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Chemical Structure| 870119-58-7 Chemical Structure| 870119-58-7
Chemical Structure| 870119-58-7

9-(3-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-9H-carbazole

CAS No.: 870119-58-7

4.5 *For Research Use Only !

Cat. No.: A263708 Purity: 97%

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Product Details of [ 870119-58-7 ]

CAS No. :870119-58-7
Formula : C24H24BNO2
M.W : 369.26
SMILES Code : CC1(C)C(C)(C)OB(C2=CC(N3C4=C(C5=C3C=CC=C5)C=CC=C4)=CC=C2)O1
MDL No. :MFCD22415352
InChI Key :YWLGYAZJWNLVKB-UHFFFAOYSA-N
Pubchem ID :58690899

Safety of [ 870119-58-7 ]

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H302
Precautionary Statements:P280-P305+P351+P338

Application In Synthesis of [ 870119-58-7 ]

* 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.

  • Downstream synthetic route of [ 870119-58-7 ]

[ 870119-58-7 ] Synthesis Path-Downstream   1~30

  • 1
  • [ 870119-56-5 ]
  • [ 870119-58-7 ]
  • C42H33N [ No CAS ]
YieldReaction ConditionsOperation in experiment
With potassium phosphate; tetrabutylammomium bromide;palladium diacetate; In N,N-dimethyl-formamide; at 130℃; for 5h; A mixed solution of 2.2 g of the above-mentioned 10-bromo-2-tert-butyl-9-phenylanthracene, 2.2 g of 9-[3-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolane-2-yl)phenyl] carbazole, 2.4 g of tripotassium phosphate, 360 mg of tetrabutyl ammonium bromide, 25 mg of palladium acetate and 60 ml of dimethylformamide was heated while stirred under nitrogen gas stream at a temperature of 130C for 5 hours. After cooling the mixed solution to room temperature, 100 ml of water was injected thereto and filtered. The solid separated by filtration was purified by silica gel column chromatography and vacuum dried to thereafter obtain a compound [130]. The results of 1H-NMR analysis of the obtained powder are as follows. 1H-NMR (CDCl3 (d=ppm)) : 1.26 (s, 9H), 7.23-7.86 (m, 22H), 8.11 (d, 2H) This compound [130] was purified by sublimation under a pressure of 1×10-3Pa at a temperature of approximately 260C by using an oil diffusion pump, and thereafter used as a light emitting device material. HPLC purity (area% at a measuring wavelength of 254 nm) was 99.4% before purification by sublimation and 99.6% after purification by sublimation.
  • 2
  • [ 185112-61-2 ]
  • [ 73183-34-3 ]
  • [ 870119-58-7 ]
YieldReaction ConditionsOperation in experiment
83% With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In 1,4-dioxane; for 6h; P3 (65 g, 1 eq), Bis (pinacolato) diboron ( bis (pinacolato) diboron) (65 g 1.5 eq), PdCl2 (dppf) (11 g, 0.1 eq), KOAc (50 g, 3 eq), Dioxane 800ml Is placed in a round bottom flask (1-neck-R.B.F.) and stirred. (6h) A silica / celite filter was applied, Compound P2 was obtained. (60 g, Step yield = 83%)
81% With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In tetrahydrofuran; at 80℃; for 5h;Inert atmosphere; In a 100 ml three-necked flask, first S15 (1.35 mmol), bis(pinacolato)diboron(1.65 mmol),(1,1'-bis (diphenylphosphine) ferrocene) dichloropalladium (II) (0.05mmol) and potassium acetate (9mmol) were added separately,While stirring, degassing and nitrogen replacement were repeated 3 times quickly, and 6 mL of tetrahydrofuran was added through a syringe.Stir at a certain speed, and heat the resulting mixed solution reactant under reflux at a reaction temperature of 80 C. for 5 h;After the reaction is completed, cool to room temperature and add 6 ml of water, extract with ether, and dry the obtained organic phase with anhydrous sodium sulfate.The solvent was distilled off and purified by column chromatography to obtain intermediate S10 (1.1 mmol, 81%).
