Structure of 2113-58-8
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CAS No. : | 2113-58-8 |
Formula : | C12H9NO2 |
M.W : | 199.21 |
SMILES Code : | O=[N+](C1=CC(C2=CC=CC=C2)=CC=C1)[O-] |
MDL No. : | MFCD00007245 |
InChI Key : | FYRPEHRWMVMHQM-UHFFFAOYSA-N |
Pubchem ID : | 16450 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H302+H312+H332 |
Precautionary Statements: | P261-P264-P270-P271-P280-P301+P312+P330-P302+P352+P312+P362+P364-P304+P340+P312-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 |
---|---|---|
100% | With hydrogen;palladium 10% on activated carbon; In ethanol; for 3h; | Palladium on carbon (10%, 0.70 g, 0.658 mmol) was added to a Parr hydrogenator bottle. The bottle was purged with nitrogen. Next, 3- nitro-l,l'-biphenyl (10 g, 50.2 mmol) and 190 mL ethanol were added to the bottle. The material was hydrogenated on a Parr hydrogenator. After 3 h, the reaction mixture was filtered through Celite and the Celite washed with dichloromethane. The filtrate was evaporated, obtained a brown oil, 8.69 g, assume quantitative yield (8.49 g). |
99.7% | Another batch of reaction was effected on the same scale except that 254 g (1.28 mol) of <strong>[2113-58-8]m-nitrobiphenyl</strong> was used, obtaining 215 g of m-aminobiphenyl (yield 99.7%). | |
94% | palladium; In ethyl acetate; | a) 3-phenylaniline To a stirring solution of <strong>[2113-58-8]3-nitrobiphenyl</strong> (1.2 g, 6.0 mmol) in ethyl acetate (25 mL) was added 10% Palladium on carbon (500 mg, 40% w/w). After stirring under a balloon of hydrogen for 24 h, the mixture was filtered through Celite and concentrated to yield the title compound as a white solid (0.956 g, 94%). MS (ESI): 170.0 (M+H)+. |
16 g (95%) | palladium-carbon; In methanol; chloroform; | Example 1 Synthesis of 3-aminobiphenyl (1): The following compound is prepared: STR26 A mixture of <strong>[2113-58-8]3-nitrobiphenyl</strong> (20 g, 100 mmol) and 10% Pd/C (2 g) in MeOH/CHCl3 (300 mL, 1:1) is hydrogenated at 40 psi for 4 hours. The mixture is suction filtered through a layer of diatomaceous earth and washed with MeOH. The filtrate is evaporated to dryness and the solid is further dried under vacuum to give 16 g (95%) of 3-aminobiphenyl. |
(a) In a manner similar to that of Example 7(b), <strong>[2113-58-8]3-nitrobiphenyl</strong> (2.48 g) gives 1.77 g of 3-aminobiphenyl, mp 27.5-28.5 C. | ||
With hydrogen;palladium 10% on activated carbon; In methanol; | Example 11; 3-aminobiphenyl: <strong>[2113-58-8]3-nitrobiphenyl</strong> (500 mg, 2.5 mmol) and 10% palladium on carbon (267 mg, 2.5 mmol) were dissolved in methanol (1 mL) and purged with nitrogen and placed under an atmosphere of hydrogen overnight. The reaction mixture was filtered and evaporated to yield 326 mg of the desired amine, which was used directly in Example 12. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60% | With toluene-4-sulfonic acid; orthoformic acid triethyl ester; copper(l) chloride; sodium nitrite; at 50℃; for 0.75h; | General procedure (Method A): To a solution of aniline (32.25 mmol) in 30 ml of benzene was added p-TSA (12.25 g, 64.5 mmol), TEOF (4.7 g, 32.25 mmol), CuCl (10 mol %) at rt, mixture was heated to 50 C. Maintaining 50 C, powdered NaNO2 (2.09 g, 32.25 mmol) was added portion wise over 15 min, frothing was observed during the addition which subsided. The reaction mixture was maintained at the same temperature for 30 min to complete the reaction, monitored by TLC. The reaction mixture was cooled to rt, filtered to remove the solid precipitated, washed with EtOAc and organic layer was evaporated to dryness to get sticky residue, which was extracted with petroleum ether (60-80) followed by evaporation of solvent to yield the crude biaryl. It was purified by recrystallization from methanol/column chromatography ethyl acetate/petroleum ether (0.5:10) as eluent. |
