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CAS No. : | 52708-37-9 | MDL No. : | MFCD00626047 |
Formula : | C18H14N2 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | DEVUXRBOPYDIDJ-UHFFFAOYSA-N |
M.W : | 258.32 | Pubchem ID : | 621047 |
Synonyms : |
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Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P264-P280-P302+P352-P337+P313-P305+P351+P338-P362+P364-P332+P313 | UN#: | N/A |
Hazard Statements: | H315-H319 | 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 palladium on activated charcoal; hydrazine hydrate In ethanol Reflux; Inert atmosphere; | |
98% | With tin(ll) chloride In methanol for 4h; Heating; | |
98% | With tin(ll) chloride In ethanol at 70℃; for 4h; |
98% | With palladium 10% on activated carbon; hydrazine hydrate In ethanol at 80℃; | |
97.82% | With iron; acetic acid at 20℃; for 16h; Cooling with ice; | 1 Synthesis of compound 2 In a 200mL single-neck flask, add compound 1 (4.00g, 13.87mmol) and 60mL glacial acetic acid successively, cool in an ice-water bath, add reduced iron powder (3.85g, 69.35mmol) in batches, magnetically stir for 10min, transfer to room temperature and continue stirring reaction for 16h. Stop the reaction, pour the reaction liquid into 150mL ice water, solids will precipitate out, filter with suction, and wash with distilled water. The solid was dissolved in DCM, filtered, and the remaining liquid was distilled under reduced pressure to remove the volatile solvent to obtain 3.50 g of viscous liquid (yield: 97.82%). |
96% | With palladium on activated charcoal; hydrazine hydrate In ethanol for 4h; Reflux; | |
95% | With tin(ll) chloride In ethanol for 6h; Heating; | |
95% | With palladium on activated charcoal; hydrazine hydrate In ethanol at 90℃; for 12h; Inert atmosphere; | |
95% | With palladium 10% on activated carbon; hydrazine hydrate In ethanol at 80℃; for 24h; Inert atmosphere; | 2.2 (2) Synthesis of Intermediate 4- (9H-carbazol-9-yl) aniline After 2.883g (0.01mol) 9- (4-nitrophenyl) -9H-carbazole was added to three 500ml flask, 300ml of absolute ethanol, a magnetic stirrer and argon gas, was heated to 80 deg.] C oil bath, was added 10% wt after the palladium on carbon 0.1g, was added and 10ml of hydrazine hydrate, the reaction was refluxed for 24h, the reaction solution was suction filtered and the filtrate was cold crystallization, the resulting cake was suction filtered and dried in vacuo 80 24h, to give the product 2.454g, 95% yield. This intermediate structure is as follows |
95% | With sodium tetrahydroborate In ethanol at 20℃; for 2h; | |
94% | With palladium 10% on activated carbon; hydrazine hydrate In ethanol for 4h; Reflux; | 2.2.2. Synthesis of N-(4-aminophenyl) carbazole (2) To a refluxed solution of compound 1 (1.44 g, 5.00 mol)and Pd/C (0.0720 g) in ethanol (10 mL) was added dropwise hydrazine monohydrate. The mixture was refluxedfor 4 h and cooled to room temperature. Pd/C was removedby filtration through Celite and the filtrate was concentrated to give compound 2 as a clear viscous liquid(1.24 g) in 94 % yield. IR (KBr): 3460, 3379 cm1 (NH2stretch). 1H NMR (500 MHz, DMSO-d6, d, ppm): 8.19(d, 2H), 7.40 (t, 2H), 7.27-7.21 (m, 4H), 7.18 (d, 2H), 6.81(d, 2H), 5.35 (s, 2H). |
90% | With tin(II) chloride dihdyrate In ethanol at 70℃; for 1.66667h; Inert atmosphere; | |
