[ CAS No. 89827-45-2 ] {[proInfo.proName]}

Name: 89827-45-2|4-Bromodibenzo[b,d]furan|97%
Brand: Ambeed
SKU: A435139
Price: 5.0 USD
Availability: InStock
Rating: 95 (26 reviews)

,{[proInfo.pro_purity]}

Cat. No.: {[proInfo.prAm]}

2D 3D

Structure of 89827-45-2 * Storage: {[proInfo.prStorage]}

Cart0 Add to My Favorites Add to My Favorites Bulk Inquiry Inquiry Add To Cart

Search after Editing

* Storage: {[proInfo.prStorage]}

For Research Only 110K+ Compounds Competitive Price 1-2 Day Shipping

Quality Control of [ 89827-45-2 ]

COA NMR CNMR HPLC LC-MS

Related Doc. of [ 89827-45-2 ]

SDS Specification

Alternatived Products of [ 89827-45-2 ]

Product Details of [ 89827-45-2 ]

CAS No. :	89827-45-2	MDL No. :	MFCD00185685
Formula :	C₁₂H₇BrO	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	DYTYBRPMNQQFFL-UHFFFAOYSA-N
M.W :	247.09	Pubchem ID :	458256
Synonyms :

Calculated chemistry of [ 89827-45-2 ]

Physicochemical Properties

Num. heavy atoms :	14
Num. arom. heavy atoms :	13
Fraction Csp3 :	0.0
Num. rotatable bonds :	0
Num. H-bond acceptors :	1.0
Num. H-bond donors :	0.0
Molar Refractivity :	61.42
TPSA :	13.14 Å²

Pharmacokinetics

GI absorption :	High
BBB permeant :	Yes
P-gp substrate :	No
CYP1A2 inhibitor :	Yes
CYP2C19 inhibitor :	Yes
CYP2C9 inhibitor :	No
CYP2D6 inhibitor :	No
CYP3A4 inhibitor :	No
Log Kp (skin permeation) :	-4.34 cm/s

Lipophilicity

Log Po/w (iLOGP) :	2.67
Log Po/w (XLOGP3) :	4.88
Log Po/w (WLOGP) :	4.35
Log Po/w (MLOGP) :	3.5
Log Po/w (SILICOS-IT) :	4.12
Consensus Log Po/w :	3.9

Druglikeness

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

Water Solubility

Log S (ESOL) :	-5.13
Solubility :	0.00182 mg/ml ; 0.00000735 mol/l
Class :	Moderately soluble
Log S (Ali) :	-4.89
Solubility :	0.00317 mg/ml ; 0.0000128 mol/l
Class :	Moderately soluble
Log S (SILICOS-IT) :	-5.82
Solubility :	0.000374 mg/ml ; 0.00000151 mol/l
Class :	Moderately soluble

Medicinal Chemistry

PAINS :	0.0 alert
Brenk :	0.0 alert
Leadlikeness :	2.0
Synthetic accessibility :	2.53

Safety of [ 89827-45-2 ]

Signal Word:	Warning	Class:	N/A
Precautionary Statements:	P305+P351+P338	UN#:	N/A
Hazard Statements:	H302-H319-H413	Packing Group:	N/A
GHS Pictogram:

Application In Synthesis of [ 89827-45-2 ]

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

Upstream synthesis route of [ 89827-45-2 ]
Downstream synthetic route of [ 89827-45-2 ]

[ 89827-45-2 ] Synthesis Path-Upstream 1~16

1
[ 132-64-9 ]
[ 89827-45-2 ]

Yield	Reaction Conditions	Operation in experiment
75%	Stage #1: With n-butyllithium In tetrahydrofuran; hexane at -70 - 0℃; for 2 h; Inert atmosphere Stage #2: With ethylene dibromide In tetrahydrofuran; hexane for 12 h;	33.6 mg (200 mmol) of dibenzofuran was dissolved in 700 ml of THF under a nitrogen atmosphere. To this was added 350 ml of n-butyl lithium (1.6 mol/1 hexane solution) at −70° C. or less. After completion of addition, the mixture was stirred at −70° C or less for 1 hour. Then, the reaction mixture was heated to 0° C. and it was stirred for 1 hour. The reaction mixture was cooled again to −70° C. or less, and 45 g (300 ml) of 1,2-dibromoethane was added dropwise. After completion of drop, the reaction mixture was stirred for 12 hours. Then, water was added to the reaction mixture, and the reaction product was extracted with ethyl acetate. The organic layer was washed with water, and the solvent was removed under a reduced pressure. The produced residue was recrystallized with hexane to obtain 37.1 g of an intermediate 1. The yield was 75percent. The structure of the compound was confirmed with NMR and mass spectrum.
74%	Stage #1: With n-butyllithium In tetrahydrofuran at -40 - 20℃; for 2.5 h; Inert atmosphere Stage #2: With ethylene dibromide In tetrahydrofuran at -78 - 20℃; for 2.5 h;	Synthesis of Intermediate 20 (0137) (0138) Under a nitrogen atmosphere, dibenzofuran (1.68 g, 10 mmol) was dissolved in tetrahydrofuran (10 mL), and mixed with n-BuLi (2.5 M, 4 mL) at −40° C. The cooling device was removed, and the reaction solution was placed in a water bath and warmed to room temperature in about 30 min, and then stirred for 2 hrs. Then, the reaction solution was cooled to −78° C., and 1,2-dibromoethane (2.82 g, 15 mmol) in tetrahydrofuran (10 mL) was added dropwise. The cooling device was removed, and the mixture was placed in a water bath and warmed to room temperature in about 30 min, and then stood for 2 hrs. (0139) After the reaction was terminated, the reaction solution was washed with a saturated sodium chloride solution, taken up in a 2 N aqueous HCl solution, stirred for 30 min, and extracted with diethyl ether. (0140) The organic layer was dried over anhydrous magnesium sulfate to remove a small amount of water contained therein, suctioned, and concentrated. The resultant compound was purified by column chromatography eluting with Hex:EA=5:1, to obtain Intermediate 20 (1.83 g, 74percent). (0141) Intermediate 20 MS(FAB): 247(M⁺)
74%	Stage #1: With n-butyllithium In tetrahydrofuran at -40 - 20℃; for 2.5 h; Inert atmosphere Stage #2: With ethylene dibromide In tetrahydrofuran at -78 - 20℃; for 2.5 h;	Under a nitrogen atmosphere, dibenzofuran (1.68 g, 10 mmol) was dissolved in tetrahydrofuran (10 mL), and mixed with n-BuLi (2.5 M, 4 mL) at −40° C. The cooling device was removed, and the reaction solution was placed in a water bath and warmed to room temperature in about 30 min, and then stirred for 2 hrs. Then, the reaction solution was cooled to −78° C., and 1,2-dibromoethane (2.82 g, 15 mmol) in tetrahydrofuran (10 mL) was added dropwise. The cooling device was removed, and the mixture was placed in a water bath and warmed to room temperature in about 30 min, and then stood for 2 hrs.After the reaction was terminated, the reaction solution was washed with a saturated sodium chloride solution, taken up in a 2 N aqueous HCl solution, stirred for 30 min, and extracted with diethyl ether.The organic layer was dried over anhydrous magnesium sulfate to remove a small amount of water contained therein, suctioned, and concentrated. The resultant compound was purified by column chromatography eluting with Hex:EA=5:1, to obtain Intermediate 16 (1.83 g, 74percent).Intermediate 16 MS(FAB): 247(M⁺)

62%	Stage #1: With n-butyllithium In tetrahydrofuran; hexane at -30 - 20℃; Inert atmosphere Stage #2: With ethylene dibromide In tetrahydrofuran; hexane at -60 - 20℃;	In an argon atmosphere, 600 ml of dehydrated tetrahydrofuran was added to 78.0 g (0.46 mol) of dibenzofuran. The resultant mixture was cooled to -30 °C and added with 300 ml (0.50 mol) of a 1.65 M hexane solution of n-butyllithium dropwise, and then, the temperature was raised to room temperature over one hour under stirring. After further stirring at room temperature for 5 h, the mixture was cooled to -60 °C and added with 60 ml (0.70 mol) of 1,2-dibromoethane dropwise over one hour. [0166] After further stirring at room temperature for 15 h, the mixture was poured into 1000 ml of iced water and then extracted with dichloromethane. The organic layer was washed with a saturated saline solution, dried over MgSO₄, filtered, and then concentrated. The concentrate was purified by silica gel chromatography and washed with tetrahydrofuran/methanol, to obtain 70 g of solid, which was identified as the following intermediate 1-9 by FD-MS analysis (yield: 62percent).
62%	Stage #1: With n-butyllithium In tetrahydrofuran; hexane at -30 - 20℃; for 6 h; Inert atmosphere Stage #2: With ethylene dibromide In tetrahydrofuran; hexane at -60 - 20℃; for 16 h;	[0182] In an argon atmosphere, 78.0 g (0.46 mol) of dibenzofuran was added with 600 ml of dehydrated tetrahydrofuran.The resultant mixture was cooled to -30 °C and added dropwise with 300 ml (0.50 mol) of a 1.65 M hexane solution ofn-butyllithium. The temperature was raised to room temperature over one hour under stirring. The mixture was stirredat room temperature for 5 h, cooled to - 60 °C, and then added dropwise with 60 ml (0.70 mol) of 1,2-dibromoethaneover one hour.[0183] After stirring at room temperature for 15 h, the mixture was poured into 1000 ml of iced water and extractedwith dichloromethane. The organic layer was washed with brine, dried over MgSO4, filtered, and then concentrated. Theconcentrate was purified by silica gel column chromatography and washed with tetrahydrofuran/methanol to obtain 70g of solid, which was identified as the following intermediate 1-3 by FD-MS (yield: 62percent).
70 g	Stage #1: With n-butyllithium In tetrahydrofuran; hexane at -30 - 20℃; for 6 h; Inert atmosphere Stage #2: With ethylene dibromide In tetrahydrofuran; hexane at -60 - 20℃; for 16 h;	Under an argon atmosphere, 600 mL of dehydrated tetrahydrofuran was added to 78.0 g of dibenzofuran and the mixture was cooled to −30° C. 300 mL of n-butyllithiumhexane solution (1.65 M) was then dropped and the mixture was heated to a room temperature over 1 hour under stirring. After being stirred for 5 hours at a room temperature, the mixture was cooled to −60° C., and 60 mL of 1,2-dibromoethane was dropped thereto over 1 hour.After being stirred for 15 hours at a room temperature, the mixture was poured into 1000 mL of ice water, and the organic phase was extracted with dichloromethane. The extracted organic phase was washed with saturated saline, dried with anhydrous magnesium sulfate, and subjected to filtration and concentration. The solids obtained were purified with silica gel chromatography (with toluene), washed with tetrahydrofuran/methanol, and dried under reduced pressure to obtain 70 g of solids. The solids were identified as Intermediate 5 by FD-MS analysis.

Reference： [1] Angewandte Chemie - International Edition, 2010, vol. 49, # 52, p. 10214 - 10216
[2] Patent: US2018/37546, 2018, A1, . Location in patent: Paragraph 0166; 0167
[3] Patent: US2017/125677, 2017, A1, . Location in patent: Paragraph 0137-0141
[4] Patent: US2017/125678, 2017, A1, . Location in patent: Paragraph 0112; 0113; 0114; 0115; 0116
[5] Patent: EP2738166, 2014, A1, . Location in patent: Paragraph 0165-0166
[6] Patent: EP2762478, 2014, A1, . Location in patent: Paragraph 0182; 0183
[7] Journal of the American Chemical Society, 1939, vol. 61, p. 2836,2842
[8] Journal of the American Chemical Society, 1984, vol. 106, # 23, p. 7150 - 7167
[9] Journal of the American Chemical Society, 1984, vol. 106, p. 3286
[10] Patent: EP2364980, 2011, A1, . Location in patent: Page/Page column 93
[11] Patent: EP2423206, 2012, A1, . Location in patent: Page/Page column 52
[12] Patent: EP2484665, 2012, A1, . Location in patent: Page/Page column 64-65
[13] Patent: US2012/273766, 2012, A1, . Location in patent: Page/Page column 71
[14] Patent: EP2527334, 2012, A1, . Location in patent: Page/Page column 88
[15] Patent: EP2617712, 2013, A1, . Location in patent: Paragraph 0161
[16] European Journal of Inorganic Chemistry, 2014, # 1, p. 256 - 264
[17] European Journal of Inorganic Chemistry, 2014, vol. 2014, # 1, p. 256 - 264
[18] Organometallics, 2015, vol. 34, # 18, p. 4433 - 4440
[19] RSC Advances, 2015, vol. 5, # 88, p. 72009 - 72018
[20] Chemistry - A European Journal, 2015, vol. 21, # 37, p. 12881 - 12884

2
[ 23197-48-0 ]
[ 89827-45-2 ]

Yield	Reaction Conditions	Operation in experiment
49%	With 3-nitropyridine; tert-Butyl peroxybenzoate; palladium diacetate In Hexafluorobenzene at 90℃;	The starting material, 3-bromo- [1,1'-biphenyl] -2-ol (32.42 g, 130.15 mmol)To a round bottom flask was added Pd (OAc) 2 (2.92 g, 13.01 mmol), 3-nitropyridine (1.62 g, 13.01 mmol) andAdd together C6F6 (195ml),After dissolving in DMI (130 ml)Tert-butyl peroxybenzoate (50.56 g, 260.30 mmol)And the mixture was stirred at 90 ° C.After the reaction was completed, the reaction mixture was extracted with CH2Cl2 and water. The organic layer was dried over MgSO4 and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 15.76 g (yield: 49percent) of the product
49%	With 3-nitropyridine; tert-Butyl peroxybenzoate; palladium diacetate In Hexafluorobenzene	3-bromo-[1,1’-biphenyl]-2-ol (32.42 g, 130.15 mmol) as a starting material, Pd(OAc)2 (2.92 g, 13.01 mmol), and 3-nitropyridine (1.62 g, 13.01 mmol) were added into a round bottom flask, then, dissolved in C5F5 (195 ml), DM1 (130 ml). After adding tert-butyl peroxybenzoate (50.56 g, 260.30 mmol), stirring at 90 D was followed. When the reaction was completed, the reaction product was extracted with CH2C12 and water, and then, the organic layer was dried with Mg504 and concentrated. Then, the concen-continued trate was passed through silica gel colunm, then recrystallized to obtain 15.76 g (yield: 49percent) of the product.

Reference： [1] Patent: KR2017/21807, 2017, A, . Location in patent: Paragraph 0138-0140
[2] Patent: US2018/72695, 2018, A1, . Location in patent: Paragraph 0090; 0091

3
[ 917477-33-9 ]
[ 89827-45-2 ]

Reference： [1] Organic Letters, 2013, vol. 15, # 11, p. 2754 - 2757

4
[ 132-64-9 ]
[ 106-93-4 ]
[ 89827-45-2 ]

Reference： [1] Patent: EP2423179, 2012, A1, . Location in patent: Page/Page column 52

5
[ 1424386-19-5 ]
[ 89827-45-2 ]

Reference： [1] Journal of the American Chemical Society, 2013, vol. 135, # 19, p. 7086 - 7089
[2] Journal of Organic Chemistry, 2018, vol. 83, # 2, p. 805 - 811

6
[ 132-64-9 ]
[ 89827-45-2 ]

Reference： [1] Bulletin of the Chemical Society of Japan, 2014, vol. 87, # 11, p. 1235 - 1244

7
[ 577-19-5 ]
[ 89827-45-2 ]

Reference： [1] Journal of the American Chemical Society, 2013, vol. 135, # 19, p. 7086 - 7089
[2] Journal of the American Chemical Society, 2013, vol. 135, # 19, p. 7086 - 7089
[3] Journal of the American Chemical Society, 2013, vol. 135, # 19, p. 7086 - 7089

8
[ 95-56-7 ]
[ 132-64-9 ]
[ 89827-45-2 ]
[ 262-12-4 ]
[ 201138-91-2 ]

Reference： [1] Environmental Science and Technology, 2005, vol. 39, # 7, p. 2128 - 2134

9
[ 89466-08-0 ]
[ 89827-45-2 ]

Reference： [1] Journal of Organic Chemistry, 2018, vol. 83, # 2, p. 805 - 811

10
[ 95-56-7 ]
[ 132-64-9 ]
[ 89827-45-2 ]
[ 262-12-4 ]
[ 108-95-2 ]

Reference： [1] Environmental Science and Technology, 2003, vol. 37, # 24, p. 5574 - 5580

11
[ 89827-45-2 ]
[ 121-43-7 ]
[ 100124-06-9 ]

Yield	Reaction Conditions	Operation in experiment
80%	Stage #1: With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1 h; Inert atmosphere Stage #2: at -78 - 20℃; for 2 h; Inert atmosphere Stage #3: With hydrogenchloride In tetrahydrofuran; hexane; water at 20℃; for 3 h;	Synthesis of dibenzofuran-4-boronic acid (0048) In a 300 ml three-necked flask, 7.2 g of 4-bromodibenzofuran was dissolved in −78° C. anhydrous tetrahydrofuran (THF) under an argon atmosphere. Then, 20 ml of an n-butyl lithium-n-hexane solution (1.6 M, 1.1 eq) was added and stirred for 1 hour. 4.23 ml (1.3 eq) of trimethoxyborane (B(OMe)₃) was added and stirred for 2 hours, and the temperature of the reaction system was increased to room temperature. 200 ml of 1 N hydrochloric acid was added into the reactant and stirred for 3 hours. An organic layer was separated, and solvents were distilled off. In the crude product thus obtained, hexane was added. Precipitated product was filtered to obtain 4.94 g of dibenzofuran-4-boronic acid as a white solid (yield 80percent). The product was measured by FAB-MS, and dibenzofuran-4-boronic acid having a molecular weight of 212 was detected.
73%	Stage #1: With n-butyllithium In tetrahydrofuran at -78 - 0℃; for 1 h; Inert atmosphere Stage #2: at -78℃; Stage #3: With hydrogenchloride In tetrahydrofuran; water for 0.5 h;	Synthesis of Intermediate 22 (0146) (0147) Under a nitrogen atmosphere, Intermediate 20 (2.47 g, 10 mmol) was dissolved in anhydrous tetrahydrofuran (40 mL), and then cooled to −78° C. n-butyllithium (2.5 M, 4 mL) was slowly added dropwise, stirred at 0° C. for 1 hr, and then cooled to −78° C. again. Trimethyl borate (12.47 g, 12 mmol) was added dropwise, and stirred for 12 hrs at normal temperature. After the reaction was terminated, a 2N aqueous HCl solution was added, stirred for 30 min, and extracted with diethyl ether. (0148) The organic layer was dried over anhydrous magnesium sulfate, suctioned, and concentrated. The resultant compound was purified by column chromatography eluting with Hex:EA=5:1, to obtain Intermediate 22 (1.55 g, 73percent). (0149) Intermediate 22 MS(FAB): 212(M⁺)
73%	Stage #1: With n-butyllithium In tetrahydrofuran at -78 - 0℃; for 1 h; Inert atmosphere Stage #2: at -78℃; for 12 h; Stage #3: With hydrogenchloride; water In tetrahydrofuran for 0.5 h;	Under a nitrogen atmosphere, Intermediate 16 (2.47 g, 10 mmol) was dissolved in anhydrous tetrahydrofuran (40 mL), and then cooled to −78° C. n-butyllithium (2.5 M, 4 mL) was slowly added dropwise, stirred at 0° C. for 1 hr, and then cooled to −78° C. again. Trimethyl borate (12.47 g, 12 mmol) was added dropwise, and stirred for 12 hrs at normal temperature. After the reaction was terminated, a 2N aqueous HCl solution was added, stirred for 30 min, and extracted with diethyl ether. The organic layer was dried over anhydrous magnesium sulfate, suctioned, and concentrated. The resultant compound was purified by column chromatography eluting with Hex:EA=5:1, to obtain Intermediate 18 (1.55 g, 73percent). Intermediate 18 MS (FAB): 212(M⁺)

Reference： [1] Patent: US9172047, 2015, B2, . Location in patent: Page/Page column 17
[2] Patent: US2017/125677, 2017, A1, . Location in patent: Paragraph 0146-0149
[3] Patent: US2017/125678, 2017, A1, . Location in patent: Paragraph 0121; 0122; 0123
[4] RSC Advances, 2015, vol. 5, # 88, p. 72009 - 72018

12
[ 89827-45-2 ]
[ 5419-55-6 ]
[ 100124-06-9 ]

Reference： [1] Patent: CN108285452, 2018, A, . Location in patent: Paragraph 0035; 0037; 0040; 0041

13
[ 95-56-7 ]
[ 132-64-9 ]
[ 89827-45-2 ]
[ 262-12-4 ]
[ 201138-91-2 ]

Reference： [1] Environmental Science and Technology, 2005, vol. 39, # 7, p. 2128 - 2134

14
[ 89827-45-2 ]
[ 73183-34-3 ]
[ 912824-85-2 ]

Yield	Reaction Conditions	Operation in experiment
90%	Stage #1: With bis-triphenylphosphine-palladium(II) chloride; potassium acetate In tetrahydrofuran at 20℃; for 0.0833333 h; Inert atmosphere Stage #2: at 80℃; for 24 h; Inert atmosphere	4-Bromodibenzofuran 10.0g (38.1 mmol) was dissolved in 300ml tetrahydrofuran and then, Bis (triphenylphosphine) palladium (II) dichloride 1.3g (1.9 mmol) was added at the room temperature was stirred for about 5 minutes dongan it. Thereafter, Bis (pinacolato) diboron 14.5g (57.2 mmol) and Potassium acetate 11.2g (114.3 mmol) and the mixture was heated under reflux for a day at 80 . When the reaction is complete, the extract was added to 200ml of ethyl acetate, and distilled under reduced pressure the organic layer was dried with magnesium sulfate. Purification of the separation results obtained therefrom by column chromatography to give Intermediate 12-3 about 10.0g (34.3 mmol, 90percent yield). The resulting compound was confirmed by LC-MS.
82%	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate In N,N-dimethyl-formamide at 90℃;	Sub-1-I-1 (15.76 g, 63.78 mmol) was dissolved in DMF (320 ml) into a round bottom flask,Bis (pinacolato) diboron (17.82 g, 70.16 mmol), Pd (dppf) Cl2 (1.56 g, 1.91 mmol) and KOAc (18.78 g, 191.35 mmol) were added and stirred at 90 ° C.When the reaction was complete, DMF was removed by distillation and extracted with CH2Cl2 and water.The organic layer was dried over MgSO4 and concentrated. The resulting compound was purified by silicagel column and recrystallized to give 15.38 g of the product (Yield: 82percent).
82%	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate In N,N-dimethyl-formamide	Sub 14-1 (15.76 g, 63.78 mmol) was added into a round bottom flask, then, dissolved in DMF (320 ml). After adding l3is(pinacolato)diboron (17.82 g, 70.16 mmol), Pd(dppCl2 (1.56 g, 1.91 mmol), KOAc (18.78 g, 191.35 mmol), stirring at 90 D was followed. When the reaction was completed, DMF was removed by distillation, and then extracting with CH2C12 and water was followed. The organic layer was dried with Mg504 and concentrated. Then, the concentrate was passed through silica gel colunm, then recrystallized to obtain 15.38 g (yield: 82percent) of the product.

Reference： [1] Patent: KR2016/6493, 2016, A, . Location in patent: Paragraph 0484; 0485; 0486; 0487; 0488
[2] Patent: KR2017/21807, 2017, A, . Location in patent: Paragraph 0138; 0141; 0142
[3] Patent: US2018/72695, 2018, A1, . Location in patent: Paragraph 0090; 0092

15
[ 89827-45-2 ]
[ 185990-03-8 ]
[ 912824-85-2 ]

Reference： [1] Chemical Science, 2015, vol. 6, # 5, p. 2943 - 2951

16
[ 89827-45-2 ]
[ 912824-85-2 ]

Reference： [1] RSC Advances, 2015, vol. 5, # 88, p. 72009 - 72018

[ 89827-45-2 ] Synthesis Path-Downstream 1~72

1
[ 132-64-9 ]
[ 89827-45-2 ]

Yield	Reaction Conditions	Operation in experiment
76%	Stage #1: dibenzo[b,d]furan With n-butyllithium In tetrahydrofuran; hexane at -40 - 20℃; Stage #2: With ethylene dibromide In tetrahydrofuran; hexane at -78 - 20℃;
75%	Stage #1: dibenzo[b,d]furan With n-butyllithium In tetrahydrofuran; hexane at -70 - 0℃; for 2h; Inert atmosphere; Stage #2: With ethylene dibromide In tetrahydrofuran; hexane for 12h;	Synthesis of Intermediate 1 33.6 mg (200 mmol) of dibenzofuran was dissolved in 700 ml of THF under a nitrogen atmosphere. To this was added 350 ml of n-butyl lithium (1.6 mol/1 hexane solution) at -70° C. or less. After completion of addition, the mixture was stirred at -70° C or less for 1 hour. Then, the reaction mixture was heated to 0° C. and it was stirred for 1 hour. The reaction mixture was cooled again to -70° C. or less, and 45 g (300 ml) of 1,2-dibromoethane was added dropwise. After completion of drop, the reaction mixture was stirred for 12 hours. Then, water was added to the reaction mixture, and the reaction product was extracted with ethyl acetate. The organic layer was washed with water, and the solvent was removed under a reduced pressure. The produced residue was recrystallized with hexane to obtain 37.1 g of an intermediate 1. The yield was 75%. The structure of the compound was confirmed with NMR and mass spectrum.
74%	Stage #1: dibenzo[b,d]furan With n-butyllithium In tetrahydrofuran at -40 - 20℃; for 2.5h; Inert atmosphere; Stage #2: With ethylene dibromide In tetrahydrofuran at -78 - 20℃; for 2.5h;	Synthesis of Intermediate 20 Synthesis of Intermediate 20 (0137) (0138) Under a nitrogen atmosphere, dibenzofuran (1.68 g, 10 mmol) was dissolved in tetrahydrofuran (10 mL), and mixed with n-BuLi (2.5 M, 4 mL) at -40° C. The cooling device was removed, and the reaction solution was placed in a water bath and warmed to room temperature in about 30 min, and then stirred for 2 hrs. Then, the reaction solution was cooled to -78° C., and 1,2-dibromoethane (2.82 g, 15 mmol) in tetrahydrofuran (10 mL) was added dropwise. The cooling device was removed, and the mixture was placed in a water bath and warmed to room temperature in about 30 min, and then stood for 2 hrs. (0139) After the reaction was terminated, the reaction solution was washed with a saturated sodium chloride solution, taken up in a 2 N aqueous HCl solution, stirred for 30 min, and extracted with diethyl ether. (0140) The organic layer was dried over anhydrous magnesium sulfate to remove a small amount of water contained therein, suctioned, and concentrated. The resultant compound was purified by column chromatography eluting with Hex:EA=5:1, to obtain Intermediate 20 (1.83 g, 74%). (0141) Intermediate 20 MS(FAB): 247(M+)

