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CAS No. : | 4316-58-9 | MDL No. : | MFCD00009665 |
Formula : | C18H12Br3N | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | ZRXVCYGHAUGABY-UHFFFAOYSA-N |
M.W : | 482.01 | Pubchem ID : | 258027 |
Synonyms : |
|
Num. heavy atoms : | 22 |
Num. arom. heavy atoms : | 18 |
Fraction Csp3 : | 0.0 |
Num. rotatable bonds : | 3 |
Num. H-bond acceptors : | 0.0 |
Num. H-bond donors : | 0.0 |
Molar Refractivity : | 104.22 |
TPSA : | 3.24 Ų |
GI absorption : | Low |
BBB permeant : | No |
P-gp substrate : | Yes |
CYP1A2 inhibitor : | No |
CYP2C19 inhibitor : | No |
CYP2C9 inhibitor : | Yes |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -4.11 cm/s |
Log Po/w (iLOGP) : | 4.33 |
Log Po/w (XLOGP3) : | 7.23 |
Log Po/w (WLOGP) : | 7.44 |
Log Po/w (MLOGP) : | 6.71 |
Log Po/w (SILICOS-IT) : | 5.72 |
Consensus Log Po/w : | 6.29 |
Lipinski : | 1.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 1.0 |
Muegge : | 2.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -7.79 |
Solubility : | 0.0000078 mg/ml ; 0.0000000162 mol/l |
Class : | Poorly soluble |
Log S (Ali) : | -7.12 |
Solubility : | 0.0000364 mg/ml ; 0.0000000755 mol/l |
Class : | Poorly soluble |
Log S (SILICOS-IT) : | -9.16 |
Solubility : | 0.00000033 mg/ml ; 0.0000000007 mol/l |
Class : | Poorly soluble |
PAINS : | 0.0 alert |
Brenk : | 0.0 alert |
Leadlikeness : | 2.0 |
Synthetic accessibility : | 2.31 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | 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 |
---|---|---|
100% | With N-Bromosuccinimide; triethylamine In N,N-dimethyl-formamide at 20℃; | |
97% | With bromine In chloroform at 0 - 20℃; for 1h; | |
94% | With N-Bromosuccinimide In N,N-dimethyl-formamide at 20℃; for 12h; Cooling with ice; | 1 Preparation of intermediate R: tris-(4-bromophenyl)amine Weigh triphenylamine (4.9g, 20mmol) in a 250mL round bottom flask,Add 30mL DMF solution under ice bath condition to make it completely dissolve,Weigh again NBS (10.9g, 61mmol) and dissolve it in 50mL DMF solution, and slowly add this solution dropwise to the round bottom flask.The ice bath was removed, and the reaction system was stirred at room temperature for 12 hours.After the reaction is complete, add 100 mL of water to the round bottom flask under ice bath conditions.A large amount of white solid precipitated in the reaction flask, and 9g of white solid (94%) was obtained after suction filtration and drying; |
91% | With N-Bromosuccinimide In N,N-dimethyl-formamide at 0 - 20℃; for 24h; Inert atmosphere; Schlenk technique; | |
90% | With N-Bromosuccinimide In N,N-dimethyl-formamide at 20℃; | |
90% | With N-Bromosuccinimide In N,N-dimethyl-formamide at 0 - 20℃; for 12h; | |
90% | With N-Bromosuccinimide In N,N-dimethyl-formamide at 0 - 20℃; | |
90% | With N-Bromosuccinimide In N,N-dimethyl-formamide at 0 - 20℃; for 4h; | |
90% | With N-Bromosuccinimide In N,N-dimethyl-formamide at 20℃; Darkness; Cooling with ice; | |
90% | With N-Bromosuccinimide In N,N-dimethyl-formamide at 20℃; for 24h; | |
89% | With bromine In dichloromethane at 20℃; for 48h; | |
87% | With N-Bromosuccinimide In N,N-dimethyl-formamide for 1h; | |
86% | With bromine In chloroform for 1h; | |
86.9% | With bromine In chloroform at 20℃; Cooling with ice; | |
85% | With bromine In chloroform at 0 - 20℃; for 1h; under light protection.; | |
85% | With N-Bromosuccinimide In N,N-dimethyl-formamide for 5h; Cooling with ice; Darkness; | 1.1 First stage: triphenylamine 2.45g was added in a 100ml round bottom flask, just so all triphenylamine was dissolved DMF ((N, N- dimethylformamide), and the mixture was ice manufacturing low-temperature environment, the dissolved 5.34gNBS 10ml of DMF, was slowly added via the funnel constant pressure to the round flask, the reaction mixture was stirred under light shielded state 5H; after completion of the reaction, water was added to the hydrolysis, to produce a precipitate, filtration, column separation, and dried to give the intermediate three bromo-triphenylamine 4.06g (yield 85%) |
85% | With N-Bromosuccinimide In tetrahydrofuran at 0 - 20℃; | 2.3. Synthesis of tris(4-bromophenyl)amine Triphenylamine (1.00 g, 4.08 mmol) was added to 20 ml of anhydrousTHF in a 50 ml two neck round bottom flask. After cooling the solution to 0 °C, N-bromosuccinimide (NBS) (2.61 g, 14.69 mmol) was added slowly to the reaction mixture. Then, the reaction mixture was warmed to room temperature and stirred for overnight. After completion,the reaction was quenched by addition of ice water and extracted with chloroform (60 ml). The organic layer was washed with brine (150ml), dried over anhydrous K2CO3, and finally isolated by filtration. The solvent was rotary evaporated, and the product was precipitated withcold hexane to obtain the pure white powder. The product was subsequently dried in a vacuum oven at RT to obtain the white powder (Yield= 1.671 mg, 85 %). 1H-NMR (500 MHz, CDCl3), δ (ppm): 7.35 (d, J =8.5 Hz, 6 H), 6.95 (d, J = 8.5 Hz, 6 H). |
83% | With bromine In chloroform at 0℃; for 2h; | |
83% | With N-Bromosuccinimide In N,N-dimethyl-formamide | |
83% | With N-Bromosuccinimide In N,N-dimethyl-formamide at 0 - 20℃; Darkness; | |
81% | With N-Bromosuccinimide In chloroform at 0 - 20℃; Inert atmosphere; Darkness; | |
80% | With bromine In chloroform at 0℃; for 0.5h; | |
80% | With bromine In dichloromethane; chloroform at -6℃; for 0.666667h; | 1 he triphenylamine (3 g) was dissolved in 20 mL of a mixed solution of chloroform and methylene chloride at a temperature below -6 ° C (ice saltBath), and a solution of liquid bromine (2 mL) in chloroform (10 mL) was slowly added dropwise. Stirring 40min, the solution gradually become yellow-green, the reaction solution into 25mL hot anhydrous ethanol, a small amount of crystals appear. Cooled to 0 ° C and filtered to give white needle crystals. And recrystallized from ethyl acetate to give 4.7 g of bromo-triphenylamine as a white bulk crystal in 80% yield, 141-142 ° C (literature value: 143-144 ° |
80% | With bromine In chloroform for 1h; Cooling with ice; | 1 Preparation of tris(4'-bromophenyl)amine Weighing (9.640 g, 39.1 mmol) of triphenylamine into a 250 mL three-neck bottle, Take 40 mL of chloroform solution and add it to the mixture with acetone bath. 6 mL of liquid bromine was slowly dropped into a three-necked bottle with a constant pressure dropping funnel to control one drop for two seconds. The dropping process keeps the temperature low and keeps stirring. After the dropwise addition, 10 mL of chloroform solution was added to the constant pressure dropping funnel to continue to drip, and the unreacted liquid bromine was washed away. After all the dropwise addition was completed, the mixture was stirred under ice bath for one hour, and the solution was changed with stirring. Green, while stirring, additionally heat 100 mL of absolute ethanol to 40 C. After the three bottles are stirred, The heated anhydrous ethanol was added to the three-necked bottle, and the solution immediately became clear and sealed with a plastic wrap. It was placed in a refrigerator and chilled overnight, suction filtered, and then washed with (20 mL × 3) anhydrous ethanol to give tris(4'-bromophenyl)amine as a white solid. Yield: 9.470 g (80%) |
80% | With N-Bromosuccinimide In N,N-dimethyl-formamide at 20℃; for 12h; | 16 Example 16, Preparation of Compound 12 Triphenylamine (5 g, 20.38 mmol) was added to a 250 ml one-necked flask, dissolved in DMF (30 g), and NBS (11.97 g, 67.23 mmol) was added dropwise.The mixture was stirred at room temperature for 12 h and the product was extracted with DCM. Yield: 80% |
79% | With bromine In chloroform at 20℃; for 2h; | |
77% | With N-Bromosuccinimide In N,N-dimethyl-formamide at 0 - 20℃; Inert atmosphere; | |
74% | With N-Bromosuccinimide In N,N-dimethyl-formamide at 20℃; for 12h; Darkness; | 5 Example 5 Dissolve triphenylamine (2.45g, 10mmol) in 250mL DMF, add dropwise N-bromosuccinimide (NBS5.95g, 35mmol) dissolved in 30mL DMF solution, stir at room temperature for 12 hours, the whole reaction process is avoided Light. After the reaction is over, put the completed round-bottom flask into the ice-water mixture prepared in advance and let it stand still, and the milky white solid will slowly precipitate out. Subsequently, the white solid was washed with absolute ethanol and dried in vacuum to obtain a crude white solid product. Finally, petroleum ether:dichloromethane=1:2 was used as the eluent for column chromatography purification to obtain the final product bromo-triphenylamine (3.57g, yield 74%), |
72% | With N-Bromosuccinimide In N,N-dimethyl-formamide at 20℃; for 3h; | |
68% | With bromine In dichloromethane at -78 - 20℃; for 0.5h; | Synthesis of Intermediate 22; 24.5 g (100 mmol) of triphenylamine was dissolved in 500 mL of methylene chloride and cooled to -78°C. Then, a dilution of 31.9 g (200 mmol) of bromine in 100 mL of methylene chloride was dropwise added thereto while stirring. After the dropwise addition was completed, the mixture was further stirred at room temperature for 30 minutes. 300 mL of cold water was added thereto and extracted with methylene chloride. An organic layer was collected and dried using magnesium sulfate to evaporate the solvent. The residue was recrystallized using a mixed solution of methylene chloride and hexane to obtain 36.7 g (yield: 68%) of Intermediate 22. This compound was identified using HR-MS. |
66% | With bromine In chloroform at 20℃; for 24h; UV-irradiation; | |
55% | With bromine In ethanol; chloroform at 0 - 40℃; for 24h; | 3.2. Preparation of tris(4-bromophenyl)amine A chloroform solution (30 mL) of triphenylamine (5.50 g,22.4 mmol) was stirred for 10 min at 0 C and then the bromine(13.46 g, 84.2 mmol)was dropped slowly. The ethanol (100 mL)wasadded when the solution color of the reaction turned green. Themixture was continually stirred for 24 h at 40 C, and a largeamount of solid was formed. After filtration, the crude product waswashed with cold ethanol (20 mL) to obtain a white powder oftris(4-bromophenyl)amine. Yield: 5.95 g (55%). Mp: 140e142 C.Anal. Calcd for C18H12Br3N: C, 44.85; H, 2.5; N, 2.9%. Found: C, 44.6;H, 2.3; N, 3.1%. 1H NMR (CDCl3, 400 MHz): d 6.93 (d, J 8.8 Hz, 6H,ArH), 7.36 (d, J 8.8 Hz, 6H, ArH). |
48% | With N-Bromosuccinimide In dichloromethane at 20℃; for 12h; | 15.1 (1) Synthesis of Compound J27 The following reagent and solvent were charged into a reaction vessel. Compound J26: 0.50 g (2.0 mmol), Dichloromethane: 20 ml. Next, NBS (1.2 g, 6.7 mmol) was added to the reaction vessel and then the reaction solution was stirred at room temperature for 12 hours. Next, a coarse product obtained by concentrating the reaction solution under reduced pressure was purified by silica gel column chromatography (mobile phase; toluene) and then subjected to dispersion washing with methanol, followed by recrystallization with a mixed solvent of heptane and methanol. Thus, 470 mg (yield: 48%) of Compound J27 were obtained. |
45.9% | With N-Bromosuccinimide In N,N-dimethyl-formamide at 0 - 20℃; for 24h; | |
38% | With bromine In chloroform at 0 - 20℃; for 1.5h; | |
With bromine; benzene | ||
With TBATB In methanol; dichloromethane | ||
With N-Bromosuccinimide In tetrachloromethane Heating; | ||
With bromine | ||
With N-Bromosuccinimide | ||
With N-Bromosuccinimide In N,N-dimethyl-formamide | ||
With N-Bromosuccinimide In N,N-dimethyl-formamide Inert atmosphere; | ||
With bromine In dichloromethane | ||
With N-Bromosuccinimide In N,N-dimethyl-formamide at 0℃; | ||
With N-Bromosuccinimide In chloroform at 20℃; for 16h; Inert atmosphere; | 1 Preparation of tribromo triphenylamine Under an argon atmosphere,Triphenylamine (5 g, 20.38 mmol) was added to the two-necked flask,Add 100ml chloroform for complete dissolution,Bromosuccinimide (11.61 g, 65.22 mmol) was further added,After 16 hours at room temperature,Extraction with ether,The ether phase was washed with saturated aqueous sodium chloride solution,Dried over anhydrous magnesium sulfate,Evaporate the solvent,The product was purified by column chromatography using petroleum ether as eluent,Got a white solid. | |
With bromine In chloroform | ||
With N-Bromosuccinimide In N,N-dimethyl-formamide | ||
1.92 g | With N-Bromosuccinimide In N,N-dimethyl-formamide at 20℃; for 12h; | |
With bromine In chloroform at 20℃; for 0.5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With nitrosyl hexafluorophosphate In dichloromethane at -78 - 20℃; Inert atmosphere; | |
