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).
Reference：
[1] Patent: US2017/331067, 2017, A1, . Location in patent: Paragraph 0260-0263
[2] Chemistry - An Asian Journal, 2016, vol. 11, # 6, p. 868 - 873
[3] Patent: KR2015/75169, 2015, A, . Location in patent: Paragraph 0206-0209
[4] Patent: KR2015/59395, 2015, A, . Location in patent: Paragraph 0162; 0163; 0164; 0165
[5] Patent: KR2015/88163, 2015, A, . Location in patent: Paragraph 0342-0345
2
[ 3842-55-5 ]
[ 68716-49-4 ]
[ 23449-08-3 ]
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).
Reference：
[1] Patent: WO2006/67931, 2006, A1, . Location in patent: Page/Page column 60
[2] Patent: EP2808323, 2014, A1,
[3] Patent: CN107880030, 2018, A,
[4] Patent: CN108440430, 2018, A,
4
[ 106-37-6 ]
[ 3842-55-5 ]
[ 23449-08-3 ]
Reference：
[1] Chemical Communications, 2016, vol. 52, # 73, p. 10956 - 10959
5
[ 3842-55-5 ]
[ 1073062-59-5 ]
Reference：
[1] Patent: JP2017/197482, 2017, A, . Location in patent: Paragraph 0204
6
[ 3842-55-5 ]
[ 89598-96-9 ]
[ 864377-31-1 ]
Yield
Reaction Conditions
Operation in experiment
95%
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; water at 80℃; for 12 h; Inert atmosphere
Under a nitrogen atmosphere, 50g (187mmol) the compound 2-chloro-4,6-diphenyl-1,3,5-triazine was dissolved in 1L of tetrahydrofuran (tetrahydrofuran, THF) added thereto 45g (224.12mmol) (3-bromophenyl) borate, and 2.1g (1.87 mmol) of tetrakis (triphenylphosphine) palladium, and the mixture was stirred. Subsequently, thereto added 64g (467mmol) of potassium carbonate saturated aqueous solution, and the resulting mixture was heated at reflux for 80 12 hours. When the reaction is complete, add water to the reaction solution, and the mixture was extracted with dichloromethane (dichloromethane, DCM), followed by removal of water with anhydrous MgSO4 filtered and concentrated under reduced pressure. Subsequently, the obtained residue was separated and purified via flash column chromatography to give 69g (95percent) compound II-1.
95%
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; water at 80℃; for 12 h; Inert atmosphere
SYNTHESIS EXAMPLE 1 Synthesis of Intermediate I-1 (0197) (0198) The compound, 2-chloro-4,6-diphenyl-1,3,5-triazine (50 g, 187 mmol) was dissolved in 1 L of THF (tetrahydrofuran) in a nitrogen environment, (3-bromophenyl)boronic acid (45 g, 224.12 mmol) 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 resulting mixture was heated and refluxed at 80° C. for 12 hours. When the reaction was complete, water was added to the reaction solution. dichloromethane (DCM) was used for an extraction, and an extract therefrom was filtered after removing moisture with anhydrous MgSO4 and then, concentrated under a reduced pressure. This obtained residue was separated and purified through flash column chromatography to obtain the intermediate I-1 (69 g and 95percent). (0199) HRMS (70 eV, EI+): m/z calcd for C21H14BrN3:387.0371, found: 387. (0200) Elemental Analysis: C, 65percent; H, 4percent
95%
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; water at 80℃; for 12 h; Inert atmosphere
In a nitrogen environment, 2-chloro-4,6-diphenyl-1,3,5-triazine (50 g, 187 mmol) was dissolved in 1 L of tetrahydrofuran (THF)To this was added (3-bromophenyl) boronic acid (45 g, 224.12 mmol)And tetrakis (triphenylphosphine) palladium(2.1 g, 1.87 mmol) were added and stirred. Saturated water-saturated potassium carbonate (64 g, 467 mmol)And the mixture was refluxed by heating at 80 ° C for 12 hours. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM). Then, water was removed with anhydrous MgSO 4,Filtered and concentrated under reduced pressure.The thus-obtained residue was purified by flash column chromatography(Flash column chromatography) to obtain intermediate II-1(69 g, 95percent).
