* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Reference：
[1] Chinese Chemical Letters, 2014, vol. 25, # 5, p. 779 - 782
2
[ 3437-95-4 ]
[ 5467-74-3 ]
[ 40133-22-0 ]
Reference：
[1] Journal of Heterocyclic Chemistry, 2000, vol. 37, # 2, p. 281 - 286
3
[ 188290-36-0 ]
[ 5467-74-3 ]
[ 40133-22-0 ]
Reference：
[1] Journal of Organic Chemistry, 2003, vol. 68, # 2, p. 578 - 580
4
[ 188290-36-0 ]
[ 5467-74-3 ]
[ 40133-22-0 ]
[ 20608-85-9 ]
Reference：
[1] Chemical Communications, 2011, vol. 47, # 42, p. 11671 - 11673
5
[ 5467-74-3 ]
[ 22090-26-2 ]
Reference：
[1] Angewandte Chemie - International Edition, 2012, vol. 51, # 15, p. 3642 - 3645
6
[ 5467-74-3 ]
[ 67-68-5 ]
[ 50907-23-8 ]
Reference：
[1] Journal of Organic Chemistry, 2017, vol. 82, # 2, p. 887 - 892
7
[ 5467-74-3 ]
[ 30483-75-1 ]
Reference：
[1] Angewandte Chemie - International Edition, 2012, vol. 51, # 15, p. 3642 - 3645
8
[ 288-32-4 ]
[ 5467-74-3 ]
[ 10040-96-7 ]
Yield
Reaction Conditions
Operation in experiment
90%
With copper(I) sulfide; N,N,N,N,-tetramethylethylenediamine In methanol at 20℃; for 24 h;
General procedure: A 10mL round bottom flask was charged with a magnetic stirring bar, benzimidazole 1 (59mg, 0.5mmol), boronic acid 2 (1.0mmol), Cu2S (4mg, 0.025mmol), and MeOH (2mL), followed with the addition of TMEDA (0.075mL, 0.5mmol). The flask was sealed with a septum, through which was inserted 18-gauche needle. This setup allowed air to go into the reaction and avoid contamination of a mixture. The reaction mixture was stirred from 400 to 600rpm for appropriate time and extracted with EtOAc (2×15mL). Combined organic layers were washed with saturated aqueous solution of ethylenediaminetetraacetic acid disodium salt (15mL), and then dried over anhydrous Na2SO4. Volatiles were removed under reduced pressure and the residue was purified by column chromatography (silica gel, hexanes – EtOAc) to yield the title product, which was characterized by 1H NMR, 13C NMR, HRMS, and melting point (if solid).
81%
With triethylamine In methanol at 20℃; for 5 h;
General procedure: In a typical reaction, arylboronic acid (1 mmol), amino-compound (1 mmol), catalyst (5 wtpercent), Et3N (2 mmol) were mixed in methanol ( 5mL) in a 25mL round bottomed flask. The reaction mixture was subjected under continuous stirring at room temperature for 5 h. Reaction was monitored from time to time using TLC. After completion of the reaction, catalyst was separated with the aid of an external magnet and reaction mixture was taken in ethyl acetate. The organiclayer was washed using brine solution, dried over sodium sulfate. After evaporating the solvent, the crude product was puried by column chromatography using 230–400 silica mesh. The recovered catalyst was washed with methanol and ethyl acetate, dried in oven and kept in desiccator for further use.
74%
With [2,2]bipyridinyl; oxygen; copper diacetate In water at 20℃; for 24 h;
General procedure: Under an O2 atmosphere, a mixture of 4-methoxyphenylboroic acid (1a, 60.8 mg, 0.40 mmol), imidazole (2a, 13.6 mg, 0.20 mmol), Cu(OAc)2 (3.6 mg, 0.020 mmol), ligand I (3.7 mg, 0.020 mmol), and Brij 30 (21.8 mg, 0.060 mmol) in H2O (4 mL) was stirred at room temperature for 24 h. The mixture was diluted with brine and extracted with AcOEt (30 mL.x.3). The organic layer was washed with H2O (10 mL.x.3) and dried over MgSO4. The solvent was removed under the reduced pressure and the residue was purified by SiO2 column chromatography using AcOEt to give N-(4-methoxyphenyl)imidazole (3aa) (23.7 mg, 68percent).
Reference：
[1] Synthesis, 2008, # 5, p. 795 - 799
[2] Tetrahedron, 2018, vol. 74, # 5, p. 606 - 617
[3] Green Chemistry, 2018, vol. 20, # 21, p. 4891 - 4900
[4] Catalysis Communications, 2018, vol. 109, p. 38 - 42
[5] Tetrahedron, 2012, vol. 68, # 38, p. 7794 - 7798
9
[ 3842-55-5 ]
[ 5467-74-3 ]
[ 23449-08-3 ]
Yield
Reaction Conditions
Operation in experiment
96%
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; water at 80℃; for 12 h; Inert atmosphere
Synthesis Example 32: Synthesis of Intermediate I-32 The compound, 2-chloro-4,6-diphenyl-1,3,5-triazine (50 g, 187 mmol) was dissolved in THF (1 L) under a nitrogen environment, (4-bromophenyl)boronic acid (45 g, 224.12 mmol, Aldrich Corporation), and tetrakis(triphenylphosphine)palladium (2.1 g, 1.87 mmol) were added thereto, and the mixture was stirred. Potassium carbonate saturated in water (64 g, 467 mmol) was added thereto, and the obtained mixture was heated and refluxed at 80° C. for 12 hours. When the reaction was complete, water was added to the reaction solution, and the mixture was extracted with dichloromethane (DCM) and then, filtered after removing moisture with anhydrous MgSO4 and concentrated under a reduced pressure. This obtained residue was separated and purified through flash column chromatography to obtain Compound I-32 (70 g and 96percent). HRMS (70 eV, EI+): m/z calcd for C21H14BrN3: 387.0371. found: 387. Elemental Analysis: C, 65percent; H, 4percent
60%
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In ethanol; water; toluene at 100℃; for 12 h;
2-chloro-4,6-diphenyl-1,3,5-triazine (20g, 1.0eq), (4- bromophenyl) boronic acid (16.5g, 1.1eq), K2CO3 (20.6g, 2.0eq), Pd (PPh3) 4 (8.6g, 0.1eq) in toluene 400 ml / 100 ml of ethanol / 50 ml H2O for 12 hours in a mixture of 100 It was stirred. And extracted with MC MC: hexane = 1: 3 to the separation column to obtain a white solid compound 72-1. (4.5g, 60percent)
60%
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; water at 80℃; for 53 h; Inert atmosphere
The compound 2-chloro-4,6-diphenyl-1,3,5-triazine (72 g, 268 mmol) was dissolved in THF (tetrahydrofuran)(4-bromophenyl) boronic acid (45 g, 224.12 mmol) andTetrakis (triphenylphosphine) palladium (2.63 g, 2.82 mmol) was added and stirred. Saturated potassuim in waterCarbonitrile (51.6 g, 373.54 mmol), and the mixture was refluxed by heating at 80 for 53 hours. After completion of the reaction,Water was added, and the mixture was extracted with dichloromethane (DCM). Then, water was removed with anhydrous MgSO 4, filtered, and concentrated under reduced pressure. thisThe residue thus obtained was separated and purified by flash column chromatography to obtain Compound I-4 (62 g, 60percent).
30%
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In 1,4-dioxane; water at 60℃; for 18 h; Inert atmosphere
Compound in a nitrogen stream to a flask 1L reaction [259-1] 40g (0.15mol), compound [241-6] 36.1g (0.18mol), potassium carbonateDissolve 41.4g (0.30mol) in 1,4-dioxane and 410mL, 180 mL of purified water and then put the temperature was raised to tetrakis (updated in about 60 Lee thereby phenyl phosphine) palladium added 5.2g (4.5mmol) and stirred under reflux for 18 hours. After completion of the reaction slowly to room temperature and coldSerious filtered and then the reaction solution. The filtered solid is extracted with dichloromethane, and saturated brine. The organic layer was separated, anhydrousDried with magnesium sulfate, filtered and concentrated under reduced pressure. Using the concentrate was purified by column chromatography method, to obtain the intermediate compound to prepare a [259-2] 17g (30percent).
Reference：
[1] Patent: US2017/331067, 2017, A1, . Location in patent: Paragraph 0260-0263
[2] Chemistry - An Asian Journal, 2016, vol. 11, # 6, p. 868 - 873
[3] Patent: KR2015/75169, 2015, A, . Location in patent: Paragraph 0206-0209
[4] Patent: KR2015/59395, 2015, A, . Location in patent: Paragraph 0162; 0163; 0164; 0165
[5] Patent: KR2015/88163, 2015, A, . Location in patent: Paragraph 0342-0345
10
[ 83819-97-0 ]
[ 5467-74-3 ]
[ 23449-08-3 ]
Yield
Reaction Conditions
Operation in experiment
70%
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran for 4 h; Reflux
Tetrahydrophenylphosphine palladium (2.1 g, 1.83 mmol) and potassium carbonate (75.7 g, 549 mmol) were added to a solution of p-bromophenylboronic acid (36.6 g, 183 mmol) and 2-iodo-4,6-diphenyl- 1,3,5-triazine (72.1g, 201mmol) (500mL) was degassed tetrahydrofuran,And the mixture was heated under reflux for 4 hours.The reaction mixture was cooled to room temperature,After which the solvent is removed.The residue was purified by silica gel column chromatography (49.5 g, 70percent of theory).
Reference：
[1] Patent: CN106699733, 2017, A, . Location in patent: Paragraph 0054; 0055; 0056; 0057
11
[ 5467-74-3 ]
[ 2620-76-0 ]
Yield
Reaction Conditions
Operation in experiment
84.9%
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran at 80℃; for 10 h; Inert atmosphere
In a 250 mL three-necked flask,Access to nitrogen,0.04 mol of intermediate M1 was added,100mlTHF,0.05 mol of phenylboronic acid,0.0004 mol of tetrakis (triphenylphosphine) palladium,Stir,Then, 0.06 mol of K2CO3 aqueous solution (2 M) was added,Heated to 80 ° C,Reflux reaction for 10 hours,Sampling point plate,The reaction is complete.Natural cooling,Extracted with 200 ml of dichloromethane,The extract was dried over anhydrous sodium sulfate, filtered, the filtrate was steamed and purified on a silica gel column,Intermediate N1 was obtained, HPLC purity 99.6percent yield 84.9percent.
84.9%
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran at 80℃; for 10 h; Inert atmosphere
(2) In a 250 mL three-necked flask,Purged with nitrogen,0.04 mol of intermediate M1 was added,100mlTHF,0.05mol phenylboronic acid,0.0004 mol of tetrakis (triphenylphosphine) palladium,Stirring,Then 0.06 mol K2CO3 aqueous solution (2M) was added,Heated to 80 ° C,The reaction was refluxed for 10 hours,Sample board, the reaction was complete.The mixture was naturally cooled and extracted with 200 ml of dichloromethane. The layers were separated, the extract was dried over anhydrous sodium sulfate, filtered, and the filtrate was rotary evaporated and purified over a silica gel column to give the intermediate N1,HPLC purity 99.6percent, yield 84.9percent.
84.9%
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; water at 80℃; for 10 h; Inert atmosphere
(2) In a 250 mL three-necked flask, purged with nitrogen, 0.04 mol of intermediate M1, 100 ml of THF, 0.05 mol of phenylboronic acid,0.0004mol tetrakis (triphenylphosphine) palladium, stirred, then add 0.06mol K2CO3 aqueous solution (2M), heated to 80 ° C, the reaction was refluxed for 10 hours, the sample point plate, the reaction was complete.The mixture was naturally cooled and extracted with 200 ml of dichloromethane. The layers were separated and the extract was dried over anhydrous sodium sulfate and filtered. The filtrate was rotary evaporated and purified on a silica gel column to give the intermediate N1 with an HPLC purity of 99.6percent and a yield of 84.9percent.
