| 98% |
With copper(II) oxide; potassium hydroxide In dimethyl sulfoxide; <i>tert</i>-butyl alcohol at 110℃; for 24h; Inert atmosphere; |
|
| 98% |
With potassium carbonate at 120℃; for 4h; |
|
| 98% |
With potassium carbonate In water at 60℃; for 1h; |
|
| 98% |
With caesium carbonate In tetrahydrofuran at 150℃; for 3h; Inert atmosphere; |
2.3. Catalytic reaction
General procedure: The catalytic O-arylation reactions were conducted in asealed stainless-steel reactor. A phenol (14 mmol), aryl halide(14 mmol), Cs2CO3 (14 mmol), tetrahydrofuran (THF, 10 mL),and the Cu2O/SiC catalyst (10 mg) were placed in the reactor.The reaction was performed under Ar at 150 °C for 3 h. Afterthe reaction, the suspension was collected and centrifuged. Thesupernatant was analyzed using gas chromatography-massspectrometry (Bruker SCION SQ 456GC-MS, Germany). Theyields and TOFs were calculated based on the aryl halide usingthe following equations:Yield = Conversion (%) selectivity (%)= (1 - na/nb) x ntp/(ntp + nbp) x 100%TOF = Amount of aryl halides (mol) x conversion (%)x selectivity (%)/(mass of Cu2O/SiC (g) x Cu2O loading (%) xreaction time (h)/M[Cu2O] (g/mol))where na is the moles of aryl halide after reaction, nb is themoles of aryl halide before reaction, ntp is the moles of targetproduct after reaction, and nbp is the moles of byproduct afterreaction. |
| 98% |
With potassium carbonate In toluene for 8h; Reflux; Inert atmosphere; |
2.3.5. General procedure for the synthesis of diaryl ethers through C-Ocross-coupling of phenols and aryl iodides
General procedure: To synthesize diaryl ethers via C-O coupling reactions (O-arylationreactions), aryl halide (1 mmol), phenol (2 mmol) and K2CO3 (2 mmol)in toluene (5 mL) were placed into a 25 mL round bottomed flaskequipped with a condenser and a mechanical stirrer. Next, CNF-phen-Cu(I) (0.01 mmol, 0.02 g) was added and the obtained mixture was stirredat reflux temperature under argon atmosphere for a definite time whichis required to proceed each reaction. The progress of the reaction wasmonitored by TLC (pure n-hexane). After completion, the reactionmixture was cooled to ambient temperature and after addition of ethylacetate (15 mL) was allowed to stir for 15 min. Afterthat, the resultingmixture was filtered and the residue was washed with water and hotethyl acetate (40 mL). After concentrating the filtrate under reducedpressure, the crude product was purified by column chromatography (nhexaneas eluent). The prepared products were identified using 1H NMRand melting points. |
| 97% |
With tetrabutylammomium bromide; caesium carbonate In 1-methyl-pyrrolidin-2-one; dihexyl ether at 120℃; for 12h; Inert atmosphere; |
|
| 97% |
With caesium carbonate In dimethyl sulfoxide at 120℃; for 12h; Green chemistry; |
|
| 96% |
With potassium carbonate In N,N-dimethyl-formamide at 110℃; |
|
| 96% |
With caesium carbonate In acetonitrile at 82℃; for 10h; |
|
| 96% |
With tetrabutylammomium bromide; caesium carbonate In dimethyl sulfoxide at 120℃; for 10h; |
2.1. General procedure for the O-arylation of phenol with aryl halides
General procedure: Polymer supported Cu(II) catalyst (0.05 g, 0.0098 mmol) in DMSO (5 mL) was taken in a 100 ml R.B flask and stirred at room temperature for 10 min. Then aryl halide (1 mmol), phenol(1 mmol), tetrabutylammonium bromide (tBu4NBr) (0.1 mmol),Cs2CO3 (1 mmol) and DMSO (5 mL) were added to it. The final reaction mixture was refluxed at 120 °C under an open air condition.The reaction mixtures were collected at different time intervals and identified by GCMS and quantified by GC. After the completion of the reaction, the catalyst was filtered off and washed with water followed by acetone and dried in oven. The filtrate was extracted with ethyl acetate (3 x 20 ml) and the combined organic layers were dried with anhydrous Na2SO4 by vacuum. The filtrate was concentrated by vacuum and the resulting residue was purified by column chromatography on silica gel to provide the desired product. |
