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Structure of 7511-49-1 * Storage: {[proInfo.prStorage]}
* 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.
With sulfated tungstate In neat (no solvent) at 130℃; for 10 h;
General procedure: In round bottom flask equipped with condenser a mixture of aryl alkyl ketones (3mmol) and sulfated tungstate (20 wt. percent) were stirred at 130 C, the progress of the reaction was monitored by TLC. After disapperance of the aryl alkyl ketones and the reaction was continued for additional time of 2 h. The reaction mixture was cooled, diluted with 30 mL of ethyl acetate and filtered to recover the catalyst. The filtrate was washed with 10 mL of water, dried over sodium sulfate and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel ( 60-120) with (PE:EA=9:1) as eluent to get pure 1,3,5-arylenzenes.
76%
With para-dodecylbenzenesulfonic acid In neat (no solvent) at 130℃; for 4 h; Green chemistry
General procedure: A mixture of acetophenone (3 mmol) and DBSA (0.6 mmol) was heated at 130 °C in a preheated oil bath for 3–8 hours. After completion of the reaction as indicated by thin layer chromatography (TLC), the reaction mixture was cooled to room temperature and diluted with equal volumes of saturated solution of NaHCO3 and brine (5 mL + 5 mL). The resulting solution was extracted with ethyl acetate (10 mL × 3) and the organic layers were combined, dried over anhydrous Na2SO4 and evaporated under reduced pressure to dryness. The crude product obtained was purified by silica gel (60–120 mesh size) column chromatography using 1–2percent ethyl acetate in heptane as the eluent to afford the desired products in pure form.
69%
With ethylenediamine; trifluoroacetic acid In nitromethane for 48 h; Reflux
General procedure: To a solution of aryl methyl ketone (1, 1.5mmol) in dry nitromethane (1.5mL) was added trifluoroacetic acid (0.045 mL, 0.6mmol) and ethylenediamine (0.020 mL, 0.3mmol). The mixture was stirred at reflux and detected by TLC. After completion of the reaction, the reaction mixture was cooled to room temperature, quenched with saturated NH4Cl, extracted with Ethyl acetate. Combined organic layers were washed with brine, dried over Na2SO4, and concentrated. The residue was purified by silica gel column chromatography to give product 2.
Reference：
[1] Synthetic Communications, 2013, vol. 43, # 16, p. 2178 - 2190
[2] RSC Advances, 2015, vol. 5, # 27, p. 21206 - 21214
[3] Journal of the Iranian Chemical Society, 2012, vol. 9, # 5, p. 791 - 798
[4] European Journal of Organic Chemistry, 2014, vol. 2014, # 14, p. 2907 - 2916
[5] Synthetic Communications, 2005, vol. 35, # 24, p. 3167 - 3171
[6] Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 2006, vol. 45, # 12, p. 2781 - 2783
[7] Chemistry - A European Journal, 2012, vol. 18, # 20, p. 6172 - 6182
[8] RSC Advances, 2016, vol. 6, # 60, p. 55319 - 55326
[9] Polyhedron, 2012, vol. 31, # 1, p. 721 - 728
[10] Tetrahedron Letters, 2017, vol. 58, # 31, p. 3032 - 3036
[11] Chemical Communications, 2018, vol. 54, # 81, p. 11475 - 11478
[12] Synthetic Communications, 2012, vol. 42, # 24, p. 3569 - 3578
[13] RSC Advances, 2015, vol. 5, # 15, p. 10869 - 10877
[14] Journal of the American Chemical Society, 2017, vol. 139, # 5, p. 2053 - 2059
[15] Journal of Materials Chemistry, 2002, vol. 12, # 2, p. 206 - 212
