Structure of 110677-45-7
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CAS No. : | 110677-45-7 |
Formula : | C19H13NO |
M.W : | 271.31 |
SMILES Code : | O=CC1=CC=C(N2C3=C(C4=C2C=CC=C4)C=CC=C3)C=C1 |
MDL No. : | MFCD19441374 |
InChI Key : | RPHLDCKUUAGNAC-UHFFFAOYSA-N |
Pubchem ID : | 9838334 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H319 |
Precautionary Statements: | P305+P351+P338 |
* 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 |
---|---|---|
Ca. 92% | With N-Bromosuccinimide; In N,N-dimethyl-formamide; toluene; at 0℃; for 0.5h; | Compound 3 (1.60 g, 5.9 mmol) was dissolved intoluene (10 mL) and cooled to 0C in an ice bath. Thena solution of NBS (2.60 g, 13.2 mmol) in DMF (15 mL)was added dropwise to the dissolved compound 3 andstirred for 30 min. The reaction mixture was pouredin ice-cold water and the obtained precipitate wasfiltered, washed with cold methanol for several times,and dried under reduced pressure. Yield ∼92%. |
82% | With bromine; In dichloromethane; for 6h;Cooling with ice; | 3,6-dibromo-9- (4-formylphenyl) carbazole: in 250mL one-neck flask, 9- (4-formylphenyl) carbazole (5.00g, 18.428mmoL) and 145mL of methylene chloride were dissolved with stirring, cooled with ice bath, was slowly added dropwise thereto and mixed 8mLDCM the liquid bromine (1.45mL, 56.115mmoL), after the completion of the dropwise addition, the reaction was 6h.After completion of the reaction, with a sufficient amount of saturated aqueous NaOH quenched, extracted with methylene chloride, dried over anhydrous Na2SO4And dried under reduced pressure the reaction was removed by rotary evaporation the solvent, the residue was recrystallized from ethanol to give a dark yellow solid 6.48g, yield% 82.0 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79.08% | With sodium hydroxide; In N,N-dimethyl-formamide; at 130℃; for 6h; | A mixture of 9H-Carbazole(5 g, 0.03 mol), and sodium hydroxide (1.2 g, 0.03 mol) in drydimethylformamide (DMF) was heated with stirring. Then 4-fluorobenzaldehyde (3.72 g, 0.03 mol) was added, and the reactionmixture was stirred at 130 C for 6 h. After cooling to roomtemperature, the mixture was poured into distilled water andextracted with ethyl acetate. The organic layer was dried withanhydrous magnesium sulfate and concentrated by vacuum evaporation.The crude product was purified by column chromatographyusing the mixture of petroleum and dichloromethane (vol.ratio 3:1) as an eluent to get the desired compound as a yellow solid(6.43 g) with a yield of 79.08%. |
74% | With potassium carbonate; In dimethyl sulfoxide; at 150℃; | The intermediate 4-(9H-carbazol-9-yl)benzaldehyde wassynthesized according to the reported procedure [33]. Asolution of 4-fluorobenzaldehyde (0.222 g, 1.79 mmol),carbazole (0. 30 g, 1.79 mmol), K2CO3(500 mg) and DMSO(10 mL) was heated at 150 C overnight. After completionof the reaction as confirmed by thin layer chromatographicanalysis (TLC), the solution was cooled to room temperatureand water was added to the reaction mixture. The mixturewas extracted thrice with DCM (3 X 10 mL) and the organiclayer was separated and dried over anhydrous Na2SO4.Afterthe solvent was evaporated a yellow solid was obtained,which is followed by recrystallization from EtOH yieldingintermediate compound 4-(9H-carbazol-9-yl)benzaldehydewith 74% yield. |
68% | In a 250 mL two-necked flask, anhydrous DMF (100 mL) was addedto a mixture of 9H-carbazole (8.40 g, 50 mmol) and potassium tertbutoxide(5.52 g, 50 mmol). The mixture was stirred at 110 C for30 min under nitrogen atmosphere. Then, 4-fluorobenzaldehyde(1.24 g, 10 mmol) was added and stirred for 36 h. Then, the reactionmixture was cooled to room temperature and the reaction solvent wasremoved by distillation under reduced pressure. The residue was extractedwith ethyl acetate and water. Further purification was carriedout by silica gel chromatography to afford Cz9PhCHO as a light yellowsolid (9.30 g, 68%). 1H NMR (300 MHz, CDCl3, δ/ppm): 10.11 (s, 1H),8.12-8.16 (m, 4H), 7.79 (d, J=8.4Hz, 2H), 7.51 (d, J=7.5 Hz, 2H),7.44 (t, J=7.2 Hz, 2H), 7.33 (t, J=7.8 Hz, 2H); 13C NMR (75 MHz,CDCl3, δ/ppm): 191.03, 143.39, 140.07, 134.64, 131.42, 126.82,126.34, 124.00, 120.88, 120.56, 109.81. HRMS (m/z): calcd forC19H13NO: 271.0997. Found: 271.0996. |
67.5% | 9- (4-formylphenyl) carbazole: in 250mL three-necked flask, carbazole (3.345g, 20mmoL), potassium t-butylate (2.245g, 20mmoL) and purified 80mL of DMF.Under nitrogen conditions, the mixed solution was magnetically stirred reaction at 110 0.5h, then slowly added dropwise thereto in dissolved 20mLDMF fluorobenzaldehyde (2.483g, 20mmoL), After dropping the reaction was stirred at this temperature for 36h.After completion of the reaction, cooled to room temperature, the mixture was poured into cold water, the reaction mixture was stirred 0.5h, filtered and the filter residue recrystallized from absolute ethanol to give a yellow solid 3.66g, yield 67.5%. | |
Ca. 60% | With potassium tert-butylate; In N,N-dimethyl-formamide; at 110℃; for 37h;Inert atmosphere; | Compound 3 was synthesized as per the reported procedure.26 In 50mL RB flask, carbazole (2.0 g,11.9 mmol) and t-BuOK (1.33 g, 11.9 mmol) were dissolvedtogether in DMF (10 mL) and heated at 110Cunder stirring for 30 min. 4-Fluorobenzaldehyde (1.5 g,11.9 mmol) was taken in 5mL of DMF and addeddropwise to the reaction mixture over 30 min. Then thereaction mixture refluxed for another 36 h at the sametemperature under nitrogen atmosphere. After completionof the reaction, the reaction mixture was cooledto room temperature and poured in excess amount ofice-cold water (700 mL), from which solid precipitated.Then the solid was filtered under reduced pressure anddried. Finally, the crude compound was purified bycolumn chromatography employing silica gel as stationaryphase and CHCl3: Hexane (1:1) as mobilephase. Yield ∼60% |
60% | To a stirred solution of carbazole 3 (6.30 g, 37.7 mmol) in anhydrousDMF (150 mL) was added potassium tert-butoxide (4.23 g, 37.7 mmol) atroom temperature under nitrogen atmosphere. The reaction mixture washeated to 110 C and then a solution of 4-fluorobenzaldehyde 4 (4.04mL g, 37.7 mmol) in anhydrous DMF (10 mL) was added dropwise intothe mixture over 50 min. The mixture was kept at 110 C for 36 h. Thenthe mixture was cooled to room temperature and poured into 500 mL icewater. The precipitate obtained was filtered, dried and recrystallized byusing acetone/water (v/v = 9:1) system to afford compound 5 as a paleyellow solid (6.15 g, 60%).mp 156-158 C; 1H NMR (500 MHz, CDCl3): δ = 7.33 (t, J = 7.0 Hz, 2H), 7.44 (t, J = 8.0, 7.0 Hz, 2H), 7.51 (d, J = 8.0 Hz, 2H), 7.80 (d, J =7.5 Hz, 2H), 8.15 (t, J = 7.5, 7.0 Hz, 4H), 10.12 (s, 1H); 13C NMR (125MHz, CDCl3): δ = 109.75, 120.49, 120.80, 123.97, 126.27, 126.84,131.37, 134.65, 140.07, 143.41, 190.95; ESI-MS: m/z 272.03 [M + H]+. | |