95%
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; water at 80℃; for 12 h; Inert atmosphere
Synthesis Example 1: Synthesis of Intermediate I-1 (0132) (0133) The compound, 2-chloro-4,6-diphenyl-1,3,5-triazine (50 g, 187 mmol, TCI Inc.) was dissolved in THF (1 L) under a nitrogen environment, (3-bromophenyl)boronic acid (45 g, 224.12 mmol, TCI Inc.) 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), filtered after removing moisture with anhydrous MgSO4, and concentrated under a reduced pressure. The obtained residue was separated and purified through column chromatography to obtain Intermediate I-1 (69 g and 95percent). (0134) FIRMS (70 eV, EI+): m/z calcd for C21H14BrN3: 387.0371. found: 387. (0135) Elemental Analysis: C, 65percent; H, 4percent
95%
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; water at 80℃; for 12 h; Inert atmosphere
Synthesis Example 1: Synthesis of Intermediate I-1 A compound, 2-chloro-4,6-diphenyl-1,3,5-triazine (50 g, 187 mmol, TCI) was dissolved in THF (1 L) under a nitrogen environment, (3-bromophenyl)boronic acid (45 g, 224.12 mmol) 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. The obtained residue was separated and purified through column chromatography to obtain Compound I-1 (69 g, 95percent). HRMS (70 eV, EI+): m/z calcd for C21H14BrN3: 387.0371. found: 387. Elemental Analysis: C, 65percent; H, 4percent
75.3%
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In ethanol; water; toluene at 90℃; for 12 h; Inert atmosphere
The compound 2-chloro-4,6-diphenyl-1,3,5-triazine (5.35 g, 20 mmol) and 3-bromo-phenylboronic acid (4.01 g, 20 mmol) were dissolved in toluene (100 ml).Add ethanol (20 ml) and aqueous potassium carbonate (2M, 20 ml).In the N2 atmosphere,Tetrakis(triphenylphosphine)palladium (345 mg, 0.3 mmol) was added and the reaction was stirred at 90 ° C for 12 hours;After the reaction is completed, distilled water is added to the reaction mixture to separate the toluene layer.Extract the water layer with dichloromethane,The extracted organic layer was dried over anhydrous magnesium sulfate and filtered.The dichloromethane was distilled off under reduced pressure, and the obtained crude product was separated by column chromatography.The eluent is petroleum ether, which gives a white solid (compound 1).The yield was 75.3percent (5.84 g).
66%
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 1 L of THF in a nitrogen atmosphere,3-bromophenyl boronic acid (45 g, 224.12 mmol) and tetrakis (triphenylphosphine) palladium (2.63 g,2.82 mmol) were added and stirred. Saturated water-saturated potassuim carbonate (51.6 g, 373.54 mmol) was added and heated at 80 ° C for 53& Lt; / RTI & gt; for a period of time. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM)The water was removed with MgSO4, filtered and concentrated under reduced pressure. The residue thus obtained was purified by flash column chromatographySeparation and purification were conducted to obtain the above compound I-5 (57 g, 66percent).