74%	Stage #1: dibenzo[b,d]furan With n-butyllithium In tetrahydrofuran at -40 - 20℃; for 2.5h; Inert atmosphere; Stage #2: With ethylene dibromide In tetrahydrofuran at -78 - 20℃; for 2.5h;	1 Synthesis of Intermediate 16 Under a nitrogen atmosphere, dibenzofuran (1.68 g, 10 mmol) was dissolved in tetrahydrofuran (10 mL), and mixed with n-BuLi (2.5 M, 4 mL) at -40° C. The cooling device was removed, and the reaction solution was placed in a water bath and warmed to room temperature in about 30 min, and then stirred for 2 hrs. Then, the reaction solution was cooled to -78° C., and 1,2-dibromoethane (2.82 g, 15 mmol) in tetrahydrofuran (10 mL) was added dropwise. The cooling device was removed, and the mixture was placed in a water bath and warmed to room temperature in about 30 min, and then stood for 2 hrs.After the reaction was terminated, the reaction solution was washed with a saturated sodium chloride solution, taken up in a 2 N aqueous HCl solution, stirred for 30 min, and extracted with diethyl ether.The organic layer was dried over anhydrous magnesium sulfate to remove a small amount of water contained therein, suctioned, and concentrated. The resultant compound was purified by column chromatography eluting with Hex:EA=5:1, to obtain Intermediate 16 (1.83 g, 74%).Intermediate 16 MS(FAB): 247(M+)
68%	Stage #1: dibenzo[b,d]furan With n-butyllithium In tetrahydrofuran at -40 - 25℃; for 2.5h; Inert atmosphere; Stage #2: With 1,1-dibromomethane at -78 - 25℃; for 2.5h; Inert atmosphere; regioselective reaction;
62%	Stage #1: dibenzo[b,d]furan With n-butyllithium In tetrahydrofuran; hexane at -30 - 20℃; Inert atmosphere; Stage #2: With ethylene dibromide In tetrahydrofuran; hexane at -60 - 20℃;	1-9 INTERMEDIATE SYNTHESIS 1-9: Synthesis of intermediate 1-9 In an argon atmosphere, 600 ml of dehydrated tetrahydrofuran was added to 78.0 g (0.46 mol) of dibenzofuran. The resultant mixture was cooled to -30 °C and added with 300 ml (0.50 mol) of a 1.65 M hexane solution of n-butyllithium dropwise, and then, the temperature was raised to room temperature over one hour under stirring. After further stirring at room temperature for 5 h, the mixture was cooled to -60 °C and added with 60 ml (0.70 mol) of 1,2-dibromoethane dropwise over one hour. [0166] After further stirring at room temperature for 15 h, the mixture was poured into 1000 ml of iced water and then extracted with dichloromethane. The organic layer was washed with a saturated saline solution, dried over MgSO4, filtered, and then concentrated. The concentrate was purified by silica gel chromatography and washed with tetrahydrofuran/methanol, to obtain 70 g of solid, which was identified as the following intermediate 1-9 by FD-MS analysis (yield: 62%).
62%	Stage #1: dibenzo[b,d]furan With n-butyllithium In tetrahydrofuran; hexane at -30 - 20℃; for 6h; Inert atmosphere; Stage #2: With ethylene dibromide In tetrahydrofuran; hexane at -60 - 20℃; for 16h;	1-3 INTERMEDIATE SYNTHESIS 1-3: Synthesis of intermediate 1-3 [0182] In an argon atmosphere, 78.0 g (0.46 mol) of dibenzofuran was added with 600 ml of dehydrated tetrahydrofuran.The resultant mixture was cooled to -30 °C and added dropwise with 300 ml (0.50 mol) of a 1.65 M hexane solution ofn-butyllithium. The temperature was raised to room temperature over one hour under stirring. The mixture was stirredat room temperature for 5 h, cooled to - 60 °C, and then added dropwise with 60 ml (0.70 mol) of 1,2-dibromoethaneover one hour.[0183] After stirring at room temperature for 15 h, the mixture was poured into 1000 ml of iced water and extractedwith dichloromethane. The organic layer was washed with brine, dried over MgSO4, filtered, and then concentrated. Theconcentrate was purified by silica gel column chromatography and washed with tetrahydrofuran/methanol to obtain 70g of solid, which was identified as the following intermediate 1-3 by FD-MS (yield: 62%).
	With n-butyllithium; diethyl ether; bromine
	With n-butyllithium 1,) THF, hexane, 25 deg C, 5 h; 2.) THF, 25 deg C, 2 h; Yield given. Multistep reaction;
	With n-butyllithium; ethylene dibromide 1.) hexane, 25 deg C, 5 h; 2.) THF, RT, 2 h; Yield given. Multistep reaction;
	Stage #1: dibenzo[b,d]furan With n-butyllithium In tetrahydrofuran; hexane at -30 - 20℃; for 6h; Stage #2: With ethylene dibromide In tetrahydrofuran; hexane at -60 - 20℃; for 16h;	2-19 Under an argon atmosphere, 600 mL of dry tetrahydrofuran were added to 78.0 g of dibenzofuran, and then the mixture was cooled to -30°C. 300 milliliters of a solution of n-butyllithium in hexane (1.65 M) were dropped to the mixture, and then the temperature of the whole was increased to room temperature over 1 hour while the whole was stirred. After having been stirred at room temperature for 5 hours, the resultant was cooled to -60°C, and then 60 mL of 1,2-dibromoethane were dropped to the resultant over 1 hour. After having been stirred at room temperature for 15 hours, the mixture was poured into 1,000 mL of ice water, and then the organic layer was extracted with dichloromethane. The organic layer was washed with a saturated salt solution, and was then dried with anhydrous magnesium sulfate. The dried product was separated by filtration, and was then concentrated. The resultant solid was purified by silica gel chromatography (toluene), washed with tetrahydrofuran and methanol, and dried under reduced pressure. As a result, 70 g of a solid were obtained. The solid was identified as Intermediate 2-19 by FD-MS analysis.
	Stage #1: dibenzo[b,d]furan With n-butyllithium In tetrahydrofuran; hexane at -65 - 20℃; for 3h; Inert atmosphere; Heating; Stage #2: With ethylene dibromide In tetrahydrofuran; hexane at -65 - 20℃; for 3h; Heating;	1.1.A In a stream of argon, 30.0g of dibenzofuran and 300 mL of dehydrated tetrahydrofuran (THF) were put in a 1000 mL-recovery flask, and the resulting solution was cooled to -65°C. Then, 120 mL (1.65 M) of a hexane solution of n-butyllithium was added. The resulting mixture was heated gradually, and allowed to react at room temperature for 3 hours. After cooling to -65°C again, 23.1 mL of 1,2-dibromoethane was added dropwise thereto, and the reaction mixture was heated gradually and a reaction was conducted for 3 hours at room temperature. The reaction solution was separated and extracted by adding 2N hydrochloric acid and ethyl acetate, and then the organic phase was washed with clean water and saturated saline and dried with sodium sulfate, and concentrated to obtain a crude product. The crude product was purified with silica gel chromatography (methylene chloride), and solids obtained were dried under reduced pressure to obtain 43.0g of white solids. The solids were identified as intermediate M1 by FD-MS (field desorption mass spectrometry) analysis.
	Stage #1: dibenzo[b,d]furan With n-butyllithium In tetrahydrofuran; hexane at -30 - 20℃; for 6h; Inert atmosphere; Stage #2: With ethylene dibromide In tetrahydrofuran; hexane at -60 - 20℃; for 16h; Inert atmosphere;	20 Under an argon atmosphere, 600 mL of dry tetrahydrofuran were added to 78.0 g of dibenzofuran, and then the mixture was cooled to -30°C. 300 mL of a solution of n-butyllithium in hexane (1.65 M) were dropped to the mixture, and then the temperature of the whole was increased to room temperature over 1 hour while the whole was stirred. After having been stirred at room temperature for 5 hours, the resultant was cooled to -60°C, and then 60 mL of 1,2-dibromoethane were dropped to the resultant over 1 hour. After having been stirred at room temperature for 15 hours, the mixture was poured into 1,000 mL of ice water, and then the organic layer was extracted with dichloromethane. The organic layer was washed with a saturated salt solution, and was then dried with anhydrous magnesium sulfate. The dried product was separated by filtration, and was then concentrated. The resultant solid was purified by silica gel chromatography (toluene), washed with tetrahydrofuran and methanol, and dried under reduced pressure. As a result, 70 g of a solid were obtained. The solid was identified as the Intermediate 20 by FD-MS analysis.
	Stage #1: dibenzo[b,d]furan With n-butyllithium In tetrahydrofuran; hexane at 20℃; for 6h; Inert atmosphere; Stage #2: With ethylene dibromide In tetrahydrofuran; hexane at -60 - 20℃; for 16h;	11 Under argon atmosphere, 600 ml of dehydrated tetrahydrofuran was added to 78.0 g (0.46 mol) of dibenzofuran, and the mixture was cooled to -30° C. Thereto, 300 ml (0.50 mol) of a 1.65M n-butyllithium-hexane solution was dropped, and the resulting mixture was heated to room temperature while stirring over 1 hour. After stirred at room temperature for 5 hours, the mixture was cooled to -60° C., and 60 ml (0.70 mol) of 1,2-dibromoethane was dropped thereto over 1 hour.After stirred at room temperature for 15 hours, the resulting mixture was poured to 1000 ml of iced water, followed by extraction with dichloromethane. After washed with saturated saline, the organic layer was dried with MgSO4, followed by filtration and concentration. The concentrated residue was purified by silica-gel chromatography, and washed with tetrahydrofuran/methanol to obtain 70 g of solids. The solids were identified as Intermediate 11 by FD-MS analysis.
	Stage #1: dibenzo[b,d]furan With n-butyllithium In tetrahydrofuran; hexane at -30 - 20℃; Inert atmosphere; Stage #2: With ethylene dibromide In tetrahydrofuran; hexane at -60 - 20℃; Inert atmosphere;	3 Synthesis Example 3 (synthesis of intermediate 3)> Under an argon atmosphere, 600 mL of tetrahydrofuran anhydrous were added to 78.0 g of dibenzofuran, and then the mixture was cooled to -30°C. 300 mL of a solution of n-butyllithium in hexane (1.65 M) were dropped to the mixture, and then the temperature of the resultant mixture was increased to room temperature over 1 hour while the mixture was stirred. After having been stirred at room temperature for 5 hours, the mixture was cooled to -60°C, and then 60 mL of 1,2-dibromoethane were dropped to the mixture over 1 hour. After having been stirred at room temperature for 15 hours, the resultant mixture was poured into 1,000 mL of ice water, and then the organic layer was extracted with dichloromethane. After having been washed with a saturated salt solution, the organic layer was dried with anhydrous magnesium sulfate, separated by filtration, and then concentrated. The resultant solid was purified by silica gel chromatography (toluene), washed with tetrahydrofuran and methanol, and dried under reduced pressure. Thus, 70 g of a solid were obtained. The solid was identified as the intermediate 3 by FD-MS analysis.
70 g	Stage #1: dibenzo[b,d]furan With n-butyllithium In tetrahydrofuran; hexane at -30 - 20℃; for 6h; Inert atmosphere; Stage #2: With ethylene dibromide In tetrahydrofuran; hexane at -60 - 20℃; for 16h;	5 Synthesis of Intermediate 5 Under an argon atmosphere, 600 mL of dehydrated tetrahydrofuran was added to 78.0 g of dibenzofuran and the mixture was cooled to -30° C. 300 mL of n-butyllithiumhexane solution (1.65 M) was then dropped and the mixture was heated to a room temperature over 1 hour under stirring. After being stirred for 5 hours at a room temperature, the mixture was cooled to -60° C., and 60 mL of 1,2-dibromoethane was dropped thereto over 1 hour.After being stirred for 15 hours at a room temperature, the mixture was poured into 1000 mL of ice water, and the organic phase was extracted with dichloromethane. The extracted organic phase was washed with saturated saline, dried with anhydrous magnesium sulfate, and subjected to filtration and concentration. The solids obtained were purified with silica gel chromatography (with toluene), washed with tetrahydrofuran/methanol, and dried under reduced pressure to obtain 70 g of solids. The solids were identified as Intermediate 5 by FD-MS analysis.
	With n-butyllithium; 1,1-dibromomethane In tetrahydrofuran at -75℃;
	With n-butyllithium; ethylene dibromide In tetrahydrofuran at -75℃;
	Stage #1: dibenzo[b,d]furan With n-butyllithium In tetrahydrofuran Stage #2: With ethylene dibromide In tetrahydrofuran
	Stage #1: dibenzo[b,d]furan With n-butyllithium In tetrahydrofuran; hexane at -78 - 0℃; for 6h; Inert atmosphere; Stage #2: With ethylene dibromide In tetrahydrofuran at 20℃; for 10h;
	Stage #1: dibenzo[b,d]furan With n-butyllithium at -40℃; Stage #2: With ethylene dibromide at -78℃;
	Stage #1: dibenzo[b,d]furan With n-butyllithium In tetrahydrofuran; hexane at -40 - 20℃; for 2.5h; Stage #2: With ethylene dibromide In tetrahydrofuran; hexane at -78 - 20℃; for 2.5h;	3 4-Bromodibenzofuran 100.00 g (99%, 588.6 mmol) of dibenzofuran are dissolved in 800 ml of anhydrous THF and admixed at -40° C. with 400 ml (640.0 mmol) of n-BuLi (1.6M in hexane). The cooling bath is removed. The reaction solution is allowed to come to room temperature in a water bath within approx. 30 min and stirred for a further two hours. Thereafter, it is cooled to -78° C. and a solution of 160.34 g (99%, 844.9 mmol, 73.55 ml) of 1,2-dibromoethane in 80 ml of anhydrous THF is added dropwise. The cooling bath is removed, and the mixture is allowed to come to room temperature in a water bath within approx. 30 min and stirred for a further two hours. Subsequently, 60 ml of saturated sodium chloride solution are added cautiously (slightly exothermic reaction, temperature rise 1-2° C.). The organic phase is removed and freed of the solvent under reduced pressure. The oily red-brown residue is taken up in 900 ml of dichloromethane and washed successively with 500 ml of HCl solution (1N) and 400 ml of water. The organic phase is dried over magnesium sulfate and freed of the solvent under reduced pressure. In the course of cooling, a yellowish solid precipitates out, which is comminuted in a mortar and washed on a frit with 2×150 ml of isopropanol. After drying, 120.36 g of beige powder are obtained (according to GC and NMR: DBF/Br-DBF ratio=10/90, corresponds to 111.93 g of Br-DBF/76% yield). After removing the solvent, a further 15.84 g of a mixture of dibenzofuran and 4-bromodibenzofuran (comprises a further approx. 7.8 g/5% Br-DBF) are obtained from the isopropanol solution. This mixture can likewise be used in the further stages. 1H NMR (CDCl3, 500 MHz): δ=7.92 (d, 3JH,H=7.8 Hz, 1H), 7.86 (dd, 3JH,H=7.7 Hz, 4JH,H=1.0 Hz, 1H), 7.65 (d, 3JH,H=8.2 Hz, 1H), 7.61 (dd, 3JH,H=7.8 Hz, 4JH,H=1.1 Hz, 1H), 7.50 (dt, 3JH,H=8.2 Hz, JH,H=1.3 Hz, 1H), 7.37 (dt, 3JH,H=7.8 Hz, JH,H=0.8 Hz, 1H), 7.21 (t, 3JH,H=7.8 Hz, 1H).

Reference： [1]Unger, Yvonne; Meyer, Dirk; Molt, Oliver; Schildknecht, Christian; Muenster, Ingo; Wagenblast, Gerhard; Strassner, Thomas [Angewandte Chemie - International Edition, 2010, vol. 49, # 52, p. 10214 - 10216]
[2]Current Patent Assignee: MERCK KGAA - US2018/37546, 2018, A1 Location in patent: Paragraph 0166; 0167
[3]Current Patent Assignee: NANJING TOPTO SEMICONDUCTOR MATERIAL CO LTD - US2017/125677, 2017, A1 Location in patent: Paragraph 0137-0141
[4]Current Patent Assignee: NANJING TOPTO SEMICONDUCTOR MATERIAL CO LTD - US2017/125678, 2017, A1 Location in patent: Paragraph 0112; 0113; 0114; 0115; 0116
[5]Murai, Masahito; Ogita, Takuya; Takai, Kazuhiko [Chemical Communications, 2019, vol. 55, # 16, p. 2332 - 2335]
[6]Current Patent Assignee: IDEMITSU KOSAN CO LTD - EP2738166, 2014, A1 Location in patent: Paragraph 0165-0166
[7]Current Patent Assignee: IDEMITSU KOSAN CO LTD - EP2762478, 2014, A1 Location in patent: Paragraph 0182; 0183
[8]Gilman et al. [Journal of the American Chemical Society, 1939, vol. 61, p. 2836,2842]
[9]Cram, D. J.; Dicker, I. B.; Lauer, M.; Knobler, C. B.; Trueblood, K. N. [Journal of the American Chemical Society, 1984, vol. 106, # 23, p. 7150 - 7167]
[10]Cram,D.J.; Degrandpre,M.; Knobler,C.B. [Journal of the American Chemical Society, 1984, vol. 106, p. 3286]
[11]Current Patent Assignee: IDEMITSU KOSAN CO LTD - EP2364980, 2011, A1 Location in patent: Page/Page column 93
[12]Current Patent Assignee: IDEMITSU KOSAN CO LTD - EP2423206, 2012, A1 Location in patent: Page/Page column 52
[13]Current Patent Assignee: IDEMITSU KOSAN CO LTD - EP2484665, 2012, A1 Location in patent: Page/Page column 64-65
[14]Current Patent Assignee: IDEMITSU KOSAN CO LTD - US2012/273766, 2012, A1 Location in patent: Page/Page column 71
[15]Current Patent Assignee: IDEMITSU KOSAN CO LTD - EP2527334, 2012, A1 Location in patent: Page/Page column 88
[16]Current Patent Assignee: IDEMITSU KOSAN CO LTD - EP2617712, 2013, A1 Location in patent: Paragraph 0161
[17]Tronnier, Alexander; Nischan, Nicole; Metz, Stefan; Wagenblast, Gerhard; Münster, Ingo; Strassner, Thomas [European Journal of Inorganic Chemistry, 2014, # 1, p. 256 - 264]
[18]Tronnier, Alexander; Nischan, Nicole; Metz, Stefan; Wagenblast, Gerhard; Münster, Ingo; Strassner, Thomas [European Journal of Inorganic Chemistry, 2014, vol. 2014, # 1, p. 256 - 264]
[19]Tenne, Mario; Metz, Stefan; Wagenblast, Gerhard; Münster, Ingo; Strassner, Thomas [Organometallics, 2015, vol. 34, # 18, p. 4433 - 4440]
[20]Chen, Shuo; Wu, Yukun; Zhao, Yi; Fang, Daining [RSC Advances, 2015, vol. 5, # 88, p. 72009 - 72018]
[21]Tronnier, Alexander; Wagenblast, Gerhard; Münster, Ingo; Strassner, Thomas [Chemistry - A European Journal, 2015, vol. 21, # 37, p. 12881 - 12884]
[22]Current Patent Assignee: BASF SE; OLEDWORKS LLC; AMS OSRAM AG; KONINKLIJKE PHILIPS ELECTRONICS NV - US2022/144869, 2022, A1 Location in patent: Paragraph 0357-0360

2
[ 89827-45-2 ]
[ 2786-05-2 ]

Reference： [1]Journal of the American Chemical Society,1939,vol. 61,p. 1365,1369

3
[ 95-56-7 ]
[ 132-64-9 ]
[ 89827-45-2 ]
[ 262-12-4 ]
[ 201138-91-2 ]

Reference： [1]Environmental Science and Technology,2005,vol. 39,p. 2128 - 2134

4
[ 89827-45-2 ]
[ 62-53-3 ]
[ 743453-07-8 ]

Yield	Reaction Conditions	Operation in experiment
93.1%	With tris(1,5-diphenylpenta-1,4-dien-3-one)dipalladium; sodium tertiary butoxide; dicyclohexyl [2’,4’,6’-tris(propan-2-yl)-[1,1‘-biphenyl]-2-yl]phosphane 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.
89.3%	With tris(1,5-diphenylpenta-1,4-dien-3-one)dipalladium; tri-tert-butyl phosphine; sodium tertiary butoxide In toluene at 90℃; for 12h; Inert atmosphere;	4.1 The specific operation is as follows: (1) Under the protection of nitrogen, add reactant 46-1 (120mmol) and sodium tert-butoxide (220mmol) into a 1000ml three-necked flask, and dissolve it with 500ml of dry toluene solution. After stirring for 10min at room temperature, Add reactant 46-2 (120mmol), tri-tert-butylphosphine (12mmol), tris(dibenzylideneacetone)dipalladium (2mmol) under conditions, then slowly increase the reaction temperature to 90°C, continue the reaction for 12h, use The reaction is monitored by TLC. After the reaction is over, cool to room temperature, add appropriate amount of distilled water under stirring, leave the organic phase after separation, collect the filtrate after drying with anhydrous magnesium sulfate, filter the filtrate with diatomaceous earth, remove the catalyst, The filtrate was spin-dried using a rotary evaporator, dissolved in petroleum ether/ethanol, recrystallized, filtered, the filter cake was rinsed with petroleum ether several times, and dried in an oven at 60°C for 5 hours to obtain intermediate 46-3 ( 27.8g, yield: 89.3%).
86%	Stage #1: 4-bromodibenzo[b,d]furan; aminobenzene With sodium tertiary butoxide In 1,4-dioxane for 1h; Inert atmosphere; Stage #2: With tris(1,5-diphenylpenta-1,4-dien-3-one)dipalladium; 1,3-bis(2,6-diisopropylphenyl)-4,5-dihydro-1H-imidazol-3-ium chloride In 1,4-dioxane for 2h; Inert atmosphere; Reflux;	1 Synthesis Example 1 Synthesis of 1,4-phenylaminodibenzofuran In a 25 ml three-necked flask, 5.0 g (20.3 mmol) of 4-bromodibenzofuran,2.3 g (25.2 mmol) of aniline,Sodium t-butoxide (t-BuONa) 5.05 g (52.7 mmol),And 100 ml of dehydrated 1,4-dioxane were added and nitrogen bubbling was performed for 1 hour. Thereafter, 581 mg (1.01 mmol) of bis (dibenzylideneacetone) palladium (0) (Pd (dba) 2), 859 mg (2.02 mmol) of 1,3-bis (2,6-diisopropylphenyl) imidazolinium chloride In addition, heating and refluxing were performed for 2 hours while stirring under a nitrogen stream. After confirming the consumption of the raw material by TLC, the formation of the desired product was confirmed by MS, and after the reaction solution was returned to room temperature, 15 ml of water was added and stirred. Then, the organic layer was extracted with diethyl ether, washed with saturated brine, dried over anhydrous magnesium sulfate, filtered and concentrated to obtain a brown viscous substance. The obtained viscous material was dissolved in 200 ml of a mixed solvent of toluene / hexane (1: 1), suction filtered through silica gel (approximately 4 cm on glass filter) and concentrated to obtain a pale yellow solid. The obtained solid was recrystallized and purified using ethanol to obtain a white solid. The target was identified by MS and 1 H-NMR.

