Structure of 1036378-83-2
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CAS No. : | 1036378-83-2 |
Formula : | C24H25BO2 |
M.W : | 356.27 |
SMILES Code : | CC1(C)C(C)(C)OB(C2=CC(C3=CC=CC=C3)=CC(C4=CC=CC=C4)=C2)O1 |
InChI Key : | DZVYZTRVAYXJNI-UHFFFAOYSA-N |
Pubchem ID : | 59757613 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H302-H315-H319-H335 |
Precautionary Statements: | P261-P264-P270-P271-P280-P301+P312-P302+P352-P304+P340-P305+P351+P338-P330-P332+P313-P337+P313-P362-P403+P233-P405-P501 |
* 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 |
---|---|---|
91% | With potassium acetate; palladium dichloride; In 1,4-dioxane; for 3h;Inert atmosphere; Reflux; | In a 2 L reaction flask under nitrogen, 65 g (210.22 mmol) of 1-bromo-3,5-diphenyl,Bis (pinacolato) diboron 64.1 g (252.26 mmol),61.9 g (630.66 mmol) of potassium acetate,7.7 g (10.51 mmol) of palladium (II) dichloride and 650 ml of 1,4-dioxane are added and the temperature is raised.After refluxing for 3 hours, the reaction mixture is filtered through celite, extracted with dichloromethane and distilled water, and then the organic layer is treated with anhydrous magnesium sulfate and concentrated under reduced pressure. After separation and purification by silica gel chromatograph,Recrystallization from dichloromethane and methanol gave 68.3 g (91%) of white solid intermediate compound [6-1]. |
89.3% | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In tetrahydrofuran; at 80℃; for 5h;Inert atmosphere; | (1) In a 250 mL three-necked flask, nitrogen gas was added, and 0.02 mol of I-14 was added to dissolve in 100 ml of tetrahydrofuran (THF). (Diphenylphosphine) ferrocene) dichloropalladium (II) and 0.05 mol potassium acetate were added, the mixture was stirred, and the mixed solution of the above reactants was heated to reflux at a reaction temperature of 80 C. for 5 hours; after the reaction was completed, cooled and 100 ml of water were added, and the mixture was filtered and dried in a vacuum oven. The obtained residue was separated and purified through a silica gel column to obtain intermediate E14; the purity by HPLC was 99.4%, and the yield was 89.3%. |
89.3% | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In tetrahydrofuran; at 80℃; for 5h;Inert atmosphere; | (1) In a 250mL three-necked bottle, nitrogen gas is added, 0.02mol of raw material I-14 is dissolved in 100ml of tetrahydrofuran (THF), and then 0.024mol of bis (pinacol) diboron, 0.0002mol of Pd (pddf) 2Cl2 and 0.05mol of potassium acetate were added, the mixture was stirred, and the mixed solution of the above reactants was heated to reflux at a reaction temperature of 80 C for 5 hours; after the reaction was completed, cooled and added 100 ml of water, and the mixture was filtered and dried in a vacuum oven. The obtained solid was dissolved in dichloromethane, and then separated and purified through a silica gel column with a dichloromethane: ethyl acetate = 3: 1 eluent to obtain intermediate E14; HPLC purity was 99.4%, and the yield was 89.3%. |
86% | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In N,N-dimethyl-formamide; at 90℃; | Sub 2-II-1 (21.61g, 69.9mmol) obtained in the above synthesis was dissolved in DMF in a round bottom flask, Bis (pinacolato) diboron (19.52g, 76.9mmol), Pd (dppf) Cl2 (1.71g, 2.1 mmol), was added KOAc (20.58g, 209.7mmol) and stirred at 90 C. When the reaction is complete, the DMF was removed by distillation and extracted with water and CH2Cl2. The resulting compound and the organic layer was dried over MgSO4 and concentrated to silicagel column and the product was recrystallized 21.41g (yield: 86%) was obtained. |
85% | With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; potassium acetate; In N,N-dimethyl-formamide; at 150℃; for 10h;Inert atmosphere; | Nitrogen environment at the 1-bromo-3 ,5-diphenylbenzene (100 g, 323 mmol) to dimethylforamide (DMF) and then dissolved in 1.0 L, here bis (pinacolato) diboron (98.6 g, 388 mmol) and (1, 1 ' -bis (diphenylphosphine) ferrocene) dichloropalladium (II) (2.64 g, 3.23 mmol), and potassiumacetate (95.1 g, 969 mmol) were placed in 150 10 sigan during heating to reflux was. After the reaction was completed, the reaction solution into water and then filter the mixture, and dried in a vacuum oven. The thus obtained residue by flash column chromatography minutes Li to give the compound I-8 (97.8 g, 85%). |
80% | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In 1,4-dioxane;Reflux; | A 500ml round flask, 5'-Bromo-m-terphenyl 150g (485.11mmol, 1eq), bis(pinacolato)diboron 184.78g (727.66mmol, 1.5eq), Pd(dppf)Cl2 17.7g (put 24.26mmol, 0.05eq), KOAc 190.4g (1940.43mmol, 4eq) was stirred under reflux into a 1,4-dioxane 2L. After the reaction was completed, the mixture was extracted with CH2Cl2/H2O, and CH2Cl2 layer was dried with MgSO4. Silica-gel column purification to give the compound C-1, 138g in 80% yield. |
