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CAS No. : | 100124-06-9 | MDL No. : | MFCD00092336 |
Formula : | C12H9BO3 | Boiling Point : | No data available |
Linear Structure Formula : | - | InChI Key : | ZXHUJRZYLRVVNP-UHFFFAOYSA-N |
M.W : | 212.01 | Pubchem ID : | 2734328 |
Synonyms : |
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Chemical Name : | Dibenzo[b,d]furan-4-ylboronic acid |
Signal Word: | Warning | Class: | |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | |
Hazard Statements: | 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 |
---|---|---|
84% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; for 12h;Reflux; | 200mL of tetrahydrofuran is introduced into the compound B-1 and diphenyl 14.8g (50mmol) prepared in Synthesis Example 5 and [b, d] furan-4-yl boronic acid (12.7g, 60mmol), followed by Pd (PPh3) 4 (2.89g, 2.5mmol) and 100mL2MK2CO3 aqueous solution, the resulting mixture was stirred for 12 hours while refluxing. The temperature was cooled to normal temperature and distilled water was extracted with chloroform. The organic layer was dried over anhydrous magnesium sulfate (MgSO4) was dried, then the solvent was removed, and subjected to silica gel column chromatography to give 16.1g (42mmol, 84%) Compound E-1. |
78% | With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In ethanol; water; toluene; at 120℃; for 15h; | Preparation of Compound 8-1 [206] Compound 7-1 (10 g, 33.8 mmol), dibenzo[b,d]furan-4-ylboronic acid (8.6 g, 40.56 mmol), Pd(PPh3)4 (2 g, 1.7mmol), K2CO3 (34 g, 321 mmol), toluene 60mL, EtOH 12mL and purified water 12mL were mixed and then stirred at 120C for 15 hours. After termination of the reaction, the resultant mixture was allowed to stand and the water layer was removed, after which the organic layer was concentrated. Silica column purification was then carried out, yielding Compound 8-1 (10.2 g, 78%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
palladium diacetate; In methanol; ethanol; hexane; water; acetone; toluene; | Synthesis Method of 3,6-di(dibenzofuran-4-yl)-9-phenyl-9H-carbazole (abbreviated as DBF2PC-II)To a 200-mL three-neck flask were added 2.0 g (5.0 mmol) of <strong>[57103-20-5]3,6-dibromo-9-phenyl-9H-carbazole</strong>, 3.2 g (11 mmol) of dibenzofuran-4-boronic acid, 10 mg (0.1 mmol) of palladium(II) acetate, 30 mg (0.1 mmol) of tris(o-tolyl)phosphine, 50 mL of toluene, 5 mL of ethanol, and 7.5 mL of a 2 mol/L aqueous potassium carbonate solution.This mixture was degassed while being stirred under reduced pressure, and then heated and stirred at 90° C. for 6.5 hours under a nitrogen stream to be reacted.After the reaction, 250 mL of toluene was added to this reaction mixture and the mixture was heated.The mixture was filtered through Celite (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 531-16855), alumina, and Florisil (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 540-00135) in this order to give a filtrate.The resulting filtrate was purified by silica gel column chromatography (a developing solvent in which the toluene/hexane ratio was 1:3).The obtained fraction was concentrated, acetone, methanol, and water were added thereto, and the mixture was irradiated with ultrasonic waves.Then, acetone and methanol were added to the obtained precipitate and the mixture was irradiated with ultrasonic waves, filtrated, washed, and dried.Thereby, 2.8 g of a target substance, white powder, was obtained in 69percent yield.A reaction scheme of the above synthesis method is illustrated in the following (E-1).The Rf values of the white powder obtained through the reaction and <strong>[57103-20-5]3,6-dibromo-9-phenyl-9H-carbazole</strong> were respectively 0.32 and 0.55, which were found by silica gel thin layer chromatography (TLC) (a developing solvent in which the ethyl acetate/hexane ratio was 1:10).The white powder obtained by the step 1 was subjected to nuclear magnetic resonance (NMR) spectroscopy.The measurement data are shown below.show the 1H NMR charts.Note that is an enlarged chart of .By the measurement results, it was confirmed that the white powder obtained by the step 1 was DBF2PC-II, which is represented by the structural formula (208).1H NMR (CDCl3, 300 M Hz): delta (ppm)=7.37 (dt, J=7.8 Hz, J=1.2 Hz, 2H), 7.44-7.56 (m, 5H), 7.60-7.69 (m, 8H), 7.75 (dd, J=7.2 Hz, J=1.5 Hz, 2H), 7.95 (dd, J=7.8 Hz, J=1.5 Hz, 2H), 8.00-8.04 (m, 4H), 8.75 (d, J=1.5 Hz, 2H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | With sodium carbonate;bis(triphenylphosphine)palladium(II) dichloride; In water; acetonitrile; | Step 1: Synthesis of 3,5-Dimethyl-2-(dibenzofuran-4-yl)pyrazine (abbreviation: Hdm4 dbfpr) First, into a recovery flask equipped with a reflux pipe were placed 1.51 g of <strong>[38557-72-1]2-chloro-3,5-dimethylpyrazine</strong>, 2.25 g of 4-dibenzofuranylboronic acid, 1.12 g of sodium carbonate, 0.048 g of bis(triphenylphosphine)palladium(II) dichloride (abbreviation: Pd(PPh3)2Cl2), 15 mL of water, and 15 mL of acetonitrile, and the air inside the flask was replaced with argon. Heating was performed by microwave irradiation (2.45 GHz, 100 W) of this reaction container for 10 minutes, so that reaction occurred. After that, water was added to this reaction solution, and extraction with dichloromethane was carried out. A solution of the obtained extract was washed with water and dried over magnesium sulfate. After the drying, the solution was filtered. After the solvent of this solution was distilled, the obtained residue was washed with methanol, so that the pyrazine derivative which was the object of the synthesis, Hdm4 dbfpr, was obtained (a pale orange powder in a yield of 65%). Note that a microwave synthesis system (Discover, produced by CEM Corporation) was used for the microwave irradiation. The synthesis scheme of Step 1 is illustrated in the following scheme (x-1). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In water; toluene; for 12h;Inert atmosphere; Reflux; | (4-Dibenzofuranyl) boronic acid ((4-dibenzofuranyl) boronic acid), 30 g (141.5 mmol), <strong>[57381-62-1]methyl-2-bromo-4-chlorobenzoate</strong> (methyl-2-bromo-5-chlorobenzoate), 37.1 g ( 148.6 mmol), tetrakistriphenylphosphine palladium 8.2 g (7.1 mmol) dissolved in toluene 550 ml was added to flask placed in a nitrogen atmosphere. Potassium carbonate (potassium carbonate) 104.2 g (707.51 mmol) was dissolved in 550 ml toluene, and the aqueous solution 353.8 ml was stirred under reflux for 12 hours. After completion of the reaction, the mixture was extracted with ethyl acetate, dried with magnesium sulfite (magnesium sulphate), filtered and the filtrate was concentrated under reduced pressure. The resulting mixture was purified by silica gel column chromatography using n-hexane / dichloromethane (7:3 volume ratio) to give the desired compound of intermediate (D) 38.2 g (80percent yield) as a white solid. |
71% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; at 90℃; for 21h;Inert atmosphere; | 50 g (200 mmol) of methyl-2-bromo-5-chlorobenzoate was dissolved in 0.5 L of tetrahydrofuran (THF) in a nitrogen environment, 46.7 g (220 mmol) of dibenzofuran-4-yl boronic acid and 4.63 g (4.01 mmol) of tetrakis(triphenylphosphine)palladium were added thereto, and the mixture was agitated. 59 g (401 mmol) of potassium carbonate saturated in water was added thereto, and the mixture was heated and refluxed at 90 °C for 21 hours. When the reaction was terminated, water was added to the reaction solution, and the mixture was extracted with dichloromethane (DCM) and treated with anhydrous MgSO4 to remove moisture and then, filtered and concentrated under a reduced pressure. The obtained residue was separated and purified through flash column chromatography, obtaining a compound I-14 (47.7 g, 71 percent). HRMS (70 eV, EI+): m/z calcd for C20H13ClO3: 336.0553, found: 336.1. Elemental Analysis: C, 71 percent; H, 4 percent |
71% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; at 80℃; for 21h;Inert atmosphere; | 50 g (200 mmol) of <strong>[57381-62-1]methyl-2-bromo-4-chlorobenzoate</strong> was dissolved in 0.5 L of tetrahydrofuran (THF) under a nitrogen atmosphere, 46.7 g (220 mmol) of dibenzofuran-4-ylboronic acid and 4.63 g (4.01 mmol) of tetrakis(triphenylphosphine) palladium were added thereto, and the mixture was agitated. Then, 59.0 g (401 mmol) of potassium carbonate saturated in water was added thereto, and the obtained mixture was heated and refluxed at 80 °C for 21 hours. When the reaction was complete, water was added thereto, and the mixture was extracted with dichloromethane (DCM) and treated with anhydrous MgSO4 to remove moisture and then, filtered and concentrated under a reduced pressure.Then, a residue obtained therefrom was separated and purified through flash column chromatography, obtaining 47.7 g (71 percent) of the intermediate I-1. HRMS (70 eV, EI+): m/z calcd for C20H13ClO3: 336.0553, found: 336.Elemental Analysis: C, 71 percent; H, 4 percent |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In 1,2-dimethoxyethane; ethanol; water; for 24h;Reflux; Inert atmosphere; | General procedure: To a mixture of 2-chloro-4-fluoropyridine (0.580 g, 4.43 mmol) and Pd(PPh3)4 (0.172 g, 0.149mmol) in 1,2-dimethoxyethane (21 mL) was added a solution of 4-(dibenzo[b,d]furanyl)boronic acid (0.960 g, 4.51mmol) in ethanol (21mL), followed by addition of 2.0 M sodium carbonate aqueous solution (21 mL). Then, the mixturewas refluxed for 1 day under nitrogen. After cooling, the solvent was removed on a rotary evaporator. The residue was dissolved in chloroform (50 mL), and then the solution was washed with water (50 mL 2) and sat. brine (50 mL). The obtained organic solution was dried over anhydrous magnesium sulfate. The solvent was removed on a rotary evaporator, and the residue was purified by silica gel column chromatography using chloroform as eluent to obtain 2-(dibenzo[b,d] furan-4-yl)-4-fluoropyridine as awhite powder (0.780 g, 2.96mmol, 67percent) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
52% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water;Inert atmosphere; Reflux; | Synthesis of Compound A (0050) Into a 200 ml three-necked flask, 1.92 g of dibenzofuran-4-boronic acid, 10.0 g (2 eq) of <strong>[57103-20-5]3,6-dibromo-9-phenylcarbazole</strong>, 20 ml of a 2 M aqueous potassium carbonate solution, and 0.73 g (0.07 eq) of phosphine tetrakistriphenylphosphinepalladium (Pd(PPh3)4) were added under an argon atmosphere. In 80 ml of THF, the reactant was heated and refluxed while stirring for 6 hours. After cooling in the atmosphere, an organic layer was separated and purified by using silica gel chromatography (a mixture solvent of chloroform and hexane). The crude product thus obtained was recrystallized using a mixture solvent of toluene and hexane to obtain 2.30 g of Compound A as a white solid (yield 52percent). (0051) The compound was measured and identified by 1H-NMR and FAB-MS. 1H-NMR(CDCl3): 8.60 (d, 1H), 8.34 (d, 1H), 7.93-8.02 (m, 3H), 7.44-7.70 (m, 11H), 7.29-7.40 (m, 2H) (0052) FAM-MS: 488 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
67% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In 1,4-dioxane;Reflux; | In a round bottom flask, 20.0 g of dibenzo[b,d]furan-4-ylboronic acid, 33.8 g of 2,8-dibromodiphenyl And [b,d]furan (<strong>[10016-52-1]2,8-dibromodibenzo[b,d]furan</strong>) is dissolved in 800 ml of 1,4-dioxan (1,4-dioxan),After placing 140 ml of K2CO3 (2M) and 3.3 g of Pd(PPh3)4, reflux stirring was carried out.The reaction was confirmed by thin layer chromatography (TLC), and after water was added, the reaction was terminated. The organic layer was extracted with methyl cellulose (MC), and after filtration under reduced pressure, 26.1 g (yield 67%) of intermediate IM1 was obtained by recrystallization. |