[16] Green Chemistry, 2010, vol. 12, # 8, p. 1370 - 1372
[17] Journal of the Chemical Society, Perkin Transactions 1, 2000, # 16, p. 2695 - 2701
[18] Journal of Chemical Research, 2007, # 12, p. 720 - 721
[19] New Journal of Chemistry, 2002, vol. 26, # 3, p. 291 - 297
[20] Advanced Synthesis and Catalysis, 2013, vol. 355, # 5, p. 957 - 972
[21] Chemistry - A European Journal, 2015, vol. 21, # 51, p. 18576 - 18579
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[25] European Journal of Organic Chemistry, 2008, # 18, p. 3129 - 3140
[26] Comptes Rendus Chimie, 2013, vol. 16, # 3, p. 252 - 256
[27] Journal of Chemical Research - Part S, 2003, # 12, p. 778 - 779
[28] Synlett, 2008, # 15, p. 2365 - 2367
[29] Synthetic Communications, 2009, vol. 39, # 22, p. 4117 - 4121
[30] RSC Advances, 2013, vol. 3, # 6, p. 1902 - 1915
[31] Tetrahedron Letters, 2012, vol. 53, # 19, p. 2436 - 2439
[32] Tetrahedron Letters, 2018, vol. 59, # 11, p. 1023 - 1027
[33] Chemical Communications, 2014, vol. 50, # 43, p. 5737 - 5740
[34] Journal of Materials Chemistry C, 2015, vol. 3, # 7, p. 1582 - 1587
[35] Macromolecules, 2003, vol. 36, # 22, p. 8353 - 8360
[36] Tetrahedron Letters, 2009, vol. 50, # 30, p. 4335 - 4339
[37] Inorganic Chemistry, 2013, vol. 52, # 13, p. 7311 - 7313
[38] Journal of Organic Chemistry, 2004, vol. 69, # 18, p. 6050 - 6058
[39] Chemistry of Materials, 2017, vol. 29, # 24, p. 10469 - 10477
[40] Journal of the Chemical Society, Perkin Transactions 2: Physical Organic Chemistry (1972-1999), 1988, p. 1251 - 1258
[41] Journal of the American Chemical Society, 1953, vol. 75, p. 5959
[42] Tetrahedron Letters, 2005, vol. 46, # 46, p. 7871 - 7875
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[44] Journal of Inclusion Phenomena and Macrocyclic Chemistry, 2011, vol. 71, # 1-2, p. 113 - 120
[45] Journal of Materials Chemistry, 2012, vol. 22, # 10, p. 4502 - 4510
[46] Patent: EP2586766, 2013, A1, . Location in patent: Paragraph 0085
[47] CrystEngComm, 2016, vol. 18, # 42, p. 8147 - 8150
[48] Angewandte Chemie - International Edition, 2016, vol. 55, # 47, p. 14614 - 14617[49] Angew. Chem., 2016, vol. 128, p. 14834 - 14837,4
[50] Chemistry - A European Journal, 2018, vol. 24, # 18, p. 4547 - 4551
2
[ 766-96-1 ]
[ 34108-77-5 ]
[ 7511-49-1 ]
Reference：
[1] Journal of the American Chemical Society, 2006, vol. 128, # 47, p. 15094 - 15095
[2] Chemical Communications, 2006, # 19, p. 2066 - 2068
[3] Dalton Transactions, 2013, vol. 42, # 37, p. 13327 - 13330
3
[ 99-90-1 ]
[ 122-51-0 ]
[ 7511-49-1 ]
Yield
Reaction Conditions
Operation in experiment
43.6%
With hydrogenchloride In benzene at 20℃; for 3 h;
4-Bromoacetophenone (7.962 g, 40 mmol) and ethyl orthoformate ester (8 mL, 48 mmol) were dissolved in benzene (24 mL) in a flask. Gaseous hydrogen chloride was bubbled through the solution at room temperature and under stirring for 3 h. The solution became brownish-red colored and the precipitate formation began during the first hour. The resulting precipitate was filtered off, washed with acetone and methanol, and dried. The yield of product recrystallized from chloroform was 43.6percent. The 1H NMR spectrum of synthesized product (see Fig. 1) was completely corresponded to that of 1,3,5-tris(4-bromophenyl)benzene. 1H NMR (500 MHz), δ: 7.68 (s, 3 H); 7.60 (d, 6 H, J = 8.5 Hz); 7.53 (d, 6 H, J = 8.5 Hz).
