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CAS No. : | 444796-09-2 | MDL No. : | MFCD28147705 |
Formula : | C18H11Br2N | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | MDXCDMSVFQIDGN-UHFFFAOYSA-N |
M.W : | 401.10 | Pubchem ID : | 22392517 |
Synonyms : |
|
Num. heavy atoms : | 21 |
Num. arom. heavy atoms : | 19 |
Fraction Csp3 : | 0.0 |
Num. rotatable bonds : | 1 |
Num. H-bond acceptors : | 0.0 |
Num. H-bond donors : | 0.0 |
Molar Refractivity : | 96.18 |
TPSA : | 4.93 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 : | No |
Log Kp (skin permeation) : | -4.22 cm/s |
Log Po/w (iLOGP) : | 3.7 |
Log Po/w (XLOGP3) : | 6.38 |
Log Po/w (WLOGP) : | 6.31 |
Log Po/w (MLOGP) : | 5.61 |
Log Po/w (SILICOS-IT) : | 5.38 |
Consensus Log Po/w : | 5.48 |
Lipinski : | 1.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 1.0 |
Muegge : | 2.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -6.95 |
Solubility : | 0.000045 mg/ml ; 0.000000112 mol/l |
Class : | Poorly soluble |
Log S (Ali) : | -6.28 |
Solubility : | 0.000213 mg/ml ; 0.000000531 mol/l |
Class : | Poorly soluble |
Log S (SILICOS-IT) : | -8.28 |
Solubility : | 0.00000213 mg/ml ; 0.0000000053 mol/l |
Class : | Poorly soluble |
PAINS : | 0.0 alert |
Brenk : | 0.0 alert |
Leadlikeness : | 2.0 |
Synthetic accessibility : | 1.95 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P273-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H302-H315-H319-H412 | 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 |
---|---|---|
80% | With palladium diacetate; tris-(o-tolyl)phosphine; sodium t-butanolate In toluene | 2.5 g (8 mmol) 4,4’-dibromo biphenyl was used(utilized) to perform a cyclization reaction to synthesize 2.08g (80percent) of 4,4’-dibromo carbazole. The 4,4’-dibromo carbazole and iodinated phenyl were dissolved in 40 ml of toluene to synthesize Intermediate C through a buchwald reaction. |
78% | With copper; potassium carbonate In N,N-dimethyl-formamide at 130℃; Inert atmosphere | Synthesis of 2,7-dibromo-9-phenyl-9H-carbazole A mixture of 32.5 g (100 mmole) 2,7-dibromo-9H-carbazole, 20.4 g (100 mmole) iodobenzene, 9.5 g (150 mmole) of copper powder, 27.6 g (200 mmole) of potassium carbonate, and 600 ml dimethylformamide were heated at 130° C. under nitrogen overnight, then cooled to room temperature, the solution was filtered. The filtrate was extracted three times with dichloromethane and water, dried with anhydrous magnesium sulfate, the solvent was evaporated in vacuum. The residue was purified by column chromatography on silica(hexane-dichloromethane) afforded a white solid (31.3 g, 78 mmol, 78percent). |
70% | With copper; potassium carbonate In 1,2-dichloro-benzene at 140℃; for 12 h; | 2,7-dibromo-9H-carbazole (3.0 g, 9.32 mmol), iodobenzene (2.1 g, 10.25 mmol), copper powder (1.8 g,27.95 mmol) and potassium carbonate (4.1 g, 29.81 mmol) were added to stirred 60 mL o-dichlorobenzene, the system at 140 °C Reflow for 12 hours. At the end of the reaction, 20 mL of distilled water was added thereto, followed by extraction with ethyl acetate, and the organic phases were combined. After drying over anhydrous magnesium sulfate, it was concentrated and column chromatography afforded 2,7-dibromo-9-phenyl-carbazole (2.4 g, 70percent yield). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92.9% | With copper(l) iodide; 1,10-Phenanthroline; potassium carbonate; In water; N,N-dimethyl-formamide; | 2,7-dibromo-9H-carbazole (3.25 g, 10.0 mmol), 1-iodobenzene(2.45 g, 12.0 mmol), K2CO3 (4.17 g, 30 mmol), CuI (0.38 g, 2.0 mmol), 1,10-Phenanthroline hydrate (0.40 g, 2.0 mmol) andDMF (30.0 mL) were added to a 100 mL flask. The mixture washeated to 160 C under nitrogen for 24 h. After cooling to roomtemperature, the reaction mixture was extracted with dichloromethaneand water. The combined organic layers were dried overNa2SO4, filtered, and evaporated under reduced pressure. The cruderesidue was purified by column chromatography with dichloromethaneand petroleum ether as eluent to afford 3.80 g of whitesolid, in 92.9% yield. 1H NMR (500 MHz, CDCl3, d): 7.94 (d, J 8.2 Hz,2H), 7.65 (t, J 7.6 Hz, 2H), 7.54-7.47 (m, 5H), 7.40 (t, J 8.2 Hz, 2H). |
80% | With palladium diacetate; tris-(o-tolyl)phosphine; sodium t-butanolate; In toluene; | 2.5 g (8 mmol) 4,4?-dibromo biphenyl was used(utilized) to perform a cyclization reaction to synthesize 2.08g (80%) of 4,4?-dibromo carbazole. The 4,4?-dibromo carbazole and iodinated phenyl were dissolved in 40 ml of toluene to synthesize Intermediate C through a buchwald reaction. |
78% | With copper; potassium carbonate; In N,N-dimethyl-formamide; at 130℃;Inert atmosphere; | Synthesis of 2,7-dibromo-9-phenyl-9H-carbazole A mixture of 32.5 g (100 mmole) 2,7-dibromo-9H-carbazole, 20.4 g (100 mmole) iodobenzene, 9.5 g (150 mmole) of copper powder, 27.6 g (200 mmole) of potassium carbonate, and 600 ml dimethylformamide were heated at 130 C. under nitrogen overnight, then cooled to room temperature, the solution was filtered. The filtrate was extracted three times with dichloromethane and water, dried with anhydrous magnesium sulfate, the solvent was evaporated in vacuum. The residue was purified by column chromatography on silica(hexane-dichloromethane) afforded a white solid (31.3 g, 78 mmol, 78%). |
70% | With copper; potassium carbonate; In 1,2-dichloro-benzene; at 140℃; for 12h; | 2,7-dibromo-9H-carbazole (3.0 g, 9.32 mmol), iodobenzene (2.1 g, 10.25 mmol), copper powder (1.8 g,27.95 mmol) and potassium carbonate (4.1 g, 29.81 mmol) were added to stirred 60 mL o-dichlorobenzene, the system at 140 C Reflow for 12 hours. At the end of the reaction, 20 mL of distilled water was added thereto, followed by extraction with ethyl acetate, and the organic phases were combined. After drying over anhydrous magnesium sulfate, it was concentrated and column chromatography afforded 2,7-dibromo-9-phenyl-carbazole (2.4 g, 70% yield). |
With potassium carbonate; | Synthesis of 2,7-dibromo-9-phenyl-9H-carbazole A mixture of 32.5 g (100 mmole) 2,7-dibromo-9H-carbazole, 20.4 g (100 mmole) iodobenzene, 9.5 g (150 mmole) of copper powder, 27.6 g (200 mmole) of potassium carbonate, and 600 ml dimethylformamide were heated at 130 C. under nitrogen overnight, then cooled to room temperature, the solution was filtered. The filtrate was extracted three times with dichloromethane and water, dried with anhydrous magnesium sulfate, the solvent was evaporated in vacuum. The residue was purified by column chromatography on silica(hexane-dichloromethane) afforded a white solid (31.3 g, 78 mmol, 78%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