61 g | With copper(l) iodide; potassium nitrite; trimethyl orthovalerate; triiodoacetic acid; at 80℃; for 2h; | At room temperature, put 138g of meta-nitroaniline, 78g of benzene, 438g of triiodoacetic acid, 85g of potassium nitrite, 191g of cuprous iodide and 7L of trimethyl orthovalerate into a 10L reactor, and stir at room temperature for 1 hour to make it Dissolve and mix well, then control the temperature to 80C and keep it under constant temperature stirring for 2 hours. Then the material obtained after the above reaction was poured into 10L of water for quenching. After cooling, the solid impurities were filtered off. The filter cake was washed with 2L of ethyl acetate and the filtrate was separated into layers. The aqueous layer was extracted with 2L of ethyl acetate, and the organic phase was extracted with 2L of water. After washing, the organic layer was evaporated to dryness. The solid was dissolved by refluxing with 1L of ethanol and then cooled to 10C and filtered. The filtered solid was washed with 1L of petroleum ether and then dried by blowing to obtain 303g of crude product. Then use 7 times the volume of ethylene glycol methyl ether to heat and dissolve, then cool and crystallize and filter to obtain 132 g of product m-nitroaniline.The filtered mother liquor must be recovered and recrystallized again to obtain 61 g of product meta-nitroaniline. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With potassium carbonate;1q-Pd(dba)2; In 1-methyl-pyrrolidin-2-one; water; at 100℃; for 1h;Conversion of starting material; | Aryliodide or bromide (0.5 mmol), arylboric acid (0.6 mmol), K2CO3 (1.0 mmol), bis-thiourea-Pd(dba)2 1q complex in NMP (2.5×10 M solution) and NMP/H2O (0.75 ml/0.25 ml) were added to a flask under aerobic conditions. The flask was sealed with rubber septa and heated at the desired temperature. The reaction mixture was diluted with ethyl acetate, washed with brine, and dried over Na2SO4. The solvent was removed and the residue was purified by a flash chromatography on silica gel to give the product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With potassium carbonate; In ethanol; water; at 80℃; for 0.75h; | General procedure: General procedure: Aryl halide (1.0 mmol), arylboronic acid (1.2 mmol), base (2.5 mmol), and Fe3O4/SiO2-Met-Pd(OAc)2 (10 mg, 0.14 mol% Pd) were added to the vessel (10 mL) with 3 mL of solvent. The mixture was continuously stirred at 80 C in an air atmosphere for the desired time until complete consumption of the starting aryl halide as monitored by TLC. After magnetic separation of the catalyst, the product was extracted with diethyl ether and purified by column chromatography (n-hexane: chloroform). In the recycling experiment, the separated catalyst was then washed with ether and dried under vacuum to remove residual solvent |
94% | With potassium carbonate; In ethanol; water; at 80℃; for 2h; | Suzuki-Miyaura coupling reaction;In a typical reaction, to a solution of 1 mmol of the aryl halide in 5 ml of water/ethanol (1:1) was added 1.1 mmol of phenyl boronic acid, 276 mg of K2CO3 (2 mmol) followed by 15 mg of the solid catalyst (1 mol%). The mixture was then stirred for the desired time at 80 C. The reaction was monitored by thin layer chromatography (TLC). After completion of reaction, the reaction mixture was cooled to room temperature and the catalyst (SBA-15/Met/Pd(II)) was recovered by centrifuge and washed with ethyl acetate and ethanol.The combined organic layer was dried over anhydrous sodium sulfate and evaporated in a rotary evaporator under reduced pressure. The crude product was purified by column chromatography. |