Reference：
[1] Russian Chemical Bulletin, 2018, vol. 67, # 8, p. 1433 - 1439[2] Izv. Akad. Nauk, Ser. Khim., 2018, # 8, p. 1433 - 1439,7
In a 100 mL-flask, 2.45 g of the last product of compound 13, 60 mL of a 47percent aqueous HBr solution, and 0.5 g of tetrabutylammonium bromide were added, and the mixture was heated under reflux with nitrogen for 6 hours. After cooling to room temperature, the mixture was extracted with ethyl acetate, washed twice with water, and the solvent was evaporated under reduced pressure to obtain 2.11 g of a crude product of Compound 14. The crude product was dissolved in 60 mL of DMF, 4.22 g of PPh3PBr2 was added, and the reaction was refluxed with nitrogen for 12 hours. After cooling to room temperature, the solvent is distilled off and the residue is dissolvedAfter ethyl acetate was washed with water twice, the solvent was distilled off again and silica gel column chromatography gave 2.77 g of compound 15 in a yield of 85percent.
Reference：
[1] Patent: CN107915753, 2018, A, . Location in patent: Paragraph 0029; 0046; 0047
Stage #1: With n-butyllithium In tetrahydrofuran; hexane at -65 - -60℃; for 1 h; Inert atmosphere Stage #2: With hydrogenchloride In tetrahydrofuran; hexane; water at -65 - -60℃; for 1 h; Inert atmosphere
A mixture of 0.8 kg of 4-bromoacetophenone by Sigma-Aldrich Japan, KK., 40 ml of sulfuric acid and 1.2 kg ofpotassium disulfate was stirred at 180°C for 18 hours. After stirring, 3.0 L of ethanol was added to the mixture, whichwas heated to reflux for 7 hours. It was then allowed to naturally cool to room temperature, producing a precipitate whichwas filtered out. After adding 3.0 L of water to the filtered precipitate and heating to reflux for 1 hour, the reaction mixturewas allowed to naturally cool to room temperature. The reaction mixture was filtered and rinsed with 0.5 L of ethanol.In this manner there was obtained 0.58 kg of 1,3,5-tris(p-bromophenyl)benzene. [0086] A solution comprising 0.58 kg of 1,3,5-tris(p-bromophenyl)benzene and 7.2 L of tetrahydrofuran was cooledto-65°C under an argon gas atmosphere. A 1.6 mol/L butyllithium n-hexane solution (2.1 L) by Wako Pure ChemicalIndustries, Ltd. was then added dropwise at -65°C to -60°C. After reaction at -65°C for 1 hour, CO2 gas was bubbledthrough for 1 hour at -65°C to -60°C. A 2.5 L portion of 1N-hydrochloric acid was added dropwise to the reaction product,and the deposited precipitate was filtered out to obtain 0.40 g of a crude product of the aromatic carboxylic acid representedby formula (5). The crude product was rinsed with tetrahydrofuran and then with hexane and dried under reducedpressure to obtain 0.29 g of the aromatic carboxylic acid represented by formula (5).