43% | With potassium carbonate; In N,N-dimethyl-formamide; at 140℃; for 18h;Schlenk technique; Inert atmosphere; | Add 4-fluorobenzaldehyde (1.27mL, 12mmol), carbazole (1670mg, 10mmol) and K2CO3 (4150mg, 30mmol) were added to a 50mL Schlenk tube, 20mL DMF was added, and heated to reflux for 18h under nitrogen protection. Dilute the cooled reaction solution with 20mL saturated sodium chloride solution, extract with 3*25mL ethyl acetate, combine the organic phases, add anhydrous MgSO4 to dry, filter to remove anhydrous magnesium sulfate, evaporate the solvent under reduced pressure,Petroleum ether: dichloromethane (6:1) column chromatography to obtain the target product with a yield of 43%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With copper(l) iodide; potassium carbonate; In N,N-dimethyl-formamide; at 140℃; for 12h;Inert atmosphere; | Scheme 4A mixture of 9H-carbazole (9.53 g, 57 mmol), 4-bromobenzaldehyde (21.1 g, 114 mmol), Copper(I) iodide (1.80 g, 9.4 mmol), K2C03 (11.8 g, 86 mmol), in 60 mL dry DMF, was heated to 140C, under nitrogen atmosphere for 12 hours. After cooling to room temperature, the inorganic solid was filtered, and the residue was poured into ice water to precipitate the product.The so-formed solid was collected, and washed by water, ethanol several times, then crystallized from CH2C12 and ethanol, to give light-yellow solid (yield: 95%). MS (ESI): 272.10 [M+H]. |
87% | With copper; potassium carbonate; In nitrobenzene; at 180℃; for 24h;Inert atmosphere; | (2) carbazole (1.0 g, 6 mmol, 6.0 eq), 4-bromobenzaldehyde (2.2 g, 12 mmol, 12.0 eq), copper powder (64 mg,1 mmol, 1.0 eq), K2CO3 (1.24 g, 9 mmol, 9.0 eq) was dissolved in 10 mL of nitrobenzene, protected with nitrogen, heated at 180 C.Should be 24h The reaction was detected by TCL plate. After the reaction was complete, the mixture was cooled to room temperature and separated on a silica gel column. The silica gel particle size was200-300 mesh, eluent ratio of ethyl acetate / petroleum ether = 1: 50, the product 2-1, the yield of 87%. |
85% | With copper(l) iodide; 18-crown-6 ether; potassium carbonate; In dimethyl sulfoxide; at 130℃; for 24h; | (1) 10 g of carbazole was added to a 250 mL three-necked flask.13.2g 4-bromobenzaldehyde,5g potassium carbonate,2.5 g of cuprous iodide and 2 g of 18-[crown]-6 ether,Add 150 mL of dimethyl sulfoxide as solvent.The oil bath is reacted at 130 C for 24 hours;After the reaction is over,After the reaction solution is cooled to room temperature,Filtering,Then, the filtrate was mixed with a 20 wt% NaCl aqueous solution to precipitate a solid.Recover solids and dry,Recrystallization 3 times with acetonitrile,The intermediate (4-(9H-carbazol-9-yl)benzaldehyde is obtained,The yield is 85%; |
84% | With 18-crown-6 ether; copper; potassium carbonate; In 1,2-dichloro-benzene; at 200℃;Inert atmosphere; | Example 1.1.1 4-(9H-carbazol-9-yl)benzaldehyde (1) 9H-carbazole (30.0 g, 179.4 mmol), 4-bromobenzaldehyde (36.5 g, 197.4 mmol), potassium carbonate (109.1 g, 789.5 mmol), and 18-crown-6 (4.7 g 17.9 mmol) were dissolved in 1,2-dicholorobenzene. The reaction mixture was degassed with argon and then copper (29.9 g, 466.5 mmol) was added. The reaction was heated to about 200 C. under argon for about 36-40 hours. The copper, potassium carbonate, and 18-crown-6 were then filtered off. The solvent was removed and the resulting residue was purified by a silica chromatography, employing 1:1 dichloromethane:hexanes as an eluent. A recrystallization was performed in tetrahydrofuran (THF)/methanol to yield the product 1 as tan solid (84% yield). 1H NMR (400 MHz, DMSO-d): δ 10.13 (s, 1H), 8.27 (d, J=7.7 Hz, 2H), 8.20 (d, J=8.4 Hz, 2H), 7.90 (d, J=8.4 Hz, 2H), 7.52 (d, J=8.1 Hz, 2H), 7.48-7.44 (m, 2H), 7.33 (t, J=7.0 Hz, 2H) |
81.7% | With tri-tert-butyl phosphine; palladium diacetate; potassium carbonate; In toluene; at 115℃; for 24h; | 0.090 g (3.7 mol%) of P(t-Bu)3 and 0.035 g (1.3 mol%) Pd(OAC)2 were added to 80 mL degassed toluene, followed by 2.5 g (0.0135 mol) of 4-bromobenzaldehyde and 2.000 g (0.0120 mol) of 9H-carbazole and 4.150 g (0.0300 mol) anhydrous K2CO3. The reaction mixture was heated to 115 C for 24 h. The solvent was removed under vacuum, and 150 mL CH2Cl2 was added. The material was washed with 2 * 50 mL 20% NaOH, washed with 1 * 50 mL brine, and dried with anhydrous MgSO4. The solvent was removed under vacuum, and the residue was purified by column chromatography on silica gel using ethyl acetate/petroleum ether (1:20, v/v) as the eluent to give 4-(9H-carbazol-9-yl)benzaldehyde as white powder (2.65 g, 81.7%). m.p.: 156-158 C. 1H NMR (CDCl3, δ, ppm): 10.13 (s, 1H, -CHO), 8.16 (dd, J = 8.5 Hz, 4H), 7.81 (d, J = 8.0 Hz, 2H), 7.52 (d, J = 8.0 Hz, 2H), 7.45 (t, J = 7.6 Hz, 2H), 7.34 (t, J = 8.0 Hz, 2H). |
80% | With tri-tert-butyl phosphine; palladium diacetate; potassium carbonate; In toluene; for 24h;Inert atmosphere; Reflux; | According to the literature,4 9H-carbazole (1.67 g, 10.00 mmol), 4-bromobenzaldehyde (2.08 g, 11.25 mmol), K2CO3 (3.46 g, 25.00 mmol), Pd(OAc)2 (0.17 g, 0.83 mmol) and P(t-Bu)3 (10%, 2.5 mL, 1.00 mmol) in anhydrous toluene (17 mL) were refluxed under N2 atmosphere for 24 h. After cooled to room temperature, the reaction mixture was filtered to remove precipitate and the solution was evaporated under vacuum. Finally, the residue was purified by silica gel column chromatography with petroleum ether/dichloromethane as the eluent (4/1, v/v). The white solid was obtained. Yield: 80%. |
80% | With copper(l) iodide; 18-crown-6 ether; potassium carbonate; In 1,2-dichloro-benzene; at 180℃; for 48h;Inert atmosphere; | 3g carbazole, 3.3g p-bromobenzaldehyde, 3.7g potassium carbonate 0.33g 18-crown-6, 0.4g cuprous iodide and18ml of o-dichlorobenzene was added to a 100ml round-bottomed flask, vacuum was evacuated under nitrogen three times after freezing, and it was stirred and refluxed at 180 C for 48 hours. After completion of the reaction, the reaction system was washed repeatedly with 5% hydrochloric acid solution, extracted three times with dichloromethane, dried with anhydrous magnesium sulfate, and then the solvent was removed, and the pure product was separated by column chromatography to obtain 3.9g, with a yield of 80%. |