85.8%	With tri-tert-butyl phosphine; potassium-t-butoxide; palladium diacetate In toluene for 1h; Inert atmosphere; Reflux;	3 Example 3: Synthesis of Intermediate C A 500 ml three-necked flask was filled with 12.3 grams of 4-Bromodibenzo[b,d]furan, 5 grams of aniline, and 12 grams of Potassium tert-butoxide (Potassium tert-butoxide, t- BuOK), 0.56 grams of palladium acetate [Pd(OAc)2] and 1.3 grams of tri-tert-butyl phosphine (P(t-Bu)3) dissolved in 250 ml of toluene and placed in nitrogen The reaction was refluxed under the system for 1 hour. It was filtered with Celite, and the filtrate was re-precipitated with Hexane to obtain a solid, which was dried to obtain 11.5 g of intermediate C, with a purity of 99% and a yield of 85.8%.
82%	With palladium diacetate; sodium tertiary butoxide; dicyclohexyl [2’,4’,6’-tris(propan-2-yl)-[1,1‘-biphenyl]-2-yl]phosphane In toluene for 5h; Inert atmosphere; Reflux;	1 Synthesis of Intermediate 1-1 In a three-necked flask,4-Bromodibenzofuran (24.6 g, 0.1 mol) was added,Aniline (14 g, 0.15 mol),Sodium tert-butoxide (20.0 g, 0.2 mol)Palladium acetate (200 mg),X-phos (400 mg) and toluene (300 mL),Heated under reflux under nitrogen for 5 hours,Cooling, washing, organic layer drying, concentration,The crude product was purified by column chromatography to give 21.8 g, yield 82%.
81%	With tri-tert-butyl phosphine; Palladium⁽⁰⁾ bis(dibenzylideneacetone); sodium tertiary butoxide In toluene at 90 - 110℃; for 12h; Inert atmosphere;	2.4; 4.4 Step 4: Synthesis of Intermediate 8 Aniline (4.7g, 50.0mmol), 4-bromodibenzofuran (12.4g, 50.0mmol), bis(dibenzylideneacetone) palladium (860mg, 1.5mmol), tri-tert-butylphosphine (600mg, 3mmol) ) And toluene (100ml), heated to 90°C under argon flow, After adding sodium tert-butoxide (288mg, 3mmol), it was heated to 110°C under argon atmosphere, and the reaction was stirred for 12 hours. Next, the reaction mixture was cooled to room temperature, water was added for liquid separation; the solvent of the obtained organic layer was concentrated, and the The obtained solid was purified by silica gel column chromatography, Intermediate 8 (10.0 g, 40.5 mmol) was obtained with a yield of 81%.
77%	With tris(1,5-diphenylpenta-1,4-dien-3-one)dipalladium; 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; sodium tertiary butoxide In 5,5-dimethyl-1,3-cyclohexadiene for 8h; Reflux; Inert atmosphere;	10.1 Synthesis of Compound (10-1) In a three-neck flask, 15.0 g (60.7 mmol) of 4-bromobenzofuran, 11.3 g (121 mmol) of aniline, 0.83 g (0.91 mmol) of Pd2(dba)3, 1.13 g (1.81 mmol) of rac-BINAP, 11.6 g (120.7 mmol) of sodium t-butoxide and 300 mL of dehydrated xylene were placed. The resultant was refluxed in an argon atmosphere for 8 hours. After completion of the reaction, insoluble matters were separated by filtration through celite. The filtrate was transferred to a dripping funnel and extracted several times with toluene. The obtained organic phase was dried with anhydrous magnesium sulfate, filtered and concentrated. The concentrated product was purified by silica gel chromatography (hexane:toluene=4:1), whereby white solids were obtained.The yield was 12.1 g and the percentage yield was 77%.
74%	With tris(1,5-diphenylpenta-1,4-dien-3-one)dipalladium; tri-tert-butyl phosphine; sodium tertiary butoxide In toluene at 40℃; for 2h; Inert atmosphere;	1 1. Synthesis example of Sub 1-1 4-bromodibenzo[b,d]furan (20.00 g, 80.94 mmol),Aniline (11.31 g, 121.41 mmol), Pd2(dba)3 (3.71 g, 4.05 mmol),Add NaOtBu (23.34 g, 242.83 mmol) and 270 mL toluene.After that, nitrogen replacement is performed, and the temperature of the reactor is adjusted to 40°C.P(t-Bu)3 (3.28 ml, 8.09 mmol) was added, and when the reaction was completed after 2 hours,After removing the water in the reaction and filtration under reduced pressure,The organic layer was dried over MgSO4 and concentrated,The resulting compound was subjected to silica gel column and recrystallization to obtain 15.53 g of a product (yield: 74%).
73%	With tri-tert-butyl phosphine; potassium-t-butoxide; palladium diacetate In toluene for 4h; Inert atmosphere; Reflux;	4 Synthesis of Dibenzofuran-4-yl-phenyl-amine (Compound 4) Under a nitrogen atmosphere, a 250 ml three-necked flask was charged with 4.66 g of Aniline and 13.59 g of 4-bromo-dibenzofuran(4-Bromo-dibenzofuran),250 ml of toluene was dissolved with stirring to add 11.22 g of potassium tert-butoxide.0.56 g of palladium acetate (palladium acetate) and 1.32 g of Tri-tert-butylphosphine were heated at reflux for 4 hours.After cooling, concentrate by filtration and separate the column (Hex:EA=10:1).Product 9.4 g, yield 73%.
67.5%	With tris(1,5-diphenylpenta-1,4-dien-3-one)dipalladium; tri-tert-butyl phosphine; sodium tertiary butoxide In toluene at 120℃; for 10h; Inert atmosphere;	2.1 (1) Synthesis of compound 5 Under nitrogen protection, aniline 1.88g (20.24mmol), 4-bromodibenzofuran 5.00g (20.24mmol), sodium tert-butoxide 2.33g (24.28mmol), tris (dibenzylideneacetone) two palladium 927mg ( Pd2(dba)3, 1.01 mmol) and 614 mg (3.04 mmol) of tri-tert-butyl phosphine were added to 50 ml of anhydrous toluene, stirred and heated to 120° C., and reacted for 10 hours. After the reaction, it was extracted three times with ethyl acetate and saturated sodium chloride solution, the organic phase was dried with anhydrous sodium sulfate, filtered, and the solvent was spin-dried with a rotary evaporator to obtain a crude product. The crude product is separated and purified by a silica gel chromatography column, and the eluent is a mixed solvent of petroleum ether/dichloromethane to obtain 3.54 g of a white solid product with a yield of 67.5%.
65.9%	With tris(1,5-diphenylpenta-1,4-dien-3-one)dipalladium; tri-tert-butyl phosphine; sodium tertiary butoxide In toluene at 115℃; for 24h; Inert atmosphere;	1 1) In a 250ml three-necked flask, under the protection of nitrogen, add 0.03mol of 4-bromobenzo[b,d]furan,0.036mol of aniline, 150ml of toluene, stir and mix, then add 0.045mol of sodium tert-butoxide, 0.0015mol Pd2(dba)3,0.0015 mol of tri-tert-butylphosphine, stirring and heating to 115 °C, refluxing reaction for 24 hours, sample point plate, showing noremaining4-bromobenzo[b,d]furan, complete reaction; naturally cooled to room temperature , Filtration, the filtrate was evaporated under reduced pressure until no fractions, over neutral silica gelcolumn to give Intermediate 2-1, HPLC purity 99.3%, yield 65.9%;
64%	With tri-tert-butyl phosphine; potassium-t-butoxide; palladium diacetate In toluene for 2h; Reflux; Inert atmosphere;	6 Example 6: Dibenzofuran-4-yl-aniline Synthesis of (Dibenzofuran-4-yl-phenyl-amine) (4) 4.66 g of Aniline and 12.35 g of 4-bromo-dibenzofuran were placed in a three-necked flask under nitrogen, and 250 ml of toluene was stirred and dissolved to add 11.22 g of potassium t-butoxide. (potassium tert-butoxide), 0.56 g of palladium acetate, 1.32 g of Tri-tert-butylphosphine, heated under reflux for 2 hours, cooled, concentrated by filtration, and subjected to column separation (Hex: EA =10:1), 8.2 grams of product was obtained, yield 64%.
42%	With tris(1,5-diphenylpenta-1,4-dien-3-one)dipalladium; C₃₂H₅₆Cl₂N₂P₂Pt; sodium tertiary butoxide In 5,5-dimethyl-1,3-cyclohexadiene at 120℃; for 15h; Inert atmosphere;	1 Synthesis of N-phenyl-dibenzo [b, d] furan-4-amine Under an argon atmosphere, 4-bromo-dibenzo [b, d] furan 5. 0g with aniline 2. 0gdissolved in 150ml dehydrated xylene, and then add bis (dibenzylideneacetone)palladium 0 • 13g, sodium t-butoxide 5. 8g, and bis(di-tert-butyl(4-dimethylaminophenyl)phosphine)dichloropalladium(II) 0. 18g and heated at 120 ° C for 15 hours. The reaction mixture was cooleduntil room temperature, water 100ml, and stirred followed by liqbis(di-tert-butyl(4-dimethylaminophenyl)phosphine)dichloropalladium(II) uidseparation. After the organic layer waswashed with water, the solvent was distilled off under reduced pressure toobtain a crude product. The crudeproduct was dissolved in toluene, the use of purified alumina column (solvent:toluene / heptane = 1/1 (volume ratio)) and the removal of the coloring component. The solvent was distilled off under reducedpressure, and then recrystallized from heptane, to obtain N- phenyl-dibenzo [b,d] furan-4-amine 2. 2g (42% yield).
	With 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; sodium tertiary butoxide In toluene at 85℃; for 6h; Inert atmosphere;	1.2.B In a stream of argon, 11.7g of intermediate M1, 10.7 mL of aniline, 0.63g of tris(dibenzylideneacetone)dipalladium(0) [Pd2(dba)3], 0.87g of 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl [BINAP], 9.1g of sodium tert-butoxide and 131 mL of dehydrated toluene were put in a 300 mL-recovery flask. A reaction was conducted at 85°C for 6 hours. After cooling, the reaction solution was fitered through cellite. A crude product obtained was purified by silica gel column chromatography (n-hexane/methylene chloride (3/1)). Solids obtained were dried under reduced pressure to obtain 10.0g of white solids. The solids were identified as intermediate M2 by FD-MS (field desorption mass spectrometry) analysis.
	With sodium tertiary butoxide In toluene at 85℃; for 6h; Inert atmosphere;	1.1.A (1) Synthesis of Intermediate (b); Synthesis Example A; 11.7 g of the intermediate (a), 10.7 mL of aniline, 0.63 g of tris(dibenzylideneacetone)dipalladium(0) (Pd2(dba)3), 0.87 g of 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (BINAP), 9.1 g of sodium tert-butoxide and 131 mL of dehydrated toluene were placed in a 300-mL recovery flask under an argon stream, and reacted at 85° C. for 6 hours.After cooling, the reaction solution was filtered with Celite, the resulting crude product was purified by silica gel chromatography (n-hexane/methylene chloride (3/1)), and the resulting solid was dried under reduced pressure, thereby providing 10.0 g of a white solid, which was identified as the intermediate (b) by analysis with FD-MS (field desorption mass spectrum).
	With 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; sodium tertiary butoxide In toluene at 130℃; for 24h; Inert atmosphere;	6 Synthesis Example 6 (synthesis of intermediate 6)> In a stream of argon, 24.7 g of the intermediate 3, 14.0 g of aniline, 28.8 g of t-butoxysodium, 1.4 g of tris(dibenzylideneacetone)dipalladium(0), 1.9 g of 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl, and 350 mL of toluene were loaded, and then the mixture was reacted at 130°C for 24 hours. After cooling, the mixture was filtered through celite, and then the filtrate was concentrated under reduced pressure. The resultant coarse product was subjected to column purification and recrystallized with toluene. The recrystallized product was taken by filtration, and was then dried. Thus, 20.7 g of a white powder were obtained. The white powder was identified as the intermediate 6 by FD-MS analysis.
	With bis(tri-tertiary-butylphosphine)palladium⁽⁰⁾; sodium tertiary butoxide In toluene at 80℃;	26-int Synthesis of Compound 26 4-Bromodibenzofuran (10 g, 40.6 mmol)And aniline (3.78 g, 40.6 mmol) were dissolved in toluene (100 ml), Sodium t-butoxide (5.5 g, 56.8 mmol) was added, the mixture was 80 degree heated with stirring, and then [bis (tri-t-butylphosphine)] palladium2% by weight.After the temperature was lowered to room temperature and the reaction was terminated,Hexane to prepare N-phenyldibenzofuran-4-amine. The compound 1 was synthesized in the same manner as in the synthesis of the compound 1, using the compound 2-2-C instead of the compound 1-1-C, to thereby prepare a compound 26.
10 g	With tris(1,5-diphenylpenta-1,4-dien-3-one)dipalladium; 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; sodium tertiary butoxide In toluene at 85℃; for 6h; Inert atmosphere;	1.2 (2) Compound D-2 Under argon conditions, the compound D-1 (11.7 g), the compound B (10.7 mL), tris(dibenzylideneacetone)dipalladium(0) (Pd2(dba)3, 0.26 mmol), 2,2′-bis(diphenylphosphino)-1,1′-binapthyl (BINAP, 0.87 g), sodium tert-butoxide (9.1 g), and dehydrated toluene (131 mL) were added to a distillation flask (300 mL) and reacted at 85° C. for 6 hours. After cooling, the reaction solution was filtered through celite. The obtained crude product was purified by silica gel chromatography using n-hexane and methylene chloride (volume ratio=3:1), and the obtained solid was dried under reduced pressure to obtain compound D-2. (10.0 g)
10 g	With tris(1,5-diphenylpenta-1,4-dien-3-one)dipalladium; 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; sodium tertiary butoxide In toluene at 85℃; for 6h; Inert atmosphere;	1.2 (2) Compound D-2 Under argon conditions, the compound D-1 (11.7 g), the compound B (10.7 mL), tris(dibenzylideneacetone)dipalladium(0) (Pd2(dba)3, 0.26 mmol), 2,2′-bis(diphenylphosphino)-1,1′-binapthyl (BINAP, 0.87 g), sodium tert-butoxide (9.1 g), and dehydrated toluene (131 mL) were added to a distillation flask (300 mL) and reacted at 85° C. for 6 hours. After cooling, the reaction solution was filtered through celite. The obtained crude product was purified by silica gel chromatography using n-hexane and methylene chloride (volume ratio=3:1), and the obtained solid was dried under reduced pressure to obtain compound D-2. (10.0 g)

Reference： [1]Current Patent Assignee: SHAANXI LIGHTE OPTOELECTRONICS MATERIAL CO.,LTD - CN113214280, 2021, A Location in patent: Paragraph 0116-0118; 0119-0121
[2]Current Patent Assignee: JILIN OLED OPTICAL AND ELECTRONIC MATERIALS CO LTD - CN113135935, 2021, A Location in patent: Paragraph 0123-0126
[3]Current Patent Assignee: YAMAGATA UNIVERSITY - JP2019/26556, 2019, A Location in patent: Paragraph 0032; 0033
[4]Current Patent Assignee: TETRAHEDRON TECHNOLOGY CORP - TW2020/16064, 2020, A Location in patent: Paragraph 0027
[5]Current Patent Assignee: SHANGHAI TAOE CHEMICAL TECHNOLOGY CO LTD - CN106478566, 2017, A Location in patent: Paragraph 0049; 0050; 0051
[6]Current Patent Assignee: EVERDISPLAY OPTRONICS (SHANGHAI) LIMITED - CN108342191, 2020, B Location in patent: Paragraph 0069; 0073-0076; 0098; 0102
[7]Current Patent Assignee: IDEMITSU KOSAN CO LTD - KR2015/132095, 2015, A Location in patent: Paragraph 0265-0270
[8]Current Patent Assignee: DUK SAN NEOLUX CO., LTD. - KR2021/100352, 2021, A Location in patent: Paragraph 0259-0261; 0305
[9]Current Patent Assignee: TETRAHEDRON TECHNOLOGY CORP - TWI614241, 2018, B Location in patent: Page/Page column 8
[10]Current Patent Assignee: SOUTH CHINA UNIVERSITY OF TECHNOLOGY - CN112538077, 2021, A Location in patent: Paragraph 0046-0050
[11]Current Patent Assignee: VALIANT CO., LTD. - CN107868037, 2018, A Location in patent: Paragraph 0077; 0078
[12]Current Patent Assignee: TETRAHEDRON TECHNOLOGY CORP - TWI644886, 2018, B Location in patent: Page/Page column 10
[13]Current Patent Assignee: CHISSO CORPORATION - KR2015/74015, 2015, A Location in patent: Paragraph 0935-0936
[14]Current Patent Assignee: IDEMITSU KOSAN CO LTD - EP2423206, 2012, A1 Location in patent: Page/Page column 52
[15]Current Patent Assignee: IDEMITSU KOSAN CO LTD - US2012/299473, 2012, A1 Location in patent: Page/Page column 44-45
[16]Current Patent Assignee: IDEMITSU KOSAN CO LTD - EP2527334, 2012, A1 Location in patent: Page/Page column 88; 89
[17]Current Patent Assignee: LG CHEM CO.,LTD. - KR2017/41646, 2017, A Location in patent: Paragraph 0556-0558
[18]Current Patent Assignee: LG DISPLAY CO.,LTD. - US2022/223793, 2022, A1 Location in patent: Paragraph 0104; 0105
[19]Current Patent Assignee: LG DISPLAY CO.,LTD. - US2022/278282, 2022, A1 Location in patent: Paragraph 0135; 0137-0138

5
[ CAS Unavailable ]
[ 89827-45-2 ]
[ 50548-37-3 ]

Yield	Reaction Conditions	Operation in experiment
75%	With copper (I) iodide; potassium carbonate; N<SUP>1</SUP>,N<SUP>2</SUP>-dimethylethane-1,2-diamine In 5,5-dimethyl-1,3-cyclohexadiene at 135℃; for 5h; Inert atmosphere;	1.1-1 Synthesis of Intermediate A-1 Under an argon atmosphere, a mixture of 1,200 g (4.86 mol) of 4-bromodibenzofuran, 573 g (9.71 mol) of acetamide, 184.98 g (971 mmol) of copper (I) iodide, 85.62 g (971 mmol) of N,N′-dimethylethylenediamine, 1,342 g (97.1 mol) of potassium carbonate, and 6 L of xylene was reacted at 135° C. for 5 h. After the reaction solution was cooled to room temperature, 4L of water was added thereto, followed by stirring for 1 h to precipitate crystals. And then the precipitated crystals were collected by filtration and washed with water and n-heptane to obtain 950 g of an intermediate A-1. The yield was 75%.
75%	With copper (I) iodide; potassium carbonate; N<SUP>1</SUP>,N<SUP>2</SUP>-dimethylethane-1,2-diamine In 5,5-dimethyl-1,3-cyclohexadiene at 135℃; for 5h; Inert atmosphere;	A-1 (A-1) Synthesis of Intermediate A-1 In argon atmosphere, a mixture of 4-bromodibenzaofuran (1200 g, 4.86 mol), acetamide (573 g, 9.71 mol), copper iodide (I) (184.98 g, 971 mmol), N,N′-dimethylethylenediamine (85.62 g, 971 mmol), potassium carbonate (1342 g, 97.1 mol), and xylene (6 L) was allowed to react at 135° C. for 5 h. After cooling to room temperature, water (4 L) was added and the resultant mixture was stirred for one hour. The precipitated crystal was collected by filtration and washed with water and n-heptane to obtain the intermediate A-1 (950 g) in a yield of 75%.
51%	With copper (I) iodide; (±)-trans-1,2-diaminocyclohexane; potassium carbonate In toluene Reflux;	6.1 Synthesis Example 6. Synthesis of Compound 203. Synthesis Example 6-(1). Synthesis of Intermediate 6-a In a 2 L-round-bottom flask reactor, 4-bromodibenzofuran (150.0 g, 0.607 mol), acetamide (53.8 g, 0.911 mol), copper iodide (57.8 g, 0.30 mol), (±)trans-1,2-diaminocyclohexane (63.9 g, 0.60 mol), potassium carbonate (167.8 g, 1.21 mol), and toluene (1500 ml) were stirred overnight together under reflux. After completion of the reaction, filtration through a silica gel pad was carried out, and the filtrate was washed many times with hot toluene. The filtrate was concentrated in a vacuum, and the concentrate was crystallized in acetonitrile, followed by filtration to afford . (70.0 g, 51%)

51%	With copper (I) iodide; potassium carbonate; (±)-trans-1,2-diaminocyclohexane In toluene Reflux;	11.1 Synthesis Example 11-(1): Synthesis of Intermediate 11-a In a 2 L-round-bottom flask reactor, 4-bromodibenzofuran (150.0 g, 0.607 mol), acetamide (53.8 g, 0.911 mol), copper iodide (57.8 g, 0.30 mol), (±)trans-1,2-diaminocyclohexane (63.9 g, 0.60 mol), and potassium carbonate (167.8 g, 1.21 mol), and toluene (1500 ml) were together stirred overnight under reflux. After completion of the reaction, filtration through a silica gel pad was carried out, and the filtrate was washed many times with hot toluene. The filtrate was concentrated in a vacuum, and the concentrate was crystallized in acetonitrile, followed by filtration to afford . (70.0 g, 51%)
51%	With copper (I) iodide; potassium carbonate; (±)-trans-1,2-diaminocyclohexane In propan-2-one Reflux;	1.1-1 In a 2 L-round bottom flask reactor 4-Bromodibenzofuran (150.0 g, 0.607 mol),Acetamide (53.8 g, 0.911 mol),Copper iodide (57.8 g, 0.30 mol),(1) Trans-1,2-diaminocyclohexane(63.9 g, 0.60 mol),Potassium carbonate (167.8 g, 1.21 mol),1500 ml of toluene was added and the mixture was refluxed overnight. After completion of the reaction, the reaction product was filtered on a silica gel pad and washed several times with hot toluene. The filtrate was concentrated under reduced pressure to give a solid, which was crystallized from acetonitrile and filtered to obtain Intermediate 1-a. (70.0 g, 51%).
51%	With copper (I) iodide; potassium carbonate; (±)-trans-1,2-diaminocyclohexane In toluene Reflux;	1.1-1 Synthesis of Intermediate 1-a In a 2-L round bottom flask, 4-bromodibenzofuran (150.0 g, 0.607 mol), acetamide (53.8 g, 0.911 mol), copper iodide (57.8 g, 0.30 mol), (±)trans-1,2-diaminocyclohexane (63.9 g, 0.60 mol), potassium carbonate (167.8 g, 1.21 mol), and toluene (1500 ml) were stirred together overnight under reflux. After completion of the reaction, filtration was conducted through a silica gel pad. The filtrate was washed many times with toluene and concentrated in a vacuum. The concentrate was crystalized in acetonitrile to afford as a crystal (70.0 g, 51%).
41%	With copper (I) iodide; (±)-trans-1,2-diaminocyclohexane; potassium carbonate In toluene Inert atmosphere; Reflux;	1.1 (1) The Compound A-4 In the round bottom flask (1 L) under nitrogen atmosphere, SM-1 (49.14 g, 0.20 mol), (1R,2R)-cyclohexane-1,2-diamine (23.11 g, 0.20 mol), acetamide (35.85 g, 0.61 mol), copper(I) iodide (38.54 g, 0.20 mol) and potassium carbonate (100 g, 0.40 mol) were dissolved in toluene (500 mL), and the mixture was stirred under reflux while heating overnight. When the reaction was completed, the organic layer was extracted and separated using ethyl acetate and distilled water after filtering through a celite pad filter. The organic layer was dried with anhydrous magnesium sulfate, filtered through a filter, and then concentrated under reduced pressure. The crude product was recrystallized using dichloromethane and hexane to obtain the compound A-4 (18.45 g, 41%).
32%	With copper (I) iodide; (±)-trans-1,2-diaminocyclohexane; potassium carbonate In toluene Reflux;	2-1 Synthesis of intermediate 2-a 2L round bottom flask, 4-bromo-modify-benzofuran reactor (100g, 0.405mol) in, (1R, 2R) - cyclohexane-1,2-diamine(46.21g, 0.404mol), acetamide (71.7g, 1.21mol), copper iodide (I) (77.08g, 0404mol), potassium carbonate (200g,0.809mol), put into 1000ml of toluene was stirred at reflux overnight. After the reaction was complete, filtered through a pad of Celite, ethyl acetateWashed with. The filtrate and the organic layer was separated and extracted with water and ethyl acetate. The organic layer with magnesium sulfateAfter the dry process was concentrated under reduced pressure filtration. Material is recrystallized from dichloromethane and petroleum ether (50g,32%) was obtained.
32%	With copper (I) iodide; potassium carbonate In toluene Reflux;	4-(4) 2L round bottom flask, 4-bromo-modify-benzofuran reactor (100g, 0.405mol), (1R, 2R) - cyclohexane-1,2-diamine (46.21g, 0.404mol), acetamide (71.7g, 1.21mol) , copper iodide (I) (77.08g, 0404mol), potassium carbonate (200g, 0.809mol), put into 1000ml of toluene was stirred at reflux overnight. After the reaction was complete, filtered through a pad of Celite, ethyl acetateWashed with. The filtrate and the organic layer was separated and extracted with water and ethyl acetate. The organic layer was filtered and concentrated under reduced pressure and then treated with anhydrous magnesium sulfate. Material is recrystallized from dichloromethane and petroleum ether was obtained (50g, 32%).
32%	With copper (I) iodide; (±)-trans-1,2-diaminocyclohexane; potassium carbonate In toluene Reflux;	2.2-1 Synthesis Example 2- (1): Synthesis of Intermediate 2-a Intermediate 2-a was synthesized according to Scheme 8 below:4-bromodibenzofuran (100 g, 0.405 mol), (1R, 2R) -cyclohexane-1,2-diamine (46.21 g, 0.404 mol) in a 2 L round bottom flask reactor Acetamide (71.7 g, 1.21 mol), copper iodide (I) (77.08 g, 0404 mol), potassium carbonate (200 g, 0.809 mol),1000 ml of toluene was added and stirred under reflux overnight. After the reaction was completed, the resultant was filtered through a pad of celite and washed with ethyl acetate.The filtrate was extracted with water and ethyl acetate to separate the organic layer. The organic layer was concentrated under reduced pressure after anhydrous treatment with magnesium sulfate. The material was recrystallized from dichloromethane and petroleum ether to obtain
	With copper (I) iodide; potassium carbonate; N<SUP>1</SUP>,N<SUP>2</SUP>-dimethylethane-1,2-diamine In xylene at 170℃; for 18h; Inert atmosphere;	3.1.D In a stream of argon, 18.7g of intermediate M1, 3.4g of acetoamide, 0.81 of copper iodide (I), 15.7g of potassium carbonate and 90 mL of xylene were put in a 300 mL-recovery flask. After stirring, 0.9 mL of N,N'-dimethylethylenediamine was put, and a reaction was conducted at 170°C for 18 hours. The reaction solution was filtered, and a crude product obtained was washed with toluene, clean water and methanol. Solids obtained were dried under reduced pressure, whereby 8.2g of solids were obtained. The solids obtained were identified as intermediate M4 by FD-MS (field desorption mass spectrometry) analysis.
	With copper atom; potassium carbonate In Bicyclo[4.4.0]decane at 190℃; for 96h; Inert atmosphere;	12 Synthesis Example 12 (synthesis of intermediate 12)> Under an argon atmosphere, 37.0 g of 1-acetamide, 49.4 g of the intermediate 3, 109 g of potassium carbonate and 2.5 g of a copper powder in 400 mL of decalin were reacted at 190°C for 4 days. After the reaction, the resultant was cooled, 200 mL of toluene were added to the resultant, and insoluble matter was taken by filtration. The product taken by filtration was dissolved in 500 mL of chloroform, and then insoluble matter was removed. After that, the residue was treated with activated carbon and concentrated. 300 mL of acetone were added to the concentrate, and then 27.6 g of the precipitated crystal were taken by filtration. The crystal was identified as the intermediate 12 by FD-MS analysis.

Reference： [1]Current Patent Assignee: IDEMITSU KOSAN CO LTD - US2020/317653, 2020, A1 Location in patent: Paragraph 0265-0267
[2]Current Patent Assignee: IDEMITSU KOSAN CO LTD - US2020/392122, 2020, A1 Location in patent: Paragraph 0341-0342
[3]Current Patent Assignee: HODOGAYA CHEMICAL CO LTD - US2017/18723, 2017, A1 Location in patent: Paragraph 0198-0199
[4]Current Patent Assignee: HODOGAYA CHEMICAL CO LTD - US2018/233669, 2018, A1 Location in patent: Paragraph 0296-0297
[5]Current Patent Assignee: HODOGAYA CHEMICAL CO LTD - KR2019/33504, 2019, A Location in patent: Paragraph 0477-0483
[6]Current Patent Assignee: HODOGAYA CHEMICAL CO LTD - US11251378, 2022, B2 Location in patent: Page/Page column 61
[7]Current Patent Assignee: LG DISPLAY CO.,LTD.; DUPONT DE NEMOURS INC - US2022/199919, 2022, A1 Location in patent: Paragraph 0038-0040
[8]Current Patent Assignee: HODOGAYA CHEMICAL CO LTD - KR2016/13678, 2016, A Location in patent: Paragraph 0268-0274
[9]Current Patent Assignee: HODOGAYA CHEMICAL CO LTD - KR2015/128583, 2015, A Location in patent: Paragraph 0377-0382
[10]Current Patent Assignee: HODOGAYA CHEMICAL CO LTD - KR2019/111856, 2019, A Location in patent: Paragraph 0268-0274
[11]Current Patent Assignee: IDEMITSU KOSAN CO LTD - EP2423206, 2012, A1 Location in patent: Page/Page column 54
[12]Current Patent Assignee: IDEMITSU KOSAN CO LTD - EP2527334, 2012, A1 Location in patent: Page/Page column 89

6
[ 89827-45-2 ]
[ 154230-29-2 ]
[ 1253190-12-3 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; water; toluene; at 90℃; for 8h;Inert atmosphere;	In the stream of argon, 8.0g of intermediate i-7, 7.7g of <strong>[154230-29-2]trans-2-(4-chlorophenyl)vinylboronic acid</strong>, 0.75g of tetrakis(triphenylphosphine)palladium(0) [Pd(PPh3)4], 10.3g of sodium carbonate (clean water 49 mL), 60 mL of dehydrated toluene and 60 mL of dehydrated THF were put in a 500 mL-recovery flask. The resulting mixture was allowed to react at 90C for 8 hours in the stream of argon. The reaction liquid was separated by adding clean water and toluene, and the aqueous phase was extracted with toluene. An organic phase obtained by mixing was washed with clean water and saturated saline, and dried with sodium sulfate, and concentrated to obtain a crude product. The crude product was purified with silica gel chromatography (toluene/hexane=1/19), and solids obtained were dried under reduced pressure to obtain 8.4g of white solids. The white solids were identified as intermediate i-8 by FD-MS analysis.

Reference： [1]Patent: EP2423179,2012,A1 .Location in patent: Page/Page column 52

7
[ 89827-45-2 ]
[ 864377-33-3 ]
[ 1422393-46-1 ]

Reference： [1]Chemistry - A European Journal,2013,vol. 19,p. 1194 - 1198

8
[ 89827-45-2 ]
[ 98-80-6 ]
[ 74104-10-2 ]

Yield	Reaction Conditions	Operation in experiment
98%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate In tetrahydrofuran; water for 12h; Reflux; Inert atmosphere;	1.2 Step 2: Synthesis of Intermediate M-2 75 g (305 mmol) of 4-bromodibenzofuranand 45g (365mmol) of phenylboronic acid dissolved in 760ml of tetrahydrofuran,And 381 ml of an aqueous solution in which 126.5 g (915 mmol) of K2CO3 was dissolved was added, followed by stirring.Subsequently, 17.62 g (15.25 mmol) of Pd(PPh3)4 were added,Stir at reflux for 12 hours under nitrogen atmosphere.When the reaction is completed, water is added to the reaction solution,It was extracted with ethyl acetate (EA), treated with anhydrous magnesium sulfate to remove moisture therefrom, filtered, and concentrated under reduced pressure.The resulting residue was isolated and purified by flash column chromatography,Intermediate M-2 (73.12 g, yield: 98%) was obtained.
95%	With potassium carbonate; palladium dichloride In ethanol; water at 20℃; for 12h;
94%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate In ethanol; water; toluene at 110℃;	7 Synthesis of Intermediate AN 27.2 g phenylboronic acid and 24.7 g 4-bromo-dibenzofuran were placed into a three-neck flask (2 L), to which 600 mL toluene and 150 mL ethanol were added to dissolve the solid. The resulting mixture was aerated with nitrogen gas for 15 minutes and then, 150 mL aqueous K2CO3 solution (3.0 eq., 2M) and 2.3 g Pd(PPh3)4(2 mol %) were sequentially added. The reaction was heated up to 110° C. and performed overnight at, and after the reaction finished, the resulting mixture was absorbed with activated carbon and filtered by suction filtration. The solvent was removed by rotary evaporation and the residual was dried and recrystallized with toluene and ethanol to produce 23.0 g Intermediate AN in 94% yield

94%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate In ethanol; water; toluene at 110℃; Inert atmosphere;	7.72 Reaction 72 27.2 g of phenylboronic acid and 4-bromo-dibenzofuran (24.7 g) were added to a 2 L three-neck flask and 600 mL of toluene was added.Dissolve with 150 mL of ethanol, pass nitrogen for 15 minutes, add an additional 150 mL of aqueous K2CO3 (3.0 eq., 2 M) solution, and finally add 2.3 g of Pd(PPh3)4 (2 mol %). The temperature was raised to 110°C and the reaction was completed overnight. Activated carbon adsorption, suction filtration, solvent removal, drying, recrystallization with toluene and ethanol, to obtain 23.0g of intermediate AN, the yield of 94%
91%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate In tetrahydrofuran; water at 80℃; for 12h;	3 Synthesis Example 3: Synthesis of Int-2 4-Bromo-dibenzofuran (80 g, 509.41 mmol), phenylboronic acid (90 g, 424.51 mmol),K2CO3 (117.34 g, 849.02 mmol) and Pd(PPh3)4 (24.53 g, 21.23 mmol) were placed in a round bottom flask,And THF (1000 mL) and distilled water (500 mL) were added thereto, and then the resultant was stirred under reflux at 80° C. for 12 hours.When the reaction was completed, after removing the aqueous layer therefrom, 93 g (91%) of the intermediate Int-2 was obtained using column chromatography.
90%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate In ethanol; water; toluene Reflux;	1.1 1) Preparation of compound 1-1 4-bromodibenzofuran in a 5L round flask(4-bromodibenzofurane)100g (407mmol, 1eq) and phenyl boronic acid50g(407mmol, 1eq), Pd(pph3)4 24g(20mmol, 0.05eq), K2CO3169 g (1221 mmol, 3 eq) was added, and toluene/ethanol (EtOH)/H 2 O were each added in 2L/350ml/350ml and stirred under reflux.After the reaction was completed, the mixture was extracted with CH2Cl2/ H2O, and the CH2Cl2 layer was dried over MgSO4.Compound 1-1 by Silica-gel column purification89.1 g was obtained in 90% yield.
90%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate In ethanol; water; toluene Reflux;	2.1 1) Preparation of compound 2-1 5L round flask 4-bromodibenzofuran 100g(407mmol, 1eq) And phenyl boronic acid 50g(407mmol, 1eq), Pd(pph3)4 24g (20mmol, 0.05eq), K2CO3 169g (1221mmol, 3eq) And added Toluene/EtOH/H2O 2L/350ml/350ml and stirred under reflux. After the reaction was completed, the mixture was extracted with CH2Cl2/ H2O, and the CH2Cl2 layer was dried over MgSO4. Silica-gel column purification gave 89.1 g of Compound 2-1 in a yield of 90%.
82%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate In ethanol; water; toluene at 80℃; for 12h; Inert atmosphere;	1 1000ml bottle was added in three 4-bromo-dibenzofuran (30g, 121.5mmol), phenylboronic acid (15.6g, 127.6mmol), tetrakistriphenylphosphine palladium (0.7g, 0.61mmol), potassium carbonate (41g, 297.1 mmol), toluene 300ml, ethanol 150ml, water 150ml, nitrogen protection reaction at 80 12h. TLC showed the reaction was complete. Spin off the toluene, ethanol, water was extracted with dichloromethane (200mlX3) and the combined organic phases over anhydrous sodium sulfate, and concentrated under reduced pressure distillation product 4-phenyl-dibenzofuran (24.4 g, 82% yield )
69 %	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate In tetrahydrofuran; water Reflux;	4.1 Step 1: Synthesis of the intermediate Int 4-1-a Add 41.8 g (169.2 mmol) of 4-bromodibenzofuran, 24.8 g (203.3 mmol) of phenylboronic acid, 46.8 g (338.3 mmol) of K2CO3 and 5.9 g (5.1 mmol) of Pd(PPh3)4 Suspend in 340 ml of THF and 170 ml of distilled water under a stream of nitrogen and then stir back into the reflux for 8 h. When the reaction is complete, the product is extracted with DCM and treated by column chromatography (hexane: DCM (20%)) to obtain 28.5 g (69%) of the intermediate Int 4-1-a as a solid.
69 %	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate In tetrahydrofuran; water Reflux; Inert atmosphere;	4.1 1st step: Synthesis of Intermediate Int 4-1-a 41.8 g (169.2 mmol) of 4-bromodibenzofuran, 24.8 g (203.3 mmol) of phenylboronic acid, 46.8 g (338.3 mmol) of K2CO3, and 5.9 g (5.1 mmol) of Pd(PPh3)4 were suspended in 340 ml of THF and 170 ml of distilled water under a nitrogen flow and then, stirred under reflux for 8 hours. When a reaction was completed, the resultant was extracted with DCM and treated through column chromatography (hexane:DCM (20%)), obtaining 28.5 g (69%) of Intermediate Int 4-1-a as a solid.