59% | With tetrakis(triphenylphosphine) palladium(0); In 1,4-dioxane; | Synthesis of 9-phenyl-2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole A mixture of 11.9 g (29.6 mmol) <strong>[444796-09-2]2,7-dibromo-9-phenyl-9H-carbazole</strong>, 18.8 g (74 mmol) of bis(pinacolato)diboron, 0.7 g (0.6 mmol) of tetrakis(triphenylphosphine)palladium, 8.7 g (89 mmol) of potassium acetate, and 500 ml 1,4 dioxane was degassed and placed under nitrogen, and then heated at 90 C. for 24 h. After finishing the reaction, the mixture was allowed to cool to room temperature. The organic phase separated and washed with ethyl acetate and water. After drying over magnesium sulfate, the solvent was removed in vacuum. The residue was purified by column chromatography on silica(hexane-dichloromethane) to give product (8.6 g, 59%) as a white solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
59% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; toluene; at 110℃; for 8h;Inert atmosphere; | Synthesis of 2-bromo-7-(5-methoxybiphenyl-2-yl)-9-phenyl-9H-carbazole A mixture of 4 g (10 mmol) of <strong>[444796-09-2]2,7-dibromo-9-phenyl-9H-carbazole</strong>, 75 g (12 mmol) of 5-methoxybiphenyl-2-ylboronic acid, 0.12 g (0.1 mmol) of tetrakis(triphenylphosphine)palladium, 15 ml of 2M Na2CO3, 20 ml of EtOH and 60 ml toluene was degassed and placed under nitrogen, and then heated at 110 C. for 8 h. After finishing the reaction, the mixture was allowed to cool to room temperature. The reaction mixture was extracted with ethyl acetate and water, dried with anhydrous magnesium sulfate, the solvent was evaporated in vacuum. The residue was purified by column chromatography on silica (hexane-dichloromethane) afforded a white solid (3 g, 5.9 mmol, 59%). |
With tetrakis(triphenylphosphine) palladium(0); In ethanol; toluene; | Synthesis of 2-bromo-7-(5-methoxybiphenyl-2-yl)-9-phenyl-9H-carbazole A mixture of 4 g (10 mmol) of <strong>[444796-09-2]2,7-dibromo-9-phenyl-9H-carbazole</strong>, 75 g (12 mmol) of 5-methoxybiphenyl-2-ylboronic acid, 0.12 g (0.1 mmol) of tetrakis(triphenylphosphine)palladium, 15 ml of 2M Na2CO3, 20 ml of EtOH and 60 ml toluene was degassed and placed under nitrogen, and then heated at 110 C. for 8 h. After finishing the reaction, the mixture was allowed to cool to room temperature. The reaction mixture was extracted with ethyl acetate and water, dried with anhydrous magnesium sulfate, the solvent was evaporated in vacuum. The residue was purified by column chromatography on silica (hexane-dichloromethane) afforded a white solid (3 g, 5.9 mmol, 59%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
59% | With tetrakis(triphenylphosphine) palladium(0); potassium acetate; In 1,4-dioxane; at 90℃; for 24h;Inert atmosphere; | Synthesis of 9-phenyl-2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxa borolan-2-yl)-9H-carbazole A mixture of 11.9 g (29.6 mmol) <strong>[444796-09-2]2,7-dibromo-9-phenyl-9H-carbazole</strong>, 18.8 g (74 mmol) of bis(pinacolato)diboron, 0.7 g (0.6 mmol) of tetrakis(triphenylphosphine)palladium, 8.7 g (89 mmol) of potassium acetate, and 500 ml 1,4 dioxane was degassed and placed under nitrogen, and then heated at 90 C. for 24 h. After finishing the reaction, the mixture was allowed to cool to room temperature. The organic phase separated and washed with ethyl acetate and water. After drying over magnesium sulfate, the solvent was removed in vacuum. The residue was purified by column chromatography on silica(hexane-dichloromethane) to give product(8.6 g, 59%) as a white solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
48.82% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; water; toluene; for 24h;Reflux; Inert atmosphere; | Example 3:Compounds of formula 6 500ml three-necked flask,Obtained above, a compound of Formula 2 6.05g (17.6mmol),2,7-dibromo-9-phenyl-carbazole 3.28g (8mmol),Tetrakis (triphenylphosphine) palladium 1.0g,20ml aqueous potassium carbonate (4.3g of potassium carbonate dissolved in 20ml of water),40ml and 200ml of toluene ethanol mix,Reflux under nitrogen for 24h.The reaction was cooled to room temperature,Then extracted with dichloromethane (2 * 200ml),The combined organic layersDried over anhydrous sodium sulfate,Concentrated to give an oil.After column chromatography,Volume ratio of ethyl acetate: petroleumEther = 1:10 ~ 1: 3 as eluentTo give a white solid 2.7g,Yield 48.82%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
35% | With copper(l) cyanide; In N,N-dimethyl-formamide; at 150℃; for 24h; | 2,7-dibromo -9-phenyl-9H-carbazole 20.0 g (50.0 mmol) and 4.48 g CuCN (50.0 mmol) dissolved in a DMF 120 mL at 24 hours after 150oC dongan stirring. After cooling the reaction solution to room temperature, it was added 60 mL of aqueous ammonia and 60 mL of water and extracted three times with 60 mL CH2Cl2. The combined organic layers were dried over magnesium sulfate and purified by separation of the residue obtained by evaporation of the solvent by silica chromatography to give the intermediate jelgwan I-14 6.08 g (yield 35%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
0.1 g | With bis(di-tert-?butyl(4-?dimethylaminophenyl)?phosphine)?dichloropalladium(II); tetrabutylammomium bromide; potassium carbonate; In toluene; for 8h;Reflux; | 2-(5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridin-2-yl)thiazole (1.5 g), 2,7- di bromo -9-phenyl-9H-carbazole (1.3 g), potassium carbonate (0.7 g), tetrabutylammonium bromide (0.1 g), Pd-132 (trademark; manufactured by Johnson-Matthey) (0.2 g) and toluene (5 ml) the flask was stirred for 8 hours at the reflux temperature into the heating. The reaction mixture was cooled to room temperature and the precipitate collected by suction filtration, washed with water, the resulting solid. In addition, recrystallized from chlorobenzene, compound (1-404): 2,2 '-(5,5'-(9-phenyl-9H-carbazole-2,7-diyl)bis(pyridin-5,2-diyl))dithiazole (0.1 g). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1.7 g | With potassium phosphate; bis(di-tert-?butyl(4-?dimethylaminophenyl)?phosphine)?dichloropalladium(II); tetrabutylammomium bromide; In water; for 4h;Reflux; | 2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)phenyl)thiazole (4.3 g), 2,7- dibromo-9 -phenyl-9H-carbazole (2.5 g), tripotassium phosphate (5.3 g), tetrabutylammonium bromide (0.1 g), Pd(PPh3)4 (0.2 g), 1,2,4-trimethylbenzene (20ml ) and water (2 ml) was stirred for 4 hours the flask was heated at the reflux temperature into. The reaction mixture was cooled to room temperature, then water was added to dissolve the inorganic salt was subjected to suction filtration. The resulting solid was purified by silica gel column chromatography purification (eluent toluene / ethyl acetate = 9/1 (volume ratio)), and further recrystallized from o-dichlorobenzene, compound (1 to 25): 2,2 '-((9-phenyl-9H-carbazole-2,7-diyl)bis(4,1-phenylene))dithiazole (1.7 g). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; sodium t-butanolate; In o-xylene; toluene; at 160℃; for 48h; | Pd2 (dba) 3 357.3 mg (0.39 mmol) and t-Bu3P mg 157.9 (0.78 mmol) of o-xylene dissolved in 50 ml after 10 minutes at room temperature in agitation. 4H-Therapie in [3,2-b: 2 ', 3'-d] pyrrole 6.76 g (46 mmol), 5,9 - dibromo -7-phenyl-7H-benzo [c] carbazole 10.6 g ( It was added to 20 mmol) and t-BuONa 2.25 g (23.41 mmol) and reflux was stirred for 48hours at 160C. After the reaction was added to cold 20 ml of distilled water and extracted with ethyl acetate. The solvent was evaporated and dried over magnesium sulfate and filtered. 143 compound after column chromatography through )(4,4'-(9-phenyl-9H-carbazole-2,7-diyl)bis(4H-difuro[3,2-b:2',3'-d]pyrrole)) to give 8.53 g (yield 82%) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; sodium t-butanolate; In o-xylene; toluene; at 160℃; for 48h; | Pd2 (dba) 3 357.3 mg (0.39 mmol) and t-Bu3P mg 157.9 (0.78 mmol) of o-xylene dissolved in 50 ml after 10 minutes room temperature in agitation. Here the furnace dithiol 4H- [3,2-b: 2 ', 3'-d] pyrrole 8.23 g (46 mmol), 2,7- dibromo-9-phenyl -9H- carbazole 7.98 g (20 mmol), t-BuONa, and 2.25 g (23.41 mmol was addedand reflux was stirred for 48hours at 160C. After the reaction was added to cold 20 ml of distilled water and the organics extracted with ethyl acetate. The solvent was evaporated and dried over magnesium sulfate and filtered. After column chromatography through 101 compound 4,4 '- (9-phenyl -9H- carbazole-2,7-diyl) bis (4H- the furnace dithiane [3,2-b: 2', 3'-d ] pyrrole) to give 10.10 g (yield: 85%) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | With copper; potassium carbonate; In 1,2-dichloro-benzene; at 180℃; for 24h; | General procedure: 9H-carbazole 5.02 g (30 mmol), bromobenzene, 4.71 g (30 mmol), copper power 1.14 g (18 mmol) and K2CO36.22 g (45 mmol) of o-dichlorobenzene was dissolved in 80 mL then 180 oC in It was stirred for 24 hours. After cooling to room temperature the reaction solution was added to 60 mL water and extracted three times with ethyl acetate 50 mL. The combined organic layers were dried over magnesium sulfate and silica jelgwan the residue obtained by evaporation of the solventSeparated by chromatography To give intermediate I-1To give the 5.47 g (75% yield). |
73% | With copper; potassium carbonate; In 1,2-dichloro-benzene; at 180℃; for 24h; | General procedure: 6.69 g (40 mmol) of 9H-carbazole, 6.28 g (40 mmol) of bromobenzene, 1.52 g (24 mmol) of copper powder, and 8.29 g (60 mmol) of K2CO3 were dissolved in 100 mL of o-dichlorobenzene, and then, the resultant solution was stirred at a temperature of 180 C. for 24 hours. The reaction solution was cooled to room (e.g., ambient) temperature, 60 mL of water was added thereto, and the result was extracted three times by using 50 mL of ethyl acetate. An organic layer obtained therefrom was dried by using magnesium sulfate, and then residues obtained by evaporation of a solvent therefore were separation-purified by using silica gel column chromatography to obtain 7.10 g of Intermediate A-1 (yield: 73%). |
73% | With copper; potassium carbonate; In 1,2-dichloro-benzene; at 180℃; for 24h; | General procedure: After dissolving 5.02 g (30 mmol) of 9H-carbazole, 4.71 g (30 mmol) of bromobenzene, 1.14 g (18 mmol) of copper power and 6.22 g (45 mmol) of K2CO3 in 80 mL of o-dichlorobenzene Followed by stirring at 180 DEG C for 24 hours.After the reaction solution was cooled to room temperature, 60 mL of water was added and extracted three times with 50 mL of ethyl acetate. The resulting organic layer was dried over magnesium sulfate and the solvent was evaporated. The obtained residue was purified by silica gel column chromatography to obtain 5.47 g (yield 75%) of Intermediate I-1. The resulting compound was identified via LC-MS. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With tris(dibenzylideneacetone)dipalladium(0) chloroform complex; 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; sodium t-butanolate; In toluene; | 2.96 g (17.8 mmol) of [2,2?]bithiophenyl was used (utilized) to prepare 3,5,3?,5?-tetrabromo-[2,2?]bithiophenyl via bromination, and then 2.16 g (55%) of 3-bromo-[2,2?] bithiophenyl was synthesized through a debromination reaction using zinc. Then, the 3-bromo-[2,2?]bithiophenyl was used to perform a nucleophilic substiution reaction (SN2 reaction) and a cyclization reaction to synthesize Intermediate D. The Intermediate C and Intermediate D were then used (utilized) to perform buchwald-Hartwig cross-coupling to synthesize 2.99 g (83%) of Compound 107. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | 2,7-Dibromo-9-phenyl-carbazole (39.9 g, 0.1 mol) and 2'-nitro-2-biphenylboronic acid (50 g) were weighed in order.0.2mol), potassium carbonate (69g, 0.5mol), 300mL water, 1L toluene in a 2L three-neck flask, nitrogen protection, stirring at room temperature, system It is white and turbid. 20 minutes later, 1 g of tetraphenylphosphine palladium is added and the mixture is heated to reflux for 12 hours. The system produces a large amount of solids which are filtered off with suction. Solid product intermediate a-3 (51, 7 g, 90% yield). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | 2,7-Dibromo-9-phenyl-carbazole (39.9 g, 0.1 mol), 2'-fluoro-2-biphenylboronic acid (43 g, 0.2 mol), and potassium carbonate (69 g, 0.5 mol) were weighed in this order. , 300mL of water, 1L of toluene in a 2L three-neck flask, nitrogen protection, stirring at room temperature, the system is white and turbid, 20 minutes after adding 1g of tetraphenylphosphine palladium, heated to reflux for 12 hours, the system produces a lot of solids, suction filtration to obtain solids in the middle Body d-1 (52.4 g, 90% yield). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | 2,7-Dibromo-9-phenyl-carbazole (39.9 g, 0.1 mol), 4'-nitro-2-biphenylboronic acid (50 g, 0.2 mol), and potassium carbonate (69 g, 0.5 mol) were weighed in turn. ), 300mL water, 1L toluene in 2L three-neck flask, nitrogen protection, stirring at room temperature, systemIt was white and turbid. After 20 minutes, 1 g of tetrakistriphenylphosphine palladium was added and the mixture was heated under reflux for 12 hours. The system produced a large amount of solids which were filtered by suction to obtain a solid product intermediate a-2 (51, 7 g, yield 90%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
51% | With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In ethanol; water; toluene; at 120℃; for 3h;Inert atmosphere; | Step 1: Under nitrogen protection, <strong>[444796-09-2]2,7-dibromo-9-phenyl-9H-carbazole</strong> (3.37 g, 8.4 mmol) was added to the reaction vessel.2-biphenylboronic acid (1.82 g, 9.2 mmol),Tetrakistriphenylphosphine ruthenium (0.09 g, 0.08 mmol), sodium carbonate (2.67 g, 25.2 mmol),Toluene 60 mL, ethanol 20 mL, and distilled water 20 mL were stirred at 120 C for 3 h.After the end of the reaction, the distilled water was stopped, the ethyl acetate was extracted, and the organic layer was dried over MgS04.The solvent was distilled off under reduced pressure, and then purified by silica gel column chromatography to afford Intermediate 1-1 (2.03 g, 51%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate; In toluene; for 10h;Inert atmosphere; Reflux; | A 250 mL three-necked flask was charged with 0.02 mol of 2,7-dibromocarbazole, 0.03 mol of bromobenzene, and 0.04 mol of sodium t-butoxide under a nitrogen atmosphere.10-4mol Pd2(dba)3, 10-4mol P(t-Bu)3 and 200mL toluene, heated under reflux for 10 hours, sampling the plate, the raw material reaction is complete;Naturally cooled to room temperature (20 ~ 25 C), filtered, collected filtrate and vacuum distillation (-0.09MPa, 85 C), column chromatography, to obtain the starting material A2; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
50.8% | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; sodium t-butanolate; In toluene; for 12h;Reflux; | Weigh 0.025 mol of the intermediate M9 obtained above and 0.01 mol of the starting material A2 in 150 mL of anhydrous toluene.After sufficient oxygen removal, 0.025 mol of sodium t-butoxide and 10-4 mol of Pd(dppf)Cl2 were added, and the mixture was heated under reflux for 12 hours, and the plate was sampled, and the raw materials were completely reacted;It was naturally cooled to room temperature (20 to 25 C), filtered, and the filtrate was collected and evaporated under reduced pressure (-0.09 MPa, 85 C), and subjected to column chromatography to give the desired product. The HPLC purity was 99.4% and the yield was 50.8%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With palladium diacetate; potassium carbonate; tri tert-butylphosphoniumtetrafluoroborate; In 5,5-dimethyl-1,3-cyclohexadiene; at 145℃;Inert atmosphere; | S1. In a 250 mL reaction flask, add <strong>[444796-09-2]2,7-dibromo-9-phenyl-9H-carbazole</strong> (12.03 g, 30 mmol), 9H-carbazole (3.34 g, 20 mmol),Tri-tert-butylphosphine tetrafluoroborate (0.35 g, 1.2 mmol), potassium carbonate (8.29 g, 60 mmol),100mL of xylene, under a nitrogen atmosphere, add palladium acetate (0.14g, 0.6mmol),The temperature was raised to 145 C for 10-24 hours, and there was almost no remaining liquid phase monitoring raw material. The heating was stopped.Cool to room temperature, wash with water, filter, and concentrate the filtrate.Beat the filter cake with ethyl acetate 2-3 times to get 8.00g 7-bromo-9-phenyl-9H-2,9'-dicarbazole, yield 82%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
9.01 g | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; water; toluene; at 85℃;Inert atmosphere; | S1. In a 250 mL reaction flask, add 2,7-dibromo-9-phenyl-9H-carbazole (12.03 g, 30 mmol), <strong>[1001911-63-2](9-phenyl-9H-carbazol-2-yl)boronic acid</strong> (5.74 g, 20 mmol),Potassium carbonate (2.76g, 20mmol), 30mL toluene, 15mL water and 15mL ethanol,Under a nitrogen atmosphere, add tetrakis(triphenylphosphine)palladium (0.04g, 0.03mmol),The temperature was raised to 85 C for 10-24 hours, and the raw materials for liquid phase monitoring basically remained. Stop heating.Cool to room temperature, wash with water, filter, and concentrate the filtrate.Beat the filter cake with ethyl acetate 2-3 times,You can get 9.01g of crude product 7-bromo-9,9'-biphenyl-9H,9'H-2,2'-dicarbazole with a yield of 80%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79% | The 250 mL two-necked flask was then added with the intermediate (2.41 g, 10 mmol), <strong>[444796-09-2]9-phenyl-2,7-dibromocarbazole</strong> (4.00 g, 10 mmol), palladium acetate (90 mg, 0.4 mmol), and tertiary Butylphosphine tetrafluoroborate (0.34g, 1.2mmol), then add NaOt-Bu (1.16g, 12mmol) to the glove box, and put in 100mL of water and oxygen detoxified toluene under argon atmosphere at 120 The reaction was allowed to proceed for 24 hours at , cooled to room temperature, and 0.4 g of NaH was added. The reaction was continued at 120 C. for 24 hours, cooled to room temperature, poured into 200 mL of ice water, and extracted three times with dichloromethane. The organic phases were combined and turned into silica gel. Column chromatography (volume ratio of dichloromethane to n-hexane of 1: 5) was separated and purified to obtain 4.3 g of the first reactant. The first reactant was a white powder with a yield of 79%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | The 250 mL two-necked flask was then added with the intermediate (2.57 g, 10 mmol), <strong>[444796-09-2]9-phenyl-2,7-dibromocarbazole</strong> (4.00 g, 10 mmol), palladium acetate (90 mg, 0.4 mmol), and tertiary Butylphosphine tetrafluoroborate (0.34g, 1.2mmol), then add NaOt-Bu (1.16g, 12mmol) to the glove box, and put in 100mL of water and oxygen detoxified toluene under argon atmosphere at 120 Reaction at for 24 