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CAS No. : | 56525-79-2 | MDL No. : | MFCD00222619 |
Formula : | C24H17N | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | PCMKGEAHIZDRFL-UHFFFAOYSA-N |
M.W : | 319.40 | Pubchem ID : | 3123295 |
Synonyms : |
|
Num. heavy atoms : | 25 |
Num. arom. heavy atoms : | 25 |
Fraction Csp3 : | 0.0 |
Num. rotatable bonds : | 2 |
Num. H-bond acceptors : | 0.0 |
Num. H-bond donors : | 1.0 |
Molar Refractivity : | 106.68 |
TPSA : | 15.79 Ų |
GI absorption : | Low |
BBB permeant : | No |
P-gp substrate : | Yes |
CYP1A2 inhibitor : | Yes |
CYP2C19 inhibitor : | Yes |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | Yes |
Log Kp (skin permeation) : | -3.53 cm/s |
Log Po/w (iLOGP) : | 3.15 |
Log Po/w (XLOGP3) : | 6.64 |
Log Po/w (WLOGP) : | 6.66 |
Log Po/w (MLOGP) : | 5.24 |
Log Po/w (SILICOS-IT) : | 6.66 |
Consensus Log Po/w : | 5.67 |
Lipinski : | 1.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 1.0 |
Muegge : | 2.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -6.61 |
Solubility : | 0.0000781 mg/ml ; 0.000000245 mol/l |
Class : | Poorly soluble |
Log S (Ali) : | -6.77 |
Solubility : | 0.0000539 mg/ml ; 0.000000169 mol/l |
Class : | Poorly soluble |
Log S (SILICOS-IT) : | -9.97 |
Solubility : | 0.0000000341 mg/ml ; 0.0000000001 mol/l |
Class : | Poorly soluble |
PAINS : | 0.0 alert |
Brenk : | 0.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 2.03 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P280 | UN#: | N/A |
Hazard Statements: | H302-H317 | 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 |
---|---|---|
76% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; water at 80℃; for 16 h; Inert atmosphere | It was dissolved in 3,6-dibromo-9H-carbazole(100 g, 308 mmol) in a nitrogen environment in 700 mL tetrahydrofuran(THF), here the phenylboronic acid(45.1 g, 370 mmol) and put tetrakis(triphenylphosphine) palladium (10.7 g, 9.24mmol) was stirred. Into a potassium carbonate (213 g, 1,540 mmol) in a saturated water was heated to reflux at 80 ° C for 16 hours. After the reaction was completed, the reaction solution into water and extracted with DCM then water was removedwith anhydrous MgSO4, filter and was concentrated under reduced pressure. Thus the resulting residue was separated and purified by flash column chromatography to obtain the compound I-23(74.8 g, 76percent). |
75% | With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; tris-(dibenzylideneacetone)dipalladium(0); potassium phosphate monohydrate In water; tolueneInert atmosphere; Reflux | Synthesis of 3,6-diphenyl-9H-carbazole 3,6-Dibromo-9H-carbazole (10.0 g, 30.8 mmol), phenylboronic acid (8.25 g, 67.7 mmol) Pd2(dba)3 (0.564 g, 0.615 mmol), dicyclohexyl(2',6'-dimethoxy-[1,1'-biphenyl]-2-yl)phosphine (SPhOS) (1.011 g, 2.462 mmol), and potassium phosphate hydrate (28.3 g, 123 mmol) were dissolved in the mixture of toluene (350 mL) and water (40 mL) in a three-necked flask. The mixture was degassed by bubbling nitrogen, then it washeated to reflux overnight. After completion of the reaction, the mixture partitioned between ethyl acetate and water. The aqueous layer was washed 3 times with ethyl acetate and the combined organic layers were washed with brine and water. The crude compound was purified by column chromatography on silica gel, eluted with hexane/DCM 1/1 (v/v) mixture. The target compound was obtained as a white solid (7.4 g, 75 percent yield). |
74% | With potassium carbonate In tetrahydrofuranInert atmosphere; Reflux | Example 10; a) 3.09 g (9.23 mmol) of 3,6-dibromocarbazole and 2.78 g (22.2 mmol) of phenylboronic acid are stirred in 140 ml of THF under argon. 12.76 g (92.30 mmol) of potassium carbonate in 46 ml of water are added. 0.27 g (0.23 mmol) of palladium tetrakis(triphenylphosphine) are added under argon and the reaction is stirred under reflux over night. At room temperature, a 1 percent aqueous solution of NaCN is added to the medium which is boiled for 20 min. At room temperature, ethyl acetate is added and the organic phase is washed with water, dried over magnesium sulfate, filtered and evaporated under reduced pressure. The crude material is purified by chromatography over silica gel (cyclohexane/ethyl acetate 4:1 ) to give 2.17 g of a white solid (74percent). 1H NMR (CDCI3, 300 MHz) 8.34 (d, J = 1.8 Hz, 2H), 8.11 (s, 1 H), 7.74- 7.68 (m, 6H), 7.52-7.45 (m, 6H), 7.37-7.32 (m, 2H). |
74% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In toluene at 80℃; for 8 h; Inert atmosphere | In the nitrogen atmosphere, 3,6-dibromocarbazole (5 g, 15.4 mmol) was added sequentially to the flask, Phenylboronic acid (4.1 g, 33.9 mmol) (Triphenylphosphine) palladium (0.7 g, 0.6 mmol) Toluene (45 ml), 2M sodium carbonate (45 ml), And the mixture was stirred at 80 ° C for 8 hours. After separating the organic phase, Concentrated under reduced pressure in an evaporator. The resulting residue was purified by silica gel column chromatography, 3,6-diphenylcarbazole (3.6 g, yield 74percent) was obtained. |
74% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In toluene at 80℃; for 8 h; Inert atmosphere | In the nitrogen atmosphere,3,6-dibromocarbazole (5 g, 15.4 mmol) was added sequentially to the flask,Phenylboronic acid (4.1 g, 33.9 mmol)(Triphenylphosphine) palladium (0.7 g, 0.6 mmol)Toluene (45 ml),2M sodium carbonate (45 ml),And stirred at 80 ° C for 8 hours.After separating the organic phase,Concentrated under reduced pressure in an evaporator.The resulting residue was purified by silica gel column chromatography,3,6-diphenylcarbazole (3.6 g, yield 74percent) was obtained. |
73% | With potassium carbonate In toluene for 10 h; Heating / reflux | Preparation of 3,6-diphenylcarbazole Reaction 5As depicted in Reaction 5, 15g (46 mmol) of 3,6-dibromocarbazole, 14g (92 mmol) of phenylboronic acid, K2CO3 (2 mol), Pd(PPh3)4 and toluene were refluxed for 10 hours. The reaction mixture was extracted with methylene chloride. The solvent was removed, and then the residue was purified by column chromatography (eluent: hexane) to give the title compound. Yield: 73percent. MS (El) (Calcd. for C24H17N: 319.14, Found: 319). |
68% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; water at 80℃; | Carbazole (16.72g, 100mmol), NBS (59.4g, 210mmol), BPO (2.42g, 10mmol), methylene chloride (300 ml) at room temperature is injected into the medal and then 2000. When reaction is completed methylene chloride and water, NaHCO 3 extracted using aqueous solution obtained after the organic layer Na 2 SO 4 dried to, for the products and re-crystallized concentrating 23.73g (73percent)obtained. Said product obtained (23.73g, 73.02mmol), phenylboronic acid (19.6g, 160.64mmol), Pd (PPh 3) 4, (8.44g, 7.3mmol), K 2 CO 3 (60.55g, 438.12mmol), THF (320 ml), water (160 ml) in 80 °C agitation return current doesn't have any error frames, turns on the light. When reaction is completed for reducing temperature a high temperature to the normal temperature after methylene chloride and a water extraction of the organic layer obtained after MgSO 4 dried to, for the products and re-crystallized concentrating 15.9g (68percent)obtained |
63% | With potassium carbonate In 1,2-dimethoxyethane; water at 80℃; for 3.5 h; | As an example of a material according to the invention, a synthetic method of a compound represented by formula (59) 9-[4-(3, 6-diphenyl-N-carbazolyl)] phenyl- 10-phenylanthracene (hereinafter referred to as DPCzPA) below will be described. [0209][0210] This compound is prepared in accordance with the synthetic method shown below. Note that 9-phenyl-10-(4-bromophenyl) anthracene is prepared in the manner shown in Example 1. [0211]First, a synthetic method of 3,6-dibromocarbazole will be shown below. A mixture of 6.5 g (20.0 mmol) 3,6-dibromocarbazole, 5.0 g (41.0 mmol) of phenylboronic acid, 93 mg (0.40 mmol) of palladium acetate, 6.9 g (5.2 mmol) of potassium carbonate, water (25 mL), 610 mg of tri(ortho-tolyl) phosphine, and dimethoxyethane (50 mL) is heated to reflux at 80 0C for 3.5 three hours. After the reaction, the solution is rinsed with water, aqueous layer is extracted with toluene, and it is rinsed together with the organic layer using saturated salt solution, and thereafter EPO <DP n="67"/>dried with magnesium sulfate. After natural filtration, the filtrate is condensed to obtain 4.1 g of 3,6-di(2-phenyl-phenyl)-carbazoleas a white solid at a yield of 63 percent. A synthetic scheme of 3,6-di(2-phenyl-phenyl)-carbazoleis shown below. |
63% | With potassium carbonate In 1,2-dimethoxyethane; water at 80℃; for 3.5 h; | [Step 2] A synthesis method of 3,6-diphenylcarbazole is described.; A synthesis scheme of 3,6-diphenylcarbazole is represented by (a-2). [Show Image] 6.5 g of 3,6-dibromocarbazole (20 mmol), 5.0 g of phenylboron acid (41 mmol), 93mg of palladium(II) acetate (0.40 mmol), 610mg of tri(ortho-tolyl)phosphine (1.9mmol) were put into a 200mL three-necked flask, and then, the inside of the flask was substituted by nitrogen. Into the mixture, 50 ml of ethyleneglycol dimethylether (abbreviation : DME), and 25 mL of a pottassium carbonate water solution (2.0 mol/L) were added. This mixture was refluxed for 3.5 hours at 80 °C. After the reaction, the reaction mixture was washed with water and a water layer was extracted with toluene. The extracted solution and an organic layer were washed with a saturated saline, and dried by magnesium sulphate. The mixture was naturally filtrated. The filtrate was condensed, and 4.1 g of an objective matter, a white powder solid was obtained at the yield 63 percent. |
63% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In 1,4-dioxane; water at 100℃; for 17 h; Inert atmosphere | A mixture of 3,6-dibromo-9H- carbazole (3.0 g, 9.2 mmol) (Aldrich), phenylboronic acid (3.0 g, 25 mmol) (Aldrich), tetrakis(triphenylphosphine)palladium (Pd(PPh3)4) (0.3 g, 0.26 mmol) (Frontier Scientific, Logan, UT) and potassium carbonate (6.5 g, 47 mmol) (Aldrich) in dioxane/water (75 mL/15 mL) (Aldrich) was degassed with bubbling argon (Airgas, San Marcos, CA) for 60 min and heated at about 100 °C on a hot plate with a silicone oil bath for about 16 hours. Upon cooling to room temperature, the whole mixture was mixed with ethyl acetate (Aldrich) and rinsed with brine. Then, the organic mixture was dried over Na2S04 (Aldrich), loaded on silica gel (Grade 135) and purified by flash column using eluents of ethyl acetate/hexanes (10percent to 30percent) (Aldrich). After removal of solvents, a white solid (Compound OSC-3) was obtained (2.1 g, in 63percent yield). Confirmed by 1 HNMR (Jeol Instruments, Peabody, MA). |
63% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In 1,4-dioxane; water at 100℃; for 16 h; | A mixture of 3,6-dibromo-9H-carbazole (3.0 g, 9.2 mmol), phenylboronic acid (3.0 g, 25 mmol), Pd(PPh3)4 (0.3 g, 0.26 mmol) and potassium carbonate (6.5 g, 47 mmol) in dioxane/water (75 mL/15 ml) was degassed and heated at about 100 °C for about 16 hours. Upon cooling to room temperature, the whole was worked up with ethylacetate/brine, the organic was dried over Na2So4, loaded on silica gel and purified by flash column using eluents of ethyl acetate/hexane (10percent to 30percent). After removal of solvents, a white solid (Compound 11 ) was obtained (2.1 g, in 63percent yield). |
48% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; water at 80℃; for 10 h; Inert atmosphere | 30 g (92.3 mmol) of 3,6-dibromo-9H-carbazole was dissolved in 0.3 L of tetrahydrofuran (THF) in a nitrogenenvironment, 28 g (231 mmol) of phenyl boronic acid and 3.2 g (2.8 mmol) of tetrakis(triphenylphosphine)palladium wereadded thereto, and the mixture was agitated. 40.8 g (277 mmol) of potassium carbonate saturated in water was addedthereto, and the mixture was heated and refluxed at 80 °C for 10 hours. When the reaction was terminated, water wasadded to the reaction solution, and the mixture was extracted with dichloromethane (DCM) and treated with anhydrousMgSO4 to remove moisture and then, filtered and concentrated under a reduced pressure. The obtained residue wasseparated and purified through flash column chromatography, obtaining a compound I-4 (14.3 g, 48 percent). HRMS (70 eV, EI+): m/z calcd for C24H17N: 319.1361, found: 319.1. HRMS (70 eV, EI+): m/z calcd for C24H17N: 319.1361, found: 319.1. |
33% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In water; N,N-dimethyl-formamide at 80℃; for 4 h; Inert atmosphere | General procedure: Under nitrogen protection system, 3-bromo -9H- carbazole 1.6mmol, tetrakistriphenylphosphine palladium 0.64mmol, anhydrous carbonatePotassium1.92mmol phenylboronic acid 1.92mmol, was dissolved in N, N- dimethylformamide: H2O = (15ml: 2ml) mixed solvent,80 stirring for 4h, after completion of the reaction, cooled to room temperature, the mixed solution was extracted with dichloromethane and water, the organic phase was dried over anhydrous magnesiumDried and evaporated, evaporated and the product after column chromatography to obtain 3-phenyl -9H- carbazole (A-1) 1.44mmol, 90percent yield. The method of the same A-1, by column chromatography to obtain a white solid product 3,6-diphenyl -9H- carbazole (A-2), producingRate of 33percent. |
38 g | Stage #1: With sodium carbonate In 1,4-dioxane; water for 1 h; Inert atmosphere Stage #2: With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine In 1,4-dioxane; waterReflux; Inert atmosphere |
3,6-dibromocarbazole (50 g, 0.154 mol), phenylboronic acid (41 g, 0.336 mol), 150ml water, 80g sodium carbonate, and 600ml dioxane were charged into a 2 liter pot with magnetic stirrer, reflux condenser and nitrogen inlet, and sparged with nitrogen for one hour. Pd2DBA3 (6g, 0.0066mol) and tri-t-butylphosphine (3 g, 0.0148mol) was quickly added from the drybox. The reaction was refluxed overnight. The next day water was added to the reaction mixture and methylene chloride extractions were preabsorbed to 141 g of activated silica and purified by column chromatography using methylene chloride/hexanes yielding 38 grams of product 3,6-diphenylcarbazole. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
57% | With potassium carbonate;palladium diacetate; tri-tert-butyl phosphine; In hexane; xylene; at 130℃; for 12h; | [Step 3] A synthesis method of 2,3-bis[4-(3,6-diphenylcarbazol-9-yl)pbenyl]quinoxaline (DPCPQ) is described. A synthesis scheme of DPCPQ was represented by (a-3). [Show Image] 2.3g of 2,3-bis(4-bromophenyl)quinoxaline (6.1 mmol), 4.3 g of 3,6-diphenyl carbazole (14 mmol), 0.061g of palladium(II) acetate (0.27 mmol), 5.6 g of potassium carbonate (41 mmol) were put into a 200 mL three-necked flask, and the inside was substituted by nitrogen. Into this mixture, 50 mL of xylene, and 1.7 g of tri(tert-butyl)phosphine (10 percent hexane solution) (0.81 mmol) were added. This mixture was stirred for 12 hours at 130 °C. After the reaction, a precipitate of the reaction mixture was filtrated by suction to be collected. The obtained solid was dissolved in chloroform and this solution was filtrated by suction through Florisil, celite, and alumina. The filtrate was condensed, the obtained solid was recombined with a mixed solvent of chloroform and hexane to be recrystallized and 3.2 g of an objective matter, a lemon-yellow powder solid was obtained at the yield 57 percent. It was confirmed by a nuclear magnetic resonance method (NMR) that this compound was DPCPQ. 3.2 g of the obtained DPCPQ was refined by sublimation at 380 °C under the following conditions: the pressure was 5.6 Pa, and an argon flow rate was 3.0 mL/min. 0.8 g of DPCPQ was collected and the collection rate was 25 percent. The analysis result of DPCPQ by proton nuclear magnetic resonance spectrometry (1HNMR) was as follows. 1HNMR (CDCl3, 300 MHz): delta =7.32-7.37 (m, 4H), 7.42-7.47 (m, 8H), 7.57-7.60 (m, 4H), 7.69-7.81 (m, 17H), 7.88-7.94 (m, 6H), 8.29-8.32 (m, 2H), 8.42-8.42 (m, 3H). FIG 8A is a 1HNMR chart of DPCPQ, and FIG. 8B is an enlarged 1HNMR chart of DPCPQ in 7.0 to 9.0 ppm. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium carbonate; copper(II) sulfate; In tridecane; at 230℃; for 24h; | (Compound 1): In a 50 milliliter round bottom flask there were added 4,4'-diiodo-1,1'-biphenyl (2.1 grams), 3,6-diphenyl carbazole (3.3 grams), potassium carbonate powder (1.4 grams), copper sulfate pentahydrate (0.06 grams), and 5 milliliters of tridecane.. The resulting mixture was heated to 230° C. and stirred at this temperature under argon for 24 hours.. After cooling to room temperature (~23° C.), the solids content resulting was ground into slurry, which slurry was then transferred to a filtration funnel, washed with hexane to remove the tridecane, followed by washing with 3 percent hydrochloric acid and water.. The solid resulting was then dissolved in hot toluene.. The insoluble residue was filtered hot.. After cooling to room temperature, the product was crystallized from the solution to yield 2.3 grams of 4,4'-bis-[9-(3,6-diphenylcarbazolyl)]-1,1'-biphenyl as a yellowish powder.. This compound had a melting point of 294° C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; at 80℃; for 16h;Inert atmosphere; | It was dissolved in 3,6-dibromo-9H-carbazole(100 g, 308 mmol) in a nitrogen environment in 700 mL tetrahydrofuran(THF), here the phenylboronic acid(45.1 g, 370 mmol) and put tetrakis(triphenylphosphine) palladium (10.7 g, 9.24mmol) was stirred. Into a potassium carbonate (213 g, 1,540 mmol) in a saturated water was heated to reflux at 80 C for 16 hours. After the reaction was completed, the reaction solution into water and extracted with DCM then water was removedwith anhydrous MgSO4, filter and was concentrated under reduced pressure. Thus the resulting residue was separated and purified by flash column chromatography to obtain the compound I-23(74.8 g, 76%). |
75% | With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; tris-(dibenzylideneacetone)dipalladium(0); potassium phosphate monohydrate; In water; toluene;Inert atmosphere; Reflux; | Synthesis of 3,6-diphenyl-9H-carbazole 3,6-Dibromo-9H-carbazole (10.0 g, 30.8 mmol), phenylboronic acid (8.25 g, 67.7 mmol) Pd2(dba)3 (0.564 g, 0.615 mmol), dicyclohexyl(2',6'-dimethoxy-[1,1'-biphenyl]-2-yl)phosphine (SPhOS) (1.011 g, 2.462 mmol), and potassium phosphate hydrate (28.3 g, 123 mmol) were dissolved in the mixture of toluene (350 mL) and water (40 mL) in a three-necked flask. The mixture was degassed by bubbling nitrogen, then it washeated to reflux overnight. After completion of the reaction, the mixture partitioned between ethyl acetate and water. The aqueous layer was washed 3 times with ethyl acetate and the combined organic layers were washed with brine and water. The crude compound was purified by column chromatography on silica gel, eluted with hexane/DCM 1/1 (v/v) mixture. The target compound was obtained as a white solid (7.4 g, 75 % yield). |
75.5% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; at 120℃; | 3,6-dibromo-9H-carbazole (5 g, 15.3 mmol) and phenylboronic acid (5.63 g, 46.15 mmol) was dissolved in tetrahydrofuran (THF) (60 ml) into a 2-necked round bottom flask, Tetrakis(triphenylphosphine)palladium(0), Pd(PPh3)4) (0.89 g, 0.77 mmol), K2CO3 (8.3 g) was dissolved in distilled water (30 ml) at 2M, and the mixture was stirred at 120 C. Then, after the reaction was completed, the reaction product was extracted with CH2Cl2 and water, and the organic layer was dried over MgSO4 and concentrated. The concentrated reaction product was purified by silica gel column chromatography to obtain 3.7 g of 3,6-diphenyl-9H-cabazole (hereinafter referred to as Sub 2) (yield: 75.5%). |
74% | With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran;Inert atmosphere; Reflux; | Example 10; a) 3.09 g (9.23 mmol) of 3,6-dibromocarbazole and 2.78 g (22.2 mmol) of phenylboronic acid are stirred in 140 ml of THF under argon. 12.76 g (92.30 mmol) of potassium carbonate in 46 ml of water are added. 0.27 g (0.23 mmol) of palladium tetrakis(triphenylphosphine) are added under argon and the reaction is stirred under reflux over night. At room temperature, a 1 % aqueous solution of NaCN is added to the medium which is boiled for 20 min. At room temperature, ethyl acetate is added and the organic phase is washed with water, dried over magnesium sulfate, filtered and evaporated under reduced pressure. The crude material is purified by chromatography over silica gel (cyclohexane/ethyl acetate 4:1 ) to give 2.17 g of a white solid (74%). 1H NMR (CDCI3, 300 MHz) 8.34 (d, J = 1.8 Hz, 2H), 8.11 (s, 1 H), 7.74- 7.68 (m, 6H), 7.52-7.45 (m, 6H), 7.37-7.32 (m, 2H). |
74% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In toluene; at 80℃; for 8h;Inert atmosphere; | In the nitrogen atmosphere, 3,6-dibromocarbazole (5 g, 15.4 mmol) was added sequentially to the flask, Phenylboronic acid (4.1 g, 33.9 mmol) (Triphenylphosphine) palladium (0.7 g, 0.6 mmol) Toluene (45 ml), 2M sodium carbonate (45 ml), And the mixture was stirred at 80 C for 8 hours. After separating the organic phase, Concentrated under reduced pressure in an evaporator. The resulting residue was purified by silica gel column chromatography, 3,6-diphenylcarbazole (3.6 g, yield 74%) was obtained. |
74% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In toluene; at 80℃; for 8h;Inert atmosphere; | In the nitrogen atmosphere,3,6-dibromocarbazole (5 g, 15.4 mmol) was added sequentially to the flask,Phenylboronic acid (4.1 g, 33.9 mmol)(Triphenylphosphine) palladium (0.7 g, 0.6 mmol)Toluene (45 ml),2M sodium carbonate (45 ml),And stirred at 80 C for 8 hours.After separating the organic phase,Concentrated under reduced pressure in an evaporator.The resulting residue was purified by silica gel column chromatography,3,6-diphenylcarbazole (3.6 g, yield 74%) was obtained. |
73% | With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In toluene; for 10h;Heating / reflux; | Preparation of 3,6-diphenylcarbazole Reaction 5As depicted in Reaction 5, 15g (46 mmol) of 3,6-dibromocarbazole, 14g (92 mmol) of phenylboronic acid, K2CO3 (2 mol), Pd(PPh3)4 and toluene were refluxed for 10 hours. The reaction mixture was extracted with methylene chloride. The solvent was removed, and then the residue was purified by column chromatography (eluent: hexane) to give the title compound. Yield: 73%. MS (El) (Calcd. for C24H17N: 319.14, Found: 319). |