Reference： [1]Current Patent Assignee: SAMSUNG SDI CO.,LTD. - CN114437091, 2022, A Location in patent: Paragraph 0218; 0224-0228
[2]Maetani, Shinji; Fukuyama, Takahide; Ryu, Ilhyong [Organic Letters, 2013, vol. 15, # 11, p. 2754 - 2757]
[3]Current Patent Assignee: NANJING TOPTO SEMICONDUCTOR MATERIAL CO LTD - US9938287, 2018, B1 Location in patent: Page/Page column 131
[4]Current Patent Assignee: NANJING TOPTO SEMICONDUCTOR MATERIAL CO LTD - CN107880055, 2018, A Location in patent: Paragraph 0363-0368
[5]Current Patent Assignee: SAMSUNG SDI CO.,LTD. - CN114437090, 2022, A Location in patent: Paragraph 0216-0219
[6]Current Patent Assignee: SOULBRAIN CO.,LTD. - KR2020/68397, 2020, A Location in patent: Paragraph 0149-0153
[7]Current Patent Assignee: SOULBRAIN CO.,LTD. - KR2020/68398, 2020, A Location in patent: Paragraph 0183-0187
[8]Current Patent Assignee: WUHAN SHANGSAI OPTOELECTRONICS TECHNOLOGY CO LTD - CN105503622, 2016, A Location in patent: Paragraph 0034; 0035; 0046; 0047
[9]Current Patent Assignee: SAMSUNG SDI CO.,LTD. - CN115745932, 2023, A Location in patent: Paragraph 0216-0220
[10]Current Patent Assignee: SAMSUNG SDI CO.,LTD. - US2023/117860, 2023, A1 Location in patent: Paragraph 0148; 0149

9
[ 89827-45-2 ]
[ 185990-03-8 ]
[ 912824-85-2 ]

Reference： [1]Chemical Science,2015,vol. 6,p. 2943 - 2951

10
[ 89827-45-2 ]
[ 1303472-74-3 ]
[ 1567814-83-8 ]

Yield	Reaction Conditions	Operation in experiment
91%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate In tetrahydrofuran; water at 90℃; for 26h; Inert atmosphere;	17 Preparation of Intermediate I-17 15 g (60.7 mmol) of 4-bromodibenzofuran was dissolved in 0.2 L of tetrahydrofuran (THF) in a nitrogen environment, 24.7 g (66.8 mmol) of 3-phenyl-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole and 0.70 g (0.61 mmol) of tetrakis(triphenylphosphine)palladium were added thereto, and the mixture was agitated. 17.9 g (121 mmol) of potassium carbonate saturated in water was added thereto, and the mixture was heated and refluxed at 90 °C for 26 hours. When the reaction was terminated, water was added to the reaction solution, and the mixture was extracted with dichloromethane (DCM) and treated with anhydrous MgSO4 to remove moisture and then, filtered and concentrated under a reduced pressure. The obtained residue was separated and purified through flash column chromatography, obtaining a compound I-17 (22.6 g, 91 %). HRMS (70 eV, EI+): m/z calcd for C30H19NO: 409.1467, found: 409.1. Elemental Analysis: C, 88 %; H, 5 %

Reference： [1]Current Patent Assignee: SAMSUNG SDI CO.,LTD.; SAMSUNG C&T CORPORATION - EP2889296, 2015, A1 Location in patent: Paragraph 0220-0223

11
[ 89827-45-2 ]
[ 168618-42-6 ]
C₁₉H₁₄OS [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
99%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; sodium carbonate In ethanol; water; toluene at 120℃; for 3h;	2 Preparation of compound 2-1 After introducing compound 4-bromodibenzofuran (50g, 202.35mmol), 2-methyithiophenylboronic acid (34g, 202.35mmol), tetrakis(triphenylphosphine)palladium (1 1.7g, 10.1 l7mmol), sodium carbonate (64g, 607.O6mmol), toluene (l000mL), ethanol (300mL), and distilled water (300mL) into a reaction vessel, the mixture was stirred at 120°C for 3 hours. After the reaction, the mixture was washed with distilled water, and extracted with ethyl acetate. The extracted organic layer was dried with magnesium sulfate, and the solvent was removed therefrom by a rotary evaporator. The products were purified by column chromatography to obtain compound 2-1 (58g, 99%).

Reference： [1]Current Patent Assignee: DOW INC - WO2015/99507, 2015, A1 Location in patent: Paragraph 238; 239

12
[ 89827-45-2 ]
[ 121-43-7 ]
[ 100124-06-9 ]

Yield	Reaction Conditions	Operation in experiment
80%	Stage #1: 4-bromodibenzofuran With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1h; Inert atmosphere; Stage #2: Trimethyl borate In tetrahydrofuran; hexane at -78 - 20℃; for 2h; Inert atmosphere; Stage #3: With hydrogenchloride In tetrahydrofuran; hexane; water at 20℃; for 3h;	Synthesis of dibenzofuran-4-boronic acid Synthesis of dibenzofuran-4-boronic acid (0048) In a 300 ml three-necked flask, 7.2 g of 4-bromodibenzofuran was dissolved in -78° C. anhydrous tetrahydrofuran (THF) under an argon atmosphere. Then, 20 ml of an n-butyl lithium-n-hexane solution (1.6 M, 1.1 eq) was added and stirred for 1 hour. 4.23 ml (1.3 eq) of trimethoxyborane (B(OMe)3) was added and stirred for 2 hours, and the temperature of the reaction system was increased to room temperature. 200 ml of 1 N hydrochloric acid was added into the reactant and stirred for 3 hours. An organic layer was separated, and solvents were distilled off. In the crude product thus obtained, hexane was added. Precipitated product was filtered to obtain 4.94 g of dibenzofuran-4-boronic acid as a white solid (yield 80%). The product was measured by FAB-MS, and dibenzofuran-4-boronic acid having a molecular weight of 212 was detected.
73%	Stage #1: 4-bromodibenzofuran With n-butyllithium In tetrahydrofuran at -78 - 0℃; for 1h; Inert atmosphere; Stage #2: Trimethyl borate In tetrahydrofuran at -78℃; Stage #3: With hydrogenchloride In tetrahydrofuran; water for 0.5h;	Synthesis of Intermediate 22 Synthesis of Intermediate 22 (0146) (0147) Under a nitrogen atmosphere, Intermediate 20 (2.47 g, 10 mmol) was dissolved in anhydrous tetrahydrofuran (40 mL), and then cooled to -78° C. n-butyllithium (2.5 M, 4 mL) was slowly added dropwise, stirred at 0° C. for 1 hr, and then cooled to -78° C. again. Trimethyl borate (12.47 g, 12 mmol) was added dropwise, and stirred for 12 hrs at normal temperature. After the reaction was terminated, a 2N aqueous HCl solution was added, stirred for 30 min, and extracted with diethyl ether. (0148) The organic layer was dried over anhydrous magnesium sulfate, suctioned, and concentrated. The resultant compound was purified by column chromatography eluting with Hex:EA=5:1, to obtain Intermediate 22 (1.55 g, 73%). (0149) Intermediate 22 MS(FAB): 212(M+)
73%	Stage #1: 4-bromodibenzofuran With n-butyllithium In tetrahydrofuran at -78 - 0℃; for 1h; Inert atmosphere; Stage #2: Trimethyl borate In tetrahydrofuran at -78℃; for 12h; Stage #3: With hydrogenchloride; water In tetrahydrofuran for 0.5h;	1 Synthesis of Intermediate 18 Under a nitrogen atmosphere, Intermediate 16 (2.47 g, 10 mmol) was dissolved in anhydrous tetrahydrofuran (40 mL), and then cooled to -78° C. n-butyllithium (2.5 M, 4 mL) was slowly added dropwise, stirred at 0° C. for 1 hr, and then cooled to -78° C. again. Trimethyl borate (12.47 g, 12 mmol) was added dropwise, and stirred for 12 hrs at normal temperature. After the reaction was terminated, a 2N aqueous HCl solution was added, stirred for 30 min, and extracted with diethyl ether. The organic layer was dried over anhydrous magnesium sulfate, suctioned, and concentrated. The resultant compound was purified by column chromatography eluting with Hex:EA=5:1, to obtain Intermediate 18 (1.55 g, 73%). Intermediate 18 MS (FAB): 212(M+)

70%	Stage #1: 4-bromodibenzofuran With n-butyllithium In tetrahydrofuran for 1h; Stage #2: Trimethyl borate In tetrahydrofuran at 20℃;	Preparation of intermediate II-4: Intermediate II-3 (6.33g, 25.61mmol) was added to a 250ml three-necked flask containing THF (50ml), -78, n-butyllithium (1.72g, 26.89mmol) was added dropwise, and kept warm after the dropwise addition After 1h, trimethyl borate (3.99g, 38.42mmol) was added dropwise, and the temperature was kept for 1h, and the temperature was raised to room temperature and stirred overnight. Hydrochloric acid (2mol / L) was added to adjust the pH to neutral, and then filtered to obtain a crude white product, which was then slurried with n-heptane to obtain intermediate II-4 (3.80g, yield: 70%).
	Stage #1: 4-bromodibenzofuran With n-butyllithium In tetrahydrofuran for 2h; Cooling with acetone-dry ice; Stage #2: Trimethyl borate In tetrahydrofuran at -78 - 0℃; for 1h; Stage #3: With hydrogenchloride In tetrahydrofuran; water at 0 - 20℃; for 8h;

Reference： [1]Current Patent Assignee: Samsung Display (in: Samsung); SAMSUNG ELECTRONICS CO.,LTD. - US9172047, 2015, B2 Location in patent: Page/Page column 17
[2]Current Patent Assignee: NANJING TOPTO SEMICONDUCTOR MATERIAL CO LTD - US2017/125677, 2017, A1 Location in patent: Paragraph 0146-0149
[3]Current Patent Assignee: NANJING TOPTO SEMICONDUCTOR MATERIAL CO LTD - US2017/125678, 2017, A1 Location in patent: Paragraph 0121; 0122; 0123
[4]Current Patent Assignee: SHAANXI LIGHTE OPTOELECTRONICS MATERIAL CO.,LTD - CN111018843, 2020, A Location in patent: Paragraph 0160; 0161; 0163
[5]Chen, Shuo; Wu, Yukun; Zhao, Yi; Fang, Daining [RSC Advances, 2015, vol. 5, # 88, p. 72009 - 72018]

13
[ 89827-45-2 ]
[ 912824-85-2 ]

Reference： [1]RSC Advances,2015,vol. 5,p. 72009 - 72018

14
[ 89827-45-2 ]
[ 916435-45-5 ]

Yield	Reaction Conditions	Operation in experiment
83%	With [bis(acetoxy)iodo]benzene; sulfuric acid; iodine; acetic anhydride; acetic acid at 20℃; for 36h; Inert atmosphere;
65%	With [bis(acetoxy)iodo]benzene; sulfuric acid; iodine; acetic anhydride; acetic acid at 20℃; for 10h; Inert atmosphere;	1.1 1) Synthesis of Intermediate 1-1 10 g (40.65 mmol) of 4-bromo dibenzofuran under nitrogen,iodine 5.1 g (20.32 mmol),6.6 g (20.32 mmol) of phenyl iodide diacetate150 mL acetic acidInto a 150 mL acetic anhydride mixed solvent, add 3 drops of sulfuric acid,Stir at room temperature for 10 hours.Terminate the reaction,Ethyl acetate is added to the mixed solution, washed with water, the layers are separated, and only the organic layer is added. Anhydrous magnesium sulfate is added and stirred. After filtration through silica pad, the solution was concentrated by column concentration under reduced pressure, and intermediate 1-1 was obtained in 65% yield.
65%	With [bis(acetoxy)iodo]benzene; sulfuric acid; iodine; acetic anhydride; acetic acid at 20℃; for 10h; Inert atmosphere;	2.(1) (1) Synthesis of Intermediate 2-1 10.0 g (40.65 mmol) of 4-bromo dibenzofuran, 5.1 g (20.32 mmol) of iodine and 6.6 g (20.32.mmol) of phenyl iodide diacetate were placed in a mixed solvent of 150 mL of acetic acid and 150 mL of acetic anhydride under nitrogen atmosphere. Three drops of sulfuric acid was added drop wisely in the solution and then stirred 10 hours at room temperature. After the reaction was completed, ethyl acetate was added into the mixed solution, and then the solution was washed with water to separate an organic layer from an aqueous layer. Anhydrous magnesium sulfate was added to the organic solution and the organic solution was stirred again. After the solution was filtered with silica pad, the solution was concentrated under reduced pressure and purified by column chromatography to give an Intermediate 2-1 (yield: 65%).

65%	With [bis(acetoxy)iodo]benzene; sulfuric acid; iodine; acetic anhydride; acetic acid at 20℃; for 10h; Inert atmosphere;	1.1 (1) Synthesis of Intermediate 1-1 10.0 g (40.65 mmol) of 4-bromo dibenzofuran, 5.1 g (20.32 mmol) of iodine and 6.6 g (20.32 mmol) of phenyl iodide diacetate were placed in a mixed solvent of 150 mL of acetic acid and 150 mL of acetic anhydride under nitrogen atmosphere. Three drops of sulfuric acid were added in the solution and then stirred 10 hours at room temperature. After the reaction was completed, ethyl acetate was added into the mixed solution, and then the solution was washed with water and organic layer was separated from aqueous layer. Anhydrous magnesium sulfate was added to the organic solution and the solution was stirred again. After the solution was filtered with silica pad, the solution was concentrated under reduced pressure and purified by column chromatography to give an Intermediate 1-1 (yield: 65%).
65%	With [bis(acetoxy)iodo]benzene; sulfuric acid; iodine; acetic anhydride In acetic acid at 20℃; for 10h; Inert atmosphere;	1.1 (1) Synthesis of Intermediate 1-1 10 g (40.65 mmol) of 4-bromo dibenzofuran, 5.1 g (20.32 mmol) of iodine and 6.6 g (20.32 mmol) of phenyl diacetate were placed into a mixed solvent of 150 mL of acetic acid and 150 mL of acetic anhydride under nitrogen atmosphere, three drops of sulfuric acid was added into the solution with drop-wise, and then the solution was stirred for 10 hours at room temperature. After reaction was completed, ethyl acetate was added into the mixed solution, then the solution was washed with water to separate an aqueous layer form an organic layer. The organic layer was placed into anhydrous magnesium sulfate and then the organic solution was stirred again. The organic solution was filtered with a silica pad, concentrated under reduced pressure and then purified by column chromatography to give intermediate 1-1 (yield: 65%).
60%	With [bis(acetoxy)iodo]benzene; sulfuric acid; iodine; acetic anhydride; acetic acid at 20℃; for 36h; Inert atmosphere;	1.1 Step 1: Synthesis of Intermediate Product (Compound 3-A) 4-bromodibenzofuran (2 g, 8.1 mmol), iodobenzene-diacetate (1.3 g, 4.0 mmol) and iodine (1.03 g, 4.0 mmol) were suspended in 10 mL of acetic anhydride and 10 mL of acetic acid. After adding a small amount of sulfuric acid, the mixture was stirred at room temperature under nitrogen flow for 36 hours. Upon completion of the reaction, the organic layer was extracted with dichloromethane. The solution was dried using anhydrous sodium sulfate. After vacuum distillation, the solution was columned and recrystallized with hexane to obtain compound 3-A (1.8 g, yield: 60%).
51%	With [bis(acetoxy)iodo]benzene; sulfuric acid; iodine; acetic anhydride; acetic acid at 20℃; for 24h;	8 Synthesis of 6-bromo-2-iododibenzo[b,d]furan A mixture of 24.7 g (100 mmol) 4-bromodibenzo[b,d]furan, 12.7 g (50 mmol) of iodine, 16.1 g (50 mmol) of phenyliododiacetate, 50 ml of acetic acid, 50 ml of acetic anhydride and 3 ml of sulfuric acid were stirred at room temperature for 24 hours. After completion of reaction, toluene was added to the reaction mixture and the mixture was washed with water. After the organic phase was dried with anhydrous magnesium sulfate, the solvent in the organic phase was distilled away under reduced pressure. The residue was purified by column chromatography on silica(hexane-dichloromethane) afforded a white solid (19 g, 51 mmol, 51%)
49%	With [bis(acetoxy)iodo]benzene; sulfuric acid; iodine In acetic acid at 20℃; Inert atmosphere;	5.a a) 50 g (0.202 mol) 4-Bromo-dibenzofuran are added to 500 ml acetic acid under nitrogen. At room temperature 32,5 g (0.101 mol) (Diacetoxy-iodo)benzene, 25.7 g (0.101 mol I2 and 16 drops of H2SO4 97% are added in four portions each within 2 h. The resulting suspension is stirred overnight, filtered, the residue is washed three times with cold methanol (50 ml each) and dried at 80°C/125 mbar overnight. The product is crystallized from Cyclohex- ane to yield 36.9 g (49.0% of theory) 6-Bromo-2-iodo-dibenzofuran as a white solid. 1 H-NMR (400 MHz, CDCI3): δ 8.25 (s, 1 H), 7.82 (d, J = 7.6 Hz, 1 H), 7.76 (d, J = 8.4 Hz, 1 H), 7.64 (d, J = 7.6 Hz, 1 H), 7.42 (d, J = 8.4 Hz, 1 H), 7.26 - 7.21 (m, 1 H).
47.7%	With [bis(acetoxy)iodo]benzene; sulfuric acid; iodine; acetic anhydride; acetic acid at 20℃; for 10h; Inert atmosphere;	2.3. Synthesis of 2-iodo-6-bromodibenzofuran (2) In a 250 mL round-bottom three-neck flask under a nitrogen atmosphere,4-bromodibenzofuran (5 g, 20 mmol), iodine (2.57 g, 10 mmol),phenyliodine diacetate (3.259 g, 10 mmol), sulfuric acid (0.01 mL),acetic acid (15 mL) and acetic anhydride (15 mL) were placed, andstirred at room temperature for 10 h. The reaction mixture was washedwith water, extracted with dichloromethane, and concentrated to givecompound (2) (3.6 g, 47.7%). 1H NMR (300 MHz, CDCl3) δ 8.27 (s, 1H),7.85 (d, 1H, J =6.0 Hz), 7.78 (d, 1H, J =6.0 Hz), 7.66 (d, 1H, J =9.0Hz), 7.44 (d, 1H, J =6.0 Hz), 7.25 (t, 1H, J =7.5 Hz). 13C NMR (75 MHz,CDCl3) δ 155.41, 153.41, 136.38, 130.79, 130.01, 126.80, 124.37,124.33, 119.80, 114.14, 104.59, 86.35. HRMS (ESI, m/z): [M + H]+calcd for C12H6BrIO, 371.86; found 372.00. Elemental analysis; found:C, 38.38; H, 1.48%; molecular formula C12H6BrIO requires C, 38.64; H,1.62; Br, 21.42; I, 34.02; O, 2.44%.
	With [bis(acetoxy)iodo]benzene; sulfuric acid; iodine In acetic anhydride; acetic acid at 20℃;
	With [bis(acetoxy)iodo]benzene; sulfuric acid; iodine In acetic anhydride; acetic acid

Reference： [1]Jang, Seokhoon; Lee, Kyung Hyung; Lee, Jun Yeob; Lee, Youngu [Journal of Materials Chemistry C, 2019, vol. 7, # 4, p. 826 - 834]
[2]Current Patent Assignee: LG DISPLAY CO.,LTD.; LG CHEM CO.,LTD. - KR2019/68103, 2019, A Location in patent: Paragraph 0210-0213
[3]Current Patent Assignee: LG DISPLAY CO.,LTD.; LG CHEM CO.,LTD. - US2020/136059, 2020, A1 Location in patent: Paragraph 0202-0203
[4]Current Patent Assignee: LG DISPLAY CO.,LTD.; LG CHEM CO.,LTD. - US2020/127214, 2020, A1 Location in patent: Paragraph 0188-0189
[5]Current Patent Assignee: LG DISPLAY CO.,LTD.; LG CHEM CO.,LTD. - US2020/194685, 2020, A1 Location in patent: Paragraph 0231-0232
[6]Current Patent Assignee: DAEGU GYEONGBUK INSTITUTE OF SCIENCE & TECHNOLOGY - US2019/359602, 2019, A1 Location in patent: Paragraph 0034; 0035; 0036
[7]Current Patent Assignee: LUMINESCENCE TECHNOLOGY CORPORATION - US2016/322569, 2016, A1 Location in patent: Paragraph 0058; 0059
[8]Current Patent Assignee: IDEMITSU KOSAN CO LTD - WO2015/140073, 2015, A1 Location in patent: Page/Page column 97
[9]Yun, Seong-Jae; Seo, Min Hye; Lee, Sungkoo [Dyes and Pigments, 2020, vol. 175]
[10]Jang, Seokhoon; Lee, Kyung Hyung; Lee, Jun Yeob; Lee, Youngu [Journal of Materials Chemistry C, 2019, vol. 7, # 31, p. 9599 - 9608]
[11]Choi, Kyung Hyun; Kim, Jae Min; Chung, Won Jae; Lee, Jun Yeob [Molecules, 2021, vol. 26, # 9]

15
[ 89827-45-2 ]
[ 73183-34-3 ]
[ 912824-85-2 ]

Yield	Reaction Conditions	Operation in experiment
90%		4-Bromodibenzofuran 10.0g (38.1 mmol) was dissolved in 300ml tetrahydrofuran and then, Bis (triphenylphosphine) palladium (II) dichloride 1.3g (1.9 mmol) was added at the room temperature was stirred for about 5 minutes dongan it. Thereafter, Bis (pinacolato) diboron 14.5g (57.2 mmol) and Potassium acetate 11.2g (114.3 mmol) and the mixture was heated under reflux for a day at 80 . When the reaction is complete, the extract was added to 200ml of ethyl acetate, and distilled under reduced pressure the organic layer was dried with magnesium sulfate. Purification of the separation results obtained therefrom by column chromatography to give Intermediate 12-3 about 10.0g (34.3 mmol, 90% yield). The resulting compound was confirmed by LC-MS.
82%	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In N,N-dimethyl-formamide; at 90℃;	Sub-1-I-1 (15.76 g, 63.78 mmol) was dissolved in DMF (320 ml) into a round bottom flask,Bis (pinacolato) diboron (17.82 g, 70.16 mmol), Pd (dppf) Cl2 (1.56 g, 1.91 mmol) and KOAc (18.78 g, 191.35 mmol) were added and stirred at 90 C.When the reaction was complete, DMF was removed by distillation and extracted with CH2Cl2 and water.The organic layer was dried over MgSO4 and concentrated. The resulting compound was purified by silicagel column and recrystallized to give 15.38 g of the product (Yield: 82%).
82%	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In N,N-dimethyl-formamide;	Sub 14-1 (15.76 g, 63.78 mmol) was added into a round bottom flask, then, dissolved in DMF (320 ml). After adding l3is(pinacolato)diboron (17.82 g, 70.16 mmol), Pd(dppCl2 (1.56 g, 1.91 mmol), KOAc (18.78 g, 191.35 mmol), stirring at 90 D was followed. When the reaction was completed, DMF was removed by distillation, and then extracting with CH2C12 and water was followed. The organic layer was dried with Mg504 and concentrated. Then, the concentrate was passed through silica gel colunm, then recrystallized to obtain 15.38 g (yield: 82%) of the product.

78%	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In 1,4-dioxane;Reflux;	3L round flask 4-bromodibenzofurane 80g(325mmol, 1eq) And bis(pinacolato)diboron 91g(358mmol, 1.1eq), Pd(dppf)Cl2 12g(16mmol, 0.05eq), KOAc 128g (1300mmol, 4eq) And 1,4-dioxane 2L was added and stirred under reflux. After the reaction was completed, the mixture was extracted with CH2Cl2/ H2O, and the CH2Cl2 layer was dried over MgSO4. Silica-gel column purification gave 75 g of Compound 1-1 in a yield of 78%.
60.5%	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In 1,4-dioxane; at 130℃; for 5h;Inert atmosphere;	In a 250mL three-necked bottle, With nitrogen, 10.0mol of raw material VIII-1, 12.0mol raw material IX-1, 0.3g Pd(dppf)Cl2, 30.0mmol of potassium acetate was added to 100mL of 1,4-dioxane, At 130 C, React for 5 hours. The target product was obtained by separation and purification through silica gel column chromatography, with HPLC purity of 99.8% and yield of 60.5%.
	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In 1,4-dioxane; at 90℃; for 48h;Inert atmosphere;	(1) In a 250 ml round bottom flask, the intermediate products 4-bromodibenzofuran (15 mmol) and potassium acetate (40 mmol) and dried 1,4-dioxane (60 ml),Pd (dppf) Cl2 (0.4 mmol) and pinacol biborate (50 mmol) were mixed and stirred under a nitrogen atmosphere at 90 C for 48 hours. The obtained intermediate was cooled to room temperature and added to water, then filtered through a pad of celite, and the filtrate was extracted with dichloromethane, It was then washed with water and dried over anhydrous magnesium sulfate. After filtration and evaporation, the crude product was purified by silica gel column chromatography to obtain intermediate product P43-1
2.68 g	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In 1,4-dioxane; water;Inert atmosphere; Reflux;	General procedure: Intermediate M4 (16g, 80mmol), pinacol borate (40.63g, 159.99mmol), potassium acetate (23.55g, 239.99mmol), Pd(dppf)2Cl2 (0.5g) were added to a 500mL single-necked flask and added 300 mL of 1,4-dioxane and 100 mL of water were refluxed overnight under the protection of nitrogen. HPLC monitoring. No raw material remained, the reaction system was passed through a silica gel column and concentrated to dryness under reduced pressure to obtain a brown oily liquid, which was directly used for the next reaction without purification.

