[ CAS No. 108714-73-4 ] {[proInfo.proName]}

Name: 108714-73-4|9,9-Dimethyl-9H-fluoren-2-amine|98%
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Quality Control of [ 108714-73-4 ]

COA NMR CNMR HPLC LC-MS

Related Doc. of [ 108714-73-4 ]

SDS Specification

Alternatived Products of [ 108714-73-4 ]

Product Details of [ 108714-73-4 ]

CAS No. :	108714-73-4	MDL No. :	MFCD09953790
Formula :	C₁₅H₁₅N	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	GUTJITRKAMCHSD-UHFFFAOYSA-N
M.W :	209.29	Pubchem ID :	22617093
Synonyms :

Calculated chemistry of [ 108714-73-4 ]

Physicochemical Properties

Num. heavy atoms :	16
Num. arom. heavy atoms :	12
Fraction Csp3 :	0.2
Num. rotatable bonds :	0
Num. H-bond acceptors :	0.0
Num. H-bond donors :	1.0
Molar Refractivity :	68.79
TPSA :	26.02 Å²

Pharmacokinetics

GI absorption :	High
BBB permeant :	Yes
P-gp substrate :	Yes
CYP1A2 inhibitor :	Yes
CYP2C19 inhibitor :	Yes
CYP2C9 inhibitor :	No
CYP2D6 inhibitor :	Yes
CYP3A4 inhibitor :	No
Log Kp (skin permeation) :	-4.92 cm/s

Lipophilicity

Log Po/w (iLOGP) :	2.31
Log Po/w (XLOGP3) :	3.74
Log Po/w (WLOGP) :	3.58
Log Po/w (MLOGP) :	3.47
Log Po/w (SILICOS-IT) :	3.77
Consensus Log Po/w :	3.38

Druglikeness

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

Water Solubility

Log S (ESOL) :	-4.05
Solubility :	0.0187 mg/ml ; 0.0000894 mol/l
Class :	Moderately soluble
Log S (Ali) :	-3.98
Solubility :	0.022 mg/ml ; 0.000105 mol/l
Class :	Soluble
Log S (SILICOS-IT) :	-5.6
Solubility :	0.000529 mg/ml ; 0.00000253 mol/l
Class :	Moderately soluble

Medicinal Chemistry

PAINS :	0.0 alert
Brenk :	1.0 alert
Leadlikeness :	2.0
Synthetic accessibility :	2.17

Safety of [ 108714-73-4 ]

Signal Word:	Warning	Class:	N/A
Precautionary Statements:	P280-P305+P351+P338-P310	UN#:	N/A
Hazard Statements:	H302-H315-H319-H332-H335	Packing Group:	N/A
GHS Pictogram:

Application In Synthesis of [ 108714-73-4 ]

* 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 [ 108714-73-4 ]
Downstream synthetic route of [ 108714-73-4 ]

[ 108714-73-4 ] Synthesis Path-Upstream 1~11

1
[ 108-86-1 ]
[ 108714-73-4 ]
[ 355832-04-1 ]

Reference： [1] Patent: US9515265, 2016, B2, . Location in patent: Page/Page column 109; 121

2
[ 108714-73-4 ]
[ 92-66-0 ]
[ 897671-69-1 ]

Yield	Reaction Conditions	Operation in experiment
92%	With [Pd(N,N'-bis(2,6-bis(di-p-tolylmethyl)-4-methylphenyl)-imidazol-2-ylidene)(acetylacetonate)Cl]; lithium hexamethyldisilazane In 1,4-dioxane at 110℃; for 3 h; Inert atmosphere; Sealed tube	General procedure: A glassvial was charged with [Pd(IPr*me)(acac)Cl],neat amine (1.1 mmol), and the arylhalide (1 mmol) in dry 1,4-dioxane (1 mL) under an atmosphere of argonand sealed with a screw cap fitted with aseptum. LiHMDS (1.1 mmol) was subsequently injected at roomtemperature under argon, the reaction mixture was then refluxed at 110 for 3 h, After this time, dioxane was evaporated, the crude product wasdissolved in CH₂Cl₂. The solution was filtered on a padof silica covered with Celite, and thepad was eluted with CH₂Cl₂. After chromatography onsilica gel, the pure complex was obtained.
81%	With tri-tert-butyl phosphine; palladium diacetate; sodium t-butanolate In toluene for 6 h; Inert atmosphere	A solution of 9,9-dimethyl-7-aminofluorene 49 mmol was added4-bromobiphenyl was dissolved in 400 mL of toluene,The solution was degassed and saturated with nitrogen,Then 2.43 mmol of 1M tri-tert-butylphosphine solution and 1.21 mmol were addedOf palladium (II) acetate,And then 146 mmol of sodium tert-butoxide was added. The reaction mixture was heated under boiling in a protective atmosphere for 6 hours,The mixture was then partitioned between toluene and water, the organic phase was washed three times with water and dried over sodium sulfate, and the mixture was stirred on a rotary evaporator, The residual residue was recrystallized from heptane / toluene after the crude product was filtered through silica gel using toluene and finallyDegassed in a high vacuum to give compound C-1. The yield was 20 g (81percent of the theoretical value).
72%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tri-tert-butyl phosphine; sodium t-butanolate In toluene for 12 h; Reflux	9,9-dimethyl-9H-fluoren-2-amine (15.0 g, 71.67 mmol) 18.4 g of 4-bromo-1,1'-biphenyl(1.43 mmmol) of tris (dibenzylideneacetone) dipalladium (0) was suspended in 239 ml of toluene, followed by addition of tri-tert-butylphosphine 1.4 mL (5.73 mmol) was added thereto, followed by reflux stirring for 12 hours. Extracted with dichloromethane and distilled water, and the organic layer is subjected to silica gel filtration. The organic solution was removed and recrystallized from dichloromethane and hexane to obtain 18.6 g (yield: 72percent) of the intermediate product (O).

Reference： [1] Journal of Organometallic Chemistry, 2018, vol. 861, p. 125 - 130
[2] Advanced Synthesis and Catalysis, 2016, vol. 358, # 10, p. 1589 - 1594
[3] Patent: CN106632219, 2017, A, . Location in patent: Paragraph 0077; 0078; 0079; 0080
[4] Patent: KR2016/102142, 2016, A, . Location in patent: Paragraph 0308; 0311-0313

3
[ 605644-46-0 ]
[ 108714-73-4 ]

Yield	Reaction Conditions	Operation in experiment
81%	With palladium 10% on activated carbon; hydrogen In ethanol for 24 h;	23.9 g (100.0 mmol) of compound 2 and 0.5 g of 10percent Pd on activated charcoal were diluted with 500 mL of ethanol and stirred for 24 hours in a hydrogen atmosphere. The reactant was filtered to remove a catalyst, concentrated, and then separated using column chromatography to obtain 16.9 g of compound 3 in light-yellow solid form with a yield of 81percent. The structure of compound 3 was identified using high-resolution mass spectrometry (HR-MS). (calc.: 209.1204, found: 209.1194)

Reference： [1] Journal of Materials Chemistry B, 2013, vol. 1, # 40, p. 5450 - 5455
[2] Patent: US8865322, 2014, B2, . Location in patent: Page/Page column 26; 37; 38
[3] Patent: CN105418515, 2016, A, . Location in patent: Paragraph 0012; 0040

4
[ 28320-31-2 ]
[ 108714-73-4 ]

Reference： [1] Patent: WO2012/15265, 2012, A1, . Location in patent: Page/Page column 15
[2] Patent: EP2468725, 2012, A1,

5
[ 63021-04-5 ]
[ 108714-73-4 ]

Reference： [1] Patent: EP2468725, 2012, A1, . Location in patent: Page/Page column 121

6
[ 4569-45-3 ]
[ 108714-73-4 ]

Reference： [1] Patent: US8865322, 2014, B2,
[2] Patent: CN105418515, 2016, A,

7
[ 86-73-7 ]
[ 108714-73-4 ]

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

8
[ 108714-73-4 ]
[ 28320-31-2 ]
[ 500717-23-7 ]

Yield	Reaction Conditions	Operation in experiment
81%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tri-tert-butyl phosphine; sodium t-butanolate In toluene at 85℃; for 3 h;	6.27 g (30 mmol) of 2-amino-9,9'-dimethylfluorene, 5.46 g (20.0 mmol) of 2-bromo-9,9'-dimethylfluorene, 366 mg (0.4 mmol) of Pd₂(bda)₃ where dba is dibenzylideneacetone, 80 mg (0.4 mmol) of PtBu₃, and 2.88 g (30 mmol) of NaOtBu were dissolved in 60 mL of toluene, and the mixture was refluxed at 85°C for 3 hours. The mixture was cooled to room temperature and subjected to extraction three times with 50 mL of water and 50 mL of diethyl ether. An organic layer was collected and dried using magnesium sulfate to evaporate the solvent. The residue was separately purified using silica gel column chromatography to obtain 6.50 g of Intermediate I-1 (Yield: 81 percent) The produced compound was identified using 1H NMR and MS/FAB. C₃₀H₂₇N:calc. 401.21, found 402.231H NMR (400MHz, CDCl₃). δ7.78 (dd, 2H), 7.56 (d, 2H), 7.36-7.30 (m, 2H), 7.14-7.09 (m, 2H), 7.02 (d, 2H), 6.94 (d, 2H), 5.85 (s, 1H), 1.65 (s, 12H)
61%	With sodium t-butanolate In toluene at 90℃; for 3 h; Inert atmosphere	Synthesis Example 7: Synthesis of Compound 65; Synthesis of Intermediate 13 [Show Image] Under a nitrogen atmosphere, 1.91 g (7.0mmol) of 9,9'-dimethyl-2-bromofluorene, 2.2 g (10.5 mmol) of 9,9'-dimethyl-2-aminofluorene, 2.0 g (21 mmol) of t-BuONa, 130 mg (0.14mmol) of Pd₂(dba)₃, and 28 g (0.14mmol) of P(t-Bu)₃ were dissolved in 30 ml of toluene, and then the mixture was stirred at 90°C for 3 hours. After the reaction was completed, the reaction product was cooled to room temperature and extracted three times with distilled water and 50 ml of diethylether. The organic layer was collected and dried using magnesium sulfate to evaporate the solvent. The residue was separated and purified using silica gel column chromatography to obtain 1.7 g (yield: 61 percent) of Intermediate 13. This compound was identified using HR-MS. C₃₀H₂₇N calc.: 401.2143; found 401.2147.

Reference： [1] Patent: EP2581365, 2013, A1, . Location in patent: Paragraph 0129
[2] Patent: EP2292602, 2011, A1, . Location in patent: Page/Page column 31

9
[ 108714-73-4 ]
[ 1260228-95-2 ]

Reference： [1] Patent: CN107556229, 2018, A,

10
[ 108714-73-4 ]
[ 1257220-47-5 ]

Reference： [1] Patent: KR2017/113427, 2017, A,
[2] Patent: KR2017/116976, 2017, A,
[3] Patent: KR2018/32517, 2018, A,
[4] Patent: CN107915722, 2018, A,

11
[ 108714-73-4 ]
[ 1242056-42-3 ]

Reference： [1] Advanced Synthesis and Catalysis, 2016, vol. 358, # 10, p. 1589 - 1594

[ 108714-73-4 ] Synthesis Path-Downstream 1~88

1
[ 108714-73-4 ]
[ 942615-28-3 ]
C₆₁H₇₁N [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
78.0%	With tri-tert-butyl phosphine; sodium t-butanolate;bis(dibenzylideneacetone)-palladium(0); In xylene; at 20 - 125℃; for 3h;	Example 1) <n="33"/>(Synthesis of Exemplified Compound 3) a) Synthesis of Intermediate Compound 1-1Intermediate was produced by using 2,7- ditertiarybutylfluorene (SIGMA-ALDRICH) as a raw material (Bull. Chem. Soc. Jpn . , 59, 97-103 (1986)). Further, the intermediate was subjected to dimethylation to produce Intermediate 1-1. b) Synthesis of Exemplified Compound 3A 200-ml three-necked flask was prepared. 4.56 g (12.0 mmol) of Compound 1-1 were loaded into the flask. In addition, 0.828 g (4.00 mmol) of Compound 1-2 and 0.96 g (10.0 mmol) of sodium tertiary butoxide were loaded into the flask. Further, 100 ml of xylene were loaded into the flask, and then 34.4 mg (0.17 mmol) of tritertiarybutylphosphine were added while the mixture was stirred in a nitrogen atmosphere at room temperature. Next, 48.9 mg (0.085 mmol) of palladium dibenzylideneacetone were added. The temperature of the resultant was increased to125C, and then the resultant was stirred for 3 hours <n="34"/>After the reaction, an organic layer was extracted with toluene, dried with anhydrous sodium sulfate, and purified with a silica gel column (mixed developing solvent of heptane and toluene) , whereby 2.53 g of Exemplified Compound 3 (white crystal) were obtained (78.0% yield).Mass spectrometry confirmed that the M+ of the compound was 817.5. In addition, differential scanning calorimetry (DSC) confirmed that the compound had a melting point of 267C and a glass transition point of 143C. (Examples 2 to 11)
78%	With sodium t-butanolate;tri-tert-butyl phosphine; bis(dibenzylideneacetone)-palladium(0); In xylene; at 125℃; for 3h;Inert atmosphere;	(Synthesis Method of Compound 2); The following reagents and solvent were placed into a reaction vessel. Note that Intermediate 4 is a reagent synthesized from 2 , 7-di-tert-butylfluorene (Sigma- Aldrich Co.) according to the method disclosed in NPL 1. Intermediate 4: 4.56 g (12.0 mmol)Intermediate 5: 0.828 g (4.00 mmol)Sodium tertiary butoxide: 0.96 g (10.0 mmol)Xylene: 100 ml[0133] Next, the inside of the reaction system was made to be nitrogen atmosphere, and the reaction solution was stirred at room temperature. Next, tri-tertiary- butylphosphine 34.4 mg (0.17 mmol) was added to the reaction solution. Next, palladium-dibenzylidene acetone 48.9 mg (0.085 mmol) was added to the reaction solution .[0134] ext, the temperature of the reaction solution wasincreased to 125C and then the reaction solution was stirred for 3 hours at this temperature (125C). After completion of the reaction, an organic layer wasextracted using toluene, dried over anhydrous sodium sulfate, and then the solvent was distilled away under reduced pressure to thereby obtain a crude product. Next, the crude product was purified by a silica gel column chromatography (developing solvent: heptane- toluene mixed solvent) , thereby obtaining white color crystals of Compound 2 (2.53 g) (yield: 78.0%).[0135] The compound was confirmed to have an + of 817.5 by mass spectrometry. Further, the compound was confirmed to have a melting point of 267C and a glass transition temperature of 143C by differential scanningcalorimetry (DSC) .

Reference： [1]Patent: WO2007/72952,2007,A1 .Location in patent: Page/Page column 32-33
[2]Patent: WO2011/40631,2011,A1 .Location in patent: Page/Page column 47-48

2
[ 108714-73-4 ]
[ 28320-31-2 ]
[ 500717-23-7 ]

Yield	Reaction Conditions	Operation in experiment
84%	With tris-(dibenzylideneacetone)dipalladium(0); sodium t-butanolate; XPhos; In toluene; at 105 - 110℃; for 2.5h;Inert atmosphere;	2-Bromo-9,9-dimethylhydrazine (12.0 g, 43.9 mmol),<strong>[108714-73-4]2-amino-9,9-dimethylhydrazine</strong> (10.1 g, 48.3 mmol),Tris(dibenzylideneacetone)dipalladium (0.4 g, 0.4 mmol),2-Dicyclohexylphosphino-2,4,6-triisopropylbiphenyl (0.4 g, 0.9 mmol) and sodium tert-butoxide (6.3 g, 65.9 mmol) were added to toluene (120 mL).Heat to 105-110 C under nitrogen, stir for 2.5 hours; cool to room temperature, wash the reaction twice with water, dry over magnesium sulfate, filter, pass the filtrate through a short silica gel column, remove the solvent under reduced pressure; use dichloromethane / ethanol The crude product was recrystallized and purified to give the crude solid intermediate VB (15.2 g, 84%).
81%	With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; at 85℃; for 3h;	6.27 g (30 mmol) of <strong>[108714-73-4]2-amino-9,9'-dimethylfluorene</strong>, 5.46 g (20.0 mmol) of 2-bromo-9,9'-dimethylfluorene, 366 mg (0.4 mmol) of Pd2(bda)3 where dba is dibenzylideneacetone, 80 mg (0.4 mmol) of PtBu3, and 2.88 g (30 mmol) of NaOtBu were dissolved in 60 mL of toluene, and the mixture was refluxed at 85C for 3 hours. The mixture was cooled to room temperature and subjected to extraction three times with 50 mL of water and 50 mL of diethyl ether. An organic layer was collected and dried using magnesium sulfate to evaporate the solvent. The residue was separately purified using silica gel column chromatography to obtain 6.50 g of Intermediate I-1 (Yield: 81 %) The produced compound was identified using 1H NMR and MS/FAB. C30H27N:calc. 401.21, found 402.231H NMR (400MHz, CDCl3). delta7.78 (dd, 2H), 7.56 (d, 2H), 7.36-7.30 (m, 2H), 7.14-7.09 (m, 2H), 7.02 (d, 2H), 6.94 (d, 2H), 5.85 (s, 1H), 1.65 (s, 12H)
61%	With sodium t-butanolate;tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; In toluene; at 90℃; for 3h;Inert atmosphere;	Synthesis Example 7: Synthesis of Compound 65; Synthesis of Intermediate 13 [Show Image] Under a nitrogen atmosphere, 1.91 g (7.0mmol) of 9,9'-dimethyl-2-bromofluorene, 2.2 g (10.5 mmol) of 9,9'-dimethyl-2-aminofluorene, 2.0 g (21 mmol) of t-BuONa, 130 mg (0.14mmol) of Pd2(dba)3, and 28 g (0.14mmol) of P(t-Bu)3 were dissolved in 30 ml of toluene, and then the mixture was stirred at 90C for 3 hours. After the reaction was completed, the reaction product was cooled to room temperature and extracted three times with distilled water and 50 ml of diethylether. The organic layer was collected and dried using magnesium sulfate to evaporate the solvent. The residue was separated and purified using silica gel column chromatography to obtain 1.7 g (yield: 61 %) of Intermediate 13. This compound was identified using HR-MS. C30H27N calc.: 401.2143; found 401.2147.

60%	With tris-(dibenzylideneacetone)dipalladium(0); sodium t-butanolate; tri tert-butylphosphoniumtetrafluoroborate; In toluene; at 90℃; for 19h;Inert atmosphere;	To a suspension of 22.6 g (82.7 mmol) of 2-bromo-9,9-dimethyl-9H-fluorene, 17.3 g (82.7 mmol) of <strong>[108714-73-4]9,9-dimethyl-9H-fluoren-2-amine</strong>, and 23. 8 g (248.1 mmol) of sodium ten-butanolate in 300 mL of of toluene were added 0.96 g (3.31 mmol) of tri-ten-butylphosphine tetrafluoroborate and 3.03 g (3.31 mmol) of Pd2(dba)3 under an argonatmosphere. The mixture was heated at 90C for 19 h. After cooling, 40 mL of saturated aqueous NH4CI solution were added. After 30 minutes, the combined phases were filtered through celite and extended with 500 mL of dichloromethane and 250 mL of water. The organic phase was separated and the aqueous phase was washed with 200 mL of dichloromethane. The combined organic phases were washed withsaturated NaCI solution, dried with MgSO4, and evaporated to dryness. The crude solid was crystallised from toluene to give the title compound as a white solid (20.0 g, 60%).
	With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; In toluene; at 110℃; for 24h;Inert atmosphere;	0.1 mol of raw material 2-amino-9,9-dimethylfluorene and 0.12 mol of raw material2-Bromo-9,9-dimethylphosphonium is dissolved in 500mL of anhydrous toluene. After deoxygenation, 0.005mol of Pd2 (dba) 3 and 0.15mol of tri-tert-butylphosphorus are added, and the reaction is performed at 110 C for 24 hours under an inert atmosphere.During the reaction, the progress of the reaction is continuously monitored by TLC. After the reaction of the raw materials is complete, cool,Filtration and rotary evaporation of the filtrate,The solvent was removed, and the crude product was passed through a silica gel column to obtain intermediate 1.

Reference： [1]Patent: CN110183332,2019,A .Location in patent: Paragraph 0107; 0108
[2]Patent: EP2581365,2013,A1 .Location in patent: Paragraph 0129
[3]Patent: EP2292602,2011,A1 .Location in patent: Page/Page column 31
[4]Patent: WO2018/206769,2018,A1 .Location in patent: Page/Page column 85; 86
[5]Patent: CN110317206,2019,A .Location in patent: Paragraph 0051-0053
[6]Patent: CN111233764,2020,A .Location in patent: Paragraph 0028; 0035

3
[ 108714-73-4 ]
[ 59951-65-4 ]
[ 1356174-65-6 ]

Yield	Reaction Conditions	Operation in experiment
80%	With tri-tert-butyl phosphine; potassium tert-butylate; bis(dibenzylideneacetone)-palladium(0); In toluene; at 80℃;Inert atmosphere;	The 2.83g (0.01mole) intermediate G1-1,2-amino -9,9-dimethylfluorene 2.09g (0.01mole) and 50 ml toluene mixed, under a nitrogen atmosphere, by adding 0.18g (0.0002mole) three (dibenzylidene acetone) a second palladium Pd 2 (dba) 3, 1.44g (0.015mole) tert butoxide potassium and 0.809g (0.0004mole, 10% toluene solution of the quality) butyl phosphinethree uncles, heating to 80 C for reaction, monitoring board, after the reaction is complete cooling to room temperature, add 100 ml toluene, the silica gel funnel to obtain filtrate, the filtrate water washing 3 times more phase, fasten it dry after silica gel column, to obtain 3.3g solid intermediate G1-2, the yield is 80%.
	With tri-tert-butyl phosphine; sodium t-butanolate;palladium diacetate; In toluene; at 100℃; for 12h;	18.6 g (88.64 mmol) of Compound 2-3, 25 g (88.64 mmol) of Compound 3-1, 0.6 g (2.7 mmol) of Pd(OAc)2, 3.6 mL (8.9 mmol) of P(t-Bu)3, 25.5 g (266 mmol) of NaOt-Bu, and 1000 mL of toluene were stirred under heat at 100C for 12 hours. After the reaction completed, the reaction product was washed with distilled water, and extracted with ethylacetate, after which the resultant organic layer was dried with MgSO4, evaporated using a rotary evaporator to remove the solvent, and then purified using column chromatography, thus obtaining 14.2 g (34.5 mmol) of Compound 3-2.