81% | With nitrosyl hexafluorophosphate In dichloromethane at -30℃; for 1h; | 2.3.2. Preparation of tris-(4-bromophenyl)ammoniumylhexafluorophosphate ([TBPA][PF6]) [TBPA][PF6] was prepared according to literature procedureswith the following modifications [45,46]. A solution of tris-(4-bromophenyl)amine (200 mg, 0.42 mmol) in CH2Cl2 (2 mL) was cooledto -30 °C. Upon addition of nitrosonium hexafluorophosphate([NO][PF6], 74 mg, 0.41 mmol), the clear solution immediatelybecame dark blue. After 1 h of stirring at -30 °C, pentane (20 mL)was added to precipitate a dark blue solid. The solid was collectedby filtering through a medium porosity glass-fritted funnel,washed with pentane (20 mL), dried under vacuum to yield211 mg (81%) dark blue powder, and stored at -30 °C. EPR (CH2Cl2,77 K): g = 2.00. λmax (CH2Cl2, nm, εM-1 cm-1): 309 (6.4 104), 367(7.2 104), 725 (1.1 105). |
With nitrosyl hexafluorophosphate In dichloromethane for 0.2h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79% | Stage #1: 2-bromothiophene With magnesium In diethyl ether for 2h; Heating; Stage #2: tri(p-bromophenyl)amine In tetrahydrofuran; diethyl ether for 12h; Heating; Further stages.; | |
75.4% | Stage #1: 2-bromothiophene With magnesium In tetrahydrofuran for 1h; Inert atmosphere; Reflux; Stage #2: tri(p-bromophenyl)amine With bis-triphenylphosphine-palladium(II) chloride In tetrahydrofuran for 16h; Inert atmosphere; Reflux; | 1; 5; 6; 1 Example 1 Weigh 2.528g of polished magnesium bar into a three-necked flask,Add 15mL of distilled tetrahydrofuran THF,Nitrogen gas for protection,5mL of 2-bromothiophene was added dropwise with a constant pressure funnel to carry out the first reflux reaction,After refluxing for 1h, the reaction was stopped to obtain Grignard reagent of 2-bromothiophene. Then weigh 4.227g of tribromotriphenylamine and 0.135g of PdCl2(PPh3)2 into a three-necked flask,Add 30mL THF and add 2-bromothiophene Grignard with stirring, under the protection of nitrogen,Heating for the second reflux reaction for 16h,Add saturated ammonium chloride to quench the reaction, and then extract the quenched product with chloroform,The extracted product was dried with anhydrous sodium acetate, and the dried product was purified by column chromatography with an eluent composed of n-hexane:dichloromethane with a volume ratio of 3:1.3.48 g of yellow-green needle-like crystal compound B was obtained,That is, trithiophene aniline with a yield of 75.4%. |
With bis-triphenylphosphine-palladium(II) chloride; iodine; magnesium 3 equiv. of 2-bromothiophene; 1.) Et2O, reflux, 1 h; 2.) THF, reflux, 4 h; Yield given. Multistep reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85.3% | With benzyltriphenylphosphonium chloride; potassium carbonate;copper(l) iodide; at 200 - 210℃; for 12h; | Example 10 Synthesis of Tris{4-[N-(3-methylphenyl)-N-phenylamino]phenyl}amine (exemplified compound I-25) Tris(4-bromophenyl)amine was mixed in an amount of 8.2 g (17.0 mmol) with 18.7 g (102.0 mmol) of N-(3-methylphenyl)-N-phenylamine, 13.5 g (102.0 mmol) of potassium carbonate, 0.5 g (2.6 mmol) of copper iodide, and 1.0 g (2.6 mmol) of benzyltriphenylphosphonium chloride. This mixture was reacted at 200-210 C. for 12 hours in a nitrogen stream. After the reaction, 100 mL of toluene and 50 mL of water were added and the resultant mixture was subjected to liquid separation. Thereafter, the organic layer was washed with water and dehydrated and dried with anhydrous sodium sulfate. After the drying agent was removed by filtration, 100 mL of hexane was added to the organic layer. The resultant solution was cooled for crystallization. Thus, the target compound (I-25) was obtained as light-yellow crude crystals in an amount of 7.9 g (yield, 85.3%). The target compound obtained had a melting point of 210-211 C. and a content as determined by HPLC of 99.2% (HPLC conditions: column, Super-ODS; eluent, methanol/tetrahydrofuran (V/V=97/3); buffer, triethylamine and acetic acid each in an amount of 0.1%; detection UV, 254 nm; flow rate, 0.8 mL/min). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium tertiary butoxide In toluene Reflux; | 5 In a round bottom flask, 5.0 g of tris(4-bromophenyl)amine, 5.2 g of 9H-carbazole, 1.5 g of t-BuONa, 0.5 g g of Pd2(dba)3 and 1.5 ml of (t-Bu)3P were dissolved in 200 ml of toluene, followed by reflux stirring. The reaction was confirmed by Thin Layer Chromatography (TLC), and the reaction was terminated after adding water. The organic layer was extracted with MC (Methylene chloride) and recrystallized after filtration under reduced pressure, thereby obtaining 5.2 g of compound 114. (70% yield) |
66.7% | With copper (I) iodide; 1,10-Phenanthroline; potassium carbonate In N,N-dimethyl-formamide at 160℃; for 72h; Inert atmosphere; | |
59% | With tri-tert-butyl phosphine; potassium carbonate In xylene at 120℃; for 24h; |
With copper oxide (I) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With tri-tert-butyl phosphine; sodium t-butanolate In toluene at 110℃; for 5.5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With anhydrous potassium acetate In 1,2-dimethoxyethane at 150℃; for 0.283333h; microwave irradiation; | |
87% | With palladium (II) [1,1'-bis(diphenylphosphanyl)ferrocene] dichloride; anhydrous potassium acetate In N,N-dimethyl-formamide at 90℃; Inert atmosphere; Schlenk technique; | |
71% | With sodium tertiary butoxide In toluene at 90℃; for 3h; | Synthesis of Intermediate 23; 84 g (330 mmol) of bis(pinacolato)diboron, 48.2 g (100 mmol) of Intermediate 22, 4.3 g (45 mmol) of t-BuONa, and 1.2 g (1.5 mmol) of Pd(dppf)2Cl2 were dissolved in 1000 mL of toluene and stirred at 90°C for 3 hours. After the reaction was completed, the reaction product was cooled to room temperature and extracted three times with distilled water and 500 ml of diethylether. An organic layer was collected and dried using magnesium sulfate to evaporate the solvent. The residue was separated and purified using silica gel column chromatography to obtain 44.2 g (yield: 71%) of Intermediate 23. This compound was identified using HR-MS. |
64% | With palladium (II) [1,1'-bis(diphenylphosphanyl)ferrocene] dichloride; anhydrous potassium acetate In 1,4-dioxane for 24h; Reflux; Inert atmosphere; | |
63% | Stage #1: tri(p-bromophenyl)amine; 4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl-4',4',5',5'-tetramethyl-1,3,2-dioxaborolane With anhydrous potassium acetate In 1,4-dioxane for 0.5h; Cooling with liquid nitrogen; Stage #2: With palladium (II) [1,1'-bis(diphenylphosphanyl)ferrocene] dichloride at 90℃; for 48h; | 6 Example 6 Bromo-triphenylamine (0.65g, 5mmol),bis(pinacolato)diboron(3.6g, 15mmol),Potassium acetate (0.78g, 8mmol),Add 100mL dioxane to a 250mL round bottom flask and stir well and degas under liquid nitrogen freezing conditions for 30 minutes. After degassing is successful, add the catalyst Pd(dppf)Cl2 (90mg, 0.1mmol),Degas again twice to remove all oxygen in the reaction system. Finally, the round bottom flask was refluxed and heated in an oil bath at 90°C for 48 hours. After the reaction is completed, it is cooled to room temperature, deionized water and dichloromethane are added, and the mixture is stirred and extracted. The organic phase after the extraction and an appropriate amount of silica gel powder are added to a spin-type bottle and spin-dried. Finally, column chromatography was performed with petroleum ether: dichloromethane=10:1 as the eluent to obtain the product pinacol borate triphenylamine (1.96g, yield 63%). |
61% | With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); zinc(II) diacetate dihydrate In dimethyl sulfoxide at 110℃; for 72h; Schlenk technique; Inert atmosphere; Darkness; | |
59% | With palladium (II) [1,1'-bis(diphenylphosphanyl)ferrocene] dichloride; anhydrous potassium acetate In 1,4-dioxane at 85℃; | |
59% | With palladium (II) [1,1'-bis(diphenylphosphanyl)ferrocene] dichloride; anhydrous potassium acetate In 1,4-dioxane at 85℃; Inert atmosphere; Schlenk technique; | |
59% | With palladium (II) [1,1'-bis(diphenylphosphanyl)ferrocene] dichloride In 1,4-dioxane at 85℃; for 12h; Inert atmosphere; | |
53% | With palladium (II) [1,1'-bis(diphenylphosphanyl)ferrocene] dichloride; anhydrous potassium acetate In 1,4-dioxane for 16h; Inert atmosphere; Reflux; | Synthesis of TPA-Bpin [41]. General procedure: A mixture of [1,1′ -Bis(diphenylphosphino)ferrocene]dichloropalladium(II) (0.20 g, 0.27 mmol), bis(pinacolato)diboron (2.44 g, 9.60 mmol), 4-bromo-N,N-diphenylamine (2.56g, 8.00 mmol), KOAc (2.16 g, 22.00 mmol) and dehydrated 1,4-dioxane(100 mL) in a round bottom flask was refluxed under argon atmospherefor 16 h. The reaction mixtures were concentrated, extracted bydichloromethane, and purified by column chromatography (petroleumether/dichloromethane = 10/4, v/v) to afford the white solids with ayield of 60% (1.78 g). |
52% | With palladium bis[bis(diphenylphosphino)ferrocene] dichloride; anhydrous potassium acetate In N,N-dimethyl-formamide at 85℃; for 12h; | |
20% | With palladium (II) [1,1'-bis(diphenylphosphanyl)ferrocene] dichloride; anhydrous potassium acetate In 1,4-dioxane at 85℃; for 12h; Inert atmosphere; | |
With palladium (II) [1,1'-bis(diphenylphosphanyl)ferrocene] dichloride; anhydrous Sodium acetate at 85℃; for 36h; Inert atmosphere; | 1.4 4) Synthesis of TPA-B (Compound 4) Under a nitrogen atmosphere, tris (4-bromophenyl) amine (4.82 g, 10 mmol) was added to a 250 mL two-necked flask bis(pinacolato) diborane(10.16 g, 40 mmol),Sodium acetate (19.6g, 200mmol), 2,4_ dioxane 120mL, catalyst bis (diphenylphosphino) ferrocene palladium chloride (82mg, 0. lmmol), warmed to 85 ° C.One and a half days of reaction, cooled to room temperature. The solvent is decanted, the reaction is poured into methylene chloride, extracted with water, dried over anhydrous sodium sulfate. The crude product was isolated on a silica gel column and a mixture of petroleum ether and ethyl acetate (8: 1) as eluent to give a white powder. | |
With palladium (II) [1,1'-bis(diphenylphosphanyl)ferrocene] dichloride; anhydrous potassium acetate In 1,4-dioxane at 110℃; for 16h; Inert atmosphere; | 2 Preparation of Tribenzoate tripropylamine Tribromo triphenylamine (5 g, 10.37 mmol), methyl acetate (3.05 g, 31.12 mmol) and bisboronate (10.54 g, 41.49 mmol) were added to a 250 mL two neck flask under argon atmosphere,1,4-dioxane was added for complete dissolution,Further [1,1'-bis (diphenylphosphino) ferrocene] palladium dichloride (379.51 mg, 518.67 μmol)The temperature was raised to 110 ° C and reacted for 16 hours.Extraction with ether,The ether phase was washed with saturated aqueous sodium chloride solution,Dried over anhydrous magnesium sulfate,Evaporate the solvent,The product was purified by column chromatography using petroleum ether as eluent,Got a white solid. | |
With tris-(dibenzylideneacetone)dipalladium(0); anhydrous potassium acetate; dicyclohexyl[2’,4’,6’-tris(propan-2-yl)[1,1’-biphenyl]-2-yl]phosphane In tetrahydrofuran at 85℃; for 2h; Inert atmosphere; | 2.5 4.2.2 4-methyl-N-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-N-(p-tolyl)aniline (4a) General procedure: A mixture of 3a (352 mg, 1.00 mmol), bis(pinacolato)diboron (257 mg, 1.01 mmol), Pd2(dba)3 (dba = dibenzylideneacetone; 14 mg, 0.015 mmol), 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (Xphos; 29 mg, 0.061 mmol), KOAc (0.29 g, 3.0 mmol) and THF (3 mL) under argon atmosphere was heated at 85 °C for 2 h. After cooled down to room temperature, the reaction was diluted with EtOAc (10 mL) and washed with water (2 * 20 mL). The organic layer was dried over anhydrous Na2SO4 and evaporated in vacuum to afford the crude product of 4a which was used in the further step. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | Stage #1: tri(p-bromophenyl)amine With n-butyllithium In tetrahydrofuran; hexane at -78 - 20℃; Stage #2: 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane In tetrahydrofuran; hexane at -78 - 20℃; | |
64% | Stage #1: tri(p-bromophenyl)amine With n-butyllithium In tetrahydrofuran at -78℃; for 1h; Inert atmosphere; Stage #2: 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane In tetrahydrofuran at -78 - 20℃; Inert atmosphere; | General procedure A for synthesis of triphenylamine substituted boronic ester (Scheme 1) General procedure: 4-Bromo substituted triphenylamine was dissolved in dry THF under nitrogen atmosphere and it was cooled to -78 ° C . n-BuLi was added with syringe and kept at -78 ° C for one hour. 2-Isopropoxy-4,4,5,5-tetramethyl-[1,3,2]dioxaborolane was added dropwise. After addition, the solution was allowed to warm up to room temperature for overnight reaction. After quenching of the reaction with ammonium chloride solution, the water layer was extracted with chloroform and the combined organic layer was dried over MgSO4. After the remove of the solvent under reduced pressure, the residue was purified by silica gel column chromatography (petroleum ether/dichloromethane 1:1) to afford the product as white solids. |
63% | Stage #1: tri(p-bromophenyl)amine With n-butyllithium In tetrahydrofuran Stage #2: 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane In tetrahydrofuran |