Reference：
[1] Patent: CN106967052, 2017, A, . Location in patent: Paragraph 0116; 0117; 0118
[2] Patent: CN106946853, 2017, A, . Location in patent: Paragraph 0094; 0095
[3] Patent: CN107417668, 2017, A, . Location in patent: Paragraph 0123; 0124
[4] Patent: KR2015/41508, 2015, A, . Location in patent: Paragraph 0218; 0242
12
[ 1899-24-7 ]
[ 5467-74-3 ]
[ 20005-42-9 ]
Yield
Reaction Conditions
Operation in experiment
7%
With tetrabutylammomium bromide; palladium diacetate; potassium carbonate In water at 20℃; for 5 h;
To a glass flask, 3 (113.8 mg, 0.650mmol), (4-bromophenyl)boronic acid (143.6 mg, 0.715 mmol), tetrabutylammonium bromide(209.6 mg, 0.650 mmol), Pd(OAc)2 (2.9 mg, 0.013 mmol) and K2CO3 (224.6 mg, 1.63 mmol)were added and then dissolved in deionized water (3 mL). The reaction mixture was stirred vigorously for 5 h at room temperature. After the white reaction mixture had become yellowand non-homogeneous, the mixture was diluted with water (10 mL), and the product was extracted with EtOAc. The organics were separated, filtered through a Celite pad, and dried with MgSO4. The organic solvent was removed under reduced pressure and the crude product was purified by dry-flash chromatography (SiO2: hexane/EtOAc = 9/1 to 7/3) to afford the title compound 5 (11 mg, 7 percent).
Reference：
[1] Organic Letters, 2018, vol. 20, # 8, p. 2273 - 2277
[2] Organic Letters, 1999, vol. 1, # 7, p. 965 - 967
[3] Journal of the Serbian Chemical Society, 2017, vol. 82, # 6, p. 641 - 649
[4] Bioorganic and Medicinal Chemistry Letters, 2002, vol. 12, # 19, p. 2681 - 2683
13
[ 123-75-1 ]
[ 201230-82-2 ]
[ 5467-74-3 ]
[ 5543-27-1 ]
Reference：
[1] Chemistry - A European Journal, 2015, vol. 21, # 20, p. 7374 - 7378
Reference：
[1] Journal of Organic Chemistry, 2017, vol. 82, # 5, p. 2450 - 2461
16
[ 25309-64-2 ]
[ 5467-74-3 ]
[ 58743-79-6 ]
Reference：
[1] Angewandte Chemie - International Edition, 2016, vol. 55, # 26, p. 7530 - 7533[2] Angew. Chem., 2016, vol. 128, # 26, p. 7656 - 7659,4
17
[ 5467-74-3 ]
[ 99-93-4 ]
[ 5731-01-1 ]
Reference：
[1] European Journal of Organic Chemistry, 2014, vol. 2014, # 23, p. 4953 - 4957
18
[ 5467-74-3 ]
[ 2050-47-7 ]
Reference：
[1] Journal of Organic Chemistry, 2001, vol. 66, # 2, p. 633 - 634
19
[ 5467-74-3 ]
[ 107-13-1 ]
[ 57775-08-3 ]
Reference：
[1] Chemistry - A European Journal, 2012, vol. 18, # 47, p. 14918 - 14922
[2] Chemical Communications, 2018, vol. 54, # 10, p. 1257 - 1260
20
[ 5467-74-3 ]
[ 100-44-7 ]
[ 2116-36-1 ]
[ 23450-18-2 ]
Yield
Reaction Conditions
Operation in experiment
63%
at 100℃; for 24 h; Sealed tube
To a 10 mL reaction tube containing a magnet was added (4-bromophenyl) boronic acid (201 mg, 1.0 mmol)Lithium tert-butoxide (80 mg, 1.0 mmol).Trifluorotoluene (2 mL) and benzyl chloride (63 mg, 0.5 mmol) were added.Stuffed rubber stopper,The reaction was performed on a 100 ° C electromagnetic heating stirrer for about 24 hours.After the reaction,Cool to room temperature,The organic solvent is removed using a rotary evaporator,And purified by column chromatography to give 1-benzyl-4-bromobenzeneAnd 1-benzyl-2-bromobenzene (82 mg, 63percent).The compound is a colorless oily liquid,
88.889 % de
Stage #1: Schlenk technique; Inert atmosphere Stage #2: at 100℃; for 24 h; Schlenk technique; Inert atmosphere
General procedure: Arylboronic acid (1.0 mmol), LiOtBu (1.0 mmol) was added to a Schlenk tube. The tube was charged with nitrogen and then PhCF3 (2 mL) and benzyl chloride (0.5 mmol) were added. The reaction mixture was stirred at 100 °C for 24 h. After the mixture was cooled down to room temperature, solvent was removed under reduced pressure to leave a crude product. The crude product was purified by column chromatography on silica gel, eluting with petroleum ether to afford the coupling product.
Reference：
[1] Patent: CN106478326, 2017, A, . Location in patent: Paragraph 0098; 0099; 0100; 0101; 0102
[2] Tetrahedron, 2016, vol. 72, # 49, p. 8022 - 8030
21
[ 5467-74-3 ]
[ 623-33-6 ]
[ 14062-25-0 ]
Reference：
[1] Angewandte Chemie - International Edition, 2014, vol. 53, # 39, p. 10510 - 10514[2] Angew. Chem., 2014, vol. 126, # 39, p. 10678 - 10682,5
22
[ 624-38-4 ]
[ 5467-74-3 ]
[ 17788-94-2 ]
Yield
Reaction Conditions
Operation in experiment
84%
With sodium carbonate In toluene
(1) Synthesis of 4,4"-dibromo-p-terphenyl Toluene 600 ml and a 2M sodium carbonate aqueous solution 300 ml were added to 1,4-diiodobenzene 33.0 g, 4-bromophenylboronic acid 48.2 g and tetrakis(triphenylphosphine)palladium (0) 4.62 g under argon atmosphere, and the mixture was refluxed for 10 hours under heating. After finishing the reaction, the mixture was immediately filtered, and the aqueous layer was removed. The organic layer was dried on sodium sulfate and then concentrated. A solid matter thus obtained was recrystallized from toluene to obtain 32.6 g of white crystal of 4,4"-dibromo-p-terphenyl (yield: 84percent)
Reference：
[1] Chemical Communications, 2007, # 27, p. 2855 - 2857
29
[ 106-40-1 ]
[ 5467-74-3 ]
Yield
Reaction Conditions
Operation in experiment
74%
Stage #1: With hydrogenchloride; sodium nitrite In methanol; water at 0 - 5℃; for 0.5 h; Stage #2: With tetrahydroxydiboron In methanol; water at 20℃; for 1 h;
General procedure: To a solution of arylamine (0.5 mmol, 1.0 equiv) in MeOH(1.0 mL) was added HCl (0.5 mL, 1.5 mmol, 3.0 equiv), followed by H2O (0.5 ml). This mixture was stirred 2 min,and the NaNO2 solution (0.25 mL) was then added. The NaNO2 solution was prepared by dissolving 35 mg ofNaNO2 in H2O (0.25 mL). This mixture was stirred 30 minat 0–5 °C, followed by HCl (135 mg, 1.5 mmol, 3.0 equivalents) in MeOH (1.0 mL). This mixture was stirred 60min. H2O (10 mL) was added to reaction mixture, then extracted with CH2Cl2 (50 mL, 3×). The combined organic layer was dried over Na2SO4, followed by evaporation to give the products.
Reference：
[1] Synlett, 2014, vol. 25, # 11, p. 1577 - 1584
[2] Chemistry - A European Journal, 2014, vol. 20, # 22, p. 6608 - 6612
30
[ 5419-55-6 ]
[ 106-37-6 ]
[ 5467-74-3 ]
Yield
Reaction Conditions
Operation in experiment
74%
Stage #1: With n-butyllithium In diethyl ether; hexane at -78℃; for 0.5 h; Stage #2: at -78 - 20℃;
Dissolve Sub 1-2-1 (1) (7g, 30mmol) in anhydrous Ether, lowering the temperature ofthe reaction to -78 ° C, was added dropwise n-BuLi (2.5M in hexane) (2.1g, 22mmol)slowly, and after I, the reaction is stirred for 30 min. After the dropwise additionTriisopropyl borate (8.5g, 30mmol) lowering the temperature of the reaction back to -78 ° C. Stirring at room temperature, diluted with water and it binds the 2N HCl. Aftercompletion of reaction, ethyl acetate and water, dried over MgSO4 and the organic layerwas extracted and concentrated and to the resulting organic silicagel column andrecrystallized to give 4.46g of Sub 1-2-2 (1). (Yield: 74percent)
51%
Stage #1: With n-butyllithium In tetrahydrofuran at -78 - 25℃; for 1 h; Stage #2: at -78 - 25℃; for 6 h;
In a 500 ml round bottom flask charged with 1,4-dibromobenzene 30 g (127 mmol) in anhydrous tetrahydrofuran (THF) and stirred. The reaction mixture is suspended in the temperature of the flask was cooled using liquid nitrogen to -78°C and was charged with n-BuLi 2.5M (115 mmol) in 45.8 mL slowly. After raising the temperature gradually to room temperature, it stirred for 1 hour. Re-cool the temperature of the flask using liquid nitrogen to -78°C and then, triisopropylborate 48 g (58.7 mL, 254 mmol) was added quickly. Then the reaction was conducted at room temperature for 6 hours, the reaction was terminated on ice and 2 N HCl aqueous solution. Extraction with methylene chloride (MC) and then the solvent was removed, by putting into hexane, After boiling the filter to dry it with a compound 13 g (Yield = 51percent) was obtained, without further purification it was used directly in the next reaction.
Reference：
[1] Patent: KR2015/121394, 2015, A, . Location in patent: Paragraph 0180-0183
[2] Patent: KR2016/73914, 2016, A, . Location in patent: Paragraph 0169-0173
31
[ 121-43-7 ]
[ 106-37-6 ]
[ 5467-74-3 ]
Reference：
[1] Organic Letters, 2016, vol. 18, # 15, p. 3630 - 3633
[2] New Journal of Chemistry, 2018, vol. 42, # 12, p. 9369 - 9372
[3] Journal of the Chemical Society - Perkin Transactions 1, 1999, # 17, p. 2513 - 2523
[4] Journal of Organic Chemistry, 2015, vol. 80, # 9, p. 4430 - 4442
32
[ 106-37-6 ]
[ 5467-74-3 ]
Reference：
[1] Journal of the American Chemical Society, 2010, vol. 132, # 6, p. 1734 - 1735
[2] Tetrahedron, 2007, vol. 63, # 35, p. 8529 - 8536
[3] Journal of Nanoscience and Nanotechnology, 2010, vol. 10, # 8, p. 5153 - 5160
[4] Journal of the American Chemical Society, 2013, vol. 135, # 4, p. 1264 - 1267
[5] Organic Letters, 2016, vol. 18, # 11, p. 2716 - 2718
33
[ 7732-18-5 ]
[ 374564-35-9 ]
[ 5467-74-3 ]
Yield
Reaction Conditions
Operation in experiment
74%
at 25℃; for 0.75 h;
General procedure: In a flask containing the appropriate potassiumorganotrifluoroborate (0.5 mmol) in distilled water(1 mL) was added montmorillonite K10 (150percent m/m). Themixture was stirred for the time indicated in Scheme 1at room temperature. After this period, the mixture wasextracted with EtOAc (3 × 10 mL) and the organic phasewas washed with water (2 × 15 mL). The organic phasewas dried over anhydrous MgSO4, filtered and the solventwas removed in vacuo to yield the corresponding boronicacids 2a-o.
