Name: 2243-47-2|[1,1'-Biphenyl]-3-amine|98%
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1
[ 2113-58-8 ]
[ 2243-47-2 ]

Yield	Reaction Conditions	Operation in experiment
100%	With hydrogen;palladium 10% on activated carbon; In ethanol; for 3h;	Palladium on carbon (10%, 0.70 g, 0.658 mmol) was added to a Parr hydrogenator bottle. The bottle was purged with nitrogen. Next, 3- nitro-l,l'-biphenyl (10 g, 50.2 mmol) and 190 mL ethanol were added to the bottle. The material was hydrogenated on a Parr hydrogenator. After 3 h, the reaction mixture was filtered through Celite and the Celite washed with dichloromethane. The filtrate was evaporated, obtained a brown oil, 8.69 g, assume quantitative yield (8.49 g).
99.7%		Another batch of reaction was effected on the same scale except that 254 g (1.28 mol) of <strong>[2113-58-8]m-nitrobiphenyl</strong> was used, obtaining 215 g of m-aminobiphenyl (yield 99.7%).
94%	palladium; In ethyl acetate;	a) 3-phenylaniline To a stirring solution of <strong>[2113-58-8]3-nitrobiphenyl</strong> (1.2 g, 6.0 mmol) in ethyl acetate (25 mL) was added 10% Palladium on carbon (500 mg, 40% w/w). After stirring under a balloon of hydrogen for 24 h, the mixture was filtered through Celite and concentrated to yield the title compound as a white solid (0.956 g, 94%). MS (ESI): 170.0 (M+H)+.

16 g (95%)	palladium-carbon; In methanol; chloroform;	Example 1 Synthesis of 3-aminobiphenyl (1): The following compound is prepared: STR26 A mixture of <strong>[2113-58-8]3-nitrobiphenyl</strong> (20 g, 100 mmol) and 10% Pd/C (2 g) in MeOH/CHCl3 (300 mL, 1:1) is hydrogenated at 40 psi for 4 hours. The mixture is suction filtered through a layer of diatomaceous earth and washed with MeOH. The filtrate is evaporated to dryness and the solid is further dried under vacuum to give 16 g (95%) of 3-aminobiphenyl.
		(a) In a manner similar to that of Example 7(b), <strong>[2113-58-8]3-nitrobiphenyl</strong> (2.48 g) gives 1.77 g of 3-aminobiphenyl, mp 27.5-28.5 C.
	With hydrogen;palladium 10% on activated carbon; In methanol;	Example 11; 3-aminobiphenyl: <strong>[2113-58-8]3-nitrobiphenyl</strong> (500 mg, 2.5 mmol) and 10% palladium on carbon (267 mg, 2.5 mmol) were dissolved in methanol (1 mL) and purged with nitrogen and placed under an atmosphere of hydrogen overnight. The reaction mixture was filtered and evaporated to yield 326 mg of the desired amine, which was used directly in Example 12.

Reference： [1]Patent: WO2012/121936,2012,A2 .Location in patent: Page/Page column 77
[2]Journal of Medicinal Chemistry,2002,vol. 45,p. 2260 - 2276
[3]Patent: EP666298,1995,A2
[4]Patent: US2002/49316,2002,A1
[5]RSC Advances,2014,vol. 4,p. 33599 - 33606
[6]Catalysis science and technology,2018,vol. 8,p. 1454 - 1467
[7]Journal of Organic Chemistry,2014,vol. 79,p. 9433 - 9439
[8]Catalysis Letters,2014,vol. 144,p. 1258 - 1267
[9]New Journal of Chemistry,2018,vol. 42,p. 1373 - 1378
[10]Journal of the Chemical Society,1958,p. 1184,1187
[11]Chemische Berichte,1903,vol. 36,p. 4083
[12]Chemische Berichte,1904,vol. 37,p. 882
[13]Journal of the Chemical Society,1927,p. 3006
[14]Journal of the American Chemical Society,1954,vol. 76,p. 2997
[15]Bulletin of the Chemical Society of Japan,1975,vol. 48,p. 1868 - 1874
[16]Recueil des Travaux Chimiques des Pays-Bas,1963,vol. 82,p. 5 - 16
[17]Arzneimittel-Forschung/Drug Research,1972,vol. 22,p. 1399 - 1404
[18]Bioorganic and Medicinal Chemistry Letters,1996,vol. 6,p. 1479 - 1482
[19]Patent: US6004536,1999,A
[20]Patent: US6211220,2001,B1
[21]Patent: WO2008/13791,2008,A2 .Location in patent: Page/Page column 32
[22]Journal of Medicinal Chemistry,2009,vol. 52,p. 3703 - 3715
[23]ChemPlusChem,2020,vol. 85,p. 247 - 253
[24]Journal of Agricultural and Food Chemistry,2021,vol. 69,p. 12039 - 12047

2
[ 2243-47-2 ]
[ 20442-79-9 ]

Yield	Reaction Conditions	Operation in experiment
71.7%	With hydrogenchloride; potassium iodide; sodium nitrite; In water;	A 10-l reactor was charged with 775 ml of conc. hydrochloric acid, 775 ml of water, and 775 g of ice, and 125 g (0.740 mol) of m-aminobiphenyl was suspended therein. To the reactor maintained below 0C, 750 ml of an aqueous solution of 56.3 g (0.816 mol) sodium nitrite was added dropwise over 30 minutes and stirring was continued for a further 50 minutes at the temperature. To the resulting diazonium salt aqueous solution maintained below 0C, 1250 ml of an aqueous solution of 185 g (1.12 mol) potassium iodide was added dropwise over one hour. After addition, stirring was continued for one hour at the temperature and then for 2 hours at room temperature. The reaction solution was extracted with ethyl acetate. The organic layer was washed with water, dried over magnesium sulfate, and distilled of the solvent, obtaining a crude crystal. Another batch of reaction was effected on the same scale. The resulting crude crystals were combined together and purified through a silica gel column with n-hexane, obtaining 297 g of m-iodobiphenyl (yield 71.7% for the two batches combined).
	With hydrogenchloride; potassium iodide; sodium nitrite; In water;	Example 3 A 10-l reactor was charged with 155 ml of conc. hydrochloric acid, 155 ml of water, and 155 g of ice, and 25 g (0.148 mol) of m-aminobiphenyl was suspended therein. To the reactor maintained below 0C, 150 ml of an aqueous solution of 11.3 g (0.164 mol) sodium nitrite was added dropwise over 30 minutes and stirring was continued for a further 50 minutes at the temperature. To the resulting diazonium salt aqueous solution maintained below 0C, 250 ml of an aqueous solution of 37 g (0.223 mol) potassium iodide was added dropwise over one hour. After addition, stirring was continued for one hour at the temperature and then for 2 hours at room temperature. The reaction solution was extracted with ethyl acetate. The organic layer was washed with water, dried over magnesium sulfate, and distilled of the solvent, obtaining a crude crystal. The crude crystal was purified through a silica gel column with n-hexane, obtaining 28 g of m-iodobiphenyl.

Reference： [1]Organic Letters,2014,vol. 16,p. 1594 - 1597
[2]Patent: EP666298,1995,A2
[3]Journal of the Chemical Society,1931,p. 1111,1112
[4]Bulletin of the Chemical Society of Japan,1975,vol. 48,p. 1868 - 1874
[5]Patent: EP666298,1995,A2

3
[ 7428-91-3 ]
[ 2243-47-2 ]

Reference： [1]Journal of Organic Chemistry,1992,vol. 57,p. 1986 - 1990

4
[ 4455-13-4 ]
[ 2243-47-2 ]
[ 80726-52-9 ]
[ 80726-53-0 ]

Reference： [1]Journal of Medicinal Chemistry,1982,vol. 25,p. 446 - 451

5
[ 4455-13-4 ]
[ 2243-47-2 ]
[ 90750-99-5 ]
[ 90750-98-4 ]

Reference： [1]Journal of Medicinal Chemistry,1982,vol. 25,p. 446 - 451

6
[ 6639-36-7 ]
[ 7428-91-3 ]
[ 2243-47-2 ]

Reference： [1]Journal of Organic Chemistry,1992,vol. 57,p. 1986 - 1990

7
[ 2243-47-2 ]
[ 109221-88-7 ]

Reference： [1]Bioorganic and Medicinal Chemistry Letters,1996,vol. 6,p. 1479 - 1482

8
[ 108-42-9 ]
[ 98-80-6 ]
[ 2243-47-2 ]

Yield	Reaction Conditions	Operation in experiment
98%	With chloro[(di(1-adamantyl)-N-butylphosphine)-2-(2-aminobiphenyl)]palladium(II); potassium carbonate In N,N-dimethyl-formamide at 80℃; Inert atmosphere;	3 3-amino-biphenyl preparation Under nitrogen, 1L four-mouth bottle, mechanical stirring, adding 500mLN, N-dimethyl formamide (DMF), 50g3-aminochlorobenzene, 57.3g phenyltheophylline boric acid, 108.4g potassium carbonate, 0.26g palladium catalyst 2GAd2 (n-bu) PPd (Chloro [(di (1-adamantyl)-N-butylphosphine) - 2 - (2-aminobiphenyl)] palladium (II)), in 80 °C reaction sleepovers. Plus 20g naoh 100 ml aqueous solution quenching, 300 ml ethyl acetate extraction, the organic phase exsolution, to obtain crystal micro purple 3-aminobiphenyl 65g, the yield is 98%.
93%	With potassium carbonate In ethanol; water at 50℃; for 5h; Inert atmosphere;
90%	With tetrabutylammomium bromide; potassium carbonate In water at 60℃; for 6h;

83%	With potassium carbonate In water; N,N-dimethyl-formamide at 80℃; for 4h; Schlenk technique;	2.4. catalytic performance for suzuki cross coupling reactions General procedure: In the Suzuki cross coupling reactions, a mixture of phenyl-boronic acid (0.6 mmol, 1.2 equiv), aryl halide (0.5 mmol, 1 equiv),K2CO3(1 mmol, 2 equiv), and Pd-Cu NWs (4 mg) were placedin a Schlenk tube (10 mL), which contained 2 mL of N,N-dimethylformamide (DMF) and water (H2O) (v/v = 1/1). Themixture was then stirred for a desired period of time at a selectedtemperature, and the reaction was monitored by thin layer chro-matography (TLC). Afterward, the reaction mixture was cooleddown to room temperature. And the catalyst was recovered byfiltration, followed by washing thoroughly with ethyl acetate andwater. The combined organic layer was dried by Na2SO4, and thefiltered residue was purified by flash column chromatography onsilica gel. As for the recycling experiments, we conducted severalparallel experiments under identical conditions and recycled thecatalyst for next run test. The target reactions would get supple-ment of catalysts from the other parallel experiments to make surethe scale of catalyst with 4 mg.
79%	With potassium phosphate; [1,1'-bis(diphenylphosphino)ferrocene]nickel(II) chloride In 1,4-dioxane at 95℃; for 16h;
72%	With (Fe₃O₄ nanoparticles)(at)PEG/Cu-Co In water at 80℃; for 4h; Green chemistry;

Reference： [1]Current Patent Assignee: BEIJING GREENCHEM TECH - CN105439871, 2016, A Location in patent: Paragraph 0076; 0077; 0078; 0079
[2]Lee, Dong-Hwan; Choi, Minkee; Yu, Byung-Woo; Ryoo, Ryong; Taher, Abu; Hossain, Shahin; Jin, Myung-Jong [Advanced Synthesis and Catalysis, 2009, vol. 351, # 17, p. 2912 - 2920]
[3]Jin, Myung-Jong; Lee, Dong-Hwan [Angewandte Chemie - International Edition, 2010, vol. 49, # 6, p. 1119 - 1122]
[4]Lv, Jing-Jing; Wang, Zheng-Jun; Feng, Jiu-Ju; Qiu, Renhua; Wang, Ai-Jun; Xu, Xinhua [Applied Catalysis A: General, 2016, vol. 522, p. 188 - 193]
[5]Indolese, Adriano F. [Tetrahedron Letters, 1997, vol. 38, # 20, p. 3513 - 3516]
[6]Allahresani, Ali; Kazemnejadi, Milad; Nasseri, Mohammad Ali; Rezazadeh, Zinat [Dalton Transactions, 2020, vol. 49, # 30, p. 10645 - 10660]

9
[ 591-19-5 ]
[ 98-80-6 ]
[ 2243-47-2 ]

Yield	Reaction Conditions	Operation in experiment
100%	With sodium carbonate In methanol Heating / reflux;	1.2.i To a solution of phenylboronic acid (10.5 g, 86.4mmol) in 100 niL of MeOH, Na2CO3 (18.3 g, 172.2mmol) and 3-bromoaniline (14.9 g, 86.4mmol) were added sequentially. To the so obtained suspension, Pd(OAc)2 (500mg, 2.16mmol) was added and the reaction was heated to reflux of solvent until a black suspension appeared; the suspension was cooled at room temperature, diluited with MeOH and the black precipitate was removed by filtration. The filtrate was concentrated under reduced pressure and the residue was splitted in water and CH2Cl2. The organic phase was dried on Na2CO3 and concentrated under reduced pressure to give 3-phenylaniline as a brown oil (14.6 g, yield 100%). 1H-NMR (CHCl3): 6.68-6.73 (IH5 m), 6.93-6.95 (IH, m), 7.03-7.08 (IH, m), 7.24-7.60 (4H, m), 7.64-7.68 (2H, m).13C-NMR (CHCl3): 114.5, 114.7, 118.2, 127.7, 129.2, 130.3, 141.9, 143.0, 147.3.
100%	With palladium diacetate; sodium carbonate In methanol Reflux; Inert atmosphere;	A Step A: 3-Phenylaniline To a solution of phenylboronic acid (12.19 g, 100 mmol) in MeOH (150 mL) were added Na2C03 (21.2 g, 200 mmol) and 3-bromoaniline (17.2 g, 100 mmol) sequentially. To the suspension was added Pd(OAc (562 mg, 2.50 mmol) and the reaction was heated to reflux until a black suspension appeared. The suspension was cooled to room temperature, diluted with MeOH, and the black precipitate was removed by filtration. The filtrate was concentrated to dryness and the residue was taken up in water and DCM. The organic phase was collected, dried over anhydrous Na2CC>3, and concentrated to dryness to give the title Compound as a brown oil (18.37 g, 100.0% yield).
100%	With palladium diacetate; sodium carbonate In methanol Reflux;	[1,1‘-biphenyl]-3-amine To a solution of phenylboronic acid (12.193 g, 100.00 mmol) in MeOH (150 mL) were added sequentially Na2C03 (21.198 g, 200.00 mmol) and 3-bromoaniline (17.202 g, 100.00 mmol), and then Pd(OAc)2 (562 mg, 2.50 mmol) was added and the reaction was heated to reflux until a black suspension appeared. The reaction was cooled to room temperature, diluted with MeOH, and the black precipitate was removed by filtration. The filtrate was concentrated to dryness and the residue was added to water and DCM. The organic phase was collected, dried over anhydrous Na2SC>4, and concentrated to dryness to give the title compound (18.373 g, 100.00% yield) as a brown oil. MS (ESI): mass calcd. for C12HnN, 169.22; m/z found, 170.0 [M+H]+.