Reference：
[1] Journal of the Chemical Society, Perkin Transactions 2: Physical Organic Chemistry (1972-1999), 1988, p. 1251 - 1258
[2] Journal of the American Chemical Society, 2004, vol. 126, # 3, p. 884 - 890
[3] RSC Advances, 2013, vol. 3, # 6, p. 1902 - 1915
[4] Patent: EP2586766, 2013, A1, . Location in patent: Paragraph 0085; 0086
24
[ 7511-49-1 ]
[ 71866-86-9 ]
Reference：
[1] Journal of the Chemical Society, Perkin Transactions 2: Physical Organic Chemistry (1972-1999), 1988, p. 1251 - 1258
[2] Inorganic Chemistry, 2013, vol. 52, # 14, p. 7862 - 7872
[3] Journal of the American Chemical Society, 2018,
A mixture of 0.8 kg of 4-bromoacetophenone by Sigma-Aldrich Japan, KK., 40 ml of sulfuric acid and 1.2 kg ofpotassium disulfate was stirred at 180C for 18 hours. After stirring, 3.0 L of ethanol was added to the mixture, whichwas heated to reflux for 7 hours. It was then allowed to naturally cool to room temperature, producing a precipitate whichwas filtered out. After adding 3.0 L of water to the filtered precipitate and heating to reflux for 1 hour, the reaction mixturewas allowed to naturally cool to room temperature. The reaction mixture was filtered and rinsed with 0.5 L of ethanol.In this manner there was obtained 0.58 kg of 1,3,5-tris(p-bromophenyl)benzene. [0086] A solution comprising 0.58 kg of 1,3,5-tris(p-bromophenyl)benzene and 7.2 L of tetrahydrofuran was cooledto-65C under an argon gas atmosphere. A 1.6 mol/L butyllithium n-hexane solution (2.1 L) by Wako Pure ChemicalIndustries, Ltd. was then added dropwise at -65C to -60C. After reaction at -65C for 1 hour, CO2 gas was bubbledthrough for 1 hour at -65C to -60C. A 2.5 L portion of 1N-hydrochloric acid was added dropwise to the reaction product,and the deposited precipitate was filtered out to obtain 0.40 g of a crude product of the aromatic carboxylic acid representedby formula (5). The crude product was rinsed with tetrahydrofuran and then with hexane and dried under reducedpressure to obtain 0.29 g of the aromatic carboxylic acid represented by formula (5).
(2-hydroxyethyl)-terminated-star-poly(1,3-butadiene), product of living anionic polymerization; monomer(s): 1,3-butadiene; 1,3,5-tri(p-bromophenyl)benzene; ethylene oxide[ No CAS ]
star-polystyrene, product of living anionic polymerization, Mw 2800 Da (by SEC in THF), PDI 1.08; monomer(s): styrene; 1,3,5-tri(p-bromophenyl)benzene[ No CAS ]
star-polystyrene, product of living anionic polymerization, Mw 131000 Da (by SEC in THF), PDI 1.13; monomer(s): styrene; 1,3,5-tri(p-bromophenyl)benzene[ No CAS ]
star-polystyrene, product of living anionic polymerization, Mw 90800 Da (by SEC in THF), PDI 1.08; monomer(s): styrene; 1,3,5-tri(p-bromophenyl)benzene[ No CAS ]
star-polystyrene-block-poly(1,3-butadiene), product of living anionic polymerization, Mw 5700 Da, PDI 1.1; monomer(s): styrene; 1,3,5-tri(p-bromophenyl)benzene; butadiene[ No CAS ]
star-poly(1,3-butadiene), product of living anionic polymerization, Mw 32500 Da (by SEC in THF), PDI 1.03; monomer(s): 1,3-butadiene; 1,3,5-tri(p-bromophenyl)benzene[ No CAS ]
star-polystyrene-block-poly(1,3-butadiene)-block-poly(methyl methacrylate), product of living anionic polymerization, Mw 7500 Da, PDI 1.1; monomer(s): styrene; 1,3,5-tri(p-bromophenyl)benzene; 1,3-butadiene; methyl methacrylate; 1,1-diphenylethylene[ No CAS ]
