[ CAS No. 474918-32-6 ] {[proInfo.proName]}

Name: 474918-32-6|2-Bromo-9,9-diphenyl-9H-fluorene|98%
Brand: Ambeed
SKU: A112312
Price: 5.0 USD
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Quality Control of [ 474918-32-6 ]

COA NMR CNMR HPLC LC-MS

Related Doc. of [ 474918-32-6 ]

SDS Specification

Alternatived Products of [ 474918-32-6 ]

Product Details of [ 474918-32-6 ]

CAS No. :	474918-32-6	MDL No. :	MFCD09907957
Formula :	C₂₅H₁₇Br	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	WNXNWOBGPRKOJF-UHFFFAOYSA-N
M.W :	397.31	Pubchem ID :	46856308
Synonyms :

Calculated chemistry of [ 474918-32-6 ]

Physicochemical Properties

Num. heavy atoms :	26
Num. arom. heavy atoms :	24
Fraction Csp3 :	0.04
Num. rotatable bonds :	2
Num. H-bond acceptors :	0.0
Num. H-bond donors :	0.0
Molar Refractivity :	111.45
TPSA :	0.0 Å²

Pharmacokinetics

GI absorption :	Low
BBB permeant :	No
P-gp substrate :	Yes
CYP1A2 inhibitor :	Yes
CYP2C19 inhibitor :	Yes
CYP2C9 inhibitor :	No
CYP2D6 inhibitor :	No
CYP3A4 inhibitor :	No
Log Kp (skin permeation) :	-3.5 cm/s

Lipophilicity

Log Po/w (iLOGP) :	3.88
Log Po/w (XLOGP3) :	7.36
Log Po/w (WLOGP) :	6.81
Log Po/w (MLOGP) :	6.66
Log Po/w (SILICOS-IT) :	7.3
Consensus Log Po/w :	6.4

Druglikeness

Lipinski :	1.0
Ghose :	None
Veber :	0.0
Egan :	1.0
Muegge :	2.0
Bioavailability Score :	0.55

Water Solubility

Log S (ESOL) :	-7.49
Solubility :	0.0000128 mg/ml ; 0.0000000323 mol/l
Class :	Poorly soluble
Log S (Ali) :	-7.19
Solubility :	0.0000257 mg/ml ; 0.0000000648 mol/l
Class :	Poorly soluble
Log S (SILICOS-IT) :	-10.98
Solubility :	0.0000000041 mg/ml ; 0.0 mol/l
Class :	Insoluble

Medicinal Chemistry

PAINS :	0.0 alert
Brenk :	0.0 alert
Leadlikeness :	2.0
Synthetic accessibility :	3.36

Safety of [ 474918-32-6 ]

Signal Word:	Warning	Class:	N/A
Precautionary Statements:	P280-P305+P351+P338	UN#:	N/A
Hazard Statements:	H302	Packing Group:	N/A
GHS Pictogram:

Application In Synthesis of [ 474918-32-6 ]

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

Upstream synthesis route of [ 474918-32-6 ]
Downstream synthetic route of [ 474918-32-6 ]

[ 474918-32-6 ] Synthesis Path-Upstream 1~13

1
[ 73183-34-3 ]
[ 474918-32-6 ]
[ 462128-39-8 ]

Yield	Reaction Conditions	Operation in experiment
91%	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate In N,N-dimethyl-formamideReflux	Preparation of Compound 50-1 Reflux in a single neck round bottom flask2-bromo-9,9-diphenyl -9H- fluorene (40g, 100.67mmol),Diboron (51.1g, 201.34mmol),PdCl2 (dppf) (2.2g, 3.02mmol), KOAc (29.6g, 302.01mmol)And DMF (400ml)mixture.The mixture was extracted with MC and dried over MgSO4,Then using a vacuum rotary evaporator to remove the DMF.Concentrate was purified by column chromatography (SiO2, hexane: dichloromethane = 1: 1) to give a white solid was isolated compound 50-1 (41g, 91percent).

Reference： [1] Patent: CN105408333, 2016, A, . Location in patent: Paragraph 0212; 0213; 0214

2
[ 61676-62-8 ]
[ 474918-32-6 ]
[ 462128-39-8 ]

Reference： [1] Organic Letters, 2002, vol. 4, # 25, p. 4439 - 4442

3
[ 736928-22-6 ]
[ 71-43-2 ]
[ 474918-32-6 ]

