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CAS No. : | 503299-24-9 | MDL No. : | MFCD24387484 |
Formula : | C24H18BrN | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | AFDFEVPHXYRVDH-UHFFFAOYSA-N |
M.W : | 400.31 | Pubchem ID : | 57746354 |
Synonyms : |
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Signal Word: | Warning | Class: | |
Precautionary Statements: | P261-P280-P301+P312-P302+P352-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 |
---|---|---|
73% | Stage #1: With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1 h; Stage #2: With Trimethyl borate In tetrahydrofuran; hexane at 20℃; for 4 h; |
2-2. Preparation of compound 10[173]N-(4-bromophenyl)-N-phenyl-[1,1’-biphenyl]-4-amine (15.0 g, 37.5 mmol) was dissolved in tetrahydrofurane (190.0 mL) and n-butyl lithium (2.5 M in hexane) (22.0 mL) was added to the mixture at -78 . The mixture was stirred for 1 hour and trimethoxyborane (6.3 mL, 56.21 mmol) was added thereto. After stirring the whole mixture for 4 hours at room temperature, the mixture was extracted with ethyl acetate (200.0 mL) and the obtained organic layer was washed with distilled water (100.0 mL). The organic solvent was removed under the reduced pressure. The obtained solid was washed with hexane, filtered and dried to obtain (4-([1,1-biphenyl]-4-yl(phenyl)amino)phenyl)boronic acid (10.0 g, 73percent). |
61% | Stage #1: With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1 h; Inert atmosphere Stage #2: With Trimethyl borate In tetrahydrofuran; hexane at -78 - 20℃; for 25 h; Stage #3: With hydrogenchloride In tetrahydrofuran; hexane at 20℃; for 1 h; |
(iii) Synthesis of 4-[N-(biphenyl-4-yl)-N-phenylamino]phenylboronic acid A synthesis scheme (C-4) of 4-[N-(biphenyl-4-yl)-N-phenylamino]phenylboronic acid is shown below. In a 300-mL three-neck flask, 7.0 g (18 mmol) of 4-bromo-4'-phenyltriphenylamine was put, and the atmosphere in the flask was substituted by nitrogen. Then, 80 mL of tetrahydrofuran (abbreviation: THF) was added thereto, and the mixture was stirred at -78° C. for 10 minutes. After that, 13 mL (21 mmol) of an n-butyllithium hexane solution (1.63 mol/L) was dropped into this solution from a syringe, and the solution was stirred at -78° C. for 1 hour. After a certain time, 3.5 mL of trimethyl borate was added to the reaction mixture and the mixture was stirred at -78° C. for 1 hour, then stirred for 24 hours while changing the temperature from -78° C. to room temperature. After stirring, 100 mL of 1M dilute hydrochloric acid was added to the solution, and the mixture was stirred at room temperature for 1 hour. After stirring, ethyl acetate was added to this solution for extraction. After extraction, the extract was washed with a saturated saline. After washing, magnesium sulfate was added to the extract for drying. After the drying, magnesium sulfate was removed by suction filtration to give a filtrate. The obtained filtrate was concentrated and recrystallized from a mixed solvent of chloroform and hexane to give 4.0 g of the target substance, 4-[N-(biphenyl-4-yl)-N-phenylamino]phenylboronic acid in a yield of 61percent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
56% | Stage #1: With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1 h; Stage #2: at -78 - 20℃; for 25 h; Stage #3: With hydrogenchloride; water In tetrahydrofuran; hexane at 20℃; for 1 h; |
Step 1: Synthesis of 4-[λT-(biphenyl-4-yl)-λT-phenyl]aminophenylboronic acid][0410]A synthetic scheme of 4-[N-(biphenyl-4-yl)-λT-phenyl]aminophenylboronic acid in Step 1 is shown in the following (η-l). [0411] <n="176"/>[0412]In a 300-mL three-neck flask, 7.0 g (18 mmol) of 4-bromo-4'-phenyltriphenylamine was put, and the atmosphere in the flask was substituted by nitrogen. Then, 80 mL of tetrahydrofuran (abbreviation: THF) was added thereto, and the mixture was stirred at -780C for 10 minutes. After that, 13 mL (21 mmol) of an n-butyllithium hexane solution (1.63 mol/L) was dropped onto this solution from a syringe, and the solution was stirred at -780C for 1 hour. After the stirring, 3.5 mL (31 mmol) of trimethyl borate was added to the reaction mixture, and the mixture was stirred at -78 0C for 1 hour and at room temperature for 24 hours. After the reaction, 100 mL of IM dilute hydrochloric acid was added to the reaction solution, and the mixture was stirred at room temperature for 1 hour. After the stirring, this solution was extracted with ethyl acetate, and an organic layer was washed with a saturated saline solution. After the washing, magnesium sulfate was added to the organic layer, and the organic layer was dried. After the drying, magnesium sulfate was removed by suction filtration to obtain filtrate. The obtained filtrate was concentrated and recrystallized with a mixture solvent of chloroform and hexane to obtain 3.6 g of an object at a yield of 56 percent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
56% | Step 1: Synthesis of 4-[lambdaT-(biphenyl-4-yl)-lambdaT-phenyl]aminophenylboronic acid][0410]A synthetic scheme of 4-[N-(biphenyl-4-yl)-lambdaT-phenyl]aminophenylboronic acid in Step 1 is shown in the following (eta-l). [0411] <n="176"/>[0412]In a 300-mL three-neck flask, 7.0 g (18 mmol) of 4-bromo-4'-phenyltriphenylamine was put, and the atmosphere in the flask was substituted by nitrogen. Then, 80 mL of tetrahydrofuran (abbreviation: THF) was added thereto, and the mixture was stirred at -780C for 10 minutes. After that, 13 mL (21 mmol) of an n-butyllithium hexane solution (1.63 mol/L) was dropped onto this solution from a syringe, and the solution was stirred at -780C for 1 hour. After the stirring, 3.5 mL (31 mmol) of trimethyl borate was added to the reaction mixture, and the mixture was stirred at -78 0C for 1 hour and at room temperature for 24 hours. After the reaction, 100 mL of IM dilute hydrochloric acid was added to the reaction solution, and the mixture was stirred at room temperature for 1 hour. After the stirring, this solution was extracted with ethyl acetate, and an organic layer was washed with a saturated saline solution. After the washing, magnesium sulfate was added to the organic layer, and the organic layer was dried. After the drying, magnesium sulfate was removed by suction filtration to obtain filtrate. The obtained filtrate was concentrated and recrystallized with a mixture solvent of chloroform and hexane to obtain 3.6 g of an object at a yield of 56 %. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With potassium carbonate In ethanol; water; toluene at 90℃; for 6.5h; | 3 Step 3: Synthesis of 4-(l-naphthyl)-4'-phenyltriphenylamine] [0519]A synthetic scheme of 4-(l-naphthyl)-4'-phenyltriphenylamine in Step 3 is shown in the following (L-3). [0520][0521]In a 100-mL three-neck flask, 8.0 g (20 mmol) of 4-bromo-4'-phenyltriphenylamine, 3.4 g (20 mmol) of 1-naphthaleneboronic acid, 44 mg (0.2 mmol) of palladium(II) acetate, and 60 mg (0.4 mmol) of tri(ø-tolyl)phosphine were put, and 20 mL of toluene, 10 mL of ethanol, and 15 mL of a potassium carbonate solution (2 mol/L) were added to this mixture. This mixture was deaerated while being stirred under low pressure. After the deaeration, the mixture was stirred under a nitrogen atmosphere at 90 0C for 6.5 hours to be reacted. [0522]After the reaction, 150 mL of toluene was added to this reaction mixture, and this suspension was filtrated through Florisil, silica gel, and then Celite. The obtained filtrate was washed with water. Then, magnesium sulfate was added to remove moisture. This suspension was filtrated through Florisil, alumina, silica gel, and then Celite to obtain filtrate. The obtained filtrate was concentrated, and methanol was added thereto. The mixture was irradiated with supersonic and then recrystallized to obtain 8.6 g of an objective white powder at a yield of 97 %. |