100%	With palladium diacetate; sodium carbonate In methanol Reflux;	A Step A: 3-Phenylaniline. To a solution of phenylboronic acid (12.19 g, 100 mmol) in MeOH (150 mL) were added Na2CO3 (21.2 g, 200 mmol) and 3-bromoaniline (17.2 g, 100 mmol) sequentially. To the suspension was added Pd(OAc)2 (562 mg, 2.50 mmol) and the reaction was heated to reflux until a black suspension appeared. The suspension was cooled to room temperature, diluted with MeOH, and the black precipitate was removed by filtration. Thefiltrate was concentrated to dryness and the residue was taken up in water and DCM. Theorganic phase was collected, dried over anhydrous Na2CO3, and concentrated to dryness to give the title compound as a brown oil (18.37 g, 100.0% yield).
100%	With palladium diacetate; sodium carbonate In methanol Reflux;	Intermediate 46: [1, 1'-Biphenyl] -3-amine To a solution of phenylboronic acid (12.193 g, 100.00 mmol) in MeOH (150 mL) were added sequentially Na 2CO 3 (21.198 g, 200.00 mmol) and 3-bromoaniline (17.202 g, 100.00 mmol), and then Pd (OAc) 2 (562 mg, 2.50 mmol) was added and the reaction was heated to reflux until a black suspension appeared. The reaction was cooled to room temperature, diluted with MeOH, and the black precipitate was removed by filtration. The filtrate was concentrated to dryness and the residue was added to water and DCM. The organic phase was collected, dried over anhydrous Na 2SO4, and concentrated to dryness to give the title compound (18.373 g, 100.00% yield) as a brown oil. MS (ESI) : mass calcd. for C 12H 11N, 169.22 m/z found, 170.0 [M+H] +.
99%	With potassium carbonate In toluene at 100℃; for 12h; Schlenk technique;	2.11 General procedure for Suzuki coupling General procedure: The catalyst (0.02% mol), aryl halide (1.12mmol), phenyl boronic acid (1.87mmol), K2CO3 (3.75mmol), 6mL of toluene were mixed in Schlenk tube at 100°C for 12h. Then the reaction media was cooled to the room temperature and extracted with 10mL of water (3 times). With help of a separatory funnel the organic phase was separated and dried with MgSO4. The dried products were shipped to analysis by 1H NMR and GC-MS.
99%	With potassium phosphate; palladium diacetate In water at 100℃; for 1h; Inert atmosphere; Green chemistry;
99%	With potassium carbonate In water at 70℃; for 0.5h; Inert atmosphere; Green chemistry;
99%	With potassium carbonate In ⁽²⁾H₈-toluene at 100℃; for 24h;
98%	With potassium carbonate In neat (no solvent) at 50℃; for 0.0666667h; Microwave irradiation;	2.9. General synthesis of Suzuki coupling reactions General procedure: A mixture of the catalyst (0.02 mol%), aryl halide (1.12 mmol), phenyl boronic acid (1.87 mmol), and K2CO3(3.75 mmol) was irritated at 50°C and 400 W for 4 min without solvent under microwave irradiation. After these reactions were completed, the mixture was extracted with toluene-water (4:2, v/v). Consequently, the organic phase was separated and dried with MgSO4. Finally, the obtained biaryl products were characterized by 1H NMR and GC-MS.
97%	With Pd(II)/C; sodium carbonate; triphenylphosphine In 1,2-dimethoxyethane at 80℃; for 9h;
97%	With tetrabutyl ammonium fluoride; potassium carbonate In water at 100℃; for 2h;
96%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; sodium carbonate In ethanol; water Reflux; Inert atmosphere;
96%	With potassium carbonate In water at 50℃; for 2.5h;	2.4 Synthesis of Biaryls 3 General procedure: In a test tube equipped with a magnetic stirrer bar, thearyl halide 1 (1 mmol) was mixed with phenyl boricacid 2 (1.2 mmol), K2CO3(2 mmol), and the Pd-catalyst(0.1mol% Pd) in 2 ml of H2Oin air. The reaction mixturewas then stirred at 50 °C for appropriate time. After completionof the reaction, the catalyst was removed by magnetand washed with ethanol and water (3 × 5 ml). The aqueouslayer was extracted with chloroform, then organic layerdried over anhydrous MgSO4.The solvent was evaporatedunder reduced pressure to give the corresponding biarylcompounds. All the products were previously reported [5,8-12] and were confirmed by the spectroscopic methodusing 1H and 13C NMR (see supporting information).
96%	With magnesium hydroxide; potassium hydroxide; barium(II) hydroxide; calcium hydroxide In water at 20℃; for 2.5h;
93%	With potassium carbonate In water at 70℃; for 2h; Inert atmosphere;	4.3. General procedure for the Suzuki reaction General procedure: In a typical run, h-BN(at)Fur(at)Pd(OAc)2 (0.05 mmol) was added to a mixture of arylboronic acid 1 (1.0 mmol), aryl bromide 2 (1.5 mmol) and K2CO3 (1.5 mmol) in water (1 mL). The resulting mixture was stirred at 70 °C under Ar protection, and the progress of the reaction was monitored by TLC. After completion of the reaction, ethyl acetate was added to the reaction mixture and the catalyst was separated. The organic phase was washed with water, dried over anhydrous Na2SO4 and the solvent was evaporated under reduced pressure. Finally, the residue was isolated by chromatography on a column of silica gel to afford the corresponding product 3.
93%	With 0.1 % Cu/C; potassium carbonate In water at 50℃; for 3.5h; Green chemistry;	2.2. Synthesis of biaryls 3 General procedure: In a test tube, 1.0 mmol of aryl halides 1, 1.2 mmol of phenylboronic acid 2 were mixed together and then 2.0 mmol of K2CO3, and the Cu/Cnano-catalyst (0.1 mol % Cu) in 2 mL of H2O, were added in air. The reaction mixture was then stirred at 50 °C for appropriate time. After completion of the reaction (monitored by TLC), the catalyst was removed by simple filtration. The recycled catalyst was was hed with ethanol and water (3 × 5 mL) and dried at 60 °C in oven for further use. The aqueous layer was extracted with ethyl acetate, and organic layer dried over anhydrous MgSO4. The solvent was evaporated under reduced pressure to give the corresponding biaryl compounds.
93%	With Co(II) creatine complex immobilized on functionalized silica-coated Fe₃O₄ nanoparticles In water at 75℃; for 2h; Green chemistry;	General procedure for the C-C bond formation catalyzed by Fe3O4SiO2-CT-Co General procedure: To a solution of phenylboronic acid derivatives (1.2mmol), aryl halides (1.0mmol), KOH (2.5mmol), and water (3.0ml), 1.5mol % of Fe3O4SiO2-CT-Co was added at 75°C with stirring under oil bath condition. After the fnalization of the reaction, the Co-coordinated MNPs catalyst (Fe3O4SiO2-CT-Co) was separated from the reaction mixture and washed with EtOH and H2O and, fnally, dried at 60°C in a vacuum oven for 12h. Subsequently, the water as a green solvent was separated from the reaction mixture by rotary evaporator and the prepared Suzuki products have been obtained in pure products with good to excellent isolated yields. Some selected products have been characterized with H and C NMR, and the data have been added in supporting material section.
92%	With potassium phosphate In ethanol at 20℃; for 2h;
92%	With potassium phosphate monohydrate In water; toluene at 95℃; for 2.5h; Inert atmosphere;
92%	With potassium carbonate In toluene at 100℃; for 48h; Schlenk technique;	General procedure for Suzuki coupling General procedure: The catalyst, (OCMCS-3aPd or OCMCS-4aPd), 0.04 (% mol), 1.2 mmol aryl halides, 1.87 mmol phenyl boronic acid, 3.75 mmol K2CO3 and 6 mL toluene were put into a Schlenk tube and stirred at 100°C for 48 h (Scheme 1). Reaction was followed by TLC. Then the reaction media was allowed to cool at room temperature. The mixture was extracted with 10 mL of water and the aqueous and organic phases were separated in a separatory funnel. The extraction was repeated three times. MgSO4 was added into the organic phase to ensure complete water removal. The products were analyzed and characterized with GC-MS and 1H NMR.
92%	With sodium acetate In 1,4-dioxane at 95℃; for 8h; Inert atmosphere; Schlenk technique;
90%	With potassium carbonate In water at 70℃; for 2h; Inert atmosphere;
89%	With potassium carbonate; sodium chloride for 0.666667h;
86%	With C₃₄H₂₆Cl₂Fe₂N₂O₆Pd₂S₂^(2-)*2Na⁽¹⁺⁾; sodium hydroxide In water at 60℃; for 4h;
85%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; sodium carbonate In ethanol; water; toluene for 18h; Reflux; Inert atmosphere;
85%	With potassium carbonate at 50℃; for 0.0833333h; Microwave irradiation;	2.4.2. General procedure General procedure: The mixture of phenyl boronic acid (1.75 mmol), aryl halide(1.12 mmol), K2CO3(3.75 mmol) and the catalyst (5 × 10-3% mol)in a Schlenk tube was exposed to the microwave irradiation (at 400 W) at 50C for 5 min. The progress of the reactions was moni-tored by thin layer chromatography (TLC). Then, reaction mediumwas extracted with toluene-water mixture (2:1 v:v) and the organicphase was dried with addition of MgSO4. Finally, chemical identi-fication of the biaryls was done on a GC-MS.
85%	With oxygen; potassium carbonate In neat (no solvent) at 50℃; for 0.0833333h; Microwave irradiation; Green chemistry;	2.4.2 General procedure for microwave assisted synthesis of biaryls General procedure: Upon determination of the optimum conditions, we employed the following procedure for the synthesis of biaryls. Phenyl boronic acid (1.75 mmol), aryl halide (1.12 mmol), K2CO3 (3.75 mmol) and the catalyst (1.5×10-3mol %) were put into a Schlenk tube and exposed to 400 W microwave irradiation for 5 min at 50 °C in solvent-free medium under oxygen atmosphere. Biaryl products were extracted into organic phase using toluene-water extraction mixture (2:1 v:v). The organic phase containing the product was separated with a separatory funnel. To remove water remaining in the organic phase, a drying agent (MgSO4) was added into the organic phase. The anhydrous organic phase was subsequently evaporated to eliminate toluene. Finally, the biaryl compounds were dissolved in acetone and shipped to GS-MS analysis.
85%	With potassium carbonate In neat (no solvent) at 50℃; for 0.1h; Schlenk technique; Microwave irradiation; Green chemistry;
85%	With potassium phosphate In 1,4-dioxane at 80℃; for 1.5h;
83%	With palladium nanoparticles supported on Fe₃O₄ loaded Schiff base modified kaolin In neat (no solvent) for 0.1h; Alkaline conditions; Microwave irradiation; Green chemistry;	2.4. General procedure for Suzuki coupling reactions General procedure: The mixture containing Pd NPsKao/Fe3O4/Pyr (0.025 mol %), arylhalide (1 mmol), Na2CO3 (3.5 mmol) and phenyl boronic acid (1.8mmol) was subjected to microwave irradiation for 6 min. Upon thecompletion of the reaction, the mixture was extracted with water:toluene (1:2) three times. The organic phase containing biaryls wasevaporated and the product was characterized by GC/MS analysis.
80%	With potassium carbonate In neat (no solvent) at 50℃; for 0.0666667h; Microwave irradiation; Green chemistry; chemoselective reaction;	2.4. Suzuki coupling reaction General procedure: Base system, reaction time, and catalysts amount parameters must be optimized to obtain C-C coupling reactions with high selectivity. Therefore, coupling reaction of 4-bromoanisol with phenylboronic acid was selected as the model reaction, and optimum conditions were determined for coupling reaction in the presence of biomaterial supported Pd catalyst. To determine the optimum catalyst amount, biomaterial supported Pd catalyst was used at different loading catalyst (2.5, 5.0,10.0, 20.0) × 10-3 mol% under microwave irradiation at 400 W insolvent insolvent-free reaction mixture (50C). Reaction time was investigated from 1 min to 5 min, and NaOH, K2CO3, KOH, and Cs2CO3 base systems were examined for optimum coupling reaction condition. Different aryl halides (1.12 mmol), K2CO3 (3.75 mmol), phenylboronic acid (1.87 mmol), and biomaterial supported Pd catalyst (0.01% mol) were mixed, and the reaction was allowed under microwave irradiation at 400 W in solvent-free media for 4 min (Scheme 2). At the end of the reaction period, the product was extracted with toluene:water (4:2, v:v). Organic phase was separated, and MgSO4 was added to remove water. The chemical identifications of synthesized biaryls were illuminated with 1H NMR and gas chromatography-mass spectroscopy (GC-MS) analyses. At the end of the coupling reaction, biomaterial supported Pd catalyst was filtered and washed with hot water and methanol to reactivate the biocatalyst. Then, the same biomaterial supported Pd catalyst was used for recycling experiments for model reaction under optimum reaction conditions for 10 times. Leaching test was applied to supernatant of all recycle experiments to determine Pd ion in the solution.
80%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate In 1,4-dioxane; water; toluene for 4h; Reflux;	4.4-4 Intermediate 4-d was synthesized according to Reaction Formula 19 General procedure: 30 g (174 mmol) of 3-bromoaniline in a 1 L reactor,Phenylboronic acid 25.5 g (209 mmol),Tetrakis(triphenylphosphine)palladium 4 g (3 mmol), potassium carbonate 48.2 g (349 mmol),150 ml of 1,4-dioxane, 150 ml of toluene,90 mL of distilled water was added and the mixture was stirred under reflux for 4 hours.After the reaction is completed, the layers are separated at room temperature,After concentrating the organic layer under reduced pressure,Separation by column chromatography gave 24 g of .(Yield 80%)
80%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate In 1,4-dioxane; water; toluene for 4h; Reflux;	4-4 Intermediate 4-d was Synthesized by Reaction 19: 3-Bromoaniline (30 g, 174 mmol), phenylboronic acid (25.5 g, 209 mmol), tetrakis(triphenylphosphine)palladium (4 g, 3 mmol), potassium carbonate (48.2 g, 349 mmol), 1,4-dioxane (150 mL), toluene (150 mL), and distilled water (90 mL) were placed in a 1 L reactor. The mixture was refluxed with stirring for 4 h. After completion of the reaction, the reaction mixture was allowed to stand at room temperature for layer separation. The organic layer was concentrated under reduced pressure and purified by column chromatography to afford Intermediate 4-d (24 g, yield 80%).
80%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate In 1,4-dioxane; water; toluene for 4h; Reflux;	4.4-4 [0118] 3-Bromoaniline (30 g, 174 mmol), phenylboronic acid (25.5 g, 209 mmol), tetrakis(triphenylphosphine)palladium (4 g, 3 mmol), potassium carbonate (48.2 g, 349 mmol), 1,4-dioxane (150 mL), toluene (150 mL), and distilled water (90 mL) were placed in a 1 L reactor. The mixture was refluxed with stirring for 4 h. After completion of the reaction, the reaction mixture was allowed to stand at room temperature for layer separation. The organic layer was concentrated under reduced pressure and purified by column chromatography to afford Intermediate 4-d (24 g, yield 80%).
78%	With potassium carbonate In water at 60℃; for 0.5h; Sonication; Green chemistry;	2.4 General procedure of C-C coupling reactions General procedure: The mixture of 1.0 mmol aryl halides, 1.8 mmol phenyl boronic acid, 3.5 mmol base, 1x10-2 mmol Pd NPsCMC/AG and 6 mL of water were sonicated at 60°C for 30 min. Formation of biphenyl compounds was followed by thin layer chromatography. After the coupling reactions, the reaction mixture was extracted with toluene. Organic phase, which containing biphenyl compounds, was separated with separation funnel and desired coupling products were obtained by evaporating of the solvent.
78%	With potassium carbonate In neat (no solvent) for 0.0833333h; Microwave irradiation; Schlenk technique; Green chemistry;	2.2.4. General procedure for Suzuki coupling reactions General procedure: In the process of determination of the fabricated catalyst efficiencyin Suzuki coupling reactions, microwave irradiation technique,which is very fast, easy to use, highly productive andnontoxic, was used. Firstly, the reaction of phenylboronic acid and4-iodoanisol was selected as the model coupling reaction for thesynthesis of biaryl compounds by Suzuki coupling reactions. Then,the effects of catalyst loading, reaction time, base type, and microwaveirradiation power on the biaryl product yield wereinvestigated on the chosen model coupling reaction. After the optimumreaction conditions were found, the general method whichwas performed for the fabrication of different biaryls by Suzukicoupling reactions was as follows: 1.87 mmol of phenyl boronicacid, 1.12 mmol of the selected aryl halide, 3.75 mmol of potassiumcarbonate, and 0.007 mol% of Pd NPsP(3-MPAP) were added in aSchlenk tube. The coupling reactions were performed in solventfreemedium using 400W microwave irradiation for 5min. Theobtained mixture was cooled to room temperature (RT) at the endof the reaction. 5mL toluene was added on the cooled mixture andit was filtered. Then, the filtrate was extracted with 5mL watertwice. MgSO4 was added on the separated organic phase whichcontains biaryl product to completely eliminate water. Then,toluene in the obtained product was evaporated at room temperature.Finally, the product yield was calculated and its chemicalstructure was identified by GC/MS analysis.
76%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; sodium carbonate In methanol at 70℃; for 24h; Inert atmosphere;	1.1. General Procedure for Suzuki coupling reactions General procedure: To a solution of phenylboronic acid (1 equiv.) in MeOH were added, Na2CO3 (2 equiv.) and 3-bromoaniline (1 equiv.). Pd(OAc)2 or Pd(PPh3)4 (equiv. varied) was added and the reaction mixture heated at reflux for several hours at 70 °C or stirring in a microwave at 100 °C. The solution was then cooled to r.t, diluted with methanol and filtered through a pad of celite to remove the black precipitate. The filtrate was then concentrated in vacuo and the residual product was then partitioned between water (15 mL) and DCM (15 mL). The organic phase was removed and the aqueous phase was further extracted with DCM (2 × 15 mL). The organic fractions were combined, dried over anhydrous MgSO4, filtered and evaporated to dryness to give the crude product. The resulting oily residue was purified using flash column chromatography and the major product fractions were evaporated to dryness to afford the title compound. The following compounds were prepared in this manner.
73%	With potassium carbonate In neat (no solvent) at 50℃; for 0.0666667h; Microwave irradiation; Green chemistry;	3.1.2. General procedure for the Suzuki coupling reaction General procedure: Phenyl boronic acid (1.75 mmol), aryl halide (1.12 mmol), K2CO3(3.75 mmol) and the catalyst (0.02%) were mixed without usingany solvent and subsequently the mixture was exposed to themicrowave irradiation (at 400 W) at 50C for 4 min. After thereaction was terminated, the organic phase was extracted fromthe mixture into toluene-water (4:2 v:v). To ensure the completeremoval of water from the organic phase, MgSO4was added intothe organic phase. The chemical composition of the synthesizedbiaryls in the organic phase were analysed by using GC-MS AgilentGC-7890 A- MS 5975.
72%	With potassium carbonate at 50℃; for 0.1h; Microwave irradiation; Schlenk technique;
72%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; sodium carbonate In methanol for 12h; Reflux;	2 4.1.1. General procedure for the Suzuki coupling reaction to obtaincompounds 4a-c General procedure: To a solution of phenylboronic acid (4.0 mmol) in 10 mL ofMeOH, Na2CO3 (8.0 mmol) and 3-bromoaniline (4.0 mmol) wereadded sequentially. To this suspension, Pd tetrakis (0.14 mmol)was added and the reaction was heated to reflux for 12 h; the suspensionwas cooled at room temperature, diluted with MeOH andthe black precipitate was removed by filtration. The filtrate was diluted with water and extracted with CH2Cl2 (3 10 mL). Theorganic phase was dried on Na2SO4 and concentrated underreduced pressure.
72%	With potassium carbonate for 0.0833333h; Schlenk technique; Microwave irradiation; Green chemistry;	2.5. General synthesis procedure for Suzuki-Miyaura reactions General procedure: Aryl halide (1.0 mmol), phenylboronic acid (1.8 mmol), K2CO3 (3.5 mmol) and Pd NPs(at)Fe3O4/CS-AG microcapsules(1.5×10-2 mmol) were placed into a Schlenk tube and the mixture was subjected to microwave irradiation at 400W for 5 min. The mixture was then diluted with water and Pd NPs(at)Fe3O4/CS-AG microcapsules were collected by an external magnet and the filtrate was extracted with toluene three times. Coupled products were obtained by evaporation of the organic phase and then characterized by GC/MS.
70%	With potassium carbonate In neat (no solvent) for 0.1h; Schlenk technique; Microwave irradiation; Green chemistry;	2.6 General method For Suzuki-Miyaura Coupling Reactions General procedure: A mixture of Pd NPsCS-AC/Fe3O4 (1.5 × 10-3 mmol),phenyl boronic acid (1.8 mmol), aryl halides (1.0 mmol),K2CO3(3.5 mmol) were added to a Schlenk tube, and it was heated under microwave irradiation at 400 W for 6 min.After the completion of coupling reaction, the mixture was cooled at room temperature, and it was extracted with water:toluene (1:2 v/v). Finally, desire biaryls were collected by evaporation of organic phase under reduced pressure and characterized by GC/MS analyses.
68.9%	With bis-triphenylphosphine-palladium(II) chloride; sodium carbonate In ethanol; water; toluene Inert atmosphere; Reflux;
62.3%	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium carbonate In 1,4-dioxane; water at 80℃; for 8h; Inert atmosphere;
62.3%	With potassium carbonate In 1,4-dioxane; water at 80℃; for 8h; Inert atmosphere;	65.a Example 65 (a) Compound 65A (212mg, 1.232mmol), phenylboronic acid (100mg, 0.821mmol), potassium carbonate (227mg, 1.643mmol) dissolved in 10ml 1.4-dioxane: water = 4:1, ventilated with N2 After 1 min, Pa(dppf)Cl2 (67mg, 0.082mmol) was added, and after N2 aeration for 1 min, the reaction was carried out at 80°C for 8 hours, and the reaction was monitored with a TLC plate. After the reaction was completed, 50mlH2O/50ml*2DCM was extracted, and the organic layers were combined. Wash once with 100ml of saturated brine, dry with anhydrous sodium sulfate, evaporate the solvent, and purify the organic phase silica gel with a flash chromatography column using a gradient of EA/PE=10-50% to obtain 87mg of orange oily liquid, which is Compound 65B, the yield was 62.3%.
	With triphenylphosphine
	Stage #1: m-Bromoaniline; phenylboronic acid With sodium carbonate; triphenylphosphine In propan-1-ol; water for 0.75h; Heating / reflux; Stage #2: With hydrogenchloride In diethyl ether; hexane; isopropyl alcohol Stage #3: With sodium hydroxide In tert-butyl methyl ether; water	10.A Example 10; 2-BUTYL-L- (3-METHANESULFONYLPROPYL)-7-PHENYL-LH-IMIDAZO [4,5-c] quinolin-4- amine; Part A A solution of 3-bromoaniline (344 g, 2.00 mol) and phenyl boronic acid (268 g, 2.2 mol) in n-propanol (3.5 L) was sparged with N2 for 10 min. To this solution was added Pd (OAc) 2 (1.35 g, 6.0 mmol), triphenylphosphine (4.72 g, 18.0 mmol), Na2C03 (1.2 L of a 2 M solution, 2.4 mol), and H2O (700 mL). The reaction was brought to reflux under a N2 atmosphere over a period of 45 min and then cooled to RT and transferred to a separatory funnel. The clear aqueous layer was drawn off (1. 1 L), and the organic layer was washed with brine (3X500 mL). The organic layer was treated with charcoal (90 g of Darco G-60) and MGS04 (160 g) and was filtered through CELITE filter agent, washing with ethyl acetate. The filtrate was concentrated (420 g of an orange oil), dissolved in 1.1 L of 1/1 hexane/isopropanol, filtered to remove insoluble solid and then diluted with an additional 1.9 L of 1/1 hexane/isopropanol. The resulting solution was cooled in an ice bath and then anhydrous HC1 in ether (1.05 L of a 2 M solution, 2.1 mol) was added. The solid was collected by filtration, washed with 700 ML diethyl ether (ET20), and dried at RT in a vacuum oven to obtain 345 g of the HC1 salt of biphenyl-3-ylamine as yellow crystals. The free base was obtained by shaking the solid with TERT-BUTYL methyl ether and 1 N NAOH followed by isolation in the usual fashion. 'H NMR (300 MHz, CDC13) : consistent with literature data (C. N. Carrigan et al., J. Med. CLIENT., 45, 2260-2276 (2002)).
78 %Chromat.	With tetrabutylammomium bromide; potassium carbonate In water at 80℃; for 12h;
21 %Chromat.	With palladium diacetate In water at 100℃; Inert atmosphere;
93 %Chromat.	With tetrabutylammomium bromide; potassium carbonate In ethanol; water at 20℃; for 2h;	Suzuki Coupling Reaction; General Procedure General procedure: Aryl halide (1.0 mmol), arylboronic acid (1.5 mmol), TBAB (0.5 mmol), K2CO3 (2.0 mmol), and catalyst 4 (0.1 mol%) were mixed in H2O/EtOH (2 mL/2 mL). The mixture was stirred at r.t. in an air atmosphere. The reaction progress was monitored by GC. After reaction completion, the mixture was diluted with H2O and Et2O. The organic layer was separated from mixture, dried over anhydrous MgSO4, and concentrated under reduced pressure. The crude reaction product was purified using column chromatography on silica gel to afford the corresponding product in good yield.
92 %Chromat.	With triethylamine In water at 50℃; for 6h;
	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; sodium carbonate In methanol for 12h; Reflux;
	With C₂₁H₂₈N₈O₄Pd⁽²⁺⁾2Cl^(1-); potassium carbonate In ethanol; water at 20℃; for 6h; Sealed tube;