80% With potassium acetate;dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; In dimethyl sulfoxide; at 60 - 80℃; for 9.25h; Under nitrogen flow, the target compound 11 (10.5 g), bis(pinacolate)diboron (9.93 g), potassium acetate (10.9 g), and anhydrous dimethylsulfoxide (190 ml) were stirred while heating to 60C for 15 min, and [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) dichloromethane complex (0.799 g) was added thereto. The resulting mixture was stirred while heating to 80C for 9 hr and then allowed to cool to room temperature. To the reaction solution, water (250 ml) and toluene (500 ml) were added, and the resulting mixture was stirred. After the water layer was reextracted twice with toluene, the organic layers were mixed. Further, magnesium sulfate and active clay were added thereto. The magnesium sulfate and active clay were removed by filtration, and the toluene was evaporated under reduced pressure. The precipitated crystal was washed with cold methanol and dried under reduced pressure to obtain a target compound 12 (9.86%, yield: 80%) as a white crystal.
76% With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; tris-(dibenzylideneacetone)dipalladium(0); potassium acetate; In 1,4-dioxane; for 24h;Inert atmosphere; Reflux; In 500 mL three-necked flask, followed by adding intermediate M7 (20g, 62.lmmol), bis (pinacolato) diboron (23.6g, 93.2mmol), CH3COOK (17.5g, 178.2mmol), 1, 4- dioxane, 300 mL, and S-phos (5.35g, 13.04mmol), N2 replaced three times, was added Pd2 (dba) 3 (3.98g, 4.35mmol) and heated to reflux. After 24h the reaction was stopped.It cooled to room temperature, filtered, and the filtrate was collected, concentrated, and purified by column chromatography (dichloromethane: n-hexane = 0-1 as the mobile phase), to receive an off-white solid 17.4g (76%),
70% With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In tetrahydrofuran; 1,4-dioxane; at 85℃; for 24h; In a 250 mL single-mouth reaction flask, Compound 5 (5.00 g, 15.52 mmol) was added separately.Potassium acetate (7.90 g, 80.70 mmol) and bis(pinacol) diboron (4.88 g, 18.62 mmol), Pd(dppf) 2Cl2 (0.23 g, 0.31 mmol),Then, 100 mL of anhydrous tetrahydrofuran was added, followed by heating to 85 C under nitrogen for 24 hours.After completion of the reaction, it was cooled to room temperature, then 100 mL of water was added, extracted with dichloromethane, and the organic phase was collected and washed with water several times.The organic phase was dried over anhydrous magnesium sulfate and the solvent was evaporated with stirring.The column chromatography eluent was ethyl acetate/petroleum ether = 10/1, yielding a white solid, 4.2 g, yield 70%.
69% With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In N,N-dimethyl-formamide; at 85℃;Inert atmosphere; A mixture of 1B (6.55 g, 20.4 mmol), bis(pinacolato)diboron (6.22 g, 24.5 mmol), [1,1?-Bis(diphenylphosphino)ferrocene]dichloropalladium (747 mg, 1.02 mmol), and potassium acetate (5.88 g, 60 mmol) in dimethylformamide (DMF) (anhydrous, 50 mL) was degassed for 45 minutes. The mixture was further degassed by being heated to about 85 C. overnight under argon. After cooling to RT, the mixture was poured into DCM (250 mL) and solids were filtered off. The filtrate was washed with water (2×300 mL), dried over sodium sulfate, and loaded onto silica gel. Flash column (gradient of 10% to 30% DCM in hexanes) and precipitation from DCM/MeOH gave 5.17 g of 1C; 69% yield, pure by HNMR.