Yield	Reaction Conditions	Operation in experiment
98.6%	at 45 - 75℃; for 5.5 h; Inert atmosphere	1) 10 mmol trifluoroacetic acid, 1.5 mmol anhydrous aluminum trichloride and 150 mmol dry benzene in a flaskMix well A liquid;2) 10 mmol of 2-bromo-9-phenyl-fluorene-9-ol and 90 mmol of dry benzene were mixed to give B solution;3) B was added dropwise to Solution A while stirring under argon, 2-bromo-9-phenyl-fluorene-9-ol in Solution BAnd A liquid trifluoroacetic acid molar ratio of 1: 1, mixing process control system temperature does not exceed 45 ;4) the system temperature to 75 , the reaction 1.5 h; and then maintain the system temperature and add 5 mmol trifluoroacetic acid; continueReaction 4h after the end of the reaction.5) separation and purification to be 2-bromo-9,9-diphenylfluorene, separation and purification operation: the reaction after the end of the system to join250 mmol of ice water; stratified, the organic phase was neutralized with saturated sodium bicarbonate to pH, extracted with ethyl acetate, and the extract was concentrated to give a white solid powder product with a yield of 98.6percent.
95.1%	Stage #1: at 64℃; for 2 h; Stage #2: at 45℃; for 5 h;	10 mmol of 2-bromo-9-phenyl-fluoren-9-ol and 170 mmol of benzene were mixed,Stirring up to 64 ° C, through the addition of sufficient hydrogen bromide gas, until the TLC monitoring to the basic disappearance of raw materials, ventilation is completed,The reaction system was heated to reflux temperature, refluxed for 2 h,Return the water at the same time using the water separator to separate the system;The system was cooled to 20 ± 2 , in 1h by adding the catalyst in batches,Heated to 45 after 5h reaction;Wherein the catalyst consists of 12 mmol of anhydrous aluminum trichloride and 3 mmol of anhydrous ferric chloride,The catalyst was added in three batches, and the weight ratio was three: 2: 1;Separation and purification to obtain 2-bromo-9,9-diphenylfluorene, separation and purification operation: the reaction after the end of the system to join240 mmo 1 ice water; layered, organic phase neutralized with saturated sodium bicarbonate to pH,ethyl acetate was added and the extract was concentrated to give the product as a white solid, yield 95.1percent.

Reference： [1] Patent: CN105016968, 2017, B, . Location in patent: Paragraph 0031; 0032; 0033; 0034; 0035; 0036; 0037
[2] Patent: CN105085163, 2017, B, . Location in patent: Paragraph 0014; 0026-0028; 0031-0033; 0034-0038; 0041-0043
[3] Journal of the American Chemical Society, 2002, vol. 124, # 39, p. 11576 - 11577
[4] Journal of Organic Chemistry, 2010, vol. 75, # 12, p. 4004 - 4013
[5] Patent: US2011/54229, 2011, A1, . Location in patent: Page/Page column 34

4
[ 71-43-2 ]
[ 474918-32-6 ]

Reference： [1] Patent: CN105085162, 2017, B, . Location in patent: Paragraph 0032; 0036

5
[ 3096-56-8 ]
[ 474918-32-6 ]

Reference： [1] Journal of the American Chemical Society, 2002, vol. 124, # 39, p. 11576 - 11577
[2] Patent: US2011/54229, 2011, A1,

6
[ 17103-26-3 ]
[ 474918-32-6 ]

Reference： [1] Patent: US2015/207075, 2015, A1, . Location in patent: Page/Page column

7
[ 108-86-1 ]
[ 474918-32-6 ]

Reference： [1] Patent: US2011/54229, 2011, A1,

8
[ 486-25-9 ]
[ 474918-32-6 ]

Reference： [1] Tetrahedron, 2014, vol. 70, # 25, p. 3847 - 3853

9
[ 3096-56-8 ]
[ 100-58-3 ]
[ 474918-32-6 ]

Reference： [1] Tetrahedron, 2014, vol. 70, # 25, p. 3847 - 3853

10
[ 688-74-4 ]
[ 474918-32-6 ]
[ 400607-31-0 ]

Reference： [1] Patent: US2012/309974, 2012, A1, . Location in patent: Page/Page column 13

11
[ 121-43-7 ]
[ 474918-32-6 ]
[ 400607-31-0 ]

Yield	Reaction Conditions	Operation in experiment
4 g	With n-butyllithium In tetrahydrofuran at -78℃;	Take 10 grams of 2-bromo-9,9-diphenylfluorene and 100 ml of anhydrous tetrahydrofuran was added to a 1 liter flask,Cooled to -78 ° C with liquid nitrogen,25.2 ml of n-butyllithium and trimethyl borate are slowly added dropwise with stirring,After the natural return to room temperature,Add appropriate amount of dilute hydrochloric acid hydrolysis,Then extracted with ethyl acetate,The organic layer was separated and dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure and 4 g of product was eluted with hexane.

Reference： [1] Patent: CN106957272, 2017, A, . Location in patent: Paragraph 0090; 0091

12
[ 121-43-7 ]
[ 7732-18-5 ]
[ 474918-32-6 ]
[ 400607-31-0 ]

Yield	Reaction Conditions	Operation in experiment
4 g	Stage #1: With n-butyllithium In tetrahydrofuran at -78℃; Stage #2: With hydrogenchloride In tetrahydrofuran	Take 10g of 2-bromo-9,9-diphenylfluorene and 100ml of anhydrous tetrahydrofuran into a 1L flask.The liquid nitrogen was cooled to -78°C, and 25.2 ml of n-butyllithium and trimethyl borate were slowly added dropwise with stirring. After the addition, the mixture was naturally returned to room temperature and added with an appropriate amount of dilute hydrochloric acid to hydrolyze ethyl acetate (Ethyl acetate). ) Extraction, separation of the organic layer, drying over anhydrous sodium sulfate, removal of the solvent under reduced pressure, and precipitation of 4 g of product as hexane.

