 12h;Reflux;	After mixing compound C-7-2 (23 g, 0.093 mmol), iodobenzene (20.9 mL, 0.186 mol), CuI (14.2 g, 0.074 mol), Cs2CO3 (91.2 g, 0.28 mol), toluene (300 mL), and ethylenediamine (9.46 mL, 0.140 mol), the mixture was stirred under reflux. After 12 hours, the mixture was cooled to room temperature, and CuI and Cs2CO3 were removed. Then, the remaining liquid was distilled under reduced pressure, and then separated with a column to obtain compound C-7-3 (28 g, 92.4 %).
91.65%	With potassium phosphate; ethylenediamine; for 12h;Reflux;	[165] After mixing compound 1-3 (10 g, 40.63 mmol), CuI (3.8 g, 20.3 mmol), K3PO4 (21.56 g, 101.58 mmol), toluene 300 mL, iodobenzene 9.09 mL, and ethylenediamine (2.7 mL, 40.63 mmol), the mixture was stirred under reflux for 12 hours. Then, the mixture was cooled to room temperature and filtered under reduced pressure. The remaining solution was washed with distilled water and extracted with methylene chloride (MC). Then, the resulting product was dried with magnesium sulfate, distilled under reduced pressure, and separated through a column to obtain compound 1-4 (12 g, 37.24 mmol, 91.65 %).
90%	With copper(l) iodide; caesium carbonate; ethylenediamine; In toluene; for 3h;Reflux;	After introducing 2-bromocarbazole 100 g (0.406 mol), iodobenzene 166 g (0.813mol), copper iodide 38.7 g (0.203 mol), ethylenediamine 27 mL (0.406 mol), cesiumcarbonate 265 g (0.813 mol), and toluene 1.3 L in a reaction container, the mixture wasstirred under reflux for 3 hours. After the reaction, the mixture was washed withdistilled water, and an organic layer was extracted with ethyl acetate. The extractedorganic layer was dried with magnesium sulfate, and the solvent was removed using arotary evaporator. The remaining substance was then purified with column chromatographyto obtain compound 2-1 (116 g, 90%).

89%	With copper(l) iodide; caesium carbonate; ethylenediamine; In toluene; for 4h;Reflux;	After mixing compound C-62-2 17 g (69.07 mmol), iodobenzene 15.4 mL (138.15 mmol), CuT 10.5 g (55.26 mmol), ethylenediamine (EDA) 6.9 mL (103.6 mmol), Cs2 CO3 56.26 g (172.6 mmol), and toluene 350 mL, the mixture was stuffed under reflux. After 4 hours, the mixture was cooled to room temperature, and filtered under reduced pressure. The remaining solution was filtered under reduced pressure, and separated with a column to obtain compound C-62-3 20 g (89 %).
85%	With copper(l) iodide; potassium carbonate; L-proline; In dimethyl sulfoxide; at 90℃; for 72h;Inert atmosphere; Sealed tube;	A pressure vessel was charged with -bromo-9H-carbazole (10 mmol), iodobenzene (20 mmol), potassium carbonate (20 mmol), L-proline (2 mmol), copper(I) iodide (1 mmol), and dimethyl sulfoxide (25 mL). After three cycles of evacuation and backfilling with nitrogen, the vessel was sealed and stirred at 90 C. for three days. After cooling, the reaction mixture was diluted with dichloromethane (200 mL), washed four times with water (200 mL), and dried over magnesium sulfate. After removing the solvent under reduced pressure, the crude product was chromatographed over silica with hexane as the eluent, giving 2-bromo-9-phenyl-9H-carbazole in 85% yield.
84.86%		Compound 1-2 (30g, 101.29mmol), iodobenzene (41.3g, 202.59mmol), CuI (9.6g, 50.64mmol), Cs2CO3 (82.5g, 253.2mmol), and toluene 600mL were mixed and heated at 50C, and ethylenediamine (6.8mL, 101.29mmol) was added. The mixture was stirred under reflux. 14 hours later, the mixture was cooled to room temperature and distilled water was added. The mixture was extracted with EA, dried with anhydrous MgSO4, distilled under reduced pressure and column separated, yielding Compound 1-3 (32g, 85.96mmol, 84.86%).
84.46%		Preparation of compound 1-3 [100] After mixing compound 1-2 (30 g, 101.29 mmol), iodobenzene (41.3 g, 202.59 mmol), CuI (9.6 g, 50.64 mmol) and Cs2CO3 (82.5 g, 253.2 mmol) with toluene (600 mL), the reaction mixture heated at 50C. Ethylenediamine (EDA) (6.8 mL, 101.29 mmol) was added to the reaction mixture and was stirred under reflux. After 14 hours, the reaction mixture was cooled to room temperature, and distilled water was added. The reaction mixture was extracted with ethyl acetate, was dried with MgSO4, was distillated under reduced pressure, and was filtered through column to obtain compound 1-3 (32 g, 85.96 mmol, 84.86 %).
84%	With tris-(dibenzylideneacetone)dipalladium(0); triphenylphosphine; sodium t-butanolate; In toluene; at 100℃;	To a round bottom flask Sub 1-1-1 (4.9g, 20mmol), Sub 1-2-1 (4.1g, 20mmol), Pd2(dba)3 (0.9g, 1mmol), PPh3 (0.5g, 2mmol), NaOt-Bu (5.8g, 60mmol), toluene (210mL) added and allowed to react at 100 C. When the reaction is complete, the ether and water are added to the resulting solution. The organic layer was dried over MgSO4, concentrated and recrystallized silicagel column and extracted Sub 1-3-1, 5.4g (yield: 84%) was obtained.
81%	With copper(l) iodide; 1,10-Phenanthroline; potassium carbonate; In N,N-dimethyl-formamide; at 80℃; for 24h;Inert atmosphere;	[271] In a 100 ml round-bottom three-neck flask under a nitrogen atmosphere, 4.2 g of Intermediate 20, 5.2 g of iodobenzene, 0.3 g of copper iodide, 0.3 g of1, 10-phenanthroline, 7.1 g of potassium carbonate and 50 ml of dimethylfomiamide were placed, and reacted at 80C for 24 hrs. The reaction solution was cooled and then extracted with dichloromethane and water. The extracted solution was concentrated, subjected to column chromatography using a solvent mixture of dichloromethane and n-hexane and then concentrated, thus obtaining 4.8 g of Intermediate 21 (yield 8 1%).[272] MS (ESI): [M+H]+ 322
79%	With copper; potassium carbonate; sodium sulfate; In nitrobenzene; at 200℃;	The obtained Sub 1-II-B1 (37.19g, 151.1mmol) was dissolved in nitrobenzene in a round bottom flask, and iodobenzene (46.24g, 226.7mmol), Na2SO4 (21.46g, 151.1mmol), K2CO3 (20.89g, 151.1mmol), and Cu (2.88g, 45.3mmol) were added to the reaction solution, followed by stirring at 200C. Upon completion of the reaction, nitrobenzene was removed by distillation, and the reaction product was extracted with CH2Cl2 and water. The extracted organic layer was dried with MgSO4 and concentrated, and then the produced organic material was separated by a silica gel column and recrystallized to obtain 38.47g of product (yield: 79%).
79%	With copper; potassium carbonate; sodium sulfate; In nitrobenzene; at 200℃;	Intermediate B 1mol and iodobenzene 1.5mol After dissolved in nitrobenzene, Na2SO4, K2CO3, the Cu It was added and the resulting mixture was stirred at 200C . After the reaction is complete when the nitrobenzene removed by distillation and extracted with water and CH2Cl2 and the organic layer over anhydrous MgSO4 Dried and concentrated to give the desired intermediate C and the resulting product was purified by column chromatography and recrystallization after (yield: 79%).
77%	With copper; potassium carbonate; In nitrobenzene; for 16h;Inert atmosphere; Reflux;	Under nitrogen atmosphere, intermediate Compound B 2.45g (10mmol), iodobenzene and 3.06g (15mmol) was dissolved in 25ml nitrobenzene, K2CO3 4.15g (30mmol) and Cu 0.19g (3mmol) was added and the mixture was refluxed for 16 hours. After completion of the reaction, MC 100ml, H2O 100ml was added and then the the MC layer was extracted, concentrated and separated by column chromatography using Hex : EA =5 : 1 and dried over anhydrous MgSO4 to give the intermediate C 2.48g (77%).
73%	With copper; potassium carbonate; sodium sulfate; In nitrobenzene; at 200℃;	Sub 1-II-1 (80.34g, 326.5mmol) nitrobenzene (653 ml) for in round bottom flask senses a rotation velocity of the disk in, iodobenzene (99.9g, 489.7mmol), Na 2 SO 4 (46.37g, 326.5mmol), K 2 CO 3 (45.12g, 326.5mmol), cu (6.22g, 97.9mmol) added 200 C stirring section. When reaction is completed the via fractional distillation to remove the nitrobenzene CH 2 Cl 2 extracted and water. Organic layer MgSO 4 to dry a silicagel column with a compound formed after the products and recrystallization 76.78g (yield: 73%)is obtained.
73%	With copper; potassium carbonate; sodium sulfate; In nitrobenzene; at 200℃;	It was dissolved Sub 1-II-1 (80.34g, 326.5mmol) obtained in the above synthesis in nitrobenzene (653ml) in a round bottom flask, iodobenzene (99.9g, 489.7mmol), Na2SO4 (46.37g, 326.5mmol), K2CO3 ( 45.12g, 326.5mmol), was added Cu (6.22g, 97.9mmol) and stirred at 200 . After completion of reaction was removed by distillation to nitrobenzene and extracted with CH2Cl2 wamul. The resulting compound and the organic layer was dried over MgSO4 and concentrated to silicagel column and the product was recrystallized 76.78g: (yield: 73%).
73%	With copper; potassium carbonate; sodium sulfate; In nitrobenzene; at 200℃;	Sub 1-II-1 (80.34g , 326.5mmol) was dissolved in nitrobenzene (653ml) in a round bottom flask, iodobenzene (99.9g, 489.7mmol), Na 2 SO 4 (46.37g,326.5mmol), K 2 CO 3 was added (45.12g, 326.5mmol), Cu ( 6.22g, 97.9mmol) and the resulting mixture was stirred at 200 . After completion ofreaction by distillation to remove nitrobenzene and the CH 2 Cl 2 and extracted with water. The organic layer is MgSO 4 and the resulting compoundwas dried and concentrated to a silicagel column and the product was recrystallized 76.78g: (yield: 73%).
73%	With copper; potassium carbonate; sodium sulfate; In nitrobenzene; at 200℃;	Sub 1-II-1 (113.37g, 460.7mmol) obtained in the above synthesis was dissolved with nitrobenzene in a round bottom flask, iodobenzene (140.97g, 691mmol), Na2SO4 (65.43g, 460.7mmol), K2CO3 (63.67g, 460.7 mmol), was added Cu (8.78g, 138.2mmol) and stirred at 200 C. After completion of reaction was removed by distillation to nitrobenzene and extracted with CH2Cl2 wamul. The resulting compound and the organic layer was dried over MgSO4 and concentrated to silicagel column and recrystallized to give the product 108.35g (73% yield).
73%	With copper; potassium carbonate; sodium sulfate; In nitrobenzene; at 200℃;	Sub-1-II-1 (80.34g, 326.5 mmol) obtained in the above Synthesis was added to a round bottom flask and dissolved in nitrobenzene 653 mL, iodobenzene (99.9 g, 489.7 mmol), Na2SO4 (46.37 g, 326.5 mmol), K2CO3 (45.12 g, 326.5 mmol), and Cu (6.22 g, 97.9 mmol) were added and the resulting mixture was stirred at 200 C. After completion of reaction, nitrobenzene was removed by distillation, extracted with water and CH2Cl2, the resulting material was purified by silicagel column, and the organic layer was dried over MgSO4, and concentrated to obtain product 76.78 g (yield: 73%).
70%	With potassium phosphate; copper(l) iodide; (-)-(1R,2R)-diaminocyclohexane; In 1,4-dioxane; at 80℃; for 8h;Inert atmosphere;	In argon stream, a mixture obtained by successively mixingthe intermediate 2 (20 g 81 mmol) iodobenzene (18.1 g 89mmol), copper iodide (1.5 g, 8 mmol), tripotassium phoshtermediatephate (34.5 g, 163 mmol), dry dioxane (100 mE), and cycloxylene hexanediamine (1.8 g, 16 mmol) was stirred at 80 C. for 8 h.After cooling the reaction liquid to room temperature, theorganic layer was separated and the organic solvent wasremoved from the organic layer by distillation under reducedpressure. The obtained residue was purified by a silica gelcolunm chromatography to obtain the intermediate 14 (18.3 g, yield: 70%). The identification of the intermediate 14 wasmade by FD-MS (field desorption mass spectrometry) analy50 sis.
69%	With tri-tert-butyl phosphine; palladium diacetate; sodium t-butanolate; In toluene; at 20℃; for 15h;Inert atmosphere;	In a 0.5 L reaction flask, 10.0 g (40.6 mmol) of the compound [119-1], 10.7 g (44.7 mmol) of the compound [119-2] 5.9 g (60.9 mmol) of sodium butoxide, and 150 ml of toluene were placed, and the mixture was stirred at room temperature. 0.1 g (0.4 mmol) of palladium acetate, 0.3 g (0.8 mmol) of tri-tert-butylphosphine (50%) And the mixture was stirred under reflux for 15 hours under a stream of nitrogen. After completion of the reaction, the mixture was slowly cooled to room temperature, and then the reaction solution was poured into a saturated ammonium chloride aqueous solution and extracted with ethyl acetate. The organic layer was separated, dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure and purified by column chromatography to obtain 9.0 g (69%) of intermediate compound [119-3].
54%	With potassium phosphate; copper(l) iodide; cis-cyclohexane-1,2-diamine; In 1,4-dioxane; for 48h;Inert atmosphere; Reflux;	A mixture solution of 2-bromo-9H-carbazole (10.0 g, 40.6 mmol), iodobenzene (12.43 g, 61.0 mmol), CuI (0.774 g, 4.06 mmol), (1R,2S)-cyclohexane-1,2-diamine (0.987 ml, 8.13 mmol), and K3PO4 (17.25 g, 81 mmol) in dioxane (150 ml) was refluxed under nitrogen for 48 h. (0125) (0126) After cooling to room temperature, the mixture was filtered through a plug of Celite and the solid was washed with DCM. The combined filtrate was evaporated and purified by column chromatography on silica gel with hexane/DCM (9/1, v/v) as eluent to yield 2-bromo-9-phenyl-9H-carbazole (7.4 g, 54%) as a white solid.
50.4%	With potassium carbonate; copper(l) chloride; In dimethyl sulfoxide; for 24h;Reflux;	A 500ml reactor 2-bromo mocha carbazole (30g, 121.9mmol), iodobenzene (38.3g, 243.8mmol), copper chloride (I) (0.24g, 2.4mmol), potassium carbonate (20.2g, 146.3mmol), dimethyl Insert the sulfoxide 240 mL was refluxed for 24 hours.After completion of reaction, after cooling to room temperature, into a 200mL ethyl acetate was filtered through a Buchner.Extract the filtrate with water 500 mL, under reduced pressure and then dry the organic layer was treated to remove the organic solvent.Hexane: ethyl acetate (10: 1) the column was isolated using as a developing solvent.19.8g of a white solid to give the 2-bromo-phenyl -N- carbazole.(50.4%).
37%	With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; for 12h;Reflux;	30.51 g (149.56 mmol) of iodobenzene, 18.32 g (74.78 mmol) of 2-bromo-9H-carbazole, 14.37 g (149.56 mmol) of sodium t-butoxide, and 1.81 ml (7.48 mmol) of tritertbutylphosphine were dissolved in 300 ml of toluene, and 0.68 g (0.75 mmol) of Pd2(dba)3 was added thereto, and refluxed and agitated for 12 hours. After the reaction was finished, extraction was performed by dichloromethane, filtering was performed by silica gel, and the column was used at a ratio of hexane:MC=9:1 (v/v) to obtain 8.99 g of 2-bromo-9-phenylcarbazole (yield 37%). 1H NMR: 7.24 (t, 1H), 7.36 (m, 3H), 7.50 (dd, 2H), 7.58 (t, 2H), 7.65 (t, 2H), 8.06 (d, 1H), 8.13 (d, 1H). GC-Mass (theoretical value: 321.02 g/mol, measured value: 321 g/mol).
	With tris-(dibenzylideneacetone)dipalladium(0); triphenylphosphine; sodium t-butanolate; In toluene; at 100℃; for 24h;	2-bromo-9H-carbazole ( 327mmol) and iodobenzene (360mmol), toluene (2800mL) Pd2(dba) 3 (8.24g, 9mmol), PPh3 (7.87g, 30mmol), NaOt-Bu ( 86.5g, 900mmol) were added to each, and refluxed under stirring for 24 hours at 100 C. ether and extracted with water and the organic layer is MgSO 4 and then dried, and concentrated to the resulting organic silicagel column and recrystallization to give the 2-bromo-9-phenyl- 9H-carbazole.
	With copper(l) iodide; 1,10-Phenanthroline; sodium hydroxide; In para-xylene; at 140℃; for 48h;	1,4-Dibromo-2-nitrobenzene (4.60 g, 0.016 mol) and phenylboronic acid (2.0 g, 0.016 mol) were refluxed in toluene (40 ml) with a catalytic amount of Pd(PPh3)4 (568 mg, 0.492 mmol). 4-Bromo-2-nitro-1-phenylbenzene (3.17 g, 0.011 mol) was formed and then refluxed in triethylphosphite to yield 2-bromocarbazole.2-Bromocarbazole (1.27 g, 5.162mmol) and iodobenzene (0.87 ml,7.741 mmol) were refluxed to yield 2-bromophenylcarbazole. After consecutive reactions with n-butyllithium and trimethylborate,boronic acid (0.622 g, 2.167 mmol) prepared would react with 2-bromothiazole (0.16 ml, 1.734 mmol). The ligand L3 was obtained as a white powder (60%). Spectral data: MS (MALDITOF):m/z 326.36 (M+). 1H NMR (CDCl3): delta (ppm) 8.17 (t, J=8.8 Hz,2H, Ar), 8.05 (s, 1H, Ar), 7.87-7.85 (m, 2H, Ar), 7.66-7.52 (m, 2H,Ar), 7.52-7.48 (m, 2H, Ar), 7.46-7.38 (m, 2H, Ar), 7.33-7.29 (m, 2H,Ar).
		2-bromo-9Hcarbazole(2 g, 8 mmol), copper(Iota) iodide (1.24 g, 6.5 mmol), cesiumcarbonate (7.98 g, 24 mmol) were added to 25 mL of anhydrous toluenesolution in 3-neck round bottom flask under N2 atmosphere. After themixture was heated at 80 C, iodobenzene (1.82 mL, 16 mmol), ethylenediamine(0.82 mL, 12.2 mmol) was added to mixture. Then themixture was refluxed at 110 C for 15 h 1H NMR (300 MHz, THF):delta(ppm) 8.14-8.11 (d, 1H), 8.07-8.04 (d, 1H), 7.67-7.62 (m, 2H),7.59-7.56 (m, 2H), 7.53-7.47 (m, 2H), 7.39-7.32 (m, 3H), 7.27-7.21 (t,1H).