hours, cooling to room temperature, adding 0.4g NaH, and continuing the reaction at 120 C for 24 hours, cooling to room temperature, pouring the reaction solution into 200 mL of ice water, extracting with methylene chloride three times, combining the organic phases, spinning into silica gel, and column Chromatography (dichloromethane: n-hexane, v: v, 1: 5) separation and purification to obtain 3.8 g of the first reactant, the first reactant is a white powder, the yield is 68%, |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | The 250 mL two-necked flask was then added with the intermediate (2.67 g, 10 mmol), <strong>[444796-09-2]9-phenyl-2,7-dibromocarbazole</strong> (4.00 g, 10 mmol), palladium acetate (90 mg, 0.4 mmol), and tertiary Butylphosphine tetrafluoroborate (0.34g, 1.2mmol), then add NaOt-Bu (1.16g, 12mmol) to the glove box, and put in 100mL of water and oxygen detoxified toluene under argon atmosphere at 120 Reaction at for 24 hours, cooling to room temperature, adding 0.4g NaH, and continuing the reaction at 120 C for 24 hours, cooling to room temperature, pouring the reaction solution into 200 mL of ice water, extracting three times with dichloromethane, combining the organic phases, spinning into silica gel, and column Chromatography (dichloromethane: n-hexane, v: v, 1: 5) isolated and purified to obtain 3.9 g of the first reactant, the first reactant was a white powder, the yield was 68%, |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | The 250 mL two-necked flask was then added with the intermediate (2.40 g, 10 mmol), <strong>[444796-09-2]9-phenyl-2,7-dibromocarbazole</strong> (4.00 g, 10 mmol), palladium acetate (90 mg, 0.4 mmol), and tertiary Butylphosphine tetrafluoroborate (0.34g, 1.2mmol), then add NaOt-Bu (1.16g, 12mmol) to the glove box, and put in 100mL of water and oxygen detoxified toluene under argon atmosphere at 120 Reaction at for 24 hours, cooling to room temperature, adding 0.4g NaH, and continuing the reaction at 120 C for 24 hours, cooling to room temperature, pouring the reaction solution into 200 mL of ice water, extracting three times with dichloromethane, combining the organic phases, spinning into silica gel, and column Chromatography (dichloromethane: n-hexane, v: v, 1: 5) separation and purification to obtain 3.9 g of the first reactant, the first reactant is a white powder, the yield is 70%, |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In ethanol; water; toluene; at 85℃; for 12h;Inert atmosphere; | <strong>[444796-09-2]2,7-dibromo-9-phenyl-9H-carbazole</strong> (1.0 g, 2.0 mmol), 2-(3-(4,4,5,5-tetramethyl-1,3,2- dioxaborolan-2-yl)-5-(1-phenyl-1Hbenzo[d]imidazol-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole(2.95 g, 5.0 mmol), K2CO3 (4.17 g, 12 mmol), Pd(PPh3)4 (0.012 g,0.01 mmol), Toluene (30.0 mL), EtOH (15.0 mL) and H2O (5.0 mL)were added to a 100 mL flask. The mixture was heated to 85 C under nitrogen for 12 h. After cooling to room temperature, thereaction mixture was extracted with dichloromethane and water.The combined organic layers were dried over Na2SO4, filtered, andevaporated under reduced pressure. The crude residuewas purifiedby column chromatography with dichloromethane and petroleumether as eluent to afford 1.40 g of white solid, in 60% yield. 1H NMR(500 MHz, CDCl3, d): 8.03 (d, J 8.1 Hz, 2H), 7.92 (s, 2H), 7.89 (d,J 7.8 Hz, 4H), 7.84-7.62 (m, 8H), 7.54 (d, J 7.3 Hz, 2H), 7.43 (t,J 7.4 Hz, 10H), 7.38-7.24 (m, 21H), 7.11 (s, 2H), 7.00 (d, J 8.1 Hz,2H). 13C NMR (500 MHz, CDCl3, d): 144.88, 144.43, 138.94, 133.01,132.58, 132.28, 132.13, 131.79, 131.78, 131.51, 131.45, 130.75, 130.46,130.28, 130.07, 126.83, 126.45, 126.05, 125.19, 123.13, 122.65, 122.34,113.21, 110.61. MS (MALDI-TOF) [m/z]: calcd for C82H53N9, 1164.3;found, 1164.2. Anal. calcd for C82H53N9: C, 84.59; H, 4.59; N 10.83.Found: C, 84.55; H, 4.62; N 10.74. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
77% | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In 1,4-dioxane; water Inert atmosphere; Reflux; | Preparation of intermediate I-6: Into a 1 L reaction flask, (76.8 g, 161.0 mmol) of intermediate I-5,2,7-dibromo-9-phenylcarbazole (64.57g, 161.0mmol), 500ml of 1,4-dioxane,Under a nitrogen atmosphere, stirring at 60 ° C, tetrakis (triphenyl) phosphine palladium (9.30 g, 8.05 mmol) and 100 ml of potassium carbonate (66.65 g, 483.0 mmol) aqueous solution were added, and the mixture was heated and refluxed overnight. The reaction liquid was cooled to room temperature, the solid was washed with methanol and ultrapure water, and recrystallized with toluene to obtain intermediate I-6 (89.16 g, yield 77%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
25 g | With sulfuric acid; nitric acid; acetic acid at 60℃; for 2h; | 10 Synthesis of Intermediate 199-1 Dissolve N-phenyl-2,7-dibromocarbazole (25g, 62.3mmol) in acetic acid (400mL),Add nitric acid (5.89g, 93.5mmol), heat to 60,Then concentrated sulfuric acid (6.72g, 68.6mmol) was slowly added dropwise to the above solution through a constant pressure dropping funnel,A solid precipitated out gradually. After dripping, continue to stir for 2 hours and cool down.Pour the reaction liquid into 1L of ice water, stir well, collect the solid by filtration, and rinse the solid with water.25g was dried and used directly in the next step. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With bis(dibenzylideneacetone)-palladium(0); sodium t-butanolate; tri tert-butylphosphoniumtetrafluoroborate In toluene at 80℃; for 8h; Inert atmosphere; | 4 General procedure: In an Ar atmosphere, 2,7-dibromo-9-phenyl-9H-carbazole (8.00 g, 20.0 mmol), B (18.5 g, 49.9 mmol), Pd (dba)2 (0.803 g, 1.40 mmol), HP (t-Bu)3BF4 (0.288 g, 1.60 mmol), and NaOt-Bu (5.75 g, 59.8 mmol) were added to 100 mL of toluene, and heated and stirred at 80° C. for 8 hours. After adding water, the resultant mixture was subjected to Celite filtering and liquid separation to concentrate an organic layer. The concentrated organic layer was purified by silica gel column chromatography to obtain C (14.7 g, yield 75%). The molecular weight of C was 981 as measured by FAB MS. |