76.6% | With tri-tert-butyl phosphine; potassium carbonate;palladium diacetate; In toluene; at 115℃; for 36h; | 0.9 g (3.7 mol %) of P(t-Bu)3 and 0.35 g (1.3 mol %) Pd(OAc)2 were added to 800 ml degassed toluene, followed by 25 g (1.1 eq., 0.1316 mol) of 4-bromobenzaldehyde and 20 g (0.1196 mol) of 9H-carbazole and 41.5 g (2.5 eq., 0.2990 mol) anhydrous K2CO3. The reaction mixture was heated to 115 C. for 24 hours. Most of the solvent was removed and the reaction stirred for another 12 hours at 115 C. Solvent was removed under vacuum, and 300 ml CH2Cl2 was added. The material was washed with 2×50 ml H2O and 2×50 ml 20% NaOH, washed with 1×50 ml brine, and dried with MgSO4. The solvent was removed, leaving the intermediate, 4-(9H-carbazol-9-yl)benzaldehyde, an orange-brown solid. 125 ml of 80% hexanes/20% EtOAc were added. The mixture was stirred, cooled and vacuum filtered, leaving an off-white solid. After washing with more hexanes/EtOAc, the white solid was recrystallized from ethanol/toluene to give 20.53 g fine white needle crystals. A second crop of crystals provided 4.34 additional grams of the intermediate, 4-(9H-carbazol-9-yl)benzaldehyde. Total yield was 24.87 g or 76.6%.; 0.9 g (3.7 mol %) of P(t-Bu)3 and 0.35 g (1.3 mol %) Pd(OAc)2 were added to 800 ml degassed toluene, followed by 25 g (1.1 eq., 0.1316 mol) of 4-bromobenzaldehyde, 20 g (0.1196 mol) of 9H-carbazole, and 41.5 g (2.5 eq., 0.2990 mol) anhydrous K2CO3. The reaction mixture was heated to 115 C. for 24 hours. Most of the solvent was removed under vacuum and the reaction stirred for another 12 hours at 115 C. The remaining solvent was removed under vacuum, and 300 ml CH2Cl2 was added to the reaction mixture. The material was washed with 2×50 ml H2O and 2×50 ml 20% NaOH, then with 1×50 ml brine, and then dried with MgSO4. The solvent was removed, leaving an orange-brown solid. 125 ml of 80% hexanes/20% EtOAc was added to the mixture, which was stirred, cooled and vacuum filtered, leaving an off-white solid. After washing with more hexanes/EtOAc, the white solid was recrystallized from ethanol/toluene to give 20.53 g fine white needle crystals of 4-(9H-carbazol-9-yl)benzaldehyde intermediate product. A second crop of crystals provided 4.34 additional grams of the 4-(9H-carbazol-9-yl)benzaldehyde intermediate product. The total yield was 24.87 g or 76.6%.1H NMR (500 MHz, CDCl3), δ 10.10 (s, 1H), 8.13 (dd, J=8.5 Hz), 7.78 (d, J=8.5 Hz, 2H), 7.49 (d, J=8 Hz, 2H), 7.43 (dd, J=8.5 Hz, 2H), 7.32 (dd, J=8.5 Hz, 2H) |
74% | With copper(l) iodide; potassium carbonate; In N,N-dimethyl-formamide; at 140℃; for 19h; | A mixture of 9.53 g (57 mmol) carbazole, 21.31 g (114 mmol) 4-bromobenzaldehyde, 11.89 g K2CO3 (86 mmol), 1.80 g (9.4 mmol) Cul in 60 ml of DMF was reacted for 19 hours at 140C. The reaction mixture was cooled to room temperature, filtered, washed with DMF and the filtrate diluted with ice. The residue was filtered and washed with water and ethanol. 1 1.36 g (74%) of a beige solid were obtained. |
73% | With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; for 18h;Reflux; Inert atmosphere; | 9H-Carbazole 1eq (30.8g), 4-Bromo-Aldehyde 1eq (34.1g), sodium-t-butoxide 2eq (35.4g), Pd2 (dba)3 0.05eq (5.3g) toluene (750ml ), and then tri-tertiary butylphosphine was stirred under reflux for 18 hours under a nitrogen flow of 0.15eq. After completion of the reaction, extraction was performed with toluene and distilled water, and the organic layer was dried over magnesium sulfate (MgSO4), filtered, and the filtrate was concentrated under reduced pressure. The organic solution was removed, followed by silica gel column with hexane:dichloromethane=7:3 (v/v), and the product solid was recrystallized from dichloromethane and acetone to obtain an intermediate a-1 (36.5g, Y=73%). |
71% | With tri-tert-butyl phosphine; palladium diacetate; potassium carbonate; In toluene; for 48h;Inert atmosphere; Reflux; | Add carbazole (2.0g, 12mmol), 4-bromobenzaldehyde(2.5g, 13.5mmol), potassium carbonate (4.15 g, 30mmol), palladium acetate (0.2g, 1.0mmol),And tri-tert-butyl phosphine (0.3 mL) in a nitrogen atmosphere,Dissolved in 20 mL of anhydrous toluene and refluxed for 48 hours.After the reaction, it was cooled to room temperature, filtered, and the filtrate was taken.The filtrate was extracted with water and dichloromethane, and the organic phase was taken.After using a rotary evaporator to remove the solvent,Purify the residue by column chromatography(Petroleum ether/CH2Cl2, V/V=1:1),2.3 g of a white solid was obtained (71% yield). |
63.4% | With 18-crown-6 ether; copper; potassium carbonate; In 1,2-dichloro-benzene; at 170℃; for 12h;Inert atmosphere; | A mixture of 4-bromobenzaldehyde (0.231 g, 1.25 mmol), 9H-carbazole(0.167 g, 1.00 mmol), copper powder (0.095 g, 1.50 mmol),potassium carbonate (0.207 g, 1.50 mmol) and 18-crown-6(0.013 g, 0.05 mmol) in 1,2-dichlorobenzene was stirred at170 oC for 12 hours under the nitrogen atmosphere. After thereaction mixture was cooled down to room temperature,excess of K2CO3 and Cu is removed by the filtration. Aportion of 100 mL of water was added into the filtrate andthen extracted three times of with a portion of 100 mL ofMC. The combined organic layer was dried over anhydrousMgSO4 then the solvent was removed using a rotary evaporator.The yield of the colorless solid was 0.172 g (63.4%).mp 160.3 oC. 1H-NMR (400 MHz, CDCl3) 10.10 (s, 1H),8.16-8.11 (m, 4H), 7.79-7.77 (d, J = 8.08 Hz, 2H), 7.52-7.49(d, J = 8.08 Hz, 2H), 7.46-7.42 (t, J = 6.96 Hz, 2H), 7.36-7.32 (t, J = 7.72 Hz, 2H), 13C-NMR (100 MHz, CDCl3) 190.92, 143.32, 139.99, 134.56, 131.32, 126.74, 126.23,123.91, 120.77, 120.45, 109.71. Anal. Calcd. For C19H13NO:C, 84.11; H, 4.83; N, 5.16; O, 5.90. Found: C, 84.10; H, 4.79; N, 5.97. |
58% | With copper; potassium carbonate; In nitrobenzene; for 6h;Inert atmosphere; | The 3.34g (20mmol) carbazole, 3.70g (20mmol) of bromobenzaldehyde, 5.0g (36mmol) and anhydrous potassium carbonate320mg (5mmol) of copper powder placed 200mL single jar, add 40mL nitrobenzene was heated under nitrogen backFlow 6h, the reaction was stopped, cooled, filtered, and evaporated under reduced pressure nitrobenzene, was added 30mL recrystallized from ethanol to give a brownBulk solids 3.12g, yield = 58% |
