Structure of 1082549-89-0
*Storage: {[sel_prStorage]}
*Shipping: {[sel_prShipping]}
The BI-3802 was designed by Boehringer Ingelheim and could be obtained free of charge through the Boehringer Ingelheim open innovation portal opnMe.com, associated with its negative control.
4.5
*For Research Use Only !
Change View
Size | Price | VIP Price | US Stock |
Global Stock |
In Stock | ||
{[ item.pr_size ]} |
Inquiry
{[ getRatePrice(item.pr_usd, 1,1,item.pr_is_large_size_no_price, item.pr_usd) ]} {[ getRatePrice(item.pr_usd,item.pr_rate,1,item.pr_is_large_size_no_price, item.discount_usd) ]} {[ getRatePrice(item.pr_usd, 1,1,item.pr_is_large_size_no_price, item.pr_usd) ]} |
Inquiry {[ getRatePrice(item.pr_usd,item.pr_rate,item.mem_rate,item.pr_is_large_size_no_price, item.vip_usd) ]} | Inquiry {[ item.pr_usastock ]} In Stock Inquiry - | {[ item.pr_chinastock ]} {[ item.pr_remark ]} In Stock 1-2 weeks - Inquiry - | Login | - + | Inquiry |
Please Login or Create an Account to: See VIP prices and availability
US Stock: ship in 0-1 business day
Global Stock: ship in 5-7 days
1-2weeks
Inquiry
{[ getRatePrice(item.pr_usd,item.pr_rate,item.mem_rate,item.pr_is_large_size_no_price, item.vip_usd) ]}
{[ getRatePrice(item.pr_usd, 1,1,item.pr_is_large_size_no_price, item.pr_usd) ]}
{[ getRatePrice(item.pr_usd,1,item.mem_rate,item.pr_is_large_size_no_price, item.pr_usd) ]}
Inquiry
{[ getRatePrice(item.pr_usd,item.pr_rate,1,item.pr_is_large_size_no_price, item.vip_usd) ]}
{[ getRatePrice(item.pr_usd, 1,1,item.pr_is_large_size_no_price, item.pr_usd) ]}
{[ getRatePrice(item.pr_usd, 1,1,item.pr_is_large_size_no_price, item.pr_usd) ]}
In Stock
- +
Please Login or Create an Account to: See VIP prices and availability
US Stock: ship in 0-1 business day
Global Stock: ship in 2 weeks
Search for reports by entering the product batch number.
Batch number can be found on the product's label following the word 'Batch'.
Search for reports by entering the product batch number.
Batch number can be found on the product's label following the word 'Batch'.
Search for reports by entering the product batch number.
Batch number can be found on the product's label following the word 'Batch'.
Search for reports by entering the product batch number.
Batch number can be found on the product's label following the word 'Batch'.
Search for reports by entering the product batch number.
Batch number can be found on the product's label following the word 'Batch'.
CAS No. : | 1082549-89-0 |
Formula : | C36H31BN2O2 |
M.W : | 534.45 |
SMILES Code : | CC1(C)C(C)(C)OB(C2=CC(N3C4=C(C5=C3C=CC=C5)C=CC=C4)=CC(N6C7=C(C8=C6C=CC=C8)C=CC=C7)=C2)O1 |
MDL No. : | N/A |
InChI Key : | ADMPYRNBAYKWOL-UHFFFAOYSA-N |
Pubchem ID : | 59372091 |
GHS Pictogram: |
![]() |
Signal Word: | Warning |
Hazard Statements: | H302-H315-H319-H335 |
Precautionary Statements: | P261-P264-P270-P271-P280-P301+P312-P302+P352-P304+P340-P305+P351+P338-P330-P332+P313-P337+P313-P362-P403+P233-P405-P501 |
* 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 |
---|---|---|
52.6% | With tetraethylammonium hydroxide;tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; at 75℃; for 48h;Heating / reflux; | 1.0 g (0.53 mmol) of M-3, 1.03 g (1.92 mmol) of (3-(9H-carbazole- 9-yl)-5-(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolane-2-yl)phenyl)-9H-carbazole, and 0.05 g of tetrakistriphenylphosphine palladium were dissolved in 30 ml_ of tetrahydrofuran (THF) under an argon atmosphere in a 100ml round flask with a thermometer, a reflux condenser, and an agitator, and 15 ml_ of 20% tetratriethyl ammonium hydroxide was added thereto. The resulting mixture was refluxed at 75 0C for 48 hours.When the reaction was complete, the reactant was cooled to room temperature, and was then extracted several times with methylenechloride and washed with water.Then, anhydrous magnesium sulfate was used to remove moisture <n="88"/>from the washed reactant. The resulting product was filtered to remove the solvent.The reactant with no solvent was purified through a silica gel column using a mixed solvent of methylenechloride/hexane in a ratio of 1 :1 and recrystallized in acetone, preparing 0.8 g (52.6%) of white CISH-3. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With tetraethylammonium hydroxide;tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; at 75℃; for 48h;Heating / reflux; | 1.0 g (0.83 mmol) of M-1 , 2.22 g (4.15 mmol) of (3-(9H-carbazole- 9-yl)-5-(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolane-2-yl)phenyl)-9H-carbazole, and 0.05 g of tetrakistriphenylphosphine palladium were dissolved in 40 ml_ of tetrahydrofuran (THF) under an argon atmosphere in a 100ml round flask with a thermometer, a reflux condenser, and an agitator. 