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10
[ 2243-47-2 ]
[ 175422-04-5 ]
biphenyl-3-yl-(2,6-dibromo-pyridin-4-yl)-amine [ No CAS ]

Reference： [1]Tetrahedron Letters,2007,vol. 48,p. 113 - 117

11
[ 42466-67-1 ]
[ 2243-47-2 ]
3-(biphenyl-3-ylamino)-2-cyano-acrylic acid ethyl ester [ No CAS ]

Reference： [1]Journal of Medicinal Chemistry,2007,vol. 50,p. 186 - 191

12
[ 5751-20-2 ]
[ 2243-47-2 ]
[ 960243-28-1 ]

Yield	Reaction Conditions	Operation in experiment
92%	In diethylene glycol dimethyl ether; for 18h;Heating / reflux;	EXAMPLE 4; N4-(3-(dimethylamino)propyl)-N2-m-biphenylpyrimidine-2,4-diamine hydrochloride (11); Preparation of 2-(3-biphenylamino)pyrimidin-4(3H)-one (9): To 2-(methylthio)-pyrimidine-4(3H)-one, 1, (790 mg, 5.5 mmol) in diglyme (5 mL) is added 3-amino-biphenyl (1.91 g, 11.2 mmol). The resulting mixture is stirred at reflux for 18 hours. The mixture is cooled to room temperature and hexane is added and a precipitate forms which is collected by filtration to afford 1.34 g (92percent yield) of the desired compound which is used without further purification. MS (ESI, pos. ion) m/z: 264 (M+1).
92%	In diethylene glycol dimethyl ether; for 18h;Heating / reflux;	EXAMPLE 3; N2-Biphenyl-3-yl-N4-(3-morpholin-4-yl-propyl)-pyrimidine-2,4-diamine (10); Preparation of 2-(3-biphenylamino)pyrimidin-4(3H)-one (8); To 2-(methylthio)-pyrimidine-4(3H)-one (790 mg, 5.5 mmol) in 5 mL of diglyme is added 3-amino-biphenyl (1.91 g, 11.2 mmol). The resulting mixture is stirred at reflux for 18 hours. The mixture is cooled to room temperature and hexanes are added to form a precipitate which is collected by filtration to afford 1.34 g (92percent yield) of the desired compound which is used without purification. MS (ESI, pos. ion) m/z: 264 (M+1).

Reference： [1]Patent: US2007/293525,2007,A1 .Location in patent: Page/Page column 16; 17
[2]Patent: US2007/293494,2007,A1 .Location in patent: Page/Page column 20

13
[ 854382-06-2 ]
[ 2243-47-2 ]
N-(3-Phenylphenyl){2-[(4-pyridylmethyl)amino](3-pyridyl)}carboxamide [ No CAS ]

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2007,vol. 17,p. 6003 - 6008

14
[ 2243-47-2 ]
[ 53592-10-2 ]

Reference： [1]Journal of the Chemical Society,1927,p. 3006

15
[ 6404-29-1 ]
[ 2243-47-2 ]
[ 911358-54-8 ]

Yield	Reaction Conditions	Operation in experiment
91%	With (benzotriazo-1-yloxy)tris(dimethylamino)phosphonium hexafluorophosphate; triethylamine In N,N-dimethyl-formamide at 20℃; for 3h;	1.1 N-Boc-caproic acid (1.1g, 4.77 mmol), 3-phenyl aniline (806 mg, 4.77 mmol) and EJOP (2.11 g, 4.77 mmol) were dissolved in DMF (10 ml_). Triethylamine (1 1.92 mmol, 1.66 rnL) was added and the reaction was stirred for 3 hours at room temperature. The reaction was then quenched with water and extracted with ethyl acetate. The organic extract was dried (Na2SO4), filtered, and evaporated. The residue was purified by silica gel column chromatography with gradient of EtOAc (25-100%) in Hexane to afford 1 (1.65 g, 91%) as a beige solid . LRMS (ESI): (calc.) 382.2; (found) 383.3 (MH)+
91%	With (benzotriazo-1-yloxy)tris(dimethylamino)phosphonium hexafluorophosphate; triethylamine In N,N-dimethyl-formamide at 20℃; for 3h;	1.1 Example 1; N-(Biphenyl-3-yl)-6-(sulfamoylamino)hexanamide (4) Step 1: tert-Butyl 6-(biphenyl-3-ylamino)-6-oxohexylcarbamate (1c) N-Boc-caproic acid (1.1 g, 4.77 mmol), 3-phenyl aniline (806 mg, 4.77 mmol) and BOP (2.11 g, 4.77 mmol) were dissolved in DMF (10 ml). Triethylamine (11.92 mmol, 1.66 ml) was added and the reaction was stirred for 3 hours at room temperature. The reaction was then quenched with water and extracted with ethyl acetate. The organic extract was dried (Na2SO4), filtered, and evaporated. The residue was purified by silica gel column chromatography with gradient of EtOAc (25-100%) in Hexane to afford 1c (1.65 g, 91%) as a beige solid. LRMS (ESI): (calc.) 382.2; (found) 383.3 (MH)+.
	With (benzotriazo-1-yloxy)tris(dimethylamino)phosphonium hexafluorophosphate; triethylamine In N,N-dimethyl-formamide

Reference： [1]Current Patent Assignee: MIRATI THERAPEUTICS, INC. - WO2006/102760, 2006, A1 Location in patent: Page/Page column 52; 53
[2]Current Patent Assignee: MIRATI THERAPEUTICS, INC. - US2007/293530, 2007, A1 Location in patent: Page/Page column 74
[3]Location in patent: scheme or table Wahhab, Amal; Smil, David; Ajamian, Alain; Allan, Martin; Chantigny, Yves; Therrien, Eric; Nguyen, Natalie; Manku, Sukhdev; Leit, Silvana; Rahil, Jubrail; Petschner, Andrea J.; Lu, Ai-Hua; Nicolescu, Alina; Lefebvre, Sylvain; Montcalm, Samuel; Fournel, Marielle; Yan, Theresa P.; Li, Zuomei; Besterman, Jeffrey M.; Deziel, Robert [Bioorganic and Medicinal Chemistry Letters, 2009, vol. 19, # 2, p. 336 - 340]

16
Pd-Cl [ No CAS ]
[ 2113-58-8 ]
[ 2243-47-2 ]

Yield	Reaction Conditions	Operation in experiment
99.9%	In ethanol;	Example 1 A 2-l atmospheric hydrogenation reactor was charged with 250 g (1.26 mol) of <strong>[2113-58-8]m-nitrobiphenyl</strong>, 12.5 g of 5% Pd-Cl, and 1250 ml of ethanol. A theoretical amount of hydrogen gas was absorbed at room temperature. The catalyst was removed by filtration and the filtrate was distilled of the solvent, obtaining 212 g of m-aminobiphenyl (yield 99.9%).

Reference： [1]Patent: EP666298,1995,A2

17
[ 2243-47-2 ]
[ 38186-88-8 ]
[ 1038826-90-2 ]

Yield	Reaction Conditions	Operation in experiment
62%		Step (a) 2-(biphenyl-3-ylamino)-5-fluoronicotinic acid<strong>[38186-88-8]2-Chloro-5-fluoronicotinic acid</strong> (1.83 g, 10.45 mmol) and potassium carbonate (1.74 g, 12.6 mmol) were added to dry DMF (20 ml). Copper (41 mg), copper(I)bromide (75 mg) and 3-aminobiphenyl (3.0 g, 17.8 mmol) were added and the reaction mixture was stirred at 150 0C for 12 hours. IM HCl was added and the product that precipitated was collected <n="49"/>by filtration, washed with IM HCl then water and dried to afford the sub-title compound(1.98 g, 62percent).APCI (-ve): 307 (M-H)

Reference： [1]Patent: WO2008/84223,2008,A2 .Location in patent: Page/Page column 47-48

18
[ 2243-47-2 ]
[ 76315-01-0 ]
[ 916337-27-4 ]

Yield	Reaction Conditions	Operation in experiment
		Intermediate 1.7: A mixture of N-benzyl-N-tert-butoxycarbonylglycine (1.0 g, 3.77 mmol) (see e.g. J. Am. Chem. Soc. 125, 10664, 2003) and chloroformic acid ethylester (0.4 mL, 4.14 mmol) in THF (20 mL), Et3N (0.63 mL, 4.52 mmol) is stirred at room temperature. After stirring for 30 min, the reaction mixture is filtered for removing inorganic salt. A solution of this crude product in THF is treated with 3-aminobiphenyl (765 mg, 4.52 mmol) and NaH (230 mg, 0.5.7 mmol) at room temperature for 30 min. After adding H2O, the reaction mixture is extracted with EtOAc. The combined organic phases are washed with H2O, brine and dried (Na2SO4). Concentration under reduced pressure affords a crude product. Then deprotection of this crude product by 4M dioxane solution of HCl (20 mL) at room temperature affords Intermediate 1.7 as white solid; ES-MS: M+H=317; HPLC: tRet=3.09 min.

Reference： [1]Patent: US2008/242662,2008,A1 .Location in patent: Page/Page column 25-26

19
[ 1202889-60-8 ]
[ 2243-47-2 ]
[ 1202890-26-3 ]

Yield	Reaction Conditions	Operation in experiment
78%	Stage #1: 4-(6-cyano-4-(methoxycarbonyl)chroman-7-yloxy)benzoic acid With oxalyl dichloride; N,N-dimethyl-formamide In dichloromethane at 20℃; for 1h; Stage #2: 3-biphenyl amine With triethylamine In dichloromethane at 20℃; for 1h;	67.A To a solution of 4-(6-cyano-4-(methoxycarbonyl)chroman-7- yloxy)benzoic acid (Preparation 2) (50 mg, 0.142 mmol) and a drop of DMF in dichloromethane (2 ml) was added oxalyl chloride (2M in dichloromethane) ( 84.91 μL, 0.170 mmol) at ambient temperature. Gas evolution was observed. The mixture was stirred for 1 hour at ambient temperature. Biphenyl-3 -amine (28.74 mg, 0.170 mmol) in dichloromethane (1 ml) and triethylamine (59.172 μL, 0.424 mmol) were added to the activated acid. The mixture was stirred for 1 hour at ambient temperature. The crude mixture was purified on silica gel (EtOAc in hexanes gradient) to provide 55.6 mg of the title compound as a thin film (78%).

Reference： [1]Current Patent Assignee: PFIZER INC - WO2009/158426, 2009, A1 Location in patent: Page/Page column 125

20
[ 626-01-7 ]
[ 98-80-6 ]
[ 2243-47-2 ]

Yield	Reaction Conditions	Operation in experiment
94%	With potassium carbonate In water monomer at 50℃; for 2h;	2.4 Synthesis of Biaryls 3 General procedure: In a test tube equipped with a magnetic stirrer bar, thearyl halide 1 (1 mmol) was mixed with phenyl boricacid 2 (1.2 mmol), K2CO3(2 mmol), and the Pd-catalyst(0.1mol% Pd) in 2 ml of H2Oin air. The reaction mixturewas then stirred at 50 °C for appropriate time. After completionof the reaction, the catalyst was removed by magnetand washed with ethanol and water (3 × 5 ml). The aqueouslayer was extracted with chloroform, then organic layerdried over anhydrous MgSO4.The solvent was evaporatedunder reduced pressure to give the corresponding biarylcompounds. All the products were previously reported [5,8-12] and were confirmed by the spectroscopic methodusing 1H and 13C NMR (see supporting information).
94%	With magnesium(II) hydroxide; potassium hydroxide; barium(II) hydroxide; calcium hydroxide In water monomer at 20℃; for 2h;
93%	With Co(II) creatine complex immobilized on functionalized silica-coated Fe₃O₄ nanoparticles In water monomer at 75℃; for 1h; Green chemistry;	General procedure for the C-C bond formation catalyzed by Fe3O4SiO2-CT-Co General procedure: To a solution of phenylboronic acid derivatives (1.2mmol), aryl halides (1.0mmol), KOH (2.5mmol), and water (3.0ml), 1.5mol % of Fe3O4SiO2-CT-Co was added at 75°C with stirring under oil bath condition. After the fnalization of the reaction, the Co-coordinated MNPs catalyst (Fe3O4SiO2-CT-Co) was separated from the reaction mixture and washed with EtOH and H2O and, fnally, dried at 60°C in a vacuum oven for 12h. Subsequently, the water as a green solvent was separated from the reaction mixture by rotary evaporator and the prepared Suzuki products have been obtained in pure products with good to excellent isolated yields. Some selected products have been characterized with H and C NMR, and the data have been added in supporting material section.