90% | With tin(II) chloride dihdyrate In ethanol at 80℃; for 1.83333h; Inert atmosphere; | 1 Weigh 6.00g product NPC (22mmol),Add 30.2g of tin(II) chloride dihydrate (134mmol) and 35ml of ethanol into the mixed system, heat to 80°C and reflux,React for 110 min under nitrogen protection. After removing the solvent by distillation under reduced pressure,Place the product in a cold water bath,Add 25-30% NaOH solution under vigorous stirring,After the system becomes milky white liquid, the product is extracted with ether,After washing with saturated brine and fully drying with anhydrous magnesium sulfate,Filter and spin-evaporate to remove the solvent,Dry to get a white viscous productN-(4-anilino)carbazole(CzPA) 5.12g, the yield is 90% |
90% | Stage #1: 9-(4-nitrophenyl)-9H-carbazole With palladium 10% on activated carbon; hydrazine hydrate In ethanol at 20℃; for 1h; Inert atmosphere; Stage #2: at 90℃; for 12h; | Step 2: synthesis of 9-(4-aminophenyl)-9H-carbazole 0.08 mol (23.05 g) of 9-(4-nitrophenyl)-9H-carbazole and 0.016mol (1.7 g) of 10% Pd/C were dispersed in 100mL of ethanol in a 250mL two-neck round-bottom flask equipped with a stirring hot plate, a condenser and an inlet of inert gas. The reaction mixture was stirred under nitrogen for 1 h at room temperature before 0.8mol (40 g) of hydrazine monohydrate was slowly added. The reaction mixture was refluxed at 90 C for 12 h. The reaction mixture was filtered to get rid of Pd/C, and then ethanol was removed by a vacuum evaporator to leave the white gel product (yield 90%) (Scheme 1). |
85% | With tin(II) chloride dihdyrate In ethyl [2]alcohol for 24h; Reflux; | 2 Synthesis of APCB 2.3.2 Synthesis of N-(4-aminophenyl)carbazole (APCB) To a solution of 5.76 g (0.02 mol) of NPCB in 40 ml ethanol, 15.8 g (0.07 mol) of SnCl2·2H2O was added. After refluxing for 24 h, the reaction mixture was condensed under reduced pressure to distill off most of the ethanol followed by neutralization with 40 wt% aqueous NaOH solution until the mixture became alkaline. The resulting mixture was then extracted with toluene, dried over anhydrous magnesium sulfate, and evaporated under reduced pressure to get 4.5 g (85% in yield) of yellowish syrup. FT-IR (KBr, cm-1): 3375, 3459 (N-H stretch). 1H NMR (DMSO-d6, 400 MHz), δ (ppm): 8.19 (d, 2H, J = 7.67 Hz), 7.40 (t, 2H, J = 7.66 Hz), 7.26∼7.17 (m, 6H), 6.79 (d, 2H, J = 8.61 Hz), 5.43 (s, 2H). |
85% | With 5%-palladium/activated carbon; hydrazine hydrate In ethanol at 80℃; | |
80% | With palladium 10% on activated carbon; hydrazine hydrate In ethanol for 10h; Reflux; | 4-(9H-Carbazol-9-yl)aniline (4b), compound 3b (0.09 mol), 10% Pd/C (0.103 g) and ethanol (20 mL) were added to a 50-mL round-bottom flask equipped with a stirring bar. The reaction mixture was heated under reflux. Hydrazine monohydrate (3 mL) was added slowly to the mixture, and then the solution was stirred under reflux for 10 h. The solution was cooled to room temperature, filtered to remove Pd/C, and then concentrated to afford a light brown viscous liquid in a yield of 80%. 1H NMR (500 MHz, CDCl3): δ 8.15 (d, J = 8.0 Hz, 2H), 7.41 (t, J = 7.5 Hz, 2H), 7.34-7.26 (m, 6H), 6.88- 6.87 (m, 2H), 3.83 (s, 2H). 4-(3,6-Dibromo-9H-carbazol-9-yl)aniline (4c), compound 4c was synthesized according the method used to prepare 4a with 3c instead of 3a to afford a white powder in a yield of 92%. 1H NMR (500 MHz, CD3CN): δ 8.34 (d, J = 2.0 Hz, 2H), 7.55 (d, J = 9.0, 2.0 Hz, 2H), 7.25-7.23 (m, 4H), 6.92-6.90 (m, 2H), 4.74 (-NH2, 2H). |
