[ CAS No. 58743-83-2 ]

Name: 58743-83-2|4-Bromo-4'-methoxy-1,1'-biphenyl|98%
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CAS No. :	58743-83-2	MDL No. :	MFCD00671954
Formula :	C₁₃H₁₁BrO	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	-
M.W :	263.13 g/mol	Pubchem ID :	-
Synonyms :

Safety of [ 58743-83-2 ]

Signal Word:	Warning	Class:
Precautionary Statements:	P233-P260-P261-P264-P271-P280-P302+P352-P304-P304+P340-P305+P351+P338-P312-P321-P332+P313-P337+P313-P340-P362-P403-P403+P233-P405-P501	UN#:
Hazard Statements:	H315-H319-H335	Packing Group:
GHS Pictogram:

Application In Synthesis of [ 58743-83-2 ]

Upstream synthesis route of [ 58743-83-2 ]
Downstream synthetic route of [ 58743-83-2 ]

[ 58743-83-2 ] Synthesis Path-Upstream 1~2

1
[ 58743-83-2 ]
[ 29558-77-8 ]

Reference： [1] Chemistry - A European Journal, 2009, vol. 15, # 17, p. 4289 - 4300
[2] RSC Advances, 2016, vol. 6, # 97, p. 95137 - 95148

2
[ 124-38-9 ]
[ 58743-83-2 ]
[ 725-14-4 ]

Reference： [1] Molecular Crystals and Liquid Crystals (1969-1991), 1985, vol. 131, p. 1 - 8

[ 58743-83-2 ] Synthesis Path-Downstream 1~26

1
[ 29558-77-8 ]
[ 77-78-1 ]
[ 58743-83-2 ]

Reference： [1]Journal of Organic Chemistry,2000,vol. 65,p. 5253 - 5263
[2]Journal of Heterocyclic Chemistry,2001,vol. 38,p. 11 - 23
[3]Journal of the Chemical Society,1936,p. 802,806
[4]Molecular Crystals and Liquid Crystals (1969-1991),1985,vol. 131,p. 1 - 8

2
[ 58743-83-2 ]
[ 105-58-8 ]
[ 96871-79-3 ]

Yield	Reaction Conditions	Operation in experiment
81%	Stage #1: 4-bromo-4'-methoxylbiphenyl With n-butyllithium In tetrahydrofuran; hexane at -76℃; for 0.666667h; Stage #2: Diethyl carbonate In tetrahydrofuran; hexane at 25℃; for 1h; Inert atmosphere;	Synthesis of 26 n-BuLi (2.7M solution in hexane, 1.5 mL, 1.1 equiv) was added over 10 min to a solution of 25 (0.90 g, 3.4 mmol) in dry THF (15 mL) at -76 °C. The reaction was allowed for 40 min. A solution of diehtylcarbonate (0.13 mL, 1.1 mmol) in dry THF (2 mL) was dropwised to the reaction mixture. And then the reaction mixture was stirred at room temperature for 1 h under Ar. The solution was poured into brine (10 mL) and CHCl3 (20 mL). Aqueous layer was extracted with CHCl3 for two times. The combined organic layer was washed with water and dried over MgSO4. A residual liquid was purifiedby column chromatography (EtOAc/Hex = 1/5) to give the compound 26 (0.51 g, 81%).
	With sodium; benzene

Reference： [1]Kim, Nam-Kyun; Sogawa, Hiromitsu; Takata, Toshikazu [Tetrahedron Letters, 2020, vol. 61, # 23]
[2]Morton; Emerson [Journal of the American Chemical Society, 1938, vol. 60, p. 284]

3
[ 29558-77-8 ]
[ 74-88-4 ]
[ 58743-83-2 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium carbonate; In N-methyl-acetamide; water;	Part A: To a solution of 12.4 grams (5.0 mmol) of 4-(4'-bromophenyl)phenol in 50 mL of dimethylformamide was added 10.1 grams of potassium carbonate followed by 10.51 grams of iodomethane and this stirred at room temperature for 48 hours. The solution was diluted with 400 mL of water and extracted with ethyl acetate. The organics were dried over magnesium sulfate filtered and concentrated to yield 14.1 grams of crude product. Purification by recrystallization from ethyl acetate hexane gave 8.2 grams of 4-(4'-bromophenyl)anisole as a white crystalline solid.

Reference： [1]Journal of Heterocyclic Chemistry,2007,vol. 44,p. 853 - 862
[2]Angewandte Chemie - International Edition,2007,vol. 46,p. 6807 - 6810
[3]Chemical Communications,2015,vol. 51,p. 12641 - 12644
[4]Molecular Crystals and Liquid Crystals (1969-1991),1985,vol. 127,p. 413 - 430
[5]Journal of Fluorine Chemistry,2006,vol. 127,p. 620 - 626
[6]Patent: US6747027,2004,B1

4
[ 75-77-4 ]
[ 58743-83-2 ]
[ 17964-17-9 ]

Yield	Reaction Conditions	Operation in experiment
95%	Stage #1: 4-bromo-4'-methoxylbiphenyl With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 2h; Stage #2: chloro-trimethyl-silane In tetrahydrofuran; hexane at 20℃; for 4h; Further stages.;
	(i) nBuLi, Et₂O, benzene, (ii) /BRN= 1209232/; Multistep reaction;

Reference： [1]Moon, Kyung-Soo; Kim, Ho-Joong; Lee, Eunji; Lee, Myongsoo [Angewandte Chemie - International Edition, 2007, vol. 46, # 36, p. 6807 - 6810]
[2]Baker,R. et al. [Journal of the Chemical Society, 1964, p. 627 - 633]

5
[ 589-87-7 ]
[ 22868-26-4 ]
[ 58743-83-2 ]

Yield	Reaction Conditions	Operation in experiment
60%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; silver(l) oxide In tetrahydrofuran at 60℃; for 36h;
60%	With silver(l) oxide In tetrahydrofuran at 60℃; for 36h;

Reference： [1]Hirabayashi, Kazunori; Mori, Atsunori; Kawashima, Jun; Suguro, Masahiro; Nishihara, Yasushi; Hiyama, Tamejiro [Journal of Organic Chemistry, 2000, vol. 65, # 17, p. 5342 - 5349]
[2]Hirabayashi, Kazunori; Kawashima, Jun; Nishihara, Yasushi; Mori, Atsunori; Hiyama, Tamejiro [Organic Letters, 1999, vol. 1, # 2, p. 299 - 301]

6
[ 5720-07-0 ]
[ 106-40-1 ]
[ 58743-83-2 ]

Yield	Reaction Conditions	Operation in experiment
67%	Stage #1: 4-bromo-aniline With tert.-butylnitrite; boron trifluoride diethyl etherate In methanol at 0℃; for 0.5h; Schlenk technique; Stage #2: 4-methoxyphenylboronic acid In methanol at 0 - 60℃; for 5h; Schlenk technique;
65%	Stage #1: 4-bromo-aniline With tert.-butylnitrite; boron trifluoride diethyl etherate at -15 - 5℃; for 0.583333h; Stage #2: 4-methoxyphenylboronic acid With (R,R)-N,N'-(2-MeC₆H₄)2-N,N'-(cyclohexane-1,2-diyl)thiourea In methanol at 20℃; for 4h;

Reference： [1]Zong, Yan; Hu, Jiefeng; Sun, Peipei; Jiang, Xiaoqing [Synlett, 2012, vol. 23, # 16, p. 2393 - 2396]
[2]Dai, Mingji; Liang, Bo; Wang, Cuihua; Chen, Jiahua; Yang, Zhen [Organic Letters, 2004, vol. 6, # 2, p. 221 - 224]

7
[ 106-37-6 ]
[ 5720-07-0 ]
[ 58743-83-2 ]
[ 13021-19-7 ]