86 g | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In 1,4-dioxane; for 3h;Inert atmosphere; Reflux; | (258.73 mmol) of 1-bromo-3,5-diphenyl, 78.8 g (310.48 mmol) of bis (pinacolato) diboron and 76.18 g (776.19 mmol) of potassium acetate in a 2 L reaction flask under nitrogen atmosphere,9.47 g (12.94 mmol) of (1,1'-bis (diphenylphosphino) ferrocene) palladidium (II) dichloride is added, 800 ml of 1,4-dioxane is added and the temperature is raised.After refluxing for 3 hours, the reaction mixture is filtered through celite, extracted with dichloromethane / distilled water, treated with anhydrous magnesium sulfate and distilled under reduced pressure. The residue was subjected to silica gel chromatography and recrystallized from dichloromethane and methanol to obtain 86 g (93 wt%) of a white solid intermediate compound [41-1] |
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In tetrahydrofuran; at 80℃; for 5h;Inert atmosphere; | In a 250 mL three-necked flask, nitrogen gas was added, 0.02 mol of the raw material A-9 was added and dissolved in 100 mL of tetrahydrofuran (THF), and then 0.024 mol of the raw material B,0.0002mol (1,1'-bis (diphenylphosphine) ferrocene) dichloropalladium (II) and 0.05mol potassium acetate were added, the mixture was stirred, and the mixed solution of the above reactants was heated to reflux at a reaction temperature of 80 C 5 hours; at the end of the reaction, cool and add 100 mL of water, and filter the mixture and dry in a vacuum oven. The obtained residue was separated and purified through a silica gel column to obtain intermediate M-9. | |
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In 1,4-dioxane; at 100℃; for 24h;Inert atmosphere; Glovebox; | In a nitrogen filled glovebox a mixture of the bromo-m-terphenyl (3.350 g, 10.834 mmol, 1.00 eq), Pd(dppf)Cl2 (0.442 g, 0.5417 mmol, 0.05 eq), B2Pin2 (4.127 g, 16.251 mmol, 1.50 eq), and KOAc (3.190 g, 32.502 mmol, 3.00 eq) in anhydrous deoxygenated 1,4-dioxane (100 mL) was placed in a mantle heated to 100 C., stirred vigorously (1000 rpm) for 24 hrs, removed from the heating mantle, allowed to cool gradually to 23 C., suction filtered through a pad of silica gel, rinsed with CH2Cl2 (4×25 mL), the resulting filtrate solution was concentrated onto celite, and purified via silica gel chromatography; 10% CH2Cl2-100% CH2Cl2 in hexanes to afford the boropinacolate ester as a white solid (3.446 g, 9.672 mmol, 89%). NMR indicated pure product. (0252) 1H NMR (500 MHz, Chloroform-d) δ 8.08 (dt, J=2.7, 1.7 Hz, 2H), 7.95 (p, J=2.0 Hz, 1H), 7.73 (dq, J=7.9, 1.5 Hz, 4H), 7.48 (tt, J=8.0, 1.5 Hz, 4H), 7.39 (ddt, J=8.3, 6.9, 1.3 Hz, 2H), 1.42 (s, 6H), 1.41 (s, 6H). 13C NMR (126 MHz, Chloroform-d) δ 141.15, 141.09, 132.49, 128.91, 128.68, 127.36, 127.31, 83.95, 24.90. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
77% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; at 65℃; for 3h;Inert atmosphere; | Compound 4 (2.5 g, 7.0 mmol), Pd(PPh3)4 (0.45 g, 0.35mmol) were added to 100 mL of dry THF solution, then 1,4-dibromobenzene (9.6 g, 15 mmol) and 2 M K2CO3 solution(7 mL), which was dissolved in H2O, was added to the reaction mixture. The reaction mixture was heated to 65 Cfor 3h under nitrogen. After the reaction was finished, extracted with diethyl ether and water. The organic layer was dried with anhydrous MgSO4 and filterd. The solvent was evaporated. The product was isolated by silica gel column chromatography using CHCl3:hexane (1:10) eluent to afford a white solid (Yield 77%). 1H NMR (300 MHz, CDCl3) δ7.80 (s, 1H), 7.74 (s, 2H), 7.69 (d, 4H), 7.58 (m, 4H), 7.48 (t,4H), 7.39 (t, 2H). |
77% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; at 65℃; for 12h;Inert atmosphere; | 1,4-dibromobenzene (1.65 g, 7.00 mmol), compound2 (2.49 g, 7.00 mmol), and Pd(PPh3)4 (0.40 g, 0.35 mmol) were addedto 100 mL of anhydrous THF. Then, 2M K2CO3 solution (20 mL), whichwas dissolved in H2O, was added to the reaction mixture. The reactionmixture was heated to 65 C for 12 h under nitrogen. After the reactionwas finished, the reaction mixture was extracted with CHCl3 and water.The organic layer was dried with anhydrous MgSO4 and filtered. Thesolvent was evaporated. The product was isolated by silica gel columnchromatography using CHCl3: n-hexane (1: 10) eluent to afford a whitesolid (2.07 g, Yield 77%). 1H NMR (300 MHz, CDCl3): δ = 7.80 (s, 1H),7.74 (s, 2H), 7.69 (d, 4H), 7.58 (m, 4H), 7.48 (t, 4H), 7.39 (t, 2H);EI + -Mass: 384. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | Compound 1 (12.0 g, 38.8 mmol) was added to300 mL of anhydrous THF and stirred at -78 C under a nitrogen atmosphere,then 2M n-BuLi (29.0 mL, 58.1 mmol) was added to thereaction mixture. Next, isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane(11.9 mL, 58.1 mmol) was added to the reaction mixture after30 min. After the reaction was finished, the reaction mixture was extractedwith diethyl ether and water. The organic layer was dried withanhydrous MgSO4 and filtered. The solvent was evaporated. The residuewas re-dissolved in CHCl3 and MeOH was added to the solution.The precipitate was filtered and washed with MeOH to afford a whitesolid (12.9 g, 93%). 1H NMR (300 MHz, CDCl3): δ = 8.03 (s, 2H), 7.90(s, 1H), 7.69 (d, 4H), 7.44(t, 4H), 7.35 (t, 2H), 1.37 (s, 12H); EI + -Mass: 356. | |