79.8% | With palladium on activated carbon; hydrazine hydrate In ethanol at 20 - 60℃; | 3.2.2. Synthesis of N-(4-aminophenyl)carbazole (II) The dried nitro compound N-(4-nitrophenyl)carbazole (monomer I in Scheme 1, 8.6 g, 30 mmol), along with the palladium carbon hydrogenation catalyst (Pd/C, 0.7 g, 10 wt%), and hydrazine hydrate (24 mL) were carefully weighed or measured. Monomer I and the Pd/C hydrogenation catalyst were then sequentially added to a 250 mL three-necked flask that was equipped with a stir bar. After the addition of ethanol (50 mL), this mixture was stirred at room temperature for 5-10 min until the reaction system was uniformly mixed, and it was then heated to 60 °C. After the temperature had become stable, the hydrazine hydrate was added dropwise to the reaction system through a constant pressure funnel at a controlled rate of 4-5 s per drop, so that the hydrazine hydrate was completely added within 2 h, and the reaction proceeded at a constant temperature for 12 h. After the reaction reached completion, Pd/C was removed via filtration through a sand core funnel. The filtrate was collected and the ethanol and hydrazine hydrate were distilled off via rotary evaporation, and the residual liquid was taken up in water to give a white precipitate. After washing with distilled water for 4-5 times, this precipitate was dried in a vacuum oven at 60 °C for 12 h. The crude product N-(4-aminophenyl)carbazole was thus obtained with a dried weight of 6.2 g, a theoretical yield of 7.7 g, and a percentage yield of 79.8%. The crude product was recrystallized from absolute ethanol under a nitrogen atmosphere at 85 °C, and the resultant crystals were dried in a vacuum oven at 60 °C for 12 h, thus yielding 5.2 g of the purified product as brown crystals.Monomer (II), brown crystals, the yield was 79.8%. Tm: 105-107 °C,FT-IR (KBr) cm-1: 3460, 3379 (NH2 stretch). 1H NMR (DMSO-d6,500 MHz, δ, ppm): 8.19 (2H, d, J 7.7 Hz), 7.39 (2H, d, J 8.3 Hz),7.24 (4H, t, J 7.5 Hz), 7.18 (2H, d, J 7.2 Hz), 6.80 (2H, d,J 7.0 Hz), 5.43 (2H, s). Found: C, 83.3; H, 5.5; N, 5.7%; molecularformula C18H14N2 requires C, 83.7; H, 5.5; N, 5.8%. |
78.3% | With hydrazine hydrate; palladium on activated charcoal In ethanol for 10h; Reflux; Inert atmosphere; | 3.2; 4.2 2) Add 5.2 g of N-p-nitrophenyl oxazole to a 250 mL three-necked flask.0.2g Pd/C, 50mL ethanol mixed,Heating under reflux in an N2 atmosphere,Slowly add 4 ml of hydrazine hydrate and heat to reflux for 10 h at reflux temperature.Cool to room temperature, filter, and steam;Recrystallization from petroleum ether gives N-p-aminophenyl oxazole,Yield 78.3%; |
65% | With tin(ll) chloride In ethanol at 70℃; for 4.5h; | |
48% | With hydrogenchloride; tin In methanol for 2h; Heating; | |
43% | With sodium tetrahydroborate; tin(ll) chloride In tetrahydrofuran; methanol at 0 - 20℃; for 3h; Inert atmosphere; | 8 Preparation of Intermediate I-8 Under a nitrogen atmosphere, I-7 (30 g, 104.1 mmol) was dissolved in 0.3 L of dm tetrahydrofuran (THF), then 0.3 L of methanol was added and the mixture was cooled to 0 ° C.After adding sodium borohydride (39.4 g, 1,041 mmol), tin (II) chloride (98.7 g, 520.5 mmol) was added and the mixture was reacted at room temperature for 3 hours. After completion of the reaction, water was added to the reaction solution, and the mixture was extracted with ethyl acetate (EA). After removal of moisture with anhydrous MgSO 4, filtration and concentration under reduced pressure.The residue thus obtained was separated and purified by flash column chromatography to obtain I-6 (11.6 g, 43%). |
With hydrogenchloride; tin | ||