Reference： [1]Patent: CN103524399,2016,B .Location in patent: Paragraph 0054-0058;0059
[2]Patent: WO2012/15265,2012,A1 .Location in patent: Page/Page column 17

4
[ 108714-73-4 ]
[ 59951-65-4 ]
[ 1356174-66-7 ]

Reference： [1]Patent: WO2012/15265,2012,A1

5
[ 108714-73-4 ]
[ 502161-03-7 ]
[ 1268835-64-8 ]

Yield	Reaction Conditions	Operation in experiment
82%	With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; at 100℃; for 5h;	10.5 g (50 mmol) of Intermediate a, 18.5 g (50 mmol) of Intermediate b, 1.35 g (3.0 mole %) of tris(dibenzylideneacetone)dipalladium(0) (Pd2(dba)3), 7.2 g (75 mmol) of sodium tert-butoxide, and 300 mg (3.0 mole%) of tri-tert-butylphosphine (P(t-Bu)3) were added to 300 mL of toluene, and the mixture was refluxed while stirring at 100C for 5 hours. The reaction mixture was cooled to room temperature and subjected to extraction with methylene chloride and H2O. Then, the resultant was dried using magnesium sulfate to evaporate the solvent. The residue was separately purified using silica gel column chromatography to obtain 18.5 g of Intermediate c (Yield: 82%). The produced compound was identified using LC-MS. C33H26N2:M+ 450.21
62%	With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; at 90℃; for 6h;Inert atmosphere;	100 mL of toluene was added to a mixture including 11.1 g (30.0 mmol) of compound 4, 7.53 g (39.0 mmol) of compound 3, 4.3 g (45.0 mmol) of NaOtBu, 1.4 g (1.5 mmol) of Pd2(dba)3, and 0.30 g (1.5 mmol) of PtBu3 and then the mixture was heated at 90 C. in a nitrogen atmosphere for 6 hours. The reaction mixture was cooled to room temperature, 30 mL of water was further added to the reaction mixture, and the reaction mixture was subjected to extraction twice with 200 mL of methylene chloride. The resultant organic layer was dried, filtered, concentrated, and then separated using column chromatography to obtain 8.38 g of compound 5 in light-green solid form with a yield of 62%. The structure of compound 5 was identified using HR-MS. (calc.: 450.2096, found: 450.2091)

Reference： [1]Patent: EP2554545,2013,A1 .Location in patent: Paragraph 0152; 0153
[2]Patent: US8865322,2014,B2 .Location in patent: Page/Page column 25-28; 38; 39

6
[ 108714-73-4 ]
[ 1028647-93-9 ]
9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluoren-2-amine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
94%	With 1,1'-bis(diisopropylphosphino)ferrocene; [Pd(dippf)(maleimide)]; sodium t-butanolate; In toluene; at 70℃; for 20h;Inert atmosphere; Sealed tube; Schlenk technique;	Examples 4a to 4i General Protocol (0096) All experiments were carried out in 20 mL headspace vials for gas chromatography that were sealed with crimped aluminium caps featuring Teflon-coated butyl rubber septa (both available, for example, from VWR). For the heating of the vessels, cylindrical aluminium blocks 8 cm high were used, corresponding precisely in their diameter to the hotplates of laboratory magnetic stirrers (e.g. Heidolph Mr 2002). These aluminium blocks were provided with ten holes 7 cm deep and the same diameter as the reaction vessels, and a hole for accommodating a temperature sensor. (0097) Vacuum distributors for connection to the Schlenk line were made for the simultaneous evacuation and refilling of ten vessels at a time. For this purpose, ten vacuum-compatible 3 mm Teflon tubes were each connected at one end with adapters to accommodate Luer-Lock syringe needles and were connected at the other end to a steel tube, which can be connected via a vacuum hose to the Schlenk line. (0098) For the implementation of the experiments, the aryl bromide (1.00 mmol), the corresponding primary amine (1.00 mmol) and sodium tert-butanolate (118 mg, 1.20 mmol) were weighed out in air into the reaction vessels, 20 mm magnetic stirring cores were added, and the vessels were given an airtight seal with septum caps, using crimping tongs. Ten reaction vessels at a time were introduced into the holes in an aluminium block, and connected to the vacuum distributor via hollow needles which were inserted through the septum caps. (0099) The reaction vessels were subsequently evacuated and charged with nitrogen gas three times in succession, in unison. When the reaction vessels had been given an inert gas atmosphere in this way, pressure compensation with the external atmosphere was produced at the vacuum line via an excess-pressure valve. Using a syringe, a stock solution of [Pd(dippf)(maleimide)](1.24 mg, 0.002 mmol) and dippf (0.85 mg, 0.002 mmol) in toluene (2 mL) was injected through the septum caps. The aluminium block was then brought to 70 C. and the needles of the vacuum distributor were removed. After a reaction time of 20 hours, the vessels were cooled and carefully opened and the reaction medium was diluted with dichloromethane (30 mL) and water (30 mL). The aqueous phase was adjusted to a pH of 7 using 1N hydrochloric acid, separated from the organic phase and extracted with dichloromethane (2×20 mL). The combined organic phases were dried over magnesium sulphate, filtered and finally analyzed by thin-layer chromatography. (0100) The solvent was removed under reduced pressure (40 C., 500 mbar) and the crude product which remained was purified by column chromatography (basic Al2O3, diethyl ether:hexane or ethyl acetate:hexane). Example 4a Synthesis of Compound 3a (0101) (0102) According to the general protocol, compound 3a was prepared starting from 1a (398 mg, 1.00 mmol) and 2a (209 mg, 1.00 mmol) and was isolated by column chromatography (Al2O3, diethyl ether:hexane=1:1) in 94% yield (496 mg, 0.94 mmol). 1H NMR (400 MHz, chloroform-d): delta=8.41 (d, J=1.3 Hz, 1H), 8.26 (d, J=7.8 Hz, 1H), 7.75-7.60 (m, 9H), 7.55-7.44 (m, 5H), 7.41-7.21 (m, 6H), 7.13 (d, J=7.0 Hz, 1H), 5.91 (s, 1H), 1.55 ppm (s, 6H), 13C NMR (101 MHz, chloroform-d): delta=155.3, 153.1, 142.6, 142.0, 141.3, 140.0, 139.3, 137.7, 134.6, 133.2, 132.5, 129.9 (2C), 128.1, 127.4 (2C), 127.0 (2C), 126.9, 126.0 (2C), 125.0, 123.9, 123.5 (2C), 122.4, 120.8, 120.3, 120.0, 119.9, 119.1, 118.1, 116.8, 112.2, 110.0, 109.9, 46.8, 27.2 ppm (2C). CHN: Calculated for C3H30N2: C, 88.94; H, 5.74; N, 5.32. found: C, 88.79; H, 5.86; N, 5.19.
94%	With 1,1'-bis(diisopropylphosphino)ferrocene; 1,1?-bis(diisopropylphosphino)ferrocene palladium(0)-maleimide; sodium t-butanolate; In toluene; at 70℃; for 20h;Schlenk technique; Sealed tube; Inert atmosphere;	General procedure: All tests were carried out in 20 mL headspace vials for the gas chromatography, which vials were sealed with aluminum flange caps with teflon-coated butyl rubber septa (both available, for example, from VWR). To control the temperatures of the vessels, 8 cm-high cylindrical aluminum blocks were used, the diameter of which exactly corresponds to that of the hot plates of laboratory magnetic stirrers (e.g. Heidolph Mr 2002). These aluminum blocks were provided with ten 7 cm deep holes with the diameter of the reaction vessels and a hole for accommodating a temperature sensor. To enable the simultaneous evacuation and refilling of ten vessels, vacuum distributors were manufactured for connection to the Schlenk line. To this end, ten 3 mm vacuum-tight teflon hoses were respectively connected at one end to adapters to accommodate Luer Lock syringe needles and at the other end to a steel tube that can be connected to the Schlenk line via a vacuum hose. To carry out the tests, the aryl bromide (1.00 mmol), the corresponding primary amine (1.00 mmol) and sodium-tert-butanolate (118 mg, 1.20 mmol) were weighed out in air into the reaction vessels, 20 mm magnetic stirring bars were added and the vessels were sealed airtight with septa caps using flanging pliers. 10 reaction vessels were respectively inserted into the holes of an aluminum block and connected to the vacuum distributor via cannulas, which were bored through the septa caps. The reaction vessels were then collectively evacuated and flushed with nitrogen three times in succession. After the reaction vessels were provided with an inert gas atmosphere in this way, a pressure equalization with the outside atmosphere was created in the vacuum line via the relief valve. A stock solution of [Pd(dippf)(maleimide)] (1.24 mg, 0.002 mmol) and dippf (0.85 mg, 0.002 mmol) in toluene (2 mL) was injected through the septa caps with the aid of a syringe. The aluminum block was then brought to 70 C. and the needles were removed from the vacuum distributor. After a reaction time of 20 hours, the vessels were carefully opened after cooling and the reaction medium was diluted with dichloromethane (30 mL) and water (30 mL). The aqueous phase was set to pH=7 with 1N hydrochloric acid, separated from the organic phase and extracted with dichloromethane (2×20 mL). The combined organic phases were dried over magnesium sulfate, filtered and then investigated using thin layer chromatography. The solvent was removed in vacuum (40 C., 500 mbar) and the remaining raw product was cleaned using column chromatography (basic Al2O3, diethyl ether:hexane or ethylacetate:hexane).
85%	With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; at 100℃; for 5h;	10.5 g (50 mmol) of Intermediate a, 19.9 g (50 mmol) of Intermediate d, 1.35 g (3.0 mole %) of Pd2(dba)3, 7.2 g (75 mmol) of sodium tert-butoxide, and 300 mg (3.0 mole%) of P(t-Bu)3 were added to 300 mL of toluene, and the mixture was refluxed while stirring at 100C for 5 hours. The reaction mixture was cooled to room temperature and subjected to extraction with methylene chloride and H2O. Then, the resultant was dried using magnesium sulfate to evaporate the solvent. The residue was separately purified using silica gel column chromatography to obtain 22.5 g of Intermediate e (Yield: 85%). The produced compound was identified using LC-MS. C39H30N2: M+ 526.24

74%

With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; at 90℃; for 6h;Inert atmosphere;

100 mL of toluene was added to a mixture including 11.9 g (30.0 mmol) of compound 7, 7.53 g (39.0 mmol) of compound 3, 4.3 g (45.0 mmol) of NaOtBu, 1.4 g (1.5 mmol) of Pd2(dba)3, and 0.30 g (1.5 mmol) of PtBu3 and then the mixture was heated at 90 C. in a nitrogen atmosphere for 6 hours. The reaction mixture was cooled to room temperature, 30 mL of water was further added to the reaction mixture, and the reaction mixture was subjected to extraction twice with 200 mL of methylene chloride. The resultant organic layer was dried, filtered, concentrated, and then separated using column chromatography to obtain 11.6 g of compound 10 in pale yellow solid form with a yield of 74%. The structure of compound 10 was identified using HR-MS. (calc.: 526.2409, found: 526.2413)

Reference： [1]Advanced Synthesis and Catalysis,2016,vol. 358,p. 1589 - 1594
[2]Patent: US2016/257650,2016,A1 .Location in patent: Paragraph 0096 - 0102
[3]Patent: US2020/31803,2020,A1 .Location in patent: Paragraph 0137-0142; 0143-0144
[4]Patent: EP2554545,2013,A1 .Location in patent: Paragraph 0152; 0154
[5]Patent: US8865322,2014,B2 .Location in patent: Page/Page column 39; 40

7
[ 605644-46-0 ]
[ 108714-73-4 ]

Yield	Reaction Conditions	Operation in experiment
88%	With palladium on activated charcoal; hydrazine hydrate; In ethanol; for 4h;Reflux;	10 g of <strong>[605644-46-0]2-nitro-9,9-dimethylfluorene</strong> was added to the reaction flask, and stirred and dissolved with 80 m of ethanol.When <strong>[605644-46-0]2-nitro-9,9-dimethylfluorene</strong> is completely dissolved into a clear solution,30 m L of hydrazine hydrate was added dropwise. After the addition was completed, 2 g of palladium on carbon catalyst was added, and then refluxed for 4 h. Finally, the color of the reaction liquid was very bright and dark red.Then directly hot filter,distillation under reduced pressure gave 7.7 g of a white solid, yield 88%, product content 99%.
81%	With palladium 10% on activated carbon; hydrogen; In ethanol; for 24h;	23.9 g (100.0 mmol) of compound 2 and 0.5 g of 10% Pd on activated charcoal were diluted with 500 mL of ethanol and stirred for 24 hours in a hydrogen atmosphere. The reactant was filtered to remove a catalyst, concentrated, and then separated using column chromatography to obtain 16.9 g of compound 3 in light-yellow solid form with a yield of 81%. The structure of compound 3 was identified using high-resolution mass spectrometry (HR-MS). (calc.: 209.1204, found: 209.1194)
		C. C step b dissolved in methanol in the resulting compound, then adding activated carbon, six hydrated ferric chloride, heating to reflux 10 min, slowly dropping 85% hydrazine hydrate, under the protection of nitrogen to continue reaction 2h, oil filtration to remove insoluble matter, the filtrate after turns on lathe does ethyl acetate extraction, drying by anhydrous sodium sulfate, concentrated to obtain yellow solid 2-amino -9,9 the base fluorene-diethyl [...], referred to as compound D;

Reference： [1]Journal of Materials Chemistry B,2013,vol. 1,p. 5450 - 5455
[2]Patent: CN109824523,2019,A .Location in patent: Paragraph 0018
[3]Patent: US8865322,2014,B2 .Location in patent: Page/Page column 26; 37; 38
[4]Patent: CN105418515,2016,A .Location in patent: Paragraph 0012; 0040

8
[ 108714-73-4 ]
[ 502161-03-7 ]
C₄₆H₃₆N₂O [ No CAS ]

Reference： [1]Patent: US8865322,2014,B2

9
[ 4569-45-3 ]
[ 108714-73-4 ]

Reference： [1]Patent: US8865322,2014,B2
[2]Patent: CN105418515,2016,A
[3]Patent: CN109824523,2019,A

10
[ 108714-73-4 ]
C₃₁H₂₈BrN [ No CAS ]
C₄₆H₄₂N₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
74%	With bis(dibenzylideneacetone)-palladium(0); sodium t-butanolate; In toluene; at 95℃; for 4h;	General procedure: Intermediates 1-1 (5.0 g, 0.018 mol), 4-bromo-N,N-dip-tolylaniline (12.5 g, 0.036 mol), Pd(dba)2 (0.8 g, 0.0009 mol), sodium-tert-butoxide (3.5 g, 0.052 mol) in TOL 200 ml was reacted at 95 C for 4 hours. Reaction after column purification separation H20:MC (n-HEXANE: MC) 11.2 g (75% yield) of compound 1 are obtained. Intermediates 20-2 (5.0 g, 0.010 mol) to <strong>[108714-73-4]9,9-dimethyl-9H-fluoren-2-amine</strong> (2.1 g, 0.010 mol) for inserting and removing manufacturing e.g. in the embodiment 1-(2) the same method used in the synthesis of <intermediate 20-3> 4.6 g (74% yield) is obtained. (m/z=622)

Reference： [1]Patent: KR2015/131700,2015,A .Location in patent: Paragraph 0104; 0347; 0354-0356

11
[ 108714-73-4 ]
C₂₈H₂₅Br [ No CAS ]
C₄₃H₃₉N [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
75%	With bis(dibenzylideneacetone)-palladium(0); sodium t-butanolate; In toluene; at 95℃; for 4h;	General procedure: Intermediates 1-1 (5.0 g, 0.018 mol), 4-bromo-N,N-dip-tolylaniline (12.5 g, 0.036 mol), Pd(dba)2 (0.8 g, 0.0009 mol), sodium-tert-butoxide (3.5 g, 0.052 mol) in TOL 200 ml was reacted at 95 C for 4 hours. Reaction after column purification separation H20:MC (n-HEXANE: MC) 11.2 g (75% yield) of compound 1 are obtained. Intermediates 21-1 (5.0 g, 0.011 mol) to <strong>[108714-73-4]9,9-dimethyl-9H-fluoren-2-amine</strong> (2.3 g, 0.011 mol) for inserting and removing manufacturing e.g. in the embodiment 1-(2) the same method used in the synthesis of <intermediate 21-2> 4.7g (yield 75%) is obtained. (m/z=569)

Reference： [1]Patent: KR2015/131700,2015,A .Location in patent: Paragraph 0104; 0362; 0366-0368

12
[ 108714-73-4 ]
[ 108-24-7 ]
[ 63021-04-5 ]

Yield	Reaction Conditions	Operation in experiment
99.7%	In acetic acid; at 25℃; for 24h;	1. 2-Amino-9,9-dimethyl-fluorene (SM, 313.9g, 1500mmol) was added to a 3L 4-neck flask, and then addthe acid (1150mL, 1207.5g) was dissolved, stir with a mechanical stirrer .Acetic anhydride (285 mL, 307.8 g, 3015 mmol) was slowly added dropwise (3.3 h)from the constantpressure dropping funnel withstirring at room temperature (about 25C).After the addition was completed,stirringwas continued at room temperature (about25 C.), during which a large amount of white precipitate was precipitated, and the reaction time was about 24 h (6 h, control 1; 24 h control 2).The reaction solution was pouredinto 5L of water and mechanically stirred at room temperature (about 25C) for 30 min.The mixture was filtered under reduced pressure and the cake was washed with water until neutral.After drying in a forced air oven (about50 C.) (12 h), a white powdered solid I (375.7 g, yield 99.7%, HPLC content 99.6%) was obtained.
	With acetic acid; In acetic anhydride; at 20℃; for 5h;	D. The resulting compound of step c dissolved in glacial acetic acid in D, slowly adding 8 times equivalent second grade acid anhydride, room temperature reaction 5h, is poured into the ice water, precipitated soil white precipitate, and washing, drying to obtain soil white solid 2-acetyl -9,9 the base fluorene-diethyl [...], referred to as compound E;
	In dichloromethane; for 3h;	25 g of 2-amino-9,9-dimethylfluorene was added to 80 ml of dichloromethane, and 12.8 ml of acetic anhydride was added dropwise with stirring.After stirring for about 3 hours, it was confirmed that the raw material was exhausted by thin layer chromatography (ethyl acetate/hexane=1/2) analysis.

Reference： [1]Patent: CN107556229,2018,A .Location in patent: Paragraph 0030; 0047
[2]Patent: CN105418515,2016,A .Location in patent: Paragraph 0012; 0041
[3]Patent: KR2019/50646,2019,A .Location in patent: Paragraph 0090; 0091

13
[ 108714-73-4 ]
[ 57102-42-8 ]
N-(4-(9H-carbazol-9-yl)phenyl)-9,9-dimethyl-9H-fluoren-2-amine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
75%	With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; at 110℃; for 5h;Inert atmosphere;	9,9 g of 50.0 (238.90 mmol) of 9- (4-bromophenyl) -9H-carbazole, 43.94 g (262.79 mmol) under nitrogen gas stream dimethyl-9H-fluoren-2-amine, 6.56 g (7.17 mmol) of Pd2 (dba) 3, 4.84 g (23.89 mmol) of P (t-bu) 3, 57.40 Mixing NaO (t-bu), and toluene (1000 ml) of g (597.26 mmol) and stirred for 5 hours at 110 . After completion of the reaction extracted with dichloromethane, which was put into the filter MgSO4. The solvent of the filtered organic layer column chromatography Using a blood desired compound 80.73 g: was obtained (yield 75%). GC-Mass (theoretical value: 450.57 g / [0101] mol, measured value: 450 g / mol)

Reference： [1]Patent: KR2016/12500,2016,A .Location in patent: Paragraph 0098-0100

14
[ 108714-73-4 ]
[ 212385-73-4 ]
[ 1267248-54-3 ]

Yield	Reaction Conditions	Operation in experiment
52%	With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; at 110℃; for 5h;Inert atmosphere;	9 - (4'-bromo-(1,1'-biphenyl)-4-yl) -9H-carbazole of 20.0 g (50.21 mmol), <strong>[108714-73-4]9,9-dimethyl-9H-fluoren-2-amine</strong> of 10.51 g (50.21 mmol), the Pd 2 (dba) 3 of 1.38 g (1.51 mmol), P (t-bu) 3 of 1.02 g (5.02 mmol), and the NaO (t-bu) and toluene (300 ml) of 12.06 g (125.54 mmol) were mixed under the nitrogen air current and it was stirred in 110 for 5 hours. It extracted in the dichloromethane after the reaction termination and the MgSO 4 was put and it filtered. The intended compound 12.06 g (yield: 52 %) was obtained using the column chromatography after the solvent of the filtered organic layer was removed

Reference： [1]Patent: KR2016/12500,2016,A .Location in patent: Paragraph 0188-0190

15
[ 955959-84-9 ]
[ 108714-73-4 ]
[ 1267248-96-3 ]

Yield	Reaction Conditions	Operation in experiment
90%	With tri-tert-butyl phosphine; bis(dibenzylideneacetone)-palladium(0); sodium t-butanolate; In toluene; for 4h;Inert atmosphere; Reflux;	Intermediate M-1 15g (46.4mmol) in a round bottom flask and 9,9-Dimethyl-9H-fluoren-2-ylamine 4.8g (23.2mmol),sodium-t- butoxide 6.7g (69.6mmol) ofIt was dissolved in toluene into a 185ml. Here Pd (dba) 2 0.53g (0.928mmol) and tri-tert-butylphosphine was placed to 0.38g (1.86mmol) in turn and the mixture was stirred under reflux for 4 hours under a nitrogen atmosphere. After completion of the reaction and then extracted with toluene the organic layer was dried and distilled over magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure. The product n- hexane / dichloromethane (8: 2 by volume) to give compound 8 as a purification by a silica gel column chromatography as a white solid 14.4g (90percent yield).
85%	With tri-tert-butyl phosphine; bis(dibenzylideneacetone)-palladium(0); sodium t-butanolate; In toluene; for 4h;Inert atmosphere; Reflux;	15 grams (46.4 millimoles) of intermediate M-1, 4.9 g (23.2 mmol) of 9,9-dimethyl-9H-indol-2-amine and 6.7 grams (69.6 millimoles) Sodium tert-butoxide (NaOt-Bu) was placed in a round bottom flask, And 160 ml of toluene was added thereto to dissolve it. Subsequently, 0.85 g (0.928 mmol) of Pd(dba)2 was sequentially added thereto. And 0.45 g (1.86 mmol) of tri-tert-butylphosphine (P(t-Bu)3), and the mixture was refluxed under a nitrogen atmosphere and stirred for 4 hours. When the reaction was completed, the resultant was extracted with toluene and distilled water, and the organic layer obtained therefrom was dried over magnesium sulfate and filtered, and the filtered solution was concentrated under reduced pressure. Subsequently, the product obtained therefrom was purified by hydrazine column chromatography using n-hexane/dichloromethane (8:2 by volume) to obtain 27.4 g of Compound I-61 (yield: 85percent).

Reference： [1]Patent: KR2016/12846,2016,A .Location in patent: Paragraph 0216; 0220; 0221; 0222
[2]Patent: TW2016/2060,2016,A .Location in patent: Paragraph 0107

16
[ 108714-73-4 ]
C₃₂H₂₂BrN [ No CAS ]
C₄₇H₃₆N₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
74%	With tris-(dibenzylideneacetone)dipalladium(0); triphenylphosphine; sodium t-butanolate; In toluene; at 100℃; for 24h;	To a round bottom flask Sub 2-1 (2) (10.0g, 20mmol), Sub 2-2 (10) (4.2g, 20mmol),Pd2 (dba) 3 (0.9g, 1mmol), PPh3 (0.5g, 2mmol ), NaOt-Bu (5.8g, 60mmol), were addedto toluene (210mL), respectively, and refluxed under stirring for 24 hours at 100 C.Organic layer is dried ether and extracted with water and silicagel column and recrystallized with MgSO4 and the resulting organic one was concentrated by Sub 2 (9)to 9.3g (yield: 74%) was obtained.