69% | With palladium diacetate; potassium carbonate; triphenylphosphine; In tetrahydrofuran; water;Reflux; | First, 100 g (310 mmol) of 3,6-dibromocarbazole (CAS 6825-20-3) E1 together with 189 g (1550 mmol) of phenylboronic acid (CAS 98-80-6) E2And 430 g (3.1 mol) of potassium carbonate was introduced into a 41 four-necked flask and dissolved in 1000 ml of tetrahydrofuran and 300 ml of water.After the mixture had been degassed for 30 minutes, 140 mg (0.62 mmol) of palladium acetate and 650 mg of triphenylphosphine were added, and the mixture was heated overnight under reflux.700 ml of water was then added to the batch and the aqueous phase was extracted several times with dichloromethane.The combined organic phases were dried over sodium sulfate and the solvent mixture was removed in vacuo.The resulting residue was dissolved in 1.5 mL of dichloromethane and filtered.The solvent was again removed in vacuo and the solid was washed with stirring with 600 mL of ethanol.Filtration and drying gave 68 g (0.21 mol, 69%) of desired material. |
68% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; at 80℃; | Carbazole (16.72g, 100mmol), NBS (59.4g, 210mmol), BPO (2.42g, 10mmol), methylene chloride (300 ml) at room temperature is injected into the medal and then 2000. When reaction is completed methylene chloride and water, NaHCO 3 extracted using aqueous solution obtained after the organic layer Na 2 SO 4 dried to, for the products and re-crystallized concentrating 23.73g (73%)obtained. Said product obtained (23.73g, 73.02mmol), phenylboronic acid (19.6g, 160.64mmol), Pd (PPh 3) 4, (8.44g, 7.3mmol), K 2 CO 3 (60.55g, 438.12mmol), THF (320 ml), water (160 ml) in 80 C agitation return current doesn't have any error frames, turns on the light. When reaction is completed for reducing temperature a high temperature to the normal temperature after methylene chloride and a water extraction of the organic layer obtained after MgSO 4 dried to, for the products and re-crystallized concentrating 15.9g (68%)obtained |
63% | With potassium carbonate;palladium diacetate; tris-(o-tolyl)phosphine; In 1,2-dimethoxyethane; water; at 80℃; for 3.5h; | As an example of a material according to the invention, a synthetic method of a compound represented by formula (59) 9-[4-(3, 6-diphenyl-N-carbazolyl)] phenyl- 10-phenylanthracene (hereinafter referred to as DPCzPA) below will be described. [0209][0210] This compound is prepared in accordance with the synthetic method shown below. Note that 9-phenyl-10-(4-bromophenyl) anthracene is prepared in the manner shown in Example 1. [0211]First, a synthetic method of 3,6-dibromocarbazole will be shown below. A mixture of 6.5 g (20.0 mmol) 3,6-dibromocarbazole, 5.0 g (41.0 mmol) of phenylboronic acid, 93 mg (0.40 mmol) of palladium acetate, 6.9 g (5.2 mmol) of potassium carbonate, water (25 mL), 610 mg of tri(ortho-tolyl) phosphine, and dimethoxyethane (50 mL) is heated to reflux at 80 0C for 3.5 three hours. After the reaction, the solution is rinsed with water, aqueous layer is extracted with toluene, and it is rinsed together with the organic layer using saturated salt solution, and thereafter EPO <DP n="67"/>dried with magnesium sulfate. After natural filtration, the filtrate is condensed to obtain 4.1 g of 3,6-di(2-phenyl-phenyl)-carbazoleas a white solid at a yield of 63 %. A synthetic scheme of 3,6-di(2-phenyl-phenyl)-carbazoleis shown below. |
63% | With potassium carbonate;palladium diacetate; Tri(p-tolyl)phosphine; In 1,2-dimethoxyethane; water; at 80℃; for 3.5h; | [Step 2] A synthesis method of 3,6-diphenylcarbazole is described.; A synthesis scheme of 3,6-diphenylcarbazole is represented by (a-2). [Show Image] 6.5 g of 3,6-dibromocarbazole (20 mmol), 5.0 g of phenylboron acid (41 mmol), 93mg of palladium(II) acetate (0.40 mmol), 610mg of tri(ortho-tolyl)phosphine (1.9mmol) were put into a 200mL three-necked flask, and then, the inside of the flask was substituted by nitrogen. Into the mixture, 50 ml of ethyleneglycol dimethylether (abbreviation : DME), and 25 mL of a pottassium carbonate water solution (2.0 mol/L) were added. This mixture was refluxed for 3.5 hours at 80 C. After the reaction, the reaction mixture was washed with water and a water layer was extracted with toluene. The extracted solution and an organic layer were washed with a saturated saline, and dried by magnesium sulphate. The mixture was naturally filtrated. The filtrate was condensed, and 4.1 g of an objective matter, a white powder solid was obtained at the yield 63 %. |
63% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In 1,4-dioxane; water; at 100℃; for 17h;Inert atmosphere; | A mixture of 3,6-dibromo-9H- carbazole (3.0 g, 9.2 mmol) (Aldrich), phenylboronic acid (3.0 g, 25 mmol) (Aldrich), tetrakis(triphenylphosphine)palladium (Pd(PPh3)4) (0.3 g, 0.26 mmol) (Frontier Scientific, Logan, UT) and potassium carbonate (6.5 g, 47 mmol) (Aldrich) in dioxane/water (75 mL/15 mL) (Aldrich) was degassed with bubbling argon (Airgas, San Marcos, CA) for 60 min and heated at about 100 C on a hot plate with a silicone oil bath for about 16 hours. Upon cooling to room temperature, the whole mixture was mixed with ethyl acetate (Aldrich) and rinsed with brine. Then, the organic mixture was dried over Na2S04 (Aldrich), loaded on silica gel (Grade 135) and purified by flash column using eluents of ethyl acetate/hexanes (10% to 30%) (Aldrich). After removal of solvents, a white solid (Compound OSC-3) was obtained (2.1 g, in 63% yield). Confirmed by 1 HNMR (Jeol Instruments, Peabody, MA). |
63% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In 1,4-dioxane; water; at 100℃; for 16h; | A mixture of 3,6-dibromo-9H-carbazole (3.0 g, 9.2 mmol), phenylboronic acid (3.0 g, 25 mmol), Pd(PPh3)4 (0.3 g, 0.26 mmol) and potassium carbonate (6.5 g, 47 mmol) in dioxane/water (75 mL/15 ml) was degassed and heated at about 100 C for about 16 hours. Upon cooling to room temperature, the whole was worked up with ethylacetate/brine, the organic was dried over Na2So4, loaded on silica gel and purified by flash column using eluents of ethyl acetate/hexane (10% to 30%). After removal of solvents, a white solid (Compound 11 ) was obtained (2.1 g, in 63% yield). |
48% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; at 80℃; for 10h;Inert atmosphere; | 30 g (92.3 mmol) of 3,6-dibromo-9H-carbazole was dissolved in 0.3 L of tetrahydrofuran (THF) in a nitrogenenvironment, 28 g (231 mmol) of phenyl boronic acid and 3.2 g (2.8 mmol) of tetrakis(triphenylphosphine)palladium wereadded thereto, and the mixture was agitated. 40.8 g (277 mmol) of potassium carbonate saturated in water was addedthereto, and the mixture was heated and refluxed at 80 C for 10 hours. When the reaction was terminated, water wasadded to the reaction solution, and the mixture was extracted with dichloromethane (DCM) and treated with anhydrousMgSO4 to remove moisture and then, filtered and concentrated under a reduced pressure. The obtained residue wasseparated and purified through flash column chromatography, obtaining a compound I-4 (14.3 g, 48 %). HRMS (70 eV, EI+): m/z calcd for C24H17N: 319.1361, found: 319.1. HRMS (70 eV, EI+): m/z calcd for C24H17N: 319.1361, found: 319.1. |
33% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In water; N,N-dimethyl-formamide; at 80℃; for 4h;Inert atmosphere; | General procedure: Under nitrogen protection system, 3-bromo -9H- carbazole 1.6mmol, tetrakistriphenylphosphine palladium 0.64mmol, anhydrous carbonatePotassium1.92mmol phenylboronic acid 1.92mmol, was dissolved in N, N- dimethylformamide: H2O = (15ml: 2ml) mixed solvent,80 stirring for 4h, after completion of the reaction, cooled to room temperature, the mixed solution was extracted with dichloromethane and water, the organic phase was dried over anhydrous magnesiumDried and evaporated, evaporated and the product after column chromatography to obtain 3-phenyl -9H- carbazole (A-1) 1.44mmol, 90% yield. The method of the same A-1, by column chromatography to obtain a white solid product 3,6-diphenyl -9H- carbazole (A-2), producingRate of 33%. |
With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; ethanol; water; for 18h;Heating / reflux; | EXAMPLE I Synthesis of 3,6-diphenyl carbazole In a 250 milliliter round bottom flask there were added 3,6-dibromocarbazole (5 grams), 50 milliliters of 1,2-dimethoxyethane, phenylboric acid (4.8 grams) dissolved in ethanol, and sodium carbonate (4.2 grams) dissolved in 20 milliliters of water.. After the resulting solution was saturated with argon, 0.49 gram of tetrakis-(triphenylphosphine) palladium was added.. The reaction mixture was heated to reflux and stirred for 18 hours.. The reaction flask was removed from the heat and cooled to room temperature, about 22 C. to about 25 C. The resulting solution was transferred to a separatory funnel, and the organic layer, which contained product, was separated from the aqueous phase.. After removal of the organic solvents by evaporation, the residue was subjected to column chromatography on silica gel to yield 3.5 grams of 3,6-diphenyl carbazole as colorless powder product.. Its chemical structure was confirmed by Proton IR analysis. | |
According to an ordinary process, 3,6-diphenylcarbazole was synthesized by reacting 3,6-dibromocarbazole and phenylboronic acid. | ||
With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In ethanol; toluene; | Manufacturing Example 8 A solution was prepared by adding 12.7 g of 3,6-dibromocarbazole, 10.0 g of phenylboronic acid, and 2.61 g of tetrakis(triphenylphosphine)palladium into 40 ml of ethanol and 170 ml of toluene. The resulting solution was blended with 90 ml of a 22% aqueous solution of sodium carbonate, and the mixture was heated under reflux in a nitrogen atmosphere for 5 hours. Insoluble materials were removed therefrom by performing hot filtration using a filter aid. Thereafter, the organic layer was separated from the aqueous layer, and the solvent was distilled off under a reduced pressure. After washing with water and drying were performed, a light brown powder was prepared. The resulting powder was subjected to a column chromatography treatment (eluant: toluene), followed by washing with hexane. Thus, 6.0 g of a colorless needle crystal of 3,6-diphenylcarbazole was produced. The physical properties thereof were as follows. melting point: 180.5 C. to 181.5 C. elemental analysis value (%): measured value/calculated value C 90.44/90.24 H 5.25/5.38 N 4.31/4.39 infrared absorption spectrum (KBr pellet method) NH stretching vibration: 3423, 3378 cm-1 | |