93% | With palladium diacetate; metformin hydrochloride; potassium carbonate; In ethanol; water; at 80℃; for 2h;Green chemistry; | General procedure: To a 5 mL flask containing a mixture of Pd(OAc)2 (0.01 mmol, 0.025 g), Met.HCl (0.02 mmol, 0.033 mg), and K2CO3 (2 mmol, 276 mg) in distilled H2O (1.5 mL) and EtOH (99%, 1.5 ml) were added aryl halide (1 mmol) and boronic acid (1.1 mmol) at 80 C, and the mixture stirred for the appropriate amount of time (see Table 2). The progress of the reaction was monitored by TLC. After completion of the reaction, the mixture was washed with EtOAc (5Χ1ml) and the organic phase separated and evaporated. Further purification was by column chromatography (EtOAc/n-hexane) gave the desired coupled product. |
93% | With Pd/C; potassium carbonate; In water; N,N-dimethyl-formamide; at 110℃; for 2.5h; | General procedure: To a tube equipped with a magnetic stir bar were added catalyst 1(7.0 mg, 0.1 mol% Pd), K2CO3 (138 mg, 2.0 equiv), arylboronicacid (1.1 equiv), and aryl bromide (0.5 mmol) in turn. Subsequently,the solvent (DMF-H2O, 3:2, 2.0 mL, v/v) was added under an airatmosphere. The reaction was then heated to 40 C and stirred untilthe aryl bromide was completely consumed as determined by TLC.After completion of the reaction, the reaction mixture was purifiedby silica gel column chromatography to afford the desired pureproduct. |
90% | With potassium carbonate; In water; at 50℃; for 3h; | General procedure: In a test tube equipped with a magnetic stirrer bar, thearyl halide 1 (1 mmol) was mixed with phenyl boricacid 2 (1.2 mmol), K2CO3(2 mmol), and the Pd-catalyst(0.1mol% Pd) in 2 ml of H2Oin air. The reaction mixturewas then stirred at 50 C for appropriate time. After completionof the reaction, the catalyst was removed by magnetand washed with ethanol and water (3 × 5 ml). The aqueouslayer was extracted with chloroform, then organic layerdried over anhydrous MgSO4.The solvent was evaporatedunder reduced pressure to give the corresponding biarylcompounds. All the products were previously reported [5,8-12] and were confirmed by the spectroscopic methodusing 1H and 13C NMR (see supporting information). |
87% | With 0.1 % Cu/C; potassium carbonate; In water; at 50℃; for 4h;Green chemistry; | General procedure: In a test tube, 1.0 mmol of aryl halides 1, 1.2 mmol of phenylboronic acid 2 were mixed together and then 2.0 mmol of K2CO3, and the Cu/Cnano-catalyst (0.1 mol % Cu) in 2 mL of H2O, were added in air. The reaction mixture was then stirred at 50 C for appropriate time. After completion of the reaction (monitored by TLC), the catalyst was removed by simple filtration. The recycled catalyst was was hed with ethanol and water (3 × 5 mL) and dried at 60 C in oven for further use. The aqueous layer was extracted with ethyl acetate, and organic layer dried over anhydrous MgSO4. The solvent was evaporated under reduced pressure to give the corresponding biaryl compounds. |
71% | With tetrabutylammomium bromide; potassium carbonate; In water; at 90℃; for 4h;Green chemistry; | General procedure: 25-ml RB was charged with 4-iodo anisole (1.0 mmol), phenyl boronic acid (1.5 mmol), GO-PMMA-Pd catalyst (0.3 mol %), K2CO3 (1 mmol), TBAB (10 mol %) and 2 ml water. The mixture was allowed to stir at 90 C for an appropriate time (Table 1) and the extent of the reaction was monitored by thin layer chromatography (TLC). After the completion of the reaction, the reaction mixture was extracted by ethyl acetate (2×25 mL) and washed with water repeatedly. The catalyst was filtered off and washed several times with ether and water (1:1) until no significant product was obtained in the wash. The recoverd catalyst was reused for the next coupling experiment. The reaction mixture was dried over anhydrous Na2SO4, concentrated in vacuum and purified by column chromatography on silica gel 60-120 mesh using petroleum ether as eluent to obtain pure product. The catalyst recoverd after 5th run was subjected to ICP-AES for Pd content analysis. The isolated products were analysed by 1H NMR and 13C NMR spectroscopy. |