97% | With potassium carbonate; tris-(o-tolyl)phosphine In ethanol; water; toluene at 90℃; for 2.5h; Inert atmosphere; | 1.3 In a 100-mL three-neck flask, 8.0 g (20 mmol) of 4-bromo-4'-phenyltriphenylamine, 3.4 g (20 mmol) of 1-naphthaleneboronic acid, 44 mg (0.2 mmol) of palladium(II) acetate, and 60 mg (0.4 mmol) of tri(o-tolyl)phosphine were put, and 20 mL of toluene, 10 mL of ethanol, and 15 mL of a potassium carbonate aqueous solution (2 mol/L) were added to this mixture. This mixture was deaerated while being stirred under low pressure. After the deaeration, the mixture was stirred under a nitrogen atmosphere at 90 0C for 2.5 hours to be reacted. After the reaction, 150 mL of toluene was added to this reaction mixture, and this suspension was filtrated through Florisil, silica gel, and then Celite. The obtained filtrate was washed with water, and magnesium sulfate was added thereto to remove moisture. This suspension was filtrated through Florisil, alumina, silica gel, and then Celite to obtain filtrate. The obtained filtrate was concentrated, methanol was added thereto, ultrasonic waves were applied thereto, and then recrystallization thereof was performed to obtain 8.6 g of an objective white solid at a yield of 97 %. A synthetic scheme of Step 3 is shown in (c-1) given below. [0197]An Rf value of the objective substance by a silica gel thin layer chromatography (TLC) (developing solvent, ethyl acetate: hexane = 1:10) was 0.43 and that of 4-bromo-4'-phenyltriphenylarnine was 0.50. [0198]The compound which was obtained through Step 3 described above was measured by a nuclear magnetic resonance method (1H NMR). The measurement data are shown below. [0199]1H NMR (CDCl3, 300 MHz): δ (ppm) = 7.07 (t, J = 7.5 Hz, IH), 7.22 - 7.61 (m, 17H), 7.83 (d, J = 7.8 Hz, IH), 7.88 - 7.91 (m, IH), 8.02 - 8.05 (m, IH) [0200] A chart of 1H NMR is shown in FIG. 9A. Further, FIG. 9B is a chart showing an enlarged portion in the range of 6 ppm to 9 ppm of FIG. 9A. [0201]Subsequently, molecular weight of the above compound was measured by a Time-of-flight mass spectrometry (abbreviation: TOF-MS) detector (Waters Micromass LCT Premier, manufactured by Waters). A mixture solution containing acetonitrile and 0.1 % of a formic acid solution (mixture rate of acetonitrile and the forminc acid solution, 80/20 vol/vol) was used as a solvent. Accordingly, a main peak with a molecular weight of 448.21 (mode is ES+) was detected. [0202]From the above measurement results, it was understood that αNBAlBP, which is the triarylamine derivative represented by the above structural formula (3), was obtained by this synthetic example. [0203]Next, FIG. 10 shows an absorption spectrum of the toluene solution of αNBAlBP and an absorption spectrum of a thin film of ccNBAlBP. An ultraviolet-visible spectrophotometer (V-550, manufactured by JASCO Corporation) was used for measurement of the absorption spectra. The spectrum of the toluene solution of αNBAlBP was measured in a quartz cell. The absorption spectrum of the solution which was obtained by subtracting the quartz cell from the measured absorption spectrum is shown in FIG. 10. In addition, as for the absorption spectrum of the thin film, a sample was manufactured by evaporation of αNBAlBP over a quartz substrate, and the absorption spectrum thereof, from which the absorption spectrum of the quartz substrate is subtracted, is shown in FIG. 10. In FIG. 10, a horizontal axis represents a wavelength (nm), and a longitudinal axis represents an absorption intensity (given unit). From FIG. 10, in the case of the toluene solution of αNBAlBP, an absorption peak on a long wavelength side was observed at around 332 nm, and in the case of the thin film, an absorption peak on a long wavelength side was observed at around 339 nm. [0204]Emission spectra of the toluene solution of αNBAlBP and the thin film of αNBAlBP are shown in FIG. 11. The measurement was performed using an ultraviolet-visible spectrophotometer (V-550, manufactured by JASCO Corporation) in a manner similar to that of the absorption spectra measurement. The emission spectrum of the toluene solution of αNBAlBP was measured in a quartz cell, and the emission spectrum of the thin film of αNBAlBP was measured by manufacturing a sample by evaporation of αNBAlBP over a quartz substrate. From FIG. 11, in the case of the toluene solution of αNBAlBP, the maximum emission wavelength was observed at around 404 nm (excitation wavelength: 365 nm), and in the case of the thin film, the maximum emission wavelength was observed at around 423 nm (excitation wavelength: 340 nm). [0205] The results of measuring the thin film of αNBAlBP by photoelectron spectrometry (AC-2, product of Riken Keiki Co., Ltd.) in the atmosphere indicated that the HOMO level of αNBAlBP was -5.52 eV. The Tauc plot of the absorption spectrum of the thin film in FIG. 10 revealed that the absorption edge was 3.27 eV. Thus, the energy gap in the solid state of αNBAlBP was estimated to be 3.27 eV, which means that the LUMO level of αNBAlBP is -2.25 eV. As thus described, it was understood that αNBAlBP has a large energy gap of 3.27 eV in the solid state. [0206]In addition, oxidation reaction characteristics of αNBAlBP were measured. The oxidation reaction characteristics were examined by a cyclic voltammetry (CV) measurement. Further, an electrochemical analyzer (ALS model 600A or 600C, manufactured by BAS Inc.) was used for the measurement. [0207]As for a solution used for the CV measurement, dehydrated JVyV-dimethylformamide (abbreviation: DMF, product of Sigma-Aldrich Inc., 99.8%, catalog No. 22705-6) was used as a solvent, and tetra-n-butylammonium perchlorate (abbreviation: W-Bu4NClO4, product of Tokyo Chemical Industry Co., Ltd., catalog No. T0836), which was a supporting electrolyte, was dissolved in the solvent such that the concentration of tetra-7-butylammonium perchlorate was 100 mmol/L. Further, the object to be measured was also dissolved in the solvent such that the concentration thereof was 2 mmol/L. Further, a platinum electrode (a PTE platinum electrode, manufactured by BAS Inc.) was used as a working electrode; a platinum electrode (a VC-3 Pt counter electrode (5 cm), manufactured by BAS Inc.) was used as an auxiliary electrode; and an Ag/Ag+ electrode (an RE5 non-aqueous solvent reference electrode, manufactured by BAS Inc.) was used as a reference electrode. Note that the measurement was performed at room temperatures (20 °C to 25°C). The scan speed at these CV measurements was set at 0.1 V/s. [0208]A scan for changing the potential of the working electrode with respect to the reference electrode from 0.22 V to 0.70 V and then from 0.70 V to 0.22 V was set to one cycle, and measurement was performed for 100 cycles. [0209]From the measurement results, it was understood that repetition of the oxidation reduction between an oxidation state and a neutral state had favorable characteristics in αNBAlBP without large change in oxidation peak even after 100 cycles of measurements. [0210]Further, the HOMO level of αNBAlBP was also calculated from the CV measurement results. [0211]First, a potential energy (eV) of the reference electrode (AgZAg+ electrode), which was used in this example, with respect to the vacuum level was calculated. That is, the Fermi level of the Ag/Ag+ electrode was calculated. It is known that the oxidation-reduction potential of ferrocene in methanol is +0.610 V [vs. SHE] with respect to a standard hydrogen electrode (Reference: Christian R. Goldsmith et al., J. Am. Chem. Soc, Vol. 