62% | Stage #1: tri(p-bromophenyl)amine With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 2h; Inert atmosphere; Stage #2: 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane In tetrahydrofuran; hexane at -78 - 20℃; Inert atmosphere; | |
62% | Stage #1: tri(p-bromophenyl)amine With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 2h; Inert atmosphere; Stage #2: 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane In tetrahydrofuran; hexane at -78 - 20℃; Inert atmosphere; | |
60% | Stage #1: tri(p-bromophenyl)amine With n-butyllithium In tetrahydrofuran; hexane at -78 - -65℃; for 1.5h; Inert atmosphere; Stage #2: 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane In tetrahydrofuran; hexane at -65 - 20℃; Inert atmosphere; | |
60% | Stage #1: tri(p-bromophenyl)amine With n-butyllithium In tetrahydrofuran; hexane at -78 - 0℃; for 1.25h; Inert atmosphere; Stage #2: 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane In tetrahydrofuran; hexane at -78 - 20℃; Inert atmosphere; | |
57% | Stage #1: tri(p-bromophenyl)amine With n-butyllithium In tetrahydrofuran at -78℃; for 1h; Inert atmosphere; Stage #2: 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane In tetrahydrofuran at -78 - 20℃; for 13h; Inert atmosphere; | |
55% | Stage #1: tri(p-bromophenyl)amine With n-butyllithium In tetrahydrofuran at -78℃; for 1h; Inert atmosphere; Stage #2: 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane In tetrahydrofuran at -78 - 20℃; for 12h; Inert atmosphere; | |
55% | Stage #1: tri(p-bromophenyl)amine With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 2h; Inert atmosphere; Stage #2: 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane In tetrahydrofuran; hexane at -78 - 20℃; for 49h; Inert atmosphere; | 2.2.1.1 Synthesis of tris(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)amine 1.93g (4.00mmol) Of tris(4-bromophenyl)amine was dissolved in anhydrous tetrahydrofuran (THF) (60mL), the solution was degassed and stirred at -78°C. 4.86mL (13.61mmol) Of n-butyllithium solution (n-BuLi, 2.8M in hexane) was added to the above mixture under Ar atmosphere and the resulting solution was stirred for 2hat -78°C. 5.83mL (28.58mmol) Of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added to the solution and the mixture was kept at -78°C for another 1h and then stirred at room temperature for 48h. The reaction was quenched with water, and the organic layer was extracted with dichloromethane (DCM). After dried over MgSO4, the solution was concentrated and the solvent mixture of DCM/hexane (3:2) was used as eluent for silica gel column chromatography to isolate the product. The obtained product was further purified by recrystallization from chloroform (CHCl3)/ethanol to give a white solid in 55% yield. 1H NMR (600MHz, C2D2Cl4): δ (ppm) 1.30 (s, 36H), 7.03 (d, 6H), 7.64 (d, 6H). MS (APLI): m/z calcd 623.3778; found 623.3667. |
54% | Stage #1: tri(p-bromophenyl)amine With n-butyllithium In tetrahydrofuran at -80℃; for 1h; Stage #2: 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane In tetrahydrofuran at -80 - 20℃; | |
34.8% | Stage #1: tri(p-bromophenyl)amine With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.5h; Inert atmosphere; Stage #2: 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane In tetrahydrofuran; hexane at -78 - 20℃; | |
15.5% | Stage #1: tri(p-bromophenyl)amine With n-butyllithium In tetrahydrofuran at -78℃; for 2h; Stage #2: 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane In tetrahydrofuran at -78 - 20℃; for 38h; | |
Stage #1: tri(p-bromophenyl)amine With n-butyllithium In tetrahydrofuran at -78 - 20℃; Stage #2: 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane In tetrahydrofuran for 24h; | ||
With n-butyllithium In tetrahydrofuran at -78℃; for 16h; | ||
With n-butyllithium In tetrahydrofuran |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With copper(l) iodide; tetrakis(triphenylphosphine) palladium(0); N-ethyl-N,N-diisopropylamine In toluene at 80℃; Inert atmosphere; | |
82% | With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; triphenylphosphine In tetrahydrofuran for 3h; Inert atmosphere; Sealed tube; Heating; | |
82% | Stage #1: tri(p-bromophenyl)amine With copper(l) iodide; tetrakis(triphenylphosphine) palladium(0); N,N-diphenylaminobenzene In dichloromethane at 20℃; for 0.5h; Stage #2: trimethylsilylacetylene In dichloromethane at 20 - 75℃; for 24.5h; |
81% | In diisopropylamine at 20℃; for 10h; Heating / reflux; | |
80% | With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triphenylphosphine In triethylamine Heating; | |
58.6% | With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine for 24h; | |
With copper(l) iodide; bis(triphenylphosphine)palladium(II) chloride; diethylamine at 50℃; for 12h; Inert atmosphere; | ||
With copper(l) iodide; trans-bis(triphenylphosphine)palladium dichloride; triethylamine | ||
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; triphenylphosphine | ||
98 %Spectr. | With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; 18-crown-6 ether; triethylamine; triphenylphosphine In water at 115℃; for 0.0833333h; Microwave irradiation; Green chemistry; | |
0.75 g | With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In tetrahydrofuran at 75℃; for 24h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With tetrakis(triphenylphosphine) palladium(0) In toluene for 12h; Heating; | |
85% | ||
85% | In toluene for 12h; Heating / reflux; | 1 First, 1 g (2 mmol) of tris(4-bromophenyl)amine (Aldrich) was dissolved in 100 ml of toluene, and then 2.9 ml (4.5 eq.) of 2-tributylstannylthiophene and 27 mg (1.1 %) of Pd(PPh3)4 were added thereto. The mixture was refluxed under a nitrogen atmosphere for 12 hours. The reaction mixture was allowed to cool to room temperature, washed with brine twice, and dried over MgSO4. After the solvent was evaporated, the obtained residue was washed with petroleum ether (PE), and dried, affording 0.87 g (yield: 85%) of tris[4-(2-thienyl)phenyl]amine as a pale yellow solid. 1H NMR (CDCl3) δ (ppm): 7.50 (d, 2H) 7.20 (m, 2H) 7.10 (d, 2H) 7.08 (dd, 1 H) |
73% | With tetrakis(triphenylphosphine) palladium(0) In toluene for 12h; Inert atmosphere; Reflux; | |
With bis-triphenylphosphine-palladium(II) chloride | ||
With tetrakis(triphenylphosphine) palladium(0) In toluene at 120℃; for 16h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79% | With nitrosonium hexafluorophosphate In dichloromethane for 0.0833333h; Inert atmosphere; | |
75.3% | With nitrosonium hexafluorophosphate at 23℃; for 0.75h; Glovebox; Inert atmosphere; | |
With nitrosonium hexafluorophosphate In dichloromethane |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With n-butyllithium; sodium bicarbonate In diethyl ether; water | 5 Synthesis of 4,4',4"-tris(triethylsilyl)triphenylamine (Example Compound (42)) EXAMPLE 5 Synthesis of 4,4',4"-tris(triethylsilyl)triphenylamine (Example Compound (42)) 4.0 g (8.3 mmol) of 4,4',4"-tribromotriphenylamine was placed in a 200-ml four-necked flask equipped with a mechanical stirrer a condenser, a nitrogen-inlet tube and a dropping funnel, and the inside atmosphere was replaced with nitrogen. 100 ml of diethyl ether was added and the 4,4',4"-tribromotriphenylamine was dissolved therein. To this ether solution, 16 ml of n-butyl lithium (1.6M hexane solution, 25.6 mmol) was gradually added dropwise at room temperature. After completion of the addition, the mixture was stirred at room temperature for 1 hour. Then, to this reaction mixture, 20 ml of a diethyl ether solution of 3.8 g (24.9 mmol) of triethylchlorosilane was gradually added dropwise under reflux conditions. After completion of the addition, the reaction mixture was stirred for 2 hours under reflux conditions. Then, the mixture was cooled on ice water bath, and 50 ml of water was added for hydrolysis. The ether layer was extracted and washed with a saturated aqueous solution of sodium hydrogen carbonate and then with two portions of water, followed by drying with anhydrous sodium sulfate. After drying, the diethyl ether was distilled off to yield a white solid, which was then recrystallized with n-hexane to yield 4.2 g of the desired product (yield 87%). m.p.: 154.0°-156.0° C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
67% | With sodium carbonate In 1,2-dimethoxyethane; water at 100℃; for 8h; | 2 Under an atmospheric argon gas flow, 1H-indene-2-boronic acid prepared in a publicly known process (J. Org. Chem., 67,169 (2002)) in an amount of 9.8 g (62 millimole), tris(4-bromophenyl)amine in an amount of 8.2 g (17 millimole), (tetrakistriphenylphosphine)palladium in an amount of 0.4 g (0.34 millimole), sodium carbonate aqueous solution in an amount of 5.4 g (52 millimole, 2M) and dimethoxyethane in an amount of 50 milliliter were placed into a three-neck flask equipped with a cooling pipe and having a capacity of 300 milliliter, and the resultant solution was stirred under heating at a temperature of 100 °C for 8 hours. After the reaction was completed, precipitated crystal was separated by filtration and washed with the uses of 50 milliliter of water and 100 milliliter of methanol and then, purifying them by means of column chromatography (silicagel, developing solvent: hexane/methylene chloride= 8/2), 6.6 g of pale yellow powder was obtained. The pale yellow powder was identified as Compound D-5-1 from the result of 1H-NMR spectrum (FIG. 2) and Field Desorption Mass Spectrum (FD-MS) measurement (yield: 67 %). Further, the 1H-NMR spectrum was obtained by means of DRX-500 (Trade name; produced by Brucker Optics Inc.; deuterated methylene chloride solvent). Furthermore, the maximum fluorescent wavelength measured about the resultant compound among toluene solution was 433 nanometers. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
52% | With potassium carbonate In tetrahydrofuran; water at 80℃; for 5h; | 15 15.05 g (60 mmol) of 1-bromo-4-naphthalene boronic acid, 12.5 g (10 mmol) of tris-4-bromophenylamine, 1.73 g (1.5 mmol) of Pd(PPh3)4, and 6.22 g (45 mmol) of K2CO3 were dissolved in 100 mL of a THF/H2O(2:1) mixed solution and then the mixture was stirred for 5 hours at a temperature of 80°C. The reaction solution was extracted three times with 600 ml of diethylether, thereby obtaining an organic layer. The organic layer was dried over magnesium sulfate and the residue obtained by evaporating the solvent was recrystallized with dichloromethane and normal hexane (n-hexane), thereby obtaining 4.47 g (yield 52%) of Intermediate 15. The obtained compound was identified by HR-MS. C48H30Br3N calc.: 856.9928; found 856.9932 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With palladium diacetate; Cs2CO3; triphenylphosphine In tetrahydrofuran for 72h; Reflux; Inert atmosphere; Schlenk technique; | |
90% | With tetrakis-(triphenylphosphine)-palladium; anhydrous sodium carbonate In ethanol; water monomer; toluene for 24h; Reflux; Inert atmosphere; | |
87% | With tetrakis-(triphenylphosphine)-palladium; potassium carbonate In 1,4-dioxane; water monomer at 90℃; for 72h; Inert atmosphere; Sealed tube; |
86% | With tetrakis-(triphenylphosphine)-palladium; Cs2CO3 In Dimethyl ether at 100℃; for 72h; Inert atmosphere; Schlenk technique; | |
85% | With tetrabutylammonium bromide; potassium carbonate In water monomer at 60℃; for 3h; | |
74% | With tetrakis-(triphenylphosphine)-palladium; anhydrous sodium carbonate In tetrahydrofuran at 70℃; for 48h; Inert atmosphere; | |
61.5% | With tetrakis-(triphenylphosphine)-palladium; potassium carbonate In 1,4-dioxane; water monomer at 90℃; for 72h; Inert atmosphere; | |
61.5% | With tetrakis-(triphenylphosphine)-palladium; potassium carbonate In 1,4-dioxane; water monomer at 90℃; for 72h; Inert atmosphere; | |
With tetrakis-(triphenylphosphine)-palladium; potassium carbonate In tetrahydrofuran | ||
With tetrakis-(triphenylphosphine)-palladium; anhydrous sodium carbonate In ethanol; water monomer; toluene |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
40% | With copper(l) iodide; potassium carbonate; In N,N-dimethyl-formamide; at 90℃; for 24h;Inert atmosphere; Darkness; | The specific preparation method includes the following steps:Add 3.6g of dihydrophenazine and 6g of anhydrous K2CO3 powder into a 200mL two-neck bottle,10g bromotriphenylboron, 0.2g CuI, then add 50mL anhydrous DMF, bubbling nitrogen for 30min,The reaction was refluxed for 24 hours at 90 in the dark, and the device was cooled to room temperature.Add a lot of water, and then suction filter the solid out,After drying, recrystallize with 1,4-dioxane to obtain the product,Then sublimation to obtain a white solid with a yield of 40%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran for 36h; Reflux; Inert atmosphere; | |
84% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In 2-ethoxy-ethanol; water at 130℃; for 4h; Reflux; Inert atmosphere; | Tris[4-(thiophen-2-yl)phenyl]amine (TPAT). Thiophene-2-boronic acid (1.02 g, 8.0 mmol) was mixed with Tris(4-bromophenyl)amine (0.63 g, 1.3 mmol) and K2CO3 (1.21 g, 8.8mmol) in ethoxyethanol/deionized water (9:1, 15 mL) in a 100 mLtwo necked round bottom flask. Pd(PPh3)4 (94.0 mg, 0.08 mmol)was added to the stirred suspension, which was then heated rapidly to 130°C and maintained under reflux conditions for 4 hours under a nitrogen atmosphere.22 After cooling to room temperature, deionized water (50 mL) was added to precipitate the main part of the product and then the mixture was wished by water and extracted with dichloromethane consecutively. The product was then dried with MgSO4 and purified on a silica gel column (petroleum ether-CH2Cl25:1 as eluent) to obtain the final product as a light yellow powder(0.54 g, yield 84%). MALDI-TOF-MS (M) (m/z):493.1 [M + H]+.1H NMR (500 MHz, CDCl3) δ 7.53 (d, J = 8.6 Hz, 6H), 7.27-7.25(m, 6H), 7.17-7.14 (m, 6H), 7.10-7.08 (m, 3H). |
81% | With tetrabutylammomium bromide; potassium carbonate In water at 60℃; for 3h; |
59% | With bis-triphenylphosphine-palladium(II) chloride; potassium carbonate In tetrahydrofuran; water for 48h; Reflux; | |
59% | With bis-triphenylphosphine-palladium(II) chloride; potassium carbonate In tetrahydrofuran-d8 for 48h; Reflux; | 2.1 Materials Tungsten trioxide (WO3) and Pdcl2(PPh3)2 were purchased from Beijing HWRK Chem Co., Ltd. 2-Thienylboronic acid, tetrabutylammonium perchlorate (TBAP) and tris(4-bromophenyl) amine were purchased from Alfa Aesar. Potassium carbonate (K2CO3), tetrahydrofuran (THF), acetonitrile (ACN), dichlormethane (DCM), and sodium chloride (NaCl) were purchased from Tianjin Hongyan Chem Co., Ltd. Lithium perchlorate (LiClO4) was purchased from Aladdin Industrial Corporation. Sodium sulfate (Na2SO4) was purchased from Beijing Liudian Chem Co., Ltd. Petroleum ether was purchased from Guangdong JHD Co., Ltd. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With copper(l) iodide; 1,10-Phenanthroline; potassium carbonate In N,N-dimethyl-formamide at 145 - 150℃; for 48h; | 1.3 Direct Synthesis of Tris(4-carbazoyl-9 ylphenyl)amine-d24 (TCTA-d24) (3b) Due to poor yields and deuteration levels of TCTA by hydrothermal methods, synthesis of TCTA-d24 was achieved using carbazole-d8 (1) and protonated tris(4-bromophenyl)amine via a modified Ullman condensation as reported by of Liu et al.[4] This involved treating protonated tris(p-bromophenyl)amine (1g, 2 mmol) with carbazole-d8 (1, 94 % D content; 1.33 g, 8 mmol) in excess, in the presence of 10 % CuI (0.15g, 0.8 mmol), 20 % 1,10-phenanthroline (0.29 g, 1.6 mmol), and K2CO3 (2.2 g, 16 mmol) in dry DMF (15 mL), under refluxing conditions (145°C -150°C oil bath temperature) for 48 hrs. DCM (10 mL) was added to dissolve the precipitate that was formed. The undissolved material was filtered off and MeOH was added to the filtrate until no further precipitation was produced. This off white precipitate was collected by filtration and washed with MeOH and water three times. The product was purified by silica column, eluting with a mixture of toluene:hexane (1:3) to give a white solid 1.2 g Yield: 80%. Isotope distribution (ESI-MS): 2.2% d20, 7.8% d21, 22.3% d22, 37.4% d23, 30.3% d24. MS and NMR results showed overall % D content of 63 +/- 1 %. 1H NMR (CD2Cl2, MeOH as an internal standard δ 3.47 (s, 3H))) δ 7.31 (s, 0.04H), 7.48 (s, 0.06H), 7.60 (m, 1.65H), 8.20 (s, 0.04H); 2H NMR (CD2Cl2) δ 7.6 (br s), 8.3 (br s); 13C (CD2Cl2) δ 109.5 (m, 6C, carbazole), 119.5 (m, 12C, carbazole), 123.2 (s, 6C, carbazole qC), 125.3 (s, 6C, triphenylamine), 125.5 (m, 6C, carbazole), 128.1 (s, 6C, triphenylamine), 132.8 (s, 6C, carbazole qC), 141.0 (s, 3C, triphenylamine qC), 146.7 (s, 3C, triphenylamine qC). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In ethanol; water; toluene Inert atmosphere; Reflux; | Tris(4-bromophenyl)amine (2.41 g, 5 mmol), 2,4-difluorophenylboronicacid (2.84 g, 18 mmol), Pd (PPh3)4 (0.58 g, 0.5 mmol),aqueous Na2CO3 (2.0 M, 15 mL), ethanol (10 mL) and toluene(30 mL) were mixed in a flask under nitrogen. The mixture washeated to reflux and maintained at this temperature overnight.Whenthe reaction was completed (judging from thin-layer chromatography),water was added to quench the reaction. Then, theproducts were extracted with CH2Cl2. The organic layer wascollected, dried over anhydrous MgSO4 and evaporated undervacuum. The solid was absorbed on silica gel and purified by columnchromatography using light petrol ether/ethyl acetate (20:1) as theeluent to give 3FT as a white solid (2.44 g, 85%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With tris-(dibenzylideneacetone)dipalladium(0); tri-ortho-cresyl phosphate; Aliquat 336; potassium carbonate In toluene at 85℃; for 48h; Inert atmosphere; | 5 Synthesis of tris(4-(thiophen-2-yl)phenyl)amine (Formula 9) Anhydrous toluene (20 ml) as a solvent was placed in a 100 ml flask equipped with a magnetic stirring bar and a condenser, and then tris(4-bromophenyl)amine (1.0 g, 2.1 mmol) (Formula 7), 4,4,5,5-tetramethyl-2-(thiophen-2-yl)-1,3,2-dioxaborolane (1.7 g, 7.88 mmol) (Formula 8), dipalladiumtris(dibenzylacetone) (Pd2(dba)3) (0.1 g, 0.11 mmol), tri-o-tolyl phosphate (P(o-tolyl)3) (0.2 g, 0.4 mmol), potassium carbonate (K2CO3) (1.1 g, 8.3 mmol) and trioctylmethylammonium chloride (Aliquat 336) (1 drop) were added thereto. After oxygen was removed from the flask by vacuum-nitrogen cycling, the mixture was stirred at reflux under a nitrogen atmosphere at 85° C. for 48 hr. The stirring was stopped, and the toluene layer was collected, filtered through a short column (eluent=chloroform), and dried. The residue was purified by column chromatography (eluent=dichloromethane/hexane (1:1)) to afford 0.88 g (yield=86%) of tris(4-(thiophen-2-yl)phenyl)amine (Formula 9). 1H-NMR (CDCl3, δ ppm) 7.07 (dd, 3H, aromatic proton), 7.13 (d, 6H, aromatic proton), 7.24 (m, 6H, aromatic proton), 7.52 (d, 6H, aromatic proton) |
57% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In 1,4-dioxane; water at 100℃; for 18h; Inert atmosphere; | |
With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In 1,2-dimethoxyethane; water at 85℃; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With copper(l) iodide; potassium carbonate; In N,N-dimethyl-formamide; at 130℃; for 36h; | A DMF (50 mL) suspension of K2CO3 (1.27 g, 9.2 mmol), tris(4-bromophenyl)amine (610 mg, 1.3 mmol), imidazole (920 mg,13.5 mmol) and CuI (210 mg, 1.1 mmol) was stirred for 36 h at130 C. After filtration, the mother solution was kept in ice bath for0.5 h, and a white precipitate was formed. The precipitate wasseparated by filtration. Then this solid was dissolved in ethanol(100 mL), and the insoluble matter was removed through filtering.The ethanol was removed by rotary evaporator to afford a whitepowder of tris(4-(1H-imidazole-1-yl)phenyl)amine. Yield: 0.45 g(80%). Mp: 243e245 C. Anal. Calcd for C27H21N7: C, 73.1; H, 4.7; N,22.1%. Found: C, 73.05; H, 4.6; N, 22.35%. 1H NMR (400 MHz,DMSO-d6): d 7.11 (s, 3H, ArH), 7.20 (d, J 8.8 Hz, 6H, ArH), 7.62 (d,J 8.8 Hz, 6H, ArH), 7.69 (s, 3H, ArH), 8.20 (s, 3H, ArH). |
70% | With copper(l) iodide; potassium carbonate; In N,N-dimethyl-formamide; at 140℃; for 48h;Inert atmosphere; | To a 250 mL three-necked flask was added (1.000 g, 2.0 mmol) of tribromoaniline, (0.850 g, 12.4 mmol) imidazole, (1.500 g, 10.8 mmol) potassium carbonate and (0.170 g, 0.8 mmol) cuprous iodide, The raw material was dissolved by measuring 10 mL of DMF, and the reaction temperature was raised to 140 C for 48 hours under nitrogen protection. After the completion of the reaction, the reaction system was quickly placed in a water bath for 0.5 h, and a large amount of blue-white solid precipitated. After suction filtration, a blue-white solid was obtained, which was dissolved in 100 mL of anhydrous ethanol, filtered, and the liquid was evaporated under reduced pressure. A white solid is obtained which is the product tris[4'-(imidazolyl)phenyl]amine. Yield: 0.650 g (70%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In 1,4-dioxane for 48h; Inert atmosphere; Reflux; | |
90% | With tetrabutylammomium bromide; potassium carbonate In water at 60℃; for 3h; | |
90% | With tetrakis(triphenylphosphine) palladium(0) at 20℃; for 24h; Inert atmosphere; Reflux; | Synthesis of tris(4′ -methoxy-[1, 1′-biphenyl]-4-yl)amine (1) Tri (4-bromophenylamine) (0.48 g, 1 mmol) and p-methoxyphenylboric acid (0.53 g, 3.5 mmol) were stirred in ethylene glycol diethylether (30 ml), followed by the addition of tetrakis (triphenylphosphine)palladium (0.12 g, 0.1 mmol). The reaction mixture was quickly heatedto refilux and stirred in N2 for 24 h. After cooling to room temperature,the reaction mixture was poured into 100 ml deionized water andextracted with dichloromethane. The organic phase was dried by magnesiumsulfate and evaporated. The crude product was purified by columnchromatography on a silica gel with dichloromethane/hexane (1:3,v/v) to yield a white solid (0.5 g, 90%). 1H NMR (500 MHz, CDCl3) 7.54 (d, J = 8.8 Hz, 6H), 7.49 (d, J = 8.7 Hz, 6H), 7.23 (d, J = 8.7 Hz,6H), 6.99 (d, J = 8.8 Hz, 6H), 3.87 (s, 9H). ESI HRMS (mass m/z): found:564.2518 [M+ + H] (calculated: 564.2533). |
63% | Stage #1: tri(p-bromophenyl)amine With tetrakis(triphenylphosphine) palladium(0) In toluene at 20℃; for 0.25h; Schlenk technique; Inert atmosphere; Stage #2: 4-methoxyphenylboronic acid With sodium carbonate In methanol; water at 80℃; for 84h; Inert atmosphere; Schlenk technique; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With tri-tert-butyl phosphine; palladium diacetate; sodium t-butanolate; In toluene; at 100℃; for 72h;Schlenk technique; Inert atmosphere; | General procedure: In a dry schlenk equipped with a magnetic stir bar,tribrominated triphenylamine derivative (1.0 mmol, 1.0 equiv.),<strong>[101-70-2]bis(4-methoxyphenyl)amine</strong> or 3,6-dimethoxycarbazole (4.5 equiv.), palladium(II) acetate (0.1 equiv.), sodiumtert-butoxide (6.0 equiv.) and anhydrous toluene (20 mL) were charged. Themixture was then degassed by argon purging for 30 min. Tri-tert-butylphosphine(0.2 equiv.) dissolved in toluene (3 mL) was added via syringe. After evacuated and refilled with argon (x5), themixture was heated (100C) for 3 days and then allowed to cool to roomtemperature. The mixture was diluted with chloroform (100 mL), washed withbrine (x2) and water, dried over anhydrous MgSO4, filtered and concentrated to give a viscous oil (ca. 3 - 4 mL) to which was added methanol (200 mL) with stirring. The precipitate was then filtered,rinsed with methanol. The crude product was purified by column chromatographyeluting with CH2Cl2/cyclohexane (50/50 ? 100/0 v/v) toyield a desired product |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
47% | With tri-tert-butyl phosphine; palladium diacetate; sodium t-butanolate In toluene at 100℃; for 72h; Schlenk technique; Inert atmosphere; | Generalprocedure for the synthesis of 1, 2, 3,4 and 5 (Buchwald-Hartwig amination) General procedure: In a dry schlenk equipped with a magnetic stir bar,tribrominated triphenylamine derivative (1.0 mmol, 1.0 equiv.),bis(4-methoxyphenyl)amine or 3,6-dimethoxycarbazole (4.5 equiv.), palladium(II) acetate (0.1 equiv.), sodiumtert-butoxide (6.0 equiv.) and anhydrous toluene (20 mL) were charged. Themixture was then degassed by argon purging for 30 min. Tri-tert-butylphosphine(0.2 equiv.) dissolved in toluene (3 mL) was added via syringe. After evacuated and refilled with argon (x5), themixture was heated (100°C) for 3 days and then allowed to cool to roomtemperature. The mixture was diluted with chloroform (100 mL), washed withbrine (x2) and water, dried over anhydrous MgSO4, filtered and concentrated to give a viscous oil (ca. 3 - 4 mL) to which was added methanol (200 mL) with stirring. The precipitate was then filtered,rinsed with methanol. The crude product was purified by column chromatographyeluting with CH2Cl2/cyclohexane (50/50 → 100/0 v/v) toyield a desired product |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In 1,4-dioxane; water; at 100℃; for 24h;Inert atmosphere; | Add tris(4-bromophenyl)amine, 4-pyridineboronic acid, potassium carbonate and palladium tetrakistriphenylphosphine to 66% 1,4-dioxane aqueous solution, and reaction is under protection of N2 at temperature of 100C , the reaction is carried out for 24 hours to obtain substance A, which is then added to distilled water a to obtain the extraction liquid; the tris(4-bromo)aniline, 4-pyridineboronic acid, potassium carbonate and tetraphenyl The dosage ratio of phosphonium palladium, 1,4-dioxane aqueous solution and distilled water a is 390.43mg:358.93mg:325mg:93.5mg:15mL:100mL; After extracting the extract obtained in S1 with dichloromethane three times, the obtained organic phase is washed three times with distilled water, and then washed three times with a saturated aqueous sodium chloride solution to obtain substance B; Dissolve substance B obtained in S2 in absolute ethanol, and then add distilled water b to obtain substance C; the dosage ratio of substance B, absolute ethanol and distilled water b is 300 mg: 10 mL: 100 mL; After the substance C obtained in S3 is subjected to suction filtration, water washing and petroleum ether washing in sequence, it is recrystallized with ethanol to obtain substance D; the molecular formula of the substance D is C33H24N4; the substance D The structural formula of is that the dosage ratio of the substance D, N,N-dimethylformamide and 1-bromooctane is 476mg: 10mL: 2mL; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85.5% | With palladium diacetate; triethylamine; tris-(o-tolyl)phosphine In dichloromethane at 85 - 90℃; for 25h; Inert atmosphere; | 1.2 Synthesis of tris[4-(2-pyridin-4-ylvinyl)phenyl]amine or compound 5 Compound 4 (1 g, 2.07 mmol, 1 eq.), palladium acetate (23 mg, 0.104 mmol, 0.05 eq.) and tris-o-tolylphosphine (95 mg, 0.311 mmol, 0.15 eq.) are introduced into a dry reactor which is then purged with nitrogen. One mL of 4-vinylpyridine (0.98 g, 9.32 mmol, 4.5 eq.) and 5.4 mL of a TEA/DMF mixture (2/1, v/v) are successively added. The mixture is stirred at 85-90° C., under nitrogen for 25 hours. Next, its temperature is brought to room temperature and the solvents are removed under high vacuum. The product is diluted with 120 mL of dichloromethane, washed with 3*30 mL of a saturated sodium carbonate solution and then dried. The volume of dichloromethane is reduced and the product is precipitated by adding hexane and cooling to 4° C. 0.943 g of compound 5 is thus obtained in the form of an orange powder (yield: 85.5%). |