Reference： [1]Patent: KR2016/6493,2016,A .Location in patent: Paragraph 0484; 0485; 0486; 0487; 0488
[2]Patent: KR2017/21807,2017,A .Location in patent: Paragraph 0138; 0141; 0142
[3]Patent: US2018/72695,2018,A1 .Location in patent: Paragraph 0090; 0092
[4]Patent: KR2020/68398,2020,A .Location in patent: Paragraph 0165-0169
[5]Patent: CN111233867,2020,A .Location in patent: Paragraph 0081-0083
[6]Patent: CN111100126,2020,A .Location in patent: Paragraph 0090-0094
[7]Patent: CN111377899,2020,A .Location in patent: Paragraph 0074-0075; 0081-0082; 0089-0093

16
[ 89827-45-2 ]
[ 209848-36-2 ]
[ 1820951-92-5 ]

Yield	Reaction Conditions	Operation in experiment
84%	With tri-tert-butyl phosphine; bis(dibenzylideneacetone)-palladium⁽⁰⁾; sodium t-butanolate In toluene Inert atmosphere; Reflux;	5 Synthesis of intermediate IM9 In an Ar atmosphere, 15.00g (60.71mmol) of 4-bromodibenzofuran, 1.75g (0.05 equivalent, 3.04mmol) of Pd(dba)2, 5.83g (1.0 equivalent) were sequentially added to a 1,000mL three-necked flask in an Ar atmosphere , 60.71mmol) of NaOtBu, 600mL of toluene, 13.31g (1.0 equivalent, 60.71mmol) of 4-(naphthalene-2-yl)aniline and 2.46g (0.2 equivalent, 12.14mmol) of tBu3P, followed by heating, refluxing and stirring . After cooling to room temperature, water was added to the reaction solution, and the organic layer was extracted. Toluene was added to the water layer, and the organic layer was further extracted. The organic layer was collected, washed with brine solution and dried with MgSO4. MgSO4 was separated by filtration, and the organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (using a mixture solvent of hexane and toluene as an eluent) to obtain Intermediate IM9 (19.69 g, yield 84%).
78%	With tris(dibenzylideneacetone)dipalladium⁽⁰⁾ chloroform complex; triphenylphosphine; sodium t-butanolate In toluene at 100℃; for 24h;	II.2 Synthesis of Sub 2(22) round bottom flask Sub 2-1(2) (4.9g, 20mmol), Sub 2-2(2) (4.4g, 20mmol), Pd2 (dba) 3 (0.9g, 1mmol), PPh3 (0.5g, 2mmol ), NaOt-Bu (5.8g, 60mmol), were added to toluene (210mL), respectively, and refluxed under stirring for 24 hours at 100°C. The organic layer was dried over MgSO4, and extracted with water and ether and recrystallized silicagel column and the resulting organics concentrated after Sub 2(22) to 6.0g (yield: 78%) was obtained

Reference： [1]Current Patent Assignee: SAMSUNG ELECTRONICS CO.,LTD.; Samsung Display (in: Samsung) - CN113121556, 2021, A Location in patent: Paragraph 0293-0297
[2]Current Patent Assignee: DUK SAN NEOLUX CO., LTD. - KR2015/117399, 2015, A Location in patent: Paragraph 0164; 0165; 0166

17
[ 89827-45-2 ]
[ 27007-53-0 ]
C₁₉H₁₀BrClO₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
55%		Under argon atmosphere, 4-bromodibenzofuran: 8.6g, tetrahydrofuran: 100mL were added in the flask and cooled to -30C. To this was slowly added butyllithium in hexane solution (1.6M): 26ml. After stirring for 30 minutes, warmed to 0C then stirred for 1 hour. Then, under an argon atmosphere was added <strong>[27007-53-0]2-bromo-5-chlorobenzoic acid methyl ester</strong>: 17.5g, tetrahydrofuran: 40mL. Previously prepared solution was added at 0C after warming to room temperature for 5 hours with stirring. Then, after aqueous ammonium chloride solution was added to the reaction solution, transferred to a separatory funnel then extracted with toluene. Then, the organic layer was dried over sodium sulfate, filtered, concentrated. The residue was purified by silica gel column chromatography to give 7.3 g of a white solid (yield 55%).

Reference： [1]Patent: CN105531278,2016,A .Location in patent: Paragraph 0268; 0269; 0270; 0270; 0271

18
[ 89827-45-2 ]
[ 102113-98-4 ]
bis(biphenyl-4-yl)dibenzofuran-4-ylamine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
80%	With tri-tert-butyl phosphine; palladium diacetate; sodium t-butanolate In toluene for 1h; Reflux; Inert atmosphere;	2 synthesis of bis(biphenyl-4-yl)dibenzofuran-4-ylamine A degassed solution of 36.6 g (147 mmol) 4-bromo-dibenzofuran and 39.5 g (123 mmol) of bis-biphenyl-4-yl-amine in 600 mL of toluene for 1 hour with N 2 saturated. Thereafter the solution first with 2:09 mL (8.6 mmol) of P(tBu)3 ,then with 1:38 g (6.1 mmol) palladium (ll) acetate are added and then 17.7 g (185 mmol) NaOtBu added in the solid state. The reaction mixture is heated under reflux for 1 h. After cooling to room temperature carefully 500 ml of water are added. The aqueous phase is washed with 3x 50 mL toluene, over MgS0 4 is dried and the solvent removed in vacuo. Thereafter, the crude product on silica gel with heptane / acetic ester (20: 1) is purified by chromatography.The yield is 57.7 g (118 mmol), corresponding to 80% of theory
75%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tri-tert-butyl phosphine; sodium t-butanolate In toluene at 110℃; for 18h;	1 Step 1: Synthesis of intermediate A1-1 4-Bromodibenzofuran (10 g (g), 40.47 mmol (mmole)),Di(4-biphenyl)amine (12.36g, 38.45mmole) and sodium tert-butoxide (11.67g, 121.41mmole) were placed in a 500ml (mL) reaction flask,Then add 100 mL of toluene. Next, after adding tris(dibenzylideneacetone) dipalladium (Pd(dba)2) (1.16g, 2.02mmole) and toluene 20mL to a 50mL scintillation vial,Add tri-tert-butylphosphine (P(t-Bu)3) (0.98g, 4.86mmole)A first mixed solution is formed, and the color of the first mixed solution is changed from dark red to dark green by heating the scintillation bottle; finally, the first mixed solution is slowly added to the reaction bottle, and the temperature is raised to 110°C for After 18 hours of reaction, a second mixed solution was formed.After confirming the completion of the reaction with a TLC tablet, the second mixed solution is cooled to room temperature,Add 300mL of deionized water and stir for 30 minutes, then let stand to separate,Extract with 200 mL of ethyl acetate each time and repeat the extraction three times,The organic layer collected by three extractions was added to magnesium sulfate (MgSO4) to remove water,Filtration and separation, concentration and drying to obtain crude product;The crude product is mixed with n-hexane and ethyl acetate (volume ratio is 10:1)The eluent was purified by column chromatography to obtain 14.8g of product (ie intermediate A1-1),The yield of this product is 75%.

Reference： [1]Current Patent Assignee: MERCK KGAA - KR2016/38006, 2016, A Location in patent: Paragraph 0296-0300
[2]Current Patent Assignee: E-RAY OPTOELECTRONICS TECHNOLOGY CO., LTD. - CN111138393, 2020, A Location in patent: Paragraph 0086-0089

19
[ 89827-45-2 ]
[ 1010068-84-4 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1.1: tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate / toluene; ethanol; water / 12 h / 80 °C / Inert atmosphere 2.1: n-butyllithium / ethanol; tetrahydrofuran / 2 h / -78 - 20 °C / Inert atmosphere 2.2: 12 h / -78 - 20 °C / Inert atmosphere

Reference： [1]Current Patent Assignee: WUHAN SHANGSAI OPTOELECTRONICS TECHNOLOGY CO LTD - CN105503622, 2016, A

20
[ 89827-45-2 ]
[ 1269508-31-7 ]
[ 1801142-51-7 ]

Yield	Reaction Conditions	Operation in experiment
90%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate In tetrahydrofuran at 80℃; for 8h; Inert atmosphere;	13 Example 13: Synthesis of HOST 1 In a nitrogen environment, Compound I-1 20 g (45.9 mmol) in tetrahydrofuran (THF) 0.2 L dissolved after, here 4-bromodibenzofuran(4-bromodibenzofuran) 11.4 g (45.9 mmol) and tetrakis (triphenylphosphine ) palladium (tetrakis (triphenylphosphine) palladium) 0.53 g (0.46 mmol) and the mixture was stirred. Into a potassium carbonate 15.9 g (115 mmol) in saturated water it was heated to reflux at 80 for 8 hours. After the reaction was completed, the reaction solution into water, extracted with dichloromethane (DCM) and then water was removed with anhydrous MgSO4, filter, and concentrate was pressure. Thus, the obtained residue was purified by purified by flash column chromatography to obtain the compound HOST1 19.6g (90%)

Reference： [1]Current Patent Assignee: SAMSUNG SDI CO.,LTD. - KR2015/83385, 2015, A Location in patent: Paragraph 0212-0215

21
[ 89827-45-2 ]
[ 106-49-0 ]
[ 1609080-05-8 ]

Yield	Reaction Conditions	Operation in experiment
78%	With tri-tert-butyl phosphine; bis(dibenzylideneacetone)-palladium⁽⁰⁾; sodium t-butanolate In toluene at 90 - 110℃; for 12h; Inert atmosphere;	2.7 Step 7: Synthesis of intermediate 8 4-methyl-1-aniline (5.4 g, 50 mmol), 4-bromodibenzofuran (12.4 g, 50 mmol), bis (dibenzylideneacetone) palladium (0.8 g, 1.5 mmol), three A mixture of tert-butylphosphine (0.6 g, 3 mmol) and toluene (100 ml) was heated to 90 ° C under an argon stream, followed by the addition of sodium tert-butoxide (0.3 g, 3 mmol) and heated under an argon atmosphere. The temperature was increased to 110 ° C, and the reaction was stirred for 12 hours. The reaction mixture was cooled to room temperature, and water was added for liquid separation; the solvent of the obtained organic layer was concentrated, and the obtained solid was purified by silica gel column chromatography to obtain Intermediate 8 (20.2 g, 39 mmol), 78% yield. rate.
77%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tri-tert-butyl phosphine; sodium t-butanolate In toluene at 60℃; for 12h; Inert atmosphere;	24 intermediate (9) Synthesis of N-(4-methylphenyl)-4-dibenzofuranamine Under a nitrogen atmosphere, 100mL round bottom 3-neck flask 4-bromoDibenzofuran 2g, p- toluidine 1.3g,Tris (dibenzylideneacetone naphthyridin-acetone) dipalladium (0) 0.2g,15% tris (t- butyl) phosphine 0.3g,T- butoxy sodium 1.2g,35ml toluene were introduced, and stirred 12 hours at 60°C .The reaction solution after cooling was purified by silica gel filtration,Concentrated, and then carried our dichloromethane and n- hexane mixed solvent to column chromatography to give the intermediate (9) 1.7g. (Yield: 77%)
77%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tri-tert-butyl phosphine; sodium t-butanolate In toluene at 60℃; for 12h; Inert atmosphere;	10 synthesis of Intermediate (10) N-(4-methylphenyl)-4-dibenzofuranamine Under a nitrogen atmosphere, 100mL round bottom 3-neck flask was charged with 4-bromo-benzofuran-modify 2g, p- toluidine 1.3g, Tris (dibenzylideneacetone) palladium (0) 0.2g, 15% tris (t- butyl) phosphine 0.3 g, t- butoxy sodium 1.2g, 35ml toluene were introduced, and stirred 12 hours at 60 °C. After cooling the reaction solution by silica gel filtration, concentrated, and then curl with dichloromethane and n- hexane mixed solventColumn chromatography by performing intermediate (10) was obtained 1.7g. (Yield: 77%)

77%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tri-tert-butyl phosphine; sodium t-butanolate In toluene at 60℃; for 12h; Inert atmosphere;	8 Synthesis of N-(4-methylphenyl)-4-dibenzofuranamine Under a nitrogen atmosphere, a 100 mL round bottom three-necked flask was charged with 2 g of 4-bromodibenzofuran, 1.3 g of p-toluidine,0.2 g of tris (dibenzylidineacetone) dipalladium (0), 0.3 g of 15% tris (t-butyl) phosphine, 1.2 g of t-butoxysodium and 35 ml of toluene were placed,At 60 Stir for 12 hours. The reaction solution was cooled, filtered through silica gel, Concentrated and then subjected to column chromatography using a mixed solvent of dichloromethane and n-hexane to obtain 1.7 g of intermediate (8). (Yield: 77%)
74%	With palladium diacetate; 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; sodium t-butanolate In toluene for 12h; Reflux;	8 [Scheme 1-1] Synthesis of [Intermediate 1-a] General procedure: 1-cyano-4-chlorobenzene (13.8 g, 0.1 mol), 2-methyl-5-aminopyridine (10.8 g, 0.1 mol), palladium acetate (0.08 g, 0.32 mmol), 2,2'-bis ( Diphenylphosphino)-1-1'-binaphthyl (0.26 g, 0.42 mmol), sodium tertiary butoxide (15.2 g, 0.16 mol) was added to 150 mL of toluene and refluxed for 12 hours. After cooling to room temperature, washed with methanol and recrystallized from dichloromethane and methanol to obtain [Intermediate 1-a] 15.3 g (yield 73%).

Reference： [1]Current Patent Assignee: EVERDISPLAY OPTRONICS (SHANGHAI) LIMITED - CN107573925, 2020, B Location in patent: Paragraph 0074; 0079; 0080; 0081; 0082
[2]Current Patent Assignee: SK CHEMICALS CO LTD - KR2016/91196, 2016, A Location in patent: Paragraph 0389-0392
[3]Current Patent Assignee: SK CHEMICALS CO LTD - KR2016/29962, 2016, A Location in patent: Paragraph 0187-0189
[4]Current Patent Assignee: SK CHEMICALS CO LTD - KR2016/84918, 2016, A Location in patent: Paragraph 0197-0200
[5]Current Patent Assignee: HODOGAYA CHEMICAL CO LTD - KR102080738, 2020, B1 Location in patent: Paragraph 0239-0243; 0425; 0438-0441

22
[ 89827-45-2 ]
[ 99-88-7 ]
N-(4-isopropylphenyl)dibenzo[b,d]furan-4-amine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
86%	With tri-tert-butyl phosphine; palladium diacetate; sodium t-butanolate; In toluene; for 5h;Reflux;	(10 mmol) of 4-bromodibenzo [b, d] furan and 1.35 g (10 mmol) of 4-isopropylaniline were introduced under nitrogen, (0.2 mmol) of Pd (OAc) 2, 0.4 ml (0.4 mmol) of 1M t-Bu3P and 2.88 g (30 mmol) of tBuONa The reaction was refluxed for 5 hours. [0126] After the reaction was completed, the reaction mixture was cooled to room temperature, and extracted with 150 ml of toluene and 150 ml of H 2 O. A small amount of water in the organic layer was removed with anhydrous MgSO 4, filtered, and the organic solvent was concentrated to obtain Hex: EA = 5: 1 to obtain 2.60 g (86%) of Intermediate-3.
70%	With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; at 60℃; for 12h;Inert atmosphere;	Under a nitrogen atmosphere, 100mL round bottom 3-neck flask 4-bromoDibenzofuran 2g,4-diisopropylaniline 1.4g,Tris (dibenzylideneacetone naphthyridin-acetone) dipalladium (0) 0.2g,15% tris (t- butyl) phosphine 0.3g,T- butoxy sodium 1.2g, 35ml toluene were introduced,And it stirred 12 hours at 60C . The reaction solution after cooling was purified by silica gel filtration,Concentrated, and then to conduct our dichloro methane and n- hexane mixed solvent to column chromatography to give the intermediate (10) 1.6g. (70% yield)
70%	With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; at 60℃; for 12h;Inert atmosphere;	In a 100 mL round-bottomed three-necked flask under nitrogen, 2 g of 4-bromodibenzofuran, 1.4 g of 4-isopropylaniline, 0.2 g of tris (dibenzylidineacetone) dipalladium (0)0.3 g of 15% tris (t-butyl) phosphine,1.2 g of t-butoxysodium and 35 ml of toluene were placed, At 60 Stir for 12 hours. The reaction solution was cooled, filtered through silica gel, concentrated and then subjected to column chromatography using a mixed solvent of dichloromethane and n-hexane to obtain 1.6 g of intermediate (9). (Yield: 70%)

50%		0.10 mol of 4-isopropylamine and 0.30 mol of sodium tert-butoxide, 400 mL of toluene were added to the reaction flask, stirred for 30 minutes, protected with nitrogen. Then, 0.12 mol of 4-bromodibenzofuran and 1.5 g of tris(dibenzylideneacetone)dipalladium were added. Finally, 4 g of tri-tert-butylphosphine was added and the temperature was raised to 100 C for 24 hours. After the reaction is completed, the reaction system is cooled, the reaction is terminated by adding water, filtering, the filtrate is separated, spin-dried toluene, a small amount of methylene chloride is added to dissolve the dried product, using petroleum ether: dichloromethane = 3: 1 (volume ratio) column separation, to give N-(4-isopropylphenyl)dibenzo[b,d]furan-4-amine (Intermediate C-1) (0.05 mol, y = 50%).
27%	With tris-(dibenzylideneacetone)dipalladium(0); 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; sodium t-butanolate; In toluene; for 7h;Reflux;	1L 3-necked flask, 4-bromo modayi benzofuran (25.0g, 101mmol), 4-isopropyl aniline (16.4g, 121mmol, 1.2eq.), Tris (dibenzylideneacetone) palladium (2.78g, 3.04mmol, 3mol%), 2,2'- bis (diphenylphosphino) -1,1'-binaphthyl (1.51g, 24.2mmol, 2.4mol%), sodium tert-butoxide(10.7g, 111mmol, 1.1 eq .) were weighed, added to dehydrated toluene (405mL), the mixture was heated under reflux for 7 hours. Was added to a saturated aqueous solution of sodium chloride to the reaction solution, extracted with toluene, the organic layer was dried over sodium sulfate, and concentrated. Using the column chromatography, the obtained crude product was purified to give the intermediate 4 (8.2g, 27.2mmol, 27% yield). It was identified as the desired compound by FDMS (field desorption mass analysis).

Reference： [1]Patent: KR2017/49296,2017,A .Location in patent: Paragraph 0122; 0123; 0124; 0125; 0126
[2]Patent: KR2016/91196,2016,A .Location in patent: Paragraph 0395-0397
[3]Patent: KR2016/84918,2016,A .Location in patent: Paragraph 0203-0205
[4]Patent: CN106146538,2016,A .Location in patent: Paragraph 0189; 0190; 0191; 0192; 0193; 0194
[5]Patent: KR2015/98631,2015,A .Location in patent: Paragraph 0409-0411

23
[ 89827-45-2 ]
[ CAS Unavailable ]
[ CAS Unavailable ]

Yield	Reaction Conditions	Operation in experiment
91%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tributylphosphine; sodium t-butanolate In toluene at 80℃; for 1h; Inert atmosphere;	8 Synthesis of Compound 63 Synthesis of Compound 63 (0326) 5.3 mmol (3.0 g) of Intermediate 8-2 and 10 mmol (2.5 g) of 3-bromodibenzofuran were diluted in 150 ml of toluene, and then, under a nitrogen atmosphere, 0.4 mmol (0.4 g) of tris(dibenzylidineacetone)dipalladium (0) (Pd2(dba)3), 0.4 mmol (0.1 ml) of tributylphosphine (PtBu3), and 24 mmol (2.3 g) of sodium t-butoxide (NaOtBu) were added thereto, and the mixture was reacted at a temperature of 80° C. for 1 hour. The reaction product was cooled at ambient temperature, an organic layer was separated therefrom and then dried by using anhydrous magnesium sulfate, and then, concentrated under reduced pressure. The obtained residual was separation-purified by silica gel column chromatography to obtain Compound 63 (3.0 g, yield of 91%). The obtained compound was identified by MS/FAB and 1H NMR. LC/MS cal: 627.74. found: 627.60.

Reference： [1]Current Patent Assignee: SAMSUNG ELECTRONICS CO.,LTD.; Samsung Display (in: Samsung) - US2016/240790, 2016, A1 Location in patent: Paragraph 0320; 0325; 0326

24
[ 108-77-0 ]
[ 89827-45-2 ]
[ 51800-19-2 ]

Yield	Reaction Conditions	Operation in experiment
75%	Stage #1: 4-bromodibenzo[b,d]furan With iodine In tetrahydrofuran at 80℃; for 2h; Stage #2: 1,3,5-trichloro-2,4,6-triazine In tetrahydrofuran at 20℃;	2.1 Step 1) Preparation of compound 2-1 The compound 4-bromodibenzo [b, d] furan (30 g, 120 mmol) was dissolved in tetrahydrofuran(2.9 g, 120 mmol) and iodine (I2)(0.6 g, 2.4 mmol) in 20 mL of tetrahydrofuran.The mixture was stirred at 80 DEG C for 2 hours and then cooled to room temperature2,4,6-trichloro-1,3,5-triazine (22 g, 120 mmol) was dissolved in tetrahydrofuranThe solution dissolved in 80 mL was slowly added dropwise.When the reaction is completed, the solvent is distilled off under reduced pressure,The residue was purified by silica column chromatography to obtain the desired compound 2-1 (28.8 g, yield 75%) was prepared
65%	Stage #1: 4-bromodibenzo[b,d]furan With iodine; magnesium In tetrahydrofuran at 80℃; for 2.5h; Stage #2: 1,3,5-trichloro-2,4,6-triazine In tetrahydrofuran at 20℃; for 3h;	1 [Preparation Example 1] Synthesis of IC-1 After dissolving magnesium (14.5 g, 598 mmol) and iodine (3.0 g, 12 mmol) in 50 ml of anhydrous tetrahydrofuran solvent, 4-bromodibenzo [b, d] furan (147.7 g, 598 mmol) was added to 130 ml of anhydrous tetrahydrofuran Add the dissolved solution for 30 minutes. The mixture is stirred at 80 ° C for 2 hours and then cooled at room temperature. Then, 1,3,5-trichlorotriazine (110.3 g, 598 mmol) dissolved in 390 ml of anhydroustetrahydrofuran is added dropwise with stirring for 3 hours.After the reaction was completed, the organic solvent was removed by distillation under reduced pressure, and the residue was purified by column chromatography. Recrystallization was performed with methanol, and the obtained crystals were filtered to obtain IC-1 (40.89 g, yield 65%).
63%	Stage #1: 4-bromodibenzo[b,d]furan With iodine; magnesium In tetrahydrofuran at 80℃; for 2.5h; Inert atmosphere; Stage #2: 1,3,5-trichloro-2,4,6-triazine In tetrahydrofuran at 20℃; for 3h; Inert atmosphere;	1.1 1) Synthesis of intermediate a-I-1 Under the protection of N2, add magnesium flakes (2.9g, 120mmol) to the three-necked flaskAnd tetrahydrofuran (THF) 30mL, the temperature of the system rises to 80,Add iodine (0.6g, 2.4mmol) and 4-bromodibenzofuran to the system(30.0g, 120mmol) dissolved completely in 30mL of THF solvent,Slowly drip into the system within 30 minutes, and control the temperature at 80°C during the dripping process.After the dropwise addition is completed, the reaction is stirred at 80°C for 2h to obtain a mixed solution.After cooling at room temperature, 2,4,6-trichloro-1,3,5-triazine (22.3 g, 120 mmol) dissolved in 80 mL of THF was added dropwise to the mixed solution, and the reaction was terminated after stirring for 3 hours to obtain a reaction solution.After the reaction, toluene (200 mL) was added to extract the reaction solution, and the organic phases were combined,Dry the organic layer with anhydrous magnesium sulfate, filter, and concentrate by distillation under reduced pressure;The crude product is purified by silica gel column chromatography,Methanol was recrystallized and filtered to obtain a solid intermediate a-I-1 (24.2 g, yield: 63%).

63%

Stage #1: 4-bromodibenzo[b,d]furan With iodine; magnesium In tetrahydrofuran at 80℃; for 2.5h; Inert atmosphere; Stage #2: 1,3,5-trichloro-2,4,6-triazine In tetrahydrofuran at 20℃; for 3h; Inert atmosphere;

1.1 Synthesis of Intermediate a-I-1 Under the protection of N2, add magnesium flakes (2.9g, 120mmol) and 30ml solution of tetrahydrofuran to thethree-necked flask, the temperature of the system rises to 80°C, and add iodine (0.6g, 2.4mmol), 4-bromodibenzofuran to the system (30.0 g, 120 mmol) was completely dissolved in 30 ml of THF solution, slowly added dropwise to the system within 30 min, and the temperature was controlled at 80° C. during the dropwise addition.After the dropwise addition was completed, the reaction was stirred at 80 °C for 2 h.After cooling at room temperature, 2,4,6-trichloro-1,3,5-triazine (22.3 g, 120 mmol) dissolved in 80 ml of THF was added dropwise to the mixed solution, and the reaction was terminated after stirring for 3 h.After the reaction, toluene and water were added to extract the reaction solution, the organic phases were combined, the organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated by distillation under reduced pressure; the crude product was purified by silica gel column chromatography, and the solid intermediate a-I-1 was obtained by methanol recrystallization and filtration (24.2 g, 63%).

Reference： [1]Current Patent Assignee: LG CHEM CO.,LTD. - KR2019/6353, 2019, A Location in patent: Paragraph 0167-0170
[2]Current Patent Assignee: DOOSAN CORP. - KR2015/42335, 2015, A Location in patent: Paragraph 0096-0099
[3]Current Patent Assignee: SHAANXI LIGHTE OPTOELECTRONICS MATERIAL CO.,LTD - CN112876462, 2021, A Location in patent: Paragraph 0170-0173
[4]Current Patent Assignee: SHAANXI LIGHTE OPTOELECTRONICS MATERIAL CO.,LTD - CN114075176, 2022, A Location in patent: Paragraph 0144-0145; 0147; 0148-0149

25
[ 89827-45-2 ]
[ 95-51-2 ]
[ 1421599-28-1 ]

Yield	Reaction Conditions	Operation in experiment
88%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tri-tert-butyl phosphine; sodium t-butanolate In 5,5-dimethyl-1,3-cyclohexadiene for 14h; Reflux;	1.1 Synthesis of intermediate product (B) 4-Bromodibenzofuran (A) (4-bromodibenzofuran, 30 g, 121.41 mmol)Xylene (500 ml)Followed by 2-chloroaniline (16.23 g, 127.48 mmol),Pd2 (dba) 3 (3.34 g, 3.64 mmol),P (t-Bu) 3 (1.74 ml, 7.28 mmol) and NaO (t-bu) (23.34 g, 242.83 mmol) were added at room temperature and refluxed for 14 hours. After completion of the reaction, water and ethyl acetate were added. The separated organic layer was dried over an silica gel filter and anhydrous magnesium sulfate, and the solvent was concentrated under reduced pressure. The resulting mixture was recrystallized from dichloromethane and hexane to obtain the title compound (31.4 g, 88% .
76%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tri-tert-butyl phosphine; sodium t-butanolate In toluene at 100℃;	2.1.1 (1) Sub 4-c-1 synthesis After dissolving 4-bromodibenzo [b, d] furan (50.0 g, 202 mmol) in Toluene in a round bottom flask, 2-chloroaniline (25.8 g, 202 mmol),Pd2(dba)3 (5.56 g, 6.07 mmol), P(t-Bu)3 (2.46 g, 12.1 mmol),NaOt-Bu (38.9 g, 405 mmol) was added and stirred at 100 ° C.When the reaction is completed, the mixture is extracted with CH2Cl2 and water, and the organic layer is dried over MgSO4 and concentrated.Thereafter, the resulting compound was recrystallized after applying a silica gel column to obtain 45.2 g (yield: 76%) of the product.
74%	With tri-tert-butyl phosphine; palladium diacetate; sodium t-butanolate In 5,5-dimethyl-1,3-cyclohexadiene for 15h; Reflux; Inert atmosphere;	2.1 First Step: Synthesis of Intermediate 6 In a 5L flask,130.0 g (0.53 mol) of 4-bromodibenzofuran,82.5 ml (0.79 mol) of 2-chloroaniline, 151.7 g (1.58 mol) of sodium tert-butoxide,11.8 g (52.6 mmol) of palladium acetate and 51.1 g (50% toluene) of tri-tert-butylphosphine mixed with 2.5 L of xylene,The mixture was heated and refluxed under a stream of nitrogen for 15 hours.When the reaction is over,After volatilizing and removing the solvent,Add 2L of methanol to it,And the crystallized solid is filteredDissolved in dichlorobenzene,Filtered on silica gel/celite,After removing the right amount of organic solvents,Recrystallized from methanol,Intermediate 6 was obtained (115.0 g, yield 74%).