20 mL of 20% tetratriethyl ammonium hydroxide was added thereto. The mixture was refluxed for reaction at 75 0C for 48 hours.When the reaction was complete, the reactant was cooled to room temperature and then extracted with methylenechloride and washed several times.Then, anhydrous magnesium sulfate was used to remove moisture from the reactant. The resulting product was filtered to remove a solvent. After removing the solvent, the reactant was purified with a silica gel column using a mixed solvent of methylenechloride/hexane in a ratio of <n="86"/>1 :1 and recrystallized in a mixed solvent of acetone/hexane, obtaining 1.54 g (85%) of CISH-1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75.8% | With tetraethylammonium hydroxide;tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; at 75℃; for 48h;Heating / reflux; | 0.8 g (0.66 mmol) of M-2, 1.42 g (2.66 mmol) of (3-(9H-carbazole- 9-yl)-5-(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolane-2-yl)phenyl)-9H-carbazole, and 0.06 g of tetrakistriphenylphosphinepalladium were dissolved in 30 mL of tetrahydrofuran (THF) under an argon atmosphere in a 100 ml round flask with a thermometer, a reflux condenser, and an agitater. Then, 15 ml_ of 20% tetratriethyl ammonium hydroxide was added thereto and refluxed for reaction at 75 0C for 48 hours.When the reaction was complete, the reactant was cooled to room temperature, and was then extracted several times with methylenechloride and washed.Then, anhydrous magnesium sulfate was used to remove moisture from the reactant, which was then filtered to remove a solvent.The reactant with no solvent was purified through a silica gel <n="87"/>column using a mixed solvent of methylenechloride/hexane in a ratio of 1 :1 , preparing 1.1 g (75.8%) of white CISH-2. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | With tetraethylammonium hydroxide;tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; at 75℃; for 48h;Heating / reflux; | 1.2 g (1.11 mmol) of M-3, 1 ,78 g (3.34 mmol) of a material G (3- (9H-carbazol-9-yl)-5-(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-yl)phenyl)-9H-carbazole, and 0.06 g (0.05 mmol) of tetraistriphenylphosphinepalladium were dissolved in 30 ml_ of THF (tetrahydrofuran) in a 250ml round flask with a thermometer, a reflux condenser, and an agitator under an argon atmosphere, and 15ml_ of 20% tetratriethylammonium hydroxide was added thereto. The resulting mixture was refluxed for reaction at 75 0C for48 hours.When the reaction was complete, the reactant was cooled to room temperature. The reactant was extracted several times with methylenechloride, and was also washed several times with water. Then, the reactant was treated with anhydrous magnesium sulfate to remove moisture. After it was filtered, the solvent was removed therefrom.The reactant with no solvent was purified through a silica gel column using a solvent of methylenechloride/hexane mixed in a ratio of 1 :2 and recrystallized a mixed solvent of acetone/hexane, obtaining 1.3 g <n="67"/>(68%) of white CISH-4. This material had a maximum light emitting wavelength of 388 nm in a chloroform solution. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With tetraethylammonium hydroxide;tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; at 75℃; for 48h;Heating / reflux; | 1.2 g (1.11 mmol) of M-4, 1 ,78 g (3.34 mmol) of a material G (3-(9H-carbazol-9-yl)-5-(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-yl)phenyl )-9H-carbazole, and 0.06 g (0.05 mmol) of tetrakistriphenylphosphinepalladium were dissolved in 30 mL of THF (tetrahydrofuran) in a 250ml round flask with a thermometer, a reflux condenser, and an agitator under an argon atmosphere, and 15ml_ of 20% tetratriethylammonium hydroxide was added thereto. The resulting mixture was refluxed for reaction at 75 0C for 48 hours.When the reaction was complete, the reactant was cooled to room temperature and then extracted several times with methylenechloride, and was also washed several times with water.Then, the reactant was treated with anhydrous magnesium sulfate to remove moisture. After it was filtered, the solvent was removed therefrom. The reactant with no solvent was purified through a silica gel <n="68"/>column using a solvent of methylenechloride/hexane mixed in a ratio of 1 :2 and recrystallized in a mixed solvent of acetone/hexane, obtaining 1.35 g (70%) of white CISH-5. This material had a maximum light emitting wavelength of 386 nm in a chloroform solution. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
