Structure of 70592-05-1
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CAS No. : | 70592-05-1 |
Formula : | C27H22O |
M.W : | 362.46 |
SMILES Code : | COC1=CC=C(/C(C2=CC=CC=C2)=C(C3=CC=CC=C3)/C4=CC=CC=C4)C=C1 |
MDL No. : | N/A |
InChI Key : | DNKXVYVXQUNHPL-UHFFFAOYSA-N |
Pubchem ID : | 11302947 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H302-H315-H319-H335 |
Precautionary Statements: | P261-P280-P301+P312-P302+P352-P305+P351+P338 |
* 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 |
---|---|---|
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; water; toluene; for 12h;Inert atmosphere; Reflux; | TPE-OMe and TPE-SMe were prepared and synthesized by Suzuki-Miyaura cross-coupling reaction using triphenyl bromide as raw material.The general synthesis method is as follows:In the mixture of bromotristyrene (3.35g, 10.8mmol) and substituted phenylboronic acid (10.00mmol) was added K2CO3 aqueous solution (2M, 15mL),Ethanol (15mL) and toluene (50mL) and Pd(PPh3)4 (0.10g, 0.10mmol),The reaction was refluxed for 12h under the protection of nitrogen.After cooling to room temperature, the reaction mixture was poured into water,It was extracted three times with dichloromethane, and the organic layer was washed with brine,Then dry on MgSO4.After removing the solvent under reduced pressure, pass through silica gel column chromatography,Petroleum ether is used as the eluent to obtain a white solid powder. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
42% | With titanium(IV) tetrachloride; zinc powder; In tetrahydrofuran; at 78℃; for 12h;Inert atmosphere; | General procedure: Benzophenone (1 g, 5.487mmol), 4-(Dimethylamino)-benzophenone (1.2 g, 5.487mmol), and zinc powder (4.3 g, 65.844mmol) were mixed in freshly distilled cold tetrahydrofuran (THF, 20mL, 0C), and titanium tetrachloride (TiCl4, 4.2mL) was added dropwise under an argon atmosphere whilst rapidly stirring over 10min. The mixture was then slowly warmed up to 78C with stirring, and the reaction was allowed to further proceed for 12h under reflux. After the reaction, the mixture was cooled to room temperature, and deionized water (DI H2O, 25mL) was added to quench the reaction. The resulting solution was filtered through a pad of celite to remove the remaining zinc powder and the filtrated solution was washed with ethyl acetate (EtOAc) and DI H2O. The collected organic extract was washed with brine and dried over anhydrous sodium sulfate (Na2SO4). The resulting residue was concentrated in vacuo and was purified by flash column chromatography (n-hex/EtOAc=9:1, v/v, TLC: Rf 0.5). TPE-N1 was collected with a 38% yield (yellowish solid). |
10.4% | With titanium(IV) tetrachloride; zinc powder; In tetrahydrofuran; at 0℃;Inert atmosphere; Reflux; | Zinc powder (2.68 g, 41 mmol) was weighed respectively, dissolved in tetrahydrofuran (30 mL), titanium tetrachloride (2.2 mL, 20 mmol) was added dropwise at 0 C, heated to reflux for 2 h under nitrogen protection, and then 4- Methoxybenzophenone (1.06 g, 5.0 mmol) and benzophenone (0.91 g, 5.0 mmol) were dissolved in 40 mL of tetrahydrofuran solution and added to the reaction system.Reflux for another 8-12h.After the reaction, it was filtered through celite, washed with dichloromethane for several times, the filtrate was concentrated under reduced pressure, separated by silica gel column chromatography (eluent is petroleum ether:dichloromethane=2:1), and purified to obtain a white solid product T1 (0.38 g, yield: 10.4%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98.1% | With boron tribromide; In dichloromethane; at -78 - 20℃; for 13h;Inert atmosphere; Schlenk technique; | (2) Under a nitrogen atmosphere, Compound 1 (1.08 g, 3.0 mmol) was added to a Schlenk tube,The compound 1 was completely dissolved by addition of lOmL anhydrous dichloromethane,After cooling to _78 C, drop the solution of boron tribromide in dichloromethane1.7 mL, 3.6 mmol)The reaction was carried out at -78 C for 1 hour and then allowed to warm to room temperature,Continue to react for 12 hours. After completion of the reaction, drop the appropriate amount of ice water quenching reaction, a white solid precipitation, filter, filter cake with deionized water 3 times, collecting filter cake and vacuum drying, white solid(1.02 g, yield 98.1%),And the structure was characterized by 1 H NMR, 13 C NMR and IR. It was confirmed that the white solid was Compound 2 and its structural formula was |