124, No. 1, pp. 83-96, 2002). On the other hand, by using the reference electrode, which was used in this example, the oxidation-reduction potential of ferrocene in methanol was calculated to be +0.11 V [vs. Ag/Ag+]. Therefore, it was understood that the potential energy of the reference electrode, which was used in this example, was lower than that of the standard hydrogen electrode by 0.50 [eV]. [0212] Here, it is also known that the potential energy of the standard hydrogen electrode with respect to the vacuum level is -4.44 eV (Reference: Toshihiro Ohnishi and Tamami Koyama, Macromolecular EL material, Kyoritsu Shuppan, pp .64-67). As described above, it was possible to calculate the potential energy of the reference electrode, which was used in this example, with respect to the vacuum level as follows: -4.44-0.50 = -4.94 [eV]. [0213]Subsequently, the calculation of the HOMO level of αNBAlBP by CV measurement is described in detail. An oxidization peak potential £pa of αNBAlBP was 0.61 V. In addition, a reduction peak potential Epc thereof was 0.54 V. Therefore, a half-wave potential (an intermediate potential between Epa and Epc) can be calculated to be 0.57 V. This shows that αNBAlBP was oxidized by electric energy of 0.57 V [vs. Ag/ Ag+], and this energy corresponds to the HOMO level. Here, as described above, the potential energy of the reference electrode, which was used in this example, with respect to the vacuum level is -4.94 [eV]; therefore, it was understood that the HOMO level of αNBAlBP was calculated as follows:-4.94-0.57 = -5.51 [eV]. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With N-Bromosuccinimide In ethyl acetate at 20℃; for 24h; | 1.2ii; C-3 (ii) Synthesis of 4-bromo-4'-phenyltriphenylamine (ii) Synthesis of 4-bromo-4'-phenyltriphenylamine A synthesis scheme (C-3) of 4-bromo-4'-phenyltriphenylamine is shown below. 10 g (31 mmol) of 4-phenyltriphenylamine was put in a 500 mL three-neck flask and 300 mL of ethyl acetate was added thereto. The mixture was stirred at room temperature. Then, 5.5 g (31 mmol) of N-bromo succinimide (abbreviation: NBS) was added to this solution in portions, and the mixture solution was stirred for 24 hours. After stirring, the solution was washed with a saturated sodium hydrogen carbonate solution, and a saturated saline in this order. After washing, magnesium sulfate was added to the organic layer for drying. After drying, the mixture was subjected to suction filtration to remove the magnesium sulfate, and thus a filtrate was obtained. The obtained filtrate was concentrated and dried to give 12 g of the target substance, powdery light brown solid of 4-bromo-4'-phenyltriphenylamine in a yield of 97%. |
96% | With N-Bromosuccinimide In ethyl acetate; toluene for 27.5h; | 2 Step 2: Synthesis of 4-bromo-4'-phenyltriphenylamine] [0515]A synthetic scheme of 4-bromo-4'-phenyltriphenylamine in Step 2 is shown in the following (L-2). [0516][0517] In a 500-mL conical flask, 6.4 g (20 mmol) of 4-phenyltriphenylamine, 250 mL of ethyl acetate, and 150 mL of toluene were added and the mixture was stirred, and then 3.6 g (20 mmol) of JV-bromo succinimide (abbreviation: NBS) was added to this solution. After that, this mixture was stirred for 27.5 hours. After the obtained suspension was washed with water, moisture was removed by magnesium sulfate. This suspension was concentrated and dried to obtain 7.7 g of an objective white powder at a yield of 96 %. |
96% | With N-Bromosuccinimide In ethyl acetate; toluene for 27.5h; | 1.2 In a 500-mL conical flask, 6.4 g (20 mmol) of 4-phenyltriphenylamine, 250 mL of ethyl acetate, and 150 mL of toluene were added and the mixture was stirred, and then 3.6 g (20 mmol) of W-Bromosuccinimide (abbreviation: NBS) was added to this solution. After that, this mixture was stirred for 27.5 hours. After the obtained suspension was washed with water, moisture was removed by magnesium sulfate. This suspension was concentrated and dried to obtain 7.7 g of an objective white powder at a yield of 96 %. A synthetic scheme of Step 2 is shown in (b-1) given below. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79% | With potassium carbonate In ethanol; water; toluene at 90℃; for 6.5h; | 4 Step 4: Synthesis of 4-[9-(biphenyl-4-yl)-9H-carbazol-3-yl)-4'-phenyl-triphenylamine (abbreviation: BCBAlBP)] [0596]A synthetic scheme of4-[9-(biphenyl-4-yl)-9H-carbazol-3-yl)-4'-phenyl-triphenylamine in Step 4 is shown in the following (N-4). [0597] [0598]In a 50-mL three-neck flask, 1.2 g (3.0 mmol) of4-bromo-4'-phenyl-triphenylamine, 1.1 g (3.0 mmol) of[9-(biphenyl-4-yl)-9H-carbazol-3-yl]boronic acid, 6.0 mg (0.03 mmol) of palladium(II) acetate, and 18 mg (0.06 mmol) of tri(o-tolyl)phosphine were put, and 20 mLof toluene,5 mL of ethanol, and 3 mL of a potassium carbonate solution (2 mol/L) were added to this mixture. This mixture was deaerated while being stirred under low pressure.After the deaeration, the mixture was stirred under a nitrogen atmosphere at 90 0C for6.5 hours to be reacted. [0599]After the reaction, 150 mL of toluene was added to this reaction mixture, and this suspension was filtrated through Florisil and then Celite. The obtained filtrate was washed with water. Then, magnesium sulfate was added to remove moisture. This suspension was filtrated through Florisil, alumina, silica gel, and then Celite to obtain filtrate. The obtained filtrate was concentrated, and acetone and methanol were added thereto. The mixture was irradiated with supersonic and then recrystallized to obtain1.5 g of an objective white powder at a yield of 79 %. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With potassium carbonate In ethanol; water; toluene at 90℃; for 13h; | 5 Step 5: Synthesis of 4-{9-[4(l-naphthyl)phenyl]-9H-carbazol-3-yl}-4'-phenyl-triphenylamine (abbreviation: NBCBAlBP)] [0683]A synthetic scheme of4-{9-[4(l-naphthyl)phenyl]-9H-carbazol-3-yl}-4'-phenyl-triphenylamine in Step 5 is shown in the following (Q-5). [0684][0685]In a 50-mL three-neck flask, 1.0 g (2.5 mmol) of 4-bromo-4'-phenyl-triphenylamine, 1.0 g (2.5 mmol) of 9-[4-(l-naphthyl)phenyl]-9H-carbazol-3-boronic acid, 4.0 mg (0.02 mmol) of palladium(II) acetate, and 6.0 mg (0.02 mmol) of tri(ø-tolyl)phosphine were put, and 20 mL of toluene, 5 mL of ethanol, and 2.5 mL of a potassium carbonate solution (2 mol/L) were added to this mixture. This mixture was deaerated while being stirred under low pressure. After the deaeration, the mixture was stirred under a nitrogen atmosphere at 90 0C for 13 hours to be reacted. [0686]After the reaction, 150 mL of toluene was added to this reaction mixture, and this suspension was filtrated through Florisil, silica gel, and then Celite. The obtained filtrate was washed with water. Then, magnesium sulfate was added to remove moisture. This suspension was filtrated through Florisil, alumina, silica gel, and then Celite to obtain filtrate. The obtained filtrate was concentrated, and acetone and methanol were added thereto. The mixture was irradiated with supersonic and then recrystallized to obtain 1.2 g of an objective white powder at a yield of 70 %. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
