2-(4-bromophenyl)-4,6-diphenyl-1,3,5-triazine

white solid powder

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 MgSO2-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)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).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).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.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.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).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;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).

Molecular Weight:388.3
XLogP3:5.7
Hydrogen Bond Acceptor Count:3
Rotatable Bond Count:3
Exact Mass:387.03711
Monoisotopic Mass:387.03711
Topological Polar Surface Area:38.7
Heavy Atom Count:25
Complexity:372
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes