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CAS No. : | 23449-08-3 | MDL No. : | MFCD00194632 |
Formula : | C21H14BrN3 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | AYHGAQGOMUQMTR-UHFFFAOYSA-N |
M.W : | 388.26 | Pubchem ID : | 1728672 |
Synonyms : |
|
Num. heavy atoms : | 25 |
Num. arom. heavy atoms : | 24 |
Fraction Csp3 : | 0.0 |
Num. rotatable bonds : | 3 |
Num. H-bond acceptors : | 3.0 |
Num. H-bond donors : | 0.0 |
Molar Refractivity : | 103.83 |
TPSA : | 38.67 Ų |
GI absorption : | High |
BBB permeant : | Yes |
P-gp substrate : | Yes |
CYP1A2 inhibitor : | Yes |
CYP2C19 inhibitor : | Yes |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | Yes |
Log Kp (skin permeation) : | -4.66 cm/s |
Log Po/w (iLOGP) : | 4.12 |
Log Po/w (XLOGP3) : | 5.65 |
Log Po/w (WLOGP) : | 5.64 |
Log Po/w (MLOGP) : | 4.57 |
Log Po/w (SILICOS-IT) : | 5.62 |
Consensus Log Po/w : | 5.12 |
Lipinski : | 1.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 1.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -6.32 |
Solubility : | 0.000186 mg/ml ; 0.00000048 mol/l |
Class : | Poorly soluble |
Log S (Ali) : | -6.23 |
Solubility : | 0.000231 mg/ml ; 0.000000594 mol/l |
Class : | Poorly soluble |
Log S (SILICOS-IT) : | -9.61 |
Solubility : | 0.0000000944 mg/ml ; 0.0000000002 mol/l |
Class : | Poorly soluble |
PAINS : | 0.0 alert |
Brenk : | 0.0 alert |
Leadlikeness : | 2.0 |
Synthetic accessibility : | 2.37 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H302-H315-H319-H335 | Packing Group: | N/A |
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 |
---|---|---|
96% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; water at 80℃; for 12 h; Inert atmosphere | Synthesis Example 32: Synthesis of Intermediate I-32 The compound, 2-chloro-4,6-diphenyl-1,3,5-triazine (50 g, 187 mmol) was dissolved in THF (1 L) under a nitrogen environment, (4-bromophenyl)boronic acid (45 g, 224.12 mmol, Aldrich Corporation), and tetrakis(triphenylphosphine)palladium (2.1 g, 1.87 mmol) were added thereto, and the mixture was stirred. Potassium carbonate saturated in water (64 g, 467 mmol) was added thereto, and the obtained mixture was heated and refluxed at 80° C. for 12 hours. When the reaction was complete, water was added to the reaction solution, and the mixture was extracted with dichloromethane (DCM) and then, filtered after removing moisture with anhydrous MgSO4 and concentrated under a reduced pressure. This obtained residue was separated and purified through flash column chromatography to obtain Compound I-32 (70 g and 96percent). HRMS (70 eV, EI+): m/z calcd for C21H14BrN3: 387.0371. found: 387. Elemental Analysis: C, 65percent; H, 4percent |
60% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In ethanol; water; toluene at 100℃; for 12 h; | 2-chloro-4,6-diphenyl-1,3,5-triazine (20g, 1.0eq), (4- bromophenyl) boronic acid (16.5g, 1.1eq), K2CO3 (20.6g, 2.0eq), Pd (PPh3) 4 (8.6g, 0.1eq) in toluene 400 ml / 100 ml of ethanol / 50 ml H2O for 12 hours in a mixture of 100 It was stirred. And extracted with MC MC: hexane = 1: 3 to the separation column to obtain a white solid compound 72-1. (4.5g, 60percent) |
60% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; water at 80℃; for 53 h; Inert atmosphere | The compound 2-chloro-4,6-diphenyl-1,3,5-triazine (72 g, 268 mmol) was dissolved in THF (tetrahydrofuran)(4-bromophenyl) boronic acid (45 g, 224.12 mmol) andTetrakis (triphenylphosphine) palladium (2.63 g, 2.82 mmol) was added and stirred. Saturated potassuim in waterCarbonitrile (51.6 g, 373.54 mmol), and the mixture was refluxed by heating at 80 for 53 hours. After completion of the reaction,Water was added, and the mixture was extracted with dichloromethane (DCM). Then, water was removed with anhydrous MgSO 4, filtered, and concentrated under reduced pressure. thisThe residue thus obtained was separated and purified by flash column chromatography to obtain Compound I-4 (62 g, 60percent). |
30% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In 1,4-dioxane; water at 60℃; for 18 h; Inert atmosphere | Compound in a nitrogen stream to a flask 1L reaction [259-1] 40g (0.15mol), compound [241-6] 36.1g (0.18mol), potassium carbonateDissolve 41.4g (0.30mol) in 1,4-dioxane and 410mL, 180 mL of purified water and then put the temperature was raised to tetrakis (updated in about 60 Lee thereby phenyl phosphine) palladium added 5.2g (4.5mmol) and stirred under reflux for 18 hours. After completion of the reaction slowly to room temperature and coldSerious filtered and then the reaction solution. The filtered solid is extracted with dichloromethane, and saturated brine. The organic layer was separated, anhydrousDried with magnesium sulfate, filtered and concentrated under reduced pressure. Using the concentrate was purified by column chromatography method, to obtain the intermediate compound to prepare a [259-2] 17g (30percent). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | Stage #1: With antimonypentachloride In dichloromethane at 0 - 60℃; for 1 h; Inert atmosphere Stage #2: at 0℃; Inert atmosphere; UV-irradiation |
11 g (50 mmol) of 4-bromobenzoyl chloride was placed in a 300 mL three-necked flask, the inside of the flask was purged with nitrogen, then 50 mL of dichloromethane and 11 g (1.0 × 102 mmol) of benzonitrile were added and the mixture was stirred at 0 ° C. under a nitrogen stream did.After stirring, 5.8 mL (50 mmol) of antimony chloride was added, gradually returned to room temperature from 0 ° C. and stirred at 60 ° C. for 1 hour. After stirring, the mixture was cooled and 80 mL of dichloromethane was added.The mixture was suction filtered to obtain a solid. The obtained solid was washed with dichloromethane to obtain 15 g of a yellow solid. A 1 L four-necked flask was charged with 600 mL of ammonia water and stirred at 0 ° C.A yellow solid was added little by little to this solution and stirred, and the color of the solid changed from yellow to white.The mixture was suction filtered to obtain a solid. The obtained solid was washed successively with water and methanol. After washing, this solid was transferred to a recovery flask, 200 mL of N, N-dimethylformamide was added, and the mixture was stirred at 153 ° C. After stirring, the mixture was suction filtered. The filtrate was transferred again to a recovery flask, and 100 mL of N, N-dimethylformamide was added and stirred at 153 ° C.After stirring, this mixture was suction filtered again. The precipitated solid from the obtained filtrate and filtrate was placed in a recovery flask and distilled under reduced pressure to reduce N, N-dimethylformamide to about 100 mL. To this mixture was added 500 mL of water, and the mixture was stirred and filtered.The resulting solid was washed with water. This solid was added to 500 mL of methanol, irradiated with ultrasonic waves, and suction filtered to obtain 16 g of a white powdery solid (intermediate A-1; 2-bromophenyl-4,6-diphenyltriazine) , Yield 81percent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | With copper(II) acetate monohydrate; sodium carbonate In toluene at 100℃; for 24 h; | General procedure: A mixture ofaldehyde 1 (6.8 mmol), amidine hydrochloride 2 (2 g,11.4 mmol), Na2CO3 (1.21 g, 11.4 mmol, 1.0 equiv) andCu(OAc)2 (10 molpercent) was stirred in toluene (20 mL) under100 °C in air for 24 h. After completion of the reaction, themixture was cooled to room temperature. The water wasadded to the reaction system and atmospheric distillation untiltoluene was evaporated. The resulting solution was filteredand residue with hot water washed 3 times. The crude productwas purified by column chromatography on silica gel usingpetroleum ether/EtOAc (100:1) as an eluent to give the correspondingproducts 7a-7x. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; water at 70℃; for 5 h; | 2.68 g (10 mmol) of 2-chloro-4,6-diphenyl-1,3,5-triazine(2-chloro-4,6-diphenyl-[1,3,5]-triazine),2.82 g (10.0 mmol) of 4-bromo-phenylboronic acid pinacol ester(4-bromo-phenylboronic acid pinacol ester),0.58 g (0.5 mmol) of Pd(PPh3)4 and 4.14 g (30.0 mmol) ofK2CO3 was dissolved in 60 mL of a mixture of THF and H2O (2:1 by volume) to obtain a solution which was then stirred at 70C for about 5 hours.And then extracted three times with 60 mL of water and 60 mL of diethyl ether.The organic layer was collected and dried over magnesium sulfate to evaporate the solvent.The residue was separated and purified by silica gel column chromatography to obtain 2.56 of Intermediate I-7(yield: 66percent). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
59.2% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In ethanol; water; toluene at 120℃; for 24 h; Inert atmosphere | 3) In a 250ml three-vial bottle,Under nitrogen protection,Add 0.05 mol intermediate S3-1,0.06 mol of dibromobenzene,100ml toluene, stirring and mixing,Add 0.0025mol Pd(PPh3)4,0.06mol potassium carbonate,50 ml of a mixed solution of water and ethanol in a volume ratio of 1:1Stirred to 120°C and refluxed for 24 hours.Sampling point board showing no intermediate S3-1 remaining,The reaction is complete; it is naturally cooled to room temperature, filtered, and the filtrate is separated. The organic phase is taken and vacuum-steamed under reduced pressure to a fraction-free, neutral silica gel column.Intermediate B1 was obtained, HPLC purity 99.3percent, yield 59.2percent; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran for 4 h; Reflux | Tetrahydrophenylphosphine palladium (2.1 g, 1.83 mmol) and potassium carbonate (75.7 g, 549 mmol) were added to a solution of p-bromophenylboronic acid (36.6 g, 183 mmol) and 2-iodo-4,6-diphenyl- 1,3,5-triazine (72.1g, 201mmol) (500mL) was degassed tetrahydrofuran,And the mixture was heated under reflux for 4 hours.The reaction mixture was cooled to room temperature,After which the solvent is removed.The residue was purified by silica gel column chromatography (49.5 g, 70percent of theory). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium carbonate;Pd(PPh3)4; In tetrahydrofuran; water; toluene; | 2,4,6-tris(4-(3-(6-(9-(2-methylpropyl)carbazol-3-yl)-9-(2-methylpropyl)carbazol-3-yl)propyl)phenyl)-1,3,5-triazine (TRZ-3Cz(MP)2). 9-BBN (0.5 M in THF, 3.30 ml, 1.65 mmol) was added dropwise into a solution of 6 (0.21 g, 0.42 mmol) in THF (2 ml) at 0 C. The mixture was stirred at room temperature for 15 minutes and then at 35 C. for 18 hours before transferring into a mixture of <strong>[30363-03-2]2,4,6-tris(4-bromophenyl)-1,3,5-triazine</strong> (0.07 g, 0.13 mmol), Pd(PPh3)4 (0.030 g, 0.026 mmol), Na2CO3 (3.82 g, 36.0 mmol), H2O (18 ml) and toluene (30 ml). The reaction mixture was stirred at 85 C. for 40 hours, cooled to room temperature, and then extracted with chloroform. The organic extracts were combined, washed with water and dried over MgSO4. Upon evaporating off the solvent, the crude product was purified by column chromatography on silica gel with hexane/methylene chloride 3:2 (v/v) as the eluent to yield TRZ-3Cz(MP)2 (0.147 g, 65%) as a pale yellow powder. 1H NMR (400 MHz, CDCl3, 298 K): delta(ppm) 8.69-8.67 (d, 6H), 8.40-8.39 (t, 6H), 8.18-8.16 (d, 3H), 8.01 (s, 3H), 7.82-7.78 (m, 6H), 7.47-7.30 (m, 27H), 4.12-4.09 (m, 12H), 2.92-2.82 (m, 12H), 2.48-2.35 (m, 6H), 2.19-2.11 (m, 6H), 1.03-0.99 (m, 36H). Calc. for C126H123N9: C, 85.82; H, 7.03; N, 7.15. Found: C, 85.43; H, 7.01; N, 7.11. 2-(4-(3-(6-(9-(2-methylpropyl)carbazol-3-yl)-9-(2-methylpropyl)carbazol-3-yl)propyl)phenyl)-4,6-diphenyl-1,3,5-triazine (TRZ-1Cz(MP)2). The procedure for the synthesis of TRZ-3Cz(MP)2 was followed to prepare TRZ-1Cz(MP)2 from 6 and 2-(4-bromophenyl)-4,6-diphenyl-1,3,5-triazine as a yellow powder in a 63% yield. 1H NMR (400 MHz, CDCl3, 298 K): delta(ppm) 8.79-8.76 (m, 4H), 8.71-8.69 (d, 2H), 8.41-8.39 (m, 2H), 8.19-8.17 (d, 1H), 8.02 (s, 1H), 7.81-7.79 (m, 2H), 7.60-7.55 (m, 6), 7.49-7.42 (m, 6H), 7.35-7.33 (m, 2H), 7.25-7.20 (m, 1H), 4.14-4.11 (m, 4H), 2.93-2.82 (m, 4H), 2.44-2.40 (m, 2H), 2.20-2.10 (m, 2H), 1.03-1.01 (m, 12H). Calc. for C56H51N5: C, 84.71; H, 6.47; N, 8.82. Found: C, 84.52; H, 6.39; N, 8.74. Tris(4-(3-(6-(9-(2-methylpropyl)carbazol-3-yl)-9-(2-methylpropyl) carbazol-3-yl)propyl)phenyl)amine (TPA-3Cz(MP)2). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60% | Stage #1: 2-(4-aminophenyl)-4,6-diphenyl-1,3,5-triazine With hydrogen bromide; sodium nitrite In water for 1h; Cooling with ice; Stage #2: With hydrogen bromide; copper(I) bromide In water at 20 - 115℃; | 1.2 (2) Synthesis of 2-(4-bromophenyl)-4,6-diphenyl-1,3,5-triazine (2) Synthesis of 2-(4-bromophenyl)-4,6-diphenyl-1,3,5-triazine A mixed solution of 2-(4-aminophenyl)4,6-diphenyl-1,3,5-triazine (13.7 mmol, 4.45 g) and 20 mL of hydrobromic acid (47%) was cooled to 0 to 5ºC over an ice bath. An aqueous solution containing sodium nitrite (13.7 mmol, 946.8 mg) and 20 mL of water was cooled over an ice bath, and slowly added dropwise to the reaction solution, which was stirred over an ice bath for 1 hour. After adding a mixed solution of copper(I) bromide (8.24 mmol, 1.18 g) and 8 mL of hydrobromic acid (47%) was slowly added dropwise to the cooled reaction solution, which was stirred for several minutes under room temperature. The reaction solution was heated to 115ºC over an oil bath and refluxed overnight. After standing to cool to room temperature, the reaction solution was cooled over an ice bath and neutralized with sodium hydrogencarbonate. Chloroform and a sodium chloride aqueous solution were added thereto, and the organic layer was separated and extracted. The organic layer was dehydrated over anhydrous magnesium sulfate, and the solvent was distilled off. 2-(4-Bromophenyl)-4,6-diphenyl-1,3,5-triazine as the target product was isolated and purified by silica gel chromatography with a mixed solvent of chloroform and hexane (1/4) (yield amount: 3.19 g, yield: 60%). 1H-NMR (CDCl3, 300 MHz) δ = 7.58 (m, 6H), 7.70 (d, 2H), 8.64 (s, 2H), 8.76 (s, 4H) MALDI-MS m/z: 388 |
60% | Stage #1: 2-(4-aminophenyl)-4,6-diphenyl-1,3,5-triazine With hydrogen bromide at 0 - 5℃; for 0.25h; Stage #2: With sodium nitrite In water at 0℃; for 1h; Stage #3: With hydrogen bromide; copper(I) bromide at 20 - 125℃; for 12h; | 2-Chloro-4,6-diphenyl-1,3,5-triazine (5.35 g, 20 mmol),4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenylamine (4.82 g, 22 mmol),Tetrakis(triphenylphosphine)palladium(0) (1.16 g, 1 mmol),One drop of quaternary ammonium chloride 336Phase transfer catalyst,Aqueous potassium carbonate solution (100ml, 2mol / L, oxygen)And toluene (100 ml, deoxygenated) was added to a two-necked flask.Under a nitrogen atmosphere,Protected from light at 65 ° C for 48 h,4-(4,6-diphenyl-1,3,5-triazin-2-yl)aniline 4.6 g (yield: 71%). Then 4-(4,6-diphenyl-1,3,5-triazin-2-yl)aniline (4.45 g, 13.7 mmol),Hydrobromic acid (48%) (20 mL),It was added to a two-necked flask and stirred at 0-5 ° C for 15 min.Take a beaker and add 946.8 mg of sodium nitrite and 20 mL of water.It was cooled to 0 ° C, transferred to a two-necked flask, and stirred for one hour in an ice bath.One hour later, a mixture of cuprous bromide (1) (1.18 g, 8.24 mmol) and hydrobromic acid (48%) (8 mL) was further added to a two-necked flask.After stirring for a few minutes at room temperature, the two-necked flask was transferred to an oil bath and reacted at 125 ° C for 12 h.2-(4-Bromophenyl)-4,6-diphenyl-1,3,5-triazine 3.19 g (yield: 60%) was obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | Stage #1: 10H-phenothiazine; 2-(4-bromobenzenyl)-4,6-diphenyl-1,3,5-triazine With potassium carbonate In toluene at 20℃; for 0.166667h; Inert atmosphere; Stage #2: With tri-tert-butyl phosphine; palladium diacetate In toluene for 24h; Inert atmosphere; Reflux; | 7 Synthesis of Compound 7 Synthesis Example 7 Synthesis of Compound 7 To a two-neck flask having been substituted with nitrogen, 2-(4-bromophenyl)-4,6-diphenyl-1,3,5-triazine (3.0 mmol, 1.17 g), phenothiazine (3.3 mmol, 657.6 mg), potassium carbonate (9.0 mmol, 1.24 g) and 30 mL of toluene were added, and stirred under room temperature for 10 minutes. A mixed solution of palladium(II) acetate (0.09 mmol, 20.2 mg), tri-tert-butylphosphine (0.33 mmol, 66.8 mg) and 30 mL of toluene was added thereto, and the mixture was heated under refluxing for 24 hours. After standing to cool to room temperature, chloroform and a sodium chloride aqueous solution were added thereto, and the organic layer was separated and extracted. The organic layer was dehydrated over anhydrous magnesium sulfate, and the solvent was distilled off. The compound 7 as the target product was isolated and purified by silica gel chromatography with a mixed solvent of chloroform and hexane (1/4) (yield amount: 1.03 g, yield: 68%). 1H-NMR (CDCl3, 300 MHz) δ = 6.72 (d, 2H), 6.95 (t, 2H), 7.02 (t, 2H), 7.19 (d, 2H), 7.46 (d, 2H), 7.56 (m, 6H), 8.77 (d, 4H), 8.86 (d, 2H) MALDI-MS m/z: 506 |