Reference：
[1] Journal of the Brazilian Chemical Society, 2018, vol. 29, # 9, p. 1777 - 1785
34
[ 13675-18-8 ]
[ 106-40-1 ]
[ 5467-74-3 ]
Reference：
[1] Chemistry - A European Journal, 2014, vol. 20, # 22, p. 6608 - 6612
[2] Journal of Organic Chemistry, 2014, vol. 79, # 21, p. 10568 - 10580
35
[ 374564-35-9 ]
[ 5467-74-3 ]
Reference：
[1] Journal of Organic Chemistry, 2009, vol. 74, # 19, p. 7364 - 7369
36
[ 589-87-7 ]
[ 5467-74-3 ]
Reference：
[1] Journal of Organic Chemistry, 2011, vol. 76, # 4, p. 1013 - 1030
37
[ 13283-31-3 ]
[ 18620-02-5 ]
[ 5467-74-3 ]
Reference：
[1] Journal of Organometallic Chemistry, 1983, vol. 259, # 3, p. 269 - 274
38
[ 13675-18-8 ]
[ 673-40-5 ]
[ 5467-74-3 ]
Reference：
[1] Chemistry - A European Journal, 2014, vol. 20, # 22, p. 6608 - 6612
39
[ 688-74-4 ]
[ 18620-02-5 ]
[ 5467-74-3 ]
Reference：
[1] Journal of the American Chemical Society, 1934, vol. 56, p. 1865,1867
[2] Journal of the American Chemical Society, 1932, vol. 54, p. 4415,4418
40
[ 106-37-6 ]
[ 13283-31-3 ]
[ 5467-74-3 ]
Reference：
[1] Journal of Organometallic Chemistry, 1983, vol. 259, # 3, p. 269 - 274
41
[ 96484-29-6 ]
[ 5467-74-3 ]
Reference：
[1] Zhurnal Obshchei Khimii, 1936, vol. 6, p. 636,638,639[2] Chem. Zentralbl., 1936, vol. 107, # II, p. 1152
[3] Zhurnal Obshchei Khimii, 1936, vol. 6, p. 636,638,639[4] Chem. Zentralbl., 1936, vol. 107, # II, p. 1152
Reference：
[1] Journal of the Chemical Society [Section] C: Organic, 1966, p. 566 - 571
46
[ 5467-74-3 ]
[ 92-86-4 ]
[ 4151-80-8 ]
Reference：
[1] Advanced Synthesis and Catalysis, 2005, vol. 347, # 1, p. 185 - 195
47
[ 5467-74-3 ]
[ 20725-34-2 ]
Reference：
[1] Patent: WO2013/189865, 2013, A1,
48
[ 5467-74-3 ]
[ 292638-85-8 ]
[ 75567-84-9 ]
Reference：
[1] Chemistry - A European Journal, 2012, vol. 18, # 47, p. 14918 - 14922
49
[ 619-44-3 ]
[ 5467-74-3 ]
[ 89901-03-1 ]
Yield
Reaction Conditions
Operation in experiment
78%
With sodium carbonate In ethanol; water; toluene at 80℃; for 4 h; Heating / reflux
A mixture of methyl 4-iodobenzoate, 9.38g (35.8 mmol), 4- bromophenylboronic acid 7.18g (35.8 mmol), Pd (PPh3) 4,2. 07g (1.79 mmol), in 180ML of toluene and 100mL of ethanol was heated to obtain a clear solution. To the solution was added 30mL of 4. OM aq. NA2CO3. The reaction mixture refluxed for 4h at 80 °C. The mixture was cooled to room temperature and diluted with 300mL ethyl acetate. The organic layer was washed with 2X300ML portions of water, 2X300ML portions of sat. aq. NACL, and dried (MGSO4). After the solution was concentrated, the residue was purified by column chromatography (eluted with 7percent ETOAC-HEPTANE) to afford the desired product in 7. 8G (78percent) as a white SOLID. 1H NMR (CDC13) 8.10 (d, 2H, J = 9. 0HZ), 7.62 (d, 2H, J = 9. 0HZ), 7.59 (d, 2H, J = 9. 3HZ), 7.48 (d, 2H, J = 9.3 Hz), 3.95 (s, 3H).
78%
With sodium carbonate In ethanol; water; toluene at 80℃; for 4 h; Heating / reflux
Example 14. 4' -Bromo-biphenyl-4-carboxylic acid methyl ester.; A mixture of methyl 4-iodobenzoate, 9.38g (35.8 mmol), 4- bromophenylboronic acid 7.18g (35.8 mmol), Pd(PPh3)4, 2.07g (1.79 mmol), in 18OmL of toluene and 10OmL of ethanol was heated to obtain a clear solution. To the solution was added 3OmL of 4.0M aq. Na2CC>3. The reaction mixture refluxed for 4h at 80 °C. The mixture was cooled to room temperature and diluted with 30OmL ethyl acetate. The organic layer was washed with 2x300mL portions of water, 2x300mL portions of sat. aq. NaCl, and dried (MgSC>4) . After the solution was concentrated, EPO <DP n="96"/>the residue was purified by column chromatography (eluted with 7percent EtOAc-Heptane) to afford the desired product in 7.8g (78percent) as a white solid. 1H NMR (CDCl3) 8.10 (d, 2H, J = 9.0Hz)Λ 7.62 (d, 2H, J = 9.0Hz), 7.59 (d, 2H, J = 9.3Hz), 7.48 (d, 2H, J = 9.3 Hz) , 3.95 (s, 3H) .
78%
With sodium carbonate In ethanol; water; toluene at 80℃; for 4 h;
Example 96; 4' -Bromo-biphenyl-4-carboxylic acid methyl ester; A mixture of methyl 4-iodobenzoate, 9.38g (35.8 mmol), 4- bromophenylboronic acid 7.18g (35.8 mmol), Pd(PPh3) 4, 2.07g (1.79 mmol), in 18OmL of toluene and 10OmL of ethanol was heated to obtain a clear solution. To the solution was added 3OmL of 4.0M aq. Na2CO3. The reaction mixture refluxed for 4h at 80 °C. The mixture was cooled to room temperature and diluted with 30OmL ethyl acetate. The organic layer was washed with 2x300mL portions of water, 2x300mL portions of sat. aq. NaCl, and dried (MgSO4) . After the solution was concentrated, the residue was purified by column chromatography (eluted with 7percent EtOAc-Heptane) to afford the desired product in 7.8g (78percent) as a white solid.
78%
With sodium carbonate In ethanol; water; toluene at 80℃; for 4 h;
A mixture of methyl 4-iodobenzoate, 9.38g (35.8 mmol), 4- BROMOPHENYLBORONIC acid 7.18g (35. 8 mmol), Pd (PPh3) 4, 2. 07G (1.79 mmol), in 180ML of toluene and LOOML of ethanol was heated to obtain a clear solution. To the solution was added 30mL of 4. OM aq. NA2CO3. The reaction mixture refluxed for 4h at 80 °C. The mixture was cooled to room temperature and diluted with 300mL ethyl acetate. The organic layer was washed with 2X300ML portions of water, 2X300ML portions of sat. aq. NaCl, and dried (MGS04). After the solution was concentrated, the residue was purified by column chromatography (eluted with 7percent ETOAC-HEPTANE) to afford the desired product in 7.8g (78percent) as a white SOLID. 1H NMR (CDC13) 8.10 (d, 2H, J = 9. 0HZ), 7. 62 (d, 2H, J = 9. 0HZ), 7. 59 (d, 2H, J = 9.3Hz), 7.48 (d, 2H, J = 9.3 Hz), 3.95 (s, 3H).
With sodium carbonate In 1,4-dioxane; water for 5 h; Heating / reflux
2.52a. methyl 4'-bromo-biphenyl-4-carboxylate 0.54 g (2.5 mmol) of methyl 4-bromo-benzoate is dissolved in 10 mL dioxane and 2.5 mL 2M-sodium carbonate solution. 0.6 g (3 mmol) of 4-bromophenyl-boric acid and 0.12 g (0.1 mmol) of tetrakis-(triphenylphosphine)-palladium are added successively and the reaction is refluxed for 5 hours. The reaction mixture is combined with water and EtOAc, filtered and the phases are separated. The aqueous phase is extracted with EtOAc and the combined organic phases are dried over MgSO4. After elimination of the drying agent and solvent the residue is triturated with acetonitrile, suction filtered and dried in the air. Yield: 100 mg (13.7percent of theory); C14H11BrO2 (M=291.15); calc.: molar peak (M+H)+: 291/293 fnd.: molar peak (M+H)+: 291/293; Rf value: 0.68 (silica gel, petroleum ether/EtOAc 8:2).
Reference：
[1] Journal of the American Chemical Society, [2] Journal of the American Chemical Society, 1932, vol. 54, p. 4415 - 4424
[3] , Gmelin Handbook: B: B-Verb.13, 4.7.2.4, page 203 - 209,
52
[ 5467-74-3 ]
[ 74386-13-3 ]
Reference：
[1] Journal of the American Chemical Society, 1932, vol. 54, p. 4415,4418
53
[ 5467-74-3 ]
[ 107-18-6 ]
[ 80793-25-5 ]
Reference：
[1] European Journal of Organic Chemistry, 2012, # 25, p. 4694 - 4698
[2] Green Chemistry, 2014, vol. 16, # 5, p. 2788 - 2797
54
[ 75-89-8 ]
[ 5467-74-3 ]
[ 106854-77-7 ]
Yield
Reaction Conditions
Operation in experiment
72%
With pyridine; copper diacetate; sodium carbonate In 1,2-dichloro-ethane at 20℃; for 14 h; Schlenk technique; Molecular sieve; Sealed tube
General procedure: In a nitrogen-filled glove box, a 25 mL Schlenk tube equipped with a magnetic stir bar was charged with Cu(OAc)2 (9.3 mg,0.05 mmol, 0.1 equiv), aryl boronic acid 1 (0.5 mmol, 1.0 equiv),Na2CO3 (106.0 mg, 1.0 mmol, 2.0 equiv) and 4 Å MS (250.0 mg). The vessel was sealed with a septum before removing from the glovebox. The tube was evacuated and backfilled with air for 3 times.Then DCE (5.0 mL), pyridine (39.6 mg, 0.5 mmol, 1.0 equiv) and CF3CH2OH (100.0 mg, 1.0 mmol, 2.0 equiv) were added respectivelyvia syringe. The mixture was stirred vigorously under a balloon ofair at room temperature for 14 h. Then the reaction solution was vacuum-filtered over a sintered-glass funnel with a tightly packedpad of Celite (1 cm thick), and the filter cake was rinsed with DCM(20 mL). The combined filtrates were concentrated. The residue was purified with silica gel column chromatography to provide the desired product.
Reference：
[1] Journal of Fluorine Chemistry, 2017, vol. 196, p. 24 - 31
55
[ 5467-74-3 ]
[ 106418-67-1 ]
Reference：
[1] Journal of the American Chemical Society, 2017, vol. 139, # 15, p. 5313 - 5316
With potassium hydrogenfluoride In methanol; water at 0℃; for 0.5 h;
General procedure: To a solution of the appropriate boronic acid, 1a-j (5 mmol) in MeOH (10 mL) was added dropwise a solution of KHF2 (1.56 g, 20 mmol) in H2O (8 mL) using an addition funnel. The mixture was stirred for 30 min and concentrated under high vacuum. The residual solid was extracted with four portions of 20percent MeOH in acetone. The combined extracts were concentrated close to the saturation point and Et2O was added until no more precipitation was observed. The solid was collected, washed with two portions of Et2O, and dried under high vacuum to give the corresponding products sufficiently pure for characterization.
Reference：
[1] Journal of the American Chemical Society, 2008, vol. 130, # 47, p. 15792 - 15793
[2] Tetrahedron Letters, 2012, vol. 53, # 32, p. 4240 - 4242
58
[ 5467-74-3 ]
[ 374564-35-9 ]
Reference：
[1] Journal of the American Chemical Society, 2013, vol. 135, # 38, p. 14012 - 14015
[2] European Journal of Organic Chemistry, 2013, # 22, p. 4909 - 4917
With sodium carbonate In water; toluene at 110℃; for 10 h;
(iv) Synthesis method of 9-(4-bromophenyl)-10-phenylanthracene 5.3 g (14 mmol) of 9-iodine-10-phenylanthracene, 2.9 g (14 mmol) of 4-bromophenyl boronic acid, and 0.18 g (0.15 mmol) of tetrakis(triphenylphosphine)palladium(0) were put into a 100 mL three-necked flask. Then, the atmosphere in the flask was substituted with nitrogen. 30 mL of toluene and 15 mL (31 mmol) of an aqueous sodium carbonate solution (2.0 mol/L) were added to the mixture. This mixture was refluxed at 110° C. for 10 hours to be reacted. After the reaction was completed, a precipitate in the reaction mixture was collected by suction filtration. The obtained solid was dissolved in toluene and subjected to suction filtration through Florisil, celite, and then alumina. The filtrate was condensed. The obtained solid was recrystallized by a mixed solvent of chloroform and hexane; then 4.1 g of objective 9-(4-bromophenyl)-10-phenylanthracene was obtained as a light yellow powdered solid in a yield of 72percent. A synthetic scheme of 9-(4-bromophenyl)-10-phenylanthracene is illustrated below (synthetic scheme b-4).
45%
With potassium carbonate In water; toluene at 80℃; for 9 h;
Next, a synthetic method of 9-phenyl-10-(4-bromophenyl) anthracene using 9-iodo- 10-phenylanthracene prepared by the above method as a starting material will be shown. A mixture of 1.0 g (2.63 mmol) of 9-iodo- 10-phenylanthracene, 542 mg (2.70 mmol) of p-bromo phenylboronic acid, 46 mg (0.03 mmol) of tetrakis (triphenylphosphine) palladium, 2M potassium carbonate solution (3 mL), and 10 mL of toluene is agitated at 80 °C 9 hours. After reaction, toluene is added and filtration is carried out using Florisil, celite, and alumina. After the filtrate is rinsed with water and saturated salt solution, it is dried with magnesium sulfate. After natural filtration, the filtrate is condensed, and when it is recrystallized with chloroform and hexane, 562 mg of 9-phenyl-10-(4-bromophenyl) anthracene is obtained as alight brown solid at a yield of 45 percent. A synthetic scheme of 9-phenyl-10-(4-bromophenyl) anthracene from 9-iodo- 10-phenylanthracene is shown below.