With hydrazine hydrate In ethanol for 9h; Heating; | ||
With tin(ll) chloride | ||
Stage #1: 9-(4-nitrophenyl)-9H-carbazole With hydrogenchloride; tin In methanol; water for 16h; Heating / reflux; Stage #2: With sodium hydrogencarbonate In methanol; water at 20℃; | 1.b A suspension of compound 2 (9.20 g, 31.9 mmol), tin granules (11.4 g, 95.7 mmol), hydrochloric acid (15.1 ml, 153.0 mmol, 37%) in methanol (200 ml) was heated under reflux for 16 h. The reaction mixture was cooled to room temperature, filtered, neutralized with excess sodium bicarbonate solution (aqueous) and the organic layer extracted into chloroform (3 x 150 ml) and the combined extracts dried (MgSO4), filtered and the solvent removed in vacuo providing a viscous oil. The crude product was purified by columned chromatography [silica gel, eluted with 2:1 hexanes:ethyl acetate, containing 1 % methanol] providing a colorless oil. 1H NMR (500MHz, CDCI3) δ/ppm: 8.19 (dt, 2H, aromatic), 7.45 (m, 2H, aromatic), 7.38 (dt, 2H, aromatic), 7.30-7.34 (m, 4H, aromatic), 6.87 (dt, 2H, aromatic), 3.84 (s, 2H, NH2). | |
With tin(ll) chloride In ethanol Reflux; | ||
With palladium 10% on activated carbon; hydrazine hydrate In ethanol for 24h; Reflux; | ||
With palladium on activated charcoal; hydrazine hydrate In ethanol for 6h; Reflux; | ||
With hydrazine hydrate | ||
With palladium on activated charcoal; hydrazine hydrate In ethanol | ||
With palladium on activated charcoal; hydrazine In ethanol | ||
With palladium on activated charcoal; hydrogen In N,N-dimethyl-formamide at 50℃; | ||
With palladium on activated charcoal; hydrazine In ethanol Reflux; | ||
With sodium tetrahydroborate; 1% Pd on activated carbon In methanol at 20℃; for 2.5h; Cooling with ice; | 2.3. Synthesis of 2-(9H-Carbazol-9-yl) Aniline and 4-(9H-Carbazol-9-yl)Aniline General procedure: 9-(2-nitrophenyl)-9H-carbazole/9-(4-nitrophenyl)-9H-carbazole(1 eq)was dissolved in 5 mLof dry methanol and catalytic amount of 1%Pd/C was added in ice-cold condition under vigorous stirring. NaBH4(2 eq.) was added in portion-wise over a period of 30 min into reactionsolution at ice-cold condition. The reaction mixture was brought toroom temperature and stirred for another 2 h. Then Pd/C was filteredoff and solvent was evaporated using rota-vapour. The residue was extractedwith ethyl acetate and the extract was washed with brine solutionand dried over Na2SO4. Finally, the evaporation of ethyl acetateusing rota-vapour producedwhite coloured solid as product. Yield: 68%. | |
With palladium on activated charcoal; hydrazine In ethanol for 18h; Reflux; | ||
With tin(ll) chloride In ethanol for 3h; Inert atmosphere; | ||
With palladium on activated charcoal; hydrazine hydrate |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91.4% | With potassium carbonate In N,N-dimethyl-formamide at 100℃; for 12h; Inert atmosphere; | General procedure: 0.1 mol (16.72 g) of carbazole and 0.1mol (14.11 g) of 4-fluoronitrobenzene were dissolved in 100mL of DMF in a 250mL two-neck round-bottom flask equipped with a stirring hot plate, a condenser and an inlet of inert gas. 0.15mol (20.7 g) of K2CO3 was gradually added into the solution and the reaction was carried out at 100 C for 12 h. After cooling the reaction solution, crystals were filtered, washed with water and recrystallized by ethanol.The obtained product was light-yellow needle crystals (yield 95%) (Scheme 1). |