25% | With potassium carbonate In ethanol; water; toluene at 90℃; for 6.5h; | 4 Step 4: Synthesis of 4-[9-(l-naphthyl)-9H-carbazol-3-yl]-4'-phenyl-triphenylamine(abbreviation: NCBAlBP)][0715]A synthetic scheme of4-[9-(l-naphthyl)-9H-carbazol-3-yl]-4'-phenyl-triphenylamine (abbreviation:NCBAlBP) in Step 4 is shown in the following (R-4). [0716][0717]In a 50-mL three-neck flask, 1.2 g (3.0 mmol) of 4-bromo-4'-phenyl-triphenylamine, 1.0 g (3.0 mmol) of9-(l-naphthyl)9H-carbazol-3-boronic acid, 6.0 mg (0.03 mmol) of palladium(II) acetate, and 0.03 mg (18 mmol) of tri(o-tolyl)phosphine were put, and 15 mL of toluene, 5 mL of ethanol, and 3 mL of a potassium carbonate solution (2 mol/L) were added to this mixture. This mixture was deaerated while being stirred under low pressure. After the deaeration, the mixture was stirred under a nitrogen atmosphere at 90 0C for 6.5 hours to be reacted. [0718]After the reaction, 150 mL of toluene was added to this reaction mixture, and this suspension was filtrated through Florisil, silica gel, and then Celite. The obtained filtrate was washed with water. Then, magnesium sulfate was added to remove moisture. This suspension was filtrated through Florisil, alumina, silica gel, and then Celite to obtain filtrate. The obtained filtrate was concentrated and purified by silica gel column chromatography (developing solvent, toluene: hexane = 1:3). The obtained fraction was concentrated, and methanol was added thereto. The mixture was irradiated with supersonic and then recrystallized to obtain 0.5 g of an objective white powder at a yield of 25 % |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: sodium t-butanolate; bis(dibenzylideneacetone)-palladium(0); tri-tert-butyl phosphine / toluene; hexane / 5 h / 80 °C / Inert atmosphere 2: N-Bromosuccinimide / ethyl acetate / 24 h / 20 °C | ||
Multi-step reaction with 2 steps 1: tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate / toluene / 5 h / Inert atmosphere; Reflux 2: tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate / toluene / 5 h / Inert atmosphere; Reflux |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | 2-2. Preparation of compound 10[173]N-(4-bromophenyl)-N-phenyl-[1,1?-biphenyl]-4-amine (15.0 g, 37.5 mmol) was dissolved in tetrahydrofurane (190.0 mL) and n-butyl lithium (2.5 M in hexane) (22.0 mL) was added to the mixture at -78 . The mixture was stirred for 1 hour and trimethoxyborane (6.3 mL, 56.21 mmol) was added thereto. After stirring the whole mixture for 4 hours at room temperature, the mixture was extracted with ethyl acetate (200.0 mL) and the obtained organic layer was washed with distilled water (100.0 mL). The organic solvent was removed under the reduced pressure. The obtained solid was washed with hexane, filtered and dried to obtain (4-([1,1-biphenyl]-4-yl(phenyl)amino)phenyl)boronic acid (10.0 g, 73%). | |
61% | (iii) Synthesis of 4-[N-(biphenyl-4-yl)-N-phenylamino]phenylboronic acid A synthesis scheme (C-4) of 4-[N-(biphenyl-4-yl)-N-phenylamino]phenylboronic acid is shown below. In a 300-mL three-neck flask, 7.0 g (18 mmol) of 4-bromo-4'-phenyltriphenylamine was put, and the atmosphere in the flask was substituted by nitrogen. Then, 80 mL of tetrahydrofuran (abbreviation: THF) was added thereto, and the mixture was stirred at -78 C. for 10 minutes. After that, 13 mL (21 mmol) of an n-butyllithium hexane solution (1.63 mol/L) was dropped into this solution from a syringe, and the solution was stirred at -78 C. for 1 hour. After a certain time, 3.5 mL of trimethyl borate was added to the reaction mixture and the mixture was stirred at -78 C. for 1 hour, then stirred for 24 hours while changing the temperature from -78 C. to room temperature. After stirring, 100 mL of 1M dilute hydrochloric acid was added to the solution, and the mixture was stirred at room temperature for 1 hour. After stirring, ethyl acetate was added to this solution for extraction. After extraction, the extract was washed with a saturated saline. After washing, magnesium sulfate was added to the extract for drying. After the drying, magnesium sulfate was removed by suction filtration to give a filtrate. The obtained filtrate was concentrated and recrystallized from a mixed solvent of chloroform and hexane to give 4.0 g of the target substance, 4-[N-(biphenyl-4-yl)-N-phenylamino]phenylboronic acid in a yield of 61%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1.1: n-butyllithium / hexane; tetrahydrofuran / 1 h / -78 °C / Inert atmosphere 1.2: 25 h / -78 - 20 °C 1.3: 1 h / 20 °C 2.1: bis(dibenzylideneacetone)-palladium(0); potassium carbonate; tris-(o-tolyl)phosphine / toluene; ethanol; water / 5 h / 90 °C / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: sodium t-butanolate; bis(dibenzylideneacetone)-palladium(0); tri-tert-butyl phosphine / toluene; hexane / 5 h / 80 °C / Inert atmosphere 2: N-Bromosuccinimide / ethyl acetate / 24 h / 20 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate In toluene at 70℃; | II.1.1 (1) Synthesis of Sub 2-I-7 After N-phenyl-[1,1′-biphenyl]-4-amine (CAS Registry Number: 32228-99-2) (13.1 g, 53.40 mmol) was dissolved in toluene (445 ml) in a round bottom flask, 1-bromo-4-iodobenzene (CAS Registry Number: 589-87-7) (22.7 g, 80.10 mmol), Pd2(dba)3 (1.5 g, 1.60 mmol), 50% P(t-Bu)3 (2.1 ml, 4.27 mmol), NaOt-Bu (15.4 g, 160.19 mmol) were added to the solution and the mixture was stirred at 70° C. When the reaction was completed, the reaction product was extracted with CH2Cl2 and water, and then the organic layer was dried with MgSO4 and concentrated. Then, the concentrate was applied to silica gel column and recrystallized to obtain 15.6 g (yield: 73%) of the product. |
61% | With tris-(dibenzylideneacetone)dipalladium(0); tris-(o-tolyl)phosphine; sodium t-butanolate In toluene at 120℃; for 3h; | 2.2-1 -1. Preparation of compound 8 -1. Preparation of compound 8[170]N-Phenyl-[1,1-biphenyl]-4-amine (15.0 g, 61.1 mmol), 1-bromo-4-iodobenzene (21.0 g, 73.32 mmol), tris(dibenzylideneacetone)dipalladium(O) (1.1 g, 1.22 mmol), tris(ortho-toluyl)phosphine (1.5 g, 4.89 mmol) and sodium tert-butoxide (8.8 g, 91.65 mmol) were dissolved in toluene (300.0 mL). The mixture was stirred for 3 hours at 120 . After cooling the mixture to room temperature, the mixture was extracted with ethyl acetate (200.0 mL) and the obtained organic layer was washed with distilled water (200.0 mL). The organic solvent was removed under the reduced pressure. The obtained solid was washed with methanol, filtered and dried. The obtained product was separated through column chromatography on silica gel and recrystallization to obtain N-(4-bromophenyl)-N-phenyl-[1,1’-biphenyl]-4-amine (15.0 g, 61 %). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1.1: n-butyllithium / tetrahydrofuran; hexane / 1 h / -78 °C 1.2: 4 h / 20 °C 2.1: palladium diacetate; dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; potassium phosphate / toluene / 8 h / Reflux |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
61% | With tris-(dibenzylideneacetone)dipalladium(0); sodium t-butanolate In toluene at 100℃; | Synthesis of 8-29 To a round bottom flask, N-(4-bromophenyl)-N-phenyl-[1,1'-biphenyl]-4-amine (9.6g, 24mmol), N-(9,9-dimethyl-9H-fluoren-3-yl)pyridin-3-amine (5.7g, 20mmol), Pd2(dba)3 (0.03 ~ 0.05mmol), P(t-Bu)3 (0.1 equivalent), NaOt-Bu (3 eq.), toluene (10.5mL after the insert / 1mmol) and the reaction proceeds at 100 °C. When the reaction is complete, water and ether and the organic layer was extracted and dried over MgSO4 silicagel column and re-crystallization and the resulting organics concentrated and then the product was 7.4g (yield: 61%) was obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With potassium phosphate; copper(l) iodide; rac-diaminocyclohexane In 1,4-dioxane for 18h; Inert atmosphere; Reflux; | 2 Synthesis of Compound (2) In a three-neck flask, 2.11 g (5 mmol) of compound (1-4), 2.20 g (5.5 mmol) of N-(4-bromophenyl)-N-(4-biphenyl)aniline, 0.95 g (5 mmol) of copper iodide, 2.12 g (10mmol) of potassium triphosphate, 1.14 g (10 mmol) of cyclohexanediamine and 20 mL of 1,4-dioxane were placed. The mixture was refluxed in a nitrogen atmosphere for 18 hours. After completion of the reaction, insoluble matters were removed by filtration through celite. The filtrate was transferred to a dripping funnel and extracted several times with toluene. The obtained organic phase was dried with anhydrous magnesium sulfate, filtered and concentrated. The resultant was puried by silica gel chromatography (hexane:toluene~3:1), whereby white solids were obtained. The yield was 2.60 g and the percentage yield was 70%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