60% | Stage #1: 10H-phenothiazine; 2-(4-bromobenzenyl)-4,6-diphenyl-1,3,5-triazine With potassium carbonate In toluene at 20℃; for 0.166667h; Stage #2: With tri-tert-butyl phosphine; palladium diacetate In toluene at 120℃; for 24h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
56% | Stage #1: 5,10-dihydrophenazine; 2-(4-bromobenzenyl)-4,6-diphenyl-1,3,5-triazine With sodium t-butanolate In toluene at 20℃; for 0.166667h; Inert atmosphere; Stage #2: With tri-tert-butyl phosphine; palladium diacetate In toluene Inert atmosphere; Reflux; | 9 Synthesis of Compound 19 Synthesis Example 9 Synthesis of Compound 19 To a two-neck flask having been substituted with nitrogen, 2-(4-bromophenyl)-4,6-diphenyl-1,3,5-triazine (1.0 mmol, 388.3 mg), 5,10-dihydrophenazine (0.5 mmol, 91.1 mg), sodium tert-butoxide (1.5 mmol, 144.2 mg) and 5 mL of toluene were added, and stirred under room temperature for 10 minutes. A mixed solution of palladium(II) acetate (0.04 mmol, 4.5 mg), tri-tert-butylphosphine (0.11 mmol, 11.2 mg) and 5 mL of toluene was added thereto, and the mixture was heated under refluxing overnight. After standing to cool to room temperature, chloroform and a sodium chloride aqueous solution were added thereto, and the organic layer was separated and extracted. The organic layer was dehydrated over anhydrous magnesium sulfate, and the solvent was distilled off. The compound 19 as the target product was isolated and purified by silica gel chromatography with a mixed solvent of chloroform and hexane (1/4) (yield amount: 446.3 mg, yield: 56%). 1H-NMR (CDCl3, 300 MHz) δ = 7.58 (m, 20H), 8.79 (d, 16H) MALDI-MS m/z: 796 |
3.72 g | With tri-tert-butyl phosphine; palladium diacetate; potassium carbonate In toluene for 24h; Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride In N,N-dimethyl-formamide at 110℃; for 6h; Inert atmosphere; | 4 Preparation of Compound 72-2 Nitrogen compound 72-1 (4.5g, 1.0eq), bis (pinacolato) diboron (bis (pinacolato) diboron) (5.9g, 2.0eq), PdCl2 (dppf) (0.26g, 0.03eq), DMF 50 ml mixture of KOAc (3.4g, 3.0eq) was stirred for 6 hours at 110 . reaction Extract the water with MC and MC: hexane = 1: 2 column separation to obtain a white solid compound 72-2. (4.8g, 96%) |
95% | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate In 1,4-dioxane at 108℃; | 1 I-b Take I-a, pinacol diborate (4.9g, 19.3mmol), [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride (565mg, 0.773mmol) ),Potassium acetate (4.55g, 46.358mmol) was dissolved in 100mL of ultra-dry 1,4-dioxane solvent, refluxed overnight at 108°C, filtered through Celite, evaporated under reduced pressure, and purified by column chromatography to obtain a white solid (yield 95%) |
93.1% | With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; potassium acetate In 1,4-dioxane at 100℃; for 7h; Reflux; | Intermediate Synthesis Example 2: Intermediate 4 Synthesis 2-(4-bromophenyl)-4,6-diphenyl-1,3,5-triazine 10.0 g (26.0 mmol), Bis(pinacolato)diboron 13.0 g (52.0 mmol), Pd(dppf)Cl2.CH2Cl2 950 mg(0.647 mmol), potassium acetate (KOAc) 10.2 g (104 mmol), and dioxane 130 mL were input into a one-neck 250 mL flask to obtain a mixture. Then, the mixture was refluxed and stirred at 100° C. for 7 hours. After completion of the reaction, the reaction product was subjected to distillation under reduced pressure to remove the solvent from the reaction product. A thus-resulting solid was dissolved in dichloromethane, and filtered using Celite, and washed with dichloromethane. A thus-resulting product was crystallized using methanol (300 mL), to obtain a solid compound (intermediate 4) 10.5 g (yield: 93.1%). |
87.3% | With tris-(dibenzylideneacetone)dipalladium(0); potassium acetate; tricyclohexylphosphine In 1,4-dioxane for 4h; Inert atmosphere; Reflux; | Synthesis of Intermediate E In a 500 ml three necked round bottom flask, 38.8 g (100 mmol) of 2-(4-bromophenyl)-4,6-diphenyltriazine, 2.7 g (3 mmol) of Pd2(dba)3,2.21 g (6 mmol) tricyclohexylphosphine, 55.9 g (220 mmol) bis(pinacorate)diborane,39.25 g (400 mmol) of potassium acetate was added thereto, replaced with nitrogen.300 ml of 1,4-dioxane was added and stirred for 4 hours while refluxing.After completion of the reaction, the mixture was extracted with Methylene Chloride, the organic layer was dried with MgSO4, purified by column chromatography and crystallized with n-Hexane to give 38 g (87.3.%) As intermediate E. |
86% | With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; potassium acetate In N,N-dimethyl-formamide at 100℃; | 2 Synthesis of Intermediate (C) 5.00 g (12.9 mmol) of 2-(4-bromophenyl)-4,6-diphenyl-1,3,5-triazine, 3.94 g (15.5 mmol) of bis(pinacolato)diboron,527 mg (0.645 mmol) of PdCl2(dppf)·CH2Cl2, and 3.80 g (38.7 mmol) of potassium acetate were added to 100mL of DMF, and then, the mixture was heated at a temperature of 100 °C while stirring. When the reaction stopped, thereaction product was cooled to room temperature and then subjected to silica gel to perform filtering under a reducedpressure, and the filtration solution was concentrated a reduced pressure. The product was refined by performingrecrystallization using ethyl acetate/toluene to obtain 4.81 g (yield of 86%) of Intermediate (C) as a target compound. LC-Mass (calculated: 435.21 g/mol, found: M+1 = 436 g/mol) |
84.5% | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate In 1,4-dioxane at 110℃; for 14h; Inert atmosphere; | 2 Synthesis of 4'-(4,6-diphenyl-l,3,5-triazin-2-yI)-2,3,5,6-tetrafluoro-[l,l'-biphenyl]-4- carbonitrile (G). 2-(4-bromopheny])-4,6-diphenyl-l,3,5-triazine (5 00 g, 12.88 mmol), bis(pinacolato)diboron (3 93 g, 15.46 mmol), [ I, G- bis(diphenylphosphino)ferrocene]palladium(II) dichloride (0.485 g, 0 644 mmol), anhydrous potassium acetate (3.81 g, 38.64 mmol) and 1,4-dioxane (50 mL) were charged into a 3- necked flask, and the resulting solution was stirred at 1 10 °C for 14 h under a nitrogen atmosphere. After cooled to room temperature, the reaction mixture was filtered through a Celite pad rinsing by ethyl acetate, and the resulting filtrate was evaporated in vacuo. The obtained residue was purified by column chromatography on silica gel using 10: 1 (v/v) hexane/ethyl acetate as eluent to afford a beige solid (4.74 g, 84.5%). NMR (500 MHz, CDCb, d): 8.79 (d, J= 8.0 Hz, 4H), 8.76 (d, ./= 8 5 Hz, 2H), 8 01 (d, J = 8.5 Hz, 2H), 7.64 7.57 (m, 6H), 1.40 (s, 12H |
78% | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate In toluene for 10h; Reflux; Inert atmosphere; | 9 Synthesis Example 9: Synthesis of Intermediate L-9 30.0 g (77.27 mmol) of Intermediate E-8, 29.43.g (115.90 mmol) of bis(pinacolato) diboron, 22.75 g (231.80 mmol) ofpotassium acetate, and 3.15 g (3.86 mmol) of Pd(dppf)C12 were added to 300 mE of toluene in a 1000 ml flask, and the mixture was heated and refluxed under a nitrogen flow for 10 hours. The resultant was added to 1500 mE of methanol, and a crystallized solid was filtered, dissolved in dichlorometh60 ane, filtered again with silica gel/Celite, and recrystallizedwith hexane after removing an appropriate amount of the organic solvent to obtain Compound E-9 (26.4 g, 78%).calcd. C27H25BN302: C, 74.49; H, 6.02; B, 2.48; N, 9.65; 0, 7.35; found: C, 74.42; H, 6.12; B, 2.40; N, 9.58; 0, 7.41.Synthesis of Intermediates E-10, E-11, E-12, and E-13 |
78% | With tris-(dibenzylideneacetone)dipalladium(0); potassium acetate; XPhos In toluene at 108℃; for 2h; | 2.1.1 Take product B-1 (10g, 25.7mmol),Add pinacol diborate (7.85g, 30.8mmol),5.03g potassium acetate,0.24g tris(dibenzylideneacetone)dipalladium,0.15g 2-dicyclohexylphosphorus-2’,4’,6’-triisopropylbiphenyl,Toluene 80mL,Warm up to 108 to start the reaction,After 2 hours of reaction,The reaction liquid is washed with water,Toluene column,Recrystallization gave 8.7 g of intermediate B-1 (20.0 mmol, yield 78%). |
76.4% | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate In toluene for 5h; Reflux; | 1-(5) 1-(5) 1-e synthesis In a 500 mL round bottom flask, (14 g, 36 mmol) obtained from Scheme 4, bispinacolato diborone (11 g, 43 mmol), palladium(II) chloride-1,1'-bis (Diphenylphosphino)ferrocene (0.9 g, 1 mmol), potassium acetate (7.1 g, 72 mmol), and 150 mL of toluene were added and refluxed for 5 hours.After the reaction was completed, the solid was filtered, the filtrate was concentrated under reduced pressure, and then column separated to obtain 12 g (yield 76.4%) of the target product. |
73.8% | With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; potassium acetate In 1,4-dioxane at 85℃; for 16h; | 2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-phenyl)-4,6-diphenyl-[1,3,5]-triazine (9) Compound 8 (582.4 mg, 1.5 mmol), bis(pinacolato)diboron (B2pin2) (398.7 mg, 1.57 mmol), anhydrous potassium acetate (KOAc) (402.3 mg, 4.1 mmol), Pd(dppf)Cl2·CH2Cl2 (30 mg, 0.04 mmol) was heated in degassed dioxane (15 mL) at 85 °C for 16 h. The organic phase was extracted with diethyl ether, washed with distilled water and dried over MgSO4. After purification by flash chromatography with hexane: dichloromethane = 4:1 as the eluent, compound 9 was obtained (482 mg, 73.8%). |
68% | With palladium bis[bis(diphenylphosphino)ferrocene] dichloride; potassium acetate In N,N-dimethyl-formamide at 90℃; for 12h; Inert atmosphere; | 3 Synthesis of Intermediate 47-1 The compound 2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine (2 g, 5.1 mmol) was added to the flask,Boronic acid(1.5 g, 6.18 mmol), potassium acetate (15.4 mmol), Pd (dppf) 2Cl2 (100 mg), 40 mlN, N-dimethylformamide, heated to 90 ° C under nitrogen for 12 hours, cooled, poured into water, extracted with dichloromethane, washed with anhydrous sulfurThe sodium acetate was dried and concentrated, and the crude product was purified by silica gel column to give 1.5 g of a white solid in 68% yield. |
66% | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate In 1,4-dioxane Reflux; | 1.6 6) Preparation of intermediate compound A-6 A 1 L round-bottom flask was charged with 2- (4-bromophenyl)-4,6-diphenyl-1,3,5-triazine [2- (4-bromophenyl)-triazine] 30 g (77.3 mmol, 1 eq) Bis(pinacolato)diboron 29.4 g (115.95 mmol, 1.5 eq) of2.8 g (3.9 mmol, 0.05 eq) of Pd (dppf) Cl2,Add 15.2 g (154.6 mmol, 2 eq) of potassium acetate (KOAc)350 mL of 1,4-dioxane was added, and the mixture was stirred under refluxAfter completion of the reaction, the mixture was extracted with MC / H2O and the MC layer was dried with MgSO4. The silica-gel column was purified to obtain 20.2 g of intermediate compound A-6 in a yield of 66%. |
64% | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate In 1,4-dioxane at 90℃; for 72h; Reflux; Inert atmosphere; | |
53% | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate In N,N-dimethyl-formamide for 16h; Reflux; | |
With potassium acetate In N,N-dimethyl-formamide | ||
With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; potassium acetate In toluene for 16h; Reflux; | 1 Preparation of Compound 1 The obtained compound 1-9 (7.74 g, 20 mmol),bis(pinacolato)diboron(6.22 g, 24 mmol),1,1'-bis(diphenylphosphino)-ferrocene-palladium(II) chloride dichloride complex (0.49 g, 0.6 mmol),Potassium acetate (5.90 g, 60 mmol) and 79 ml of toluene were reacted under reflux for 16 hours.After cooling, add 26 ml of water, stir for 30 minutes, and separate the organic phase.Filtration through a short bed of diatomaceous earth, followed by evaporation of the organic solvent,The obtained crude product was recrystallized from heptane / toluene; under argon atmosphere,The obtained solid 1-10 (6.53 g, 15 mmol), Compound 1-6 (3.96 g, 14.3 mmol),Tetrakis(triphenylphosphine)palladium (0.35 g, 0.3 mmol), toluene (43 ml),Aqueous sodium carbonate (2M, 21 ml) was added to the flask and refluxed for 8 hours.After cooling to room temperature, it was extracted with toluene, and the organic phase was washed with brine.After drying the organic phase, it is purified by column chromatography.The compound 1 8.58g was obtained.The yield was 78%. | |
With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; potassium acetate In toluene for 16h; Reflux; | 1 Preparation of Compound 1 The resulting bromide 1-3 (7.74 g, 20 mmol),Bornazolium diborate (6.22 g, 24 mmol),1,1'-bis(diphenylphosphino)-ferrocene-palladium(II) dichloride dichloromethane complex (0.49 g, 0.6 mmol), potassium acetate (5.90 g, 60 mmol) and 79 ml of toluene The reaction was carried out under reflux for 16 hours.After cooling, add 26 ml of water, stir for 30 minutes, and separate the organic phase.Filtration through a short bed of diatomaceous earth, followed by evaporation of the organic solvent,The obtained crude product was recrystallized from heptane / toluene; under argon atmosphere,The obtained solid 1-4 (10.22 g, 15 mmol), compound 1-5 (4.23 g, 14.3 mmol), tetrakis(triphenylphosphine)palladium (0.35 g, 0.3 mmol),Toluene (43 ml), aqueous sodium carbonate (2M, 21 ml) was added to the flask.The reaction was refluxed for 8 hours, cooled to room temperature and extracted with toluene.The organic phase is washed with saturated brine and the organic phase is dried.Purification by column chromatography gave Compound 1. 5.The yield was 75%. | |
With potassium acetate; bis(dibenzylideneacetone)-palladium(0); tricyclohexylphosphine In 1,4-dioxane for 12h; Reflux; | 1 Synthesis Example 1: Preparation of Compound TM1 Compound E1 (41.4 g, 106.6 mmol), pinacol diborate (29.8 g, 117.3 mmol), KOAc (31.4 g, 319.8 mmol), Pd(dba) 2 (1.7 g, 3 mmol) were sequentially added to the reaction flask. PCy3 (1.7 g, 6 mmol) and dioxane (500 ml) were stirred under reflux for 12 hours. After completion of the reaction, the mixture was cooled to EtOAc. | |
With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; potassium acetate In toluene for 16h; Reflux; | 1 Preparation of Compound 1 The resulting bromide 1-3 (7.74 g, 20 mmol), boranoic acid pinacol ester (6.22g, 24mmol), 1,1'-bis(diphenylphosphino)-ferrocene-palladium dichloride (II) Dichloromethane complex (0.49 g, 0.6 mmol), potassium acetate (5.90 g, 60 mmol) And 79 ml of toluene were reacted under reflux for 16 hours, cooled, added with 26 ml of water, stirred for 30 minutes, the organic phase was separated, filtered through a short bed of celite, and then the organic solvent was evaporated. The obtained crude product was recrystallized from heptane / toluene; the obtained solid 1-4 (10.22 g, 15 mmol), compound 1-5 (4.48 g, 14.3 mmol), tetrakis(triphenylphosphine)palladium (0.35) g, 0.3 mmol), toluene (43 ml), aqueous sodium carbonate (2M, 21 ml) was added to the flask. The reaction was refluxed for 8 hours, cooled to room temperature and extracted with toluene. The organic phase is washed with saturated brine, and the organic phase is dried and purified by column chromatography. Compound 1. 9.18 g was obtained in 75% yield. | |
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate In 1,4-dioxane at 100℃; for 12h; | 2; 3; 4; 6 Add 100mmol of 2-(4-bromophenyl)-4,6-diphenyltriazine, 110mmol of pinacol diborate, 29.4g of potassium acetate (300mmol), and 800ml of dioxane into the reaction flask, And add 1mol% Pd(dppf)Cl2. React at 100°C for 12h. After the completion of the reaction, the reaction was stopped, and the reactant was cooled to room temperature, water was added, the organic phase was separated, and concentrated to obtain a white solid, filtered and washed with water, and the obtained solid was recrystallized and purified with toluene to obtain a white powder M2. Wherein, the added amount of Pd(dppf)Cl2 is 1 mol% of 2-(4-bromophenyl)-4,6-diphenyltriazine. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | Stage #1: 2-(4-bromobenzenyl)-4,6-diphenyl-1,3,5-triazine With n-butyllithium In tetrahydrofuran at -78℃; for 1h; Inert atmosphere; Stage #2: With iodine In tetrahydrofuran at 20℃; for 1h; Inert atmosphere; | 4.5 (5) Synthesis of Compound Represented by Formula 4-e 23.2 g (59.8 mmol) of the compound represented by the formula 4-d obtained from the above Reaction Scheme 21 was dissolved in 230 ml of tetrahydrofuran in a nitrogen stream, and then 45 ml of 1.6 M normal-butyl lithium 71.76 mmol) is slowly added dropwise, and the mixture is stirred for 1 hour while maintaining the temperature at -78 ° C. Thereafter, 18.2 g (71.76 mmol) of iodine was slowly added dropwise thereto, and the mixture was stirred at room temperature for 1 hour. When the reaction is completed, 200 ml of sodium thiosulfate aqueous solution is added dropwise and stirred for 30 minutes. The mixture was extracted with ethyl acetate and water, and the organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure to obtain 23.2 g of a compound represented by the formula 4-e. (Yield: 89%) |