Reference： [1] Patent: TWI603960, 2017, B, . Location in patent: Paragraph 0069; 0070

13
[ 474918-32-6 ]
[ 400607-31-0 ]

Reference： [1] Patent: WO2015/73343, 2015, A1,

[ 474918-32-6 ] Synthesis Path-Downstream 1~88

1
[ 80-10-4 ]
[ 474918-32-6 ]
[ 1008530-48-0 ]

Yield	Reaction Conditions	Operation in experiment
83%	With n-butyllithium; In tetrahydrofuran; at -78 - 20℃; for 18h;	Synthesis Example 4: Preparation of a compound represented by Formula 6; [Show Image] <strong>[474918-32-6]2-bromo-9,9'-diphenylfluorene</strong> (represented by Formula 15) which is an intermediate was synthesized using a method introduced in Organic Letters 2002, vol. 4, No. 25, pp. 4439-4442. Then, 2.01 g (5.06 mmol) of Formula 15 was dissolved in 100 ml of THF, and 3.5 ml (5.6 mmol) of n-BuLi and 0.63 g (2.49 mmol) of dichlorodiphenylsilane were added thereto at -78C. The temperature was gradually increased to room temperature and the mixture was reacted for 18 hour. The solvent was evaporated under reduced pressure and the result was purified using silica gel column chromatography, and as an eluant, a solution of chloroform and hexane (1:1 v/v) to produce 1.69 g of a compound of Formula 6 (Yield 83 %).

Reference： [1]Patent: EP1892244,2008,A1 .Location in patent: Page/Page column 18-19

2
[ 2401-73-2 ]
[ 474918-32-6 ]
[ 1008530-49-1 ]

Yield	Reaction Conditions	Operation in experiment
65%	With n-butyllithium; In tetrahydrofuran; at -78 - 20℃; for 18h;	Synthesis Example 5: Preparation of a compound represented by Formula 7; [Show Image] 1.24 g of the compound represented by Formula 7_was produced in the same manner as in Synthesis Example 4, except that 1,3-dichloro-1,1,3,3-tetramethyldisiloxane was used instead of dichlorodiphenylsilane (Yield 65 %).

Reference： [1]Patent: EP1892244,2008,A1 .Location in patent: Page/Page column 19

3
[ 3096-56-8 ]
[ 474918-32-6 ]

Reference： [1]Journal of the American Chemical Society,2002,vol. 124,p. 11576 - 11577
[2]Patent: US2011/54229,2011,A1

4
phenylmagnesium bromide [ No CAS ]
[(4-methoxy-1,3-η³-cyclohexenyl)PdCl]2 [ No CAS ]
[ 474918-32-6 ]

Reference： [1]Journal of the American Chemical Society,2002,vol. 124,p. 11576 - 11577

5
[ 474918-32-6 ]
2,5-bis-(9,9-diphenyl-9H-fluoren-2-yl)-thiophene [ No CAS ]

Reference： [1]Organic Letters,2002,vol. 4,p. 4439 - 4442

6
[ 474918-32-6 ]
5,5'-bis-(9,9-diphenyl-9H-fluoren-2-yl)-[2,2']bithiophenyl [ No CAS ]

Reference： [1]Organic Letters,2002,vol. 4,p. 4439 - 4442

7
[ 474918-32-6 ]
5,5''-bis-(9,9-diphenyl-9H-fluoren-2-yl)-[2,2';5',2'']terthiophene [ No CAS ]

Reference： [1]Organic Letters,2002,vol. 4,p. 4439 - 4442

8
[ 474918-32-6 ]
5,5'''-bis-(9,9-diphenyl-9H-fluoren-2-yl)-[2,2';5',2'';5'',2''']quaterthiophene [ No CAS ]

Reference： [1]Organic Letters,2002,vol. 4,p. 4439 - 4442

9
[ 121-43-7 ]
[ 474918-32-6 ]
dimethyl 9,9-diphenyl-9H-fluoren-2-ylboronate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
		The compound <strong>[474918-32-6]2-bromo-9,9-diphenyl-9H-fluorene</strong> (3.00 g, 7.55 mmol) was dissolved in anhydrous THF (150 mL), and n-butyl lithium (6.14 mL, 1.6 M in hexanes, 1.3 eq.) was added to the solution at -78C. The mixture solution was stuffed at -78C for2 h. To the solution, trimethyl borate (1.1 mL, 1.3 eq.) was added at -78C. After stuffing the solution for 1 h, 5 mL of 6 N HC1 solution was added to the solution, and the resulting biphasic solution was stirred rapidly for 2 h at room temperature. After the reaction, the organic layer was extracted with methylene chloride, and washed with brine, dried over MgSO4, and the solvent removed under vacuum. The crude product was purified by silicachromato gram with methylene chloride, and the mixture of methylene chloride and methanol (9:1). After purification, 2 g of compound lb white powder was obtained (73.3% yield).

