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CAS No. : | 750573-24-1 | MDL No. : | MFCD28100481 |
Formula : | C30H19BrN2 | Boiling Point : | No data available |
Linear Structure Formula : | - | InChI Key : | SJOKONNBSXFPSN-UHFFFAOYSA-N |
M.W : | 487.39 | Pubchem ID : | 59770826 |
Synonyms : |
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Signal Word: | Warning | Class: | |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | |
Hazard Statements: | H302-H315-H319-H335 | Packing Group: | |
GHS Pictogram: |
* 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.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65.4% | Step 4: Synthesis of Intermediate (F)35.0 g (72 mmol) of the intermediate (E) was dissolved in 350 ml of tetrahydrofuran and added with 61.5 ml (98 mmol) of an n-butyllithium hexane solution (1.6M) under an argon atmosphere at -70 C. The obtained solution was agitated at -70 C. to 40 C. for 1 hour. The reaction flux was frozen to -70 C. and slowly added with 29.3 ml (144 mmol) of isopropyl tetramethyl dioxaborolane in a dropwise fashion. The obtained solution was agitated at -70 C. for 1 hour, and heated to room temperature and agitated for 6 hours. The obtained reaction solution was added with 200 ml of water and agitated for 20 minutes.After the reaction solution was separated into two liquid layers, an organic layer thereof was dried with anhydrous sodium sulfate. After the organic solvent was removed under a reduced pressure, the obtained residue was purified with silica gel column chromatography to provide 25.1 g (yield 65.4%) of the intermediate (F). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
38% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In toluene; at 130℃; for 48h;Inert atmosphere; | <strong>[890042-13-4]4,4,5,5-tetramethyl-2-(triphenylen-2-yl)-1,3,2-dioxaborolane</strong> (0.65g, 1.84mmol), 9,9′-(5-bromo-1,3-phenylene)bis(9H-carbazole) (0.91g, 1.87mmol), tetrakis(triphenylphosphine) palladium(0) (0.06g, 0.06mmol), and 1M Na2CO3 (7.3ml) in 40ml of Toluene was stirred at 130C for 48h under nitrogen atmosphere. After the reaction had finished, the mixture was washed three times with distilled water and extracted with chloroform. The organic layer was separated, dried over anhydrous magnesium sulfate, and evaporated under reduced pressure. The crude product was purified by silica gel column chromatography using n-hexane-tetrahydrofuran (5:1). The final product was obtained as a white powder after purification by vacuum sublimation at a synthetic yield of 38%. 1H NMR (400MHz, CDCl3) 8.97 (s, 1H), 8.79-8.77 (d, J=8.8Hz, 1H), 8.71-8.67 (m, 4H), 8.22-8.20 (d, J=7.6Hz, 4H), 8.16 (s, 2H), 8.02-8.00 (d, J=8.8Hz, 1H), 7.88 (s, 1H), 7.72-7.62 (m, 8H), 7.52-7.48 (t, J=8.4Hz, 4H), 7.37-7.33 (t, J=6.8Hz, 4H) ppm; 13C NMR (CDCl3, 400MHz) 142.5, 138.6, 137.8, 135.5, 128.2, 128, 127.9, 127.7, 127.3, 127.2, 127, 126.2, 125.5, 125.3, 124.2, 123.8, 122.5, 122.2, 122, 121.6, 121.4, 121.3, 121.2, 119.8, 118.5, 118.4ppm. ESI-MS [M+H]+: m/z calcd. 635.2487; found 635.2460. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In 1,4-dioxane; for 3h;Inert atmosphere; Reflux; | A three-necked flask of 2000ml, equipped with mechanical stirring, Ar gas protection.Was added 3,5-bis (carbazol-9-yl) bromobenzene 9.72 g (molecular weight 486,0.02mol), with boronic acid pinacol ester 5.6 g (molecular weight 254.2, 0.022mol) frequency, Pd (dppf) Cl23.2g (0.0044mol), potassium acetate 36g (molecular weight 138,0.26mol), 1,4-dioxane 500ml.Mechanical agitation, ventilation kept under reduced pressure Ar atmosphere for three times, the reaction was monitored by TLC (thin layer chromatography), to the starting material completely disappeared after 3 hours reflux the reaction was complete.Allowed to cool, the reaction system was divided into two layers, the organic layer was separated, evaporated to dryness, to give the product 9.72g, 91.0% yield. |