49% | With copper(l) iodide; 18-crown-6 ether; potassium carbonate; In 1,2-dichloro-benzene; for 48h;Inert atmosphere; Reflux; | Carbazole (5.00 g, 29.90 mol),4-bromobenzaldehyde (5.55 g, 29.9 mmol), K2CO3 (6.20 g,44.86 mmol), 18-crown-6 (550.00 mg, 2.08 mmol), CuI (680.00 mg, 3.57 mmol) wereadded to 1,2-dichlorobenzene (30 mL), then refluxed under nitrogen for 48 h.After cooling, the reaction mixture was quenched with (NH4)2CO3solution and extracted with CH2Cl2, then dried overanhydrous MgSO4. After removal of the solvent, the residue waspurified by column chromatography on silica gel using CH2Cl2/petroleum(1:1, v/v) as eluent followed by recrystallization from mixture of CH2Cl2and ethanol to give the product as white powder. Yield: 49%. 1H NMR(500 MHz, DMSO, δ): 10.14 (s, 1H), 8.29 (d, J= 7.77 Hz, 2H), 8.22 (d, J = 7.77 Hz,2H), 7.93 (d, J = 7.77 Hz, 2H), 7.54(d, J = 8.44 Hz, 2H), 7.49 (t, J = 7.77 Hz, 7.77 Hz, 2H), 7.36 (t, J = 7.77 Hz, 7.26 Hz, 2H). |
With copper; potassium carbonate; In nitrobenzene; for 24h;Reflux; Inert atmosphere; | A mixture of carbazole (1.67 g, 10 mmol), 4-bromobenzaldehyde (2.00 g, 10.8 mmol), K2CO3 (5.52 g, 40 mmol) and Cu (0.45 g, 7 mmol) in anhydrous nitrobenzene was refluxed and stirred for 24 h under nitrogen gas protection. After reaction, the mixture was cooled down to room temperature and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography to yield pure product. 1H NMR (400 MHz, CDCl3) δ=10.09 (s, 1H), 8.20 (d, J = 8.0 Hz, 2H), 8.10 (d, J = 8.4 Hz, 2H), 7.75 (d, J = 8.4 Hz, 2H), 7.55 (d, J = 8.4 Hz, 2H), 7.49 (t, J = 8.4 Hz, 2H), 7.40 (t, J = 7.6 Hz, 2H). 13C NMR (100 MHz, CDCl3) δ= 191.06, 143.32, 140.08, 134.63, 131.42, 126.74, 126.42, 124.06, 120.97, 120.63, 109.90. | |
900 mg | With copper(l) iodide; caesium carbonate; In N,N-dimethyl-d6-formamide; at 110℃; for 1h;Inert atmosphere; Microwave irradiation; | Weigh 1.67g of carbazole and 2.035g of p-bromobenzaldehyde in a 30ml microwave reaction tube, and then weigh 1.93g of cesium carbonate as an acid binding agent. 190mg of cuprous iodide was used as a catalyst, oxygen was passed through argon to ensure that the system was in an anaerobic environment, and finally 10ml of anhydrous DMF was added as a solvent. Put the microwave reaction tube into a microwave reactor and react at 110 C for 1 hour. Extraction was continued, and after column chromatography, 900 mg of p-aldehyde phenylcarbazole was obtained as a white powder. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With methanol; sodium tetrahydroborate; In tetrahydrofuran; at 20℃; for 1.5h; | Example 1.1.2 4-(9H-carbazol-9-yl)phenyl)methanol (2) <strong>[110677-45-7]4-(9H-carbazol-9-yl)benzaldehyde</strong> (1) (8.0 g, 29.5 mmol) was dissolved in a (2:1) mixture of tetrahydrofuran/methanol. Sodium borohydride (1.4 g, 38.3 mmol) was added portion wise to the reaction mixture. The reaction mixture was stirred for about 1.5 hours at room temperature and the solvents were then removed. Deionized water was then added to the crude material, and 1M HCl was added dropwise until the solution was neutral. The material was then extracted with ethyl acetate and washed with water. The ethyl acetate was then removed and the product 2 was precipitated out of dichloromethane/hexanes to yield white solid 2 (91% yield). 1H NMR (400 MHz, DMSO-d): δ 8.25 (d, J=7.7 Hz, 2H), 7.60 (dd, J1=8.4 Hz, J2=20.2 Hz, 4H), 7.45-7.41 (m, 2H), 7.35 (d, J=8.4 Hz, 2H), 7.28 (t, J=7.0 Hz, 2H), 5.42-5.40 (m, 1H), 4.65 (d, J=5.5 Hz, 2H) |
83% | With sodium hydroxide; sodium tetrahydroborate; In tetrahydrofuran; methanol; water; at 20℃; for 16h; | 4.3 g (0.1585 mol) of the intermediate, <strong>[110677-45-7]4-(9H-carbazol-9-yl)benzaldehyde</strong>, 0.3 g (0.5 equivalents, 0.007925 mol) NaBH4, and 2.3 ml 20% NaOH were added to a mixture of 75 ml THF and 75 ml MeOH. The solution was stirred for 16 hours at 20 C. Most of the solvent was removed under vacuum and the remainder poured into 200 ml H2O. The mixture was neutralized with 3M HCl, extracted with 3×50 ml CH2Cl2, and washed with 2×40 ml H2O and 1×40 ml brine. The solvent was removed under vacuum, and the residue was taken up in 20 ml hot CH2Cl2. Hexanes were added drop-wise until the desired intermediate, (4-(9H-carbazol-9-yl)phenyl)methanol, precipitated out. 3.58 g of fine needles of the alcohol product were obtained. The total yield of intermediate, (4-(9H-carbazol-9-yl)phenyl)methanol, was 3 was 3.58 g or 83%. |
82.57% | With sodium tetrahydroborate; sodium hydroxide; In tetrahydrofuran; methanol; at 20℃; for 16h; | 2.200 g (0.008 mol) of <strong>[110677-45-7]4-(9H-carbazol-9-yl)benzaldehyde</strong>, 0.153 g (0.5 eq, 0.004 mol) of NaBH4, and 1.2 mL 20% NaOH were added to a mixture of 37 mL THF and 37 mL MeOH. The solution was stirred for 16 h at room temperature. The reaction mixture was poured into 100 mL H2O, and then neutralized with 3 M HCl. The solution was extracted with CH2Cl2 (3 × 50 mL) and then dried over anhydrous MgSO4. After filtering, the solvent was removed under vacuum, and the residue was taken up in 10 mL hot CH2Cl2. Hexanes were added dropwise until (4-(9H-carbazol-9-yl)phenyl)methanol precipitated out. 1.83 g of fine needles of the alcohol product was obtained. The total yield of (4-(9H-carbazol-9-yl)phenyl)methanol was 1.83 g (82.57%). m.p.: 120-122 C. 1H NMR (CDCl3, δ, ppm): 8.15 (d, J = 7.4 Hz, 2H), 7.63 (d, J = 8.8 Hz, 2H), 7.58 (d, J = 8.4 Hz, 2H), 7.42 (t, J = 7.4 Hz, 2H), 7.32 (d, J = 8.2 Hz, 2H), 7.29 (t, J = 7.4 Hz, 2H), 4.85 (d, J = 5.6 Hz, 2H), 1.81 (t, J = 5.6 Hz, 1H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90.34% | With potassium tert-butylate; In tetrahydrofuran; for 24h;Inert atmosphere; | A mixture of 2 (2.71 g,10 mmol), potassium tert-butylate (1.68 g, 15 mmol), andCH3PPh3Br (4.28 g, 12 mmol) in dry THF (100 mL) under nitrogenwas stirred for 24 h the mixturewas poured into distilled water and extracted with ethyl acetate. The organic layer was dried withanhydrous magnesium sulfate and concentrated by vacuum evaporation.The crude product was purified by column chromatographyusing the mixture of petroleum and dichloromethane (vol.ratio 5:1) as an eluent to get the desired compound as a white solid(2.43 g) with a yield of 90.34%. |
67% | Experimental procedure: In a 100ml three-necked flask, add methyltriphenylphosphonium bromide (1.7g, 11.2mmol) in sequence,Potassium tert-butoxide (0.33 g, 13.4 mmol) and 30 mL THF. After reacting for 30 minutes, the color of the solution was light yellow. 1 g (7.5 mmol) of 9-phenyl-9H-carbazole-3-carbaldehyde was dissolved in an appropriate amount of THF and added dropwise to the above mixture.The color of the solution immediately became dark yellow. N2 protection,Reaction at room temperature for 15-16h. The color of the solution is dark yellow,Pour the reaction solution into 100ml ice water, Extract the organic phase with dichloromethane, separate the organic phase,Dry the organic phase with anhydrous sodium sulfate, filter,Rotary evaporation to remove the solvent, column chromatography to separate the target product,The eluent is petroleum ether: dichloromethane = 10:1,0.67 g of light yellow target product was obtained, and the yield was 67%. | |