Yield	Reaction Conditions	Operation in experiment
1: 30% 2: 22%	With disodium[(N,N’-bis(2-hydroxy-5-sulfonatobenzyl)-1,2-diphenyl-1,2-diaminoethano)palladate(II)]; caesium carbonate In water at 80℃; for 1h;	Catalysis experiments and gas chromatographic analysis of the reaction mixtures General procedure: Stock solutions of the catalysts (Na2[Pd(HSS)], Na2[Pd(PrHSS)], Na2[Pd(BuHSS)],Na2[Pd(dPhHSS)], rac-Na2[Pd(CyHSS)], Na2[Pd(cis-CyHSS)]) Na2[Pd(trans-CyHSS)]) were prepared by dissolving 5.0×10-7 mol complex in 6 mL water. In general, 0.5 mmol aryl-halide, 0.75 mmol boronic acid derivative (1.5 mmol in the reactions of aryl-dihalides), and 0.5 mmolbase (Cs2CO3) were used in each reaction. Good quality distilled water was used as solvent, the organic phase was comprised of the substrates. 3 mL of water was used in each reaction. The reactions were carried out at 80 °C in 30-120 min reaction time. At the end of the reactions, the mixtures were allowed to cool to room temperature and then were extracted by chlorofom (2 mL). After separation of the phases (15-20 min) the organic phase was removed by a Pasteur pipette and filtered through a short MgSO4 plug.
	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; caesium carbonate In methanol; toluene Heating;

Reference： [1]Bunda, Szilvia; Joó, Ferenc; Kathó, Ágnes; Udvardy, Antal; Voronova, Krisztina [Molecules, 2020, vol. 25, # 17]
[2]Sinclair, David J.; Sherburn, Michael S. [Journal of Organic Chemistry, 2005, vol. 70, # 9, p. 3730 - 3733]

8
[ 2170-13-0 ]
[ 58743-83-2 ]

Reference： [1]Journal of Heterocyclic Chemistry,2001,vol. 38,p. 11 - 23

9
[ 58743-83-2 ]
[ 40501-41-5 ]

Reference： [1]Molecular Crystals and Liquid Crystals (1969-1991),1985,vol. 131,p. 1 - 8

10
[ 58743-83-2 ]
4-bromo-2-methyl-2H-pyrazol-3-ylamine [ No CAS ]
(4-bromo-2-methyl-2H-pyrazol-3-yl)-(4'-methoxy-biphenyl-4-yl)-amine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With sodium t-butanolate In toluene at 80℃; for 48h;	1.19 Example 1.19; Preparation of (4-Bromo-2-methyl-2H-pyrazol-3-yl)-(4'-methoxy-biphenyl-4-yI)-amine(Compound 13).A 20-mL scintillation vial was charged with 4'-bromo-4-methoxy-biphenyl (263.1 mg, 1 mmol), 3-amino-4-bromo-2-methyl pyrazole (176.0 mg, 1 mmol), sodium fert-butoxide (134.5 mg, 1.4 mmol), tris(dibenzylideneacetone)dipalladium(0) (45.8 mg, 0.05 mmol), BESfAP (62.3 mg, 0.1 mmol) and toluene (2 mL) under nitrogen atmosphere. The reaction mixture was heated at 800C for 48 hours. It was then allowed to cool to room temperature, taken up in ether/ethyl acetate, filtered and concentrated. The crude material was subjected to column chromatography on silica gel (Biotage, eluent hexanes/ethyl acetate 70/30) to afford Compound 13 as a yellow solid. LCMS m/z (%) = 358 (M+H 79Br, 100), 360 (M+H 81Br, 98).

Reference： [1]Current Patent Assignee: PFIZER INC - WO2006/60762, 2006, A2 Location in patent: Page/Page column 72

11
[ 589-87-7 ]
[ 5720-07-0 ]
[ 58743-83-2 ]

Yield	Reaction Conditions	Operation in experiment
99%	With caesium carbonate In water; N,N-dimethyl-formamide at 20℃; Inert atmosphere;	General procedure for Suzuki cross coupling reaction General procedure: The Suzuki coupling reactions were carried out in a test tube (13 mm) using an organic synthesizer. Aryl iodides, bromides and chlorides (0.1 mmol) base (150 mol%), arylboronic acid (0.15 mmol) and Pd catalysts 3-5 atom% were placed in a test tube. The argon gas was supplied from the balloon with argon exchange 2 times without degassing. Solvent was added and stirred at 1000 rpm at specified temperature for the desired time. Completion of the reaction was monitored by TLC. After completion, the reaction was cooled and quenched by 1M HCl, extract with EtOAc. The organic layer was evaporated, dried and the yields were reported as NMR or isolated yield after purification by silica gel column chromatography (eluted with EtOAc/Hexane). The products were confirmed by 1H NMR spectra and mass comparing with the pure, commercially available compounds and reported NMR in the literature which exactly matched with the reported values.1-18
95%	With sodium carbonate In 1-methyl-pyrrolidin-2-one at 100℃; for 8h; Inert atmosphere;
84%	With potassium fluoride In toluene at 80℃; for 3.5h;

With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate In water; N,N-dimethyl-formamide at 110℃; Inert atmosphere; Sealed tube;

General procedure: To a solution of 4-Methylphenylboronic acid (2.8g,21mmol) in DMF/water (v/v, 1:1) was added 1-bromo-4-iodobenzene (4g, 14mmol) , Tetrakis (triphenylphosphine)palladium (0.8g, 0.7mmol) and K2CO3 (5.8g, 42mmol), themixture was stirred at 110oC in a sealed tube under N2 over night. The reaction mixture was cooled and poured into an ice-wate rmixture solution, filtering to get solid material. The residue was purified by column chromatography on silica gel (petroleum ether) to yield the title compound

Reference： [1]Karanjit, Sangita; Kashihara, Masaya; Nakayama, Atsushi; Shrestha, Lok Kumar; Ariga, Katsuhiko; Namba, Kosuke [Tetrahedron, 2018, vol. 74, # 9, p. 948 - 954]
[2]Nikitin, Oleg M.; Polyakova, Olga V.; Sazonov, Petr K.; Yakimansky, Alexander V.; Goikhman, Mikhail Ya.; Podeshvo, Irina V.; Magdesieva, Tatiana V. [New Journal of Chemistry, 2016, vol. 40, # 12, p. 10465 - 10473]
[3]Suzuki, Ken; Fontaine, Arnaud; Hori, Yoji; Kobayashi, Tohru [Synlett, 2007, # 20, p. 3206 - 3208]
[4]Ding, Yuyang; Mao, Liufeng; Xu, Dengfeng; Xie, Hui; Yang, Ling; Xu, Hongjiang; Geng, Wenjun; Gao, Yong; Xia, Chunguang; Zhang, Xiquan; Meng, Qingyi; Wu, Donghai; Zhao, Junling; Hu, Wenhui [Bioorganic and Medicinal Chemistry Letters, 2015, vol. 25, # 14, p. 2744 - 2748]

12
[ 106-37-6 ]
[ 5720-07-0 ]
[ 58743-83-2 ]