91%	With 0.1 % Cu/C; potassium carbonate In water monomer at 50℃; for 3h; Green chemistry;	2.2. Synthesis of biaryls 3 General procedure: In a test tube, 1.0 mmol of aryl halides 1, 1.2 mmol of phenylboronic acid 2 were mixed together and then 2.0 mmol of K2CO3, and the Cu/Cnano-catalyst (0.1 mol % Cu) in 2 mL of H2O, were added in air. The reaction mixture was then stirred at 50 °C for appropriate time. After completion of the reaction (monitored by TLC), the catalyst was removed by simple filtration. The recycled catalyst was was hed with ethanol and water (3 × 5 mL) and dried at 60 °C in oven for further use. The aqueous layer was extracted with ethyl acetate, and organic layer dried over anhydrous MgSO4. The solvent was evaporated under reduced pressure to give the corresponding biaryl compounds.
89%	With tripotassium phosphate tribasic In 1,4-dioxane at 80℃; for 1h;
87%	With potassium carbonate In water monomer; acetone at 60℃; for 7h;
75%	With potassium carbonate In water monomer at 60℃; for 2h;
	With palladium (II) [1,1'-bis(diphenylphosphanyl)ferrocene] dichloride; sodium hydroxide In tetrahydrofuran for 12h; Reflux;
	With tetrakis-(triphenylphosphine)-palladium; anhydrous sodium carbonate In N,N-dimethyl-formamide at 160℃; for 0.5h; Microwave irradiation;
	With C₂₁H₁₉N₄O₂Pd⁽¹⁺⁾*Cl^(1-); potassium carbonate In water monomer; N,N-dimethyl-formamide at 80℃; for 8h; Inert atmosphere;	2.4. Catalytic activity over Suzuki-Miyaura reaction General procedure: The solvent/solvent mixture used in the reaction was de- gassed through the Freeze-pump-claw method [28,29] . A three- neck round bottom flask equipped with water condenser, magnetic stir bar and a N 2 -inlet. The flask was charged with degassed sol- vent (100 mL), base i.e. potassium carbonate (0.75 mmol) and 1-4 (0.1-0.6 mmol). The phenylbronic acid (0.6 mmol) and aryl halide (0.5 mmol) was added by glass syringe through a rubber septum. The mixture was allowed to stir at 25-100 °C for 2-12 h and then cooled to room temperature. It was further filtered through the bed of silica. The reaction progress was monitored periodically by TLC. The product was extracted with ethyl acetate (3 ×10 mL). The combined organic phase was washed with brine (2 ×10 mL) and dried over Na 2 SO 4 . The solvent was removed under reduced pres- sure to afford crude. The residue obtained was purified through column chromatography on silica gel eluting with ethyl acetate. Column chromatography was performed to obtain the pure prod- uct with eluting the column ethyl acetate: hexane (5: 95; v/v) sol- vent mixture. Product was characterized by ESI-MS, 1 H-NMR and 13 C-NMR.
90 %Chromat.	With [Cu(L-tryp)(azpy)_1/2(H₂O)(NO₃)]∝; sodium hydroxide In N,N-dimethyl-formamide at 80℃; for 12h;

Reference： [1]Sarvi, Iraj; Gholizadeh, Mostafa; Izadyar, Mohammad [Catalysis Letters, 2017, vol. 147, # 5, p. 1162 - 1171]
[2]Lamei, Kamran; Eshghi, Hossein; Bakavoli, Mehdi; Rostamnia, Sadegh [Applied Organometallic Chemistry, 2017, vol. 31, # 11]
[3]Haqjow, Hanif; Raoufi, Farveh [Research on Chemical Intermediates, 2021, vol. 47, # 10, p. 4113 - 4128]
[4]Lamei, Kamran; Eshghi, Hossein; Bakavoli, Mehdi; Rounaghi, Seyyed Amin; Esmaeili, Elaheh [Catalysis Communications, 2017, vol. 92, p. 40 - 45]
[5]Keyhaniyan, Mahdi; Shiri, Ali; Eshghi, Hossein; Khojastehnezhad, Amir [New Journal of Chemistry, 2018, vol. 42, # 24, p. 19433 - 19441]
[6]Mejias, Nereida; Pleixats, Roser; Shafir, Alexandr; Medio-Simon, Mercedes; Asensio, Gregorio [European Journal of Organic Chemistry, 2010, # 26, p. 5090 - 5099]
[7]Allahresani, Ali; Chahkandi, Mohammad; Nasseri, Mohammad Ali; Reiser, Oliver; Sheikh, Safoora [RSC Advances, 2022, vol. 12, # 15, p. 8833 - 8840]
[8]Lacivita, Enza; Patarnello, Daniela; Stroth, Nikolas; Caroli, Antonia; Niso, Mauro; Contino, Marialessandra; De Giorgio, Paola; Di Pilato, Pantaleo; Colabufo, Nicola A.; Berardi, Francesco; Perrone, Roberto; Svenningsson, Per; Hedlund, Peter B.; Leopoldo, Marcello [Journal of Medicinal Chemistry, 2012, vol. 55, # 14, p. 6375 - 6380]
[9]Tang, Jing; Liu, Feng; Nagy, Eva; Miller, Lena; Kirby, Karen A.; Wilson, Daniel J.; Wu, Bulan; Sarafianos, Stefan G.; Parniak, Michael A.; Wang, Zhengqiang [Journal of Medicinal Chemistry, 2016, vol. 59, # 6, p. 2648 - 2659]
[10]Bagri, Sanjay Singh; Chaurasia, Bhaskar; Gaur, Pratiksha; Mehrotra, Ripul; Raidas, Mohan Lal; Shukla, Satyendra Nath [Journal of Molecular Structure, 2021, vol. 1225]
[11]Bhasin, K. K.; Husain, Ahmad; Kumar, Girijesh; Kumar, Rakesh; Nar, Kuldeep Kaur; Rani, Pooja; Singh, Amit Pratap [CrystEngComm, 2021, vol. 23, # 44, p. 7855 - 7864]

21
[ 33018-91-6 ]
[ 2243-47-2 ]
C₂₁H₂₅NO₃ [ No CAS ]

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2009,vol. 19,p. 336 - 340

22
[ 60142-89-4 ]
[ 2243-47-2 ]
C₂₄H₃₂N₂O₃ [ No CAS ]

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2009,vol. 19,p. 336 - 340

23
[ 2243-47-2 ]
[ 6160-65-2 ]
[ 1510-25-4 ]

Yield	Reaction Conditions	Operation in experiment
96%	With dmap; In dichloromethane; at 20.0℃; for 1.0h;Inert atmosphere;	To a stirred solution of biphenyl-3-ylamine (338 mg, 2 mmol) in DCM (5 mL), thiocarbonyldiimidazole (TCDI) (535 mg, 3 mmol) and DMAP (48.8 mg, 0.04 mmol) were added and the reaction mixture stirred at r.t under N2 for 1 h (until TLC showed no starting material remaining). The reaction mixture was then purified by a silica plug (DCM). The solvent was then removed in vacuo to leave a colourless oil (407 mg, 96%). Rf: 0.86 (1:1 DCM/hex). 1H NMR (CDCl3): delta 7.16 (ddd, 1H, J 8, 2, 1 Hz, H6'), 7.34-7.48 (m, 6H, H4'', H5', H4', H3'', H5'', H2'), 7.52 (m, 2H, H2'', H6''). 13C NMR (CDCl3): delta 124.4 (CH), 124.5 (CH), 126.2 (CH), 127.2 (CH), 128.2 (CH), 129.1 (CH), 130.0 (CH), 131.8 (C), 135.7 (NCS), 139.5 (C), 143.0 (C).

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2011,vol. 21,p. 6782 - 6787

24
[ 1219-33-6 ]
[ 2243-47-2 ]
[ 1333331-70-6 ]

Yield	Reaction Conditions	Operation in experiment
	In diphenylether; at 250℃; for 0.166667h;	5-(Benzyloxy)-4-oxo-4H~pyran-2-carboxylic acid (36.9 g, 150 mmol) and 3-aminobiphenyl (25.35 g, 150 mmol) were combined in diphenyl ether (110 ml). The mixture was heated to 250 C (pre-heated block) in an open flask. After 10 min, the mixture was cooled to room temperature. The residue was purified by silica gel chromatography to provide 3-(benzyloxy)-l- (biphenyl-3-yl)pyridin-4(lH)-one. NMR S (400 MHz, <¾-DMSO): 7.55 (d5 J=7.6 Hz, 1H), 7.46 (m, 4H), 7.44-7.31 (m, 5H), 7.29-7.11 (m, 4H), 6.51 (d, J=7.2 Hz, 1H), 5.17 (s, 2H).MS (M+H)+ 354.

Reference： [1]ACS Medicinal Chemistry Letters,2015,vol. 6,p. 318 - 323
[2]Patent: WO2011/109254,2011,A1 .Location in patent: Page/Page column 115

25
[ 1392620-48-2 ]
[ 2113-58-8 ]
[ 2243-47-2 ]

Yield	Reaction Conditions	Operation in experiment
35%; 25%	With triethylsilane; palladium dichloride; In tetrahydrofuran; for 96h;Inert atmosphere; Reflux;	General procedure: To a solution of aryl alkyl sulfide (0.23 mmol, 1.0 equiv) and PdCl2 (0.007 mmol, 3 mol %, 1.2 mg) in 2 mL of THF was added triethylsilane (amount indicated in Table 3) under argon atmosphere (color of the reaction mixture turned to black). The resulting mixture was stirred at room temperature (or at the indicated temperature in Table 3). After completion of the reaction, to the reaction mixture was added 4 mL of H2O (gas evolves). The aqueous layer was extracted with CH2Cl2 (4 mL × 2), and the combined organic layer was dried over Na2SO4 and evaporated. The residue was purified by silica gel column chromatography using hexane/ethyl acetate as eluent.

Reference： [1]Tetrahedron Letters,2012,vol. 53,p. 4313 - 4316

26
[ 2243-47-2 ]
trifluoromethylsilver [ No CAS ]
[ 366-04-1 ]

Yield	Reaction Conditions	Operation in experiment
74%	Stage #1: 3-biphenyl amine With hydrogenchloride In water at 0℃; for 0.0833333h; Inert atmosphere; Schlenk technique; Stage #2: With tert.-butylnitrite at 0℃; for 0.25h; Inert atmosphere; Schlenk technique; Stage #3: trifluoromethylsilver at -78 - 20℃; for 4h; Inert atmosphere; Schlenk technique;
74%	Stage #1: 3-biphenyl amine With hydrogenchloride In water at 0℃; for 0.0833333h; Schlenk technique; Stage #2: With tert.-butylnitrite In water at -196 - 20℃; Schlenk technique; Inert atmosphere; Stage #3: trifluoromethylsilver In water at -78 - 20℃; for 5h; Schlenk technique; Inert atmosphere;	Trifluoromethylation Procedure 1 (Table 1); General Procedure General procedure: An oven-dried Schlenk tube (A) equipped with a magnetic stir bar was charged with AgF (132.2 mg, 1.05 mmol, 3.5 equiv), sealed with a septum, and degassed by alternating vacuum evacuation and nitrogen backfill (three times) before freshly distilled EtCN (3 mL)was added. To the resulting suspension, which was precooled to -78 °C (dry ice-acetone bath), was added TMSCF3 (149.3 mg, 1.05 mmol, 3.5 equiv) by microsyringe. The mixture was allowed towarm to r.t. and stirring was continued for an additional 15 min. In due course, AgF solid dissolved and a gray, dark solution of [Ag-CF3] formed. Another Schlenk tube (B) equipped with a magnetic stir bar was charged with the aniline (ArNH2; 0.30 mmol, 1.0 equiv) in freshly distilled EtCN (1.5 mL). To the resulting solution, which was precooled to 0 °C (ice bath), aq HCl (12 M; 50.0 μL, 0.60mmol, 2.0 equiv) was added; precipitate formed immediately. After 5 min stirring, t-BuONO (37.7 mg, 0.33 mmol, 1.1 equiv) was added by microsyringe, and the mixture was allowed to stir at 0 °C for 15 min. The resulting suspension in Schlenk tube (B) was degassed by alternating vacuum evacuation at -196 °C (liquid nitrogen), then the solution was allowed to warm to r.t. under a nitrogen atmosphere (three times), and finally cooled to -78 °C (dry ice-acetone bath). The gray, dark solution of [AgCF3] in Schlenk tube (A), which was precooled to -78 °C (dry ice-acetone bath), was added to Schlenk tube (B) (ArN2+Cl-) by syringe at -78 °C (dry ice-acetone bath) over a period of 1 h. After the addition was complete, the reaction mixture was stirred for 3 h at -78 °C (dry ice-acetone bath), allowed to warm to r.t., and stirring was continued for an additional 1 h. An off-white precipitate was observed, and the reaction mixture was diluted with EtOAc (3 mL) and filtered through a short silica gel column. The solvent was removed under reduced pressure with a rotatory evaporator, and the crude residue was purified by silica gel column chromatography to give the desired trifluoromethylation product 3. The yields of products 3a, 3f, 3g, 3l, 3o, 3r, 3x, and 3zb are based on the 19F NMR spectra with 4-F3COC6H4OMe as internal standard. Analytical data for the representative product ethyl 4-(trifluoromethyl)benzoate (3i) are provided below. Data for other products can be found in the literature.

Reference： [1]Wang, Xi; Xu, Yan; Mo, Fanyang; Ji, Guojing; Qiu, Di; Feng, Jiajie; Ye, Yuxuan; Zhang, Songnan; Zhang, Yan; Wang, Jianbo [Journal of the American Chemical Society, 2013, vol. 135, # 28, p. 10330 - 10333]
[2]Wang, Xi; Xu, Yan; Zhou, Yujing; Zhang, Yan; Wang, Jianbo [Synthesis, 2014, vol. 46, # 16, p. 2143 - 2148]

27
[ 2243-47-2 ]
[ 183322-18-1 ]
[ 1456819-76-3 ]

Yield	Reaction Conditions	Operation in experiment
93%	In isopropyl alcohol at 80℃; for 0.25h; Microwave irradiation;	General procedure for 4-anilinoquinazolines 5-18, 34-36 General procedure: A mixture of 4-chloroquinazoline (23a-c,[1] 23d-f, 31-33[3]) (0.5 mmol) and the appropriate aniline (0.5 mmol) in i-PrOH (1 mL) was microwave irradiated at 80 °C (power set point 60 W; ramp time1 min; hold time 15 min). After cooling, the obtained precipitate was collected by filtration to give compounds 5-18 and 33-35 as hydrochlorides.

Reference： [1]Conconi, Maria Teresa; Marzaro, Giovanni; Urbani, Luca; Zanusso, Ilenia; Di Liddo, Rosa; Castagliuolo, Ignazio; Brun, Paola; Tonus, Francesca; Ferrarese, Alessandro; Guiotto, Adriano; Chilin, Adriana [European Journal of Medicinal Chemistry, 2013, vol. 67, p. 373 - 383]

28
[ 2243-47-2 ]
[ 3177-24-0 ]
[ 336191-17-4 ]
[ 1570262-37-1 ]

Yield	Reaction Conditions	Operation in experiment
		Step 1 : tert-Butyl 2,8-diazaspiro[4.5]decane-2-carboxylate (69 mg, 0.287 mol) was added to a cooled solution of the 2,4-dichloropyrimidine-5-carbonitrile (50 mg, 0.287 mmol) and Hunig's base (50 uL, 0.287 mmol) in CH2CI2 (1.5 mL) and the reaction mixture was stirred for 3 hours at 0 °C. The solvent was removed under reduced pressure, then the mixture was diluted with CH3CN (2 mL) and the biphenyl-3 -amine (97 mg, 0.575 mol) was added. The mixture was then heated to 80 °C overnight. Upon cooling, the reaction mixture was diluted with ethyl acetate, washed with 0 and then brine and the organic extracts were dried ( a2S04), filtered and concentrated in vacuo. The residue was purified by silica gel chromatography (ethyl acetate/hexanes) provided a mixture of the two possible isomers which was separated by the reverse phase chromatography to afford tert-butyl 8-[2-(biphenyl-3- ylamino)-5-cyanopyrimidin-4-yl]-2,8-diazaspiro[4.5]decane-2-carboxylate. MS ESI calcd. for C3oH35 602 [M + H]+ 511 , found 51 1.