44% | With potassium tert-butylate; In tetrahydrofuran; at 0 - 20℃; | Example 1.3.2 9-(4-vinylphenyl)-9H-carbazole (8) <strong>[110677-45-7]4-(9H-carbazol-9-yl)benzaldehyde</strong> (1) (13.38 g, 49.37 mmol) was dissolved in tetrahydrofuran (200 mL) and then methyltriphenylphosphonium bromide (19.38 g, 54.31 mmol) was added. The reaction mixture was cooled to about 0 C. Potassium t-butoxide was then added. The reaction mixture was stirred at about 0 C. for about 5 minutes, then allowed to warm to room temperature and then stirred overnight. The reaction was then concentrated in vacuo, poured into water, and then extracted with ethyl acetate. The ethyl acetate layer was then dried down and the crude product was run through a silica plug using 1:4 dichloromethane:hexanes to yield an off white solid 8 (44% yield). 1H NMR (400 MHz, CDCl3): δ 8.16 (d, J=8.8 Hz, 2H), 7.65 (d, J=8.4 Hz, 2H), 7.54 (d, J=8.4 Hz, 2H), 7.45-7.40 (m, 4H), 7.32-7.29 (m, 2H), 6.84 (dd, J1=17.6 Hz, 32=10.6 Hz, 1H), 5.87 (d, J=17.2 Hz, 1H), 5.38 (d, J=11.0 Hz, 1H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With pyridine; In acetonitrile; for 4h;Reflux; | (2) To 100 ml of a three-necked flask equipped with electromagnetic stirring, 7.5 g of (<strong>[110677-45-7]4-(9H-carbazol-9-yl)benzaldehyde</strong> was added.Completely dissolved with 20 mL of anhydrous acetonitrile,2mL anhydrous pyridine as a catalyst,Then add 2.8 g of malononitrile,Heating and refluxing for 4 h,After the reaction is over,The reaction solution was mixed with a 15 wt% NaCl aqueous solution to precipitate a solid.Recover solids and dry,Recrystallization 3 times with acetonitrile,The target product (4-(9H-carbazol-9-yl)benzylidene)malononitrile was obtained.The yield was 83%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
62% | With potassium tert-butylate; In tetrahydrofuran; isopropyl alcohol; at 0 - 20℃; for 6h; | 4.0 g (0.01474 mol) of the 4(9H-carbazole-9-yl)benzaldehyde and 14.1 g (1.5 eq., 0.02211 mol) of Wittig Salt VI [5] were added to a mixture of 150 ml dry THF and 250 ml IPA under N2. The solution was cooled to 0 C., and 16.5 ml (1.1 eq., 0.01621 mol) of 1 M t-Bu3O-K+ were added drop-wise. The temperature was allowed to rise slowly to 20 C., and the reaction was stirred for 6 hours. After removing most of the solvent, 250 ml CH2Cl2 were added. The solution was washed with 3×50 ml H2O and 1×50 ml brine, dried with MgSO4, and evaporated, leaving a thick, yellow slurry that was purified through a short silica gel column eluting with CH2Cl2 followed by 85% CH2Cl2/15% MeOH. The total yield of the intermediate product, Wittig Salt VII, was 6.25 g or 62%.1H NMR (500 MHz, CDCl3), δ 8.13 (d, J=7.5 Hz, 2H), 7.76 (d, J=7.5 Hz, 2H), 7.55-7.04 (m, 12H), 4.10 (d, J=24 Hz, 2H), 3.90 (s, 6H), 2.40 (t, J=11 Hz, 6H), 1.44 (m, 12H), 0.90 (t, J=11 Hz, 9H) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
25% | With copper(I) oxide; In N,N-dimethyl acetamide; at 190℃; for 72h; | A DMAc solution (60 mL) of 4-iodobenzaldehyde (3.48 g,15.00 mmol), carbazole (3.01 g, 18.00 mmol), and copper(I) oxide (2.57 g, 18.00 mmol) was stirred at 190 Cfor 3 days. After cooling to room temperature, the productmixture was washed with water. After removal ofthe organic solvent, the residue was purified by columnchromatography on silica gel using methylene chlorideand n-hexane (1:5, v/v) as an eluent. Further purificationwas performed by precipitation in n-hexane to obtain1 as a light yellow solid. Yield (1.02 g, 25%). mp160-162 C. 1H NMR (400 MHz, DMSO-d6) 7.33(t, 2 H, -Ph-carbazole), 7.46 (t, 3 H, -Ph-carbazole),7.52 (d, 2 H, -Ph-carbazole), 7.91 (d, 2 H, -carbazole-Ph), 8.20 (d, 2 H, -carbazole-Ph), 8.27 (d, 2 H, -Ph-carbazole), 10.12 (s, 1 H, -Ph-CHO); 13C NMR(100.64 MHz, DMSO-d6) 100.86, 120.67, 120.78,123.24, 126.53, 126.72, 131.41, 134.58, 139.45, 142.20,192.23. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
58% | With piperidine; In acetonitrile; at 80℃; for 6h;Inert atmosphere; | Compound 1 (271 mg, 1.0 mmol), 2-cyanoaceticacid (126 mg, 1.50 mmol), piperidine (0.1 mL, 1.0 mmol) werestirred in dry acetronitrile (20 mL) and the solution was heated at80 C for 6 h under N2. After cooling to room temperature, solventswere removed by rotary evaporation, and the residue was purifiedby silica gel column chromatography with CH2Cl2: CH3OH (v: v, 10:1) as eluent to afford D1 as yellow solids (196 mg, 58%). M.p.207e208 C. 1H NMR (500 MHz, DMSO-d6, ppm): d 8.49 (s, 1H),8.36 (d, J 8.6 Hz, 2H), 8.28 (d, J 7.7 Hz, 2H), 7.92 (d, J 8.6 Hz,2H), 7.56 (d, J 8.3 Hz, 2H), 7.48 (t, J 7.1 Hz, 2H), 7.34 (t, J 7.0 Hz,2H). 13C NMR (126 MHz, DMSO-d6, ppm): d 140.08,139.34,138.47,131.59, 130.39, 126.11, 125.79, 123.01, 120.83, 120.18, 119.87, 116.78,109.32, 107.32, 109.72, 96.08, 85.46. Anal. Calcd. for C22H14N2O2: C78.09, H 4.17, N 8.28. Found: C 78.26, H 4.29, N 8.45. HRMS (ESI, m/z): [MH] calcd. for C22H13N2O2, 337.0983; found, 339.1036. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium tert-butylate; In tetrahydrofuran; at 20℃;Inert atmosphere; | [Step 2; Synthesis of (E)-4-bromo-4'-(9H-carbazol-9-yl)stilbene] Next, 9.44 g (18.4 mmol) of 4-bromobenzyl triphenylphosphonium bromide obtained in Step 1 and 5.00 g (18.4 mmol) of <strong>[110677-45-7]4-(9H-carbazol-9-yl)benzaldehyde</strong> were placed into a 300 mL three-neck flask, and nitrogen substitution was carried out in the three-neck flask. Then, 50 mL of tetrahydrofuran (THF) was added thereto. A suspension in which 2.07 g (18.4 mmol) of potassium tert-butoxide was mixed in 50 mL of THF was dropped into this mixture. After the completion of the dropping, the reaction mixture was stirred at room temperature for 24 hours. After the completion of the reaction, water was added to the reaction mixture, and the precipitate was collected by suction filtration. 4.41 g of a yellow powdered solid, (E)-4-bromo-4'-(9H-carbazol-9-yl)stilbene, which was the target substance, was obtained in a yield of 56.4%. It was confirmed that (Z)-4-bromo-4'-(9H-carbazol-9-yl)stilbene which is an isomer of the target substance was included in the obtained filtrate. A synthetic scheme (a-2) of (E)-4-bromo-4'-(9H-carbazol-9-yl)stilbene is shown below. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72.58% | Preparation of compound 2-2 [95] The compound 2-1(18 g, 55.86 mmol) was dissolved in THF (200 mL) and n-buLi (24.58 mL, 61.45 mmol, 2.5 M in Hexane) was slowly added thereto at -78C. 1 hours later, DMF (5.6 mL, 72.65 mmol) was added and the mixture was stirred for 12 hours at room temperature. Distilled water was added thereto and the product was extracted with EA. After drying with MgSO4 and distilling under reduced pressure, a compound 2-2 (11 g, 40.54 mmol, 72.58 %) was given by column separation. | |