45%
With potassium carbonate In toluene at 80℃; for 9 h;
First, 1.0 g (2.63 mmol) of 9-iodine-10-phenylanthracene, 542 mg (2.70 mmol) of /7-bromophenyl boronic acid, 46 mg (0.03 mmol) of tetrakis(triphenylphosphine)palladium (O) (abbreviation: Pd(PPh3)4), 3 mL (6 mmol) of an aqueous solution containing 2 mol/L of a potassium carbonate (K2CO3), and 10 mL of toluene were stirred at 80°C for 9 hours. After the reaction, toluene was added to the product. Then, this solution was filtrated through florisil, celite, and alumina. Subsequently, the filtrate was washed with water and saturated saline in this order. After the washing, the washed filtrate was dried with magnesium sulfate. The product EPO <DP n="97"/>was naturally filtrated and then the filtrate was concentrated. Thereafter, the concentrated filtrate was recrystallized by chloroform and hexane. Thus, 562 mg (yield: 45percent) of a light brown solid of 9-(4-bromophenyl)-10-phenylanthracene, which was target matter, was obtained (synthetic scheme (b-6)).
45%
With potassium carbonate In toluene at 80℃; for 9 h;
(iv) Synthesis of 9-phenyl-10-(4-bromophenyl)anthracene (abbreviation: PA).; A mixture of 1.0 g (2.63 mmol) of 9-iodo-lO-phenylanthracene, 542 mg (2.70 mmol) of p-bromo phenylboronic acid, 46 mg (0.03 mmol) of Pd(PPli3)4 (0), 3 mL (6 mmol) of K2CO2 of 2M, and 10 mL of toluene was stirred for 9 hours at 800C. After reaction, toluene was added and filtration was carried out using Florisil.(R)., celite, and alumina. A filtrate was washed with water and saturated saline, and then dried with magnesium sulfate. After natural filtration, the filtrate was condensed, and when it was recrystallized with chloroform and hexane, 562 mg of9-phenyl-10-(4-bromophenyl)anthracene that is a target substance is obtained as a light brown solid at a yield of 45 percent
45%
With potassium carbonate In water; toluene at 80℃; for 9 h;
(iv) Synthesis of 9-phenyl-10-(4-bromophenyl)anthracene (abbr.: PA) Synthetic Scheme (f-4) of 9-phenyl-10-(4-bromophenyl)anthracene (abbr.: PA) is shown below. 1.0 g (2.63 mmol) of 9-iodo-10-phenylanthracene, 542 mg (2.70 mmol) of p-bromophenylboronic acid, 46 mg (0.03 mmol) of tetrakis(triphenylphosphine)palladium(0) (Pd(PPh3)4), 3 mL (6 mmol) of an aqueous potassium carbonate (K2CO3) solution (2 mol/L), and 10 mL of toluene were collected, mixed, and stirred for 9 hours at 80° C. After the reaction, toluene was added and the mixture was filtered through florisil, Celite.(R)., and alumina. The filtrate was washed with water and a saturated aqueous sodium chloride solution and then dried with magnesium sulfate. After natural filtration, the filtrate was concentrated and the obtained solid was recrystallized with chloroform and hexane, thereby obtaining 562 mg of objective 9-phenyl-10-(4-bromophenyl)anthracene as a light-brown solid with a yield of 45percent.
45%
With potassium carbonate In water; toluene at 80℃; for 9 h;
(iv) Synthesis of 9-phenyl-10-(4-bromophenyl)anthracene (abbreviation: PA) The following shows a synthesis scheme (f-4) of 9-phenyl-10-(4-bromophenyl)anthracene (abbreviation: PA). 1.0 g (2.63 mmol) of 9-iodo-10-phenylanthracene, 542 mg (2.70 mmol) of p-bromophenylboronic acid, 46 mg (0.03 mmol) of tetrakis(triphenylphosphine)palladium(0) (Pd(PPh3)4), 3 mL (6 mmol) of a potassium carbonate (K2CO3) aqueous solution (2 mol/L), and 10 mL of toluene were stirred at 80° C. for 9 hours. After the reaction, toluene was added therein, and the mixture was filtered through Florisil, Celite, and alumina. The filtrate was washed with water and a saturated saline solution and then dried with magnesium sulfate. After the solution was filtered naturally, the filtrate was concentrated and recrystallized with chloroform and hexane; thus, 562 mg of a light brown solid of 9-phenyl-10-(4-bromophenyl)anthracene that was an object was obtained (yield: 45percent).
45%
With potassium carbonate In toluene at 80℃; for 9 h;
1.0 g (2.63 mmol) of 9-iodo-lO-phenylanthracene, 542 mg (2.70 mmol) of p-bromophenylboronic acid, 46 mg (0.03 mmol) of Pd(PPli3)4, 3 ml (6 mmol) of 2 mol/L potassium carbonate (K2CO3) solution, and 10 ml of toluene were stirred for 9 hours at 800C. After the reaction, toluene was added, and the mixture was filtered through Florisil, Celite, and alumina. The filtrate was washed with water and a saturated saline solution, then dried with magnesium sulfate. After natural filtration, the filtrate was concentrated, and recrystallized with chloroform and hexane. The target substance of 9-(4-bromophenyl)-10-phenylanthracene was obtained as a light brown solid, weighing 562 mg in a yield of 45percent (synthesis scheme j-6)). [0414]j-6)
45%
With magnesium sulfate In toluene
(4) Synthesis of 9-(4-Bromophenyl)-10-phenylanthracene (abbreviation. PA) Were mixed 1.0 g (2.6 mmol) of 9-iodine-10-phenylanthracene obtained by the above Step 1(3), 540 mg (2.7 mmol) of p-bromophenylboronic acid, 46 mg (30 μmol) of tetrakis(triphenylphosphine)palladium(0), 3.0 mL (6.0 mmol) of 2.0 mol/L potassium carbonate aqueous solution, and 10 mL of toluene, and the mixture was stirred at 80° C. for 9 hours to be reacted. After the reaction, toluene was added therein, and the mixture was filtered through Florisil (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 540-00135), celite (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 531-16855), and alumina. The obtained filtrate was washed with water and saturated saline, and magnesium sulfate was added so that the moisture was removed. This suspending solution was naturally filtered and the obtained filtrate was concentrated, so that a solid was obtained. The obtained solid was recrystallized with a mixed solution of chloroform and hexane, whereby 560 mg of a light-brown solid of 9-(4-Bromophenyl)-10-anthracene (abbreviation: PA), which was the object of the synthesis, was obtained in a yield of 45percent (synthesis scheme (a-4)).
45%
With potassium carbonate In water; toluene at 80℃; for 9 h;
(4) Synthesis of 9-(4-Bromophenyl)-10-phenylanthracene (abbreviation: PA)Were mixed 1.0 g (2.6 mmol) of 9-iodine-lO-phenylanthracene obtained by the above Step 1(3), 540 mg (2.7 mmol) of /?-bromophenylboronic acid, 46 mg (30 μmol) of tetrakis(triphenylphosphine)palladium(0), 3.0 mL(6.0 mmol) of 2.0 mol/L potassium carbonate aqueous solution, and 10 mL of toluene, and the mixture was stirred at 80 0C for 9 hours to be reacted. After the reaction, toluene was added therein, and the mixture was filtered through Florisil (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 540-00135), celite (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 531-16855), and alumina. The obtained filtrate was washed with water and saturated saline, and magnesium sulfate was added so that the moisture was removed. This suspending solution was naturally filtered and the obtained filtrate was concentrated, so that a solid was obtained. The obtained solid was recrystallized with a mixed solution of chloroform and hexane, whereby 560 mg of a light-brown solid of 9-(4-Bromophenyl)-10-anthracene (abbreviation: PA), which was the object of the synthesis, was obtained in a yield of 45 percent (synthesis scheme (a-4)).
45%
With potassium carbonate In water; toluene at 80℃; for 9 h; Inert atmosphere
In a 50 mL three-necked flask were put 1.0 g (2.63 mmol) of 9-iodo-10-phenylanthracene, 542 mg (2.70 mmol) of p-bromophenyl boronic acid, 46 mg (0.03 mmol) of tetrakis(triphenylphosphine)palladium(0), 3 mL of an aqueous potassium carbonate solution (2 mol/l), and 10 mL of toluene. This mixture was stirred under nitrogen stream at 80° C. for 9 hours. After the mixture was stirred, to this mixture was added about 20 mL of toluene. Then, the mixture was suction-filtered through Florisil (a product of Wako Pure Chemical Industries, Ltd., Catalog No. 540-00135), Celite (a product of Wako Pure Chemical Industries, Ltd., Catalog No. 531-16855), and alumina. The obtained filtrate was washed with water and a saturated saline solution, followed by drying with magnesium sulfate. This mixture was gravity filtered, and the obtained filtrate was concentrated to give a solid. This solid was recrystallized with chloroform/hexane, whereby 9-(4-bromophenyl)-10-phenylanthracene was obtained as 562 mg of a light brown solid at a yield of 45percent. The synthesis scheme of Step 1 is illustrated in (b-1) below.
45%
With potassium carbonate In toluene
[Step 1] Synthesis of 9-(4-bromophenyl)-10-phenylanthracene A synthesis scheme of 9-(4-bromophenyl)-10-phenylanthracene is shown in (a-4). Into a 50 mL three-neck flask were put 1.0 g (2.63 mmol) of 9-iodo-10-phenylanthracene and 542 mg (2.70 mmol) of p-bromophenyl boronic acid. The atmosphere in the flask was replaced with nitrogen. After that, 10 mL of toluene and 3 mL of potassium carbonate aqueous solution (2.0 M) were added to the flask. This mixture was degassed under reduced pressure, then 46 mg (0.03 mmol) of tetrakis(triphenylphosphine)palladium(0) was added to the mixture. The mixture was stirred under a nitrogen stream at 80° C. for 9 hours. After the stirring, about 20 mL of toluene was added to this mixture. Then, the mixture was subjected to suction filtration through Florisil (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 540-00135), Celite (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 531-16855), and alumina. The obtained filtrate was washed with water and a saturated saline, and then dried with magnesium sulfate. This mixture was gravity filtered, and the obtained filtrate was concentrated to give a solid. The obtained solid was recrystallized with chloroform/hexane to give 0.56 g of a light-brown solid, which was the object of the synthesis, in a yield of 45percent.
45%
With potassium carbonate In water; toluene at 80℃; for 9 h;
Step 3: Synthesis of 9-(4-bromophenyl)-10-phenylantracene A mixture containing 1.0 g (2.6 mmol) of 9-iodine-10-phenylanthracene, 540 mg (2.7 mmol) of p-bromophenylboronic acid, 46 mg (30 μmol) of tetrakis(triphenylphosphine)palladium(0) (Pd(PPh3)4), 3.0 mL of an aqueous solution of potassium carbonate (2.0 mol/L), and 10 mL of toluene was stirred at 80° C. for 9 hours. After the reaction, toluene was added to the mixture, and the mixture was filtered through Florisil (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 540-00135), Celite (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 531-16855), and alumina. The obtained filtrate was washed with water and brine, followed by drying with magnesium sulfate. This mixture was gravity filtered, and the obtained filtrate was concentrated to give a solid, which was subjected to recrystallization with a mixed solvent of chloroform and hexane, resulting in 560 mg of a pale yellow solid which szx a target substance in 45percent yield. The synthetic scheme of 9-(4-bromophenyl)-10-phenylanthracene is illustrated in (A-3).
45%
With potassium carbonate In toluene
Step 3: Synthesis of 9-(4-bromophenyl)-10-phenylanthracene A mixture containing 1.0 g (2.6 mmol) of 9-iodine-10-phenylanthracene, 540 mg (2.7 mmol) of p-bromophenylboronic acid, 46 mg (30 μmol) of tetrakis(triphenylphosphine)palladium(0) (abbreviated to Pd(PPh3)4), 3.0 mL (6.0 mmol) of a potassium carbonate aqueous solution (2.0 mol/L), and 10 mL of toluene was stirred at 80° C. for 9 hours. After the stirring, toluene was added to the mixture, and the mixture was filtered through Florisil (produced by Wako Pure Chemical Industries, Ltd., catalog number: 540-00135), Celite (produced by Wako Pure Chemical Industries, Ltd., catalog number: 531-16855), and alumina. The obtained filtrate was washed with water and brine, followed by drying with magnesium sulfate. This mixture was gravity filtered, and the obtained filtrate was concentrated to give a solid, which was subjected to recrystallization with a mixed solvent of chloroform and hexane, resulting in 560 mg of a light brown solid which was a target substance in a yield of 45percent. The synthetic scheme of 9-(4-bromophenyl)-10-phenylanthracene is shown in (A-3).