70% | With trans-bis(triphenylphosphine)palladium dichloride; potassium carbonate In N,N-dimethyl-formamide Reflux; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With tetrakis(triphenylphosphine) palladium(0); lithium tert-butoxide In 1,4-dioxane at 120℃; Sealed tube; | 1 [0116] A mixture of tris-bromotriphenylamine 3a (123 mg, 0.25 mmol, 1 equiv.), 5-N-methylbenzimidazoyloxazole (600 mg, 3 mmol, 3 equiv.), lithium tert-butoxide (460 mg, 6 mmol, 6 equiv.), tetrakis(triphenylphosphine)palladium(0) (180 mg, 10mol%) in dry dioxane (5 mL) was stirred overnight at 120°C in a sealed tube. Dichloromethane and water were added. After decantation, the resulting organic layer was washed with brine, dried over MgSO4, filtered and concentrated to dryness. The crude residue was purified by column chromatography (dichloromethane/methanol = 100/0 to 90/10), dissolved in a minimal amount of dichloromethane and precipitated with diethyl ether to afford the desired compound 5aBzim in 83% yield (700 mg, 0.83 mmol) as a yellow solid. |
33% | With tetrakis(triphenylphosphine) palladium(0); lithium tert-butoxide In 1,4-dioxane at 120℃; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
35% | With tetrakis(triphenylphosphine) palladium(0); lithium tert-butoxide In 1,4-dioxane at 120℃; for 2h; Sealed tube; | 1 Preparation of compound 5aPy Preparation of compound 5aPy [0112] A mixture of tris-bromotriphenylamine 3a (123 mg, 0.25 mmol, 1 equiv.), 5-pyridyloxazole (112 mg, 0.77 mmol, 3 equiv.), lithium tert-butoxide (92 mg, 1.1 mmol, 4.5 equiv.), tetrakis(triphenylphosphine)palladium(0) (44 mg, 0.04 mmol, 0.15 equiv.) in dry dioxane (2 mL) was stirred for 2 h at 120°C in a sealed tube. Dichloromethane and water were added. After decantation, the resulting organic layer was washed with brine, dried over MgSO4, filtered and concentrated to dryness. The crude residue was purified by column chromatography (dichloromethane/methanol = 100/0 to 90/10), dissolved in a minimal amount of dichloromethane and precipitated with diethyl ether to afford the desired compound 5aPy in 35 % yield (60 mg, 0.09 mmol) as a yellow solid. 1H NMR (300 MHz, CDCl3) δ 8.69 (d, J = 5. 0, 2H), 8.09 (d, J = 8.6, 2H), 7.67 (s, 1H), 7.58 (d, J = 5.7, 2H), 7.30 (d, J = 8.6, 2H) 13C NMR (75 MHz, CDCl3) δ 162.2, 150.5, 148.8, 148.6, 134.8, 128.2, 127.1, 124.6, 122.3, 117.9 MS (ES+) m/z 678.3 Anal. (C42H27N7O3.0.5H2O) Calcd: C, 73.46; H, 4.11; N, 14.28 Found : C, 73.62; H, 3.89; N, 13.96 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With bis(dibenzylideneacetone)-palladium(0); sodium t-butanolate; XPhos In toluene at 110℃; for 24h; Schlenk technique; Inert atmosphere; | |
54% | With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate In toluene at 100℃; for 3h; | 15.2 (2) Synthesis of Compound J28 The following reagents and solvent were charged into a reaction vessel. Tris(dibenzylideneacetone)dipalladium(0): 48 mg (0.052 mmol), Tri(t-butyl)phosphine: 42 mg (0.21 mmol) , Toluene: 5 ml. Next, the reaction solution was stirred at room temperature for 15 minutes. After that, the following reagents and a solvent were charged into the reaction solution. Compound J27: 250 mg (0.52 mmol), Aniline: 580 mg (6.2 mmol) , t-Butoxysodium: 600 mg (6.2 mmol). Next, the reaction solution was heated to 100° C. and then stirred at the temperature (100° C.) for 3 hours. After the completion of the reaction, the reaction solution was cooled and then the reaction solution was concentrated under reduced pressure to provide a coarse product. Next, the coarse product was purified by silica gel column chromatography (developing solvent; toluene) to provide 150 mg (yield: 54%) of Compound J28. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In 1,2-dimethoxyethane; water; for 20h;Inert atmosphere; Reflux; | To a mixture of tris(4-bromotriphenylamine) (2.0 g; 0.00415 mole), 1- thianthrenylboronic acid (3.6 g; 0.037 mole), tetrakis(triphenyl phosphine) palladium (0.72 g; 0.00062 mole) in ethyleneglycoldimethyl ether (70 ml) was added potassium carbonate (3.0 g; 0.022 mole) in water (50 ml). The reaction mixture was magnetically stirred and refluxed under nitrogen atmosphere for 20 hours, allowed to cool and the solvent removed under reduced pressure. The residue was dissolved in dichloromethane and extracted with brine (The product was not completely soluble in dichloromethane). The organic phase was washed with water, dried over anhydrous magnesium sulphate and solvent removed to give a green solid. To the solid methanol was added, stirred for 6h and filtered off under suction. The product was washed with diethyl ether and dried under vacuum at 70 C. Crude yield 3.15 g. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
56% | With tricyclohexylphosphine tetrafluoroborate; palladium diacetate; potassium carbonate In N,N-dimethyl acetamide at 120℃; for 72h; Inert atmosphere; | 2.5.2. SM1 A mixture of tris(4-bromophenyl)amine (0.96 g, 2.0 mmol), 1a (4.70 g, 12.0 mmol), anhydrous DMAc (12.0 mL), K2CO3 (2.49 g,18 mmol), Pd(OAc)2 (39 mg, 0.18 mmol), and PCy3*HBF4 (132 mg,0.36 mmol) was stirred at 120 °C for 3 d under N2 atmosphere. After being cooled to room temperature, water (50 mL) and DCM (50 mL) were added, the organic layer was separated, the aqueous one was extracted with DCM (50 mL x 2), and the combined organic layers were washed with brine (50 mL x 3), dried over anhydrous MgSO4, and evaporated to dryness. The residue was chromatographically purified on a silica gel column eluting with DCM to afford SM1 as a light red solid (1.58 g, 56%). Melting point (Mp) 121 °C. FTIR (KBr, cm-1): 2800-3000 (C-H), 1698, 1656 (C=O), 1588, 1536, 1502,1467 (C-C), 1435, 1388, 1349, 1320 (C-N), 1263, 1237, 1179, 1104,1065, 958, 885, 859, 802. 1H NMR (400 MHz, CDCl3): δ (ppm) 8.67(d, J 8.4 Hz, 1H), 8.59 (d, J 7.2 Hz, 1H), 8.55 (d, J 7.6 Hz, 1H), 7.81 (d, J 7.6 Hz, 1H), 7.72 (t, J 8.0 Hz, 1H), 7.56 (d, J 8.4 Hz, 1H),7.34 (s, 1H), 7.27 (d, J 3.6 Hz, 1H), 7.16 (s, 2H), 4.13 (t, J 7.6 Hz,2H), 0.78e1.69 (m, 15H). 13C NMR (100 MHz, CDCl3): δ (ppm) 163.45, 163.18, 146.96, 145.96, 139.12, 137.77, 131.17, 130.83, 130.14,129.91, 129.54, 129.29, 128.93, 127.99, 127.75, 127.51, 127.11, 126.88,124.82, 123.57, 123.50, 122.52, 40.44, 31.94, 29.51, 29.40, 28.40,27.34, 22.78, 14.08. Anal. calcd for C90H84N4O6S3: C, 76.46; H, 5.99;N, 3.96. Found: C, 76.17; H, 5.89; N, 4.07%. MALDI-TOF (m/z): M+ calculated for C90H84N4O6S3, 1413.8; found: 1413.8. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70.3% | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate In 1,4-dioxane at 80℃; for 24h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In ethanol; water; toluene for 12h; Reflux; Inert atmosphere; | 2.2 Synthesis of tris(4-(pyrimidin-5-yl)phenyl)amine (TPMTPA) The synthetic route of tris(4-(pyrimidin-5-yl)phenyl)amine (TPMTPA) is outlined in Scheme 1. In a two-necked 150 mL round bottom flask equipped with a magnetic stir bar, areflux condenser, and nitrogen atmosphere, toluene (24 mL), ethanol (12 mL), and 2 M aqueous Na2CO3 (18 mL) wereadded to a mixture of tris(4-bromophenyl)amine (1.21g,2.5 mmol), 5-pyrimidinylboronic acid (1.00 g, 8 mmol), and tetrakis(triphenylphosphine)platinum (0.23 g, 0.2 mmol). The mixture was refluxed for 12 h under nitrogen inlet. After cooled to room temperature, the reaction mixture was extracted with dichloromethane and distilled water. The dichloromethane phase was dried over Na2SO4 and then filtered. After the solvent was removed under reduced pressure, the crude product was purified by silica gel column chromatography using dichloromethane/ethyl acetate (1:1) as the eluent. Further purification by sublimation gave a white solidof TPMTPA (0.83 g) (69%). 1H NMR (400 MHz, CDCl3) δ 9.23 (s, 3H), 9.01 (s, 6H), 7.57 (d, J=8.6 Hz, 6H), 7.33 (d, J=8.6 Hz, 6H). 13C NMR (101 MHz, CDCl3) δ 157.26,154.51, 147.73, 133.59, 129.31, 128.14, 125.07. HRMS (EI,m/z): [M]+ Calcd. for C30H21N7, 479.1858; found, 479.1860.Anal. Calcd. (%) for C30H21N7: C, 75.14; H, 4.41; N, 20.45; found: C, 75.15; H, 4.44; N, 20.41. |
60% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; water at 85℃; for 48h; Inert atmosphere; | |
60% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; water at 75℃; for 48h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In ethanol; water; toluene Inert atmosphere; Reflux; | Tris{4-[5′-(5,5-dimethyl-1,3-dioxan-2-yl)-2,2′-bithien-5-yl]phenyl}amine (3a). In an inert atmosphere, degassed solutions of tris(4-bromophenyl)amine (0.92 g, 1.91 mmol) and 1 (2.79 g, 6.87 mmol) in toluene/ethanol mixture (50/5 mL) and 2 M solution of aq. Na2CO3 (10.3 mL) were added to Pd(PPh3)4 (238 mg, 0.2 mmol). The reaction mixture was stirred under reflux for 11 h, and then it was cooled to room temperature and poured into 100 mL of water and 100 mL of toluene. The organic phase was separated, washed with water, dried over sodium sulfate and filtered. The solvent was evaporated in vacuum and the residue was dried at 1 Torr. The product was purified by column chromatography on silica gel (eluent toluene: ethyl acetate = 20: 1) to give pure compound 3a (1.67 g, 81%) as a yellow solid. M.p. = 247-248 °C. 1H NMR (250 MHz, CDCl3): δ [ppm] 0.8 (s, 9H), 1.28 (s, 9H), 3.61 (d, 6H, J = 11 Hz), 3.74 (d, 6H, J = 11 Hz), 5.61 (s, 3H), 7.01-7.06 (overlapping peaks, 6H), 7.09-7.17 (overlapping peaks, 12H), 7.46 (d, 6H, J = 8.54 Hz). Calcd (%) for C60H57NO6S6: C, 66.70; H, 5.32; N, 1.30; S, 17.80. Found: C, 66.57; H, 5.33; N, 1.27; S, 17.81. MALDI-MS: found m/z 1080.63; calculated for [M]+ 1080.51. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
50% | Stage #1: tri(p-bromophenyl)amine With n-butyllithium; N,N,N,N,-tetramethylethylenediamine In hexane at -78℃; for 1h; Schlenk technique; Stage #2: With copper dichloride at 20℃; for 10h; Schlenk technique; | Preparation of N,N,N',N'-tetrakis(4-bromophenyl)biphenyl-4,4'-diamine An oven-dried 500 mL Schlenk flask was charged with tris(4-bromophenyl)amine (24.1 g, 50 mmol), then ether (350 mL) and N,N,N',N'-tetramethylethylenediamine (8.2 mL) were added through a rubber septum. The reaction mixture was cooled to -78 °C. Upon slow addition of a n-BuLi solution (34 mL, 1.6 M in hexanes, 55 mmol), and the mixture was stirred for 1 h at -78 °C. Solid CuCl2 (10.8 g, 80 mmol) was added, and the reaction mixture was then allowed to slowly warm to room temperature and stirred for an additional 10 h. The reaction mixture was exposed to air, stirred for 30 min and concentrated in vacuo. Approximately chloroform (100 mL) and water (100 mL) were added, and the layers were separated. The aqueous layer was subsequently washed with chloroform (50 mL) three times. The organic extracts were combined, dried with MgSO4, and filtered. The volatile chloroform was removed under vacuum to leave a green solid. Purification by column chromatography (petroleum ether) yielded the pure product as a white solid (10.1 g, 50%). 1HNMR (DMSO-d, 500 MHz, 25 °C): 7.61 (d, 4H), 7.5 (d, 8H), 7.09 (d, 4H), 7.0 (d, 8H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In ethanol; water; toluene for 1.5h; Inert atmosphere; Reflux; | 3 Synthesis of Compound G 3.00 g (6.27 mmol) of Compound E, 1.24 g (6.27 mmol) of Compound F, 25 mL of toluene, 12.5 mL of ethanol, and 6.3 mL of a 2 M aqueous solution of sodium carbonate were added to a reaction vessel, and the inner atmosphere of the vessel was replaced with argon. 0.43 g (0.38 mmol) of Pd(PPh3)4 was added thereto, followed by stirring under reflux for about 1.5 hours. After cooling, an organic layer was extracted, dried with anhydrous magnesium sulfate, and filtered, and the filtrate was concentrated using a rotary evaporator. The crude product thus obtained was separated by silica gel column chromatography (developing solution: toluene/hexane) to produce 2.94 g (Yield 85%) of Compound G as a solid white powder. The molecular weight of Compound G was measured by FAB-MS, and a value of 553.00 (C30H21Br2N) was obtained. |
43% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In ethanol; water; toluene for 6.5h; Reflux; Inert atmosphere; | Synthesis of Intermediate 5 Under a nitrogen atmosphere,Tris (4-bromophenyl) amine (14.5 g, 30.1 mmol),3-Biphenylboronic acid (3.00 g, 15.0 mmol),Toluene (60 ml),Nitrogen bubbling was performed on ethanol (30 ml) solution for 30 minutes,Tetrakis (triphenylphosphine) palladium (0) (347 mg, 0.300 mmol) at room temperature,2.0 M aqueous sodium carbonate solution (19 ml)Is added,And heated under reflux for 6 hours.After cooling to room temperature,The reaction mixture was extracted with methylene chloride,The organic layer was washed with brine, dried with magnesium sulfate,And concentrated under reduced pressure.The residue was purified by silica gel column chromatography (hexane / methylene chloride = 19: 1 → 1: 9 → 1: 4)Intermediate 5 (3.60 g, yield 43%) was obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
45% | Stage #1: 4-(benzo[b]thiophen-3-yl)-N,N-diphenylaniline With tert.-butyl lithium In tetrahydrofuran at -78 - -60℃; for 0.5h; Inert atmosphere; Stage #2: With Triisopropyl borate In tetrahydrofuran at -78℃; Inert atmosphere; Stage #3: tri(p-bromophenyl)amine With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In ethanol; water; toluene at 70 - 80℃; for 2h; Inert atmosphere; | 56.2.A; 56.2.B Synthesis of M64 A. In and cooled to -78 °C the M56-1 38g (100mmol), dry THF 500ml to 1000ml three-necked flask with a mechanical stirrer fitted under the protection of nitrogen gas was added dropwise 2.4M n- butyllithium 50ml (120mmol) to this solution maintaining the reaction for 30 minutes under the following -60 °C changed from tan to dark black and the temperature was raised to room temperature and was stirred and then cooled to -78 °C and added dropwise Triisopropyl borate 30g (159.5mmol) and the solution allowed to stand overnight. Stirred for 30 minutes and then stopped (cancellation) by the addition of saturated aqueous ammonium chloride solution and separating and extracting the award and merging of the organic phase and dried over anhydrous magnesium sulfate rotational dehydration, and was dispersed in petroleum ether and suction filtered obtaining a white solid It is then used in the reaction of the next step directly. B. The above prepared under the protection of nitrogen gas three-necked flask with a mechanical stirrer, 1000ml fitted material (100mmol), tree - (p- bromophenyl) amine 9.6g (20mmol), tetrakis triphenylphosphine palladium 1.2g , toluene 300ml, ethanol 120ml, put the sodium carbonate 52g and water 200ml, and when after the reaction in 70 °C for 60 min solution turns brown from yellow to react, stirred under 80 °C for 60 min observing the presence or absence of the solid granules, and stopping the stirring and the solid disappears. (Ethyl acetate: petroleum ether = 1: proceed to TLC in 8 proportion of, and to stop the reaction overnight was allowed to stand and then aliquots ( ), washed and extracted Water and merge, dry the organic phase rotation dehydration (Spin Dry water ), and then dispersed with dichloromethane yielded a white solid compound M56 12.3g then after obtaining a white solid 15g recrystallized from toluene / dichloromethane and a 45% yield of the last two steps. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
50% | Stage #1: C20H13NS With tert.-butyl lithium In tetrahydrofuran at -78 - -60℃; for 0.5h; Inert atmosphere; Stage #2: With Triisopropyl borate In tetrahydrofuran at -78℃; for 0.5h; Inert atmosphere; Stage #3: tri(p-bromophenyl)amine With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In ethanol; water; toluene at 70 - 80℃; for 2h; Inert atmosphere; | 59.2.A; 59.2.B Synthesis of M64 A. under the protection of nitrogen gas with a mechanical stirrer, 1000ml three-necked flask is equipped with a M64-1 25g (66.65mmol), dry THF 500ml, and the input to -78 cooled and 2.4M n-butyllithium 50ml (120mmol) of one solution is to drip the thermal reactions proceed for 120 minutes and then held at -60 and then turned into a dark black to yellowish brown, and cooled to -78 °C from -20 °C and the drip Triisopropyl borate 30g (159.5mmol) then the solution emerald color varies from amber stirred and allowed to stand overnight. By stirring and fractions after stopping (cancellation) was added for 30 bungan extracts the award and merging of the organic phase and dried over anhydrous magnesium sulfate and rotary dehydration conducting an ultrasonic treatment was dispersed in petroleum ether and suction filtration of the pale yellow after obtaining the oil-phase material is used in the reaction of the next step directly. B. The above prepared a 1000ml three-necked flask which is equipped with a mechanical stirrer under nitrogen gas protection material (46.65mmol),3,3 '- dibromo-2,2'-benzo (b) thiophene 8.4g (20mmol), tetrakis triphenylphosphine palladium 1.2g, toluene 300ml, 120ml ethanol, sodium carbonate 52g and water 200ml the In under 60 minutes and 70 No reaction then the solution is changing from yellow to brown reaction for 60 minutes under 80 °C and observing the presence or absence of the solid granules to agitation and the agitation stopped and the solid disappears. (Ethyl acetate: petroleum ether = 1: proceed with TLC to 8 proportional and stop the reaction overnight and washed aliquot ( ) was left and water to extract the award and merges the organic phase, dry, rotating dewatering (SpinDry) one through the dispersion and then with dichloromethane then 15g. obtained as a white solid recrystallized from toluene / dichloromethane yielded a white solid 9.1g M3 is a 45% yield of the last two steps. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; toluene; at 110℃; for 24h;Inert atmosphere; | The second stage: three bromine was added 2.39g triphenylamine in 250ml dual-port round-bottomed flask, 1.86gQuinoline boronic acid, palladium tetrakistriphenylphosphine 0.1g (catalyst), 30ml of toluene, 15ml of ethanol, 20ml concentration of 2mol / L sodium carbonate solution, the mixture was stirred under nitrogen protection reaction at 110 24h; After completion of the reaction, After the reaction was cooled to room temperature and repeatedly with dichloromethane and liquid separation, all combined organic phase was separated by column chromatography and drying, to give the final product 2.44g (85% yield). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
51% | With tris-(dibenzylideneacetone)dipalladium(0); triphenylphosphine; sodium t-butanolate In toluene at 100℃; for 24h; | III.1 Synthesis of 1-1 Sub 1(1) (9.6g, 20mmol), Sub 2 (1) (44.1g, 60mmol), Pd2(dba) 3 (2.7g, 3mmol), PPh3 (1.5g, 6mmol), NaOt- after addition of Bu (16.5g,180mmol), each of the toluene (630mL), stirred and refluxed for 24 hours at 100 ° C.The organic layer was dried over MgSO4, and extracted with water and ether andrecrystallized silicagel column and the resulting organics concentrated to a final productafter 1-1 24.9g: was obtained (yield: 51%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In toluene at 80℃; for 24h; Inert atmosphere; Schlenk technique; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: potassium carbonate; tetrakis(triphenylphosphine) palladium(0) / toluene / 24 h / 80 °C / Inert atmosphere; Schlenk technique 2: 1,10-Phenanthroline; caesium carbonate; copper(l) iodide / N,N-dimethyl-formamide / Reflux; Inert atmosphere; Schlenk technique |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; potassium phosphate; palladium diacetate In 1,2-dimethoxyethane at 80℃; for 48h; Inert atmosphere; | Tris{4-[2,6-bis(trifluoromethyl)pyridin-4-yl]phenyl}amine (4) In a fume hood, an oven-dried Schlenk flask equipped with magnetic stirring bar was filled with N2 and evacuated (three cycles). Under N2 atmosphere, Pd(OAc)2 (1.7 mg, 0.0075 mmol, 3 mol% Pd), SPhos (6.2mg, 0.015 mmol, 6 mol%), K3PO4 (239 mg, 1.125 mmol, 4.5 equiv), 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,6-bis(trifluoromethyl)pyridine (341 mg, 1 mmol, 4 equiv), tris(4-bromophenyl)amine(121 mg, 0.25 mmol, 1 equiv), and DME (2 mL) were added in order. The Schlenk flask was closed and the mixture was heated at 80 °C in an oil bath for 48 h. The progress of reaction was monitored by GC-MS and TLC. Upon completion of reaction, the Schlenk flask was cooled to r.t. and exposed to air. The mixture was extracted into EtOAc, washed with water and brine, and dried (anhyd Na2SO4). The crude product was purified by column chromatography (silica gel); light yellow solid; yield: 151 mg (0.25 mmol, 68%); mp 262-263 °C; Rf = 0.4 (hexanes-CH2Cl2 1:1).FT-IR (ATR): 1593, 1515, 1389, 1329, 1260, 1187, 1129, 1064, 898,855, 824, 725 cm-1.1H NMR (700 MHz, CDCl3): δ = 8.05 (s, 6 H), 7.69 (d, J = 8.6 Hz, 6 H),7.34 (d, J = 8.6 Hz, 6 H).13C NMR (176 MHz, CDCl3): δ = 151.3 (3 C), 149.4 (q, 2JC-F = 35.6 Hz, 6C), 148.6 (3 C), 131.0 (3 C), 128.7 (6 CH), 125.1 (6 CH), 120.9 (q, 1JC-F =274.7 Hz, 6 CF3), 120.3 (6 CH).GC-MS (EI): m/z (%) = 884 (100) [M]+, 865 (10), 756 (7), 670 (11), 554(27), 432 (32), 301 (38).HRMS (ESI-Orbitrap): m/z [M + H]+ calcd for C39H19F18N4: 885.13168;found: 885.12840. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
47% | With tetrakis(triphenylphosphine) palladium(0) In N,N-dimethyl-formamide at 110℃; for 2.5h; Inert atmosphere; | 1.2 Synthesis of formula (1-1) 2.0 g of tributylphenylamine (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 0.24 g of Pd (PPh3) 4 were placed in a reaction vessel and purged with nitrogen, Of 7.8 g (purity 86.7%) of 5-tributylstyrene-2,2'-bithiophene previously prepared in [1](DMF) solution. After stirring at 110 DEG C for 2.5 hours, the reaction solution was reprecipitated with 1.5 L of methanol. SlurryWas stirred at room temperature for 15 hours, filtered, and then 90 mL of toluene, 10 mL of ethanol and 0.75 g of activated carbon were added to the obtained filtrateAnd the mixture was stirred under reflux conditions for 1 hour. The resultant filtrate was cooled to 0 deg. C while stirring, and stirring was continued at 0 deg. C for 2 hours. The slurry was filtered, and the filtrate was dried (80 DEG C, 2 hours) to obtain 1.4 g of the target thiophene derivative 1 (yield: 47%). |
1.4 g | With tetrakis(triphenylphosphine) palladium(0) In N,N-dimethyl-formamide at 110℃; for 2.5h; Inert atmosphere; | 2.2 The thiophene derivative 3 (TP3) represented by the formula (X4) was synthesized by the following method. Tributylphenylamine(Tokyo Chemical Industry Co., Ltd.)2.0 g and Pd(PPh3)4 0.24g were placed in a reaction vessel and replaced with nitrogen.100 mL of a dimethylformamide (DMF) solution of 7.8 g (purity: 86.7%) of 5-tributylstannyl-2,2'-dithiophene synthesized in [1] was added.After stirring at 110 ° C for 2.5 hours, the reaction solution was reprecipitated with 1.5 L of methanol.After the slurry was stirred at room temperature for 15 hours,Filtration, adding 90 mL of toluene to the obtained filtrate,10 mL of ethanol and 0.75 g of activated carbon were stirred under reflux for 1 hour.Filtration was carried out while hot, and the obtained filtrate was cooled to 0 ° C under stirring, and stirring was continued at 0 ° C for 2 hours.The slurry was filtered, and the filtrate was dried (80 ° C, 2 hours) to give TP3 (yield: 1.4 g, yield 47%).The measurement results of 1H-NMR and TOF-MS are shown below. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