51% | To a solution of 0.90 g 9-(4-bromo-phenyl)-9H-carbazole (1) (2.8 mmol) in 30 ml anhydrous Et2O was added 1.34 ml of 2.5 M n-BuLi in hexane (3.4 mmol) at -78 C under nitrogen atmosphere. After the reaction mixture was warmed to 0 C, 0.26 ml DMF(3.4 mmol) was added at -78 C. The resulting mixture was allowed to warm to room temperature and stirred at room temperature overnight. Then the mixture was poured into ice water and 5% HCl (aq.) (5 ml) was added and the two layers were separated. The aqueous layer was extracted with Et2O (3 × 20 ml) and the combined organic layer was washed with brine (15 ml), dried with MgSO4 and evaporated under reduced pressure, a yellow power was obtained by crystallized from ethanol (0.39 g, yield:51%). m.p. 148-150 C refPreviewPlaceHolder[31]. 1H NMR (300 MHz, CDCl3) δppm 10.12-10.20 (s, 1H), 8.12-8.16 (m, 4H), 7.78-7.86 (d, 2H), 7.49-7.63 (d, 2H), 7.32-7.44 (t, 2H), 7.19-7.30 (t, 2H). MS(M+) 271.0997. Anal. Calc. for C19H13ON: C, 84.13%; H, 4.80%; N, 5.17%. Found: C, 84.40%; H, 4.77%; N, 5.12%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69% | With copper(l) iodide; 18-crown-6 ether; potassium carbonate; In 1,2-dichloro-benzene; at 180℃; for 48h;Schlenk technique; Inert atmosphere; | The compound 8 was synthesized as described inliterature.24 In a typical reaction, 249.4 mg (1.5 mmol) of 9H-carbazole, 283.2 mg (1.5 mmol) of 4-bromobenzaldehyde,58.0 mg (0.22 mmol) of 18-crown-6, 303.9 mg (2.2 mmol)of K2CO3, 42.3 mg (15 mmol%) CuI and 1.5 mL of o-dichlorobenzene were added to a 10 mL Schlenk tube. The mixture was refluxed under nitrogen atmosphere at 180 C for 48 h. After, the reaction was quenched with aqueous 20% HCl and extracted with chloroform. The organic phase was dried with anhydrous Na2SO4 and concentrated under vacuum. The product was purified by silica flash column chromatography(mobile phase: ethyl acetate/hexane 5%). The compound 8 was obtained as a white solid in 69% yield. 1H NMR (400 MHz,DMSO-d6) δ 10.14 (s, 1H), 8.28 (d, J 7.67 Hz, 2H), 8.21 (d,J 8.35 Hz, 2H), 7.92 (d, J 8.32 Hz, 2H), 7.53 (d, J 8.32 Hz,2H), 7.47 (t, J 7.63 Hz, 2H), 7.34 (t, J 7.38 Hz, 2H); 13C NMR(100 MHz, DMSO-d6) δ 193.1, 143.1, 140.4, 135.5, 132.3,127.6, 127.4, 124.2, 121.7, 121.6, 110.8; infrared (IR)(attenuated total reflectance, ATR) ν / cm-1 3050, 2824, 2743,1702, 1595, 1510, 1479, 1450, 1361, 1336, 1198, 1161, 1123,1103, 916, 830, 749, 720, 633, 620, 567, 529, 502. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
28.07% | In dimethyl sulfoxide; at 200℃; for 12h; | Preparation of compound 2-3 [97] After the compound 2-2(11 g, 40.54 mmol), and 5-bromopyridine-2,3-diamine (7.6 g, 40.54 mmol) were dissolved in DMSO (200 mL),the mixture was heated at 200C for 12 hours. After cooling to room temperature, the product was washed with distilled water and extracted with EA. After drying with MgSO4 and distilling under reduced pressure, acompound 2-3 (5 g, 11.38 mmol, 28.07 %) was given by column separation. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | Under nitrogen, to a solution of 0.16 ml (1.2 mmol) of 2-methylbenzothiazole in 10 ml of anhydrous THF at -78 C was added dropwise, 0.56 ml (1.4 mmol) of 2.5 M n-BuLi in hexane. The mixture was stirred at -78 C for 30 min, then 0.27 g (1.0 mmol) of <strong>[110677-45-7]4-(9H-carbazol-9-yl)benzaldehyde</strong> in 5 ml of anhydrous THF was added dropwise. The reaction was stirred at -78 C for 1 h, then allowed to warm to ambient temperature and stirred overnight. Next, 0.20 ml of acetic acid was added, and the mixture was diluted with 50 ml of CH2Cl2. The solution was dried over MgSO4, filtered, and concentrated in vacuo. A yellow power was obtained by recyrstallized from ethanol. (0.38 g, yield: 75%). m.p. 176.5-178 C. 1H NMR (300 MHz, CDCl3) δppm 7.88-7.94 (d, 2H), 7.70-7.72 (d, 1H), 7.52-7.59 (d, 1H), 7.50-7.51 (d, 2H), 7.40-7.43 (m, 2H), 7.27-7.30 (m, 6H), 7.26 (m, 2H), 5.44-5.46 (m, 1H), 3.55-3.57 (m, 2H), 2.84-2.85 (s, 1H). MS(M+) 420.1356. Anal. Calc. for C27H20N2OS: C, 77.12%; H, 4.79%; N, 6.66%. Found: C, 77.20%; H, 4.84%; N, 6.72%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | In dimethyl sulfoxide; at 120℃; for 12h; | A mixture of the corresponding 0.41 g <strong>[110677-45-7]4-(9H-carbazol-9-yl)benzaldehyde</strong> (2) (1.50 mmol), 0.20 ml 2-aminothiophenol (1.87 mmol), and 30 ml DMSO was heated in an oil bath to 120 C, held at that temperature for 12 h, then poured into water and extracted with CH2Cl2 (3 × 10 ml). The combined organic layer was dried with anhydrous Na2SO4 and evaporated to dryness. The crude compound was stirred for 15 min in 30 ml of boiling ethanol, then the solution was cooled, and the pure product was isolated by filtration. (0.48 g, yield: 86%). m.p. 190-193 C. 1H NMR (300 MHz, CDCl3) δppm 8.11-8.17 (m, 2H), 7.82-7.97 (m, 4H), 7.72-7.75 (d, 2H), 7.50-7.59 (d, 2H), 7.41-7.46 (d, 2H), 7.25-7.34 (m, 4H). MS(M+) 376.1382. Anal. Calc. for C25H16N2S: C, 79.78%; H, 4.26%; N, 7.45%. Found: C, 80.02%; H, 4.12%; N, 7.27%. |
80% | In 1-methyl-pyrrolidin-2-one; at 110℃; for 48h;Inert atmosphere; | Compound 1b (1.37 g, 5 mmol), 2-aminothiophenol (0.55 mL, 5 mmol)And NMP (10 mL) were heated in an oil bath at 110 C for 48 hours,It was then poured into 1: 1 ethanol / water.The precipitate was collected and recrystallized from ethanol to obtain compound 2b in a yield of 80%. |
65.6% | In dimethyl sulfoxide; at 150 - 160℃; for 3.5h; | A mixture of <strong>[110677-45-7]4-(9H-carbazol-9-yl)benzaldehyde</strong> (1.626g, 6mmol), 2-aminothiophenol (0.825g, 6.6mmol) and DMSO (24mL) was heated to 150-160C in oil bath for 3.5h. The mixture was cooled to RT and poured into sodium chloride aqueous solution and then the resulting precipitate was filtered. The light-yellow crystal was obtained after recrystallization with ethyl acetate as solvent. Yield: 65.6%. Mp: 223.3-223.6C. MS (ESI): m/z 377.3 [M+H+]. 1H NMR (500MHz, CD2Cl2, TMS):δ 8.39 (d, J=8.5Hz, 2H), 8.20 (d, J=7.5Hz, 2H), 8.14 (d, J=8.5Hz, 1H), 8.01 (d, J=8.0Hz, 1H), 7.78 (d, J=8.5Hz, 2H), 7.59-7.55 (t, 3H), 7.49-7.46 (m, 3H), 7.36-7.33 (t, 2H); 13C NMR (125MHz, CD2Cl2, TMS): 166.91, 154.04, 140.48, 140.22, 135.15, 132.22, 129.05, 127.19, 126.52, 126.15, 125.45, 123.67, 123.15, 121.77, 120.38, 120.30, 109.83. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