70.6% | With copper(l) iodide; ethylenediamine; sodium iodide In 1,4-dioxane at 110℃; for 24h; Schlenk technique; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
64% | With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate In toluene for 6h; Inert atmosphere; | (Synthesis of Intermediate 1) General procedure: 4-(9-phenyl-9H-carbazol-3-yl)aniline (3.0 g, 8.97 mmol), 4-iodobiphenyl (2.51 g, 8.97 mmol), and sodium-t-butoxide (1.2 g, 13.5 mmol) were added into a reaction container on which a nitrogen substitution process was performed, and toluene (600 mL) was added as a solvent into the reaction container. Next, a tris(tert-butylphosphine)toluene solution (P(t-Bu)3tol.sol) (0.26 g, 0.27 mmol) and tris(dibenzylideneacetone)dipalladium(0) (Pd2(dba)3) (0.25 g, 0.45 mmol) were added, an inside of the container was substituted with nitrogen, and a solution in the container was stirred for six hours. The reaction solution was diluted with toluene (100 mL). The diluted reaction solution was filtered using Celite, and then, the filtered reaction solution was cleaned using a saturated saline solution to obtain an organic layer. The obtained organic layer was dried using anhydrous magnesium sulfate and then was filtered. A filtrate was concentrated by a rotary evaporator. An obtained crude product was refined by a silica gel chromatography, and an obtained solid was recrystallized to form 2.9 g of Intermediate 1. A yield of the obtained Intermediate 1 was 67%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With tri-tert-butyl phosphine; palladium diacetate; sodium t-butanolate; at 110℃; for 24h;Inert atmosphere; Darkness; | 9,9-Dimethyl-9,10-dihydroacridine(2.8 mmol), 2-(4-bromophenyl)-4,6-diphenylwas added to a 250 mL three-necked flask under a nitrogen atmosphere.-1,3,5-triazine 1.1 g (2.8 mmol), 0.90 g of sodium t-butoxide,59.8 mg of palladium acetate, tri-tert-butylphosphine, heated to 110 C, and stirred for 24 hours in the dark.After completion of the reaction, the solvent in thereactionsystem was suspended, extracted three times with dichloromethane and water to give an organic phase.Dichloromethane was distilled off under reduced pressure, and purified by silica gel columnto yield 1.30 g of product of formula P20. |
90% | With tri-tert-butyl phosphine; palladium diacetate; sodium t-butanolate; In toluene; at 110℃; for 24h;Inert atmosphere; | Under a nitrogen atmosphere,Add <strong>[6267-02-3]9,9-dimethyl-9,10-dihydroacridine</strong> to a 250 ml three-necked flask(2.8mmol),2-(4-bromophenyl)-4,6-diphenyl-1,3,5-triazine 1.1 g (2.8 mmol), 0.90 g of sodium t-butylate,Add 59.8 mg of palladium acetate,Tri-tert-butylphosphine,Heated to 110 C,The reaction was stirred for 24 hours in the dark.After the reaction,The solvent in the reaction system is suspended,Extract three times with dichloromethane and water.Take the organic phase.Distilling off the dichloromethane under reduced pressure,Purified on silica gel column,The product of the formula P20 was obtained in 1.30 g, yield 90%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; water at 80℃; for 12h; Inert atmosphere; | 32 Synthesis Example 32: Synthesis of Intermediate I-32 Synthesis Example 32: Synthesis of Intermediate I-32 The compound, 2-chloro-4,6-diphenyl-1,3,5-triazine (50 g, 187 mmol) was dissolved in THF (1 L) under a nitrogen environment, (4-bromophenyl)boronic acid (45 g, 224.12 mmol, Aldrich Corporation), and tetrakis(triphenylphosphine)palladium (2.1 g, 1.87 mmol) were added thereto, and the mixture was stirred. Potassium carbonate saturated in water (64 g, 467 mmol) was added thereto, and the obtained mixture was heated and refluxed at 80° C. for 12 hours. When the reaction was complete, water was added to the reaction solution, and the mixture was extracted with dichloromethane (DCM) and then, filtered after removing moisture with anhydrous MgSO4 and concentrated under a reduced pressure. This obtained residue was separated and purified through flash column chromatography to obtain Compound I-32 (70 g and 96%). HRMS (70 eV, EI+): m/z calcd for C21H14BrN3: 387.0371. found: 387. Elemental Analysis: C, 65%; H, 4% |
96.5% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; water; toluene for 12h; Reflux; | 1-(4) 1-(4) 1-d synthesis In a 500 mL round bottom flask obtained from Scheme 3 (10 g, 37 mmol), bromophenylboronic acid (7.5 g, 37 mmol), potassium carbonate (10.33 g, 75 mmol), tetrakistriphenyl Phosphine palladium (0.86 g, 1 mmol), 60 mL of water, 100 mL of toluene, and 100 mL of tetrahydrofuran were added and refluxed for 12 hours.When the reaction was completed, the mixture was cooled to room temperature, and crystals were precipitated using methanol and filtered to obtain 14 g (yield 96.5%) of the target product. |
82% | With tetrakis(triphenylphosphine) palladium(0); tetrabutyl-ammonium chloride; potassium carbonate In ethanol; water; toluene at 78℃; for 10h; Inert atmosphere; | Synthesis of compound 3 2-Chloro-4,6-diphenyl-1,3,5-triazine (10.00 g, 37.35 mmol), p-bromophenylboronic acid (7.50 g, 37.35 mmol), tetrakis (triphenylphosphine) palladium ( 2.15g, 1.87mmol), potassium carbonate (10.32g, 74.70mmol), tetrabutylammonium chloride (0.43g, 1.86mmol), toluene (80mL), ethanol (40mL) and deionized water (20mL) were added to the round bottom In the flask, the temperature was increased to 78 ° C under nitrogen protection, and the mixture was stirred for 10 hours. The reaction solution was cooled to room temperature, and toluene (300 mL) was added for extraction. The organic phases were combined, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure. The crude product was purified by silica gel column chromatography using n-heptane as a mobile phase, and then purified by recrystallization using a dichloromethane / ethyl acetate system to obtain a white solid intermediate ID-1 (11.89 g, yield 82%). |
80% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In 1,4-dioxane; water; toluene at 100℃; for 12h; | 4.4 (4) Synthesis of Compound Represented by Formula 4-d 20.0 g (74.7 mmol) of chlorodiphenyltriazine, 18.0 g (89.7 mmol) of 4-bromophenylboronic acid,1.7 g (1.5 mmol) of tetrakis (triphenylphosphine) palladium, 20.7 g (149.4 mmol) of potassium carbonate, 100 ml of 1,4-dioxane, 100 ml of toluene and 50 ml of distilled water were added and stirred at 100 ° C for 12 hours . When the reaction is complete, extract using ethyl acetate and distilled water. The organic layer was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and recrystallized from methylene chloride and acetone to obtain 23.2 g of a compound represented by the formula (4-d). (Yield: 80%) |
80% | With tetrakis(triphenylphosphine) palladium(0); tetrabutyl-ammonium chloride; potassium carbonate In ethanol; water; toluene at 78℃; for 8h; Inert atmosphere; | 1 Step 1): SM1 (30g, 112.05mmol), SM2 (22.50g, 112.05mmol), tetrakis(triphenylphosphine)palladium (6.47g, 5.60mmol), potassium carbonate (46.39g, 336.7mmol), tetrabutylammonium chloride (1.56g, 5.60mmol), toluene (240mL), ethanol (120mL) and deionized water (60mL) were added to the three-necked flask, raise the temperature to 78 °C under nitrogen protection and stir for 8 hours; the reaction solution was cooled to room temperature, and toluene (150 mL) was added for extraction, combine the organic phase, dry the organic phase with anhydrous magnesium sulfate, and filter to obtain the filtrate, the filtrate was concentrated under reduced pressure to obtain crude product; The obtained crude product was purified by silica gel column chromatography using n-heptane as the mobile phase. After that, recrystallize and purify with dichloromethane/ethyl acetate system (1:3), intermediate-11 (34.8 g, 80% yield) was obtained. |
80% | With tetrakis(triphenylphosphine) palladium(0); tetrabutyl-ammonium chloride; potassium carbonate In ethanol; water; toluene at 78℃; for 8h; Inert atmosphere; | Combine SM1 (30g, 112.05mmol), SM2 (22.50g, 112.05mmol), tetrakis(triphenylphosphine) palladium (6.47g, 5.60mmol), potassium carbonate (46.39g, 336.7mmol), tetrabutylammonium chloride (1.56g, 5.60mmol), toluene (240mL), ethanol (120mL) and deionized water (60mL) were added to a three-necked flask, heated to 78°C under nitrogen protection, and stirred for 8 hours; the reaction solution was cooled to room temperature and toluene was added (150mL) was extracted, the organic phases were combined, the organic phase was dried with anhydrous magnesium sulfate, filtered to obtain the filtrate, and the filtrate was concentrated under reduced pressure to obtain the crude product; the crude product was purified by silica gel column chromatography using n-heptane as the mobile phase, and then purified with two The chloromethane/ethyl acetate system (1:3) was recrystallized and purified to obtain Intermediate-2-1 (34.8 g, yield 80%). |
75.4% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; water at 80℃; for 10h; Inert atmosphere; | (3) In a 250 ml three-neck bottle in, inject the nitrogen, adding 0.04 µM intermediate Y, 150 ml of THF, 0.05 µM bromophenylacetic boric acid, 0.0004 µM (triphenylphosphine) palladium four, stirring, then adding 0.06 µM K of the2CO3Aqueous solution (2 M), heating to 80 °C, reflux reaction for 10 hours, sampling [...], the reaction is complete. Natural cooling, for 200 ml dichloromethane extraction, layered, extraction solution dried with anhydrous sodium sulfate, filtered, filtrate and steaming and, over silica gel column purification, to obtain the intermediate A1, HPLC purity 99.5%, yield 75.4%. |
69% | Stage #1: 2-chloro-4,6-diphenyl-1,3,5-triazine; 4-Bromophenylboronic acid With tetrakis(triphenylphosphine) palladium(0) In tetrahydrofuran for 0.5h; Inert atmosphere; Stage #2: With potassium carbonate In tetrahydrofuran; water at 80℃; Inert atmosphere; | |
60% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In ethanol; water; toluene at 100℃; for 12h; | 4 Preparation of Compound 72-1 2-chloro-4,6-diphenyl-1,3,5-triazine (20g, 1.0eq), (4- bromophenyl) boronic acid (16.5g, 1.1eq), K2CO3 (20.6g, 2.0eq), Pd (PPh3) 4 (8.6g, 0.1eq) in toluene 400 ml / 100 ml of ethanol / 50 ml H2O for 12 hours in a mixture of 100 It was stirred. And extracted with MC MC: hexane = 1: 3 to the separation column to obtain a white solid compound 72-1. (4.5g, 60%) |
60% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; water at 80℃; for 53h; Inert atmosphere; | 4 Synthesis of Intermediate I-4 The compound 2-chloro-4,6-diphenyl-1,3,5-triazine (72 g, 268 mmol) was dissolved in THF (tetrahydrofuran)(4-bromophenyl) boronic acid (45 g, 224.12 mmol) andTetrakis (triphenylphosphine) palladium (2.63 g, 2.82 mmol) was added and stirred. Saturated potassuim in waterCarbonitrile (51.6 g, 373.54 mmol), and the mixture was refluxed by heating at 80 for 53 hours. After completion of the reaction,Water was added, and the mixture was extracted with dichloromethane (DCM). Then, water was removed with anhydrous MgSO 4, filtered, and concentrated under reduced pressure. thisThe residue thus obtained was separated and purified by flash column chromatography to obtain Compound I-4 (62 g, 60%). |
51% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran for 3h; Reflux; | Synthesis of Intermediate 1-5 2-chloro-4,6-diphenyl-1 ,3,5-triazine (5 g, 18.6mmol) and (4-bromophenyl)boronic acid (4.88 g, 24.3mmol) were added to tetrahydroffiran (80 ml), and 2 Mpotassium carbonate (40 ml) was added thereto. Subsequently, tetrakis(triphenylphosphine)palladium (0) (0.65 g,0.6 mmol) was added thereto, and the obtained mixture was heated up, refluxed and stirred for 3 hours, and cooled down to room temperature. Subsequently, a precipitate therein was filtered. The filtered precipitate was washed by using dichloromethane and hexane and then, purified through sublimation to obtain Intermediate 1-5 (3.7 g). A yield was 51%. |
30% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In 1,4-dioxane; water at 60℃; for 18h; Inert atmosphere; | Preparation of intermediate compound [259-2] Compound in a nitrogen stream to a flask 1L reaction [259-1] 40g (0.15mol), compound [241-6] 36.1g (0.18mol), potassium carbonateDissolve 41.4g (0.30mol) in 1,4-dioxane and 410mL, 180 mL of purified water and then put the temperature was raised to tetrakis (updated in about 60 Lee thereby phenyl phosphine) palladium added 5.2g (4.5mmol) and stirred under reflux for 18 hours. After completion of the reaction slowly to room temperature and coldSerious filtered and then the reaction solution. The filtered solid is extracted with dichloromethane, and saturated brine. The organic layer was separated, anhydrousDried with magnesium sulfate, filtered and concentrated under reduced pressure. Using the concentrate was purified by column chromatography method, to obtain the intermediate compound to prepare a [259-2] 17g (30%). |
30% | With tetrakis(triphenylphosphine) palladium(0); tetrabutylammomium bromide; potassium carbonate In ethanol; water; toluene at 40℃; for 5h; Inert atmosphere; Reflux; | 1 1. Synthesis of Intermediate A-1 Add 2-chloro-4,6-diphenyl-1,3,5-triazine (18.73g, 70mmol) and 4-bromophenylboronic acid (14.00g, 70mmol) to a 500mL three-necked flask with nitrogen protection and reflux device. ), potassium carbonate (30.69g, 140mmol), tetrabutylammonium bromide (4.5g, 14mmol), 120mL of toluene, 30mL of ethanol and 30mL of ultrapure water, protected by nitrogen, turn on the heating and stir, and wait until the temperature rises to 40 At the time, tetrakistriphenylphosphine palladium (0.45g, 0.4mmol) was added and the temperature was raised to reflux for 5h. After the reaction was completed, the reaction solution was cooled to room temperature, extracted with 200mL of toluene, washed with 400mL of ultrapure water, and washed with anhydrous The sodium sulfate was dried, and then concentrated until no more liquid flowed out. The product was purified through a column. The eluent was petroleum ether and ethyl acetate (4:1, volume ratio) to obtain Intermediate A-1 (8.15g, Yield 30%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | Stage #1: benzonitrile; 4-chlorobenzoyl chloride With antimonypentachloride In dichloromethane Inert atmosphere; Stage #2: With ammonium hydroxide In dichloromethane Inert atmosphere; | |