Reference：
[1] Patent: CN105566200, 2016, A, . Location in patent: Paragraph 0326; 0327; 0328; 0329
[2] Patent: US2017/84845, 2017, A1, . Location in patent: Paragraph 0197-0200
[3] Patent: KR2017/11338, 2017, A, . Location in patent: Paragraph 0390; 0392-0395
[4] Patent: US2017/222158, 2017, A1, . Location in patent: Paragraph 0132; 0133; 0134; 0135
[5] Patent: US2017/331067, 2017, A1, . Location in patent: Paragraph 0184-0187
[6] Patent: CN108409730, 2018, A, . Location in patent: Paragraph 0054; 0058; 0059; 0060
[7] Patent: KR2015/59395, 2015, A, . Location in patent: Paragraph 0168; 0169; 0170; 0171
7
[ 108-36-1 ]
[ 3842-55-5 ]
[ 864377-31-1 ]
Yield
Reaction Conditions
Operation in experiment
40.4%
Stage #1: With n-butyllithium In tetrahydrofuran-d8 at -78℃; for 1 h; Stage #2: at 20℃; for 5 h;
1,3-Dibromobenzene 28 g(0.119 mol) was dissolved in THF 600 mL, and then n-BuLi 47.5 mL was slowly added dropwise thereto at -78°C, followed by stirring for 1 hour. 2-Chloro-4,6-diphenyl-1,3,5-triazine 47.5 mL was slowly added dropwise thereto, and the resultant mixture was stirred at room temperature for 5 hours after the temperature was slowly raised. After the reaction is completed, extraction with EA and distilled water and column separation were sequentially performed, thereby obtaining Compound 9-1 15.7 g (40.43 mmol, 40.4percent).
28%
With n-butyllithium In tetrahydrofuran at -78 - 20℃; for 12 h;
1,3-dibromobenzene was dissolved in THF and cooled into the temperature of —78° C. n-l3uLi (60 mE, 2.5M) was slowly dropped into the solution, and 2-chioro-4,6-diphenyl-1,3,5-triazine (40 g, 149.7 mmol), whichdissolved in THF, was slowly dropped. The solution was slowly heated up to the room temperature and stirred forhours. After completion of the reaction, the resultant was re-precipitated by THF/MeOH and MC (methylenechloride)/hexane such that 2-(3-bromophenyl)-4,6-diphenyl-15-triazine (16 g, yield: 28percent) was obtained.
Reference：
[1] Patent: EP2857395, 2015, A1, . Location in patent: Paragraph 0076
[2] Patent: US2018/130953, 2018, A1, . Location in patent: Paragraph 0211; 0212
[3] Patent: JP2016/108255, 2016, A, . Location in patent: Paragraph 0087-0089
8
[ 591-18-4 ]
[ 3842-55-5 ]
[ 864377-31-1 ]
Yield
Reaction Conditions
Operation in experiment
30%
Stage #1: With n-butyllithium In tetrahydrofuran at -78℃; for 1.5 h; Inert atmosphere Stage #2: at 20℃; for 1.5 h; Inert atmosphere
To a round bottom flask, 1-bromo-3-iodo-benzene (60.0 g, 212 mmol), 480 mL of tetrahydrofuran were added and the temperature falls to -78° C under a nitrogen condition . After 30 minutes, 126 mL of 1.6 M n-butyllithium (202 mmol) was slowly added dropwise . After 1 hour, 2-chloro-4,6-diphenyl-1,3,5-triazine 62.4 g (233 mmol) was dissolved in 250 mL of tetrahydrofuran, after dropping a solution slowly comes to room temperature and then stirred for 30 minutes. After stirring for about 1 hour at room temperature, 2N hydrochloric acid was added dropwise to the reaction solution until the acid is an aqueous solution. The combined organic layer was then extracted, concentrated and then separated by column chromatography to give <4-a> 24.7g (yield 30percent).
2-(2,4-Dihydroxy-5-hexylphenyl)-4,6-diphenyl-s-triazine[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With hydrogenchloride;aluminium trichloride; In 5,5-dimethyl-1,3-cyclohexadiene;
EXAMPLE 19 2-(2,4-Dihydroxy-5-hexylphenyl)-4,6-diphenyl-s-triazine To a 350 mL sulfonation flask equipped with a mechanical stirrer, condenser and a nitrogen atmosphere are charged 21.4 g (80 mmol) of 2-chloro-4,6-diphenyl-s-triazine, and 100 mL of xylene (mixture of isomers). To the beige suspension are added 11.3 g (85 mmol) of aluminum chloride in one portion. The mixture is warmed to ca. 80 C. for 45 minutes. 18.8 g (96 mmol) of 4-hexylresorcinol are then added in five portions over 40 minutes to the now homogeneous solution. The reaction mixture is heated at 90 C. for 24 hours. After cooling to room temperature, the contents of the flask are poured into 100 mL of 12% aqueous hydrochloric acid. The precipitate formed is removed by filtration, washed to pH 7 with water, rinsed with methanol and dried at 70 C. under vacuum. The title compound is obtained as a crude orange product (29.2 g) and melts at 209-213 C. It can be used without further purification.