Reference： [1]Patent: KR2015/93995,2015,A .Location in patent: Paragraph 0207; 0209-0211

17
[ 108714-73-4 ]
[ 1242056-42-3 ]

Reference： [1]Advanced Synthesis and Catalysis,2016,vol. 358,p. 1589 - 1594
[2]Patent: US2020/31803,2020,A1

18
[ 108714-73-4 ]
[ 92-66-0 ]
[ 897671-69-1 ]

Yield	Reaction Conditions	Operation in experiment
92%	With [Pd(N,N'-bis(2,6-bis(di-p-tolylmethyl)-4-methylphenyl)-imidazol-2-ylidene)(acetylacetonate)Cl]; lithium hexamethyldisilazane; In 1,4-dioxane; at 110℃; for 3h;Inert atmosphere; Sealed tube;	General procedure: A glassvial was charged with [Pd(IPr*me)(acac)Cl],neat amine (1.1 mmol), and the arylhalide (1 mmol) in dry 1,4-dioxane (1 mL) under an atmosphere of argonand sealed with a screw cap fitted with aseptum. LiHMDS (1.1 mmol) was subsequently injected at roomtemperature under argon, the reaction mixture was then refluxed at 110 for 3 h, After this time, dioxane was evaporated, the crude product wasdissolved in CH2Cl2. The solution was filtered on a padof silica covered with Celite, and thepad was eluted with CH2Cl2. After chromatography onsilica gel, the pure complex was obtained.
84%	With tris-(dibenzylideneacetone)dipalladium(0); sodium t-butanolate; XPhos; In toluene; at 108℃; for 2h;Inert atmosphere;	4-bromobiphenyl (10.0 g, 42.9 mmol),2-amino-9,9-dimethyl-fluorene (9.88g, 47.2mmol),Tris(dibenzylideneacetone)dipalladium (0.39 g, 0.43 mmol), 2-dicyclohexylphosphino-2,4,6-triisopropylbiphenyl (0.41 g, 0.86 mmol) and sodium tert-butoxide ( 6.18g, 64.3mmol)Add toluene (80 mL), heat to 108 C under nitrogen, stir for 2 h;After cooling to room temperature, the reaction solution was washed with water and dried over magnesium sulfate.After filtration, the filtrate was removed under reduced pressure; using dichloromethane/ethanol systemThe crude product was recrystallized and purified to give pale-yellow solid intermediate II-A (13.1 g, 84%).
84%	With tris-(dibenzylideneacetone)dipalladium(0); sodium t-butanolate; XPhos; In toluene; at 105 - 110℃; for 1h;Inert atmosphere;	4-bromobiphenyl (10.0 g, 42.9 mmol),<strong>[108714-73-4]2-amino-9,9-dimethylhydrazine</strong> (9.88 g, 47.2 mmol),Tris(dibenzylideneacetone)dipalladium (0.39 g, 0.43 mmol),2-Dicyclohexylphosphino-2,4,6-triisopropylbiphenyl (0.41 g, 0.86 mmol) and sodium tert-butoxide (6.18 g, 64.3 mmol) were added to toluene (100 mL).Heating to 105-110 C under nitrogen protection, stirring for 1 h;After cooling to room temperature, the reaction solution was washed with water and dried over magnesium sulfate.After filtration, the filtrate was passed through a short silica gel column, and the solvent was removed under reduced pressure;The crude product was recrystallized and purified using a dichloromethane/ethanol system.The light gray solid intermediate II-A (13.1 g, 84%) was obtained.

82.7%	With tris-(dibenzylideneacetone)dipalladium(0); sodium t-butanolate; In toluene; at 80℃; for 6h;	<strong>[108714-73-4]2-amino-9,9-dimethylhydrazine</strong> 63.0 g (300 mmol), 4-bromobiphenyl 61.0 g (360 mmol) and sodium tert-butoxide 72 g (0.65 mol) were added to the three-necked flask.Pd2 (dba) 10.4 g (0.5 mmol), toluene 500 m L, and reacted at 80 C (bath temperature) for 6 h with stirring. Pour into 500 m L of water, extract with toluene (3 × 100 mL), combine the extracts, decolorize with 10 g of activated carbon, and concentrate under reduced pressure to obtain a dark gray solid, which is recrystallized from toluene: cyclohexane = 1:3 mixed solvent. White solid 2-(4-biphenyl)amino-9,9-dimethylhydrazine (1) 89.8 g, yield 82.7%, purity 99.5%,
81%	With tri-tert-butyl phosphine; palladium diacetate; sodium t-butanolate; In toluene; for 6h;Inert atmosphere;	A solution of 9,9-dimethyl-7-aminofluorene 49 mmol was added4-bromobiphenyl was dissolved in 400 mL of toluene,The solution was degassed and saturated with nitrogen,Then 2.43 mmol of 1M tri-tert-butylphosphine solution and 1.21 mmol were addedOf palladium (II) acetate,And then 146 mmol of sodium tert-butoxide was added. The reaction mixture was heated under boiling in a protective atmosphere for 6 hours,The mixture was then partitioned between toluene and water, the organic phase was washed three times with water and dried over sodium sulfate, and the mixture was stirred on a rotary evaporator, The residual residue was recrystallized from heptane / toluene after the crude product was filtered through silica gel using toluene and finallyDegassed in a high vacuum to give compound C-1. The yield was 20 g (81% of the theoretical value).
81%	With tris-(dibenzylideneacetone)dipalladium(0); sodium t-butanolate; XPhos; In toluene; at 105 - 110℃; for 1h;Inert atmosphere;	4-bromobiphenyl (10.0 g, 42.9 mmol),<strong>[108714-73-4]2-amino-9,9-dimethylhydrazine</strong> (9.9 g, 47.2 mmol),Tris(dibenzylideneacetone)dipalladium (0.4 g, 0.4 mmol),2-Dicyclohexylphosphino-2,4,6-triisopropylbiphenyl (0.4 g, 0.9 mmol) and sodium tert-butoxide (6.2 g, 64.4 mmol) were added to toluene (100 mL).Heated to 105-110 C under nitrogen protection,Stir for 1 hour;The mixture was cooled to room temperature, and the reaction mixture was washed twice with water, dried over magnesium sulfate, filtered, and then filtered, and the filtrate was passed through a silica gel column, and the solvent was removed under reduced pressure.The light gray solid intermediate I-B (12.5 g, 81%) was obtained.
72%	With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; for 12h;Reflux;	<strong>[108714-73-4]9,9-dimethyl-9H-fluoren-2-amine</strong> (15.0 g, 71.67 mmol) 18.4 g of 4-bromo-1,1'-biphenyl(1.43 mmmol) of tris (dibenzylideneacetone) dipalladium (0) was suspended in 239 ml of toluene, followed by addition of tri-tert-butylphosphine 1.4 mL (5.73 mmol) was added thereto, followed by reflux stirring for 12 hours. Extracted with dichloromethane and distilled water, and the organic layer is subjected to silica gel filtration. The organic solution was removed and recrystallized from dichloromethane and hexane to obtain 18.6 g (yield: 72%) of the intermediate product (O).
60%	With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In 5,5-dimethyl-1,3-cyclohexadiene; toluene; for 12h;Inert atmosphere; Reflux;	Add 9,9-Dimethyl-9H-fluoren-2-ylamine (9,9-Dimethyl-9H-fluoren-2-ylamine) (17.4 g, 83.0 mmol),4-bromo-biphenyl (15.5 g, 66.4 mmol),Sodium tert-butoxide (NaOtBu) (12.0 g, 124.5 mmol),Pd2 (dba) 3 (4.6 g, 5.0 mmol) and tri-tert-butylphosphine (P (tBu) 3)(6.0 g, 50% in toluene) put in xylene (400 ml)And then heated and refluxed under a stream of nitrogen for 12 hours. After removing xylene,Process the remainder via column chromatography to obtain 18.0 g of intermediateA-38-1 (60%).
60%	With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In 5,5-dimethyl-1,3-cyclohexadiene; toluene; for 12h;Inert atmosphere; Reflux;	Add <strong>[108714-73-4]9,9-dimethyl-9H-fluoren-2-ylamine</strong> (17.4 g, 83.0 mmol),4-bromo-biphenyl (15.5 g, 66.4 mmol), sodium tert-butoxide (NaOtBu) (12.0 g, 124.5 mmol), Pd2 (dba) 3(4.6 g, 5.0 mmol) and tri-tert-butylphosphine (P (t-Bu) 3) (6.0 g,50% in toluene) in xylene (400 ml),It was then heated and refluxed under a stream of nitrogen for 12 hours. After removing the xylene,The residue was processed by column chromatography to obtain 18.0 g of intermediateA-38-1 (60%).
	With tris-(dibenzylideneacetone)dipalladium(0); tert-butylphosphine; sodium t-butanolate; In toluene;Inert atmosphere; Reflux;	Step c1The aryl halides were weighed according to a molar ratio of 1:0.95:0.001:0.004:1.5.9,9-alkyl-2-aminoindole compound, Pd2 (DBA) 3, tert-butylphosphine, sodium t-butoxide, ready for use;Step c2, dissolving the aryl halide obtained in step c1 in a toluene solvent,The mass ratio of the aryl halide to the toluene is 1:10,Then adding the 9,9-alkyl-2-aminoindole compound weighed in step c1,Pd2 (DBA) 3, tert-butylphosphine, sodium tert-butoxide, under the protection of nitrogen,The temperature is raised to reflux, and the reaction is carried out for 2 to 4 hours to obtain a reaction liquid c, which is ready for use;Step c3, adding the reaction liquid c obtained in the step c2 to 1 volume of purified water,After the water is separated, the organic layer is passed through a silica gel column at 60 to 70 C.After the effluent was distilled out 3/5 times the volume of toluene, 3 times of isopropanol was quickly added.Stirring conditions are lowered to 15 C, filtered, and dried.A synthetic product of an aryl halide and a 9,9-alkyl-2-aminoindole compound is obtained.a method for preparing a silicon-containing organic electroluminescent material according to the embodiment,The aryl halide in step c1 is 4-bromobiphenyl,9,9-alkyl-2-aminoindole compound is9,9-dimethyl-2-Amino.

Reference： [1]Journal of Organometallic Chemistry,2018,vol. 861,p. 125 - 130
[2]Advanced Synthesis and Catalysis,2016,vol. 358,p. 1589 - 1594
[3]Patent: CN110128279,2019,A .Location in patent: Paragraph 0049; 0050
[4]Patent: CN110105225,2019,A .Location in patent: Paragraph 0102-0103
[5]Patent: CN109824523,2019,A .Location in patent: Paragraph 0019
[6]Patent: CN106632219,2017,A .Location in patent: Paragraph 0077; 0078; 0079; 0080
[7]Patent: CN110183332,2019,A .Location in patent: Paragraph 0071; 0072
[8]Patent: KR2016/102142,2016,A .Location in patent: Paragraph 0308; 0311-0313
[9]Patent: TW2019/43698,2019,A .Location in patent: Paragraph 0193-0196
[10]Patent: TW2019/43699,2019,A .Location in patent: Paragraph 0222-0223
[11]Patent: CN110128460,2019,A .Location in patent: Paragraph 0063; 0080-0084; 0095; 0112-0116

19
[ 39195-66-9 ]
[ 108714-73-4 ]
C₄₃H₃₁NO₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
85%	With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; at 100℃; for 72h;Inert atmosphere;	9, 9-dimethyl-9H-fluoren-2-amine (15.5 g, 74.1 mmol) was dissolved in 0.35 L of toluene under a nitrogen atmosphere,To this was added intermediate I-1 (50.8 g, 222.2 mmol), tris (diphenylideneacetone) dipalladium (0) (2.0 g, 2.22 mmol), tris-tert-butylphosphine (1.80 g , 4.23 mmol) and sodium tert-butoxide (15.7 g, 162.9 mmol) were sequentially added, and the mixture was heated under reflux at 100 C. for 3 days.After completion of the reaction, water was added to the reaction solution, and the mixture was extracted with dichloromethane (DCM). After removal of moisture with anhydrous MgSO 4, filtration and concentration under reduced pressure.The residue thus obtained was separated and purified by flash column chromatography to obtain Compound 1 (37.4 g, 85%).

Reference： [1]Patent: JP2016/505611,2016,A .Location in patent: Paragraph 0182-0184

20
[ 63676-27-7 ]
[ 108714-73-4 ]
C₄₃H₃₁NS₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
93%	With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; at 100℃; for 25h;Inert atmosphere;	Under a nitrogen atmosphere, 9,9-dimethyl -9H- fluorene-2-amine (19.4g, 92.9mmol) after dissolved in toluene 0.35 L, this intermediate I-2 (50g, 204.3mmol ), tris (di-phenylene) dipalladium (0) (2.55g, 2.79mmol) ,tris -tert- butyl phosphine (2.26g, 11.1mmol), and sodium tert- butoxide (19.6g, 204.4mmol) in that order, and the mixture was heated to reflux at 100 25 hours.After completion of the reaction, water was added to the reaction solution was extracted with dichloromethane (DCM), anhydrous MgSO4After removal of the moisture, filtered, and concentrated in vacuo.The thus obtained residue was separated and purified by flash column chromatography to give compound 3 (54.0g, 93%).

Reference： [1]Patent: JP2016/505611,2016,A .Location in patent: Paragraph 0186-0188

21
[ 108-86-1 ]
[ 108714-73-4 ]
[ 355832-04-1 ]

Yield	Reaction Conditions	Operation in experiment
80%	With tris-(dibenzylideneacetone)dipalladium(0); sodium t-butanolate; XPhos; In toluene; for 2h;Inert atmosphere; Reflux;	Bromobenzene (10g, 63.7mmol),2-amino-9,9-dimethyl-fluorene (14.7g, 70.1mmol),Tris(dibenzylideneacetone)dipalladium (1.2 g, 1.3 mmol),2-dicyclohexylphosphorus-2,4,6-triisopropylbiphenyl (1.2 g, 2.5 mmol)And sodium tert-butoxide (9.2 g, 95.5 mmol) was added to toluene (150 mL).Heating to reflux temperature under nitrogen protection, stirring for 2 h;After cooling to room temperature, the reaction solution was washed with water and dried over magnesium sulfate.After filtration, the filtrate was passed through a short silica gel column, and the solvent was removed under reduced pressure;The crude product was recrystallized and purified using a dichloromethane/ethanol system.14.5 g of a white solid intermediate 4-B was obtained in a yield of 80%.
	With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; at 100℃;	General procedure: Sub 3-1 (1 eq.), Sub 3-2 (1.1 eq.), Pd2(dba)3 (0.05 eq.),P(t-Bu)3 (0.1 eq.), NaOt-Bu (3 eq.), and toluene (10.5 mE/immol starting material) were added to a round-bottomedflask and then, the reaction was performed thereon at atemperature of 1000 C. When the reaction stopped, and extraction process was performed thereon by using ether and water, and then, an organic layer was dried and concentrated by using Mg504, and then, the obtained organic material was purified by silicagel colunm chromatography and recrystallized obtain Sub 3.

Reference： [1]Patent: CN109593042,2019,A .Location in patent: Paragraph 0075; 0076
[2]Patent: US9515265,2016,B2 .Location in patent: Page/Page column 109; 121

22
[ 108714-73-4 ]
[ 1161009-88-6 ]
(9,9-dimethyl-9H-fluoren-2-yl)-(9,9-spirobifluoren-4-yl)amine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
92%	With 1,1'-bis-(diphenylphosphino)ferrocene; palladium diacetate; sodium t-butanolate; In toluene; for 20h;Reflux;	1 ,1 '-Bis(diphenylphosphino)ferrocene (0.83 g, 1.49 mmol), palladium acetate (0.34 mg, 1.49 mmol) and sodium tert-butoxide (9.3 g, 97.1 mmol) are added to a solution of fluoren-2-yl-amine (15.6 g, 97.1 mmol) and 4-bromo-9,9-spiro-bifluorene (30.0 g, 97.1 mmol) in degassed toluene (500 ml), and the mixture is heated under reflux for 20 h. The reaction mixture is cooled to room temperature, extended with toluene and filtered through Celite. The filtrate is extended with water, re-extracted with toluene, and the combined organic phases are dried and evaporated in vacuo. The residue is filtered through silica gel (heptane/dichloromethane) and crystallised from heptane/toluene. (9,9-dimethyl-9H-fluoren-2-yl)-(9,9- spirobifluoren-4-yl)-amine is obtained as a off-white solid (36.0 g, 92% of theory).

Reference： [1]Patent: WO2017/12687,2017,A1 .Location in patent: Page/Page column 48; 49

23
[ 108714-73-4 ]
[ 1285719-59-6 ]
C₃₉H₃₀N₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
97%	With 1,1'-bis(diisopropylphosphino)ferrocene; [Pd(dippf)(maleimide)]; sodium t-butanolate; In toluene; at 70℃; for 20h;Inert atmosphere;	Example 3a Use of [Pd(Dippf)(Maleimide)] as Palladium Complex (0089) A dry three-necked flask with reflux condenser, gas inlet, excess-pressure valve and magnetic stirring rod was charged with the aryl bromide 132 (7.97 g, 20.0 mmol), the amine 131 (4.17 g, 20.0 mmol), 1,1?-bis(diisopropylphosphino)ferrocene (8.5 mg, 0.02 mmol) and sodium tert-butanolate (2.35 g, 24.0 mmol) and was brought under a nitrogen atmosphere by multiple evacuation and gas admission. Toluene (30 mL) and [Pd(dippf)(maleimide)](24.9 mg, 0.04 mmol, from example 2) in toluene (10 mL) were added and the mixture was heated at 70 C. for 20 hours. The reaction was monitored by thin-layer chromatography and it was found that after this time full conversion had been reached. After cooling had taken place to room temperature, water (60 mL) was added and the reaction mixture was extracted with dichloromethane (150 mL). The organic phase was separated off, dried over magnesium sulphate (5 g) and filtered through basic aluminium oxide (10 g). The solvent was removed under reduced pressure (40 C., 10 mbar) and the slightly yellow residue was washed with diethyl ether (3×20 mL). Drying under reduced pressure (2 h, 10-2 mbar) gave the product as a colourless solid (10.2 g, 19.4 mmol, 97%). (0090) 1H NMR (400 MHz, chloroform-d): delta=8.41 (d, J=1.3 Hz, 1H), 8.26 (d, J=7.8 Hz, 1H), 7.75-7.60 (m, 9H), 7.55-7.44 (m, 5H), 7.41-7.21 (m, 6H), 7.13 (d, J=7.0 Hz, 1H), 5.91 (s, 1H), 1.55 ppm (s, 6H). (0091) 13C NMR (101 MHz, chloroform-d): delta=155.3, 153.1, 142.6, 142.0, 141.3, 140.0, 139.3, 137.7, 134.6, 133.2, 132.5, 129.9 (2C), 128.1, 127.4 (2C), 127.0 (2C), 126.9, 126.0 (2C), 125.0, 123.9, 123.5 (2C), 122.4, 120.8, 120.3, 120.0, 119.9, 119.1, 118.1, 116.8, 112.2, 110.0, 109.9, 46.8, 27.2 ppm (2C). (0092) Elemental analysis: Calculated for C3H30N2: C, 88.94; H, 5.74; N, 5.32. found: C, 88.64; H, 5.91; N, 5.22.
97%	With 1,1'-bis(diisopropylphosphino)ferrocene; 1,1?-bis(diisopropylphosphino)ferrocene palladium(0)-maleimide; sodium t-butanolate; In toluene; at 70℃; for 20h;Inert atmosphere;	The aryl bromide 132 (7.97 g, 20.0 mmol), the amine 131 (4.17 g, 20.0 mmol), 1,1?-bis(diisopropylphosphino)ferrocene (8.5 mg, 0.02 mmol) and sodium-tert-butanolate (2.35 g, 24.0 mmol) were introduced in a dry three-necked flask with reflux condenser, gas inlet, relief valve, and magnetic stirring rod and brought under a nitrogen atmosphere by repeated evacuation and gassing. Toluene (30 mL) and [Pd(dippf)(maleimide)] (24.9 mg, 0.04 mmol, from example 2) were added to toluene (10 mL) and the mixture heated for 20 hours to 70 C. The reaction was followed by thin-layer chromatography and it was determined that after this period the full conversion was achieved. After cooling to room temperature, water (60 mL) was added and extracted using dichloromethane (150 mL). The organic phase was separated off, dried over magnesium sulfate (5 g) and filtered through basic aluminum oxide (10 g). The solvent was removed in the vacuum (40 C., 10 mbar) and the slightly yellow residue washed with diethyl ether (3×20 mL). After drying in vacuum (2 h, 10-2 mbar), the product was obtained as a colorless solid (10.2 g, 19.4 mmol, 97%). 1H NMR (400 MHz, chloroform-d): Gamma=8.41 (d, J=1.3 Hz, 1H), 8.26 (d, J=7.8 Hz, 1H), 7.75-7.60 (m, 9H), 7.55-7.44 (m, 5H), 7.41-7.21 (m, 6H), 7.13 (d, J=7.0 Hz, 1H), 5.91 (s, 1H), 1.55 ppm (s, 6H). 13C NMR (101 MHz, chloroform-d): delta=155.3, 153.1, 142.6, 142.0, 141.3, 140.0, 139.3, 137.7, 134.6, 133.2, 132.5, 129.9 (2C), 128.1, 127.4 (2C), 127.0 (2C), 126.9, 126.0 (2C), 125.0, 123.9, 123.5 (2C), 122.4, 120.8, 120.3, 120.0, 119.9, 119.1, 118.1, 116.8, 112.2, 110.0, 109.9, 46.8, 27.2 ppm (2C).