81% | Stage #1: benzonitrile; 4-chlorobenzoyl chloride With antimonypentachloride In dichloromethane at 0 - 60℃; for 1h; Inert atmosphere; Stage #2: With ammonium hydroxide at 0℃; Inert atmosphere; UV-irradiation; | 1-1 Synthesis of Intermediate A-1 11 g (50 mmol) of 4-bromobenzoyl chloride was placed in a 300 mL three-necked flask, the inside of the flask was purged with nitrogen, then 50 mL of dichloromethane and 11 g (1.0 × 102 mmol) of benzonitrile were added and the mixture was stirred at 0 ° C. under a nitrogen stream did.After stirring, 5.8 mL (50 mmol) of antimony chloride was added, gradually returned to room temperature from 0 ° C. and stirred at 60 ° C. for 1 hour. After stirring, the mixture was cooled and 80 mL of dichloromethane was added.The mixture was suction filtered to obtain a solid. The obtained solid was washed with dichloromethane to obtain 15 g of a yellow solid. A 1 L four-necked flask was charged with 600 mL of ammonia water and stirred at 0 ° C.A yellow solid was added little by little to this solution and stirred, and the color of the solid changed from yellow to white.The mixture was suction filtered to obtain a solid. The obtained solid was washed successively with water and methanol. After washing, this solid was transferred to a recovery flask, 200 mL of N, N-dimethylformamide was added, and the mixture was stirred at 153 ° C. After stirring, the mixture was suction filtered. The filtrate was transferred again to a recovery flask, and 100 mL of N, N-dimethylformamide was added and stirred at 153 ° C.After stirring, this mixture was suction filtered again. The precipitated solid from the obtained filtrate and filtrate was placed in a recovery flask and distilled under reduced pressure to reduce N, N-dimethylformamide to about 100 mL. To this mixture was added 500 mL of water, and the mixture was stirred and filtered.The resulting solid was washed with water. This solid was added to 500 mL of methanol, irradiated with ultrasonic waves, and suction filtered to obtain 16 g of a white powdery solid (intermediate A-1; 2-bromophenyl-4,6-diphenyltriazine) , Yield 81%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; water; toluene at 80℃; for 24h; Inert atmosphere; | 19 Example 19 P 18 synthetic: under the protection of the argon, will 3-bromo -10, 10-dioxide-oxaneones (10mmol, 3 . 88g), M 14 (25mmol, 10 . 28g), potassium carbonate (2.0MinH 2 O, 10 ml, 20mmol), Pd (PPh 3) 4 (0.4mmol, 461mg), THF (50 ml), toluene (100 ml) in 250 ml three-mouth bottle, 80 °C reaction under 24h. After the reaction, water washing after methylene chloride extraction, column separation to obtain the white solid 5.21g, yield 88%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | With tri-tert-butyl phosphine; palladium diacetate; sodium t-butanolate; In toluene; at 110℃; for 24h;Inert atmosphere; Reflux; | M 10 synthetic: under the protection of the argon, the 2-(4-bromophenyl)-4, 6 diphenyl -1, 3, 5 triazine (10mmol, 3 . 88g), M 1 (20mmol, 3 . 02g) input 250 ml in the reaction bottle of the three-port, by adding 100 ml of toluene to dissolve them. After dissolving, butyl sodium alcoholate joins uncle sequentially (4.8g, 50mmol), three extra butyl phosphine (0.5 ml, 1M/L) and palladium acetate (112 mg, 0 . 5mmol), system is greenish black. After finishing the feeding, heating to 110 C, reflux, reaction 24h. After the reaction, water washing after methylene chloride extraction, column separation to obtain the yellow solid 3.63g, yield 84%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With tris-(dibenzylideneacetone)dipalladium(0); triphenylphosphine; sodium t-butanolate; In tetrahydrofuran; toluene;Reflux; | triphenylen-2-ylboronic acid (5.4g, 20mmol) was dissolved in a THF 2-(4-bromophenyl)-4,6-diphenyl-1,3,5-triazine (7.8g, 20mmol), Pd2(dba)3 (0.9g, 1mmol), PPh3 (0.5g, 2mmol), followed by the addition of NaOt-Bu (5.8g, 60mmol), toluene (210 mL), stirred and refluxed. When the reaction is complete, the organic layer was dried over MgSO4, and extracted with water and ether and recrystallized silicagel column and the resulting organic compound and then concentrated and compound 5-6 was obtained 7.5g (70% yield). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
42.9% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In toluene at 80 - 90℃; for 24h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; water at 80℃; for 20h; Inert atmosphere; | 4 Synthesis of Compound 30 The compound 1-3 (20 g, 39.6 mmol) was dissolved in 0.2 L of tetrahydrofuran (THF) in a nitrogen atmosphere, and then I-4 (15.3G, 39.6 mmol) and tetrakis (triphenylphosphine) palladium (0.45 g, 0.39 mmol) were added and stirred. Saturated with waterPotassuim carbonate (9.7 g, 99 mmol) was added, and the mixture was refluxed by heating at 80 DEG C for 20 hours. After completing the reaction,Water was added to the solution, extracted with dichloromethane (DCM), and then dehydrated with anhydrous MgSO 4, filtered, concentrated under reduced pressureRespectively. The residue thus obtained was separated and purified by flash column chromatography to obtain the compound 30 (24 g, 87%) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; at 90℃; for 1h; | 4-bromo-triazine (20g, 51.5mmol) and 3,5-phenylboronic acid(9.8g, 51.5mmol) and potassium carbonate (K2CO3) (21.3g, 155mmol) intetrahydrofuran (THF) (300mL) , dissolved in H2O (100ml) and it was heated to 90°C. And tetrakis (triphenylphosphine) palladium (Pd (PPh3) 4) (1.2 g,1.03 mmol) was added and refluxed for 1 hour. After cooling to room temperature, the water layer was removed. Magnesium sulfate (MgSO4) was added to the organic layer and then filtered. And after Concentrated ,purified by column chromatography to obtain the compound of formula 1A (21 g, yield 90percent). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | With palladium diacetate; sodium t-butanolate; XPhos In 1,4-dioxane at 80℃; for 16h; Inert atmosphere; | 1 In a 20-mL glass tube equipped with a screw cap, were placed CP-Cz (0.11 g), 2- parabromophenyl-4, 6-diphenyl- 1,3,5 -triazine (Trz-Ph-Br, 0.12 g), NaOtBu (0.065 g), Pd(OAc)2 (0.014 g), and XPhos (0.037 g). The tube was then capped and evacuate/refill with argon three times. 0.6 mL of anhydrous 1,4-dioxane was filled in under argon. The mixture was stirred at 80 °C for 16 h. For work-up, the mixture was diluted with DCM and filtered through silica gel. After removing the volatiles, flash chromatography (gradient 0 to 30% DCM in hexanes) was used to purify the product. Yield: 0.23 g, 72%. |
49% | With palladium diacetate; sodium t-butanolate; XPhos In 1,4-dioxane at 80℃; Schlenk technique; | 7 In a 10 mL Schlenk tube,89.1 mg of Compound 1 was dissolved in 0.5 mL of 1,4-dioxane.Add 97.2 mg Trz-PhBr, 11.3 mg in sequencePd(OAc)2, 30.0mg XPhos and52.7 mg NaOt-Bu, stirred at 80 ° C overnight,The obtained material is subjected to column chromatography separation,Obtained a white solid,The yield was 49%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; for 12.0h;Reflux; Inert atmosphere; | Reagent 1 (100.0 g, 257.55 mmol) and Reagent 2 (58.5 g, 206.43 mmol) were put into 1,000 ml of tetrahydrofuran under a nitrogen atmosphere, and the resulting mixture was stirred and refluxed. Thereafter, potassium carbonate (71.2 g, 515.11 mmol) was dissolved in 200 ml of water, the resulting solution was introduced into the mixture, the resulting mixture was sufficiently stirred, and then tetrakistriphenyl-phosphinopalladium (8.9 g, 7.73 mmol) was introduced thereinto. After the reaction for 12 hours, the temperature of the product was lowered to normal temperature and a produced solid was filtered. After the filtration, the solid was washed with 100 ml of tetrahydrofuran, 500 ml of ethyl acetate, 500 ml of water, and 300 ml of ethanol. The resulting product was dried to prepare Compound 1A (112.6 g, 88%). Reagents 1 and 2 were purchased from Aldrich and TCI, respectively. |
81% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; for 8.0h;Inert atmosphere; Reflux; | In a nitrogen atmosphere2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine (reagent 1-1, 50 g, 129 mmol)(4-chloronaphthalen-1-yl) boronic acid (reagent 1-2, 29.2 g, 142 mmol)Were added to 600 ml of tetrahydrofuran and stirred and refluxed.After this, potassium carbonate (53 g, 386 mmol)Was dissolved in 60 ml of water, and the mixture was sufficiently stirred. Then, tetrakistriphenylphosphinopalladium (4.5 g, 4 mmol) was added thereto.After 8 hours of reaction, the temperature was lowered to room temperature and filtered. The filtrate was extracted with chloroform and water, and then the organic layer was dried with magnesium sulfate.The organic layer was then distilled under reduced pressure and recrystallized using ethyl acetate.The resulting solid was filtered and dried to give Intermediate 1-1 (49 g, 81%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With potassium phosphate; copper(l) iodide; (S,S)-1,2-diaminocyclohexane; In toluene; at 100℃;Inert atmosphere; | Compound 1 (0.60 g, 2.12 mmol), compound 2 (0.9 g, 2.32 mmol),tripotassium phosphate (0.89 g, 4.19 mmol), copper iodide (8 mg,0.04 mmol), and trans-1,2-diaminocyclohexane (0.21 g, 1.48 mmol)were dissolved in distilled toluene (40 mL), and the reaction mixture was refluxed at 100 C in N2 for 12 h. There after, the reaction mixturewas cooled to 25 C and filtered through Celite. It was concentrated under vacuum. The residue was purified by silica gel column chromatography using dichloromethane (DCM)/hexane (1:5 v/v) as the eluent to give a pure compound 3, which was a white-green solid (1.13 g);yield 90%. mp 255.6 C. IR (KBr, cm-1) ν: 2957, 1604, 1516, 1452,1370, 1219, 838, 772, 692. 1H NMR (CDCl3, 500 MHz, ppm): δ9.02-9.01 (2H, d, J=8.5 Hz), 8.82-8.80 (4H, dd, J=8.3, 1.5 Hz), 8.43(1H, s), 8.20-8.19 (1H, d, J=7.6 Hz), 7.85-7.84 (1H, d, J=7.7 Hz),7.83-7.81 (2H, dd, J=6.7, 1.8 Hz), 7.62 (1H, s), 7.61-7.60 (1H, t,J=1.7 Hz), 7.60-7.58 (3H, d, J=7.3 Hz), 7.57-7.56 (1H, t,J=1.7 Hz), 7.54-7.53 (2H, d, J=8.3 Hz), 7.44-7.40 (2H, m),7.38-7.35 (1H, td, J=7.5, 1.1 Hz), 7.34-7.31 (1H, t, J=7.5 Hz),7.29-7.26 (1H, td, J=7.4, 1.1 Hz), 1.53 (6H, s). 13C NMR (CDCl3,125 MHz, ppm): δ 170.91, 153.36, 153.31, 141.71, 140.86, 140.76,139.56, 136.10, 134.94, 132.80, 132.67, 130.70, 129.01, 128.70,127.07, 126.82, 126.40, 125.81, 124.01, 123.32, 122.56, 120.43,120.26, 119.41, 111.41, 109.92, 104.07, 46.81, 27.94; Uv-Vis (CHCl3) λ max/nm (ε/105 mol-1 dm3 cm-1): 362 (0.24); Found: [M+H]+590.2468; molecular formula C42H30N4 requires [M+H]+ 590.2470. |
With potassium tert-butylate; tri tert-butylphosphoniumtetrafluoroborate; In toluene; for 24h;Inert atmosphere; Reflux; | Added to the reaction bottle 0.1 µM intermediate 1, 0.1 µM intermediate 2, 20g tert-butanolate, 5g arrowhead three uncles acetate butyl phosphine tetrafluoroborate salts and toluene (1000 ml), under the protection of nitrogen heating reflux for 24 hours, cooling, removing the toluene, adding dichloromethane, washing, drying, the crude product of column, then methylene chloride and ethanol to recrystallize the purified product, compound 5. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium <i>tert</i>-butylate; tri tert-butylphosphoniumtetrafluoroborate In toluene for 24h; Reflux; | 3 Embodiment 3:The preparation of compound 8, it can be used for the electron transport layer, light emitting layer, a hole transporting layer Added to the reaction bottle 0.1 µM intermediate 1, 0.1 µM intermediate 2, 20g tert-butanolate, 5g arrowhead three uncles acetate butyl phosphine tetrafluoroborate salts and toluene (1000 ml), under the protection of nitrogen heating reflux for 24 hours, cooling, removing the toluene, adding dichloromethane, washing, drying, the crude product of column, then methylene chloride and ethanol to recrystallize the purified product, compound 8. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
77% | With copper(l) iodide; 1,10-Phenanthroline; potassium hydroxide; In 5,5-dimethyl-1,3-cyclohexadiene; for 4.0h;Inert atmosphere; Reflux; | In a nitrogen atmosphereThe compound of formula IA (10 g, 50 mmol) and the compound of formula IB (19 g, 50 mmol)Was added to 250 ml of xylene and potassium hydroxide (5.6 g, 99 mmol), 1,10-phenanthroline (10 g, 19 mmol) was added with stirring.Then, by heating, copper iodide (2.8 g, 15 mmol) was slowly added under reflux. After the reaction was completed for about 4 hours, the reaction was terminated. After completion of the reaction, the temperature was lowered to room temperature, the salt was filtered through a filter, and the organic layer was distilled. Thereafter, the distillate was extracted twice with chloroform and water, and the organic layer was distilled off under reduced pressure Recrystallization with ethanol gave Intermediate 1 (19 g, 77percent). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
63% | With tri-tert-butyl phosphine; palladium diacetate; sodium t-butanolate In toluene for 24h; Reflux; | 1.4 Step 4:Preparation of compound S1, the reaction is as follows: The reaction flask was charged with 10H, 10'H-9,9'-spircridine (1.2 mmol, 0.42 g) and 2- (4-Bromophenyl) -4,6-diphenyl-1,3,5-triazine (2.8 mmol, 1.09 g), 50 ml of toluene as a solvent, 60 mg of palladium acetate,Tri-t-butylphosphine (0.5 mmol, 0.11 g), and 0.48 g of sodium t-butoxide. The reaction was stirred under heating and refluxing for 24 hours, after cooling,The mixture is poured into 200 ml of water and the product is extracted with methylene chloride. The organic phase is dried over anhydrous magnesium sulphate and the solvent is removed after separationThe mixture was purified by silica gel column chromatography to give a yellow solid. After drying under vacuum to obtain high purity product sublimation(0.72 g, yield 63%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With tri-tert-butyl phosphine; palladium diacetate; sodium t-butanolate In toluene at 80℃; for 24h; Inert atmosphere; | |
50% | With palladium diacetate; sodium t-butanolate; tri tert-butylphosphoniumtetrafluoroborate In toluene at 110℃; for 5h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | With copper(II) acetate monohydrate; sodium carbonate In toluene at 100℃; for 24h; | General Procedure for the Preparation 7a-7x General procedure: A mixture ofaldehyde 1 (6.8 mmol), amidine hydrochloride 2 (2 g,11.4 mmol), Na2CO3 (1.21 g, 11.4 mmol, 1.0 equiv) andCu(OAc)2 (10 mol%) was stirred in toluene (20 mL) under100 °C in air for 24 h. After completion of the reaction, themixture was cooled to room temperature. The water wasadded to the reaction system and atmospheric distillation untiltoluene was evaporated. The resulting solution was filteredand residue with hot water washed 3 times. The crude productwas purified by column chromatography on silica gel usingpetroleum ether/EtOAc (100:1) as an eluent to give the correspondingproducts 7a-7x. |
4.5 g | With sodium carbonate; copper(l) chloride at 90 - 100℃; | 1 Synthesis of TM-6: Add 3.7g (20mmol) of m-bromobenzaldehyde to a 100ML dry three-neck round bottom bottle,Benzene hydrochloride 7g (50mmol),Na2CO311g (80mmol),CuCl0.8g (8mmol),Toluene 50mL,Set 90 to react overnight,After the TLC monitoring reaction is complete,Wash three times,Then filter through diatomaceous earth to remove CuCl,After concentrating the organic phase, adding ethanol to form a precipitate to obtain a crude product.The crude product was purified by toluene and ethanol to form a precipitate to obtain 4.5 g of white solid with a purity of 99%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; at 70℃; for 5h; | 2.68 g (10 mmol) of 2-chloro-4,6-diphenyl-1,3,5-triazine(2-chloro-4,6-diphenyl-[1,3,5]-triazine),2.82 g (10.0 mmol) of 4-bromo-phenylboronic acid pinacol ester(4-bromo-phenylboronic acid pinacol ester),0.58 g (0.5 mmol) of Pd(PPh3)4 and 4.14 g (30.0 mmol) ofK2CO3 was dissolved in 60 mL of a mixture of THF and H2O (2:1 by volume) to obtain a solution which was then stirred at 70C for about 5 hours.And then extracted three times with 60 mL of water and 60 mL of diethyl ether.The organic layer was collected and dried over magnesium sulfate to evaporate the solvent.The residue was separated and purified by silica gel column chromatography to obtain 2.56 of Intermediate I-7(yield: 66%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In 1,4-dioxane; water at 120℃; for 3h; | General procedure: To one neck r.b.f was added compound D (9 g, 16.83 mmol), a mixture of Compound E (4.9 g, 18.5 mmol), Tetrakis(triphenylphosphine)palladium(0) (1.94 g, 1.68 mmol), Pottasium carbonate (4.65 g, 33.66 mmol), 1,4-dioxane/water(100ml/25ml) refluxed at 120 °C for 3 hours. Extraction with MC and drying over MgSO4. Column Purification HX:MC=4:1 packing then down to 4:1 top side after removal HX: MC=3:1 to obtain Compound F (9.4 g, 87%). The compounds as shown in Table 6 below were similarly prepared. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; toluene; for 24h;Inert atmosphere; Reflux; | 2-(4-Bromophenyl)-4,6-diphenyl-1,3,5-triazine (2.71 g, 7.0 mmol), <strong>[864377-33-3](3-(9H-carbazol-9-yl)phenyl)boronic acid</strong> (2.01 g, 7.0 mmol), tetrakis(triphenylphosphine)palladium(0) (0.24 g, 0.21 mmol), 2 MNa2CO3 (20 mL), ethanol (3 mL) and toluene (30 mL) weresequentially added to a 100 mL round bottom flask. Themixture was refluxed under nitrogen atmosphere for 24 h.After the reaction completed, the mixture was extracted with50 mL dichloromethane twice. The organic layer was storedand evaporated under reduced pressure. Then, the crudeproduct was isolated by silica gel column chromatographyand further purified by vacuum sublimation. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With 18-crown-6 ether; tri-tert-butyl phosphine; palladium diacetate; potassium carbonate; In 5,5-dimethyl-1,3-cyclohexadiene; toluene; at 120℃; for 21h;Inert atmosphere; | Under an argon stream, 2-(4-bromophenyl)-4,6-diphenyl-1,3,5-triazine (621 mg)<strong>[10537-08-3]2-chlorocarbazole</strong> (339 mg), palladium acetate (7.2 mg), A toluene solution (96 muL) of 1 M tri (tert-butyl) phosphine, potassium carbonate (332 mg), And 18-crown-6-ether (84.6 mg) were suspended in xylene (8.0 mL)Followed by stirring at 120 C. for 21 hours. After allowing the reaction mixture to cool,Water was added. The precipitated solid was washed with water,After washing with methanol, then with hexane,A white powder (yield 729 mg, yield 90%) of the objective 2-chloro-9- [4-(4,6-diphenyltriazin-2-yl)phenyl]carbazole was obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65.8% | With bis(di-tert-butyl(4-dimethylaminophenyl)phosphine)dichloropalladium(II); tetrabutylammomium bromide; sodium fluoride In water; N,N-dimethyl-formamide at 75℃; for 5h; | 1.1 1. Preparation of compound c Compound a (1.0 g, 2.58 mmol) and compound b (675 mg, respectively) were sequentially added to a 100 mL three-necked flask.2.83 mmol), tetrabutylammonium bromide (250 mg, 0.78 mmol), bis(di-tert-butyl-4-dimethylaminophenylphosphine) palladium chloride(20 mg, 0.03 mmol), NaF (270 mg, 6.44 mmol) was added N,N-dimethylformamide (40 mL) and distilled water (8 mL)In the mixed solution, the reaction was carried out at 75 ° C for 5 hours, the reaction was stopped, the reaction solution was cooled to room temperature, and poured into dichloromethane (150 mL) for use.Washed to neutrality, the organic phase was dried over anhydrous magnesium sulfate, filtered, concentrated under reduced pressure and column chromatography0.85 g, the yield was 65.8%. |