Reference： [1]Patent: WO2013/122402,2013,A1 .Location in patent: Paragraph 196; 201; 202
[2]Patent: WO2013/162284,2013,A1 .Location in patent: Paragraph 164; 165
[3]Journal of Materials Chemistry,2012,vol. 22,p. 215 - 224
[4]Patent: WO2015/99484,2015,A1 .Location in patent: Paragraph 181-182
[5]Patent: WO2014/3440,2014,A1 .Location in patent: Paragraph 172; 173; 178; 179
[6]Patent: US9312502,2016,B2 .Location in patent: Page/Page column 27; 28; 29
[7]Patent: WO2012/39561,2012,A1 .Location in patent: Page/Page column 20
[8]Patent: WO2012/169821,2012,A1 .Location in patent: Page/Page column 16
[9]Patent: KR2015/61811,2015,A .Location in patent: Paragraph 0109-0111
[10]Patent: WO2017/196081,2017,A1 .Location in patent: Paragraph 269; 270; 272; 272
[11]Patent: EP2930168,2015,A1 .Location in patent: Paragraph 0089; 0092; 0290
[12]Patent: KR101565039,2015,B1 .Location in patent: Paragraph 0098-0101
[13]Patent: KR2015/102733,2015,A .Location in patent: Paragraph 0121-0125
[14]Patent: KR101550768,2015,B1 .Location in patent: Paragraph 0151 - 0154
[15]Patent: KR2015/98171,2015,A .Location in patent: Paragraph 0138; 0142; 0151-0154
[16]Patent: KR2015/87787,2015,A .Location in patent: Paragraph 0140; 0149-0152
[17]Patent: KR2015/89427,2015,A .Location in patent: Paragraph 0136; 0137; 0138; 0143; 0144
[18]Patent: KR101614738,2016,B1 .Location in patent: Paragraph 0198-0200
[19]Journal of Physical Chemistry B,2012,vol. 116,p. 4603 - 4614
[20]Patent: US9306171,2016,B2 .Location in patent: Page/Page column 154
[21]Patent: KR2015/129282,2015,A .Location in patent: Paragraph 0125-0130
[22]Journal of Materials Chemistry C,2019,vol. 7,p. 9671 - 9677
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[24]Patent: KR101649950,2016,B1 .Location in patent: Paragraph 0085; 0086
[25]Patent: US2013/48975,2013,A1 .Location in patent: Paragraph 0050; 0051; 0052; 0053
[26]Patent: KR2015/43669,2015,A .Location in patent: Paragraph 0127; 0132; 0133
[27]Journal of Organometallic Chemistry,2017,vol. 829,p. 92 - 100
[28]Patent: KR2017/96767,2017,A .Location in patent: Paragraph 0153; 0154
[29]Polyhedron,2014,vol. 82,p. 71 - 79
[30]Dyes and Pigments,2018,vol. 156,p. 369 - 378

14
[ 3652-90-2 ]
[ 1001911-63-2 ]

Reference： [1]Patent: WO2012/39561,2012,A1
[2]Patent: WO2012/169821,2012,A1
[3]Patent: WO2013/122402,2013,A1
[4]Patent: WO2013/162284,2013,A1
[5]Patent: WO2014/3440,2014,A1
[6]Patent: KR2015/61811,2015,A
[7]Patent: KR101565039,2015,B1
[8]Patent: KR2015/102733,2015,A
[9]Patent: KR101649950,2016,B1
[10]Journal of Organometallic Chemistry,2017,vol. 829,p. 92 - 100
[11]Polyhedron,2014,vol. 82,p. 71 - 79

15
[ 3652-90-2 ]
[ 1235563-74-2 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 2: copper(l) iodide; caesium carbonate; lithium chloride / N,N-dimethyl-formamide / 48 h / 150 °C

Reference： [1]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]

16
[ 3652-90-2 ]
[ 98-80-6 ]
[ 88590-00-5 ]

Yield	Reaction Conditions	Operation in experiment
97%	With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; toluene; at 120℃; for 5h;	After dissolving <strong>[3652-90-2]2-bromo-9H-carbazole</strong> (50 g, 203.1 mmol), phenylboronic acid (30 g, 243.8 mmol), and Pd(PPh3)4 (12 g, 10.15 mmol) in 2M Na2CO3 (500 mL), toluene(1000 mL), and ethanol (500 mL) of a flask, the mixture was under reflux at 120C for 5 hours. After completion of the reaction, the mixture was extracted with ehthyl acetate. The remaining moisture was removed from the obtained organic layer with magnesium sulfate. The product was dried, and purified by column chromatography to obtain compound 2-1 (48.3 g, yield: 97%).
86%	With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; toluene; for 5h;Reflux;	Preparation of compound 3-2<strong>[3652-90-2]2-bromo-9H-carbazole</strong> (20.0 g, 81.2 mmol), phenylboronic acid (11.9 g, 97.5 mmol), Pd(PPh3)4 (4.7 g, 4.06 mmol), 2M K2C03 (121.0 mL), toluene (250.0 mL), and EtOH (121.0 mL) in a flask were stilTed under reflux for 5 hrs. After completing the reaction, the organic layer was extracted with EA and dried by removing the remaining moisture with MgSO4. The layer was separated by column chromatography to obtain compound3-2 (17.0 g, 86 %).
86%	With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; toluene; for 5h;Reflux;	Preparation of compound 3-2[120]2-Bromo-9H-carbazole (20.0 g, 81.2 mmol), phenylboronic acid (11.9 g, 97.5 mmol), Pd(PPh3)4 (4.7g, 4.06 mmol), 2M K2CO3 (121.0 mL), toluene (250.0 mL), and EtOH (121.0 mL) were stirred under reflux in a flask for 5 hrs. After completing the reaction, the organic layer was extracted with EA, was dried by removing the remaining moisture with MgSO4, and was separated through column chromatography to obtain compound 3-2 (17.0 g, 86 %).

71%

With palladium diacetate; potassium carbonate; tris-(o-tolyl)phosphine; In ethanol; water; toluene; for 6h;Inert atmosphere; Reflux;

12.1 g (50 mmol) of [3652-90-2]2-bromo-9H-carbazole,6.71 g (55 mmol) of phenylboronic acid,22.8 g (165 mmol) of potassium carbonate,100 mL of toluene,25mL of ethanol and 82mL of tap water was added 300mL flask,Degassing under reduced pressure,The flask was then purged with nitrogen.To the mixture was added 112 mg (0.50 mmol) of palladium acetateAnd 304 mg (1.0 mmol) of tris (o-tolyl) phosphine were heated under reflux for about 6 hours,And react. After cooling to room temperature, the reaction solution was separated into an organic layer and an aqueous layer. The resulting organic layer was washed with saturated brine. After adding magnesium sulfate to the solution to dry the moisture, the filtration was performed. The solution was concentrated and the resulting mixture was purified by silica gel column chromatography.The resulting solution was concentrated and the resulting mixture was recrystallized using ethanol. The precipitated solid was filtered at room temperature, the resulting residue was dried under reduced pressure,Thus, a white solid of 8.6 g of the desired product was obtained in a yield of 71%.In addition, the synthesis scheme of Step 1 is shown in the following formula (d-1).

Reference： [1]Patent: WO2015/167300,2015,A1 .Location in patent: Paragraph 232; 233; 234
[2]Patent: WO2015/84021,2015,A1 .Location in patent: Paragraph 183; 184
[3]Patent: WO2015/167199,2015,A1 .Location in patent: Paragraph 119; 120
[4]Angewandte Chemie - International Edition,2020,vol. 59,p. 6775 - 6779
Angew. Chem.,2020,vol. 132,p. 6841 - 6845,5
[5]Patent: CN107129459,2017,A .Location in patent: Paragraph 0649; 0650; 0651; 0652; 0653; 0654; 0655
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[7]Bulletin of the Korean Chemical Society,2011,vol. 32,p. 2461 - 2464

17
[ 3652-90-2 ]
[ 591-50-4 ]
[ 1246669-45-3 ]

Reference： [1]Journal of Physical Chemistry B,2012,vol. 116,p. 4603 - 4614

18
[ 109-04-6 ]
[ 3652-90-2 ]
[ 1352932-32-1 ]

Yield	Reaction Conditions	Operation in experiment
99%	With 1-methyl-1H-imidazole; copper(l) iodide; lithium tert-butoxide; In toluene; at 130℃; for 24h;Inert atmosphere;	<strong>[3652-90-2]2-bromocarbazole</strong> was added sequentially to a dry three-necked flask equipped with a reflux condenser and a magnetic rotor(3.69 g, 15.00 mmol, 1.0 eq), cuprous iodide (286 mg, 1.5 mmol, 0.1 eq)Lithium tert-butoxide (2.40 g, 30.00 mmol, 2.0 eq), nitrogen was purged three times,Then 2-bromopyridine (1.71 mL, 18.00 mmol, 1.2 eq) was added,1-methylimidazole (298 uL, 3.75 mmol, 0.25 eq) and toluene (56.6 mL).The reaction mixture was refluxed at 130 C for 24.0 hours and TLC thin layer chromatography was carried out until the reaction of <strong>[3652-90-2]2-bromocarbazole</strong> was completed. Saturated sodium sulfite solution 30mL quenching, filtration, ethyl acetate fully washed insoluble,The organic phase was separated from the mother liquor and the aqueous phase was extracted three times with 30 mL of ethyl acetate. The organic phases were combined,Dried over anhydrous sodium sulfate, filtered, the solvent was removed by distillation under reduced pressure and excess 2-bromopyridine,The resulting crude product was purified by silica gel column chromatography eluting with petroleum ether / dichloromethane = 1: 1-0: 1 to give 4.79 g of a white solid in 99% yield.
99%	With 1-methyl-1H-imidazole; copper(l) iodide; potassium carbonate; In toluene; at 120℃; for 144h;Glovebox; Sealed tube;	2-Bromo-9H-carbazole 1 (3.91 g, 15.89 mmol, 1.0 eq), CuI (0.30 g, 1.59 mmol, 0.1 eq) and K2CO3 (4.39 g, 31.78 mmol, 2.0 eq) were added to a dry pressure tube equipped with a magnetic stir bar. Then the tube was taken into a glove box. Solvent toluene (60 mL), 1-methyl-1H-imidazole (0.63 mL, 7.95 mmol, 0.5 eq) and 2-bromopyridine (4.55 mL, 47.68 mmol, 3.0 eq) were added. The mixture was bubbled with nitrogen for 10 minutes. The tube was sealed before being taken out of the glove box and the mixture was stirred in an oil bath at a temperature of 120 C. for 6 days, cooled to ambient temperature, filtered and washed with ethyl acetate. The filtrate was concentrated under reduced pressure to remove the solvent and the excess 2-bromopyridine (otherwise it is difficult to separate the desired product and 2-bromopyridine by silica gel column). The residue was purified through column chromatography on silica gel using dichloromethane as eluent to obtain the desired product 2-bromo-9-(pyridin-2-yl)-9H-carbazole 2 as an off-white solid 5.11 g in 99% yield. 1H NMR (DMSO-d6, 400 MHz): delta 7.33 (t, J=7.6 Hz, 1H), 7.45-7.50 (m, 3H), 7.74 (d, J=8.4 Hz, 1H), 7.78 (d, J=8.0 Hz, 1H), 7.95 (d, J=2.0 Hz, 1H), 8.11 (td, J=8.0, 2.0 Hz, 1H), 8.19 (d, J=8.4 Hz, 1H), 8.24 (d, J=7.6 Hz, 1H), 8.72 (dd, J=4.8, 1.6 Hz, 1H).1H NMR (CDCl3, 400 MHz): delta 7.32 (t, J=7.6 Hz, 2H), 7.41-7.47 (m, 2H), 7.60 (d, J=8.0 Hz, 1H), 7.77 (d, J=8.4 Hz, 1H), 7.91-7.95 (m, 2H), 8.01 (d, J=2.0 Hz, 1H), 8.07 (d, J=8.0 Hz, 1H), 8.72-8.73 (m, 1H). 13C NMR (CDCl3, 100 MHz): delta 111.10, 114.35, 119.01, 119.78, 120.21, 121.26, 121.30, 121.61, 123.16, 123.64, 124.06, 126.58, 138.65, 139.60, 140.29, 149.78, 151.26.
95%	With 1-methyl-1H-imidazole; copper(l) iodide; lithium tert-butoxide; In toluene;Inert atmosphere; Heating;	Preparation process: To a 48 mL sealed tube with a magnetic rotor, <strong>[3652-90-2]2-bromocarbazole</strong> (3.69 g, 15 mmol), 2-bromopyridine 0002 (1.42 mL, 15 mmol),Cuprous iodide (0.3mmoL, 0.02equiv),1-methylimidazole (0.3mmol, 0.2equiv),t-BuOLi (18 mmol, 1.2 equiv) and toluene (50 mL). The resulting mixture was sparged with nitrogen for 10 minutes and heated to 120 C. and stirred for 8 hours.Cool to room temperature, quench the reaction with water, extract with ethyl acetate, combine the organic phases, wash with an appropriate amount of saturated aqueous sodium chloride solution, and dry with anhydrous sodium sulfate.The solvent was distilled off under reduced pressure, and the obtained crude product was separated and purified by silica gel column chromatography.The eluent was petroleum ether: ethyl acetate = 25: 1, and the product 2-1 was obtained with a yield of 95%.

93%

With 1-methyl-1H-imidazole; copper(l) iodide; lithium tert-butoxide; In toluene; for 18h;Inert atmosphere; Sealed tube;

[3652-90-2]2-bromocarbazole (3.69 g, 15 mmol) was added sequentially to a 48 mL sealed tube with a magnetic rotor.2-bromopyridine (1.57 mL, 16.5 mmol), cuprous iodide (0.3 mmL, 0.02 equiv),1-Methylimidazole (0.3 mmol, 1.2 equiv), t-BuOLi (18 mmol, 1.2 equiv) and toluene (50 mL), and the obtained mixture was bubbled with nitrogen for 10 minutes and then heated to 120 C for 8 hours.Cool to room temperature, quench with water and extract with EtOAc.The organic phases were combined, washed with aq. saturated aqueous sodium chloride and dried over anhydrous sodium sulfate.The solvent was distilled off under reduced pressure, and the obtained crude product was purified by silica gel column chromatography.The eluent was petroleum ether: ethyl acetate = 25:1,A white solid was obtained in a yield of 93%

Reference： [1]Patent: CN106366069,2017,A .Location in patent: Paragraph 0033; 0034; 0035; 0036;-0084; 0172-0175
[2]Inorganic Chemistry,2017,vol. 56,p. 8244 - 8256
[3]Patent: US10020455,2018,B2 .Location in patent: Page/Page column 681; 682; 685
[4]Journal of Organic Chemistry,2017,vol. 82,p. 1024 - 1033
[5]Patent: CN110615787,2019,A .Location in patent: Paragraph 0105-0109
[6]Patent: CN108840886,2018,A .Location in patent: Paragraph 0142; 0144; 0145; 0147
[7]Patent: CN109748938,2019,A .Location in patent: Paragraph 0081-0085
[8]Patent: CN110590856,2019,A .Location in patent: Paragraph 0084-0088
[9]Patent: CN107383108,2017,A .Location in patent: Paragraph 0154
[10]Patent: CN107698623,2018,A .Location in patent: Paragraph 0149
[11]Patent: CN108017675,2018,A .Location in patent: Paragraph 0202-0204
[12]Patent: CN108948095,2018,A .Location in patent: Paragraph 0160; 0161
[13]Patent: WO2015/27060,2015,A1 .Location in patent: Paragraph 00113
[14]Patent: US2012/302753,2012,A1 .Location in patent: Page/Page column 28-29
[15]Patent: US2015/274762,2015,A1 .Location in patent: Paragraph 0160; 0161
[16]Patent: US2019/19964,2019,A1 .Location in patent: Paragraph 0443
[17]Journal of Catalysis,2018,vol. 363,p. 63 - 68
[18]Inorganic Chemistry,2019,vol. 58,p. 14349 - 14360

19
[ 3652-90-2 ]
[ 1126522-69-7 ]
[ 1345202-03-0 ]

Yield	Reaction Conditions	Operation in experiment
65%	With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; toluene; for 12h;Inert atmosphere; Reflux;	17.66 g (71.7 mmol) of a 2-bromo-carbazole compound and 22.08 g (59.8 mmol) of N-phenyl-carbazole boronic acid pinacolate were mixed with 100 mL of tetrahydrofuran and 100 mL of a 2M potassium carbonate aqueous solution, and the mixture was heated and refluxed under a nitrogen flow for 12 hours in a 500 mL round-bottomed flask having an agitator and a nitrogen atmosphere. When the reaction was complete, hexane was poured into the reactant. Then, a solid produced therein was filtered and dissolved in a solution prepared by mixing toluene and tetrahydrofuran in a volume ratio of 50:50, and activated carbon and anhydrous magnesium sulfate were added thereto. The mixture was agitated. The solution was filtered and recrystallized using dichloromethane and hexane, obtaining 19 g (yield of 65%) of a compound D.

Reference： [1]Patent: US2013/56720,2013,A1 .Location in patent: Paragraph 0215-0217

20
[ 3652-90-2 ]
[ 1591-31-7 ]
[ 1393835-87-4 ]

Yield	Reaction Conditions	Operation in experiment
70%	With 1,10-Phenanthroline; potassium carbonate; copper(l) chloride; In dimethyl sulfoxide; at 150℃; for 12h;Inert atmosphere;	22.22 g (90.3 mmol) of a 2-bromocarbazole compound, 37.94 g (135.5 mmol) of 4-iodobiphenyl and 18.72 g (135.5 mmol) of potassium carbonate were dissolved in 400 mL of dimethylsulfoxide, and 3.26 g (135.47 mmol) of 1,10-phenanthroline and 1.79 g (18.06 mmol) of copper chloride (I) were added therein in a dropwise fashion in a 1,000 mL round-bottomed flask having an agitator and a nitrogen atmosphere. The reaction solution was agitated under a nitrogen flow for 12 hours at 150 C. When the reaction was complete, distilled water was poured into the reactant. Then, a solid produced therein was dissolved in chlorobenzene, and activated carbon and anhydrous magnesium sulfate were added thereto. The mixture was agitated. The solution was filtered and recrystallized using chlorobenzene and methanol, obtaining 25 g (yield=70%) of a compound E.

Reference： [1]Patent: US2013/56720,2013,A1 .Location in patent: Paragraph 0221-0223
[2]Patent: KR2017/96767,2017,A .Location in patent: Paragraph 0151; 0152

21
[ 3652-90-2 ]
[ 106-94-5 ]
[ 1482521-68-5 ]

Yield	Reaction Conditions	Operation in experiment
83.7%	With potassium carbonate In N,N-dimethyl-formamide at 60℃; for 48h; Inert atmosphere;	2-Bromo-9-propyl-9H-carbazole (6) To a mixture of 2-bromo-9H-carbazole (1.50 g,6.09 mmol) and anhydrous K2CO3 (2.56 g, 18.53 mmol) in dry DMF (10 ml) was added 1-bromopropane (1.58 ml, 18.53mmol) at rt. The resulting light brown suspension was heated at 60°C with stirring under nitrogen for 48 h, after which the TLC control (CHCl3:hexane, 1:1) showed the total consumption of starting material. After cooling to rt, the mixture was poured into water (250 ml), extracted with CH2Cl2 (2 x 75 ml) and the organic phase washed with water. The organic extract was dried, evaporated to dryness and vacuum dried. The orange-reddish oil residue thus obtained was flash-chromatographed (CHCl3:Hex,1:3) furnishing 1.47 g of 6 as a colourless solid (83.7%); mp 60-62°C; νmax/cm-1 (KBr) 3058, 2978, 2958, 2944, 2925, 2871, 1623, 1591, 1491, 1474, 1468, 1451, 1434,1322, 1220, 1158, 1126, 1064, 1053, 1000, 924, 900,839, 812, 759, 747, 721; δH/ppm (CHCl3; 300 MHz)0.99 (3H, t, -CH2-CH2-CH3, J 7.4), 1.91 (2H, sext, -CH2-CH2-CH3, J 7.2), 4.23 (2H, t, CH2-CH2-CH3,J 7.2), 7.21-7.28 (1H, m, Ar(C6)-H, partially overlapped),7.33 (1H, dd, Ar(C3)-H, Jo 8.3, Jm 1.6), 7.41 (1H,d, Ar(C8)-H, Jo 8.2), 7.44-7.53 (1H, m, Ar(C7)-H), 7.55(1H, d, Ar(C1)-H, Jm 1.6), 7.94 (1H, d, Ar(C4)-H, Jo 8.3),8.06 (1H, d, Ar(C5)-H, Jo 7.8). Anal. calcd forC15H14BrN: C, 62.52; H, 4.90; Br, 27.73; N, 4.86.Found: C, 62.21; H, 4.83; N, 5.01.
	With sodium hydroxide In water; dimethyl sulfoxide at 90℃;	2-Bromo-9-dodecylcarbazole General procedure: A mixture of 50% aqueous NaOH (12 mL), DMSO (40 mL) and 2-bromocarbazole (2 g, 8.16 mmol) was slowly added 1-bromododecane (2.45 mL, 9.80 mmol) at room temperature. The mixture was stirred overnight at 90 C and cooled to room temperature and then added the brine. The organic phase extracted with dichloromethane was dried over MgSO4. The solvent was removed and residue was purified by silica gel column chromatography using petroleum ether as the eluent. 2.53 g of yellow liquid was obtained (75% yield). 1H NMR (500 MHz, CDCl3): δ 8.06 (d, 1H), 7.94 (d, 1H), 7.54 (s, 1H), 7.45 (t, 1H), 7.40 (d, 1H), 7.33 (d, 1H),7.25 (t, 1H), 4.25 (t, 2H), 1.86 (q, 2H), 1.56-1.23 (m, 18H), 0.88 ppm(t, 3H).

Reference： [1]Barata, Patricia D.; Prata, Jose V. [Supramolecular Chemistry, 2013, vol. 25, # 12, p. 782 - 797]
[2]Bu, Lingyu; Li, Yiping; Wang, Jianfeng; Sun, Mingxiao; Zheng, Meng; Liu, Wei; Xue, Shanfeng; Yang, Wenjun [Dyes and Pigments, 2013, vol. 99, # 3, p. 833 - 838]

22
[ 3652-90-2 ]
[ 143-15-7 ]
[ 1482521-70-9 ]

Yield	Reaction Conditions	Operation in experiment
75%	With sodium hydroxide In water; dimethyl sulfoxide at 90℃;	2-Bromo-9-dodecylcarbazole General procedure: A mixture of 50% aqueous NaOH (12 mL), DMSO (40 mL) and 2-bromocarbazole (2 g, 8.16 mmol) was slowly added 1-bromododecane (2.45 mL, 9.80 mmol) at room temperature. The mixture was stirred overnight at 90 C and cooled to room temperature and then added the brine. The organic phase extracted with dichloromethane was dried over MgSO4. The solvent was removed and residue was purified by silica gel column chromatography using petroleum ether as the eluent. 2.53 g of yellow liquid was obtained (75% yield). 1H NMR (500 MHz, CDCl3): δ 8.06 (d, 1H), 7.94 (d, 1H), 7.54 (s, 1H), 7.45 (t, 1H), 7.40 (d, 1H), 7.33 (d, 1H),7.25 (t, 1H), 4.25 (t, 2H), 1.86 (q, 2H), 1.56-1.23 (m, 18H), 0.88 ppm(t, 3H).