| 96% |
With tetrabutylammomium bromide; potassium carbonate In dihexyl ether; dimethyl sulfoxide at 130℃; for 12h; Open air atmosphere; |
|
| 96% |
With Cu-Fe-hydrotalcite In N,N-dimethyl-formamide at 140℃; for 7h; |
2.2 Catalytic reaction
General procedure: The catalytic o-arylation reaction was carried out in a magnetically stirred round bottom flask (capacity: 25 cm3), at the following reaction conditions: reaction mixture = 1 mmol aryl halides + 1.2 mmol phenol or naphthol + 3 ml solvent (DMF) + catalyst (50 mg), bath temperature = 140 °C and reaction time = 7-15 h. The reaction was monitored by TLC. After completion of the reaction, the catalyst was separated by filtration and the filtrate was treated with water, followed by extraction with ethyl acetate to give the crude product, which was subsequently purified by column chromatography on silica gel with petroleum ether/ethyl acetate as eluent. The catalyst was further washed with acetone, dried and reused. The reaction product was isolated by column chromatography and was characterized by comparison of its NMR spectra with that reported earlier. |
| 96% |
With caesium carbonate at 130℃; for 0.5h; Inert atmosphere; |
|
| 96% |
With tetrabutylammomium bromide; caesium carbonate In N,N-dimethyl-formamide at 145℃; for 24h; Inert atmosphere; |
2.3 General procedure for CuO-Fe3O4-catalyzed O-arylation of phenols with aryl halides
General procedure: To a stirred solution of phenol (2.2mmol) in DMF (15.0mL) under an argon atmosphere were added CuO-Fe3O4 (0.2mmol), TBAB (0.2mmol), Cs2CO3 (326mg, 1.0mmol) and aryl halide (2.0mmol). The reaction mixture was stirred at the required temperature (145°C) for 24 h. At the end of reaction, the catalyst was removed by a magnet and the resulting mixture was quenched with water and extracted with EtOAc. The organic phases were dried over MgSO4, followed by evaporation under reduced pressure to remove the solvent. The residue was purified by column chromatography on silica gel to afford the desired product. |
| 96% |
With caesium carbonate In N,N-dimethyl-formamide at 130℃; for 24h; |
|
| 95% |
With ethyl dimethylaminomethylphosphonate hydrochloride; copper(l) iodide; potassium carbonate In toluene at 110℃; for 18h; |
|
| 95% |
With caesium carbonate In N,N-dimethyl-formamide at 110℃; for 13h; |
|
| 95% |
With potassium phosphate; copper(l) iodide; tetrabutylammomium bromide In N,N-dimethyl-formamide for 22h; Heating; |
|
| 95% |
With potassium fluoride supported on Clinoptilolite In dimethyl sulfoxide at 110℃; for 8h; Inert atmosphere; |
|
| 95% |
With C17H17CuN2O3Pol; tetra(n-tert-butyl)ammonium bromide; caesium carbonate In acetonitrile at 70℃; for 12h; |
|
| 95% |
With caesium carbonate In N,N-dimethyl-formamide at 22℃; for 240h; Inert atmosphere; |
|
| 95% |
With L-valine; cobalt(II) diacetate tetrahydrate; caesium carbonate; zinc In acetonitrile Inert atmosphere; Heating; Green chemistry; |
General procedure for O-arylation of phenol