71% | With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate In toluene at 100℃; for 12h; | 1.2 (Synthesis of Intermediate Compound 15-2) 2,7-dibromo-9-phenyl-9H-carbazole (1 eq), intermediate compound 15-1 (2 eq), Pd2(dba)3 (0.1 eq), P(t-Bu)3 (0.2 eq), and sodium tert-butoxide (5 eq) were used to react in the same manner as in Reaction Formula 2-a to obtain Intermediate compound 15-2 (yield: 71%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
45% | With copper(l) iodide; 1,10-Phenanthroline; potassium carbonate In N,N-dimethyl-formamide at 160℃; for 12h; | 1.1 (Synthesis of Intermediate Compound 3-1) 2,7-dibromo-9-phenyl-9H-carbazole (1 eq), 3-(9H-carbazol-9-yl)-5-(diphenylamino)phenol (2 eq), Cul (0.1 eq), 1,10-phenanthroline (0.2 eq), and K2CO3 (4 eq) were dissolved in DMF, and then stirred at about 160° C. for about 12 hours. After cooling, the solvent was removed at reduced pressure, and the resultant was washed three times with dichloromethane and water, and then separated to obtain an organic layer. The obtained organic layer was dried with MgSO4, and then dried at reduced pressure. Intermediate compound 3-1 was obtained by column chromatography (yield: 45%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With bis(dibenzylideneacetone)-palladium(0); sodium t-butanolate; tri tert-butylphosphoniumtetrafluoroborate In toluene at 80℃; for 8h; Inert atmosphere; | 1 In an Ar atmosphere, 2,7-dibromo-9-phenyl-9H-carbazole (8.00 g, 20.0 mmol), B (18.5 g, 49.9 mmol), Pd (dba)2 (0.803 g, 1.40 mmol), HP (t-Bu)3BF4 (0.288 g, 1.60 mmol), and NaOt-Bu (5.75 g, 59.8 mmol) were added to 100 mL of toluene, and heated and stirred at 80° C. for 8 hours. After adding water, the resultant mixture was subjected to Celite filtering and liquid separation to concentrate an organic layer. The concentrated organic layer was purified by silica gel column chromatography to obtain C (14.7 g, yield 75%). The molecular weight of C was 981 as measured by FAB MS. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | With copper (I) iodide; tris(2,4-pentanedionato)iron(III); potassium carbonate In 1-methyl-pyrrolidin-2-one at 180℃; for 12h; | 10 The synthesis of Compound AH was carried out by adding 2,7-dibromo-9-phenyl-9H-carbazole (8.0 g, 20 mmol) and a compound including AG (17.17 g, 40.1 mmol), Cul (0.19 g, 1.0 mmol), tris(2,4-pentanedionato)iron(III) (Fe(III)(acac)3, 0.71 g, 2.0 mmol), and K2CO3 (18.5 g, 80 mmol) to NMP (400 mL), and heated and stirred at 180° C. for 12 hours. The resultant mixture was concentrated, dissolved in CH2Cl2, and subjected to Celite filtering by adding water and liquid separation to concentrate an organic layer. The concentrated organic layer was purified by silica gel column chromatography to obtain Compound AH (14.3 g, yield 65%). The molecular weight of Compound AH was 1096 as measured by FAB MS. |
50% | With potassium carbonate In N,N-dimethyl-formamide at 180℃; for 24h; Inert atmosphere; | Synthesis of intermediate 2-2a After adding 2,7-dibromo-9-phenyl-9H-carbazole (1eq.), 3,5-bis (diphenylamino) phenol (2.5eq.), Potassium carbonate (5eq.) To DSMO,The mixture was stirred at 180 degrees Celsius for 24 hours under a nitrogen atmosphere.After cooling, the mixture was washed 5 times with ethyl acetate and water, and the obtained organic layer was dried over regsvr4 and then dried under reduced pressure.Intermediate 2-2a was obtained by column chromatography. (Yield: 50%) |
50% | With potassium carbonate In N,N-dimethyl-formamide at 180℃; for 24h; Inert atmosphere; | Synthesis of intermediate 2-2a After adding 2,7-dibromo-9-phenyl-9H-carbazole (1eq.), 3,5-bis (diphenylamino) phenol (2.5eq.), Potassium carbonate (5eq.) To DSMO,The mixture was stirred at 180 degrees Celsius for 24 hours under a nitrogen atmosphere.After cooling, the mixture was washed 5 times with ethyl acetate and water, and the obtained organic layer was dried over regsvr4 and then dried under reduced pressure.Intermediate 2-2a was obtained by column chromatography. (Yield: 50%) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With [1,3-bis(2,6-di-isopropylphenyl)-4,5-dihydroimidazol-2-ylidene]chloro[3-phenylallyl]palladium(II); sodium carbonate In 1,2-dimethoxyethane; water at 80℃; Inert atmosphere; | 1.1 Synthesis of compound 1 (1) In an argon atmosphere, add 40.1 g (100 mmol) of 2,7-dibromo-9-phenyl-9H-carbazole and 36.7 g (220 mmol) of (2-nitrophenyl)boronic acid to the reaction vessel.[1,3-bis(2,6-di-isopropylphenyl)-4,5-dihydroimidazol-2-ylidene]chloro[3-phenylallyl]palladium(II) catalyst 648 mg , 200ml (300mmol) of 1.5M sodium carbonate aqueous solution and 1000ml of ethylene glycol dimethyl ether (DME), heated at 80 and stirred overnight. Cooled to room temperature, added 800ml of water, solids separated out, filtered, and the crude product was purified by silica gel column chromatography (eluent: ethyl acetate/hexane) to obtain 39.3g of compound 2,7-bis(2-nitrophenyl)-9-phenyl-9H-carbazole, the yield is 81%, and the HPLC purity is 99.6%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With potassium iodate; acetic acid; potassium iodide for 2h; Reflux; | 1.1 Step 1: Preparation of compound A-1 36.9 mmol of 2,7-dibromo-9-phenylcarbazole (CAS: 444796-09-2) was dissolved in 150.0 mL of glacial acetic acid, and 14.5 mmol of potassium iodate, 24.0 mmol of potassium iodide and a drop of concentrated Sulfuric acid, heated and refluxed, stirred for 2 hours, cooled to room temperature, filtered, the filter cake was washed with water, saturated sodium bisulfite aqueous solution, and separated and purified with a silica gel column to obtain compound A-1, a white solid, with a yield of 87%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium tertiary butoxide In toluene at 100℃; for 24h; Inert atmosphere; | Synthesis of intermediate 2-3c Intermediate 2-3b (2.1eq.), 2,7-dibromo-9-phenyl-9H-carbazole (1eq.), Tris (dibenzylideneacetone) dipalladium (0) (0.05eq.),Tory tert-butylphosphine (0.1eq.),After dissolving sodium t-butoxide (3eq.) In toluene,The mixture was stirred at 100 degrees Celsius for 24 hours under a nitrogen atmosphere.After cooling, the mixture was washed with ethyl acetate and water three times, and the obtained organic layer was dried over regsvr4 and then dried under reduced pressure. Intermediate 2-3c was obtained by column chromatography. (Yield: 65%) |