64% | With copper(l) iodide; 1,10-Phenanthroline; potassium hydroxide In 5,5-dimethyl-1,3-cyclohexadiene for 18h; Reflux; | 9 General procedure: L round bottom flask formula diphenyl amine 20 g (118 mmol), 1- bromo-4-iodo-benzene 33.4 g (118mmol), potassium hydroxide 13.2 g (236 mmol) the mixture was stirred into 400 ml of xylene. 1,10 nansseu page in five minutesAnd stirred to give after adding a rolrin gave 7 g (35.5 mmol). If the materials are somewhat rust Cooper iodide 6.75 g(35.5 mmol) was added raising the temperature back to the mixture was heated under reflux for 18 hours. Using ethyl acetate and water to the impuritiesGave was removed after the removal of water into the anhydrous magnesium sulfate. The filter is then the solution of ethyl acetate and ethanolUsing recrystallization to give the formula M 2-1 24 g (63%) |
With tris-(dibenzylideneacetone)dipalladium(0); triphenylphosphine; sodium t-butanolate In toluene at 100℃; for 24h; | 1-5.2 (2) Synthesis of Sub 5 General procedure: Sub 5-3 (1 equiv) and Sub 5-4 (1.1 equiv) were added to toluene, followed by the addition of Pd2 (dba) 3 (0.05 equiv), PPh3 (0.1 equiv) and NaOt-Bu (3 equiv) It stirred at reflux for 24 hours at 100 degreeC. After extraction with ether and water, the organic layer was dried over MgSO 4, concentrated, and the resulting organic material was silicagel column and recrystallized to obtain Sub 5. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93.1% | With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; potassium acetate In 1,4-dioxane for 5h; Inert atmosphere; Reflux; | 5 After adding Intermediate 2-77 (15.0g, 37.5mmol), Compound 4-77 (19.0g, 75mmol) and 50mL 1,4-dioxane into the reaction vessel, ventilate 3 times, and add tris(dioxane) under nitrogen atmosphere. Benzylacetone) two palladium 0.35g (0.38mmol), tricyclohexylphosphine 0.53g (1.9mmol) and potassium acetate 7.36g (75mmol), heated to reflux, stirred for 5h, the reaction was completed. The mixture was extracted with dichloromethane, then the extracted organic layer was dried using sodium sulfate, and the solvent was removed using a rotary evaporator. The remaining material was purified by column chromatography to obtain Intermediate 3-77 (15.6g, yield 93.1%). |
81% | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate In toluene for 12h; Reflux; | Synthesis of Intermediate K-7 Round bottom flask was charged with N-(4-bromophenyl)-N-phenylbiphenyl-4-amine 20 g (49.96 mmol), Pd(dppf)Cl2 1.22 g (1.50 mmol), Bis(pinacolato)diboron 15.22 g (59.95 mmol), after suspending the Potassium Acetate 14.71 g (149.88 mmol) in 250 ml toluene is stirred under reflux for 12 hours. After completion of the reaction after cooling to room temperature, filter, and concentrated to a silica gel filter and the filtrate. Recrystallized with acetone to give the compound K-7 18 g (yield 81%). |
81% | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate In toluene for 12h; Reflux; | 20 g (49.96 mmol) of N-(4-bromophenyl)-N-phenylbiphenyl-4-amine, 1.22 g (1.50 mmol) of Pd(dppf)Cl2, 15.22 in a round bottom flask Gm (59.95 mmol) of bis(pinacolyl)diboron and 14.71 g (149.88 mmol) of potassium acetate were suspended in 250 ml of toluene and then refluxed and stirred for 12 hours. When the reaction was completed, the resultant was cooled to room temperature and then filtered, and the filtered solution was filtered over silica gel and concentrated. The concentrated solution was recrystallized from acetone to give 18 g of Intermediate K-7 (yield 81%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: potassium acetate; (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride / toluene / 12 h / Reflux 2: bis(dibenzylideneacetone)-palladium(0); tri-tert-butyl phosphine; caesium carbonate / 1,4-dioxane / 12 h / Inert atmosphere; Reflux | ||
Multi-step reaction with 2 steps 1: potassium acetate; (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride / toluene / 12 h / Reflux 2: tri-tert-butyl phosphine; tris-(dibenzylideneacetone)dipalladium(0); caesium carbonate / 1,4-dioxane / 12 h / Inert atmosphere; Reflux |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With bis[tris( 1,1-dimethylethyl)phosphine]-palladium; sodium t-butanolate In 5,5-dimethyl-1,3-cyclohexadiene for 4h; Inert atmosphere; Heating; | 2 Synthesis of Compound 2-1-50 Compound 2-1(10.00, 32.57mmol), in 500ml round bottom flask in a nitrogen atmosphere N-([1,1'-biphenyl]-4-yl) -N-(4-bromophenyl) - [1,1'- biphenyl]-4-amine (16.25g, 34.20mmol) in a xylene 180ml completely dissolved and then sodium tert-butoxide (4.07g, 42.35mol) was added and, Bis (tri-tert-butylphosphine) palladium(0) (0.16g , 0.31mmol) were placed and stirred with heating for 3 hours. It was cooled down to room temperature and concentrated under reduced pressure to remove the base Xylene was recrystallized from 180ml ethyl acetate to the compound 2-2-49: to produce a (16.64g, yield 73%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; water for 6h; Inert atmosphere; Reflux; | 14 Preparation of Compound 14 To a 500 ml round-bottom flask in a nitrogen atmosphere was added Compound A-1 (17.52 g, 28.42 mmol), N- (4-bromophenyl) -N-phenyl- [1,1'-biphenyl] -4-amine(10 g, 25.84 mmol) was dissolved in 280 ml of tetrahydrofuran. To the mixture was added 2M potassium carbonate aqueous solution (140 ml), tetrakis- (triphenylphosphine) palladium (1.30 g, 1.12 mmol)And the mixture was heated with stirring for 6 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized from 310 ml of tetrahydrofuran to obtain Compound 14 (17.23 g, 85%). |
85% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; water for 6h; Inert atmosphere; Heating; | 5 Production of Compound 5 [Compound 5] Under a nitrogen atmosphere in a 500 ml round bottom flask,Compound E-2 (17.52 g, 28.42 mmol), N-(4-bromophenyl)-N-phenyl-[1,1'-biphenyl]-4-amine (10 g, 25.84 mmol) was completely dissolved After tetrahydrofuran 280ml,After adding 2M aqueous potassium carbonate solution (140 ml) and adding tetrakis(triphenylphosphine)palladium (1.30 g, 1.12 mmol), Heat stirring for 6 hours. The temperature was lowered to room temperature, the aqueous layer was removed, dried over anhydrous magnesium sulfate and concentrated under reduced pressure.Recrystallization was performed using 310 ml of tetrahydrofuran to produce Compound 5 (17.23 g, 85%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With bis(tri-t-butylphosphine)palladium(0); sodium t-butanolate In 5,5-dimethyl-1,3-cyclohexadiene for 5h; Reflux; Inert atmosphere; | 5 Synthesis of Compound 1-5 In a nitrogen atmosphere, 500 mlA round bottom flask was charged with the above compound A (10.0 g, 27.25 mmol), N- (4-bromophenyl) -N-phenyl- [1,1'-biphenyl] -4-amine(11.99 g, 29.97 mmol) was dissolved in 250 ml of xylene, Sodium-tert-butoxide (3.41 g, 35.43 mol) was added,Bis (tri-tert-butylphosphine) palladium (0.14 g, 0.27 mmol)Followed by heating and stirring for 5 hours.The temperature was lowered to room temperature, and the salt was removed by filtration. The xylene was concentrated under reduced pressure and recrystallized from ethyl acetate (280 ml) to obtain the compound 1-5 (15.91 g, yield: 85%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In ethanol; water; toluene at 70℃; for 16h; Inert atmosphere; | 1 Synthesis of arylamine derivatives (Compounds 1-5); The following components were added to a reaction vessel substituted with nitrogen and heated, and stirred at 70 ° C for 16 hours.N- (biphenyl-4-yl) -N- (4-bromophenyl) aniline 8.0 N-(9,9-dimethyl-9H-fluoren-2-yl)-N-{3’-(4,4,5,5-tetramethyl-[1,3,2]dioxaboran-2-yl)biphenyl-4-yl} aniline 11.4g 7.5g of potassium carbonate in toluene 64ml water 64ml Ethanol 16ml tetrakis (triphenylphosphine) palladium 0.8g After heating in the above manner, the mixture was cooled to room temperature, and after adding ethyl acetate and water, the organic layer was collected by a liquid separation operation. After the organic layer was concentrated, recrystallization was performed using a mixed solvent of THF and acetone,9.54 g (yield 69%) of white powder of the arylamine derivative (compound 1-5) used for formation of a 2nd hole transport layer was obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