Reference： [1]Bu, Lingyu; Li, Yiping; Wang, Jianfeng; Sun, Mingxiao; Zheng, Meng; Liu, Wei; Xue, Shanfeng; Yang, Wenjun [Dyes and Pigments, 2013, vol. 99, # 3, p. 833 - 838]

23
[ 3652-90-2 ]
[ 59965-20-7 ]
[ 1612786-04-5 ]

Reference： [1]Journal of Polymer Science, Part A: Polymer Chemistry,2014,vol. 52,p. 890 - 911

24
[ 3652-90-2 ]
[ 59965-20-7 ]
[ 1612786-05-6 ]

Reference： [1]Journal of Polymer Science, Part A: Polymer Chemistry,2014,vol. 52,p. 890 - 911

25
[ 3652-90-2 ]
[ 111-83-1 ]
[ 1356465-23-0 ]

Yield	Reaction Conditions	Operation in experiment
93%	Stage #1: 2-bromo-9H-carbazole With tetrabutylammomium bromide; sodium hydroxide In dimethyl sulfoxide at 20℃; Stage #2: 1-bromo-octane In dimethyl sulfoxide at 20℃; for 8h;	5 The compound 2-bromocarbazole (2.46 g, 10 mmol), DMS0 (100 mL), the appropriate amount of TBAB and sodium hydroxide solution (25 mL, 50 wt%) were added to the 250 mL three-necked flask, and the mixture was stirred for several minutes at room temperature, bromo-n-octane (2.3 mL, 1 mmol) was added dropwise and reacted at room temperature for 8 h. The reaction was stopped, adjusted to pH = 7 with hydrochloric acid, extracted with ethyl acetate, washed with saturated brine, and dried over anhydrous magnesium sulfate. The filtrate was evaporated to remove the solvent by rotary evaporation. The crude product was purified by silica gel (200-300 mesh) column chromatography [eluent, petroleum ether] to give 2-bromo-N-octylcarbazole (3.33 g) as a white solid in yield 93%.
68.6%	In toluene at 80℃; for 16h; Inert atmosphere; Alkaline conditions;
65%	With N-benzyl-N,N,N-triethylammonium chloride; sodium hydroxide In dimethyl sulfoxide for 8.5h;	7 Synthesis of Intermediate 7 (9-octyl-2-bromo-carbazole) Three in 250mL flask, followed by adding 3.8g (15.4mmol) 2- Bromocarbazole, 100mLDMSO, 0.25g (1.1mmol) TEBA and the 25mL solution of sodium hydroxide (50wt%), magnetically stirred solution of 3.3 within 0.5h g (16.9mmol) 1- bromo-n-octane, the reaction temperature 8h, the reaction was stopped, the reaction mixture was added hydrochloric acid to adjust PH = 7, extracted with ethyl acetate (3 × 50mL), and the combined organic layers were washed with saturated brine 3 times anhydrous magnesium sulfate overnight, filtered and the solvent was distilled off, the residue with petroleum ether as eluent column chromatography, a yellow oily liquid in a yield of 65%.

Reference： [1]Current Patent Assignee: DONGGUAN UNIVERSITY OF TECHNOLOGY - CN106905354, 2017, A Location in patent: Paragraph 0078; 0079
[2]Zhou, Pei; Dang, Dongfeng; Xiao, Manjun; Wang, Qiong; Zhong, Juan; Tan, Hua; Pei, Yong; Yang, Renqiang; Zhu, Weiguo [Journal of Materials Chemistry A, 2015, vol. 3, # 20, p. 10883 - 10889]
[3]Current Patent Assignee: DONGGUAN UNIVERSITY OF TECHNOLOGY - CN105238092, 2016, A Location in patent: Paragraph 0080; 0081

26
[ 3652-90-2 ]
[ 124-41-4 ]
[ 6933-49-9 ]

Reference： [1]RSC Advances,2015,vol. 5,p. 83122 - 83128

27
[ 3652-90-2 ]
[ 1246669-45-3 ]

Reference： [1]Patent: EP2930168,2015,A1
[2]Patent: KR101550768,2015,B1
[3]Patent: KR2015/98171,2015,A
[4]Patent: KR2015/43669,2015,A
[5]Patent: KR2015/89427,2015,A
[6]Patent: KR101614738,2016,B1
[7]Patent: WO2017/196081,2017,A1
[8]Dyes and Pigments,2018,vol. 156,p. 369 - 378

28
[ 3652-90-2 ]
[ 50488-34-1 ]
2-bromo-9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
99%	With 1-methyl-1H-imidazole; copper(l) iodide; lithium tert-butoxide; In toluene; at 130℃; for 24h;Inert atmosphere;	to with magnetic rotor and the condensation of the 100 ml dry three-mouth bottle is sequentially added in 2 - bromo carbazole (7.38 g, 30 mmol, 1.0 equivalent), cuprous iodide (113.8 mg, 0.3 mmol, 0 . 01 equivalent), 1 - methyl imidazole (49.26 mg, 0.6 mmol, 0 . 02 equivalent), [...] (4.84 g, 60 mmol, 2.0 equivalent). Replacing the nitrogen three times, then adding the syringe 2 - bromo -4 - tert-butyl pyridine (7.71 g, 36 mmol, 1.2 equivalents), 1 - methyl imidazole (49.3 mg, 0.6 mmol, 0 . 02 equivalent), 50 ml toluene, the oil bath temperature is raised to 130 C reaction 24 hours. Cooling to room temperature, vacuum distillation, to remove the solvent, then dry sample, using silica gel column chromatography column to carry out the separation and purification, eluent petroleum ether/ethyl acetate=20 is: 1, to obtain white solid 11.31 g, yield 99%.
99%	With 1-methyl-1H-imidazole; copper(l) iodide; lithium tert-butoxide; In toluene; at 130℃; for 24h;Inert atmosphere;	2-Bromocarbazole (7.38 g, 30 mmol, 1.0 eq.) was added sequentially to a 100 mL dry three-necked flask with a magnetic rotor and a condenser.Cuprous iodide (113.8 mg, 0.3 mmol, 0.01 eq.),1-methylimidazole (49.26 mg, 0.6 mmol, 0.02 equivalents),Lithium tert-butoxide (4.84 g, 60 mmol, 2.0 eq.).Pumping nitrogen three times,Then <strong>[50488-34-1]2-bromo-4-tert-butylpyridine</strong> (7.71 g, 36 mmol, 1.2 eq.) was added via a syringe.1-methylimidazole (49.3 mg, 0.6 mmol, 0.02 equivalents),50 mL of toluene, the temperature of the oil bath was raised to 130 C for 24 hours.The mixture was cooled to room temperature, distilled under reduced pressure, and the solvent was removed, followed by dry loading, and separation and purification were carried out using a silica gel column chromatography column.The eluent is petroleum ether / ethyl acetate = 20:1,11.31 g of a white solid were obtained in a yield of 99%.
96%	With 1-methyl-1H-imidazole; copper(l) iodide; potassium carbonate; In toluene; at 115 - 125℃; for 96h;Inert atmosphere;	To a pressure vessel equipped with a magnetic stir bar wasadded 2-bromo-9H-carbazole (2461 mg, 10.0 mmol, 1.0 eq),Cul (762 mg, 4.0 mmol, 0.4 eq), and K2C03 (2764 mg, 20.0mmol, 2.0 eq). Then the vessel was evacuated and back-filledwith nitrogen, and the evacuation and back-fill procedure wasrepeated twice. Then solvent toluene (60 mL), 1-methyl-1H-imidazole (792 uL, 10.0 mmol, 1.0 eq) and <strong>[50488-34-1]2-bromo-4-tert-butylpyridine</strong> (5353 mg, 25.0 mmol, 2.5 eq) were addedunder the protection ofnitrogen. The mixture was stirred in anoil bath at a temperature of 115-125 C. for 4 days. Then themixture was cooled to ambient temperature. The solvent wasremoved under reduced pressure and the residue was purifiedthrough column chromatography on silica gel using dichloromethane as an eluent to obtain the desired product,2-bromo-9-(4-tert-butylpyridin-2-yl)-9H-carbazole, as a colorless sticky liquid (3635 mg in 96% yield). ?H NMR(DMSO-d5, 400 MHz): oe 1.39 (s, 9H), 7.36 (t, J=8.0 Hz, 1H),7.48-7.55 (m, 3H), 7.71-7.73 (m, 2H), 7.94 (d, J=2.0 Hz, 1H),8.23 (d, J=8.0 Hz, 1H), 8.28 (d, J=8.0 Hz, 1H), 8.66 (d, J=5.5Hz, 1H).

96%

With copper(l) iodide; potassium carbonate; In toluene; at 115 - 125℃; for 96h;Inert atmosphere;

10250] To a pressure vessel equipped with a magnetic stir bar was added 2-bromo-9H-carbazole (2461 mg, 10.0 mmol, 1.0 eq), Cul (762 mg, 4.0 mmol, 0.4 eq), and K2C03 (2764 mg, 20.0 mmol, 2.0 eq). Then the vessel was evacuated and backfilled with nitrogen. The evacuation and back fill procedure was repeated for another two cycles. Then toluene (60 mE), 1-methyl-1H-imidazole (792 uL, 10.0 mmol, 1.0 eq) and [50488-34-1]2-bromo-4-tert-butylpyridine (5353 mg, 25.0 mmol, 2.5 eq) were added under nitrogen. The mixture was stirred in an oil bath at a temperature of 115-125 C. for 4 days. Then the mixture was cooled to ambient temperature. The solvent was removed under reduced pressure and the residue was purified through column chromatography on silica gel using dichioromethane as eluent to obtain the desired product 2-bromo-9-(4-tert-butylpyridin-2-yl)-9H-carbazole as a colorless sticky liquid 3635 mg in 96% yield. ?H NMR (DMSO-d5, 400 MHz): oe 1.39 (s, 9H), 7.36 (t, J=8.0 Hz, 1H), 7.48-7.55 (m, 3H), 7.71-7.73 (m, 2H), 7.94 (d, J=2.0 Hz, 1H), 8.23 (d, J=8.0 Hz, 1H), 8.28 (d, J=8.0 Hz, 1H), 8.66 (d, J=5.5 Hz, 1H).

Reference： [1]Patent: CN109748937,2019,A .Location in patent: Paragraph 0231; 0232; 0233
[2]Patent: CN109678907,2019,A .Location in patent: Paragraph 0232-0234
[3]Patent: US9224963,2015,B2 .Location in patent: Page/Page column 4; 6
[4]Patent: US2016/359125,2016,A1 .Location in patent: Paragraph 0249; 0250

29
[ 3652-90-2 ]
[ 1592-95-6 ]
[ 1345202-03-0 ]

Yield	Reaction Conditions	Operation in experiment
75%	With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; water; toluene; at 120℃; for 7h;	After dissolving (9-phenyl-9H-carbazol-3-yl)boronic acid (50 g, 174.10 mmol), 2-bromo-9H-carbazole (43 g, 174.10 mmol), and Pd(PPh3)4(6.0 g, 5.22 mmol) in toluene (870 mL), ethanol (200 mL), and H2O (200mL) of a flask, a mixture was under reflux at 120C for 7 hrs. After completion of the reaction, the mixture was extracted with ethyl acetate. The obtained organic layer was dried with magnesium sulfate to remove the remaining moisture, and subjected to column chromatography to obtain compound3(53.5 g, yield: 75 %)

Reference： [1]Patent: WO2016/52962,2016,A1 .Location in patent: Paragraph 183-184

30
[ 3652-90-2 ]
[ 1351692-34-6 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1.1: tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; triphenylphosphine; sodium t-butanolate / toluene / 100 °C 2.1: n-butyllithium / diethyl ether; hexane / 0.5 h / -78 °C 2.2: -78 - 20 °C 3.1: tetrakis(triphenylphosphine) palladium⁽⁰⁾; sodium hydroxide / tetrahydrofuran; water / 80 - 90 °C

Reference： [1]Current Patent Assignee: DUK SAN NEOLUX CO., LTD. - KR2015/61811, 2015, A

31
[ 3652-90-2 ]
[ 1679-18-1 ]
[ 1900703-41-4 ]

Yield	Reaction Conditions	Operation in experiment
85%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate In ethanol; water; toluene at 40 - 100℃; for 5h; Inert atmosphere;	3 Synthesis of 2-(4-chlorophenyl)-9H-carbazole A stream of nitrogen under 50.0 g (203.17 mmol) of 2-bromo-9H-carbazole, 31.77 g (203.17 mmol) of (4-chlorophenyl) boronic acid, 84.24 g (84.24 mmol) of K2CO3, 1000 ml / 250 ml / 250 ml put Toluene / H2O / EtOH was stirred in. At 40°C into the Pd (PPh3) 4 g of 11.74 (5 mol%) it was stirred at 100°C for 5 hours. After completion of the reaction and extracted with methylene chloride and the filter insert MgSO4. After removing the solvent by using a filter in the organic layer was purified by column chromatography 47.97 g: of 2- (yield 85%) (4-chlorophenyl) to obtain an -9H-carbazole [0083] GC-Mass (theoretical value:. 277.75 g / mol, measured value: 277 g / mol)

Reference： [1]Current Patent Assignee: DOOSAN CORP. - KR2016/40784, 2016, A Location in patent: Paragraph 0080-0082

32
[ 3652-90-2 ]
[ 929099-71-8 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1: dmap / tetrahydrofuran / 3 h / 20 °C / Inert atmosphere 2: tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tri-tert-butyl phosphine; caesium carbonate / 24 h / Reflux; Inert atmosphere 3: methoxybenzene; trifluoroacetic acid / dichloromethane / 0.5 h / 20 °C / Inert atmosphere

Reference： [1]Current Patent Assignee: JILIN OLED OPTICAL AND ELECTRONIC MATERIALS CO LTD - CN105906549, 2016, A

33
[ 3652-90-2 ]
[ 24424-99-5 ]
[ 1247868-53-6 ]

Yield	Reaction Conditions	Operation in experiment
93%	With dmap In tetrahydrofuran at 20℃; for 3h; Inert atmosphere;	5 Under the nitrogen protection system, 12.3 g of 2-bromocarbazole were weighed, di-tert-butyl dicarbonate (16.4 g), 4-dimethylaminopyridine (0.9 g) and THF (850 ml) into 1L round bottom three-necked flask, the reaction was stirred at room temperature for 3 h, after completion of the reaction, the organic phase was extracted, suspended, after elution with n-hexane solvent and silica gel column chromatography, 16.1 g of the first intermediate was obtained in a yield of 93%.
84%	With dmap In tetrahydrofuran at 20℃; for 12h; Inert atmosphere;

Reference： [1]Current Patent Assignee: JILIN OLED OPTICAL AND ELECTRONIC MATERIALS CO LTD - CN105906549, 2016, A Location in patent: Paragraph 0129; 0130
[2]Elmabruk, Asma; Das, Banibrata; Yedlapudi, Deepthi; Xu, Liping; Antonio, Tamara; Reith, Maarten E. A.; Dutta, Aloke K. [ACS Chemical Neuroscience, 2019, vol. 10, # 1, p. 396 - 411]

34
[ 3652-90-2 ]
[ 654664-63-8 ]
C₃₀H₁₉N [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
87%		2-Bromocarbazole (20.1 g, 81.6 mmol) and triphenylene-2-boronic acid (23 g, 84.5 mmol) were dissolved in tetrahydrofuran (200 ml), potassium carbonate (K2CO3, potassium carbonate, 40.4 g, 292.8 mmol)Was added to the reaction solution together with water, and the mixture was heated and stirred in a nitrogen state for about one hour.After stirring for one hour, tetrakis (triphenylphosphine) palladium (2.3 g, 1.95 mmol) was added and the mixture was heated with stirring for 6 hoursAfter completion of the reaction, the temperature was lowered to room temperature, and tetrahydrofuran was removed by distillation under reduced pressure, followed by filtration under reduced pressure. The solid obtained by filtration was recrystallized from tetrahydrofuran and ethanol to obtain the formula P1 (28 g, yield 87%)
81%	With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; for 12h;Inert atmosphere; Reflux;	2-bromo-carbazole (10.0 g, 40.6 mmol),Triphenylene2-boronic acid (13.2 g, 48.5mmol), and potassium carbonate (17.0 g, 123mmol) and tetrahydrofuran (100 mL) and a mixture of water (50 mL) was suspended within. After filling nitrogen,Tetrakis (triphenylphosphine) palladium (0.9 g, 0.7 mmol) was added to the suspension. Under nitrogen, the mixture was stirred for about 12 hours at reflux.After cooling to room temperature the resulting solids were filtered. To a pale yellow solid of the purified using a THF / EtOH P1 of white solid (13 g, 81%) was obtained.

Reference： [1]Patent: KR2015/135091,2015,A .Location in patent: Paragraph 0204; 0205; 0206
[2]Patent: KR2016/29689,2016,A .Location in patent: Paragraph 0198; 0199; 0200

35
[ 3652-90-2 ]
[ 182918-13-4 ]
[ 1612875-94-1 ]

Yield	Reaction Conditions	Operation in experiment
82.4%	With potassium carbonate In N,N-dimethyl-formamide at 100℃; for 8h; Inert atmosphere;	7 Under argon atmosphere, a 300 mL three-necked flask was charged with intermediate (j) (5.6 g, 21 mmol)2-Bromocarbazole (5.43 g, 22.1 mmol),Potassium carbonate (3.48 g, 25.2 mmol),Dimethylformamide (DMF, 50 mL) was added and the mixture was refluxed at 100 for 8 hours. After the reaction solution was cooled to room temperature, insoluble materials were removed by filtration, and the organic solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography to obtain intermediate (k) (10.9 g, yield 82.4%).

Reference： [1]Current Patent Assignee: IDEMITSU KOSAN CO LTD - KR2015/92145, 2015, A Location in patent: Paragraph 0320-0321

36
[ 3652-90-2 ]
[ 2915-16-4 ]
C₂₈H₁₈BrN₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
97%	With caesium carbonate; In N,N-dimethyl acetamide; at 70℃; for 16.5h;Inert atmosphere;	2-Bromocarbazole (10.0 g, 40.6 mmol), dimethylacetamide (50 ml) and cesium carbonate (26.5 g, 81.3 mmol) were sequentially added to a 250 ml double neck round bottom reaction flask, and The reaction system was filled with nitrogen, and the system was heated to 70 C in an oil bath for 30 minutes, and then <strong>[2915-16-4]2-chloro-4,6-diphenylpyrimidine</strong> (10.8 g, 40.6 mmol) was added with another 50 ml of dimethyl Amide, after 16 hours of reaction, the system was cooled and the reaction was filtered and washed with 50 ml of dimethylacetamide and 100 ml of tetrahydrofuran, and then the solid in the white porcelain funnel was washed with a large amount of water, and the remaining solid in the funnel was poured into 200. The mixture was heated to 65 C for 30 minutes in THF and filtered hot to afford compound 4-4-b (14.9 g, 97%).
90%	With potassium carbonate; In N,N-dimethyl-formamide; at 100℃; for 8h;Inert atmosphere;	Under an atmosphere of argon, a 300 mL three-necked flask was charged with intermediate (a) (5.6 g, 21 mmol) 2-Bromocarbazole (5.43 g, 22.1 mmol), Potassium carbonate (3.48 g, 25.2 mmol), Dimethylformamide (DMF, 50 mL) was added and the mixture was refluxed at 100 for 8 hours. After the reaction solution was cooled to room temperature, insolubles were removed by filtration, and the organic solvent was distilled off under reduced pres<strong>[2915-16-4]su</strong>re. The re<strong>[2915-16-4]su</strong>lting residue was purified by silica gel column chromatography to obtain intermediate (h) (9.0 g, yield 90%).