With hydrogenchloride;aluminium trichloride; In 5,5-dimethyl-1,3-cyclohexadiene;
Example 19 2-(2,4-Dihydroxy-5-hexylphenyl)-4,6-diphenyl-s-triazine To a 350 mL sulfonation flask equipped with a mechanical stirrer, condenser and a nitrogen atmosphere are charged 21.4 g (80 mmol) of 2-chloro-4,6-diphenyl-s-triazine, and 100 mL of xylene (mixture of isomers). To the beige suspension are added 11.3 g (85 mmol) of aluminum chloride in one portion. The mixture is warmed to ca. 80 C. for 45 minutes. 18.8 g (96 mmol) of 4-hexylresorcinol are then added in five portions over 40 minutes to the now homogeneous solution. The reaction mixture is heated at 90 C. for 24 hours. After cooling to room temperature, the contents of the flask are poured into 100 mL of 12% aqueous hydrochloric acid. The precipitate formed is removed by filtration, washed to pH 7 with water, rinsed with methanol and dried at 70 C. under vacuum. The title compound is obtained as a crude orange product (29.2 g) and melts at 209-213 C. It can be used without further purification.
Next, 4.36 g (100.0 mmoles) of a 55percent dispersion of sodium hydride and 70 ml of dehydrated DMF were placed in a 2000-ml three-necked flask and the mixture was stirred in a stream of nitrogen. To this mixture was added dropwise a solution of 10.4 g (40.6 mmoles) of the aforementioned solid C in 150 ml of dehydrated DMF over 10 minutes. Upon completion of the dropwise addition, the mixture was stirred continuously for 1 hour. Then, to the mixture was added dropwise a solution of 20.9 g (78.0 mmoles) of 2-chloro-4,6-diphenyl-1,3,5-triazine in 300 ml of dehydrated over 1 hour. Upon completion of the dropwise addition, the mixture was stirred continuously for 3 hours. Thereafter, 900 g of water was added, the crystals separated were collected by filtration, reslurried twice with 450 g of water, further reslurried with 450 g of methanol, the solvent was distilled off under reduced pressure, and 42.0 g of brown crystals was obtained. The brown crystals were purified by crystallization from THF and methanol and stripped of the solvent under reduced pressure to give 13.4 g (18.6 mmoles, 46percent yield) of a light brown solid or Compound 114: APCI-MS, m/z 719 [M+1]+; melting point, 498°C.
In a 2000-ml three-necked flask that had been deaerated and filled with nitrogen were placed 4.80 g (110.0 mmoles) of a 55% dispersion of sodium hydride and 70 ml of dehydrated DMF and the mixture was stirred in a stream of nitrogen. To this mixture was added dropwise a solution of 13.5 g (52.7 mmoles) of indolo[2,3-a]carbazole in 150 ml of dehydrated DMF over 10 minutes. Upon completion of the dropwise addition, the mixture was stirred for 1 hour or so and to this mixture was added dropwise a solution of 29.4 g (110.0 mmoles) of 2-chloro-4,6-diphenyl-1,3,5-triazine in 150 ml of dehydrated DMF over 1 hour. Upon completion of the dropwise addition, the mixture was stirred for 3 hours, 900 g of water was added, and the crystals separated were collected by filtration. The crystals were reslurried twice with 450 g of water, further reslurried with 450 g of methanol, the solvent was distilled off under reduced pressure, and 35.0 g of crystals was obtained. Purification of the crystals by crystallization from THF/methanol gave 24 g (33.4 mmoles, 63.4% yield) of a yellow solid or Compound 37: APCI-MS, m/z 719 [M+1]+; melting point, 426C.