20% | With tetrakis-(triphenylphosphine)-palladium; anhydrous sodium carbonate In ethanol; water monomer; toluene at 120℃; for 4h; | |
20% | With tetrakis-(triphenylphosphine)-palladium; anhydrous sodium carbonate In ethanol; water monomer; toluene at 120℃; for 4h; | 7 [Example 7] Synthesis of compound H1-80 Compound 2-1 (4.8g, 11.34mmol), N-(4-bromophenyl)-N-phenyl-[1,1'-biphenyl]-4-amine (5g, 12.47mmol), Pd (PPh3)4 (0.4g, 0.34mmol), sodium carbonate (Na2CO3) (3.0g, 28.35mmol), toluene (57mL), EtOH (14mL), and distilled water (14mL) were added to the reaction vessel and heated at 120°C Reflux for 4 hours. After the reaction was completed, the mixture was added dropwise to methanol, and then the resulting solid was filtered. The obtained solid was purified by column chromatography through recrystallization to obtain compound H1-80 (1.4 g, yield: 20.0%) |
20% | With tetrakis-(triphenylphosphine)-palladium; anhydrous sodium carbonate In ethanol; water monomer; toluene at 120℃; for 4h; | 5 Example 5: Preparation of compound H1-80 In the reaction vessel, 4.8 g of compound 5-1 (11.34 mmol),5g of N-(4-bromophenyl)-N-phenyl-[1,1'-biphenyl]-4-amine (12.47mmol), 0.4g of tetrakis(triphenylphosphine)palladium (Pd( PPh3)4) (0.34mmol), 3.0g of sodium carbonate (Na2CO3) (28.35mmol), 57mL of toluene, 14mL of ethanol and 14mL of distilled water,And the mixture was stirred at 120°C for 4 hours. After the reaction was completed, the mixture was added dropwise to methanol, and the resulting solid was filtered. Purify the obtained solid by column chromatography,To obtain 1.4 g of compound H1-80 (yield: 20.0%). |
20% | With tetrakis-(triphenylphosphine)-palladium; anhydrous sodium carbonate In ethanol; water monomer; toluene at 120℃; for 4h; | 10 Example 10: Preparation of Compound H1-68 Compound 7 (4.8 g, 11.34 mmol), N-(4-bromophenyl)-N-phenyl-[1,1′-biphenyl]-4-amine (5 g, 12.47 mmol), Pd(PPh3)4 (0.4 g, 0.34 mmol), Na2CO3 (3.0 g, 28.35 mmol), 57 mL of toluene, 14 mL of ethanol, and 14 mL of distilled water were added to a flask and stirred at 120° C. for 4 hours. After the reaction was completed, the mixture was added dropwise to methanol and the resulting solid was filtered. The resulting solid was purified by column chromatography to obtain compound H1-68 (1.4 g, yield: 20.0%). |
20% | With tetrakis-(triphenylphosphine)-palladium; anhydrous sodium carbonate In ethanol; toluene at 120℃; for 4h; | 8 Example 8: Preparation of Compound H1-68 Compound 7 (4.8 g, 11.34 mmol), N-(4-bromophenyl)-N-phenyl-[1,1′-biphenyl]-4-amine (5 g, 12.47 mmol), Pd(PPh3)4 (0.4 g, 0.34 mmol), Na2CO3 (3.0 g, 28.35 mmol), 57 mL of toluene, 14 mL of ethanol, and 14 mL of distilled water were added to a flask and stirred at 120° C. for 4 hours. After the reaction was completed, the mixture was added dropwise to methanol and the resulting solid was filtered. The resulting solid was purified by column chromatography to obtain compound H1-68 (1.4 g, yield: 20.0%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | With tri-tert-butyl phosphine; palladium diacetate; potassium carbonate; In o-xylene; at 130℃; for 12h;Inert atmosphere; | Under nitrogen flow,In a 100 mL three-necked flask,6.0 g (30.0 mmol) of <strong>[10537-08-3]2-chlorocarbazole</strong>,11.9 g (30.0 mmol) of 4-(N-phenyl-N- (4-biphenyl)amino)bromobenzene,6.2 g (45.0 mmol) of potassium carbonate,40 mL of o-xylene, 67 mg (0.30 mmol) of palladium acetate,212 mg (1.0 mmol) of tri (tert-butyl) phosphine was added and the mixture was stirred at 130 C. for 12 hours. After cooling to room temperature,30 mL of pure water and 30 mL of tetrahydrofuran were added,The organic layer was separated. The organic layer was washed with water and saturated brine,Dried over anhydrous magnesium sulfate, and concentrated under reduced pressure.The residue was purified by silica gel column chromatography (mixed solvent of toluene and hexane),11.8 g (22.8 mmol) of a pale yellow powder of 2-chloro-9- (4- (N-phenyl-N- (4-biphenyl) amino) phenyl) carbazole was isolated (yield 76%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
77% | With bis(tri-t-butylphosphine)palladium(0); sodium t-butanolate In 5,5-dimethyl-1,3-cyclohexadiene for 4h; Inert atmosphere; Reflux; | 15 Synthesis of Compound 15 Under a nitrogen atmosphere, Compound G (10.0 g, 22.88 mmol) and N-(4-bromophenyl)-4-phenylbiphenyl- 4-amine (9.61 g, 24.03 mmol) were completely dissolved in150 ml of xylene in a 500 ml-round bottom flask, and then sodium-tert-butoxide (2.86 g, 29.75 mol) was added thereto, bis(tri-tert-butylphosphine) palladium (0.12 g, 0.23 mmol) was put thereinto, and then the resulting mixture was heated and stirred for 4 hours. The temperature was lowered to normal temperature, the resulting mixture was filtered to remove the salt, and then xylene was concentrated under reduced pressure, and the residue was recrystallized with 180 ml of ethyl acetate to prepare Compound 15 (13.39 g, yield: 77%). MS[M+H]=757 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | With bis(tri-t-butylphosphine)palladium(0); sodium t-butanolate In 5,5-dimethyl-1,3-cyclohexadiene for 4h; Inert atmosphere; Reflux; | 16 Synthesis of Compound 16 Under a nitrogen atmosphere, Compound H (10.0 g, 22.88 mmol) and N-(4-bromophenyl)-N-phenylbiphenyl- 4-amine (9.61 g, 24.03 mmol) were completely dissolved in150 ml of xylene in a 500 ml-round bottom flask, and then sodium-tert-butoxide (2.86 g, 29.75 mol) was added thereto, bis(tri-tert-butylphosphine) palladium (0.12 g, 0.23 mmol) was put thereinto, and then the resulting mixture was heated and stirred for 4 hours. The temperature was lowered to normal temperature, the resulting mixture was filtered to remove the salt, and then xylene was concentrated under reduced pressure, and the residue was recrystallized with 130 ml of ethyl acetate to prepare Compound 16 (12.24 g, yield: 71%). MS[M+H]=757the |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78.1% | With palladium diacetate; sodium t-butanolate; tri tert-butylphosphoniumtetrafluoroborate In toluene at 105 - 110℃; for 6h; Inert atmosphere; | 1 Preparation of intermediate 1: O-nitroaniline (4.2 g, 30.0 mmol),N-(4-bromophenyl)-N-phenyl-[1,1'-biphenyl]-4-amine (12.0 g, 30 mmol),Sodium tert-butoxide (4.3 g, 45 mmol) and 100 g of toluene were replaced with nitrogen, and then palladium acetate (67 mg, 0.3 mmol) and P(t-Bu)3·HBF4 (148 mg, 0.6 mmol) were reacted at 105-110 ° C for 6.0 hrs. , TLC tracks the progress of the reaction.After the reaction was completed, the reaction was quenched by adding 200 g of water, layered, and washed with water.The organic phase was de-solvented under reduced pressure to a fraction free, and