Reference： [1]Patent: US2016/257650,2016,A1 .Location in patent: Paragraph 0088-0095
[2]Patent: US2020/31803,2020,A1 .Location in patent: Paragraph 0129-0133

24
[ 108714-73-4 ]
C₁₈H₁₁BrO₂ [ No CAS ]
C₃₃H₂₅NO₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
83%	With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; potassium tert-butylate; In toluene; at 85℃; for 7h;	Synthesis of Intermediate D-3 2.28 g (6.7 mmol) of Intermediate D-2, 2.1 g (10 mmol) of <strong>[108714-73-4]9,9-dimethyl-9H-fluoren-2-amine</strong>, 0.45 g (0.5 mmol) of Pd2(dba)3, 0.1 g (0.5 mmol) of P(tBu)3, and 2.25 g (20.0 mmol) of KOtBu were dissolved in 250 mL of toluene and stirred at a temperature of about 85 C. for 7 hours. The result mixture was cooled to room temperature, and an organic layer was extracted therefrom three times using 150 mL of water and 150 mL of diethyl ether. The obtained organic layer was dried by using MgSO4, filtered, and the solvent was removed therefrom by evaporation. The obtained residue was separated and purified through silica gel chromatography to obtain 2.61 g of Intermediate D-3 (yield: 83%). The compound thus obtained was identified by LC-MS. C33H27NO2: M+ 469.2

Reference： [1]Patent: US2017/62720,2017,A1 .Location in patent: Paragraph 0361; 0366; 0367

25
[ 108714-73-4 ]
C₁₈H₁₁ BrO₂ [ No CAS ]
C₃₃H₂₅NO₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
80.9%	With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; potassium tert-butylate; In toluene; at 85℃; for 7h;	Synthesis of Intermediate B-3 3.35 g (9.5 mmol) of Intermediate B-2, 3.14 g (15 mmol) of <strong>[108714-73-4]9,9-dimethyl-9H-fluoren-2-amine</strong>, 0.45 g (0.5 mmol) of Pd2(dba)3, 0.1 g (0.5 mmol) of P(tBu)3, and 2.25 g (20.0 mmol) of KOtBu were dissolved in 250 mL of toluene and stirred at a temperature of about 85 C. for 7 hours. The resulting mixture was cooled to room temperature, and an organic layer was extracted therefrom three times using 150 mL of water and 150 mL of diethyl ether. The obtained organic layer was dried using MgSO4, filtered, and the solvent was removed therefrom by evaporation. The obtained residue was separated and purified through silica gel chromatography to obtain 3.59 g of Intermediate B-3 (yield: 80.9%). The compound thus obtained was identified by LC-MS. C33H25NO2: M+ 467.2

Reference： [1]Patent: US2017/62720,2017,A1 .Location in patent: Paragraph 0321; 0326; 0327

26
[ 108714-73-4 ]
[ 696-62-8 ]
N,N-di(4-methoxyphenyl)-2-amino-9,9-dimethylfluorene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
59%	With 18-crown-6 ether; copper; potassium carbonate; In 1,2-dichloro-benzene; at 175℃; for 12h;Inert atmosphere;	1st step reaction: with mechanical stirring in a 250 ml three-necked flask is added 10.0g (48mmol) 2 - amino - 9, 9 - dimethylfluorene, 28.1g (120mmol) 4 - iodo anisole, 16.6g (120mmol) potassium carbonate, 7.6g (120mmol) copper powder, 3.2g (12mmol) 18 - crown ether -6, add 70 ml ortho-dichlorobenzene as solvent, stirring, under the protection of nitrogen, for 175 C under, reaction 12h. The condiments filtered, filtrate slowly pouring in the ethanol, the resulting crude product was toluene/hexane recrystallization (V: V=1:2), to obtain flaxen N, double-N - (4 - methoxyphenyl) - 9, 9 - dimethyl wuwu powder end 12.0g, yield 59%.
56.6%	With 18-crown-6 ether; copper; potassium carbonate; In 1,2-dichloro-benzene; at 175℃; for 20h;Inert atmosphere;	In a 250 mL round-bottom flask equipped with a stirring bar under nitrogen atmosphere, a mixture of 15.0 g (71.7 mmol) of 2-amino-9,9-dimethylfluorene, 41.9 g (179.2 mmol) of 4-iodoanisole, 11.4 g (179.2 mmol) of copper, 24.8 g (179.2 mmol) of potassium carbonate and 4.7 g (17.9 mmol) of 18-crown-6 in 80 mL of dried o-dichlorobenzene was heated with stirring at 175 C for 20 h. The reaction mixture was hot filtered, and the filtrate was poured into 500 mL of stirred ethanol slowly. The precipitated product was collected by filtration and then recrystallized from toluene/n-hexane to afford white crystals 17.1 g in 56.6% yield with a melting point of 149 C. IR (KBr): 1243 cm1, 1035 cm1 (-C-O-Cstretch). 1H NMR (300 MHz, DMSO-d6, d, ppm): 7.64 (d, J 6.7 Hz, 1H, Hf), 7.59 (d, J 8.3 Hz, 1H, He), 7.45 (d, J 6.6 Hz, 1H, Hi), 7.27 (t,J 7.4 Hz, 1H, Hg), 7.20 (t, J 7.4 Hz, 1H, Hh), 7.02 (d, J 9.0 Hz, 4H,Hb), 6.97 (d, J 2.1 Hz, 1H, Hc), 6.90 (d, J 9.0 Hz, 4H, Ha), 6.74 (dd,J 8.3, 2.2 Hz, 1H, Hd), 3.74 (s, 6H, -OCH3), 1.31 (s, 6H, -CH3).

Reference： [1]Patent: CN106631840,2017,A .Location in patent: Paragraph 0068; 0069
[2]Polymer,2017,vol. 116,p. 89 - 98

27
[ 108714-73-4 ]
[ 13438-50-1 ]
C₃₁H₂₃N [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
31.9 g	With bis(tri-t-butylphosphine)palladium(0); sodium t-butanolate; In toluene; for 3h;Inert atmosphere; Reflux;	The compound <strong>[13438-50-1]3-bromofluoranthene</strong> (30 g, 98 mmol) and 2-amino-9,9-dimethylfluorene (20.5 g, 98 mmol) were completely dissolved in 200 ml of toluene in a nitrogen atmosphere and then NaOt-Bu (11.3 g, 117.6 mmol) The mixture was stirred while increasing the temperature. After refluxing began, Bis (tri-tert-butylphosphine) palladium (0) (0.5 g, 0.98 mmol) was slowly added dropwise. After 3 hours, the reaction was terminated, the temperature was lowered to room temperature, the reaction mixture was concentrated under reduced pressure, and then subjected to column purification to obtain 31.9 g of intermediate A

Reference： [1]Patent: KR2016/126420,2016,A .Location in patent: Paragraph 0175; 0177-0178

28
[ 108714-73-4 ]
[ 1161009-88-6 ]
bis-(9,9-spirobifluoren-4-yl)-(9,9-dimethyl-9H-fluoren-2-yl)amine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
79%	With bis(tri-tert-butylphosphine)palladium(0); sodium t-butanolate; In 5,5-dimethyl-1,3-cyclohexadiene; for 6h;Inert atmosphere; Reflux;	o a 500 ml round-bottomed flask under nitrogen was added compound F (10.0 g, 25.25 mmol),9,9-dimethyl-9H-fluoren-2-amine (2.38 g, 11.36 mmol) was completely dissolved in xylene (250 ml), sodium tert-butoxide (1.33 g, 13.89 mol) was added,Bis (tri-tert-butylphosphine) palladium (0) (0.13 g, 0.25 mmol) was added thereto, followed by heating and stirring for 6 hours.After the temperature was lowered to room temperature and the salts were removed by filtration, the xylene was concentrated under reduced pressure and recrystallized from 380 ml of tetrahydrofuran to obtain Compound 15 (16.78 g, yield: 79%).

Reference： [1]Patent: KR2017/82824,2017,A .Location in patent: Paragraph 0170-0173

29
[ 89827-45-2 ]
[ 108714-73-4 ]
N-(9,9-dimethyl-9H-fluoren-2-yl)dibenzo[b,d]furan-4-amine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
83.4%	With 1,1'-bis-(diphenylphosphino)ferrocene; palladium diacetate; sodium t-butanolate; In toluene; at 80℃; for 12h;Inert atmosphere;	Briefly, a mixture of arylbromide (1.0 eq), arylamine (1.05 eq), Pd(OAc)2 (0.01 eq), 1,1?-Bis(diphenylphosphino)ferrocene (DPPF) (0.04 eq), sodiumtert-butoxide (1.5 eq), and toluene was taken in a round bottom flask and heated at 80 C. for 12 h under N2 atmosphere. After completion of the reaction, the volatiles were removed under vacuum, and the resulting solution was extracted with dichloromethane (3×60 mL). The combined organic extract was washed with brine solution, dried over Na2SO4, and concentrated to leave a yellow solid. Further, the crude product was purified by column chromatography on silica gel by using hexane/dichloromethane mixture (2:1 v/v) as an eluent. The analysis data of the obtained products, i.e. Intermediates A11 to A14, are listed in the following Table 2.
83.4%	With 1,1'-bis-(diphenylphosphino)ferrocene; palladium diacetate; sodium t-butanolate; In toluene; at 80℃; for 12h;Inert atmosphere;	General procedure: The intermediate A6 to A8 can be prepared according to the above-mentioned schematic I. The starting materials Ar1-NH2 (arylamine) and Br-Ar2 (arylbromide) are listed in Table 2 below. Briefly, aryl bromide (1.0 eq), arylamine (1.05 eq),Pd (OAc) 2 (0.01 eq),1,1'-bis (diphenylphosphino) ferrocene(1,1'-Bis (diphenylphosphino) ferrocene, DPPF) (0.04 eq),Sodium tert-butoxide (1.5 eq) and toluene were placed in a pressure tube and heated at 80 C for 12 hours under N 2 atmosphere.After completion of the reaction, the volatiles were removed in vacuo,The resulting solution was extracted with dichloromethane (3 x 60 mL).The combined organic extracts were washed with brine solution, dried over Na2SO4 and concentrated to give a yellow solid.The crude product was further purified by column chromatography on silica gel using hexane / dichloromethane mixture (2: 1 v / v) as eluent.The obtained product, i.e.,Analytical data for intermediates A11 to A14 are listed in Table 2 below.
83.4%	With 1,1'-bis-(diphenylphosphino)ferrocene; palladium diacetate; sodium t-butanolate; In toluene; at 80℃; for 12h;Inert atmosphere;	General procedure: Briefly, aryl bromide (1.0 eq), arylamine (1.05 eq), Pd (OAc) 2 (0.01 eq), 1,1'-bis (diphenylphosphino) ferrocene (DPPF) (0%) .04 eq), sodium tert-butoxide (1.5 eq), andThe mixture of toluene was taken in a round bottom flask and heated at 80 C. for 12 hours under N 2 atmosphere. After the reaction was complete, the volatiles were removed in vacuo and the resulting solution was extracted with dichloromethane (3 × 60 mL). The combined organic extracts are washed with brine solution andDry over O 4 and concentrate to leave a yellow solid. In addition, the crude product was purified by silica gel column chromatography by using hexane / dichloromethane mixture (2: 1 v / v) as eluent. The obtained products, ie intermediates A11 to A14The analytical data of are listed in Table 2 below.

83.4%	With 1,1'-bis-(diphenylphosphino)ferrocene; palladium diacetate; sodium t-butanolate; In toluene; at 80℃; for 12h;Inert atmosphere;	General procedure: Briefly, aryl bromide (1.0 eq), arylamine (1.05 eq), Pd (OAc) 2 (0.01 eq), 1,1'- bis (diphenylphosphino) ferrocene , DPPF (0.04 eq), sodium tert-butoxide (1.5 eq) and toluene were placed in a round-bottomed flask and heated at 80 C for 12 hours under N 2 atmosphere. After completion of the reaction, the volatiles were removed in vacuo and the resulting solution was extracted with dichloromethane (3 x 60 mL). The combined organic extracts were washed with brine solution, dried over Na2SO4 and concentrated to give a yellow solid. The crude product was further purified by column chromatography on silica gel using hexane / dichloromethane mixture (2: 1 v / v) as eluent. The analytical data of the obtained products, that is, the intermediates A11 to A13, are listed in Table 2 below.
83.4%	With 1,1'-bis-(diphenylphosphino)ferrocene; palladium diacetate; sodium t-butanolate; In water; toluene; at 80℃; for 12h;Inert atmosphere;	General procedure: aryl bromide (1.0 eq),Arylamine (1.05 eq),Pd (OAc) 2 (0.01 eq),1,1'-bis (diphenylphosphino) ferrocene (DPPF) (0.04 eq),Sodium tert-butoxide (1.5 eq),Take a mixture of water and toluene in a pressure tube,Heat at 80 C. for 12 hours under N 2 atmosphere.After the reaction is complete, the volatiles are removed under vacuum,The resulting solution was extracted with dichloromethane (3 × 60 mL).The combined organic extracts are washed with a salt solution,Dry over Na2SO4 and concentrate to leave a yellow solid.In addition, hexane / dichloromethane mixtureThe crude product was purified by silica gel column chromatography by using (2: 1 v / v) as eluent.Product obtained,That is, analytical data of Intermediates A11 to A14 are described in Table 2 below.
83.4%	With 1,1'-bis-(diphenylphosphino)ferrocene; palladium diacetate; sodium t-butanolate; In toluene; at 80℃; for 12h;Inert atmosphere;	General procedure: Briefly, aryl bromide (1.0 eq), arylamine (1.05 eq), Pd (OAc) 2 (0.01 eq), 1,1'-bis (diphenylphosphino)ferrocene (0.04 eq), sodium tert-butoxide (1.5 eq) and toluene were placed in a pressure tube and heated at 80C for 12 hours under N2 atmosphere. After completion of the reaction, the volatiles were removed in vacuo and the resulting solution was extracted with dichloromethane (3-60 mL). The combined organic extracts were washed with brine solution, dried over Na2SO4 and concentrated to give a yellow solid. Further, the crude product was dissolved in hexane / dichloromethane was purified by column chromatography on silica gel using a dichloromethane mixture (2: 1 v / v) as eluent.

Reference： [1]Patent: US2017/213971,2017,A1 .Location in patent: Paragraph 0089; 0090
[2]Patent: KR2019/10321,2019,A .Location in patent: Paragraph 0166-0175
[3]Patent: JP2019/19102,2019,A .Location in patent: Paragraph 0059; 0060; 0061; 0062
[4]Patent: KR2019/11128,2019,A .Location in patent: Paragraph 0127; 0133; 0135; 0136
[5]Patent: JP2019/14698,2019,A .Location in patent: Paragraph 0058; 0061-0064
[6]Patent: KR2019/10273,2019,A .Location in patent: Paragraph 0150; 0152; 0158; 0159

30
[ 108714-73-4 ]
C₁₅H₁₄BrN [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
89%	With N-Bromosuccinimide; In chloroform; at 20℃; for 2h;Inert atmosphere;	70 g (1.0 eq) of <strong>[108714-73-4]9,9-dimethyl-9H-fluoren-2-amine</strong> was dissolved in 700 ml of CHCl 3 in a 1000 ml round bottom flask under nitrogen atmosphere and 62.5 g (1.05 eq) of NBS were added Then, the mixture was stirred at room temperature for 2 hours. Thereafter, the solution was reduced in pressure, dissolved in ethyl acetate, washed with water with water, the organic layer was separated, and the solvent was removed by decompression. This was subjected to column chromatography to obtain 76.5 g of Intermediate A-1 (yield 89%).
84.97%	With N-Bromosuccinimide; In N,N-dimethyl-formamide; at 0℃;	9,9'-dimethyl-9H-fluorene-2-amine (50.00 g, 238.90 mmol) was dissolved in N, N-dimethylformamide (DMF) (200 ml) and the temperature was lowered to 0 C. N-bromosuccinimide (NBS) (42.52 g, 238.90 mmol) was dissolved in N, N-dimethylformamide (DMF) (150 ml) and slowly added to the solution, followed by stirring. After the completion of the reaction, the temperature was raised to room temperature, and water was added thereto, followed by reverse precipitation and filtration. The obtained solid was layered with chloroform and sodium thiosulfate solution. Resolving with hexane after solvent removal gave the compound 1-A (58.50 g, 84.97% yield).
81%	With N-Bromosuccinimide; In chloroform; at 0 - 20℃; for 1h;	<strong>[108714-73-4]9,9-dimethyl-9H-fluorene-2-amine</strong> (60.0 g, 0.29 mol) was dissolved in 500 mL of CHCl3, NBS (46.8 g, 0.29 mol) was added in 5 portions at 0 C and stirred at room temperature for 1 hour.Thereafter, the solution was reduced in pressure, dissolved in ethyl acetate, washed with water, and then the organic layer was separated and reduced in pressure to remove any solvent.Intermediate D1 was obtained (67.1 g, yield 81%,) using column chromatography.

81%	With N-Bromosuccinimide; In chloroform; at 0 - 20℃; for 1h;	The 9,9-dimethyl -9H- fluoren-2-amine (60.0g, 0.29mol) was dissolved in CHCl3 500mL After addition of NBS (46.8g, 0.29mol) at 0 C 5 times, and stirred at room temperature for 1 hour. Then, after the solution was under reduced pressure, dissolved in ethyl acetate, washed with water, and the organic layer was separated and reduced pressure, whereby the solvent was completely removed. Obtained by column chromatography of Intermediate A1 (67.1g, yield 81%).
80%	With N-Bromosuccinimide; In N,N-dimethyl-formamide; at 0 - 20℃; for 3h;	<strong>[108714-73-4]9,9-dimethyl-9H-fluorene-2-amine</strong>(150 g, 716.7 mmol) was added to DMF (400 ml) and dissolved. NBS (177.98 g, 716.7 mmol) was slowly added dropwise at 0 C and the mixture was stirred at room temperature for 3 hours.After extraction with water and chloroform at room temperature, the white solid was recrystallized from hexane to give the above compound A1 (165 g, yield, 80%).

Reference： [1]Patent: KR2017/113427,2017,A .Location in patent: Paragraph 0267; 0269; 0270; 0271
[2]Patent: KR2020/5488,2020,A .Location in patent: Paragraph 0237-0240
[3]Patent: KR2018/32517,2018,A .Location in patent: Paragraph 0228-0231
[4]Patent: CN107915722,2018,A .Location in patent: Paragraph 0122-0125
[5]Patent: KR2018/33000,2018,A .Location in patent: Paragraph 0224-0228
[6]Patent: KR2017/100283,2017,A .Location in patent: Paragraph 0185-0187

31
[ 108714-73-4 ]
[ 2052-07-5 ]
N‐[1,1'‐biphenyl]‐2‐yl}‐9,9‐dimethylfluoren‐2‐amine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
83%	With 1,1'-bis-(diphenylphosphino)ferrocene; palladium diacetate; sodium t-butanolate; In toluene; at 80℃; for 12h;Inert atmosphere;	General procedure: Reactants B3 to B5 were synthesized by the Scheme I-I. The Reactants B3 to B5 can be prepared according to the above Scheme I-I. The starting materials Ar1-NH2 (arylamine) and Br-Ar2 (arylbromide) to prepare the Reactants B3 to B5 are listed in the following Table 5. (0121) A mixture of arylbromide (1.0 eq), arylamine (1.05 eq), Pd(OAc)2 (0.01 eq), 1,1?-Bis(diphenylphosphino)ferrocene (DPPF) (0.04 eq), sodium tert-butoxide (1.5 eq), and toluene was taken in a pressure tube and heated at 80 C. for 12h under N2 atmosphere. After completion of the reaction, the volatiles were removed under vacuum, and the resulting solution extracted with 60 mL dichloromethane for 3 times. The combined organic extract was washed with brine solution, dried over Na2SO4, and concentrated to leave a yellow solid. Further, the crude product was purified by column chromatography on silica gel by using hexane/dichloromethane mixture (2:1 v/v) as an eluent. The analysis data of the obtained products, i.e. Reactants B3 to B5, are listed in the following Table 5.
83%	With 1,1'-bis-(diphenylphosphino)ferrocene; palladium diacetate; sodium t-butanolate; In toluene; at 80℃; for 12h;Inert atmosphere;	General procedure: Aryl bromide (1.0 equivalent), arylamine (1.05 equivalent), Pd (OAc) 2 (0.01 equivalent), 1,1'-bis (diphenylphosphino) ferrocene (DPPF) (0.04 equivalent) ), Sodium tert-butoxide (1.5 equivalents) and tolueneThe mixture was placed in a pressure tube and heated at 80 C. for 12 hours under N 2 atmosphere. After completion of the reaction, the volatiles were removed under vacuum and the resulting solution was extracted three times with 60 mL of dichloromethane. The combined organic extracts were washed with brine solution, dried over Na2SO4 and concentrated to leave a yellow solid. In addition, the crude product was purified by column chromatography on silica gel using hexane / dichloromethane mixture (2: 1 v / v) as eluent. Analytical data of the resulting products, ie, Reactants B3 to B5, are listed in Table 5 below.
80%	With tris-(dibenzylideneacetone)dipalladium(0); sodium t-butanolate; XPhos; In toluene; at 105 - 110℃; for 4h;Inert atmosphere;	2-bromobiphenyl (15.0 g, 64.4 mmol),<strong>[108714-73-4]2-amino-9,9-dimethylhydrazine</strong> (14.8 g, 70.8 mmol),Tris(dibenzylideneacetone)dipalladium (0.59 g, 0.64 mmol),2-Dicyclohexylphosphine-2,4,6-triisopropylbiphenyl (0.61 g, 1.29 mmol) and sodium tert-butoxide (9.28 g, 96.5 mmol) were added to toluene (150 mL).Heating to 105-110 C under nitrogen protection, stirring for 4 h;After cooling to room temperature, the reaction solution was washed with water and dried over magnesium sulfate.After filtration, the filtrate was passed through a short silica gel column, and the solvent was removed under reduced pressure;The crude product was recrystallized and purified using a dichloromethane/n-heptane system.The gray solid intermediate II-B (18.7 g, 80%) was obtained.

71%

With tris-(dibenzylideneacetone)dipalladium(0); sodium t-butanolate; XPhos; In toluene; at 105 - 110℃; for 2h;Inert atmosphere;

2-Bromobiphenyl (10.0 g, 42.9 mmol), <strong>[108714-73-4]2-amino-9,9-dimethylhydrazine</strong> (9.9 g, 47.2 mmol), tris(dibenzylideneacetone)dipalladium (0.4 g, 0.4 mmol) , 2-dicyclohexylphosphine-2,4,6-triisopropylbiphenyl (0.4 g, 0.9 mmol) and sodium tert-butoxide (6.2 g, 64.4 mmol) were added to toluene (100 mL) under nitrogen Heating to 105-110 C, stirring for 2 hours; cooling to room temperature, the reaction solution was washed twice with water, dried over magnesium sulfate, filtered, the filtrate was passed through a short silica gel column, solvent was removed under reduced pressure; using dichloromethane / n-heptane system The crude product was recrystallized and purified to give the crude solid Intermediate II-B (11.0 g, 71%).

Reference： [1]Patent: US2017/279050,2017,A1 .Location in patent: Paragraph 0121
[2]Patent: JP2019/26602,2019,A .Location in patent: Paragraph 0104; 0105; 0106; 0107
[3]Patent: CN110105225,2019,A .Location in patent: Paragraph 0106-0108
[4]Patent: CN110183332,2019,A .Location in patent: Paragraph 0080; 0081

32
[ 108714-73-4 ]
[ 174621-52-4 ]
N-(4-(1H-indol-1-yl)phenyl)-9,9-dimethyl-9H-fluoren-2-amine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
65%	With palladium diacetate; XPhos; In toluene; at 150℃; for 8h;Inert atmosphere;	In a round bottom flask Intermediate 1-1 (12 g, 44 mmol) and 9,9-dimethyl-2-fluorenylamine (9.3 g,(6.5 g, 66 mmol), palladium acetate (0.3 g) and x-phos (0.6 g) were added, and 200 mL of toluene was added as a solvent,Nitrogen protection, heating at 150 C, stirring and refluxing for 8 hours,The reaction was complete, cooled, washed with water, extracted with dichloromethane and dried. The product was purified by column chromatography to give 11 g of product in a yield of 65%.

Reference： [1]Patent: CN107266346,2017,A .Location in patent: Paragraph 0047; 0049; 0052; 0053

33
[ 108714-73-4 ]
[ 1257220-44-2 ]

Reference： [1]Patent: KR2017/116976,2017,A

34
[ 108714-73-4 ]
[ 1621397-55-4 ]
[ 2170321-86-3 ]

Yield	Reaction Conditions	Operation in experiment
10.2 g	With tributylphosphine; bis(dibenzylideneacetone)-palladium⁽⁰⁾; sodium t-butanolate In toluene for 3h; Reflux;	2 Preparation of intermediate compound [119-1] In a 500 mL reaction flask, 10 g (24.31 mmol) of the compound [10-1] Dimethyl-9H-fluorene-2-amine (5.08 g, 24.31 mmol), Sodium tert-butoxide 3.5g (36.47mmol) tributylphosphine 0.24ml (0.4862mmol), tris (dibenzylideneacetone) dipalladium (0) 220mg (0.2431mmol), was added to 100mL toluene and the mixture was stirred under reflux for 3 hours. After completion of the reaction, the reaction mixture was extracted with ethyl acetate / distilled water and subjected to anhydrous magnesium sulfate treatment. Separation and purification were conducted by silica gel chromatography to obtain 9.2 g (70 wt%) of an intermediate compound [119-1] as a white solid.
9.2 g	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tributylphosphine; sodium t-butanolate In toluene for 3h; Reflux;	2 Preparation of intermediate compound [119-1] 10 g (24.31 mmol) of compound [10-1], 5.08 g (24.31 mmol) of 9,9-dimethyl-9H-Fluorene-2-amine, 3.5 g (36.47 mmol) were added to a 500 mL reaction flask.Sodium tert-butoxide, 0.24 ml (0.4862 mmol) of tributylphosphine,220 mg (0.2431 mmol) of tris(dibenzylideneacetone)dipalladium (0),100 mL of toluene was stirred at reflux for 3 hours.After the reaction was completed, it was extracted with ethyl acetate/distilled water.It was filtered through anhydrous magnesium sulfate.Separation and purification by silica gel chromatography,Thus prepared 9.2 g (70 weight percent)Intermediate compound of white solid [119-1].