50%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tri-tert-butyl phosphine; sodium t-butanolate In toluene at 130℃; for 12h;	1 Synthesis Example 1: Synthesis of Int-1 4-Bromo-dibenzofuran (25 g, 101.18 mmol), 2-chloroaniline (19.36 g, 151.77 mmol),Pd2(dba)3 (4.63 g, 5.06 mmol), P(t-Bu)3 (3.7 mL,15.18 mmol) and NaO(t-Bu) (11.67 g, 121.41 mmol) in a round bottom flask and then,The mixture was stirred under reflux in a toluene (35 mL) solvent at 130°C for 12 hours.When the reaction was completed, the resultant was processed by column chromatography to obtain 15 g (50%) of the intermediate (Int-1).
	With S-Phos; sodium t-butanolate In 5,5-dimethyl-1,3-cyclohexadiene for 8h; Reflux;	6.1 (1) In the reaction flask, add 4-bromodibenzofuran (50mmol),2-chloroaniline (60mmol), Pd (dba) 0.9g (0.785mmol, 0.5%),S-Phos, xylene 500mL and sodium tert-butoxide 30g (300mmol),Heat to reflux for 8h; stop the reaction after the reaction is completed; cool to room temperature,Filtration, and the obtained solid was purified by toluene recrystallization to obtain yellow powder M1
	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tri-tert-butyl phosphine; sodium t-butanolate In toluene Inert atmosphere; Reflux;	1 Add compound 1-a (80g, 0.324mol) in a 2L three-necked flask,Compound 1-b (43.4g, 1.05eq),Sodium tert-butoxide (62.2g, 2eq),Tri-tert-butyl phosphine (26ml, 0.04eq) and toluene (800ml), under the protection of N2, add tridibenzylideneacetone palladium (5.9g, 0.02eq), heat and reflux and stir the reaction for 24h, TLC monitors compound 1- a basically disappeared. The reaction was stopped, 500ml was added for stirring and extraction, the aqueous phase was then extracted with 400ml DCM, the organic phases were combined, the filtrate was concentrated to dryness under reduced pressure, and it was directly used in the next step without purification.
64 %	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tri-tert-butyl phosphine; sodium t-butanolate In toluene at 130℃;	15 Synthesis Example 15: Synthesis of Intermediate Int-20 4-bromodibenzofuran (50 g, 202.36 mmol), 2-chloroaniline (38.72 g, 303.53 mmol), Pd2(dba)3 (9.26 g, 10.12 mmol), P(t-bu)3 (7.39 ml, 30.35 mmol), and NaO(t-Bu) (29.17 g, 303.53 mmol) were dissolved in toluene (650 ml) in a round-bottomed flask and then, stirred under reflux at 130° C. for 12 hours. When a reaction was completed, after removing an aqueous layer therefrom, column chromatography (hexane:DCM 20%) was conducted, obtaining 38 g (64%) of Intermediate Int-20.

Reference： [1]Current Patent Assignee: SAMSUNG C&T CORPORATION - KR2015/28115, 2015, A Location in patent: Paragraph 0420; 0421; 0422; 0423; 0424; 0425
[2]Current Patent Assignee: DUK SAN NEOLUX CO., LTD. - KR2020/37544, 2020, A Location in patent: Paragraph 0521; 0531-0534
[3]Current Patent Assignee: SAMSUNG SDI CO.,LTD.; SAMSUNG ELECTRONICS CO.,LTD. - CN107857772, 2018, A Location in patent: Paragraph 0216-0220
[4]Current Patent Assignee: SAMSUNG SDI CO.,LTD. - CN114437090, 2022, A Location in patent: Paragraph 0194-0199
[5]Current Patent Assignee: YANTAI XIANHUA CHEM-TECH CO LTD - CN111018855, 2020, A Location in patent: Paragraph 0075-0079
[6]Current Patent Assignee: NANJING TOPTO SEMICONDUCTOR MATERIAL CO LTD - CN113429413, 2021, A Location in patent: Paragraph 0048-0052
[7]Current Patent Assignee: SAMSUNG SDI CO.,LTD. - US2022/267344, 2022, A1 Location in patent: Paragraph 0165; 0167-0168

26
[ 89827-45-2 ]
[ 1338919-70-2 ]

Reference： [1]Patent: KR2015/28115,2015,A
[2]Patent: CN107857772,2018,A
[3]Patent: KR2020/37544,2020,A
[4]Patent: CN113429413,2021,A

27
[ 89827-45-2 ]
[ 90-41-5 ]
[ 1252914-36-5 ]

Yield	Reaction Conditions	Operation in experiment
75%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tri-tert-butyl phosphine In toluene; <i>tert</i>-butyl alcohol at 90℃; for 2h; Inert atmosphere;	10 Synthesis of intermediate 10-1 (0.16 mol) of 2-aminobiphenyl, 40 g (0.24 mol) of 4-bromodibenzofuran and 18.4 g (0.192 mol)Tert-butanolThen dissolved in 400 ml of toluene, and under the protection of nitrogen, 3.2 ml (0.0016 mol) of tri-t-butylphosphine and1.46 g (0.0016 mol) of Pd2 (dba) 3, and the mixture was heated to 90 ° C with stirring for about 2 hours. The resulting reaction was passed through a diatomaceous earth funnel and the filtrate was evaporated through a rotary evaporator to give 40 g of intermediate 10-1 (yield: 75%).
42%	With tri-tert-butyl phosphine; potassium <i>tert</i>-butylate; palladium diacetate In toluene for 2h; Reflux; Inert atmosphere;	11 Example 11: Synthesis of Biphenyl-2-yl-dibenzofuran-4-yl-amine (Compound 6) 9.11 g of 2-Aminobiphenyl and 12.35 g of 4-Bromo-dibenzofuran were placed in a three-necked flask under nitrogen and dissolved in 250 ml of toluene followed by 11.22 g of potassium tert-butoxide, 0.56 g of palladium acetate, 1.32 g of Tri- Butylphosphine, heated to reflux for 2 hours. After cooling, the filtrate was concentrated and the column was separated (Hex: EA = 10: 1). The product was obtained and the yield was 42%.

Reference： [1]Current Patent Assignee: BEIJING GREEN GUARDEE TECHNOLOGY CO LTD - CN106565433, 2017, A Location in patent: Paragraph 0094; 0095; 0096; 0097
[2]Current Patent Assignee: TETRAHEDRON TECHNOLOGY CORP - CN106588674, 2017, A Location in patent: Paragraph 0088; 0089; 0090

28
[ 89827-45-2 ]
[ 92-67-1 ]
[ 1318338-47-4 ]

Yield	Reaction Conditions	Operation in experiment
90%	With palladium diacetate; triphenylphosphine; sodium tertiary butoxide In toluene at 80℃; for 8h; Inert atmosphere;	1 Under an argon atmosphere, 8.46 g (50 mmol) of compound Y1-1, 12.35 g (50 mmol) of compound Y2-1, 9.61 g (100 mmol) of sodium t-butoxide were dissolved in 500 ml of dehydrated toluene, .23 g (1.0 mmol) of palladium acetate and 0.20 g (1.0 mmol) of triphenylphosphine were added under stirring, and the mixture was reacted at 80 ° C for 8 hours. After cooling, it was filtered through a Celite/silica gel funnel, and the filtrate was evaporated to remove organic solvent, and the residue was recrystallized from toluene and dried.15.09 g (45 mmol) of compound B-1 was obtained in a yield of 90%.
90%	With 1,1'-bis(diphenylphosphanyl)ferrocene; tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; sodium tertiary butoxide In toluene at 120℃; for 16h;	12 Under nitrogen atmosphere, 4-amino-1,1'-biphenyl (1.6 g, 9.5 mmol, 1 eq), 4-bromodibenzofuran (2.8 g, 11.4 mmol, 1.2 eq), tris(dibenzylidene) acetone)dipalladium (173mg, 0.19mmol, 0.02eq), 1,1'-bis(diphenylphosphino)ferrocene (107mg, 0.19mmol, 0.02eq) and sodium tert-butoxide (1.3g, 14.2mmol) , 1.5eq) was dispersed in 20mL of toluene.The reaction was carried out at 120°C for 16 hours.After the reaction was complete, the solvent was spun dry and the crude product was further purified by column chromatography using petroleum ether:dichloromethane (50:50).The intermediate product 12 was obtained in a yield of 2.8 g (90% yield).
73%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tri-tert-butyl phosphine; sodium tertiary butoxide In toluene for 5h; Inert atmosphere; Reflux;	Synthesis of Intermediate 21 Synthesis of Intermediate 21 (0142) (0143) Under a nitrogen atmosphere, Intermediate 13 (1.69 g, 10 mmol) and Intermediate 20 (2.47 g, 10 mmol) were mixed and dissolved in toluene (30 mL). Pd2dba3 (0.18 g, 0.2 mmol), t-Bu3P (1 M, 0.4 ml, 0.4 mmol), and t-BuONa (2.88 g, 30 mmol) were added and refluxed for 5 hrs. (0144) After the reaction was terminated, the reactants were cooled to normal temperature, and toluene (200 mL) and H2O (200 mL) were added. After extraction, the organic layer was dried over anhydrous magnesium sulfate to remove a small amount of water contained therein, suctioned, and concentrated. The resultant compound was purified by column chromatography eluting with Hex:EA=5:1, to obtain Intermediate 21 (2.45 g, 73%). (0145) Intermediate 21 MS(FAB): 335(M+)

73%

With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tri-tert-butyl phosphine; sodium tertiary butoxide In toluene for 5h; Inert atmosphere; Reflux;

1 Synthesis of Intermediate 17 Under a nitrogen atmosphere, Intermediate 9 (1.69 g, 10 mmol) and Intermediate 16 (2.47 g, 10 mmol) were dissolved in toluene (30 mL). Pd2dba3 (0.18 g, 0.2 mmol), t-Bu3P (1 M, 0.4 ml, 0.4 mmol), and t-BuONa (2.88 g, 30 mmol) were added and refluxed for 5 hrs. After the reaction was terminated, the reactants were cooled to normal temperature, and toluene (200 mL) and H2O (200 mL) were added. After extraction, the organic layer was dried over anhydrous magnesium sulfate to remove a small amount of water contained therein, suctioned, and concentrated. The resultant compound was purified by column chromatography eluting with Hex:EA=5:1, to obtain Intermediate 17 (2.45 g, 73%). Intermediate 17 MS(FAB): 335(M+)

Reference： [1]Current Patent Assignee: CHANGCHUN HAIPU RUNSI TECHNOLOGY CO LTD - CN109232492, 2019, A Location in patent: Paragraph 0076-0077
[2]Current Patent Assignee: JI HUA LABORATORY - CN114195794, 2022, A Location in patent: Paragraph 0201; 0202; 0203
[3]Current Patent Assignee: NANJING TOPTO SEMICONDUCTOR MATERIAL CO LTD - US2017/125677, 2017, A1 Location in patent: Paragraph 0142-0145
[4]Current Patent Assignee: NANJING TOPTO SEMICONDUCTOR MATERIAL CO LTD - US2017/125678, 2017, A1 Location in patent: Paragraph 0117; 0118; 0119; 0120

29
[ 23197-48-0 ]
[ 89827-45-2 ]

Yield	Reaction Conditions	Operation in experiment
49%	With 3-nitropyridine; tert-Butyl peroxybenzoate; palladium diacetate In Hexafluorobenzene at 90℃;	synthesis of Sub 1-I-1 The starting material, 3-bromo- [1,1'-biphenyl] -2-ol (32.42 g, 130.15 mmol)To a round bottom flask was added Pd (OAc) 2 (2.92 g, 13.01 mmol), 3-nitropyridine (1.62 g, 13.01 mmol) andAdd together C6F6 (195ml),After dissolving in DMI (130 ml)Tert-butyl peroxybenzoate (50.56 g, 260.30 mmol)And the mixture was stirred at 90 ° C.After the reaction was completed, the reaction mixture was extracted with CH2Cl2 and water. The organic layer was dried over MgSO4 and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 15.76 g (yield: 49%) of the product
49%	With 3-nitropyridine; tert-Butyl peroxybenzoate; palladium diacetate In Hexafluorobenzene	I.1.1 (1) Synthesis of Sub 14-1 3-bromo-[1,1’-biphenyl]-2-ol (32.42 g, 130.15 mmol) as a starting material, Pd(OAc)2 (2.92 g, 13.01 mmol), and 3-nitropyridine (1.62 g, 13.01 mmol) were added into a round bottom flask, then, dissolved in C5F5 (195 ml), DM1 (130 ml). After adding tert-butyl peroxybenzoate (50.56 g, 260.30 mmol), stirring at 90 D was followed. When the reaction was completed, the reaction product was extracted with CH2C12 and water, and then, the organic layer was dried with Mg504 and concentrated. Then, the concen-continued trate was passed through silica gel colunm, then recrystallized to obtain 15.76 g (yield: 49%) of the product.

Reference： [1]Current Patent Assignee: DUK SAN NEOLUX CO., LTD. - KR2017/21807, 2017, A Location in patent: Paragraph 0138-0140
[2]Current Patent Assignee: DUK SAN NEOLUX CO., LTD. - US2018/72695, 2018, A1 Location in patent: Paragraph 0090; 0091

30
[ 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

31
[ 89827-45-2 ]
[ 1644542-43-7 ]
[ 1644542-22-2 ]

Yield	Reaction Conditions	Operation in experiment
82%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tri-tert-butyl phosphine; sodium t-butanolate In toluene at 110℃; for 24h; Inert atmosphere;	9 Example 9: Synthesis of Compound 9 Under nitrogen protection,A solution of bipyrazole pyrene intermediate 101 mmol,4-bromodibenzo [b, d] furan220 mmol,Tris (dibenzylideneacetone) dipalladium 5.0 mmol,Sodium tert-butoxide,Tri-tert-butylphosphine 20 mmol was placed in a reaction vessel,And dissolved in 500 ml of toluene,110 reflux reaction 24h,The reaction was carried out by thin layer chromatography (TLC). The reaction was completed, cooled to room temperature, passed through a silica gel funnel, washed with methylene chloride, spin dried, recrystallized from dichloromethane / petroleum ether,After drying, 83 mmol of compound 9 was obtained in a yield of 82%.

Reference： [1]Current Patent Assignee: JILIN OLED OPTICAL AND ELECTRONIC MATERIALS CO LTD - CN104262347, 2017, B Location in patent: Paragraph 0061; 0062; 0063

32
[ 89827-45-2 ]
[ 17169-81-2 ]
[ 2055969-72-5 ]

Yield	Reaction Conditions	Operation in experiment
80%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tri-tert-butyl phosphine; sodium t-butanolate In toluene at 100℃;	1 Sub 6-28 synthesis The reaction vessel was charged with 4-bromodibenzo [b, d] furan (34 g, 138 mmol)Triazene-2-amine (30.5 g, 125.5 mmol)Tris (dibenzylideneacetone) dipalladium (5.74 g, 6.3 mmol)Tri-tert-butylphosphine (2.54 g, 12.5 mmol)Sodium tert-butoxide (36.2 g, 376.4 mmol) and toluene (1320 mL) at 100 ° C. After completion of the reaction, the organic material was extracted with ether and water, and the organic layer was dried over magnesium sulfate. The product was concentrated on a silica gel column and recrystallized to obtain 41 g of product Sub6-28 in a yield of 80%.
80%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tri-tert-butyl phosphine; sodium t-butanolate at 100℃;	2 Synthesis of Sub2-28 4-bromobenzo[b,d]furan (34g, 138mmol) and triphenylene-2-amine (30.5g, in order) were added to the reaction vessel.125.5 mmol), tris(dibenzylideneacetone)dipalladium (5.74 g, 6.3 mmol), tri-tert-butylphosphine (2.54 g, 12.5 mmol), sodium tert-butoxide (36.2 g, 376.4 mmol), toluene 1320 mL The reaction was carried out at 100 °C. After completion of the reaction, the organic layer was extracted with diethyl ether and water, and then evaporated.The product was obtained by a silica gel column and recrystallization to give 41 g of product.Sub2-28, the yield was 80%.
80%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tri-tert-butyl phosphine; sodium t-butanolate In toluene at 100℃;	2 Synthesis of Sub2-28 4-Bromobenzo[b,d]furan (34g, 138mmol) and triphenylene-2-amine (30.5g, in order) were added to the reaction vessel.125.5 mmol), tris(dibenzylideneacetone)dipalladium (5.74 g, 6.3 mmol), tri-tert-butylphosphine (2.54 g, 12.5 mmol), sodium tert-butoxide (36.2 g, 376.4 mmol), toluene 1320 mL The reaction was carried out at 100 °C. After the reaction is over,Extract the organics with ether and water,The organic layer was dried and concentrated with magnesium sulfate.The product was obtained by silica gel column and recrystallization.41g of product Sub2-28,The yield was 80%.

80%

With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tri-tert-butyl phosphine; sodium t-butanolate In toluene at 100℃;

3 Synthesis of Sub7-28 4-bromobenzo[b,d]furan (34g, 138mmol), triphenylene-2-amine (30.5g, 125.5mmol), tris(dibenzylideneacetone)dipalladium (5.74g) were added to the reaction vessel in this order. , 6.3 mmol), tri-tert-butylphosphine (2.54 g, 12.5 mmol),The reaction was carried out at 100 ° C with sodium tert-butoxide (36.2 g, 376.4 mmol) and 1320 mL of toluene. After completion of the reaction, the organic layer was extracted with diethyl ether and water, and then evaporated.The product was obtained by a silica gel column and recrystallization to give 41 g of product.Sub7-28, yield 80%.

Reference： [1]Current Patent Assignee: JILIN OLED OPTICAL AND ELECTRONIC MATERIALS CO LTD - CN107056626, 2017, A Location in patent: Paragraph 0067; 0089; 0096-0098
[2]Current Patent Assignee: JILIN OLED OPTICAL AND ELECTRONIC MATERIALS CO LTD - CN108623479, 2018, A Location in patent: Paragraph 0032; 0034
[3]Current Patent Assignee: JILIN OLED OPTICAL AND ELECTRONIC MATERIALS CO LTD - CN108623480, 2018, A Location in patent: Paragraph 0033; 0035
[4]Current Patent Assignee: JILIN OLED OPTICAL AND ELECTRONIC MATERIALS CO LTD - CN108623469, 2018, A Location in patent: Paragraph 0038; 0040

33
[ 89827-45-2 ]
[ 769-92-6 ]
[ 1438401-13-8 ]

Yield	Reaction Conditions	Operation in experiment
70%	With tri-tert-butyl phosphine; bis(dibenzylideneacetone)-palladium⁽⁰⁾; sodium t-butanolate In toluene
66%	With tri-tert-butyl phosphine; bis(dibenzylideneacetone)-palladium⁽⁰⁾; sodium t-butanolate In toluene at 90 - 110℃; for 12h; Inert atmosphere;	2.2 Synthesis of intermediate 6 4-tert-Butyl-1-aniline (14.9 g, 100 mmol),4-Bromo-dibenzofuran (24.7 g, 100 mmol),Bis (dibenzylideneacetone) palladium (1.7 g, 3 mmol),Tri-tert-butylphosphine (1.2 mg, 6 mmol) was added to toluene (200 ml)Heated to 90 ° C under a stream of argon,Additional sodium t-butoxide (0.6 mg, 6 mmol)Followed by heating to 110 ° C under an argon atmosphere,The reaction was stirred for 12 hours;The reaction mixture was cooled to room temperature,Add water for liquid separation,The resulting organic layer solvent was concentrated,Get solid,The resulting solid was purified by silica gel column chromatography,The target product Intermediate 6 (20.8 g, 66 mmol) was obtained,Yield 66%.

Reference： [1]Current Patent Assignee: EVERDISPLAY OPTRONICS (SHANGHAI) LIMITED - CN107573357, 2018, A Location in patent: Paragraph 0044
[2]Current Patent Assignee: EVERDISPLAY OPTRONICS (SHANGHAI) LIMITED - CN107286027, 2017, A Location in patent: Paragraph 0072; 0076; 0077; 0078

34
[ 89827-45-2 ]
[ 18628-07-4 ]
9-(dibenzo[b,d]furan-4-yl)-9H-3,9’-bicarbazole [ No CAS ]

Reference： [1]Chemistry - A European Journal,2017,vol. 23,p. 16044 - 16050

35
[ 4106-66-5 ]
[ 89827-45-2 ]
C₂₄H₁₅NO₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
80%	With tri-tert-butyl phosphine; bis(dibenzylideneacetone)-palladium(0); sodium t-butanolate; In toluene; for 4h;Inert atmosphere; Reflux;	Under argon atmosphere5.0 g of <strong>[4106-66-5]3-aminodibenzofuran</strong>,6.7 g of 4-bromodibenzofuran,0.8 g of bis (dibenzylideneacetone) palladium (0)1.1 g of tri-tert-butylphosphine,3.9 g of sodium tert-butoxide was added, and the mixture was refluxed with 140 mL of toluene for 4 hours.After air cooling, water was added to the reaction mixture, the organic layer was separated, dried over magnesium sulfate,The solvent was distilled.The resulting crude product was purified by silica gel column chromatography (toluene / hexane mixed solvent) to obtain 7.6 g (yield: 80%) of Intermediate F.

Reference： [1]Patent: KR2017/94020,2017,A .Location in patent: Paragraph 0262; 0263; 0264

36
[ 89827-45-2 ]
[ 1197989-83-5 ]
[ 916434-69-0 ]

Yield	Reaction Conditions	Operation in experiment
76%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate In tetrahydrofuran; water Inert atmosphere; Reflux;

Reference： [1]Yun, Ju Hui; Kang, Yu Jin; Han, Si Hyun; Lee, Jun Yeob [Journal of Materials Chemistry C, 2018, vol. 6, # 2, p. 320 - 325]

37
[ 89827-45-2 ]
[ 82-05-3 ]
C₂₉H₁₈O₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
60%		Under a nitrogen atmosphere, 1-bromodibenzofuran (44 g, 178 mmol) and tetrahydrofuran were added to the reaction vesselIn 500 mL, 71 mL (2.5M, 178 mmol) of n-butyllithium was gradually added dropwise at a low temperature of -78C.After completion of the addition, the mixture was stirred at -78C for 30 minutes and stirred at room temperature for 3 hours. Then, benzoxanone (41 g, 178 mmol) dissolved in 500 mL of tetrahydrofuran was added dropwise at a low temperature of -78C, and the mixture was stirred at room temperature for 16 hours and then was stopped. reaction,Aqueous ammonium chloride solution was added and ethyl acetate was added to extract the organics. The organic layer was dried over anhydrous MgSO 4 , and the organic solvent was distilled off under reduced pressure. The compound was purified on a silica gel column to obtain S 1 (42.4 g, 60%).

Reference： [1]Patent: CN107698490,2018,A .Location in patent: Paragraph 0050-0053

38
[ 89827-45-2 ]
[ 1381986-21-5 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1: CyJohnPhos; sodium t-butanolate; palladium diacetate / o-xylene / Inert atmosphere; Reflux 2: tetrahydrofuran; hexane / 6.17 h / -78 - 20 °C / Inert atmosphere 3: acetic acid; phosphoric acid / 3 h / 0 - 20 °C / Inert atmosphere
	Multi-step reaction with 3 steps 1.1: potassium carbonate / toluene / 0.5 h / Inert atmosphere 1.2: Reflux; Inert atmosphere 2.1: tetrahydrofuran / Cooling with liquid nitrogen 3.1: phosphoric acid / dichloromethane / 0 - 20 °C
	Multi-step reaction with 3 steps 1: caesium carbonate; palladium diacetate; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene / 24 h / Reflux; Inert atmosphere 2: tetrahydrofuran / 20 °C / Inert atmosphere 3: hydrogenchloride; acetic acid / 12 h / Reflux

Multi-step reaction with 3 steps 1: palladium diacetate; bis[2-(diphenylphosphino)phenyl] ether; caesium carbonate / toluene / 110 °C / Inert atmosphere 2: tetrahydrofuran; diethyl ether / -78 - -40 °C / Inert atmosphere 3: trifluoroborane diethyl ether / dichloromethane / 20 °C / Inert atmosphere

Reference： [1]Current Patent Assignee: LUMINESCENCE TECHNOLOGY CORPORATION - CN107652307, 2018, A
[2]Current Patent Assignee: BEIJING TUOCAI PHOTOELECTRIC TECH - CN108929338, 2018, A
[3]Zhang, Qing; Wang, Yaxiong; Yoon, Sung Joon; Chung, Won Jae; Ye, Shaofeng; Guo, Runda; Leng, Panpan; Sun, Shuaiqiang; Lee, Jun Yeob; Wang, Lei [Journal of Materials Chemistry C, 2020, vol. 8, # 5, p. 1864 - 1870]
[4]Chen, Tianheng; Chen, Zhanxiang; Gao, Jie; Gong, Shaolong; Huang, Chih-Wei; Huang, Zhongyan; Lu, Chen-Han; Wu, Chung-Chih; Xiang, Yepeng; Yang, Chuluo; Zeng, Weixuan; Zeng, Xuan [Journal of Materials Chemistry C, 2019, vol. 7, # 29, p. 9087 - 9094]

39
[ 89827-45-2 ]
[ 20474-15-1 ]
C₃₇H₂₅NO [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
67%	With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene;Reflux;	7 g of I2,4-bromodibenzo[b,d]furan, 6.5 g of the above procedure,t-BuONa (sodium tert-butoxide) 3g, Pd2(dba)3 (tris(dibenzylideneacetone)dipalladium) 0.7g,After 1 ml of (t-Bu)3P (tri-t-butylphosphine) was dissolved in 150 ml of toluene, stirring was performed under reflux.After completion of the reaction, distilled water and EA (ethanol) were used for extraction and column purification to give a compound.(yield 67%)

Reference： [1]Patent: CN104471022,2018,B .Location in patent: Paragraph 0085; 0086; 0088

40
[ 89827-45-2 ]
[ 86-74-8 ]
[ 1651195-14-0 ]

Yield	Reaction Conditions	Operation in experiment
80%	With copper; potassium carbonate In N,N-dimethyl acetamide at 170℃; for 12h; Inert atmosphere;	Synthesis of Intermediate 2 24.7 g (100 mmol) of the intermediate 1 was dissolved in 200 ml of N,N-dimethyl acetamide under a nitrogen atmosphere. To this were added 17.6 g (105 mmol) of carbazole, 14.3 g (150 mmol) of copper powder, and 27.6 g (200 mmol) of potassium carbonate. Then the mixture was stirred at 170° C. for 12 hours. After cooling the reaction solution, it was poured into 500 ml of water. The precipitated solid was filtered. The filtered solid was dissolved in ethyl acetate, and an insoluble matter was removed with filtration. The solvent was removed from the filtrate under a reduced pressure. The obtained solid was recrystallized with methanol to obtain 33.3 g of an intermediate 2. The yield was 80%. The structure of the compound was confirmed with NMR and mass spectrum.
80 %	With copper; potassium carbonate In N,N-dimethyl acetamide at 170℃; Inert atmosphere;	(Synthesis of Intermediate 2) Under nitrogen atmosphere, 24.7 g of intermediate 1 (100 mmol) was dissolved in 200 ml of N,N-dimethylacetamide, 17.6 g (105 mmol) of carbazole, 14.3 g (150 mmol) of copper powder, 27.6 g (200 mmol) of potassium carbonate. ) was added and stirred at 170° C. for 12 hours. After cooling the reaction solution, it was poured into 500 ml of water, and the precipitated solid was collected by filtration. The filtered solid was dissolved in ethyl acetate, the insoluble matter was removed by filtration, and the solid obtained by removing the solvent under reduced pressure was recrystallized with methanol to obtain 33.3 g of Intermediate 2. Yield was 80%.