Reference： [1]Journal of Organic Chemistry,2010,vol. 75,p. 4004 - 4013
[2]Patent: WO2015/73343,2015,A1 .Location in patent: Page/Page column 16

10
[ 474918-32-6 ]
[ 98-80-6 ]
[ 1158844-76-8 ]

Yield	Reaction Conditions	Operation in experiment
63%	With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In 1,4-dioxane;Reflux;	In a round-bottomed flask, 15.0 g of 2-bromo-9,9-dimethyl-9H-fluorene and 5.1 g of phenylboronic acid were dissolved in 200 ml of 1,4-dioxane and placed in 60 ml of K2CO3 After (2M) and 1.3 g of Pd(PPh3)4 were stirred at reflux. The reaction was confirmed by thin layer chromatography (TLC). After adding water, the reaction was completed. The organic layer was extracted with dichloromethane (MC) and depressurizedAfter filtration, column purification was performed to obtain 10.43 g (yield 63%) of Intermediate IM1-1.
	With sodium carbonate;bis-triphenylphosphine-palladium(II) chloride; In ethanol; water; toluene; at 100℃; for 12h;	A vessel was charged with Compound (113) (23.0 g, 58 mmol), phenylboronic acid (10.6 g, 87 mmol), PdCl2(PPh3)2 (4.1 g, 5.8 mmol), aqueous 2 M sodium carbonate solution (150 mL), toluene (300 mL) and ethanol (100 mL), and the mixture was stirred at 100 C. for 12 hours. The reaction mixture was worked up according to the same procedure for synthesis of Compound (102) to obtain Compound (114) (11 g, 32 mmol).
10.7 g	With bis-triphenylphosphine-palladium(II) chloride; sodium carbonate; In ethanol; water; toluene; at 100℃; for 12h;	(1) Synthesis of Intermediate 1-1: To a three-necked flask was added 23 g (58 mmol) of 2-bromo-9,9-diphenylfluorene (Compound 1-a), 10.6 g (87 mmol) of phenylboronic acid, (5.8 mmol) of bis-triphenylphosphine palladium dichloride, 150 ml of a 2M aqueous solution of sodium carbonate, 300 ml of toluene and 100 ml of ethanol, the reaction was heated to 100 C and the reaction was stirred for 12 hours. Cooled to room temperature and then extracted with dichloromethane (200 ml). The organic phase was washed with distilled water (150 ml), then dried over magnesium sulfate and distilled under reduced pressure. Column chromatography (n-hexane: dichloromethane 20: 1) To obtain intermediate 1-1 (10.7 g of 27 mmol

Reference： [1]Patent: CN107963973,2018,A .Location in patent: Paragraph 0108; 0109; 0112-0114
[2]Patent: US2011/54229,2011,A1 .Location in patent: Page/Page column 34
[3]Patent: CN106632185,2017,A .Location in patent: Paragraph 0059; 0062; 0065

11
[ 108-86-1 ]
[ 474918-32-6 ]

Reference： [1]Patent: US2011/54229,2011,A1

12
[ 474918-32-6 ]
[ 1158844-77-9 ]

Reference： [1]Patent: US2011/54229,2011,A1

13
[ 474918-32-6 ]
[ 1158844-78-0 ]

Reference： [1]Patent: US2011/54229,2011,A1

14
[ 1679-18-1 ]
[ 474918-32-6 ]
[ 1221237-90-6 ]

Yield	Reaction Conditions	Operation in experiment
73%	With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; water; for 5h;Heating;	Preparation of Structural Formula 18D; 2-bromo-9,9-diphenylfluorene (15 g, 37.8 mmol), and 4-chlorobenzene boronic acid (6.5 g, 41.5 mmol)) were dissolved in 150 ml of tetrahydrofurane, 100 ml of 2M potassium carbonate aqueous solution and Pd(PPh3)4 (437 mg, 0.38 mmol) were added thereto, and heated and agitated for 5 hours. After the temperature was lowered to normal temperature, the organic layer was extracted, concentrated, and recrystallized with ethanol to obtain the Structural Formula 18D (11.9 g, yield 73%). MS: [M+ H]+ = 430

Reference： [1]Patent: EP2343277,2011,A2 .Location in patent: Page/Page column 38

15
[ 474918-32-6 ]
[ 1221237-91-7 ]

Reference： [1]Patent: EP2343277,2011,A2

16
[ 474918-32-6 ]
[ 1221237-18-8 ]