54% | With tetraethylammonium hydroxide;tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; at 75℃; for 48h;Heating / reflux; | 1.2 g (0.71 mmol) of M-5, 0.95 g (1.78 mmol) of a material G (3- (9H-carbazol-9-yl)-5-(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-yl)phenyl)-9 H-carbazole, and 0.05 g (0.043 mmol) of tetrakistriphenylphosphinepalladium were dissolved in 30 ml_ of THF (tetrahydrofuran) in a 250ml round flask with a thermometer, a reflux condenser, and an agitator, and 15mL of 20% tetratriethylammonium hydroxide was added thereto. The resulting mixture was refluxed for reaction at 75 0C for 48 hours. When the reaction was complete, the reactant was cooled to room temperature and then extracted several times with methylenechloride, and was also washed several times with water.Then, the reactant was treated with anhydrous magnesium sulfate to remove moisture. After it was filtered, the solvent was removed therefrom. <n="71"/>The reactant with no solvent was purified through a silica gel column using a solvent of methylenechloride/hexane mixed in a ratio of 2:3 and recrystallized with a mixed solvent of acetone/hexane, obtaining 0.9 g(54%) of white CISH-8. This material had a maximum light emitting wavelength of 386 nm in a chloroform solution. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73.3% | With tetraethylammonium hydroxide;tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; at 75℃; for 48h;Heating / reflux; | 1 2 g (1 27 mmol) of M-1 , 1 ,71 g (3.19 mmol) of a material G (3- (9H-carbazol-9-yl)-5-(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-yl)phenyl)-9H-carbazole), and 0 06 g (0.05 mmol) of tetrakistriphenylphosphine palladium were dissolved in 30 mL of THF (tetrahydrofuran) in a 250ml round flask with a thermometer, a reflux condenser, and an agitator, and15ml_ of 20% tetratriethylammonium hydroxide was added thereto The resulting mixture was refluxed for reaction at 75 0C for 48 hours.When the reaction was complete, the reactant was cooled to room temperature and then extracted several times with methylenechloride and washed several times with water.Then, the reactant was treated with anhydrous magnesium sulfate to remove moisture. After the resulting product was filtered, the solvent was removed.The reactant without the solvent was purified through a silica gel column using a solvent of methylenechloride/hexane mixed in a ratio of 2:3 and recrystallized in a mixed solvent of methylenechloride/hexane, obtaining 1.49 g (73.3%) of white CISH-1. This material had a maximum light emitting wavelength of 365 nm in a chloroform solution. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78.8% | With tetraethylammonium hydroxide;tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; at 75℃; for 48h;Heating / reflux; | 1.2 g (1.27 mmol) of M-2, 1 ,71 g (3.19 mmol) of a material G (3-(9H-carbazol-9-yl)-5-(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-yl)phenyl)-9H-carbazole, and 0.06 g (0.05 mmol) of tetrakistriphenylphosphinepalladium were dissolved in 30 ml_ of THF(tetrahydrofuran) in a 250 ml round flask with a thermometer, a reflux condenser, and an agitator under an argon atmosphere, and 15ml_ of 20% tetratriethylammonium hydroxide was added thereto. The resulting mixture was refluxed for reaction at 75 0C for 48 hours.When the reaction was complete, the reactant was cooled to room temperature and extracted several times with methylenechloride, and was also washed several times with water. Then, the washed reactant was treated with anhydrous magnesium sulfate to remove moisture. After the resulting product was filtered, the solvent was removed therefrom.The reactant with no solvent was purified through a silica gel column using a solvent of methylenechloride/hexane mixed in a ratio of 2:3 and recrystallized in a mixed solvent of methylenechloride/hexane, obtaining 1.6 g (78.8%) of white CISH-2. This material had a maximum <n="65"/>light emitting wavelength of 363 nm in a chloroform solution. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65.4% | Step 4: Synthesis of Intermediate (F)35.0 g (72 mmol) of the intermediate (E) was dissolved in 350 ml of tetrahydrofuran and added with 61.5 ml (98 mmol) of an n-butyllithium hexane solution (1.6M) under an argon atmosphere at -70 C. The obtained solution was agitated at -70 C. to 40 C. for 1 hour. The reaction flux was frozen to -70 C. and slowly added with 29.3 ml (144 mmol) of isopropyl tetramethyl dioxaborolane in a dropwise fashion. The obtained solution was agitated at -70 C. for 1 hour, and heated to room temperature and agitated for 6 hours. The obtained reaction solution was added with 200 ml of water and agitated for 20 minutes.After the reaction solution was separated into two liquid layers, an organic layer thereof was dried with anhydrous sodium sulfate. After the organic solvent was removed under a reduced pressure, the obtained residue was purified with silica gel column chromatography to provide 25.1 g (yield 65.4%) of the intermediate (F). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1.3 g | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; for 24h;Inert atmosphere; Reflux; | Intermediate 2 (2 g, 3.7 mmol), 1,3,5-tribromo benzene (5.9 g, 18.7 mmol), tetrakis (triphenylphosphine) palladium (0) (0.1 g, 0.1 mmol) in the THF It was dissolved in a nitrogen stream. Put potassium carbonate (1 M, 30 ml) was stirred and refluxed for 24 hours up to temperature. After the distilled water and extracted with MC, by the MC / Hexane solvent mixture as a developing solvent to conduct column chromatography to give the intermediate 3 in 1.3 g. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
64.4% | With potassium carbonate;tetrakis(triphenylphosphine) palladium(0); In tetrahydrofuran; water; toluene; for 9h;Reflux; | Step 5: Synthesis of Intermediate (G)45.1 g (84 mmol) of the intermediate (F), 20.0 g (84 mmol) of 3,5-dibromopyridine, and 2.44 g (2.1 mmol) of tetrakis-(triphenyl phosphine) palladium were suspended in 600 ml of tetrahydrofuran and 400 ml of toluene, and then the suspension was added with a solution in which 23.3 g (169 mmol) of potassium carbonate was dissolved in 400 ml of water. The obtained mixture was heated and refluxed for 9 hours. The reaction fluid was separated into two layers, and an organic layer thereof was cleaned with a sodium chloride saturated aqueous solution and dried with anhydrous sodium sulfate.The organic solvent was removed by distillation under a reduced pressure, and the residue was recrystallized by toluene. The precipitated crystals were separated by filtration and cleansed with toluene to provide 30.7 g (64.4%) of the intermediate (G). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Step 2: Synthesis of Intermediate (K)10.3 g of the intermediate (F) synthesized in Example 2, 3.0 g of 1,4-dibromobenzene, 17.58 g of potassium carbonate, and 0.73 g of tetrakis-(triphenylphosphine) palladium were suspended in 200 ml of tetrahydrofuran, 200 ml of toluene, and 50 ml of purified water, and heated and refluxed under a nitrogen atmosphere for 24 hours.15 ml of an n-butyl lithium hexane solution (1.6M) was added and then the obtained solution was agitated at -70 C. for 30 minutes, and the reaction fluid was slowly added with 47.9 ml (235 mmol) of isopropyl tetramethyl dioxaborolane in a dropwise fashion. After the obtained solution was agitated at -70 C. for 1 hour, it was heated to room temperature and agitated for 6 hours. To the obtained reaction solution, 200 ml of water was added and agitated for 20 minutes. After the reaction solution was separated into two liquid layers, an organic solvent thereof was removed under a reduced pressure. The obtained residue was purified with silica gel column chromatography to provide 6 g of the intermediate (K). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In 1,4-dioxane; for 3h;Inert atmosphere; Reflux; | A three-necked flask of 2000ml, equipped with mechanical stirring, Ar gas protection.Was added 3,5-bis (carbazol-9-yl) bromobenzene 9.72 g (molecular weight 486,0.02mol), with boronic acid pinacol ester 5.6 g (molecular weight 254.2, 0.022mol) frequency, Pd (dppf) Cl23.2g (0.0044mol), potassium acetate 36g (molecular weight 138,0.26mol), 1,4-dioxane 500ml.Mechanical agitation, ventilation kept under reduced pressure Ar atmosphere for three times, the reaction was monitored by TLC (thin layer chromatography), to the starting material completely disappeared after 3 hours reflux the reaction was complete.Allowed to cool, the reaction system was divided into two layers, the organic layer was separated, evaporated to dryness, to give the product 9.72g, 91.0% yield. |
72% | With tetrakis(triphenylphosphine) palladium(0); potassium acetate; In 1,4-dioxane; at 80℃; for 12h;Inert atmosphere; | The purified compound (1) (1.7 g, 3.5 mmol), bis(pinacolato)diboron (0.93 g, 3.6 mmol),potassium acetate (0.68 g, 6.9 mmol) and tetrakis(triphenylphosphine)palladium(0) (0.2 g,0.2mmol) were dissolved in 1,4-dioxane (50mL) and a nitrogen atmosphere. After themixedsolution was stirred for 12 h at 80C, the reaction mixture was cooled to room temperature.The mixture extracted with dichloromethane (50 mL × 3 times) and dried over anhydrousMgSO4. The crude product was subjected to flash column chromatography (ethyl acetate:n-hexane = 1: 10) to give compound (2) (1.3 g, 72%). 1H NMR (CDCl3, 300 MHz); δ = 7.68(d, -CH-), 7.5 (d, -CH-), 7.45 (d, -CH-), 7.35 (m-CH-), 7.29(t, -CH3), 7.18(m, -CH-), 1.5(-CH3). |