then recrystallized from toluene to afford 10.7 g of Intermediate 1.The yield was 78.10%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1.1: sodium t-butanolate; tri tert-butylphosphoniumtetrafluoroborate; palladium diacetate / toluene / 6 h / 105 - 110 °C / Inert atmosphere 2.1: 2 h / 10 - 20 °C / Inert atmosphere 2.2: 6 h / 20 - 25 °C / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1.1: sodium t-butanolate; tri tert-butylphosphoniumtetrafluoroborate; palladium diacetate / toluene / 6 h / 105 - 110 °C / Inert atmosphere 2.1: 2 h / 10 - 20 °C / Inert atmosphere 2.2: 6 h / 20 - 25 °C / Inert atmosphere 3.1: triethylamine / dichloromethane / 24 h / -5 - 20 °C / Inert atmosphere 3.2: 0.5 h / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With palladium diacetate; 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; sodium t-butanolate In toluene at 110℃; for 15h; | 2 In a dry 2L three-necked flask, 27.5 g (60.1 mmol) of the product obtained by [Reaction formula 21] and 21.9 g (54.6 mmol) of N- (4-bromophenyl-)-N-phenyl-benzidine were added,An additional 600 ml of toluene which was dried and degassed was added as a solvent.Added 15.7 g (163.8 mmol) of sodium tert-butoxide, 0.25 g of catalyst palladium acetate (2% mol) and 1.4 g of ligand 1,1'-binapthyl-2,2'-bisdiphenylphosphine (BINAP, 4% mol) ). The temperature was raised to 110 ° C, and the reaction was carried out for 15 hours. After the reaction is completed, cool to room temperature, add activated carbon for adsorption, suction filter, spin off the solvent, recrystallize with toluene and ethanol to obtain 37.8 g of intermediate (21) with a yield of 89%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate In toluene for 5h; Inert atmosphere; Reflux; | 5 After adding Intermediate 1-77 (15.0 g, 61.1 mmol), Compound 3-77 (14.4 g, 61.1 mmol) and 50 mL of toluene into the reaction vessel, ventilate 3 times, and add tris(dibenzylidene) under a nitrogen atmosphere. Acetone) two palladium 0.56g (0.61mmol), tri-tert-butylphosphine 0.62g (3.05mmol) and sodium tert-butoxide 11.74g (122.2mmol), heated to reflux, stirred for 5h, the reaction was completed. The mixture was extracted with dichloromethane, then the extracted organic layer was dried using sodium sulfate, and the solvent was removed using a rotary evaporator. The remaining material was purified by column chromatography to obtain Intermediate 2-77 (21.2g, yield 87%). |
78.33% | With tris-(dibenzylideneacetone)dipalladium(0); triphenylphosphine; sodium t-butanolate In toluene at 105℃; for 24h; Inert atmosphere; | 10.1 Take the synthesis of intermediate B14 as an example: 1) In a 250 ml three-necked flask, add 0.01 mol of intermediate B4, 0.012 mol of raw material N1, and 150 ml of toluene under nitrogen protection.Then add 5 × 10-5mol Pd2 (dba) 3, 5 × 10-5mol P (Ph) 3, 0.03mol sodium tert-butoxide, heat to 105 ° C, reflux for 24 hoursSampling plate, showing no bromide remaining, the reaction is complete;Cool to room temperature, filter,The filtrate was spin-evaporated to no fractions and passed through a neutral silica gel column to obtain intermediate C1; the purity by HPLC was 97.24% and the yield was 78.33%; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With potassium phosphate; tetrakis(triphenylphosphine) palladium(0) In ethanol; water; toluene for 6h; Reflux; | 4.3 3) Preparation of compound HT-689 Compound HT-689-P1 (10g, 15.07mmol) and N- (4-bromophenyl) -N-phenyl- [1,1'-biphenyl] -4-amine (N- (4-bromophenyl) -N -phenyl- [1,1'-biphenyl] -4-amine) (7.2g, 18.08mmol) was dissolved in 100ml of toluene, 20ml of ethanol (Ethanol), and 20ml of H2O, then Pd (PPh3) 4 (1.37g, 1.19 mmol) and K3PO4 (9.6 g, 45.21 mmol) were added and stirred at reflux for 6 hours. After completion of the reaction, methylene chloride (MC) was dissolved in the reaction solution, extracted with distilled water, and the organic layer was dried over anhydrous MgSO4, and then the solvent was removed with a rotary evaporator, followed by column chromatography with dichloromethane and hexane as a developing solvent. Purified with to obtain compound HT-689 (12g, 93%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; potassium acetate / 1,4-dioxane / 5 h / Inert atmosphere; Reflux 2: tris-(dibenzylideneacetone)dipalladium(0); potassium carbonate / toluene; ethanol; water / 5 h / Inert atmosphere; Reflux |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate / toluene / 5 h / Inert atmosphere; Reflux 2: tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate / toluene / 5 h / Inert atmosphere; Reflux |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate In toluene at 100℃; | II.1.2 (2) Synthesis of Sub 2-7 After Sub 2-I-7 (15.6 g, 38.97 mmol) was dissolved in toluene (325 ml) in a round bottom flask, naphthalen-1-amine (CAS Registry Number: 134-32-7) (8.4 g, 58.45 mmol), Pd2(dba)3 (1.1 g, 1.17 mmol), 50% P(t-Bu)3 (1.5 ml, 3.12 mmol), NaOt-Bu (11.2 g, 116.91 mmol) were added the solution and the mixture was stirred at 100° C. When the reaction was completed, the reaction product was extracted with CH2Cl2 and water, and then the organic layer was dried with MgSO4 and concentrated. Then, the concentrate was applied to silica gel column and recrystallized to obtain 14.1 g (yield: 78%) of the product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate / toluene / 100 °C 2: tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate / toluene / 3 h / 120 °C |
Yield | Reaction Conditions | Operation in experiment |
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With dicyclohexyl({2’,6’-dimethoxy-[1,1‘-biphenyl]-2-yl})phosphane; tris-(dibenzylideneacetone)dipalladium(0); sodium tertiary butoxide In 5,5-dimethyl-1,3-cyclohexadiene at 140℃; for 7h; | 8 Synthesis of Compound P92 M2 (20 mmol), S1 (22 mmol), sodium tert-butoxide (25 mmol), tris(dibenzylideneacetone) dipalladium (0.2 mmol), S-Phos (0.4 mmol), and 150 mL of xylene were added to the reaction flask , heated to 140°C and reacted for 7h, TLC monitored the reaction to complete, after cooling, water and dichloromethane were added for extraction, the organic phase was concentrated and purified by column chromatography to obtain P92. |
Tags: 503299-24-9 synthesis path| 503299-24-9 SDS| 503299-24-9 COA| 503299-24-9 purity| 503299-24-9 application| 503299-24-9 NMR| 503299-24-9 COA| 503299-24-9 structure
Precautionary Statements-General | |
Code | Phrase |
P101 | If medical advice is needed,have product container or label at hand. |
P102 | Keep out of reach of children. |
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Prevention | |
Code | Phrase |
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P202 | Do not handle until all safety precautions have been read and understood. |
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P211 | Do not spray on an open flame or other ignition source. |
P220 | Keep/Store away from clothing/combustible materials. |
P221 | Take any precaution to avoid mixing with combustibles |
P222 | Do not allow contact with air. |
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P230 | Keep wetted |
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P232 | Protect from moisture. |
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P265 | Wash skin thouroughly after handling. |
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P272 | Contaminated work clothing should not be allowed out of the workplace. |
P273 | Avoid release to the environment. |
P280 | Wear protective gloves/protective clothing/eye protection/face protection. |
P281 | Use personal protective equipment as required. |
P282 | Wear cold insulating gloves/face shield/eye protection. |