53% | With Pd(memantine)2Cl2; sodium hydroxide; In ethanol; at 80℃; for 24h; | General procedure: In the reaction tube with a magnetic bar was added the solution of aryl bromides (0.5 mmol) and phenylboronic acid (91 mg, 0.75 mmol), NaOH (24 mg, 0.6 mmol), complex 1 (0.0001-0.02 mol%, dissolved in DMA) and ethanol (3 mL). After stirred for the required time in the preset conditions, the reaction mixture was cooled to room temperature, and then quenched by 1 mL brine and 3 mL water, and extracted with ethyl acetate (3×5 mL). The combined organic layer was dried over anhydrous MgSO4 and the filtrate was concentrated to dryness under reduced pressure. The crude products were purified by column chromatography (petroleum ether, ethyl acetate) on silica gel. |
With C24H20Cl2NPPdS; potassium carbonate; palladium; In toluene; at 100℃; for 24h; | General procedure: A 100 ml round bottom flask was fitted with a reflux condenser and a magnetic stirrer bar. The flask was charged with toluene (15 ml) and the appropriate amount of catalyst reagents and the internal standard (n-Decane: 2.59 mmol). The contents were thoroughly mixed and an initial sample (t0) was then taken. The reaction flask was placed in an oil bath at the desired temperature and the reaction mixture allowed to heat/reflux with stirring. A sample was taken and analyzed every 10 min for the first hour and every 30 min thereafter until t3h. In cases where conversionwas not complete after 3 h, the reaction mixturewas then allowed to stir for a total of 24 h. The reaction at 140 C was performed in a sealed tube. All catalytic reactions were done under aerobic conditions. Percentage conversions were determined by GC with n-decane as the internal standard and the coupling products were characterized by mass spectrometry (Table 4) as well as 1H NMR spectroscopy (Entry 5, Table 4 only). | |
With C31H33Cl2N2PPd; potassium hydroxide; In decane; N,N-dimethyl-formamide; at 150℃; for 3h;Catalytic behavior; | General procedure: The Suzuki-Miyaura cross-coupling reactions were performed in acarousel using 24 × 150 mm quick-thread glass reaction tubes. Thegeneral procedure is similar to that given for the Mizoro-Heck Crosscouplingreactions, however, boronic acid is used herein instead of analkene. The GC was initially calibrated using standard samples ofboronic acid, toluene, n-decane and the aryl halide in order to accuratelydetermine the retention times of these compounds. Also, the reactionmixture in the reaction vessel was sampled to determine time zerovalues and analysed by GC to determine the ratios of the various components.The required catalyst amount (mol %) was then added and thereaction proceeded with a stirring rate of 600 rpm. Upon the elapse ofthe reaction time, the aryl halide conversion to biphenyl was calculatedby analysing the retention peak areas of the aryl halide with reference ton-decane as an internal standard. The NMR data of the isolated productsare given in the Supplementary Information (SI2). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With C22H24Cl2N6O2Pd2; potassium carbonate; In ethanol; water; for 4h;Reflux;Catalytic behavior; | General procedure: In a 10 mL glass tube containing a Teflon-coated stir bar was placed p-bromobenzaldehyde 2e (0.05 g, 0.27 mmol, 1 equiv), phenylboronic acid 1a (0.05 g, 0.40 mmol, 1.5 equiv), 2M K2CO3 (0.33 mL, 0.67 mmol, 2.5 equiv), 4-AAP-Pd(II) (0.28 mg, 0.3 mol % Pd) and EtOH (2 mL). The mixture was stirred at reflux for 4 h. After cooling, the mixture was diluted with ether Et2O (5 mL), washed with sat. aq. NaHCO3 (3 mL), brine (3 mL) and dried over Na2SO4. Evaporation of the solvent and purification of the residue over a silica gel column (Hex: AcOEt 90:10), furnished the biphenyl 3q. |