87.5% | With n-butyllithium; In tetrahydrofuran; at -78℃; for 2h;Inert atmosphere; | Compound 3 (10.0 g, 32.3 mmol) was dissolved in400 mE of an anhydrous tetrahydroffiran solvent under a nitrogen atmosphere. 24.3 mE of a 2M normal butyl lithium solution and 9.9 mE of isopropoxy-4,4,5,5-tetramethyl-1 ,3, 2-dioxaborolane were added thereto at -78 C., and the obtained mixture was stirred for 2 hours. When a reaction was complete, the resultant was extracted with chloroform and distilled water and treated with anhydrous magnesium sulfate. The obtained resulting material was reprecipitated by using chloroform and methanol to obtain 10.1 g of a white solid (a yield of 87.5%). |
86.9% | With n-butyllithium; In tetrahydrofuran; at -78℃;Enzymatic reaction; | Compound 3 (6.0 g, 38.7 mmol) was dissolved in 100 mL of anhydrous THF solution and stirred at -78 C, the 2.0 M n-BuLi (12.4 mL) was added. Then isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4 mL) was added to the reaction mixture. After the reaction was finished, extracted with diethyl ether and water. The organic layer was dried by evaporator. Which product was recrystallized from dichloromethane(CHCl3) and methanol (Yield 86.9%). 1H NMR(300 MHz, CDCl3) δ 7.71 (s, 3H), 7.62 (d, 4H), 7.46 (t, 4H),7.40 (t, 2H), 1.37 (s, 12H). |
79.2% | With n-butyllithium; In tetrahydrofuran; at -78℃;Inert atmosphere; | 1.5 g (4.85 mmol) of Intermediate (2) was placed in a flask, and 100 ml of anhydrous THF was added under nitrogen, followed by stirring.2.91 ml (5.82 mol) of 2M n-BuLi was slowly added while maintaining the temperature at -78 C. At -78 [deg.] C, 3.48 ml of 2-isopropoxy-4,4,5,5-tetramethyl- [l, 3,2] dioxaborolane were added. When the reaction was completed, ethyl acetate (EA) and water were used for extraction.The solvent was evaporated to obtain 1.369 g (yield: 79.2%) of a white solid compound (intermediate (3)) which was a product in the ethyl acetate (EA) layer. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; toluene; for 20h;Reflux; Inert atmosphere; | 1.20 g (3.0 mmol) of <strong>[57103-20-5]3,6-dibromo-9-phenylcarbazole</strong>, 2.35 g (6.6 mmol) of TPDOB, 8.0 ml of 2 M potassium carbonate aqueous solution, 60 ml of toluene and 30 ml of ethanol and nitrogen bubbling was carried out for 1 hour .40.21 g (0.18 mmol) of Pd (PPh 3) was added and refluxed for 4 hours.The organic layer was extracted with toluene and washed with saturated brine.The organic layer was dried over anhydrous magnesium sulfate, filtered, concentrated and purified by silica gel column chromatography (developing solvent: hexane / toluene = 5/1 => 3/1) to obtain a white solid.Confirmation of the target substance was carried out by 1 H-NMR, MS. (Yield 1.27 g, yield 60percent) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In N,N-dimethyl-formamide; at 150℃; for 5h;Inert atmosphere; | Synthesis Example 42: Synthesis of Intermediate I-42 Compound I-48 (27.8 g, 105.00 mmol) was dissolved in dimethylforamide (DMF, 1 L) under a nitrogen environment, bis(pinacolato)diboron (32.0 g, 126.01 mmol), (1,1′-bis(diphenylphosphine)ferrocene)dichloropalladium (II) (0.86 g, 1.05 mmol), and potassium acetate (25.8 g, 262.51 mmol) were added thereto, and the mixture was heated and refluxed at 150 C. for 5 hours. When the reaction was complete, water was added to the reaction solution, and the mixture was filtered and dried in a vacuum oven. This obtained residue was separated and purified through flash column chromatography to obtain Compound I-42 (33 g and 88%). HRMS (70 eV, EI+): m/z calcd for C24H25BO2: 356.1948. found: 356. Elemental Analysis: C, 81%; H, 7% |
80% | With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; potassium acetate; palladium diacetate; In toluene; at 100℃; for 2h;Inert atmosphere; | In the nitrogen,Clean and dry 1000ml three-mouth bottle,Proportionately add 8a,Boric acid pinacol ester,Toluene,Potassium acetate,Palladium acetate,s-Phos,Stir and warm up to 100C and keep warm for 2h.Sampling GC test, 7a reaction completed, cooling to below 30C, waterWash, remove the solvent, petroleum ether beating, get 8b;GC: 98.5%, yield: 80%; |