Reference： [1]Patent: EP2343277,2011,A2

17
[ 87199-17-5 ]
[ 474918-32-6 ]
[ 1334287-59-0 ]

Yield	Reaction Conditions	Operation in experiment
70%	With bis-triphenylphosphine-palladium(II) chloride; potassium carbonate; In tetrahydrofuran; toluene; at 90℃;Inert atmosphere;	Compound 4-formyl phenylboronic acid (300 mg, 0 . 76mmol), 2-bromo -9,9 the base fluorene-diethyl [...] (103 mg, 0 . 67mmol), double (triphenylporphyrin phosphorus) palladium dichloride Pd (PPh3)2Cl2(23.51 mg, 0 . 034mmol), dissolved in 10 ml tetrahydrofuran mixed solvent of toluene and (Vtoluene: VTHF= 1:1) in, under the protection of nitrogen 90 C reflux reaction, thin-layer chromatography tracking to the reaction is complete. The solution obtained after the organic solvent, a revolving off, the extraction with ethyl acetate, the organic layer three times washing with water, saturated NaCl solution to a washing, drying by anhydrous sodium sulfate, reducing pressure and evaporating the solvent. The crude product using petroleum ether and ethyl acetate mixed solvent (20:1) column, to obtain 4 - (9,9 the [...] -diphenyl -9H-fluoren-2-yl) benzaldehyde (white solid, 251.1 mg, yield 70%).

Reference： [1]European Journal of Organic Chemistry,2011,p. 4788 - 4798
[2]Patent: CN105418515,2016,A .Location in patent: Paragraph 0153; 0154; 0155

18
[ 87199-17-5 ]
[ 474918-32-6 ]
7-[4-(9,9-diphenyl-9H-fluoren-2-yl)styryl]-9,9-diethyl-2-(N,N-diphenylamino)-9H-fluorene [ No CAS ]

Reference： [1]European Journal of Organic Chemistry,2011,p. 4788 - 4798

19
[ 688-74-4 ]
[ 474918-32-6 ]
[ 400607-31-0 ]

Yield	Reaction Conditions	Operation in experiment
		9,9-Diphenyl-2-Fluorene Boric acid Dissolved 4.6 g of 9,9-Diphenyl-2-Bromo Fluorene (see J. AM. CHEM. SOC. 2002, 124, 11576-11577) in 100 ml of THF, stirred under Nitrogen gas field and cooled to -78 C. Constantly dripped it to the volume of 7 ml, and after stirred for 2 hours, dripped in 4 ml of Tributyl Borate. The reaction lasted for 4 hours with temperature constant, then warmed up to the room temperature and stirred overnight. After cooled to -10 C., dripped in 10% diluted HCl, the PH value reached 1, and stirred for 2 hours. Then later, followed with liquid separated, extracted by Methylene Chloride, concentrated, and further purified by silica gel column chromatography, 3 g of product can be reached, with 80% of purity.

Reference： [1]Patent: US2012/309974,2012,A1 .Location in patent: Page/Page column 13

20
[ 333174-61-1 ]
[ 474918-32-6 ]
2,5-bis(9,9-diphenylfluoren-2-yl)-1,1-dimethyl-3,4-diphenylsilole [ No CAS ]

Reference： [1]Chemistry - A European Journal,2014,vol. 20,p. 1931 - 1939

21
C₂₃H₁₈Cl₂SiZn₂ [ No CAS ]
[ 474918-32-6 ]
2,5-bis(9,9-diphenylfluoren-2-yl)-1-methyl-1,3,4-triphenylsilole [ No CAS ]

Reference： [1]Chemistry - A European Journal,2014,vol. 20,p. 1931 - 1939

22
[ 1054451-31-8 ]
[ 474918-32-6 ]
[ 1601479-57-5 ]

Yield	Reaction Conditions	Operation in experiment
55%	With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; water; toluene; for 12h;Reflux; Inert atmosphere;	General procedure: A mixture of 2 (0.83 g, 2.2 mmol), 5 (0.48 g, 1 mmol), Pd(PPh3)4 (0.11g, 0.1mmol), and K2CO3 (1.1 g, 8.0 mmol) in toluene/ethanol/water (100 mL, 8/1/1 v/v/v) was heated to reflux for 12 h under nitrogen. Then the reaction mixture was cooled to room temperature and poured into water. The organic layer was extracted with dichloromethane, and the combined organic layers were washed with a saturated brine solution and water, and dried over anhydrous magnesium sulfate. After filtration and solvent evaporation, the residue was purified by silica-gel column chromatography using hexane/dichloromethane as eluent. White solid of (TPE)2PF was obtained in 56% yield.