Reference： [1]Current Patent Assignee: MERCK KGAA - US2018/37546, 2018, A1 Location in patent: Paragraph 0168
[2]Current Patent Assignee: KONICA MINOLTA, INC. - JP2016/149521, 2016, A Location in patent: Paragraph 0242

41
[ 89827-45-2 ]
[ 2208328-14-5 ]
[ CAS Unavailable ]

Yield	Reaction Conditions	Operation in experiment
90.1%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tri-tert-butyl phosphine; sodium t-butanolate In toluene at 120℃; for 12h; Inert atmosphere;	21 Intermediate 6B 3.03g and 4-bromobenzofuran 2.96g, sodium tert-butoxide 5.7g, toluene 100mL, solution levelUnder a nitrogen atmosphere for 30 minutes, add 0.2 g of Pd2(dba)3, inject 10% tri-tert-butylphosphine 10ml with a syringe, turn on stirring, addHeated to 120 degrees Celsius, 12 hours after the reaction, the reaction solution was washed with water, the organic phase was concentrated, and silica gel column chromatography (PE:EA=20:1 to 1:1) 4.23 g of a white solid was obtained with a yield of 90.1%.

Reference： [1]Current Patent Assignee: BEIJING ETERNAL MATERIAL TECHNOLOGY CO LTD - CN107759527, 2018, A Location in patent: Paragraph 0123; 0124; 0125

42
[ 89827-45-2 ]
[ 79-44-7 ]
[ 88818-41-1 ]

Yield	Reaction Conditions	Operation in experiment
55%	Stage #1: 4-bromodibenzofuran With n-butyllithium In tetrahydrofuran at -78℃; for 1.5h; Stage #2: N,N-Dimethylcarbamoyl chloride In tetrahydrofuran at 20℃; for 4h;	1-1 Production Example 1-1: Preparation of Compound 1-1 4-Bromobenzofuran (Compound A-1, 10 g, 40 mmol) was added to 500 mL of anhydrous tetrahydrofuran and cooled to -78 ° C.Then, n-butyllithium (18 mL, 45 mmol) was slowly added dropwise over 30 minutes while stirring, followed by reaction for 1 hour.Then, dimethylcarbamyl chloride (5 g, 49 mmol) was added thereto, slowly warmed to room temperature, and reacted for 4 hours.After the reaction was terminated by pouring water, the water layer and the organic layer were separated, and the organic layer was subjected to distillation under reduced pressure to obtain Compound A-2 (5.3 g, 55%).(Z) -N'-cyanobenzimidamide (4 g, 27 mmol) was added thereto while stirring, and the mixture was refluxed. After reaction for 20 hours, the resulting solid was filtered, and the filtrate was again dissolved in chloroform. After neutralization and extraction with water saturated with calcium carbonate, the organic layer was dried with magnesium sulfate. The organic layer was then distilled under reduced pressure and recrystallized from ethanol. The resulting solid was filtered and dried to give Compound 1-1 (6 g, 71%).
55%	Stage #1: 4-bromodibenzofuran In tetrahydrofuran at -78℃; for 1.5h; Stage #2: N,N-Dimethylcarbamoyl chloride With n-butyllithium In tetrahydrofuran at -78 - 20℃; for 4h;	1 Preparation of Compound 1-1 4-Bromobenzofuran (Compound A-1, 10 g, 40 mmol) was added to 500 mL of anhydrous tetrahydrofuran and cooled to -78 ° C. Then, n-butyllithium (18 mL, 45 mmol) was slowly added dropwise over 30 minutes while stirring, followed by reaction for 1 hour. Then, dimethylcarbamyl chloride (5 g, 49 mmol) was added thereto, slowly warmed to room temperature, and reacted for 4 hours. After the reaction was terminated by pouring water, the water layer and the organic layer were separated, and the organic layer was subjected to distillation under reduced pressure to obtain Compound A-2 (5.3 g, 55%). 3 mL of phosphorus oxychloride Was added to 200 mL of acetonitrile and stirred (Z) -N'-cyanobenzimidamide (4 g, 27 mmol) was added and refluxed. After reaction for 20 hours, the resulting solid was filtered, and the filtrate was again dissolved in chloroform. After neutralization and extraction with water saturated with calcium carbonate, the organic layer was dried with magnesium sulfate. The organic layer was then distilled under reduced pressure and recrystallized from ethanol. The resulting solid was filtered and dried to give Compound 1-1 (6 g, 71%).

Reference： [1]Current Patent Assignee: LG CHEM CO.,LTD. - KR2017/141144, 2017, A Location in patent: Paragraph 0138; 0139; 0140
[2]Current Patent Assignee: LG CHEM CO.,LTD. - KR2018/32518, 2018, A Location in patent: Paragraph 0199-0202

43
[ 89827-45-2 ]
[ 122-39-4 ]
[ 1469898-72-3 ]

Yield	Reaction Conditions	Operation in experiment
75%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tri-tert-butyl phosphine; sodium t-butanolate In toluene at 100℃; Inert atmosphere;	2.1 Step one: synthesis of intermediate 6 The intermediate 4 (8.5 g, 50 mmol) and intermediate 5 (12.4 g, 50 mmol) is dissolved in 200 ml of toluene, under stirring conditions, exhaust 30 minutes later, then quickly tertiary butanol sodium (480 mg, 5 mmol), 3-tert-butylphosphine (1.1 g, 5 mmol) and double Bis(dibenzylideneacetone)palladium (864 mg, 1.5 mmol), heating to 100 °C, overnight reaction, cooling to room temperature, adding water and dichloromethane stirring, extraction, the combined organic phase, and drying with anhydrous sodium sulfate, concentrated under reduced pressure, finally with silica gel column chromatography, showering liquid is petroleum ether, to obtain pure intermediates 6 (12.5 g, 37.5 mmol), yield is 75%.

Reference： [1]Current Patent Assignee: EVERDISPLAY OPTRONICS (SHANGHAI) LIMITED - CN107573246, 2018, A Location in patent: Paragraph 0031-0032

44
[ 89827-45-2 ]
[ 1110690-60-2 ]

Yield	Reaction Conditions	Operation in experiment
88%	Stage #1: 4-bromodibenzofuran With lithium diisopropyl amide In tetrahydrofuran at -10℃; for 1h; Inert atmosphere; Stage #2: With iodine In tetrahydrofuran for 17h; Inert atmosphere;	2.1; 23.1 (1) Synthesis of Intermediate-6 Put 24.7g (100mmol, 1.0eq.) 4-bromodibenzofuran into a dry 2L three-necked flask, dissolve it with 300ml dry tetrahydrofuran, pour nitrogen through it, and reduce to -10.Add 44ml of 2.5M (110mmol, 1.1eq.) LDA dropwise. When the addition is over, continue to stir at this temperature for 1 hour, add 38.1g (150mmol, 1.5eq.) iodine in batches, remove the cooling environment, and continue the reaction Overnight for 17 hours, when the reaction is over,Add 4M HCl solution dropwise, stir for 1 hour, stand still, separate layers, wash the upper organic phase with water 3 times, and extract the lower organic phase with dichloromethane and wash 3 times with water.Combine the organic phases, dry, spin off the solvent, and purify with a chromatography column to obtain 32.8 g of Intermediate-6 with a yield of 88%.
83%	Stage #1: 4-bromodibenzofuran With lithium diisopropyl amide In tetrahydrofuran at -10℃; for 1h; Inert atmosphere; Stage #2: With iodine In tetrahydrofuran	2.11 (11) Synthesis of Intermediate-18 In a dry 2 L three-necked flask, 24.7 g (100 mmol, 1.0 eq.) of 4-bromodibenzofuran was added, dissolved in 300 ml of dry tetrahydrofuran, and passed through nitrogen to -10 ° C. 44 ml of 2.5 M (110 mmol) was added dropwise. , 1.1 eq.) of LDA, after the end of the dropwise addition, continue to stir at this temperature for 1 hour, add 30.1 g (150 mmol, 1.5 eq.) of iodine in portions, remove the cooling environment, continue the reaction overnight, until the reaction is over, drop Add 4M HCl solution, stir for 1 hour, let stand, layer, the upper organic phase is washed 3 times with water, the lower organic phase is extracted with dichloromethane, washed 3 times, the organic phase is combined, dried, solvent is removed, and chromatographed The column was purified to give 31 g of Intermediate -18.

Reference： [1]Current Patent Assignee: NANJING TOPTO SEMICONDUCTOR MATERIAL CO LTD - CN107936957, 2020, B Location in patent: Paragraph 0079-0083; 0151-0155
[2]Current Patent Assignee: NANJING TOPTO SEMICONDUCTOR MATERIAL CO LTD - CN108178763, 2018, A Location in patent: Paragraph 0086; 0127; 0129; 0130

45
[ 89827-45-2 ]
[ 164461-18-1 ]
C₂₈H₁₆O [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
89%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate In ethanol; water; toluene at 110℃; Inert atmosphere;	2.1 (1) Synthesis of Intermediate-8 24.7 g (100 mmol, 1.0 eq.) of 4-bromodibenzofuran and 27.1 g (110 mmol, 1.1 eq.) of 1-indoleboronic acid were added to a 2 L three-necked flask, dissolved in 1000 ml of toluene and 100 ml of ethanol, and passed through nitrogen. For 15 minutes, 150 ml of 2M aqueous solution containing 41.5 g (300 mmol, 3.0 eq.) of K2CO3 was added, and finally 2.3 g of Pd(PPh3)4 (2 mol%) was added. The temperature was raised to 110 ° C and the reaction was completed overnight. Adding activated carbon adsorption, suction filtration, solvent removal, drying, recrystallization from toluene and ethanol to give 32.8 g of intermediate-8, yield 89%

Reference： [1]Current Patent Assignee: NANJING TOPTO SEMICONDUCTOR MATERIAL CO LTD - CN108178763, 2018, A Location in patent: Paragraph 0086; 0087; 0089; 0090

46
[ 89827-45-2 ]
[ 5419-55-6 ]
[ 100124-06-9 ]

Yield	Reaction Conditions	Operation in experiment
94%	Stage #1: 4-bromodibenzofuran With n-butyllithium In tetrahydrofuran at -78℃; for 1.5h; Inert atmosphere; Stage #2: Triisopropyl borate In tetrahydrofuran at 20℃; for 8h;	4.1 (5-(4-([2,2':6',2"-teridopyridine]-4'-yl)phenyl)-5H-benzofuro[3,2-c]indole)Preparation (1) 4-bromodibenzofuran (7.4 g, 30 mmol, 1 eq) in a 50 ml three-necked flask,Add dry tetrahydrofuran solution, cool to -78 ° C, replace N2, three times,To ensure the oxygen-free environment of the system, add n-butyl lithium (2.5M, 13.2ml,After 33 mmol, 1.1 eq), the reaction was kept at -78 ° C for 1.5 h, and triisopropyl borate (ρ = 0.815 g/ml, 7.6 ml, 33 mmol, 1.1 eq) was added dropwise. After the addition was completed, the temperature was raised to room temperature for 8 h. After the dropwise addition of dilute hydrochloric acid, the reaction was quenched, distilled under reduced pressure to give tetrahydrofuran, dissolved in dichloromethane, washed with anhydrous magnesium sulfate, dried, filtered, and the filtrate was recrystallized.White solid product4-boronic acid dibenzofuran6 g (yield 94%).
	Stage #1: 4-bromodibenzofuran With n-butyllithium In tetrahydrofuran at -78℃; for 1.5h; Inert atmosphere; Stage #2: Triisopropyl borate In tetrahydrofuran at 20℃; for 8h;	1.1 1 Preparation of dibenzo[b,d]furan-4-ylboronic acid: 4-bromodibenzofuran (1 eq), added to a dry tetrahydrofuran solution, cooled to -78 ° C, and replaced N2 three times to ensure the system's oxygen-free environment,After adding n-butyllithium (2.5 M, 1.1 eq) dropwise, the reaction was kept at -78 ° C for 1.5 h.Triisopropyl borate (ρ=0.815g/ml, 1.1eq) was added dropwise, and the mixture was added to room temperature after the addition was completed. After 8 hours, the reaction was quenched with dilute hydrochloric acid.Tetrahydrofuran was distilled off under reduced pressure, dissolved in dichloromethane was added, washed with water, dried over anhydrous magnesium sulfate, filtered, and the filtrate was recrystallized, to give the product as a white solid (94%);

Reference： [1]Current Patent Assignee: WUHAN SHANGSAI OPTOELECTRONICS TECHNOLOGY CO LTD - CN109897029, 2019, A Location in patent: Paragraph 0063-0066
[2]Current Patent Assignee: HUAZHONG UNIVERSITY OF SCIENCE & TECHNOLOGY - CN108285452, 2018, A Location in patent: Paragraph 0035; 0037; 0040; 0041

47
[ 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

48
[ 89827-45-2 ]
[ 578-95-0 ]
C₂₅H₁₇NO₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
47%	Stage #1: 4-bromodibenzofuran With n-butyllithium In tetrahydrofuran at -78 - 30℃; for 3.5h; Inert atmosphere; Stage #2: 10H-acridin-9-one In tetrahydrofuran at -78 - 30℃; for 15h; Inert atmosphere;	56 (1) Synthesis of intermediates 3-7 Under nitrogen protection, 16.8 g (100 mmol) of compound F-7 and tetrahydrofuran 500 mL were added, and 63 mL of n-butyllithium (1.6 M) was added dropwise at -78 °C, and the reaction was carried out at low temperature for 30 minutes, and the temperature was raised to 30 °C for 3 hours. , again cool down to -78 °C. Add 500 mL of 9(10H)-acridone solution (Compound A-1) (0.2 Μ, 9.5 g (100 mmol)), slowly warm to 30 °C, react for 15 hours, then add ammonium chloride aqueous solution to quench the reaction, chloroform extraction. The solvent was removed by rotary distillation and passed through a silica gel column to afford 17.3 g of solid intermediate 3-7 (yield 47%).
47%	Stage #1: 4-bromodibenzofuran With n-butyllithium In tetrahydrofuran at -78℃; for 0.5h; Inert atmosphere; Stage #2: 10H-acridin-9-one at -78 - 30℃; for 15h;	73.1 (1) Synthesis of intermediates 3-4 Under nitrogen protection, 16.8 g (100 mmol) of the compound of the formula F-4, tetrahydrofuran 500 mL, -78 ° C was added.Under the conditions, add 63mL of n-butyl lithium (1.6M), react at low temperature for 30 minutes, heat up to 30 ° C for 3 hours, and then cool down again -At 78 ° C, add 500 mL of 9 (10H)-acridone (compound of formula A-1) solution (0.2 M, 9.5 g (100 mmol)), slowly riseWarm to 30 ° C, reaction for 15 hours, add ammonium chloride aqueous solution to quench the reaction, chloroform extraction, rotary distillation to remove the solvent, through silica gel column17.3 g of solid intermediate 3-4 were obtained (yield 47%);

Reference： [1]Current Patent Assignee: NINGBO LUMILAN NEW MATERIAL CO LTD - CN109206416, 2019, A Location in patent: Paragraph 0405-0408
[2]Current Patent Assignee: NINGBO LUMILAN NEW MATERIAL CO LTD - CN109232419, 2019, A Location in patent: Paragraph 0546; 0547; 0548; 0549; 0550; 0551; 0552; 0553

49
[ 89827-45-2 ]
[ 1917361-78-4 ]
[ 1917359-52-4 ]

Yield	Reaction Conditions	Operation in experiment
75%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate In 1,4-dioxane; water at 120℃; for 4h;	20 Preparation of Compound 245 A mixture of Compound 237-5 (9 g, 14.52 mmol), 4-bromodibenzo[b,d]furan (3.5 g, 14.52 mmol), Pd(PPh3)4 (1.67 g, 1.45 mmol), K2CO3 (4 g, 27.04 mmol), and 1,4-dioxane (150 ml)/H2O (30 ml) was stirred at 120° C. in a one-neck round bottom flask for 4 hours. The reactant at 120° C. was filtered, and then washed with 1,4-dioxane at 110° C. and with methanol to obtain Compound 245 (7.2 g, 75%).

Reference： [1]Current Patent Assignee: LT SAMBO CO LTD - US10177319, 2019, B2 Location in patent: Page/Page column 201-202

50
[ 89827-45-2 ]
[ 1917361-75-1 ]
[ 1917361-53-5 ]

Yield	Reaction Conditions	Operation in experiment
78%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate In 1,4-dioxane; water at 120℃; for 4h;	71 Preparation of Compound 239 General procedure: A mixture of Compound 239-1 (9 g, 14.52 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (4.27 g, 15.97 mmol), Pd(PPh3)4 (1.67 g, 1.45 mmol), K2CO3 (4 g, 27.4 mmol), and 1,4-dioxane (150 ml)/H2O (30 ml) was stirred at 120° C. in a one-neck round bottom flask for 4 hours. The reactant at 120° C. was filtered, and then washed with 1,4-dioxane at 110° C. and with methanol to obtain Compound 239 (8.4 g, 80%)

Reference： [1]Current Patent Assignee: LT SAMBO CO LTD - US10177319, 2019, B2 Location in patent: Page/Page column 200; 218

51
[ 89827-45-2 ]
[ 931-51-1 ]
[ 1698876-03-7 ]

Yield	Reaction Conditions	Operation in experiment
88%	Stage #1: cyclohexylmagnesiumchloride With zinc(II) chloride In tetrahydrofuran; 2-methyltetrahydrofuran; toluene at 20℃; for 1h; Inert atmosphere; Stage #2: 4-bromodibenzofuran With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; tris-(dibenzylideneacetone)dipalladium⁽⁰⁾ In tetrahydrofuran; 2-methyltetrahydrofuran; toluene at 50℃; for 12h;	1.1 Example 1: Synthesis of Compound Step 1: Under N2 atmosphere, to 5 THF (300.0 mL) was added 6 cyclohexylmagnesium chloride (445.0 mL, 1.3 M in THF/7 toluene (62/38, v/v)) at room temperature, and 8 zinc chloride (410.0 mL, 2.0 M in 9 2-methyltetrahydrofuran) was added dropwise with stirring, it was reacted at room temperature for 1 h (white solid precipitated). Then 10 4-bromodibenzo[b,d]furan (82.0 g, 331.9 mmol), 11 2-dicyclohexylphorspine-2′,6′-dimethoxylbiphenyl (12.0 g, 29.2 mmol) and 12 tris(dibenzylideneacetone)dipalladium (9.0 g, 9.8 mmol) were mixed together and added to the reaction mixture quickly. The reaction was heated to 50° C. for 12 h, and was monitored by TLC. After the reaction was completed, it was cooled to room temperature, and quenched with saturated NH4Cl solution (200 mL). After filtration, the residue was washed with EA. The filtrate was combined and extracted with EA (2100 mL). The organic phase was washed with saturated NaCl solution (2100 mL), dried over anhydrous Na2SO4 and evaporated to dryness. The residue was purified by column chromatography (silica gel (200300 mesh), eluent: petroleum ether) to give 13 4-cyclohexyldibenzo[b,d]furan as yellow oil (74.0 g, 295.6 mmol, 88.0%).

Reference： [1]Current Patent Assignee: BEIJING SUMMER SPROUT TECHNOLOGY CO LTD - US2019/81253, 2019, A1 Location in patent: Paragraph 0109-0110

52
[ 89827-45-2 ]
[ 1651187-33-5 ]
[ 2375831-28-8 ]

Yield	Reaction Conditions	Operation in experiment
75%	With potassium phosphate; copper(l) iodide; trans-1,2-cyclohexanediamine In toluene at 110℃; for 12h; Inert atmosphere;	2 Compound 1 - 6 synthesis of Under the environment of nitrogen, will (9.48 g, 20 mmol) intermediate 1 - 6 - 3, (5 g, 20 mmol) compound 1 - 3 - 7, (1.91 g, 10 mmol) cuprous iodide, (2.28 g, 20 mmol) anti-form link oneself diamine, (12.72 g, 40 mmol) potassium phosphate and 100 ml toluene is added to 300 ml bottle in three, heating and stirring to 110 °C reaction 12 hours, the end of the reaction, cooling to room temperature, filtered and the filtrate, rotary evaporated most of the solvent, dichloromethane is used for dissolving water washing 3 times, to collect organic the fluid mixes purified by silica gel column, to obtain compound 1 - 3, yield 75%.

Reference： [1]Current Patent Assignee: TCL TECHNOLOGY GROUP CORPORATION - CN109575002, 2019, A Location in patent: Paragraph 0198; 0199; 0202; 0203

53
[ 89827-45-2 ]
[ 50548-43-1 ]
bis(dibenzofuran-4-yl)amine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
74.8%	With tris-(dibenzylideneacetone)dipalladium(0); triphenylphosphine; sodium t-butanolate; In toluene; at 105℃; for 24h;Inert atmosphere;	In a 250 ml three-necked flask, 0.01 mol of raw material O1 was added under nitrogen protection.0.012 mol of raw material P1, 150 ml of toluene were stirred and mixed.Then add 5×10-5 mol Pd2(dba)3, 5×10-5 mol P(Ph)3,0.03 mol of sodium tert-butoxide, heated to 105 C, refluxed for 24 hours, sampling plate,Show no bromine residue remaining, the reaction is complete; naturally cool to room temperature, filter,The filtrate is steamed to no fraction, and passed through a neutral silica gel column to obtain the target product intermediate B1;HPLC purity 99.03%, yield 74.8%;

Reference： [1]Patent: CN109574926,2019,A .Location in patent: Paragraph 0090; 0095-0097

54
[ 89827-45-2 ]
[ 225931-80-6 ]
[ 787618-22-8 ]
C₁₂H₇O^(1-)*Pd⁽²⁺⁾*Br^(1-)*C₃₀H₄₃O₂P [ No CAS ]

Reference： [1]Chemical Science,2019,vol. 10,p. 5837 - 5842

55
[ 89827-45-2 ]
[ 2217-41-6 ]
[ 2376824-90-5 ]

Yield	Reaction Conditions	Operation in experiment
91%	With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; sodium t-butanolate In toluene at 85℃; for 12h;	2.1 Synthesis Step 1: Synthesis of Intermediate 2 To a 75 ml three-necked flask, 30 ml of toluene, 2.7 g of 1-aminotetrahydronaphthalene, 2.25 g of 4-bromodibenzofuran, and 2.2 g of sodium tert-butoxide were sequentially added.Tris(dibenzylideneacetone)palladium 0.18g, 2-cyclohexylphosphine-2,6-methoxy-1,1-biphenyl 0.22g, after three times of nitrogen replacement, the system is heated to 85 degrees, the heat preservation reaction 12 Hours, the system shrinks directly after cooling down,Column chromatography, dichloromethane (DCM):Petroleum ether (PE) = 1:20 gave 2.28 g of a yellow solid. The yield was 91%.

Reference： [1]Current Patent Assignee: AAC ACOUSTIC TECHNOLOGIES HOLDINGS INC. - CN109678729, 2019, A Location in patent: Paragraph 0109; 0112-0114

56
[ 89827-45-2 ]
[ 16452-11-2 ]
C₂₂H₁₄ClNO [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
75%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tri-tert-butyl phosphine; sodium t-butanolate In toluene at 100℃;	2.1.1 (1) Sub 4-c-1 synthesis After dissolving 4-bromodibenzo [b, d] furan (50.0 g, 202 mmol) in a round bottom flask with Toluene,1-chloronaphthalen-2-amine (35.9 g, 202 mmol), Pd2 (dba) 3 (5.56 g, 6.07 mmol),P (t-Bu) 3 (2.46 g, 12.1 mmol), NaOt-Bu (38.9 g, 405 mmol) was added and stirred at 100 ° C.When the reaction is completed, the mixture is extracted with CH2Cl2 and water, and the organic layer is dried over MgSO4 and concentrated.Thereafter, the resulting compound was recrystallized after applying a silica gel column to obtain 52.2 g (yield: 75%) of the product.

Reference： [1]Current Patent Assignee: DUK SAN NEOLUX CO., LTD. - KR2020/37543, 2020, A Location in patent: Paragraph 0569; 0582-0585

57
[ 89827-45-2 ]
[ 1010068-85-5 ]
C₃₀H₁₈O₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
74%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate In ethanol; water; toluene Reflux;	1.3 3) Preparation of compound 1-3 In a 3L round flask, compound 1-2 53g (183.95mmol, 1.1eq) and4-bromodibenzofurane 41.3g (167.23mmol, 1eq),Pd(pph3)4 9.6g(8.36mmol, 0.05eq), K2CO3 69.2g(501.70mmol, 3eq) and Toluene/EtOH/H2O respectively1.6L/334ml/334ml was added and stirred under reflux.After the reaction was completed, the mixture was extracted with CH2Cl2/H2O, and the CH2Cl2 layer was dried over MgSO4. Silica-gel column purification to compound1-3 51 g were obtained in 74% yield.

Reference： [1]Current Patent Assignee: SOULBRAIN CO.,LTD. - KR2020/68397, 2020, A Location in patent: Paragraph 0149; 0158-0161

58
[ 89827-45-2 ]
[ 1010068-85-5 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1.1: potassium carbonate; tetrakis(triphenylphosphine) palladium⁽⁰⁾ / toluene; ethanol; water / Reflux 2.1: n-butyllithium / tetrahydrofuran / -78 - 20 °C 2.2: -78 - 20 °C
	Multi-step reaction with 2 steps 1.1: tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate / toluene; ethanol; water / Reflux 2.1: n-butyllithium / tetrahydrofuran / -78 - 20 °C 2.2: -78 - 20 °C

Reference： [1]Current Patent Assignee: SOULBRAIN CO.,LTD. - KR2020/68397, 2020, A
[2]Current Patent Assignee: SOULBRAIN CO.,LTD. - KR2020/68398, 2020, A

59
[ 89827-45-2 ]
[ 63503-60-6 ]
[ 1801420-58-5 ]

Yield	Reaction Conditions	Operation in experiment
77%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; sodium carbonate In ethanol; water; toluene at 100℃; for 17h; Inert atmosphere;	1 Synthesis of Intermediate 17a Under nitrogen condition, a mixture of 3-chlorophenylboronic acid (7.8 g, 60 mmol), 4-bromodibenzo[b,d]furan (16.3 g, 66 mmol), 60 ml of 2M Na2CO3 (aq), 60 ml of ethanol, 120 ml of toluene, and Pd(PPh3)4 (0.69 g, 1.2 mmol) was added and then heated at 100° C. for 17 hours. After the reaction was finished, the mixture was extracted with ethyl acetate and water, and then the organic layer was evaporated under reduced pressure. The residue was purified by column chromatography on silica to give Intermediate 17a (12.9 g, 77%) as a white solid.
76%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate In tetrahydrofuran; water for 6h; Reflux;	20.20-1 20-1. Preparation of compound 20-1 In a 1000-mL, 4-neck round-bottom flask, 13.3 g (0.054 mol) of 4-bromodibenzo[b,d]furan was added and diluted with 350 mL of tetrahydrofuran. To this dilution, 9.4 g of (3-chlorophenyl)boronic acid, 54 mL of 3M-potassium carbonate aqueous solution, and 1.0 g of tetrakis(triphenylphosphine)palladium (0) were added, and the reaction solution was refluxed for 6 hours. After the reaction solution was cooled to room temperature, tetrahydrofuran was concentrated, methanol was added, and the precipitated solid was vacuum filtered. The collected solid compounds were vacuum dried to obtain 11.4 g of compound 20-1 (yield 76%)
77 %	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; sodium carbonate In ethanol; water; toluene at 100℃; Inert atmosphere;	1 Synthesis of Intermediate 17a Under nitrogen condition, a mixture of 3-chlorophenylboronic acid (7.8 g, 60 mmol), 4-bromodibenzo[b,d]furan (16.3 g, 66 mmol), 60 ml of 2M Na2CO3 (aq), 60 ml of ethanol, 120 ml of toluene, and Pd(PPh3)4 (0.69 g, 1.2 mmol) was added and then heated at 100° C. for 17 hours. After the reaction was finished, the mixture was extracted with ethyl acetate and water, and then the organic layer was evaporated under reduced pressure. The residue was purified by column chromatography on silica to give Intermediate 17a (12.9 g, 77%) as a white solid.