77% | With potassium acetate;bis(dibenzylideneacetone)-palladium(0); tricyclohexylphosphine; In 1,4-dioxane; at 83 - 85℃; for 24h;Inert atmosphere; | The compound entitled was synthesized in accordance with the following scheme. Into a 1L four-necked glass flask equipped with a thermometer, a reflux condenser and a stirrer, 3,5-diphenylchlorobenzene 15.0 g (56.7 mmol) synthesized as the reference example 1, pinacolate diborane 20.2 g (79.5 mmol), potassium acetate 8.35 g (85.1 mmol) and dehydrated 1,4-dioxane 750ml were added, and nitrogen was passed through the solution for 1 hour and 30 minutes. Then dibenzylideneacetone palladium(0) 1.96 g (3.41 mmol) and tricyclohexylphosphine 2.29 g (8.17 mmol) were added, which were reacted for 24 hours at 83 to 85 C with stirring. After completion of the reaction, the reaction mixture was cooled down to room temperature and separated with the addition of saturated saline and ethyl acetate, and the organic layer obtained was dried with anhydrous magnesium sulfate. After filtration, the filtrate was concentrated under reduced pressure, and the obtained concentrate was purified by silica-gel column chromatography (eluents; hexane-chloroform) to obtain 2-(m-terphenyl-5'-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborane 15.6 g as white solid (isolation yield; 77 %). |
69% | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In N,N-dimethyl-formamide; for 10h;Inert atmosphere; | To a 1000 ml flask was added 50.0 g (188.86 mmol) of the intermediate 5-chloro-1,1 ': 3,1'-terphenyl, Bis pinacolato diboron 62.35 g (245.51 mmol), 55.60 g (566.67. Mmol) of potassium acetate, 9.25 g (11.33 mmol) of Pd (dppf) Cl2 After adding 670 mL of dimethylformamide, And heated under reflux in a nitrogen stream for 10 hours. The resulting mixture was added to 1500 mL of methanol, and the crystallized solid component was filtered, and then dichloromethane-soluble silica gel / celite was filtered. An appropriate amount of an organic solvent was removed and then recrystallized from a nucleic acid to obtain a compound L-5(46.34, 69% yield). The result of elemental analysis of the resulting compound L-5 is as follows. |
67% | With tris-(dibenzylideneacetone)dipalladium(0); potassium acetate; tricyclohexylphosphine; In 1,4-dioxane; at 80℃; for 23h;Inert atmosphere; | 7.94 g (30.0 mmol) of TPCl synthesized in (1), 8.37 g (33.0 mmol) of pinacol diboron,4.41 g (45.0 mmol) of potassium acetate and 180 ml of dioxane were added and nitrogen bubbling was carried out for 1 hour.0.69 g (0.75 mmol) of tris (dibenzylideneacetone) dipalladium [Pd 2 (dba) 3] and 1.05 g (3.75 mmol) of tricyclohexylphosphine (PCy 3) were added and stirred under a nitrogen atmosphere at 80 C. for 23 hours did.The reaction mixture was cooled to room temperature and then filtered through Celite. The organic layer was extracted with chloroform and washed with saturated brine. The extract was dried over anhydrous magnesium sulfate, filtered, concentrated, and purified by silica gel column chromatography (eluting with chloroform / hexane = 1/3, column elution started, followed by elution with chloroform alone) A solid was obtained. Confirmation of the target product was carried out by 1 H-NMR (yield 7.20 g, yield 67%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69% | With potassium phosphate;tris-(dibenzylideneacetone)dipalladium(0); tricyclohexylphosphine; In 1,4-dioxane; water; at 80 - 83℃; for 20h;Inert atmosphere; | Into a 300 ml four-necked glass flask equipped with a thermometer, a reflux condenser and a stirrer, 2-(m-terphenyl-5'-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborane 11.3 g (31.7 mmol), bis(4-chlorophenyl)sulfone 3.50 g (12.2 mmol), 1.35 mol/l potassium phosphate aqueous solution 63.0 ml (85.1 mmol) and 1,4-dioxane 175 ml were added, and nitrogen was passed through the solution for 1 hour. Then, tris(dibenzylidene)acetone dipalladium(0) 270 mg (290 µmol) and tricyclohexylphosphine 210 mg (750 µmol) were added, which were reacted for 20 hours at 80 to 83C with stirring. After completion of the reaction, the reaction mixture was cooled down to room temperature and separated with the addition of water and ethyl acetate, and the organic layer obtained was dried with anhydrous magnesium sulfate. After filtration, the filtrate was concentrated under reduced pressure, and the obtained concentrate was purified in a sequence of silica-gel column chromatography (eluent; toluene), recrystallization (ethyl acetate), sublimation to obtain bis(4-(m-terphenyl-5'-yl)phenyl)sulfone 5.70 g as white solid (isolation yield; 69 %). Bis(4-(m-terphenyl-5'-yl)phenyl)sulfone is a novel compound, which is represented by the following property values. EI-MS; 307, 674 (M) 1H-NMR (CDCl3, δ(ppm)); 7.34 to 7.56 (12H, m), 7.60 to 7.92 (18H, m), 8.04 to 8.14(4H, m) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In ethanol; water; toluene; for 3h;Reflux; Inert atmosphere; | Example 3; Synthesis of Example Compound A-6; [0109][Chem. 16] [0110] The following reagents and solvents were placed in a 200 mL round-bottomed flask.F-l: 1.9 g (5 mmol)F-4: 4.3 g (12 mmol)Tetrakis (triphenylphosphine) palladium(O) : 137 mg (0.12 mmol) Toluene: 50 mLEthanol: 20 mL30 wt% Aqueous sodium carbonate solution: 30 mL[0111] The