65% | With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium tertiary butoxide In toluene at 100℃; for 24h; Inert atmosphere; | Synthesis of intermediate 2-3c Intermediate 2-3b (2.1eq.), 2,7-dibromo-9-phenyl-9H-carbazole (1eq.), Tris (dibenzylideneacetone) dipalladium (0) (0.05eq.),Tory tert-butylphosphine (0.1eq.),After dissolving sodium t-butoxide (3eq.) In toluene,The mixture was stirred at 100 degrees Celsius for 24 hours under a nitrogen atmosphere.After cooling, the mixture was washed with ethyl acetate and water three times, and the obtained organic layer was dried over regsvr4 and then dried under reduced pressure. Intermediate 2-3c was obtained by column chromatography. (Yield: 65%) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84 % | With tri-tert-butyl phosphine; bis(dibenzylideneacetone)-palladium(0); sodium t-butanolate In toluene Reflux; | 1.ii ii) Synthesis of compound 1 3.27g (8.15mmol) of intermediate 1 and 1.91g (9.78mmol) of 3,6-dimethyl-9H-carbazole were dissolved in 50ml of anhydrous toluene, and then in 10 Mole % of Pd(dba)2 and 20 mole % of P(t-Bu)3, and 2.35 g (24.44 mmol) of sodium tert-butoxide (NaOtBu) were heated at reflux for 8 hours. After removing the organic solvent, the obtained product was separated and purified by silica gel column chromatography to obtain 3.53 g of 7-bromo-3',6'-dimethyl-9-phenyl-9H-2,9' - Bicarbazole (Compound 1). Its yield was 84%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94 % | With caesium carbonate In 1-methyl-pyrrolidin-2-one at 120℃; | 1 Synthetic intermediate (002-a) Dissolve 2,7-dibromocarbazole (1eq) in N-methylpyrrolidone (NMP) (100mL), then add cesium carbonate (5eq) and fluorobenzene (3eq), stir at 120°C for 24 hours, then add 1L water, the white solid was filtered, washed repeatedly with water, dehydrated and then separated and purified by silica gel chromatography to obtain a white solid intermediate (002-a) with a yield of 94%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
59 % | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate In 1,4-dioxane; water at 90℃; | 1 Synthetic intermediate (002-b) Place pinacol diboronate (1.5eq), intermediate (002-a) (1eq), [1,1'-bis(diphenylphosphino)ferrocene] di Palladium chloride (0.05eq), potassium acetate (4eq), and then add 250mL of a mixed solution of dioxane and water in a ratio of 3:1, stir and react at 90°C for 12 hours, cool to room temperature, spin dry after the reaction is completed, Use dichloromethane and water solution, dry with magnesium sulfate and then spin dry, and then use silica gel chromatography column for separation and purification. The solid intermediate (002-b) was obtained in 59% yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72 % | With tris-(dibenzylideneacetone)dipalladium(0); N-ethyl-N,N-diisopropylamine; Xantphos In 1,4-dioxane at 110℃; Inert atmosphere; | 2 The reaction formula is as follows: Add 2-1 (2,7-dibromo-9-phenylcarbazole) (28.8g, 72.0mmol) and 4-tert-butylphenylselenol (12.84g, 60.0mmol) in a 500mL three-necked flask,Pd2(dba)3 (1.37g, 1.5mmol), Xantphos (1.74g, 3.0mmol) and N,N-diisopropylethylamine (15.5g, 20.9mL, 120.0mmol), take 300mL of 1,4-di Add oxane into the bottle, raise the temperature to reflux, stir and react under the protection of argon for 12 hours, then cool to room temperature, pour the reaction solution into 1.2L deionized water, stir for 1 hour, extract and separate the organic phase with dichloromethane After adding anhydrous sodium sulfate to dry, the obtained organic phase was filtered to remove the solvent, and the crude product was separated by silica gel column to obtain product 2-2 (23.0 g, yield: 72%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
50 % | With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In ethanol; water; toluene at 70℃; | 10.1 (1) Synthesis of intermediate 121-1 10mmol of 2,7-dibromo-9-phenyl-9H-carbazole (1eq.), 11mmol of cyclohexylboronic acid (1.1eq.),0.3mmol of Pd(PPh3)4(0.03eq.),20 mmol of K2CO3 (2 eq.) and toluene, ethanol, and H2O (100 mL, 10 mL, and 20 mL, respectively) were added to a single-neck round bottom flask, followed by stirring at a temperature of 70° C. for 6 hours.Once the reaction was complete, the work-up process was performed using H2O and diethyl ether, followed by column chromatography (eluent:Dichloromethane and hexane at a volume ratio of 1:10) to separate the resulting organic layer.The resulting organic layer was recrystallized from diethyl ether to obtain 2.0 g of Intermediate 121-1. (yield=50%, purity≥99.9%) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72 % | With trifluorormethanesulfonic acid; benzene-d6 at 80℃; | 2.1 1) Preparation of Compound 79-P3 20g (49.86 mmol) of compound 79-P4 was dissolved in 804g of benzene-D6 and 187g of CF3SO3H and stirred at 80°C for 1 hour. After completion of the reaction,it was quenched with Na2CO3 in D2O.After quenching, ethyl acetate was added to the mixed solution to dissolve it, and the organic layer was separated,dried over anhydrous MgSO4 , and then the solvent was removed using a rotary evaporator.Thereafter, the mixture was purified by column chromatography using dichloromethane and hexane as developing solvents to obtain 14.8 g of compound 79-P3 (72% yield). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
64.3 % | With bis-triphenylphosphine-palladium(II) chloride; potassium carbonate In ethanol; water; toluene Reflux; Inert atmosphere; | 4 Synthesis of Compound 4 Intermediate 1 (0.3g, 0.52mmol), 2,7-dibromo-9-phenylcarbazole (0.1g, 0.25mmol) and potassium carbonate (0.1g, 0.72mmol) were added to the flask,Add toluene (1 mL), ethanol (0.5 mL), deionized water (0.5 mL) and Pd(PPh3)2Cl2 (5 mg), and reflux for 5 h under nitrogen protection.TLC showed that the reaction was complete. After cooling, a solid was precipitated, filtered, and washed with deionized water and ethanol in sequence. The filter cake was dissolved with 5 mL of chlorobenzene under reflux, passed through a small amount of silica gel while it was hot, rinsed with chlorobenzene, concentrated to near dryness,The solid was precipitated, filtered and rinsed with ethanol to obtain 0.18 g of a light yellow solid with a yield of 64.3%. |
Tags: 444796-09-2 synthesis path| 444796-09-2 SDS| 444796-09-2 COA| 444796-09-2 purity| 444796-09-2 application| 444796-09-2 NMR| 444796-09-2 COA| 444796-09-2 structure
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P390 | Absorb spillage to prevent material damage. |
P391 | Collect spillage. Hazardous to the aquatic environment |