Reference： [1]Patent: WO2014/31438,2014,A2 .Location in patent: Paragraph 00239

29
[ 2243-47-2 ]
[ 3177-24-0 ]
[ 336191-17-4 ]
[ 1570258-91-1 ]

Reference： [1]Patent: WO2014/31438,2014,A2

30
[ 3279-90-1 ]
[ 2243-47-2 ]
[ 1611467-15-2 ]

Yield	Reaction Conditions	Operation in experiment
86%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; sodium t-butanolate; XPhos In toluene at 100℃; for 9h; Inert atmosphere;	6-[(1,1'-Biphenyl)-3-ylamino]-3,4-dihydroquinolin-2(1H)-one (11f): General procedure: Toluene (4.5mL) was added to a flask containing 6-bromo-3,4-dihydroquinolin-2(1H)-one (300mg, 1.33mmol), 3-(trifluoromethoxy)aniline (231μL, 1.73mmol), Pd2(dba)3 (15.2mg, 0.02mmol), 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (31.6mg, 0.07mmol) and NaOt-Bu (192mg, 2.00mmol) under an argon atmosphere. The mixture was stirred at 100°C for 9h. After cooling, the reaction mixture was diluted with EtOAc, and filtered through a pad of Celite. The filtrate was concentrated in vacuo. Crude material was purified by flash chromatography with n-hexane/EtOAc (2:3) to afford the desired diaryl amine 11i

Reference： [1]Takeuchi, Tomoki; Oishi, Shinya; Kaneda, Masato; Misu, Ryosuke; Ohno, Hiroaki; Sawada, Jun-Ichi; Asai, Akira; Nakamura, Shinya; Nakanishi, Isao; Fujii, Nobutaka [Bioorganic and Medicinal Chemistry, 2014, vol. 22, # 12, p. 3171 - 3179]

31
[ 591-27-5 ]
[ 98-80-6 ]
[ 2243-47-2 ]

Yield	Reaction Conditions	Operation in experiment
91%	Stage #1: m-Hydroxyaniline With fluorosulfonyl fluoride; triethylamine In ethanol; water at 20℃; for 4h; Stage #2: phenylboronic acid With palladium diacetate; triethylamine In ethanol; water at 20℃; for 6h;	3 Example 3: Preparation of 3-aminobiphenyl In the air, 1mmol of 3-aminophenol, 3mmol of triethylamine,4mL of 50% ethanol aqueous solution was added to a 10mL flask, and sulfonyl fluoride gas was slowly introduced,The reaction was stirred magnetically at room temperature. After 4 hours of reaction, 1mmol of phenylboronic acid,3mmol of triethylamine, 0.2mmol of palladium acetate, continue to react at room temperature for 6 hours,After the reaction is over, add 20mL saturated saline to quench the reaction,The reaction mixture was extracted with 40 mL of ethyl acetate to extract the reaction product, and the organic phases were combined,The filtrate is concentrated and separated by column chromatography to obtain the final product.The structure of the product was identified by hydrogen nuclear magnetic resonance spectroscopy and mass spectrometry, and the separation yield reached 91%.
70%	With potassium phosphate; 1,3-bis[(diphenylphosphino)propane]dichloronickel(II); 4-methyl-N-phenyl-N-tosylbenzenesulfonamide In 1,4-dioxane at 110℃; Inert atmosphere; Schlenk technique; chemoselective reaction;

Reference： [1]Current Patent Assignee: ZUNYI MEDICAL UNIVERSITY - CN111362805, 2020, A Location in patent: Paragraph 0023-0025
[2]Chen, Liangshun; Lang, Hongyue; Fang, Lei; Zhu, Mengyun; Liu, Jinqian; Yu, Jianjun; Wang, Limin [European Journal of Organic Chemistry, 2014, vol. 2014, # 23, p. 4953 - 4957]

32
[ 2243-47-2 ]
[ 79-04-9 ]
[ 89473-63-2 ]

Yield	Reaction Conditions	Operation in experiment
75%	With triethylamine In dichloromethane at 20℃; Inert atmosphere;	N-([1,1'-biphenyl]-3-yl)-2-chloroacetamide (1d) General procedure: In a dichloromethanesolution (2-3 mL) of chloroacetylchloride (1.1 eq), adichloromethane solution (8-10 mL) of the appropriate amine (1 eq) andtriethylamine (1.1 eq) was added dropwise and the reaction mixture was stirredovernight at room temperature under a nitrogen atmosphere. The reaction mixturewas evaporated and the residue was extracted with ethyl acetate-brine. Theorganic layer was dried over Na2SO4 and upon rotary evaporationgave the desired product, which was pure in most cases (by TLC). In certaincases, chromatography was applied for further purification
	With potassium carbonate In acetonitrile at 0℃; for 2h;

Reference： [1]Papadopoulou, Maria V.; Bloomer, William D.; Rosenzweig, Howard S.; O'Shea, Ivan P.; Wilkinson, Shane R.; Kaiser, Marcel; Chatelain, Eric; Ioset, Jean-Robert [Bioorganic and Medicinal Chemistry, 2015, vol. 23, # 19, p. 6467 - 6476]
[2]Wang, Yong; Chan, Fung-Yi; Sun, Ning; Lui, Hok-Kiu; So, Pui-Kin; Yan, Siu-Cheong; Chan, Kin-Fai; Chiou, Jiachi; Chen, Sheng; Abagyan, Ruben; Leung, Yun-Chung; Wong, Kwok-Yin [Chemical Biology and Drug Design, 2014, vol. 84, # 6, p. 685 - 696]

33
[ 585-79-5 ]
[ 98-80-6 ]
[ 2243-47-2 ]

Yield	Reaction Conditions	Operation in experiment
85%	With potassium carbonate; hydrazine hydrate In water; N,N-dimethyl-formamide at 80℃; for 5h;	2.4 Preparation of Aminobiphenyls in the Presenceof Ni7-Pd3(at)BIHPS General procedure: Aryl halide (1.0 mmol), phenylboronic acid (1.1 mmol),K2CO3(2.0 mmol), Ni7-Pd3BIHPS (0.03 g) and H2O/DMF (2:1, 3 mL) were mixed and heated at 80 °C for anappropriate time (monitored by TLC). Then, hydrazinehydrate (80 wt%, 6 eq) was added to the reaction vessel.After completion of the reduction process, the mixturewas filtered and washed with water. The organic layer wasextracted with ethyl acetate (3 × 15 mL) and dried overMgSO4.Then the organic solution was concentrated andpurified by column chromatography to obtain the finalproduct.
84%	With β-D-mannose; palladium diacetate; potassium carbonate In water; N,N-dimethyl-formamide at 130℃; for 1h; Microwave irradiation; Green chemistry;
	Multi-step reaction with 2 steps 1: potassium phosphate / water; ethanol / 3 h / 20 °C 2: sodium tetrahydroborate / water / 6 h / 20 °C

Reference： [1]Beigbaghlou, Somayyeh Sarvi; Javad Kalbasi, Roozbeh; Marjani, Katayoun; Habibi, Azizollah [Catalysis Letters, 2018, vol. 148, # 8, p. 2446 - 2458]
[2]Rohilla, Sandeep; Pant, Pradeep; Jain, Nidhi [RSC Advances, 2015, vol. 5, # 40, p. 31311 - 31317]
[3]Doherty; Knight; Backhouse; Bradford; Saunders; Bourne; Chamberlain; Stones; Clayton; Lovelock [Catalysis science and technology, 2018, vol. 8, # 5, p. 1454 - 1467]

34
[ 2243-47-2 ]
[ 2498-50-2 ]
(E)-4-(3-(biphenyl-3-yl)triaz-1-enyl)benzimidamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
51%		General procedure: The synthesis of DMZ analogues followed previously reported procedure [19a], see Scheme 2. <strong>[2498-50-2]4-Aminobenzamidine dihydrochloride</strong> (212mg, 1.0mmol) was added to a stirred solution of 12N HCl (0.27mL) and water (1.5mL) in a 10mL flask at 0C and stirring was continued for 15min. To the mixture was added (dropwise) cold (?0C) NaNO2 solution (76mg in 0.27mL water, 1.1 eq.) and stirring was continued for 15min before cold (?0C) NaOAc solution (328mg in 1.5mL water, 4.0 eq.) was added dropwise over 15min to adjust the pH to 6.0. Cold (?0C) aromatic amine solution (1.0mmol in 1.0mL methanol) was added dropwise to the above solution and stirring was continued for another 1-12hat 0C. After the reaction was completed, the solvent was removed under reduced pressure. Water (100mL) was added to the residue and the aqueous mixture was washed with dichloromethane (2×15mL). The aqueous layer was then basified with 2.5% NaOH solution to make the pH>10.0. The desired compound was then extracted from the aqueous layer with ethyl acetate (2×100mL). The organic layer was washed with brine and dried with sodium sulfate. Finally, the solvent was removed under reduced pressure and the final product was obtained with purity >95%.

Reference： [1]European Journal of Medicinal Chemistry,2016,vol. 118,p. 266 - 275

35
[ 2113-57-7 ]
[ 2243-47-2 ]
bis([1,1'-biphenyl]-3-yl)amine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
85%	With palladium diacetate; sodium tertiary butoxide; tricyclohexylphosphine In toluene at 95℃; for 8h;	6 Synthesis of Compound 5 3-aminobiphenyl (54 g, 319 mmol), 3-bromobiphenyl (70 g, 301 mmol), Pd(OAc)2 (0.33 g, 1.47 mmol), tricyclohexylphosphine (0.84 g, 2.8 mmol), NaOt-Bu (57 g, 593 mmol), and 280 mL of toluene were added to a flask and stirred at 95° C. for 8 hours. After the reaction was completed, the mixture was cooled to room temperature. The organic layer was extracted with ethyl acetate, and residual moisture was removed using magnesium sulfate. The residue was dried, and separated by column chromatography to obtain compound 5 (60.23 g, yield: 85%).
85%	With palladium diacetate; sodium tertiary butoxide; tricyclohexylphosphine In toluene at 95℃; for 8h;	4 Synthesis of Compound 5 3-aminobiphenyl (54 g, 319 mmol), 3-bromobiphenyl (70 g, 301 mmol), Pd(OAc)2 (0.33 g, 1.47 mmol), tricyclohexylphosphine (0.84 g, 2.8 mmol), NaOt-Bu (57 g, 593 mmol), and 280 mL of toluene were added to a flask and stirred at 95° C. for 8 hours. After the reaction was completed, the mixture was cooled to room temperature. The organic layer was extracted with ethyl acetate, and residual moisture was removed using magnesium sulfate. The residue was dried, and separated by column chromatography to obtain compound 5 (60.23 g, yield: 85%).
76%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tri-tert-butyl phosphine; sodium tertiary butoxide In toluene at 60℃; for 12h; Inert atmosphere;	23 Synthesis of Intermediate (8) di([1,1'-biphenyl]-3-yl)amine Under a nitrogen atmosphere, 100mLRound bottom 3-neck flask was charged with 3-amino-1,1'-biphenyl 2.0g, 3-bromo-1,1'-biphenyl 2.0g, tris (dibenzylideneacetone naphthyridin-acetone) dipalladium (0) 0.2g, 15% tris (t- butyl) phosphine 0.8g, T- butoxy sodium 2.9g,Ml of toluene 50ml, And it 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 (8) 2.1g. (Yield: 76%)

76%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tri-tert-butyl phosphine; sodium tertiary butoxide In toluene at 60℃; for 12h; Inert atmosphere;	9 synthesis of Intermediate (9) di([1,1'-biphenyl]-3-yl)amine 100mL 3-neck round bottom flask under a nitrogen atmosphere, 3-amino-1,1'-biphenyl 2.0g, 3-bromo-1,1'-biphenyl 2.0g, Tris (dibenzylideneacetone) palladium (0) 0.2g, 15% tris (t- butyl) phosphine 0.8g, t- butoxy sodium 2.9g, 50ml toluene were introduced, and stirred 12 hours at 60°C . Carried out after cooling the reaction solution by silica gel filtration, column chromatography, and then was concentrated in dichloromethane and n- hexane mixed solvent to give the intermediate (9) 2.1g. (Yield: 76%)
76%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tri-tert-butyl phosphine; sodium tertiary butoxide In toluene at 60℃; for 12h; Inert atmosphere;	7 Synthesis of di([1,1'-biphenyl]-3-yl) amine Under a nitrogen atmosphere, 100 mL 2.0 g of 3-amino-1,1'-biphenyl, 2.0 g of 3-bromo-1,1'-biphenyl, 0.2 g of tris (dibenzylidineacetone) dipalladium (0) 0.8 g of 15% tris (t-butyl) phosphine,2.9 g of t-butoxysodium and 50 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 2.1 g of Intermediate (9). (Yield: 76%)
30.0g	With sodium tertiary butoxide In 5,5-dimethyl-1,3-cyclohexadiene at 120℃; for 6h; Inert atmosphere;	73 Under a nitrogen atmosphere, and added at 120 will have a [1,1'-biphenyl] -3-amine (19.0g), 4- bromo-1,1'-biphenyl (25.0g), Pd-132 (0.8g), NaOtBu (15.5g) and xylene(200ml) was stirred for 6 hours the flask was heated. The reaction mixture was cooled toroom temperature so far, water and ethyl acetate were added for liquid separation. Then,the use of silica gel column chromatography (eluent: toluene / heptane = 5/5 (volumeratio)) to be purified. Solid with heptane were distilled off under reduced pressure andthe solvent obtained was washed to obtain bis ([1,1'-biphenyl] -3-yl) amine (30.0g).
	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tri-tert-butyl phosphine; sodium tertiary butoxide In toluene at 70℃;	2.a a. Secondary Amine General procedure: a. Secondary Amine (0569) The desired secondary amine can be prepared according to the scheme below: where Ra and Rb represent the desired substituents. (0570) Equimolar amounts of the appropriate aniline and bromoaryl can be reacted in toluene at 70 C with 1 mol equivalent of sodium t-butoxide for 2-4 hrs using a catalyst of Pd2(DBA)3:P(t-Bu)3 1:2 at a 1 mol % ratio to the reagents. The resulting solution can be evaporated, chromatographed with toluene eluent through alumina plug and the secondary amine isolated by evaporation and addition of methanol. The bromides and anilines for the sec amines are generally commercially available.
30 g	With sodium tertiary butoxide In 5,5-dimethyl-1,3-cyclohexadiene at 120℃; for 6h; Inert atmosphere;	18 Synthesis Example 18: Synthesis of Compound (1-2676) In a nitrogen atmosphere, a flask containing [1,1′-biphenyl]-3-amine (19.0 g), 3-bromo-1,1′-biphenyl (25.0 g), Pd-132 (0.8 g), NaOtBu (15.5 g), and xylene (200 ml) was heated and stirred for six hours at 120° C. The reaction liquid was cooled to room temperature, subsequently water and ethyl acetate were added thereto, and the mixture was partitioned. Subsequently, purification was performed by silica gel column chromatography (developing liquid: toluene/heptane=5/5 (volume ratio)). A solid obtained by distilling off the solvent under reduced pressure was washed with heptane, and thus di([1,1′-biphenyl]-3-yl)amine (30.0 g) was obtained.

Reference： [1]Current Patent Assignee: DOW INC - US2022/69228, 2022, A1 Location in patent: Paragraph 0158-0160
[2]Current Patent Assignee: DOW INC - US2022/33414, 2022, A1 Location in patent: Paragraph 0140-0142
[3]Current Patent Assignee: SK CHEMICALS CO LTD - KR2016/91196, 2016, A Location in patent: Paragraph 0384-0386
[4]Current Patent Assignee: SK CHEMICALS CO LTD - KR2016/29962, 2016, A Location in patent: Paragraph 0183-0185
[5]Current Patent Assignee: SK CHEMICALS CO LTD - KR2016/84918, 2016, A Location in patent: Paragraph 0192-0194
[6]Current Patent Assignee: SK INC; KWANSEI GAKUIN UNIVERSITY - CN105431439, 2016, A Location in patent: Paragraph 1673; 1674; 1675
[7]Current Patent Assignee: LG CHEM CO.,LTD. - US2017/25608, 2017, A1 Location in patent: Paragraph 0569
[8]Current Patent Assignee: SK INC; KWANSEI GAKUIN UNIVERSITY - US2018/94000, 2018, A1 Location in patent: Paragraph 0574

36
[ 1000339-52-5 ]
[ 2243-47-2 ]
3-([1,1'-biphenyl]-3-ylamino)-2-nitrobenzonitrile [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
82%	With N-ethyl-N,N-diisopropylamine; In tetrahydrofuran; at 85℃; for 48h;	Synthesis of 3-([1,1?-biphenyl]-3-ylamino)-2-nitrobenzonitrile Biphenylamine (4.6 g, 27 mmol) and <strong>[1000339-52-5]3-fluoro-2-nitrobenzonitrile</strong> (5.0 g, 30.1 mmol) was added into THF (20 mL) and N,N-diisopropylethylamine (20 mL) and heated at 85 C. for 2 days. The solvent was then evaporated and the residue was then purified by column chromatography using THF:hexane (1:4, v/v) as the eluent. 7.0 g (82% yield) of a red solid was obtained.

Reference： [1]Patent: US2016/218303,2016,A1 .Location in patent: Paragraph 0211; 0212

37
[ 2243-47-2 ]
[ 41046-70-2 ]
[ 79-04-9 ]
C₂₁H₁₈INO₃ [ No CAS ]

Reference： [1]Organic and Biomolecular Chemistry,2017,vol. 15,p. 1956 - 1960

38
[ 2243-47-2 ]
[ 2713-29-3 ]
[ 79-04-9 ]
C₂₀H₁₅FINO₂ [ No CAS ]

Reference： [1]Organic and Biomolecular Chemistry,2017,vol. 15,p. 1956 - 1960

39
[ 1220631-66-2 ]
[ 2243-47-2 ]
6-([ 1,1‘-biphenyl]-3-ylamino)-8-((4-methoxybenzyl)(methyl)amino)imidazo[1,2-b]pyridazine-3-carbonitrile [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
77%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; caesium carbonate; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene In N,N-dimethyl acetamide at 125℃; for 2h; Sealed tube; Inert atmosphere;	Nitrogen was bubbled through a solution of 6-chloro-8-((4- methoxybenzyl)(methyl)amino)imidazo[l,2-b]pyridazine-3-carbonitrile (75 mg, 0.229 mmol) in dimethylacetamide (DMA, 2 mL) for 15 minutes and then [l,l'-biphenyl]-3- amine (77 mg, 0.458 mmol) was added, followed by Pd2(dba)3 (41.9 mg, 0.046 mmol), Xantphos (53.0 mg, 0.092 mmol) and cesium carbonate (298 mg, 0.915 mmol). The reaction vessel was sealed and heated to 125 °C for 2 hours. The reaction was cooled to room temperature and ethyl acetate and water were added. The suspension was filtered and the filtrate layers separated. The organic layer was dried over sodium sulfate, filtered, concentrated and purified using flash chromatography providing the coupling product (90 mg, 77% yield). LC retention time 1.17 min [J]. MS (E+) m/z: 461 (MH+).