reaction solution was refluxed for 3 hours under heating and stirring in a nitrogen atmosphere. Upon completion of the reaction, water was added to the reaction solution, followed by stirring. The precipitated crystals were separated by filtration and washed with water, ethanol, and acetone to obtain a crude product. The crude product was dissolved in chlorobenzene under heating, subjected to hot filtration, and recrystallized twice with achlorobenzene solvent. The obtained crystals were vacuum dried at 100C and purified by sublimation at 10~4 Pa and 340C. As a result, 2.4 g (yield: 70%) of high-purityExample Compound A-6 was obtained. [MALDI-TOF-MS]Observed value: m/z = 678.25Calculated value: 678.29[0112] The Ti energy of Example Compound A-6 was measured as in Example 1. The Τχ energy was 443 nm on a wavelength basis .[0113] The energy gap of Example Compound A-6 wasdetermined as in Example 1. The energy gap of ExampleCompound A-6 was 3.6 eV. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
32% | With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In ethanol; water; toluene; at 85℃; for 3h;Inert atmosphere; | Synthesis of Example Compound B-3[0134][Chem. 21][7a] [B-3][0135] The following reagents and solvents were placed in a 200 mL round-bottomed flask. [7a] : 1 g (2 mmol)[13] (terphenylboronic acid): 1.4 g (4 mmol)Pd(PPh)4 ( (tetrakis (triphenylphosphine) palladium(O) ) : 0.23 g (0.2 mmol)Toluene: 50 mLEthanol: 20 mL30 wt% Aqueous sodium carbonate solution: 30 mL[0136] The reaction solution was refluxed for 3 hours under heating and stirring in a nitrogen atmosphere. Upon completion of the reaction, water was added to the reaction solution, followed by stirring. Precipitated crystals were separated by filtration and washed with water, ethanol, and acetone to obtain a crude product. The crude product was dissolved in chlorobenzene under heating, subjected to hot filtration, and recrystallized twice with a chlorobenzene solvent. The obtained crystals were vacuum dried at 100 C and purified by sublimation at 10"4 Pa and 340 C. As a result, 0.51 g (yield: 32%) of high-purity Example Compound B-3 was obtained.[MALDI-TOF-MS]Observed value: m/z = 800.9Calculated value: 800.3The i energy of Example Compound B-3 measured as in Example 1 was 461 nm on a wavelength basis.[0137] The energy gap of Example Compound B-3 measured as in Example 1 was 3.6 eV. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
45% | With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In ethanol; water; toluene; at 85℃; for 3h;Inert atmosphere; | Synthesis of Example Compound B-9[0142][Chem. 23][0143] Example Compound B-9, i.e., an asymmetric compound, was synthesized as follows through two reaction stages. First Stage[0144] The following reagents and solvents were placed in a 500 mL round-bottomed flask.[7a] : 5 g (10 mmol)[13] (terphenylboronic acid): 3.5 g (10 mmol)Pd(PPh)4 ( (tetrakis (triphenylphosphine) palladium(O) ) : 0.57 g (0.5 mmol)Toluene: 150 mLEthanol: 40 mL30 wt% Aqueous sodium carbonate solution: 60 mL[0145] The reaction solution was refluxed for 3 hours under heating and stirring in a nitrogen atmosphere. Upon completion of the reaction, water was added to the reaction solution, followed by stirring. Precipitated crystals were separated by filtration and washed with water and ethanol to obtain a crude product. The crude product was purified by column chromatography (filler: silica gel, developing solvent: heptane/ethyl acetate = 5/1), dissolved in toluene under heating, subjected to hot filtration, andrecrystallized twice with a toluene solvent. The obtained crystals were vacuum dried at 100C. As a result, 2.9 g (yield: 45%) of an intermediate [15] was obtained. The intermediate [15] was used as a raw material for thereaction of the second stage. |
Yield | Reaction Conditions | Operation in experiment |
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32% | With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In ethanol; water; toluene; at 85℃; for 3h;Inert atmosphere; | Synthesis of Example Compound C-3[0149]Chem. 24][0150] The following reagents and solvents were placed in a 200 mL round-bottomed flask.[7b] : 1 g (2 mmol)[13] (terphenylboronic acid): 1.4 g (4 mmol)Pd(PPh) 4 (tetrakis (triphenylphosphine ) palladium ( 0 ) ) : 0.23 g (0.2 mmol)Toluene: 50 mLEthanol: 20 mL30 wt% Aqueous sodium carbonate solution: 30 mL[0151] The reaction solution was refluxed for 3 hours under heating and stirring in a nitrogen atmosphere. Upon completion of the reaction, water was added to the reaction solution, followed by stirring. Precipitated crystals were separated by filtration and washed with water, ethanol, and acetone to obtain a crude product. The crude product was dissolved in chlorobenzene under heating, subjected to hot filtration, and recrystallized twice with a chlorobenzene solvent. The obtained crystals were vacuum dried at 100 C and purified by sublimation at 10~4 Pa and 325C. As a result, 0.51 g (yield: 32%) of high-purity Example Compound C-3 was obtained.[MALDI-TOF- S]Observed value: m/z = 800.9Calculated value: 800.3The Ti energy of Example Compound C-3 measured as in Example 1 was 472 nm on a wavelength basis.[0152] The energy gap of Example Compound C-3 measured as in Example 1 was 3.2 eV. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