71% | With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; potassium acetate; In N,N-dimethyl-formamide; at 100℃; for 24h; | 13.68 g (28.07 mmol) of Intermediate (G), 10.69 g (42.10 mmol) of 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi(1,3,2-dioxaborolane), 1.23 g (1.68 mmol) of PdCl2(dppf).CH2Cl2, and 8.26 g (84.20 mmol) of potassium acetate were mixed with 140 mL of dimethyl formamide, followed by stirring at a temperature of 100 C. for 24 hours. Once the reaction was complete, the resulting mixture was cooled to room temperature and filtered through silica gel under reduced pressure. The obtained filtrate was concentrated under reduced pressure, and the resulting product was separated and purified by silica gel column chromatography and recrystallized using dichloromethane/n-hexane to obtain a desired compound, 10.62 g of Intermediate (H) (at a yield of 71%). LC-Mass (calculated value: 534.25 g/mol, measured value: M+1=535 g/mol) |
70% | With tetrakis(triphenylphosphine) palladium(0); potassium acetate; In 1,4-dioxane; for 12h;Inert atmosphere; Reflux; | 9,9'-(5-bromo-1,3-phenylene)bis(9H-carbazole) (6 g, 12.3 mmol), Bis(pinacolato)diboron(4.7 g, 18.4 mmol), potassium acetate (3.6 g, 37 mmol), and Pd(PPh3)4 (0.4 g, 0.3 mmol) were dissolved in distilled 1,4-dioxane. The reaction mixture was refluxed for 12 hours under nitrogen and then allowed to cool to room temperature. After the mixture washed with ethyl acetate, the solvent was removed under vacuum. The crude material was purified by column chromatography on silica gel (ethyl acetate:hexane=1:3 as eluent) to give the title compound 1 (yield: 70%). 1HNMR(CDCl3): δ (ppm) 8.20 (d, 6H), 7.60-7.40 (m, 9H), 7.35-7. 26 (m, 4H),1.30-1.45 (m, 12H). |
70% | With tetrakis(triphenylphosphine) palladium(0); potassium acetate; In 1,4-dioxane; for 12h;Reflux; Inert atmosphere; | 9,9-(5-bromo-1,3-phenylene)bis(9H-carbazole) (6 g,12.3 mmol), Bis(pinacolato)diboron (4.7 g, 18.4 mmol),potassium acetate (3.6 g, 37 mmol), and Pd(PPh34(0.4 g, 0.3 mmol) were dissolved in distilled 1,4-dioxane.The reaction mixture was refluxed for 12 hours undernitrogen and then allowed to cool to room temperature.After the mixture washed with ethyl acetate, the solventwas removed under vacuum. The crude material waspurified by column chromatograph on silica gel (ethylacetate:hexane = 1:3 as eluent) to give the title compound1 (yield: 70%). 1H NMR (CDCl3: (ppm) 8.20 (d, 6H),7.60-7.40 (m, 9H), 7.35-7.26 (m, 4H), 1.30-1.45 (m, 12H). |
65% | With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; potassium acetate; In 1,4-dioxane; at 60 - 80℃; for 14h;Inert atmosphere; | Intermediate compound (1) (16.4 g, 33.6 mmol),Bis (pinacolato) diboron (17.1g, 67.2mmol)And potassium acetate (32.97 g, 336 mmol) dissolved in 1,4-dioxane (200 ml),It was then stirred at about 60 C for about 15 minutes under a nitrogen atmosphere.Pd(dppf)CH2Cl2 (0.82 g, 1.0 mmol) was added to the reaction mixture and stirred at about 80 C for about 14 hours.The reaction mixture was cooled to room temperature, extracted with toluene, dried over MgSO 4 to remove water, and then separated by column chromatography (hexane: methylene chloride (MC) = 1:3, v/v).The intermediate compound (2) (11.76 g, yield: 65%) was obtained. |
53% | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In 1,4-dioxane; for 12h;Reflux; | Compound 1-2 64 g (131 mmol),50 g (197 mmol) of bis (pinacolato) diboron,Pd(dppf)Cl2 ([1,1'-bis (diphenylphosphine)ferrocene]dichloropalladium (II)), 4.8 g (6.55 mmol),25.7 g (262 mmol) of potassium acetate was suspended in 500 mL of 1,4-dioxane, and then refluxed and stirred for 12 hours.Extraction with dichloromethane and distilled waterThe high organic layer is filtered through silica gel. The organic solution was removed and recrystallized to obtain 37.1 g (yield 53%) of compound 1-3. |
3 g | With 1,1'-bis-(diphenylphosphino)ferrocene; potassium acetate; In 1,4-dioxane; for 24h;Inert atmosphere; Reflux; | 9H-carbazole (6.0 g, 35.7 mmol), and 1,3,5-tribromobenzene (5.0 g, 15.0 mmol), cooper (I) iodide (CuI, 0.7 g, 3.6 mmol), potassium carbonate (4.9 g, 35.7 mmol), 1,10-phenanthroline (1,10-phenanthroline, 0.6 g, 3.6 mmol) is dissolved in DMF to insert.Looking up the temperature under the flow of nitrogen was stirred under reflux for 12 hours.After extracting the reaction solution was subjected to column chromatography on MC MC / Hexane solvent mixture as a developing solvent to give the intermediate 1 of about 2 g. Intermediate 1 (4 g, 8.2 mmol) and 4,4,4 ', 4', 5,5,5 ', 5'-octamethyl-2,2'-bi (1,3,2- dioxane)See above) (3.12 g, 12.3 mmol), potassium acetate (2.4 g, 24.0 mmol), 1,1 '- bis (diphenylphosphino) ferrocene (1,1'-bis (diphenylphosphino) ferrocene, 0.2 g, 0.2 mmol) put in 1,4-dioxane (1,4-dioxane) was stirred at reflux for 24 hours under a nitrogen gas stream is dissolved.After having poured to terminate the reaction, distilled water and extracted with MC.MC / Hexane solvent mixture to a column chromatography with a developing solvent to obtain the intermediate 2 LE of 3 g. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