38 g | 3,6-dibromocarbazole (50 g, 0.154 mol), phenylboronic acid (41 g, 0.336 mol), 150ml water, 80g sodium carbonate, and 600ml dioxane were charged into a 2 liter pot with magnetic stirrer, reflux condenser and nitrogen inlet, and sparged with nitrogen for one hour. Pd2DBA3 (6g, 0.0066mol) and tri-t-butylphosphine (3 g, 0.0148mol) was quickly added from the drybox. The reaction was refluxed overnight. The next day water was added to the reaction mixture and methylene chloride extractions were preabsorbed to 141 g of activated silica and purified by column chromatography using methylene chloride/hexanes yielding 38 grams of product 3,6-diphenylcarbazole. |
Yield | Reaction Conditions | Operation in experiment |
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EXAMPLE II Synthesis of 4,4'-Bis-[9-(3,6-diphenylcarbazolyl)]-1-1,1'-biphenyl In a 50 milliliter round bottom flask there were added 4,4'-diiodo-1,1'-biphenyl (2.1 grams), 3,6-diphenyl carbazole (3.3 grams), potassium carbonate powder (1.4 grams), copper sulfate pentahydrate (0.06 grams), and 5 milliliters of tridecane. The resulting mixture was heated to 230° C. and stirred at this temperature under argon for 24 hours. After cooling to room temperature (~23° C.), the solids content resulting was ground into slurry, which slurry was then transferred to a filtration funnel, washed with hexane to remove the tridecane, followed by washing with 3 percent hydrochloric acid and water. The solid resulting was then dissolved in hot toluene. The insoluble residue was filtered hot. After cooling to room temperature, the product was crystallized from the solution to yield 2.3 grams of 4,4'-bis-[9-(3,6-diphenylcarbazolyl)]-1,1'-biphenyl as a yellowish powder. This compound had a melting point of 294° C. Its chemical structure was confirmed by proton analysis. |
Yield | Reaction Conditions | Operation in experiment |
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With sodium carbonate; In ethanol; water; | EXAMPLE I Synthesis of 3,6-Diphenyl Carbazole In a 250 milliliter round bottom flask there were added 3,6-dibromocarbazole (5 grams), 50 milliliters of 1,2-dimethoxyethane, phenylboric acid (4.8 grams) dissolved in ethanol, and sodium carbonate (4.2 grams) dissolved in 20 milliliters of water. After the resulting solution was saturated with argon, 0.49 gram of tetrakis-(triphenylphosphine) palladium was added. The reaction mixture was heated to reflux and stirred for 18 hours. The reaction flask was removed from the heat and cooled to room temperature, about 22° C. to about 25° C. The resulting solution was transferred to a separatory funnel, and the organic layer, which contained product, was separated from the aqueous phase. After removal of the organic solvents by evaporation, the residue was subjected to column chromatography on silica gel to yield 3.5 grams of 3,6-diphenyl carbazole as colorless powder product. Its chemical structure was confirmed by Proton IR analysis. |
Yield | Reaction Conditions | Operation in experiment |
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33% | 3.6-Diphenyl-9H-carbazole The same method as employed in the preparation of Intermediate 7 but starting from 3,6-dibromo-9H-carbazole gave after flash chromatography the title compound as a white solid in a 33percent yield. M.p.: 145-147 °C. 1H NMR (CDCl3, 300 MHz) delta 8.32 (d, 2H,J= 1.2 Hz), 8.09 (s, 1H), 7.72-7.66 (m, 6H), 7.50-7.43 (m, 6H), 7.35-7.30 (m, 2H). |
Yield | Reaction Conditions | Operation in experiment |
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71% | With sodium t-butanolate;tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; In toluene; at 110℃; for 10h; | Next, a synthetic method of DPCzPA by coupling reaction of 3, 6-diphenylcarbazole and 9-phenyl-10-(4-bromophenyl) anthracene will be shown. A mixture of 819 mg (2.0 mmol) of 9-phenyl-10-(4-bromophenyl) anthracene, 666 mg (2.1 mmol) of 3, 6-diphenylcarbazole, 14 mg (0.02 mmol) of dibenzylidine palladium (II), 1.0 g (10 mmol) of t-butoxy sodium, 0.1 mL of tri(t-butyl) phosphine, 20 mL of toluene is refluxed at 110 0C for 10 hours. After the reaction, the solution is rinsed with water, aqueous layer is extracted with toluene, and it is rinsed together with the organic layer using saturated salt solution, and thereafter dried with magnesium sulfate. An oily product obtained by natural filtration and condensation is dissolved in toluene, and filtered through celite, Florisil, and alumina. The filtrate is condensed, and purified by silica gel column chromatography (toluene). Recrystallization is carried out using dichloromethane and hexane to obtain 937 mg of DPCzPA at a yield of 71 percent. A synthetic scheme of DPCzPA by coupling reaction of 3, 6-diphenylcarbazole and 9-phenyl-10-(4-bromophenyl) anthracene is shown below. |
Yield | Reaction Conditions | Operation in experiment |
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69% | A solution was prepared by stirring tris(dibenzylideneacetone)dipalladium(0) chloroform complex (0.104 g), tri(t-butyl)phosphine (0.162 g), and toluene (5 ml) under nitrogen atmosphere at 60°C for 10 min. This solution was added to a mixture heated to 60°C of 2,6-bis(3-bromophenyl)-4-phenylpyridine (1.30 g), <strong>[56525-79-2]3,6-diphenylcarbazole</strong> (2.68 g), t-butoxysodium (1.18 g), and toluene (25 ml) under nitrogen atmosphere, and the resulting mixture was stirred at 110°C for 8 hr. The mixture was allowed to cool to room temperature and concentrated, and methanol was added thereto. The resulting precipitate was collected by filtration and washed with a water/methanol mixture solution. The precipitate was purified by silica-gel column chromatography (n-hexane/toluene = 1/1) and washed with an N,N-dimethylformamide/ethanol mixture solution and a methylene chloride/methanol mixture solution and then dried under reduced pressure to obtain a target compound 24 (1.81 g, yield: 69percent) as a white crystal. This white crystal was purified by sublimation to yield 1.35 g of a white solid. The white solid was confirmed to be a target compound 24 by DEI-MS (m/z = 924 (M+)). The compound had a vaporization temperature of 570°C and a glass transition temperature of 172°C. The melting point was not observed. |
Yield | Reaction Conditions | Operation in experiment |
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6% | With potassium phosphate; copper(l) iodide; In 1,4-dioxane; for 15h;Heating / reflux; | Preparation of 4'-naphthyl-<strong>[56525-79-2]3,6-diphenylcarbazole</strong> Reaction 6As depicted in Reaction 6, a solution of 1Og (31.3 mmol) of carbazole, 13.5g (31.3 mmol) of 1,4-dibromonaphthalene, CuI, diaminohexane and K3PO4 in dioxane was refluxed for 15 hours. After completion of the reaction, the reaction mixture was <n="32"/>extracted with ethyl acetate. After the solvent was removed under reduced pressure, the residue was purified by column chromatography to give the title compound. The product was collected by filtration under reduced pressure and dried. Yield: 6percent. MS (El) (Calcd. for C34H22BrN: 523.09, Found: 523). |
Yield | Reaction Conditions | Operation in experiment |
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28% | With potassium phosphate;tris-(dibenzylideneacetone)dipalladium(0); DavePhos; In toluene; at 100℃; for 24h;Inert atmosphere; | b) 4.00 g of S-9 (12.5 mmol), 3.75 g of S-1 (5.69 mmol), 0.40 g (1.02 mmol) 2-of dicyclo- hexylphosphino-2'-(N,N-dimethylamino)biphenyl and 3.38 g (15.93 mmol) of potassium phosphate are stirred under argon in 47 ml toluene. 0.31 g (0.34 mmol) of tris(dibenzylidene- acetone) palladium(ll) are added and the reaction is stirred at 1000C for 24h. At room temperature, a 1 percent aqueous solution of NaCN is added to the medium which is boiled for 20 min. Ethyl acetate is added and the organic phase is washed with water, dried over magnesium sulfate, filtered and evaporated under reduced pressure. The crude product is purified by chromatography over silica gel (dichloromethane/cyclohexane 1 :1 ) and further purified by preparative HPLC to give 1.6 g of a white solid (28percent). 1H NMR (CDCI3, 300 MHz) 8.42 (m, 4H), 7.77-7.69 (m, 16H), 7.56-7.44 (m, 12H), 7.41-7.30 (m, 8H), 7.17-7.13 (m, 6H), 6.99-6.96 (m, 2H). |
Yield | Reaction Conditions | Operation in experiment |
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73% | In toluene; | Preparation of 3,6-diphenylcarbazole As depicted in Reaction 5, 15 g (46 mmol) of 3,6-dibromocarbazole, 14 g (92 mmol) of phenylboronic acid, K2CO3 (2 mol), Pd(PPh3)4 and toluene were refluxed for 10 hours. The reaction mixture was extracted with methylene chloride. The solvent was removed, and then the residue was purified by column chromatography (eluent:hexane) to give the title compound. Yield: 73percent. MS (EI) (Calcd. for C24H17N, 319.14. Found: 319). |
Yield | Reaction Conditions | Operation in experiment |
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96% | With sodium t-butanolate;tri-tert-butyl phosphine; bis(dibenzylideneacetone)-palladium(0); In water; xylene; at 140℃; for 6h;Inert atmosphere; | Method of Synthesizing 2-[4-(3,6-Diphenyl-9H-carbazol-9-yl)phenyl]-3-phenylquinoxaline (abbreviation: Cz1PQ-III)First, into a 200-mL three-neck flask were placed 2.2 g (6.0 mmol) of 2-(4-bromophenyl)-3-phenylquinoxaline, 1.9 g (6.0 mmol) of <strong>[56525-79-2]3,6-diphenyl-9H-carbazole</strong>, and 1.1 g (12.0 mmol) of sodium tert-butoxide.The air in the flask was replaced with nitrogen, and 60 mL of xylene was placed into this flask.The mixture was degassed by stirring under reduced pressure.To this mixture were added 0.2 mL of tri(tert-butyl)phosphine and 71 mg (0.12 mmol) of bis(benzylideneacetone)palladium(0).This mixture was stirred under a nitrogen stream at 140° C. for 6 hours.After the predetermined time had elapsed, water was added to the obtained mixture, and the mixture was separated into an organic layer and an aqueous layer.Organic substances were extracted with toluene from the aqueous layer.The solution of the obtained extract was combined with the organic layer, and the mixture was washed with saturated brine and dried with magnesium sulfate.The obtained mixture was gravity filtered, and the filtrate was concentrated to give an oily substance.This oily substance was purified by silica gel column chromatography (with a developing solvent of toluene), followed by recrystallization from toluene, whereby 3.0 g of a yellow powder of Cz1PQ-III, which is the substance to be produced, was obtained in 81percent yield.By a train sublimation method, 3.2 g of the obtained yellow powder of Cz1PQ-III, which is the substance to be produced, was sublimated and purified.In the sublimation and the purification, the yellow powder was heated at 300° C. under a pressure of 2.3 Pa with a flow rate of argon gas of 5 mL/min.After that, 3.1 g of a yellow powder of Cz1PQ-III, which is the substance to be produced, was obtained in 96percent yield.The synthesis scheme of Cz1PQ-III is illustrated in the following (a-3).Further, 1H NMR data of the obtained compound are as follows: 1H NMR (CDCl3, 300 MHz): delta=7.34-7.38 (m, 2H), 7.43-7.53 (m, 9H), 7.60-7.86 (m, 14H), 8.22-8.26 (m, 2H), 8.40 (d, J=1.5 Hz, 2H). |
Yield | Reaction Conditions | Operation in experiment |