82% | With cesium fluoride In dimethyl sulfoxide at 150℃; for 24h; Inert atmosphere; | 2.3 (3) Synthesis of the intermediate N- (4- (9H-carbazol-9-yl) phenyl) -4-nitro-N- (4-nitrophenyl)aniline The 2.583g (0.01mol) 4- (9H-carbazol-9-yl) aniline and 5.305ml (0.05mol) was added to 250ml of fluoronitrobenzene three flask, DMSO as a solvent, a magnetic stirrer and argon gas, heating to an oil bath at 150 , added 3.038g (0.02mol), cesium fluoride (CsF), the reaction was refluxed for 24h. The reaction mixture was poured into ice water, extracted with methylene chloride, the solvent was distilled off under reduced pressure, the product with dichloromethane: n-hexane = 1: 2 (volume ratio) as the mobile phase, silica as the stationary phase for the column chromatography, collecting the product and spin dry, vacuum dried at 80 24h, to give the product 4.104g, 82% yield. The intermediate structures such asunder |
78% | With cesium fluoride In dimethyl sulfoxide at 150℃; for 15h; |
75% | With cesium fluoride In N,N-dimethyl-formamide at 150℃; for 24h; Inert atmosphere; | 3 Synthesis 2.3.3 2.3.3 Synthesis of 4,4'-dinitro-4"-N-carbazolyltriphenylamine (DNCzTPA) To a solution of 2.58 g (10 mmol) of APCB and 2.2 ml (21 mmol) of 4-fluoronitrobenzene in 50 ml of DMF, 1.52 g (10 mmol) of cesium fluoride was added with stirring at one portion, and then heated at 150 °C for 24 h under nitrogen atmosphere. The resulting mixture was then poured into 500 ml of methanol to yield a yellow precipitate followed by filtration, washing thoroughly by ethanol and drying in vacuum to afford 3.75 g (75% in yield) of yellow solid. DSC: m.p. 296 °C and FT-IR (KBr, cm-1): 1579, 1308 (NO2 stretch). 1H NMR (DMSO-d6, 400 MHz), δ (ppm): 8.28∼8.25 (m, 6H), 7.75 (d, 2H, J = 8.61 Hz), 7.53 (d, 2H, J = 8.59 Hz), 7.53∼7.46 (m, 4H), 7.36 (d, 4H, J = 9.14 Hz), 7.32 (t, 2H, J = 7.82 Hz). |
70% | With potassium carbonate In N,N-dimethyl-formamide at 150℃; for 10h; Dean-Stark; Inert atmosphere; | 2.2.3. Synthesis of 4,4'-dinitro-4''-N-carbazolyltriphenylamine (3) A mixture of 9.041 g (0.035 mol) of compound 2,10.12 g (0.072 mol) of 4-fluoronitrobenzene, 7.245 g(0.0525 mol) of anhydrous potassium carbonate, 80 mL of dry N,N-dimethylformamide (DMF) was in a 250-mL, three-necked, round-bottomed flask equipped with amechanical stirrer, a Dean-Stark strap, a reflux condenserand a nitrogen purge. The mixture was refluxed at 150 C with stirring for 10 h under a nitrogen atmosphere. After being poured into water (500 mL), the red precipitatewas collected by filtration and dried under vacuum. The crude product was crystallized from DMF to obtain redcrystals. Yield, 70 %, Tm: 282 C. IR (KBr): 1578,1311 cm1 (NO2 stretch). 1H NMR (500 MHz, DMSO-d6, d,ppm): 8.50 (d, 4H), 8.03 (d, 2H), 7.87 (d, 2H), 7.72 (m,8H), 7.57 (m, 4H). |
66.4% | With potassium carbonate In N,N-dimethyl-formamide at 20 - 160℃; Inert atmosphere; | 3.2.3. Synthesis of 4,4'-dinitro-4"-N-carbazolyltriphenylamine (III) Monomer II (9.0 g, 35 mmol), p-fluoronitrobenzene(10.8 g, 77 mmol) and potassium carbonate (10.6 g, 77 mmol) were placed in a 250 mL round-bottom flask that was equipped with a stir bar and then dissolved in DMF (80 mL). Under nitrogen protection, this reaction mixture was stirred for 5-10 min at room temperature until it was thoroughly mixed, and heated to 150-160 °C to reach a reflluxs tate. This refllux was maintained at this temperature for 24 h. After the reaction was finished, the solution was cooled to room temperature, and it was then slowly poured into ice water. This mixture was slowly