68% With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In 1,4-dioxane; at 80℃; for 24h;Inert atmosphere; Step 1 in the manufacturing of the compound (3.0 g, 9.3 mmol), bis (pinacolato) di boron (2.6 g, 10 mmol), potassium acetate (2.7 g, 28 mmol) and [bis (diphenylphosphino)ferrocene] dichloropalladium (0) complex (0.32 g, 0.39 mmol) and then the presence of nitrogen, for 24 hours at 80 dissolved in dioxane (60 ml), and stirred. After the reaction was terminated, cooled to ambient temperature, the reaction mixture was filtered through celite. Pour water to the filtrate, extracted with ethyl acetate, and wash the organic layer extracted with brine. The washed organic layer was dried over magnesium sulfate and purified by column chromatography (silica gel), the desired compound (2.3 g, 68%) was obtained.
68% With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; at 100℃; for 26h;Inert atmosphere; 4 was prepared as follows: a mixture of compound 3 (see Kido, J.; Su, S. -J.; Sasabe, H.; and, Takeda, T., Chem. Mater. 2008, 20(5), 1691-1693, which is incorporated by reference herein for its relevant teachings) (5.45 g, 16.9 mmol), bis(pinacolato)diboron (9.020 g, 35.52 mmol), [1,1'-bis(diphenylphosphino)-ferrocene]dichloropalladium(II) (0.743 g, 1.02 mmol), potassium acetate (4.980, 50.75 mmol) and anhydrous toluene (110 mL) was degassed with argon for 1 h. while stirring. The reaction mixture was then maintained under argon at 100 C. while stirring for 25 h. until TLC (SiO2, 4:1 hexanes-dichloromethane) confirmed consumption of the starting material. Upon completion, the reaction was cooled to RT and about 500 mL ethyl acetate added. The organics were then washed with saturated NaHCO3, H2O and brine, dried over MgSO4, filtered and concentrated in vacuo. The crude product was purified via flash chromatography (SiO2, 4:1 hexanes-dichloromethane to 100% dichloromethane) to afford Compound 4 (4.26 g, 68%) as a white solid.
With potassium acetate;1,1'-bis-(diphenylphosphino)ferrocene; tris-(dibenzylideneacetone)dipalladium(0); In 1,4-dioxane;Inert atmosphere; Reflux; Step 2. 3-Bromophenyl carbazole (9.5 g, 29.5 mmol), bis(pinacolato)diboron (11.2 g, 44.2 mmol), potassium acetate (8.7 g), tris(dibenzylideneacetone)dipalladium (200 mg) and 1,1'-bis(diphenylphosphino)ferrocene (400 mg) are suspended in 200 mL of dioxane and heated to reflux under nitrogen atmosphere overnight. After cooling down and evaporation the residue is subjected to column chromatography on silica gel, providing 9-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-9H-carbazole b(6.0 g, colorless crystals).
With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; potassium acetate; In N,N-dimethyl-formamide; for 6h;Reflux; 9-(3-bromo-phenyl)-9H-carbazole (9-(3-bromophenyl)-9H-carbazole, 5g, 15.5mmol), bis(pinacolato)diboron (bis(pinacolato)diboron, 6.3g , 24.8mmol), KOAc 4.5g (46.5mmol), were dissolved Pd (dppf) Cl2CH2Cl2 1.13g (1.55mmol) in DMF100ml was refluxed for 6 hours. After cooling to room temperature after completion of the reaction was isolated by extraction with EA / H2O (Sat'd NaHCO3). The organic layer was dried over MgSO4 and evaporated under reduced pressure to remove the solvent. Separated by column chromatography to obtain the desired product compound 2-2.
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In 1,4-dioxane; at 85℃; for 4h;Inert atmosphere; In a 500mL reaction flask, add intermediate M4 (11g, 34.45mmol), diboronic acid pinacol ester (13.12g, 51.68mmol), PdCl2 (dppf) (5.04g, 6.89mmol), CH3COOK (6.76g, 68.9mmol) Add 1,4-dioxane (10mL) and stir,Heated to 85 under nitrogen protection,After 4 hours of reaction, the reaction was monitored by TLC until the reaction was complete. The temperature was lowered to room temperature, filtered, and the reaction solution was concentrated.The product was separated and purified on a silica gel column, and concentrated to obtain a crude product, which was filtered with 100 mL of n-hexane to obtain intermediate M5.