Synthesis of Comparative Compound 1. 3,6-Diphenyl-9H-carbazole (4.00 g, 12.52 mmol) was dissolved in anhydrous DMF (170 mL) and treated with NaH (0.751 g, 18.79 mmol, 60percent dispersion in mineral oil) while stirring vigorously at room temperature providing yellow solution. Once H2 evolution stopped, the solution was stirred for 1 hour, and then treated with 2-chloro-4,6-diphenyl-1,3,5-triazine (5.03 g, 18.79 mmol), and left stirred overnight at room temperature. After stirring for ?30 minutes, reaction solution had significant white precipitate swirling around. The crude mixture was quenched with water and filtered. The white precipitate was washed with water, MeOH, and EtOH. The material was recrystallized from toluene (400 mL) to obtain the target, Comparative Compound 1 with 99.86percent purity. One more recrystallization from toluene gave a purity of 100percent to afford 6.0 g (87percent yield).
2-(6-bromodibenzofuran-4-yl)-4,6-diphenyl-1,3,5-triazine[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
34%
The 80g (245 mmole) of <strong>[201138-91-2]4,6-dibromo-dibenzofuran</strong> been dissolved by heating in a dry flask 500ml of dry THF. The reaction mixture was cooled to -78 . At this temperature was slowly added dropwise 57ml of n-phenyl lithiumDibutyl ether (115 mmol) of 1.9M solution. The batch was stirred for another hour at -73 deg.] C. Then 65g of 2-chloro-4,6-diphenyl-1,3,5-triazine (245 mmol) was dissolved in 150ml of THF and added dropwise at -70 deg.] C. When the addition was complete, the reaction mixture was slowly warmed to room temperature and stirred at room temperature overnight, quenched with water and then evaporated in a rotary evaporator, during which a white solid precipitated. The batch was then cooled to room temperature, filtered off by suction and has precipitated solid was rinsed with methanol. The yield was 40g (84 mmole), corresponding to 34% of the theoretical.
34%
80 g (245 mmol) <strong>[201138-91-2]4,6-dibromdibenzofuran</strong> are dissolved in a heated flask in 500 ml of dried THF. The reaction mixture is cooled to -78 C. At this temperature 57 ml of a 9 M solution of phenyllithium in dibutyl ether (115 mmol) are slowly added dropwise. The mixture is stirred at -73 C for 1 hour. Subsequently, 65 g of 2-chloro-4,6-diphenyl-1, 3,5-triazine (245 mmol) dissolved in 150 ml THF and added dropwise at -70 C . After completion of the addition, the reaction mixture is slowly warmed to room temperature.Stirred room temperature, quenched with water and then concentrated on a rotary evaporator. This precipitates a white solid. The mixture is then cooled to room temperature and the precipitated solid is suction filtered and washed with methanol. The yield is 40 g (84 mmol) corresponding to 34% of theory.
3-(9-carbazolyl) carbazole (3.8g) under nitrogen dissolved in 60 ml dry N, N '-dimethyl formamide. Adding 0.7g of sodium hydride, and stirring at room temperature 1 hour. N then dissolved in dry, N '-dimethyl formamide in the 2-chloro -4, 6 diphenyl -1, 3, 5-triazine (U-1, 3.6g) solution (25 ml) is added to the reaction mixture. The reaction further stirring 3 hours. In water is poured into the reaction mixture, to precipitate the product. Then with methanol-hexane for cleaning solid, and drying under vacuum, in order to obtain 5.4g of the 2, 4-diphenyl-6-(-carbazolyl 3-N) carbazole -9 the [...] -yl)-1, 3, 5-triazine, i.e. compound 2-1 (84%).