P301 + P310 | IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician. |
P301 + P312 | IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell. |
P301 + P330 + P331 | IF SWALLOWED: Rinse mouth. Do NOT induce vomiting. |
P302 + P334 | IF ON SKIN: Immerse in cool water/wrap in wet bandages. |
P302 + P350 | IF ON SKIN: Gently wash with plenty of soap and water. |
P303 + P361 + P353 | IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower. |
P304 + P312 | IF INHALED: Call a POISON CENTER or doctor/physician if you feel unwell. |
P304 + P340 | IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing. |
P304 + P341 | IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P305 + P351 + P338 | IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing. |
P306 + P360 | IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes. |
P307 + P311 | IF exposed: call a POISON CENTER or doctor/physician. |
P308 + P313 | IF exposed or concerned: Get medical advice/attention. |
P309 + P311 | IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician. |
P332 + P313 | IF SKIN irritation occurs: Get medical advice/attention. |
P333 + P313 | IF SKIN irritation or rash occurs: Get medical advice/attention. |
P335 + P334 | Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages. |
P337 + P313 | IF eye irritation persists: Get medical advice/attention. |
P342 + P311 | IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician. |
P370 + P376 | In case of fire: Stop leak if safe to Do so. |
P370 + P378 | In case of fire: |
P370 + P380 | In case of fire: Evacuate area. |
P370 + P380 + P375 | In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion. |
P371 + P380 + P375 | In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion. |
Storage | |
Code | Phrase |
P401 | |
P402 | Store in a dry place. |
P403 | Store in a well-ventilated place. |
P404 | Store in a closed container. |
P405 | Store locked up. |
P406 | Store in corrosive resistant/ container with a resistant inner liner. |
P407 | Maintain air gap between stacks/pallets. |
P410 | Protect from sunlight. |
P411 | |
P412 | Do not expose to temperatures exceeding 50 oC/ 122 oF. |
P413 | |
P420 | Store away from other materials. |
P422 | |
P402 + P404 | Store in a dry place. Store in a closed container. |
P403 + P233 | Store in a well-ventilated place. Keep container tightly closed. |
P403 + P235 | Store in a well-ventilated place. Keep cool. |
P410 + P403 | Protect from sunlight. Store in a well-ventilated place. |
P410 + P412 | Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF. |
P411 + P235 | Keep cool. |
Disposal | |
Code | Phrase |
P501 | Dispose of contents/container to ... |
P502 | Refer to manufacturer/supplier for information on recovery/recycling |
Physical hazards | |
Code | Phrase |
H200 | Unstable explosive |
H201 | Explosive; mass explosion hazard |
H202 | Explosive; severe projection hazard |
H203 | Explosive; fire, blast or projection hazard |
H204 | Fire or projection hazard |
H205 | May mass explode in fire |
H220 | Extremely flammable gas |
H221 | Flammable gas |
H222 | Extremely flammable aerosol |
H223 | Flammable aerosol |
H224 | Extremely flammable liquid and vapour |
H225 | Highly flammable liquid and vapour |
H226 | Flammable liquid and vapour |
H227 | Combustible liquid |
H228 | Flammable solid |
H229 | Pressurized container: may burst if heated |
H230 | May react explosively even in the absence of air |
H231 | May react explosively even in the absence of air at elevated pressure and/or temperature |
H240 | Heating may cause an explosion |
H241 | Heating may cause a fire or explosion |
H242 | Heating may cause a fire |
H250 | Catches fire spontaneously if exposed to air |
H251 | Self-heating; may catch fire |
H252 | Self-heating in large quantities; may catch fire |
H260 | In contact with water releases flammable gases which may ignite spontaneously |
H261 | In contact with water releases flammable gas |
H270 | May cause or intensify fire; oxidizer |
H271 | May cause fire or explosion; strong oxidizer |
H272 | May intensify fire; oxidizer |
H280 | Contains gas under pressure; may explode if heated |
H281 | Contains refrigerated gas; may cause cryogenic burns or injury |
H290 | May be corrosive to metals |
Health hazards | |
Code | Phrase |
H300 | Fatal if swallowed |
H301 | Toxic if swallowed |
H302 | Harmful if swallowed |
H303 | May be harmful if swallowed |
H304 | May be fatal if swallowed and enters airways |
H305 | May be harmful if swallowed and enters airways |
H310 | Fatal in contact with skin |
H311 | Toxic in contact with skin |
H312 | Harmful in contact with skin |
H313 | May be harmful in contact with skin |
H314 | Causes severe skin burns and eye damage |
H315 | Causes skin irritation |
H316 | Causes mild skin irritation |
H317 | May cause an allergic skin reaction |
H318 | Causes serious eye damage |
H319 | Causes serious eye irritation |
H320 | Causes eye irritation |
H330 | Fatal if inhaled |
H331 | Toxic if inhaled |
H332 | Harmful if inhaled |
H333 | May be harmful if inhaled |
H334 | May cause allergy or asthma symptoms or breathing difficulties if inhaled |
H335 | May cause respiratory irritation |
H336 | May cause drowsiness or dizziness |
H340 | May cause genetic defects |
H341 | Suspected of causing genetic defects |
H350 | May cause cancer |
H351 | Suspected of causing cancer |
H360 | May damage fertility or the unborn child |
H361 | Suspected of damaging fertility or the unborn child |
H361d | Suspected of damaging the unborn child |
H362 | May cause harm to breast-fed children |
H370 | Causes damage to organs |
H371 | May cause damage to organs |
H372 | Causes damage to organs through prolonged or repeated exposure |
H373 | May cause damage to organs through prolonged or repeated exposure |
Environmental hazards | |
Code | Phrase |
H400 | Very toxic to aquatic life |
H401 | Toxic to aquatic life |
H402 | Harmful to aquatic life |
H410 | Very toxic to aquatic life with long-lasting effects |
H411 | Toxic to aquatic life with long-lasting effects |
H412 | Harmful to aquatic life with long-lasting effects |
H413 | May cause long-lasting harmful effects to aquatic life |
H420 | Harms public health and the environment by destroying ozone in the upper atmosphere |
Sorry,this product has been discontinued.
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