star-polystyrene-block-poly(1,3-butadiene)-block-poly(methyl methacrylate), product of living anionic polymerization; monomer(s): styrene; 1,3,5-tri(p-bromophenyl)benzene; 1,3-butadiene; methyl methacrylate; 1,1-diphenylethylene[ No CAS ]
1-[4'-{N'-butyl-1,6,7,12-tetrakis(4-methyl-phenoxy)perylene-3,4:9,10-tetracarboxylic bisimide-N-propargyl-yl}-phenyl-4-yl]-3,5-bis(4-bromophenyl)-benzene[ No CAS ]
1,3-bis[4'-{N'-butyl-1,6,7,12-tetrakis(4-methyl-phenoxy)perylene-3,4:9,10-tetracarboxylic bisimide-N-propargyl-yl}-phenyl-4-yl]-5-(4-bromophenyl)-benzene[ No CAS ]
A 300 mL capacity three-necked flask was flame dried and backfilled with Ar. A 1.55 g (2.86 mmol) quantity of <strong>[7511-49-1]1,3,5-tris(4-bromophenyl)benzene</strong> and 200 mL of THF were added and the mixture was cooled to -78 C. with liquid nitrogen/MeOH. A 7 mL (11.2 mmol) quantity of n-BuLi was then added and the mixture was stirred for 2 hours at -78 C. To the cloudy, yellowish-white solution was added 2.03 mL (11.3 mmol) of CIPPh2 in dropwise fashion. The transparent yellow solution was stirred for 1 hour at -78 C. and then gradually returned to room temperature. The solution was extracted with saturated brine and CH3CO2Et. The organic layer obtained was dried with MgSO4 and the solvent was distilled off. To the yellow residue obtained were added 50 mL of CH2Cl2 and 4 mL of H2O2, and the mixture was stirred for 3 hours in an ice bath. The reaction solution was extracted with saturated brine and dried with MgSO4. The solvent was distilled off. The brown residue obtained was purified by silica gel column chromatography (CH2Cl2: hexane=4:1), yielding target compound 2 in the form of white crystals.
With cesium fluoride;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; for 48h;Inert atmosphere; Reflux;
Anhydrous 1,2-dimethoxyethane (150 mL) was placed in a two-neck 250-mL round bottom flask equipped with a magnetic stirring bar and a reflux condenser under nitrogen atmosphere. 4-Methoxycarbonylphenylboronic acid (2.98 g, 16.6 mmol), CsF (5.03 g, 33.1 mmol), Pd(PPh3)4 (574 mg, 0.50 mmol), and 1,3 ,5-tris(4-bromo-phenyl) benzene (2.00 g, 3.68 mmol) were added to the flask, and the reaction mixture was refluxed for 48 h under nitrogen atmosphere. The solution was cooled to room temperature and evaporated under vacuum. The residue was dissolved in CHCl3, washed with water and dried over MgS04. The solvent was evaporated under vacuum. Further purification was achieved by dissolving the product in 50 mL of diethyl ether and the solution was heated for 20 min and placed in the refrigerator for 1 h. The white product was collected by filtration and dried in vacuum overnight (2.1 g, 80%): mp 218 C;-NMR (CDC13, 400 MHz) delta 8.17 (d, 6H, J = 8.0Hz), 7.93 (s, 3H), 7.86 (d, 6H, J = 8.4Hz), 7.80 (d, 6H, J = 8.4Hz), 7.77 (d, 6H, J = 8.4Hz), 3.90 (s, 9H); 13C-NMR (CDCI3, 100 MHz) delta 167.4, 145.4, 142.3, 141.1, 139.7, 130.6, 129.5, 128.3, 128.2, 127.4, 125.6, 52.6; FT-IR (KBr, 4000-400 cm-1) 3428 (br), 2947 (w), 1932 (w), 1719 (s), 1607 (m), 1434 (m), 1277 (s), 1180 (m), 1110 (s), 1004 (m), 824 (s), 772 (s).