Yield	Reaction Conditions	Operation in experiment
90%	With palladium diacetate at 20℃; for 3h; Green chemistry;
82%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; caesium carbonate In methanol; toluene for 12h; Reflux; Inert atmosphere; regiospecific reaction;	4.2.1. 4-Bromo-4'-methoxybiphenyl (4)²³ The reaction was carried out by following the reflux-12 h procedure, using p-dibromobenzene (2, 0.50 g, 2.12 mmol), 4-methoxyphenyl boronic acid (3a, 0.22 g, 1.41 mmol), cesium carbonate (0.92 g, 2.82 mmol), Pd(PPh3)4 (0.13 g, 0.11 mmol), toluene (20 mL), and methanol (10 mL). Compound 4 was isolated by column chromatography (silica gel, cyclohexane/AcOEt 8/2) as a white solid (0.31 g, 82% yield), mp: 143-145 °C; 1H NMR (400 MHz, CDCl3) δ: 7.53 (dd, 4H, J=7.6, 8.8 Hz, ArH), 7.40 (d, 2H, J=8.3 Hz, ArH), 6.97 (d, 2H, J=8.8 Hz, ArH), 3.84 (s, 3H, OCH3) ppm; MS m/z (%): 264 (M+, 0.2), 262 (0.2), 184 (100), 169 (47), 152 (5).
80%	Stage #1: 1.4-dibromobenzene With 3,3’-(pyridine-2,6-diylbis(1H-imidazole-3-ium-1,3-diyl))bis(propane-1-sulfonate); palladium diacetate; potassium carbonate In water; acetonitrile at 30℃; for 0.166667h; Inert atmosphere; Schlenk technique; Stage #2: 4-methoxyphenylboronic acid In water; acetonitrile at 20℃; for 12h; Inert atmosphere; Schlenk technique;

80%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; caesium carbonate In methanol; toluene at 100℃; for 16h; Inert atmosphere;	18.A Step A: Step A: 4-bromo-4'-methoxy-1,1'-biphenyl To a solution of (4-methoxyphenyl)boronic acid (5 g, 32.9 mmol) in toluene/MeOH (200 mL/100 mL) was added 1,4-dibromobenzene (11.6 g, 49.4 mmol), Pd(PPh3)4 (1.9 g, 1.65 mmol) and Cs2CO3 (21.4 g, 65.8 mmol). The resulting solution was stirred at 100° C. for 16 hours under N2 atmosphere. TLC showed the reaction was completed. After cooled to room temperature, the reaction mixture was diluted with 50 mL of EA, washed with water, brine. The organic phase was dried over anhydrous sodium sulfate and concentrated in vacuo. The residue was purified by chromatography column to afford 4-bromo-4'-methoxy-1,1'-biphenyl (7.0 g, 80% yield). LCMS (ES+): m/z 263.1 [M+H]+.
80%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; caesium carbonate In methanol; toluene at 100℃; for 16h; Inert atmosphere;	A Step A: 4-bromo-4'-methoxy-1,1'-biphenyl To a solution of (4-methoxyphenyl)boronic acid (5 g, 32.9 mmol) in toluene/ MeOH (200 mL/100 mL) was added 1,4-dibromobenzene (11.6 g, 49.4 mmol), Pd(PPh3)4 (1.9 g, 1.65 mmol) and Cs2CO3 (21.4 g, 65.8 mmol). The resulting solution was stirred at 100 °C for 16 hours under N2 atmosphere. TLC showed the reaction was completed. After cooled to room temperature, the reaction mixture was diluted with 50 mL of EA, washed with water, brine. The organic phase was dried over anhydrous sodium sulfate and concentrated in vacuo. The residue was purified by chromatography column to afford 4-bromo-4'-methoxy-1,1'-biphenyl (7.0 g, 80% yield). LCMS (ES+): m/z 263.1 [M+H]+.
69%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; sodium carbonate In toluene at 90 - 100℃; for 14h; Inert atmosphere;
67%	With potassium hydroxide In water at 60℃; for 10h;
34%	With palladium diacetate; caesium carbonate; triphenylphosphine In toluene at 110℃; for 16h; Inert atmosphere;
	Stage #1: 1.4-dibromobenzene; 4-methoxyphenylboronic acid With tetrakis(triphenylphosphine) palladium⁽⁰⁾ In tetrahydrofuran for 0.25h; Inert atmosphere; Stage #2: With sodium carbonate In tetrahydrofuran; 1,2-dimethoxyethane; water at 70℃; for 12h; Inert atmosphere;	Synthesis of 25 Under an argon atmosphere 19 (2.0 g, 13.1 mmol), 1,4-dibromobenzene (6.2 g, 26.3 mmol, 2 eq.) and Pd(PPh3)4 (0.23 g, 0.2 mmol) were dissolved in dry THF (44 mL, 0.3 M). After stirring for 15 min, a solution of Na2CO3 (5.58 g, 52.6 mmol) in H2O (14 mL, 60 eq.) was added to the reaction mixture. And then some droplets of ethylene glycol were added to the mixture and heated to 70 °C for 12 h. After cooling to room temperature, the mixture was filtered through celite using ethyl acetate. The resulting organic layer was washed with saturated aqueous solution of ammonium chloride and brine. The combined organic layers were dried over anhydrous MgSO4 and evaporated under reduced pressure. The crude product was suspended in boiling ethanol (60 mL) and filtered while being hot. (Gray filter cake was obtained). Residual filtrate was crystallized by cold EtOH.

Reference： [1]Boruah, Preeti Rekha; Ali, Abdul Aziz; Chetia, Mitali; Saikia, Bishwajit; Sarma, Diganta [Chemical Communications, 2015, vol. 51, # 57, p. 11489 - 11492]
[2]Location in patent: experimental part Guillén, Elena; Hierrezuelo, Jesús; Martínez-Mallorquín, Rocio; López-Romero, J. Manuel; Rico, Rodrigo [Tetrahedron, 2011, vol. 67, # 14, p. 2555 - 2561]
[3]Prajapati; Schulzke; Kindermann; Kapdi [RSC Advances, 2015, vol. 5, # 65, p. 53073 - 53085]
[4]Current Patent Assignee: ARVINAS; YALE UNIVERSITY - US2018/179183, 2018, A1 Location in patent: Paragraph 1606
[5]Current Patent Assignee: ARVINAS; YALE UNIVERSITY - WO2020/51564, 2020, A1 Location in patent: Paragraph 0909; 0910
[6]Moorthy, Jarugu Narasimha; Koner, Apurba L.; Samanta, Subhas; Roy, Ankur; Nau, Werner M. [Chemistry - A European Journal, 2009, vol. 15, # 17, p. 4289 - 4300]
[7]Dey, Deepa; Bhattacharya, Tamalika; Majumdar, Biju; Mandani, Sonam; Sharma, Bhagwati; Sarma, Tridib K. [Dalton Transactions, 2013, vol. 42, # 38, p. 13821 - 13825]
[8]Mills, L. Reginald; Graham, Joshua M.; Patel, Purvish; Rousseaux, Sophie A. L. [Journal of the American Chemical Society, 2019, vol. 141, # 49, p. 19257 - 19262]
[9]Kim, Nam-Kyun; Sogawa, Hiromitsu; Takata, Toshikazu [Tetrahedron Letters, 2020, vol. 61, # 23]

13
[ 58743-83-2 ]
[ 247174-71-6 ]
[ 337534-45-9 ]

Yield	Reaction Conditions	Operation in experiment
39%	Stage #1: 4-bromo-4'-methoxylbiphenyl With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1h; Stage #2: 1-[1H-imidazol-4⁽⁵⁾-yl]-2-methylpropan-1-one In tetrahydrofuran; hexane at -78 - 20℃; Stage #3: With water; ammonium chloride In tetrahydrofuran; hexane	4.1. General procedure for method A and 1-[1,1'-biphenyl]-3-yl-1-(1H-imidazol-4-yl)-2-methyl-1-propanol (5) General procedure: n-BuLi in hexane (1.6 M; 6.4 mL, 10.2 mmol) was added to a cooled (-78 °C) solution of 2a (2.11 g, 9.05 mmol) in THF (30 mL) and the mixture was stirred at -78 °C for 1 h. A solution of 4 (400 mg, 2.89 mmol) in THF (10 mL) was added to the mixture and the solution was allowed to warm to rt. The reaction was quenched with aqueous NH4Cl solution and the aqueous phase was extracted with AcOEt. The extract was dried over MgSO4 and concentrated under reduced pressure. The residue was chromatographed on silica gel (CH2Cl2/MeOH = 20:1) and recrystallized from AcOEt-hexane to give 5 (450 mg, 1.54 mmol, 53%) as a colorless powder.