65.8% | With dichloro bis((p-dimethylaminophenyl)-ϖ-di-tert-butylphosphine)palladium(II); tetrabutylammomium bromide; sodium fluoride In water; N,N-dimethyl-formamide at 75℃; for 5h; | 5'-(4-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenyl)-[2,2'-bithiophene]-5-carbaldehyde (3). General procedure: In a 100mL 3-necked flask, 2-(4-bromophenyl)-1-phenyl-1H-benzo[d]imidazole (1) (1.0g,2.86 mmol), (5'-formyl-[2,2'-bithiophen]-5-yl)boronic acid(750 mg, 3.15 mmol), tetra-n-butylammonium bromide (TBAB)(277 mg, 0.86 mmol), N,N-dimethylformamide (DMF) (40 mL),Pd(amphos)Cl2 (20 mg, 0.03 mmol), H2O (8 mL), and NaF (300 mg,7.16 mmol) were added in turn. Following this, the reaction mixturewas stirred for 5 h at 75 °C and then poured into dichloromethane (DCM). The organic layer was washed with water and dried overanhydrous MgSO4. After removing the solvent, the crude productobtained was purified by column chromatography (PE/DCM 1/1,v/v; where PE is petroleum ether, boiling range: 60-90 °C) to give ayellow solid (790 mg, 59.6% yield). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | Stage #1: 9‐ethyl‐6,6,8‐trimethyl‐5H,6H,11H‐benzo[b]carbazol‐11‐one; 2-(4-bromobenzenyl)-4,6-diphenyl-1,3,5-triazine With sodium t-butanolate In toluene for 0.5h; Inert atmosphere; Stage #2: With tetrakis(triphenylphosphine) palladium(0) In toluene at 115℃; for 6h; | 5 Example 5 Synthesis of Compound 41: Taking 9-ethyl-6,6,8-trimethyl-5H-benzo[b]carbazole-11(6H)-one (3.03 g, 10.0 mmol),2-(4-bromophenyl)-4,6-diphenyl-1,3,5-triazine (4.26 g, 11.0 mmol),Sodium tert-butoxide (4.93 g, 50.0 mmol) was dissolved in 100 mL of toluene.Under nitrogen for 0.5 h, tetrakis(triphenylphosphine)palladium (1.16 g, 1.0 mmol) was added.The temperature was raised to 115 ° C, and the reaction was kept for 6 hours.After the completion of the reaction, the mixture was cooled to room temperature, poured into 100 g of a saturated aqueous solution of sodium chloride, and the layers were separated, and the organic phase was washed with a saturated aqueous solution of sodium chloride, dried and evaporated to give 6.6 g of a yellow green solid.Recrystallization from n-hexane,An off-white solid particle (5.55 g, yield 91%) was obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
67% | With tris-(dibenzylideneacetone)dipalladium(0); potassium <i>tert</i>-butylate; tert-butyldiphenylphosphine In toluene at 100℃; for 24h; Glovebox; | a a Preparation of FTRZ: 2-(4-Bromophenyl)-4,6-diphenyl-1,3,5-triazine (0.344 g, 0.89 mmol),Tris(dibenzylideneacetone)dipalladium(0) (21.1 mg, 0.036 mmol),tert-Butyldiphenylphosphine (17.9 mg, 0.074 mmol),9- (4- (hexyloxy) phenyl) -9H- fluorene (0.253 g, 0.74 mmol) in a reaction tube,Potassium tert-butoxide (0.103 g, 0.88 mmol) was weighed into a glove box.Toluene (3 mL) was added and the reaction was carried out at 100 ° C for 24 h.The reaction tube was cooled to room temperature and the substrate was extracted three times with dichloromethane.The water in the organic phase was removed with anhydrous magnesium sulfate.The solvent was removed by rotary evaporation and separated by column ( petroleum ether / dichloromethane = 5:1)0.322 g of a white solid were obtained (yield: 67%). |
67% | With tris-(dibenzylideneacetone)dipalladium(0); potassium <i>tert</i>-butylate; tert-butyldiphenylphosphine In toluene at 100℃; for 12h; Inert atmosphere; | 1 2-(4-(9-(4-(hexyloxy)phenyl)-9H-fluoren-9-yl)phenyl)-4,6-diphenyl-1,3,5-triazine (FTRZ) Preparation: 2-(4-bromophenyl)-4,6-diphenyl-1,3,5-triazine (0.344g, 0.89mmol), tris(dibenzylideneacetone)dipalladium(0)(21.3mg , 0.036mmol) solution, tert-butyldiphenylphosphine (17.9mg, 0.074mmol), 9-(4-(hexyloxy)phenyl)-9H-fluorene (0.253mg, 0.74mmol) and potassium tert-butoxide ( 0.103 mg, 0.88 mmol) was dissolved in 3 mL of toluene (anhydrous), and stirred at 100°C for 12 hours under a nitrogen atmosphere.The resulting mixture was extracted 3 times with dichloromethane and water, filtered, and concentrated under reduced pressure. The residue solid was purified by silica gel column chromatography (eluent: petroleum ether/dichloromethane = 5/1 volume) to obtain 0.322 g of white solid with a yield of 67%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; water for 10h; Reflux; Inert atmosphere; | 8 Synthesis Example 8: Synthesis of Intermediate L-8 30.0 g (83.51 mmol) of Intermediate L-7, 28.35 g (100.21 mmol) of 1-bromo-4-iodebenzene, 23.08 g (167.02 mmol) of potassium carbonate, and 4.83 g (4.18 mmol) of Pd(PPh3)4 (tetrakis(triphenylphosphine)palladium (0)) were added to 350 mE of tetrahydrofuran and 100 mE of water in a 1000 ml flask, and the mixture was heated and refluxedunder a nitrogen flow for 10 hours. The resultant was added to 1500 mE of methanol, and a crystallized solid was filtered, dissolved in dichloromethane, filtered again with silica gel/Celite, and recrystallized with methanol after removing an appropriate amount of the organic solvent toobtain Compound E-8 (37.3 g, 83%).calcd. C21H14BrN3: C, 64.96; H, 3.63; Br, 20.58; N, 10.82; found: C, 64.91; H, 3.58; Br, 20.63; N, 10.86. |
82% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In water; toluene for 8h; Inert atmosphere; Reflux; | 1 Preparation of Compound 1-3 Compound 1-1 (5.39 g, 15 mmol), under an argon atmosphereTo the flask was added bromoiodobenzene (4.05 g, 14.3 mmol), tetrakis(triphenylphosphine)palladium (0.35 g, 0.3 mmol), toluene (43 ml), aqueous sodium carbonate (2M, 21 ml), and refluxed for 8 hours. Cool to room temperature and extract with toluene.The organic phase is washed with saturated brine.After drying the organic phase, it is purified by column chromatography.Obtaining bromide 1-3 4.76g,The yield was 82%. |
82% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In water; toluene for 8h; Inert atmosphere; Reflux; | 1 Preparation of Compound 1-3 Compound 1-1 (5.39 g, 15 mmol), p-bromoiodobenzene (4.05 g, 14.3 mmol), tetrakis(triphenylphosphine)palladium (0.35 g, 0.3 mmol), under argon atmosphere, Toluene (43 ml), aqueous sodium carbonate (2M, 21 ml) was added to the flask. The reaction was refluxed for 8 hours, cooled to room temperature and extracted with toluene. The organic phase is washed with saturated brine and the organic phase is dried. Purification by column chromatography gave bromide 1-3 4.76 g, The yield was 82%. |
80.44% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In water; toluene at 70℃; for 11h; Inert atmosphere; | 1 Preparation of compound 1-9 Under the protection of nitrogen,Add 1-7 (35.92 g, 100.08 mmol) to a 2 L reactor.1-8 (28.19 g, 100.08 mmol), potassium carbonate (1.24 g, 9.00 mmol),Stir 200 mL of toluene. The temperature in the reactor rose to 70 ° C.Add Pd(PPh3)4 (1.04g, 0.90mmol),100 mL of distilled water was stirred, and the mixture was stirred under reflux for 11 hours to sufficiently react.After the reaction was terminated by adding 70 mL of distilled water, the mixture was filtered under reduced pressure, and the solid was washed with distilled water.It is then recrystallized from acetone, toluene, and THF.Sublimate after obtaining a solid.Recrystallization of toluene,Compound 1-9 31.13g was obtained.The yield was 80.44%. |
80.44% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In water; toluene at 70℃; for 11h; Inert atmosphere; | 1 Preparation of Compound 1-3 Under the protection of nitrogen,To a 2 L reactor, 1-1 (35.92 g, 100.08 mmol), 1-2 (28.19 g, 100.08 mmol), potassium carbonate (1.24 g, 9.00 mmol), and toluene (200 mL) were added. The temperature in the reaction vessel was raised to 70 ° C, and Pd (PPh3) 4 (1.04 g, 0.90 mmol) was added, and 100 mL of distilled water was stirred.The mixture was stirred under reflux for 11 h and fully reacted.After the reaction was terminated by adding 70 mL of distilled water, the mixture was filtered under reduced pressure, and the solid was washed with distilled water, and then recrystallized from acetone, toluene, and THF to obtain a solid and then sublimed.The toluene was recrystallized to give Intermediate 1-3 31.13 g, yield 80.44%. |
80.44% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In water; toluene at 70℃; for 11h; Inert atmosphere; | 1 Preparation of Compound 1-3 1-1 (35.92 g, 100.08 mmol), 1-2 (28.19 g, 100.08 mmol), was added to a 2 L reactor under nitrogen.Potassium carbonate (1.24 g, 9.00 mmol) and toluene (200 mL) were stirred.The temperature in the reaction vessel was raised to 70 ° C, and Pd(PPh3) 4 (1.04 g, 0.90 mmol) was added thereto, and 100 mL of distilled water was stirred, and the mixture was stirred under reflux for 11 hours to sufficiently react.After the reaction was terminated by adding 70 mL of distilled water, the mixture was filtered under reduced pressure, and the solid was washed with distilled water, and then recrystallized from acetone, toluene, and THF.After obtaining a solid, it is sublimed, and the toluene is recrystallized.Intermediate 1-3 31.13g is obtained,The yield was 80.44%. |
80% | With tetrakis(triphenylphosphine) palladium(0); tetrabutylammomium bromide; potassium carbonate In ethanol; water; toluene at 72℃; for 10h; Inert atmosphere; | 2.1.1 Take Intermediate A-1 (12g, 33.4mmol),Add bromoiodobenzene (9.45g, 33.4mmol),9.21g potassium carbonate,1.5g tetrabutylammonium bromide,0.38g tetratriphenylphosphine palladium,Toluene 80mL,40mL of ethanol,40mL of water,Under nitrogen protection,Warm up to 72 to start the reaction,After 10 hours of reaction,The reaction liquid is washed with water,Toluene column,Recrystallization gave 10.36g of product B-1 (26.7mmol, yield 80%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79% | With copper(l) iodide; In 1,4-dioxane; for 12h;Reflux; | Intermediate 1-5 (0.75 g, 1.9 mmol), 9H,9H?-3,3?- bicarbazole (0.28 g, 0.8 mmol), copper iodide (0.19 g, 1.0 mmol), and potassium phosphate (1.07 g, 5.1 mmol) were dried under vacuum for 2 hours, and 40 ml of 1,4-dioxane was added thereto. Subsequently, (±)-trans-1 ,2-diamino cyclohexane (0.11 g, 1.0 mmol) was added thereto, and the obtained mixture was heated up, refluxed and stirred for 12 hours, cooled down to room temperature, and filtered to obtain a precipitate. The filtered precipitate was washed with ethylacetate, dichloro methane, and hexane and then, sublimated to obtain Dopant 5 (0.6 g). A yield was 79%. Dopant 5: mass analysis (FAR) mlz 948 [(M+H)]. ?H NMR (400 MHz, CDC13): oe 9.07 (d, 4H, J=8.8 Hz), 8.84 (d, 8H, J=8.4 Hz), 8.51 (s, 2H), 8.28 (d, 2H, J=7.6 Hz), 7.90-7.84 (m, 6H), 7.69-7.60 (m, 16H), 7.49 (t, 2H, J=15.6 Hz), 7.38 (t, 2H, J=15.2 Hz). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
34% | With copper(l) iodide; trans-1,2-Diaminocyclohexane In 1,4-dioxane for 12h; Reflux; | 7 Synthesis Example 7: Dopant 7 Intermediate 1-5 (0.67 g, 1.7 mmol), 9H,9H’-2,2’- bicarbazole (0.25 g, 0.7 mmol), copper iodide (0.17 g, 0.9 mmol), and potassium phosphate (0.96 g, 4.5 mmol) were dried under vacuum for 2 hours, and 1 ,4-dioxane (40 ml) was added thereto. Subsequently, (±)-trans-1 ,2-diamino cyclohexane (0.10 g, 0.9 mmol) was added thereto, and the obtained mixture was heated up, refluxed and stirred for 12 hours, cooled down to room temperature, and filtered to obtain a precipitate. The filtered precipitate was washed by using ethylacetate, dichloro methane, and hexane and purified through sublimation to obtain Dopant 7 (0.2 g). A yield was 34%.Dopant 7: mass analysis (FAR) mlz 948 [(M+H)]. H NMR (400 MHz, DMSO): ö 9.02 (d, 1H, J=8.4 Hz), 8.78 (d, 1H, J=7.2 Hz), 8.72-8.69 (m, 4H), 8.55-8.53 (m, 5H), 8.39-8.29 (m, 4H), 8.14 (d, 2H, J=8.8 Hz), 8.07-8.01 (m, 3H), 7.93-7.88 (m, 3H), 7.83-7.69 (m, 5H), 7.65-7.48 (m, 12H), 7.38-7.34 (m, 2H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With tri-tert-butyl phosphine; palladium diacetate; sodium t-butanolate; at 110℃; for 24h;Inert atmosphere; Darkness; | Under a nitrogen atmosphere, 10H-spiro[acridine-9,9'-oxime] 1.0 g(2.8 mmol), 2-(4-bromophenyl)-4,6-diphenylwas added successively to a 250 mL three-necked flask.-1,3,5-triazine 1.1 g (2.8 mmol), 0.90 g of sodium t-butoxide,59.8 mg of palladium acetate, tri-tert-butylphosphine, heated to 110 C, and stirred for 24 hours in the dark.After completion of the reaction, the solvent in thereactionsystem was suspended, extracted three times with dichloromethane and water to give an organic phase.Dichloromethane was distilled off under reduced pressure, and purified by silica gel columnto yield 1.45 g of product of formula P19 (yield: 83%). |
83% | With tri-tert-butyl phosphine; palladium diacetate; sodium t-butanolate; In toluene; at 110℃; for 24h;Inert atmosphere; | Under a nitrogen atmosphere,Add in 250ml three-necked flask10H-spiro [acridine-9,9'-]1.0g (2.8 mmol), 2-(4-bromophenyl)-4,6-diphenyl-1,3,5-triazine 1.1 g (2.8 mmol),0.90 g of sodium t-butylate,Add 59.8 mg of palladium acetate,Tri-tert-butylphosphine,Heated to 110 C,The reaction was stirred for 24 hours in the dark.After the reaction,The solvent in the reaction system is suspended,Extract three times with dichloromethane and water.Take the organic phase.Distilling off the dichloromethane under reduced pressure,Purified on silica gel column,The product of the formula P19 was obtained in 1.45 g, yield 83%. |
83% | With tri-tert-butyl phosphine; palladium diacetate; sodium t-butanolate; In toluene; at 110℃; for 24h;Inert atmosphere; Darkness; | 10H-spiro[acridine-9,9'-oxime] 1.0 g (2.8 mmol) was added to a 250 ml three-necked flask under a nitrogen atmosphere. 2-(4-Bromophenyl)-4,6-diphenyl-1,3,5-triazine 1.1 g (2.8 mmol), 0.90 g of sodium t-butylate. Further, 59.8 mg of palladium acetate and trit-butylphosphine were added, and the mixture was heated to 110 C, and stirred for 24 hours in the dark. After completion of the reaction, the solvent in the reaction system was suspended, extracted three times with dichloromethane and water, and the organic phase was taken. Dichloromethane was distilled off under reduced pressure, and purified by silica gel column. The product of the formula P19 was obtained in 1.45 g, yield 83%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With tri-tert-butyl phosphine; palladium diacetate; sodium t-butanolate In toluene at 110℃; for 12h; Inert atmosphere; | 28.1 Synthesis of Intermediate 5-1 Under nitrogen, was added 19.5g (100mmol) 9(10Η)-acridine-one (Compound A-1), 0.65g of palladium acetate (3mmol), 2.25g tri-tert-butylphosphine (11.0 mmol), 42.5 g of compound E-1 (110 mmol), 28.5 g of sodium t-butoxide,100 mL of toluene was reacted at 110 °C for 12 hours, cooled to room temperature, extracted with chloroform, and the solvent was evaporated to give 63.8 g of solid intermediate 5-1 (yield: 87%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With tri-tert-butyl phosphine; cesium acetate; sodium t-butanolate In toluene at 110℃; for 12h; Inert atmosphere; | 1.3 The preparation method of the 9,10-dihydroacridine derivative represented by the formula C-1 specifically comprises the following steps: (3) Synthesis of 9,10-dihydroacridine derivative C-1 Under gas protection, 8 g of intermediate 2-1 (20 mmol), 0.13 g of cesium acetate (0.6 mmol), 0.45 g of tri-tert-butylphosphine (2.2 mmol), 8.5 g of compound E-1 (22 mmol), 5.7 g of sodium t-butoxide were added. 300 mL of toluene was reacted at 110 °C for 12 hours, and after cooling to room temperature, the mixture was extracted with chloroform, and the solvent was evaporated to give a solid compound C-1 (yield: 82%). |