45%
With potassium carbonate In water; toluene at 80℃; for 9 h;
(4) Synthesis of 9-phenyl-10-(4-bromophenyl)anthracene; A mixture of 1.0 g (2.63 mmol) of 9-iodo-10-phenylanthracene, 542 mg (2.70 mmol) of p-bromo phenylboronic acid, 46 mg (0.03 mmol) of tetrakis(triphenylphosphine)palladium, 3 mL of a 2 mol/L aqueous potassium carbonate solution, and 10 mL of toluene was stirred for 9 hours at 80 0C. After the reaction, toluene was added, and the mixture was filtered through florisil, Celite.(R)., and alumina. The filtrate was washed with water and a saturated aqueous sodium chloride solution in this order and then dried with magnesium sulfate. Subsequently, the filtrate was filtered naturally. After concentrating the filtrate, the filtrate was recrystallized with chloroform and hexane, thereby obtaining 562 mg of 9-phenyl-10-(4-bromophenyl)anthracene as a light-brown solid (yield: 45 percent). A synthesis scheme of9-phenyl-10-(4-bromophenyl)anthracene from 9-iodo-10-phenylanthracene is shown below.
45%
With potassium carbonate In toluene at 80℃; for 9 h;
A mixture of 1.0 g (2.63 mmol) of 9-iodo-10-phenylanthracene, 542 mg (2.70 mmol) of p-bromo phenylboronic acid, 46 mg (0.03 mmol) of tetrakis(triphenylphosphine)palladium (abbreviation: Pd(PPli3)4 ), 3 mL (6 mmol) of potassium carbonate solution (2 mol/L), and 10 mL of toluene was stirred for 9 hours at 80 °C. After reaction, toluene was added and filtration was carried out using florisil.(R)., celite, and alumina. A filtrate was washed with water and saturated saline, and then dried with magnesium sulfate. After a mixed solution was naturally filtered and a EPO <DP n="63"/>filtrate was concentrated, an obtained solid was recrystallized with a mixture of chloroform and hexane. Then, 562 mg of 9-phenyl-10-(4-bromophenyl)anthracene (PA) that was a target substance and was a light brown solid was obtained in a yield of 45 percent (Synthesis Scheme (b-4)).
45%
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In water; toluene at 80℃; for 9 h;
A mixture containing 1.0 g (2.6 mmol) of 9-iodine-10-phenylanthracene, 540 mg (2.7 mmol) of p-bromophenylboronic acid, 46 mg (30 μmol) of tetrakis(triphenylphosphine)palladium(0) (abbreviated to Pd(PPh3)4), 3.0 mL (6.0 mmol) of a potassium carbonate aqueous solution (2.0 mol/L), and 10 mL of toluene was stirred at 80 °C for 9 hours. After the stirring, toluene was added to the mixture, and the mixture was filtered through Florisil (produced by Wako Pure Chemical Industries, Ltd., catalog number: 540-00135), Celite (produced by Wako Pure Chemical Industries, Ltd., catalog number: 531-16855), and alumina. The obtained filtrate was washed with water and brine, followed by drying with magnesium sulfate. This mixture was gravity filtered, and the obtained filtrate was concentrated to give a solid, which was subjected to recrystallization with a mixed solvent of chloroform and hexane, resulting in 560 mg of a light brown solid which was a target substance in a yield of 45percent.
Reference：
[1] Patent: WO2017/196081, 2017, A1,
[2] Dyes and Pigments, 2018, vol. 156, p. 369 - 378
69
[ 39806-90-1 ]
[ 5467-74-3 ]
[ 1191616-45-1 ]
Yield
Reaction Conditions
Operation in experiment
76%
With tetrakis(triphenylphosphine) palladium(0); caesium carbonate In 1,2-dimethoxyethane; water at 90℃; for 0.116667 h; Microwave irradiation; Inert atmosphere
General procedure: 4-Iodo-1-methyl-1H-pyrazole 1 (101 mg, 0.5 mmol) and phenylboronic 2 (59 mg, 0.5 mmol) were dissolved in DME (3 mL) and H2O (1.2 mL) in a microwave vial under a nitrogen atmosphere. Pd(PPh3)4 (2 mmolpercent, 11.6 mg) and Cs2CO3 (407.3 mg, 1.25 mmol) were added, and the reaction mixture was irradiated in a microwave apparatus at 90 °C for 5–12 min. After the reaction mixture was cooled to ambient temperature, the product was concentrated, and the crude mixture was purified by silica gel column chromatography using petroleum ether/acetone as eluent to give the title compound.
Reference：
[1] Chinese Chemical Letters, 2014, vol. 25, # 5, p. 705 - 709
With tetrabutyl ammonium fluoride;palladium bis[bis(diphenylphosphino)ferrocene] dichloride; In tetrahydrofuran; at 65℃;Inert atmosphere;
Step 1 : Synthesis of 4-bromo-4'-fluoro- 1,1 '-biphenylTo THF (90 mL) degassed by purging argon was added 4- flouroiodobenzene (4.5g, 20.2 mmol), 4-bromophenylboronic acid (4g, 20.2 mmol), and tetrabutylammonium flouride (1M in THF, 40.5 mL, 40.5 mmol), and the mixture was degassed again. Pd(dppf)Cl2 (732 mg, 1 mmol) was added and the mixture was degassed again for 15 minutes. The reaction mixture was heated at 65°C in an oil bath overnight. TLC (heptane eluent) showed the reaction was complete. The reaction mixture was diluted with ethyl acetate and extracted with brine. The organic layer was dried (sodium sulfate) and concentrated to yield the crude product. Purification by column chromatography (60-120 mesh silica, heptane eluent) yielded 3.2 g of 4- bromo-4'-fluoro- 1 , 1 '-biphenyl.
With cesium fluoride;tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; for 30h;Heating / reflux;
For the synthesis of 4-bromo-4"-nitro-l,l :4',1 "-terphenylene 0.74 mmol 4-iodo-4'- nitrobiphenyle, 0.76 mmol (1.02 equivalents) of 4-bromo phenyl boronic acid, 2.22 mmol (3.0 equivalents) of caesium fluoride, and 0.037 mmol (5 mol-%) of tetrakis(triphenyl-phosphine)- palladium(O) were put in a 100 mL 2 -neck- flask equipped with a reflux condenser, dissolved in 50 mL of abs. tetrahydrofurane under an argon atmosphere, and refluxed for 30 h. The organic phase was diluted with 50 mL of dichloromethane, washed with water, dried over sodium sulphate, and concentrated. The crude product was purified by flash-chromatography (/z-hexane/ethyl acetate/dichloromethane 10:5:1 containing 5 % of triethylamine) to give the desired product as an amorphous yellow solid. Yield 42 %. 1H-NMR (CDCl3, delta, ppm): 7.50 (2 H, d, J= 8.5), 7.59 (2 H, d, J= 8.5), 7.68-7.72 (4 H, m), 7.77 (2 H, d, J= 8.5), 8.31 (2 H, d, J = 8.5).
With sodium hydrogencarbonate;bis-triphenylphosphine-palladium(II) chloride; In 1,2-dimethoxyethane; water; at 80℃; for 18h;
A mixture of 4-bromophenylboronic acid (1G, 5MMOL), 3, 5-dimethyl-4-iodoisoxazole (0.93g, 4.2 MMOL), bis (triphenylphospine) palladium (LI) chloride (59mg, 2MOL%), NAHC03 (1.06g, 12. 6MMOL) in DME (5mL) and H20 (5mL) was heated to 80 C under N2 for 18h. The reaction mixture was partitioned between 1 N HCI and EtOAc. The organic layer was washed with saturated NAHC03, brine, dried over NA2SO4AND concentrated. The residue was purified by silica gel chromatography (5% EtOAc in hexanes) to give the title compound as a white solid (0.9g, 86%). H NMR (CDCl3) : No. 2. 26 (s, 3H), 2.40 (s, 3H), 7.13 (d, 2H, J = 8.3 Hz), 7.58 (d, 2H, J = 8.3 Hz).
86%
With sodium hydrogencarbonate;bis-triphenylphosphine-palladium(II) chloride; In 1,2-dimethoxyethane; water; at 80℃; for 18h;
A mixture of 4-bromophenylboronic acid (1 g, 5 mmol), <strong>[10557-85-4]3,5-dimethyl-4-iodoisoxazole</strong> (0.93 g, 4.2 mmol), bis(triphenylphospine)palladium(II) chloride (59 mg, 2 mol %), NaHCO3 (1.06 g, 12.6 mmol) in DME (5 mL) and H2O (5 mL) was heated to 80 C. under N2 for 18 h. The reaction mixture was partitioned between 1 N HCl and EtOAc. The organic layer was washed with saturated NaHCO3, brine, dried over Na2SO4 and concentrated. The residue was purified by silica gel chromatography (5% EtOAc in hexanes) to give the title compound as a white solid (0.9 g, 86%). 1H NMR (CDCl3): delta 2.26 (s, 3H), 2.40 (s, 3H), 7.13 (d, 2H, J=8.3 Hz), 7.58 (d, 2H, J=8.3 Hz).
With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; water; at 80℃;
B. (2-methyl-1, 2, 3, 4-TETRAHYDRO-ISOQUINOLIN-7-YL)-R7- (3-TRIFLUOROMETHYL-PYRIDIN-2-Y)- QUINAZOLIN-4-YL]-AMINE (COMPOUND 2); 1. 2- (-BROMOPHENYL)-3- (TRIFLUOROMETHYL)-PYRIADINE; To a de-gassed mixture of 2-bromo-3- (trifluoromethyl)-pyridine (2.26 mmol), 4- bromo-phenylbronic acid (2.49 mmol), and 2M NA2C03 (5.65 mmol), in DME (10 mL) under nitrogen add Pd (PPh3) 4 (0. 09 MMOL). STIR the mixture at 80C for overnight, concentrate, extract with EtOAc. Dry over NA2S04, concentrate under vacuum, and purify by flash chromatography (4: 1 hexanes/EtOAc) to give 2- (4-BROMO PHENYL)-3- (TRIFLUOROMETHYL)- pyridine.
With sodium carbonate;tetrakis(triphenylphosphine)palladium (0); In toluene;
(1) Synthesis of 4,4"-dibromo-p-terphenyl Toluene 600 ml and a 2M sodium carbonate aqueous solution 300 ml were added to 1,4-diiodobenzene 33.0 g, 4-bromophenylboronic acid 48.2 g and tetrakis(triphenylphosphine)palladium (0) 4.62 g under argon atmosphere, and the mixture was refluxed for 10 hours under heating. After finishing the reaction, the mixture was immediately filtered, and the aqueous layer was removed. The organic layer was dried on sodium sulfate and then concentrated. A solid matter thus obtained was recrystallized from toluene to obtain 32.6 g of white crystal of 4,4"-dibromo-p-terphenyl (yield: 84percent)
With copper(I) sulfide; N,N,N,N,-tetramethylethylenediamine; In methanol; at 20℃; for 24h;
General procedure: A 10mL round bottom flask was charged with a magnetic stirring bar, benzimidazole 1 (59mg, 0.5mmol), boronic acid 2 (1.0mmol), Cu2S (4mg, 0.025mmol), and MeOH (2mL), followed with the addition of TMEDA (0.075mL, 0.5mmol). The flask was sealed with a septum, through which was inserted 18-gauche needle. This setup allowed air to go into the reaction and avoid contamination of a mixture. The reaction mixture was stirred from 400 to 600rpm for appropriate time and extracted with EtOAc (2×15mL). Combined organic layers were washed with saturated aqueous solution of ethylenediaminetetraacetic acid disodium salt (15mL), and then dried over anhydrous Na2SO4. Volatiles were removed under reduced pressure and the residue was purified by column chromatography (silica gel, hexanes - EtOAc) to yield the title product, which was characterized by 1H NMR, 13C NMR, HRMS, and melting point (if solid).
81%
With triethylamine; In methanol; at 20℃; for 5h;
General procedure: In a typical reaction, arylboronic acid (1 mmol), amino-compound (1 mmol), catalyst (5 wt%), Et3N (2 mmol) were mixed in methanol ( 5mL) in a 25mL round bottomed flask. The reaction mixture was subjected under continuous stirring at room temperature for 5 h. Reaction was monitored from time to time using TLC. After completion of the reaction, catalyst was separated with the aid of an external magnet and reaction mixture was taken in ethyl acetate. The organiclayer was washed using brine solution, dried over sodium sulfate. After evaporating the solvent, the crude product was puried by column chromatography using 230-400 silica mesh. The recovered catalyst was washed with methanol and ethyl acetate, dried in oven and kept in desiccator for further use.