Reference： [1]Location in patent: experimental part Kaku, Tomohiro; Tsujimoto, Saori; Matsunaga, Nobuyuki; Tanaka, Toshimasa; Hara, Takahito; Yamaoka, Masuo; Kusaka, Masami; Tasaka, Akihiro [Bioorganic and Medicinal Chemistry, 2011, vol. 19, # 7, p. 2428 - 2442]

14
[ 104-92-7 ]
[ 5467-74-3 ]
[ 58743-83-2 ]

Yield	Reaction Conditions	Operation in experiment
97%	With potassium carbonate; palladium dichloride In ethanol; water at 20℃; for 0.5h;	General procedure for the Suzuki reaction of aryl bromides with arylboronic acids General procedure: A mixture of aryl bromide (0.5 mmol), arylboronic acid (0.75 mmol), PdCl2 (0.0025 mmol, 0.44 mg), K2CO3 (1 mmol) was stirred in distilled water (2 mL) and ethonal (2 mL) at room temperature in air for the indicated time. After the completion of the reaction, the mixture was quenched by brine (15 mL), extracted with diethyl ether (4×10 mL), dried by anhydrous MgSO4, concentrated under vacuum and the product was afforded by column chromatography on silica gel (200-300 mesh) eluted with petroleum ether and ethyl acetate.
94%	With potassium carbonate In ethyl acetate at 90℃; for 1.5h;
87%	With C₁₂H₁₂Cl₂N₄O₂Pd; caesium carbonate In water at 60℃; for 4h;	General procedure for the Reaction of Arylboronic Acids and Halobenzenes General procedure: In an oven dried 10 mL round bottom flask were added arylboronic acid 1 (1.0 mmol), halobenzene 2 (1.0 mmol), Cs2CO3 (0.5 equiv) and catalyst C4 (1.0 mol%) in water (1mL). The reaction mixture was allowed to stir at 60 oC for completion. After completion of reaction (monitored by TLC) the crude residue was extracted into in ethylacetate (10 mL x 3) and dried over anhydrous sodium sulphate, filtered and evaporated under reduced pressure. The crude mixture was separated using silica-gel column chromatography by eluting with ethylacetate/hexanes.

7 %Spectr.

With C₁₆H₂₈Cl₂N₄O₂Pd; potassium carbonate In methanol; carbon dioxide at 120℃; for 1h; Supercritical conditions;

Reference： [1]Qiu, Jun; Wang, Limin; Liu, Mingtao; Shen, Qiang; Tang, Jun [Tetrahedron Letters, 2011, vol. 52, # 48, p. 6489 - 6491]
[2]Han, Yi; Di, Jia-Qi; Zhao, Ai-Dong; Zhang, Zhan-Hui [Applied Organometallic Chemistry, 2019, vol. 33, # 10]
[3]Thunga, Sanjeeva; Poshala, Soumya; Anugu, Naveenkumar; Konakanchi, Ramaiah; Vanaparthi, Satheesh; Kokatla, Hari Prasad [Tetrahedron Letters, 2019, vol. 60, # 31, p. 2046 - 2048]
[4]Location in patent: experimental part Fernandes, Ricardo R.; Lasri, Jamal; DaSilva, M. Fatima C. Guedes; Palavra, Antonio M. F.; Dasilva, Jose A. L.; Dasilva, Joao J. R. Frausto; Pombeiro, Armando J. L. [Advanced Synthesis and Catalysis, 2011, vol. 353, # 7, p. 1153 - 1160]

15
[ 5720-07-0 ]
[ 589-21-9 ]
[ 58743-83-2 ]

Yield	Reaction Conditions	Operation in experiment
72%	With bis-triphenylphosphine-palladium(II) chloride; sodium dodecyl-sulfate; potassium carbonate; p-toluenesulfonyl chloride In water at 60℃;	Typical procedure for Pd-catalyzed Suzuki cross-coupling of arylhydrazines with aryl boronic acids General procedure: A mixture of arylhydrazine 1 (0.24mmol, 1.2equiv.), aryl boronic acid 2 (0.2 mmol), K2CO3(0.6 mmol, 3.0 equiv.), p-toluenesulfonylchloride (0.24 mmol, 1.2 equiv.), sodium dodecyl sulfate (0.02 mmol, 10 mol %), and PdCl2(PPh3)2(0.01 mmol, 5 mol %) was stirred at 60 °C in water (2.0 mL) for 4-8 h under air.After completion of the reaction (indicated by TLC), the mixture was quenched with saturatedNaCl solution, extracted by EtOAc,and dried with Na2SO4. The crude product was purified by flash columnchromatography to provide the corresponding product 3.

Reference： [1]Liu, Jin-Biao; Zhou, He-Ping; Peng, Yi-Yuan [Tetrahedron Letters, 2014, vol. 55, # 17, p. 2872 - 2875]

16
[ 613-37-6 ]
[ 58743-83-2 ]

Yield	Reaction Conditions	Operation in experiment
32 %Chromat.	With N-Bromosuccinimide; [bis(acetoxy)iodo]benzene; nickel dibromide In water-d2 at 25℃; for 24h; Sealed tube; Inert atmosphere;	2.3. Standard procedure for catalytic bromination General procedure: To 2 mL CF3COOH (or D2O), 0.25 mmol substrate, 0.5 mmol oxidizing agent, 0.375 mmol NBS and 5 mol% catalyst were added. The reagents were taken in a specially designed tube (10 mL), were purged with N2 gas, and sealed; the mixture was stirred for 24 h at room temperature. Next, the volatiles were removed under reduced pressure. The brominated products were analyzed by 1HNMR spectroscopy and the yields were calculated by GC/MS using dodecane as an internal standard.
32.0 %Chromat.	With N-Bromosuccinimide; [bis(acetoxy)iodo]benzene; nickel dibromide In water-d2 at 20℃; for 24h; Inert atmosphere; Sealed tube;

Reference： [1]Bhattacharya, Moumita; Cluff, David B.; Das, Siddhartha [Inorganica Chimica Acta, 2014, vol. 423, # 1, p. 238 - 241]
[2]Bhattacharya, Moumita; Cluff, David B.; Das, Siddhartha [Inorganica Chimica Acta, 2014, vol. 423, # PA, p. 238 - 241]

17
[ 58743-83-2 ]
[ 189628-37-3 ]
(5-bromo-2-chlorophenyl)(4'-methoxy-[1, 1'-biphenyl]-4-yl)methanol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
60%		General procedure: To a cold (-78 oC) solution of 4-bromo-4'-methylbiphenyl 14d (2.5g, 10mmol) in THF (25mL) was added n-BuLi (2.5M in hexane; 4 mL, 10 mmol) and the mixture was stirredat -78 oC for 1 h. To the reaction mixture was added a solution of 10c(2.34 g, 11mmol) in THF (20 mL) and the mixture was stirred at -78 oCfor 3h. To the reaction mixture was added saturated ammonium chloride solutionand EtOAc, then the organic layer was separated and washed with brine, driedover Na2SO4, filtered and evaporated in vacuo. Theresulting residue was purified by column chromatography on silica gel(EtOAc/petroleum ether = 1:10) to give the title compound.