81% | With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; C4H9Na In toluene at 110℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | With tri-tert-butyl phosphine; palladium diacetate; sodium t-butanolate In toluene at 110℃; for 12h; Inert atmosphere; | 37.3 The preparation method of the 9,10-dihydroacridine derivative represented by the formula C-46 specifically comprises the following steps: (3) Synthesis of 9,10-dihydroacridine derivative C-46 Under nitrogen, 10.0 g of compound 2-4 (20 mmol), 0.13 g of palladium acetate (0.6 mmol), 0.45 g of tri-tert-butylphosphine (2.2 mmol), and 8.5 g of compound E-1 (22 mmol) were added. 5.7g sodium tert-butoxide, 300mL of toluene, reacted at 110 ° C for 12 hours. After cooling to room temperature, chloroform was extracted, and the solvent was evaporated to dryness, and then silica gel column was afforded 13.5 g of solid compound C-46 (yield: 84%). |
70% | With tri-tert-butyl phosphine; C4H9Na In toluene at 110℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With tris-(dibenzylideneacetone)dipalladium(0); sodium t-butanolate; tri tert-butylphosphoniumtetrafluoroborate In o-xylene at 130℃; for 16h; Inert atmosphere; | 1 Synthesis of Compound C2 In a 100 ml three-necked flask that had been degassed and filled with nitrogen, 2 g (5.8 mmol) of 10H-spiro[acridine-9,4'-cyclopenta-[2,1-b:3,4-b']-dithiophene], 2.8 g (7 mmol) of 2-(4-bromophenyl)-4,6-diphenyl-1,3,5-triazine, 0.1 g (0.012 mmol) of Pd2(dba)3, 0.06 g (0.024 mmol) of tri-tert-butylphosphonium tetrafluoroborate, 1.2 g (4.2 mmol) of sodium tert-butoxide, and 40 ml of o-xylene were added, and then heated at 130° C. for 16 hours. After cooling to room temperature, the mixture was filtered to give a solid. The solid was washed with water and MeOH, and then filtered to give compound C2 (3.4 g, 89%) as a dark yellow solid. 1H NMR (CDCl3, 500 MHz): chemical shift (ppm) 9.09 (d, 2H), 8.9-8.8 (d, 4H), 7.68-7.58 (m, 8H), 7.17 (d, 2H), 7.02 (d, 2H), 6.98 (m, 2H), 6.67 (d, 4H), 6.46 (d, 2H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With tri-tert-butyl phosphine; palladium diacetate; caesium carbonate In toluene at 110℃; for 20h; Inert atmosphere; | |
70% | With tri-tert-butyl phosphine; palladium diacetate; caesium carbonate In toluene at 100℃; for 24h; Inert atmosphere; | 2 Synthesis of Example 2: Under the protection of nitrogen, 3,6-bis (dibenzo [b, d] thiophen-2-yl) -9H-carbazole 531 mg was added to a 100 mL two-port reactor equipped with a reflux tube,2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine 426mg,30 mg of palladium acetate, 1 mL of tri-tert-butylphosphine, 650 mg of cesium carbonate, and 30 mL of toluene.The resulting solution was heated to 100 ° C and stirred under reflux for 24 hours.After cooling to room temperature,A large amount of water and methylene chloride were added to extract the organic phase and dried over anhydrous sodium sulfate. After the organic liquid phase was distilled off, the product was purified by column chromatography with petroleum ether and methylene chloride.Obtained after drying3,6-bis (dibenzo [b, d] thiophen-2-yl) -9- (4- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl ) -9H-carbazoleLight yellow solid powder (yield 587mg, yield 70%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With tri-tert-butyl phosphine; palladium diacetate; caesium carbonate In toluene at 100℃; for 24h; Inert atmosphere; | 4 Synthesis of Example 4: Under nitrogen protection, 500 mg of 3,6-bis (dibenzo [b, d] furan-2-yl) -9H-carbazole was added to a 100 mL two-port reactor equipped with a reflux tube,2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine 426mg, palladium acetate 30mg,Tri-tert-butylphosphine 1mL,650 mg of cesium carbonate and 30 mL of toluene.The resulting solution was heated to 100 ° C and stirred under reflux for 24 hours.After cooling to room temperature, a large amount of water and methylene chloride were added to extract the organic phase and dried over anhydrous sodium sulfate. After the organic liquid phase was distilled off, the product was purified by column chromatography with petroleum ether and methylene chloride.Obtained after drying3,6-bis (dibenzo [b, d] furan-2-yl) -9- (4- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl ) -9H-carbazoleLight yellow solid powder (yield 564mg, yield 70%). |
With tri-tert-butyl phosphine; palladium diacetate; caesium carbonate In toluene at 110℃; for 20h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74% | With tri-tert-butyl phosphine; palladium diacetate; caesium carbonate In toluene at 110℃; for 20h; Inert atmosphere; | |
74% | With tri-tert-butyl phosphine; palladium diacetate; caesium carbonate In toluene at 100℃; for 24h; Inert atmosphere; | 1 Synthesis of Example 1: Under the protection of nitrogen,100mL with a reflux tube installedAdd 2- (dibenzo [b, d] thiophen-2-yl) -9H-carbazole 349mg to the two-port reactor,2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine 426mg, palladium acetate 30mg,Tri-tert-butylphosphine 1mL,650 mg of cesium carbonate and 30 mL of toluene.The resulting solution was heated to 100 ° C and stirred under reflux for 24 hours.After cooling to room temperature, add a large amount of water and dichloromethane to extract the organic phase and dry with anhydrous sodium sulfate, after distilling off the organic liquid phase,The product was purified by column chromatography with petroleum ether and methylene chloride.After drying3- (dibenzo [b, d] thiophen-2-yl) -9- (4- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl)- 9H-carbazole light yellow solid powder (yield 485mg, yield 74%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With tri-tert-butyl phosphine; palladium diacetate; caesium carbonate In toluene at 100℃; for 24h; Inert atmosphere; | 3 Synthesis of Example 3: Under the protection of nitrogen,In a 100 mL two-port reactor equipped with a reflux tube, add 3- (dibenzo [b, d] furan-2-yl) -9H-carbazole 333 mg, 2- (4-bromophenyl) -4,6-di Phenyl-1,3,5-triazine 426mg,Palladium acetate 30mg, tri-tert-butylphosphine 1mL,650 mg of cesium carbonate and 30 mL of toluene.The resulting solution was heated to 100 ° C and stirred under reflux for 24 hours.After cooling to room temperature, a large amount of water and methylene chloride were added to extract the organic phase and dried over anhydrous sodium sulfate. After the organic liquid phase was distilled off, the product was purified by column chromatography with petroleum ether and methylene chloride.After drying3- (dibenzo [b, d] furan-2-yl) -9- (4- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl)- 9H-carbazole light yellow solid powder (yield 480 mg, yield 75%). |
With tri-tert-butyl phosphine; palladium diacetate; caesium carbonate In toluene at 110℃; for 20h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With tetrakis(triphenylphosphine) palladium(0); tetrabutylammomium bromide; sodium carbonate In 1,4-dioxane; water at 80℃; for 6h; Inert atmosphere; | 2 Intermediate 1 - 6 - 2 synthesis of Under the environment of nitrogen, will (17.5 g, 60 mmol) intermediate 1 - 3 - 5, (20.6 g, 60 mmol) intermediate 1 - 6 - 1, (2.08 g, 1.2 mmol) four triphenyl phosphine palladium, (12.7 g, 120 mmol) sodium carbonate, (3.9 g, 12 mmol) tetrabutyl ammonium bromide, 150 ml of 1, 4 - dioxane and 30 ml water is added to a 500 ml three-opening in the bottle, heating 80 °C stirring for 6 hours, the end of the reaction, the reaction liquid inverted in 500 ml of pure water, the separated solid filtered, the filter residue recrystallization purification, to obtain intermediate 1 - 6 - 2, yield 70%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); potassium carbonate In ethanol; lithium hydroxide monohydrate; toluene for 3h; Reflux; Inert atmosphere; | 3.1.2. 2-(4-(anthracen-9-yl)phenyl)-4,6-diphenyl-1,3,5-triazine (p-TAN) A mixture of 2-(4-bromophenyl)-4,6-diphenyl-1,3,5-triazine (5.00 g,12.88 mmol), 9-anthracene boronic acid (4.00 g, 18.01 mmol), K2CO3(3.56 g, 25.76 mmol) and Pd(PPh3)2Cl2 (0.10 g, 0.142 mmol) was addedto a round bottle flask, followed by toluene (30 mL), ethanol (15 mL)and deionized water (15 mL) and the resulting mixture was refluxed for3 h under N2 protection. After phase separation, the organic layer wasconcentrated under vacuum and purified by column chromatography toafford a white solid (8.32 g, 95.0%). 1H NMR (400 MHz, CDCl3, δ): 9.00(d, J = 8.3 Hz, 2H), 8.85 (dd, J = 8.0, 1.6 Hz, 4H), 8.55 (s, 1H), 8.09 (d, J= 8.5 Hz, 2H), 7.74 (d, J = 8.8 Hz, 2H), 7.71-7.58 (m, 8H), 7.53-7.46(m, 2H), 7.42-7.36 (m, 2H). |
86% | With palladium (II) [1,1'-bis(diphenylphosphanyl)ferrocene] dichloride; potassium carbonate In ethanol; lithium hydroxide monohydrate; toluene for 21.5h; Inert atmosphere; Reflux; | 2-(4-(anthracen-9-yl)phenyl)-4,6-diphenyl-i,3,5-triazine A flask was flushed with nitrogen and charged with 2-(4-bromophenyl)-4,6-diphenyl-i,3,5- triazine (65 g, 167.4 nimol), anthracen-9-ylboronic acid (40.9 g, 184.2 mol), Pd(dppf)Cl2 (0.6 g, 0.84 mmol), and K2C03 (46.3 g, 334.8 mmol). A mixture of deaerated toluene/ ethanol/ water (3.9:1.3:1, 1030 mL) was added and the reaction mixture was heated to reflux under a nitrogen atmosphere for 21.5 h. Without cooling down, the formed precipitate was collected by suction filtration and washed with toluene. The crude product was dissolved in hot chloroform and filtered over a pad of Florisil. After rinsing with additional chloroform and dichloromethane, the combined filtrates were concentrated in vacuo and the obtained precipitate was isolated by suction filtration, washed with chloroform and dried to yield 69.6 g (86%) of a pale yellow solid. HPLC: 99-67% |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate In toluene Reflux; | Compound P1 Synthesis In a round bottom flask, 4.8 g of 9H-2,9'-bicarbazole (Sub C1)5 g of 2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine, t-BuONa 2.9 g,0.4 g of Pd2 (dba) 3,(t-Bu) 3P 0.8 mlWas dissolved in 30 ml of toluene, and the mixture was stirred under reflux.After confirming the reaction by TLC, water was added and the reaction was terminated. The organic layer was extracted with MC, filtered under reduced pressure, purified by column and recrystallized9- (4- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl) -9H-2,9'- bicarbazole (Product P1)6.4 g (yield 75%) was obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
17.34% | With bis-triphenylphosphine-palladium(II) chloride; 2-Ethylhexanoic acid; potassium carbonate; tricyclohexylphosphine In 5,5-dimethyl-1,3-cyclohexadiene at 100℃; Inert atmosphere; | 2 Synthesis of 4'-(4,6-diphenyl-l,3,5-triazin-2-yI)-3,4,5,6-tetrafluoro-[l,l'-biphenyl]-2- carbonitrile (K) Bis(triphenyiphosphine)paladiurn(II) dichloride (0.57 mmol, 0 40 g), 2, 3,4,5- tetrafluorobenzonitrile (11.42 mmol, 2.00 g), 2-(4-bromophenyl)-4,6-diphenyl-l,3,5-triazine (17.13 mmol, 6.65 g), potassium carbonate (34.27 mmol, 4.74 g), 2-ethyl hexanoic acid (2.28 mmol, 0.33 g) and tricycohexylphosphine (1 .71 mmol, 0.48 g) put into 3 neck round flask under nitrogen atmosphere. After nitrogen gas flow m a minute, it was dissolved in xylene dire temperature of mixture was increased to 100 C and then stirred overnight. The reaction quenched by brine solution at room temperature, and the mixture extracted by chloroform and dried over MgSOr and then concentrated by vacuum evaporator system. The mixture was purified by column chromatography on silica gel using n-hexane/chloroform as an eluent. A white powdery product was obtained (0.96 g, 17.34% yield). NMR (500 MHz, CDCb) d 7.58 - 7.65 (m, 6H), 7.68 (d, ./ = 8.5 Hz, 8.79 (d, ./ = 7 Hz, 4H), 8.94 (d, ,/ = 8.5 Hz, 2H).i9F NMR (470 MHz, CDCb) d -152.45 (id. JF = 23 5, 4.7 Hz, IF), -143.95 (td, JF = 18.8, 9.4 Hz, IF), -137.47 (qd, JF = 21.2, 9.4, 4.7 Hz., IF), -129.61- -129.69 (m, IF) MS (APCI) m/z 483.10 [(M+HG]. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate In 1,4-dioxane at 110℃; for 12h; Inert atmosphere; | 1 Specific preparation process: 100ml1 under nitrogen4-Dioxane solvent was added with 2,3,4,5-tetraphenylpyrrole (3.71g, 10.0mmol),4-bromotriphenyltriazine(4.27g, 11.0mmol),Tris (dibenzylideneacetone) dipalladium (0.58g, 0.5mmol)And tri-tert-butyl phosphorus (15%, 0.15 mmol), and stirred at 110 ° C for 12 hours.After the reaction was cooled to room temperature, it was filtered through a silica gel funnel.The solution was concentrated under reduced pressure and subjected to column chromatography with dichloromethane and n-hexane.The final product (5.77 g, 8.5 mmol) was obtained,The yield was 85%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In 1,4-dioxane; at 110℃; for 12h;Inert atmosphere; | Specific preparation process: 100ml under nitrogenTo the 1,4-dioxane solvent was added <strong>[3469-20-3]2,3-diphenylindole</strong> (1.70 g, 10.0 mmol)And 4-bromotriphenyltriazine (4.27g, 11.0mmol),Tris (dibenzylideneacetone) dipalladium (0.58 g, 0.5 mmol) and tri-tert-butyl phosphorus (15%, 0.15 mmol) were stirred at 110 C for 12 hours.After the reaction was cooled to room temperature, the mixture was filtered through a silica gel funnel, and the solution was concentrated under reduced pressure.The final product (4.90 g, 8.5 mmol) was obtained in a yield of 85%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79% | Stage #1: 2-(4-bromobenzenyl)-4,6-diphenyl-1,3,5-triazine With n-butyllithium In tetrahydrofuran at -78℃; for 1h; Stage #2: Trimethyl borate In tetrahydrofuran at 20℃; | The intermediate I-D-1 (11.89 g, 30.62 mmol)Add to a 250 mL three-necked flask containing THF (100 mL), and dropwise add n-butyllithium (1.99 g, 31.09 mmol) at -78 ° C.Incubate for 1h after drippingTrimethyl borate (4.61 g, 44.42 mmol) was added dropwise, and the temperature was kept at room temperature for 1 h, followed by stirring overnight; hydrochloric acid (2 mol / L) was added to adjust the pH to neutral, and then filtered to obtain a white crude product. White solid intermediate ID (8.54 g, yield 79%). |
65% | With n-butyllithium In tetrahydrofuran at -78 - 20℃; | 2 Step (2): Intermediate-11 (20g, 51.51mmol) was added to a three-necked flask containing THF (1L), and n-butyllithium (3.46g, 54.08mmol) was added dropwise at -78 °C. Trimethyl borate (8.02g, 77.26 mmol), continue to hold for 1h, warm to room temperature and stir overnight. Hydrochloric acid (2mol/L) was added to adjust the pH to neutral, and then filtered to obtain a white crude product, which was slurried with 3 volumes of n-heptane to obtain a white solid intermediate-12 (11.82g, yield 65%). |
65% | Stage #1: 2-(4-bromobenzenyl)-4,6-diphenyl-1,3,5-triazine With n-butyllithium In tetrahydrofuran at -78℃; for 1h; Stage #2: Trimethyl borate In tetrahydrofuran at 20℃; | Add the middle -2-1 (20g, 51.51mmol) into a three-necked flask containing THF (1L), add n-butyllithium (3.46g, 54.08mmol) dropwise at -78°C, keep it warm for 1h and then drop it. Add trimethyl borate (8.02g, 77.26mmol), continue to incubate for 1h, then warm to room temperature and stir overnight. Hydrochloric acid (2mol/L) was added to adjust the pH to neutral, and then filtered to obtain a white crude product, which was beaten with 3 times of n-heptane to obtain a white solid intermediate-3-1 (11.82g, yield 65%). |