Reference： [1]Current Patent Assignee: BRISTOL-MYERS SQUIBB CO - WO2017/87590, 2017, A1 Location in patent: Page/Page column 82; 83

40
[ 1171919-75-7 ]
[ 2243-47-2 ]
tert-butyl (3R)-3-[(2-sulfanylacetyl)amino]piperidine-1-carboxylate [ No CAS ]
[ 530-62-1 ]
(R)-tert-butyl 3-(5-([1,1’-biphenyl]-3-yl)-4-oxo-4,5-dihydro-3H-1-thia-3,5,8-triazaacenaphthylene-2-carboxamido)piperidine-1-carboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
23.2%		To a 2-5 mL Biotage microwave vial with a stir bar were added 3-aminobiphenyl (370.5 mg, 2.189 mmol), 2-chloro-4- iodonicotinonitrile (578 mg, 2.186 mmol), Pd(OAc)2(9.6 mg, 0.043 mmol), DPEPhos (36.1 mg, 0.0671 mmol), and CS2CO3(988 mg, 3.03 mmol). The vial was sealed and treated with dioxane (4.35 mL), evacuated/flushed with argon 4X, and stirred at 150 C under argon for 30. The reaction was then cooled to room temperature, treated with tert-butyl (3R)-3-[(2- sulfanylacetyl)amino]piperidine-l -carboxylate (Intermediate 22) in dioxane (4.05 mL, 0.65 M, 2.63 mmol) via syringe, evacuated/flushed with argon 4X, and stirred at 150 C for 15 min. The reaction was then cooled to room temperature, treated with solid CDI (1.409 g, 8.689 mmol) in one portion under air, resealed and evacuated/flushed with argon 4X, and stirred at 150 C for 15 min. The reaction was diluted with EtOAc (10 mL), and washed with 0.5 M citric acid/brine (2 x 8 mL) and 2 M K2CO3(1 x 5 mL), dried over anhydrous Na2SC>4, filtered, and concentrated to dryness. The reaction mixture was purified by flash column chromatography to give the title compound as a beige foam (289 mg, 23.2% yield).

Reference： [1]Patent: WO2017/100668,2017,A1 .Location in patent: Page/Page column 475

41
[ 589-87-7 ]
[ 2243-47-2 ]
N-(4-iodophenyl)[1,1′-biphenyl]-3-amine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
85%	With palladium diacetate; 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; sodium t-butanolate In toluene at 110℃;	2.4 Synthesis of Intermediate J Add in a dry 2L three-necked flask42.5g of bromoiodobenzene and28g 3-aminobiphenyl,Then dry and degassed 1000 ml of toluene was added as a solvent.Add 43.3g sodium tert-butoxide, 0.7g catalyst palladium acetate (2% mol)And 3.7 g of ligand 1,1'-binaphthyl-2,2'-bisdiphenylphosphine (BINAP, 4% mol).Warm up to 110°C,The reaction ended overnight.Cool to room temperatureAdd activated carbon adsorption,Suction filtrationSpin off the solvent,Recrystallization from toluene and ethanol,41.4 g of intermediate J are obtained,The yield is 85%.

Reference： [1]Current Patent Assignee: NANJING TOPTO SEMICONDUCTOR MATERIAL CO LTD - CN107663214, 2018, A Location in patent: Paragraph 0096-0099

42
[ 2243-47-2 ]
[ 36847-10-6 ]
C₁₆H₁₂BrN₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
68%	With palladium diacetate; 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; sodium t-butanolate; In toluene; at 110℃;	35.7g in a dry 2L three-necked flask 4.6-dibromopyrimidine and 27.9 g 3-aminobiphenyl, Then dry and degassed 800 mL of toluene was added as a solvent. Add 43.2g of sodium tert-butoxide, 0.67g catalyst palladium acetate (2% mol) and 3.7g Ligand 1,1'-binaphthyl-2,2'-bisdiphenylphosphine (BINAP, 4% mol). The temperature was raised to 110C and the reaction ended overnight. Cool to room temperature, add activated carbon adsorption, suction filtration, remove solvent, Recrystallization from toluene and ethanol, 33.3 g of intermediate K was obtained (yield 68%).

Reference： [1]Patent: CN107686484,2018,A .Location in patent: Paragraph 0133-0136

43
[ 1008106-86-2 ]
[ 2243-47-2 ]
C₁₈H₁₆BNO₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
88%	With palladium diacetate; 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; sodium t-butanolate In toluene at 110℃;	1 Synthesis of intermediate B In a dry 2L three-necked flask, 37.2 g of 2-iodophenylboronic acid and 28 g of 3-aminobiphenyl were added. Then dry and degassed 600 mL of toluene was added as a solvent. Add 43.2g of sodium tert-butoxide, 0.7g catalyst palladium acetate (2% mol) and 3.7g ligand 1,1'-binaphthyl-2,2'-bisdiphenylphosphine (BINAP, 4% mol). The temperature was raised to 110°C and the reaction was completed overnight. Cool to room temperature Add activated carbon adsorption, suction filtration, remove the solvent, Recrystallization from toluene and ethanol gave 38.2 g of intermediate B (yield 88%).

Reference： [1]Current Patent Assignee: NANJING TOPTO SEMICONDUCTOR MATERIAL CO LTD - CN107686484, 2018, A Location in patent: Paragraph 0065-0068

44
[ 573-17-1 ]
[ 2243-47-2 ]
C₂₆H₁₉N [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
87%	With palladium diacetate; 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; sodium t-butanolate In toluene at 110℃;	8 Synthesis of Intermediate Ae 25.7 g 9-bromophenanthrene and 18.6 g 3-aminobiphenyl (1.1 eq.) were placed into a dry three-neck flask (2 L), to which 500 mL dry and degassed toluene was added to dissolve the solid. Then, 28.8 g sodium tert-butoxide, 0.45 g catalyst palladium diacetate (2% mol) and 2.5 g 1,1′-binaphthyl-2,2′-bis(diphenylphosphino)(BINAP, 4% mol) ligand were added. The resulting was heated up to 110° C. and reacted overnight. After the reaction finished and being cooled down to room temperature, the resulting mixture was absorbed with activated carbon and filtered by suction filtration. The solvent was removed by rotary evaporation and the residual was recrystallized with toluene and ethanol to produce 30.1 g Intermediate Ae in 87% yield.
87%	With palladium diacetate; 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; sodium t-butanolate In toluene at 110℃;	8.89 Reaction 89 25.7 g of 9-bromophenanthrene and 18.6 g (1.1 eq.) of 3-aminobiphenyl were added to a dry 2L three-necked flask, followed by addition of500 mL of dried and degassed toluene was used as a solvent. 28.8 g of sodium tert-butoxide, 0.45 g of palladium acetate catalyst (2% mol) and2.5 g of 1,1'-binaphthyl-2,2'-bisdiphenylphosphine (BINAP, 4% mol). The temperature was raised to 110°C and the reaction was completed overnight. Cool toThe mixture was adsorbed on activated carbon at room temperature, suction-filtered, the solvent was removed by spin-drying, and the residue was recrystallized from toluene and ethanol to obtain 30.1 g of intermediate Ae.87%

Reference： [1]Current Patent Assignee: NANJING TOPTO SEMICONDUCTOR MATERIAL CO LTD - US9938287, 2018, B1 Location in patent: Page/Page column 144; 145
[2]Current Patent Assignee: NANJING TOPTO SEMICONDUCTOR MATERIAL CO LTD - CN107880055, 2018, A Location in patent: Paragraph 0437-0440

45
[ 2398-37-0 ]
[ 2243-47-2 ]
C₁₉H₁₇NO [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
89%	With palladium diacetate; 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; sodium t-butanolate In toluene at 110℃;	1 Synthesis of Intermediate (2) 28.1 g 1-bromo-3-methoxylbenzene and 27.9 g 3-amino bibenzene were added into a dry 2 L three-neck flask, followed by 600 mL dry and degassed toluene added to dissolve. Then, 43.2 g sodium tert-butoxide (3 eq.), 0.67 g catalyst palladium diacetate (2% mol) and 3.7 g 1,1′-binaphthyl-2,2′-bis(diphenylphosphino) (BINAP, 4% mol) ligand were added. The reaction mixture was heated up to 110° C. and reacted overnight. After the reaction finished and the reaction mixture was cooled down to room temperature, the residual was absorbed by the added activated carbon, filtered by suction filtration and removed with solvent by rotary evaporation to produce 36.8 g Intermediate (2) at a yield of 89%.

Reference： [1]Current Patent Assignee: NANJING TOPTO SEMICONDUCTOR MATERIAL CO LTD - US2018/105534, 2018, A1 Location in patent: Paragraph 0033-0034

46
[ 60-12-8 ]
[ 2243-47-2 ]
[ 530-62-1 ]
phenethyl [1,1'-biphenyl]-3-ylcarbamate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
74%	Stage #1: 3-biphenyl amine; 1,1'-carbonyldiimidazole With dmap In acetonitrile at 100℃; for 15h; Inert atmosphere; Stage #2: 2-phenylethanol In acetonitrile at 100℃; for 8h; Inert atmosphere;	7 4.1.5. General procedure for the preparation of compounds 1-2a-c,3a-b General procedure: A stirred solution of the previously obtained amine (1 mmol),CDI (4 mmol, 0.648 g), and DMAP (0.2 mmol, 0.024 g) in CH3CN(8 mL) was heated at 100 C for 15 h under N2 atmosphere. Thena solution of the suitable alcohol (1.2 mmol) in CH3CN (1 mL)was added. The mixture was stirred at 100 C for 8 h and concentrated.
	Stage #1: 3-biphenyl amine; 1,1'-carbonyldiimidazole With dmap In acetonitrile Reflux; Stage #2: 2-phenylethanol In acetonitrile Reflux;

Reference： [1]Lauria, Simone; Perrotta, Cristiana; Casati, Silvana; Di Renzo, Ilaria; Ottria, Roberta; Eberini, Ivano; Palazzolo, Luca; Parravicini, Chiara; Ciuffreda, Pierangela [Bioorganic and Medicinal Chemistry, 2018, vol. 26, # 9, p. 2561 - 2572]
[2]Casati, Silvana; Ciuffreda, Pierangela; Ottria, Roberta; Yancheva, Denitsa; Šmelcerović, Andrija; Lazarević, Jelena; Zvezdanović, Jelena [Chemico-Biological Interactions, 2020, vol. 326]

47
[ 98-00-0 ]
[ 2243-47-2 ]
[ 530-62-1 ]
furan-2-ylmethyl [1,1'-biphenyl]-3-ylcarbamate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
68%	Stage #1: 3-biphenyl amine; 1,1'-carbonyldiimidazole With dmap In acetonitrile at 100℃; for 15h; Inert atmosphere; Stage #2: (2-furyl)methyl alcohol In acetonitrile at 100℃; for 8h; Inert atmosphere;	8 4.1.5. General procedure for the preparation of compounds 1-2a-c,3a-b General procedure: A stirred solution of the previously obtained amine (1 mmol),CDI (4 mmol, 0.648 g), and DMAP (0.2 mmol, 0.024 g) in CH3CN(8 mL) was heated at 100 C for 15 h under N2 atmosphere. Thena solution of the suitable alcohol (1.2 mmol) in CH3CN (1 mL)was added. The mixture was stirred at 100 C for 8 h and concentrated.
	Stage #1: 3-biphenyl amine; 1,1'-carbonyldiimidazole With dmap In acetonitrile Reflux; Stage #2: (2-furyl)methyl alcohol In acetonitrile Reflux;

Reference： [1]Lauria, Simone; Perrotta, Cristiana; Casati, Silvana; Di Renzo, Ilaria; Ottria, Roberta; Eberini, Ivano; Palazzolo, Luca; Parravicini, Chiara; Ciuffreda, Pierangela [Bioorganic and Medicinal Chemistry, 2018, vol. 26, # 9, p. 2561 - 2572]
[2]Casati, Silvana; Ciuffreda, Pierangela; Ottria, Roberta; Yancheva, Denitsa; Šmelcerović, Andrija; Lazarević, Jelena; Zvezdanović, Jelena [Chemico-Biological Interactions, 2020, vol. 326]

48
[ 591-50-4 ]
[ 13331-27-6 ]
[ 2243-47-2 ]

Yield	Reaction Conditions	Operation in experiment
87%	With potassium carbonate; hydrazine hydrate In water; N,N-dimethyl-formamide at 80℃; for 3.5h;	2.4 Preparation of Aminobiphenyls in the Presenceof Ni7-Pd3(at)BIHPS General procedure: Aryl halide (1.0 mmol), phenylboronic acid (1.1 mmol),K2CO3(2.0 mmol), Ni7-Pd3BIHPS (0.03 g) and H2O/DMF (2:1, 3 mL) were mixed and heated at 80 °C for anappropriate time (monitored by TLC). Then, hydrazinehydrate (80 wt%, 6 eq) was added to the reaction vessel.After completion of the reduction process, the mixturewas filtered and washed with water. The organic layer wasextracted with ethyl acetate (3 × 15 mL) and dried overMgSO4.Then the organic solution was concentrated andpurified by column chromatography to obtain the finalproduct.

Reference： [1]Beigbaghlou, Somayyeh Sarvi; Javad Kalbasi, Roozbeh; Marjani, Katayoun; Habibi, Azizollah [Catalysis Letters, 2018, vol. 148, # 8, p. 2446 - 2458]

49
[ 108-86-1 ]
[ 13331-27-6 ]
[ 2243-47-2 ]

Yield	Reaction Conditions	Operation in experiment
82%	With potassium carbonate; hydrazine hydrate In water; N,N-dimethyl-formamide at 80℃; for 6.5h;	2.4 Preparation of Aminobiphenyls in the Presenceof Ni7-Pd3(at)BIHPS General procedure: Aryl halide (1.0 mmol), phenylboronic acid (1.1 mmol),K2CO3(2.0 mmol), Ni7-Pd3BIHPS (0.03 g) and H2O/DMF (2:1, 3 mL) were mixed and heated at 80 °C for anappropriate time (monitored by TLC). Then, hydrazinehydrate (80 wt%, 6 eq) was added to the reaction vessel.After completion of the reduction process, the mixturewas filtered and washed with water. The organic layer wasextracted with ethyl acetate (3 × 15 mL) and dried overMgSO4.Then the organic solution was concentrated andpurified by column chromatography to obtain the finalproduct.

Reference： [1]Beigbaghlou, Somayyeh Sarvi; Javad Kalbasi, Roozbeh; Marjani, Katayoun; Habibi, Azizollah [Catalysis Letters, 2018, vol. 148, # 8, p. 2446 - 2458]

50
[ 2243-47-2 ]
C₆₁H₃₇BrIN₃O₂ [ No CAS ]
C₇₃H₄₆N₄O₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
76%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tri-tert-butyl phosphine; sodium t-butanolate In toluene at 90℃; for 3h; Inert atmosphere;	3.7 (7) Synthesis of Compound 95 46 g (43.8 mmol, 1.0 eq.) of intermediate-17 and 9 g (52.6 mmol, 1.2 eq.) of 3-aminobiphenyl were added to a dry 3 L three-necked flask, followed by addition of dry and degassed 1000 ml of toluene as solvent. Nitrogen gas was passed for 15 minutes. Further add 12.6 g (131.4 mmol, 3.0 eq.) sodium t-butoxide, 0.8 g (2% mol) catalyst Pd2 (dba) 3 and 3.5 ml (4% mol) P(t-bu) 3 in toluene solution (m /v, 10%). The temperature was raised to 90 ° C and the reaction was carried out for 3 hours. After completion of the reaction, the mixture was cooled to room temperature, adsorbed with activated carbon, suction filtered, and the solvent was evaporated, and then recrystallized from toluene and ethanol to give 42 g of compound 95 in a yield of 76%

Reference： [1]Current Patent Assignee: NANJING TOPTO SEMICONDUCTOR MATERIAL CO LTD - CN108178765, 2018, A Location in patent: Paragraph 0111; 0136; 0138; 0139

51
m-pyridin-4-ylbromobenzene [ No CAS ]
[ 2243-47-2 ]
N-(3-(pyridin-4-yl)phenyl)[1,1'-biphenyl]-3-amine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
85%	With palladium diacetate; sodium t-butanolate In toluene at 120℃; for 48h; Inert atmosphere;	2.1 Example 2 (8) according to the present invention can be synthesized by the following method. (1) Add 3-benzidine to a 500 ml three-necked bottle(34g, 200mmol),4-(3-bromophenyl)pyridine (47 g,200 mmol), sodium tert-butoxide (60 g, 600 mmol) was added to 200 g of toluene, and palladium acetate was added under the protection of N2.After reacting at 120 ° C for 48 h, the reaction was completed by TLC.The water (200 ml) was washed three times, decolorized by adding activated carbon, dried and dried to obtain a gray solid, and the product was recrystallized from ethyl acetate.Drying under vacuum gave N-(3-(pyridin-4-yl)phenyl)-[1,1'-biphenyl]-3-amine 55 g, 85% yield.

Reference： [1]Current Patent Assignee: WUHAN SHANGSAI OPTOELECTRONICS TECHNOLOGY CO LTD - CN108203405, 2018, A Location in patent: Paragraph 0061-0063

52
[ 1171919-75-7 ]
[ 2243-47-2 ]
tert-butyl (3R)-3-[(2-sulfanylacetyl)amino]piperidine-1-carboxylate [ No CAS ]
(R)-tert-butyl 3-(5-([1,1’-biphenyl]-3-yl)-4-oxo-4,5-dihydro-3H-1-thia-3,5,8-triazaacenaphthylene-2-carboxamido)piperidine-1-carboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
23.2%		To a 2-5 mL Biotage microwave vial with a stir bar were added 3-aminobiphenyl (370.5 mg, 2.189 mmol) , <strong>[1171919-75-7]2-chloro-4-iodonicotinonitrile</strong> (578 mg, 2.186 mmol) , Pd (OAc)2(9.6 mg, 0.043 mmol) , DPEPhos (36.1 mg, 0.0671 mmol) , and Cs2CO3(988 mg, 3.03 mmol) . The vial was sealed and treated with dioxane (4.35 mL) , evacuated/flushed with argon 4X, and stirred at 150 under argon for 30. The reaction was then cooled to room temperature, treated with tert-butyl (3R) -3- [ (2-sulfanylacetyl) amino] piperidine-1-carboxylate (Intermediate 22) in dioxane (4.05 mL, 0.65 M, 2.63 mmol) via syringe, evacuated/flushed with argon 4X, and stirred at 150 for 15 min. The reaction was then cooled to room temperature, treated with solid CDI (1.409 g, 8.689 mmol) in one portion under air, resealed and evacuated/flushed with argon 4X, and stirred at 150 for 15 min. The reaction was diluted with EtOAc (10 mL) , and washed with 0.5 M citric acid/brine (2 x 8 mL) and 2 M K2CO3(1 x 5 mL) , dried over anhydrous Na2SO4, filtered, and concentrated to dryness. The reaction mixture was purified by flash column chromatography to give the title compound as a beige foam (289 mg, 23.2yield) .