Reference： [1]Dyes and Pigments,2014,vol. 106,p. 87 - 93

23
[ 474918-32-6 ]
[ 551951-04-3 ]
[ 1610059-33-0 ]

Yield	Reaction Conditions	Operation in experiment
51%	With 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone; copper(l) iodide; 18-crown-6 ether; potassium carbonate; at 180℃; for 48h;	3,3?,6,6?-tetra-tert-butyl-9?-(9,9-diphenyl-9H-fluoren-2-yl)-9?H-9,3?:6?,9?-tercarbazole (2DPF-TCz), 9?-(9,9?-spirobi[fluoren]-2-yl)-3,3?,6,6?-tetra-tert-butyl-9?H-9,3?:6?,9?-tercarbazole (2SBF-TCz), 9?,9-(9,9-diphenyl-9H-fluorene-2,7-diyl)bis(3,3?,6,6?-tetra-tert-butyl-9?H-9,3?:6?,9?-tercarbazole) (27DPF-TCz), and 2,7-bis(3,3?,6,6?-tetra-tert-butyl-9?H-[9,3?:6?,9?-tercarbazol]-9?-yl)-9,9??-spirobi[fluorene] (27SBF-TCz) were synthesized by a similar procedure: A mixture of <strong>[474918-32-6]2-bromo-9,9-diphenyl-9H-fluorene</strong> (2-bromo-9,9?-spirobi[fluorene], 2,7-dibromo-9,9-diphenyl-9H-fluorene, and 2,7-dibromo-9,9?-spirobi[fluorene]) (1.5 mmol), TCz (1.6 mmol or 3.2 mmol), CuI (0.06 mmol), 18-crown-6 (0.06 mmol), K2CO3 (4.5 mmol), and DMPU (5 mL) was heated at 180 C for 48 h. After cooling, the mixture was treated with water and extracted with diethyl ether. The organic extraction was dried over MgSO4 with removal of the volatiles. The residue was purified by column chromatography on silica gel using petroleum ether/ethyl acetate as an eluent.

Reference： [1]Tetrahedron,2014,vol. 70,p. 3847 - 3853

24
[ 486-25-9 ]
[ 474918-32-6 ]

Reference： [1]Tetrahedron,2014,vol. 70,p. 3847 - 3853

25
[ 3096-56-8 ]
[ 100-58-3 ]
[ 474918-32-6 ]

Reference： [1]Tetrahedron,2014,vol. 70,p. 3847 - 3853

26
2,4-dichloro-6-(naphthalen-2-yl)-1,3,5-triazine [ No CAS ]
[ 474918-32-6 ]
2-chloro-4-(9,9-diphenyl-9H-fluoren-2-yl)-6-(naphthalen-2-yl)-1,3,5-triazine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
63%		A dry glass jar was charged with <strong>[474918-32-6]2-bromo-9,9-diphenyl-9H-fluorene</strong> (3.23 g, 10 mmol), 40 mL of dry THF, and magnesium turnings (0.36 g, 15 mmol), and the reactionmixture was stirred at 50C under nitrogen. GC-MS analysis of an aliquot of the reaction mixture (quenched with D20 and extracted with EtOAc) was done periodically to check the reaction progress. Upon complete conversion, this Grignard solution was slowly added to a solution of 2,4-dichloro-6-(naphthalen-2-yl)-1,3,5-triazine Id (2.76 g, 10 mmol) in dry THF (20 mL), at room temperature. The reaction mixture was stirred at roomtemperature, with periodic analysis by LC-MS, until complete conversion. The solvent was removed by rotatory evaporation, and the solid was redissolved in chloroform, dried loaded with silica gel, and purified by silica gel chromatography with chlorofornilhexanes gradient (20-40%), to give the desired intermediate compound If (3.5 g, 63% yield).

Reference： [1]Patent: WO2015/73343,2015,A1 .Location in patent: Page/Page column 21

27
[ 474918-32-6 ]
[ 400607-31-0 ]

Reference： [1]Patent: WO2015/73343,2015,A1

28
[ 474918-32-6 ]
C₅₇H₃₉N₃ [ No CAS ]

Reference： [1]Patent: WO2015/73343,2015,A1

29
[ 17103-26-3 ]
[ 474918-32-6 ]

Yield	Reaction Conditions	Operation in experiment
	With acetic acid;	2-Bromo-9,9-diphenyl-9H-fluorene (2-1) 30 g (103 mmol) of methyl 4'-bromobiphenyl-2-carboxylate are dissolved in 500 ml of dried THE in a flask which has been dried by heating. The clear solution is cooled to -10 C., and 102 ml (307 mmol) of a freshly prepared 3 M 2-phenylmagnesium bromide solution are then added. The reaction mixture is slowly warmed to room temperature and then quenched using NH4Cl (500 ml). The mixture is subsequently partitioned between ethyl acetate and water, and the organic phase is washed three times with water, dried over Na2SO4 and evaporated in a rotary evaporator. 400 ml of acetic acid are carefully added to the residue. 80 ml of fuming HCl are subsequently added. The batch is heated to 75 C. and kept at this temperature for 5 h. A white solid precipitates out during this time. The batch is then cooled to room temperature, and the precipitated solid is filtered off with suction and rinsed with methanol. The residue is dried at 40 C. in vacuo. The yield is 29.4 g (74 mmol) (72% of theory).