stirred to obtain a brownish yellow flocculent precipitate. After the ice had completely melted, this mixture was filtered. The filter cake was then dried via suction filtration, washed repeatedly with water for 7-8 times, washed repeatedly with distilled water for 3-4 times, and finally washed 3-4 times with anhydrous methanol. It was dried in a vacuum oven at 60 °C for 12 h. The crude product 4,4'-dinitro-4"-N-carbazolyltriphenylamine was thus obtained at a dried weight of 11.6 g, a theoretical yield of 17.5 g, and a percentage yield of 66.4%. Monomer (III), brownish yellow powder, the yield was 66.4%. Tm:281-283 °C, FT-IR (KBr) cm-1: 1578, 1311 (NO2 stretch). 1H NMR(DMSO-d6, 500 MHz, δ, ppm): 8.25 (6H, d, J 8.1 Hz), 7.75 (2H, d,J 8.2 Hz), 7.53 (2H, d, J 7.4 Hz), 7.48 (4H, d, J 7.6 Hz), 7.36 (4H,d, J 9.1 Hz), 7.31 (2H, t, J 6.8 Hz). Found: C, 72.0; H, 4.0; N, 11.3%;molecular formula C30H20N4O4 requires C, 72.0; H, 4.0; N, 11.2%. |
With cesium fluoride In dimethyl sulfoxide | ||
With copper; potassium carbonate In 5,5-dimethyl-1,3-cyclohexadiene; dimethyl sulfoxide at 142℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
62% | Stage #1: 4-(9H-carbazol-9-yl)aniline With hydrogenchloride; sodium nitrite In 1,4-dioxane; water Stage #2: With potassium iodide In 1,4-dioxane; water at 70 - 80℃; for 0.5h; | |
Multi-step reaction with 2 steps 1.1: BF3*Et2O; tert-butyl nitrite / tetrahydrofuran / 0.33 h / cooling 1.2: 86 percent / K2CO3 2.1: 94 percent / MeI / 14 h / 110 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With tri-tert-butyl phosphine; sodium t-butanolate In N,N-dimethyl-formamide; toluene at 100℃; for 48h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With tri-tert-butyl phosphine; sodium t-butanolate In N,N-dimethyl-formamide; toluene at 100℃; for 48h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With tris(dibenzylideneacetone)dipalladium (0); tri-tert-butyl phosphine; sodium t-butanolate In toluene for 36h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With tri-tert-butyl phosphine; sodium t-butanolate In toluene for 36h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With tri-tert-butyl phosphine; sodium t-butanolate In toluene for 32h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With tris(dibenzylideneacetone)dipalladium (0); tri-tert-butyl phosphine; sodium t-butanolate In toluene for 36h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With copper(I) oxide In diphenylether at 190℃; for 24h; | Synthesis of 4-(9H-carbazol-9-yl)benzenamine (A): 4-(9H- carbazol-9-yl)benzenamine (A) was prepared through the Ullmann Reaction following the procedures reported in the literature {Macromolecules 2004, 37, 5531-5537). A mixture of 4-iodobenzenamine (2.19 g, 10 mmol), copper (I) oxide(2.18 g, 20 mmol) and carbazole (3.35 g, 20 mmol) in 40 ml 1- phenoxybenzene was heated to 190°C in an oil bath for 24 h under N2 atmosphere. The reaction mixture was cooled to room temperature and then filtered by fast silica gel column to remove excess copper complex and 1-phenoxybenzene. The filtrate was evaporated to dryness and passed through a silica gel column using hexane and ethyl acetate mixture (6:1) as eluent to give product, yielding 2.37 g (92%). 1H NMR (400 MHz, CDCl3): δ(ppm) 8.164-8.144 (d, J= 8.0 Hz, 2H), 7.432-7.395 (t, J= 8.0 Hz, 2H), 7.353-7.277 (m, 6H), 6.912-6.891 (d, J= 7.6 Hz, 2H), 4.019 (w, 2H). |