74%
With [2,2]bipyridinyl; oxygen; copper diacetate; In water; at 20℃; under 760.051 Torr; for 24h;
General procedure: Under an O2 atmosphere, a mixture of 4-methoxyphenylboroic acid (1a, 60.8 mg, 0.40 mmol), imidazole (2a, 13.6 mg, 0.20 mmol), Cu(OAc)2 (3.6 mg, 0.020 mmol), ligand I (3.7 mg, 0.020 mmol), and Brij 30 (21.8 mg, 0.060 mmol) in H2O (4 mL) was stirred at room temperature for 24 h. The mixture was diluted with brine and extracted with AcOEt (30 mL×3). The organic layer was washed with H2O (10 mL×3) and dried over MgSO4. The solvent was removed under the reduced pressure and the residue was purified by SiO2 column chromatography using AcOEt to give N-(4-methoxyphenyl)imidazole (3aa) (23.7 mg, 68%).
With pyridine; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical;copper diacetate; In 1,2-dichloro-ethane; at 20℃; for 24h;Molecular sieve;
A mixture of <strong>[188554-13-4]2-hydroxy-4-pyridinecarboxaldehyde</strong> (123 mg, 0.001 mol), 4-bromo- phenylboronic acid (400 mg, 0.002 mol), Cu(OAc)2 (18 mg, 0.0001 mol), pyridine (162 ml, 0.002 mol), TEMPO (172 mg, 0.0011 mol) and molecular sieves in DCM (2 ml) was stirred at room temperature for 24 hours. Then, the solids were filtered through a celite pad and the filtrate was treated with Na2CO3 (aqueous saturated solution). The organic layer was separated, dried over Na2SO4 and the solvent evaporated. The residue was purified by column chromatography (eluents: DCM and DCM/EtOAc; 9/1), yielding 0.180 g of intermediate compound 1-6 (65 %).
With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In water; toluene; for 7h;Heating / reflux;
Synthesis Example 1 (Synthesis of a compound (AN-1)); Under the atmosphere of argon, 10 g of <strong>[63279-58-3]1-bromo-4-iodonaphthalene</strong> and 6 g of 4-bromophenylboronic acid which were synthesized in accordance with conventional processes were dissolved into 150 ml of toluene, and 45 ml of a 2M aqueous solution of sodium carbonate was added. Then, 1 g of tetrakistriphenylphosphinepalladium was added, and the resultant mixture was heated under the refluxing condition for 7 hours. After one night, the formed organic layer was extracted with toluene, washed with water and a saturated aqueous solution of sodium chloride. The organic layer was dried with anhydrous sodium sulfate, and the solvent was removed by distillation. The residue was purified in accordance with the silica gel column chromatography (the solvent of development: toluene/hexane), and 6.3 g of 1-bromo-4-(4-bromophenyl)-naphthalene was obtained (the yield: 58percent). The obtained 1-bromo-4-(4-bromophenyl)naphthalene in an amount of 6 g was mixed with 10 g of 10-phenylathracene-9-boronic acid synthesized in accordance with a conventional process and 150 ml of DME. Then, 1.1 g of tetrakistriphenylphosphinepalladium and 50 ml of a 2M aqueous solution of sodium carbonate were added, and the atmosphere was purged with argon. After the resultant mixture was heated under the refluxing condition for 7.5 hours, the mixture was cooled by leaving standing, and formed crystals were separated by filtration. The separated crystals were washed with water, methanol and then heated toluene, and 8.3 g of the object compound (AN-1) was obtained as a light yellow solid substance (the yield: 70percent). When the obtained compound was examined in accordance with the field desorption mass spectroscopy (FDMS), it was found that m/z=708, which agreed with C56H36=708, and the above compound was identified to be Compound AN-1.
With potassium hydrogenfluoride; In methanol; water; at 0℃; for 0.5h;
General procedure: To a solution of the appropriate boronic acid, 1a-j (5 mmol) in MeOH (10 mL) was added dropwise a solution of KHF2 (1.56 g, 20 mmol) in H2O (8 mL) using an addition funnel. The mixture was stirred for 30 min and concentrated under high vacuum. The residual solid was extracted with four portions of 20% MeOH in acetone. The combined extracts were concentrated close to the saturation point and Et2O was added until no more precipitation was observed. The solid was collected, washed with two portions of Et2O, and dried under high vacuum to give the corresponding products sufficiently pure for characterization.
Synthesis Example 4: Synthesis of Compound 8; Compound 8 was synthesized according to Reaction Scheme 3 below: [Show Image] Intermediate 8d was synthesized by reacting Compound 1d with 4-bromophenylboronic acid through a Suzuki coupling reaction. 6.27 g (18 mmol) of Intermediate 8c and 4.67 g (15 mmol) of Intermediate 8d were added to a mixed solvent of THF and K2CO3 solution, 0.52 g (3 mol%) of Pd(PPh3)4 was added thereto while stirring, and the mixture was heated for 12 hours. The mixture was cooled to room temperature and subject to extraction using dichloromethane. Then, an organic layer was collected, and the solvent was removed by drying the organic layer using anhydrous magnesium sulfate under reduced pressure. The resulting product was filtered using column chromatography (ethyl acetate:dichloromethane=3:7) to obtain 6.8 g of yellow solid Compound 8 (Yield: 85%). 1H NMR (500MHz, CDCl3) delta 8.79(dd, 2H), 8.41(d, 2H), 8.12-8.08(m, 3H), 8.06-7.93(m, 5H), 7.87-7.79(m, 3H), 7.74(dd, 2H), 7.69-7.60(m, 5H), 7.38-7.31(m, 4H).
With bathophenanthroline; water; copper diacetate; manganese(III) triacetate dihydrate; In 1,4-dioxane; at 90℃;
General procedure: In a 25mL round bottom flask (oven-dried overnight) was added the phenyl boronic acid (1a, 1.0 mmol) followed by the addition of 1,4-dioxane (6mL). To this solution, manganese (III) acetate. dihydrate (5molpercent), Bphen (3e, 10molpercent), Cu(OAc)2 (5molpercent), nitrile (0.5mmol) and water (0.5mmol) were added sequentially. The reaction was then stirred at room temperature for 10min and slowly brought to 90°C under air. The reaction was allowed to run for overnight at the same temperature. After the completion, the reaction mixture was quenched and extracted with ethyl acetate and water. The organic layer was collected, and the aqueous layer was again extracted with ethyl acetate for three more times. The combined organic layer was further washed with sodium bicarbonate and brine solution. The organic layer was then dried over sodium sulfate, filtered and evaporated using rotavap. The crude compound obtained was further purified using column chromatography (EA:hexane 10:90).
With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In water; diethylene glycol; at 80℃; for 12h;
Compound (126) (10 g, 21.08 mmol), 4-bromophenylboronic acid (4.23 g, 21.1 mmol), tetrakis(triphenylphosphine)palladium (Pd(PPh3)4) (2.43 g, 21.1 mmol), aqueous 1.0 M potassium carbonate solution (105 mL) and diethyleneglycol (DME) (100 mL) were mixed, and the mixture was stirred at 80° C. under reflux for 12 hours. After cooling to ambient temperature, the organic layer was extracted with dichloromethane (200 mL), and the extract was washed with distilled water (200 mL), dried over magnesium sulfate, and distilled under reduced pressure. Purification via silica gel column chromatography (n-hexane: dichloromethane=7:1) gave Compound (127) (2.4 g, 4.4 mmol).
With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In water; diethylene glycol; at 80℃; for 12h;
Compound (144) (10 g, 21.1 mmol), 4-bromophenylboronic acid (4.2 g, 42.2 mmol), tetrakis(triphenylphosphine)palladium 1.0 (Pd(PPh3)4) (2.4 g, 2.1 mmol), aqueous 2.0 M potassium carbonate solution (105 mL) and diethyleneglycol (100 mL) were suspended, and the suspension was stirred at 80° C. under reflux for 12 hours. After cooling to ambient temperature, the organic layer was extracted with dichloromethane (700 mL), and the extract was washed with distilled water (400 mL), dried over magnesium sulfate, and distilled under reduced pressure. Purification via silica column chromatography (n-hexane:dichloromethane=7:1) gave Compound (146) (2.7 g, 4.4 mmol).
With pyridine; oxygen; copper diacetate; In dichloromethane; at 20℃; for 16h;Molecular sieve;
To a mixture of compound XLI-1 (3.7 g, 26.6 mmol), compound XLI-2 (10.6 g, 53.4 mmol), Cu(OAc)2 and Py. in dichloromethane (400 mL) was added to powdered 4A molecular sieves. The reaction mixture was flushed with 02 and stirred at room temperature for 16 hours. The mixture was filtered through celite, the filtrated was concentrated, and the residue was purified by column chromatography (PE:EA=10:1) to give compound XLI-3 (4.5 g, yield 57.5percent).
Using similar reaction conditions as described in step i of intermediate 9, 4-bromo pyridine (2g, 8.44 mmol) was coupled with ( 4-bromophenyl) boronic acid (1 g, 9.2 mmol) in sodiumcarbonate (3.57 g, 33.7 mmol), Pd(PPh3)4 (487 mg, 0.422 mmol) and toluene/ethanol/water(50/50/20 ml) to afford 2.2 g of the crude product which was taken as such for next reaction.LCMS: 235.9 rn/z = (M+2).
With 1,2-bis(diphenylphosphino)ethane nickel(II) chloride; trifluoroacetic acid; In 1,4-dioxane; water; at 20 - 120℃; for 12h;
Add 100 mmol of o-aminobenzonitrile, 200 mmol of p-bromobenzeneboronic acid, 5 mmol of nickel catalyst to the appropriate amount of mixed solvent in the reaction vessel (mixture of 1,4-dioxane and water in a volume ratio of 4:1) at room temperature.Ni(dppe)Cl2 and 400 mmol of trifluoroacetic acid were then stirred and warmed to 90 ° C, and the reaction was stirred at this temperature for 24 hours.After the reaction is completed, the reaction mixture is rotary evaporated to dryness, and then a sufficient amount of ethyl acetate is added to dissolve it, followed by washing with an appropriate amount of a saturated aqueous solution of sodium hydrogencarbonate and a saturated aqueous solution of sodium chloride, and the organic layer is separated. After the aqueous layer and the aqueous layer were extracted with ethyl acetate for three times, the organic layer was combined (the organic layer washed with the combined aqueous solution and the organic layer obtained by ethyl acetate extraction), dried over anhydrous sodium sulfate and evaporated under reduced pressure. Fast column chromatography(Eluation was carried out with a mixture of petroleum ether and ethyl acetate in a volume ratio of 1:0.5 as an eluent), and the eluent was collected and evaporated to remove the eluent to give 2-amino-4'- as a pale yellow solid. Bromo-benzophenone, the characterization data was as above, the yield was 86.8percent, and the purity was 94.6percent.