Reference： [1]Patent: CN109988152,2019,A .Location in patent: Paragraph 0168-0170
[2]Patent: KR2015/92145,2015,A .Location in patent: Paragraph 0303-0305

37
[ 4926-28-7 ]
[ 3652-90-2 ]
[ 1404169-08-9 ]

Yield	Reaction Conditions	Operation in experiment
95%	With 1-methyl-1H-imidazole; copper chloride (I); lithium tert-butylate In toluene at 130℃; for 2.5h; Inert atmosphere;	15 Example 15: Preparation of 2-bromo-9- (4-methyl-2-pyridyl) carbazole 2-bromocarbazole was added sequentially to a dry three-necked flask equipped with a reflux condenser and a magnetic rotor(492.2 mg, 2.00 mmol, 1.0 eq), cuprous chloride (2.0 mg, 0.02 mmol, 0.01 eq)Lithium tert-butoxide (240.2 mg, 3.00 mmol, 1.5 eq), nitrogen was purged three times,Then 4-methyl-2-bromopyridine (334.0 uL, 3.00 mmol, 1.5 eq)1-methylimidazole (3.2 uL, 0.04 mmol, 0.02 eq) and toluene (7.6 mL).The reaction mixture was refluxed at 130 ° C for 2.5 hours and TLC thin layer chromatography was carried out until the reaction of 2-bromocarbazole was completed. Saturated sodium sulfite solution 5mL quenching, filtration, ethyl acetate fully washed insoluble,The organic phase in the mother liquor was separated, dried over anhydrous sodium sulfate, filtered, and the solvent was distilled off under reduced pressure.The resulting crude product was purified by silica gel column chromatography eluting with petroleum ether / dichloromethane = 10: 1-1:Obtained 643.2 mg of white solid in 95% yield.
95%	With 1-methyl-1H-imidazole; copper chloride (I); lithium tert-butylate In toluene at 130℃; for 2.5h; chemoselective reaction;
95%	With 1-methyl-1H-imidazole; copper (I) iodide; lithium tert-butylate In toluene at 20 - 130℃; for 48h; Inert atmosphere;

93%	With 1-methyl-1H-imidazole; copper (I) iodide; potassium carbonate In toluene at 120℃; for 72h; Inert atmosphere; Sealed tube;	1 Synthesis of 2-bromo-9-(4-methyl-2-pyridyl)-oxazole: 2-bromocarbazole (246 mg, 1 mmol), 2-bromo-, was added sequentially to a 48 mL sealed tube with a magnetic rotor. 4-methylpyridine (516 mg, 3 mmol), cuprous iodide (29 mg, 0.15 mmol), 1-methylimidazole (41 mg, 0.5 mmol), potassium carbonate (276 mg, 2 mmol) and toluene (5 mL). The mixture was bubbled with nitrogen for 10 minutes and then heated to 120 ° C and stirred for 3 days. After cooling to room temperature, the reaction was quenched with EtOAc (EtOAc)EtOAc. The solvent was evaporated to dryness, and the obtained crude product was purified by silica gel column chromatography, eluent: petroleum ether / ethyl acetate = 25:1 to afford 312 mg of white solid.
93%	With 1-methyl-1H-imidazole; copper (I) iodide; lithium tert-butylate In toluene at 130℃; for 10h; Inert atmosphere;	1 Example 1: Compound Pt5 can be synthesized as follows: Synthesis of Br-Cab-Py-Me: To a dry three-necked flask with a reflux condenser and a magnetic rotor, 2-bromocarbazole (12600 mg, 51.20 mmol, 1.00 equiv), cuprous iodide (97 mg, 0.51 mmol, 0.01 eq.), lithium t-butoxide ( 6150 mg, 76.80 mmol, 1.50 eq.), three times of nitrogen was added, then 1-methylimidazole (83 mg, 1.02 mmol, 0.02 eq.), 2-bromo-4-methylpyridine (9690 mg, 56.32 mmol, 1.10 eq.) and Toluene (200 mL). The reaction mixture was stirred and refluxed at 130 ° C for 10 hours, and was subjected to TLC thin layer chromatography until the reaction of the starting material 2-bromocarbazole was completed. The reaction was quenched by the addition of 200 mL of water, filtered, and ethyl acetate was washed thoroughly, and the organic phase was separated, dried over anhydrous sodium sulfate, filtered and evaporated. The obtained crude product was separated and purified by silica gel column chromatography, eluting solvent ( petroleum ether / ethyl acetate = 20:110:1), Br-Cab-Py-Me was obtained as a white solid, 16.06 g, yield 93%.
93%	With 1-methyl-1H-imidazole; copper (I) iodide; lithium tert-butylate In toluene at 120℃; for 8h; Sealed tube; Inert atmosphere;	3 Synthesis of 2-bromo-9-(4-methyl-2-pyridyl)carbazole: 2-bromocarbazole 0001 (1 eq, 15 mmol) was added sequentially to a 48 mL sealed tube with a magnetic rotor.2-bromo-4-methylpyridine 0008 (1.1 eqiv 16.5 mmol), cuprous iodide (0.3 mmL, 0.02 equiv),1-Methylimidazole (0.3 mmol, 1.2 equiv), t-BuOLi (18 mmol, 1.2 equiv) and toluene (50 mL), and the mixture obtained was stirred under nitrogen for 10 minutes and then heated to 120 ° C for 8 hours.After cooling to room temperature, the reaction was quenched with water and ethyl acetate.After washing with an appropriate amount of a saturated aqueous solution of sodium chloride, dried over anhydrous sodium sulfate.The solvent was distilled off under reduced pressure, and the obtained crude product was purified by silica gel column chromatography.The eluent was petroleum ether: ethyl acetate = 25:1,A white solid was obtained in a yield of 93%.
93%	With 1-methyl-1H-imidazole; copper (I) iodide; lithium tert-butylate In toluene Inert atmosphere; Heating;	1.1 (1) Synthesis of 1-1: Preparation process: 2-bromocarbazole (3.69 g, 15 mmol), 2-bromo-4-methylpyridine 0002 (1.42 mL, 15 mmol),Cuprous iodide (0.3mmoL, 0.02equiv),1-methylimidazole (0.3 mmol, 0.2 equiv), t-BuOLi (18 mmol, 1.2 equiv), and toluene (50 mL),The resulting mixture was sparged with nitrogen for 10 minutes and heated to 120 ° C and stirred for 8 hours.Cool to room temperature, quench the reaction with water, extract with ethyl acetate, combine the organic phases, wash with an appropriate amount of saturated aqueous sodium chloride solution, and dry with anhydrous sodium sulfate.The solvent was distilled off under reduced pressure,The obtained crude product was separated and purified by silica gel column chromatography,The eluent was petroleum ether: ethyl acetate = 25: 1 to obtain a white solid with a yield of 93%.
93%	With 1-methyl-1H-imidazole; copper (I) iodide In toluene at 120℃; Inert atmosphere; Sealed tube; Alkaline conditions;	5.1 (1) Synthesis of 2-bromo-9- (4-methylpyridin-2-yl) carbazole: Preparation process: To a 48 mL sealed tube with a magnetic rotor, 2-bromocarbazole (3.69 g, 15 mmol), 2-bromo-4-methylpyridine (2.8 g, 16.5 mmol), and cuprous iodide (0.3 mmL, 0.02 equiv), 1-methylimidazole (0.3 mmol, 1.2 equiv), t-BuOLi (18 mmol, 1.2 equiv), and toluene (50 mL). The resulting mixture was bubbled with nitrogen for 10 minutes and heated to 120 ° C with stirring 8 hour. Cool to room temperature, quench the reaction with water, extract with ethyl acetate, combine the organic phases, wash with an appropriate amount of saturated aqueous sodium chloride solution, and dry with anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the obtained crude product was separated and purified by silica gel column chromatography. The eluent was petroleum ether: ethyl acetate = 25: 1 to obtain a white solid with a yield of 93%.
91%	With 1-methyl-1H-imidazole; copper chloride (I); lithium tert-butylate In toluene at 130℃; for 12h;	The compounds Compound Pd7 and Compound Pt7 in the present invention can be synthesized as follows: To a dry three-necked flask with a magnetic rotor, 2-bromoindazole (3.7293 g, 15.00 mmol, 99%, 1.00 equiv) was added in succession.Cuprous chloride (0.0151 g, 0.15 mmol, 0.01 equiv) and lithium tert-butoxide (1.8190 g, 22.50 mmol, 1.50 equiv).Nitrogen was purged three times and then 2-bromo-4-methylpyridine (2.53 mL, 22.5 mmol, 99%, 1.5 equiv) was added under nitrogen protection.1-Methylimidazole (24.2 μL, 0.30 mmol, 0.02 eq) and toluene (56.6 mL).The reaction flask was then placed in a 130°C oil bath.After stirring for 12 hours, the reaction was completed by thin layer chromatography.It was cooled to room temperature, filtered through celite, and the insolubles were thoroughly washed with ethyl acetate.The resulting filtrate was washed with water (50 mL) and dried over anhydrous sodium sulfate.The mixture was filtered, concentrated, and the crude product was purified by flash silica gel column chromatography (eluent: petroleum ether/dichloromethane = 10/1 to 1/1) to afford C1 as a white solid, 4.60619 g, 91% yield.
91%	With 1-methyl-1H-imidazole; copper chloride (I); lithium tert-butylate In toluene at 130℃; for 12h; Inert atmosphere;	3 Synthesis of Br-Cab-Py-Me: Add to the dry three-necked flask with a magnetic rotor2-bromocarbazole (3.7293 g, 15 mmol, 99%, 1.0 eq),Cuprous chloride (0.0151g, 0.15mmol, 0.01 equivalents)And lithium tert-butoxide (1.8190 g, 22.5 mmol, 1.5 eq.). Pumping nitrogen three times,Subsequent addition of 2-bromo-4-methylpyridine under nitrogen(2.53mL, 22.5mmol, 99%, 1.5 equivalents),1-methylimidazole (24.2 μL, 0.3 mmol, 0.02 eq.) and toluene (56.6 mL).The reaction vial was then placed in a 130 ° C oil bath. After stirring for 12 hours,The reaction was monitored by thin layer chromatography. Cool to room temperature and filter through celite.The ethyl acetate was thoroughly washed with insolubles. The filtrate was washed with water (50 mL).Dry over anhydrous sodium sulfate. Filtered, concentrated,The crude product was separated and purified by flash chromatography on silica gel column chromatography.(eluent: petroleum ether / dichloromethane = 10/1 ~ 1 / 1) to get Br-Cab-Py-Me,White solid 4.6019 g, yield 91%.
86%	With 1-methyl-1H-imidazole; copper chloride (I); lithium tert-butylate In toluene at 130℃; for 12h; Schlenk technique; Inert atmosphere;
75%	With copper (I) iodide; potassium carbonate; <i>L</i>-proline In dimethyl sulfoxide at 120℃; for 72h; Schlenk technique; Inert atmosphere;	2 Synthesis of 2-(3-amino-5-methylphenol)-9-(2-pyridyl)carbazole 4103: General procedure: The synthesis method of 2-bromo-9-(4-methylpyridin-2-yl)carbazole 4203 is synthesized with 2-bromo-9-(2-pyridyl)carbazole.However, 2-bromopyridine was replaced with 4-methyl-2-bromopyridine 4201 (light brown solid was used directly in the next step). _: To a 25 ml Shrek tube was added 2-bromo-9-(2-pyridyl)carbazole 4101 (1 equiv), 3-amino-5-methylphenol 4102 (1.2 equiv),Cuprous iodide (10%), L-proline (L-Pro, 20%), cesium carbonate (2 equiv) and dimethyl sulfoxide (0.5 M).The resulting mixture was sparged with nitrogen for 10 minutes and stirred at 120 ° C for 3 days.After cooling, water and ethyl acetate (EA) were added, and the mixture was filtered.The aqueous phase was extracted with ethyl acetate and the organic phases were combined.Wash with brine and dry the organic phase with anhydrous Na2SO4.The obtained solution was purified by silica gel chromatography using PE:EA=8:1 as an eluent.The target product 4103 (brown viscous liquid, yield 75%) was obtained.
40%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; sodium tertiary butoxide In 1,3-dimethylbenzene for 18h; Reflux; Inert atmosphere;	synthesis of 2-Bromo-9-(4-methylpyridin-2-yl)-9H-carbazole In a 500 mL three-neck round-bottom flask was added 2,2′-bis(diphenylphosphino)-1,1′-binaphthalene (1.1 g, 1.8 mmol), Pd2(dba)3 (0.56 g, 0.61 mmol) in 250 mL of m-xylene. The reaction mixture was degassed by bubbling nitrogen for 30 minutes and heated to 80° C. for 15 minutes. The reaction mixture was cooled to room temperature and 2-bromo-9H-carbazole (5.0 g, 20.3 mmol), 2-bromo-4-methylpyridine (4.2 g, 24.4 mmol) and sodium tert-butoxide (2.9 g, 30.5 mmol) were added. The reaction was again degassed for 15 minutes and heated to reflux for 18 hours. After cooling to room temperature, the reaction mixture was diluted with 250 mL of water and extracted with EtOAc (3×150 mL). The combined organic layers were washed with water (2×150 mL), brine (1×150 mL) and dried over NaSO4. After removal of the solvents under reduced pressure, the crude material was first chromatographed on a silica gel column with DCM and then on a neutral alumina column with 3/1 hexane/DCM (v/v) to give 2.8 g (40%) of 2-Bromo-9-(4-methylpyridin-2-yl)-9H-carbazole as a white solid. The product was confirmed by GC/MS and NMR.
	With 1-methyl-1H-imidazole; copper (I) iodide; lithium tert-butylate In toluene at 130℃;
	With copper (I) iodide; potassium carbonate; <i>L</i>-proline In dimethyl sulfoxide at 130℃; for 24h;	6.4 4) Synthesis of Intermediate Compound BD50-4 2-bromo-4-(tert-butyl)pyridine (1.0 eq), 2-bromo-9H-carbazole (1.2 eq), CuI (0.01 eq), K2CO3 (2.0 eq), and L-proline (0.02 eq) were dissolved in dimethyl sulfoxide (0.1M) and stirred at a temperature of 130° C. for 24 hours. The reaction mixture was cooled at room temperature, and then subjected to an extraction process three times utilizing dichloromethane and water to obtain an organic layer. The obtained organic layer was dried by utilizing magnesium sulfate and concentrated, and column chromatography was utilized to synthesize Intermediate compound BD50-4 (yield: 68

Reference： [1]Current Patent Assignee: ZHEJIANG UNIVERSITY OF TECHNOLOGY - CN106366069, 2017, A Location in patent: Paragraph 0089; 0090; 0091; 0092
[2]Zhao, Xiangdong; She, Yuanbin; Fang, Kun; Li, Guijie [Journal of Organic Chemistry, 2017, vol. 82, # 2, p. 1024 - 1033]
[3]Li, Guijie; Zheng, Jianbing; Fang, Xiaoli; Xu, Kewei; Yang, Yun-Fang; Wu, Jiang; Cao, Linyu; Li, Jian; She, Yuanbin [Organometallics, 2021, vol. 40, # 4, p. 472 - 481]
[4]Current Patent Assignee: AAC ACOUSTIC TECHNOLOGIES HOLDINGS INC.; NANJING TECH UNIVERSITY - CN108178774, 2018, A Location in patent: Page/Page column 8; 9
[5]Current Patent Assignee: ZHEJIANG UNIVERSITY OF TECHNOLOGY; AAC ACOUSTIC TECHNOLOGIES HOLDINGS INC. - CN108484676, 2018, A Location in patent: Paragraph 0193; 0194; 0195
[6]Current Patent Assignee: AAC ACOUSTIC TECHNOLOGIES HOLDINGS INC.; NANJING TECH UNIVERSITY - CN109748938, 2019, A Location in patent: Paragraph 0119-0123
[7]Current Patent Assignee: NANJING JIANUOLIN OPTOELECTRONICS TECHNOLOGY CO LTD - CN110615787, 2019, A Location in patent: Paragraph 0077-0081
[8]Current Patent Assignee: NANJING JIANUOLIN OPTOELECTRONICS TECHNOLOGY CO LTD - CN110590856, 2019, A Location in patent: Paragraph 0153-0157
[9]Current Patent Assignee: AAC ACOUSTIC TECHNOLOGIES HOLDINGS INC.; ZHEJIANG UNIVERSITY OF TECHNOLOGY - CN107892704, 2018, A Location in patent: Paragraph 0197; 0198
[10]Current Patent Assignee: AAC ACOUSTIC TECHNOLOGIES HOLDINGS INC.; ZHEJIANG UNIVERSITY OF TECHNOLOGY - CN108299507, 2018, A Location in patent: Paragraph 0138; 0139; 0143; 0144
[11]Fleetham, Tyler; Golden, Jessica H.; Idris, Muazzam; Hau, Han-Ming; Muthiah Ravinson, Daniel Sylvinson; Djurovich, Peter I.; Thompson, Mark E. [Inorganic Chemistry, 2019, vol. 58, # 18, p. 12348 - 12357]
[12]Current Patent Assignee: NANJING TECH UNIVERSITY; AAC ACOUSTIC TECHNOLOGIES HOLDINGS INC. - CN108840886, 2018, A Location in patent: Paragraph 0142; 0148; 0149; 0150; 0163; 0165; 0166; 0167
[13]Current Patent Assignee: UNIVERSAL DISPLAY CORP - US9461254, 2016, B2 Location in patent: Page/Page column 192
[14]Li, Guijie; Chen, Qidong; Zheng, Jianbing; Wang, Qunmin; Zhan, Feng; Lou, Weiwei; Yang, Yun-Fang; She, Yuanbin [Inorganic Chemistry, 2019, vol. 58, # 21, p. 14349 - 14360]
[15]Current Patent Assignee: Samsung Display (in: Samsung); SAMSUNG ELECTRONICS CO.,LTD. - US2022/177503, 2022, A1 Location in patent: Paragraph 0595; 0599

38
[ 52718-95-3 ]
[ 3652-90-2 ]
methyl 2-(2-bromo-9H-carbazol-9-yl)pyridine-3-carboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
97%	With copper(l) iodide; potassium carbonate; L-proline; In toluene; at 105 - 115℃; for 24h;Inert atmosphere;	For example, LI-Br-1 can be synthesized as follows: Synthesis of methyl 2-(2-bromo-9H-carbazol-9-yl)pyridine-3-carboxylate: A mixture of 2-bromo-9H-carbazole (1.23 g, 10 mmol, 1.0 eq), <strong>[52718-95-3]methyl 2-bromopyridine-3-carboxylate</strong> (1.51 g, 7 mmol, 1.4 eq), CuI (0.19 g, 1.0 mmol, 0.2 eq), K2CO3 (1.38 g, 10 mmol, 2.0 eq), and L-proline (0.12 g, 1.0 mmol, 0.2 eq) in toluene (15 mL) was stirred at 105-115 C. for 1 day under nitrogen then cooled to ambient temperature. The solvent was removed under reduced pressure and the residue was purified through column chromatography on silica gel using dichloromethane as eluent to obtain a sticky liquid 1.85 g in 97% yield. 1H NMR (DMSO-d6, 400 MHz): delta 3.32 (s, 3H), 7.22 (d, J=8.0 Hz, 1H), 7.31 (t, J=7.2 Hz, 1H), 7.41 (d, J=8.0 Hz, 1H), 7.45 (dd, J=8.4, 16 Hz, 1H), 7.48 (d, J=1.6 Hz, 1H), 7.74 (dd, J=8.0, 4.8 Hz, 1H), 8.19 (d, J=8.0 Hz, 1H), 8.24 (d, J=8.0 Hz, 1H), 8.49 (d, J=8.0, 2.0 Hz, 1H), 8.93 (d, J=8.4, 2.0 Hz, 1H).
	With copper(l) iodide; potassium carbonate; L-proline; In toluene; at 120℃; for 24h;Inert atmosphere; Sealed tube;	The synthesis of 2-bromo-9-(3-methoxycarbonylpyridin-2-yl)carbazole 4402 is the same as that of 2-bromo-9-(2-pyridyl)carbazole, but 2-bromopyridine is replaced by <strong>[52718-95-3]4-methoxycarbonyl-2-bromopyridine</strong> 4401 was heated at 120 C for 1 day to give the titled product4402 (light brown solid was used directly for next step). _: 2-bromocarbazole (3.69 g, 15 mmol) was added sequentially to a 48 mL sealed tube with a magnetic rotor.2-bromopyridine (1.57 mL, 16.5 mmol), cuprous iodide (0.3 mmL, 0.02 equiv),1-Methylimidazole (0.3 mmol, 1.2 equiv), t-BuOLi (18 mmol, 1.2 equiv) and toluene (50 mL), and the obtained mixture was bubbled with nitrogen for 10 minutes and then heated to 120 C for 8 hours.Cool to room temperature, quench with water and extract with EtOAc.The organic phases were combined, washed with aq. saturated aqueous sodium chloride and dried over anhydrous sodium sulfate.The solvent was distilled off under reduced pressure, and the obtained crude product was purified by silica gel column chromatography.The eluent was petroleum ether: ethyl acetate = 25:1,A white solid was obtained in a yield of 93%

Reference： [1]Patent: US2016/359125,2016,A1 .Location in patent: Paragraph 0275; 0276
[2]Patent: CN108840886,2018,A .Location in patent: Paragraph 0142; 0144; 0145; 0147; 0195; 0197; 0198