NaH 0.45 g (18.72 mmol, 60% in mineral oil) and 12 mL DMF and 2.1 g mixed compound 4-2 (12.48 mmol) and 20 mL DMF to dissolve Add. After stirred for 30 minutes Add and dissolve 3.6 g of the compound 2-1 (13.73 mmol) in 25 mL DMF. 12 hours under a reduced pressure, the resulting solid was filtered and then distilled water was stirred. Recrystallized from EA to give the compound 124 2.6 g (6.50 mmol, 54.24%).
With tetrakis(triphenylphosphine) palladium(0); caesium carbonate; In ethanol; water; toluene; at 120℃; for 3h;
Preparation of compound 4-2[223]After introducing compound 4-1 (20 g, 70.4 mmol), compound A (12.5 g, 46.7 mmol), Cs2CO3(30 g, 93.3 mmol), Pd(PPh3)4(5 g, 4.67 mmol), toluene 150 mL, EtOH 50 mL, and H2O 50 mL into a flask, the mixture was stirred under reflux at 120C for 3 hours. After the reaction is completed, an organic layer was extracted with ethyl acetate, and remaining moisture was removed with magnesium sulfate and dried. The remaining product was then separated with column chromatography to obtain compound 4-2 (7.5 g, 41%).
2-(4-fluoro-3-methylphenyl)-4,6-diphenyl-1,3,5-triazine[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
86.3%
With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In tetrahydrofuran; ethanol;Reflux;
Take 2.0 g of 2-chloro-4,6-diphenyl-1,3,5-triazine (7.49 mmol)Add in a dry 250 ml two-necked bottle, then add 3.97 g of sodium carbonate and100 mL of a mixture of tetrahydrofuran and ethanol, 1.5 g<strong>[139911-27-6](4-fluoro-3-methylphenyl)boronic acid</strong> (9.74 mmol),(volume ratio = 4:1). After deaeration with nitrogen, 0.087 g of tetrakis(triphenylphosphine)palladium (0.075 mmol) was added.Stir and heat to reflux. After the 2-chloro-4,6-diphenyl-1,3,5-triazine reaction is completely consumed,After cooling to room temperature, the obtained crude product was purified by column chromatography.Obtained a white powder (2.2 g),The yield was 86.3%.
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; water; toluene; for 12h;Reflux;
13 g of compound 1-3 (49 mmol), 14.5 g of 2-chloro-4,6-diphenyl-1,3,5-triazine (54 mmol), 2.8 g of tetrakis(triphenylphosphine)palladium (2.4 mmol), 17 g of potassium carbonate (123 mmol), 240 mL of toluene, 30 mL of ethanol, and 60 mL of distilled water were introduced into a reaction vessel, and the mixture was stirred under reflux for 12 hours. After completion of the reaction, the mixture was washed with distilled water, extracted with ethyl acetate, and the extracted organic layer was dried with magnesium sulfate. The solvent was removed with a rotary evaporator, and the resulting product was purified by column chromatography to obtain 18 g of compound 1-4 (yield: 100%).
Prepare the format reagent, 2.67g of 2-chloro-4,6-diphenyl-1,3,5-triazine,0.4 mol of magnesium was added to 50 tetrahydrofuran, and the temperature was raised to reflux reaction.Gradually adding the remaining 24gA saturated solution of 2-chloro-4,6-diphenyl-1,3,5-triazine in tetrahydrofuran was kept at reflux for about 1 h, and was used.Add 29.6 g of 1-bromo-3-iodo-2-toluene and 300 ml of tetrahydrofuran to another three-necked flask and mix well.Nitrogen protection, cooling to -5 C, transfer the prepared format reagent to the dropping funnel,Slowly add dropwise to keep the temperature of the system not exceeding 10 C.After the addition was completed, stir for 30 minutes and then slowly increase to room temperature.After 5 hours, the reaction of the starting material was completed, and a saturated aqueous solution of ammonium chloride was added dropwise to the reaction solution.After stirring for 5 min, dichloromethane was extracted, and the organic phase was dried under reduced pressure.The residue was subjected to column chromatography to give 25.7 g of Intermediate 39-1. (yield 64%)
2-(4-chloronaphthalen-1-yl)-4,6-diphenyl-1,3,5-triazine[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
71%
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; for 12.0h;Reflux; Inert atmosphere;
Reagent 6-1 (50.0 g, 187.27 mmol) and Reagent 2 (42.5 g, 205.99 mmol) were put into 1,000 ml of tetrahydrofuran under a nitrogen atmosphere, and the resulting mixture was stirred and refluxed. Thereafter, potassium carbonate (51.8 g, 374.53 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 (6.5 g, 5.62 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 6A (52.3 g, 71%). Reagents 6-1 and 2 were purchased from Aldrich and TCI, respectively.