32% | With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In ethanol; water; toluene; at 85℃; for 3h;Inert atmosphere; | Synthesis of Example Compound C-9[0153][Chem. 25] [0154] Example compound C-9, i.e., an asymmetric compound, was synthesized as follows through two reaction stages.First: Stage[0155] The following reagents and solvents were placed in a 500 mL round-bottomed flask.[7b] : 5 g (10 mmol)[13] (terphenylboronic acid): 3.5 g (10 mmol)Pd (PPh) 4 (tetrakis (triphenylphosphine) palladium(O) ) : 0.57 g (0.5 mmol)Toluene: 150 mLEthanol: 40 mL30 wt% Aqueous sodium carbonate solution: 60 mL[0156] The reaction solution was refluxed for 3 hours under heating and stirring in a nitrogen atmosphere. Upon completion of the reaction, water was added to the reaction solution, followed by stirring. Precipitated crystals were separated by filtration and washed with water and ethanol to obtain a crude product. The crude product was purified by column chromatography (filler: silica gel, developing solvent: heptane/ethyl acetate = 5/1), dissolved in toluene under heating, subjected to hot filtration, andrecrystallized twice with a toluene solvent. The obtained crystals were vacuum dried at 100C. As a result, 2.1 g (yield: 32%) of an intermediate [17] was obtained. The intermediate [17] was used as a raw material for thereaction of the second stage. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
21% | With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In ethanol; water; toluene; at 85℃; for 3h;Inert atmosphere; | Synthesis of Example Compound -3[0120][Chem. 18][0121] The following reagents and solvents were placed in a 200 mL round-bottomed flask.[3] : 1 g (2 mmol)[13] (terphenylboronic acid): 1.4 g (4 mmol)Pd(PPh)4 (tetrakis (triphenylphosphine) palladium ( 0 ) ) : 0.23 g (0.2 mmol)Toluene: 50 mLEthanol: 20 mL30 wt% Aqueous sodium carbonate solution: 30 mL[0122] The reaction solution was refluxed for 3 hours under heating and stirring in a nitrogen atmosphere. Upon completion of the reaction, water was added to the reaction solution, followed by stirring. Precipitated crystals were separated by filtration and washed with water, ethanol, and acetone to obtain a crude product. The crude product was dissolved in toluene under heating, subjected to hotfiltration, and recrystallized twice with a toluene solvent. The obtained crystals were vacuum dried at 100 C andpurified by sublimation at 10~4 Pa and 320C. As a result, 0.33 g (yield: 21%) of high-purity Example Compound A-3 was obtained.[0123] The compound obtained was identified by mass spectroscopy.Matrix-assisted laser desorption ionization-time-of-flight mass spectroscopy (MALDI-TOF-MS )Observed value: m/z = 801.0Calculated value: C28H22O = 800.3The T i energy of Example Compound A-3 measured as in Example 1 was 471 nm on a wavelength basis.[0124] The energy gap of Example Compound A-3 determined as in Example 1 was 3.4 eV. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
55% | With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In ethanol; water; toluene; for 3h;Inert atmosphere; Reflux; | Synthesis of illustrative compound A-5[0120][0121] A 200-mL recovery flask was charged with the following reagents and solvents:F-1: 1.85 g (5 mmol)F-4: 4.3 g (12 mmol)Tetrakis (triphenylphosphine) palladium ( 0 ) : 137 mg (0.12 mmol) Toluene: 50 mLEthanol: 20 mLSodium carbonate aqueous solution (concentration: 30% by weight) : 30 mL[0122] Then, the atmosphere inside the reaction system wasreplaced by a nitrogen atmosphere, and thereafter, the reaction solution was stirred under refluxing for 3 hours. After the completion of the reaction, water was added to the reaction solution and further stirred, and a deposited crystal was filtered out. Then, thecrystal was washed with water, ethanol and acetone successively to obtain a crude product. Then, the crude product was heated and dissolved in chlorobenzene, and hot filtered, and thereafter, recrystallized twice with a chlorobenzene solvent to obtain a purified crystal. Then, the obtained crystal was vacuum dried at 100C, and thereafter, refined by sublimation under the conditions of 1 x 10"4 Pa and 380C to obtain 1.8 g of high-purity illustrative compound A-5 (yield: 55%) .[0123] [MALDI-TOF-MS]Observed value: m/z = 668.22, calculated value: 668.84 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76.4% | With potassium acetate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In 1,4-dioxane; at 80℃;Inert atmosphere; | Synthesis Example 3This example illustrates the synthesis of Compound 33, 4,6- di([1 ,1 ':3',1 "-terphenyl]-5'-yl)-2-(3-(pyrimidin-5-yl)phenyl)pyrimidine.