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2015,vol. 25,p. 2744 - 2748

18
[ 696-62-8 ]
[ 5467-74-3 ]
[ 58743-83-2 ]

Yield	Reaction Conditions	Operation in experiment
88%	With potassium carbonate In N,N-dimethyl-formamide at 80℃; for 1.5h;	2.4. General procedure for Suzuki-Miyaura cross-coupling General procedure: A round bottom flask (50 mL) equipped with condenser was chargedwith aryl halide (1.0 mmol), arylboronic acid (1.2 mmol), K2CO3(2 mmol), Pd(II)-AMP-CellAl2O3 (40 mg) and dimethyl formamide(DMF) (5 mL). The mixture was stirred in an oil bath at 80 °C. Uponcompletion of the reaction as monitored by thin layer chromatography(TLC) (petroleum ether:ethyl acetate, 95:0.5), the reaction mixture wasfiltered. The filtrate was extracted with ethyl acetate (3 × 5 mL). Thecombined organic layers were collected, dried over anhydrous Na2SO4,and concentrated in vacuum to afford the crude products. These productswere purified by silica gel column chromatography (Ether /EtOAc = 9:1 v/v).
83%	With bis-triphenylphosphine-palladium(II) chloride; Aliquat 336; potassium carbonate In tetrahydrofuran; water Reflux;
76%	With sodium carbonate In water; toluene at 100℃; for 12h; Inert atmosphere;	1.1 Step 1: Synthesis of 4-bromo-4'-methoxy-1,1'-biphenyl (21): To a mixture of compound 19 (200 mg, 0.85 mmol)and compound 20 (257 mg, 1.28 mmol)in toluene- water (9: 1)(35 mL)was added Na2CO3 (181 mg, 1.70 mmol)and the reaction mixture was degassed with N2 for 20 min. PdCl2(dppf complex (60 mg, 0.08 mmol)was added and the reaction mixture was heated to 100 °C for 12 h. After completion of the reaction, the mixture was filtered through a Celite pad, filtrate was concentrated and purified by silica gel column chromatography [gradient elution with EtOAc: Hexane (10:90)] to afford compound 21 (200 mg, 76%). 1H NMR (400 MHz, CD2Cl2): d 7.51 (dd, J= 17.5, 7.0, 2.2 Hz, 4H), 7.41 (dd, J = 8.7, 2.1 Hz, 2H), 6.97 (dd, J= 8.7, 2.1 Hz, 2H), 3.85 (s, 3H).

Reference： [1]Mhaldar, Pradeep; Pore, Dattaprasad; Rashinkar, Gajanan; Vibhute, Sandip [Reactive and Functional Polymers, 2020, vol. 152]
[2]Sen, Choong Ping; Valiyaveettil, Suresh [RSC Advances, 2016, vol. 6, # 97, p. 95137 - 95148]
[3]Current Patent Assignee: SRX CARDIO LLC - WO2020/252383, 2020, A2 Location in patent: Paragraph 00232; 00248

19
[ 58743-83-2 ]
[ 1202355-37-0 ]

Reference： [1]RSC Advances,2016,vol. 6,p. 95137 - 95148

20
[ 121-43-7 ]
[ 58743-83-2 ]
[ 156642-03-4 ]

Yield	Reaction Conditions	Operation in experiment
58%	Stage #1: 4-bromo-4'-methoxylbiphenyl With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1h; Inert atmosphere; Stage #2: Trimethyl borate In tetrahydrofuran; hexane at -78 - 5℃;	18.B Step B: Step B: (4'-methoxy-[1,1'-biphenyl]-4-yl)boronic acid To a solution of 4-bromo-4'-methoxy-1,1'-biphenyl (2 g, 7.63 mmol) in dry THF (30 mL) was added n-BuLi (9.2 ml, 22.9 mmol, 2.5 M in hexane) dropwise at -78° C. under N2 atmosphere. 1 hour later, (CH3O)3B (2.38 g, 22.9 mmol) was added dropwise at -78° C. The resulting solution was stirred for 1 hour at -78° C. and overnight at 5° C. After quenched with saturated NH4Cl solution, the mixture was extracted with EA (30 mL*2.) The combined organic layer was dried over anhydrous sodium sulfate. The residue was purified by chromatography column to afford (4'-methoxy-[1,1'-biphenyl]-4-yl)boronic acid (1.0 g, 58% yield). 1H NMR (400 MHz, DMSO-d6): δ 8.06 (s, 2H), 7.84 (d, J=7.6 Hz, 2H), 7.63 (d, J=7.6 Hz, 2H), 7.58 (d, J=7.6 Hz, 2H), 7.02 (d, J=7.6 Hz, 2H), 3.80 (s, 3H).
58%	Stage #1: 4-bromo-4'-methoxylbiphenyl With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1h; Inert atmosphere; Stage #2: Trimethyl borate In tetrahydrofuran; hexane at -78 - 5℃;	B Step B: (4'-methoxy-[ biphenyl]-4-yl)boronic acid To a solution of 4-bromo-4'-methoxy-1,1'-biphenyl (2 g, 7.63 mmol) in dry THF (30 mL) was added n-BuLi (9.2 ml, 22.9 mmol, 2.5 M in hexane) dropwise at -78 oC under N2 atmosphere.1 hour later, (CH3O)3B (2.38 g, 22.9 mmol) was added dropwise at -78 oC. The resulting solution was stirred for 1 hour at -78 oC and overnight at 5 °C. After quenched with saturated NH4Cl solution, the mixture was extracted with EA (30 mL x 2.) The combined organic layer was dried over anhydrous sodium sulfate. The residue was purified by (2081) chromatography column to afford (4'-methoxy-[1,1'-biphenyl]-4-yl)boronic acid (1.0 g, 58% yield). 1H NMR (400 MHz, DMSO-d6): d 8.06 (s, 2H), 7.84 (d, J = 7.6 Hz, 2H), 7.63 (d, J = 7.6 Hz, 2H), 7.58 (d, J = 7.6 Hz, 2H), 7.02 (d, J = 7.6 Hz, 2H), 3.80 (s, 3H).

Reference： [1]Current Patent Assignee: ARVINAS; YALE UNIVERSITY - US2018/179183, 2018, A1 Location in patent: Paragraph 1608
[2]Current Patent Assignee: ARVINAS; YALE UNIVERSITY - WO2020/51564, 2020, A1 Location in patent: Paragraph 0911; 0912

21
[ 4482-01-3 ]
[ 5720-07-0 ]
[ 106-40-1 ]
[ 58743-83-2 ]

Yield	Reaction Conditions	Operation in experiment
91%	Stage #1: o-benzenedisulfonimide; 4-bromo-aniline With acetic acid at 0 - 5℃; for 0.166667h; Inert atmosphere; Stage #2: With isopentyl nitrite for 0.166667h; Inert atmosphere; Stage #3: 4-methoxyphenylboronic acid With bis[(trifluoromethanesulfonyl)imidate]-2-(dicyclohexyl(2’,6’-dimethoxybiphenyl))phosphine gold(I); caesium carbonate In tetrahydrofuran at 20℃; for 2h; Inert atmosphere; chemoselective reaction;	3.19 4.3 4-Methoxybiphenyl (4a): representative procedure for the Au catalysed Suzuki-Miyaura couplings General procedure: In a oven-dried flask and under nitrogen flow, benzenediazonium o-benzenedisulfonimide (1a, 161mg, 0.5mmol) was added to a suspension of 4-methoxyphenylboronic acid (3a, 91mg, 0.6mmol), [bis(trifluoromethanesulfonyl)imidate](triphenylphosphine)gold(I) (2:1) toluene adduct (39mg, 0.025mmol, 5mol%), Cs2CO3 (325mg, 1mmol) in THF (5mL). The resulting mixture was stirred at room temperature for 2h; the completion of the reaction was confirmed by the absence of azo coupling with 2-naphthol. Then, the reaction mixture was poured into diethyl ether/water (100mL, 1:1). The aqueous layer was separated and extracted with diethyl ether (50mL). The combined organic extracts were washed with water (50mL), dried with Na2SO4 and evaporated under reduced pressure. GC-MS analyses of the crude residue showed 4-methoxybiphenyl (4a), MS (EI): m/z 184 (M+) as the major product, besides traces of biphenyl, MS (EI): m/z 154 (M+), 4,4'-dimethoxybiphenyl, MS (EI): m/z 214 (M+), N-phenyl-o-benzenedisulfonimide, MS (EI): m/z 295 (M+). The crude residue was purified on a short column, eluting with petroleum ether/diethyl ether (9:1). The only isolated product was the title compound (4a, 81mg, 88% yield).

Reference： [1]Barbero, Margherita; Dughera, Stefano [Tetrahedron, 2018, vol. 74, # 39, p. 5758 - 5769]

22
[ 2005-10-9 ]
[ 58743-83-2 ]
6-(4'-methoxy-[1,1'-biphenyl]-4-yl)benzo[c]chromen-5-ium perchlorate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
43%	Stage #1: 4-bromo-4'-methoxylbiphenyl With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1.5h; Inert atmosphere; Stage #2: 6H-benzo[c]chromen-6-one In tetrahydrofuran; hexane at -78 - 20℃; for 2h; Inert atmosphere; Stage #3: With perchloric acid; acetic anhydride In diethyl ether; water at 0℃;	4.4. 6-(40-Methoxy-[1,10-biphenyl]-4-yl)benzo[c]chromen-5-iumperchlorate (15) 4-bromo-4'-methoxybiphenyl 6 (0.671 g, 2.55 mmol) was dissolved in 10 mL of anhydrous THF in an oven dried round bottom flask. The solution was cooled to 78 C in a dry ice/acetone bath and sparged with Ar for 45 min. 1.6 M n-BuLi in hexane (1.70 mL,2.72 mmol) was added dropwise via syringe and the reaction was stirred for 1.5 h at 78 C. During this time 6H-benzo[c]chromen-6-one 9 (0.500 g, 2.55 mmol) was dissolved in 10 mL of anhydrous THF in a separate oven dried round bottom flask. The solution was cooled to 78 C in a dry ice/acetone bath and sparged with Ar for 30 min. The aryllithium solution was transferred to the solution containing 9 at 78 C via cannula under Ar pressure. The cooling bath was removed, and the reaction was allowed to stir for 2 h. 50 mL of sat. NH4Cl was added to the reaction and subsequently extracted 3x with 25 mL of Et2O. The combined organics were dried with MgSO4, filtered, and concentrated under reduced pressure. The crude product was dissolved in 25 mL of diethyl ether and cooled to 0 C in an ice bath and stirred very rapidly. A chilled (0 C) solution of 70% perchloric acid in acetic anhydride (1:3 by volume) was slowly added drop-wise to the stirring ethereal solution until a colored precipitate formed. The crude product was filtered and recrystallized in glacial acetic acid to yield a red-orange powder (0.508 g, 43%). mp 270e271 C. 1H NMR (400 MHz, CDCl3/CF3CO2D): d 8.90 (d, J 8.5 Hz, 1H), 8.86 (d, J 8.5 Hz, 1H), 8.76 (dd,J 8.3 Hz, J 1.5 Hz, 1H), 8.59 (t, J 7.9 Hz, 1H), 8.36 (d, J 8.5 Hz,2H), 8.27 (dd, J 8.4 Hz, J 1.1 Hz, 1H), 8.17 (t, J 8.3 Hz, 1H), 8.12(td, J 7.9 Hz, J 1.5 Hz, 1H), 8.07-8.01 (m, 3H), 7.77 (d, J 9.0 Hz,2H), 7.12 (d, J 8.8 Hz, 2H), 3.95 (s, 3H). 13C NMR (100 MHz, CDCl3/CF3CO2D): d 183.7, 160.6, 151.6, 150.2, 143.9, 139.7, 136.2, 134.9,134.3,132.1, 131.2, 131.0,129.2,128.2, 127.3, 124.1,124.0, 121.5, 120.5,119.8, 115.3, 55.9. IR (ATR) nmax: 1592, 1483, 1078 cm1. HRMS (ESI)m/z calcd for C26H19O2 [M] 363.1385, found 363.1373.

Reference： [1]Meyer, Samantha M.; Charlesworth-Seiler, Eva M.; Patrow, Joel G.; Kitzrow, Jonathan P.; Gerlach, Deidra L.; Reinheimer, Eric W.; Dahl, Bart J. [Tetrahedron, 2020, vol. 76, # 23]

23
[ 90-47-1 ]
[ 58743-83-2 ]
9-(4'-methoxy-[1,1'-biphenyl]-4-yl)xanthylium perchlorate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
47%	Stage #1: 4-bromo-4'-methoxylbiphenyl With magnesium; ethylene dibromide In tetrahydrofuran Reflux; Inert atmosphere; Stage #2: xanth-9-one In tetrahydrofuran at 0 - 20℃; for 2h; Inert atmosphere; Stage #3: With perchloric acid; acetic anhydride In diethyl ether; water at 0℃; for 0.5h;	4.10. 9-(40methoxy-[1,10-biphenyl]-4-yl)xanthylium perchlorate (24) Magnesium (0.132 g, 5.42 mmol) was placed into an oven-dried round bottom flask and flushed with Ar for 30 min while stirring. 4-Bromo-4'-methoxybiphenyl 6 (1.43 g, 5.42 mmol), anhydrous THF(8 mL), and 2 drops of 1,2-dibromoethane were then added. The reaction was heated to reflux, stirred for 30 min under Ar, and allowed to cool back to rt over 1 h. During this time xanthone 18 (0.532 g, 2.71 mmol) was dissolved in 16 mL of anhydrous THF in a separate oven dried round bottom flask. The flask was cooled to0 C with an ice bath and sparged for 30 min with Ar. The arylmagnesium bromide solution was transferred to the solution containing 18 at 0 C via cannula under Ar pressure. The cooling bath was removed, and the reaction was stirred for 2 h. 50 mL of sat. NaHCO3 was added to the reaction and subsequently extracted 3x with 100 mL of CH2Cl2. The combined organics were washed dried with Na2SO4, filtered, and concentrated under reduced pressure. The crude intermediate was purified via column chromatography using gradient elution (5% EtOAc in hexane/50% EtOAc in hexane) but not characterized further. The purified intermediate was dissolved in 10 mL of diethyl ether and 70% aq. HClO4 was added dropwise at rt until a colored precipitate formed. The reaction was allowed to stir for 30 min and filtered to yield a red solid. The solid was recrystallized in glacial acetic acid to yield small red needles (0.595 g, 47%). mp 230e231 C. 1H NMR (400 MHz, CDCl3/CF3CO2D): d 8.51 (ddd, J 8.6 Hz, J 7.0 Hz, J 1.2 Hz, 2H), 8.37 (d,J 8.8 Hz, 2H) 8.33 (dd, J 8.7 Hz, J 1.3 Hz, 2H), 8.01-7.94 (m, 4H),7.78 (d, J 8.1 Hz, 2H), 7.73 (d, J 8.8 Hz, 2H), 7.10 (d, J 8.8 Hz, 2H)3.94 (s, 3H). 13C NMR (100 MHz, CDCl3/CF3CO2D): d 174.9, 160.2,158.3, 145.7, 144.0, 132.0, 131.9, 131.4, 129.4, 128.7, 128.6, 127.3,123.5,120.0,114.8, 55.6. IR (ATR) nmax: 1596,1578,1083 cm1. HRMS(ESI) m/z calcd for C26H19O2 [M] 363.1385, found 363.1382.

Reference： [1]Meyer, Samantha M.; Charlesworth-Seiler, Eva M.; Patrow, Joel G.; Kitzrow, Jonathan P.; Gerlach, Deidra L.; Reinheimer, Eric W.; Dahl, Bart J. [Tetrahedron, 2020, vol. 76, # 23]

24
[ 58743-83-2 ]
[ 1066-54-2 ]
[ 878131-55-6 ]

Yield	Reaction Conditions	Operation in experiment
69%	With copper(l) iodide; trans-bis(triphenylphosphine)palladium dichloride; water; 1,8-diazabicyclo[5.4.0]undec-7-ene In benzene at 60℃; for 24h; Inert atmosphere; Darkness;	9 Synthesis of compound 12 Add 4-bromo-4-methoxybiphenyl (2.7g, 10.12mmol), DBU (9.2g, 60.43mmol), bistriphenylphosphine palladium dichloride (425mg) into a 100mL two-necked flask, cuprous iodide (191mg), under the protection of argon, ventilate three times, add benzene 40mL, add Trimethylsilylacetylene (0.71mL), water (70ul), Heat to 60°C for 24h in the dark. After the reaction, the reaction solution was cooled to room temperature, and the solvent was removed by rotary evaporation. Add dichloromethane to disperse, filter with suction, wash the residue with water several times, methanol washed to obtain a brown crude product, after recrystallization with a large amount of toluene, compound 12 was obtained as a white solid (1.4 g, 69%).