72% | With tetrakis(triphenylphosphine) palladium(0); potassium acetate; In 1,4-dioxane; at 80℃; for 12h;Inert atmosphere; | The purified compound (1) (1.7 g, 3.5 mmol), bis(pinacolato)diboron (0.93 g, 3.6 mmol),potassium acetate (0.68 g, 6.9 mmol) and tetrakis(triphenylphosphine)palladium(0) (0.2 g,0.2mmol) were dissolved in 1,4-dioxane (50mL) and a nitrogen atmosphere. After themixedsolution was stirred for 12 h at 80C, the reaction mixture was cooled to room temperature.The mixture extracted with dichloromethane (50 mL × 3 times) and dried over anhydrousMgSO4. The crude product was subjected to flash column chromatography (ethyl acetate:n-hexane = 1: 10) to give compound (2) (1.3 g, 72%). 1H NMR (CDCl3, 300 MHz); δ = 7.68(d, -CH-), 7.5 (d, -CH-), 7.45 (d, -CH-), 7.35 (m-CH-), 7.29(t, -CH3), 7.18(m, -CH-), 1.5(-CH3). |
71% | With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; potassium acetate; In N,N-dimethyl-formamide; at 100℃; for 24h; | 13.68 g (28.07 mmol) of Intermediate (G), 10.69 g (42.10 mmol) of 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi(1,3,2-dioxaborolane), 1.23 g (1.68 mmol) of PdCl2(dppf).CH2Cl2, and 8.26 g (84.20 mmol) of potassium acetate were mixed with 140 mL of dimethyl formamide, followed by stirring at a temperature of 100 C. for 24 hours. Once the reaction was complete, the resulting mixture was cooled to room temperature and filtered through silica gel under reduced pressure. The obtained filtrate was concentrated under reduced pressure, and the resulting product was separated and purified by silica gel column chromatography and recrystallized using dichloromethane/n-hexane to obtain a desired compound, 10.62 g of Intermediate (H) (at a yield of 71%). LC-Mass (calculated value: 534.25 g/mol, measured value: M+1=535 g/mol) |
70% | With tetrakis(triphenylphosphine) palladium(0); potassium acetate; In 1,4-dioxane; for 12h;Inert atmosphere; Reflux; | 9,9'-(5-bromo-1,3-phenylene)bis(9H-carbazole) (6 g, 12.3 mmol), Bis(pinacolato)diboron(4.7 g, 18.4 mmol), potassium acetate (3.6 g, 37 mmol), and Pd(PPh3)4 (0.4 g, 0.3 mmol) were dissolved in distilled 1,4-dioxane. The reaction mixture was refluxed for 12 hours under nitrogen and then allowed to cool to room temperature. After the mixture washed with ethyl acetate, the solvent was removed under vacuum. The crude material was purified by column chromatography on silica gel (ethyl acetate:hexane=1:3 as eluent) to give the title compound 1 (yield: 70%). 1HNMR(CDCl3): δ (ppm) 8.20 (d, 6H), 7.60-7.40 (m, 9H), 7.35-7. 26 (m, 4H),1.30-1.45 (m, 12H). |
70% | With tetrakis(triphenylphosphine) palladium(0); potassium acetate; In 1,4-dioxane; for 12h;Reflux; Inert atmosphere; | 9,9-(5-bromo-1,3-phenylene)bis(9H-carbazole) (6 g,12.3 mmol), Bis(pinacolato)diboron (4.7 g, 18.4 mmol),potassium acetate (3.6 g, 37 mmol), and Pd(PPh34(0.4 g, 0.3 mmol) were dissolved in distilled 1,4-dioxane.The reaction mixture was refluxed for 12 hours undernitrogen and then allowed to cool to room temperature.After the mixture washed with ethyl acetate, the solventwas removed under vacuum. The crude material waspurified by column chromatograph on silica gel (ethylacetate:hexane = 1:3 as eluent) to give the title compound1 (yield: 70%). 1H NMR (CDCl3: (ppm) 8.20 (d, 6H),7.60-7.40 (m, 9H), 7.35-7.26 (m, 4H), 1.30-1.45 (m, 12H). |