93% | With potassium carbonate; In water; at 50℃; for 2.5h; | General procedure: In a test tube equipped with a magnetic stirrer bar, thearyl halide 1 (1 mmol) was mixed with phenyl boricacid 2 (1.2 mmol), K2CO3(2 mmol), and the Pd-catalyst(0.1mol% Pd) in 2 ml of H2Oin air. The reaction mixturewas then stirred at 50 C for appropriate time. After completionof the reaction, the catalyst was removed by magnetand washed with ethanol and water (3 × 5 ml). The aqueouslayer was extracted with chloroform, then organic layerdried over anhydrous MgSO4.The solvent was evaporatedunder reduced pressure to give the corresponding biarylcompounds. All the products were previously reported [5,8-12] and were confirmed by the spectroscopic methodusing 1H and 13C NMR (see supporting information). |
90% | With sodium hydroxide; In ethanol; water; at 25℃; for 3h; | General procedure: The Pd/IL-NH2/SiO2/Fe3O4 catalyst (19 mg, Pd: 0.5 mmol %), aryl halide (0.5 mmol), arylboronic acid (0.75 mmol), base (1 mmol), and solvent (3 mL) were added into a 10 mL glass test tube. Then the reaction was allowed to proceed at room temperature (25 C). After the reaction was finished as monitored by thin layer chromatography (TLC), the catalyst was magnetically separated and washed two times with ethyl acetate (1 mL). To obtain the GC yield, the combined organic phase was analyzed by a gas chromatograph (GC) equipped with a flame ionization detector (FID) using dodecane as an internal standard (Angilent 7890A, HP-5, 30 m 0.32 mm). To obtain the isolated yield, the combined organic phase was concentrated and the products were purified by column chromatography over silica gel. For reuse of the catalyst, after magnetically recovered, the catalyst was successively rinsed with ethyl acetate (1 mL 2) and water (0.5 mL), and dried at room temperature ready for the next cycle. |
90% | With potassium carbonate; In water; at 90℃; for 0.333333h;Green chemistry; | General procedure: In a typicalprocedure,iodobenzene (1.0 mmol, 0.203 g), phenylboronicacid (1.2 mmol, 0.146 g), potassium carbonate(1.5 mmol, 0.207 g), ZrO2ECP-Pd nanocatalyst (0.31 mol%,0.005 g), and water (3 mL) were allowed to react at 90 C. Uponthe completion of the reaction which was monitored by TLC,the reaction mixture was cooled to room temperature and thecatalyst was separated by centrifuge. The resulting solution wasextracted with ethyl acetate (310 mL). The organic layerswere combined, dried with sodium sulfate, and filtered. Thefiltrate was concentrated by vacuum and purified by thinlayerchromatography usingn-hexane/ethyl acetate (50/1) to affordthe pure product (0.150 g, %98 yield). |
90% | With 0.1 % Cu/C; potassium carbonate; In water; at 50℃; for 3.5h;Green chemistry; | General procedure: In a test tube, 1.0 mmol of aryl halides 1, 1.2 mmol of phenylboronic acid 2 were mixed together and then 2.0 mmol of K2CO3, and the Cu/Cnano-catalyst (0.1 mol % Cu) in 2 mL of H2O, were added in air. The reaction mixture was then stirred at 50 C for appropriate time. After completion of the reaction (monitored by TLC), the catalyst was removed by simple filtration. The recycled catalyst was was hed with ethanol and water (3 × 5 mL) and dried at 60 C in oven for further use. The aqueous layer was extracted with ethyl acetate, and organic layer dried over anhydrous MgSO4. The solvent was evaporated under reduced pressure to give the corresponding biaryl compounds. |