Reference： [1]Current Patent Assignee: DONGHUA UNIVERSITY - CN109456301, 2021, B Location in patent: Paragraph 0063-0066

25
[ 66107-30-0 ]
C₁₄H₁₄O₂Zn*MgBr*2LiCl [ No CAS ]
[ 58743-83-2 ]

Yield	Reaction Conditions	Operation in experiment
35%	In 2-methyltetrahydrofuran; 1-methyl-pyrrolidin-2-one; at 80℃; for 0.5h;Glovebox; Microwave irradiation; Inert atmosphere;	General procedure: In a glovebox, (het)arylpivalate 1 (0.2 mmol) and NMP (1.5 mL) were added to thediarylzinc 2 (0.3 mmol, prepared by mixing zinc bromide, lithium chloride, and the corresponding aryl magnesium bromidein 1.5 mL of THF) in a reaction tube. The reaction mixturewas then heated at 80 C for 0.5 h under MW irradiation.After completion of the reaction, the mixture was concentratedunder vacuum, and saturated NH4Cl added. The mixturewas extracted with CH2Cl2 several times. The combinedorganic layers were dried over anhydrous MgSO4, concentratedin vacuo, and the residue was purified by column chromatographyon silica gel to give the coupling product 3.

Reference： [1]Journal of Chemical Research,2021,vol. 45,p. 869 - 875

26
[ 58743-83-2 ]
[ 125163-12-4 ]
N-(4-fluoro-5-methoxy-2-nitrophenyl)-4'-methoxy[1,1'-biphenyl]-4-amine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
26%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; sodium tertiary butoxide; dicyclohexyl[2’,4’,6’-tris(propan-2-yl)[1,1’-biphenyl]-2-yl]phosphane In toluene at 100℃; for 16h;	9.1 Step 1: N-(4-Fluoro-5-methoxy-2-nitrophenyl)-4'-methoxy-[1,1'-biphenyl]-4-amine. A mixture of 4-fluoro-5-methoxy-2-nitroaniline (155 mg, 0.84 mmol), 1-bromo-4-(4-methoxyphenyl)benzene (200 mg, 0.76 mmol), tris(dibenzylideneacetone)dipalladium(0) (35 mg, 0.04 mmol), XPhos (36 mg, 0.08 mmol), sodium tert-butoxide (146 mg, 1.52 mmol), and toluene (2 mL) was degassed with 2 vacuum/N2 cycles, stirred at 100 °C for 16 h, and then allowed to cool to rt. The mixture was diluted with EtOAc (15 mL) and water (10 mL). Celite was added, and the mixture was filtered through Celite. The filter cake was washed with EtOAc (10 mL). The organic layer was washed with brine (10 mL), dried (Na2SO4), filtered, concentrated, and then purified by silica gel chromatography (0-15% EtOAc in hexanes) to give N-(4-fluoro-5-methoxy-2-nitrophenyl)-4'-methoxy-[1,1'-biphenyl]-4-amine (73 mg, 26%) as an orange solid. 1H NMR (400 MHz, DMSO-d6): δ 9.74 (s, 1H), 8.02 (d, J = 11.9 Hz, 1H), 7.67 (m, 4H), 7.48 (d, J = 8.6 Hz, 2H), 7.04 (d, J = 8.8 Hz, 2H), 6.85 (d, J = 7.8 Hz, 1H), 3.83-3.81 (m, 3H), 3.81-3.80 (m, 3H); LCMS: 369.2 [M+H]+.
26%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; sodium tertiary butoxide; dicyclohexyl[2’,4’,6’-tris(propan-2-yl)[1,1’-biphenyl]-2-yl]phosphane In toluene at 100℃; for 16h;	9.1 Step 1: N-(4-Fluoro-5-methoxy-2-nitrophenyl)-4'-methoxy-[1,1'-biphenyl]-4-amine. A mixture of 4-fluoro-5-methoxy-2-nitroaniline (155 mg, 0.84 mmol), 1-bromo-4-(4-methoxyphenyl)benzene (200 mg, 0.76 mmol), tris(dibenzylideneacetone)dipalladium(0) (35 mg, 0.04 mmol), XPhos (36 mg, 0.08 mmol), sodium tert-butoxide (146 mg, 1.52 mmol), and toluene (2 mL) was degassed with 2 vacuum/N2 cycles, stirred at 100 °C for 16 h, and then allowed to cool to rt. The mixture was diluted with EtOAc (15 mL) and water (10 mL). Celite was added, and the mixture was filtered through Celite. The filter cake was washed with EtOAc (10 mL). The organic layer was washed with brine (10 mL), dried (Na2SO4), filtered, concentrated, and then purified by silica gel chromatography (0-15% EtOAc in hexanes) to give N-(4-fluoro-5-methoxy-2-nitrophenyl)-4'-methoxy-[1,1'-biphenyl]-4-amine (73 mg, 26%) as an orange solid. 1H NMR (400 MHz, DMSO-d6): δ 9.74 (s, 1H), 8.02 (d, J = 11.9 Hz, 1H), 7.67 (m, 4H), 7.48 (d, J = 8.6 Hz, 2H), 7.04 (d, J = 8.8 Hz, 2H), 6.85 (d, J = 7.8 Hz, 1H), 3.83-3.81 (m, 3H), 3.81-3.80 (m, 3H); LCMS: 369.2 [M+H]+.

Reference： [1]Current Patent Assignee: METACRINE INC - WO2022/72491, 2022, A1 Location in patent: Paragraph 00417
[2]Current Patent Assignee: METACRINE INC - WO2022/72491, 2022, A1 Location in patent: Paragraph 00417