65% | With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; potassium acetate; In 1,4-dioxane; at 60 - 80℃; for 14h;Inert atmosphere; | Intermediate compound (1) (16.4 g, 33.6 mmol),Bis (pinacolato) diboron (17.1g, 67.2mmol)And potassium acetate (32.97 g, 336 mmol) dissolved in 1,4-dioxane (200 ml),It was then stirred at about 60 C for about 15 minutes under a nitrogen atmosphere.Pd(dppf)CH2Cl2 (0.82 g, 1.0 mmol) was added to the reaction mixture and stirred at about 80 C for about 14 hours.The reaction mixture was cooled to room temperature, extracted with toluene, dried over MgSO 4 to remove water, and then separated by column chromatography (hexane: methylene chloride (MC) = 1:3, v/v).The intermediate compound (2) (11.76 g, yield: 65%) was obtained. |
53% | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In 1,4-dioxane; for 12h;Reflux; | Compound 1-2 64 g (131 mmol),50 g (197 mmol) of bis (pinacolato) diboron,Pd(dppf)Cl2 ([1,1'-bis (diphenylphosphine)ferrocene]dichloropalladium (II)), 4.8 g (6.55 mmol),25.7 g (262 mmol) of potassium acetate was suspended in 500 mL of 1,4-dioxane, and then refluxed and stirred for 12 hours.Extraction with dichloromethane and distilled waterThe high organic layer is filtered through silica gel. The organic solution was removed and recrystallized to obtain 37.1 g (yield 53%) of compound 1-3. |
3 g | With 1,1'-bis-(diphenylphosphino)ferrocene; potassium acetate; In 1,4-dioxane; for 24h;Inert atmosphere; Reflux; | 9H-carbazole (6.0 g, 35.7 mmol), and 1,3,5-tribromobenzene (5.0 g, 15.0 mmol), cooper (I) iodide (CuI, 0.7 g, 3.6 mmol), potassium carbonate (4.9 g, 35.7 mmol), 1,10-phenanthroline (1,10-phenanthroline, 0.6 g, 3.6 mmol) is dissolved in DMF to insert.Looking up the temperature under the flow of nitrogen was stirred under reflux for 12 hours.After extracting the reaction solution was subjected to column chromatography on MC MC / Hexane solvent mixture as a developing solvent to give the intermediate 1 of about 2 g. Intermediate 1 (4 g, 8.2 mmol) and 4,4,4 ', 4', 5,5,5 ', 5'-octamethyl-2,2'-bi (1,3,2- dioxane)See above) (3.12 g, 12.3 mmol), potassium acetate (2.4 g, 24.0 mmol), 1,1 '- bis (diphenylphosphino) ferrocene (1,1'-bis (diphenylphosphino) ferrocene, 0.2 g, 0.2 mmol) put in 1,4-dioxane (1,4-dioxane) was stirred at reflux for 24 hours under a nitrogen gas stream is dissolved.After having poured to terminate the reaction, distilled water and extracted with MC.MC / Hexane solvent mixture to a column chromatography with a developing solvent to obtain the intermediate 2 LE of 3 g. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With palladium diacetate; sodium carbonate; triphenylphosphine; In 1,2-dimethoxyethane; water; for 1h;Reflux; Inert atmosphere; | Under a nitrogen atmosphere, 3.9 g (8 mmol) of the compound (C), 2.95 g (8 mmol) of the compound (F)0.21 g (0.8 mmol) of triphenylphosphine,sodium carbonate4.23 g (40 mmol) was added to 40 mL of dimethoxyethane and 40 mL of water, and the mixture was stirred. 0.045 g (0.2 mmol) of palladium acetate was added, and the mixture was heated under reflux for 1 hour. After cooling to room temperature, the precipitated crystals were collected by filtration and washed with water. The solution was dissolved in THF, unnecessary substances were removed by filtration, methanol was added, and the precipitated crystals were collected by filtration to obtain 3.62 g (yield 70%) of exemplified compound 1. FIG. 4 shows a 1 H-NMR chart of Exemplary Compound 1. |
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