  • 3
  • [ 123291-15-6 ]
  • [ 870119-58-7 ]
  • C59H39N3 [ No CAS ]
YieldReaction ConditionsOperation in experiment
With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; water; for 6h;Heating / reflux; To a mixture of the target compound 5 (1.86g), the target compound 12 (3.84 g), dimethoxyethane (80 ml), and water (12 ml), tetrakis(triphenylphosphine)palladium (0.37 g) and potassium carbonate (3.32 g) were sequentially added. The resulting mixture was stirred while heating under reflux for 6 hr. To the resulting solution, brine (100 ml) was added. After extraction with dichloromethane (2 x 100 ml), anhydrous magnesium sulfate and active clay were added to the organic layer. The mixture was stirred, filtered, and concentrated to obtain a solid content. The solid content was purified by silica-gel column chromatography to obtain a target compound 13 (2.16 g). The obtained compound was confirmed to be a target compound 13 by DEI-MS (m/z = 789 (M+)). The compound had a vaporization temperature of 541C and a glass transition temperature of 125C. The melting point was not detected.
YieldReaction ConditionsOperation in experiment
71.8% With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In toluene; for 10h;Reflux; General procedure: 9-(4- bromophenyl)-9H-carbazole 24 g (34mmol),the bis pinacolrato diboron 20.4 g (41 mmol), the palladium(II)chloridation-1,1'-bis(diphenyl phosphino)ferrocene 1.4 g (1 mmol), potassiumacetate 6.7 g (68mmol), toluene 240 ml is put in dried 500mL reactor and it mixes reflux for 10 hours. After solid is filtered after thecompletion of reaction the filtrate is reduced pressureand it concentrates. It separated according to the methylene chloride and heptane into the column chromatography and 003c3-c003e 20.5 g was obtained. (yield71.5%)
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In N,N-dimethyl-formamide; at 90 - 100℃; General procedure: After the bromine compound (1 equivalent) was dissolved in DMF,Bis (pinacolato) diboron (1.1 eq.), Pd (dppf) Cl2 (0.03 mmol)After addition of KOAc (3 eq) And stirred at 90 to 100 C. When the reaction was complete, DMF was removed by distillation and extracted with CH2Cl2 and water.The organic layer was dried over MgSO4 and concentrated. The resulting compound was purified by silicagel column and recrystallized to give product Sub2.
  • 5
  • [ 870119-58-7 ]
  • [ 108-36-1 ]
  • [ 854952-41-3 ]
YieldReaction ConditionsOperation in experiment
With potassium acetate;tetrakis(triphenylphosphine) palladium(0); In water; toluene;Inert atmosphere; Reflux; Step 3. 1,3-Dibromobenzene (16 g, 64.9 mmol), <strong>[870119-58-7]9-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-9H-carbazole</strong> b(6.0 g, 11.6 mmol), potassium acetate (saturated solution of 6.6 g in water) and tetrakis(triphenylphosphine)palladium (0) (380 mg) are heated to reflux in 150 mL of toluene overnight under nitrogen atmosphere. After cooling down, evaporation and column chromatography 9-(3'-bromo-[1,1'-biphenyl]-3-yl)-9H-carbazole (5.8 g) is obtained.
  • 6
  • [ 625-92-3 ]
  • [ 870119-58-7 ]
  • [ 1013405-25-8 ]
  • 7
  • [ 26452-80-2 ]
  • [ 870119-58-7 ]
  • [ 1262678-75-0 ]
  • 8
  • [ 626-05-1 ]
  • [ 870119-58-7 ]
  • [ 1013405-24-7 ]
  • 9
  • [ 3934-20-1 ]
  • [ 870119-58-7 ]
  • [ 1262678-76-1 ]
  • 10
  • [ 1193-21-1 ]
  • [ 870119-58-7 ]
  • [ 1262678-77-2 ]
  • 11
  • [ 870119-58-7 ]
  • [ 108-36-1 ]
  • [ 1116499-73-0 ]
  • 12
  • [ 870119-58-7 ]
  • [ 4774-14-5 ]
  • [ 1262678-78-3 ]
  • 14
  • [ 5394-23-0 ]
  • [ 870119-58-7 ]
  • [ 1233221-55-0 ]
YieldReaction ConditionsOperation in experiment