90% | With tetrabutylammomium bromide; potassium carbonate; In water; at 40℃; for 0.583333h; | General procedure: Typically, a 10-mL round-bottom flask was charged withiodobenzene (1.0 mmol, 0.204 g), phenylboronic acid(1.1 mmol, 0.134 g), K2CO3(1.2 mmol, 0.165 g), TBAB(0.2 mmol, 0.064 g), H2O(3 mL) and 0.0015 g of γ-Fe2O3/AEPH2-TC-Pd (0.1 mol%). The resultant mixture was heatedunder stirring at 40 C for 10 min. After completion of thereaction (as judged by TLC), the reaction mixture wasallowed to cool down to room temperature and the nanocatalystwas easily separated by using a proper magnetic field,washed with EtOH and vacuum-dried at 50 C to be ready for utilizing in successive runs. Subsequently, the reactionmixture was extracted with ethyl acetate (5 × 5 mL). Combinedorganic phase was dried over anhydrous Na2SO4,andsolvent was next removed on a rotary evaporator. Thereafter,the obtained crude product was chromatographed on silicagel (eluted with n-hexane:ethyl acetate; 50:1), to afford thecorresponding pure product (0.148 g, % 98 yield). |
85% | With potassium carbonate; In water; at 60℃; for 3h;Catalytic behavior; | General procedure: Aryl halide (1 mmol), arylboronic acid (1.2 mmol), K2CO3 (3 mmol) and 25 mg (0.07 mol%) Pdo-catalyst (Pdo-Mont.) were added to 10 ml of water and the reaction mixture was stirred at 60 C for a stipulated time period. The progress of the reactions was monitored by TLC. After completion of the reaction, the mixture was cooled to room temperature (∼25 C), and ethyl acetate (10 ml) was added to the mixture followed by separation of the solid catalyst by filtration through sintered funnel (G-3). The recovered catalyst was washed with acetone, dried in a desiccator and stored for another run. The organic extract was washed with water, dried over Na2SO4 and concentrated to give the crude products, which was finally purified by silica gel column chromatography using ethyl acetate and hexane as eluents. The products were identified by 1H NMR, mass spectrometry and melting point determination followed by their comparison with the standard literature data [54,55 |
85% | With potassium carbonate; In water; at 80℃; for 0.75h; | General procedure: Potassium carbonate (1.5 mmol, 0.207 g) was added to a mixture of iodobenzene (1.0 mmol, 0.203 g) and phenylboronic acid (1.2 mmol, 0.146 g), in water (3 mL) at 80 C. Then, to the resulting mixture ZrO2(at)AEPH2-PPh2-Pd(0) (0.2 mol%, 0.004 g) was added under stirring. After the completion of the reaction (20 min) which was monitored by TLC, the nanocatalyst was recovered by centrifugation, washed with ethyl acetate and dried under vacuum at 100 C for 24 h. The reaction mixture was then extracted with ethyl acetate (5 × 5 mL) and the combined organic layer was dried over anhydrous Na2SO4. After evaporation of the solvent, the crude product was purified by thin layer chromatography using n-hexane/ethyl acetate (50/1) to afford the pure product (0.145 g, % 95 yield). |
84% | With potassium carbonate; In ethanol; water; at 60℃; for 3h;Green chemistry; | General procedure: A mixture of aryl halide (0.125mmol), phenylboronic acid(0.126mmol), K2CO3(0.187mmol), in 0.5ml H2O:EtOH(1:1) and Pd(II)NA2SMNP (0.0006g, 0.02mol%) wasstirred at 60C for the appropriate of time. The progressof the reaction was monitored by TLC. After completionthe reaction, the catalyst was removed with an externalmagnet and washed with EtOH, dried and used directly fora subsequent round of reaction without further purification.Then, desired product (liquid phase) was extracted byplate chromatography eluted with n-hexane/EtOAc (10:1). |