Reference： [1]Current Patent Assignee: CMDL CO LTD - KR2017/138799, 2017, A Location in patent: Paragraph 0074; 0076-0078
[2]Current Patent Assignee: CMDL CO LTD - CN109867652, 2019, A Location in patent: Paragraph 0069-0073

35
[ 108714-73-4 ]
[ 1260228-95-2 ]

Reference： [1]Patent: CN107556229,2018,A

36
[ 911836-38-9 ]
[ 108714-73-4 ]
C₃₁H₂₅N [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
89%	With palladium diacetate; 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; sodium t-butanolate; In toluene; at 110℃;	In a dry 2L three-necked flask add 28.3 g of 1-bromo-5-phenylnaphthalene and 23 g2-Amino-9,9'-dimethylhydrazine, followed by dry and degassed 600 mL of toluene as solvent.28.8 g of sodium tert-butoxide (3 eq.), 0.45 g of palladium acetate catalyst (2% mol) and 2.5 g of ligand 1,1'-binaphthyl-2,2'-bisdiphenylphosphine (BINAP, 4% mol ). Warm up to 110C,The reaction ended overnight. Cool to room temperature, add activated carbon adsorption, suction filtration, spin off the solvent,Recrystallization from toluene and ethanol gave 36.6 g of intermediate g with a yield of 89%.

Reference： [1]Patent: CN107880055,2018,A .Location in patent: Paragraph 0209-0212

37
[ 108714-73-4 ]
C₂₅H₁₁Br₃I₂O₂ [ No CAS ]
C₄₀H₂₄Br₂INO₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
58%		35.6 g (42.7 mmol, 1.0 eq.) was added to a dry 1 L three-necked flask.Intermediate -7 and 8.9 g (42.7 mmol, 1.0 eq.)<strong>[108714-73-4]2-amino-9,9-dimethylhydrazine</strong>,Add 400 ml of toluene and stir to dissolve, and add 4.9 g (51.2 mmol, 1.2 eq) of sodium t-butoxide.With nitrogen for 15 minutes, 0.4 g (0.42 mmol, 0.01 eq) of tris(dibenzylideneacetone)dipalladium was added.Add 1.7 ml (0.84 mmol, 0.02 eq) of a solution of tri-tert-butylphosphine in toluene (10%),Nitrogen protection, heating to 90 C, reaction for 3 hours, the reaction is completed. Cool to room temperature,Filtering, washing the filter cake with water, washing the filter cake with ethanol, pulping with ethanol 3 times, and re-crystallizing the filter cake with toluene.Finally, 20.6 g of Intermediate-8 was obtained in a yield of 58%.

Reference： [1]Patent: CN108164544,2018,A .Location in patent: Paragraph 0100; 0102; 0103

38
[ 108714-73-4 ]
[ 580-13-2 ]
[ 1263001-82-6 ]

Yield	Reaction Conditions	Operation in experiment
84%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tri-tert-butyl phosphine; sodium t-butanolate In toluene Reflux;	1 The synthesis of IA1 below is as follows. In a round bottom flask, 36.6 g of 2-bromonaphthyl group, 44.4 g of 9,9-dimethyl-9H-indole-2-amine, 33.9 g of t-BuONa, and 3.2 g of Pd2(dba)3, (t- Bu) 3P 1.7 ml was dissolved in 350 ml of toluene, and stirred under reflux. The reaction was confirmed by thin layer chromatography (TLC), and after adding water, the reaction was completed. The organic layer was extracted with dichloromethane (MC) and filtered under reduced pressure.Thereafter, column purification and recrystallization were carried out to obtain IA1g (yield 84%).
18 g	With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; sodium t-butanolate In toluene at 80℃; for 16h; Inert atmosphere;	9 Synthesis of C48-3 Place 2-amino-9,9-dimethylfluorene (12.0g, 57.3mmol) and 2-bromonaphthalene (14.3g, 68.8mmol) in a 250mL three-necked flask, then add sodium tert-butoxide (8.27g, 86.0mmol) and toluene (250mL), after full stirring, nitrogen replaces the air in the bottle, then add the catalyst [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride (420mg, 0.573mmol) and 2-bicyclohexylphosphine-2',6'-dimethoxybiphenyl (470mg, 1.15mmol), heated to 80 °C and reacted for 16h. After cooling to room temperature, the reaction solution was poured into saturated aqueous ammonium chloride solution, extracted with ethyl acetate (150 mL, three times), the organic phases were combined, washed with saturated brine, dried over anhydrous sodium sulfate, filtered and concentrated to obtain a brown oil. The crude product was purified by silica gel column chromatography (petroleum ether/dichloromethane, 5/1) to obtain 18 g of white solid.

Reference： [1]Current Patent Assignee: DONGJIN SEMICHEM CO.,LTD. - CN108250083, 2018, A Location in patent: Paragraph 0097; 0100; 0101; 0102
[2]Current Patent Assignee: BEIJING ETERNAL MATERIAL TECHNOLOGY CO LTD - CN112010761, 2020, A Location in patent: Paragraph 0099-0100; 0105-0106

39
[ 108714-73-4 ]
[ 19111-87-6 ]
N-(9,9-dimethyl-9H-fluoren-2-yl)triphenylen-2-amine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
73%	With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; at 100℃; for 24h;	Step1:The reactor was added 2-amino-9,9-dimethyl-fluorene (1.67g, 8mmol),2-bromo-triphenylene (2.05 g, 6.67 mmol),Pd2(dba)3 (0.17g, 0.2mmol),P(t-Bu)3 (0.14, 0.67 mmol),NaOt-Bu (2.24g, 20mmol),Toluene solution 100mL,Reaction at 100 C for 24 h,After the reaction, the organic phase was extracted with diethyl ether and water.The organic layer was dried over MgSO 4Concentrated organic matter, column chromatography,Recrystallization gave Intermediate 1-a (1.56 g, 73%).
31.9 g	With bis(tri-t-butylphosphine)palladium(0); sodium t-butanolate; In toluene; for 3h;Inert atmosphere; Reflux;	Under nitrogen atmosphere, afier completely dissolving 2-bromotriphenylene (30 g, 98 mmol) and 2-amino- 9,9-dimethylfluorene (20.5 g, 98 mmol) in 200 ml of toluene, NaOt-Bu (11.3 g, 117.6 mmol) was added thereto, and the result was stirred while raising a temperature until reflux. When the result started to reflux, bis(tri-tert-butylphosphine) palladium(0) (0.5 g, 0.98 mmol) was slowly added dropwise thereto. The reaction was complete afier 3 hours and the result was cooled to room temperater, concentrated under reduced pressure, and then colunm purified to prepare 31.9 g of Intermediate A. MS[M+H]+=436
	With tri-tert-butyl phosphine; palladium diacetate; sodium t-butanolate; In toluene; at 80℃; for 8h;Inert atmosphere;	Step 1: Under the argon atmosphere, bromide A-1 (4.77 g, 15 mmol), amine compound B-1 (3.14 g, 15 mmol),Sodium tert-butoxide (2.88 g, 30 mmol) was added to 150 ml of dehydrated toluene.Palladium acetate (0.07 g, 0.3 mmol) and tri-tert-butylphosphine (0.06 g, 0.3 mmol) were added under stirring, and the mixture was reacted at 80 C for 8 hours.After cooling, it was filtered through a celite/silica funnel and filtered.The liquid is removed by distillation under reduced pressure to remove the organic solvent.The obtained residue was recrystallized from toluene, and the obtained solid was filtered and dried to give Intermediate M-1.

Reference： [1]Patent: CN109503391,2019,A .Location in patent: Paragraph 0063; 0065
[2]Patent: US2018/244659,2018,A1 .Location in patent: Paragraph 0145; 0146; 0147
[3]Patent: CN109293516,2019,A .Location in patent: Paragraph 0095; 0096; 0097

40
[ 86-76-0 ]
[ 108714-73-4 ]
(2-dibenzofuranyl)-(2-9,9-dimethylfluorenyl)amine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
51%	With tris-(dibenzylideneacetone)dipalladium(0); sodium t-butanolate; tri tert-butylphosphoniumtetrafluoroborate; In toluene; at 90℃; for 15h;Inert atmosphere;	To a suspension of 9.0 g (36.4 mmol) of 2-bromodibenzo[b,d]furan, 11.4 g (54.6 mmol)of <strong>[108714-73-4]9,9-dimethyl-9H-fluoren-2-amine</strong>, and 10.5 g (109.2 mmol) of sodium tenbutanolatein 200 mL of toluene were added 0.42 g (1.46 mmol) of tri-tenbutylphosphine tetrafluoroborate and 1 .33 g (1 .46 mmol) of Pd2(dba)3 under an argon atmosphere. The mixture was heated at 90C for 15 h. After cooling, 100 mL of saturated aqueous NH4CI solution were added. After 30 minutes, the combined phases were filteredthrough celite and extended with 100 mL of toluene. The organic phase was separated, and the aqueous phase was washed with 100 mL of toluene. The combined organic phases were dried with MgSO4 and evaporated to dryness. The crude solid was crystallised from toluene/cyclohexane. The crude solid was purified with column chromatography (heptane/dichloromethane) to give the title compound as a white solid(6.9 g, 51 %).

Reference： [1]Patent: WO2018/206769,2018,A1 .Location in patent: Page/Page column 85; 86

41
[ 108714-73-4 ]
[ 171408-76-7 ]
N-(9,9-dimethyl-9H-fluoren-2-yl)-9,9'-spirobi(fluorene)-7-amine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
94%	With tri-tert-butyl phosphine; palladium diacetate; sodium t-butanolate In toluene at 110℃; for 12h;	3-4 (1) 39.4g (0.1mol) of 2-bromo-9,9'-spirobifluorene (MW:394), (1,1'-biphenyl)-2-amine (MW:169.1) 17.75g (0.105) mol), palladium(II) acetate (molecular weight 224.51) 0.22g,Tri-tert-butyl phosphine (MW: 202.32) 0.44 g (0.0022 mol), toluene 350 mL and sodium tert-butoxide (MW: 96.10) 11.5 g,Put it in a 500mL reaction flask, insert a condenser, stir the reaction with a thermometer, heat up to 110°C, react for 12hrs,After the reaction is over, the temperature is lowered, and 140 mL of ethanol is added, then filtered, washed with water, and dried.Obtained 49.18g (0.094mol) of N(9,9-dimethyl-9H-fluoren-2-yl)-9,9'-spirobisfluoren-2-amine (MW: 523.2) with a yield of 94%;
94%	With tri-tert-butyl phosphine; palladium diacetate; sodium t-butanolate In toluene at 110℃; for 12h;	3.1; 7.1 (1) Combine 2-bromo-9,9'-spirobifluorene (MW: 395.30) 39.53g (0.1mol),9,9-Dimethyl-2-aminofluorene (MW: 209.29) 21.98 g (0.105 mol), sodium tert-butoxide (MW: 96.10) 19.22 g (0.2 mol), palladium (II) acetate (MW: 224.51) 0.22g, tri-tert-butyl phosphorus) (MW:202.32) 0.44g (0.0022mol) and 350mL of toluene, put in a 500mL reaction flask, insert a condenser and thermometer, stir the reaction, heat up to 110, react for 12h; wait for reaction After cooling down, add 140mL ethanol, filter, wash with water, and dry to obtain N-(9,9-dimethyl-9H-fluoren-2-yl)-9,9'-spirobisfluoren-2-amine ( MW: 523.2) 49.18g (0.094mol), yield 94%;
74%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tri-tert-butyl phosphine; sodium t-butanolate In toluene for 3h; Inert atmosphere; Reflux;	5.5-1 5-1. Preparation of compound 5-1 12.1 g (0.058 mol) of compound 9,9-dimethyl-9H-fluoren-2-amine was added to a 500-mL, 3-neck round-bottom flask under a nitrogen atmosphere, and the mixture was diluted with 300 mL of toluene.To this dilution, 22.9 g of 2-bromo-9,9'-spirobi[fluorene], 0.27 g of tris(dibenzylideneacetone)dipalladium (0),0.12 g of tri-(t-butyl)phosphine and 7.2 g of sodium t-butoxide were added.The reaction solution was refluxed for 3 hours, cooled, and poured into excess methanol to precipitate a solid. The obtained solid was filtered, dried in vacuo, and separated by column to obtain 22.5 g of compound 5-1 (yield 74%)

74%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tri-tert-butyl phosphine; sodium t-butanolate In toluene for 3h; Inert atmosphere; Reflux;	5.5-1 5-1. Preparation of compound 5-1 12.1 g (0.058 mol) of compound 9,9-dimethyl-9H-fluoren-2-amine was added to a 500-mL, 3-neck round-bottom flask under a nitrogen atmosphere, and the mixture was diluted with 300 mL of toluene. In this dilution, 22.9 g of 2-bromo-9,9'-spirobi[fluorene], 0.27 g of tris(dibenzylideneacetone)dipalladium(0), 0.12 g of tri-(t-butyl)phosphine, and 7.2 g of sodium t-butoxide was added. The reaction solution was refluxed for 3 hours, cooled, and poured into excess methanol to precipitate a solid. The obtained solid was filtered, dried in vacuo, and separated by column to obtain compound 5-1 22.5 g (yield 74%).
	With tri-tert-butyl phosphine; palladium diacetate; sodium t-butanolate In toluene at 80℃; for 8h; Inert atmosphere;	1 Example 1: Preparation of Compound 1 Bromide B1 (5.93 g, 15 mmol), amine compound A-1 (3.14 g, 15 mmol), sodium t-butoxide (2.88 g, 30 mmol) were added to 150 ml of dehydrated toluene under argon atmosphere, and palladium acetate was added thereto with stirring. 0.07 g, 0.3 mmo 1), tri-tert-butylphosphine (0.06 g, 0.3 mmol), and reacted at 80 ° C for 8 hours. After cooling, it was filtered through a celite/silica funnel, and the filtrate was evaporated to remove organic solvent. The residue obtained was crystallized from toluene, and the obtained solid was filtered and dried to give Intermediate M-1.
	With tri-tert-butyl phosphine; palladium diacetate; sodium t-butanolate In toluene at 80℃; for 8h; Inert atmosphere;	1 Synthesis of Compound HT2-1 of Example 1 Bromide B-1 (5.93 g, 15 mmol) under argon atmosphere,Amine compound A-1 (3.14 g, 15 mmol),Sodium tert-butoxide (2.88 g, 30 mmol) was added to 150 ml of dehydrated toluene.Palladium acetate (0.07 g, 0.3 mmol) was added with stirring.Tri-tert-butylphosphine (0.06 g, 0.3 mmol) was reacted at 80 ° C for 8 hours.After cooling, it was filtered through a celite/silica gel funnel.The filtrate was subjected to distillation under reduced pressure to remove an organic solvent, and the obtained residue was recrystallized from toluene.The obtained solid was collected by filtration and dried to give Intermediate M-1.

Reference： [1]Current Patent Assignee: YANTAI XIANHUA CHEM-TECH CO LTD - CN111434648, 2020, A Location in patent: Paragraph 0058-0061; 0064-0065; 0067-0070; 0073-0074
[2]Current Patent Assignee: YANTAI XIANHUA CHEM-TECH CO LTD - CN111484468, 2020, A Location in patent: Paragraph 0062-0066; 0086-0089
[3]Current Patent Assignee: EL & M SPA - KR2021/128618, 2021, A Location in patent: Paragraph 0139-0142
[4]Current Patent Assignee: EL & M SPA - KR2021/128617, 2021, A Location in patent: Paragraph 0134-0137
[5]Current Patent Assignee: CHANGCHUN HAIPU RUNSI TECHNOLOGY CO LTD - CN108912038, 2018, A Location in patent: Paragraph 0080; 0087-0089
[6]Current Patent Assignee: CHANGCHUN HAIPU RUNSI TECHNOLOGY CO LTD - CN109053547, 2018, A Location in patent: Paragraph 0097; 0129-0131

42
[ 108714-73-4 ]
[ 204530-94-9 ]
C₄₇H₃₅N [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
87%	With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; for 4h;Inert atmosphere; Reflux;	17.9 grams (63.07 millimoles) of <strong>[204530-94-9]1-(4-bromophenyl)naphthalene</strong>, 6.0 grams (28.67 millimoles) 2-amino-9,9-dimethyl-9H-indole and 8.3 g (86.01 mmol) of sodium tributoxide was placed in a round bottom flask, and 200 ml of toluene was added thereto to dissolve it. Subsequently, 0.165 g (0.287 mmol) of Pd(dba) 2 and 0.145 g (0.72 mmol) of tri-tert-butylphosphine (P(t-Bu) 3 ) were sequentially added thereto, and the mixture was subjected to a nitrogen atmosphere. It was refluxed and stirred for 4 hours. When the reaction was completed, the resultant was extracted with toluene and distilled water, the organic layer was dried over magnesium sulfate and filtered, and the filtered solution was concentrated under reduced pressure. Subsequently, the product was purified by column chromatography using hexane/dichloromethane (7:3 by volume) to obtain 15.3 g of pale beige solid compound H-204 (yield: 87%).

Reference： [1]Patent: TW2016/2060,2016,A .Location in patent: Paragraph 0126

43
[ 89827-45-2 ]
[ 108714-73-4 ]
[ 1427556-50-0 ]

Yield	Reaction Conditions	Operation in experiment
83.4%	With 1,1'-bis(diphenylphosphino)ferrocene; palladium diacetate; sodium t-butanolate; In toluene; at 80℃; for 12h;Inert atmosphere;	Intermediates A6 to A9 can be prepared according to Scheme I above. The starting materials Ar 1 - NH 2 (arylamine) and Br - Ar 2 (aryl bromide) are listed in Table 2 below.Briefly, aryl bromide (1.0 eq), aryl amine (1.05 eq), Pd (OAc) 2 (0.01 eq), 1,1'-bis (diphenylphosphino) ferrocene (0.04 eq) , Sodium tert-butoxide (1.5 eq) and toluene was placed in a pressure tube and heated under N 2 atmosphere at 80 C. for 12 hours.After the reaction was complete, the volatiles were removed under vacuum and the resulting solution was extracted with dichloromethane (3 x 60 mL).The combined organic extracts were washed with brine (brine) solution, dried over Na2SO4 and concentrated to leave a yellow solid.In addition, the crude product was purified by silica gel column chromatography by using hexane / dichloromethane mixture (2: 1 v / v) as eluent.The analytical data of the products obtained, ie intermediates A 6 to A 9, are listed in Table 2 below.

Reference： [1]Patent: JP6446099,2018,B1 .Location in patent: Paragraph 0057-0060

44
[ 108714-73-4 ]
[ 350-46-9 ]
N-(4-nitrophenyl)-2-amino-9,9-dimethylfluorene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
80%	With triethylamine; In dimethyl sulfoxide; at 100℃; for 40h;Inert atmosphere;	7.1 g (50.0 mmol) of 4-fluoronitrobenzene and 12.6 g (60.0 mmol) were placed in a 250 mL three-necked flask equipped with mechanical stirring under nitrogen.2-Amino-9,9-dimethylfluorene, 6.1 g (60.0 mmol) of triethylamine, then 53.6 mL of dimethyl sulfoxide was added and reacted at 100 C for 40 h. The mixture was discharged into an ice-water mixture at room temperature, suction filtered, and the cake was recrystallized from ethanol and N,N-dimethylformamide.Obtaining 13.2 g of 4-nitrophenyl-2-amino-9,9-dimethylfluorene in a yield of 80%
80%	With triethylamine; In dimethyl sulfoxide; at 100℃; for 40h;Inert atmosphere;	Under nitrogen conditions,7.1 g (50.0 mmol) of 4-fluoronitrobenzene was added to a 250 mL three-necked flask equipped with mechanical stirring.12.6 g (60.0 mmol) of <strong>[108714-73-4]2-amino-9,9-dimethylhydrazine</strong>,6.1 g (60.0 mmol) of triethylamine was then added to 53.6 mL of dimethyl sulfoxide and reacted at 100 C for 40 h. The mixture was discharged into an ice-water mixture at room temperature, suction filtered, and the cake was recrystallized from ethanol and N,N-dimethylformamide.4-3.2 mg of 4-nitrophenyl-<strong>[108714-73-4]2-amino-9,9-dimethylhydrazine</strong> was obtained.Yield 80%;

Reference： [1]Patent: CN108912003,2018,A .Location in patent: Paragraph 0164; 0167
[2]Patent: CN108929297,2018,A .Location in patent: Paragraph 0168-0169; 0171

45
[ 1153-85-1 ]
[ 108714-73-4 ]
[ 1268835-64-8 ]

Yield	Reaction Conditions	Operation in experiment
85%	With tris-(dibenzylideneacetone)dipalladium(0); 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; sodium t-butanolate; In toluene; at 130℃; for 24h;Inert atmosphere;	Under the protection of argon, compound D1 (32.2 g, 100 mmol) and compound E3 (31.4 g, 150 mmol) were added to the reaction flask.Sodium tert-butoxide (28.8 g, 300 mmol), tris(dibenzylideneacetone) dipalladium (1.4 g, 1.5 mmol),1,1'-binaphthyl-2,2'-bisdiphenylphosphine (1.9 g, 3 mmol) and toluene (350 ml) were reacted at 130 C for 24 hours.After cooling, the mixture was filtered, and the filtrate was concentrated under reduced pressure.The obtained crude product was subjected to column purification and recrystallization from toluene.After filtration, it was dried to give Compound F7 (38.3 g, 85%).

Reference： [1]Patent: CN109232377,2019,A .Location in patent: Paragraph 0139-0141

46
[ 108714-73-4 ]
C₃₁H₄₁BrO₄ [ No CAS ]
C₄₆H₅₅NO₄ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
96%	With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In 5,5-dimethyl-1,3-cyclohexadiene; at 100℃; for 8h;Inert atmosphere;	5 g of the upper intermediate Int. -3 and 2.5 g of <strong>[108714-73-4]2-amino-9,9-dimethylhydrazine</strong> are mixed,Add 50 ml of xylene,1.3 g of sodium t-butoxide and 82 mg of Pd2 (dba) 3 were added, 0.2 ml of a 10% tri-tert-butylphosphine hexane solution was added under nitrogen atmosphere, and the mixture was heated to 100 C, stirred for 8 hours, and cooled to room temperature. Add 50 ml of water and stir for 30 minutes, and separate the upper organic phase. Washed with water, dried and concentrated under reduced pressure.Recrystallization from toluene gave 5.9 g of intermediate Int-4, yellow solid, yield 96%.