With potassium phosphate;tris-(dibenzylideneacetone)dipalladium(0); tricyclohexylphosphine; In 1,4-dioxane; water; at 80 - 100℃;Inert atmosphere; Example 11; This example illustrates the preparation of phenanthroline derivative Compound 15, using Suzuki coupling of 4,7-dichloro-1,10-phenanthroline with the boronic ester shown below. Take 2.5 g of dichloro-phen (10 mM) in glove box and add 8.0 g (22 mM) boronic ester. Add 0.30 g Pd2 DBA3 (0.30 mM), 0.2 g tricylcohexylphosphine (0.70 mM) and 7.5 g potassium phosphate (34 mM) and dissolve all into 60 mL dioxane and 30 mL water. Mix and heat in glove box in mantle at 100 C for 1 hr then warm gently (minimum rheostat setting) under nitrogen overnight. Solution immediately is dark purple but on reaching 80 C it is a tan brown slurry which slowly becomes clear brown. As the solution refluxes (air condensor) no ppt forms. Cool and work up by removing from glove box and filter off orange gum from the dioxane after adding more water (on celite). Dissolve into chloroform and then chromatograph on column of silica/florisil/alumina (B) and elute with DCM (elutes blue PL fraction in very low amount as a pale yellow solution). Change to 50:50 methanol/DCM and elute orange solution which appears to be bulk of the material. Product seems to be extremely soluble but ?crystallizes? as a white powder from acetone/methanol/DCM mixture. Recover 5.6 g of white product sent for nmr in DCM (colorless solution with blue PL). The structure was confirmed by NMR analysis as Compound 15:
  • 15
  • [ 870119-58-7 ]
  • [ 1229012-68-3 ]
  • [ 1009362-85-9 ]
YieldReaction ConditionsOperation in experiment
With potassium phosphate;tris-(dibenzylideneacetone)dipalladium(0); tricyclohexylphosphine; In 1,4-dioxane; water; at 80 - 100℃;Inert atmosphere; Example 9; This example illustrates the preparation of phenanthroline derivative Compound 1, using Suzuki coupling of 2,9-dichloro-4,7-diphenyl 1,10-phenanthroline from Example 1 with the boronic ester shown below. Take 2.0 g of dichloro-phen (5 mM) in glove box and add 4.0 g (11 mM) boronic ester. Add 0.15 g Pd2 DBA3 (0.15 mM), 0.1 g tricyclohexylphosphine (0.35 mM) and 3.75 g potassium phosphate (17 mM) and dissolve all into 30 mL dioxane and 15 mL water. Mix and heat in glove box in mantle at 110 C for 1 hr then warm gently (minimum rheostat setting) under nitrogen overnight. Solution immediately is dark purple but on reaching 80 C it is a tan brown slurry which slowly becomes clear brown with a dense ppt. As the solution refluxes (air condensor) a flocculent ppt forms. Cool and work up by removing from glove box and filter off white fibers from the dioxane after adding more water. Dissolve into chloroform and then evaporate and ppt in toluene by adding methanol as off white fine needles. Collect by filtration and wash well with methanol to isolate 3.55 g material. The structure was confirmed by NMR analysis as Compound 1:
  • 16
  • [ 5315-25-3 ]
  • [ 870119-58-7 ]
  • [ 1360431-90-8 ]
  • 17
  • [ 870119-58-7 ]
  • [ 19493-44-8 ]
  • [ 1330750-08-7 ]
  • 18
  • [ 185112-61-2 ]
  • [ 870119-58-7 ]
  • [ 342638-54-4 ]
  • 19
  • [ 3764-01-0 ]
  • [ 870119-58-7 ]
  • 2,4,6-tris(3-(carbazol-9-yl)phenyl)pyrimidine [ No CAS ]
  • 20
  • potassium phosphate [ No CAS ]
  • [ 870119-58-7 ]
  • [ 177775-86-9 ]
  • [ 1414941-49-3 ]
YieldReaction ConditionsOperation in experiment
94% tris-(dibenzylideneacetone)dipalladium(0); In water; toluene; A solution of 1-(3-bromo-9H-carbazol-9-yl)ethanone (2.000 g, 6.94 mmol), <strong>[870119-58-7]9-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-9H-carbazole</strong> (2.56 g, 6.94 mmol), Pd2(dba)3 (0.064 g, 0.069 mmol), SPhos (0.057 g, 0.139 mmol) and potassium phosphate tribasic hydrate (4.80 g, 20.82 mmol) in toluene (100 mL) and water (10 mL) was stirred at 70 C. under nitrogen overnight. After cooling to room temperature, the organic phase was isolated. Upon evaporation of the solvent, the residue was purified by column chromatography on silica gel with hexane:DCM (1:4, v/v) as eluent to yield 1-(3-(3-(9H-carbazol-9-yl)phenyl)-9H-carbazol-9-yl)ethanone (2.9 g, 94%) as a white solid.