45% | With triethylamine; In neat (no solvent); at 70℃; for 4h;Sealed tube; Irradiation; | General procedure: In a typical reaction, a mixture of aryl halid (0.2mmol),arylboronic acid (0.22 mmol), Et3N(0.4 mmol) and TiO2-AA-Pd nano hybrid (0.15mol%) was added in a10 mL Pyrex test tube and sealed with septum cap. Then thereaction mixture transferred into a reactor chamber and irradiate dunder magnetic stirring using a CFL lamp (philips,wavelength in the range 390-750nm, 40W, 1.1Wm-2) asthe visible light source at 70C for appropriate time. Aftercompletion of the reaction, TiO2-AA-Pd nanohybrid wasextracted by adding of ethanol (5mL) followed by centrifugingand decantation (3 × 5mL ethanol). Then, desired product(liquid phase) was extracted by plate chromatographyeluted with n-hexane/EtOAc (10/2). |
With potassium carbonate; In water; for 2h;Reflux;Catalytic behavior; | General procedure: To a mixture of Pd(II)-β-CD (0.001mol%, based on palladium, 0.23mL from a solution of 1mg in 100mL water, see Table2 for amount of catalyst) in 2mL water was added aryl halide (0.2mmol), arylboronic acid (0.24mmol), and K2CO3 (0.3mmol). The resulting mixture was stirred at reflux for 1-12h (Table2). After cooling, the product was extracted with n-hexane (2×3mL) and dried over Na2SO4. The product was purified by flash chromatography and characterized with 1H and 13CNMR (in CDCl3 and DMSO solvents) to afford biaryls 3a-s in 56-100% yields. All products are known and most of them are commercially available (see supporting information). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With tetrabutyl ammonium fluoride; caesium carbonate; In 1,4-dioxane; water; at 80℃; for 6h; | General procedure: For catalyst test, in a typical method, 1mmol of aryl halide, 2 mmol of PTMS, 1 mmol of TBAF, 1 mmol of Cs2CO3, 0.3 mol% (0.10 g) of NHC-Pd/SBA-15/IL were mixed to react in 2 mL dioxane:H2O (2:1) at 80C for 8 h afterwards, the reaction mixture was cooled to room temperature and the catalyst was separated by filtration and with DCM. Work-up step was performed by DCM (organic solvent) and distilled water. Then, the organic solution was evaporated and the residue was purified by column chromatography and the product. All obtained products are known and characterized and compared with physical and instrumental methods. |
87% | With TAd-PEPPSI; sodium hydroxide; In 1,4-dioxane; water; at 80℃; for 4h;Inert atmosphere; | General procedure: Under nitrogen, a 20mL Schlenk tube containing a stirring bar was charged with sodium hydroxide (120mg, 3.0mmol), TAd-PEPPSI (6.4mg, 0.010mmol), aryl bromide 5 (1.0mmol), trimethoxyphenylsilane 6 (224μL, 1.2mmol) and 1,4-dioxane (4mL)/H2O (2mL). The mixture was stirred at 80C for 4h. After the mixture was allowed to cool to room temperature, water (5mL) was added and the mixture was extracted with three portions of ethyl acetate (15mL), dried with MgSO4, and filtered. The solvent was removed under reduced pressure to give the crude product. The product was isolated by PTLC (hexane/ethyl acetate). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | With palladium diacetate; silver nitrate; at 150℃; for 36h;Inert atmosphere; | General procedure: Aryl bromides (0.5 mmol) and AgNO3 (85 mg, 0.5 mmol) and Pd(OAc)2 (11.2 mg, 0.05 mmol) were added to Schlenk tubes. Benzene (4 ml) was added to the tubes using a syringe. The mixture was then stirred in a sealed tube under argon atmosphere. Then the mixture was stirred at 150 C until complete consumption of the starting material was monitored by TLC. After completion of the reaction, the mixture was diluted with ethyl acetate, passed through a fritted glass filter to remove the inorganic