Reference： [1]Patent: CN105733562,2019,B .Location in patent: Paragraph 0098; 0110; 0111; 0112

47
[ 108714-73-4 ]
[ 583-55-1 ]
[ 1357150-72-1 ]

Yield	Reaction Conditions	Operation in experiment
73%	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; sodium t-butanolate; In toluene; at 100℃; for 2h;Inert atmosphere;	A mixture of 10 g (35.3 mmol) of 1-bromo-2-iodobenzene, 7.4 g (35.3 mmol) of <strong>[108714-73-4]9,9-dimethyl-9H-fluoren-2-amine</strong>, 0.52 g (0.7 mmol) of Pd(dppf)Cl2, 6.8 g (70.6 mmol) of sodium tert-butoxide, and 60 ml of toluene was degassed and placed under nitrogen, and then heated at 100 C. for 2 h. After the reaction was finished, the mixture was allowed to cool to room temperature and then filtered to remove the solvent. The crude product was purified by column chromatography, yielding 9.4 g of yellow solid (73%). 1H NMR (CDCl3, 400 MHz): chemical shift (ppm) 8.11 (d, 1H), 7.65 (d, 1H), 7.55 (d, 2H), 7.43 (m, 1H), 7.31 (m, 1H), 7.18 (m, 2H), 6.68-6.74 (m, 2H), 6.50-6.56 (m, 2H) , 4.11 (s, 1H), 1.68 (s, 6H).

Reference： [1]Patent: US2019/123284,2019,A1 .Location in patent: Paragraph 0023-0024

48
[ 108714-73-4 ]
[ 474918-32-6 ]
N-(9,9-dimethyl-9H-fluoren-2-yl)-9,9-diphenyl-9H-fluoren-2-amine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
81%	With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene;Reflux;	To a round bottom flask was added 9,9-dimethyl-9H-fluorene-2-amine (Sub A1) 4.9 g, <strong>[474918-32-6]2-bromo-9,9-biphenyl-9H-fluorene</strong> (SubB1) 37 g, t-BuONa , 32.2 g of Pd2(dba)3 and 32.3 ml of P(t-Bu)3 were dissolved in 200 ml of toluene, and the mixture was stirred under reflux. After confirming the reaction by TLC, water was added and the reaction was terminated. The organic layer was extracted with MC, filtered under reduced pressure, and then subjected to column purification and recrystallization to obtain an intermediate product, N-(9,9-dimethyl-9H-fluoren-2-yl)-9,9-biphenyl-9H-amine (Sub C1) (yield: 81%).

Reference： [1]Patent: KR2019/31645,2019,A .Location in patent: Paragraph 0191-0193

49
[ 955959-84-9 ]
[ 108714-73-4 ]
[ 1267248-50-9 ]

Yield	Reaction Conditions	Operation in experiment
63%	With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; for 4h;	9,9-Dimethyl-9H-fluorene-2-amine (9,9-dimethyl-9H-fluoren-2-amine) (10 g, 1 eq) 4- (4-bromophenyl) dibenzo [b, d] furan (4- (4-bromophenyl) dibenzo [b, d] furan) (28 g, 1.2 eq) Pd2 (dba) 3 (2.4 g, 0.03 eq), t-BuONa (12.5 g, 1.5 eq), t-Bu 3P (1.05 g, 0.06 eq), 400 ml of toluene is placed in a round bottom flask (1-neck-R.B.F.) and stirred. (4h) MC / Hx = 1/5 N- (4- (dibenzo [b, d] furan-4-yl) phenyl) -9,9-dimethyl-9H-fluorene-2-amine (N- (4- (dibenzo [b, d] furan-4-yl) phenyl) -9,9-dimethyl-9H-fluoren-2-amine. (12 g, step yield = 63percent)

Reference： [1]Patent: KR2019/58859,2019,A .Location in patent: Paragraph 0188-0190

50
[ 50548-45-3 ]
[ 108714-73-4 ]
C₂₇H₂₁NO [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
86%	With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; potassium tert-butylate; In toluene; at 100℃; for 20h;	5 grams (g) of <strong>[50548-45-3]1-bromodibenzo[b,d]furan</strong> (Intermediate (a)), 6.4 g of 9,9-dimethyl-9H-fluoren-2-amine (Intermediate (b)), 6.4 g of potassium tert-butoxide (KtOBu), 0.3 g of P(tBu)3, and 0.4 g of Pd2 (dba)3 were diluted in toluene, followed by stirring at a temperature of 100 C. under reflux. After a 20-hour lapse, the temperature was lowered to room temperature. Subsequently, the reaction was terminated utilizing water. An organic layer was extracted therefrom three times utilizing ethyl acetate. Then, the organic layer was dried utilizing anhydrous magnesium sulfate, followed by filtration under reduced pressure. The obtained residue was separated and purified through column chromatography to thereby obtain 6.5 g of Intermediate 1-1 (yield: 86%). The compound thus obtained was identified by liquid chromatography-mass spectrometry (LC-MS). C27H21NO: calc'd: M+375.16 foun'd: 375.26

Reference： [1]Patent: US2019/185460,2019,A1 .Location in patent: Paragraph 0400

51
[ 108714-73-4 ]
[ 1421789-14-1 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 5 steps 1: dichloromethane / 3 h 2: nitric acid; sulfuric acid / 2 h / 5 - 10 °C 3: potassium hydroxide / ethanol / 4 h / Reflux 4: hypophosphoric acid; sodium nitrite; sulfuric acid / water; tetrahydrofuran / 0 - 10 °C 5: iron; aluminum (III) chloride / 1,4-dioxane / 8 h / Reflux

Reference： [1]Current Patent Assignee: WISCHEM - KR2019/50646, 2019, A

52
[ 26608-06-0 ]
[ 108714-73-4 ]
[ 1427556-50-0 ]

Yield	Reaction Conditions	Operation in experiment
80%	With tris-(dibenzylideneacetone)dipalladium(0); sodium t-butanolate; XPhos; In toluene; at 105 - 110℃; for 2h;Inert atmosphere;	<strong>[26608-06-0]3-bromodibenzofuran</strong> (10.0 g, 40.5 mmol),2-bromo-9,9-dimethylhydrazine (9.3 g, 44.5 mmol),Tris(dibenzylideneacetone)dipalladium (0.4 g, 0.4 mmol),2-Dicyclohexylphosphino-2,4,6-triisopropylbiphenyl (0.4 g, 0.8 mmol) and sodium tert-butoxide (5.8 g, 60.7 mmol) were added to toluene (100 mL).Heated to 105-110 C under nitrogen protection,After stirring for 2 hours; cooling to room temperature, the reaction solution was washed twice with water, dried over magnesium sulfate, filtered, and then filtered, and the filtrate was passed through a silica gel column, and the solvent was removed under reduced pressure. The crude product was recrystallized and purified using dichloromethane/n-heptane system. The pale yellow solid intermediate VII-B (12.1 g, 80%) was obtained.

Reference： [1]Patent: CN110183332,2019,A .Location in patent: Paragraph 0125; 0126

53
[ 26608-06-0 ]
[ 108714-73-4 ]
C₄₈H₄₁NO [ No CAS ]

Reference： [1]Patent: CN110183332,2019,A

54
[ 108714-73-4 ]
[ 2245-43-4 ]
C₃₁H₃₃N [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
81.25%	With tris-(dibenzylideneacetone)dipalladium(0); sodium t-butanolate; XPhos; In toluene; at 108℃; for 3h;Inert atmosphere;	The intermediate I-A-1 (5.00 g, 17.17 mmol) in the above Synthesis Example 1 was2-amino-9,9-dimethylindole (3.70 g, 17.68 mmol),Tris(dibenzylideneacetone)dipalladium (0.31 g, 0.34 mmol),2-Dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (0.32 g, 0.69 mmol)And sodium tert-butoxide (2.47 g, 25.75 mmol) was added to toluene (50 mL).Heat to 108 C under nitrogen, stir for 3 h; then cool to room temperature,The reaction solution was washed with deionized water and dried over anhydrous magnesium sulfate.After filtration, the filtrate was passed through a short silica gel column, and the solvent was removed under reduced pressure;The crude product was recrystallized and purified using a dichloromethane/n-heptane system.The white solid intermediate I-J (5.85 g, 81.25%) was obtained.
70%	With tris-(dibenzylideneacetone)dipalladium(0); sodium t-butanolate; XPhos; In toluene; at 70 - 105℃; for 2h;Inert atmosphere; Reflux;	Under nitrogen protection, 1- (4-bromophenyl) adamantane 43.75mmol, 2-amino-9,9-dimethylfluorene 43.75mmol, 128mL toluene and 65.625mmol sodium tert-butoxide were added to the reaction flask, and stirred. And heated to 70-80 C, and then slowly added Pd2 (dba) 3 0.218mmol, x-PHOS 0.436mmol, after the addition, continue to warm to 100-105 C and reflux for 2h, the reaction is completed, the temperature is reduced, and dichloro Methane extraction, washing the organic phase with water, drying, filtering and concentrating. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it was recrystallized to LC> 99.5%, and dried to obtain intermediate 9 (yield 70%).

Reference： [1]Patent: CN110183333,2019,A .Location in patent: Paragraph 0123-0126
[2]Patent: CN110563647,2019,A .Location in patent: Paragraph 0103-0105; 0128; 0129

55
[ 108714-73-4 ]
[ 92-66-0 ]
1-(4'-bromobiphenyl-4-yl)adamantane [ No CAS ]
C₄₉H₄₅N [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
65%		Under nitrogen protection, 95.535 mmol of 4-bromo-4'-adamantylbiphenyl, 95.535 mmol of 2-amino-9,9-dimethylfluorene, 702 mL of toluene, and 286.605 mmol of sodium tert-butoxide were added to the reaction flask. Stir, heat up to 70 C, slowly add Pd2dba3 0.95535mmol, s-PHOS 1.9107mmol, after the addition, continue to warm to 102 C and reflux for 2h, then lower the temperature to 70 C, add 4-bromobiphenyl 93.624mmol, continue The temperature was raised to 102 C. and the reaction was refluxed for 8 h. After the reaction was completed, the temperature was lowered, and the mixture was extracted with dichloromethane. The organic phase was washed with water, dried, filtered, and concentrated. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it was recrystallized to LC> 99.95%. Compound 3 was dried. Yield: 65%.

Reference： [1]Patent: CN110240546,2019,A .Location in patent: Paragraph 0048; 0051-0052

56
[ 108714-73-4 ]
[ 92-66-0 ]
2-bromo-7-adamantyl-9,9-dimethylfluorene [ No CAS ]
C₅₂H₄₉N [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
58%		Under the protection of nitrogen, 2-bromo-7-adamantyl-9,9-dimethylfluorene 82.797mmol, 2-amino-9,9-dimethylfluorene 82.797mmol, toluene 675mL, tertiary Sodium butoxide 248.391mmol, stir, heat up to 70-80 , slowly add Pd2dba3 0.82797mmol, s-PHOS 1.6560mmol, after the addition,Continue to raise the temperature to 105 C for 4h, and then lower the temperature to 70 C.81.141 mmol of 4-bromobiphenyl was added, and the temperature was further increased to 105 C. under reflux for 6 hours. After the reaction was completed, the temperature was lowered, and the mixture was extracted with dichloromethane. The organic phase was washed with water, dried, filtered, and concentrated. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it was recrystallized to LC> 99.95%. Compound 4 was dried. Yield: 58%.

Reference： [1]Patent: CN110240546,2019,A .Location in patent: Paragraph 0053; 0056-0057

57
[ 108714-73-4 ]
[ 94994-62-4 ]
C₂₃H₂₃F₃O₃S [ No CAS ]
C₅₅H₄₈N₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
60%		Under nitrogen protection, 5-((3r, 5r, 7r) -adamantane-1-yl)-[1,1'-biphenyl] -2-yltrifluoromethanesulfonate 82.287mmol 82.287mmol of 2-amino-9,9-dimethylfluorene, 720mL of toluene, 246.86mmol of sodium tert-butoxide, stir, heat to 70 C, slowly add Pd2dba30.82287mmol, s-PHOS 1.6457mmol Continue to heat up to 105 C and reflux for 6h, then cool down to 70 C, add 80.641mmol of <strong>[94994-62-4]2-bromo-9-phenylcarbazole</strong>, continue to heat up to 105 C and reflux for 4h. After the reaction is complete, cool down and extract with methylene chloride The organic phase was washed with water, dried, filtered and concentrated. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it was recrystallized to LC> 99.95%. Compound 10 was dried. Yield: 60%.

Reference： [1]Patent: CN110240546,2019,A .Location in patent: Paragraph 0079-0082

58
[ 108714-73-4 ]
[ 28320-31-2 ]
1-(4'-bromobiphenyl-4-yl)adamantane [ No CAS ]
C₅₂H₄₉N [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
78%		Under nitrogen protection, 4-bromo-4'-adamantylbiphenyl 82.797mmol, 2-amino-9,9-dimethylfluorene 82.797mmol, toluene 608mL, sodium tert-butoxide 248.391mmol, Stir, heat up to 70 C, slowly add Pd2dba3 0.82797mmol, s-PHOS1.6560mmol. After the addition is complete, continue to warm to 105 C and reflux for 2h, then lower the temperature to 70 C, add 2-bromo-9,9-di Methyl hydrazone was 81.141 mmol, and the temperature was further increased to 105 C. under reflux for 3 hours. After the reaction was completed, the temperature was lowered, and the mixture was extracted with dichloromethane. The organic phase was washed with water, dried, filtered and concentrated. After passing through the column with a mixed solvent of toluene and n-heptane, it was recrystallized to LC> 99.95%. Dried to get compound 19. Yield: 78%.

Reference： [1]Patent: CN110240546,2019,A .Location in patent: Paragraph 0111-0113

59
[ 108714-73-4 ]
[ 2245-43-4 ]
[ 28320-31-2 ]
C₄₆H₄₅N [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
65%		Under nitrogen, 82.797 mmol of 4-adamantyl bromobenzene, 82.797 mmol of 2-amino-9,9-dimethylfluorene, 482 mL of toluene, 248.391 mmol of sodium tert-butoxide were added to the reaction flask, and the temperature was raised to At 70 C, slowly add Pd2dba3 0.82797mmol and s-PHOS 1.6560mmol. After the addition, continue to warm to 105 C and reflux for 2h, then lower the temperature to 70 C, add 2-bromo-9,9-dimethylfluorene 81.141mmol The temperature was further increased to 105 C. and the reaction was refluxed for 6 h. After the reaction was completed, the temperature was lowered, and the mixture was extracted with dichloromethane. The organic phase was washed with water, dried, filtered, and concentrated. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it was recrystallized to LC> 99.95%. Compound 11 was dried. Yield: 65%.

Reference： [1]Patent: CN110240546,2019,A .Location in patent: Paragraph 0083-0085

60
[ 1153-85-1 ]
[ 108714-73-4 ]
1-(4'-bromobiphenyl-4-yl)adamantane [ No CAS ]
C₅₅H₄₈N₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
70%		Under the protection of nitrogen, 4-bromo-4'-adamantylbiphenyl 82.797mmol was added to the reaction flask,82.797mmol of 2-aminobiphenyl, 608mL of toluene, 248.391mmol of sodium tert-butoxide, stirred, heated to 70 C, slowly added Pd2dba30.82797mmol, s-PHOS 1.6560mmol, after the addition, continued to warm to 105 C under reflux After 2h, the temperature was lowered to 70 C, and 3-bromo-9-phenylcarbazole 81.141mmol was added. The temperature was further increased to 105 C and the reaction was refluxed for 4h. After the reaction was completed, the temperature was lowered, and the organic phase was washed with water, dried, and filtered. concentrate. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it was recrystallized to LC> 99.95%. Compound 7 was dried. Yield: 70%.

Reference： [1]Patent: CN110240546,2019,A .Location in patent: Paragraph 0067-0070

61
[ 108714-73-4 ]
[ 1028647-93-9 ]
1-(4'-bromobiphenyl-4-yl)adamantane [ No CAS ]
C₆₁H₅₂N₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
72%		Under nitrogen protection, 4-bromo-4'-adamantylbiphenyl 82.797mmol, 2-aminobiphenyl 82.797mmol, toluene 608mL, sodium tert-butoxide 248.391mmol were added to the reaction flask, stirred and heated to 70 C Slowly add Pd2dba30.82797mmol and s-PHOS 1.6560mmol. After the addition, continue to warm to 105 C and reflux for 2h, then lower the temperature to 70 C and add 3- (4-bromophenyl) -9-phenyl-9H -Carbazole 81.141 mmol, continued to warm to 105 C. and refluxed for 5 h. After the reaction was completed, the temperature was reduced, and the mixture was extracted with dichloromethane. The organic phase was washed with water, dried, filtered and concentrated. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it was recrystallized to LC> 99.95%. Compound 8 was dried. Yield: 72%.

Reference： [1]Patent: CN110240546,2019,A .Location in patent: Paragraph 0071-0074

62
[ 26608-06-0 ]
[ 108714-73-4 ]
2-bromo-7-adamantyl-9,9-dimethylfluorene [ No CAS ]
C₅₂H₄₇NO [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
53%		Under nitrogen protection, 2-bromo-7-adamantyl-9,9-dimethylfluorene 82.797mmol, 2-amino-9,9-dimethylfluorene 82.797mmol, toluene 675mL,248.391mmol of sodium tert-butoxide, stir, heat up to 70 C, slowly add Pd2dba3 0.82797mmol, s-PHOS 1.6560mmol, after the addition, continue to warm to 105 C and reflux for 4h, then lower the temperature to 70 C, add 4- Brominated biphenyl 81.141 mmol, continued to warm to 105 C. and refluxed for 6 h. After the reaction was completed, the temperature was reduced, and the mixture was extracted with dichloromethane. The organic phase was washed with water, dried, filtered, and concentrated. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it was recrystallized to LC> 99.95%. Compound 9 was dried. Yield: 53%.

Reference： [1]Patent: CN110240546,2019,A .Location in patent: Paragraph 0075-0078

63
[ 108714-73-4 ]
[ 2245-43-4 ]
[ 59951-65-4 ]
C₄₇H₄₃N [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
81%		Under nitrogen, 82.797 mmol of 4-adamantyl bromobenzene, 82.797 mmol of 2-amino-9,9-dimethylfluorene, 482 mL of toluene, 248.391 mmol of sodium tert-butoxide were added to the reaction flask, and the temperature was raised to At 70 C, slowly add Pd2dba30.82797mmol and s-PHOS 1.6560mmol. After the addition, continue to warm to 105 C and reflux for 2h, and then lower the temperature to 70 C. Add 1-bromo-4-phenylnaphthalene 81.141mmol and continue to warm The reaction was refluxed for 8 hours at 105 C. After the reaction was completed, the temperature was lowered and the mixture was extracted with dichloromethane. The organic phase was washed with water, dried, filtered, and concentrated. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it was recrystallized to LC> 99.95%. Compound 13 was dried. Yield: 81%.

Reference： [1]Patent: CN110240546,2019,A .Location in patent: Paragraph 0089-0091

64
[ 108714-73-4 ]
[ 2245-43-4 ]
[ 22082-99-1 ]
C₄₇H₄₃N [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
80%		Under nitrogen protection, 82.797mmol of 4-adamantyl bromobenzene, 82.797mmol of 2-amino-9,9-dimethylfluorene, 482mL of toluene, 248.391mmol of sodium tert-butoxide were added to the reaction flask, and the temperature was raised to At 70 C, slowly add Pd2dba3 0.82797mmol and s-PHOS 1.6560mmol. After the addition, continue to raise the temperature to 105 C under reflux for 2h, and then lower the temperature to 70 C.81.141 mmol of 2- (4-bromophenyl) naphthalene was added, and the temperature was further increased to 105 C. under reflux for 12 h. After the reaction was completed, the temperature was lowered and the mixture was extracted with dichloromethane. The organic phase was washed with water, dried, filtered and concentrated. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it was recrystallized to LC> 99.95%. Compound 21 was dried. Yield: 80%.

Reference： [1]Patent: CN110240546,2019,A .Location in patent: Paragraph 0117-0120

65
[ 108714-73-4 ]
[ 60631-83-6 ]
[ 2245-43-4 ]
C₄₉H₄₅N [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
62%	Stage #1: 9,9-dimethyl-9H-fluoren-2-ylamine; 4-(1-Adamantyl)bromobenzene With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; sodium t-butanolate In toluene at 70 - 105℃; for 2h; Inert atmosphere; Stage #2: 4’-Bromo-[1,1’:3’,1”]terphenyl In toluene at 70 - 105℃; for 24h;	22 Under nitrogen, 82.797 mmol of 4-adamantyl bromobenzene, 82.797 mmol of 2-amino-9,9-dimethylfluorene, 482 mL of toluene, 248.391 mmol of sodium tert-butoxide were added to the reaction flask, and the temperature was raised to At 70 ° C, slowly add Pd2dba3 0.82797mmol and s-PHOS 1.6560mmol. After the addition, continue to warm to 105 ° C and reflux for 2h, and then lower the temperature to 70 ° C.81.141 mmol of 4'-bromo-1,1 ': 3', 1 ”-terphenyl was continued to reflux at 105 ° C for 24 hours. After the reaction was completed, the temperature was lowered and the mixture was extracted with dichloromethane. The organic phase was washed with water, dried, filtered, and concentrated. Recrystallize after passing through the column with dichloroethane to LC> 99.95%. Dry to obtain compound 22. Yield: 62%.

Reference： [1]Current Patent Assignee: SHAANXI LIGHTE OPTOELECTRONICS MATERIAL CO.,LTD - CN110240546, 2019, A Location in patent: Paragraph 0121-0124

66
[ 108714-73-4 ]
[ 1190360-23-6 ]
[ 1246021-35-1 ]

Yield	Reaction Conditions	Operation in experiment
63%	With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene;Reflux;	In a round bottom flask, 20.0 g of the above <strong>[1190360-23-6]3-bromo-9,9-dimethyl-9H-fluorene</strong> (<strong>[1190360-23-6]3-bromo-9,9-dimethyl-9H-fluorene</strong>) and 16.9 g of 9,9-dimethyl-9H-fluoren-2-amine, 10.5 g of t-BuONa, 2.7 g of Pd2 (dba) 3, and 3.3 ml of (t-Bu) 3P were dissolved in 400 ml of toluene, and then stirred under reflux.The reaction was confirmed by thin-layer chromatography, and after adding water, the reaction was completed.The organic layer was extracted with methyl cellulose, filtered under reduced pressure, and then recrystallized to obtain 18.5 g (yield 63%) of OP1.

Reference： [1]Patent: CN110551087,2019,A .Location in patent: Paragraph 0163-0166

67
[ 108714-73-4 ]
[ 23801-23-2 ]
C₃₁H₂₁Br [ No CAS ]
C₆₈H₄₇N [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
77%		Intermediate I-34 (see Synthesis Example 13) 1.78 g (5.0 mmol), <strong>[108714-73-4]9,9-dimethyl-9H-fluoren-2-amine</strong> 1.04 g (5.0 mmol), Pd (dba) (Tris (dibenzylideneacetone)dipalladium (0)) 0.09 g (0.1 mmol), 0.01 g (0.1 mmol) of P t Bu (Tri-tert-butylphosphine) and 1.38 g (10.0 mmol) of KO t Bu were dissolved in 20 mL of toluene,followed by 2 hours at 85 C. Was stirred. The reaction solution was cooled to room temperature, and extracted three times with 20 mL of water and 20 mL ofdiethyl ether. The organic layer obtained therefrom was dried over magnesium sulfate, the solvent was evaporated, and the residue obtained was dissolved in 20mL of toluene again. Intermediate I-42 (see Synthesis Example 2) 2.37 g (5.0 mmol), Pd (dba) 0.09 g (0.1 mmol), P t Bu 0.01 g (0.1 mmol) and KO tBu 1.38 g(10.0 mmol) was added, followed by stirring at 85 C. for 2 hours. The reaction solution was cooled to room temperature, and extracted three times with 20 mL ofwater and 20 mL of diethyl ether. The organic layer thus obtained was dried over magnesium sulfate, and the residue obtained by evaporation of the solvent wasseparated and purified through silica gel column chromatography to obtain Compound 48 (3.38 g, 77% yield). The produced compound was confirmed by MS /FAB and H NMR.