Reference： [1]Patent: US2015/207075,2015,A1 .Location in patent: Page/Page column

30
[ 13716-12-6 ]
[ 1372775-52-4 ]
[ 474918-32-6 ]
N-[1,1'-biphenyl]-2-yl}-N-[1,1'-biphenyl]-4-yl}-9,9-diphenyl-9H-fluoren-3-yl-amine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With palladium diacetate; In toluene;	Biphenyl-2-ylbiphenyl-4-yl-(9,9-diphenyl-9H-fluoren-3-yl)amine (2-1) 17 g of biphenyl-2-ylbiphenyl-4-ylamine (53 mmol) and 21 g of <strong>[474918-32-6]2-bromo-9,9-diphenyl-9H-fluorene</strong> (53 mmol) are dissolved in 350 ml of toluene: the solution is degassed and saturated with N2. 2.1 ml (2.1 mmol) of a 1 M solution of tri-tert-butylphosphine and 0.24 g (1.06 mmol) of palladium(II) acetate are then added, and 12.7 g of sodium tert-butoxide (132 mmol) are subsequently added. The reaction mixture is heated at the boil for 5 h under a protective atmosphere. The mixture is subsequently partitioned between toluene and water, and the organic phase is washed three times with water, dried over Na2SO4 and evaporated in a rotary evaporator. After the crude product has been filtered through silica gel with toluene, the residue which remains is recrystallised from heptane/toluene and finally sublimed in a high vacuum. The purity is 99.9%. The yield is 25 g (74% of theory).

Reference： [1]Patent: US2015/207075,2015,A1 .Location in patent: Page/Page column

31
[ 578027-21-1 ]
[ 474918-32-6 ]
C₄₃H₂₉NO [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
80%	With tri-tert-butyl phosphine; palladium diacetate; sodium t-butanolate; In toluene; at 80℃; for 8h;Inert atmosphere;	INTERMEDIATE SYNTHESIS 2-1 (Synthesis of intermediate 2-1) [0129] Under an argon atmosphere, into a mixture of 19.9 g (50.0 mmol) of <strong>[474918-32-6]2-bromo-9,9'-diphenylfluorene</strong>, 13.0 g (50.0 mmol) of the intermediate 1-3, and 9.6 g (100.0 mmol) of t-butoxysodium, 250 ml of dry toluene was added, and the resultant mixture was stirred. After adding 225 mg (1.0 mmol) of palladium acetate and 202 mg (1.0 mmol) of tri-t-butylphosphine, the mixture was allowed to react at 80 C for 8 h. [0130] After cooling, the reaction mixture was filtered through celite/silica gel. The filtrate was condensed under reduced pressure. The obtained residue was recrystallized from toluene and the crystal was collected by filtration and dried to obtain 23.0 g of a white solid, which was identified as the intermediate 2-1 by FD-MS analysis (yield: 80%).

Reference： [1]Patent: EP2891648,2015,A1 .Location in patent: Paragraph 0129-0130

32
[ 62-53-3 ]
[ 474918-32-6 ]
[ 860465-14-1 ]

Yield	Reaction Conditions	Operation in experiment
90%	With tri-tert-butyl phosphine; bis(dibenzylideneacetone)-palladium(0); sodium t-butanolate; In toluene; for 3h;Reflux; Inert atmosphere;	Under an argon (Ar) atmosphere, 3.0 g of Compound A, 0.70 g of aniline, 0.22 g of Pd(dba)2, 0.73 g of NaOt-Bu, and 0.31 g of t-Bu3P were added to a 200 mL, three necked flask, followed by heating and refluxing in 75 mL of a toluene solvent for about 3 hours. After air cooling, water was added, an organic layer was separated, and solvents were distilled. The crude product thus obtained was separated by silica gel column chromatography (using hexane and toluene) to obtain 2.78 g (yield 90%) of Compound B as a white solid. (0132) The molecular weight of Compound B measured by FAB-MS was 409.
75%	With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; at 40℃;	<strong>[474918-32-6]2-bromo-9,9-diphenyl-9H-fluorene</strong> (35.27g, 88.8mmol) as the starting material was dissolved in toluene in a round bottom flask, and aniline (16.53g, 177.5mmol), Pd2(dba)3 (2.44g, 2.7mmol), 50% P(t-Bu)3 (3.5ml, 7.1mmol), and NaOt-Bu (25.6g, 266.3mmol) were added to the reaction solution, followed by stirring at 40C. Upon completion of the reaction, 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 27.27g of product (yield: 75%).
70%	With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene;Reflux;	In a round-bottom flask, 10.0 g of <strong>[474918-32-6]2-bromo-9,9-diphenyl-9H-fluorene</strong>, 2.6 g of aniline, 3.6 g of t-BuONa, and 0.9 g of Pd2 (dba) were dissolved in 130 ml of toluene. After 3 and 1.1 ml of (t-Bu)3P was stirred at reflux.The reaction was confirmed by thin layer chromatography, and after addition of water, the reaction was completed.The organic layer was extracted with dichloromethane (MC), and after filtration under reduced pressure, column purification and recrystallization were performed to obtain 7.22 g (yield 70%) of OP1.