39
[ 3430-17-9 ]
[ 3652-90-2 ]
2-bromo-9-(3-methylpyridin-2-yl)-9H-carbazole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
91%	With 1-methyl-1H-imidazole; copper(l) chloride; lithium tert-butoxide In toluene at 130℃; for 2.5h; Inert atmosphere;	14 Example 14: Preparation of 2-bromo-9- (3-methyl-2-pyridyl) carbazole Into a dry three-necked flask with a reflux condenser and a magnetic rotor2-bromocarbazole (492.2 mg, 2.00 mmol, 1.0 eq), cuprous chloride (2.0 mg, 0.02 mmol, 0.01 eq)Lithium tert-butoxide (240.2 mg, 3.00 mmol, 1.5 eq), nitrogen was purged three times,Then 3-methyl-2-bromopyridine (334.2 uL, 3.00 mmol, 1.5 eq)1-methylimidazole (3.2 uL, 0.04 mmol, 0.02 eq) and toluene (7.6 mL).The reaction mixture was refluxed at 130 ° C for 2.5 hours and TLC thin layer chromatography was carried out until the reaction of 2-bromocarbazole was completed. Saturated sodium sulfite solution 5mL quenching, filtration, ethyl acetate fully washed insoluble,The organic phase in the mother liquor was separated, dried over anhydrous sodium sulfate, filtered, and the solvent was distilled off under reduced pressure.The crude product was purified by silica gel column chromatography eluting with petroleum ether / ethyl acetate = 40: 1-1: 1,A white solid was obtained 611.9 mg, yield 91%.
91%	With 1-methyl-1H-imidazole; copper(l) chloride; lithium tert-butoxide In toluene at 130℃; for 2.5h; chemoselective reaction;

Reference： [1]Current Patent Assignee: ZHEJIANG UNIVERSITY OF TECHNOLOGY - CN106366069, 2017, A Location in patent: Paragraph 0085; 0086; 0087; 0088
[2]Zhao, Xiangdong; She, Yuanbin; Fang, Kun; Li, Guijie [Journal of Organic Chemistry, 2017, vol. 82, # 2, p. 1024 - 1033]

40
[ 3510-66-5 ]
[ 3652-90-2 ]
[ 1674393-11-3 ]

Yield	Reaction Conditions	Operation in experiment
92%	With 1-methyl-1H-imidazole; copper(l) chloride; lithium tert-butoxide In toluene at 130℃; for 3h; Inert atmosphere;	16 Example 16: Preparation of 2-bromo-9- (5-methyl-2-pyridyl) carbazole 2-bromocarbazole was added sequentially to a dry three-necked flask equipped with a reflux condenser and a magnetic rotor(492.2 mg, 2.00 mmol, 1.0 eq), 5-methyl-2-bromopyridine (516.1 mg, 3.00 mmol, 1.5 eq)Cupric chloride (2.0 mg, 0.02 mmol, 0.01 eq), lithium tert-butoxide (240.2 mg, 3.00 mmol, 1.5 eq)The nitrogen was purged three times and then 1-methylimidazole (3.2 uL, 0.04 mmol, 0.02 eq) and toluene (7.6 mL) were added.The reaction mixture was refluxed at 130 ° C for 3 hours and TLC thin layer chromatography was carried out until the reaction of 2-bromocarbazole was completed. Saturated sodium sulfite solution 5mL quenching, filtration, ethyl acetate fully washed insoluble,The organic phase in the mother liquor was separated, dried over anhydrous sodium sulfate, filtered, and the solvent was distilled off under reduced pressure.The resulting crude product was purified by silica gel column chromatography eluting with petroleum ether / dichloromethane = 10: 1-1:Obtained 617.1 mg of white solid in 92% yield.
92%	With 1-methyl-1H-imidazole; copper(l) chloride; lithium tert-butoxide In toluene at 130℃; for 2h; chemoselective reaction;

Reference： [1]Current Patent Assignee: ZHEJIANG UNIVERSITY OF TECHNOLOGY - CN106366069, 2017, A Location in patent: Paragraph 0093; 0094; 0095; 0096
[2]Zhao, Xiangdong; She, Yuanbin; Fang, Kun; Li, Guijie [Journal of Organic Chemistry, 2017, vol. 82, # 2, p. 1024 - 1033]

41
[ 624-28-2 ]
[ 3652-90-2 ]
[ 2059135-30-5 ]

Yield	Reaction Conditions	Operation in experiment
98%	With 1-methyl-1H-imidazole; copper(l) chloride; lithium tert-butoxide In toluene at 130℃; for 5h; Inert atmosphere;	17 Example 17: Preparation of 2-bromo-9- (5-bromo-2-pyridyl) carbazole 2-bromocarbazole was added sequentially to a dry three-necked flask equipped with a reflux condenser and a magnetic rotor(246.1 mg, 1.0 mmol, 1.0 eq), cuprous chloride (1.0 mg, 0.01 mmol, 0.01 eq)Lithium tert-butoxide (120.1 mg, 1.5 mmol, 1.5 eq), nitrogen was purged three times,Followed by the addition of 2,5-dibromopyridine (355.3 mg, 1.5 mmol, 1.5 eq)1-methylimidazole (1.6 uL, 0.02 mmol, 0.02 eq) and toluene (4 mL).The reaction mixture was refluxed at 130 ° C for 5.0 hours and TLC thin layer chromatography was carried out until the reaction of 2-bromocarbazole was completed. Saturated sodium sulfite solution quenched, filtered, ethyl acetate fully washed insoluble,The organic phase in the mother liquor was separated, dried over anhydrous sodium sulfate, filtered,The solvent and excess 2,5-dibromopyridine were removed by distillation under reduced pressure,The resulting crude product was purified by silica gel column chromatography, eluent:Petroleum ether / dichloromethane = 1: 1 to give 397.8 mg of a white solid in 98% yield.
80%	With 1-methyl-1H-imidazole; copper(l) chloride; lithium tert-butoxide In toluene at 130℃; for 5h; chemoselective reaction;

Reference： [1]Current Patent Assignee: ZHEJIANG UNIVERSITY OF TECHNOLOGY - CN106366069, 2017, A Location in patent: Paragraph 0097; 0098; 0099; 0100
[2]Zhao, Xiangdong; She, Yuanbin; Fang, Kun; Li, Guijie [Journal of Organic Chemistry, 2017, vol. 82, # 2, p. 1024 - 1033]

42
[ 3652-90-2 ]
[ 357927-50-5 ]
2-bromo-9-(4-fluoropyridin-2-yl)-9H-carbazole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
93%	With 1-methyl-1H-imidazole; copper(l) chloride; lithium tert-butoxide; In toluene; at 130℃; for 4h;Inert atmosphere;	2-bromocarbazole was added sequentially to a dry three-necked flask equipped with a reflux condenser and a magnetic rotor(246.1 mg, 1.00 mmol, 1.0 eq), cuprous chloride (1.0 mg, 0.01 mmol, 0.01 eq)Lithium tert-butoxide (120.1 mg, 1.50 mmol, 1.5 eq), nitrogen was purged three times,Then <strong>[357927-50-5]4-fluoro-2-bromopyridine</strong> (155.0 uL, 1.50 mmol, 1.5 eq)1-methylimidazole (1.6 uL, 0.02 mmol, 0.02 eq) and toluene (3.8 mL).The reaction mixture was refluxed at 130 C for 4.0 hours and TLC thin layer chromatography was carried out until the reaction of 2-bromocarbazole was completed. Saturated sodium sulfite solution 3mL quenching, filtration, ethyl acetate fully washed insoluble,The organic phase in the mother liquor was separated, dried over anhydrous sodium sulfate, filtered, and the solvent was distilled off under reduced pressure.The resulting crude product was purified by silica gel column chromatography, eluent: petroleum ether / dichloromethane = 5: 1-1:To give 319.1 mg of a white solid in 93% yield.

Reference： [1]Patent: CN106366069,2017,A .Location in patent: Paragraph 0101; 0102; 0103; 0104
[2]Journal of Organic Chemistry,2017,vol. 82,p. 1024 - 1033

43
[ 3652-90-2 ]
[ 4595-60-2 ]
2-bromo-9-(pyrimidin-2-yl)-9H-carbazole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
96%	With 1-methyl-1H-imidazole; copper(l) chloride; lithium tert-butoxide; In toluene; at 130℃; for 7h;Inert atmosphere;	2-bromocarbazole was added sequentially to a dry three-necked flask equipped with a reflux condenser and a magnetic rotor(492.2 mg, 2.00 mmol, 1.0 eq), <strong>[4595-60-2]2-<strong>[4595-60-2]bromopyrimidine</strong></strong> (476.9 mg, 3.00 mmol, 1.5 eq)Cupric chloride (2.0 mg, 0.02 mmol, 0.01 eq), lithium tert-butoxide (240.2 mg, 3.00 mmol, 1.5 eq)The nitrogen was purged three times and then 1-methylimidazole (3.2 uL, 0.04 mmol, 0.02 eq) and toluene (7.6 mL) were added. The reaction mixture was refluxed at 130 C for 7.0 hours and TLC thin layer chromatography was carried out until the reaction of 2-bromocarbazole was completed. Saturated sodium sulfite solution 5mL quenching, filtration, ethyl acetate fully washed insoluble,The organic phase in the mother liquor was separated, dried over anhydrous sodium sulfate, filtered, and the solvent was distilled off under reduced pressure.The resulting crude product was purified by silica gel column chromatography, eluent: petroleum ether / dichloromethane = 5: 1-1:Obtained 621.7 mg of white solid in 96% yield.

Reference： [1]Patent: CN106366069,2017,A .Location in patent: Paragraph 0105; 0106; 0107; 0108
[2]Journal of Organic Chemistry,2017,vol. 82,p. 1024 - 1033

44
[ 56423-63-3 ]
[ 3652-90-2 ]
2-bromo-9-(pyrazin-2-yl)-9H-carbazole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
93%	With 1-methyl-1H-imidazole; copper(l) chloride; lithium tert-butoxide; In toluene; at 130℃; for 7h;Inert atmosphere;	2-bromocarbazole was added sequentially to a dry three-necked flask equipped with a reflux condenser and a magnetic rotor(246.1 mg, 1.00 mmol, 1.0 eq), cuprous chloride (1.0 mg, 0.01 mmol, 0.01 eq)Lithium tert-butoxide (120.1 mg, 1.50 mmol, 1.5 eq), nitrogen was purged three times,Then <strong>[56423-63-3]<strong>[56423-63-3]2-bromopyrazin</strong>e</strong> (135.7 uL, 1.50 mmol, 1.5 eq) was added,1-methylimidazole (1.6 uL, 0.02 mmol, 0.02 eq) and toluene (3.8 mL).The reaction mixture was refluxed at 130 C for 7.0 hours and TLC thin layer chromatography was carried out until the reaction of 2-bromocarbazole was completed. Saturated sodium sulfite solution 5mL quenching, filtration, ethyl acetate fully washed insoluble,The organic phase in the mother liquor was separated, dried over anhydrous sodium sulfate, filtered,The solvent and the excess <strong>[56423-63-3]<strong>[56423-63-3]2-bromopyrazin</strong>e</strong> were removed by distillation under reduced pressure, and the resulting crude product was purified by silica gel column chromatography,Eluent: petroleum ether / dichloromethane = 5: 1-1: 1 to give 300.6 mg of a white solid in 93% yield.

Reference： [1]Patent: CN106366069,2017,A .Location in patent: Paragraph 0109; 0110; 0111; 0112
[2]Journal of Organic Chemistry,2017,vol. 82,p. 1024 - 1033

45
[ 2005-43-8 ]
[ 3652-90-2 ]
2-bromo-9-(quinolin-2-yl)-9H-carbazole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
94%	With 1-methyl-1H-imidazole; copper(l) chloride; lithium tert-butoxide; In toluene; at 130℃; for 3h;Inert atmosphere;	2-bromocarbazole was added sequentially to a dry three-necked flask equipped with a reflux condenser and a magnetic rotor(246.1 mg, 1.00 mmol, 1.0 eq), <strong>[2005-43-8]2-bromoquinoline</strong> (312.1 mg, 1.50 mmol, 1.5 eq)Cupric chloride (1.0 mg, 0.01 mmol, 0.01 eq), lithium tert-butoxide (120.1 mg, 1.50 mmol, 1.5 eq)The nitrogen was purged three times and then 1-methylimidazole (1.6 uL, 0.02 mmol, 0.02 eq) and toluene (3.8 mL) were added.The reaction mixture was refluxed at 130 C for 3.0 hours and TLC thin layer chromatography was carried out until the reaction of 2-bromocarbazole was completed. Saturated sodium sulfite solution 5mL quenching, filtration, ethyl acetate fully washed insoluble,The organic phase in the mother liquor was separated, dried over anhydrous sodium sulfate, filtered, and the solvent was distilled off under reduced pressure.The resulting crude product was purified by silica gel column chromatography eluting with petroleum ether / dichloromethane = 5: 1-3: 1,A white solid of 351.6 mg, yield 94%

Reference： [1]Patent: CN106366069,2017,A .Location in patent: Paragraph 0113; 0114; 0115; 0116
[2]Journal of Organic Chemistry,2017,vol. 82,p. 1024 - 1033

46
[ 2516-40-7 ]
[ 3652-90-2 ]
2-bromo-9-(benzothiazol-2-yl)-9H-carbazole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
79%	With 1-methyl-1H-imidazole; copper(l) chloride; lithium tert-butoxide; In toluene; at 130℃; for 48h;Inert atmosphere;	2-bromocarbazole was added sequentially to a dry three-necked flask equipped with a reflux condenser and a magnetic rotor(123.1 mg, 0.5 mmol, 1.0 eq), cuprous chloride (0.5 mg, 0.005 mmol, 0.01 eq)Lithium tert-butoxide (60.0 mg, 0.75 mmol, 1.5 eq), nitrogen was purged three times,Then <strong>[2516-40-7]2-<strong>[2516-40-7]bromobenzothiazole</strong></strong> (160.6 mg, 0.75 mmol, 1.5 eq) was added,1-methylimidazole (0.82 uL, 0.01 mmol, 0.02 eq) and toluene (4 mL).The reaction mixture was refluxed at 130 C for 48 hours and TLC thin layer chromatography was carried out until the reaction of 2-bromocarbazole was completed. Saturated sodium sulfite solution quenched, filtered, ethyl acetate fully washed insoluble,The organic phase in the mother liquor was separated, dried over anhydrous sodium sulfate, filtered,The solvent and excess <strong>[2516-40-7]2-<strong>[2516-40-7]bromobenzothiazole</strong></strong> were removed by distillation under reduced pressure,The resulting crude product was purified by silica gel column chromatography, eluent:Petroleum ether / dichloromethane = 1: 1 to give a pale yellow solid58.5 mg, yield 79%.

Reference： [1]Patent: CN106366069,2017,A .Location in patent: Paragraph 0121; 0122; 0123; 0124
[2]Journal of Organic Chemistry,2017,vol. 82,p. 1024 - 1033

47
[ 3034-53-5 ]
[ 3652-90-2 ]
[ 2059135-36-1 ]

Yield	Reaction Conditions	Operation in experiment
93%	With 1-methyl-1H-imidazole; copper(l) chloride; lithium tert-butoxide In toluene at 130℃; for 11h; chemoselective reaction;
92%	With 1-methyl-1H-imidazole; copper(l) iodide; lithium tert-butoxide In toluene at 130℃; for 8h; Inert atmosphere;	24 Example 24: Preparation of 2-bromo- (2-thiazolyl) carbazole 2-bromocarbazole was added sequentially to a dry three-necked flask equipped with a reflux condenser and a magnetic rotor(492.2 mg, 2.0 mmol, 1.0 eq), cuprous iodide (3.8 mg, 0.02 mmol, 0.01 eq)Lithium tert-butoxide (240.2 mg, 3.0 mmol, 1.5 eq), nitrogen was purged three times,Then 2-bromothiazole (270.4 mg, 3.0 mmol, 1.5 eq) was added,1-methylimidazole (3.3 mg, 0.04 mmol, 0.02 eq) and toluene (8 mL).The reaction mixture was refluxed at 130 ° C for 8 hours and TLC thin layer chromatography was carried out until the reaction of 2-bromocarbazole was completed. Saturated sodium sulfite solution quenched, filtered, ethyl acetate fully washed insoluble,The organic phase in the mother liquor was separated, dried over anhydrous sodium sulfate, filtered,The solvent and the excess 2-bromothiazole were removed by distillation under reduced pressure, and the resulting crude product was purified by silica gel column chromatography,Eluent: petroleum ether / dichloromethane = 10: 1 to give 606.5 mg of a white solid in 92% yield.

Reference： [1]Zhao, Xiangdong; She, Yuanbin; Fang, Kun; Li, Guijie [Journal of Organic Chemistry, 2017, vol. 82, # 2, p. 1024 - 1033]
[2]Current Patent Assignee: ZHEJIANG UNIVERSITY OF TECHNOLOGY - CN106366069, 2017, A Location in patent: Paragraph 0125; 0126; 0127; 0128

48
[ 3652-90-2 ]
[ 924648-24-8 ]
[ 2101438-52-0 ]

Yield	Reaction Conditions	Operation in experiment
95%	With 1,10-Phenanthroline; copper(l) chloride; potassium hydroxide In o-xylene at 100 - 140℃; for 21h; Inert atmosphere;	2-bromo-9-(3,5-dihexylphenyl)-9H-carbazole A 2L flask fitted with overhead stirrer and condenser was charged with l,3-dihexyl-5- iodobenzene (9.0g, 36.57mmol) and 2-bromocarbazole (27.23g, 73.14mmol, 2 equivt). O- xylene (370ml) was added and stirred. Nitrogen was bubbled through the suspension for 1 hr then KOH pellets (5.13g, 91.42mmol, 2.5 equivt) was added and stirred for 10 min. CuCl (1.08g, 10.9mmol, 0.3 equivt) was added followed by 1,10-phenanthroline (3.95g, 21.91 mmol, 0.6 equivt), a brownish cloudy solution obtained. The reaction mixture heated to 100°C for 1 hr then the rest of CuCl( 0.73g, 7.37mmol, , 0.2 equivt) and 1,10-phenanthroline (2.64g, 14.34 mmol, 0.4 equivt) were added. The temperature of the reaction mixture was increased to 140°C and heated for 20 hr. TLC showed no bromocarbazole remained. The reaction was allowed to coolto room temperature which resulted in the formation of a large amount of black precipitate. Water (300ml) was added and stirred for 10 min then transferred to a separatory funnel and allowed to separate. The aqueous layer was extracted with EtOAc and the combined organic layer was washed with water (200ml x2) and brine (200mlx2), dried over MgS04, evaporated to dryness, a brownish liquid which was purified by silica colulmn using heptane as eluent (17.05g, colorless oil, 99.75% HPLC, 95% yield). (0253) 1H-NMR (600MHz, CDC13, TMS): S= 8.10 (d, 1H), 7.98(d, 1H), 7.52 (d, 1H), 7.42(m, 1H), 7.37 (m, 2H), 7.29(m, 1H), 7.13 (m, 3H), 2.69(t, 4H), 1.68(m, 4H), 1.36(m, 12H), 0.90(t, 6H).

Reference： [1]Current Patent Assignee: Sumitomo Chemical (w/o Dongwoo Fine-Chem); SUMITOMO CHEMICAL COMPANY LIMITED - WO2017/103586, 2017, A1 Location in patent: Page/Page column 43-45

49
[ 3652-90-2 ]
[ 22918-01-0 ]
2-bromo-9-(4-chloropyridin-2-yl)-9H-carbazole [ No CAS ]

Reference： [1]Journal of Organic Chemistry,2017,vol. 82,p. 8634 - 8644

50
[ 3652-90-2 ]
[ 175205-81-9 ]
9-(4-trifluoromethylpyridin-2-yl)-9H-carbazol-2-ol [ No CAS ]

Reference： [1]Journal of Organic Chemistry,2017,vol. 82,p. 8634 - 8644

51
[ 3652-90-2 ]
[ 175205-81-9 ]
2-bromo-9-(4-(trifluoromethyl)pyridin-2-yl)-9H-carbazole [ No CAS ]

Reference： [1]Journal of Organic Chemistry,2017,vol. 82,p. 8634 - 8644
[2]Inorganic Chemistry,2019,vol. 58,p. 12348 - 12357

52
[ 3652-90-2 ]
[ 86-58-8 ]
C₂₁H₁₄N₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
67%	With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; at 125℃; for 24h;Inert atmosphere;	Synthesis of Intermediate 1-a (0207) 2-bromo-9H-carbazole (2.35 grams (g), 10 millimoles (mmol)), a phenylboronic acid (1.34 g, 11 mmol), and tetrakis(triphenylphosphine)palladium(0) (Pd(PPh3)4 (0.8 g, 0.7 mmol) potassium carbonate (K2CO3, 3.4 g, 25 mmol) were loaded into a 2-neck flask. The flask was purged with nitrogen and the mixture was reacted at a temperature of 125?C for 24 hours. The resultant was cooled to room temperature, and an extraction process was performed thereon by using ethyl acetate/water (EA/H2O) to obtain an organic layer. (0208) The organic layer was dried by using magnesium sulfate (MgSO4) and condensed. The resultant was subjected to column chromatography (hexane:EA=2:1 at a volumetric ratio), thereby completing the preparation of Intermediate 1-a (Yield=67%).