40% | With tetrakis(triphenylphosphine) palladium(0); tri-tert-butyl phosphine; potassium carbonate; In water; toluene; at 100℃; for 2h;Inert atmosphere; | General procedure: A mixture of 9-(3-(9H-carbazol-9-yl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-9H-carbazole 1 (3.9 g,7.30 mmol), <strong>[4181-20-8]tris(4-iodophenyl)amine</strong> 3b (1 g, 1.61 mmol),Pd(Ph3P)4 (0.37 g, 0.32mmol), t-Bu3P 50% in toluene(0.3 mL, 0.64mmol), and K2CO3 (4.4 g, 31.8 mmol) in 100 mL of toluene and 50 mL of distilled water was stirred at 100C for 2 days under argon. After completion of the reaction,the mixture was extracted with dichloromethane. The organic layers were then separated, dried over magnesium sulfate, filtered,and concentrated. The residues were purified by column chromatography using silica gel as the stationary phase and an n-hexane: dichloromethanemixture as the eluent to give the requisiteproduct 4b. Yield: 40%; |
40% | With tetrakis(triphenylphosphine) palladium(0); tri-tert-butyl phosphine; potassium carbonate; In water; toluene; at 100℃; for 48h;Inert atmosphere; | To a solution of 9- (3- (9H-carbazol-9-yl) -5- (4,4,5,5-tetramethyl-1,3,2-dioxa (3.9 g, 7.30 mmol), tris (4-iodophenyl) amine (Formula b) (1 g, 1.61 mmol), Pd Pd3P)4(0.37 g, 0.32 mmol), in toluene t-Bu3P 50% (0.3ml, 0.64 mmol) and K2CO3and the mixture of (4.4 g, 31.8 mmol) under an argon atmosphere for 2 days And stirred at 100 C.After completion of the reaction, the mixture was extracted with dichloromethane.Then, the organic layer was separated, MgSO4was then dried filtered and concentrated.The obtained residue was purified by silica gel column chromatography using n-hexane: dichloromethane as an eluent to obtain a product of formula (2a) as a beige solid (yield: 40%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
61% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In water; toluene; at 100℃;Inert atmosphere; | General procedure: A mixture of <strong>[1082549-89-0]9-(3-(9H-carbazol-9-yl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-9H-carbazole</strong> 1 (2.16g, 4.04 mmol), 4-iodo-N,N-diphenylbenzenamine 3a (1 g,2.69 mmol), Pd(Ph3P)4 (0.31 g, 0.27 mmol), and K2CO3 (1.86 g, 13.47 mmol) in 100 mL of toluene and 50 mL of distilled water was stirred at 100 C overnight under argon. After completion of the reaction, the mixture was extracted with dichloromethane. The organic layers were then separated, dried over magnesium sulfate, filtered, and concentrated. The residues were purified by column chromatography using silica gel as the stationary phase and an n-hexane: dichloromethane mixture as the eluent to give the requisite product 4a. Yield: 61% |
61% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; at 100℃;Inert atmosphere; | To a solution of 9- (3- (9H-carbazol-9-yl) -5- (4,4,5,5-tetramethyl-1,3,2-dioxa (2.1 g, 4.04 mmol) and 4-iodo-N, N-diphenylbenzenamine (a) (1 g, 2.69 mmol) ), Pd (Pd3P)4(0.31 g, 0.27 mmol) and K2CO3(1.86 g, 13.47 mmol) was stirred overnight at 100 C. under an argon atmosphere.After completion of the reaction, the mixture was extracted with dichloromethane.Then, the organic layer was separated, MgSO4was then dried filtered and concentrated.The obtained residue was purified by silica gel column chromatography using n-hexane: dichloromethane as an eluent to obtain a white solid (yield: 61%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In 1,4-dioxane; at 95℃; for 24h; | General procedure: N- (biphenyl-4-yl) -N- (4-bromophenyl)-9,9-dimethyl-9H-fluoren-2-amine (5.2 g, 0.010 mol) inbis (pinacolato) dibron (2.5 g, 0.012 mol),PdCl2 (dppf) (0.4 g, 0.0005 mol), potassium-acetate (2.7 g,0.020 mol) 1,4-dioxane , add 100 mL wasreacted by stirring for 24 hours at 95 . After the reaction cooled to H20:After layer separation the MC columnpurification ( n - Hexane : MC ) to the intermediate 1-1 to obtain 4.0 g (yield 71%) |
72% | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In 1,4-dioxane; at 95℃; for 24h; | General procedure: Intermediate 1-1 (5.2 g, 0.010 mol), bis(pinacolato)dibron (2.5 g, 0.012 mol) PdCl2(dppf) (0.4 g, 0.0005 mol), potassium-acetate (2.7 g, 0.020 mol), 100 mL 4-dioxane was reacted with stirring for 24 hours at 95 C the end of the reaction after cooling by H2O:. after layer separation the MC column purification (n-Hexane: MC) to the intermediate 1-2, 4.0 g (yield: 71%) was obtained. (M / z = 563). |