Stage #1: 2-(4-bromobenzenyl)-4,6-diphenyl-1,3,5-triazine With n-butyllithium In tetrahydrofuran; ethanol; hexane at -90℃; for 0.5h; Inert atmosphere; Stage #2: Trimethyl borate In tetrahydrofuran; ethanol; hexane at 90℃; for 0.5h; | 1.1 Example 1 (1) Put 38.83g (0.1mol) of 2-(4-bromophenyl)-4,6-diphenyl-1,3,5-triazine and 260mL of tetrahydrofuran into the reactor and stir until all are dissolved. Add 85 mL of diethoxymethane, replace with nitrogen for 30 minutes, reduce the temperature of the reaction system to below -90 with an absolute ethanol bath through liquid nitrogen, and slowly add n-butyl lithium n-hexane through a constant pressure funnel while maintaining this temperature The solution is 50 mL (2.5 mol/L). After the addition, keep this temperature for 30 minutes, and then slowly drop 18.18 g of trimethyl borate through a constant pressure funnel. After the addition, keep this temperature for 30 minutes and naturally warm to room temperature. Add 15% by mass dilute hydrochloric acid to adjust the pH to 6-7, divide the water layer, extract the water layer twice with 15 mL of ethyl acetate each time, combine the organic layers, and dry the organic layer with anhydrous magnesium sulfate for 1 h After that, the mother liquor was filtered. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97.8% | With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate In toluene at 80℃; for 20h; Inert atmosphere; | 1 (Synthesis Example 1) Synthesis of Compound 1 2- (4-bromophenyl) -4,6-diphenyltriazine2.00 g (5.15 mmol),0.594 g (6.18 mmol) of sodium tert-butoxide,1.31 g (7.73 mmol) of diphenylamine,99.7 mg (0.109 mmol) of tris (dibenzylideneacetone) dipalladium (0) was placed in a 100 mL three-necked flask,The atmosphere in the flask was replaced with nitrogen.To this mixture were added 30 mL of toluene and 1.0 mL of a 0.75 mol / L solution of tri (tert-butyl) phosphine in toluene.After nitrogen bubbling this mixture for 30 minutes, under a nitrogen atmosphere,Stirred at 80 ° C. for 20 hours.After stirring, the mixture was celite,Suction filtration was performed through silica gel to obtain a filtrate. Water was added to the obtained filtrate to wash it. After washingSeparate the organic and aqueous layers,The organic layer was dried by adding magnesium sulfate. After drying,This mixture was subjected to suction filtration to obtain a filtrate. The solid obtained by concentrating the obtained filtrate was washed with a mixed solvent of acetone and methanol to obtain 2.40 g of Compound 1 in a yield of 97.8% |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | With palladium diacetate; sodium t-butanolate; tri tert-butylphosphoniumtetrafluoroborate In toluene at 120℃; for 12h; Inert atmosphere; | 1.3 Select a 50mL two-necked flask, add the donor unit (a) (340mg, 1mmol) under the protection of argon,2-(4-bromophenyl)-4,6-diphenyl-1,3,5-triazine (0.46g, 1.2mmol), palladium acetate (11.2mg, 0.05mmol),Sodium tert-butoxide (192.2mg, 2mmol),Tri-tert-butylphosphorus tetrafluoroborate (37.7 mg, 0.13 mmol) and 10 mL of toluene were reacted at 120°C for 12 hours.After cooling to room temperature,The inorganic salt was filtered off through diatomaceous earth and separated by silica gel column chromatography to obtain a green powder with a yield of 73%. |
70% | With palladium diacetate; sodium t-butanolate; tri tert-butylphosphoniumtetrafluoroborate In toluene for 24h; Reflux; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In 1,4-dioxane; water at 120℃; for 4h; | Preparation of Compound 1 General procedure: In a one neck round bottom flask, a mixture of 9-(9-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)dibenzo[b,d]furan-4-yl)-9H-carbazole (7.2 g, 15.6 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (5 g, 18.8 mmol), tetrakis(triphenylphosphine)palladium(0) (1.8 g, 1.56 mmol), potassium carbonate (4.3 g, 31.2 mmol) and 1,4-dioxane/water (100 ml/25 ml) was refluxed for 4 hours at 120° C. After filtering at 120° C., the result was washed with 1,4-dioxane, distilled water and MeOH to obtain Compound 1(C) (6.6 g, 75%). |
71% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In 1,4-dioxane; water at 120℃; for 4h; | 10 Preparation of compound 1 General procedure: In one neck round bottom flask (One neck r.b.f)9-(9-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)dibenzo[b,d]furan-4-yl)-9H-carbazole (7.2 g, 15.6 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (5 g, 18.8 mmol), tetrakis (triphenylphosphine) palladium (0) (1.8 g, 1.56 mmol), potassium carbonate (4.3 g, 31.2 mmol), 1,4-dioxane/water(100ml/25ml) The mixture was refluxed at 120°C for 4 hours.After filtering at 120° C., it was washed with 1,4-dioxane, distilled water, and MeOH to obtain compound 1 (G). (6.6 g, 75%) |
71 % | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In 1,4-dioxane; water at 120℃; | 2 Preparation of compound 2-1 General procedure: 9-(9-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)dibenzo[b,d]furan-4-yl)-9H-carbazole 7.2 g, 15.6 mmol),2-Chloro-4,6-diphenyl-1,3,5-triazine (5 g, 18.8 mmol),Tetrakis(triphenylphosphine)palladium(0) (1.8 g, 1.56 mmol),A mixture of potassium carbonate (4.3 g, 31.2 mmol) and 1,4-dioxane/water (100 mL/25 mL) was refluxed in a round bottom flask at 120°C for 4 hours.Thereafter, the mixture was filtered at 120 °C,And then with 1,4-dioxane,Washed with distilled water and MeOH to obtain compound 2-1(C).(6.6 grams, 75%) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In 1,4-dioxane; water at 120℃; for 4h; | Preparation of Compound 129 General procedure: In a one neck round bottom flask, a mixture of 9-(9-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)dibenzo[b,d]furan-3-yl)-9H-carbazole (6.5 g, 14.1 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (4.54 g, 16.9 mmol), M tetrakis(triphenylphosphine)palladium(0) (1.6 g, 1.41 mmol), potassium carbonate (3.9 g, 28.2 mmol) and 1,4-dioxane/water (80 ml/28.2 ml) was refluxed for 4 hours at 120° C. After filtering at 120° C., the result was washed with 1,4-dioxane, distilled water and MeOH to obtain Compound 129(F) (5.4 g, 68%). |
71% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In 1,4-dioxane; water at 120℃; for 4h; | 11 Preparation of compound 129 General procedure: In one neck round bottom flask (One neck r.b.f)9-(9-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)dibenzo[b,d]furan-3-yl)-9H-carbazole (6.5 g, 14.1 mmol),2-chloro-4,6-diphenyl-1,3,5-triazine (4.54 g, 16.9 mmol), tetrakis (triphenylphosphine) palladium (0) (1.6 g, 1.41 mmol), potassium carbonate ( 3.9 g, 28.2 mmol) and 1,4-dioxane/water (80 ml/28.2 ml) mixture was refluxed at 120° C. for 4 hours.After filtering at 60°C, it was washed with 1,4-dioxane, distilled water, and MeOH at 60°C to obtain compound 129 (H) (5.4 g, 68%). |
71 % | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In 1,4-dioxane; water at 120℃; | 3 Preparation of compound 2-129 9-(9-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)dibenzo[b,d]furan-3-yl)-9H-carbazole (6.5 g, 14.1 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (4.54 g, 16.9 mmol), tetrakis(triphenylphosphine)palladium(0) (1. 6 g, 1.41 mmol), potassium carbonate (3.9 g, 28.2 mmol), and a mixture of 1,4-dioxane/water (80 mL/28.2 mL) were refluxed in a round-bottomed flask at 120°C for 4 hours. Thereafter, the mixture was filtered at 120° C., and then washed with 1,4-dioxane, distilled water, and methanol (MeOH) to obtain compound 2-129(F) (5.4 g, 68%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With palladium diacetate; sodium tertiary butoxide; tri-tert-butylphosphonium hydrogen tetrafluoroborate In toluene at 110℃; for 24h; Inert atmosphere; | |
84% | With potassium-t-butoxide; palladium diacetate; tri-tert-butylphosphonium hydrogen tetrafluoroborate In toluene at 120℃; for 18h; Inert atmosphere; | 2.3.1. General procedure for synthesis of BuCz-TRZ, PhBuCz-TRZ, BuCz-MeTRZ 2-(4-Bromophenyl)-4,6-diphenyl-1,3,5-triazine (1548.1 mg, 4.00mmol, 1.00 equivalent) or 2-(4-bromo-3-methylphenyl)-4,6-diphenyl-1,3,5-triazine (1604.2 mg, 4.00 mmol, 1.00 equivalent) and BuCz(1341.2 mg, 4.80 mmol, 1.20 equivalent) or PhBuCz (1705.1 mg, 4.80mmol, 1.20 equivalent), Pd(OAc)2 (0.25 mmol), [(t-Bu)3PH]BF4 (116.1mg, 0.40 mmol, 0.10 equivalent) or 2-(Dicyclohexylphosphino)-2,4,6-Triisopropylbiphenyl (Xphos) (190.7 mg, 0.40 mmol, 0.10 equivalent)and t-BuOK (10 mmol) were dissolved in dry toluene (150 mL) under N2atmosphere. After stirring at 120 C for 18-24 h, the reaction solventwas removed by vacuum distillation, and the residue was purified bycolumn chromatography on silica gel to afford the crude product.Repeated recrystallization from CHCl3/CH3OH gave the pure product. BuCz-TRZ: white solid, yield: 84%. 1H NMR (400 MHz, Chloroformd)δ 9.01 (d, J = 8.5 Hz, 2H), 8.88-8.80 (dd, J = 6.4, 1.6 Hz, 4H), 8.19 (d,J = 17.0 Hz, 2H), 7.82 (d, J = 8.4 Hz, 2H), 7.62 (m, 6H), 7.52 (t, J = 1.4Hz, 4H), 1.51 (s, 18H). MALDI-TOF-MS, (m/z): [M]+ calcd for C41H38N4:586.3097; Found: 586.3091. |
80% | With palladium diacetate; tri-tert-butylphosphonium hydrogen tetrafluoroborate In toluene at 120℃; for 24h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With potassium-t-butoxide; palladium diacetate; dicyclohexyl(2’,4’,6’-triisopropyl-[ 1,1’-bi-phenyl]-2-yl)phosphane In toluene at 120℃; for 24h; Inert atmosphere; | 2.3.1. General procedure for synthesis of BuCz-TRZ, PhBuCz-TRZ, BuCz-MeTRZ 2-(4-Bromophenyl)-4,6-diphenyl-1,3,5-triazine (1548.1 mg, 4.00mmol, 1.00 equivalent) or 2-(4-bromo-3-methylphenyl)-4,6-diphenyl-1,3,5-triazine (1604.2 mg, 4.00 mmol, 1.00 equivalent) and BuCz(1341.2 mg, 4.80 mmol, 1.20 equivalent) or PhBuCz (1705.1 mg, 4.80mmol, 1.20 equivalent), Pd(OAc)2 (0.25 mmol), [(t-Bu)3PH]BF4 (116.1mg, 0.40 mmol, 0.10 equivalent) or 2-(Dicyclohexylphosphino)-2,4,6-Triisopropylbiphenyl (Xphos) (190.7 mg, 0.40 mmol, 0.10 equivalent)and t-BuOK (10 mmol) were dissolved in dry toluene (150 mL) under N2atmosphere. After stirring at 120 C for 18-24 h, the reaction solventwas removed by vacuum distillation, and the residue was purified bycolumn chromatography on silica gel to afford the crude product.Repeated recrystallization from CHCl3/CH3OH gave the pure product. |
75% | With palladium diacetate; tri-tert-butylphosphonium hydrogen tetrafluoroborate In toluene at 120℃; for 24h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; water at 65℃; for 24h; Inert atmosphere; | 2.2 Synthesis of 1-(4,6-diphenyl-1,3,5-triazine)-9-fluorenone In a two-neck flask under nitrogen atmosphere, 9-fluorenone-1-boronic acid (1.40 g, 6.25 mmol), 2-(4'-bromophenyl)-4,6-diphenyl-1,3,5-triazine (2.31 g, 5.94 mmol), Pd(PPh3)4 (360.94 mg, 0.31 mmol) and potassium carbonate (1.64 g, 11.88 mmol) were dissolved in 30 ml THF and 5 ml water. The mixture was stirred and heated at 65 °C for 24 h. After cooling down to the room temperature, the mixture was concentrated under reduced pressure to remove THF and then extracted by DCM (3x20 ml). The crude product (2.23 g, 4.58 mmol, 90%) was used directly without further purification due to poor solubility. MS (EI) calculated for C34H21N3O: 487.56, found: 487.24 [M+H]+. |
90% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran at 65℃; for 24h; Inert atmosphere; | |
85% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; water for 18h; Reflux; Inert atmosphere; | 1.1-1 Synthesis of the following intermediate A-1 In a nitrogen atmosphere, (9-oxo-9H-fluoren-1-yl)boronic acid (3.36g, 15mmol),2-(4-bromophenyl)-4,6-diphenyl-1,3,5-triazine (15mmol),Tetrakis(triphenylphosphine)palladium (1.73g, 1.5mmol) and potassium carbonate (4.14g, 30mmol) were dissolved in a mixed solvent of 300mL of tetrahydrofuran and 50mL of water, and heated to reflux for 18 hours.After the reaction stopped, it was cooled to room temperature, the tetrahydrofuran was removed by rotary evaporation, the liquid was separated with dichloromethane, the organic phase was collected, rotary dried, and separated by column chromatography to obtain Intermediate A-1 (6.23g).The yield was 85%. |
80% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; water for 24h; Inert atmosphere; Reflux; | 3 <Preparation Example 3> Synthesis of the following compound 3 Under the protection of nitrogen, 9-fluorenone-1-boronic acid (5.0g, 22.32mmol),2-(4-Bromophenyl)-4,6-diphenyl-1,3,5-triazine (8.66g, 22.32mmol), Tetra(triphenylphosphine) palladium (773.39mg, 0.67mmol),Anhydrous potassium carbonate (6.16g, 44.64mmol) is placed in a 250ml round bottom flask,And add 90ml tetrahydrofuran and 22ml distilled water.The above mixture was heated to reflux for 24 hours.After the reaction is over, the temperature is reduced to room temperature, filtered with suction, and washed with a large amount of distilled water,Then, it was purified by recrystallization with dichloromethane/ethanol to obtain Intermediate 2 (8.70 g, yield about 80%), which was dried for later use.Under the protection of nitrogen, place 2-bromo-triphenylamine (5.79g, 17.86mmol) in a 250ml two-necked flask,Add 77ml of anhydrous tetrahydrofuran to dissolve it, then place it at minus 78 degrees Celsius,Add 2.4M n-butyllithium solution (8.18ml, 19.64mmol) dropwise,After stirring for 1 hour at minus 78 degrees Celsius, intermediate 2 (8.72g, 17.86mmol) was added, stirred overnight and then quenched by adding 20ml of distilled water.The reaction solution was decompressed to remove tetrahydrofuran, and 40ml of dichloromethane was added to extract 3 times,Remove the dichloromethane under reduced pressure, add ethanol to recrystallize, and place the solid obtained after suction filtration and drying in a 250ml flask.Add 100ml of acetic acid and stir for 10 minutes, then add 3ml of concentrated hydrochloric acid and heat to 110°C and reflux for 3 hours.At the end of the reaction, the temperature dropped to room temperature, the reaction solution was poured into 500ml ice water, the product precipitated,After suction filtration, silica gel column chromatography was performed with the eluent of dichloromethane and petroleum ether to obtain compound 3 (10.22g, 14.29mmol, yield about 80%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In ethanol; water; toluene at 110℃; for 6h; | 7 Preparation of Compound 21 After adding 2-(4-bromophenyl)-4,6-diphenyl-1,3,5-triazine (7.8 g, 20.2 mmol), Pd(PPh3)4 (1.0 g, 0.92 mmol), K2CO3 (7.6 g, 55.2 mmol) and toluene/EtOH/H2O to Compound 21-2 (10.5 g, 19.8 mmol), the result was stirred for 6 hours at 110° C. After the reaction was completed, the result was cooled to room temperature, and extracted with distilled water and EA. After drying the organic layer with anhydrous MgSO4, the solvent was removed using a rotary evaporator, and with dichloromethane and hexane as a developing solvent, the result was purified using column chromatography to obtain target Compound 21 (12.7 g, 93%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In ethanol; water; toluene at 110℃; for 6h; | 4 Preparation of Compound 15-1 After adding 2-(4-bromophenyl)-4,6-diphenyl-1,3,5-triazine (9.5 g, 24.6 mmol), Pd(PPh3)4 (1.3 g, 1.16 mmol), K2CO3 (9.6 g, 69.6 mmol) and toluene/EtOH/H2O to Compound 1-4 (10 g, 22.3 mmol), the result was stirred for 6 hours at 110° C. After the reaction was completed, the result was cooled to room temperature, and extracted with distilled water and EA. After drying the organic layer with anhydrous MgSO4, the solvent was removed using a rotary evaporator, and with dichloromethane and hexane as a developing solvent, the result was purified using column chromatography to obtain target Compound 15-1 (12.3 g, 88%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In water; toluene at 100℃; for 10h; Inert atmosphere; | 2 Synthesis of n-46 In a 50 ml three-necked flask, under the protection of nitrogen, add intermediate p-38-2 (3.47 g, 0.01 mol), raw material 6 (0.01 mol),Potassium carbonate (0.012mol), toluene (25ml), water (5ml), tetrakis(triphenylphosphine)palladium (0.5mmol), stirred at 100°C for 10 hours, and cooled to room temperature after the reaction.Water was added to the reaction system and extracted with dichloromethane. The obtained extract was dried by adding magnesium sulfate, filtered and spin-dried in order; the crude product was purified by chromatography (ethyl acetate/n-hexane, 1/10) to obtain n- 46 (5.69 g, 87% yield). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With palladium diacetate; sodium t-butanolate; tri tert-butylphosphoniumtetrafluoroborate In toluene at 110℃; for 8h; Inert atmosphere; | |