Reference： [1]Patent: US2017/256727,2017,A1 .Location in patent: Paragraph 0205; 0206; 0207; 0208

53
[ 3652-90-2 ]
[ 612-55-5 ]
2-bromo-9-(2-naphthyl)carbazole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
88.3%	With 1,10-Phenanthroline; 18-crown-6 ether; potassium carbonate; copper(l) chloride In 1-methyl-pyrrolidin-2-one at 180℃; Inert atmosphere;	2.1 Step 1: Synthesis of Intermediate F 2-Bromo-carbazole (8.24 g, 33.46 mmol), 2-iodo-naphthalene (11.05 g, 43.5 mmol), CuCl (0.33 g, 3.35 mmol), 18-crown-6 (0.88 g, 3.35 mmol), 1,10-o-phenanthroline (0.60 g, 3.35 mmol), K2CO3 (11.56 g, 83.65 mmol) were added to N-methyl pyrrolidone (190 mL) in a three-neck round bottom flask, protected by nitrogen, heated to 180° C., and reacted overnight. Heating was stopped and the reaction was cooled to room temperature. The reaction solution was filtered through celite. The filtrate was poured into a large amount of water, extracted with DCM several times, dried over anhydrous Na2SO4, filtered and rotary evaporated to dryness. Purified via silica gel column chromatography (PE/DCM=50:1) to give intermediate F (11.0 g, 29.55 mmol) as a white solid with a yield of 88.3%
	With copper; potassium carbonate In 5,5-dimethyl-1,3-cyclohexadiene Reflux;

Reference： [1]Current Patent Assignee: BEIJING SUMMER SPROUT TECHNOLOGY CO LTD - US2020/277283, 2020, A1 Location in patent: Paragraph 0108; 0109
[2]Current Patent Assignee: LG CHEM CO.,LTD. - KR2017/96767, 2017, A Location in patent: Paragraph 0155; 0156

54
[ 1832665-30-1 ]
[ 3652-90-2 ]

Yield	Reaction Conditions	Operation in experiment
63%	With sodium azide; copper(I) thiophene-2-carboxylate; sodium hydrogencarbonate; triphenylphosphine In N,N-dimethyl acetamide at 100℃; for 12h; Inert atmosphere; Schlenk technique;
63%	With sodium azide; copper(I) thiophene-2-carboxylate; sodium hydrogencarbonate; triphenylphosphine In N,N-dimethyl acetamide at 100℃; for 12h; Inert atmosphere; Schlenk technique;	7 Synthesis of Compound 2g: Under nitrogen protection, the iodinated salt 1g (50.7mg, 0.1mmol), NaN3 (7.8mg, 0.12mmol), PPh3 (39.3mg, 0.15mmol), NaHCO3 (42.5mg, 0.2mmol), CuTc (1.9mg, 0.01 (mmol) and dry DMA (1 mL) were added to a dry Schlenk reaction tube. The reaction was stirred at 100° C. for 12 h, then cooled to room temperature, diluted with water (10 mL), added with ethyl acetate (10 mL*3), dried over anhydrous sodium sulfate, filtered, and concentrated to give a white solid. 2 g (15.5 mg, 63%).

Reference： [1]Wang, Ming; Fan, Qiaoling; Jiang, Xuefeng [Organic Letters, 2018, vol. 20, # 1, p. 216 - 219]
[2]Current Patent Assignee: EAST CHINA NORMAL UNIVERSITY - CN107935913, 2018, A Location in patent: Paragraph 0062-0065

55
[ 3652-90-2 ]
[ 1228267-13-7 ]
[ 2134586-90-4 ]

Yield	Reaction Conditions	Operation in experiment
85%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; sodium hydroxide In tetrahydrofuran; water at 80℃;	1.5 Sub 1-1 synthesis General procedure: In the synthesis, The obtained Sub 1-IV-1 (4.83 g, 12.25 mmol)Was dissolved in THF (40 ml) in a round bottom flask,2-bromo-9H-carbazole (3.01 g, 12.25 mmol),Pd (PPh3) 4 (0.57 g, 0.49 mmol),NaOH (1.47 g, 36.75 mmol),Water (20 ml)And the mixture was stirred at 80 ° C.After the reaction was completed, the reaction mixture was extracted with CH2Cl2 and water. The organic layer was dried over MgSO4 and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 4.51 g (yield: 85%) of the product.

Reference： [1]Current Patent Assignee: DUK SAN NEOLUX CO., LTD. - KR2017/103105, 2017, A Location in patent: Paragraph 0171; 0173; 0174; 0183; 0184

56
[ 3652-90-2 ]
[ 100124-06-9 ]
[ 1922121-95-6 ]

Yield	Reaction Conditions	Operation in experiment
74%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate In tetrahydrofuran; water for 3h; Reflux; Inert atmosphere;	8 Preparation Example 8: Preparation of compound int A 2-bromo-9H-carbazole (50 g, 222.2 mmol) and dibenzo[b,d]furan-4-ylboronic acid (47.1 g, 222.2 mmol) were added to tetrahydrofuran (1000 ml) in a nitrogen atmosphere. It was stirred and refluxed.Thereafter, potassium carbonate (92.1 g, 666.7 mmol) was dissolved in water (92ml), stirred sufficiently, and tetrakistriphenyl-phosphinopalladium (7.7 g, 6.7 mmol) was added. After the reaction for 3 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again added to chloroform (1481 ml) to dissolve it, and after washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound is recrystallized from chloroform and ethyl acetate to form a white solid compound IntA (54.8 g, yield 74%,
72%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate In tetrahydrofuran; water for 12h; Reflux; Inert atmosphere;	Synthesis Example A: Synthesis of Intermediate A In a nitrogen atmosphere, 2-bromo-9H-carbazole (15.0 g, 60.9 mmol) and dibenzo [b,d]furan-4-ylboronic acid (14.2 g, 67 mmol) were added to 300 ml of THF, followed by stirring and reflux. After that, potassium carbonate (33.7g, 243.8mmol) was dissolved in 100ml of water and thoroughly stirred, and then tetrakis(triphenylphosphine)palladium(0) (2.1g, 1.8mmol) was added. After the reaction for 12 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.6 g of Intermediate A. (yield 72%,)
3 g	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate In tetrahydrofuran; water at 80℃;	18 In a 250 ml three-neck round bottom flask, 2-bromocarbazole (3 g), Dibenzofuran A mixture of 4-boronic acid (3.1 g),Tetrahydrofuran (60 ml), potassium carbonate (8.4 g) and water (60 ml) were added and stirred. Tetrakis (triphenylphosphine) palladium (0) (0.4 g) was added to the mixture, and the mixture was heated to 80 ° C. The reaction solution was layered to remove water, and the organic layer was concentrated under reduced pressure to remove the solvent. Column separation was performed on the material produced by concentration to obtain 3 g of the title compound

3 g	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate In tetrahydrofuran; water at 80℃;	18 3 g of 2-bromocarbazole, 3.1 g of dibenzofuran-4-boronic acid, 60 mL of tetrahydrofuran, 8.4 g of potassium carbonate and 60 mL of water were added to a 250 mL three-neck round bottom flask and stirred. 0.4 g of tetrakis (triphenylphosphine) palladium (0) was added to the mixture, and the mixture was heated to 80 ° C. The reaction solution was layered to remove water, and the organic layer was concentrated under reduced pressure to remove the solvent. The material produced by concentration was subjected to column separation to obtain 3 g of the title compound.
3 g	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate In tetrahydrofuran; water at 80℃;	22 Synthesis of Intermediate 22-1 2-bromocarbazole (3 g), dibenzofuran-4-boronic acid (3.1 g), tetrahydrofuran (60 mL), potassium carbonate (8.4 g) and water (60 mL) in a 250 mL three-necked round bottom flask was added and stirred. Tetrakis(triphenylphosphine)palladium (0) (0.4 g) was added to this mixed solution, and it heated at 80 °C. The reaction solution was separated and the water was removed, and the organic layer was concentrated under reduced pressure to remove the solvent.The material produced by concentration was obtained by column separation 3 g of the title compound.

Reference： [1]Current Patent Assignee: LG CHEM CO.,LTD. - KR2020/86233, 2020, A Location in patent: Paragraph 0311-0313
[2]Current Patent Assignee: LG CHEM CO.,LTD. - KR2021/89523, 2021, A Location in patent: Paragraph 0172-0174
[3]Current Patent Assignee: DAEJOO ELECTRONIC MATERIALS CO LTD - KR2017/126059, 2017, A Location in patent: Paragraph 0195-0198
[4]Current Patent Assignee: DAEJOO ELECTRONIC MATERIALS CO LTD - KR2018/131662, 2018, A Location in patent: Paragraph 0221-0224
[5]Current Patent Assignee: DAEJOO ELECTRONIC MATERIALS CO LTD - KR2019/106313, 2019, A Location in patent: Paragraph 0434-0438

57
[ 3652-90-2 ]
[ 732276-63-0 ]
2-bromo-N-(2-decyltetradecyl)carbazole [ No CAS ]

Reference： [1]New Journal of Chemistry,2018,vol. 42,p. 2750 - 2757

58
[ 3652-90-2 ]
[ 1001911-63-2 ]
C₅₀H₃₀N₂O [ No CAS ]

Reference： [1]Patent: KR2018/24306,2018,A

59
[ 3652-90-2 ]
[ 1001911-63-2 ]
9-phenyl-9H,9'H-2,2'-bicarbazole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
56%	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In toluene;Reflux;	General procedure: To a round bottom flask was added 7.4 g (21.3 mmol) of Intermediate 1-c,7.0 g (27.7 mmol) of bispinacolorodiboron,0.8 g (0.1 mmol) of diphenylphosphinoferrocene palladium dichloride,6 g (63.9 mmol) of potassium acetate,70 ml of toluene was added and the mixture was refluxed. After completion of the reaction, the reaction solution was filtered and then separated by column chromatography to obtain 5.8 g of [intermediate 1-d]. (Yield: 70%). Except that 2-bromocarbazole was used instead of 2-chloro-4,6-diphenyl-1,3,5-triazine used in Synthesis Example 1-5, [Intermediate 10-a] was obtained by following the same procedure except that 9-phenylcarbazole-2-boronic acid was used in place of [Intermediate 1-d]. (Yield: 56%)
49%	With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; for 4h;Reflux; Inert atmosphere;	In a nitrogen atmosphere, 2-bromo-9H-carbazole (30.0 g, 122.5 mmol) and (9-phenyl-9H-carbazol-2-yl) boronic acid (35.2 g, 122.5 mmol) were added to 300 ml of tetrahydrofuran and stirred and It was refluxed. Thereafter, potassium carbonate (33.9 g, 244.9 mmol) was dissolved in 100 ml of water, stirred sufficiently, and then tetrakistriphenyl-phosphinopalladium (4.2 g, 3 mol%) was added thereto. After 4 hours the reaction was lowered to room temperature and filtered. The filtrate was dissolved in chloroform and extracted with water, and then the organic layer was dried over magnesium sulfate. Thereafter, the organic layer was dried, and then compound sub 5 (24.5 g, 49%) was prepared through ethyl acetate recrystallization.
49%	With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; for 4h;Inert atmosphere; Reflux;	In a nitrogen atmosphere, 2-bromo-9H-carbazole (30.0 g, 122.5 mmol) and (9-phenyl-9H-carbazol-2-yl) boronic acid (35.2 g, 122.5 mmol) were added to 300 ml of tetrahydrofuran and stirred and It was refluxed. Thereafter, potassium carbonate (33.9 g, 244.9 mmol) was dissolved in 100 ml of water, stirred sufficiently, and then tetrakistriphenyl-phosphinopalladium (4.2 g, 3 mol%) was added thereto. After the reaction for 4 hours, the temperature was lowered to room temperature and filtered. The filtrate was dissolved in chloroform and extracted with water, and then the organic layer was dried over magnesium sulfate. Thereafter, the organic layer was dried, and then compound sub 5 (24.5 g, yield: 49%) was prepared through ethyl acetate recrystallization.

Reference： [1]Patent: KR2018/24306,2018,A .Location in patent: Paragraph 0483; 0594-0598
[2]Patent: KR2020/10117,2020,A .Location in patent: Paragraph 0149; 0170-0173
[3]Patent: KR2020/10137,2020,A .Location in patent: Paragraph 0220-0223

60
[ 3652-90-2 ]
[ 124-38-9 ]
[ 57955-18-7 ]

Yield	Reaction Conditions	Operation in experiment
54%	Stage #1: 2-bromo-9H-carbazole With copper(l) iodide; sodium iodide; N,N`-dimethylethylenediamine In 1,4-dioxane at 120℃; for 24h; Inert atmosphere; Sealed tube; Stage #2: carbon dioxide With 1,4-diaza-bicyclo[2.2.2]octane; copper(I) oxide; phenylsilane; ammonia In 1,4-dioxane; 1-methyl-pyrrolidin-2-one at 130℃; for 24h; Sealed tube;	General procedure for the cyanation of aryl iodide with CO₂ and NH₃ General procedure: Under nitrogen atmosphere, Cu2O (10 mol %), DABCO (25 mol %), and a stirring bar were added into a 10 mL oven-dried sealed glass tube (as shown in Figure S1). Then NMP (0.5 mL), aryl iodides (0.125 mmol, 1.0 equiv.) and PhSiH3 (0.75 mmol, 6 equiv.) were injected by syringe. The tube wasthen sealed and CO2 (0.67 mmol, 5.4 equiv., 15 mL) as well as NH3 (0.67 mmol, 5.4 equiv., 15 mL) were injected by syringe after N2 was removed under vacuum. Finally, the mixture was stirred for 24 hr in a pre-heated-to-130 °C alloyed block. After the reaction was finished, the tube was cooled to room temperature and the pressure was carefully released. The yield of were measured by GC analysis using dodecane as the internal standard or by flash chromatography on silica gel (petroleumether/ethyl acetate).
79 %Chromat.	Stage #1: 2-bromo-9H-carbazole With copper(l) iodide; sodium iodide; N,N`-dimethylethylenediamine In 1,4-dioxane at 100℃; for 10h; Inert atmosphere; Stage #2: carbon dioxide With diethoxymethylane; ammonia; copper(II) acetylacetonate; cobalt(II) chloride In 1,4-dioxane; 1-methyl-pyrrolidin-2-one at 160℃; for 10h; Sealed tube;	38 Example 38: Preparation of 2-cyanocarbazole from 2-bromocarbazole (38) Under a nitrogen atmosphere, cuprous iodide (3.0 mol%, 0.7 mg), sodium iodide (1.0 equiv., 18.7 mg) and magnets were added to a previously baked 10 mL glass pressure tube. Dioxane (0.2 mL), 2-bromoindazole (0.125 mmol, 1.0 equiv., 26.3 mg) and N,N'-dimethylethylenediamine (10.0 mol%, 1.1 mg) were then added. After the addition, the glass pressure tube was placed in a metal module that had been preheated to 100° C. and stirred for 10 hours. After cooling to room temperature, copper acetylacetonate (20 mol%, 6.6 mg), cobalt chloride (3 mol%, 0.5 mg), N-methylpyrrolidone (0.5 mL) and diethoxymethylsilane (3.0) were added under a nitrogen atmosphere. Equiv., 50.4mg). The air inside the tube was removed and charged with carbon dioxide (5.0 equiv., 15 mL) and ammonia gas (5.0 equiv., 15 mL). After the addition was completed, the reactor was placed in a metal module preheated to 160C and stirred for 10 hours. After the reaction was completed, the reaction system was cooled to room temperature and pressure was slowly released. Using dodecane as an internal standard, passing gas The working curve of the phase chromatography determined that the yield was 79%

Reference： [1]Wang, Hua; Dong, Yanan; Zheng, Chaonan; Sandoval, Christian A.; Wang, Xue; Makha, Mohamed; Li, Yuehui [Chem, 2018, vol. 4, # 12, p. 2883 - 2893]
[2]Current Patent Assignee: CHINESE ACADEMY OF SCIENCES - CN108017557, 2018, A Location in patent: Paragraph 0146-0148

61
[ 108-86-1 ]
[ 3652-90-2 ]
[ 94994-62-4 ]

Yield	Reaction Conditions	Operation in experiment
	With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; for 10h;Inert atmosphere; Reflux;	250mL three-neck bottle,Under an atmosphere of nitrogen gas,Add 0.02 mol of 2-bromocarbazole,0.03 mol of bromobenzene,0.04 mol of sodium t-butoxide,10-4mol Pd2(dba)3,10-4 mol P(t-Bu)3 and 200 mL toluene,Heating and refluxing for 10 hours, sampling the plate, the raw material reaction is complete;Naturally cool to room temperature (20 ~ 25 C), filter, collect the filtrate and steam under reduced pressure (-0.09MPa, 85 C),Performing column chromatography to obtain the target product starting material A1;
	With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; for 10h;Inert atmosphere; Reflux;	A 250 mL three-necked flask was charged with 0.02 mol of 2-bromocarbazole, 0.03 mol of bromobenzene, 0.04 mol of sodium t-butoxide, and 10-4 mol of Pd2(dba)3 under a nitrogen atmosphere.10-4mol P(t-Bu)3 and 200mL toluene, heated under reflux for 10 hours, takeSample board, the raw material reaction is complete;Naturally cooled to room temperature (20 ~ 25 C), filtered, collected filtrate and vacuum distillation (-0.09MPa, 85 C), column chromatography, to obtain the target product A1;

Reference： [1]Patent: CN108203428,2018,A .Location in patent: Paragraph 0049; 0051
[2]Patent: CN108203427,2018,A .Location in patent: Paragraph 0046; 0047

62
[ 3652-90-2 ]
[ 92-66-0 ]
[ 1393835-87-4 ]

Yield	Reaction Conditions	Operation in experiment
	With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; for 10h;Inert atmosphere; Reflux;	250mL three-neck bottle,Under an atmosphere of nitrogen gas,Add 0.02 mol of 2-bromocarbazole,0.03 mol of 4-bromobiphenyl,0.04 mol of sodium t-butoxide,10-4mol Pd2(dba)3,10-4 mol P(t-Bu)3 and 200 mL toluene,Heating and refluxing for 10 hours, sampling the plate, the raw material reaction is complete; naturally cooling to room temperature (20 ~ 25 C), filtering, collecting the filtrate for steam distillation under reduced pressure (-0.09MPa, 85 C), column chromatography, to obtain the raw material A2
	With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; for 10h;Inert atmosphere; Reflux;	A 250 mL three-necked flask was charged with 0.02 mol of 2-bromocarbazole, 0.03 mol of 4-bromobiphenyl, and 0.04 mol of sodium t-butoxide under a nitrogen atmosphere.10-4mol Pd2(dba)3, 10-4mol P(t-Bu)3 and 200mL toluene, heated under reflux for 10 hours, sampling the plate, the raw material reaction is complete;Naturally cooled to room temperature (20 ~ 25 C), filtered, collected filtrate and vacuum distillation (-0.09MPa, 85 C), column chromatography, to obtain the starting material A3;

Reference： [1]Patent: CN108203428,2018,A .Location in patent: Paragraph 0135; 0136
[2]Patent: CN108203427,2018,A .Location in patent: Paragraph 0129; 0131

63
[ 3652-90-2 ]
[ 222-21-9 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1: (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate / N,N-dimethyl-formamide / 3 h / 130 °C 2: tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate / tetrahydrofuran; water / 24 h / Reflux 3: trifluorormethanesulfonic acid / 48 h / 20 °C

Reference： [1]Current Patent Assignee: SAMSUNG ELECTRONICS CO.,LTD.; Samsung Display (in: Samsung); DUK SAN NEOLUX CO., LTD. - US10020452, 2018, B2

64
[ 3652-90-2 ]
[ 73183-34-3 ]
[ 1242412-60-7 ]

Yield	Reaction Conditions	Operation in experiment
92%	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate In N,N-dimethyl-formamide at 85℃; for 4h; Sealed tube; Inert atmosphere;	2.1 Step 1 : 2-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)-9H-carbazole To a mixture containing 2-bromo-9H-carbazole (1 g, 4.06 mmol), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(l,3,2-dioxaborolane) (1.548 g, 6.10 mmol), potassium acetate (1.196 g, 12.19 mmol) and Pd(dppf)Cl2 (0.149 g, 0.203 mmol) in a screw cap vial was added DMF (15 mL). The vial was fitted with a Teflon lined septum cap. The system was evacuated under vacuum (via a needle from a nitrogen/vacuum manifold line) and backfilled with nitrogen gas. The procedure was repeated three times. The needle was removed and the vial was heated at 85 °C for 4 h. The reaction mixture was cooled to room temperature, diluted with EtOAc (100 mL) and washed with 10% LiCl aq. solution (25 mL X 2) and sat. aq. NaCl solution (25 mL), dried (NaiSCL), filtered and concentrated to obtain a crude residue. The crude residue was re-dissolved in DCM (20 mL), adsorbed on to silica gel (15 g) and purified on the ISCO silica gel chromatography system using a 40 g ISCO silica gel column with Hex/EtOAc (0%-50%) over a 15 min gradient to obtain 2-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)-9H- carbazole (2A) (1.1 g, 3.75 mmol, 92% yield), m/z (294, M+H).
38%	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate In N,N-dimethyl-formamide at 130℃; for 3h;	3 Synthesis Method of Intermediate J 2-Bromocarbazole, bis(pinacolato)diboron, palladium chloride (PdCl2) (dppf), and KOAc were dissolved in dimethylformamide, followed by stirring at 130° C. for 3 hours. After the completion of the reaction, the reaction product was cooled to room temperature, and then added with ether and distilled water, followed by stirring at room temperature. An organic was separated from a water layer, and the separation was repeatedly carried out twice by the same method. The resultant product produced through the concentration of the organic layer was recrystallized by acetonitrile so as to give a required intermediate J (yield: 38%).