Reference： [1]Current Patent Assignee: LUMINESCENCE TECHNOLOGY CORPORATION - US2020/235306, 2020, A1 Location in patent: Paragraph 0073-0074
[2]Current Patent Assignee: EL & M SPA - KR2021/128618, 2021, A Location in patent: Paragraph 0235-0238
[3]Current Patent Assignee: LUMINESCENCE TECHNOLOGY CORPORATION - US2020/235306, 2020, A1 Location in patent: Paragraph 0073-0074

60
[ 89827-45-2 ]
[ 16807-13-9 ]
[ 1639782-99-2 ]

Yield	Reaction Conditions	Operation in experiment
70%	With copper(l) iodide; potassium carbonate In N,N-dimethyl-formamide at 80℃; for 24h;	1 Synthesis of Intermediate II-1 3-iodocarbazole 2.93g (10.0mmol), 4-bromodibenzofuran 2.96g (12.0mmol), CuI 0.2g (2.0mmol) and After dissolving K2CO34.1g (30.0mmol) in 100mL of DMF (N,N-dimethylformamide), the mixture was stirred at 80°C for 24 hours.After cooling the reaction solution to room temperature, it was extracted three times with 30 mL of water and 40 mL of diethyl ether.The collected organic solvent layer was dried over magnesium sulfate, and the residue obtained by evaporating the solvent was separated and purified by silica gel column chromatography to obtain 3.21 g (yield 70%) of Intermediate II-1.

Reference： [1]Current Patent Assignee: Samsung Display (in: Samsung); SAMSUNG ELECTRONICS CO.,LTD. - KR102136786, 2020, B1 Location in patent: Paragraph 0206; 0224-0225

61
[ 89827-45-2 ]
[ 1268519-74-9 ]
[ 2055366-24-8 ]

Yield	Reaction Conditions	Operation in experiment
73%	With tri-tert-butyl phosphine; bis(dibenzylideneacetone)-palladium⁽⁰⁾; sodium t-butanolate In toluene at 90 - 110℃; for 12h; Inert atmosphere;	1.4 Step 4: Synthesis of Intermediate 7 Combine 9,9-diphenyl-9H-fluoren-2-amine (16.7g, 50.0mmol), 4-bromobenzofuran (12.4g, 50.0mmol), bis(dibenzylideneacetone)palladium (860mg, 1.5mmol), a mixture of tri-tert-butylphosphine (600mg, 3mmol) and toluene (100ml), Heat to 90°C under argon gas flow, add sodium tert-butoxide (288mg, 3mmol), heat to 110°C under argon gas atmosphere, and stir to react for 12 hours. The reaction mixture was cooled to room temperature, water was added for liquid separation; the solvent of the obtained organic layer was concentrated, and the obtained solid was purified by silica gel column chromatography. Intermediate 7 (18.2 g, 36.5 mmol) was obtained with a yield of 73%.

Reference： [1]Current Patent Assignee: EVERDISPLAY OPTRONICS (SHANGHAI) LIMITED - CN108342191, 2020, B Location in patent: Paragraph 0049; 0061-0064

62
[ 89827-45-2 ]
[ 2570228-22-5 ]
[ 2570227-65-3 ]

Yield	Reaction Conditions	Operation in experiment
92%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate In tetrahydrofuran; water at 80℃; for 12h; Inert atmosphere;	6 Synthesis of Intermediate I-2 Intermediate I-1 (130 g, 364 mmol) was dissolved in 1.0 L of tetrahydrofuran (THF) under a nitrogen atmosphere, and 4-chlorophenylboronic acid (68.4 g, 437 mmol) purchased from Tokyo Chemical Industry Co., Ltd., and tetrakis(triphenylphosphine) palladium (8.41 g, 7.28 mmol) were added thereto and stirred therewith. Potassium carbonate (126 g, 910 mmol) saturated in water was added thereto and then, heated and refluxed at 80° C. for 12 hours. When a reaction was complete, water was added to the reaction solution, and the mixture was extracted with dichloromethane (DCM), treated with anhydrous magnesium sulfate to remove moisture, and filtered under a reduced pressure. This obtained residue was separated and purified through flash column chromatography to obtain Intermediate I-2 (147 g, 93%).
92%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate In tetrahydrofuran; water at 80℃; for 12h; Inert atmosphere;	6 Synthesis Example 2: Synthesis of Intermediate I-2 General procedure: Intermediate I-1 (130g, 364mmol) was dissolved in 1.0L of tetrahydrofuran (THF) under a nitrogen atmosphere, and 4-chlorophenylboronic acid (68.4g, 437mmol) purchased from Tokyo Chemical Industry Co., Ltd. was added thereto. ) And tetrakis(triphenylphosphine)palladium (8.41g, 7.28mmol) and stirred with it.A saturated solution of potassium carbonate (126 g, 910 mmol) in water was added thereto, and then heated at 80°C and refluxed for 12 hours.When the reaction was completed, water was added to the reaction solution, and the mixture was extracted with dichloromethane (DCM), treated with anhydrous magnesium sulfate to remove moisture, and filtered under reduced pressure.The resulting residue was separated and purified by flash column chromatography to obtain Intermediate I-2 (147 g, 93%).

Reference： [1]Current Patent Assignee: SAMSUNG SDI CO.,LTD. - US2020/407348, 2020, A1 Location in patent: Paragraph 0102-0103; 0118-0121
[2]Current Patent Assignee: SAMSUNG SDI CO.,LTD. - CN112142719, 2020, A Location in patent: Paragraph 0157-0162; 0181-0186

63
[ 89827-45-2 ]
[ 2570228-26-9 ]
[ 2570227-69-7 ]

Yield	Reaction Conditions	Operation in experiment
95%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate In tetrahydrofuran; water at 80℃; for 12h; Inert atmosphere;	13 Synthesis of Intermediate I-2 Intermediate I-1 (130 g, 364 mmol) was dissolved in 1.0 L of tetrahydrofuran (THF) under a nitrogen atmosphere, and 4-chlorophenylboronic acid (68.4 g, 437 mmol) purchased from Tokyo Chemical Industry Co., Ltd., and tetrakis(triphenylphosphine) palladium (8.41 g, 7.28 mmol) were added thereto and stirred therewith. Potassium carbonate (126 g, 910 mmol) saturated in water was added thereto and then, heated and refluxed at 80° C. for 12 hours. When a reaction was complete, water was added to the reaction solution, and the mixture was extracted with dichloromethane (DCM), treated with anhydrous magnesium sulfate to remove moisture, and filtered under a reduced pressure. This obtained residue was separated and purified through flash column chromatography to obtain Intermediate I-2 (147 g, 93%).

Reference： [1]Current Patent Assignee: SAMSUNG SDI CO.,LTD. - US2020/407348, 2020, A1 Location in patent: Paragraph 0102-0103; 0146-0149

64
[ 89827-45-2 ]
[ 2570228-22-5 ]
[ 2570227-69-7 ]

Yield	Reaction Conditions	Operation in experiment
95%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate In tetrahydrofuran; water at 80℃; for 12h; Inert atmosphere;	13 Synthesis Example 2: Synthesis of Intermediate I-2 General procedure: Intermediate I-1 (130g, 364mmol) was dissolved in 1.0L of tetrahydrofuran (THF) under a nitrogen atmosphere, and 4-chlorophenylboronic acid (68.4g, 437mmol) purchased from Tokyo Chemical Industry Co., Ltd. was added thereto. ) And tetrakis(triphenylphosphine)palladium (8.41g, 7.28mmol) and stirred with it.A saturated solution of potassium carbonate (126 g, 910 mmol) in water was added thereto, and then heated at 80°C and refluxed for 12 hours.When the reaction was completed, water was added to the reaction solution, and the mixture was extracted with dichloromethane (DCM), treated with anhydrous magnesium sulfate to remove moisture, and filtered under reduced pressure.The resulting residue was separated and purified by flash column chromatography to obtain Intermediate I-2 (147 g, 93%).

Reference： [1]Current Patent Assignee: SAMSUNG SDI CO.,LTD. - CN112142719, 2020, A Location in patent: Paragraph 0157-0162; 0223-0228

65
[ 100124-06-9 ]
[ 89827-45-2 ]

Yield	Reaction Conditions	Operation in experiment
89%	With tetrabutylammomium bromide; copper(ll) bromide In water at 100℃; Sealed tube;	1. Preparation of aryl bromides General procedure: To a stirred solution of arylboronic acids 1 (1 mmol), CuBr2 (335 mg, 1.5 mmol), TBAB (33 mg, 0.1 mmol) water (5mL) in a sealed tube for 5-12 h at 100 °C. After completion of the reaction as indicated by TLC, the mixture was extracted with EtOAc (2×5 mL). The organic layer was dried by anhydrous Na2SO4, concentrated in vacuo, and the residue was isolated by simply column chromatography (PE/EA 40:1-20:1) to afford products, respectively.

Reference： [1]Tang, Yan-Ling; Xia, Xian-Song; Gao, Jin-Chun; Li, Min-Xin; Mao, Ze-Wei [Tetrahedron Letters, 2021, vol. 64]

66
[ 89827-45-2 ]
[ 51800-19-2 ]
[ 1699739-83-7 ]

Yield	Reaction Conditions	Operation in experiment
79%	Stage #1: 4-bromodibenzo[b,d]furan With iodine; magnesium In tetrahydrofuran at 80℃; for 2.5h; Inert atmosphere; Stage #2: 2,4-dichloro-6-(dibenzo[b,d]furan-4-yl)-1,3,5-triazine In tetrahydrofuran at 20℃; for 3h; Inert atmosphere;	1.2 2) Synthesis of intermediate a-II-1 Under the protection of N2, add magnesium flakes to the three-necked flask(1.52g, 63.7mmol) and 30mL of THF, the temperature of the system was increased to 80°C, and iodine (0.32g, 1.26mmol) was added to the system.Compound 4-bromodibenzofuran (15.73g, 63.7mmol)Dissolve completely in 30mL of THF solvent, slowly drip into the system within 30 minutes, and control the temperature at 80°C during the dripping process.After the addition is complete, stir and react for 2h at 80°C.A mixed solution is obtained. After cooling at room temperature, the intermediate a-I-1 (20.13g, 63.7mmol) dissolved in 40mL THF was added dropwise to the mixed solution,After stirring for 3 hours, the reaction was terminated to obtain a reaction solution. After the reaction,Add toluene (200mL) to extract the reaction solution, combine the organic phases,The organic layer was dried with anhydrous magnesium sulfate, filtered, and concentrated by distillation under reduced pressure; the crude product was purified by silica gel column chromatography.Recrystallize and filter methanol to obtain solid intermediate a-II-1(22.5g, yield: 79%).
79%	Stage #1: 4-bromodibenzo[b,d]furan With iodine; magnesium In tetrahydrofuran at 80℃; for 2.5h; Inert atmosphere; Stage #2: 2,4-dichloro-6-(dibenzo[b,d]furan-4-yl)-1,3,5-triazine In tetrahydrofuran at 20℃; for 3h; Inert atmosphere;	1.1 Synthesis of Intermediate Sub A-1 Under the protection of N2, magnesium chips (1.52g, 63.7mmol) and 30ml of tetrahydrofuran were added to the three-necked flask, the temperature of the system was raised to 80°C, and iodine (0.32g, 1.26mmol), 4-bromodibenzo were added to the system. Furan ((15.73g, 63.7mmol) was completely dissolved in 30ml of THF solution, slowly added dropwise to the system in 30min, and the temperature was controlled at 80°C during the dropwise addition. The dropwise addition was completed, and stirred under 80°C temperature conditions Reaction 2h.The intermediate aI-1 (20.13g, 63.7mmol) dissolved in 40mlTHF was added dropwise to the mixed solution after cooling at normal temperature, and the reaction was terminated after stirring for 3h. After the reaction was completed, toluene and water were added to extract the reaction solution, and the combined For the organic phase, the organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated by distillation under reduced pressure; the crude product was purified by silica gel column chromatography, recrystallized from methanol and filtered to obtain a solid intermediate Sub A-1 (22.5 g, 79%).

Reference： [1]Current Patent Assignee: SHAANXI LIGHTE OPTOELECTRONICS MATERIAL CO.,LTD - CN112876462, 2021, A Location in patent: Paragraph 0170; 0171; 0174; 0175
[2]Current Patent Assignee: SHAANXI LIGHTE OPTOELECTRONICS MATERIAL CO.,LTD - CN114075176, 2022, A Location in patent: Paragraph 0144-0147; 0150-0151

67
[ 89827-45-2 ]
[ CAS Unavailable ]
[ 1609080-03-6 ]

Yield	Reaction Conditions	Operation in experiment
81%	With bis(tri-t-butylphosphine)palladium⁽⁰⁾; sodium t-butanolate In toluene at 110℃; for 4h;	2.2-1 Step 2-1: Preparation of intermediate compound 9 Compound 7 (1.0 eq.), compound 8 (1.2 eq.), and NaOt-Bu (2.0 eq.) were placed in a round bottom flask and dissolved in anhydrous toluene. After raising the bath temperature to 110 °C, Pd((t-Bu)3P)2 (3 mol%) was added dropwise and stirred for 4 hours. After the reaction, the organic layer was separated by washing with dichloromethane and water, water was removed with MgSO 4 , and passed through a Celite-Silica pad. The passed solution was concentrated under reduced pressure, and purified through column chromatography to obtain an intermediate compound 9 (yield 81%).
81%	With bis(tri-t-butylphosphine)palladium⁽⁰⁾; sodium t-butanolate In toluene at 110℃; for 4h;	1.1-5 Step 1-5) Preparation of intermediate compound 1-i Compound 1-g (1.0 eq.), compound 1-h (1.2 eq.), and NaOt-Bu (2.0 eq.) were placed in a round bottom flask and dissolved in anhydrous toluene. After raising the bath temperature to 110°C, Pd((t-Bu)3P)2 (3 mol%) was added dropwise and stirred for 4 hours. After the reaction, the organic layer was separated by washing with dichloromethane and water, water was removed with MgSO 4 , and passed through a Celite-Silica pad. The passed solution was concentrated under reduced pressure and purified through column chromatography to obtain intermediate compound 1-i (yield 81%).

Reference： [1]Current Patent Assignee: LG CHEM CO.,LTD. - KR2021/90333, 2021, A Location in patent: Paragraph 0249-0253
[2]Current Patent Assignee: LG CHEM CO.,LTD. - KR2021/108270, 2021, A Location in patent: Paragraph 0160; 0181-0184

68
[ 89827-45-2 ]
[ 16245-79-7 ]
C₂₆H₂₉NO [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
14.1 g	With tris(dibenzylideneacetone)dipalladium⁽⁰⁾ chloroform complex; 1,1'-bis-(diphenylphosphino)ferrocene; sodium t-butanolate In toluene at 60 - 100℃; for 1h; Inert atmosphere;	(Synthesis of Intermediate 8) Under a nitrogen atmosphere, 30.52 g of Pd2 (dba) 3CHCl30.52 and 1.1 g of dppf were dissolved in 5 mL of toluene (deoxygenated), and the mixture was stirred at 60 ° C. to prepare a catalytic solution.Separately, under a nitrogen atmosphere, 10.0 g of 4-bromodibenzofuran, 8.7 g of p-octylaniline, and 7.8 g of sodium-t-butoxide were dissolved in 100 mL of toluene (deoxidized) and stirred at 60 ° C., and the above catalyst was used. The solution was added with a syringe and stirred at 100 ° C. for 1 hour.After cooling the reaction solution to room temperature, the solvent was distilled off.The obtained residue was purified by silica gel column chromatography to obtain 14.1 g of a white solid of Intermediate 8.

Reference： [1]Current Patent Assignee: MITSUBISHI CHEMICAL HOLDINGS CORPORATION; Mitsubishi Chemical Corp (in: MCHC Group) - JP2021/127325, 2021, A Location in patent: Paragraph 0229-0232

69
[ 89827-45-2 ]
[ 4854-84-6 ]
C₃₇H₂₂N₂O₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
31.1%	With tri-tert-butyl phosphine; Palladium⁽⁰⁾ bis(dibenzylideneacetone); sodium tertiary butoxide In 5,5-dimethyl-1,3-cyclohexadiene for 0.333333h; Reflux;	38 Preparation 38: Synthesis of compound 2-198 (LT20-30-136) In a one-necked 250 mL flask, 1.9 g (9.8 mmol) of intermediate (20), 5.0 g (20.1 mmol) of 4-Bromodibenzofuran, 20.6 g (1.0 mmol) of Pd (dba), 50% P ( t-Bu) 31.0 mL (2.0 mmol), NaOtBu 2.8 g (29.3 mmol) and xylene 40 mL were refluxed and stirred for 20 minutes. After cooling to room temperature, impurities were removed through celite filtration. After removing the solvent, it was dissolved in dichloromethane and purified by silica gel column chromatography (DCM:HEX). The obtained solid was filtered with a mixed solution (dichloromethane/hexane) to obtain 1.6 g (yield: 31.1%) of compound 2-198 (LT20-30-136) as a white solid.

Reference： [1]Current Patent Assignee: LAPTO CO LTD - KR2022/30351, 2022, A Location in patent: Paragraph 0540-0542

70
[ 89827-45-2 ]
[ 89415-43-0 ]
[ 578027-21-1 ]

Yield	Reaction Conditions	Operation in experiment
2.1 g	With tetrakis-(triphenylphosphine)-palladium; potassium carbonate In tetrahydrofuran; lithium hydroxide monohydrate at 100℃; for 4h; Inert atmosphere;	12.1 (1) Synthesis of Intermediate 12-1 4-bromodibenzofuran [4-bromodibenzofuran] (2.47 g, 10 mmol), 4-aminophenylboronic acid [4-aminophenylboronic acid] (1.64 g, 12 mmol), Pd(PPh3)4 (578 mg, 0.5 mmol) ) and K2CO3 (4.15 g, 30 mmol) were added to the RBF. After nitrogen substitution, THF (25 mL) and water (25 mL) were added, and the mixture was stirred at 100 °C for 4 hours. After extraction with ethyl acetate and water, the organic layers were collected, and the organic layer was dried using MgSO4 and filtered. The filtrate was dried with a vacuum rotary concentrator to remove the organic solvent. After column purification, 2.1 g of Intermediate 12-1 was obtained by crystallization under DCM/Heptane conditions.

Reference： [1]Current Patent Assignee: LG CHEM CO.,LTD. - WO2022/75735, 2022, A1 Location in patent: Paragraph 382-385

71
[ 89827-45-2 ]
[ 98-80-6 ]
[ 2226031-12-3 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1.1: potassium carbonate; tetrakis(triphenylphosphine) palladium⁽⁰⁾ / tetrahydrofuran; water / 12 h / 80 °C 2.1: n-butyllithium / tetrahydrofuran / 6 h / -78 °C 2.2: 12 h / -78 - 20 °C
	Multi-step reaction with 2 steps 1.1: tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate / tetrahydrofuran; water / 8 h / Reflux 2.1: n-butyllithium / tetrahydrofuran / 5.5 h / -78 °C 2.2: 4 h / -78 - 20 °C

Reference： [1]Current Patent Assignee: SAMSUNG SDI CO.,LTD. - CN114437090, 2022, A
[2]Current Patent Assignee: SAMSUNG SDI CO.,LTD. - CN115745932, 2023, A

72
[ 89827-45-2 ]
[ 2226031-12-3 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1.1: potassium carbonate; tetrakis(triphenylphosphine) palladium⁽⁰⁾ / water; tetrahydrofuran / 12 h / Reflux; Inert atmosphere 2.1: n-butyllithium / tetrahydrofuran; hexane / 6 h / -78 - 20 °C / Inert atmosphere 2.2: 12 h / -78 - 20 °C / Inert atmosphere
	Multi-step reaction with 2 steps 1.1: potassium carbonate; tetrakis(triphenylphosphine) palladium⁽⁰⁾ / tetrahydrofuran; water / 8 h / Reflux; Inert atmosphere 2.1: n-butyllithium / tetrahydrofuran / 5 h / -78 °C / Inert atmosphere 2.2: 4 h / -78 - 20 °C / Inert atmosphere

Reference： [1]Current Patent Assignee: SAMSUNG SDI CO.,LTD. - CN114437091, 2022, A
[2]Current Patent Assignee: SAMSUNG SDI CO.,LTD. - US2023/117860, 2023, A1

Same Skeleton Products

Related Products

Historical Records

Purity	Size	Price	VIP Price	USA Stock *0-1 Day	Global Stock *5-7 Days	Quantity
{[ item.p_purity ]}	{[ item.pr_size ]}	{[ getRatePrice(item.pr_usd, 1,1) ]} {[ getRatePrice(item.pr_usd,item.pr_rate,item.mem_rate) ]}	{[ getRatePrice(item.pr_usd, 1,1) ]}	Inquiry {[ getRatePrice(item.pr_usd,item.pr_rate,item.mem_rate) ]} {[ getRatePrice(item.pr_usd,1,item.mem_rate) ]}	{[ item.pr_usastock ]}	Inquiry -	{[ item.pr_chinastock ]}	Inquiry -

[ CAS No. 89827-45-2 ] {[proInfo.proName]}

Quality Control of [ 89827-45-2 ]

Related Doc. of [ 89827-45-2 ]

Product Details of [ 89827-45-2 ]

Calculated chemistry of [ 89827-45-2 ]

Physicochemical Properties

Pharmacokinetics

Lipophilicity

Druglikeness

Water Solubility

Medicinal Chemistry

Safety of [ 89827-45-2 ]

Application In Synthesis of [ 89827-45-2 ]

[ 89827-45-2 ] Synthesis Path-Upstream 1~16

[ 89827-45-2 ] Synthesis Path-Downstream 1~72

Precautionary Statements-General

Prevention

Response

Storage

Disposal

Physical hazards

Health hazards

Environmental hazards

Inquiry

Precautionary Statements-General
Code	Phrase
P101	If medical advice is needed,have product container or label at hand.
P102	Keep out of reach of children.
P103	Read label before use
Prevention
Code	Phrase
P201	Obtain special instructions before use.
P202	Do not handle until all safety precautions have been read and understood.
P210	Keep away from heat/sparks/open flames/hot surfaces. - No smoking.
P211	Do not spray on an open flame or other ignition source.
P220	Keep/Store away from clothing/combustible materials.
P221	Take any precaution to avoid mixing with combustibles
P222	Do not allow contact with air.
P223	Keep away from any possible contact with water, because of violent reaction and possible flash fire.
P230	Keep wetted
P231	Handle under inert gas.
P232	Protect from moisture.
P233	Keep container tightly closed.
P234	Keep only in original container.
P235	Keep cool
P240	Ground/bond container and receiving equipment.
P241	Use explosion-proof electrical/ventilating/lighting/equipment.
P242	Use only non-sparking tools.
P243	Take precautionary measures against static discharge.
P244	Keep reduction valves free from grease and oil.
P250	Do not subject to grinding/shock/friction.
P251	Pressurized container: Do not pierce or burn, even after use.
P260	Do not breathe dust/fume/gas/mist/vapours/spray.
P261	Avoid breathing dust/fume/gas/mist/vapours/spray.
P262	Do not get in eyes, on skin, or on clothing.
P263	Avoid contact during pregnancy/while nursing.
P264	Wash hands thoroughly after handling.
P265	Wash skin thouroughly after handling.
P270	Do not eat, drink or smoke when using this product.
P271	Use only outdoors or in a well-ventilated area.
P272	Contaminated work clothing should not be allowed out of the workplace.
P273	Avoid release to the environment.
P280	Wear protective gloves/protective clothing/eye protection/face protection.
P281	Use personal protective equipment as required.
P282	Wear cold insulating gloves/face shield/eye protection.
P283	Wear fire/flame resistant/retardant clothing.
P284	Wear respiratory protection.
P285	In case of inadequate ventilation wear respiratory protection.
P231 + P232	Handle under inert gas. Protect from moisture.
P235 + P410	Keep cool. Protect from sunlight.
Response
Code	Phrase
P301	IF SWALLOWED:
P304	IF INHALED:
P305	IF IN EYES:
P306	IF ON CLOTHING:
P307	IF exposed:
P308	IF exposed or concerned:
P309	IF exposed or if you feel unwell:
P310	Immediately call a POISON CENTER or doctor/physician.
P311	Call a POISON CENTER or doctor/physician.
P312	Call a POISON CENTER or doctor/physician if you feel unwell.
P313	Get medical advice/attention.
P314	Get medical advice/attention if you feel unwell.
P315	Get immediate medical advice/attention.
P320
P302 + P352	IF ON SKIN: wash with plenty of soap and water.
P321
P322
P330	Rinse mouth.
P331	Do NOT induce vomiting.
P332	IF SKIN irritation occurs:
P333	If skin irritation or rash occurs:
P334	Immerse in cool water/wrap n wet bandages.
P335	Brush off loose particles from skin.
P336	Thaw frosted parts with lukewarm water. Do not rub affected area.
P337	If eye irritation persists:
P338	Remove contact lenses, if present and easy to do. Continue rinsing.
P340	Remove victim to fresh air and keep at rest in a position comfortable for breathing.
P341	If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing.
P342	If experiencing respiratory symptoms:
P350	Gently wash with plenty of soap and water.
P351	Rinse cautiously with water for several minutes.
P352	Wash with plenty of soap and water.
P353	Rinse skin with water/shower.
P360	Rinse immediately contaminated clothing and skin with plenty of water before removing clothes.
P361	Remove/Take off immediately all contaminated clothing.
P362	Take off contaminated clothing and wash before reuse.
P363	Wash contaminated clothing before reuse.
P370	In case of fire:
P371	In case of major fire and large quantities:
P372	Explosion risk in case of fire.
P373	DO NOT fight fire when fire reaches explosives.
P374	Fight fire with normal precautions from a reasonable distance.
P376	Stop leak if safe to do so. Oxidising gases (section 2.4) 1
P377	Leaking gas fire: Do not extinguish, unless leak can be stopped safely.
P378
P380	Evacuate area.
P381	Eliminate all ignition sources if safe to do so.
P390	Absorb spillage to prevent material damage.
P391	Collect spillage. Hazardous to the aquatic environment
P301 + P310	IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician.
P301 + P312	IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell.
P301 + P330 + P331	IF SWALLOWED: Rinse mouth. Do NOT induce vomiting.
P302 + P334	IF ON SKIN: Immerse in cool water/wrap in wet bandages.
P302 + P350	IF ON SKIN: Gently wash with plenty of soap and water.
P303 + P361 + P353	IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower.
P304 + P312	IF INHALED: Call a POISON CENTER or doctor/physician if you feel unwell.
P304 + P340	IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing.
P304 + P341	IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing.
P305 + P351 + P338	IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing.
P306 + P360	IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes.
P307 + P311	IF exposed: call a POISON CENTER or doctor/physician.
P308 + P313	IF exposed or concerned: Get medical advice/attention.
P309 + P311	IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician.
P332 + P313	IF SKIN irritation occurs: Get medical advice/attention.
P333 + P313	IF SKIN irritation or rash occurs: Get medical advice/attention.
P335 + P334	Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages.
P337 + P313	IF eye irritation persists: Get medical advice/attention.
P342 + P311	IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician.
P370 + P376	In case of fire: Stop leak if safe to Do so.
P370 + P378	In case of fire:
P370 + P380	In case of fire: Evacuate area.
P370 + P380 + P375	In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion.
P371 + P380 + P375	In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion.
Storage
Code	Phrase
P401
P402	Store in a dry place.
P403	Store in a well-ventilated place.
P404	Store in a closed container.
P405	Store locked up.
P406	Store in corrosive resistant/ container with a resistant inner liner.
P407	Maintain air gap between stacks/pallets.
P410	Protect from sunlight.
P411
P412	Do not expose to temperatures exceeding 50 oC/ 122 oF.
P413
P420	Store away from other materials.
P422
P402 + P404	Store in a dry place. Store in a closed container.
P403 + P233	Store in a well-ventilated place. Keep container tightly closed.
P403 + P235	Store in a well-ventilated place. Keep cool.
P410 + P403	Protect from sunlight. Store in a well-ventilated place.
P410 + P412	Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF.
P411 + P235	Keep cool.
Disposal
Code	Phrase
P501	Dispose of contents/container to ...
P502	Refer to manufacturer/supplier for information on recovery/recycling