General procedure: (2) According to the reaction formula, compound M6 is prepared as follows: a mixture of compound M5 (25.40 g, 56.95 mmol), pinacol biborate (15.85 g, 62.64 mmol) and potassium acetate (16.74 g, 170.90 mmol) are dissolved In anhydrous 1,4-dioxane (200.0 mL). The resulting mixture was degassed with nitrogen for 15 min, and then tris(dibenzylideneacetone) dipalladium (CAS number: 51364-51-30, 52 g, 0.57 mmol) and2-dicyclohexylphosphino-2', 4', 6'-triisopropylbiphenyl(0.54 g, 1.14 mmol). After refluxing at 110C for 12 hours under nitrogen, the mixture was filtered immediately. The filtrate was cooled to 0C in the refrigerator, the product was precipitated, and filtered again to obtain compound M6 as a white powder, yield: 65%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With potassium phosphate; tetrakis(triphenylphosphine) palladium(0); In 1,4-dioxane; water; at 120℃; for 2h; | A-5 8.0g (16.02mmol), 9,9 '- (5- (4,4,5,5- tetramethyl-dioxa -1,3,2- borane-2-yl) phenyl-1,3- Rennes) bis (9H- cover)(<strong>[1082549-89-0]9,9'-(5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,3-phenylene)bis(9H-carbazole)</strong>)10.3g(19.22mmol), Tetrakis (triphenylphosphine) palladium (0) 0.93g (0.8mmol), K3PO4 to 10.2g (48.06mmol), 1,4- dioxane (1,4-dioxane), 160mL, 2 hours at 120 C under 32mL H2O It was stirred while refluxing. After the reaction is a rear solid cooling to room temperature produced after the completion of the filter was washed with dichloromethane (dicholoromethane), ethyl acetate (EA), methanol (MeOH). After the solid in dichloromethane (dichloromethane) to all dissolved after silica gel with excess filter to give 10.3g of the desired compound 1-12 (78%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | With potassium phosphate; tetrakis(triphenylphosphine) palladium(0); In 1,4-dioxane; water; at 120℃; for 7h; | E-4 8.0g (18.17mmol), 9,9 '- (5- (4,4,5,5- tetramethyl-dioxa -1,3,2- borane-2-yl) -1 , 3- phenylene)bis (9H-)(<strong>[1082549-89-0]9,9'-(5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,3-phenylene)bis(9H-carbazole)</strong>)11.85g(21.8mmol), Tetrakis (triphenylphosphine) palladium (0) 1.05g (0.91mmol), K3PO4 11.57g (54.51mmol) 1,4-dioxane (1,4-dioxane), 160mL, 32mL H2O under 7 hours at 120C It was stirred while refluxing. After the reaction was extracted with distilled water and dichloromethane (dichloromethane). Purified to remove the solvent by rotary evaporation The organic layer was dried over anhydrous MgSO4 dichloromethane and hexane by column chromatography as a developing solvent to obtain 9.5g of the desired compound 1-157 (68%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; water; toluene; at 120℃; for 6h; | Compound 6-3 5g (12.81mmol ) and ((3,5-di(9H-carbazol-9-yl)phenyl)boronicacid) 6.37g (14.09mmol),Pd(PPh3)4 0.74g (0.64mmol), K2CO3 3.5g (25.62mmol) toluene 50ml,ethanol (EtOH) 5ml and 5ml H2O was refluxed at 120C for 6 hour.After cooling to room temperature after completion of the reaction and extracted with distilled water and EA (ethyl acetate). The organic layer was dried over anhydrous MgSO4 then the solvent removed by rotary evaporator and EA (ethyl acetate) and hexane (Hexane) gave after washing to give 6.4g the title compound 85 (69%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
77% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; water; toluene; at 120℃; for 6h; | Compound 8-5 5g (12.81mmol ) and (3,5-di(9H-carbazol-9-yl)phenyl)boronicacid) 6.37g(14.09mmol),Pd(PPh3)4 0.74g (0.64mmol), K2CO3 3.5g (25.62mmol) toluene 50ml,ethanol (EtOH) 5ml and 5ml H2O was refluxed at 120C for 6 hour.After cooling to room temperature after completion of the reaction and extracted with distilled water and EA (ethyl acetate). The organic layer was dried over anhydrous MgSO4 then the solvent removed by rotary evaporator and EA (ethyl acetate) and hexane (Hexane) gave after washing to give 7.1g the title compound 110 (77%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
38% | With tetrakis(triphenylphosphine) palladium(0); water; potassium carbonate; In ethanol; toluene; for 12h;Reflux; | Compound1-1-1 4g (8.82 mmol), 9,9'- (5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,3-phenylene) bis (9H-carbazole), 3.45g (8.02 mmol), (tetrakis(triphenylphosphine) palladium), 0.92g (0.80 mmol), potassium carbonate, 3.33g(24.06 mmol ), toluene, H2O, ethanol mixed solutionwas refluxed for 12 hours. When the reaction is complete the resulting solid isdried and then filtered (filter) to give the title compound 24; 2.4g (38%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