18%; 32% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; water; toluene; for 2.5h;Reflux; Inert atmosphere; | Under a nitrogen atmosphere,Tris (4-bromophenyl) amine (2.63 g, 6.15 mmol),MCPB (1.76 g, 6.15 mmol),Toluene (30 ml),To a solution of ethanol (15 ml)Tetrakis (triphenylphosphine) palladium (0) (0.28 g, 0.246 mmol) at room temperature,2 M sodium carbonateAqueous solution (7.5 ml) was added,It was refluxed for 2.5 hours.After cooling to room temperature,The reaction mixture was extracted with toluene,The organic layer was washed with brine,Drying with magnesium sulfate,And concentrated under reduced pressure.The residue was purified by silica gel column chromatography (hexane / methylene chloride = 5/1 ? 3/1) and reprecipitated with methylene chloride / methanol to give Intermediate 1 (1.27 g, yield 32percent),And Intermediate 6 (0.91 g, yield 18percent). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
26% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; water; toluene; for 2h;Reflux; Inert atmosphere; | Under a nitrogen atmosphere,Tris (4-bromophenyl) amine (6.70 g, 15.67 mmol),MCPB (3 g, 10.45 mmol),Toluene (52 ml),Ethanol (26 ml)Tetrakis (triphenylphosphine) palladium (0) (0.60 g, 0.522 mmol) at room temperature,A 2 M aqueous solution of sodium carbonate (13 ml) was added,And refluxed for 2 hours.After cooling to room temperature,The reaction mixture was extracted with toluene, the organic layer was washed with brine, dried over magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane / methylene chloride = 5/1 ? 3/1 ? 2/1) and recrystallized from toluene / cyclohexane to give Intermediate 1 (1.75 g, yield 26percent Was obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In ethanol; water; toluene for 8h; Reflux; Inert atmosphere; | tris{4-[5'-(5,5-dimethyl-2-phenyl-1,3-dioxan-2-yl)-2,2′-bithien-5-yl]phenyl}amine (4) In an inert atmosphere, degassedsolutions of tris(4-bromophenyl)amine (0.8 g, 2.0 mmol) andcompound 3 (2.88 g, 6.0 mmol) in toluene/ethanol mixture (50/5 mL) and 2 M solution of aq. Na2CO3 (9 mL) were added toPd(PPh3)4 (173 mg, 0.14 mmol). The reaction mixture was stirredunder reflux for 8 h, and then it was cooled to room temperatureand poured into 75 mL of water and 100 mL of toluene. The organicphasewas separated, washed with water, dried over sodium sulfateand filtered. The solvent was evaporated in vacuum and the residuewas dried at 1 Torr. The product was purified by column chromatographyon silica gel (eluent toluene: triethylamine 99.9: 0.1) togive pure compound 4 (1.74 g, 80%) as yellow solid.M.p. 115-116 C. 1H NMR (250 MHz, CDCl3): d [ppm] 0.88 (s, 9H),1.16 (s, 9H), 3.59 (d, 6H, J 11 Hz), 3.69 (d, 6H, J 11 Hz), 6.64 (d,3H, J 3.7 Hz), 6.93e6.97 (overlapping peaks, 3), 7.07e7.13(overlapping peaks, 12H), 7.32-7.49 (overlapping peaks, 15H), 7.57(d, 6). 13C NMR (125 MHz, CDCl3) : δ [ppm] 22.21, 22.67, 30.03,72.43, 99.55, 122.73, 123.06, 124.37, 124.60, 126.48, 126.73, 126.84,128.35,128.51,128.93,136.06,138.03,140.02,142.80,145.95,146.39.Calcd (%) for C78H69NO6S6: C, 71.58; H, 5.31; S, 14.70; N, 1.07. Found:C, 71.41; H, 5.45; S, 14.57; N, 1.01. MALDI-MS: found m/z 1308.73;calculated for [M] 1308.81 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
63% | Stage #1: tri(p-bromophenyl)amine; 10-(9,9-diethyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-fluoren-2-yl)-9,9-dimethyl-9,10-dihydroacridine With potassium carbonate In 1,4-dioxane for 0.5h; Inert atmosphere; Stage #2: With tetrakis(triphenylphosphine) palladium(0) In 1,4-dioxane at 105℃; for 24h; Inert atmosphere; | 2.3.1. Synthesis of tris(4-(7-(9,9-dimethylacridin-10(9H)-yl)-9,9-diethyl-9H-fluoren-2-yl)phenyl)amine (TPA-3FA) A mixture of tris(4-bromophenyl)amine (100 mg, 0.207 mmol),10-(9,9-diethyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-fluoren-2-yl)-9,9-dimethyl-9,10-dihydroacridine (460 mg,0.829 mmol) and K2CO3 (2 M, 15.0 mL) solution in dioxane (50 mL)was placed in a 3-neck round bottom flask. Then, the reactionmixture was degassed with argon for 30 min and then Pd(PPh3)4(48 mg, 0.04 mmol) was added. The reaction mixture was vigorouslystirred under inert atmosphere at 105 °C for 24 h. Upon reaction completion, the reaction mixture was diluted with ethylacetate (EtOAc) and added water, then the EtOAc layer was separated and the aqueous phase was extracted with EtOAc again. Thecombined EtOAc layers were washed with brine solution(2 50 mL), and dried over anhydrous Na2SO4. Finally, the organic solvent was concentrated under reduced pressure and the residuewas purified by column chromatography on silica gel eluted withEtOAc/hexanes (1:9 to 2:8). The product was further purified byrecrystallization in ethanol and precipitated with CH2Cl2/hexanesto afford TPA-3FA as a pale green solid (200 mg, 63%). FTIR (neat,cm-1) 2973, 1513, 1265. 1H NMR (300 MHz, CDCl3, δ ): 7.97 (d,J 7.5 Hz, 3H), 7.84 (d, J 8.4 Hz, 3H), 7.68-7.61 (m, 12H), 7.48 (d,J 7.5 Hz, 6H), 7.34-7.25 (m, 12H), 7.0-6.90 (m, 12H), 6.35 (d,J 7.2 Hz, 6H), 2.09 (q, J 6.9 Hz, 12H), 1.73 (s, 18H), 0.44 (t,J 6.6 Hz, 18H). 13C NMR (75 MHz, CDCl3, d): 153.044, 151.083,146.794, 141.295, 141.080, 139.870, 139.809, 139.763, 135.887,129.957, 129.852, 128.029, 126.467, 125.854, 125.808, 125.410,124.521, 121.825, 121.059, 120.447, 120.309, 113.967, 56.585, 36.012,32.949, 31.616, 8.731. HRMS (FAB) calcd for C114H103N4 [MH]1528.8138, found 1528.8216. Anal. calcd for C114H102N4: C 89.61, H6.73, N 3.67; found C 89.63, H 6.71, N 3.65. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With tetrabutylammomium bromide; potassium carbonate In water at 60℃; for 3h; | |
75% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In N,N-dimethyl-formamide at 90℃; for 48h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With tri-tert-butyl phosphine; potassium <i>tert</i>-butylate; palladium diacetate In toluene at 100℃; for 8h; Inert atmosphere; Schlenk technique; Sealed tube; | 1 A compound represented by the following chemical formula (126) was synthesized by a synthetic route (S19) shown below. A stirrer,200 mL argon-substitutedOf Schlenk tube was charged with N-phenyldibenzo [b, d] thiophen-4-amine(1.65 g, 6.0 mmol),Tris (4-bromophenyl) amine (0.964 g, 2.0 mmol),Palladium acetate (27 mg, 0.12 mmol), toluene (50 mL),Tri-t-butylphosphine (24 mg, 0.12 mmol),And potassium t-butoxide (1.35 g, 12.0 mmol) were charged,After sealing, the mixture was stirred at 100 ° C. for 8 hours. after that,The reaction vessel was allowed to cool to near room temperature, the lid was opened, and water (50 mL) was added thereto.The contents were transferred to a separating funnel, the organic phase and the aqueous phase were separated, the aqueous phase was removed,The organic phase was further washed with water. The organic phase was dried over sodium sulfate.Thereafter, sodium sulfate was removed by filtration, and the organic phase was concentrated.The resulting mixture, which was concentrated,Silica gel column chromatography(Developing solvent: hexane / dichloromethane = 3/1)The target compound was obtained (yield 1.70 g, yield 80.0%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
32% | With potassium dihydrogenphosphate; copper(l) iodide; (S,S)-1,2-diaminocyclohexane In 1,4-dioxane at 80℃; for 48h; Inert atmosphere; | |
32% | With potassium phosphate; copper(l) iodide; trans-1,2-cyclohexanediamine In 1,4-dioxane at 80℃; for 48h; Inert atmosphere; | 2 Preparation of compound of formula 2 Compound 2-2 (2 g, 0.006 mol), tris(4-bromophenyl)amine (1 g, 0.002 mol), potassium phosphate (5 g, 0.024 mol), CuI in a 250 mL 1-neck flask under nitrogen atmosphere (0.2 g, 0.0015 mol), trans-1,2-diaminocyclohexane (0.68 mL, 0.006 mol), 1,4-dioxane (100 mL) was added. The reaction was allowed to proceed at 80°C for 48 hours. After completion of the reaction, quenched and the organic solvent was removed under reduced pressure. The mixture in the solid state was purified by column chromatography (methylene chloride:hexane = 1:7 volume ratio) to obtain the final compound of formula (2). Yield and NMR data of the compound of Formula 2 are as follows.Yield: 0.8 g (32%) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With N-Bromosuccinimide In N,N-dimethyl-formamide at 0 - 20℃; for 3h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75.4% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In N,N-dimethyl-formamide at 120℃; Inert atmosphere; | 1.1 Example 1 1. In a 100 mL round bottom flask, add 2,5-dihydroxyphenylboronic acid pinacolate (1.92g, 8mmol), tris(4-bromo Phenyl)amine (0.96g, 2mmol), tetratriphenylphosphine palladium (0.12g, 0.1mmol), evacuated with nitrogen three times, then added 35mL DMF and 10mL of 2M K2CO3 solution were refluxed at 120C overnight. After the reaction is complete, add 50mL of distilled water to the reaction solution In the reaction solution was extracted 3 times with ethyl acetate, then ethyl acetate was washed with water to remove a small amount of DMF, and the ethyl acetate was dried with anhydrous sodium sulfate Ethyl acid ester, spin off ethyl acetate, polar ethyl acetate: dichloromethane = 1:4 through the column, to give a purple-black solid 4- (tri (2,5- Dihydroxybenzene)) Triphenylamine 0.86g, yield 75.4%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
77% | With potassium phosphate; copper(l) iodide; trans-1,2-cyclohexanediamine In 1,4-dioxane at 110℃; for 48h; | 1 Preparation of compound of formula 1 In a 1-neck flask, compound 1 (1 g, 0.00367 mol), tris(4-bromophenyl)amine (0.6 g, 0.0012 mol), copper iodide (0.07 g, 0.000367 mol) prepared as above ), potassium phosphate (2 g, 0.0147 mol), 1,2-trans-cyclohexane diamine (0.4 mL, 0.00367 mol) was added, and 1,4-dioxane (100 mL) was added and stirred. The reaction was allowed to proceed at 110°C for 48 hours. After the reaction was completed, the mixture was cooled at room temperature, and the organic layer was separated by work-up with methylene chloride and distilled water. Subsequently, all of the solvent of the organic layer was evaporated and subjected to column chromatography (methylene chloride:hexane = 1:10 volume ratio) to obtain the final compound of formula (1). The yield and NMR data of the obtained compound of formula 1 are described below.Yield: 1 g (77%) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In ethanol; water; toluene at 70℃; for 24h; | 1 Synthesis of compound 1i Tris (4-bromophenyl) amine (20 mmol, 9.64 g), compound 1h (3.3 eq. 66 mmol, 20.8 g), toluene (100 ml) and ethanol (20 ml) were placed in a three-necked flask and dissolved. 40 ml of a 2M aqueous solution of potassium carbonate was added, and then tetrakis (triphenylphosphine) palladium (0.6 mmol, 0.69 g) was added, and the mixture was heated and stirred at 70 ° C. for 24 hours. After completion of the reaction, the mixture was diluted with methanol (200 ml), and the precipitated solid was collected by filtration and dried under vacuum (50 ° C., 16 hours). This crude product was dissolved in toluene (300 ml) by heating, filtered using a silica gel pad, and concentrated. This was recrystallized twice from toluene = 20 ml per 1 g of the purified raw material to obtain a pale yellow solid compound 1i. Yield 10.5 g, yield 65%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
35% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; methanol at 90℃; for 24h; Inert atmosphere; | 2.S1 4,4,4-tribromotriphenylamine (5mmol, 2.41g),4-pyridineboronic acid (3mmol, 3.69g),Palladium tetrakistriphenylphosphorus (0.15mmol, 173.3mg) and potassium carbonate (3mmol, 414mg) are mixed in a 1:1 volume ratio of methanol and tetrahydrofuran mixed solution,The crude product of 4-4-dibromo-4pyridyl-triphenylamine (Br-TPA-PY) was obtained by reacting at 90°C for 24 hours under nitrogen protection (the NMR results are shown in Figure 4).Purified by column chromatography,A light yellow solid is obtained,The solid has a faint blue fluorescence and the yield is 35% |
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; methanol Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
55% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; methanol at 90℃; for 24h; Inert atmosphere; | 1.S1 Combine 4,4,4-tribromotriphenylamine (5mmol, 2.41g) with 4-boronophenyl phenyl ether (10mmol, 2.14g), palladium tetrakistriphenylphosphorus (0.25mmol, 288.75mg) and potassium carbonate (10mmol , 1.38g) was added to the mixed solution of methanol and tetrahydrofuran with a volume ratio of 1:1 to dissolve, and reacted at 90°C for 24 hours under nitrogen protection to obtain crude 4-4-diphenyl ether-4 bromo-triphenylamine (OPY- TPA-Br) (the NMR results are shown in Figure 2), purified by column chromatography to obtain a light yellow solid, the solid has a light blue fluorescence, the yield is 55% |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
36% | With potassium phosphate; copper(l) iodide; trans-1,2-Diaminocyclohexane In 1,4-dioxane at 80℃; for 48h; Inert atmosphere; | 1.2 (2) Preparation of organic compounds The intermediate (a) (3g, 0.007mol), tris(4-bromophenyl)amine (1.14g, 0.0023mol), potassium phosphate (2.2g, 0.0092mol), CuI in a 250mL one-neck flask under nitrogen atmosphere (0.1g, 0.0002mol), trans-1,2-diaminocyclohexane (0.37mL, 0.0023mol), and 1,4-dioxane (100mL) are added. The reaction proceeds at 80° C. for 48 hours. After completion of the reaction, it is quenched and the organic solvent is removed under reduced pressure. The solid mixture is purified by column chromatography (MC:MeOH = 8:1) to obtain an organic compound of the following [Formula 1] (yield 36%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
35% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; water at 80℃; for 12h; Inert atmosphere; | 8.1; 9.1 (1) Synthesis of intermediate (j) In a 500 mL two-neck flask under nitrogen atmosphere, tris(4-bromophenyl)amine (0.48 g, 0.002 mol), the above intermediate (d) (1.21 g, 0.004 mol), Pd (pph3) 4 (0.2 g, 0.0002 mol) was added, and THF (100 mL) was added and stirred. When all the substances are dissolved in the flask, add potassium carbonzte solution (2N, 100mL). The reaction proceeds by refluxing at 80° C. for 12 hours. After completion of the reaction, the mixture was cooled at room temperature and extracted with EA/distilled water to separate the organic layer. After all of the solvent of the separated organic layer is blown off, it is purified by column chromatography (MC: Hx = 1:4) to obtain the following intermediate (j) (yield: 35%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
58% | With potassium phosphate; copper(l) iodide; (1R,2R)-1,2-diaminocyclohexane In 1,4-dioxane at 110℃; for 48h; | 2 The intermediate (g) (1g, 2.8mmol), tris(4-bromophenyl)amine (0.44g, 0.92mmol), copper iodide (0.07g, 0.367mol), potassium phosphate (2g, 0.0147mol) in a one-neck flask , 1,2-trans-cyclohexane diamine (0.4mL, 3.67mmol) was added, and 1,4-dioxane (100mL) was added and stirred. The reaction proceeds at 110° C. for 48 hours. After completion of the reaction, it is cooled at room temperature, and the organic layer is separated by working up with MC and distilled water. All of the solvent of the organic layer is blown off and purified by column chromatography (MC: Hx = 1:8) to obtain an organic compound of the following [Formula 2] (yield: 58%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With potassium phosphate; copper(l) iodide; (1R,2R)-1,2-diaminocyclohexane In 1,4-dioxane at 110℃; for 48h; | 1.2 (2) Synthesis of organic compounds Next, the intermediate (1) (1g, 2.88mmol), tris(4-bromophenyl)amine (0.44g, 0.92mmol),Copper iodide (0.07g, 0.367mol), potassium phosphate (2g, 0.0147mol), 1,2-trans-cyclohexanediamine (0.4mL, 3.67mmol) was added, 1,4-dioxane (100mL) was added and stirred. The reaction proceeds at 110° C. for 48 hours. After completion of the reaction, it is cooled at room temperature, and the organic layer is separated by working up with MC and distilled water. All of the solvent of the organic layer is blown off and purified by column chromatography (MC: Hx = 1:10) to obtain an organic compound of the following [Formula 1] (yield: 70%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
37% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; water at 80℃; for 12h; Inert atmosphere; | 18 (18) intermediate (r) Referring to the above reaction scheme, in a 500 mL two-neck flask under a nitrogen atmosphere, tris(4-bromophenyl)amine (0.68 g, 0.002 mol), the intermediate (g) (1.21 g, 0.004 mol), Pd (pph3) 4 ( 0.2 g, 0.0002 mol) was added, and THF (100 mL) was added and stirred. When all the substances are dissolved in the flask, add potassium carbonzte solution (2N, 100mL). The reaction proceeds by refluxing at 80° C. for 12 hours. After completion of the reaction, the mixture was cooled at room temperature and extracted with EA/distilled water to separate the organic layer. After all of the solvent of the separated organic layer was blown off, it was purified by column chromatography (MC: Hx = 1:4) to obtain the following intermediate (r) (yield: 37%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
56% | With tetrakis-(triphenylphosphine)-palladium In N,N-dimethyl-formamide at 100℃; for 24h; Inert atmosphere; Darkness; | 23 General procedure: Under an argon atmosphere, m-4 (250 mg, 0.42 mmol), 1,4-dibromobenzene (47.5 mg, 0.2 mmol), tetrakis(triphenylphosphine) palladium (24 mg, 0.2 mmol) were added to a 100 mL two-necked flask. 0.02 mmol), add DMF (15 mL) after pumping and ventilate, react at 100°C in the dark for 24 hours, a solid is precipitated, after cooling, suction filtration, washing with toluene, washing with ethanol, and silica gel column separation with dichloromethane to obtain yellow solid O4 -1 (54 mg, 40% yield). |
Tags: 4316-58-9 synthesis path| 4316-58-9 SDS| 4316-58-9 COA| 4316-58-9 purity| 4316-58-9 application| 4316-58-9 NMR| 4316-58-9 COA| 4316-58-9 structure
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P315 | Get immediate medical advice/attention. |
P320 | |
P302 + P352 | IF ON SKIN: wash with plenty of soap and water. |
P321 | |
P322 | |
P330 | Rinse mouth. |
P331 | Do NOT induce vomiting. |
P332 | IF SKIN irritation occurs: |
P333 | If skin irritation or rash occurs: |
P334 | Immerse in cool water/wrap n wet bandages. |
P335 | Brush off loose particles from skin. |
P336 | Thaw frosted parts with lukewarm water. Do not rub affected area. |
P337 | If eye irritation persists: |
P338 | Remove contact lenses, if present and easy to do. Continue rinsing. |
P340 | Remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P341 | If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P342 | If experiencing respiratory symptoms: |
P350 | Gently wash with plenty of soap and water. |
P351 | Rinse cautiously with water for several minutes. |
P352 | Wash with plenty of soap and water. |
P353 | Rinse skin with water/shower. |
P360 | Rinse immediately contaminated clothing and skin with plenty of water before removing clothes. |
P361 | Remove/Take off immediately all contaminated clothing. |
P362 | Take off contaminated clothing and wash before reuse. |
P363 | Wash contaminated clothing before reuse. |
P370 | In case of fire: |
P371 | In case of major fire and large quantities: |
P372 | Explosion risk in case of fire. |
P373 | DO NOT fight fire when fire reaches explosives. |
P374 | Fight fire with normal precautions from a reasonable distance. |
P376 | Stop leak if safe to do so. Oxidising gases (section 2.4) 1 |
P377 | Leaking gas fire: Do not extinguish, unless leak can be stopped safely. |
P378 | |
P380 | Evacuate area. |
P381 | Eliminate all ignition sources if safe to do so. |
P390 | Absorb spillage to prevent material damage. |
P391 | Collect spillage. Hazardous to the aquatic environment |
P301 + P310 | IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician. |
P301 + P312 | IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell. |
P301 + P330 + P331 | IF SWALLOWED: Rinse mouth. Do NOT induce vomiting. |
P302 + P334 | IF ON SKIN: Immerse in cool water/wrap in wet bandages. |
P302 + P350 | IF ON SKIN: Gently wash with plenty of soap and water. |
P303 + P361 + P353 | IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower. |
P304 + P312 | IF INHALED: Call a POISON CENTER or doctor/physician if you feel unwell. |
P304 + P340 | IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing. |
P304 + P341 | IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P305 + P351 + P338 | IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing. |
P306 + P360 | IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes. |
P307 + P311 | IF exposed: call a POISON CENTER or doctor/physician. |
P308 + P313 | IF exposed or concerned: Get medical advice/attention. |
P309 + P311 | IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician. |
P332 + P313 | IF SKIN irritation occurs: Get medical advice/attention. |
P333 + P313 | IF SKIN irritation or rash occurs: Get medical advice/attention. |
P335 + P334 | Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages. |
P337 + P313 | IF eye irritation persists: Get medical advice/attention. |
P342 + P311 | IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician. |
P370 + P376 | In case of fire: Stop leak if safe to Do so. |
P370 + P378 | In case of fire: |
P370 + P380 | In case of fire: Evacuate area. |
P370 + P380 + P375 | In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion. |
P371 + P380 + P375 | In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion. |
Storage | |
Code | Phrase |
P401 | |
P402 | Store in a dry place. |
P403 | Store in a well-ventilated place. |
P404 | Store in a closed container. |
P405 | Store locked up. |
P406 | Store in corrosive resistant/ container with a resistant inner liner. |
P407 | Maintain air gap between stacks/pallets. |
P410 | Protect from sunlight. |
P411 | |
P412 | Do not expose to temperatures exceeding 50 oC/ 122 oF. |
P413 | |
P420 | Store away from other materials. |
P422 | |
P402 + P404 | Store in a dry place. Store in a closed container. |
P403 + P233 | Store in a well-ventilated place. Keep container tightly closed. |
P403 + P235 | Store in a well-ventilated place. Keep cool. |
P410 + P403 | Protect from sunlight. Store in a well-ventilated place. |
P410 + P412 | Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF. |
P411 + P235 | Keep cool. |
Disposal | |
Code | Phrase |
P501 | Dispose of contents/container to ... |
P502 | Refer to manufacturer/supplier for information on recovery/recycling |
Physical hazards | |
Code | Phrase |
H200 | Unstable explosive |
H201 | Explosive; mass explosion hazard |
H202 | Explosive; severe projection hazard |
H203 | Explosive; fire, blast or projection hazard |
H204 | Fire or projection hazard |
H205 | May mass explode in fire |
H220 | Extremely flammable gas |
H221 | Flammable gas |
H222 | Extremely flammable aerosol |
H223 | Flammable aerosol |
H224 | Extremely flammable liquid and vapour |
H225 | Highly flammable liquid and vapour |
H226 | Flammable liquid and vapour |
H227 | Combustible liquid |
H228 | Flammable solid |
H229 | Pressurized container: may burst if heated |
H230 | May react explosively even in the absence of air |
H231 | May react explosively even in the absence of air at elevated pressure and/or temperature |
H240 | Heating may cause an explosion |
H241 | Heating may cause a fire or explosion |
H242 | Heating may cause a fire |
H250 | Catches fire spontaneously if exposed to air |
H251 | Self-heating; may catch fire |
H252 | Self-heating in large quantities; may catch fire |
H260 | In contact with water releases flammable gases which may ignite spontaneously |
H261 | In contact with water releases flammable gas |
H270 | May cause or intensify fire; oxidizer |
H271 | May cause fire or explosion; strong oxidizer |
H272 | May intensify fire; oxidizer |
H280 | Contains gas under pressure; may explode if heated |
H281 | Contains refrigerated gas; may cause cryogenic burns or injury |
H290 | May be corrosive to metals |
Health hazards | |
Code | Phrase |
H300 | Fatal if swallowed |
H301 | Toxic if swallowed |
H302 | Harmful if swallowed |
H303 | May be harmful if swallowed |
H304 | May be fatal if swallowed and enters airways |
H305 | May be harmful if swallowed and enters airways |
H310 | Fatal in contact with skin |
H311 | Toxic in contact with skin |
H312 | Harmful in contact with skin |
H313 | May be harmful in contact with skin |
H314 | Causes severe skin burns and eye damage |
H315 | Causes skin irritation |
H316 | Causes mild skin irritation |
H317 | May cause an allergic skin reaction |
H318 | Causes serious eye damage |
H319 | Causes serious eye irritation |
H320 | Causes eye irritation |
H330 | Fatal if inhaled |
H331 | Toxic if inhaled |
H332 | Harmful if inhaled |
H333 | May be harmful if inhaled |
H334 | May cause allergy or asthma symptoms or breathing difficulties if inhaled |
H335 | May cause respiratory irritation |
H336 | May cause drowsiness or dizziness |
H340 | May cause genetic defects |
H341 | Suspected of causing genetic defects |
H350 | May cause cancer |
H351 | Suspected of causing cancer |
H360 | May damage fertility or the unborn child |
H361 | Suspected of damaging fertility or the unborn child |
H361d | Suspected of damaging the unborn child |
H362 | May cause harm to breast-fed children |
H370 | Causes damage to organs |
H371 | May cause damage to organs |
H372 | Causes damage to organs through prolonged or repeated exposure |
H373 | May cause damage to organs through prolonged or repeated exposure |
Environmental hazards | |
Code | Phrase |
H400 | Very toxic to aquatic life |
H401 | Toxic to aquatic life |
H402 | Harmful to aquatic life |
H410 | Very toxic to aquatic life with long-lasting effects |
H411 | Toxic to aquatic life with long-lasting effects |
H412 | Harmful to aquatic life with long-lasting effects |
H413 | May cause long-lasting harmful effects to aquatic life |
H420 | Harms public health and the environment by destroying ozone in the upper atmosphere |
Sorry,this product has been discontinued.
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