  • 21
  • [ 870119-58-7 ]
  • [ 1084334-28-0 ]
  • [ 1370653-74-9 ]
YieldReaction ConditionsOperation in experiment
61% With potassium phosphate monohydrate;tris-(dibenzylideneacetone)dipalladium(0); In water; toluene;Reflux; Inert atmosphere; Comparative Examples 2: Synthesis of Comparative Compound CC-2 [0167] A solution of 4-(3-bromophenyl)dibenzo[b,d]thiophene (7.15 g, 21.08 mmol), 9-(3- (4,4, 5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)phenyl)-9H-carbazole (7.78 g, 21.08 mmol), SPhos (0.173 g, 0.422 mmol), Pd2(dba)3 (0.192 g, 0.211 mmol) and potassium phosphate monohydrate (9.71 g, 42.2 mmol) in toluene (200 mL) and water (10 mL) was refluxed under nitrogen overnight. After cooling to room temperature, the organic phase was isolated and evaporated to dryness. The residue was purified by column chromatography on silica gel with hexane:DCM (9 : 1 to 1 : 1 , v/v) as eluent, recrystallization from heptane, and sublimation under vacuum to yield CC-2 (6.4g, 61%) as white crystals
  • 22
  • [ 870119-58-7 ]
  • [ 177775-86-9 ]
  • [ 1414941-49-3 ]
YieldReaction ConditionsOperation in experiment
94% With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; tripotassium phosphate "n" hydrate;tris-(dibenzylideneacetone)dipalladium(0); In water; toluene; at 70℃;Inert atmosphere; A solution l-(3-bro (2.000 g, 6.94 mmol), 9-(3- (4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)phenyl)-9H-carbazole (2.56 g, 6.94 mmol), Pd2(dba)3 (0.064 g, 0.069 mmol), SPhos (0.057 g, 0.139 mmol) and potassium phosphate tribasic hydrate (4.80 g, 20.82 mmol) in toluene (100 mL) and water (10 mL) was stirred at 70C under nitrogen overnight. After cooling to room temperature, the organic phase was isolated. Upon evaporation of the solvent, the residue was purified by column chromatography on silica gel with hexane:DCM (1 :4, v/v) as eluent to yield l-(3-(3-(9H-carbazol-9-yl)phenyl)-9H-carbazol-9- yl)ethanone (2.9 g, 94%) as a white solid.
  • 23
  • [ 870119-58-7 ]
  • [ 1414941-45-9 ]
  • [ 1414941-50-6 ]
YieldReaction ConditionsOperation in experiment
66% With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; potassium phosphate;tris-(dibenzylideneacetone)dipalladium(0); In water; toluene; at 100℃;Inert atmosphere; A mixture solution of (3 -bromophenyl)(3 -(dibenzo [b, ]thiophen-4- yl)phenyl)diphenylsilane (3 g, 5.02 mmol), 9-(3-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2- yl)phenyl)-9H-carbazole (2.039 g, 5.52 mmol), tris(dibenzylideneacetone)dipalladium (0) (Pd2(dba)3) (0.092 g, 0.100 mmol), dicyclohexyl(2',6'-dimethoxy-[l, -biphenyl]-3-yl)phosphine (SPhos) (0.082 g, 0.201 mmol), and potassium phosphate tribasic (K3P04) (1.066 g, 5.02 mmol) in toluene (40 mL) and water (4 mL) was heated at 100 C under nitrogen overnight. The reaction mixture was quenched with water, extracted with DCM, washed with brine and water, and dried over Na2S04. Upon evaporation of the solvent, the residue was purified by column chromatography with hexane:DCM(9.25:0.75, v/v) as eluent. The crude product was dissolved in DCM, precipitated with methanol, and filtered to yield Compound 23 (2.2 g, 66%) as a colorless glass.
  • 24
  • [ 870119-58-7 ]
  • [ 1414960-14-7 ]
  • [ 1414941-54-0 ]
YieldReaction ConditionsOperation in experiment