<Reaction Scheme 2> In the reaction vessel, <strong>[117635-21-9]1,4-dibromo-2,5-dihexylbenzene</strong> (0.81 g, 2.0 0 mmol),20 ml of tetrahydrofuran was added, and at -78 C.,The mixture was stirred. Thereafter, 1.6 M n-butyllithium (n-BuLi) hexane solution (2.53 ml, 4.00 mmol) was added dropwise and after stirring for 1 hour, 3,5-diphenyl- 1-chlorotriazine was added , And the mixture was stirred at room temperature for 3 hours.After completion of the reaction, water was added to the reaction mixture,The mixture was extracted with chloroform, and the organic layer was concentrated. after that,Tetrahydrofuran was added to and dissolved in the resulting residue,Purification was carried out by reprecipitation twice using methanol to obtain a compound B.
2-(3-chloro-4-fluorophenyl)-4,6-diphenyl-1,3,5-triazine[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
82%
With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In water; toluene;Reflux;
13.4 grams (g) (50 millimoles, mmol) of 2-chloro-4,6-diphenyl-1,3,5-triazine, 9.59 g (55 mmol) of 3-chloro-4-fluorophenyl)boronic acid, 3.5 g (3 mmol) of tetrakis(triphenylphosphine)palladium (0) (Pd(PPh3)4), and 10.6 g (100 mmol) of sodium carbonate were dissolved in a mixed solution of 100 milliliters (mL) of toluene and 50 mL of water, and the resulting solution was stirred under reflux. When the reaction was complete, the reaction solution was cooled to room temperature. The aqueous solution layer was extracted therefrom, and the remaining product was filtered through silica gel under reduced pressure. The filtrate was purified by silica gel column chromatography and recrystallized with dichloromethane (DCM)/methanol (MeOH) to obtain 14.8 g (yield: 82%) of Intermediate A. LC-Mass (calculated: 361.80 g/mol, measured: M+1=362 g/mol) (wherein ?g/mol? denotes ?grams per mole?)
2,4-diphenyl-6-(thianthren-1-yl)-1,3,5-triazine[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
67%
With potassium phosphate; tris-(dibenzylideneacetone)dipalladium(0); tricyclohexylphosphine; In 1,4-dioxane; at 110℃; for 18h;Inert atmosphere;
The specific reaction steps are as follows:Thianthrene-1-boronic acid (3.84mmol, 1.00g),2-Chloro-4,6-diphenyl-1,3,5-triazine (4.22 mmol, 1.13 g),Potassium phosphate (19.20 mmol, 4.07 g), tricyclohexylphosphine (0.31 mmol, 86 mg), Pd2 (dba) 3 (0.192 mmol,176 mg), 1,4-dioxane 100 mL was sequentially added to the reactor, and after passing nitrogen for 15 minutes,The reaction was heated at 110 C for 18 h. After the reaction is over, the system is returned to room temperature.The organic phase was extracted with dichloromethane and brine, and the solvent was evaporated under reduced pressure.The crude product was separated and purified by column chromatography. The eluent was petroleum ether/dichloromethane 5:1.The product of structure 1 was obtained in a yield of 67%. Structure 1 formula: C27H17N3S2;
2,4-diphenyl-6-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl)-1,3,5-triazine[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
85%
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; at 80℃; for 12h;
Sub 1-I-22 (17.0 g, 63.5 mmol), 1,3-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzene (16.77 g, 50.8 mmol) , K2CO3 (26.33 g, 190.5 mmol) and Pd (PPh3) 4 (3.67 g, 3.2 mmol) were added to a round-bottomed flask and dissolved in THF (190 mL) and water (95 mL) for 12 hours at 80 C. It was refluxed. After the reaction was completed, the reaction was cooled to room temperature, extracted with CH2Cl2, and washed with water. The organic layer was dried over MgSO 4, concentrated, and the resulting organic was separated using a silica gel column to give Sub 1-22 (23.5 g, 85%).