70% | With palladium diacetate; sodium t-butanolate; tri tert-butylphosphoniumtetrafluoroborate In toluene at 110℃; for 14h; Inert atmosphere; | 1.3 M2 (1.07g, 1.5mmol), 4-bromophenyl-diphenyl-s-triazine (580mg, 1.5mmol) and toluene (40ml) were added to a 100ml vial,After blowing in nitrogen for 10 minutes, add palladium acetate (45mg, 0.2mmol),Tri-tert-butylphosphine tetrafluoroborate (116mg, 0.4mmol), sodium tert-butoxide (288mg, 3mmol), heated to 110 for 14 hours, after the completion of the reaction,Filter with diatomaceous earth, and distill the filtrate to remove organic solvents.Separated by column chromatography (petroleum ether/dichloromethane=3/1), a pale yellow solid compound 1 (1.07 g, yield 70%) was obtained. The hydrogen nuclear magnetic spectrum of compound 1 is shown in Fig. 4, and the electroluminescence spectrum of compound 1 under different doping concentrations is shown in Fig. 2. The electroluminescence spectrum was measured by the SPEX CCD3000 spectrometer of JY company in France. The measurements are all done in the atmosphere at room temperature. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With palladium diacetate; potassium carbonate; tris-(o-tolyl)phosphine In tetrahydrofuran; water at 60℃; for 2h; Inert atmosphere; | (Synthesis of IM-3) General procedure: IM-2 (1.05 eq., 105 mmol, 40.7 g), 2-chloro-4,6-diphenyl-1,3,5-triazine (1.0 eq., 100 mmol, 26.8 g), potassium carbonate aqueous solution ( 2.0M, 100ml),Tetrahydrofuran (300 ml) was placed in a three-necked flask and replaced with nitrogen, and then palladium acetate (4 mol%, 4 mmol, 0.90 g) and tri (o-tolyl) phosphine (6 mol%, 6 mmol, 1.83 g) were placed in the three-necked flask. In a nitrogen atmosphere, the mixture was heated and stirred at 60 ° C. for 2 hours.After completion of the reaction, the obtained reaction mixture solution was diluted with water (500 ml) and methanol (500 ml), the precipitated solid was collected by filtration, washed with water, rinsed with methanol, and vacuum dried (50 ° C., 16 h). Was done.The obtained crude product was dissolved in chloroform, passed through a short silica gel column, and concentrated.The precipitated solid was dispersed in ethyl acetate (500 ml), ultrasonically washed for 10 minutes, and then filtered.Further, the obtained sample was recrystallized from toluene (15 ml): ethyl acetate (30 ml) / sample (1 g) to obtain IM-3. The yield of IM-3 was 34.5 g, and the yield of IM-3 was 70%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butylphosphine tetrafluoroborate; sodium t-butanolate In toluene at 120℃; for 24h; Inert atmosphere; | 2.3.2. General procedure for syntheses of Cz-TRZ, 1-MeCz-TRZ, 1-MeCz-Pm General procedure: 2- (4-bromophenyl)-4,6-diphenyl-1,3,5-triazine or 2-(4-chlorophenyl)-4,6-diphenyl-1,3-pyrimidine (5.00 mmol), Cz or 1-MeCz (5.50mmol), tris(dibenzylideneacetone)dipalladium (0.25 mmol), tri-tertbutylphosphinetetrafluoroborate (0.75 mmol) and sodium tert-butoxide(10.00 mmol) were dissolved in dry toluene (150 mL) under N2 atmosphere.After stirring at 120 C for 24 h under N2 atmosphere, the reactionsolvent was removed by vacuum distillation, and the residue waspurified by column chromatography on silica gel to afford the crudeproduct. Repeated recrystallization from methanol/chloroform gave thepure products as white powders. Cz-TRZ: Yield: 82%. 1H NMR (400 MHZ, CDCl3) : 9.06 (d, J = 8.3Hz, 1H), 8.89-8.82 (m, 2H), 8.21 (d, J = 7.8 Hz, 1H), 7.85 (d, J = 8.2 Hz,1H), 7.64 (ddt, J = 20.1, 13.6, 6.6 Hz, 4H), 7.49 (t, J = 7.6 Hz, 1H), 7.37(t, J = 7.4 Hz, 1H). 13C NMR (126 MHZ, CDCl3) 170.83 (s), 140.63 (s),139.46 (s), 135.15 (s), 133.98 (s), 131.65 (s), 129.64 (s), 128.02 (s),127.70 (s), 125.74 (s), 125.15 (s), 122.77 (s), 119.42 (s), 119.40 (s),108.92 (s). TOF-EI-MS (m/z): calcd. for C33H22N4 474.1844, found474.1847 [M+]. Anal. calcd (%) for C33H22N4, C, 83.52; H, 4.67; N,11.81; Found: C, 83.51; H, 4.70; N, 11.83. |
80.9% | With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate In toluene for 5h; Inert atmosphere; Reflux; | 1.1 Under nitrogen protection, compound 1-a (5.02g, 388.26g/mol, 12.92mmol), compound 1-b (1.1eq, 2.37g, 167.21g/mol, 14.21mmol), sodium tert-butoxide (1.1eq, 1.37g, 96.1g/mol, 14.21mmol), tris(dibenzylideneacetone) two palladium (0.05eq, 0.59g, 915.72g/mol, 0.65mmol), tri-tert-butylphosphine (0.05eq, 0.13g, 202.32g/mol, 0.65mol) and toluene (50ml) were added to the reaction flask. After the addition, the temperature was raised to reflux and reacted for 5 hours. After the reaction was completed, the temperature was reduced to room temperature, and 50ml of water was added and stirred for 15 minutes. The filtrate was obtained by filtration. The filtrate was passed through diatomaceous earth. After filtration, the liquid was separated to obtain the organic phase. The organic phase was dried over anhydrous magnesium sulfate and spin-dried. After purification by column chromatography, compound 1-c (4.9 g, yield 80.4%) was obtained |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With tri-tert-butyl phosphine; palladium diacetate; sodium t-butanolate In toluene at 110℃; for 12h; Inert atmosphere; | 1 The indolo[3,2-B]carbazole (0.256g, 1mmol), 2-(4-bromophenyl)-4,6-diphenyl-1,3,5-triazine (0.814g, 2.1mmol), sodium tert-butoxide (0.288g, 3mmol) and palladium acetate (0.022g, 0.1mmol) were added to the reaction flask, evacuated three times, under the protection of nitrogen, add tri-tert-butyl phosphine (0.061g, 0.3 mmol), and finally add 20 mL of toluene, raise the temperature to 110° C., and react at this temperature for 12 hours. After the reaction, the reaction solid was obtained by suction filtration, and then recrystallized with dichloromethane and methanol, and the final product p-TRZ-ICz was obtained by suction filtration, and the final yield was 93%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butylphosphine tetrafluoroborate; sodium t-butanolate In toluene at 120℃; for 24h; Inert atmosphere; | 2.3.2. General procedure for syntheses of Cz-TRZ, 1-MeCz-TRZ, 1-MeCz-Pm General procedure: 2- (4-bromophenyl)-4,6-diphenyl-1,3,5-triazine or 2-(4-chlorophenyl)-4,6-diphenyl-1,3-pyrimidine (5.00 mmol), Cz or 1-MeCz (5.50mmol), tris(dibenzylideneacetone)dipalladium (0.25 mmol), tri-tertbutylphosphinetetrafluoroborate (0.75 mmol) and sodium tert-butoxide(10.00 mmol) were dissolved in dry toluene (150 mL) under N2 atmosphere.After stirring at 120 C for 24 h under N2 atmosphere, the reactionsolvent was removed by vacuum distillation, and the residue waspurified by column chromatography on silica gel to afford the crudeproduct. Repeated recrystallization from methanol/chloroform gave thepure products as white powders. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
67% | Stage #1: 3-bromo-10H-phenothiazine; 4-(dimethylamino)benzene-boronic acid With cesium fluoride; bis(dibenzylideneacetone)-palladium(0); tri tert-butylphosphoniumtetrafluoroborate In 1,4-dioxane at 120℃; for 16h; Schlenk technique; Inert atmosphere; Stage #2: 2-(4-bromobenzenyl)-4,6-diphenyl-1,3,5-triazine With sodium t-butanolate In 1,4-dioxane at 120℃; for 20h; Schlenk technique; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
56% | Stage #1: 3-bromo-10H-phenothiazine; 4-methoxyphenylboronic acid With cesium fluoride; bis(dibenzylideneacetone)-palladium(0); tri tert-butylphosphoniumtetrafluoroborate In 1,4-dioxane at 120℃; for 16h; Schlenk technique; Inert atmosphere; Stage #2: 2-(4-bromobenzenyl)-4,6-diphenyl-1,3,5-triazine With sodium t-butanolate In 1,4-dioxane at 120℃; for 20h; Schlenk technique; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | Stage #1: 3-bromo-10H-phenothiazine; phenylboronic acid With cesium fluoride; bis(dibenzylideneacetone)-palladium(0); tri tert-butylphosphoniumtetrafluoroborate In 1,4-dioxane at 120℃; for 16h; Schlenk technique; Inert atmosphere; Stage #2: 2-(4-bromobenzenyl)-4,6-diphenyl-1,3,5-triazine With sodium t-butanolate In 1,4-dioxane at 120℃; for 20h; Schlenk technique; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | Stage #1: 3-bromo-10H-phenothiazine; 4-trifluoromethylphenylboronic acid With cesium fluoride; bis(dibenzylideneacetone)-palladium(0); tri tert-butylphosphoniumtetrafluoroborate In 1,4-dioxane at 120℃; for 16h; Schlenk technique; Inert atmosphere; Stage #2: 2-(4-bromobenzenyl)-4,6-diphenyl-1,3,5-triazine With sodium t-butanolate In 1,4-dioxane at 120℃; for 20h; Schlenk technique; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68.3% | With tri-tert-butyl phosphine; potassium <i>tert</i>-butylate; palladium diacetate In 1,4-dioxane; water; toluene for 6h; Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); potassium carbonate In ethanol; lithium hydroxide monohydrate; toluene for 5h; Inert atmosphere; Reflux; | 1.4 4. Synthesis of intermediates 1-4 2,4-Diphenyl-6-(4-bromophenyl)-1,3,5-triazine (8.0 g, 20.60 mmol), p-chlorophenylboronic acid (3.86 g, 24.72 mmol), potassium carbonate ( 8.54g, 61.79mmol) was added to the three-necked flask, toluene (48mL), ethanol (24mL) and deionized water (24mL) were added, under nitrogen protection, bis(triphenylphosphine) palladium dichloride (0.16g) was added, The reaction was heated to reflux for 5h. After cooling to room temperature, a solid was precipitated, which was filtered off with suction. The filter cake was recrystallized with 150 mL of toluene to obtain 8.0 g of an off-white solid with a yield of 92%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; palladium diacetate; sodium t-butanolate In o-xylene at 185℃; for 4h; | 1 1. Synthesis of the Compound Host1-1 In a flask, the compound A1 (13.67 g, 50 mmol), the compound C1 (23.30 g, 60 mmol), Pd(OAc)2 (0.55 g, 2.49 mmol), S-Phos (2.04 g, 4.98 mmol), NaOt-Bu (8.6 g, 90.14 mmol) and o-xylene (500 ml) were mixed and heated at 185°C. for 4 hours. After cooling to room temperature, distilled water was added. The organic layer was extracted with ethyl acetate and distilled under reduced pressure. The obtained solid was separated by a column to obtain the compound Host1-1 (20.3 g, yield: 70.0%). |
20.5 g | Stage #1: 12H-benzo[4,5]thieno[2,3-a]carbazole With trifluorormethanesulfonic acid; benzene-d6 In 1,2-dichloro-benzene at 70 - 150℃; Stage #2: 2-(4-bromophenyl)-4,6-diphenyl-1,3,5-triazine With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; palladium diacetate; sodium t-butanolate In o-xylene at 185℃; | 17 Synthesis of Compound J-2 In a flask, compound J-1 (20.0 g, 9.0 mmol) and 1200 mL of 1,2-dichlorobenzene were added, and then the mixture was stirred at 150° C. in which compound J-1 was completely dissolved. 800 mL of benzene-D6 and triflic acid (67.6 g, 450.4 mmol) were added at 70° C. After 3 hours, the mixture was cooled to room temperature. Thereafter, 40 mL of D2O was added and stirred for 10 minutes. After neutralization with an aqueous K3PO4 solution, an organic layer was extracted with ethyl acetate, and residual moisture was removed with magnesium sulfate. The organic layer was distilled under reduced pressure and separated by column chromatography to obtain compound J-2 (15 g, yield: 72.99%). (0132) Synthesis of Compound J (0133) In a flask, compound J-2 (14 g, 49.8 mmol), compound J-3 (23.21 g, 59.78 mmol), Pd(OAc)2 (0.55 g, 2.49 mmol), S-phos (2.04 g, 4.98 mmol), NaOt-bu (8.6 g, 90.14 mmol), and 500 mL of o-xylene were added, and the mixture was heated to 185° C. for 4 hours. Thereafter, the mixture was cooled to room temperature, and then distilled water was added. An organic layer was extracted with ethyl acetate, and distilled under reduced pressure. The obtained solid was separated by column chromatography to obtain compound J (20.5 g, yield: 70.0%). |
20.5 g | Stage #1: 12H-benzo[4,5]thieno[2,3-a]carbazole With trifluorormethanesulfonic acid; benzene-d6 In 1,2-dichloro-benzene at 70℃; Stage #2: 2-(4-bromophenyl)-4,6-diphenyl-1,3,5-triazine With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; palladium diacetate; sodium t-butanolate In o-xylene at 185℃; | 17 Synthesis of Compound J-2 In a flask, compound J-1 (20.0 g, 9.0 mmol) and 1200 mL of 1,2-dichlorobenzene were added, and then the mixture was stirred at 150° C. in which compound J-1 was completely dissolved. 800 mL of benzene-D6 and triflic acid (67.6 g, 450.4 mmol) were added at 70° C. After 3 hours, the mixture was cooled to room temperature. Thereafter, 40 mL of D2O was added and stirred for 10 minutes. After neutralization with an aqueous K3PO4 solution, an organic layer was extracted with ethyl acetate, and residual moisture was removed with magnesium sulfate. The organic layer was distilled under reduced pressure and separated by column chromatography to obtain compound J-2 (15 g, yield: 72.99%). (0132) Synthesis of Compound J (0133) In a flask, compound J-2 (14 g, 49.8 mmol), compound J-3 (23.21 g, 59.78 mmol), Pd(OAc)2 (0.55 g, 2.49 mmol), S-phos (2.04 g, 4.98 mmol), NaOt-bu (8.6 g, 90.14 mmol), and 500 mL of o-xylene were added, and the mixture was heated to 185° C. for 4 hours. Thereafter, the mixture was cooled to room temperature, and then distilled water was added. An organic layer was extracted with ethyl acetate, and distilled under reduced pressure. The obtained solid was separated by column chromatography to obtain compound J (20.5 g, yield: 70.0%). |
20.5 g | Stage #1: 12H-benzo[4,5]thieno[2,3-a]carbazole With trifluorormethanesulfonic acid; benzene-d6 In 1,2-dichloro-benzene at 70℃; Stage #2: 2-(4-bromophenyl)-4,6-diphenyl-1,3,5-triazine With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; palladium diacetate; sodium t-butanolate In o-xylene at 185℃; | 17 Synthesis of Compound J-2 In a flask, compound J-1 (20.0 g, 9.0 mmol) and 1200 mL of 1,2-dichlorobenzene were added, and then the mixture was stirred at 150° C. in which compound J-1 was completely dissolved. 800 mL of benzene-D6 and triflic acid (67.6 g, 450.4 mmol) were added at 70° C. After 3 hours, the mixture was cooled to room temperature. Thereafter, 40 mL of D2O was added and stirred for 10 minutes. After neutralization with an aqueous K3PO4 solution, an organic layer was extracted with ethyl acetate, and residual moisture was removed with magnesium sulfate. The organic layer was distilled under reduced pressure and separated by column chromatography to obtain compound J-2 (15 g, yield: 72.99%). (0132) Synthesis of Compound J (0133) In a flask, compound J-2 (14 g, 49.8 mmol), compound J-3 (23.21 g, 59.78 mmol), Pd(OAc)2 (0.55 g, 2.49 mmol), S-phos (2.04 g, 4.98 mmol), NaOt-bu (8.6 g, 90.14 mmol), and 500 mL of o-xylene were added, and the mixture was heated to 185° C. for 4 hours. Thereafter, the mixture was cooled to room temperature, and then distilled water was added. An organic layer was extracted with ethyl acetate, and distilled under reduced pressure. The obtained solid was separated by column chromatography to obtain compound J (20.5 g, yield: 70.0%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
59.1 % | With potassium phosphate; tetrakis(triphenylphosphine) palladium(0) In ethanol; water; toluene Reflux; | 9 Preparation Example 9: Synthesis of Compound 2-62 (LT20-35-469) In a one-neck 250 mL flask, 2-(4-bromophenyl)-4,6-diphenyl-1,3,5-triazine (2-(4-bromophenyl)-4,6-diphenyl-1,3, 5-triazine) 5.0 g (12.9 mmol), (4'-cyano-[1,1-diphenyl]-4-yl)boronic acid ((4'-cyano-[1,1'-biphenyl]-4 -yl)boronic acid) 2.9 g (12.9 mmol), Pd(PPh3)4 744.1 mg (643.9 μmol), K3PO410.9 g (51.5 mmol), toluene 60 mL, ethanol 30 mL and water 15 mL were mixed. After that, the mixture was stirred under reflux for 12 hours.After the reaction was completed, the mixture was cooled to room temperature, filtered, washed with water and ethanol, and dried.The dried solid was dissolved in chloroform, purified by column chromatography (CHCl3:EA), and solidified with ethyl acetate to obtain 3.7 g (yield: 59.1%) of Compound 2-62 (LT20-35-469) as a white solid. |
Tags: 23449-08-3 synthesis path| 23449-08-3 SDS| 23449-08-3 COA| 23449-08-3 purity| 23449-08-3 application| 23449-08-3 NMR| 23449-08-3 COA| 23449-08-3 structure
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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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