Reference： [1]Current Patent Assignee: BRISTOL-MYERS SQUIBB CO - WO2021/67657, 2021, A1 Location in patent: Page/Page column 35
[2]Current Patent Assignee: SAMSUNG ELECTRONICS CO.,LTD.; Samsung Display (in: Samsung); DUK SAN NEOLUX CO., LTD. - US10020452, 2018, B2 Location in patent: Page/Page column 47; 48

65
[ 3652-90-2 ]
[ 127654-70-0 ]
C₁₈H₁₀BrClIN [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
78%	With potassium tert-butylate; In N,N-dimethyl-formamide; for 3h;Reflux;	70.00 g (1.0 eq) of 2-bromo-9H-carbazole and 52.14 g (1.5 eq) of KOtBu were placed in 1.0 L of DMF (dimethylformamide) and heated and stirred. At the start of the reflux, 80.23 g (1.1 eq) of <strong>[127654-70-0]1-chloro-3-fluoro-2-iodobenzene</strong> was added. After the reaction was completed after 3 hours, the reaction was poured into water and the crystals were dropped and filtered.The filtered solid was completely dissolved in CHCl3, washed with water, and again decompressed to remove the solvent, which was purified by column chromatography. 107.3 g (yield 78%) of the compound of the formula 1-a was obtained.

Reference： [1]Patent: KR101891031,2018,B1 .Location in patent: Paragraph 0108-0111

66
[ 3652-90-2 ]
[ 7236-62-6 ]
[ 2092555-62-7 ]

Yield	Reaction Conditions	Operation in experiment
68%	With sodium hydride In dimethyl sulfoxide at 25℃; for 72h; Inert atmosphere;
68%	With sodium hydride In dimethyl sulfoxide at 20℃; for 72h; Inert atmosphere;	2 Preparation of compound 2-2 Sodium hydride (0.1 g, 0.04 mol) was added to a 100 mL 2-neck flask under a nitrogen atmosphere and stirred for 1 hour. Compound 2-1 (1.5 g, 0.0088 mol) was added thereto, dissolved in DMSO (50 mL), and slowly added dropwise. After adding compound 2-1, 2-bromocarbazole (2.2 g, 0.0088 mol) was dissolved in DMSO (50 ml) and added. The reaction was allowed to proceed at room temperature for 72 hours. After the reaction was completed, the precipitate was filtered, and the filtrate was received to remove the solvent under reduced pressure. The crude mixture was purified by column chromatography (ethyl acetate:hexane = 1: 20) to give compound 2-2. Yield and NMR data of Compound 2-2 are as follows.Yield: 2 g (68%)

Reference： [1]Lee, Sungkoo; Seo, Min Hye [Chemistry - A European Journal, 2018, vol. 24, # 66, p. 17419 - 17423]
[2]Current Patent Assignee: KOREA INSTITUTE OF INDUSTRIAL TECHNOLOGY - KR2020/69184, 2020, A Location in patent: Paragraph 0149-0150; 0156-0159

67
[ 244-76-8 ]
[ 3652-90-2 ]
2-{9H-pyrido[2,3-b]indol-9-yl}-9H-carbazole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
30%	With potassium dihydrogenphosphate; copper(l) iodide; (1R,2R)-1,2-diaminocyclohexane In toluene at 120℃; for 28h; Sealed tube; Inert atmosphere;	3.1 Step 1: Synthesis of 9-(9H-carbazol-2-yl)-9H-pyridine [2,3-b]indole 9-(9H-carbazol-2-yl)-9H-pyridine [2,3 -b] indol-4 synthesized by the following reaction formula 4: 2-bromocarbazole (123 mg, 0.5 mmol),Porphyrin (252 mg, 1.5 mmol), CuI (19 mg, 0.1 mmol), trans-1,2-cyclohexanediamine (11 mg, 0.1 mmol), potassium phosphate (212 mg, 1.0 mmol),Toluene (3 mL) was placed in a 38 mL sealed tube.After bubbling nitrogen for 5 minutes, the temperature was raised to 120 ° C.The reaction was refluxed for 28 h. After completion of the reaction, the pad was filtered over Celite, and the filter cake was rinsed with ethyl acetate. The obtained filtrate was subjected to distillation under reduced pressure to remove the solvent, and the obtained product was purified on silica gel column ( petroleum ether: ethyl acetate=10:1→5:1) to give white solid 9-(9H-carbazole-2- Base)-9H-pyridine [2,3-b]indole (50 mg, yield 30%).

Reference： [1]Current Patent Assignee: AAC ACOUSTIC TECHNOLOGIES HOLDINGS INC. - CN109369644, 2019, A Location in patent: Paragraph 0117-0121

68
[ 3652-90-2 ]
[ 20442-79-9 ]
9-([1,1'-biphenyl]-3-yl)-2'-bromo-2,9'-bicarbazole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
84.2%	With dipotassium hydrogenphosphate; copper(I) thiophene-2-carboxylate; potassium iodide; In 1-methyl-pyrrolidin-2-one; at 110℃; for 36h;Inert atmosphere;Catalytic behavior;	In 1L with mechanical stirring, thermometer, To the three-necked flask of the heating reaction apparatus, 54.1 g (0.22 mol) of 2-bromocarbazole, 28.0 g (0.1 mol) of <strong>[20442-79-9]3-iodobiphenyl</strong>, 33.1 g (0.02 mol) of potassium iodide, and 153.3 g (0.88 mol) of dipotassium hydrogen phosphate were added. , Further, 300 mL of N-methylpyrrolidone was added to dissolve the solvent. After argon protection, 5.7 g (0.03 mol) of cuprous 2-thiophenecarboxylate was added to control the reaction temperature to 110 C. After continuous mechanical stirring for 36 h, the reaction was terminated by high performance liquid chromatography, and the reaction was terminated by adding water. The reaction mixture was extracted with 300 mL of dichloromethane, and the organic layer was washed with aq. The solvent was recovered under reduced pressure to give a crude product, which was recrystallized from toluene (300 mL) and methanol (300 mL) to give 47.5 g of white powder, yield: 84.2%, content: 99.2%.

Reference： [1]Patent: CN109232381,2019,A .Location in patent: Paragraph 0011; 0022-0024; 0026; 0028

69
[ 3652-90-2 ]
[ 89488-29-9 ]
2-bromo-9-(4-methoxypyridin-2-yl)-9H-carbazole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
95%	With 1-methyl-1H-imidazole; copper(l) iodide; lithium tert-butoxide; for 15h;	According to a dry three-necked bottle with a reflux condenser and a magnetic rotor2-bromocarbazole (12600 mg, 51.20 mmol, 1.00 equivalent) was added in a second time.<strong>[89488-29-9]2-bromo-4-methoxypyridine</strong> (10400 mg, 55.31 mmol, 1.10 equivalents),Cuprous iodide (98 mg, 0.50 mmol, 0.01 eq.), lithium t-butoxide (6147 mg, 76.80 mmol, 1.50 eq.).Pumping nitrogen three times,Then 1-methylimidazole (83 mg, 1.00 mmol, 0.02 eq.) was added.Toluene (200 mL).The reaction mixture was stirred at reflux at 120 C for 15 hours.TLC thin layer chromatography was carried out until the reaction of the starting material 2-bromocarbazole was completed.filter,Ethyl acetate is sufficient to wash insoluble matter,Wash the filtrate with water,The organic phase in the mother liquor is separated,Dry over anhydrous sodium sulfate,filter,The solvent was distilled off under reduced pressure.The obtained crude product was separated and purified by silica gel column chromatography.Eluent (petroleum ether / ethyl acetate = 15:1-10:1),The intermediate Br-Cab-Py-OMe was obtained as a white solid, 17.46 g, yield 95%.
95%	With 1-methyl-1H-imidazole; copper(l) iodide; lithium tert-butoxide; In toluene; at 120℃; for 15h;Inert atmosphere;	Add to the dry three-necked bottle with reflux condenser and magnetic rotor2-bromocarbazole (12600 mg, 51.20 mmol, 1.00 equivalent),<strong>[89488-29-9]2-bromo-4-methoxypyridine</strong> (10400 mg, 55.31 mmol, 1.10 equivalents),Cuprous iodide (98 mg, 0.50 mmol, 0.01 eq.),Lithium tert-butoxide (6147 mg, 76.80 mmol, 1.50 equivalents),Pump nitrogen three times, then add 1-methylimidazole(83mg, 1.00mmol, 0.02 equivalents),Toluene (200 mL). The reaction mixture was stirred at reflux at 120 C for 15 hours.TLC thin layer chromatography was carried out until the reaction of the starting material 2-bromocarbazole was completed. filter,The ethyl acetate was thoroughly washed with insoluble matter, and the filtrate was washed with water.The organic phase in the mother liquor is separated, dried over anhydrous sodium sulfate, and filtered.The solvent was distilled off under reduced pressure. The obtained crude product was separated and purified by silica gel column chromatography.Eluent (petroleum ether / ethyl acetate = 15:1-10:1),The intermediate Br-Cab-Py-OMe was obtained as a white solid, 17.46 g.The yield was 95%.

Reference： [1]Inorganic Chemistry,2019,vol. 58,p. 14349 - 14360
[2]Patent: CN109608506,2019,A .Location in patent: Paragraph 0292-0296
[3]Patent: CN108299507,2018,A .Location in patent: Paragraph 0170; 0171; 0172; 0173
[4]Inorganic Chemistry,2019,vol. 58,p. 12348 - 12357

70
[ 3652-90-2 ]
[ CAS Unavailable ]
[ 2361518-39-8 ]

Yield	Reaction Conditions	Operation in experiment
89.3%	Stage #1: 2-bromo-9H-carbazole With potassium <i>tert</i>-butylate In N,N-dimethyl-formamide at 20℃; for 1h; Stage #2: 1-bromo-3-hexyldecyl In N,N-dimethyl-formamide at 130℃; for 65h;	2.1.1. 2-Bromo-9-(3-hexyldecyl)-9H-carbazole (2) 2-Bromo-9H-carbazole (9.0 g, 35.5 mmol) and potassium tert-butoxide(6.5 g, 44.3 mmol) are dissolved in 100 ml DMF at room temperaturefor 1 h, and then 1-bromo-3-hexyldecyl (16.7 g, 54.5 mmol) isadded. The mixture is heated to 130 °C for 65 h. Then it was poured intowater and extracted with petroleum ether. The organic phase wascombined and dried over anhydrous Na2SO4.Then the solvent wasevaporated under vacuum and the residue was subjected to columnchromatography on silica gel with petroleum ether. After removal ofthe solvent, the product (2) is obtained (yield: 89.3%).1H NMR (600 MHz, CDCl3) δ 8.05 (d, J=7.7 Hz, 1H), 7.92 (d,J=8.2 Hz, 1H), 7.51 (d, J=1.3 Hz, 1H), 7.48-7.44 (m, 1H), 7.37 (d,J=8.2 Hz, 1H), 7.31 (dd, J=8.2, 1.5 Hz, 1H), 7.23 (t, J=7.5 Hz, 1H),4.10 (d, J=7.5 Hz, 2H), 2.15-2.03 (m, 1H), 1.39-1.18 (m, 27H), 0.86(dt, J=11.7, 7.1 Hz, 6H)

Reference： [1]Li, Feng; Song, Xin; Zhang, Kaili; Shahid, Bilal; Wang, Quanliang; Yu, Liangmin; Zhu, Dangqiang; Sun, Mingliang [Dyes and Pigments, 2019, vol. 170]

71
[ 3652-90-2 ]
[ 122-39-4 ]
[ 929099-71-8 ]

Yield	Reaction Conditions	Operation in experiment
99%	With tris(dibenzylideneacetone)dipalladium⁽⁰⁾ chloroform complex; lithium hexamethyldisilazane; tri tert-butylphosphoniumtetrafluoroborate In tetrahydrofuran at 65℃; for 12h; Inert atmosphere;	18 Example-18 In an argon atmosphere, 2-bromocarbazole (492 mg, 2.00 mmol), diphenylamine (379 mg, 2.24 mmol),Tris (dibenzylideneacetone) dipalladium / chloroform adduct (11 mg, 11 μmol)Tetrahydrofuran (6 mL) was added to a mixture of tri-tert-butylphosphonium tetrafluoroborate (15 mg, 51 μmol).Lithium bis (trimethylsilyl) amide (1M tetrahydrofuran solution,4.4 mL, 4.4 mmol)Stir at 65 ° C. for 12 hours.After cooling to room temperature, the reaction solution is filtered using silica gel,Washed with chloroform.The filtrate was concentrated under reduced pressure, and the resulting crude product was purified by silica gel column chromatography (hexane / ethyl acetate = 9/1),The target 2- (diphenylamino) carbazole was obtained as a pale yellow solid (664 mg, 1.99 mmol, 99% yield).

Reference： [1]Current Patent Assignee: TOSOH CORPORATION; SAGAMI CHEMICAL RESEARCH INSTITUTE - JP2019/137613, 2019, A Location in patent: Paragraph 0094-0096

72
[ 3652-90-2 ]
[ 2412557-24-3 ]

Yield	Reaction Conditions	Operation in experiment
61%	With potassium permanganate In propan-2-one at 20℃; for 6h;	1 At room temperature, 2-bromocarbazole (2.5 g, 10 mmol) was dissolved in 100 mL of acetone, and potassium permanganate powder (4.0 g, 25 mmol) was added under stirring. The reaction was carried out for 6h under the state. After the reaction was completed, the solvent was evaporated, and the residue was washed with chloroform. The remaining residue was neutralized with sodium thiosulfate solution and extracted with chloroform. The organic phases were combined, and the solvent was evaporated after drying. The crude product was recrystallized from chloroform and n-hexane to obtain 1.5 g of a white solid with a yield of 61%.
38%	With 4-dimethylaminopyridine; copper(I) bromide dimethylsulfide complex; oxygen In 1,2-dichloro-ethane at 60℃; for 17h;	Will S3 (0.8mmol),Cuprous bromide dimethyl sulfide CuBr·DMS (0.16mmol)And 4-dimethylaminopyridine DMAP (0.32 mmol) was placed in a 100 ml vial containing a stir bar.The gas atmosphere in the reaction flask was replaced by O2 balloon purge with O2 for 10 minutes.10 mL of 1,2-dichloroethane (DCE) was added via syringe.The reaction was placed in an oil bath at 60 ° C for 17 h.After 17 h, the reaction was cooled to room rt and diluted with 45 mL dichloromethane (DCM).Wash with 45 mL of saturated NH 4Cl solution.The organics were washed with 15 mL of water and dried over anhydrous sodium sulfate.Filtration and concentration in vacuo gave a crude material.The crude product was then purified by silica gel chromatography (hexane: methylene chloride = 5:1).A white solid S4 (0.15 mmol, 38%) was obtained.

Reference： [1]Current Patent Assignee: VELISP NEW MAT SUZHOU - CN114573499, 2022, A Location in patent: Paragraph 0093-0095
[2]Current Patent Assignee: TIANMA MICROELECTRONICS CO., LTD. - CN110156663, 2019, A Location in patent: Paragraph 0115-0118

73
[ 3652-90-2 ]
[ 18162-48-6 ]
[ 2389057-52-5 ]

Yield	Reaction Conditions	Operation in experiment
75%	Stage #1: 2-bromo-9H-carbazole With sodium hydroxide In tetrahydrofuran at 20℃; for 0.5h; Cooling with ice; Stage #2: tert-butyldimethylsilyl chloride In tetrahydrofuran at 20℃; for 2h; Cooling with ice;	2.2.1 (1) Synthesis of Intermediate 1 In 60% sodium hydroxide (4.8 g, 120 mmol THF suspension (150 mL), under ice cooling, drop a THF solution (200 mL) of 2-bromocarbazole (24.6 g, 100 mmol), and then stir at room temperature for 30 minute.Under ice cooling, a THF solution (40 mL) of TBSCl (18.1 g, 120 mmol) was dropped, and the mixture was stirred at room temperature for 2 hours. After adding water (66 mL) and extracting 3 times with ethyl acetate (50 mL), the resulting organic layer was dried with magnesium sulfate to remove magnesium sulfate by filtration, and the solvent was distilled off from the resulting filtrate to obtain a light brown solid. Hexane (150 mL) was added to the obtained light brown solid and filtered. Methanol (333 mL) was added to the filtrate, and it was refluxed for 30 minutes, then cooled to room temperature, filtered, and the filtrate was recovered to obtain Intermediate 1 as a white solid (yield 27.1 g, yield 75%).
70%	Stage #1: 2-bromo-9H-carbazole With sodium hydride In N,N-dimethyl-formamide; mineral oil at 23℃; for 0.25h; Inert atmosphere; Stage #2: tert-butyldimethylsilyl chloride In N,N-dimethyl-formamide; mineral oil at 23℃; for 3h; Inert atmosphere;

Reference： [1]Current Patent Assignee: NISSAN CHEMICAL CORPORATION - TW2021/10799, 2021, A Location in patent: Paragraph 0132-0133
[2]Mills, L. Reginald; Graham, Joshua M.; Patel, Purvish; Rousseaux, Sophie A. L. [Journal of the American Chemical Society, 2019, vol. 141, # 49, p. 19257 - 19262]

74
[ 3652-90-2 ]
[ 1001911-63-2 ]
C₄₂H₂₆N₂O₂ [ No CAS ]

Reference： [1]Patent: KR2020/10117,2020,A

75
[ 3652-90-2 ]
[ 1001911-63-2 ]
C₅₄H₃₆N₂Si [ No CAS ]

Reference： [1]Patent: KR2020/10137,2020,A

76
[ 3652-90-2 ]
[ 1427213-44-2 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: copper(l) chloride; 18-crown-6 ether; 1,10-Phenanthroline; potassium carbonate / 1-methyl-pyrrolidin-2-one / 180 °C / Inert atmosphere 2: (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate / 1,4-dioxane / Inert atmosphere; Reflux

Reference： [1]Current Patent Assignee: BEIJING SUMMER SPROUT TECHNOLOGY CO LTD - US2020/277283, 2020, A1

77
[ 3652-90-2 ]
[ 74-88-4 ]
[ 108793-89-1 ]

Yield	Reaction Conditions	Operation in experiment
92%	Stage #1: 2‐bromo‐9H‐carbazole With sodium hydride In tetrahydrofuran at 0 - 20℃; for 0.5h; Inert atmosphere; Stage #2: iodomethane In tetrahydrofuran at 20℃; for 2h; Inert atmosphere;
72%	Stage #1: 2‐bromo‐9H‐carbazole With sodium hydride In N,N-dimethyl-formamide; mineral oil at 0 - 20℃; for 1h; Inert atmosphere; Stage #2: iodomethane In N,N-dimethyl-formamide; mineral oil at 20℃; Inert atmosphere;
60%	With sodium hydroxide In lithium hydroxide monohydrate; dimethyl sulfoxide at 20℃; for 18h;	2-Bromo-9-methyl-9H-carbazole (KI) 2-bromocarbazole (3.00 g, 12.2 mmol) was dissolved in DMSO (10 mL). To the solution was added NaOH (0.975 g, 24.4 mmol) as a solution in H2O (2 mL). To the resulting light brown solution was slowly added Mel (1.50 mL, 24.4 mmol). The resulting mixture was stirred at room temperature for 18h. To the mixture was added aq. sat. NaCI solution (10 mL). The resulting mixture was extracted with CH2CI2 (4xl5mL). The combined organic layers were dried over Na2SO4 and concentrated. To the resulting brown solution (product + DMSO) was added H2O (10 mL) and the light brown precipitate was filtered off. The crude was recrystallized from MeOH to yield the title product as a white solid (1.88 g, 60%). XH NMR (300 MHz, CDCI3) 6: 8.09-8.02 (m, 1H), 7.97-7.90 (m, 1H), 7.58-7.46 (m, 2H), 7.43-7.30 (m, 2H), 7.29-7.21 (m, 1H), 3.81 (s, 3H).

60%

With sodium hydroxide In lithium hydroxide monohydrate; dimethyl sulfoxide at 20℃; for 18h;

2-Bromo-9-methyl-9H-carbazole (KI) 2-bromocarbazole (3.00 g, 12.2 mmol) was dissolved in DMSO (10 mL). To the solution was added NaOH (0.975 g, 24.4 mmol) as a solution in H2O (2 mL). To the resulting light brown solution was slowly added Mel (1.50 mL, 24.4 mmol). The resulting mixture was stirred at room temperature for 18h. To the mixture was added aq. sat. NaCI solution (10 mL). The resulting mixture was extracted with CH2CI2 (4xl5mL). The combined organic layers were dried over Na2SO4 and concentrated. To the resulting brown solution (product + DMSO) was added H2O (10 mL) and the light brown precipitate was filtered off. The crude was recrystallized from MeOH to yield the title product as a white solid (1.88 g, 60%). XH NMR (300 MHz, CDCI3) 6: 8.09-8.02 (m, 1H), 7.97-7.90 (m, 1H), 7.58-7.46 (m, 2H), 7.43-7.30 (m, 2H), 7.29-7.21 (m, 1H), 3.81 (s, 3H).