(3a) 4,4,5,5-tetramethyl-2-[1 ,1 ':3',1 "-terphenyl]-5'-yl-1 ,3,2-dioxaborolaneTo an 1 L RB flask equipped with an magnetic stirrer and a condenser which was attached to a nitrogen line, were added 3,5- diphenylphenyl trifluoromethanesulfonate (18.92 g, 50.0 mmol),4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1 ,3,2-dioxaborolane (29.20, 1 15.0 mmol), potassium acetate (39.5 g, 300.0 mmol) and dry dioxane (350 mL). The mixture was bubbled with nitrogen while the system was purged with nitrogen for 15 min. Pd(dppf)2CI2 (2.45 g, 3.0 mmol) was then added and the nitrogen purging was continued for another 15 min after which, the mixture was stirred and heated at 80 C (oil bath) under nitrogenovernight. The original light brown color turned to dark within 10 min of reaction. After cooling to ambient temperature, water (200 ml_) was added, and the mixture was stirred for 30 min and then allowed to stand at ambient temperature for 3 hour. The organic layer was separated, and the aqueous phase was extracted with toluene (2 x 150 ml_). The organic extracts were combined, washed with water, aqueous 10% HCI and brine (150 ml_ each) and dried over MgSO4 (20 g). After filtering, the solvent was removed by rotary evaporation. The light orange solid material was dissolved in dichloromethane/hexane (1/1 , 150 ml_) and the solution was passed through a short silica gel column and eluted withdichloromethane/hexane gradient (1/1 , 2/1 and 1/0). The product containing fractions were collected, and the solvent was removed by rotary evaporation. The residue was crystallized from dichloromethane/CH3CN to give the product as a white crystalline material (13.6 g, 76.4% yield) in a purity of 95% by HPLC analysis. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
63% | With sodium carbonate;palladium diacetate; triphenylphosphine; In 1,2-dimethoxyethane; at 80℃; for 18h;Inert atmosphere; | (3b) 4,6-di([1 ,1 ':3',1 "-terphenyl]-5'-yl)-2-chloropyrimidineA 250 ml_ 3-neck round-bottomed flask equipped with magnetic stir bar, thermometer, reflux condenser and nitrogen bubbler was charged with 2,4,6-trichloropyrimidine (2.20 g, 12.0 mmol), 4,4,5,5-tetramethyl-2- [1 ,1 ':3',1 "-terphenyl]-5'-yl-1 ,3,2-dioxaborolane from step (3a) (8.56 g, 24.0 mmol), triphenylphosphine (157 mg, 0.60 mmol), 1 ,2-dimethoxyethane (80 ml_) and sodium carbonate (2 M, 24 ml_, 48.0 mmol). With stirring, the system was purged with nitrogen (with N2 flowing in from the top of condenser and bubbling into the solution through a side arm) for 20 min. Palladium acetate (67 mg, 0.3 mmol) was added and the system was purged for another 15 min. The reaction was then stirred and refluxed at 80 C (heating block) under nitrogen for 18 hour. During the time some solid was formed. After cooling to ambient temperature, more solid was formed. The solid was filtered and washed with water. The crude product was dissolved in dichloromethane (200 mL) and the solution was washed with water, brine and dried over magnesium sulfate. The solution was then passed through a short Alumina (basic) column and eluted with dichloromethane. The product containing fractions (that exhibited blue fluorescence under UV lamp) were collected. The solvent was removed by rotary evaporation and the residue was crystallized fromdichloromethane/acetonitrile to give the product as a white fibrous material (4.3 g, 63%) in 97% purity by UPLC. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | With potassium phosphate; palladium diacetate; tris-(o-tolyl)phosphine; In 1,2-dimethoxyethane; water; at 100℃;Inert atmosphere; | Compound 1 (3.0 g, 5.5 mmol) and compound 2(3.3 g, 12.1 mmol) were added to Pd(OAc)2 (50 mg,0.22 mmol), tris(2-methylphenyl)phosphine (155 mg,0.44 mmol), K3PO4 (9.4 g, 44 mmol), and solvent(dimethoxyethane:water = 4:1) in a 500 mL roundbottomedflask under a nitrogen atmosphere. Thetemperature was raised to 100 C. When the reaction wascompleted, extraction of the product was performed withwater and chloroform. The organic extract was dried withadded MgSO4 and then filtered. The solvent was removedunder vacuum. The remaining crude mixture was passedthrough a column of silica with MC:Hexane (1:5) and thenre-crystallized from chloroform to obtain a yellow solid.The final step yield was 73%.1H-NMR (300 MHz, CDCl3(ppm): 8.01-7.94 (m,8 H), 7.87 (t, 2 H), 7.83-7.79 (m, 6 H), 7.77 (s, 5 H),7.73 (d, 1 H), 7.64-7.60 (m, 4 H), 7.55-7.48 (m, 9 H),7.45-7.39 (m, 4 H), 7.38-7.25 (m, 2 H), 1.29 (s, 9 H).Fab+-MS 963 m/z. Anal. Calcd for C66H50: C, 94.02; H,5.98 Found: C, 93.98; H, 5.88. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