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium carbonate; In 1,2-dimethoxyethane; water;Inert atmosphere; Reflux;
To a stuffed mixture of XXXII-1 (1.5 g, 9.15 mmol), XXXII-2 (1.83 g, 9.15 mmol), and K2C03 (3.79 g, 27.45 mmol) in DME/H20 (50 mL, v:v=5:1) was added Pd(dppf)C12 (1.34 g, 1.83 mmol) under N2 protection. The reaction mixture was heated to reflux overnight. The mixture was poured into water, extracted with EtOAc (150 mLx3). The combined organic layer was washed with brine, dried over anhydrous Na2SO4 and concentrated. The residue was purified by flash chromatography on silica gel (PE:EA=10:1-*5:1-*3:1) to afford XXXII-3 (600 mg, 21% yield).
methyl 6-(4-bromophenyl)-5-nitronicotinate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium phosphate; In tetrahydrofuran; water; at 75℃; for 2.5h;Inert atmosphere;
THF (46 mL) was added tripotassium phosphate (3M in H20, 4.6 mL, 13.8 mmol). After purging with N2 (vacuum/N2 x 3), the reaction was heated at 75 °C with stirring. After 2.5 h, the reaction was cooled to room temperature and concentrated. The residue was partitioned between EtOAc and H20, the organic phase was separated, washed with sat.NaC1, dried over sodium sulfate, filtered, and concentrated. The residue was purified by flash chromatography (Teledyne ISCO CombiFlash Rf, gradient of 0percent to 100percent using solvent AIB=CH2C12/EtOAc over 12 column volumes, RediSep Si02 80 g, loaded as DCM solution). A 62:26 mixture (by LCMS) of methyl 6-(4-bromophenyl)-5- nitronicotinate and methyl 6-(4?-bromo- [1,1 ?-biphenyll -4-yl)-5 -nitronicotinate (1.79 g)was obtained as a pale yellow solid, which was used as in the next step: Methyl 6-(4- bromophenyl)-5-nitronicotinate: HPLC: RT=1.31 mm (Waters Acquity UPLC BEH C18 1.7 um 2.0 x 50 mm, CH3CN/H20/0.1percentTFA, 1 mm gradient, wavelength=254nm); MS (ES): m/z= 337/339 79Br/81Br [M+lf?; methyl 6-(4?-bromo-[1,1?-biphenylj-4-yl)-5- nitronicotinate: HPLC: RT=1.53 mm (Waters Acquity UPLC BEH C18 1.7 um 2.0 x 50mm, CH3CN/H20/0. 1percentTFA, 1 mm gradient, wavelength=254nm); MS (ES): m/z=413/415 79Br/81Br [M+1j.In a 100 mL RB flask was added a mixture of methyl 6-(4-bromophenyl)-5- nitronicotinate and methyl 6-(4?-bromo- [1,1 ?-biphenyll -4-yl)-5 -nitronicotinate (1.79 g,) and 1,2-bis(diphenylphosphino)ethane (2.54 g, 6.38 mmol) in 1,2-dichlorobenzene (22 mL). The flask was placed in a pre-heated heating block at 170 °C. After 1 h, the mixture was cooled to room temperature, then concentrated in vacuo under high vacuum.The residue was dissolved in THF and a small amount of MeOH, 5i02 (20 g) was added, concentrated in vacuo then dried under vacuum overnight. The material was then purified by flash chromatography (Teledyne ISCO CombiFlash Rf, gradient of 0percent to 60percent using solvent AIBCH2C12/EtOAc over 12 column volumes, RediSep 5i02 120 g). A 3:1 mixture of methyl 7-bromo-5H-pyrido[3,2-bjindole-3-carboxylate and methyl 7-(4-bromophenyl)-5H-pyrido[3,2-bjindole-3-carboxylate (0.95 g) was obtained as a yellow solid: HPLC for methyl 7-bromo-5H-pyrido[3 ,2-bj indole-3-carboxylate: RT=0. 82 mm(Waters Acquity UPLC BEH C18 1.7 urn 2.0 x 50 mm, CH3CN/H20/0.05percentTFA, 1 mm gradient, wavelength=254nrn); MS (ES): m/z= 305/307 79Br/81Br [M+1jIn a 250 mL RB flask was added a mixture of rnethyl 7-brorno-5H-pyrido[3,2- bj indole-3 -carboxylate and rnethyl 7-(4-brornophenyl)-5H-pyrido [3 ,2-bj indole-3 - carboxylate (1.05 g, 3.44 rnrnol), 1,4-dirnethyl-5-(tributylstannyl)-1H-1,2,3-triazole (1.50 g, 3.88 rnrnol), and TEA (0.96 mL, 6.89 mmol) in DMF (49 mL), and the clear, orangesolution was purged by bubbling a nitrogen strearn through the solution for 5 mm. While purging, copper(i) iodide (107.6 rng, 0.565 mmol) and Pd(Ph3P)4 (262.5 rng, 0.227 rnrnol) were added, then the flask was fitted with a septurn, and heated in a heating block at 95°C. After 3.5 h, the reaction cooled to roorn ternperature, concentrated in vacuo, then dried under vacuurn overnight. The residue was purified by flash chrornatography(Teledyne ISCO CornbiFlash Rf, gradient of 0percent to 75percent using solvent A/B=CH2C12/acetone over 15 column volurnes, RediSep 5i02 120 g, loaded as DCM solution). Fractions containing pure product were cornbined and set aside, fractions containing irnpure product were cornbined, 5i02 (10 g) was added, and concentrated. The rnaterial was then repurified by flash chrornatography (Teledyne ISCO CornbiFlash Rf,gradient of 0percent to 70percent using solvent AIB=CH2C12/acetone over 15 column volurnes, RediSep 5i02 220 g). Once again, pure product was cornbined with product above and set aside. Irnpure product fractions were cornbined, 2 g 5i02 was added, concentrated, dried under vacuurn overnight. Repurified by flash chrornatography (Teledyne ISCO CornbiFlash Rf, gradient of 0percent to 70percent using solvent AIB=CH2C12/acetone over 20column volurnes, RediSep 5i02 40 g). Fractions containing pure product were cornbined with above product fractions and concentrated. The product, rnethyl 7-(1,4-dirnethyl-1H- 1,2,3 -triazol-5 -yl)-5H-pyrido[3 ,2-bj indole-3 -carboxylate (431.1 rng, 39percent) was obtained as ayellow solid: HPLC: RT=0.916 mm (Waters Acquity UPLC BEH C18 1.7 urn 2.0 x 50 mm, CH3CN/H20/0. 1percentTFA, 1.5 mm gradient, wavelength=254nrn); MS (ES): m/z=322 [M+ljt
methyl 7-bromo-5H-pyrido[3,2-b]indole-3-carboxylate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
0.95 g
THF (46 mL) was added tripotassium phosphate (3M in H20, 4.6 mL, 13.8 mmol). After purging with N2 (vacuum/N2 x 3), the reaction was heated at 75 °C with stirring. After 2.5 h, the reaction was cooled to room temperature and concentrated. The residue was partitioned between EtOAc and H20, the organic phase was separated, washed with sat.NaC1, dried over sodium sulfate, filtered, and concentrated. The residue was purified by flash chromatography (Teledyne ISCO CombiFlash Rf, gradient of 0percent to 100percent using solvent AIB=CH2C12/EtOAc over 12 column volumes, RediSep Si02 80 g, loaded as DCM solution). A 62:26 mixture (by LCMS) of methyl 6-(4-bromophenyl)-5- nitronicotinate and methyl 6-(4?-bromo- [1,1 ?-biphenyll -4-yl)-5 -nitronicotinate (1.79 g)was obtained as a pale yellow solid, which was used as in the next step: Methyl 6-(4- bromophenyl)-5-nitronicotinate: HPLC: RT=1.31 mm (Waters Acquity UPLC BEH C18 1.7 um 2.0 x 50 mm, CH3CN/H20/0.1percentTFA, 1 mm gradient, wavelength=254nm); MS (ES): m/z= 337/339 79Br/81Br [M+lf?; methyl 6-(4?-bromo-[1,1?-biphenylj-4-yl)-5- nitronicotinate: HPLC: RT=1.53 mm (Waters Acquity UPLC BEH C18 1.7 um 2.0 x 50mm, CH3CN/H20/0. 1percentTFA, 1 mm gradient, wavelength=254nm); MS (ES): m/z=413/415 79Br/81Br [M+1j.In a 100 mL RB flask was added a mixture of methyl 6-(4-bromophenyl)-5- nitronicotinate and methyl 6-(4?-bromo- [1,1 ?-biphenyll -4-yl)-5 -nitronicotinate (1.79 g,) and 1,2-bis(diphenylphosphino)ethane (2.54 g, 6.38 mmol) in 1,2-dichlorobenzene (22 mL). The flask was placed in a pre-heated heating block at 170 °C. After 1 h, the mixture was cooled to room temperature, then concentrated in vacuo under high vacuum.The residue was dissolved in THF and a small amount of MeOH, 5i02 (20 g) was added, concentrated in vacuo then dried under vacuum overnight. The material was then purified by flash chromatography (Teledyne ISCO CombiFlash Rf, gradient of 0percent to 60percent using solvent AIBCH2C12/EtOAc over 12 column volumes, RediSep 5i02 120 g). A 3:1 mixture of methyl 7-bromo-5H-pyrido[3,2-bjindole-3-carboxylate and methyl 7-(4-bromophenyl)-5H-pyrido[3,2-bjindole-3-carboxylate (0.95 g) was obtained as a yellow solid: HPLC for methyl 7-bromo-5H-pyrido[3 ,2-bj indole-3-carboxylate: RT=0. 82 mm(Waters Acquity UPLC BEH C18 1.7 urn 2.0 x 50 mm, CH3CN/H20/0.05percentTFA, 1 mm gradient, wavelength=254nrn); MS (ES): m/z= 305/307 79Br/81Br [M+1jIn a 250 mL RB flask was added a mixture of rnethyl 7-brorno-5H-pyrido[3,2- bj indole-3 -carboxylate and rnethyl 7-(4-brornophenyl)-5H-pyrido [3 ,2-bj indole-3 - carboxylate (1.05 g, 3.44 rnrnol), 1,4-dirnethyl-5-(tributylstannyl)-1H-1,2,3-triazole (1.50 g, 3.88 rnrnol), and TEA (0.96 mL, 6.89 mmol) in DMF (49 mL), and the clear, orangesolution was purged by bubbling a nitrogen strearn through the solution for 5 mm. While purging, copper(i) iodide (107.6 rng, 0.565 mmol) and Pd(Ph3P)4 (262.5 rng, 0.227 rnrnol) were added, then the flask was fitted with a septurn, and heated in a heating block at 95°C. After 3.5 h, the reaction cooled to roorn ternperature, concentrated in vacuo, then dried under vacuurn overnight. The residue was purified by flash chrornatography(Teledyne ISCO CornbiFlash Rf, gradient of 0percent to 75percent using solvent A/B=CH2C12/acetone over 15 column volurnes, RediSep 5i02 120 g, loaded as DCM solution). Fractions containing pure product were cornbined and set aside, fractions containing irnpure product were cornbined, 5i02 (10 g) was added, and concentrated. The rnaterial was then repurified by flash chrornatography (Teledyne ISCO CornbiFlash Rf,gradient of 0percent to 70percent using solvent AIB=CH2C12/acetone over 15 column volurnes, RediSep 5i02 220 g). Once again, pure product was cornbined with product above and set aside. Irnpure product fractions were cornbined, 2 g 5i02 was added, concentrated, dried under vacuurn overnight. Repurified by flash chrornatography (Teledyne ISCO CornbiFlash Rf, gradient of 0percent to 70percent using solvent AIB=CH2C12/acetone over 20column volurnes, RediSep 5i02 40 g). Fractions containing pure product were cornbined with above product fractions and concentrated. The product, rnethyl 7-(1,4-dirnethyl-1H- 1,2,3 -triazol-5 -yl)-5H-pyrido[3 ,2-bj indole-3 -carboxylate (431.1 rng, 39percent) was obtained as ayellow solid: HPLC: RT=0.916 mm (Waters Acquity UPLC BEH C18 1.7 urn 2.0 x 50 mm, CH3CN/H20/0. 1percentTFA, 1.5 mm gradient, wavelength=254nrn); MS (ES): m/z=322 [M+ljt
methyl 7-(1,4-dimethyl-1H-1,2,3-triazol-5-yl)-5H-pyrido[3,2-b]indole-3-carboxylate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
39%