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In N,N-dimethyl-formamide; at 90℃; for 15.5h;Inert atmosphere;
To the reaction vessel, 1,3,5-tris (4-bromophenyl) benzene (99.00 g, 182.29 mmol), bis (pinacolato) diboron (B2 (pinacol) 2, 145.81 g, 574.20 mmol), potassium acetate (KOAc, 107.34 g, 1093.72 mmol) and N, N'-dimethylformamide (DMF, 1.5 L), and argon gas was bubbled. After 30 minutes, bubbling was stopped and dichloro [1,1'-bis (diphenylphosphino) ferrocene] palladium (Pd (dppf) Cl 2, 4.47 g, 5.47 mmol) was added under an argon stream, And the mixture was stirred at 90 C. for 15 hours. After completion of the reaction, the reaction solution was allowed to flow into water (5 L) and crystallized. The crystallized product was collected by filtration and washed with water. The resulting wet solid was dissolved in toluene and dried over magnesium sulfate (MgSO 4). After removing magnesium sulfate by filtration, the filtrate was concentrated. The concentrated residue was again dissolved in toluene (2 L), then galleon earth (200 g) was added and stirred for 20 minutes. After filtering off the galleon earth, the filtrate was concentrated. Isopropyl alcohol (IPA, 1 L) was added to the concentrated residue and dispersed and washed. The obtained solid was collected by filtration and then dried at 80 C. under reduced pressure to obtain a white powder intermediate 3 (1,3,5-tris (4-pinacolatoborylphenyl) benzene, 92.93 g) Rate: 86.6%).
With tris-(dibenzylideneacetone)dipalladium(0); potassium chloride; tetrabutylammonium acetate; potassium carbonate; In N,N-dimethyl-formamide; at 100℃; for 48h;Inert atmosphere;
Synthesis of 1,3,5-tris(stilbenyl)benzene 2. 1,3,5-tris(bromophenyl)benzene (0.1 g, 0.184 mmol), styrene (0.172 g, 1.657 mmol), K2CO3 (0.038 mg, 0.276 mmol), KCl (0.014 g, 0.184 mmol), Pd2(dba)3 (0.016 g, 0.017 mmol), and n-Bu4NOAc (0.111 mg, 0.368 mmol) were added to a 25 mL dry storage tube, under a N2 atmosphere. DMF (0.6 mL) and styrene (0.172 g) were added to the flask. The reaction mixture was degassed through freeze-pump-thaw cycles. The reaction mixture was heated to 100 C. for 48 hours and was monitored by TLC (10% EtOAc/Hexanes). Once complete the reaction mixture was filtered through celite. The filtrate was extracted with CH2Cl2 (3*15 mL) and washed with brine solution (3*15 mL). The organic layers were collected, dried with anhydrous MgSO4, and solvent was removed under vacuum. The crude brown solid obtained was run through a silica plug (10% EtOAc/Hexane 20 mL) and the solvent was removed under vacuum. 2 (0.06 g, 54%) was obtained as a grey solid. This compound was previously reported, although its characterization was limited to UV/Vis spectroscopy. The experimental lambdamax obtained for 2 matched that described here. Further characterization is provided as follows. 1H NMR (400 MHz, CDCl3, 298 K) delta 7.90 (s, central Ar-H, 3H), 7.78 (d, J=8 Hz, 1-vinyl aryl-H, 6H), 7.72 (d, J=8 Hz, 1-vinyl-aryl-H 6H), 7.63 (d, J=7 Hz, 2-vinyl aryl-H, 6H), 7.46 (m, 2-vinyl aryl, 6H), 7.46 (m, 2-vinyl aryl-H, 3H), 7.12 (broad stilbenyl-H, 6H). 13C NMR (100 MHz, CDCl3, 298 K) delta 142, 140.3, 137.4, 136.8, 129.1, 128.8, 128.3 127.9, 127.7, 127.1, 126.7, 124.9. FT-IR (ATR) 1594, 1510, 1492, 1450, 1393, 1180, 1154, 1072, 1027, 960, 857, 812, 794, 77, 724, 695.