69%	With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene;Reflux;	In a round bottom flask, 30.0 g of the above <strong>[474918-32-6]2-bromo-9,9-diphenyl-9H-fluorene</strong>,5.6 g of aniline, 11 g of t-BuONa, 2.8 g of Pd2 (dba) 3 and 3.5 ml of (t-Bu)3P were dissolved in 500 ml of toluene, followed by reflux stirring.The reaction was confirmed by thin layer chromatography (TLC), and after adding water, the reaction was terminated. Using methyl cellulose (MC) to extract the organic layer,After decompression filtration,Recrystallization was carried out to obtain 21.3 g (yield 69%) of OP1.
69%	With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene;Reflux;	In a round bottom flask, 30.0 g of the above <strong>[474918-32-6]2-bromo-9,9-diphenyl-9H-fluorene</strong>, 5.6 g of aniline, t- BuONa 11g, Pd2(dba)3 2.8g, and (t-Bu)3P 3.5ml were dissolved in 500 ml of toluene, and then stirred under reflux. The reaction was confirmed by thin layer chromatography (TLC), and after adding water, the reaction was terminated. The organic layer was extracted with methyl cellulose (MC), filtered under reduced pressure, and then recrystallized to obtain 21.3 g (yield 69%) of OP1.
64%	With tris-(dibenzylideneacetone)dipalladium(0); triphenylphosphine; sodium t-butanolate; In toluene; at 100℃; for 24h;	To a round bottom flask Sub 2-1-1 (1.9g, 20mmol), Sub 2-2-1 (5.5g, 20mmol), Pd2 (dba) 3 (0.9g, 1mmol), PPh3 (0.5g, 2mmol), NaOt-Bu (5.8g, 60mmol), were added to toluene (210mL), respectively, and stirred at reflux for 24 hours, 100 C thereby. The organic layer was dried over MgSO4, and extracted with water and ether and recrystallized silica gel column and the resulting organic one was concentrated to a Sub 2-9 5.2g (yield: 64%) was obtained.

Reference： [1]Patent: US2018/83209,2018,A1 .Location in patent: Paragraph 0130-0132
[2]Patent: EP2930168,2015,A1 .Location in patent: Paragraph 0206; 0207; 0290
[3]Patent: CN107915648,2018,A .Location in patent: Paragraph 0112; 0113; 0114
[4]Patent: CN108929261,2018,A .Location in patent: Paragraph 0136; 0137; 0138
[5]Patent: CN108976162,2018,A .Location in patent: Paragraph 0141; 0142; 0143
[6]Patent: KR2015/69256,2015,A .Location in patent: Paragraph 0174-0176

33
[ 62-53-3 ]
[ 474918-32-6 ]
C₆₇H₄₆N₂ [ No CAS ]

Reference： [1]Patent: EP2930168,2015,A1

34
[ 474918-32-6 ]
7,7-diphenyl-5,7-dihydroindeno[2,1-b]carbazole [ No CAS ]

Reference： [1]Patent: WO2015/190789,2015,A1
[2]Patent: KR2015/128590,2015,A

35
[ 474918-32-6 ]
C₅₂H₃₄N₄ [ No CAS ]

Reference： [1]Patent: WO2015/190789,2015,A1
[2]Patent: KR2015/128590,2015,A

36
[ 95-51-2 ]
[ 474918-32-6 ]
C₃₁H₂₂ClN [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
82%	With tri-tert-butyl phosphine; palladium diacetate; sodium t-butanolate; In toluene; at 140℃; for 4h;	After introducing <strong>[474918-32-6]2-bromo-9,9-diphenyl-9H-fluorene</strong> (8 g, 0.020 mol), 2-chloroaniline (3.1 mL, 0.030 mol), Pd(OAc)2 (181 mg, 0.805 mmol), P(t-Bu)3 (50% in toluene) (0.8 mL, 1.61 mmol), NaOt-Bu (4.8 g, 0.056 mol), and toluene 58 mL in a flask, the resulting mixture was stirred at 140C for 4 hours. After completing the reaction, the mixture was washed with distilled water and extracted with ethyl acetate (EA). The organic layer was dried with MgSO4, the solvent was removed with a rotary evaporator, and the residue was purified with column chromatography to obtain compound 1-1 (7.3 g, 82%).

Reference： [1]Patent: WO2015/190789,2015,A1 .Location in patent: Paragraph 169; 170; 171

37
[ 87199-17-5 ]
[ 474918-32-6 ]
C₅₅H₄₂N₂ [ No CAS ]

Reference： [1]Patent: CN105418515,2016,A

38
[ 74-31-7 ]
[ 474918-32-6 ]
C₆₁H₄₃N₃ [ No CAS ]