With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; potassium phosphate;tris-(dibenzylideneacetone)dipalladium(0); In water; toluene;Inert atmosphere; Reflux; A mixture solution of (3-bromophenyl)(3-(dibenzo[£,<10~5="" torr)="" yield="" compound="" 27="" (1.9="" g)="" as="" a="" colorless="" glass.<="" td="">
  • 25
  • [ 870119-58-7 ]
  • [ 1414941-47-1 ]
  • [ 1414941-57-3 ]
YieldReaction ConditionsOperation in experiment
88% With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; K3H2PO5;tris-(dibenzylideneacetone)dipalladium(0); In water; toluene; at 100℃;Inert atmosphere; A mixture solution of (3-bromophenyl)(3'-(dibenzo[^<="" td="">
  • 26
  • [ 870119-58-7 ]
  • [ 1414941-48-2 ]
  • [ 1414941-58-4 ]
YieldReaction ConditionsOperation in experiment
80% With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; potassium phosphate;tris-(dibenzylideneacetone)dipalladium(0); In water; toluene; at 60℃;Inert atmosphere; A suspension of (3-bromophenyl)(3-(dibenzo[^<i]thiophen-2-yl)phenyl)diphenylsilane (3.16 g, 5.29 mmol), 9-(3-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)phenyl)-9H-carbazole (1.952 g, 5.29 mmol), Pd2(dba)3 (0.048 g, 0.053 mmol), SPhos (0.043 g, 0.106 mmol) and K3P04 (2.435 g, 10.57 mmol) in toluene (200 mL) and water (5 mL) was heated at 60 C under nitrogen overnight. After cooling to room temperature, the organic phase was isolated and evaporated to dryness. The residue was purified by column chromatography on silica gel with hexane:DCM (9: 1 to 7:3, v/v) as eluent to yield Compound 31 (3.2 g, 80%) as a white solid. [0131] Example 10: Synthesis of Compound 32
  • 27
  • [ 870119-58-7 ]
  • 1-(3-(3-bromophenyl)-9H-carbazol-9-yl)ethanone [ No CAS ]
  • 1-(3-(3'-(9H-carbazol-9-yl)[1,1'-biphenyl]-3-yl)-9H-carbazol-9-yl)ethanone [ No CAS ]
YieldReaction ConditionsOperation in experiment
89% With tris-(dibenzylideneacetone)dipalladium(0); In water; toluene; A mixture solution of 1-(3-(3-bromophenyl)-9H-carbazol-9-yl)ethanone (2.50 g, 6.86 mmol), <strong>[870119-58-7]9-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-9H-carbazole</strong> (2.53 g, 6.86 mmol), Pd2(dba)3 (0.063 g, 0.069 mmol), (SPhos) (0.056 g, 0.137 mmol) and K3PO4 (4.74 g, 20.59 mmol) in toluene (180 mL) and water (5 mL) was refluxed under N2 overnight. After cooling to room temperature, the organic solution was isolated. Upon evaporation of the solvent, the residue was purified by column chromatography on silica gel with hexane/DCM (1/1 to 1/4, v/v) as eluent to yield 1-(3-(3'-(9H-carbazol-9-yl)[1,1'-biphenyl]-3-yl)-9H-carbazol-9-yl)ethanone (3.2 g, 89%) as a white solid.
  • 28
  • [ 870119-58-7 ]
  • 1-(3-(3-bromophenyl)-9H-carbazol-9-yl)ethanone [ No CAS ]
  • 3-(3'-(9H-carbazol-9-yl)[1,1'-biphenyl]-3-yl)-9H-carbazole [ No CAS ]
  • 29
  • [ 760212-52-0 ]
  • [ 870119-58-7 ]
  • [ 1236181-30-8 ]
YieldReaction ConditionsOperation in experiment
56% With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In tetrahydrofuran; water; at 80℃;Inert atmosphere; A mixture of compound 1C (3.0 g, 8.15 mmol), compound 1F (2.85 g, 8.15 mmol), tetrakistriphenylphosphine palladium (471 mg, 0.408 mmol), and sodium carbonate (3.09 g, 29.2 mmol) in tetrahydrofuran (THF)/ water (50 mL/30 mL) was degassed for about 45 minutes. The mixture then heated to reflux (about 80 C.) overnight under argon. After cooling to RT, the reaction mixture was poured into DCM (300 mL) then washed with saturated sodium bicarbonate (200 mL), water (200 mL), and brine (200 mL). The organic phase was then collected, dried over magnesium sulfate, and loaded onto silica gel. A flash column (gradient of 25% to 40% ethyl acetate in DCM) and precipitation from ethyl acetate/ methanol gave 2.34 g of HTH-1; 56% yield, pure by HNMR.
 

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