56.7% | With boron tribromide; In dichloromethane; at 20℃; for 4h;Cooling with ice; | The tetraarylenes derivatives 6’ (2 g, 5.52 mmol) was added into the 100 mL round bottom flask and drying them. The DCM (40 mL) was added into the flask under ice-salt bath, and the BBr3 (1.5 mL, 16.5 mmol) was added after 15 min. And then the solution was stirred at room temperature for 4 h after another 15 min. The reaction mixture was poured into NaHCO3 aqueous solution and extracted with DCM. The organic layer was dried and evaporated. The residue was purified by column chromatography on silica gel (SiO2, PE : EA = 10:1, V/V) to give white solid (1.09 g, 56.7%). 1H NMR (400 MHz, CDCl3, ppm): δ = 7.14 - 7.01 (m, 15 H), 6.90 (d, J = 8.6 Hz, 2 H), 6.56 (d, J = 8.7 Hz, 2 H), 4.73 (s, 1 H). |
With hydrogen bromide; In acetic acid; for 12h;Reflux; | Compound A (4.4 mmol, 1.72 g),Was dissolved in glacial acetic acid, 48% hydrobromic acid (50ml) was added,Stirred at reflux for 12 hours,Evaporation of the solvent, adding toluene re-steaming,Extracted with ethyl acetate, washed twice with sodium bicarbonate and saturated saline respectively, dried over anhydrous magnesium sulfate,Column chromatography (n-hexane / ethyl acetate = 10: 1) gave the product compound B. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With n-butyllithium; In tetrahydrofuran; at -20℃; for 3h;Inert atmosphere; | Diphenylmethane (12 mmol, 2.02 g)Dissolved in 50ml of tetrahydrofuran, minus 20 ,Under nitrogen, 2.5 M n-butyllithium (10 mmol, 4 ml) was added dropwise,4-Methoxybenzophenone (12 mmol, 3.03 g)Warmed to room temperature, stirred for 3 hours,Quenched with water, extracted with methylene chloride,Unscrew the solvent, add toluene,P-toluenesulfonic acid (1.8 mmol, 0.342 g),Reflux for 6 hours,Cool at room temperature, washed with 5% sodium bicarbonate twice, anhydrous magnesium sulfate dare to spin out the solvent to give a yellow crude product,Recrystallization gave white solid product Compound A, 80%. |
74% | The diphenylmethane 4’ (3 g, 18 mmol) and the THF (20 mL) were added into the 100 mL flask. Replacing the gas in the flask 3 times under argon atmosphere, and the n-BuLi (7.5 mL, 18 mmol) was added at 0 oC dropwise, and the solution was stirred for 1 h. After that, the mixture was added into the 4-methoxylbenzophenone 5’ (3.4 g, 16 mmol) solution of THF (30 mL) at 0 oC. The solution was stirred at 30 oC for 6 h after 15 min. The mixture was poured into the solution of NH4Cl and was extracted with EA. The organic layer was washed with NaCl saturated aqueous solution, and dried with anhydrous sodium sulfate. The residue was evaporated and was added into the p-toluene sulfonic acid (0.69 g, 4 mmol) solution of toluene (120 mL). The solution was stirred at 120 oC for 6 h. The mixture was washed with saturated NaCl aqueous solution, dried, concentrated and purified by column chromatography on silica gel (SiO2, PE : DCM = 10:1, V/V) to give white solid (4.29 g, 74.0%). 1H NMR (400 MHz, CDCl3, ppm): δ = 7.10 - 6.98 (m, 15 H), 6.93 (d, J = 8.8 Hz, 2 H), 6.60 (d, J = 8.8 Hz, 2 H), 3.65 (s, 3 H). | |
5.93 g | (1) Under a nitrogen atmosphere,In SchlenkTube added dibenzyl burn(3.16 g, 20 mmol) and 80 mL of dry tetrahydrofuran. 2.2 M n-butyllithium in hexane (9. lmL, 20 mmo 1) was added dropwise at 0 C and the reaction was carried out at 0 C for 0.5 h.4-methoxybenzoylbenzene (3.40 g, 16 mmol) was added and the temperature was allowed to warm to room temperature and stirring was continued for 6 hours. After completion of the reaction, the reaction was quenched by the addition of saturated aqueous ammonium chloride solution, extracted with dichloromethane, the organic phase was collected, dried over anhydrous Na2S04,The solvent was evaporated to give the crude product as an intermediate. The intermediate was dissolved in 80 mL of dry toluene in a 250 mL round bottom flask,A catalytic amount of hydrated p-toluenesulfonic acid was added(570 mg, 3.0 mmol) and refluxed for 12 hours. After completion of the reaction, the mixture was cooled to room temperature, and the toluene solution was washed with 10 wt% aqueous NaHC03 solution. The organic phase was collected, the organic phase was collected, dried over anhydrous Na2S04, and the product was chromatographed on silica gel using petroleum ether as eluant. And the residue was dried in vacuo to give a white solid (5.93 g, yield 90.1%). The structure was characterized by Guru NMR. It was confirmed that the white solid was Compound 1, |