salts and the solvent was removed with the aid of an rotary evaporator. The residue was purified by column chromatography on silica gel using petroleum ether/ethyl acetate as eluent to provide the desired product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With polystyrene-supported-diiodobis(theophylline)palladium(II) complex; In methanol; at 25℃; for 2h; | General procedure: Under aerial atmosphere, a test tube was charged with arenediazonium tetrafluoroborate salt (0.5mmol), PS-NHC-Pd(II) complex (17mg, 1mol%), and MeOH (1mL). After the addition of arylboronic acid (0.55mmol), the mixture was stirred at room temperature for an appropriate time. The progress of the reaction was monitored by TLC. After the completion of the reaction, the mixture was filtered to recover the catalyst and the filtrate was concentrated under vacuuo. Furthermore, the reaction mixture was extracted with CH2Cl2 (2×5mL) and the combined organic layer was washed with water (2×5mL). The organic layer was dried over Na2SO4 and the solvent evaporated under reduced pressure. The residue was purified by a preparative thin layer chromatography plate, using 10% EtOAc in n-hexane as eluent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99.9% | In ethanol; | Example 1 A 2-l atmospheric hydrogenation reactor was charged with 250 g (1.26 mol) of <strong>[2113-58-8]m-nitrobiphenyl</strong>, 12.5 g of 5% Pd-Cl, and 1250 ml of ethanol. A theoretical amount of hydrogen gas was absorbed at room temperature. The catalyst was removed by filtration and the filtrate was distilled of the solvent, obtaining 212 g of m-aminobiphenyl (yield 99.9%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With Pd/Al(OH)3; In toluene; at 140℃; for 28h;Inert atmosphere; | General procedure: To a tube equipped with a magnetic stir bar were added the Pd catalyst 1 (11.2 mg, 0.4 mol% Pd) and 1.0 equiv. of aryl chloride (0.2 mmol) in turn. Subsequently, the solvent (toluene, 2.0 mL) and phenylmagnesium bromide (0.3 mmol, 1.5 equiv) were added under N2 atmosphere, respectively. The reaction was then heated to 140 C and stirred until aryl chloride was completely consumed as determined by TLC. At last, the reaction mixture was purified by silica gel column chromatography to afford the desired pure coupling product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With potassium carbonate; In 1-methyl-pyrrolidin-2-one; at 110℃; for 5h;Schlenk technique; Inert atmosphere; Green chemistry; | General procedure: An oven-dried Schlenk tuble equipped with a magnetic stirring bar was charged with MCM-41-N,N-Pd(OAc)2 (49 mg, 0.02 mmol Pd), aryl iodide (3.2 mmol), triarylbismuth (1.0 mmol), and K2CO3 (4.0 mmol) followed by anhydrous NMP (3 mL) under Ar. The reaction mixture was stirred in an oil bath at 110 C for 5-24 h. The reaction mixture was cooled to room temperature and filtered. The MCM-41-N,N-Pd(OAc)2 complex was washed with distilled water (2×5 mL), NMP (2×5 mL) and Et2O (2×5 mL) and reused in the next run. The filtrate was quenched with water, and extracted with ethyl acetate (2×30 mL). The combined ethyl acetate extract was washed with dilute hydrochloric acid (10 mL), saturated sodium bicarbonate solution (10 mL), brine (2×10 mL), and dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure and the residue was purified by flash column chromatography on silica gel. |
Tags: 2113-58-8 synthesis path| 2113-58-8 SDS| 2113-58-8 COA| 2113-58-8 purity| 2113-58-8 application| 2113-58-8 NMR| 2113-58-8 COA| 2113-58-8 structure
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H420 | Harms public health and the environment by destroying ozone in the upper atmosphere |
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