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83% | With tri-tert-butyl phosphine; sodium t-butanolate;bis(dibenzylideneacetone)-palladium(0); In hexane; toluene; at 80℃; for 5h;Inert atmosphere; | Example 5In Example 5, a method for synthesizing 9-[4-(benzoxazol-2-yl)phenyl]-<strong>[56525-79-2]3,6-diphenyl-9H-carbazole</strong> (abbreviation: CzBOxIII) represented by Structural Formula (170), which is one of the benzoxazole derivatives of the present invention, will be specifically described. Synthesis of 9-(4-[Benzoxazol-2-yl)phenyl]-<strong>[56525-79-2]3,6-diphenyl-9H-carbazole</strong>A synthesis scheme of 9-(4-[benzoxazol-2-yl)phenyl]-<strong>[56525-79-2]3,6-diphenyl-9H-carbazole</strong> is illustrated in (G-1). In a 100 mL three-neck flask were put 1.0 g (3.7 mmol) of 2-(4-bromophenyl)benzoxazole, 1.2 g (3.7 mmol) of 3,6-diphenyl-9H-carabazole, and 0.77 g (8.0 mmol) of sodium tert-butoxide. The atmosphere in the flask was replaced with nitrogen. To this mixture were added 15 mL of toluene and 0.10 mL of a 10percent hexane solution of tri(tert-butyl)phosphine. This mixture was degassed by reducing the pressure in the flask by using an aspirator. After that, the atmosphere in the flask was replaced with nitrogen. To this mixture was added 0.030 g (0.052 mmol) of bis (dibenzylideneacetone)palladium(0), followed by stirring under a nitrogen stream at 80° C. for 5 hours. After that, toluene was added to this mixture, and this suspension was suction filtered through Celite 545 (produced by Kishida Chemical Co., Ltd., Catalog No. 020-14815), whereby a filtrate was obtained.The filtrate obtained was washed with a saturated aqueous sodium hydrogen carbonate solution and saturated brine in that order. After that, magnesium sulfate was added to the organic layer to dry it. Next, this mixture was suction filtered. The resulting filtrate was concentrated to give a compound, which was then purified by silica gel column chromatography. The column chromatography was performed by using toluene as a developing solvent. The fraction obtained was concentrated to give a solid. This solid was recrystallized with a mixed solvent of dichloromethane and ethanol to give 1.8 g of a white powdered solid in a yield of 95percent.Sublimation purification of 1.8 g of the white solid obtained was performed by a train sublimation method. Under a reduced pressure of 4.0 Pa and with an argon flow rate of 5 mL/min, the sublimation purification was performed at 280° C. for 21 hours, whereby 1.5 g of the resulting substance was obtained in a yield of 83percent.The compound obtained through the above synthesis method was measured by a nuclear magnetic resonance (NMR) method. The following are the measurement data: 1H NMR (CDCl3, 300 MHz): delta=7.32-7.86 (m, 20H), 8.41 (sd, J=2.0 Hz, 2H), 8.53 (d, J=8.8 Hz, 2H) |
Yield | Reaction Conditions | Operation in experiment |
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31% | With 18-crown-6 ether; potassium carbonate;copper; In 1,2-dichloro-benzene; at 200℃; for 48h;Inert atmosphere; | Into a reactor, 6.1 g (19 mmoles) of <strong>[56525-79-2]3,6-diphenylcarbazole</strong>, 6.3 g (23 mmoles) of Intermediate Compound (A), 0.2 g of copper powder, 1.7 g of 18-crown-6 and 2.9 g (21 mmoles) of potassium carbonate were placed and 30 ml of o-dichlorobenzene was added as the solvent. The resultant mixture was heated at 200° C. in a silicone oil bath under a nitrogen stream and the reaction was allowed to proceed for 48 hours. After the reaction was completed, the reaction mixture was filtered under suction before being cooled and the obtained filtrate was concentrated using an evaporator. To the obtained oily product, 30 ml of methanol was added. The formed solid substance was separated by filtration under a reduced pressure and a gray solid substance was obtained. The obtained solid substance was recrystallized from benzene and 3.0 g (the yield: 31percent) of white crystals were obtained. It was confirmed by 90 MHz 1H-NMR and FD-MS (the field desorption mass analysis) that the obtained crystals were the target substance (A5). The result of the measurement by FD-MS is shown in the following:FD-MS calcd. for C37H25N3=511; found: m/z=511 (M+, 100) |
Yield | Reaction Conditions | Operation in experiment |
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33% | With 18-crown-6 ether; potassium carbonate;copper; In 1,2-dichloro-benzene; at 200℃; for 48h;Inert atmosphere; | Into a reactor, 6.1 g (19 mmoles) of <strong>[56525-79-2]3,6-diphenylcarbazole</strong>, 8.9 g (23 mmoles) of Intermediate Compound (C), 0.2 g of copper powder, 1.7 g of 18-crown-6 and 2.9 g (21 mmoles) of potassium carbonate were placed and 30 ml of o-dichlorobenzene was added as the solvent. The resultant mixture was heated at 200° C. in a silicone oil bath under a nitrogen stream and the reaction was allowed to proceed for 48 hours. After the reaction was completed, the reaction mixture was filtered under suction before being cooled and the obtained filtrate was concentrated using an evaporator. To the obtained oily product, 30 ml of methanol was added. The formed solid substance was separated by filtration under a reduced pressure and a gray solid substance was obtained. The obtained solid substance was recrystallized from benzene and 3.9 g (the yield: 33percent) of white crystals were obtained. It was confirmed by 90 MHz 1H-NMR. and FD-MS that the obtained crystals were the target substance (A3). The result of the measurement by FD-MS is shown in the following:FD-MS calcd. for C45H30N4=626; found: m/z=626 (M+, 100) |
Yield | Reaction Conditions | Operation in experiment |
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With potassium carbonate; In hexane; dichloromethane; | Example 9 Synthesis of Carbazole Derivative 9 3,6-Diphenylcarbazole (2.80 g, 8.77 mmol), 1-bromo-3-iodobenzene (22.18 g, 87.7 mmol), copper powder (0.279 g) and potassium carbonate (4.85 g) were mixed together, and the mixture was heated in a nitrogen atmosphere at 190° C. for 9 hours. The resultant mixture was cooled to room temperature and diluted with methylene chloride, followed by washing with water and drying, to thereby obtain a pale brown liquid. Next, the obtained liquid is purified through silica gel column chromatography using a solvent mixture of methylene chloride/hexane (2/3 by volume), to thereby obtain 3.59 g of 9-(3-bromophenyl)-<strong>[56525-79-2]3,6-diphenylcarbazole</strong>. | |
3.59 g | With copper; potassium carbonate; at 190℃; for 9h;Inert atmosphere; | 3,6-Diphenylcarbazole (2.80 g, 8.77 mmol), 1-bromo-3-iodobenzene (22.18 g, 87.7 mmol), copper powder (0.279 g) and potassium carbonate (4.85 g) were mixed together, and the mixture was heated in a nitrogen atmosphere at 190° C. for 9 hours. The resultant mixture was cooled to room temperature and diluted with methylene chloride, followed by washing with water and drying, to thereby obtain a pale brown liquid. Next, the obtained liquid is purified through silica gel column chromatography using a solvent mixture of methylene chloride/hexane (2/3 by volume), to thereby obtain 3.59 g of 9-(3-bromophenyl)-<strong>[56525-79-2]3,6-diphenylcarbazole</strong>. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
27 g | With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene;Reflux; | Pd2DBA3 (1 .2124 g, 1 .32 mmol), tri-t-butylphosphine (0.5334 g, 2.6 mmol), 210 ml toluene, 4-chloro-2-(4-t-butylphenyl) pyridine (12.6 g, 0.0512 mol), <strong>[56525-79-2]3,6-diphenylcarbazole</strong> (19.6 g, 0.0613 mol) were combined in the drybox followed by, sodium-t-butoxide (5.89 g, 0.0613 mol). The mixture was refluxed overnight. The reaction mixture was preabsorbed and purified by silica column chromatography with methylene chloride/hexanes. Product cuts were concentrated to 27 grams of ligand. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
50.7% | With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; for 12h;Heating; | 10 g (1 eq, 0.0293 mol) of Intermediate H, and 10.28 g (1.1 eq, 0.0322 mol) <strong>[56525-79-2]3,6-diphenyl-9H-carbazole</strong> were dissolved in 500 ml of toluene. 0.56 g (0.02 eq, 0.0005 mmol) of Pd2(dba)3, 6.5 g (1.2 eq, 0.035 mol) of Na(t-bu)O, 0.47 g (0.08ea, 0.0028 mmol) of P(t-Bu)3 were added to the solution, and then heated while stirring for about 12 hours. [0152] The reaction solution from the completed reaction was filtered through Celite, and the filtered product was separated by column chromatography to obtain 9.12 g of Intermediate K with a yield of about 50.7percent. [0153] GC-Mass (calc.; 614.09 g/mol. found; 613 g/mol). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
63.7% | With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; for 12h;Heating; | 20 g (1 eq, 0.057 mol) of Intermediate A, and 20.12 g (1.1 eq, 0.063 mol) <strong>[56525-79-2]3,6-diphenyl-9H-carbazole</strong> were dissolved in 400 ml of toluene. 0.97 g (0.02 eq, 0.00114 mmol) of Pd2(dba)3, 8.4 g (1.2 eq, 0.068 mol) of Na(t-bu)O, 0.13 g (0.08ea, 0.0045 mmol) of P(t-Bu)3 were added to the solution, and then heated while stirring for about 12 hours. [0133] The reaction solution from the completed reaction was filtered through Celite, and the filtered product was separated by column chromatography to obtain 22.8 g of Intermediate D with a yield of about 63.7percent. [0134] GC-Mass (calc.; 629.17 g/mol. found; 628 g/mol). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | Synthesis of Comparative Compound 1. 3,6-Diphenyl-9H-carbazole (4.00 g, 12.52 mmol) was dissolved in anhydrous DMF (170 mL) and treated with NaH (0.751 g, 18.79 mmol, 60percent dispersion in mineral oil) while stirring vigorously at room temperature providing yellow solution. Once H2 evolution stopped, the solution was stirred for 1 hour, and then treated with 2-chloro-4,6-diphenyl-1,3,5-triazine (5.03 g, 18.79 mmol), and left stirred overnight at room temperature. After stirring for ?30 minutes, reaction solution had significant white precipitate swirling around. The crude mixture was quenched with water and filtered. The white precipitate was washed with water, MeOH, and EtOH. The material was recrystallized from toluene (400 mL) to obtain the target, Comparative Compound 1 with 99.86percent purity. One more recrystallization from toluene gave a purity of 100percent to afford 6.0 g (87percent yield). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With tributylphosphine; bis(dibenzylideneacetone)-palladium(0); sodium t-butanolate; In toluene; at 100℃; for 16h;Inert atmosphere; | 11 g (34.4 mmol) of the intermediate I-4 was dissolved in 0.11 L of toluene in a nitrogen environment, intermediate I-3(11.5g, 36.2mmol), 0.95 g (1.03 mmol) of tris(dibenzylideneacetone)dipalladium (0), 0.83 g (4.12 mmol) of tris-tert butylphosphine and 3.97 g (41.3 mmol) of sodium tertiarybutoxide were sequentially added thereto, and the mixture was heated and refluxed at 100 °C for 16 hours. When the reaction was terminated, water was added to the reaction solution, and the mixture was extracted with dichloromethane (DCM) and treated with anhydrous MgSO4 to remove moisture and then, filtered and concentrated under a reduced pressure. The obtained residue was separated and purified through flash column chromatography, obtaining a compound A-1 (14.5 g, 70 percent). HRMS (70 eV, EI+): m/z calcd for C45H31NO: 601.2406, found: 602.2. Elemental Analysis: C, 90 percent; H, 5 percent |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With tributylphosphine; bis(dibenzylideneacetone)-palladium(0); sodium t-butanolate; In toluene; at 100℃; for 12h;Inert atmosphere; | 10 g (31.3 mmol) of the intermediate I-4 was dissolved in 0.1 L of toluene in a nitrogen environment, 10.5 g (32.9 mmol) of the intermediate I-7, 0.86 g (0.94 mmol) of tris(dibenzylideneacetone)dipalladium (0), 0.76 g (3.76 mmol) of tris-tertiarybutylphosphine, and 3.61 g (37.6 mmol) of sodium tertiarybutoxide were sequentially added thereto, and the mixture was heated and refluxed at 100 °C for 12 hours. When the reaction was terminated, water was added to the reaction solution, and the mixture was extracted with dichloromethane (DCM) and treated with anhydrous MgSO4 to remove moisture and then, filtered and concentrated under a reduced pressure. The obtained residue was separated and purified through flash column chromatography, obtaining a compound A-5 (16.6 g, 88 percent). HRMS (70 eV, EI+): m/z calcd for C45H31 NO: 601.2406, found: 601.2. Elemental Analysis: C, 90 percent; H, 5 percent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With tributylphosphine; bis(dibenzylideneacetone)-palladium(0); sodium t-butanolate; In toluene; at 100℃; for 6h;Inert atmosphere; | 10 g (31.3 mmol) of the intermediate I-4 was dissolved in 0.1 L of toluene in a nitrogen environment, 0.86 g (0.94 mmol) of tris(dibenzylideneacetone)dipalladium (0), 0.76 g (3.76 mmol) of tris-tertiarybutylphosphine, and 3.61 g (37.6 mmol) of sodium tertiarybutoxide were sequentially added thereto, and the mixture was heated and refluxed at 100 °C for 6 hours. When the reaction was terminated, water was added to the reaction solution, and the mixture was extracted with dichloromethane (DCM) and treated with anhydrous MgSO4 to remove moisture and then, filtered and concentrated under a reduced pressure. The obtained residue was separated and purified through flash column chromatography, obtaining a compound A-7 (15.9 g, 82 percent). HRMS (70 eV, EI+): m/z calcd for C45H31 NS: 617.2177, found: 617.2. Elemental Analysis: C, 87 percent; H, 5 percent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With tributylphosphine; bis(dibenzylideneacetone)-palladium(0); sodium t-butanolate; In toluene; at 100℃; for 12h;Inert atmosphere; | 10 g (31.3 mmol) of the intermediate I-4 was dissolved in 0.1 L of toluene in a nitrogen environment, 14.6 g (32.9 mmol) of the intermediate I-13, 0.86 g (0.94 mmol) of tris(dibenzylideneacetone)dipalladium (0), 0.76 g (3.76 mmol) of tris-tertiarybutylphosphine and 3.61 g (37.6 mmol) of sodium tertiarybutoxide were sequentially added thereto, and the mixture was heated and refluxed at 100 °C for 12 hours. When the reaction was terminated, water was added to the reaction solution, and the mixture was extracted with dichloromethane (DCM) and treated with anhydrous MgSO4 to remove moisture and then, filtered and concentrated under a reduced pressure. The obtained residue was separated and purified through flash column chromatography, obtaining a compound A-88 (21.6 g, 95 percent). HRMS (70 eV, EI+): m/z calcd for C55H35NO: 725.2719, found: 725.3. Elemental Analysis: C, 91 percent; H, 5 percent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With tributylphosphine; bis(dibenzylideneacetone)-palladium(0); sodium t-butanolate; In toluene; at 100℃; for 24h;Inert atmosphere; | 10 g (31.3 mmol) of the intermediate I-4 was dissolved in 0.1 L of toluene in a nitrogen environment, 10.5 g (32.9 mmol) of the intermediate I-16, 0.86 g (0.94 mmol) of tris(dibenzylideneacetone)dipalladium (0), 0.76 g (3.76 mmol) of tris-tertiarybutylphosphine, and 3.61 g (37.6 mmol) of sodium tertiarybutoxide were sequentially added thereto, and the mixture was heated and refluxed at 100 °C for 24 hours. When the reaction was terminated, water was added to the reaction solution, and the mixture was extracted with dichloromethane (DCM) and treated with anhydrous MgSO4 to remove moisture and then, filtered and concentrated under a reduced pressure. The obtained residue was separated and purified through flash column chromatography, obtaining a compound A-1 (17.0 g, 90 percent). HRMS (70 eV, EI+): m/z calcd for C45H31 NO: 601.2406, found: 601.2. Elemental Analysis: C, 90 percent; H, 5 percent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With tributylphosphine; bis(dibenzylideneacetone)-palladium(0); sodium t-butanolate; In toluene; at 100℃; for 48h;Inert atmosphere; | 10 g (31.3 mmol) of the intermediate I-4 was dissolved in 0.12 L of toluene in a nitrogen environment, 13.0 g (32.9 mmol) of the intermediate I-33, 0.86 g (0.94 mmol) of tris(dibenzylideneacetone)dipalladium (0), 0.76 g (3.76 mmol) of tris-tert butylphosphine and 3.61 g (37.6 mmol) of sodium tertiarybutoxide were sequentially added thereto, and the mixture was heated and refluxed at 100 °C for 48 hours. When the reaction was terminated, water was added to the reaction solution, and the mixture was extracted with dichloromethane (DCM) and treated with anhydrous MgSO4 to remove moisture and then, filtered and concentrated under a reduced pressure. The obtained residue was separated and purified through flash column chromatography, obtaining a compound D-151 (18.0 g, 85 percent). HRMS (70 eV, EI+): m/z calcd for C51H35NO: 677.2719, found: 677.3. Elemental Analysis: C, 90 percent; H, 5 percent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With tributylphosphine; bis(dibenzylideneacetone)-palladium(0); sodium t-butanolate; In toluene; at 100℃; for 37h;Inert atmosphere; | 10 g (31.3 mmol) of the intermediate I-4 was dissolved in 0.12 L of toluene in a nitrogen environment, 13.5 g (32.9 mmol) of the intermediate I-38, 0.86 g (0.94 mmol) of tris(dibenzylideneacetone)dipalladium (0), 0.76 g (3.76 mmol) of tris-tert butylphosphine and 3.61 g (37.6 mmol) of sodium tertiarybutoxide were sequentially added thereto, and the mixture was heated and refluxed at 100 °C for 37 hours. When the reaction was terminated, water was added to the reaction solution, and the mixture was extracted with dichloromethane (DCM) and treated with anhydrous MgSO4 to remove moisture and then, filtered and concentrated under a reduced pressure. The obtained residue was separated and purified through flash column chromatography, obtaining a compound D-154 (19.3 g, 89 percent). HRMS (70 eV, EI+): m/z calcd for C51 H35NS: 693.2490, found: 693.2. Elemental Analysis: C, 88 percent; H, 5 percent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium carbonate; In 1,4-dioxane; dichloromethane; water; | (2a) Preparation of 3,6-diphenylcarbazole 25g 3,6-dibromocarbazole and 20.5g phenylboronic acid were mixed in 150mL water and 300mL dioxane in glove box. Stir vigorously and add 45g sodium carbonate. Finally add 3g Pd2DBA3 and 1.5g tri-t-butylphosphine. Stir and reflux overnight then cool and remove from glove box. Add water to precipitate white solid then filter and collect. Dissolve in dichloromethane and chromatograph on silica eluting with DCM:hexanes 1:2 and elute product as colorless solution which on evaporation and washing with hexanes gives the desired product in ~80percent yield as a fluffy white solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1.4 g | With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; tris-(dibenzylideneacetone)dipalladium(0); sodium t-butanolate; In m-xylene;Reflux; Inert atmosphere; | 3,6-Diphenyl-9H-carbazole (3.0 g, 9.39 mmol), 4-chlorobenzo[4,5]thieno[3,2-d]pyrimidine (2.280 g, 10.33 mmol), sodium 2-methylpropan-2-olate (2.257 g, 23.48 mmol), Pd2dba3 (0.430 g, 0.470 mmol), and dicyclohexyl(2',6'-dimethoxy-[1,1'-biphenyl]-2-yl)phosphine (SPhos) (0.386 g, 0.939 mmol) were charged into a 250-mL round-bottom-flask (RBF), diluted in m-xylene (94 ml), degassed and heated to reflux overnight. Then the mixture was cooled down to room temperature and was diluted by DCM, filtered through a pad of Celite and washed with DCM. The solvent was evaporated and the crude solid was purified by column chromatography on silica, eluted with 30-50percent DCM in heptanes gradient mixture, then by 50/45/5 (v/v/v) DCM/heptanes/ethyl acetate mixture. After evaporation of the solvent, the yellow solid is triturated in methanol, then the solid was crystallized from heptanes/toluene mixture to provide 1.4 g of the pure Compound 1 (4-(3,6-diphenyl-9H-carbazol-9-yl) benzo [4,5] thieno [3,2-d]pyrimidine). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
31.1% | With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; tris-(dibenzylideneacetone)dipalladium(0); sodium t-butanolate; In 5,5-dimethyl-1,3-cyclohexadiene; at 140℃; | (5) A mixture of 4-chloro-2-phenylbenzofuro[3,2-d]pyrimidine (2 g, 7.12 mmol), <strong>[56525-79-2]3,6-diphenyl-9H-carbazole</strong> (2.276 g, 7.12 mmol) and sodium 2-methylpropan-2-olate (1.369 g, 14.25 mmol) in xylene (120 mL) was degassed , then Pd2(dba)3 (0.130 g, 0.142 mmol) and dicyclohexyl(2',6'-dimethoxy-[1,1'-biphenyl]-2-yl)phosphine (SPhos) (0.234 g, 0.570 mmol) were then added and heated at 140 °C overnight. The reaction solution was purified by silica gel column chromatography using heptane/DCM/ethyl acetate 80/20/2 to 4/6/0.2 (v/v/v) gradient mixture to afford Compound 6987 as a light yellow solid. (1.25 g, 31.1percent). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | (2) 3,6-Diphenyl-9H-carbazole (1.117 g, 3.50 mmol)was dissolved in DMF (15 mL) and a 60percent dispersion of sodium hydride (0.168 g, 4.20 mmol) was added as one portion. The reaction solution was stirred under nitrogen for 30 minutes at room temperature, then 4-chloro-2-phenylbenzo[4,5]thieno[3,2-d]pyrimidine (0.83 g, 2.80 mmol) was added in one portion and stirring continued at room temperature for 2 hrs. The reaction solution was quenched with water, filtered and triturated three times with EtOH. The product was recrystallized from toluene/EtOH yielding 1.1g (68percent) of the title compound 99.9percent pure. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; tris-(dibenzylideneacetone)dipalladium(0); sodium t-butanolate; In 5,5-dimethyl-1,3-cyclohexadiene;Inert atmosphere; Reflux; | 3,6-Diphenyl-9H-carbazole (2.000 g, 6.26 mmol) and 1-chlorobenzo[4,5]thieno[2,3-c]pyridine (1.376 g, 6.26 mmol) were dissolved in xylene (150 ml), then sodium 2-methylpropan-2-olate (1.204 g, 12.52 mmol), Pd2(dba)3 (120 mg) and dicyclohexyl(2',6'-dimethoxy-[1,1'-biphenyl]-2-yl)phosphine (0.129 g, 0.313 mmol) were added to the reaction solution. The reaction solution was degassed and heated to reflux under N2 atm. overnight. Then it was cooled down to room temperature, filtered through celite pad and evaporated. The residue was subjected to column chromatography on silica gel, eluted with hexane/DCM 9/1 to 1/1 (v/v) gradient mixture, providing white solid, which was crystallized from hexane/DCM. 1-(3,6-Diphenyl-9H-carbazol-9-yl)benzo[4,5]thieno[2,3-c]pyridine to form white crystals of the Comparison Compound 6961 (2.7 g, 5.37 mmol, 86 percent yield). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium carbonate; In dichloromethane; N,N-dimethyl-formamide; | Example 9 2-{3-Phenyl-6-[(E)-((Z)-1-propenyl)buta-1,3-dienyl]carbazol-9-yl}-8a-azabenzo[fg]naphthacene-8,9-dione 32 g (102-4 mmol) of <strong>[56525-79-2]3,6-diphenyl-9H-carbazole</strong>, 42 g (112 mmol) of 2-bromo-8a-azabenzo[fg]naphthacene-8,9-dione and 2.3 (10-2 mmol) of 1,3-di[2-pyridyl]-1,3-propanedione, 28.3 g (204 mmol) of potassium carbonate and 1.9 g (10.2 mmol) of copper iodide are stirred under reflux in 1000 ml of DMF for 90 h. The solution is diluted with water and extracted twice with ethyl acetate, the combined organic phases are dried over Na2SO4 and evaporated in a rotary evaporator and purified by chromatography (EtOAc/hexane:2/3). The residue is recrystallised from toluene and from dichloromethane and finally sublimed in a high vacuum, purity is 99.9percent. The yield is 46 g (75 mmol), corresponding to 68percent of theory. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