Reference： [1]Patent: WO2018/103058,2018,A1 .Location in patent: Page/Page column 475

53
[ 2243-47-2 ]
ethyl 5-(chlorocarbonyl)-6,6-dimethyl-3-[1-(trimethylsilyl)cyclobutanecarbox amido]-5,6-dihydropyrrolo[3,4-c]pyrazole-2(4H)-carboxylate [ No CAS ]
N-([1,1'-biphenyl]-3-yl)-6,6-dimethyl-3-[1-(trimethylsilyl)cyclobutanecarboxamido]-4,6-dihydropyrrolo[3,4-c]pyrazole-5(1H)-carboxamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
80%	Stage #1: 3-biphenyl amine; ethyl 5-(chlorocarbonyl)-6,6-dimethyl-3-[1-(trimethylsilyl)cyclobutanecarbox amido]-5,6-dihydropyrrolo[3,4-c]pyrazole-2(4H)-carboxylate With N-ethyl-N,N-diisopropylamine In 1,4-dioxane at 90℃; for 4h; Inert atmosphere; Stage #2: With N,N-dimethylethylenediamine In 1,4-dioxane at 20℃; for 1.5h;	9 N-([1,1'-Biphenyl]-3-yl)-6,6-dimethyl-3-[1-(trimethylsilyl)cyclobutanecarboxamido]-4,6-dihydropyrrolo[3,4-c]pyrazole-5(1H)-carboxamide (Compound No. IV-71) To a solution of 101 mg (0.230 mmol) of ethyl 5-(chlorocarbonyl)-6,6-dimethyl-3-[1-(trimethylsilyl)cyclobutanecarboxamido]-5,6-dihydropyrrolo[3,4-c]pyrazole-2(4H)-carboxylate synthesized in the same way as in Reference Example 4 in 2 ml of 1,4-dioxane, 0.13 ml (0.75 mmol) of DIPEA and 119 mg (0.700 mmol) of [1,1'-biphenyl]-3-amine were added at room temperature in a nitrogen atmosphere and reacted at 90° C. for 4 hours with stirring. Subsequently, the reaction solution was cooled to room temperature, and 0.13 ml (1.2 mmol) of N,N-dimethylethane-1,2-diamine was added thereto at room temperature and then reacted at room temperature for 1.5 hours with stirring. After completion of the reaction, ethyl acetate was added to the reaction solution, followed by washing with a 5% aqueous potassium bisulfate solution. After separation into an organic layer and an aqueous layer, the aqueous layer was subjected to extraction twice with ethyl acetate. The whole organic layer thus obtained was dried over anhydrous magnesium sulfate, then filtered, and concentrated under reduced pressure. The obtained concentration residue was suspended in an ethyl acetate/n-hexane mixed solvent and stirred at room temperature, and then, the solid remaining without being dissolved was collected by filtration, washed with n-hexane, and then dried under reduced pressure to obtain 92.4 mg of the title compound (yield: 80%) as a white solid. Mass spectrum (CI, m/z): 502 [M+1]+. 1H-NMR spectrum (400 MHz, DMSO-d6) δ: 12.28 & 11.71 (br s, total 1H), 9.60 (s, 1H), 8.20 (br s, 1H), 7.84 (t, J=1.8 Hz, 1H), 7.66-7.54 (m, 3H), 7.51-7.43 (m, 2H), 7.39-7.28 (m, 2H), 7.25-7.19 (m, 1H), 4.67 (br s, 2H), 2.56-2.40 (m, 2H), 2.29-2.13 (m, 2H), 1.93-1.75 (m, 2H), 1.69 (br s, 6H), 0.10 (s, 9H).

Reference： [1]Current Patent Assignee: UBE INDUSTRIES LIMITED - US2018/186818, 2018, A1 Location in patent: Paragraph 0570; 0571; 0572; 0573; 0574

54
[ 617-35-6 ]
[ 2243-47-2 ]
[ 200345-71-7 ]

Yield	Reaction Conditions	Operation in experiment
71%	With oxygen; palladium diacetate; acetic acid In dimethyl sulfoxide at 80℃; for 24h; Schlenk technique; Molecular sieve; regioselective reaction;
71%	With oxygen; palladium diacetate; acetic acid In dimethyl sulfoxide at 80℃; for 24h; Schlenk technique; Molecular sieve;	32 Example 32 Synthesis of Ethyl 6-Phenyl-1H-indole-2-carboxylate Take a 25 mL Schlenk reaction tube and add 68 mg of [1,1'-biphenyl]-3-amine, 9 mg of palladium acetate and 80 mg of molecular sieve.93 mg of ethyl 2-oxopropionate, 96 mg of acetic acid and 2 mL of dimethyl sulfoxide were injected, followed by a 200 mL oxygen balloon, and stirred at 80 ° C for 24 hours.After the reaction was completed, 15 mL of ethyl acetate was added to dilute the reaction solution, and the filtrate was washed twice with 10 mL of saline.The organic phase was separated, and the aqueous phase was extracted with ethyl acetate.Column chromatography was carried out to obtain the objective product as a pure product, 75 mg, yield 71%.

Reference： [1]Ren, Long; Nan, Guanglei; Wang, Yongcheng; Xiao, Zhiyan [Journal of Organic Chemistry, 2018, vol. 83, # 23, p. 14472 - 14488]
[2]Current Patent Assignee: CHINESE ACADEMY OF MEDICAL SCIENCES - CN109748840, 2019, A Location in patent: Paragraph 0167-0170

55
[ 2243-47-2 ]
[ 1256544-27-0 ]
C₂₈H₁₉NO [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
86%	With palladium diacetate; triphenylphosphine; sodium t-butanolate In toluene at 80℃; for 8h; Inert atmosphere;	3 Preparation of compound N-1: Under an argon atmosphere, 8.46 g (50 mmol) of 3-aminobiphenyl,14.86 g (50 mmol) of 9-bromo-dibenzo[2,1-B]furan,9.60 g (100 mmol) of sodium tert-butoxide dissolved in 500 ml of dehydrated toluene,0.23g (1mmol) of palladium acetate was added with stirring.0.20 g (1 mmol) of triphenylphosphine was reacted at 80 ° C for 8 hours.After cooling, it was filtered through a pad of Celite/silica gel.The filtrate is subjected to distillation under reduced pressure to remove the organic solvent.The resulting residue was recrystallized from toluene and dried.16.58 g (43 mmol) of compound N-1 was obtained in a yield of 86%.

Reference： [1]Current Patent Assignee: CHANGCHUN HAIPU RUNSI TECHNOLOGY CO LTD - CN108912048, 2018, A Location in patent: Paragraph 0090;

56
[ 57102-42-8 ]
[ 2243-47-2 ]
C₃₀H₂₂N₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
83%	With palladium diacetate; triphenylphosphine; sodium t-butanolate In toluene at 80℃; for 8h; Inert atmosphere;	6.2 Step 2: Under an argon atmosphere, 12.89 g (40 mmol) of the intermediate B'-1,6.77 g (40 mmol) of compound A'-1, 7.69 g (80 mmol) of sodium tert-butoxide dissolved in 400 ml of dehydrated toluene.0.18 g (0.8 mmol) of palladium acetate and 0.16 g (0.8 mmol) of triphenylphosphine were added under stirring, and the mixture was reacted at 80 ° C for 8 hours.The mixture was cooled, passed through a Celite/silica gel funnel, and the filtrate was evaporated to remove solvent.Drying gave 13.63 g (33.2 mmol) of intermediate C'-1.The yield was 83%.

Reference： [1]Current Patent Assignee: CHANGCHUN HAIPU RUNSI TECHNOLOGY CO LTD - CN108863906, 2018, A Location in patent: Paragraph 0142; 0143; 0145

57
[ 2243-47-2 ]
[ 53554-29-3 ]
ethyl 2-([1,1'-biphenyl]-3-ylamino)-4-hydroxypyrimidine-5-carboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
87.6%	In ethanol; for 24h;Reflux; Sealed tube;	General procedure: To a Radley reaction carousel tube, add 1 equivalent 1, 1.1 equivalents of the amine, a stir bar, and 5 mL 95% ethanol. Reflux while stirring for 24 hours. After cooling to room temperature the resulting precipitate was collected by vacuum filtration, washing with 10 mL deionized water and 5 mL chloroform.

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2019,vol. 29

58
[ 26608-06-0 ]
[ 2243-47-2 ]
C₂₃H₂₃F₃O₃S [ No CAS ]
C₄₆H₃₉NO [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
53%		Under nitrogen protection, 5-((3r, 5r, 7r) -adamantane-1-yl)-[1,1'-biphenyl] -2-yltrifluoromethanesulfonate 82.287mmol 82.287mmol of 3-aminobiphenyl, 720mL of toluene, 246.86mmol of sodium tert-butoxide, stir and heat to 70 C, slowly add Pd2dba3 0.82287mmol, 1.6457mmol of s-PHOS, after the addition, continue to warm to 105 C and reflux After 6 hours of reaction, the temperature was lowered to 70 C., <strong>[26608-06-0]3-bromodibenzofuran</strong> was added to 80.641 mmol, and the temperature was further increased to 105 C. and refluxed for 4 h. After the reaction was completed, the temperature was lowered, and the organic phase was extracted with water, dried, filtered, and concentrated. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it was recrystallized to LC> 99.95%. Compound 18 was dried. Yield: 53%.

Reference： [1]Patent: CN110240546,2019,A .Location in patent: Paragraph 0107-0110

59
[ 26608-06-0 ]
[ 2243-47-2 ]
1-(4'-bromobiphenyl-4-yl)adamantane [ No CAS ]
C₄₆H₃₉NO [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
65%		Under nitrogen protection, 4-bromo-4'-adamantyl biphenyl 82.797mmol, 3-aminobiphenyl 82.797mmol, toluene 608mL, sodium tert-butoxide 248.391mmol were added to the reaction flask, stirred, and heated to 70 C Slowly add Pd2dba30.82797mmol and s-PHOS 1.6560mmol. After the addition, continue to warm to 105 C and reflux for 2h, then lower the temperature to 70 C, add <strong>[26608-06-0]3-bromodibenzofuran</strong> 81.141mmol, continue to raise to 105 C and reflux After 8 hours of reaction, the reaction was completed, the temperature was lowered, and the mixture was extracted with dichloromethane. The organic phase was washed with water, dried, filtered, and concentrated. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it was recrystallized to LC> 99.95%. Dried compound 17. Yield: 65%.

Reference： [1]Patent: CN110240546,2019,A .Location in patent: Paragraph 0103-0106

60
[ 2243-47-2 ]
[ 28320-31-2 ]
N-((1,1'-biphenyl)-3-yl)-9,9-dimethyl-9H-fluorene-2-amine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
80%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tri-tert-butyl phosphine; sodium t-butanolate In toluene at 120℃; for 10h; Inert atmosphere;	4.1 Step 1: Synthesis of Intermediate 19-1 Add 3-aminobiphenyl (9.4g, 55.3mmol), 2-bromo-9,9-dimethyl-9H-fluorene (15.1g, 55.3mmol), and sodium tert-butoxide (10.6g, 110.6mmol) into the reaction In the bottle,Replace with nitrogen 3 times, add toluene (110ml) under nitrogen protection, and replace 3 times with nitrogen,Add tris(dibenzylideneacetone) bispalladium (0.5g, 0.553mmol) under nitrogen protection,50% tri-tert-butyl phosphine (0.45g, 1.106mmol), nitrogen replacement 3 times,The temperature was raised to 120°C and stirred for 10h. Cool to room temperature, add 100ml of water and stir for 30min,The solid is dried by suction filtration,The solid compound was separated and purified by column chromatography to obtain 16 g of solid compound with a yield of 80%.
75.5%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; triphenylphosphine; sodium t-butanolate In toluene at 105℃; for 24h;	1 Take the synthesis of intermediate B1 as an example In a 250 ml three-necked flask, under the protection of nitrogen, add 0.01 mol of raw material O1, 0.012 mol of raw material P1,150ml of toluene was stirred and mixed, and then 5 × 10-5mol of Pd2(dba)3, 5 × 10-5mol of P(Ph)3, and 0.03mol of sodium tert-butoxide were heated to 105 °C and refluxed for 24 hours.Sampling plate showed no bromide remaining and the reaction was complete; naturally cooled to room temperature, filtered, and the filtrate was rotary evaporated to no fractions, passed through a neutral silica gel column to obtain the target product intermediate B1; HPLC purity 99.53%, yield 75.5 %

Reference： [1]Current Patent Assignee: JILIN OLED OPTICAL AND ELECTRONIC MATERIALS CO LTD - CN112961134, 2021, A Location in patent: Paragraph 0079-0082
[2]Current Patent Assignee: VALIANT CO., LTD. - CN110343049, 2019, A Location in patent: Paragraph 0073; 0076-0078

61
[ 92-66-0 ]
[ 2243-47-2 ]
N-([1,1’-biphenyl]-4-yl)-[1,1‘-biphenyl]-3-amine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
77.8%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tetrakis(triphenylphosphine) palladium⁽⁰⁾; sodium t-butanolate In toluene at 105℃; for 24h; Inert atmosphere;	1.1 (1) Preparation of intermediate A1 In a 250-ml three-necked flask, under the protection of nitrogen, add 0.01 mol of raw material O1, 0.012 mol of raw material P1, 150 ml of toluene and mix, then add 5 × 10-5 mol Pd2 (dba) 3, 5 × 10-5 mol P (Ph) 3 0.03mol sodium tert-butoxide, heated to 105 ° C, reacted under reflux for 24 hours, sampled the plate, showing no bromide remaining, the reaction is complete; naturally cooled to room temperature, filtered, and the filtrate was spin-evaporated to no fractions, passed through a neutral silica gel To obtain the target product intermediate A1; HPLC purity 99.67%, yield 77.8%

Reference： [1]Current Patent Assignee: VALIANT CO., LTD. - CN110642732, 2020, A Location in patent: Paragraph 0116-0119

62
[ 2243-47-2 ]
[ 2245-43-4 ]
C₂₈H₂₉N [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
79.9%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; sodium t-butanolate; XPhos In toluene at 105 - 110℃; for 2h; Inert atmosphere;	Intermediate 1-A (20.0g, 68.67mmol), 3-aminobiphenyl (11.62g, 68.67mmol), tris (dibenzylideneacetone) dipalladium (0.32g, 0.68mmol), 2-dicyclohexyl Phosphorus-2 ', 4', 6'-triisopropylbiphenyl (0.327g, 0.34mmol) and sodium tert-butoxide (13.19g, 137.34mmol) were added to toluene (160mL),Heated to 105-110°C under the protection of nitrogen,Stir for 2h; then cool to room temperature, wash the reaction solution with deionized water 150mL and dry with anhydrous sodium sulfate. After filtration, pass the filtrate through a short silica gel column and remove the solvent under reduced pressure; use dichloromethane: n-heptane (v / v ) = 1: 3 system, the crude product was recrystallized and purified by dichloromethane / n-heptane to obtain intermediate 1 (20.85 g, 79.9%). Intermediate 1 is a pale white solid.

Reference： [1]Current Patent Assignee: SHAANXI LIGHTE OPTOELECTRONICS MATERIAL CO.,LTD - CN111072668, 2020, A Location in patent: Paragraph 0109-0111

63
[ 2243-47-2 ]
[ 19230-27-4 ]
C₃₀H₂₃ClN₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
94%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tri-tert-butyl phosphine; sodium t-butanolate In toluene at 80℃; for 2h; Inert atmosphere;	1 General procedure for synthesis A A V1 : General procedure: I0 (1.00 equivalents), 10-1 (2.10 equivalents), tris(dibenzylideneacetone)dipalladium Pd2(dba)3 (0.02 equivalents; CAS: 51364-51-3), tri-terf-butyl-phosphine (P(u)3, CAS: 13716-12-6 , 0.08 equivalents) and sodium te/f-butoxide (NaOu; 5.00 equivalents) are stirredunder nitrogenatmosphere in toluene at 80°C for 2 h. After cooling down to room temperature (rt) the reaction mixture is extracted between toluene and brine and the phases are separated. The combined organic layers are dried over MgSCU and then the solvent is removed under reduced pressure. The crude product obtained is purified by recrystallization or column chromatography and 11 is obtained as solid.

Reference： [1]Current Patent Assignee: CYNORA GMBH - WO2020/200884, 2020, A1 Location in patent: Page/Page column 40; 44

64
[ 2243-47-2 ]
[ 57013-94-2 ]
[ 56970-25-3 ]

Reference： [1]Journal of Organic Chemistry,2020,vol. 85,p. 13895 - 13905

65
9-(4-bromophenyl)-9-phenyl-9H-fluorene [ No CAS ]
[ 2243-47-2 ]
C₃₇H₂₇N [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
93%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; potassium <i>tert</i>-butylate In toluene at 85℃; for 2h;	1 Preparation of Intermediate C-1 Compound A-1 (0.85g, 5mmol), Intermediate B-1 (1.99g, 5mmol), Pd2(dba)3 (0.27g, 0.3mmol) and KOtBu (0.07g, 0.6mmol) was dissolved in 50ml of toluene and stirred at 85°C for 2h. After cooling to room temperature, the reaction was terminated with water, and extracted three times with ethyl acetate. The organic phase was dried over anhydrous magnesium sulfate and distilled under reduced pressure, and then purified by silica gel column chromatography to obtain Intermediate C-1 (2.26g, 4.65mmol). The yield is 93%.