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P260	Do not breathe dust/fume/gas/mist/vapours/spray.
P261	Avoid breathing dust/fume/gas/mist/vapours/spray.
P262	Do not get in eyes, on skin, or on clothing.
P263	Avoid contact during pregnancy/while nursing.
P264	Wash hands thoroughly after handling.
P265	Wash skin thouroughly after handling.
P270	Do not eat, drink or smoke when using this product.
P271	Use only outdoors or in a well-ventilated area.
P272	Contaminated work clothing should not be allowed out of the workplace.
P273	Avoid release to the environment.
P280	Wear protective gloves/protective clothing/eye protection/face protection.
P281	Use personal protective equipment as required.
P282	Wear cold insulating gloves/face shield/eye protection.
P283	Wear fire/flame resistant/retardant clothing.
P284	Wear respiratory protection.
P285	In case of inadequate ventilation wear respiratory protection.
P231 + P232	Handle under inert gas. Protect from moisture.
P235 + P410	Keep cool. Protect from sunlight.
Response
Code	Phrase
P301	IF SWALLOWED:
P304	IF INHALED:
P305	IF IN EYES:
P306	IF ON CLOTHING:
P307	IF exposed:
P308	IF exposed or concerned:
P309	IF exposed or if you feel unwell:
P310	Immediately call a POISON CENTER or doctor/physician.
P311	Call a POISON CENTER or doctor/physician.
P312	Call a POISON CENTER or doctor/physician if you feel unwell.
P313	Get medical advice/attention.
P314	Get medical advice/attention if you feel unwell.
P315	Get immediate medical advice/attention.
P320
P302 + P352	IF ON SKIN: wash with plenty of soap and water.
P321
P322
P330	Rinse mouth.
P331	Do NOT induce vomiting.
P332	IF SKIN irritation occurs:
P333	If skin irritation or rash occurs:
P334	Immerse in cool water/wrap n wet bandages.
P335	Brush off loose particles from skin.
P336	Thaw frosted parts with lukewarm water. Do not rub affected area.
P337	If eye irritation persists:
P338	Remove contact lenses, if present and easy to do. Continue rinsing.
P340	Remove victim to fresh air and keep at rest in a position comfortable for breathing.
P341	If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing.
P342	If experiencing respiratory symptoms:
P350	Gently wash with plenty of soap and water.
P351	Rinse cautiously with water for several minutes.
P352	Wash with plenty of soap and water.
P353	Rinse skin with water/shower.
P360	Rinse immediately contaminated clothing and skin with plenty of water before removing clothes.
P361	Remove/Take off immediately all contaminated clothing.
P362	Take off contaminated clothing and wash before reuse.
P363	Wash contaminated clothing before reuse.
P370	In case of fire:
P371	In case of major fire and large quantities:
P372	Explosion risk in case of fire.
P373	DO NOT fight fire when fire reaches explosives.
P374	Fight fire with normal precautions from a reasonable distance.
P376	Stop leak if safe to do so. Oxidising gases (section 2.4) 1
P377	Leaking gas fire: Do not extinguish, unless leak can be stopped safely.
P378
P380	Evacuate area.
P381	Eliminate all ignition sources if safe to do so.
P390	Absorb spillage to prevent material damage.
P391	Collect spillage. Hazardous to the aquatic environment
P301 + P310	IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician.
P301 + P312	IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell.
P301 + P330 + P331	IF SWALLOWED: Rinse mouth. Do NOT induce vomiting.
P302 + P334	IF ON SKIN: Immerse in cool water/wrap in wet bandages.
P302 + P350	IF ON SKIN: Gently wash with plenty of soap and water.
P303 + P361 + P353	IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower.
P304 + P312	IF INHALED: Call a POISON CENTER or doctor/physician if you feel unwell.
P304 + P340	IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing.
P304 + P341	IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing.
P305 + P351 + P338	IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing.
P306 + P360	IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes.
P307 + P311	IF exposed: call a POISON CENTER or doctor/physician.
P308 + P313	IF exposed or concerned: Get medical advice/attention.
P309 + P311	IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician.
P332 + P313	IF SKIN irritation occurs: Get medical advice/attention.
P333 + P313	IF SKIN irritation or rash occurs: Get medical advice/attention.
P335 + P334	Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages.
P337 + P313	IF eye irritation persists: Get medical advice/attention.
P342 + P311	IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician.
P370 + P376	In case of fire: Stop leak if safe to Do so.
P370 + P378	In case of fire:
P370 + P380	In case of fire: Evacuate area.
P370 + P380 + P375	In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion.
P371 + P380 + P375	In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion.
Storage
Code	Phrase
P401
P402	Store in a dry place.
P403	Store in a well-ventilated place.
P404	Store in a closed container.
P405	Store locked up.
P406	Store in corrosive resistant/ container with a resistant inner liner.
P407	Maintain air gap between stacks/pallets.
P410	Protect from sunlight.
P411
P412	Do not expose to temperatures exceeding 50 oC/ 122 oF.
P413
P420	Store away from other materials.
P422
P402 + P404	Store in a dry place. Store in a closed container.
P403 + P233	Store in a well-ventilated place. Keep container tightly closed.
P403 + P235	Store in a well-ventilated place. Keep cool.
P410 + P403	Protect from sunlight. Store in a well-ventilated place.
P410 + P412	Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF.
P411 + P235	Keep cool.
Disposal
Code	Phrase
P501	Dispose of contents/container to ...
P502	Refer to manufacturer/supplier for information on recovery/recycling

Physical hazards
Code	Phrase
H200	Unstable explosive
H201	Explosive; mass explosion hazard
H202	Explosive; severe projection hazard
H203	Explosive; fire, blast or projection hazard
H204	Fire or projection hazard
H205	May mass explode in fire
H220	Extremely flammable gas
H221	Flammable gas
H222	Extremely flammable aerosol
H223	Flammable aerosol
H224	Extremely flammable liquid and vapour
H225	Highly flammable liquid and vapour
H226	Flammable liquid and vapour
H227	Combustible liquid
H228	Flammable solid
H229	Pressurized container: may burst if heated
H230	May react explosively even in the absence of air
H231	May react explosively even in the absence of air at elevated pressure and/or temperature
H240	Heating may cause an explosion
H241	Heating may cause a fire or explosion
H242	Heating may cause a fire
H250	Catches fire spontaneously if exposed to air
H251	Self-heating; may catch fire
H252	Self-heating in large quantities; may catch fire
H260	In contact with water releases flammable gases which may ignite spontaneously
H261	In contact with water releases flammable gas
H270	May cause or intensify fire; oxidizer
H271	May cause fire or explosion; strong oxidizer
H272	May intensify fire; oxidizer
H280	Contains gas under pressure; may explode if heated
H281	Contains refrigerated gas; may cause cryogenic burns or injury
H290	May be corrosive to metals
Health hazards
Code	Phrase
H300	Fatal if swallowed
H301	Toxic if swallowed
H302	Harmful if swallowed
H303	May be harmful if swallowed
H304	May be fatal if swallowed and enters airways
H305	May be harmful if swallowed and enters airways
H310	Fatal in contact with skin
H311	Toxic in contact with skin
H312	Harmful in contact with skin
H313	May be harmful in contact with skin
H314	Causes severe skin burns and eye damage
H315	Causes skin irritation
H316	Causes mild skin irritation
H317	May cause an allergic skin reaction
H318	Causes serious eye damage
H319	Causes serious eye irritation
H320	Causes eye irritation
H330	Fatal if inhaled
H331	Toxic if inhaled
H332	Harmful if inhaled
H333	May be harmful if inhaled
H334	May cause allergy or asthma symptoms or breathing difficulties if inhaled
H335	May cause respiratory irritation
H336	May cause drowsiness or dizziness
H340	May cause genetic defects
H341	Suspected of causing genetic defects
H350	May cause cancer
H351	Suspected of causing cancer
H360	May damage fertility or the unborn child
H361	Suspected of damaging fertility or the unborn child
H361d	Suspected of damaging the unborn child
H362	May cause harm to breast-fed children
H370	Causes damage to organs
H371	May cause damage to organs
H372	Causes damage to organs through prolonged or repeated exposure
H373	May cause damage to organs through prolonged or repeated exposure
Environmental hazards
Code	Phrase
H400	Very toxic to aquatic life
H401	Toxic to aquatic life
H402	Harmful to aquatic life
H410	Very toxic to aquatic life with long-lasting effects
H411	Toxic to aquatic life with long-lasting effects
H412	Harmful to aquatic life with long-lasting effects
H413	May cause long-lasting harmful effects to aquatic life
H420	Harms public health and the environment by destroying ozone in the upper atmosphere

[ CAS No. 58743-83-2 ]

Quality Control of [ 58743-83-2 ]

Related Doc. of [ 58743-83-2 ]

Product Details of [ 58743-83-2 ]

Safety of [ 58743-83-2 ]

Application In Synthesis of [ 58743-83-2 ]

[ 58743-83-2 ] Synthesis Path-Upstream 1~2

[ 58743-83-2 ] Synthesis Path-Downstream 1~26

Related Functional Groups of [ 58743-83-2 ]

Bromides

Aryls

Ethers

Precautionary Statements-General

Prevention

Response

Storage

Disposal

Physical hazards

Health hazards

Environmental hazards

Inquiry

Related Functional Groups of
[ 58743-83-2 ]