38.5% | Synthesis of 3,6-Diphenyl-9-tosyl-9H-carbazole 3-Bromo-9-tosyl-9H-carbazole (4.20 g, 13.2 mmol), <strong>[56525-79-2]3,6-diphenyl-9H-carbazole</strong> (4.87 g, 12.5 mmol) and copper(I) oxide (4.54 g, 31.8 mmol) were added to dodecylbenzene (12.3 mL), and the mixture was heated to 220°C under a nitrogen gas environment for 20 hours. After completing the reaction, copper (I) oxide was removed by filtration, and then the filtrate was purified by silica gel column chromatography (developing solvent: hexane/dichloromethane = 50/50) (yield amount: 3.24 g (5.07 mmol), yield: 38.5percent). 1H-NMR (500 MHz, CDCl3) : delta (ppm) 8.58 (d, J = 8.5 Hz, 1H), 8.43 (d, J = 1.5 Hz, 2H), 8.41 (d, J = 8.5 Hz, 1H), 8.14 (d, J = 2.0 Hz, 1H), 7.92 (d, J = 7.5 Hz, 1H), 7.84 (d, J = 8.5 Hz, 2H), 7.75-7.72 (m, 6H), 7.68 (dd, J = 1.5 Hz, J=2.0Hz, 2H), 7.59-7.56 (m, 1H), 7.52-7.45 (m, 5H), 7.42-7.39 (m, 1H), 7.37-7.35 (m, 2H), 2.34 (s, 3H) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
40% | With sodium hydride; In tetrahydrofuran; mineral oil; at 0 - 60℃; for 15.5h; | To a mixture of 1 ,2,4,5- tetrafluoro-3,6-bis(trifluoromethyl)benzene (0.286 g, 1 .0 mmol) (Synquest Laboratory, Alachua, FL), 3,6,-diphenyl-9/-/-carbazole (1 .5 g, 4.5 mmol) (TCI America, Portland, OR) in anhydrous tetrahydrofuran (THF) (15 mL) (Aldrich, St Louis, MO), was added sodium hydride (60percent in mineral oil, 0.20 g, 5 mmol) (Aldrich) at 0 °C. The resulting mixture was stirred at 0 °C for 30 min, then 60 °C for 15 hours on a hot plate with a silicone oil bath. Yellow precipitate formed, and the mixture was diluted with 200 mL of THF, washed with brine, dried over Na2S04 (Aldrich), loaded on silica gel (Aldrich, Grade 135) and purified by flash column using eluents of dichloromethane/hexanes (30percent to 60percent) (Aldrich). The desired fractions were collected, concentrated and filtered to give a yellow solid (EC-1 ) (0.57 g, in 40percent yield). Confirmed by liquid-chromatograph-mass-spectrometer (LCMS) (using atmospheric pressure chemical ionization [APCI]) (Shimadzu Scientific Instruments, Tokyo, Japan): calculated for C 04H65F6N4 (M+H): 1483; found: 1483. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
63% | With tri-tert-butyl phosphine; palladium diacetate; potassium carbonate; In 5,5-dimethyl-1,3-cyclohexadiene; at 120℃; for 12h;Inert atmosphere; | Synthesis of Compound 3 (0059) 2.00 g of compound D, 1.76 g of <strong>[56525-79-2]3,6-diphenyl-9H-carbazole</strong>, 1.1 mg of palladium (II) acetate (Pd(OAc)2), 3.0 mg of tri-tert-butylphosphine ((t-Bu)3P), and 2.08 g of potassium carbonate (K2CO3) were added in a 100 mL three-necked flask under an argon atmosphere, and the mixture was heated and stirred at 120° C. for 12 hours in 50 mL of a xylene solvent. The mixture was cooled in air, an organic layer was separated by adding water, and the solvent was removed by distillation. The obtained crude product was purified by silica gel column chromatography (using a mixed solvent of chloroform and hexane), and was then recrystallized by a mixed solvent of toluene and hexane to obtain 2.01 g of white solid compound 3 (yield: 63percent) (0060) Chemical shift values of compound 3 measured by 1H-NMR were 8.75 (d, 1H), 8.44 (d, 2H), 8.16 (q, 2H), 7.84 (q, 2H), 7.67 to 7.76 (m, 12H), 7.46 to 7.57 (m, 9H), and 7.32 to 7.46 (m, 3H). The molecular weight of compound 3 measured by FAB-MS |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | With rubidium carbonate; tri-tert-butyl phosphine; palladium diacetate; In 5,5-dimethyl-1,3-cyclohexadiene; for 24h;Reflux; | 4-bromo-spiro-9,9'-spirobifluorene , <strong>[56525-79-2]3,6-diphenyl-9-H-carbazole</strong> and 29. 2g Rb2CO3 suspended in 250mL of xylene. To the suspension to provide 0. 95g (4. 2mmol) Pd(OAc) 2 and 12. 6ml 1M The butylphosphine solution. The mixture was stirred under reflux for 24 hours. After cooling, the organic phase was separated,150mL of water three times, and then concentrated to dryness in vacuo. The residue was extracted with hot toluene, recrystallized three times from toluene,Then sublimation under high vacuum. The yield was 19. 6g (30. 9mmol), corresponding to 66percent of the theoretical value. Purity according to HPLCIt was 99.9percent. |
66% | With rubidium carbonate; tri-tert-butyl phosphine; palladium diacetate; In para-xylene; for 24h;Reflux; | 19.2 g (47 mmol) 4-Brom-9-spirobifluorene, 15 g (47 mmol) 3,6-Diphenyl-9-H-carbazole and 29.2 g Rb2CO3 are suspended in 250 mL p-Xylol. To the suspension are given 0.95 g (4.2 mmol) Pd(OAc)2 and 12.6 ml of a 1M solution of Tri-tert-butylphosphine. The mixture is stirred 24 h under reflux. After cooling the organic phase is separated, washed three times with 150 mL water and is subsequently concentrated to dryness in vacuo. The residue is hot extracted with toluene, recrystallized three times from toluene and subsequently sublimated at high vacuum. Yield is 19.6 g (30.9 mmol) corresponding to 66percent of theory. Purity is according to HPLC 99.9percent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; for 12h;Inert atmosphere; Reflux; | After a 500 mL 3 gu filled with nitrogen to a round bottom flask, toluene (100 mL) was injected.Cutting off the light and then, the Flask formula D (10.0 g, 34.6 mmol), the general formula G (11.0 g, 34.6 mmol), tris (dibenzylideneacetone) dipalladium(1.58 g, 1.73 mmol), Tree-tert-butylphosphine (1.68 mL, 6.93 mmol) and sodium-tert-butoxide (6.65 g, 69.1 mmol)It was added.Then, the mixture was stirred under reflux for 12 hours and the reaction mixture was cooled to room temperature.The cooled reaction mixtureWas dissolved in tetrahydrofuran (THF, 50 mL), was added to the 1L reaction vessel, methanol (300 mL) is contained.Then, 30 minutesStirred, filtered and the resulting precipitate was collected by obtained the title compound (Formula 1e, 15.0 g, 82percent) of light gray solid whileAll |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | With potassium carbonate; copper(II) iodide; 1-(2-pyridyl)-3-(2-pyridyl)-1,3-propanedione; In N,N-dimethyl-formamide; for 90h;Reflux; | 3,6-diphenyl -9H- carbazole of 32g (102-4 mmol), 42g (112Mmol) and 2-bromo-8a- Azabenzo [fg] naphthacene-8,9-dione, 2.3g (10-2 mmol) and 1,3-di [2-pyridyl] -1,3-propane dione, 28.3g (204 mmolAnd potassium carbonate Le), and copper iodide 1.9 g (10.2 mmol), at reflux, It is stirred for 90 hours in DMF of 1000ml. The solution was diluted with water, and extracted twice with ethyl acetate, the combined organic phases were dried over Na2SO4, and evaporated in a rotary evaporator and purified by chromatography (EtOAc / Hexane: 2/3). The residue and toluene, recrystallized from dichloromethane, finally sublimed in high vacuum, purity 99.9percentIt is. The yield was 46g (75 mmol), corresponding to 68percent of the theoretical value. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
30% | With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; at 100℃; for 40h;Inert atmosphere; | In a nitrogen environment I-23(73 g, 229 mmol) dissolved in 1,000 mL of toluene, here 2,7-dibromo-9,9-dimethyl-9H-fluorene(121 g, 344 mmol), tris(diphenoquinone alkylpiperidinyl) dipalladium(o) (2.10 g, 2.29 mmol), tristertbutylphosphine(2.32 g, 11.5 mmol) and sodium tertbutoxide(26.4 g, 275 mmol) sequentially into 100 ° C it is heated tor eflux for 40 hours. After the reaction was completed, the reaction solution into water and extracted with dichloromethane(DCM) and then water was removed with anhydrous MgSO4, filter and was concentrated under reduced pressure. Thus separated and purified the resulting residue was purified by flash column chromatography compound to obtain a I-24(40.6 g, 30percent) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
24% | General procedure: To a well-stirred suspension of 4.0 g (100 mmol) of sodium hydride, 60percent by weight dispersion in mineral oil, in 500 mL of THF are added in portions while cooling with ice, at about +10° C., 16.7 g (100 mmol) of carbazole [51555-21-6]?Caution Evolution of hydrogen Foaming After the addition has ended, the mixture is stirred for a further 30 min and then 20.7 g (100 mmol) of 1,3,5-tricyano-2-fluoro-4,6-dichlorobenzene [25751-93-7] are added in portions while cooling with ice in such a way that the temperature does not exceed +20° C. After the addition has ended, the mixture is stirred at +10° C. for a further 2 h, then the cooling bath is removed, and the mixture is allowed to warm to 20-25° C., stirred for a further 2 h and then heated to 40° C. for another 6 h. After cooling to room temperature, 12.0 g (300 mmol) of sodium hydride, 60percent by weight dispersion in mineral oil, are added, the reaction mixture is cooled to +10° C., and then 95.8 g (300 mmol) of <strong>[56525-79-2]3,6-diphenylcarbazole</strong> [56525-79-2] are added in portions?Caution Evolution of hydrogen Foaming After the addition has ended, the mixture is stirred at +10° C. for a further 2 h, then the cooling bath is removed, and the mixture is allowed to warm to 20-25° C., stirred for a further 2 h and then heated to 60° C. for another 16 h. After cooling to room temperature, the reaction is ended by dropwise addition of 30 mL of MeOH and the reaction mixture is then concentrated almost to dryness under reduced pressure. The residue is subjected to hot extractive stirring twice with 600 mL each time of a mixture of 400 mL of methanol and 200 mL of water and then once with 500 mL of methanol. Purification is effected by recrystallization from dioxane (about 3.5 mL/g) three times, then recrystallization from DMF (about 2 mL/g) five times and fractional sublimation twice (p about 1×10?5mbar, T about 330-340° C.). Yield: 22.9 g (24.0 mmol) 24percent. Purity: 99.9percent by HPLC. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69% | With sodium hydride; In tetrahydrofuran; at 0 - 60℃; for 15.5h; | To a solution of 4-bromo-2,3,5,6-tetrafluorobenzonitrile (0.356 g, 1.4 mmol), 9H-3,6,-diphenylcarbazole (2.01 g, 6 mmol) in anhydrous THF (15 mL), was added sodium hydride (60percent in mineral oil, 0.28 g, 7 mmol) at 0 °C. The resulting mixture was stirred at 0 °C for 30 min, then 60 °C for 15 hours. Yellow precipitate formed, and diluted with THF (200 mL), washed with brine, dried over Na2So4, loaded on silica gel and purified by flash column using eluents of dichloromethane/hexane (30percent to 100percent). The desired fractions were collected, concentrated and filtrtation to give a yellow solid (Compound 23) (1.4 g, in 69percentyield). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