1-trityl-3,5-dimethyl-1H-pyrazol-4-ylboronate pinacol ester[ No CAS ]
1,3,5-tri[4-(1-trityl-3,5-dimethyl-1H-pyrazol-4-yl)phenyl]benzene[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In 1,2-dimethoxyethane; at 80℃; for 18h;Inert atmosphere;
To a 100 mL Schenk flask backfilled with N2was added 1,3,5-tri(4-bromophenyl)benzene (717 mg, 1.32 mmol),1-trityl-3,5-dimethyl-1H-pyrazol-4-ylboronatepinacol ester (2.108 g, 4.54 mmol), K2CO3 (1.799 g, 13.02mmol) and DME (40 mL). The suspension was degassed for 0.5 h, before additionof Pd(PPh3)4 (46 mg, 0.04 mmol) and the reaction washeated to 80 C for 18 h. under N2, monitoring the progress by TLC.After complete reaction, the solvent was removed in vacuo, the residue suspended in H2O (50 mL) and theorganics were extracted into DCM (3 x 50 mL). The combined organic phases driedover MgSO4 and concentrated invacuo to yield the intermediate, 1,3,5-tri[4-(1-trityl-3,5-dimethyl-1H-pyrazol-4-yl)-phenyl]benzene asan off-white coloured solid which was used in the next step without furtherpurification. Despite attempts to triturate and wash the solid in commonsolvents, an analytically pure intermediate could not be produced. Crude 1,3,5-tri[4-(1-trityl-3,5-dimethyl-1H-pyrazol-4-yl)-phenyl]benzenewas suspended in a mixture of MeOH andDCM mixture (3:2 vol., 75 mL). TFA (18 mL, 157 mmol) was then added and thecontents were then heated to reflux at for 18 h, monitoring the progress byTLC. Upon completion, the solvent was removed in vacuo. The resulting solid was triturated in toluene (15 mL),filtered and washed sequentially with CHCl3, H2O, MeOHand finally Et2O (3 mLeach). Residual TFA was removed by suspendingin H2O and adjusting the pH to 5 with 2M NaOH. Finally the compound was filtered and driedovernight at 50 C to yield1,3,5-tri[4-(3,5-dimethyl-1H-pyrazol-4-yl)-phenyl]benzene,(532 mg, 0.904 mmol, 68.5%) as a light yellow powder. 1H NMR (300MHz, DMSO-d6)delta = 2.27 (br s, 18 H), 7.43 (d, J = 8.1 Hz, 6H), 7.92 (d, J = 8.1 Hz, 6H), 7.95(s, 3H).13C NMR (500MHz, DMSO-d6) delta = 11.6, 116.41, 123.90,127.21, 129.11, 133.56, 137.46, 141.4. HRMS (ESI) Calcd for C39H37N6[M+H]: 589.307422; Found: 589.308492.
1,3,5-tri[4-(1-trityl-1H-pyrazol-4-yl)phenyl]benzene[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In 1,2-dimethoxyethane; at 80℃; for 18h;Inert atmosphere;
To a 100 mL Schenk flask backfilled with N2was added 1,3,5-tri(4-bromophenyl)benzene (684 mg, 1.26 mmol), 1-trityl-1H-pyrazol-4-ylboronate pinacol ester (1.898g, 4.35 mmol), K2CO3 (1.799 g, 13.02 mmol) and DME (40mL). The suspension was degassed for 0.5 h, before addition of Pd(PPh3)4(46 mg, 0.04) mmol) and the reaction was heated to 80 C for 18 h. under N2,monitoring the progress by TLC. After complete reaction, the solvent wasremoved in vacuo, the residuesuspended in H2O (50 mL) and the organics were extracted into DCM (3x 50 mL). The combined organic phases dried over MgSO4 andconcentrated in vacuo to yield theintermediate, 1,3,5-tri[4-(1-trityl-1H-pyrazol-4-yl)-phenyl]benzene asa light yellowsolid which was used in the next step without further purification.An NMR sample of the intermediate