Reference： [1]Current Patent Assignee: CHANGCHUN HAIPU RUNSI TECHNOLOGY CO LTD - CN111960953, 2020, A Location in patent: Paragraph 0093-0094; 0097

66
[ 1190360-23-6 ]
[ 2243-47-2 ]
9,9-dimethyl-N-([1,1'-biphenyl]-3-yl)-9H-fluorene-3-amine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
82%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; sodium t-butanolate In 5,5-dimethyl-1,3-cyclohexadiene at 110℃; for 0.5h; Inert atmosphere;	1.1 Step 1: Pd2 (dba) 3 (587 mg, 1.28 mmol) and BINAP (1.59 g, 2.56 mmol) were placed in a 500 mL three-necked flask and xylene (130 mL) was added. N2 was introduced into this solution for 20 minutes until the complexion did not change. [1,1'-Biphenyl] -3-amine (5.6 g, 32.9 mmol), 3-bromo-9,9-dimethylfluorene (6.0 g, 21.9 mmol), and sodium t-butoxide (5. 3 g, 54.91 mmol) were added in that order. Then, N2 was introduced for 10 minutes, and the reaction was carried out at 110 ° C. with stirring until the reaction of the raw materials was completed. The pressure was reduced and the solvent was removed by rotary evaporation. Purified by column chromatography, compound 9,9-dimethyl-N-([1,1'-biphenyl] -3-yl) -9H-fluorene-3-amine (6.5 g, yield 82%) was obtained.
82%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; sodium t-butanolate In 5,5-dimethyl-1,3-cyclohexadiene at 110℃; Inert atmosphere;	2.1 step 1: Pd2(dba)3 (587 mg, 1.28 mmol), BINAP (1.59 g, 2.56 mmol) were added to a 500 mL three-necked flask, and xylene (130 mL) was added. Pour N2 into this solution for 20 minutes until the color no longer changes, add [1,1'-biphenyl]-3-amine (5.6g, 32.9mmol), 3-bromo-9,9-dimethylfluorene successively (6.0 g, 21.9 mmol), sodium tert-butoxide (5.3 g, 54.91 mmol). Continue to feed N2 for 10 minutes, and stir the reaction at 110°C until the raw material reaction is complete. The solvent was removed under reduced pressure and purified by column chromatography to obtain compound 9,9-dimethyl-N-([1,1'-biphenyl]-3-yl)-9H-fluoren-3-amine (6.5g, product Rate 82%).

Reference： [1]Current Patent Assignee: BEIJING SUMMER SPROUT TECHNOLOGY CO LTD - JP2021/31496, 2021, A Location in patent: Paragraph 0163-0164
[2]Current Patent Assignee: BEIJING SUMMER SPROUT TECHNOLOGY CO LTD - CN112430191, 2021, A Location in patent: Paragraph 0194-0197

67
[ 2243-47-2 ]
3-bromo-2,9,9-trimethyl-9H-fluorene [ No CAS ]
N-([1,1'-biphenyl]-3-yl)-2,9,9-trimethyl-9H-fluorene-3-amine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
79%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; sodium t-butanolate In toluene at 110℃; Inert atmosphere;	1.5 Step 5: Pd2 (dba) 3 (2.05 g, 2.24 mmol), BINAP (2.98 g, 4.48 mmol) Into a 500 mL three-necked flask Toluene (200 mL) was added. N2 was introduced into this solution for 20 minutes until the complexion did not change. 3-Bromo 2,9,9 trimethyl-9H-fluorene (12.6 g, 44 mmol), [1,1'-biphenyl] -3-amine (11.1 g, 66 mmol), And sodium t-butoxide (12.86 g, 134 mmol) were added in sequence. Then, N2 was introduced for 10 minutes, The reaction system was heated to 110 ° C. until the reaction of 3-bromo2,9,9trimethyl-9H-fluorene was completed. The reaction solution was filtered through alkaline aluminum oxide and 00424 and washed with trol to remove the solvent. Product N- ([1,1'-biphenyl] -3-yl) -2,9,9trimethyl-9H-fluorene-3-amine by column chromatography (PE: trol = 10: 1-5: 1) (13.1 g, yield 79%) was obtained.

Reference： [1]Current Patent Assignee: BEIJING SUMMER SPROUT TECHNOLOGY CO LTD - JP2021/31496, 2021, A Location in patent: Paragraph 0099; 0104

68
[ 2243-47-2 ]
C₁₈H₉ClOS [ No CAS ]
C₃₀H₁₉NOS [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
76%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tri-tert-butyl phosphine; sodium t-butanolate In toluene at 125℃;	1.3 (3) Synthesis example of Sub 2-24 Sub 2-24-b (25.3 g, 81.9 mmol) was put in a round bottom flask and dissolved in toluene (410 mL), and then [1,1'-biphenyl]-3-amine (20.8 g, 122.9 mmol), Pd2( dba)3 (2.25 g, 2.46 mmol), P(t-Bu)3 (0.99 g, 4.92 mmol), NaOt-Bu (15.7 g, 163.9 mmol) were added, followed by reflux stirring at 125°C. When the reaction was completed, extraction was performed with CH2Cl2 and water, the organic layer was dried over MgSO4 and concentrated, and the resulting compound was recrystallized using a silica gel column to obtain 27.5 g (yield 76%) of the product.

Reference： [1]Current Patent Assignee: DUK SAN NEOLUX CO., LTD. - KR2021/30522, 2021, A Location in patent: Paragraph 0310-0311; 0316-0317

69
[ 2243-47-2 ]
[ 1620783-10-9 ]
C₂₄H₁₈ClNO [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
83.6%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tri-tert-butyl phosphine; sodium t-butanolate In toluene at 90℃; for 5h; Inert atmosphere;	3 Under the protection of nitrogen, the raw material D-039 (30.00mmol) and raw material E-039 (30.00mmol) were dissolved in 140.00ml toluene solution, and tris(dibenzylideneacetone)dipalladium (0.30mml), tri-tert-butyl Phosphine (1.50mmol) and sodium tert-butoxide (60.00mmol), stir well, heat up to 90°C, and reflux for 5h; after the reaction is over, lower the temperature to 75°C, filter with diatomaceous earth to remove the salt and The catalyst, the filtrate is cooled to room temperature, washed with water three times, the organic phase is retained, and then the aqueous phase is extracted with ethyl acetate; after the organic phases are combined, they are dried with anhydrous magnesium sulfate, and the solvent is removed with a rotary evaporator; dichloride is used Methane completely dissolves the solid organic matter, then slowly drips it into the petroleum ether solution, stirs evenly, there is precipitation, the solid is filtered off with suction, and then rinsed with absolute ethanol and petroleum ether, and dried to prepare Intermediate 3 (9.33) g, yield: 83.6%);

Reference： [1]Current Patent Assignee: JILIN OLED OPTICAL AND ELECTRONIC MATERIALS CO LTD - CN112940026, 2021, A Location in patent: Paragraph 0075; 0108-0109; 0112

70
[ 2243-47-2 ]
[ 171408-76-7 ]
N-([1,1'-biphenyl]-3-yl)-9,9'-spirobifluorene-2-amine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
83.8%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; sodium t-butanolate; XPhos In toluene at 70℃; for 1h; Inert atmosphere;	Synthesis of Intermediate D-1 General procedure: Under the protection of nitrogen, add NM-1 (30g, 159mmol), M-1 (15.6g, 168mmol), 240mL of ultra-dry toluene into a 500mL three-necked flask;Stir and raise the temperature to 70°C, add sodium tert-butoxide (22.8g, 237mmol), X-Phos (1.32g, 3.18mmol), Pd2(dba)3 (1.47g, 1.59mmol) in sequence, and heat to reflux for 1h. Reduce to room temperature, wash with water three times, add 20g anhydrous magnesium sulfate to dry, and let stand for 30 minutes;Suction filtration, high pressure concentration. After passing through a column chromatography column, intermediate D-1 (34.8 g, 89.3%) was obtained.
80%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tri-tert-butyl phosphine; sodium t-butanolate In toluene at 120℃; for 10h; Inert atmosphere;	4.1 (1) Synthesis of Intermediate 35-1 Add 3-aminobiphenyl (55.5mmol), 2-bromo-9,9'-spirobifluorene (55.5mmol), sodium tert-butoxide (110.6mmol) into the reaction flask, replace with nitrogen 3 times, and add under nitrogen protection Toluene (110mL), nitrogen replacement 3 times, adding tris(dibenzylideneacetone) bispalladium (0.555mmol), 50% tri-tert-butylphosphine (1.106mmol) under nitrogen protection, nitrogen replacement 3 times, and heating to 120 After stirring for 10 hours, TLC confirmed the completion of the reaction. After cooling to room temperature, adding 100 mL of water and stirring for 30 min, suction filtration to obtain the solid and drying, the product was purified by column chromatography to obtain 21.5 g of solid compound with a yield of 80%.
78%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tri-tert-butyl phosphine; sodium t-butanolate In toluene for 1h; Inert atmosphere; Reflux;	3.3-1 3-1. Preparation of compound 3-1 Compound [1,1`-biphenyl]-3-amine 9.8 g (0.058 mol) was added to a 500-mL, 3-neck round-bottom flask under a nitrogen atmosphere, and diluted with 250 mL of toluene.To this dilution, 22.9 g of 2-bromo-9,9'-spirobi[fluorene], 0.27 g of tris(dibenzylideneacetone)dipalladium (0),0.12 g of tri-(t-butyl)phosphine and 7.2 g of sodium t-butoxide were added.The reaction solution was refluxed for 1 hour, cooled, and poured into excess methanol to precipitate a solid. The obtained solid was filtered, dried in vacuo, and separated by column to obtain 21.9 g of compound 3-1 (yield 78%)

78%

With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tri-tert-butyl phosphine; sodium t-butanolate In toluene for 1h; Inert atmosphere; Reflux;

3.3-1 3-1. Preparation of compound 3-1 Compound [1,1`-biphenyl]-3-amine 9.8 g (0.058 mol) was added to a 500-mL, 3-neck round-bottom flask under a nitrogen atmosphere, and diluted with 250 mL of toluene. In this dilution, 22.9 g of 2-bromo-9,9'-spirobi[fluorene], 0.27 g of tris(dibenzylideneacetone)dipalladium(0), 0.12 g of tri-(t-butyl)phosphine, and 7.2 g of sodium t-butoxide was added. The reaction solution was refluxed for 1 hour, cooled, and poured into excess methanol to precipitate a solid. The obtained solid was filtered, dried in vacuo, and separated by column to obtain Compound 3-1 21.9 g (yield 78%).

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 - CN112961131, 2021, A Location in patent: Paragraph 0077-0080
[3]Current Patent Assignee: EL & M SPA - KR2021/128618, 2021, A Location in patent: Paragraph 0127-0130
[4]Current Patent Assignee: EL & M SPA - KR2021/128617, 2021, A Location in patent: Paragraph 0122-0125

71
[ 2243-47-2 ]
[ 495-71-6 ]
1-([1,1'-biphenyl]-3-yl)-2,5-diphenyl-1H-pyrrole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
80%	With trifluoroacetic acid In toluene at 110℃; for 3.5h;	1-(4-tert-Butylphenyl)-2,5-diphenyl-1H-pyrrole (1a); Typical Procedure for the Preparation of Pyrroles 1 General procedure: A 300-mL flask was charged with 4-tert-butylaniline (5.8 mL, 36 mmol), 1,4-diphenyl-1,4-butanedione (7.06 g, 29.6 mmol), and toluene (120 mL). TFA (4.6 mL, 60 mmol) was added at room temperature and the mixture was stirred at 110 °C for 3 h. The reaction was quenched with sat. aq NaHCO3 at 0 °C; pyrrole 1a precipitated immediately. The white precipitates were filtered off and washed with H2O and Et2O to afford 1a (8.69 g, 24.7 mmol, 83% yield) as a white solid.

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

72
[ 694-80-4 ]
[ 2243-47-2 ]
[ 88590-00-5 ]

Yield	Reaction Conditions	Operation in experiment
69%	With caesium carbonate In dimethyl sulfoxide at 180℃; for 0.416667h; Microwave irradiation; Green chemistry;	Synthesis of 9H-Carbazoles under Microwave Irradiation; General Procedure General procedure: Aniline 1 (1.2 mmol), 1,2-dihaloarene 2(1 mmol), Cs2CO3 (3 mmol), PdNPs/mBC (15 mol%, 16 mg of Pd) and DMSO (5 mL) were added to a vessel tube with a magnetic stirring bar. The resulting mixture was heated at 180 °C under microwave irradiation (200 W) for 25 min. The progress of the reaction was monitored by TLC and GC-MS. The crude product was treated with EtOAc. The catalyst was recovered with the aid of a permanent magnet on the outer wall of the reaction flask and washed several times with the same solvent. The reaction mixture was washed with a brine (2 ×) and then dried (anhyd Na2SO4). The solvent was removed under reduced pressure and the desired 9H-carbazole was purified by silica gel column chromatography using PE/EtOAc gradient as eluent.

Reference： [1]Steingruber, H. Sebastián; Mendioroz, Pamela; Volpe, María A.; Gerbino, Darío C. [Synthesis, 2021, vol. 53, # 21, p. 4048 - 4058]

73
[ 2243-47-2 ]
[ 474918-32-6 ]
C₃₇H₂₇N [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
84.3%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; sodium t-butanolate; XPhos In toluene at 70℃; for 1h; Inert atmosphere;	Synthesis of Intermediate D-1 General procedure: Under the protection of nitrogen, add NM-1 (30g, 159mmol), M-1 (15.6g, 168mmol), 240mL of ultra-dry toluene into a 500mL three-necked flask;Stir and raise the temperature to 70°C, add sodium tert-butoxide (22.8g, 237mmol), X-Phos (1.32g, 3.18mmol), Pd2(dba)3 (1.47g, 1.59mmol) in sequence, and heat to reflux for 1h. Reduce to room temperature, wash with water three times, add 20g anhydrous magnesium sulfate to dry, and let stand for 30 minutes;Suction filtration, high pressure concentration. After passing through a column chromatography column, intermediate D-1 (34.8 g, 89.3%) was obtained.

Reference： [1]Current Patent Assignee: SHAANXI LIGHTE OPTOELECTRONICS MATERIAL CO.,LTD - CN113214280, 2021, A Location in patent: Paragraph 0116-0118; 0119-0121

74
[ 1591-31-7 ]
[ 2243-47-2 ]
N-([1,1’-biphenyl]-4-yl)-[1,1‘-biphenyl]-3-amine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
75%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; sodium t-butanolate In toluene at 100℃; for 4h; Inert atmosphere;	1.1 first step: At room temperature, under the protection of nitrogen, add tridibenzylidene acetone dipalladium (2.3g, 2.5mmol), 1,1'-binaphthyl-2,2'-bisdiphenylphosphine (3.13g, 5mmol) into toluene ( 300mL).Pour N into this solution2For 20 minutes, 4-phenyliodobenzene (14.0g, 50mmol), 3-phenylaniline (10.0g, 60.0mmol), sodium tert-butoxide (10.56g, 110mmol) were added successively.Continue to access N2After 10 minutes, the system was heated to 100°C for 4 hours.The reaction solution was filtered and washed with tol, the solvent was removed, and the column chromatography gave intermediate 7 (11.24 g, 35 mmol, yield: 75%) as a pale yellow oil.

Reference： [1]Current Patent Assignee: BEIJING SUMMER SPROUT TECHNOLOGY CO LTD - CN113620815, 2021, A Location in patent: Paragraph 0142-0145

75
[ 2243-47-2 ]
C₁₇H₁₇Br [ No CAS ]
C₂₉H₂₇N [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
83%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; (±)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl; sodium t-butanolate In toluene at 20 - 120℃; for 2h; Inert atmosphere;	2.1 The first step: At room temperature under nitrogen protection, Pd2(dba)3 (910 mg, 0.99 mmol), BINAP (1.18 g, 1.99 mmol), intermediate 5 (6 g, 19.9 mmol), [1,1'-biphenyl]- 3-amine (5.5 g, 30 mmol) and t-BuONa (3.8 g, 39.8 mmol) were added with toluene (100 mL), and the system was heated to 120° C. to react for 2 h. After the reaction was completed, it was purified by column chromatography to obtain Intermediate 7 (6.7 g, 16.4 mmol, 83% yield) as a colorless oil.
83%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; sodium t-butanolate In toluene at 120℃; for 2h; Inert atmosphere;	2.6 Step 6 At room temperature under nitrogen protection, Pd2(dba)3 (910 mg, 0.99 mmol), BINAP (1.18 g, 1.99 mmol), intermediate 9 (6 g, 19.9 mmol), [1,1'-biphenyl]-3 - Amine (5.5 g, 30 mmol) and tBuONa (3.8 g, 39.8 mmol) were added to toluene (100 mL), and the system was heated to 120° C. to react for 2 h. After the reaction was completed, it was purified by column chromatography to obtain Intermediate 10 (6.7 g, 16.4 mmol, 83% yield) as a colorless oil.

Reference： [1]Current Patent Assignee: BEIJING SUMMER SPROUT TECHNOLOGY CO LTD - CN113683518, 2021, A Location in patent: Paragraph 0189-0192
[2]Current Patent Assignee: BEIJING SUMMER SPROUT TECHNOLOGY CO LTD - CN113683517, 2021, A Location in patent: Paragraph 0175; 0193-0195

76
[ 2243-47-2 ]
[ 4295-06-1 ]
N-([1,1'-biphenyl]-3-yl)-2-methylquinolin-4-amine [ No CAS ]