24% | Under nitrogen atmosphere, a stirred slurry of 1.00 g 4-(2-benzothiazolyl)-benzyl triphenyl phosphonium bromide (1.77 mmol) in 30 ml anhydrous THF was cooled to -78 C, 0.70 ml of 2.5 M n-BuLi in hexane (1.77 mmol) was added and the mixture was warmed to room temperature over 2 h. Then a solution of 0.48 g <strong>[110677-45-7]4-(9H-carbazol-9-yl)benzaldehyde</strong> (2) (1.77 mmol) in 10 ml THF was added dropwise with vigorous stirring at -78 C. The reaction was warmed to room temperature and stirred for 12 h. Then the THF was evaporated at reduced pressure and the residue was separated by column chromatography (petroleum ether/methylene chloride 1:3) to give a yellow power.(0.20 g, yield: 24%). m.p. 263-265 C. 1H NMR (300 MHz, CDCl3): δppm 8.11-8.13 (m, 1H), 7.94-7.82 (m, 1H), 7.69-7.71 (m, 2H), 7.60-7.62 (m, 4H), 7.51-7.53 (d, 2H), 7.42-7.45 (d, 2H), 7.38-7.40 (m, 2H), 7.26-7.36 (d, 2H), 7.21-7.24 (m, 4H), 7.15-7.18 (m, 2H). MS(M+): 478.1528. Anal. Calc. for C33H22N2S: C, 82.85%; H, 4.60%; N, 5.86%. Found: C, 82.91%; H, 4.58%; N, 5.77%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With ammonium acetate; acetic acid; for 2h;Inert atmosphere; Reflux; | Synthesis of (2-(4-(9H-carbazol-9-yl)phenyl)-1-phenyl-1H-phenanthro[9,10-d]imidazole (M1): a mixture of <strong>[110677-45-7]4-(9H-carbazol-9-yl)benzaldehyde</strong> (1.00 g, 3.70 mmol), phenanthrene-9,10-dione (767.50 mg, 3.70 mmol), aniline (0.85 g, 18.50 mmol), ammonium acetate (1.14 g, 14.80 mmol), and acetic acid (10 mL) were refluxed under nitrogen in an oil bath. After 2 h, the mixture was cooled and filtered. The solid product was washed with an acetic acid/water mixture (1:1, 150 mL) and water. It was then purified by chromatography using CH2Cl2/petroleum ether (1:1) as eluent to obtain the product as white powder. Yield: 75%. 1H NMR (500 MHz, DMSO, δ): 8.96 (d, J = 8.30 Hz, 1H), 8.91 (d, J = 8.45 Hz, 1H), 8.74 (d, J = 7.36 Hz, 1H), 8.26 (d, J = 7.83 Hz, 2H), 7.89 (d, J = 8.22 Hz, 2H), 7.84-7.76 (m, 6H), 7.73 (t, J = 7.50 Hz, 6.43 Hz, 1H), 7.66 (d, J = 7.94 Hz, 2H), 7.59 (t, J = 6.97 Hz, 7.68 Hz, 1H), 7.46 (t, J = 7.50 Hz, 7.14 Hz, 2H), 7.40 (d, J = 8.61 Hz, 2H), 7.38 (t, J = 7.68 Hz, 7.68 Hz, 1H), 7.32 (t, J = 7.68 Hz, 7.68 Hz, 2H), 7.11 (d, J = 8.47 Hz, 1H); 13C NMR (500 MHz, CDCl3, Hz): 140.53, 130.80, 130.40, 130.14, 129.15, 128.39, 127.42, 126.61, 126.39, 126.02, 124.19, 123.57, 123.18, 120.91, 120.35, 120.20, 109.78; FTIR (KBr, ν, cm-1) 3058, 1625, 1532, 1475, 1451, 1429, 1378, 1358, 1241, 1225, 1174, 1147, 1111, 1018, 1004, 929, 844, 750, 724, 667, 620, 563, 535; MALDI-TOF (m/z): [M+] calcd for C39H25N3: 535.64; Found: 535.90. Anal. calcd for C39H25N3: C 87.45, H 4.70, N 7.84; Found: C 87.45, H 4.66, N 8.03. |
75% | With ammonium acetate; acetic acid; at 120℃; for 2h;Inert atmosphere; | A mixture of<strong>[110677-45-7]4-(9H-carbazol-9-yl)benzaldehyde</strong> (1.00 g,3.70 mmol),phenanthrene-9,10-dione (767.50 mg,3.70 mmol), aniline(0.85 g,18.50 mmol), ammonium acetate (1.14 g,14.80 mmol), and acetic acid (10 mL) were refluxed undernitrogen in an oil bath. After 2 h, the mixture was cooledand filtered. The solid product was washed with an aceticacid/water mixture (1:1,150 mL) and water. It was thenpurified by chromatography using CH2Cl2/petroleum ether(1:1) as eluent to obtain the product as white powder.Yield: 75%. 1H NMR (500 MHz, DMSO, d): 8.96 (d, J =8.30 Hz, 1H), 8.91 (d, J = 8.45 Hz, 1H), 8.74 (d, J = 7.36 Hz,1H), 8.26 (d, J = 7.83 Hz, 2H), 7.89 (d, J = 8.22 Hz, 2H),7.84-7.76 (m,6H), 7.73 (t, J = 7.50 Hz, 6.43 Hz, 1H), 7.66(d, J = 7.94 Hz, 2H), 7.59 (t, J = 6.97 Hz, 7.68 Hz, 1H), 7.46(t, J = 7.50 Hz, 7.14 Hz, 2H), 7.40 (d, J = 8.61 Hz, 2H), 7.38(t, J = 7.68 Hz, 7.68 Hz, 1H), 7.32 (t, J = 7.68 Hz, 7.68 Hz,2H), 7.11 (d, J = 8.47 Hz, 1H); 13C NMR (500 MHz, CDCl3,Hz): 140.53, 130.80, 130.40, 130.14, 129.15, 128.39,127.42, 126.61, 126.39, 126.02, 124.19, 123.57, 123.18,120.91, 120.35, 120.20, 109.78; FTIR (KBr, m, cm1) 3058,1625, 1532, 1475, 1451, 1429, 1378, 1358, 1241, 1225,1174, 1147, 1111, 1018, 1004, 929, 844, 750, 724, 667,620, 563, 535; MALDI-TOF (m/z): [M+] calcd for C39H25N3:535.64; Found: 535.90. Anal. calcd for C39H25N3: C 87.45,H 4.70, N 7.84; Found: C 87.45, H 4.66, N 8.03. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | With sodium hydroxide; In ethanol; at 20℃; for 12h; | The a (217mg, 0.8mmol), acetophenone (0.8mmol), NaOH (40mg, 1mmol) placed in a single neck flask 25mL, 10mL of absolute ethanol was added, stirred at room temperature 12h, TLC monitoring, the majority of starting material spot disappeared, stop reaction. The solvent was evaporated, the remaining solid was washed with water until neutral, dried and separated by column chromatography to give B as a yellow solid, yield 65%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
53.7% | With dihydrogen peroxide; sodium hydroxide; In 1,4-dioxane; at 0 - 100℃; for 14h; | A portionof compound 2 (0.061 g, 0.220 mmol), hydrogen peroxide(0.5 mL, 0.220 mmol) and sodium hydroxide (0.009 g, 0.220mmol) was dissolved in 1 mL of dioxane and the mixturewas stirred for 2 h at 0 oC. Then the reaction mixture washeated up to 100 oC and stirred for 12 h. The reactionmixture was cooled down the room temperature and filtered.The filtrate was adjusted to pH 2 with HCl solution, andfiltered again. The crude residue was purified by recrystallizationusing n-hexane. The yield of the yellowish white solidwas 0.034 g (53.7%). mp 213.0 oC. 1H-NMR (400 MHz,MeOH-d3) 8.31-8.28 (d, J = 8.80 Hz, 2H), 8.15-8.13 (d, J= 7.68 Hz, 2H), 7.72-7.69 (d, J = 8.44 Hz, 2H), 7.47-7.38(m, 4H), 7.29-7.26 (t, J = 7.68 Hz, 2H). Anal. Calcd. ForC19H13NO2: C, 79.43; H, 4.56; N, 4.88; O, 11.14. Found: C,79.82; H, 4.47; N, 4.79. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
51% | With sodium hydroxide; In ethanol; at 20℃; for 12h; | The 4- (9- (9H- carbazol-yl)) benzaldehyde (217mg, 0.8mmol), 1- (4- methoxyphenyl) ethanone (0.8mmol),NaOH (40mg, 1mmol) placed in a single neck flask 25mL, 10mL of absolute ethanol was added, stirred at room temperature 12h,Monitored by TLC the disappearance of most of the spot of the material, the reaction was stopped. The solvent was evaporated, the remaining solid was washed with water until neutral,Drying, column chromatography, a yellow solid a, yield 51% |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