Reference： [1]Mills, L. Reginald; Monteith, John J.; Dos Passos Gomes, Gabriel; Aspuru-Guzik, Alán; Rousseaux, Sophie A. L. [Journal of the American Chemical Society, 2020, vol. 142, # 30, p. 13246 - 13254]
[2]Zhang, Wen; Lin, Song [Journal of the American Chemical Society, 2020, vol. 142, # 49, p. 20661 - 20670]
[3]Current Patent Assignee: ERACAL THERAPEUTICS - WO2022/53541, 2022, A1 Location in patent: Page/Page column 134
[4]Current Patent Assignee: ERACAL THERAPEUTICS - WO2022/53541, 2022, A1 Location in patent: Page/Page column 134

78
[ 3652-90-2 ]
[ 1391729-66-0 ]
[ 1415349-62-0 ]

Yield	Reaction Conditions	Operation in experiment
91%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate In tetrahydrofuran; water for 12h; Reflux;	10.1 Step 1: Synthesis of Intermediate 2-71-1 18.23 g (40.94 mmol) of 9-(4-phenylphenyl)-3-(tetramethyl-1,3,2-dioxaborolane-2-yl)-9H-carbazole, 11.08 g (45.03 mmol) of 3-bromo-9H-carbazole, and 11.32 g (81.88 mmol) of potassium carbonate, and 1.42 g (1.23 mmol) of tetrakis(triphenylphosphine)palladium (0) (Pd(PPh3)4) were suspended in 180 ml of tetrahydrofuran (THF) and 75 ml of distilled water in a round-bottomed flask and then, refluxed and stirred for 12 hours. Subsequently, the mixture was extracted with dichloromethane and distilled water, and an organic layer therefrom was filtered with silica gel. The organic solution was then removed therefrom, and a solid product therefrom was recrystallized with dichloromethane and n-hexane to obtain 18.05 g of Intermediate 2-71-1 (Yield=91%).

Reference： [1]Current Patent Assignee: SAMSUNG SDI CO.,LTD. - US2020/266358, 2020, A1 Location in patent: Paragraph 0386-0387

79
[ 3652-90-2 ]
[ 2217-77-8 ]
[ 1393835-87-4 ]

Yield	Reaction Conditions	Operation in experiment
92%	With potassium carbonate; copper(II) nitrate In acetonitrile at 0℃; for 4h;	4; 17 Add the substrate biphenyl-4-hydrazine 0.2mmol (44mg), 2-bromocarbazole 0.2mmol (50mg), copper nitrate 3mg (7mol%), potassium carbonate 55mg (2eq.), and acetonitrile to a 50mL Schlenk tube. , Add magnets, and stir at 0°C for 4h. After the reaction is over, add 50 mL of saturated brine, extract three times with 3*50 mL of dichloromethane, add anhydrous sodium sulfate to dry for 30 minutes, and then use a rotary evaporator to remove the low-boiling solvent. After the reaction liquid was vaporized by rotating and passed through the column, the target product was obtained with a yield of 92%.

Reference： [1]Current Patent Assignee: XINXIANG RUNYU NEW MATERIAL TECH - CN112010798, 2020, A Location in patent: Paragraph 0057-0060; 0100

80
[ 3652-90-2 ]
[ 100-63-0 ]
[ 94994-62-4 ]

Yield	Reaction Conditions	Operation in experiment
98%	With cobalt(II) phthalocyanine; N,N,N,N,-tetramethylethylenediamine In acetonitrile at 60℃; for 12h; Schlenk technique;	8; 21 Add the substrate phenylhydrazine 0.6mmol (65mg), 2-bromocarbazole 0.2mmol (50mg), cobalt(II) phthalocyanine 11mg (10mol%), TMEDA93mg (4eq.), 2mL acetonitrile to a 50mL Schlenk tube, add magneton, The reaction was stirred at 60°C for 12h. After the reaction is over, add 50 mL of saturated brine, extract three times with 3*50 mL of dichloromethane, add anhydrous sodium sulfate to dry for 30 minutes, and then use a rotary evaporator to remove the low-boiling solvent. After the reaction liquid was vaporized by rotating and passed through the column, the target product was obtained with a yield of 98%.

Reference： [1]Current Patent Assignee: XINXIANG RUNYU NEW MATERIAL TECH - CN112010798, 2020, A Location in patent: Paragraph 0073-0076; 0100

81
[ 3652-90-2 ]
[ 108-95-2 ]
[ 1916473-32-9 ]

Yield	Reaction Conditions	Operation in experiment
88%	With sodium hydroxide In 1,4-dioxane at 90 - 100℃; for 8h; Inert atmosphere;	2 Example 2 First, add 12.3g (0.05mol) 2-bromocarbazole, 50g (0.49mol) tetrahydrofurfuryl alcohol, 4g (0.1mol) sodium hydroxide, 0.5g catalyst, under nitrogen protection, add 12.3g (0.05mol) 2-bromocarbazole, Raise the temperature to 100110.After that, the temperature was maintained and the reaction was stirred for 6 hours.The reaction system is cooled to 25-30°C, the catalyst and other insoluble materials are filtered, concentrated under reduced pressure, the residue is washed with water, dried, and toluene ethanol is crystallized to obtain the target product 2-(tetrahydro-2-furanmethoxy)carbazole. 11.5g; yield 86%.
7.1 g	With caesium carbonate; copper(l) chloride In 5,5-dimethyl-1,3-cyclohexadiene for 8h; Inert atmosphere; Reflux;	1 In a nitrogen atmosphere, put 2-bromo-9H-carbazole (7.4g), phenol (5.6g), cesium carbonate (19.5g), copper(I) chloride (0.30g) and xylene (120ml) in In the flask, reflux for 8 hours. After the reaction, water and ethyl acetate were added to the reaction solution and stirred, and then the organic layer was separated and washed with water. Then, the organic layer was concentrated to obtain a crude product. After purifying the crude product with a silica gel column (eluent: ethyl acetate/toluene=1/9 (volume ratio)), the fraction containing the target product is concentrated,Thus, oily 2-phenoxy-9H-carbazole (7.1 g) was obtained.

Reference： [1]Current Patent Assignee: ALLCHEMY - CN113105384, 2021, A Location in patent: Paragraph 0045-0048
[2]Current Patent Assignee: CHISSO CORPORATION; KWANSEI GAKUIN UNIVERSITY - CN111560031, 2020, A Location in patent: Paragraph 1107-1112

82
[ 267221-88-5 ]
[ 3652-90-2 ]
4-(9H-carbazol-2-yl)-N,N-diphenylaniline [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
91%	With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; at 80℃; for 12h;	General procedure: 3-bromo-9H-carbazole (492.21 mg, 2 mmol), <strong>[267221-88-5]N,N-diphenyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline</strong> (965.35 mg, 2.6mmol), potassium carbonate (414.63 g, 3 mmol), terakis(triphenylphosphine)palladium (115.56 mg, 0.1 mmol) were dissolved in amixture solution of tetrahydrofuran (15 ml) and water (5 ml) andrefluxed under nitrogen at 80 C for 12 h. Then, the mixture wasextracted with dichloromethane and washed with water. The organiclayer was dried over anhydrous MgSO4 and the residue was purified on asilica gel column using petroleum ether/dichloromethane mixture (3:1,v/v) as eluent to afford the product as white powder (1180.6 mg, yield:89%).

Reference： [1]Dyes and Pigments,2021,vol. 188

83
[ 3652-90-2 ]
[ 6797-79-1 ]
C₁₈H₁₀BrClIN [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
75.4%	Stage #1: 2-bromo-9H-carbazole With potassium <i>tert</i>-butylate In N,N-dimethyl-formamide for 0.5h; Inert atmosphere; Reflux; Stage #2: 4-chloro-2-fluoro-1-iodobenzene In N,N-dimethyl-formamide for 3h; Inert atmosphere; Reflux;	Synthesis of Intermediate B Under the protection of N2, weigh 2bromo-9H-carbazole (80g, 325.07mmol), Potassium tert-butoxide (54.7g, 487.6mmol) and DMF (400mL) were placed in a 1000mL three-necked flask and stirred at reflux for 30min until it became clear, then 4-chloro-2-fluoro-1-iodobenzene (80.2g, 312.9mmol) was added , After refluxing for 3h, After the reaction solution was cooled to room temperature, the reaction solution was poured into water, extracted with dichloromethane, the organic phase was collected, and washed with water until it became neutral, and then 1 time anhydrous magnesium sulfate was added to remove water for 30 minutes. After concentrating the filtrate, it was purified by a silica gel column, the eluent dichloromethane: n-heptane v/v=1:4, and finally 117 g of off-white product of intermediate B-1 was obtained, with a yield of 75.4%.

Reference： [1]Current Patent Assignee: SHAANXI LIGHTE OPTOELECTRONICS MATERIAL CO.,LTD - CN112321595, 2021, A Location in patent: Paragraph 0154-0156

84
[ 3652-90-2 ]
[ 832114-00-8 ]
[ 2639272-11-8 ]

Yield	Reaction Conditions	Operation in experiment
88%	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium phosphate In tetrahydrofuran; water at 65℃; for 20h; Sealed tube; Inert atmosphere;	1.1 Step 1: Preparation of 4-(9H-carbazol-2-yl)-3,5-dimethylisoxazole To a mixture containing 2-bromo-9H-carbazole (750 mg, 3.05 mmol), 3,5- dimethyl-4-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)isoxazole (748 mg, 3.35 mmol), and Pd(dppf)Cl2 (55.7 mg, 0.076 mmol) in a screw cap vial was added THF (15 mL) followed by aqueous solution of potassium phosphate, tribasic (3.05 mL, 9.14 mmol).The vial was fitted with a Teflon lined septum cap. The system was evacuated under vacuum (via a needle from a nitrogen/vacuum manifold line) and backfilled with nitrogen gas. The procedure was repeated three times. The needle was removed and the vial was heated at 65 °C for 20 h. The reaction mixture was cooled to room temperature and diluted with EtOAc (15 mL). The aqueous layer thus obtained was aspirated using a Pasteur pipette, dried (NaiSCri), filtered and concentrated to obtain a crude product. The crude product was dissolved in a small amount of DCM and loaded on to a 24 g ISCO silica gel column and purified using the Teledyne ISCO system, eluting over a 15 min gradient with 0%-100% hexanes/ethyl acetate to obtain 4-(9H-carbazol-2-yl)-3,5- dimethylisoxazole (1C) (700 mg, 2.67 mmol, 88% yield), m/z (263, M+H).

Reference： [1]Current Patent Assignee: BRISTOL-MYERS SQUIBB CO - WO2021/67657, 2021, A1 Location in patent: Page/Page column 32-33

85
[ 3652-90-2 ]
[ 35708-19-1 ]
[ 2650504-73-5 ]

Yield	Reaction Conditions	Operation in experiment
50%	With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; sodium t-butanolate In toluene at 50℃; for 6h; Inert atmosphere; Reflux;	1.1 (1) Add 2-bromocarbazole (9.10g, 37mmol) into a 500mL three-necked flask with nitrogen protection and reflux device,Methyl 2-aminobenzoate (8.41g, 37mmol),100mL of toluene, protected by nitrogen,Turn on stirring and heating, wait until the temperature rises to 50°C,Sequentially add sodium tert-butoxide (5.28g, 55mmol),2-Dicyclohexylphosphorus-2,6-dimethoxy-biphenyl (S-phos) (0.15g, 0.37mmol),Tris(dibenzylideneacetone)dipalladium (Pd2(dba)3) (0.1g, 0.18mmol); the temperature is raised to toluene reflux,After the reaction is completed for 6 hours, stop stirring and heating after the reaction is completed. When the temperature drops to room temperature, start to process the resulting reaction solution; add 80 mL of ultrapure water to the reaction solution, stir and separate, and extract the aqueous phase twice with 100 mL of toluene each time. Combine the organic phases and wash them three times with 100 mL of ultrapure water each time; dry with anhydrous sodium sulfate, pass through a silica gel column, rinse the column with 200 mL of toluene after finishing, concentrate the organic phase to the remaining 80 mL, and heat to completely dissolve the solids. After cooling and crystallization, the solid was filtered, and recrystallized with 45 mL of dichloroethane to obtain a white solid intermediate B-1 (7.26 g, yield 50%).

Reference： [1]Current Patent Assignee: SHAANXI LIGHTE OPTOELECTRONICS MATERIAL CO.,LTD - CN112876455, 2021, A Location in patent: Paragraph 0135-0137

86
[ 3652-90-2 ]
[ 2650519-97-2 ]

Yield	Reaction Conditions	Operation in experiment
93%	With hydrogen fluoride; water-d2 In 1,4-dioxane at 100 - 120℃;	7.S71-7.S75 S71) Obtain each component carbazole compound, hydrofluoric acid catalyst, deuterium water and 1,4-dioxane solvent, wherein the carbazole compound: the hydrofluoric acid catalyst: the deuterium water: the The molar ratio of 1,4-dioxane solvent is 1:(0.05-0.1):(20-40):(5-10).The molecular structural formula of the carbazole compound is:Wherein, said R1 is any one of hydrogen, methyl, vinyl, and phenyl; said R2 and R3 are ester groups, cyano groups, carbonyl groups, hydroxyl groups, alkoxy groups, alkyl groups, tert-butyl groups, bromine groups. Any of, chlorine, fluorine, iodine, amide, amine, borate, alkynyl, alkenyl, phenyl, heterocyclic aryl. In the embodiment of the present application, the carbazole compound is 2-bromocarbazole.The fluoric acid catalyst is any one of trifluoromethanesulfonic acid, trifluoroacetic acid, and pentafluoropropionic acid.S72) Add the hydrofluoric acid catalyst, the deuterium water, the carbazole compound, and the 1,4-dioxane solvent into the reactor to obtain a mixed solution.Specifically, into the 10 mL reactor, add 0.98 mmol of the hydrofluoric acid catalyst, 0.44 g, 22 mmol of the deuterium water, 1 mmol of the 2-bromocarbazole, and 9.5 mol of the 1,4-dioxane. Ring solvent. In the embodiment of the present application, the reaction liquid includes but is not limited to a reaction flask.S73) Heat treatment of the mixed solution.Specifically, the mixed solution is heated at a temperature of 100-120° C. for 11-13 hours to make the mixed solution fully react.S74) After the reaction of the mixed solution is completed, a saturated ammonium chloride solution is added to the reactor for quenching.Specifically, 99-101 ml of the ammonium chloride solution, preferably 100 ml of the ammonium chloride solution is added to the reactor, so that the mixed solution in the reactor undergoes a quenching reaction.S75) Adding a dichloromethane solvent to the reactor, extracting, combining the organic phases, and rotating and concentrating to obtain a deuterated carbazole compound.Specifically, 99-101 ml of the dichloromethane solvent, preferably 100 ml of the dichloromethane solvent is added to the reactor. Wherein, the dichloromethane solvent can be used to extract three to four times, and the organic phases extracted several times can be combined into a 250ml eggplant-shaped bottle, using a rotary evaporator, the rotating speed is 120rpm, the temperature is 37°C, and the vacuum degree is 0.1Mpa , Treat for 3min, get deuterated carbazole compound, namely deuterated 2-bromocarbazole. Among them, the deuterated 2-bromocarbazole was 236 mg, the yield was 93%, the deuteration rate was 97%, and the analytical purity was 99%.

Reference： [1]Current Patent Assignee: ANHUI SHOLON NEW MATERIAL TECHNOLOGY CO LTD - CN112876406, 2021, A Location in patent: Paragraph 0151-0166

87
[ 3652-90-2 ]
[ 63503-60-6 ]
[ 2102336-15-0 ]

Yield	Reaction Conditions	Operation in experiment
93%	With tetrakis-(triphenylphosphine)-palladium; potassium carbonate In ethanol; lithium hydroxide monohydrate; toluene at 85℃; Inert atmosphere;	3 The synthetic method of compound 3 is as follows: Under the protection of nitrogen, in a 2L three-necked flask, sequentially add 3-a (60g, 244mmol, 1eq), 3-b (42g, 269mmol, 1.1eq), tetrakistriphenylphosphine palladium (4.2g, 3.6mmol, 0.015) eq), potassium carbonate (85g, 615mmol, 2.75eq), 500mL of toluene, 125mL of ethanol and 125mL of water. After the addition is complete, the temperature is raised to 85 and the reaction is stirred. The progress of the reaction is monitored by HPLC. When compound 3-a ≤1%, the reaction is stopped After the reaction solution was naturally cooled to room temperature, 200 mL of water was added, stirred for 10 min, filtered with suction, washed with water, washed with ethanol, and dried at 85°C for 12 hours to obtain 62.9 g of intermediate 3-c with a yield of 93%.
93%	With tetrakis-(triphenylphosphine)-palladium; potassium carbonate In ethanol; lithium hydroxide monohydrate; toluene at 85℃; Inert atmosphere;	3 Under nitrogen protection, in a 2L three-necked flask, were sequentially added 3-a (60g, 244mmol, 1eq), 3-b (42g, 269mmol, 1.1eq), tetrakistriphenylphosphine palladium (4.2g, 3.6mmol, 0.015 eq), potassium carbonate (85g, 615mmol, 2.75eq), 500mL of toluene, 125mL of ethanol and 125mL of water were added, and the temperature was raised to 85°C to stir the reaction. The reaction progress was monitored by HPLC. When compound 3-a was less than or equal to 1%, the reaction was stopped. After the reaction solution was naturally cooled to room temperature, 200 mL of water was added, stirred for 10 min, suction filtered, washed with water, rinsed with ethanol, and dried at 85°C for 12 hours to obtain intermediate 3-c, 62.9 g, yield 93%,

Reference： [1]Current Patent Assignee: NANJING TOPTO SEMICONDUCTOR MATERIAL CO LTD - CN113480527, 2021, A Location in patent: Paragraph 0037
[2]Current Patent Assignee: NANJING TOPTO SEMICONDUCTOR MATERIAL CO LTD - CN114031610, 2022, A Location in patent: Paragraph 0076-0080

88
[ 3652-90-2 ]
[ 1268137-13-8 ]
[ 2803223-66-5 ]

Yield	Reaction Conditions	Operation in experiment
58%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tri-tert-butyl phosphine; sodium tertiary butoxide In 5,5-dimethyl-1,3-cyclohexadiene at 130℃; for 7h; Inert atmosphere; Reflux;	15 Preparation Example 15, Preparation of Compound 355 2-Bromocarbazole (50.0g, 203.1mmol), Sub1-I-A161.2g, 223.4mmol), Pd2(dba)3 (1.8g, 2.0mmol), tri-tert-butylphosphine (0.8g, 4.1mmol) ), sodium tert-butoxide (39.0 g, 406.3 mmol), and xylene (500 mL) were added to the three-necked flask, heated to 130° C. under nitrogen protection, heated under reflux and stirred for 7 h. After the reaction, the solution was cooled to room temperature, toluene and water were added to extract the reaction solution, the organic phases were combined, the organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated; the crude product was purified by silica gel column chromatography (dichloromethane/n-heptane). , the solid compound Sub 1-I-A11 (48.3 g, 58%) was obtained.

Reference： [1]Current Patent Assignee: SHAANXI LIGHTE OPTOELECTRONICS MATERIAL CO.,LTD - CN114736198, 2022, A Location in patent: Paragraph 0176-0178

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[ 3652-90-2 ] Synthesis Path-Upstream 1~7

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P303 + P361 + P353	IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower.
P304 + P312	IF INHALED: Call a POISON CENTER or doctor/physician if you feel unwell.
P304 + P340	IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing.
P304 + P341	IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing.
P305 + P351 + P338	IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing.
P306 + P360	IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes.
P307 + P311	IF exposed: call a POISON CENTER or doctor/physician.
P308 + P313	IF exposed or concerned: Get medical advice/attention.
P309 + P311	IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician.
P332 + P313	IF SKIN irritation occurs: Get medical advice/attention.
P333 + P313	IF SKIN irritation or rash occurs: Get medical advice/attention.
P335 + P334	Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages.
P337 + P313	IF eye irritation persists: Get medical advice/attention.
P342 + P311	IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician.
P370 + P376	In case of fire: Stop leak if safe to Do so.
P370 + P378	In case of fire:
P370 + P380	In case of fire: Evacuate area.
P370 + P380 + P375	In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion.
P371 + P380 + P375	In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion.
Storage
Code	Phrase
P401
P402	Store in a dry place.
P403	Store in a well-ventilated place.
P404	Store in a closed container.
P405	Store locked up.
P406	Store in corrosive resistant/ container with a resistant inner liner.
P407	Maintain air gap between stacks/pallets.
P410	Protect from sunlight.
P411
P412	Do not expose to temperatures exceeding 50 oC/ 122 oF.
P413
P420	Store away from other materials.
P422
P402 + P404	Store in a dry place. Store in a closed container.
P403 + P233	Store in a well-ventilated place. Keep container tightly closed.
P403 + P235	Store in a well-ventilated place. Keep cool.
P410 + P403	Protect from sunlight. Store in a well-ventilated place.
P410 + P412	Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF.
P411 + P235	Keep cool.
Disposal
Code	Phrase
P501	Dispose of contents/container to ...
P502	Refer to manufacturer/supplier for information on recovery/recycling