Reference： [1]Patent: KR102052070,2019,B1 .Location in patent: Paragraph 0043-0046

68
[ 108714-73-4 ]
C₂₂H₁₄BrN [ No CAS ]
C₃₇H₂₈N₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
83%	With potassium carbonate; In toluene; at 95℃; for 24h;	<strong>[108714-73-4]9,9-dimethyl-9H-fluoren-2-amine</strong> (6.5g, 0.031mol), Pd (pph3) 4 (1.6g, 0.0013mol), in Intermediate 15-1 (10.0g, 0.027mol)TOL 300ml was added to potassium carbonate (11.1g, 0.081mol) and reacted at 95 C for 24 hours. After the completion of the reaction, the mixture was cooled, and the layers were separated into H20: MC and purified by column (n-Hexane: MC) to obtain 11.2 g (yield 83%) of intermediate 15-2.

Reference： [1]Patent: KR101550429,2015,B1 .Location in patent: Paragraph 0187; 0191-0195

69
[ 108714-73-4 ]
[ 1097884-37-1 ]
C₃₃H₂₆N₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
79%	With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In toluene; at 95℃; for 24h;	<strong>[108714-73-4]9,9-dimethyl-9H-fluoren-2-amine</strong> (6.5g, 0.031mol / sigma aldrich), Pd (pph3) 4 (1.8g, 0.0015mol), in Intermediate 1-3 (10.0g, 0.031mol),TOL 300ml was added to potassium carbonate (12.8g, 0.0935mol) and reacted at 95 C for 24 hours. After the completion of the reaction, the mixture was cooled and separated by H20: MC, followed by column purification (n-Hexane: MC), to obtain 11.0 g (yield 79%) of intermediate 7-1.

Reference： [1]Patent: KR101550429,2015,B1 .Location in patent: Paragraph 0157-0161

70
[ 108714-73-4 ]
[ 2113-57-7 ]
N-((1,1'-biphenyl)-3-yl)-9,9-dimethyl-9H-fluoren-2-amine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
90%	With tris-(dibenzylideneacetone)dipalladium(0); sodium t-butanolate; XPhos; In toluene; at 108℃; for 4h;Inert atmosphere;	Combine 2-amino 9,9-dimethylfluorene (4g, 17.31mmol), 3-bromobiphenyl (3.70g, 17.65mmol), tris (dibenzylideneacetone) dipalladium (0.16g, 0.17mmol), 2-Dicyclohexylphosphonium-2 ', 4', 6'-triisopropylbiphenyl (0.17g, 0.35mmol) and sodium tert-butoxide (2.49g, 25.96mmol) were added to toluene (30mL) under nitrogen protection It was heated to 108 C and stirred for 4h; after the reaction liquid was cooled to room temperature, the reaction liquid was washed with water until neutral. Afterwards, magnesium sulfate was added to the organic phase for drying. After filtration, the filtrate was removed under reduced pressure to remove the solvent; dichloromethane / n-heptane (v / v) = 1: 5 is the mobile solid crude product purified by silica gel column chromatography to obtain solid intermediate II-C (5.7g, yield 90%).

Reference： [1]Patent: CN110903260,2020,A .Location in patent: Paragraph 0106; 0125-0126

71
[ 108714-73-4 ]
[ 2351-50-0 ]
C₂₃H₂₁N [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
67%	With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; at 100℃;	2L round bottom flask <strong>[108714-73-4]9,9-dimethyl-9H-fluoren-2-amine</strong> (25.2 g, 120 mmol), 1-iodo-4-vinylbenzene (23 g, 100 mmol), Pd2(dba)3 (4.6 g, 5 mmol), P(t-Bu)3 (2 g, 10 mmol), NaOt-Bu (29 g, 300 mmol), After adding toluene (960 mL), the reaction was performed at 100C. After the reaction was completed, the mixture was extracted with ether and water, and the organic layer was dried over MgSO4, concentrated, and the resulting organic material was silicagel column and recrystallized to obtain 20.9 g (67%) of the product.

Reference： [1]Patent: KR102109353,2020,B1 .Location in patent: Paragraph 0300-0304; 0312

72
[ 108714-73-4 ]
[ 942615-32-9 ]
C₃₀H₂₇N [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With tris-(dibenzylideneacetone)dipalladium(0); sodium t-butanolate; In toluene; at 100℃; for 8h;	(4) In the reaction bottle, add 35.7g (100mmol) of 2-amino-9,9-dimethylfluorene,<strong>[942615-32-9]4-bromo-9,9-dimethylfluorene</strong> 32g (110mmol), Pd2 (dba) 3 0.9g (0.785mmol, 0.5%),500mL of toluene and 40g (300mmol) of sodium tert-butoxide, react at 100 for 8h; the reaction is completed,Stop the reaction; cool to room temperature, concentrate, and recrystallize tolueneGet M4;
	With tris-(dibenzylideneacetone)dipalladium(0); sodium t-butanolate; In toluene; at 100℃; for 8h;	(4) In the reaction bottle, add 35.7g (100mmol) of 2-amino-9,9-dimethylfluorene,<strong>[942615-32-9]4-bromo-9,9-dimethylfluorene</strong> 32g (110mmol), Pd2 (dba) 3 0.9g (0.785mmol, 0.5%),500mL of toluene and 40g (300mmol) of sodium tert-butoxide, react at 100 for 8h;After the reaction,Stop the reaction; cool to room temperature, concentrate, and recrystallize tolueneGet M4;

Reference： [1]Patent: CN111233764,2020,A .Location in patent: Paragraph 0038; 0045
[2]Patent: CN111233764,2020,A .Location in patent: Paragraph 0058; 0065

73
[ 97511-04-1 ]
[ 108714-73-4 ]
C₂₇H₂₁NS [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; sodium t-butanolate; In toluene; at 90℃; for 5h;Inert atmosphere;	In a 1000ml single-necked bottle, add 20.9g (100mmol) 2-amino-9,9'-dimethylfluorene, 28.7g (110mmol) 2-bromo-dibenzothiophene, 0.7g (1mmol) [1,1' -Bis(diphenylphosphine)ferrocene]palladium dichloride, 500ml toluene, 14.4g (150mmol) sodium tert-butoxide, vacuum exchange for nitrogen 3 times, the reaction is heated to 90C for 5h. When the reaction is complete, stop the reaction. After cooling to room temperature, the reaction solution was separated, the organic phase was concentrated, methanol was added and stirred for 1 h, and suction filtration was performed to obtain light yellow powder M9.

Reference： [1]Patent: CN111217714,2020,A .Location in patent: Paragraph 0082-0084

74
[ 97511-04-1 ]
[ 108714-73-4 ]
C₇₄H₅₂N₂S₂ [ No CAS ]

Reference： [1]Patent: CN111217714,2020,A

75
[ 108714-73-4 ]
[ 3972-65-4 ]
[ 944418-46-6 ]

Yield	Reaction Conditions	Operation in experiment
	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tri-tert-butyl phosphine; sodium t-butanolate In toluene at 110 - 120℃; Inert atmosphere;	1 In a 250mL three-neck flask, under the protection of nitrogen, add 0.02mol raw material 1, 0.022mol raw material 2, 0.05mol sodium tert-butoxide, 0.2mmol Pd2(dba)3 and 0.2mmol tri-tert-butylphosphine into 150mL toluene Stir and mix, heat to 110-120°C, reflux and react for 12-16 hours, and the reaction is complete; naturally cool to room temperature, filter, and the filtrate is evaporated under reduced pressure until there is no fraction, and passed through a neutral silica gel column.The reactant F-1 is obtained;

Reference： [1]Current Patent Assignee: VALIANT CO., LTD. - CN111471061, 2020, A Location in patent: Paragraph 0059-0061

76
[ 108714-73-4 ]
[ 154542-81-1 ]
[ 2478531-86-9 ]

Yield	Reaction Conditions	Operation in experiment
66.5%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tri-tert-butyl phosphine; sodium t-butanolate In toluene Reflux;	Under the protection of nitrogen, the raw material 1, raw material 2, tert-butanol sodium, tris(dibenzylideneacetone)dipalladium, tri-tert-butylphosphine and toluene are added to the reaction flask, and the temperature is raised to reflux.After cooling down to room temperature, add water and stir, filter to obtain the filtrate,Separate the liquids to obtain the organic phase, dry with anhydrous magnesium sulfate and spinDry and purify by column chromatography to obtain -b (yield66.5%)

Reference： [1]Current Patent Assignee: NANJING TOPTO SEMICONDUCTOR MATERIAL CO LTD - CN111548278, 2020, A Location in patent: Paragraph 0165

77
[ 108714-73-4 ]
[ 2039-82-9 ]
[ 1638541-95-3 ]

Yield	Reaction Conditions	Operation in experiment
78.6%	With tri-tert-butyl phosphine; bis(dibenzylideneacetone)-palladium⁽⁰⁾; sodium t-butanolate In toluene at 100℃; for 6h;	2.1 (1) Preparation Example 1: Synthesis of Intermediate 9-1 9,9-dimethyl-9H-fluoren-2-amine (10 g, 0.048 mol, Alfa aeser), 1-bromo-4-vinylbenzene (9.62 g, 0.048 mol, sigma aldrich), Sodium tert-butoxide (9.18 g, 0.096 mol, sigma aldrich), catalyst Pd(dba)2 (1.37 g, 0.0024 mol, sigma aldrich), tri-tert-Butylphosphine (0.97 g, 0.0048 mol, sigma aldrich) in 200 mL of Toluene and then 6 hours at 100 It was stirred and reacted. After the reaction was completed, extraction was performed and column purification was performed to obtain 11.7 g (78.6% yield) of .

Reference： [1]Current Patent Assignee: P&H TECH CO.,LTD. - KR2020/110545, 2020, A Location in patent: Paragraph 0107-0110

78
[ 108714-73-4 ]
[ 19654-19-4 ]
C₂₈H₂₂N₂S [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
72%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tri-tert-butyl phosphine; sodium t-butanolate In toluene for 3h; Inert atmosphere; Reflux;	39.39-1 39-1. Preparation of compound I6-1 In a 500-mL, 3-neck round-bottom flask, 12.1 g (0.058 mol) of 9,9-dimethyl-9H-fluoren-2-amine was added under a nitrogen atmosphere and diluted with 320 mL of toluene.In this dilution, 16.8 g of 2-(4-bromophenyl)benzo[d]thiazole,Tris(dibenzylideneacetone)dipalladium (0) 0.27 g, tri-(t-butyl)phosphine 0.12 g, and sodium t-butoxide 7.2 g were added. The reaction solution was refluxed for 3 hours, cooled, and poured into excess methanol to precipitate a solid. The obtained solid was filtered, dried in vacuo, and separated by column to obtain 17.5 g of compound I6-1 (yield 72%).
69%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tri-tert-butyl phosphine; sodium t-butanolate In toluene for 3h; Inert atmosphere; Reflux;	15-15-1 15-1. Preparation of compound J6-1 In a 500-mL, 3-neck round bottom flask, 12.1 g (0.058 mol) of 9,9-dimethyl-9H-fluoren-2-amine was added in a nitrogen atmosphere, and then diluted with 320 mL of toluene. To this diluted solution, 16.9 g of 2-(4-bromophenyl)benzo[d]thiazole, 0.27 g of tris(dibenzylideneacetone)dipalladium(0), 0.12 g of tri-(t-butyl)phosphine, and 7.2 g of sodium t-butoxide was added. The reaction solution was refluxed for 3 hours, cooled, and poured into an excess of methanol to precipitate a solid. The obtained solid was filtered, dried in vacuo, and then separated by a column to give 16.8 g of compound J6-1 (yield 69%).

Reference： [1]Current Patent Assignee: EL & M SPA - KR102260561, 2021, B1 Location in patent: Paragraph 0466-0470
[2]Current Patent Assignee: EL & M SPA - KR102212689, 2021, B1 Location in patent: Paragraph 0292-0296

79
[ 108714-73-4 ]
[ 769-92-6 ]
[ 944418-46-6 ]

Yield	Reaction Conditions	Operation in experiment
87%	With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; bis(η3-allyl-μ-chloropalladium(II)); sodium t-butanolate In 5,5-dimethyl-1,3-cyclohexadiene at 120℃; for 4h; Inert atmosphere;	24.1 Step 1: Synthesis of N-(4-t-butylphenyl)-9,9-dimethyl-9H-fluoren-2-amine In a three-neck flask were put 11.5 g (55 mmol) of 9,9-dimethyl-9H-fluoren-2-amine, 11.7 g (55 mmol) of 4-t-butylaniline, 15.9 g (165 mmol) of sodium-tert-butoxide, and 180 mL of xylene. The mixture was degassed under reduced pressure, and then the air in the flask was replaced with nitrogen. Then, 200 mg (0.55 mmol) of allylpalladium(II) chloride dimer (abbreviation: [(Allyl)PdCl]2) and 900 mg (2.20 mmol) of 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (abbreviation: Sphos (registered trademark)) were added to this mixture, and the mixture was stirred at 120° C. under a nitrogen stream for approximately 4 hours. After that, the temperature of the flask was lowered to approximately 60° C., approximately 3 mL of water was added, a precipitated solid was separated by filtration, and the solid was washed with toluene. The filtrate was concentrated, and the obtained toluene solution was purified by silica gel column chromatography. The obtained fraction was concentrated and dried under reduced pressure, whereby 16.4 g of a target brown oily substance was obtained in a yield of 87%. The synthesis scheme of N-(4-t-butyl)-9,9-dimethyl-9H-fluoren-2-amine in Step 1 is shown below.

Reference： [1]Current Patent Assignee: SEMICONDUCTOR ENERGY LABORATORY CO LTD - US2021/5814, 2021, A1 Location in patent: Paragraph 0873

80
[ 108714-73-4 ]
[ 25109-28-8 ]
[ 2572528-98-2 ]

Yield	Reaction Conditions	Operation in experiment
92%	With di-tert-butyl(2,2-diphenyl-1-methyl-1-cyclopropyl)phosphine; ϖ-allylpalladium (II) chloride dimer; sodium tertiary butoxide In 5,5-dimethyl-1,3-cyclohexadiene at 50 - 90℃; for 6h; Inert atmosphere;	2.1 Step 1: Step 1: Synthesis of N-(4-cycrohexylphenyl)-N-(9,9-dimethyl-9H-fluoren-2yl)amine In a three-neck flask were put 10.5 g (50 mmol) of 9,9-dimethyl-9H-fluoren-2-amine, 12.0 g (50 mmol) of 4-cyclohexyl-1-bromobenzene, 14.4 g (150 mmol) of sodium-tert-butoxide, and 250 mL of xylene. This mixture was degassed under reduced pressure, and then the air in the flask was replaced with nitrogen. The mixture was heated while being stirred at approximately 50° C. Then, 183 mg (0.50 mmol) of allylpalladium(II) chloride dimer (abbreviation: [(Allyl)PdCl]2) and 821 mg (2.0 mmol) of di-tert-butyl(1-methyl-2,2-diphenylcyclopropyl)phosphine (abbreviation: cBRIDP (registered trademark)) were added, and the mixture was heated at 90° C. for approximately 6 hours. After that, the temperature of the flask was lowered to approximately 60° C., approximately 4 mL of water was added to the mixture, and a precipitated solid was separated by filtration. The filtrate was concentrated, and the obtained solution was purified by silica gel column chromatography. The obtained solution was concentrated to give a condensed toluene solution. This toluene solution was dried at approximately 60° C. in a vacuum, whereby a 17.3 g of a target brown oily substance was obtained in a yield of 92%. The synthesis scheme of Step 1 is shown below.
92%	With di-tert-butyl(2,2-diphenyl-1-methyl-1-cyclopropyl)phosphine; ϖ-allylpalladium (II) chloride dimer; sodium tertiary butoxide In 5,5-dimethyl-1,3-cyclohexadiene at 0.5 - 90℃; for 0.6h; Inert atmosphere;	5.2 Step 2: Synthesis of N-(4-cyclohexylphenyl)-N-(9,9-dimethyl-9H-fluoren-2yl)amine In a three-neck flask were put 10.5 g (50 mmol) of 9,9-dimethyl-9H-fluoren-2-amine, 12.0 g (50 mmol) of 4-cyclohexyl-1-bromobenzene, 14.4 g (150 mmol) of sodium-tert-butoxide, and 250 mL of xylene. The mixture was degassed under reduced pressure, and then the air in the flask was replaced with nitrogen. The mixture was stirred while being heated to approximately 50° C. Then, 183 mg (0.50 mmol) of allylpalladium(II) chloride dimer (abbreviation: [(Allyl)PdCl]2) and 821 mg (2.0 mmol) of di-tert-butyl(1-methyl-2,2-diphenylcyclopropyl)phosphine (abbreviation: cBRIDP (registered trademark)) were added, and the mixture was heated at 90° C. for approximately six hours. After that, the temperature of the flask was lowered to approximately 60° C., approximately 4 mL of water was added to the mixture, and a precipitated solid was separated by filtration. The filtrate was concentrated, and the obtained solution was purified by silica gel column chromatography. The obtained solution was concentrated to give a condensed toluene solution. This toluene solution was dried at approximately 60° C. in a vacuum, whereby a 17.3 g of a target brown oily substance was obtained in a yield of 92%. The synthesis scheme of Step 2 is shown below.
92%	With di-tert-butyl(2,2-diphenyl-1-methyl-1-cyclopropyl)phosphine; ϖ-allylpalladium (II) chloride dimer; sodium tertiary butoxide In 5,5-dimethyl-1,3-cyclohexadiene at 0.5 - 90℃; for 0.6h; Inert atmosphere;	3.2 Step 2: Synthesis of N-(4-cyclohexylphenyl)-N-(9,9-dimethyl-9H-fluoren-2yl)amine In a three-neck flask were put 10.5 g (50 mmol) of 9,9-dimethyl-9H-fluoren-2-amine, 12.0 g (50 mmol) of 4-cyclohexyl-1-bromobenzene, 14.4 g (150 mmol) of sodium-tert-butoxide, and 250 mL of xylene. The mixture was degassed under reduced pressure, and then the air in the flask was replaced with nitrogen. The mixture was stirred while being heated to approximately 50° C. Then, 183 mg (0.50 mmol) of allylpalladium(II) chloride dimer (abbreviation: [(Allyl)PdCl]2) and 821 mg (2.0 mmol) of di-tert-butyl(1-methyl-2,2-diphenylcyclopropyl)phosphine (abbreviation: cBRIDP (registered trademark)) were added, and the mixture was heated at 90° C. for approximately six hours. After that, the temperature of the flask was lowered to approximately 60° C., approximately 4 mL of water was added to the mixture, and a precipitated solid was separated by filtration. The filtrate was concentrated, and the obtained solution was purified by silica gel column chromatography. The obtained solution was concentrated to give a condensed toluene solution. This toluene solution was dried at approximately 60° C. in a vacuum, whereby a 17.3 g of a target brown oily substance was obtained in a yield of 92%. The synthesis scheme of Step 2 is shown below.

51%

With tri-tert-butyl phosphine; Palladium⁽⁰⁾ bis(dibenzylideneacetone); sodium tertiary butoxide In toluene at 60℃; for 4h; Inert atmosphere;

6.2 (2) Synthesis of A-29-2 500ml three-neck bottle, nitrogen protection,Add 100 ml of dry toluene,2.09 g (0.01 mol) 9,9-dimethylfluoren-2-amine,2.39 g (0.01 mol) 4-cyclohexylbromobenzene,0.0575 g (0.0001 mol) Pd(dba)2 (bisdibenzylideneacetone palladium),0.4 g (0.0002 mol) of 10% tri-tert-butylphosphine in toluene,1.15 g (0.012 mol) sodium tert-butoxide,Heated to 60°C for 4 hours,Cool down, add water and liquid, and concentrate the organic layer to dryness.Separation by silica gel column chromatography, elution with petroleum ether:ethyl acetate=15:1 (volume ratio),1.87 g of the compound represented by A-29-2 was obtained with a yield of 51%.

Reference： [1]Current Patent Assignee: SEMICONDUCTOR ENERGY LABORATORY CO LTD - US2021/5814, 2021, A1 Location in patent: Paragraph 0463
[2]Current Patent Assignee: SEMICONDUCTOR ENERGY LABORATORY CO LTD - US2022/77391, 2022, A1 Location in patent: Paragraph 0377
[3]Current Patent Assignee: SEMICONDUCTOR ENERGY LABORATORY CO LTD - US2022/77391, 2022, A1 Location in patent: Paragraph 0377
[4]Current Patent Assignee: BEIJING YINQING MATERIAL TECH; FUYANG QINGHUHUA MATERIAL TECH; BEIJING YINQING SCIENCE AND TECH - CN114436868, 2022, A Location in patent: Paragraph 0073-0074; 0076; 0080-0082

81
[ 108714-73-4 ]
[ 25109-28-8 ]
[ 2572528-96-0 ]