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; at 60℃; for 3h;
30 g (181.9 mmol) of (5-cyano-2-fluorophenyl) boronic acid,2-chloro-4- (dibenzo [b, d] furan-4-yl) -6-phenyl-1,3,5-triazine(181.9 mmol), 200 mL of tetrahydrofuran and 100 mL of water are mixed and heated to 60 C. Potassium carbonate (545.6 mmol) and tetrakistriphenylphosphinepalladium (1 mmol) were added and the mixture was stirred for 3 hours under reflux.After the reaction, the reaction solution returned to room temperature was filtered to obtain a solid, and the solid was recrystallized twice with tetrahydrofuran / ethanol to obtain 53.2 g of compound 1-G (yield 83%).
5-(4,6-diphenyl-1,3,5-triazin-2-yl)-2-fluorobenzonitrile[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
90%
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; at 60℃; for 3h;
30 g (181.9 mmol) of (3-cyano-4-fluorophenyl) boronic acid,2-chloro-4,6-diphenyl-1,3,5-triazine (181.9 mmol),Mix 200 mL of tetrahydrofuran and 100 mL of water,Heat to 60 C.Potassium carbonate (545.6 mmol)And tetrakistriphenylphosphinepalladium (1 mmol)Was added and stirred for 3 hours in a reflux state.After the reaction, the reaction solution returned to room temperature was filtered to obtain a solid, and this solid was recrystallized twice with tetrahydrofuran / ethanol,57.6 g of compound 1-A was obtained (yield 90%).
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; for 12.0h;Reflux;
2-chloro-4,6-diphenyl-1,3,5-triazine 2-chlorobenzo [d] thiazole (30.0 g, 112.3 mmol) and (2) in a nitrogen atmosphere. , 4,6-trichlorophenyl) boronic acid ((2,4,6-trichlorophenyl) boronic acid) (25.2 g,112.3 mmol) was added to 300 ml of tetrahydrofuran and stirred and refluxed. Thereafter, potassium carbonate (46.6 g, 337.0 mmol) was dissolved in 100 ml of water, sufficiently stirred, and then tetrakistriphenyl-phosphinopalladium (3.9 g, 3 mol%) was added thereto. After the reaction for 12 hours, the temperature was lowered to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled under reduced pressure. The distillate was extracted with chloroform and water, and the organic layer was dried over magnesium sulfate. The organic layer was dried and recrystallized with ethyl acetate to prepare F-1 (27.7 g, 77%).
10-bromo-7-(4,6-diphenyl-1,3,5-triazin-2-yl)-7H-benzo[c]carbazole[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With sodium hydride; In N,N-dimethyl-formamide; at 80℃; for 12h;Inert atmosphere;
Dissolve E10-1 (30.0 g), 2-chloro-4,6-diphenyl-1,3,5-triazine (27.1 g) and NaH (3.2 g) in 400 ml of dry DMF under a nitrogen atmosphere Reaction at 80 C for 12h.After cooling, slowly add a small amount of water, remove the solvent by rotary evaporation, extract with dichloromethane and wash and separate the solution with water.Column chromatography and recrystallization gave Intermediate E10-2.
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