56.8% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; toluene; for 24h;Reflux; Inert atmosphere; | Synthesis procedure is the same method as compound A1, the yield of the final product was 56.8%. A mixture of intermediate Ib (10mmol), dibenzo[b,d]furan-4-ylboronic acid (10mmol), Pd(PPh3)4 (0.25g, 0.21 mmol), Na2CO3 solution (2M, 12ml, 24mmol), ethanol (15ml) and toluene (50ml) was loaded into a 250ml three-necked flask. The mixture was degassed and refluxed under nitrogen atmosphere for 24 hours. After cooling, water (50ml) was added to the mixture. The crude product was collected by filtration and the solid powder was washed several times with methanol to remove impurities. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
32% | With tris-(dibenzylideneacetone)dipalladium(0); potassium acetate; tricyclohexylphosphine; In 1,4-dioxane; at 80℃; for 16h;Inert atmosphere; | In a four-necked flask, 3,5-bis(carbazol-9-yl)chlorobenzene (4g, 9mmol), bis(pinacolato)diboron (2.4g, 9.4mmol), KOAc (2.5g , 25.8mmol), Pd2(dba)3 (258mg, 0.284mmol), tricyclohexylphosphine (385mg, 1.4mmol) and anhydrous 1,4-dioxane (120ml). The mixture in a nitrogen atmosphere, reacted at 80 deg. C overnight for 16 hours. The reaction solution was poured into water, extracted with ethyl acetate and washed with saturated NaCl (aq). Subsequently, dried over anhydrous magnesium sulfate and the solvent was removed with an evaporator. The residue was purified by column chromatography and obtained 1.5g of product.Yield 32%. |
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In 1,4-dioxane;Inert atmosphere; | Under a protective atmosphere, put the first intermediate, bipinacol borate, 1,1'-bis(diphenylphosphopalladium)ferrocene dichloride in 1,4-bis In the oxane, the reaction produces intermediate 2 (intermediate 2); |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
36% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; toluene; for 24h;Reflux; Inert atmosphere; | Synthesis procedure is the same manner as in compound A1, the final yield of product was 36%. A mixture of intermediate Ib (10mmol), dibenzo[b,d]furan-4-ylboronic acid (10mmol), Pd(PPh3)4 (0.25g, 0.21 mmol), Na2CO3 solution (2M, 12ml, 24mmol), ethanol (15ml) and toluene (50ml) was loaded into a 250ml three-necked flask. The mixture was degassed and refluxed under nitrogen atmosphere for 24 hours. After cooling, water (50ml) was added to the mixture. The crude product was collected by filtration and the solid powder was washed several times with methanol to remove impurities. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
42% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In toluene; at 100℃;Inert atmosphere; | General procedure: A mixture of dibromosilane derivatives A (0.5 g, 1 equiv.),4,4,5,5-tetramethyl-1,3,2-dioxaborolane derivatives B (3 quiv.),Pd(Pd3P)4 (0.2 equiv.) in toluene (30 mL) was added dropwiseK2CO3 (2 M aq. 15 mL) and stirred overnight at 100 C under argon.After the completion of the reaction, the mixture was extractedwith dichloromethane. The organic layers were separated, driedover magnesium sulfate, filtered, and concentrated. The residueswere purified by silica gel column chromatography and thenrecrystallized in acetone or ethanol to give the requisite productsDM4CzDBPSi, DM2CzDBPSi, DP4CzDBPSi. 2.2.2. Dimethyldi(4-(3,5-bis-carbazol-9-yl-phenyl)phenyl)silane(DM4CzDBPSi)Yield: 42%; white solid; m.p.: 349 C; FT-IR (KBr pellet): max3433, 3055, 2953, 1592, 1480, 1454, 1333, 1312, 1229, 1155, 1113,820, 747, 723 cm1; 1H NMR (500 MHz, CDCl3) d 8.19 (d, 8H,J 7 Hz), 7.96 (d, 4H, J 2 Hz), 7.83 (t, 2H, J 2 Hz), 7.69e7.74 (q,8H, J 8.5 Hz), 7.62 (d, 8H, J 8.0 Hz), 7.44e7.48 (m, 8H), 7.32e7.35(m, 8H), 0.62 (s, 6H); 13C NMR (125 MHz, CDCl3) d 144.6, 140.6,140.1, 139.9, 138.4, 135.1, 126.7, 126.3, 124.3, 123.9, 123.7, 120.6,120.5, 109.8, 31.0; GC-MS: 1025.24 for C74H53N4Si [MH]; HRMS(m/z, FAB) Calcd for C74H53N4Si [MH] 1025.4040, found1025.4038. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
30% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In toluene; at 100℃;Inert atmosphere; | General procedure: A mixture of dibromosilane derivatives A (0.5 g, 1 equiv.),4,4,5,5-tetramethyl-1,3,2-dioxaborolane derivatives B (3 quiv.),Pd(Pd3P)4 (0.2 equiv.) in toluene (30 mL) was added dropwiseK2CO3 (2 M aq. 15 mL) and stirred overnight at 100 C under argon.After the completion of the reaction, the mixture was extractedwith dichloromethane. The organic layers were separated, driedover magnesium sulfate, filtered, and concentrated. The residueswere purified by silica gel column chromatography and thenrecrystallized in acetone or ethanol to give the requisite productsDM4CzDBPSi, DM2CzDBPSi, DP4CzDBPSi. |