57% | With sodium hydroxide; In ethanol; at 20℃; for 12h; | The 4-(9-(9H-carbazolyl)) benzaldehyde (217 mg, 0 . 8mmol), 1-(4-methyl phenyl) ethanone (0.8mmol), NaOH (40 mg, 1mmol) in 25 ml single-port the bottle, by adding 10 ml anhydrous ethanol, stirring the mixture at room temperature for 12h, TLC monitoring, most of the point of disappearance of the raw materials, to stop the reaction. Evaporate the solvent, the remaining solid washing with water to neutral, drying, column chromatography separation, a to get the yellow solid, yield 57%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
54% | With sodium hydroxide; In ethanol; at 20℃; for 12h; | The 4-(9-(9H-carbazolyl)) benzaldehyde (217 mg, 0 . 8mmol), 1-(4-fluoro-phenyl) ethanone (0.8mmol), NaOH (40 mg, 1mmol) in 25 ml single-port the bottle, by adding 10 ml anhydrous ethanol, stirring the mixture at room temperature for 12h, TLC monitoring, most of the point of disappearance of the raw materials, to stop the reaction. Evaporate the solvent, the remaining solid washing with water to neutral, drying, column chromatography separation, a to get the yellow solid, yield 54%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | With sodium hydroxide; In methanol; at 20℃; for 12h; | The 4- (9- (9Η-P P sat specifically yl)) benzoic acid (217mg, 0 8mmol.), 4,4 '- phenethyl-linked pay (0 · 8mmol), Na0H (40mg, lmmol) placed in 25mL single neck flask was added 10mL of anhydrous ethanol, stirred at room temperature 12h, TLC monitoring, the majority of starting material spot disappeared, the reaction was stopped. The solvent was evaporated, the remaining solid was washed with water until neutral, dried and separated by column chromatography to give a yellow solid a, yield 73% |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | With sodium hydroxide; In ethanol; chloroform; at 20℃; | The 816 mg (4.8mmol) α- acetonaphthone , 240 mg (6mmol) sodium hydroxide in 100 ml of water, adding 6 ml ethanol, 12 drip enable its dissolution. The 1302 mg (4.8mmol) 4-(9-(9H-carbazolyl)) benzaldehyde dissolved in 18 ml in chloroform, in the above-mentioned is dripped into the ethanol solution, stirring the mixture at room temperature for overnight, to stop the reaction. Overhanging organic solvent, water and dilute, dichloromethane extraction, drying, recrystallized (petroleum ether: ethyl acetate = 15 the [...] 1), to get the yellow cluster crystal a1.37g, yield = 68%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | With sodium hydroxide; In ethanol; dichloromethane; water; at 20℃; | The 528mg (3mmol) 4- isobutyl acetophenone, 160mg (4mmol) sodium hydroxide was placed in 100mL single jarWas added 10 drops of water, 20 mL of ethanol and dissolved; the 813mg (3mmol) 4- (9- (9H- carbazolyl)) benzoateAldehyde was dissolved in 10mL of dichloromethane, ethanol and added dropwise to the mixture, stirred at room temperature overnight, filtered, ethanol, washed with petroleum ether, and dried to give a pale yellow solid (LJZ-5-13) 851mg, Yield = 66% . |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
58% | With sodium hydroxide; In ethanol; dichloromethane; water; at 20℃; for 6h; | The 786mg (3mmol) 3,5- di-tert-butyl-4-methoxyacetophenone, 160mg (4mmol) of sodium hydroxide is placed100mL single-mouth bottle, add 10 drops of water, 20mL ethanol and dissolved; the 813mg (3mmol) 4- (9- (9H-Carbazol-yl)) benzaldehyde was dissolved in 10mL of dichloromethane, ethanol and added dropwise to the mixture, stirred at room temperature 6h,Filtered, ethanol, washed with petroleum ether, and dried to give a khaki solid (LJZ-5-1) 890mg, yield = 58%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
63% | With potassium hydroxide; In ethanol; dichloromethane; water; at 20℃; | The 768mg (3mmol) 3,5- two trifluoromethyl acetophenone, 160mg (4mmol) sodium hydroxide was placed in 100mLSingle neck flask was added 10 drops of water, 20 mL of ethanol and dissolved; the 813mg (3mmol) 4- (9- (9H- carbazoleYl)) benzaldehyde was dissolved in 10mL of dichloromethane, ethanol and added dropwise to the mixture, stirred overnight at room temperature, overFiltered, ethanol, washed with petroleum ether, and dried to give a yellow solid (LJZ-5-31) 956mg, Yield = 63%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With sodium hydroxide; In ethanol; dichloromethane; water; at 20℃; | The 726mg (3mmol) 4- methoxy-4'-diphenyl ether, 160mg (4mmol) of sodium hydroxide in 100mL single-neck flask, add 10 drops of water, 20mL ethanol and dissolved; the 813mg (3mmol) 4- (9- (9H-Carbazol-yl)) benzaldehyde was dissolved in 10mL of dichloromethane, ethanol and added dropwise to the mixture, stirred at room temperature overnight, filtered, ethanol, washed with petroleum ether, and dried to give a yellow solid (LJZ-5-47) 1.45g , yield = 92%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | With sodium hydroxide; In ethanol; dichloromethane; water; at 20℃; | The 534mg (3mmol) 6- acetyl-1,4-benzo-dioxane, 160mg (4mmol) of sodium hydroxide in 100mL single-neck flask, add 10 drops of water, 20mL ethanol and dissolved; the 813mg (3mmol) 4- (9- (9H-Carbazol-yl)) benzaldehyde was dissolved in 10mL of dichloromethane, ethanol and added dropwise to the mixture, stirred at room temperature overnight, filtered, ethanol, washed with petroleum ether, and dried to give a pale yellow solid (LJZ-5-32) 842mg the yield was 65%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With sodium hydroxide; In ethanol; dichloromethane; water; at 20℃; for 6h; | The 678mg (3mmol) 4- benzyloxy acetophenone, 160mg (4mmol) sodium hydroxide was placed in 100mL single jarWas added 10 drops of water, 10 mL of ethanol and dissolved; the 813mg (3mmol) 4- (9- (9H- carbazolyl)) benzoateAldehyde was dissolved in 10mL of dichloromethane, ethanol and added dropwise to the mixture, stirred at room temperature 6h, filtered, ethanol,Washed with petroleum ether and dried to give a pale yellow powder (LJZ-6-23) 1.31g, yield 91%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
821 mg | With sodium hydroxide; In ethanol; dichloromethane; water; at 20℃; | The 420mg (3mmol) 2- methyl-5-acetyl-thiophene, 160mg (4mmol) sodium hydroxide was placed in 100mL singleNeck flask was added 10 drops of water, 20 mL of ethanol and dissolved; the 813mg (3mmol) 4- (9- (9H- carbazol-yl))Benzaldehyde was dissolved in 10mL of dichloromethane, ethanol and added dropwise to the mixture, stirred at room temperature overnight, filtered,Ethanol, washed with petroleum ether and dried to give a yellow solid (LJZ-5-14) 821mg. |
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