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CAS No. : | 108847-20-7 |
Formula : | C12H9BO2S |
M.W : | 228.07 |
SMILES Code : | OB(C1=C2C(C3=CC=CC=C3S2)=CC=C1)O |
MDL No. : | MFCD01318182 |
InChI Key : | GOXNHPQCCUVWRO-UHFFFAOYSA-N |
Pubchem ID : | 2734329 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H315-H319-H335 |
Precautionary Statements: | P261-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 potassium carbonate;palladium diacetate; tris-(o-tolyl)phosphine; In ethanol; water; toluene; at 80℃; for 6h;Inert atmosphere; | [Example 1] This example will give descriptions of a method of synthesizing 2-[4-(dibenzothiophen-4-yl)phenyl]-1-phenyl-1H-benzimidazole (abbreviation: DBTBIm-II) represented by the following Structural formula (108). [Show Image] [Synthesis of 2-[4-(dibenzothiophen-4-yl)phenyl]-1-phenyl-1H-benzimidazole (abbreviation: DBTBIm-II)] The synthesis scheme of 2-[4-(dibenzothiophen-4-yl)phenyl]-1-phenyl-1H-benzimidazole (abbreviation: DBTBIm-II) is illustrated in (B-1). [Show Image] In a 500-mL three-neck flask were put 5.1 g (15 mmol) of <strong>[2620-76-0]2-(4-bromophenyl)-1-phenyl-1H-benzimidazole</strong>, 3.7 g (16 mmol) of dibenzothiophen-4-boronic acid, and 0.2 g (0.7 mmol) of tri(ortho-tolyl)phosphine. The air in the flask was replaced with nitrogen. To this mixture were added 16 mL of a 2.0 mmol/L aqueous solution of potassium carbonate, 55 mL of toluene, and 18 mL of ethanol. Under reduced pressure, this mixture was stirred to be degassed. Then, 33 mg (0.2 mmol) of palladium(II) acetate was added to this mixture, and the mixture was stirred at 80 C for 6 hours under a nitrogen stream. After a predetermined time, water was added to the obtained mixture, and the aqueous layer was extracted with chloroform. The extracted solution and the organic layer were combined and washed with saturated brine, followed by drying with magnesium sulfate. This mixture was gravity filtered. The resulting filtrate was concentrated to give an oily substance. This oily substance was purified by silica gel column chromatography. The silica gel column chromatography was carried out using toluene as a developing solvent. The obtained fractions were concentrated to give a solid. Hexane was added to this solid, followed by irradiation with ultrasonic waves. Suction filtration was carried out, whereby 5.8 g of a white powder was obtained in 88% yield, which was the substance to be produced. By a train sublimation method, 2.8 g of the obtained white powder was purified. In the purification, the white powder was heated at 235 C under a pressure of 2.4 Pa with a flow rate of argon gas of 5 mL/min. After the purification, 2.2 g of a pale yellow glassy solid was obtained in a yield of 79%, which was the substance to be produced. A nuclear magnetic resonance (NMR) method identified this compound as 2-[4-(dibenzothiophen-4-yl)phenyl]-1-phenyl-1H-benzimidazole (abbreviation: DBTBIm-II), which was the substance to be produced. 1H NMR data of the obtained substance are as follows: 1H NMR (CDCl3, 300 MHz): δ (ppm) = 7.27-7.30 (m, 2H), 7.32-7.60 (m, 10H), 7.67-7.75 (m, 4H), 7.82-7.85 (m, 1H), 7.83 (dd, J = 8.4Hz, 1.5 Hz, 1H), 8.13-8.19 (m, 2H). FIGS. 9A and 9B illustrate the 1H NMR charts. Note that FIG. 9B is a chart showing an enlarged part of FIG. 9A in the range of 7.0 ppm to 8.5 ppm. Further, FIG. 10A shows an absorption spectrum of a toluene solution of DBTBIm-II, and FIG. 10B shows an emission spectrum thereof. FIG. 11A shows an absorption spectrum of a thin film of DBTBIm-II, and FIG. 11B shows an emission spectrum thereof. The absorption spectrum was measured using an