THF (46 mL) was added tripotassium phosphate (3M in H20, 4.6 mL, 13.8 mmol). After purging with N2 (vacuum/N2 x 3), the reaction was heated at 75 °C with stirring. After 2.5 h, the reaction was cooled to room temperature and concentrated. The residue was partitioned between EtOAc and H20, the organic phase was separated, washed with sat.NaC1, dried over sodium sulfate, filtered, and concentrated. The residue was purified by flash chromatography (Teledyne ISCO CombiFlash Rf, gradient of 0percent to 100percent using solvent AIB=CH2C12/EtOAc over 12 column volumes, RediSep Si02 80 g, loaded as DCM solution). A 62:26 mixture (by LCMS) of methyl 6-(4-bromophenyl)-5- nitronicotinate and methyl 6-(4?-bromo- [1,1 ?-biphenyll -4-yl)-5 -nitronicotinate (1.79 g)was obtained as a pale yellow solid, which was used as in the next step: Methyl 6-(4- bromophenyl)-5-nitronicotinate: HPLC: RT=1.31 mm (Waters Acquity UPLC BEH C18 1.7 um 2.0 x 50 mm, CH3CN/H20/0.1percentTFA, 1 mm gradient, wavelength=254nm); MS (ES): m/z= 337/339 79Br/81Br [M+lf?; methyl 6-(4?-bromo-[1,1?-biphenylj-4-yl)-5- nitronicotinate: HPLC: RT=1.53 mm (Waters Acquity UPLC BEH C18 1.7 um 2.0 x 50mm, CH3CN/H20/0. 1percentTFA, 1 mm gradient, wavelength=254nm); MS (ES): m/z=413/415 79Br/81Br [M+1j.In a 100 mL RB flask was added a mixture of methyl 6-(4-bromophenyl)-5- nitronicotinate and methyl 6-(4?-bromo- [1,1 ?-biphenyll -4-yl)-5 -nitronicotinate (1.79 g,) and 1,2-bis(diphenylphosphino)ethane (2.54 g, 6.38 mmol) in 1,2-dichlorobenzene (22 mL). The flask was placed in a pre-heated heating block at 170 °C. After 1 h, the mixture was cooled to room temperature, then concentrated in vacuo under high vacuum.The residue was dissolved in THF and a small amount of MeOH, 5i02 (20 g) was added, concentrated in vacuo then dried under vacuum overnight. The material was then purified by flash chromatography (Teledyne ISCO CombiFlash Rf, gradient of 0percent to 60percent using solvent AIBCH2C12/EtOAc over 12 column volumes, RediSep 5i02 120 g). A 3:1 mixture of methyl 7-bromo-5H-pyrido[3,2-bjindole-3-carboxylate and methyl 7-(4-bromophenyl)-5H-pyrido[3,2-bjindole-3-carboxylate (0.95 g) was obtained as a yellow solid: HPLC for methyl 7-bromo-5H-pyrido[3 ,2-bj indole-3-carboxylate: RT=0. 82 mm(Waters Acquity UPLC BEH C18 1.7 urn 2.0 x 50 mm, CH3CN/H20/0.05percentTFA, 1 mm gradient, wavelength=254nrn); MS (ES): m/z= 305/307 79Br/81Br [M+1jIn a 250 mL RB flask was added a mixture of rnethyl 7-brorno-5H-pyrido[3,2- bj indole-3 -carboxylate and rnethyl 7-(4-brornophenyl)-5H-pyrido [3 ,2-bj indole-3 - carboxylate (1.05 g, 3.44 rnrnol), 1,4-dirnethyl-5-(tributylstannyl)-1H-1,2,3-triazole (1.50 g, 3.88 rnrnol), and TEA (0.96 mL, 6.89 mmol) in DMF (49 mL), and the clear, orangesolution was purged by bubbling a nitrogen strearn through the solution for 5 mm. While purging, copper(i) iodide (107.6 rng, 0.565 mmol) and Pd(Ph3P)4 (262.5 rng, 0.227 rnrnol) were added, then the flask was fitted with a septurn, and heated in a heating block at 95°C. After 3.5 h, the reaction cooled to roorn ternperature, concentrated in vacuo, then dried under vacuurn overnight. The residue was purified by flash chrornatography(Teledyne ISCO CornbiFlash Rf, gradient of 0percent to 75percent using solvent A/B=CH2C12/acetone over 15 column volurnes, RediSep 5i02 120 g, loaded as DCM solution). Fractions containing pure product were cornbined and set aside, fractions containing irnpure product were cornbined, 5i02 (10 g) was added, and concentrated. The rnaterial was then repurified by flash chrornatography (Teledyne ISCO CornbiFlash Rf,gradient of 0percent to 70percent using solvent AIB=CH2C12/acetone over 15 column volurnes, RediSep 5i02 220 g). Once again, pure product was cornbined with product above and set aside. Irnpure product fractions were cornbined, 2 g 5i02 was added, concentrated, dried under vacuurn overnight. Repurified by flash chrornatography (Teledyne ISCO CornbiFlash Rf, gradient of 0percent to 70percent using solvent AIB=CH2C12/acetone over 20column volurnes, RediSep 5i02 40 g). Fractions containing pure product were cornbined with above product fractions and concentrated. The product, rnethyl 7-(1,4-dirnethyl-1H- 1,2,3 -triazol-5 -yl)-5H-pyrido[3 ,2-bj indole-3 -carboxylate (431.1 rng, 39percent) was obtained as ayellow solid: HPLC: RT=0.916 mm (Waters Acquity UPLC BEH C18 1.7 urn 2.0 x 50 mm, CH3CN/H20/0. 1percentTFA, 1.5 mm gradient, wavelength=254nrn); MS (ES): m/z=322 [M+ljt
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; toluene; at 60 - 65℃; for 24h;Inert atmosphere;
Under nitrogen protection,The resulting intermediate A-1 (20.1 g, 0.05 mol) and p-bromophenylboronic acid (20.1 g,0.1 mol) was put into a solution of 200 g of toluene and 50 g of THF, and then an aqueous solution of potassium carbonate (300 mL, 1 mol / L)Finally, the catalyst Pd (PPh3) 4 (0.58 g, 0.5 mmol) was charged.The reaction system was heated to 60 to 65 ° C and stirred for 24 hours.After completion of the reaction, 100 mL of water was added to the reaction system,Quenching reaction,Filtration is not no,The resulting filtrate was washed with deionized water,Concentrated under reduced pressure,The crude material was crystallized from ethyl acetate or petroleum ether,To give a white solid,The intermediate B-1 was obtained78.1percent.
75%
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; toluene; at 60 - 65℃; for 24h;Inert atmosphere;
Under nitrogen protection,The intermediate a (20.05 g, 0.05 mol) obtained in the previous step and p-bromophenylboronic acid (20.08 g, 0.1 mol) were charged into a mixed solvent of 200 g of toluene and 50 g of THF,Then, an aqueous solution of potassium carbonate (300 mL, 1 mol / L)Finally, catalyst Pd (PPh3) 4 (0.58 g, 0.5 mmol) was charged.The reaction system was warmed to 60-65 ° C and stirred for 24 hours.After the reaction was completed, 100 mL of water was added to the reaction system to quench the reaction and the insoluble materials were filtered off to obtain a filtrate. After washing with deionized water and concentrated under reduced pressure, the crude product was crystallized from ethyl acetate or petroleum ether to give a white solid For the intermediate b, yield 75percent.
With pyridine; copper diacetate; sodium carbonate; In 1,2-dichloro-ethane; at 20℃; for 14h;Schlenk technique; Molecular sieve; Sealed tube;
General procedure: In a nitrogen-filled glove box, a 25 mL Schlenk tube equipped with a magnetic stir bar was charged with Cu(OAc)2 (9.3 mg,0.05 mmol, 0.1 equiv), aryl boronic acid 1 (0.5 mmol, 1.0 equiv),Na2CO3 (106.0 mg, 1.0 mmol, 2.0 equiv) and 4 A MS (250.0 mg). The vessel was sealed with a septum before removing from the glovebox. The tube was evacuated and backfilled with air for 3 times.Then DCE (5.0 mL), pyridine (39.6 mg, 0.5 mmol, 1.0 equiv) and CF3CH2OH (100.0 mg, 1.0 mmol, 2.0 equiv) were added respectivelyvia syringe. The mixture was stirred vigorously under a balloon ofair at room temperature for 14 h. Then the reaction solution was vacuum-filtered over a sintered-glass funnel with a tightly packedpad of Celite (1 cm thick), and the filter cake was rinsed with DCM(20 mL). The combined filtrates were concentrated. The residue was purified with silica gel column chromatography to provide the desired product.
With potassium tert-butylate; copper diacetate; In dichloromethane; at 25℃; for 72h;
A solution of ethyl lH-l,2,3-triazole-5-carboxylate (example 23a; 500 mg, 3.54 mmol, Eq: 1) and (4-bromophenyl)boronic acid (1.07 g, 5.31 mmol, Eq: 1.5) in CH2C12 (30 mL) was treated with copper (II) acetate (322 mg, 1.77 mmol, Eq: 0.5) and KotBu (596 mg, 5.31 mmol, Eq: 1.5), at 25 °C under Air. The mixture was stirred at this temperature for 72h, before being diluted with CH2C12. The organic phase was washed with water (lx), dried over Na2S04, filtered and evaporated. MPLC (Si02; heptane/EtOAc, gradient from 100:0 to 0: 100 within 40 min) gave the title compound (82 mg, 8percent) as a white solid. MS (ESI): m/z = 298.0 [M+H]+.
General procedure: In a flask containing the appropriate potassiumorganotrifluoroborate (0.5 mmol) in distilled water(1 mL) was added montmorillonite K10 (150% m/m). Themixture was stirred for the time indicated in Scheme 1at room temperature. After this period, the mixture wasextracted with EtOAc (3 × 10 mL) and the organic phasewas washed with water (2 × 15 mL). The organic phasewas dried over anhydrous MgSO4, filtered and the solventwas removed in vacuo to yield the corresponding boronicacids 2a-o.
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; at 80℃; for 16h;
2.59 g (10 mmol) of <strong>[40000-20-2]<strong>[40000-20-2]5-bromo-1,10-phenanthrolin</strong>e</strong>, 2 g (10 mmol) of (4-bromophenyl)boronic acid, 0.58 g (0.5 mmol) of Pd(PPh3)4, and 4.15 g (30.0 mmol) of K2CO3 were dissolved in 180 mL of a mixed solution of THF and H2O (2/1) and stirred at a temperature of 80° C. for 16 hours. The obtained reaction solution was cooled to room temperature and an organic layer was extracted therefrom three times by using 100 mL of water and 100 mL of diethylether. The extracted organic layer was dried by using magnesium sulfate, and a solvent was evaporated therefrom. Then, the residue obtained therefrom was separated and purified by silica gel column chromatography to obtain 2.0 g (yield: 60percent) of Intermediate 94-1. The obtained compound was identified by LC-MS. C18H11BrN2: M+1 335.18.
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In toluene; at 50 - 150℃;Inert atmosphere;
(1) In a 500 mL three-necked flask, 3-bromo-9H-carbazole (39.37 g, 160 mmol), naphthalen-2-ylboronic acid (19.51 g, 160 mmol), potassium carbonate (44.44 g, 320 mmol),Add 250 mL of toluene under a nitrogen atmosphere,Add tetrakis(triphenylphosphine)palladium (0.37 g, 0.32 mmol),The temperature is raised to 50-150 C for 4 to 48 hours, and the liquid phase monitoring reaction is completed.Cool to room temperature, wash with water, filter, separate by column chromatography,3-phenyl-9H-carbazole 32.70g, yield 84%
(4-(3-phenyl-9H-carbazol-9-yl)phenyl)boronic acid[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
87%
With palladium diacetate; sodium t-butanolate; tri tert-butylphosphoniumtetrafluoroborate; In toluene; at 50 - 150℃;Inert atmosphere;
(2) In a 500mL three-necked bottle,<strong>[103012-26-6]<strong>[103012-26-6]3-phenyl-9H-carbazol</strong>e</strong> (14.60 g, 60 mmol),(4-Bromophenyl)boronic acid (12.05 g, 60 mmol), sodium tert-butoxide (11.52 g, 120 mmol), tri-tert-butylphosphine tetrafluoroborate (0.07 g, 0.24 mmol),Palladium acetate (0.03 g, 0.12 mmol) was added under a nitrogen atmosphere.The temperature is raised to 50-150 C for 4 to 48 hours, the liquid phase monitoring reaction is completed, and cooled to room temperature.Washed, filtered, separated by column chromatography,18.96 g of (4-(<strong>[103012-26-6]3-phenyl-9H-carbazol</strong>-9-yl)phenyl)boronic acid was obtained in a yield of 87%.
87%
With tri-tert-butylphosphine tetrafluoroborate; palladium diacetate; sodium t-butanolate; In toluene; at 50 - 150℃;Inert atmosphere;
(2) In a 500 mL three-necked flask, <strong>[103012-26-6]<strong>[103012-26-6]3-phenyl-9H-carbazol</strong>e</strong> (14.60 g, 60 mmol), (4-bromophenyl)boronic acid (12.05 g, 60 mmol), sodium tert-butoxide (11.52 g, 120 mmol), tri-tert-butylphosphine tetrafluoroborate (0.07 g, 0.24 mmol), 200 mL of toluene was added, and palladium acetate (0.03 g, 0.12 mmol) was added under a nitrogen atmosphere, and the temperature was raised to 50 to 150 C for 4 to 48 hours. The liquid phase monitoring reaction is completed, cooled to room temperature, washed with water, filtered, and separated by column chromatography to obtain 18.96 g of (4-(<strong>[103012-26-6]3-phenyl-9H-carbazol</strong>-9-yl)phenyl)boronic acid, yield 87%.
With tetrakis(triphenylphosphine) palladium(0); caesium carbonate; In methanol; water; for 12.0h;Reflux;
Add 4-bromo-2-aminopyrimidine (8.70 g, 50.0 mmol), 4-bromo-phenylboronic acid (11.0 g, 55.0 mmol), tetratriphenylphosphine palladium (2.89 g, 2.5 mmol), cesium carbonate (10.8 g , 33.0 mmol) was dissolved in methanol / water (200 mL, 1/1), refluxed and stirred for 12 h.Ethyl acetate and water were added.After the organic phase was separated, it was washed twice with saturated saline.The solvent was removed by vacuum rotary evaporation, and the residue was purified by silica gel chromatography to obtain solid compound 8a (7.50 g, 30.0 mmol) in a 60% yield.
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