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Response | |
Code | Phrase |
P301 | IF SWALLOWED: |
P304 | IF INHALED: |
P305 | IF IN EYES: |
P306 | IF ON CLOTHING: |
P307 | IF exposed: |
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P322 | |
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P341 | If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P342 | If experiencing respiratory symptoms: |
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P352 | Wash with plenty of soap and water. |
P353 | Rinse skin with water/shower. |
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P361 | Remove/Take off immediately all contaminated clothing. |
P362 | Take off contaminated clothing and wash before reuse. |
P363 | Wash contaminated clothing before reuse. |
P370 | In case of fire: |
P371 | In case of major fire and large quantities: |
P372 | Explosion risk in case of fire. |
P373 | DO NOT fight fire when fire reaches explosives. |
P374 | Fight fire with normal precautions from a reasonable distance. |
P376 | Stop leak if safe to do so. Oxidising gases (section 2.4) 1 |
P377 | Leaking gas fire: Do not extinguish, unless leak can be stopped safely. |
P378 | |
P380 | Evacuate area. |
P381 | Eliminate all ignition sources if safe to do so. |
P390 | Absorb spillage to prevent material damage. |
P391 | Collect spillage. Hazardous to the aquatic environment |
P301 + P310 | IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician. |
P301 + P312 | IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell. |
P301 + P330 + P331 | IF SWALLOWED: Rinse mouth. Do NOT induce vomiting. |
P302 + P334 | IF ON SKIN: Immerse in cool water/wrap in wet bandages. |
P302 + P350 | IF ON SKIN: Gently wash with plenty of soap and water. |
P303 + P361 + P353 | IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower. |
P304 + P312 | IF INHALED: Call a POISON CENTER or doctor/physician if you feel unwell. |
P304 + P340 | IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing. |
P304 + P341 | IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P305 + P351 + P338 | IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing. |
P306 + P360 | IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes. |
P307 + P311 | IF exposed: call a POISON CENTER or doctor/physician. |
P308 + P313 | IF exposed or concerned: Get medical advice/attention. |
P309 + P311 | IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician. |
P332 + P313 | IF SKIN irritation occurs: Get medical advice/attention. |
P333 + P313 | IF SKIN irritation or rash occurs: Get medical advice/attention. |
P335 + P334 | Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages. |
P337 + P313 | IF eye irritation persists: Get medical advice/attention. |
P342 + P311 | IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician. |
P370 + P376 | In case of fire: Stop leak if safe to Do so. |
P370 + P378 | In case of fire: |
P370 + P380 | In case of fire: Evacuate area. |
P370 + P380 + P375 | In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion. |
P371 + P380 + P375 | In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion. |
Storage | |
Code | Phrase |
P401 | |
P402 | Store in a dry place. |
P403 | Store in a well-ventilated place. |
P404 | Store in a closed container. |
P405 | Store locked up. |
P406 | Store in corrosive resistant/ container with a resistant inner liner. |
P407 | Maintain air gap between stacks/pallets. |
P410 | Protect from sunlight. |
P411 | |
P412 | Do not expose to temperatures exceeding 50 oC/ 122 oF. |
P413 | |
P420 | Store away from other materials. |
P422 | |
P402 + P404 | Store in a dry place. Store in a closed container. |
P403 + P233 | Store in a well-ventilated place. Keep container tightly closed. |
P403 + P235 | Store in a well-ventilated place. Keep cool. |
P410 + P403 | Protect from sunlight. Store in a well-ventilated place. |
P410 + P412 | Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF. |
P411 + P235 | Keep cool. |
Disposal | |
Code | Phrase |
P501 | Dispose of contents/container to ... |
P502 | Refer to manufacturer/supplier for information on recovery/recycling |
Physical hazards | |
Code | Phrase |
H200 | Unstable explosive |
H201 | Explosive; mass explosion hazard |
H202 | Explosive; severe projection hazard |
H203 | Explosive; fire, blast or projection hazard |
H204 | Fire or projection hazard |
H205 | May mass explode in fire |
H220 | Extremely flammable gas |
H221 | Flammable gas |
H222 | Extremely flammable aerosol |
H223 | Flammable aerosol |
H224 | Extremely flammable liquid and vapour |
H225 | Highly flammable liquid and vapour |
H226 | Flammable liquid and vapour |
H227 | Combustible liquid |
H228 | Flammable solid |
H229 | Pressurized container: may burst if heated |
H230 | May react explosively even in the absence of air |
H231 | May react explosively even in the absence of air at elevated pressure and/or temperature |
H240 | Heating may cause an explosion |
H241 | Heating may cause a fire or explosion |
H242 | Heating may cause a fire |
H250 | Catches fire spontaneously if exposed to air |
H251 | Self-heating; may catch fire |
H252 | Self-heating in large quantities; may catch fire |
H260 | In contact with water releases flammable gases which may ignite spontaneously |
H261 | In contact with water releases flammable gas |
H270 | May cause or intensify fire; oxidizer |
H271 | May cause fire or explosion; strong oxidizer |
H272 | May intensify fire; oxidizer |
H280 | Contains gas under pressure; may explode if heated |
H281 | Contains refrigerated gas; may cause cryogenic burns or injury |
H290 | May be corrosive to metals |
Health hazards | |
Code | Phrase |
H300 | Fatal if swallowed |
H301 | Toxic if swallowed |
H302 | Harmful if swallowed |
H303 | May be harmful if swallowed |
H304 | May be fatal if swallowed and enters airways |
H305 | May be harmful if swallowed and enters airways |
H310 | Fatal in contact with skin |
H311 | Toxic in contact with skin |
H312 | Harmful in contact with skin |
H313 | May be harmful in contact with skin |
H314 | Causes severe skin burns and eye damage |
H315 | Causes skin irritation |
H316 | Causes mild skin irritation |
H317 | May cause an allergic skin reaction |
H318 | Causes serious eye damage |
H319 | Causes serious eye irritation |
H320 | Causes eye irritation |
H330 | Fatal if inhaled |
H331 | Toxic if inhaled |
H332 | Harmful if inhaled |
H333 | May be harmful if inhaled |
H334 | May cause allergy or asthma symptoms or breathing difficulties if inhaled |
H335 | May cause respiratory irritation |
H336 | May cause drowsiness or dizziness |
H340 | May cause genetic defects |
H341 | Suspected of causing genetic defects |
H350 | May cause cancer |
H351 | Suspected of causing cancer |
H360 | May damage fertility or the unborn child |
H361 | Suspected of damaging fertility or the unborn child |
H361d | Suspected of damaging the unborn child |
H362 | May cause harm to breast-fed children |
H370 | Causes damage to organs |
H371 | May cause damage to organs |
H372 | Causes damage to organs through prolonged or repeated exposure |
H373 | May cause damage to organs through prolonged or repeated exposure |
Environmental hazards | |
Code | Phrase |
H400 | Very toxic to aquatic life |
H401 | Toxic to aquatic life |
H402 | Harmful to aquatic life |
H410 | Very toxic to aquatic life with long-lasting effects |
H411 | Toxic to aquatic life with long-lasting effects |
H412 | Harmful to aquatic life with long-lasting effects |
H413 | May cause long-lasting harmful effects to aquatic life |
H420 | Harms public health and the environment by destroying ozone in the upper atmosphere |
Sorry,this product has been discontinued.
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