83% | With copper(I) oxide In diphenylether at 190℃; for 24h; | 1 Step 1: Carbazole was reacted with 4-iodoaniline by using Cu20 as a catalyst and diphenyl ether as a solvent at 1900 C. for 24 hours to give the compound represented by formula 3 with the yield of 83%. |
75% | With copper(II) oxide In N,N-dimethyl-formamide at 160℃; for 24h; | 1 Example 1 prepration of 4-(9H-carbazol-9-yl)aniline In the three-port flask 4-iodo aniline (1.10g, 5mmol), carbazole (0.93g, 5 . 56mmol), 1.07g copper oxide in N, N-diethyl formamide solvent heated to 160 °C reflux reaction 24 hours after cooling to room temperature, poured into water, extracted with toluene, anhydrous magnesium sulphate drying, the crude product using petroleum ether: dichloromethane = 1:1 for elution medicinal preparation column chromatography purification, yield: 75% |
In diphenylether; hexane; ethyl acetate | Synthesis of 4-(9H-carbazol-9-yl)benzenamine (A): 4-(9H-carbazol-9-yl)benzenamine (A) was prepared through the Ullmann Reaction following the procedures reported in the literature (Macromolecules 2004, 37, 5531-5537). A mixture of 4-iodobenzenamine (2.19 g, 10 mmol), copper (I) oxide (2.18 g, 20 mmol) and carbazole (3.35 g, 20 mmol) in 40 ml 1-phenoxybenzene was heated to 190° C. in an oil bath for 24 h under N2 atmosphere. The reaction mixture was cooled to room temperature and then filtered by fast silica gel column to remove excess copper complex and 1-phenoxybenzene. The filtrate was evaporated to dryness and passed through a silica gel column using hexane and ethyl acetate mixture (6:1) as eluent to give product, yielding 2.37 g (92%). 1H NMR (400 MHz, CDCl3): δ(ppm) 8.164-8.144 (d, J=8.0 Hz, 2H), 7.432-7.395 (t, J=8.0 Hz, 2H), 7.353-7.277 (m, 6H), 6.912-6.891 (d, J=7.6 Hz, 2H), 4.019 (w, 2H). | |
With copper(I) oxide In diphenylether at 190℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | at 110℃; for 16h;Inert atmosphere; | In the three-port flask 4 - (9H-carbazole-9-yl) aniline (5g, 19.36mmol), 2,7-dibromo -9,9-dihexylacrylamide-fluorenylmethylchloroformate (23.82g, 48 . 39mmol), then adding DPPF (214.61 mg, 3871 . 12umol), Pd2(dba)3(354.49 mg, 387 . 12umol), to the temperature rise under the protection of argon 110 C reaction 16 hours later, to room temperature. The reaction solution with ethyl acetate extraction, the product using petroleum ether: dichloromethane = 10:1 for elution chromatography method for purifying medicinal preparation column, yield: 78%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; at 110℃; for 12h;Inert atmosphere; | Under a nitrogen flow 4-(9H-carbazol-9-yl)aniline (5.17g, 20.0mmol), 4-(4-bromophenyl)dibenzo[b, d]thiophene (6.79g, 20.0mmol), Pd2(dba)3 (0.91g, 1.00mmol), (t-Bu)3P (0.80g, 4.0mmol), sodium tert-butoxide (5.76g, 60.0mmol) to put in 100ml toluene was stirred for 12 hours at 110 C. After completion of the reaction and extracted with methylene chloride and the filter insert MgSO4. The solvent of the organic layer was filtered to give a TCA-3 (7.24g, yield 70%) by column chromatography. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate In toluene at 110℃; for 12h; Inert atmosphere; | 4 Synthesis of TCA-4 Under a nitrogen flow 4-(9H-carbazol-9-yl)aniline (5.17g, 20.0mmol), 4-(3-bromophenyl)dibenzo[b,d]thiophene (6.79g, 20.0mmol), Pd2(dba)3 (0.91g, 1.00mmol), (t-Bu)3P (0.80g, 4.0mmol), sodium tert-butoxide (5.76g, 60.0mmol) to put in 100ml toluene was stirred for 12 hours at 110 ° C . After completion of the reaction and extracted with methylene chloride and the filter insert MgSO4. The solvent of the filtered organic layer was purified by column chromatography to give a TCA-4 (7.76g, 75% yield). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate / toluene / 12 h / 110 °C / Inert atmosphere 2: tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate / toluene / 12 h / 110 °C / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With 1,1'-bis-(diphenylphosphino)ferrocene; palladium diacetate; sodium t-butanolate In toluene at 110℃; for 18h; Inert atmosphere; | 1 Step 2: Toluene (25 mE) containing the compound (0.60 g, 2.32 mmol) represented by formula 3 prepared in step 1), the compound (3.80 g, 6.97 mmol) represented by formula 4, and sodium tertiary butoxide (NaOtl3u, 2.24 g, 23.25 mmol) was refluxed with nitrogen gas for 20 minutes, to which Pd(OAc)2 (20.87 mg, 0.093 mmol) and 1,1’-bis (diphenylphosphino)ferrocene (DPPF) (103 mg, 0.186 mmol) were added thereafter. The reaction mixture was heated at 1100 C. with stirring for 18 hours. Upon completion of the reaction, the mixture was diluted with diethyl ether (50 ml), which was filtered with celite bed. The filtrate was washed with diethyl ether twice. The filtered mixture was concentrated under reduced pressure, to which water (50 ml) was added, followed by extraction with diethyl ether (2x100 ml). The organic layer was washed with brine (50 ml) and dried over anhydrous sodium sulfate. The solvent was concentrated under reduced pressure. The residue was purified by column chromatography (silica gel; ethyl acetate/hexane=1/99) to give the compound 5 (CzPAF-Br, 1.90 g, 70%). |
30% | With 1,1'-bis-(diphenylphosphino)ferrocene; tris-(dibenzylideneacetone)dipalladium(0); sodium t-butanolate In toluene at 100℃; for 24h; Inert atmosphere; | 1 Add 0.92g CzPA (4mmol),8.8g 2,7-dibromo-9,9-dioctylfluorene (16mmol),1.92g sodium tert-butoxide (10mmol),0.05g 1,1'-bis(diphenylphosphino)ferrocene (DPPF)(0.09mmol), and 0.05g tris(dibenzylideneacetone)dipalladium(0)(Pd2(dba)3)(0.05 mmol) is added to 12mL toluene,Under nitrogen atmosphere, the temperature was raised to 100°C for 24 hours.Stop the reaction and wait until the reaction solution is cooled to room temperature,Extract with dichloromethane,The extract is fully dried with anhydrous magnesium sulfate,Filter and spin-evaporate to remove the solvent toluene, and apply the column method toChoose petroleum ether: dichloromethane = 40:1 mixed solvent as the chromatography liquid for purification, and finally obtain the pure yellow-green solid product N-(4-(9-carbazole)phenyl)-7-bromo-N- (2-(7-Bromo-9,9-dioctyl-fluorene))-9,9-octyl-fluoren-2-amine (CzPAF-Br) 1.28g, yield 30%. |
With 1,1'-bis-(diphenylphosphino)ferrocene; sodium isopropylate; palladium diacetate In toluene at 90 - 120℃; Inert atmosphere; | In practice, the first reactant is added to the vessel from 1 millimol to 6 millimoles.4 mmol - 30 mmol of the second reactant 1 ml - 30 ml of toluene and 1 mmol - 13 mmol of sodium isopropoxide,Add 0.1 mmol to 5 mmol of 1,1'-bis(diphenylphosphino)ferrocene and 0.01 mmol to 0.06 mmol of palladium acetate under an argon atmosphere.Reaction at 90 degrees Celsius - 120 degrees Celsius for 9 hours - 36 hours,Obtaining a mixture comprising the first intermediate product, and then separating and purifying to obtain the first intermediate product |
Tags: 52708-37-9 synthesis path| 52708-37-9 SDS| 52708-37-9 COA| 52708-37-9 purity| 52708-37-9 application| 52708-37-9 NMR| 52708-37-9 COA| 52708-37-9 structure
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