49% | With palladium diacetate; tetraethylammonium hydroxide; tricyclohexylphosphine; In tetrahydrofuran; at 80℃; | In a 250 mL round-bottomed flask, compound 6 (1.4 g,2.10 mmol), compound 2 (1.876 g, 5.26 mmol), Pd(OAc)2(113.5 mg, 0.17 mmol), and tricyclohexylphosphine(94 mg, 0.34 mmol) were placed with anhydrous THFsolvent. It was raised to 80 C and (Et)4NOH wasadded to reaction flask. After reaction is completed, it isextracted by chloroform and water. After removing waterfrom the mixture, it was filtered by using MgSO4. Themixture was columned under EA:Hexane (1:10) mixedsolvent. The product was concentrated under reduced pressureand re-precipitated with methanol to obtain puresolid material in light yellow color. The final step yieldwas 49%.1H-NMR (300 MHz, THF) (ppm): 8.53-8.50 (s, 1 H),8.18-8.12 (d, 2 H), 8.12-8.08 (d, 2 H), 8.08-8.00 (m,3 H), 7.98-7.93 (m, 3 H), 7.93-7.86 (m, 6 H), 7.86-7.82(m, 4 H), 7.79-7.68 (m, 8 H), 7.67-7.62 (d, 2 H),7.53-7.46 (m, 5 H), 7.46-7.36 (m, 10 H), 7.34-7.28 (m,4 H). Fab+-MS 963 m/z. Anal. Calcd for C76H50: C,94.77; H, 5.23 Found: C, 94.67; H, 5.23. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80.4% | With palladium diacetate; tetraethylammonium hydroxide; tricyclohexylphosphine; In tetrahydrofuran; for 6h;Inert atmosphere; Reflux; | 0.64 g (0.674 mmol) of intermediate 9 and 0.2641 g (0.741 mmol) of intermediate 3, 0.0276 g of Pd (OAc) 0.283 g of tricyclohexylphosphine was placed in a flask, and 30 ml of anhydrous THF was added under nitrogen atmosphere and stirred.15 ml of 20% by weight of (Et) 4NOH was added and the mixture was refluxed and stirred for 6 hours.After completion of the reaction, the reaction mixture was extracted with chloroform and water and purified by column chromatography with a mixture ratio of chloroform: hexane = 1: 10 (volume ratio).Thereafter, the obtained liquid was evaporated using an evaporator,0.362 g (yield 80.4%) of white solid compound 4-6 was obtained |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
7.5% | With palladium diacetate; potassium carbonate; tricyclohexylphosphine; In tetrahydrofuran; for 6h;Inert atmosphere; Reflux; | 0.8 g (2.16 mmol) of intermediate (12) and 0.924 g (2.59 mmol) of intermediate (3)0.0888 g of Pd (OAc) 2,0.912 g of tricyclohexylphosphine was placed in a flask, and 30 ml of anhydrous THF was added under nitrogen atmosphere and stirred.15 ml of 2M K2CO3 was added, and the mixture was refluxed and stirred for 6 hours. After completion of the reaction, the reaction mixture was extracted with chloroform and water, and purified by column chromatography with a mixed ratio of ethyl acetate (EA): hexane = 1: 10 (volume ratio).Thereafter, the obtained liquid was evaporated using an evaporator, 0.6455 g (yield 7.5%) of yellow solid compound (Intermediate (13)) was obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
21.1% | With palladium diacetate; tetraethylammonium hydroxide; tricyclohexylphosphine; In tetrahydrofuran; for 6h;Reflux; Inert atmosphere; | 0.8 g (2.22 mmol) of intermediate (6)And 1.7416 g (4.89 mmol) of intermediate (3), 0.182 g of Pd (OAc) 2,0.187 g of tricyclohexylphosphine was placed in a flask, and 60 ml of anhydrous THF was added under nitrogen atmosphere and stirred.20 ml of 20% by weight of (Et) 4NOH were added,The mixture was refluxed and stirred for 6 hours. After completion of the reaction, the reaction mixture was extracted with chloroform and water, and purified by column chromatography at a mixture ratio of chloroform: hexane = 1: 5 (volume ratio).Thereafter, the obtained liquid was evaporated to obtain 0.309 g (yield: 21.1%) of an amorphous solid compound (Formula 8).[HRMS (FAB +, m / z): calcd. ForC52H34, 658.2661; Found, 658.2656]Yellow solid combination4.51 g (yield 38.2%) of water (Intermediate (6)) was obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
13% | With tetrakis(triphenylphosphine) palladium(0); sodium hydroxide; In toluene; at 60℃; | 0.7 g (1.35 mmol) of 9,10-dibromo-1,5-di-o-tolyl-anthracene, 1.11 g (3.11 mmol) of 4,4,5,5-tetramethyl-2-[1,1;3,1]terphenyl-5-yl-[1,3,2]dioxaborolane and 0.15 g (0.135 mmol) of tetrakis(triphenylphosphine)palladium(0) were added in 3-neck round flask, and 80 mLof anhydrous toluene was added. 10 mL of 2M NaOH was added at 60C. The solutionwas stirred overnight. After completion of the reaction, the solution was extracted usingchloroform and H2O. Small amount of H2O remaining in the chloroform layer was removedusing MgSO4. After obtaining solid by evaporation of product in the chloroform layer,column refinementwas performed under chloroform : hexane=1 : 3 condition. The productobtained by column was dissolved in small amount of chloroform and re-precipitated usingmethanol before filtering. 0.15 g of yellow solid was obtained by evaporating the filteredsolid. (13% yield) 1H-NMR (300MHz, DMSO) δ(ppm) : 8.44(d, 2H), 7.92-7.79(m, 14H), 7.75-7.73(d,2H), 7.59-7.48(m, 12H), 7.43-7.41(d, 2H), 7.19-7.13(t, 2H), 7.05-7.01(t, 2H), 6.87-6.79(m,2H), 6.66-6.59(t, 2H), 2.05(d, 6H). Fab+-MS: 814 m/z |