54% | With sodium hydride; In tetrahydrofuran; mineral oil; at 0 - 60℃; for 24.5h; | To a solution of <strong>[56525-79-2]3,6-diphenyl-9H-carbazole</strong> (Compound 11 )(1.51 g, 4.5 mmol) and 2,3,5,6-tetrafluro-4-(4'-cyanophenyl)benzonitrile (Compound 10) (0.277 g, 1 mmol) in anhydrous THF (25 ml) was added sodium hydride (60percent in mineral oil, 0.2 g, 5 mmol) at about 0 °C and stirred for about 30 min. The mixture was heated at about 60 °C for about 24 hours. Upon cooling to room temperature, the whole was worked up with dichloromethane/brine, dried over Na2So4, then purified by flash column using eluents of dicholoromethane/hexane(20percent to 60percent). The yellow desired fractions were collected and concentrated to give a bright yellow solid (EM-9) (0.80 g, in 54percent yield). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
64% | With sodium hydride; In tetrahydrofuran; mineral oil; at 0 - 65℃; for 17h; | To a solution of <strong>[56525-79-2]3,6-diphenyl-9H-carbazole</strong> (Compound 11 ) (1.18 g, 3.68 mmol) and Compound 21 (0.30 g, 0.77 mmol) in anhydrous tetrahydrofuran(THF) (45 ml) was added sodium hydride (NaH) (60percent in mineral oil, 0.155 g, 3.87 mmol) at about 0 °C. The mixture was stirred at about 0 °C for about one hour(until H2(g) fully evolved) then heated at about 65 °C for about 16 hours. The resulting mixture was worked up with ethyl acetate/brine and dried over magnesium sulfate. The crude material was purified thrice by column chromatography on a silica gel column using eluents of 35percent to 60percent dichloromethane in hexanes, then 0percent to 40percent dichloromethane in hexane, then finally 25percent to 40percent dichloromethane in hexane. The product was dried by rotary evaporation and recrystallized from dichloromethane/hexane to yield EM-16 (0.78 g, 64percent yield) as a yellow solid. Confirmed by 1HNMR. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
5% | With sodium hydride; In tetrahydrofuran; mineral oil; at 0 - 60℃; for 16.3h; | To a solution of 5-(4-cyano-2,3,5,6-tetrafluorophenyl)pyrimidine-2-carbonitrile (Compound 22) (0.12 g, 0.43 mmol),9H-<strong>[56525-79-2]3,6-diphenylcarbazole</strong> (0.58 g, 1.73 mmol) in THF (10 mL), was added sodium hydride (60percent in mineral oil, 0.10 g, 2.5 mmol) at about 0 °C. After stirred at room temperature for about 20 min., the mixture was heated at about 60 °C for about 16 hours. The resulting mixture was worked up with dichloromethane/brine, the organic phase was dried and purified by flash column using eluents of dichloromethane/hexane (20percent to 50percent). The orange fraction was collected and concentrated to give a orange solid (EM-18) (0.05g, in 5percent yield). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; at 110℃; for 24h;Inert atmosphere; | Under nitrogen protection,Diphenylcarbazole 142.0 mmol of <strong>[56525-79-2]3,6-diphenylcarbazole</strong>,(Or meta) chloride30.0 mmol,1.5 mmol of tris (dibenzylideneacetone) dipalladium,Sodium tert-butoxide 120.0 mmol,Tri-tert-butylphosphine 6.0 mmol,500 ml of toluene was dissolved,110 reflux reaction 24h,The end point of the reaction was determined by thin layer chromatography (TLC)After completion of the reaction,Cooled to room temperature,Silicone funnel,DCM rinse,Drying,Dichloromethane,Petroleum ether recrystallization,Filtration,After drying, 23.4 mmol of the compound (17)Yield 78percent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79% | With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; at 110℃; for 24h;Inert atmosphere; | 141.0 mmol of <strong>[56525-79-2]3,6-diphenylcarbazole</strong>, 30.0 mmol of tetraphenyl diphenyl ether meta-chloro compound, 1.5 mmol of tris (dibenzylideneacetone) dipalladium, 120.0 mmol of sodium t-butoxide, , Tri-tert-butylphosphine 6.0mmol, dissolved 500ml toluene, refluxed at 110 ° C for 24 hours, the reaction end point was determined by thin layer chromatography (TLC), the reaction was completed, cooled to room temperature, filtered through a silica gel funnel, DCM, , And recrystallized from petroleum ether. After filtration and drying, 23.7 mmol of compound (13) was obtained, and the yield was 79percent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
4.5 g | With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; at 20℃; for 12h;Reflux; Inert atmosphere; | To the reaction flask3-Bromo-9-phenyl-9H-carbazole6.24 g (18.78 mmol), <strong>[56525-79-2]3,6-diphenyl-9H-carbazole</strong>5 g (15.65 mmol),TertButoxy sodium 2.25 g (23.48 mmol),Add 150 ml of toluene and stir at room temperature.Tris(Dibenzylideneacetone)Dipalladium (0)0.43 g (0.47 mmol),0.16 mL (0.47 mmol) of tri-tert-butylphosphine (50 wtpercent)And the mixture was refluxed under nitrogen flow for 12 hours.After completion of the reaction, the reaction mixture was slowly cooled to room temperature, and then the reaction solution was poured into a saturated aqueous solution of ammonium chloride and extracted with ethyl acetate.The organic layer was separated, dried over anhydrous magnesium sulfate and filtered.The filtrate was concentrated under reduced pressure and purified by column chromatography to obtain 4.5 g (51percent by weight) of the target compound [31] as a white solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
4.8 g | With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; at 20℃; for 12h;Reflux; Inert atmosphere; | To the reaction flask 9 - ([1,1'-biphenyl] -3-yl)-3-bromo-9H-carbazole 7.48 g (18.78 mmol), <strong>[56525-79-2]3,6-diphenyl-9H-carbazole</strong>5 g (15.65 mmol),2.25 g (23.48 mmol) of sodium butoxide,Add 150 ml of toluene and stir at room temperature. , 0.43 g (0.47 mmol) of tris (dibenzylideneacetone) dipalladium (0)0.16 mL (0.47 mmol) of tri-tert-butylphosphine (50 wtpercent) And the mixture was refluxed under nitrogen flow for 12 hours.After completion of the reaction, the reaction mixture was slowly cooled to room temperature, and then the reaction solution was poured into a saturated aqueous solution of ammonium chloride and extracted with ethyl acetate.The organic layer was separated, dried over anhydrous magnesium sulfate and filtered.The filtrate was concentrated under reduced pressure and purified by column chromatography to obtain 4.8 g (48 wtpercent) of the target compound [42] as a white solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | With sodium hydride; In tetrahydrofuran; mineral oil; at 0 - 60℃; for 17.5h; | To a mixture of 5?-(4-cyanophenyl)-4?,6?-difluoro- [1,1:3,1?-terphenyl]-2?,4,4?-tricarbonitrile (Compound 2) (0.30 g, 0.68 mmol) and <strong>[56525-79-2]3,6-diphenyl-9H-carbazole</strong> (0.67 g, 2.0 mmol) in anhydrous tetrahydrofuran (THF) (15 ml) was added sodium hydride (NaH) (60percent in mineral oil, 0.16 g, 4 mmol) at about 0°C. The mixture was stirred at room temperature for about 1.5 hour, then heated at about 60°C for about 16 hours. The whole was worked up with dichloromethane/brine, dried over Na2SO4, loaded on silica gel and purified by flash column using eluents of dichloromethane/hexanes (20percent to 100percent). The desired fractions were collected, concentrated, recrystallized in dichloromethane/ hexanes to give a light yellow solid (0.467 g, in 66percent yield). Confirmed by LCMS (APCI): calculated for C70H5N5(M+H): 1041 found: 1041. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1.8 g | With tris-(dibenzylideneacetone)dipalladium(0); sodium t-butanolate; tri tert-butylphosphoniumtetrafluoroborate; In toluene; for 8h;Inert atmosphere; Reflux; | In the argon atmosphere, 2,6-dichloropyrazine (0.6 g, 3.9 mmol) was added sequentially, 3,6-dibromocarbazole (2.6 g, 8 mmol), (Dibenzylideneacetone) dipalladium (0.07 g, 0.08 mmol) Tri-t-butylphosphonium tetrafluoroborate (0.09 g, 0.3 mmol) (0.5 g, 5.5 mmol) and anhydrous toluene (20 mL), And heated to reflux for 8 hours. After the reaction solution was allowed to cool to room temperature, Separating the organic layer, The organic solvent was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography, A solid of 1.8 g was obtained. For the resulting compound, As a result of FD-MS, Identified as compound BH-1. |
1.8 g | With tris-(dibenzylideneacetone)dipalladium(0); sodium t-butanolate; tri tert-butylphosphoniumtetrafluoroborate; In toluene; for 8h;Inert atmosphere; Reflux; | In the argon atmosphere,Add it in sequence2,6-dichloropiperidine(0.6 g, 3.9 mmol),3,6-dibromocarbazole (2.6 g, 8 mmol),(Dibenzylideneacetone) dipalladium (0.07 g, 0.08 mmol)Tri-butyl-tetrafluoroborate (0.09 g, 0.3 mmol)(0.5 g, 5.5 mmol) and anhydrous toluene (20 mL),And heated to reflux for 8 hours.After the reaction solution was allowed to cool to room temperature,Separating the organic layer,The organic solvent was distilled off under reduced pressure.The resulting residue was purified by silica gel column chromatography,A solid of 1.8 g was obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | With tri-tert-butyl phosphine; sodium carbonate; In o-xylene; at 100℃; for 12h;Inert atmosphere; | To a 50 mL three-necked flask equipped with nitrogen was added 0.72 g (1 mmol) of 2,6-bis (9- (4-bromophenyl) fluorenyl) pyridine, 0.65 g (2.05 mmol) of 3,6-phenylcarbazole , 0.265 g (2.50 mmol) of sodium carbonate, 4 mL of o-xylene and 20.17 mg (0.1025 mmol) of tri-tert-butylphosphine. 3, The molar ratio of 6-phenylcarbazole to 2,6-bis (9- (4-bromophenyl) fluorenyl) pyridine was 2.05: 1, 3,6-phenylcarbazole with tri-tert-butylphosphine The molar ratio was 1: 0.05. The reaction was carried out at 100 ° C for 12 hours. After cooling to room temperature, 20 mL of water and 60 mL of dichloromethane were added. The organic layer was separated and extracted with dichloromethane three times. The combined organic layers were dried over anhydrous magnesium sulfate and evaporated to remove the solvent. The phosphorescent host material 5 was purified by column chromatography (dichloromethane / petroleum ether = 1: 8) to obtain pure phosphorescent material. Yield 66percent. MS (EI) m / z: 1193 |
Tags: 56525-79-2 synthesis path| 56525-79-2 SDS| 56525-79-2 COA| 56525-79-2 purity| 56525-79-2 application| 56525-79-2 NMR| 56525-79-2 COA| 56525-79-2 structure
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