ultraviolet-visible spectrophotometer (V-550, produced by JASCO Corporation). The measurements were performed with samples prepared in such a manner that the solution was put in a quartz cell while the thin film was obtained by evaporation onto a quartz substrate. The absorption spectrum of the solution was obtained by subtracting the absorption spectra of quartz and toluene from those of quartz and the solution, and the absorption spectrum of the thin film was obtained by subtracting the absorption spectrum of a quartz substrate from those of the quartz substrate and the thin film. In FIGS. 10A and 10B and FIGS. 11A and 11B, the horizontal axis represents wavelength (nm) and the vertical axis represents intensity (arbitrary unit). In the case of the toluene solution, absorption peaks were observed at around 294 nm, 315 nm, and 337 nm, and emission wavelength peaks were 371 nm and 386 nm (excitation wavelength: 315 nm). In the case of the thin film, absorption peaks were observed at around 234 nm, 298 nm, 319 nm, and 338 nm, and an emission wavelength peak was 401 nm (excitation wavelength: 316 nm). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
47% | palladium diacetate; In ethanol; hexane; acetone; toluene; | Step 1:Synthesis of 3,6-di-(dibenzothiophen-4-yl)-9-phenyl-9H-carbazole (abbreviated as DBT2PC-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 dibenzothiophene-4-boronic acid, 10 mg (0.1 mmol) of palladium(II) acetate, 30 mg (0.1 mmol) of tri(ortho-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 hours in a nitrogen atmosphere to be reacted.After the reaction, this reaction mixture solution was cooled to room temperature, and then filtered to give a residue while being washed with water, ethanol, toluene, and hexane in this order.The residue was purified by silica gel column chromatography (a developing solvent in which the toluene/hexane ratio was 1:3).The fraction thus obtained was concentrated, acetone and ethanol were added thereto, and the mixture was irradiated with ultrasonic waves.Then, recrystallization gave 1.4 g of a white powder in 47percent yield.The synthesis scheme of Step 1 is shown in (A-1).The obtained white powder was subjected to nuclear magnetic resonance (NMR) spectroscopy.The measurement data are shown below.1H NMR (CDCl3, 300 MHz): delta=7.44-7.70 (m, 15H), 7.82-7.86 (m, 4H), 8.15-8.22 (m, 4H), 8.57 (d, J=1.5 Hz, 2H) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | A mixture of <strong>[1357572-66-7]9-bromo-7H-benzo[c]carbazole</strong> 1-2 (1.16 g, 4 mmol), dibenzo [b,d] thiophen-4-ylboronic acid (1.00 g, 4.4 mmol) in tetrahydrofuran (20 mL) and 2 M K2CO3 (20 mL) was added into a round bottom flask and bubbled with argon stirring for 15 min. Pd(PPh3)4 (0.092 g, 0.08 mmol) was added to the mixture, and the reaction was refluxed for 5 h under argon atmosphere. The reaction mixture was cooled down to room temperature, poured into H2O and then extracted with dichloromethane three times. The combined organic layer was dried over anhydrous sodium sulfate. The solvent was removed in vacuum and the crude product was purified by SiO2 column chromatography, affording an orange solid (1.20 g, 75%). IR (KBr, disk) ν 3402.79, 3061.27, 1440.63, 1382.53 cm-1. 1H NMR (400 MHz, CDCl3, δ): 8.86 (d, J = 8.4 Hz, 1H), 8.71 (d, J = 8.4 Hz, 1H), 8.57 (s, 1H), 8.24 (dd, J = 8.8, 6.4 Hz, 2H), 8.06 (d, J = 8.0 Hz, 1H), 7.98 (s, 1H), 7.92 (t, J = 7.2 Hz, 1H), 7.88 (dd, J = 6.0, 2.4 Hz, 1H), 7.84-7.75 (m, 2H), 7.71-7.62 (m, 3H), 7.58-7.48 (m, 3H). HRMS (ESI, m/z): [M-H]+ calcd for: C28H16NS, 398.1003, found, 398.1007. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In toluene; for 12h;Reflux; Inert atmosphere; | Round bottom flask was charged with 4-benzothiophene boronic acid 21.5g (94.3mmol), <strong>[57381-62-1]methyl 2-bromo-4-chlorobenzoate</strong> 23.5g(94.3mmol) and the mixture of the aqueous solution of potassium carbonate dissolved in 117ml 19.5g (141.5mmol) was dissolved was added to toluene (313ml)It was added and stirred. Here tetrakistriphenylphosphine-palladium was added to 1.09g (0.94mmol) Under nitrogen atmosphereIt was stirred at reflux for 12 hours. After the end of the reaction the ethyl acetate extract was extracted with gun with magnesium sulfateAnd concentrated under reduced pressure and the crude was filtered and the filtrate. The product n- hexane / ethyl acetate (9: 1 by volume) as a silica gel curlColumn and purified by chromatography to give the desired compound of intermediate M-28 to give a 31g (yield 93percent) |
80% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; at 80℃; for 18h;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, 50.2 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 18 hours. When the reaction was complete, 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. Then, a residue obtained therefrom was separated and purified through flash column chromatography, obtaining 56.5 g (80 percent) of the intermediate I-5. HRMS (70 eV, EI+): m/z calcd for C20H13ClO2S: 352.0325, found: 352.Elemental Analysis: C, 68 percent; H, 4 percent |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
47% | With palladium diacetate; potassium carbonate; tris-(o-tolyl)phosphine; In ethanol; water; toluene; at 90℃; for 6h;Inert atmosphere; | 2.0 g (5.0 mmol) of <strong>[57103-20-5]3,6-dibromo-9-phenyl-9H-carbazole</strong>,Dibenzothiophene-4-boronic acid3.2 g (11 mmol),Palladium (II) acetate (10 mg, 0.1 mmol)(O-tolyl) phosphine (30 mg, 0.1 mmol)Toluene (50 mL), ethanol (5 mL) and 2 mol / L aqueous potassium carbonate solution (7.5 mL) were placed in a 200 mL three-necked flask, and the mixture was stirred under reduced pressure. Then, the mixture was heated at 90 ° C for 6 hours Stir to cause a reaction. After the reaction, the above-mentioned mixed solution was cooled to room temperature, and then filtered while washing with water, ethanol, toluene and hexane to obtain a filtrate. The resulting filtrate was purified by silica gel column chromatography (developing solvent: toluene: hexane = 1: 3). The resulting rinsing was concentrated, and acetone and ethanol were added and ultrasonic waves were applied. After recrystallization, the white powder of the object was obtained at a yield of 1.4 g and a yield of 47percent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
48% | The fourth intermediate <strong>[2050-48-8]4,4'-sulfonylbis(bromobenzene)</strong> (4.92 g, 13.16 mmol) andDibenzothiophene-4-boronic acid (2.00 g, 8.77 mmol) was added to a three-neck bottle.Dissolve in 50 mL of tetrahydrofuran (THF), add 8.7 mL of 2M K2CO3 aqueous solution, stir with argon gas for 30 min, and add 0.10 g of Pd(PPh3)4.Heat to 75 C for 16 h. After the reaction solution is cooled to room temperature,Add 30 mL of ethanol and spin dry in a rotary evaporator.The crude product was purified by silica gel column chromatography eluting with a mixture of n-hexane and methylene chloride in a volume ratio of 4:5. The obtained solid was white powder after vacuum drying. The mass was 2.01 g and the yield was 48%. . |
Tags: Dibenzothiophene-4-boronic acid | Organoboron | Thiophenes | Boronic Acids | Organometallic Reagents | Heterocyclic Building Blocks | Boronic Acids/Esters | 108847-20-7
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