Yield	Reaction Conditions	Operation in experiment
70%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; sodium tertiary butoxide In toluene at 80℃; for 3h;	4.78 g (20 mmol) of 1-bromo-4-cyclohexylbenzene, 2.09 g (10 mmol) of 2-amino-9,9-dimethyl-9H-fluorene, 0.46 g (0.5 mmol) of tris(dibenzylideneacetone)dipalladium(0) (Pd2dba3), and 2.88 g (30 mmol) of sodium tert-butoxide were dissolved in 60 ml of toluene and stirred at about 80° C. for about 3 hours. After cooling the reaction solution to room temperature, 40 ml of water was added, and extraction with 50 ml of ethyl ether was performed three times. The organic layer thus obtained was dried with MgSO4, and solvents were evaporated. The residue thus obtained was separated by silica gel chromatography to obtain 3.68 g (yield 70%) of Compound 83. The compound thus produced was identified through MS/FAB and 1H NMR. (C39H43N: M+cal.: 525.34, found: 525.24)
40%	With di-tert-butyl(2,2-diphenyl-1-methyl-1-cyclopropyl)phosphine; ϖ-allylpalladium (II) chloride dimer; sodium tertiary butoxide In 5,5-dimethyl-1,3-cyclohexadiene at 0.5 - 120℃; for 0.5h; Inert atmosphere;	4.1 Step 1: Synthesis of N,N-bis(4-cyclohexylphenyl)-9,9,-dimethyl-9H-fluoren-2-amine (Abbreviation: dchPAF) Step 1: Synthesis of N,N-bis(4-cyclohexylphenyl)-9,9,-dimethyl-9H-fluoren-2-amine (Abbreviation: dchPAF) In a three-neck flask were put 10.6 g (51 mmol) of 9,9-dimethyl-9H-fluoren-2-amine, 18.2 g (76 mmol) of 4-cyclohexyl-1-bromobenzene, 21.9 g (228 mmol) of sodium-tert-butoxide, and 255 mL of xylene. The mixture was degassed under reduced pressure, and then the air in the flask was replaced with nitrogen. The mixture was stirred while being heated to approximately 50° C. Then, 370 mg (1.0 mmol) of allylpalladium(II) chloride dimer (abbreviation: [(Allyl)PdCl]2) and 1660 mg (4.0 mmol) of di-tert-butyl(1-methyl-2,2-diphenylcyclopropyl)phosphine (abbreviation: cBRIDP (registered trademark)) were added, and the mixture was heated at 120° C. for approximately five hours. After that, the temperature of the flask was lowered to approximately 60° C., and approximately 4 mL of water was added to the mixture, so that a solid was precipitated. The precipitated solid was separated by filtration. The filtrate was concentrated, and the obtained solution was purified by silica gel column chromatography. The obtained solution was concentrated to give a condensed toluene solution. The toluene solution was dropped into ethanol for reprecipitation. The precipitate was collected by filtration at approximately 10° C. and the obtained solid was dried at approximately 80° C. under reduced pressure, whereby 10.1 g of a target white solid was obtained in a yield of 40%. The synthesis scheme of Step 1 is shown below. Analysis results by nuclear magnetic resonance (1H-NMR) spectroscopy of the white solid obtained in Step 1 are shown below. The results show that dchPAF was synthesized in this synthesis example. 1H-NMR. δ (CDCl3): 7.60 (d, 1H, J=7.5 Hz), 7.53 (d, 1H, J=8.0 Hz), 7.37 (d, 2H, J=7.5 Hz), 7.29 (td, 1H, J=7.5 Hz, 1.0 Hz), 7.23 (td, 1H, J=7.5 Hz, 1.0 Hz), 7.19 (d, 1H, J=1.5 Hz), 7.06 (m, 8H), 6.97 (dd, 1H, J=8.0 Hz, 1.5 Hz), 2.41-2.51 (brm, 2H), 1.79-1.95 (m, 8H), 1.70-1.77 (m, 2H), 1.33-1.45 (brm, 14H), 1.19-1.30 (brm, 2H). Then, 5.6 g of the obtained solid was purified by a train sublimation method. The purification by sublimation was conducted by heating at 215° C. under a pressure of 3.0 Pa with the argon flow rate of 12.0 mL/min. After the purification by sublimation, 5.2 g of a pale yellowish white solid was obtained at a collection rate of 94%. The refractive index of dchPAF was measured by a spectroscopic ellipsometer (M-2000U, produced by J.A. Woollam Japan Corp.). A film used for the measurement was formed to a thickness of approximately 50 nm with the material of each layer over a quartz substrate by a vacuum evaporation method. The results show that dchPAF is a material with a low refractive index: the ordinary refractive index is within the range of 1.50 to 1.75 in the entire blue emission region (from 455 nm to 465 nm), and the ordinary refractive index at 633 nm is within the range of 1.45 to 1.70.
40%	With di-tert-butyl(2,2-diphenyl-1-methyl-1-cyclopropyl)phosphine; ϖ-allylpalladium (II) chloride dimer; sodium tertiary butoxide In 5,5-dimethyl-1,3-cyclohexadiene at 0.5 - 120℃; for 0.5h; Inert atmosphere;	2.1 Step 1: Synthesis of N,N-bis(4-cyclohexylphenyl)-9,9,-dimethyl-9H-fluoren-2-amine (Abbreviation: dchPAF) Step 1: Synthesis of N,N-bis(4-cyclohexylphenyl)-9,9,-dimethyl-9H-fluoren-2-amine (Abbreviation: dchPAF) In a three-neck flask were put 10.6 g (51 mmol) of 9,9-dimethyl-9H-fluoren-2-amine, 18.2 g (76 mmol) of 4-cyclohexyl-1-bromobenzene, 21.9 g (228 mmol) of sodium-tert-butoxide, and 255 mL of xylene. The mixture was degassed under reduced pressure, and then the air in the flask was replaced with nitrogen. The mixture was stirred while being heated to approximately 50° C. Then, 370 mg (1.0 mmol) of allylpalladium(II) chloride dimer (abbreviation: [(Allyl)PdCl]2) and 1660 mg (4.0 mmol) of di-tert-butyl(1-methyl-2,2-diphenylcyclopropyl)phosphine (abbreviation: cBRIDP (registered trademark)) were added, and the mixture was heated at 120° C. for approximately five hours. After that, the temperature of the flask was lowered to approximately 60° C., and approximately 4 mL of water was added to the mixture, so that a solid was precipitated. The precipitated solid was separated by filtration. The filtrate was concentrated, and the obtained solution was purified by silica gel column chromatography. The obtained solution was concentrated to give a condensed toluene solution. The toluene solution was dropped into ethanol for reprecipitation. The precipitate was collected by filtration at approximately 10° C. and the obtained solid was dried at approximately 80° C. under reduced pressure, whereby 10.1 g of a target white solid was obtained in a yield of 40%. The synthesis scheme of Step 1 is shown below. Analysis results by nuclear magnetic resonance (1H-NMR) spectroscopy of the white solid obtained in Step 1 are shown below. The results show that dchPAF was synthesized in this synthesis example. 1H-NMR. δ (CDCl3): 7.60 (d, 1H, J=7.5 Hz), 7.53 (d, 1H, J=8.0 Hz), 7.37 (d, 2H, J=7.5 Hz), 7.29 (td, 1H, J=7.5 Hz, 1.0 Hz), 7.23 (td, 1H, J=7.5 Hz, 1.0 Hz), 7.19 (d, 1H, J=1.5 Hz), 7.06 (m, 8H), 6.97 (dd, 1H, J=8.0 Hz, 1.5 Hz), 2.41-2.51 (brm, 2H), 1.79-1.95 (m, 8H), 1.70-1.77 (m, 2H), 1.33-1.45 (brm, 14H), 1.19-1.30 (brm, 2H). Then, 5.6 g of the obtained solid was purified by a train sublimation method. The purification by sublimation was conducted by heating at 215° C. under a pressure of 3.0 Pa with the argon flow rate of 12.0 mL/min. After the purification by sublimation, 5.2 g of a pale yellowish white solid was obtained at a collection rate of 94%. The refractive index of dchPAF was measured by a spectroscopic ellipsometer (M-2000U, produced by J.A. Woollam Japan Corp.). A film used for the measurement was formed to a thickness of approximately 50 nm with the material of each layer over a quartz substrate by a vacuum evaporation method. The results show that dchPAF is a material with a low refractive index: the ordinary refractive index is within the range of 1.50 to 1.75 in the entire blue emission region (from 455 nm to 465 nm), and the ordinary refractive index at 633 nm is within the range of 1.45 to 1.70.

With di-tert-butyl(2,2-diphenyl-1-methyl-1-cyclopropyl)phosphine; ϖ-allylpalladium (II) chloride dimer; sodium tertiary butoxide In 5,5-dimethyl-1,3-cyclohexadiene at 50 - 120℃; for 5h; Inert atmosphere;

1.1 Step 1: Step 1: Synthesis of N,N-bis(4-cyclohexylphenyl)-9,9,-dimethyl-9H-fluoren-2-amine (Abbreviation: dchPAF) In a three-neck flask were put 10.6 g (51 mmol) of 9,9-dimethyl-9H-fluoren-2-amine, 18.2 g (76 mmol) of 4-cyclohexyl-1-bromobenzene, 21.9 g (228 mmol) of sodium-tert-butoxide, and 255 mL of xylene. This mixture was degassed under reduced pressure, and then the air in the flask was replaced with nitrogen. The mixture was stirred while being heated to approximately 50° C. Then, 370 mg (1.0 mmol) of allylpalladium(II) chloride dimer (abbreviation: [(Allyl)PdCl]2) and 1660 mg (4.0 mmol) of di-tert-butyl(1-methyl-2,2-diphenylcyclopropyl)phosphine (abbreviation: cBRIDP (registered trademark)) were added, and the mixture was heated at 120° C. for approximately 5 hours. After that, the temperature of the flask was lowered to approximately 60° C., and approximately 4 mL of water was added to the mixture, so that a solid was precipitated. The precipitated solid was separated by filtration. The filtrate was concentrated, and the obtained solution was purified by silica gel column chromatography. The obtained solution was concentrated to give a concentrated toluene solution. The toluene solution was dropped into ethanol for reprecipitation. The precipitate was collected by filtration at approximately 10° C. and the obtained solid was dried at approximately 80° C. under reduced pressure, whereby 10.1 g of a target white solid was obtained in a yield of 40%. The synthesis scheme of dchPAF in Step 1 is shown below. Analysis results by nuclear magnetic resonance spectroscopy (1H-NMR) of the white solid obtained in Step 1 are shown below. 0449) Analysis results by nuclear magnetic resonance spectroscopy (1H-NMR) of the white solid obtained in Step 1 are shown below. FIG. 14 show the 1H-NMR chart. The results show that dchPAF was synthesized in this synthesis example. (0450) 1H-NMR. δ (CDCl3): 7.60 (d, 1H, J=7.5 Hz), 7.53 (d, 1H, J=8.0 Hz), 7.37 (d, 2H, J=7.5 Hz), 7.29 (td, 1H, J=7.5 Hz, 1.0 Hz), 7.23 (td, 1H, J=7.5 Hz, 1.0 Hz), 7.19 (d, 1H, J=1.5 Hz), 7.06 (m, 8H), 6.97 (dd, 1H, J=8.0 Hz, 1.5 Hz), 2.41-2.51 (brm, 2H), 1.79-1.95 (m, 8H), 1.70-1.77 (m, 2H), 1.33-1.45 (brm, 14H), 1.19-1.30 (brm, 2H). (0451) Then, 5.6 g of the obtained solid was purified by a train sublimation method. The purification by sublimation was conducted by heating at 215° C. under a pressure of 3.0 Pa with the argon flow rate of 12.0 mL/min. After the purification by sublimation, 5.2 g of a pale yellowish white solid was obtained at a collection rate of 94%. (0452) Next, an ultraviolet-visible absorption spectrum (hereinafter, simply referred to as an absorption spectrum) of dchPAF in a toluene solution and an emission spectrum thereof were measured. The absorption spectrum was measured with an ultraviolet-visible light spectrophotometer (V-550, manufactured by JASCO Corporation), and the emission spectrum was measured with a fluorescence spectrophotometer (FS920, manufactured by Hamamatsu Photonics K.K.), both of which were measured at room temperature. A quartz cell was used for the measurement cell. FIG. 15 shows measurement results of the absorption spectrum and emission spectrum. The horizontal axis represents the wavelength and the vertical axes represent the absorption intensity and emission intensity. The absorption intensity shown in FIG. 15 is a result obtained by subtraction of an absorption spectrum of only toluene in a quartz cell from the measured absorption spectrum of the toluene solution in the quartz cell. (0453) As shown in FIG. 15, the organic compound dchPAF has an emission peak at 354 nm. (0454) Next, the organic compound dchPAF was subjected to a mass spectrometry (MS) analysis by liquid chromatography-mass spectrometry (LC-MS). (0455) In the LC-MS analysis, liquid chromatography (LC) separation was carried out with ACQUITY UPLC (registered trademark) manufactured by Waters Corporation, and MS analysis (mass spectrometry) was carried out with Xevo G2 Tof MS manufactured by Waters Corporation. Acquity UPLC BEH C8 (2.1×100 mm, 1.7 μm) was used as a column for the LC separation, and the column temperature was 40° C. Acetonitrile was used for Mobile Phase A and a 0.1% aqueous solution of formic acid was used for Mobile Phase B. Furthermore, a sample was prepared in such a manner that dchPAF was dissolved in toluene at a given concentration and the mixture was diluted with acetonitrile. The injection amount was 5.0 μL. (0456) In the LC separation, the ratio of Mobile Phase A to Mobile Phase B was 95:5 for 10 minutes after the start (0 minutes) of the measurement. (0457) In the MS analysis, ionization was carried out by an electrospray ionization (ESI) method. At this time, the capillary voltage and the sample cone voltage were set to 3.0 kV and 30 V, respectively, and detection was performed in a positive mode. A component with m/z of 525 underwent the ionization under the above-described conditions was collided with an argon gas in a collision cell to dissociate into product ions. Energy (collision energy) for the collision with argon was 50 eV The measurement mass range was set to m/z (mass-to-charge ratio)=100 to 1500. The detection result of the dissociated product ions by time-of-flight (TOF) MS are shown in FIG. 16. (0458) FIG. 16 shows that product ions of dchPAF are mainly detected at m/z of around 525. Note that the result in FIG. 16 shows characteristics derived from dchPAF and therefore can be regarded as important data for identifying dchPAF contained in a mixture. (0459) Note that a fragment ion at m/z of 367, which was observed in measurement with a collision energy of 50 eV, is estimated to be derived from N-(4-cyclohexylphenyl)-N-(9,9-dimethyl-9H-fluoren-2yl)amine generated in such a manner that a C-N bond of dchPAF was cut, and this is the characteristics of dchPAF. (0460) FIG. 82 shows the results of measuring the refractive index of dchPAF by a spectroscopic ellipsometer (M-2000U, produced by J.A. Woollam Japan Corp.). A film used for the measurement was formed to a thickness of approximately 50 nm with the material of each layer over a quartz substrate by a vacuum evaporation method. Note that a refractive index of an ordinary ray, n, Ordinary, and a refractive index of an extraordinary ray, n, Extra-ordinary are shown in FIG. 82. (0461) FIG. 82 shows that dchPAF is a material with a low refractive index: the refractive index of an ordinary ray is within the range of 1.50 to 1.75 in the entire blue light emitting region (from 455 nm to 465 nm), and the refractive index at 633 nm is within the range of 1.45 to 1.70.

Reference： [1]Current Patent Assignee: SAMSUNG ELECTRONICS CO.,LTD.; Samsung Display (in: Samsung) - US2021/234098, 2021, A1 Location in patent: Paragraph 0185-0187
[2]Current Patent Assignee: SEMICONDUCTOR ENERGY LABORATORY CO LTD - US2022/77391, 2022, A1 Location in patent: Paragraph 0369-0374
[3]Current Patent Assignee: SEMICONDUCTOR ENERGY LABORATORY CO LTD - US2022/77391, 2022, A1 Location in patent: Paragraph 0369-0374
[4]Current Patent Assignee: SEMICONDUCTOR ENERGY LABORATORY CO LTD - US2021/5814, 2021, A1 Location in patent: Paragraph 0448-0461

82
[ 108714-73-4 ]
[ 1346635-65-1 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1.1: NBS / N,N-dimethyl-formamide / 0 - 20 °C 2.1: sulfuric acid / 1 h / 20 °C 2.2: 1 h / 0 - 20 °C
	Multi-step reaction with 2 steps 1.1: NBS / dichloromethane / 0 °C 2.1: hydrogenchloride; NaNO₂ / lithium hydroxide monohydrate / 0.5 h / 0 °C 2.2: 0 - 20 °C

Reference： [1]Current Patent Assignee: BEIJING SUMMER SPROUT TECHNOLOGY CO LTD - JP2021/31496, 2021, A
[2]Wei, Jia-Jia; Yang, Yong-Jian; Liu, Xiang-Yang; Li, Runlai; Li, Shu-an [Chemistry - A European Journal, 2022, vol. 28, # 39]

83
[ 108714-73-4 ]
[ 495-71-6 ]
[ 2650505-65-8 ]

Yield	Reaction Conditions	Operation in experiment
91%	With trifluoroacetic acid In toluene at 110℃; for 1.5h;	1-(4-tert-Butylphenyl)-2,5-diphenyl-1H-pyrrole (1a); Typical Procedure for the Preparation of Pyrroles 1 General procedure: A 300-mL flask was charged with 4-tert-butylaniline (5.8 mL, 36 mmol), 1,4-diphenyl-1,4-butanedione (7.06 g, 29.6 mmol), and toluene (120 mL). TFA (4.6 mL, 60 mmol) was added at room temperature and the mixture was stirred at 110 °C for 3 h. The reaction was quenched with sat. aq NaHCO3 at 0 °C; pyrrole 1a precipitated immediately. The white precipitates were filtered off and washed with H2O and Et2O to afford 1a (8.69 g, 24.7 mmol, 83% yield) as a white solid.

Reference： [1]Ozaki, Tomoya; Kaga, Atsushi; Saito, Hayate; Yorimitsu, Hideki [Synthesis, 2021, vol. 53, # 17, p. 3019 - 3028]

84
[ 97511-05-2 ]
[ 108714-73-4 ]
[ 1792218-68-8 ]

Yield	Reaction Conditions	Operation in experiment
84.7%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; sodium t-butanolate; XPhos In toluene at 70℃; for 1h; Inert atmosphere;	Synthesis of Intermediate D-1 General procedure: Under the protection of nitrogen, add NM-1 (30g, 159mmol), M-1 (15.6g, 168mmol), 240mL of ultra-dry toluene into a 500mL three-necked flask;Stir and raise the temperature to 70°C, add sodium tert-butoxide (22.8g, 237mmol), X-Phos (1.32g, 3.18mmol), Pd2(dba)3 (1.47g, 1.59mmol) in sequence, and heat to reflux for 1h. Reduce to room temperature, wash with water three times, add 20g anhydrous magnesium sulfate to dry, and let stand for 30 minutes;Suction filtration, high pressure concentration. After passing through a column chromatography column, intermediate D-1 (34.8 g, 89.3%) was obtained.
98 %	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tri-tert-butyl phosphine; sodium t-butanolate In hexane; toluene at 100℃;	41 Reference example 41 4-bromodibenzothiophene (2.56 g, 9.74 mmol),2-amino-9,9-dimethylfluorene (2.43 g, 11.6 mmol),Toluene (33.5 mL) was added to sodium t-butoxide (1.63 g, 17.0 mmol), and allinine (1.47 mL, 15.3 mmol) was added thereto.After degassing,1M hexane solution of tri-t-butylphosphine (190 μL, 190 μmol),Tris(dibenzylideneacetone)dipalladium(0) (93.5 mg, 102 μmol) was added and stirred at 100° C. for 14 hours.After cooling to room temperature, add water (30 mL),Extracted three times with ethyl acetate (30 mL).The organic layers were combined, washed with water (10 mL) and saturated brine (10 mL), dried over magnesium sulfate, and concentrated under reduced pressure.By washing the obtained crude product with methanol,A yellow-green solid of N-(9,9-dimethyl-9H-fluoren-2-yl)dibenzo[b,d]thiophen-4-amine was obtained.(2.21 g yield, 80% yield).In addition, the washing liquid is concentrated under reduced pressure,The resulting residue was washed with ethanol to give N-(9,9-dimethyl-9H-fluoren-2-yl)dibenzo[b,d]thiophen-4-amineof yellow-green solid was obtained (total yield 3.72 g, yield 98%).

Reference： [1]Current Patent Assignee: SHAANXI LIGHTE OPTOELECTRONICS MATERIAL CO.,LTD - CN113214280, 2021, A Location in patent: Paragraph 0116-0118; 0119; 0123
[2]Current Patent Assignee: SAGAMI CHEMICAL RESEARCH INSTITUTE; TOSOH CORPORATION - WO2023/282236, 2023, A1 Location in patent: Paragraph 0734-0736

85
[ 185112-61-2 ]
[ 108714-73-4 ]
[ 2341915-30-6 ]

Yield	Reaction Conditions	Operation in experiment
91.3%	With Palladium⁽⁰⁾ bis(dibenzylideneacetone); sodium tertiary butoxide; 2,4,6-tri-tert-butylpyrimidine In toluene at 100℃; for 6h; Inert atmosphere;	3 Synthesis of compound 3-3: Compound 3-1 (10 mmol), compound 3-2 (10 mmol), Pd(dba) 2 (0.1 mmol),TTBP (0.2 mmol) and sodium tert-butoxide (30 mmol) were dissolved in toluene,Stir at 100 °C for 6 h under nitrogen atmosphere.After cooling, the solvent was removed by rotary evaporation.Extraction and washing with water,The organic phase column chromatography gave compound 3-3,Yield: 91.3%.

Reference： [1]Current Patent Assignee: TCL TECHNOLOGY GROUP CORPORATION - CN113816894, 2021, A Location in patent: Paragraph 0141-0144

86
[ 22439-61-8 ]
[ 108714-73-4 ]
[ 1429508-81-5 ]

Yield	Reaction Conditions	Operation in experiment
85.1%	With tri-tert-butyl phosphine; bis(dibenzylideneacetone)-palladium⁽⁰⁾; sodium t-butanolate In toluene at 100℃; for 6h; Inert atmosphere;	5 Synthesis of compound 5-1 Accurately weigh 2-amino-9,9-dimethylfluorene (20.9g, 100mmol), 2-bromodibenzothiophene (26.3g, 100mmol), tris(dibenzylideneacetone)dipalladium (1.73g, 3mmol), sodium tert-butoxide (14.4g, 0.15mol) was added successively in the three-necked flask of 1000mL, about 500mL of anhydrous toluene was added, and tri-tert-butylphosphine (mass-to-body ratio) was added dropwise to the reaction system after pumping and filling nitrogen three times. 10% 12 mL), then warmed to 100 °C and reacted for 6 hours. After the reaction was completed, it was passed through silica gel and rinsed twice with ethyl acetate. The organic phases were combined, spin-dried and beaten with petroleum ether to obtain about 33.3 g of compound 5-1, yield: 85.1%.
	With tri-tert-butyl phosphine; palladium diacetate; sodium t-butanolate In toluene Reflux; Inert atmosphere;	30 Preparation of intermediate A-16: General procedure: Under nitrogen protection, a-16 (15.79g, 60.00mmol),b-16 (11.96g, 60.00mmol), sodium tert-butoxide (10.38g, 108.00mmol)Add to 300ml toluene, add Pd(OAc)2(0.16g, 0.72mmol) under stirring,P(t-Bu)3 (2.88 mL of 0.50 M in toluene, 1.44 mmol),The mixed solution of the above reactants was heated to reflux for 5h. After the reaction,The reaction solution was cooled to room temperature, distilled water was added, extracted with dichloromethane, allowed to stand for liquid separation,The collected organic layer was dried with anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by distillation under reduced pressure.Cooling and crystallization, suction filtration, recrystallization of the obtained solid with toluene/methanol (volume ratio 8:1),The intermediate A-16 (18.77g, 82%) was obtained, and the purity of the solid detected by HPLC was ≧99.41%.

Reference： [1]Current Patent Assignee: GUANGZHOU ZHUIGUANG TECH - CN114957229, 2022, A Location in patent: Paragraph 0162-0165
[2]Current Patent Assignee: CHANGCHUN HYPERIONS TECH CO LTD - CN116063261, 2023, A Location in patent: Paragraph 0163-0166; 0177-0180; 0306-0308

87
[ 108714-73-4 ]
[ 2088537-45-3 ]
[ 2761520-23-2 ]

Yield	Reaction Conditions	Operation in experiment
57 %	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tri-tert-butyl phosphine; sodium t-butanolate In toluene Inert atmosphere; Reflux;	16.16-1 16-1.Preparation of compound C9-1 12.1 g (0.058 mol) of 9,9-dimethyl-9H-fluoren-2-amine was added to a 500-mL, three-necked round-bottom flask under a nitrogen atmosphere and diluted with 360 mL of toluene.In this diluted solution, 23.2 g of 4-(3-bromophenyl)-6-phenyldibenzo[b,d]furan, 0.27 g of tris(dibenzylideneacetone)dipalladium(0), and tri-(t-butyl)phos 0.12 g of pin and 7.2 g of sodium t-butoxide were added.The reaction solution was refluxed for 3 hours, cooled, and poured into an excess of methanol to precipitate a solid.The obtained solid was filtered, dried in vacuo, and then separated by a column to obtain 17.5 g of compound C9-1 (yield: 57%).

Reference： [1]Current Patent Assignee: EL & M SPA - KR102392487, 2022, B1 Location in patent: Paragraph 0216-0219

88
[ 108714-73-4 ]
[ 2088537-45-3 ]
[ 2761519-83-7 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tri-tert-butyl phosphine; sodium t-butanolate / toluene / 3 h / Inert atmosphere; Reflux 2: palladium diacetate; tri-tert-butyl phosphine; sodium t-butanolate / o-xylene / 5 h / Reflux

Reference： [1]Current Patent Assignee: EL & M SPA - KR102392487, 2022, B1

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[ CAS No. 108714-73-4 ] {[proInfo.proName]}

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