was produced by trituration in pentane (40mL). The resulting pale yellow solid was filtered and washed with pentane (5mL) before drying at 50 C.1HNMR (500MHz, DMSO-d6)delta = 7.21 - 7.26 (m, 18H), 7.33 - 7.38 (m, 27H), 7.58 (d, J = 8.6 Hz, 6H), 7.71(d, J = 8.6 Hz, 6H), 7.75 (d, J = 0.9 Hz, 3H), 7.81 (s, 3H), 7.99 (d, J = 0.9Hz, 3 H).13C NMR (500MHz,CD2Cl2) delta = 79.5, 121.8, 124.9, 126.4, 128.2, 128.3,129.8, 130.8, 132.6, 137.6, 139.4, 142.4, 143.8. Crude 1,3,5-tri[4-(1-trityl-1H-pyrazol-4-yl)-phenyl]benzenewas suspended in a mixture of MeOH andDCM mixture (3:2 vol., 75 mL). TFA (18 mL, 157 mmol) was then added and thecontents were then heated to reflux at for 18 h, monitoring the progress byTLC. Upon completion, the solvent was removed in vacuo. The resulting solid was triturated in toluene (15 mL),filtered and washed sequentially with CHCl3, H2O, MeOHand finally Et2O (3 mLeach). Residual TFA was removed by suspendingin H2O and adjusting the pH to 5 with 2M NaOH. Finally the compound was filtered and driedovernight at 50 C to yield1,3,5-Tri[4-(1H-pyrazol-4-yl)-phenyl]benzene,(461 mg, 0.913 mmol, 72.5%) as a light yellow powder. 1H NMR (500MHz, DMSO-d6)delta = 7.75 (d, J = 8.3 Hz, 6H), 7.87 (d, J = 8.3 Hz, 6H), 7.90 (s, 3H), 8.01 (brs, 3H), 8.28 (br s, 3H), 13.00 (br s, 3H).13CNMR (500MHz, DMSO-d6)delta = 120.74, 123.51, 125.57, 127.51, 132.39, 136.3, 137.56, 141.53. HRMS(ESI) Calcd for C33H25N6 [M+H]: 505.213521;Found: 505.214194.
With potassium phosphate; tetrakis(triphenylphosphine) palladium(0); In 1,4-dioxane;Inert atmosphere; Reflux;
1,3,5-tris(3',5'-dicarboxybiphenyl-4-yl)benzene 1,3,5-Tris(4-bromophenyl)benzene (0.980 g, 1.81 mmol), dimethyl isophthalate-5-pinacolboronate (2.08 g, 6.50 mmol), K3PO4 (tribasic, 3.84 g, 18.1 mmol) and 1,4-dioxane (100 mL) are added into a 200 mL round-bottomed flask equipped with a magnetic stirrer and water jacketed condenser. The resulting suspension is degassed for 15 min. by sparging with nitrogen gas. Pd(PPh3)4 (0.157 g, 0.136 mmol) is added, and the mixture is heated to reflux overnight under a nitrogen atmosphere. After cooling to room temperature, the reaction mixture is poured in H2O (100 mL) and the precipitate is collected by filtration and washed with a minimal amount of THF. The crude material is dissolved in dioxane/H2O (10:1, 110 mL), KOH (1.72 g, 30.6 mmol) is added and the mixture is heated to reflux for 12 hours. The solvent is removed by evaporation and the residue is dissolved in H2O (100 mL). The residual solids are filtered off and the filtrate is acidified with concentrated HCl (20 mL). The target compound is collected by filtration, washed with H2O and acetone and dried under vacuum to yield 0.783 g of 1 (0.980 mmol as a white powder, 54%): mp>300 C.; 1H NMR (400 MHz, DMSO-d6): delta 13.39 (s, 6H), 8.43 (s, 3H), 8.42 (s, 6H), 8.04 (d, 3J=8.2 Hz, 6H), 8.02 (s, 3H), 7.86 (d, 3J=8.2 Hz, 6H) ppm; 13C NMR (100 MHz, DMSO-d6): delta 166.9, 141.4, 140.9, 140.3, 138.1, 132.5, 131.6, 129.3, 128.4, 127.8, 124.9 ppm; HRMS (EI) calcd. for C48H30O12 (m/e): 798.1737. found: 798.1751.
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