General procedure: An oven-dried sealed tube equipped with a magneticstirring bar was charged with aryl iodide (0.65 mmol),Co(OAc)24H2O (15 mol%), l-valine (30 mol%), cesiumcarbonate (2 equiv.), and phenol (0.78 mmol). Acetonitrilesolvent (2.5 cm3) was added and the sealed tube wasevacuated using a vacuum pump, filled with nitrogen,and tightly sealed. It was then stirred in a pre-heated oil bath for 24-48 h. After the completion of the reaction, thereaction mixture was extracted with 15 cm3 of EtOAc andthe EtOAc layer was separated and washed with water.The aqueous layer was collected and further extractedtwo more times with EtOAc (2 × 15 cm3). The combinedorganic layers were dried over anhydrous Na2SO4andevaporated using a rotatory evaporator. The residue waslater purified by column chromatography (silica 100-200mesh) using hexane-EtOAc mixture as the eluent. 1-(4-Methoxyphenoxy)-2-methyl-4-nitrobenzene (3i,C14H13NO4)Pale yellow liquid; yield: 29 mg (17%);Rf = 0.70 (hexane); 1H NMR (500 MHz, CDCl3):δ = 8.13(s, 1H), 7.96 (dd, J = 9.0, 3.5 Hz, 1H), 6.99 (d, J = 9.0 Hz,2H), 6.94 (d, J =9.0 Hz, 2H), 6.67 (d, J = 9.0 Hz, 1H), 3.83(s, 3H), 2.96 (s, 3H) ppm; 13C NMR (125 MHz, CDCl3):δ = 162.29, 156.92, 148.38, 142.10, 128.66, 126.64, 123.15,121.51, 115.26, 55.69, 16.36 ppm; HRMS (QToF): m/zcalculated for C14H13NO4([M+H]+) 260.0923, found260.0931. |
| 95% |
With sodium hydroxide In water at 80℃; for 2h; |
|
| 94% |
With caesium carbonate; copper(II) oxide In dimethyl sulfoxide at 110℃; Inert atmosphere; |
|
| 93% |
With copper(I) oxide; trans-1,2-bis(2'-pyridylidenamino)cyclohexane; caesium carbonate In acetonitrile at 82℃; for 24h; |
|
| 93% |
With tetrabutylammomium bromide; caesium carbonate In dimethyl sulfoxide at 120℃; for 12h; |
General procedure for O-arylation reaction of phenols witharyl halides
General procedure: Cu- catalyst (0.05 g) in DMSO (5 mL) was taken in a 100 mLround bottom flask and stirred at room temperature for 10 min.Then aryl halide (1 mmol), phenol (1 mmol), tetrabutylammoniumbromide (tBu4NBr) (0.1 mmol), Cs2CO3(1 mmol) and DMSO (5 mL)were added to it. The final reaction mixture was heated at 120Cunder an open air condition. The reaction mixtures were collectedat different time intervals and identified by GC-MS and quantifiedby GC. After the completion of the reaction, the catalyst was fil-tered off and washed with water followed by acetone and dried inoven. The filtrate was extracted with ethyl acetate (3 × 20 mL) andthe combined organic layers were dried with anhydrous Na2SO4byvacuum. The filtrate was concentrated by vacuum and the result-ing residue was purified by column chromatography on silica gelto provide the desired product. |
| 93% |
With potassium carbonate In N,N-dimethyl-formamide at 100℃; for 24h; |
|
| 93% |
With copper(l) iodide; 2-(2-benzoylhydrazine-1-carbonyl)-1-benzylpyrrolidine 1-oxide; caesium carbonate In acetonitrile at 80℃; for 12h; Inert atmosphere; Sealed tube; |
4.2. General procedure for the C-N and C-O coupling reaction
General procedure: CuI (19.2 mg, 0.1 mmol, 10 mol%), Cs2CO3 (650 mg, 2.0 mmol) and L2 (34 mg, 0.1 mmol, 10 mol%) were added to a re-sealable 25 mL test tubes with Teflon septa. The tube was evacuated and backfilled three times with nitrogen. Add the corresponding solvent (EtOH or CH3CN, 1 mL) via syringe under countercurrent nitrogenflow, continue adding halides (1.5 mmol) and nucleophile (1.0 mmol), seal the test tube. The reaction mixture was heated at 80 °C for 12 h, and then allowed to cool to room temperature. After the reaction mixture was diluted with CH2Cl2, the precipitate was removed by filtration and washed with water. After extraction, the organic phase was dried over anhydrous sodium sulfate and concentrated by rotary evaporation. The residue was purified by column chromatography. |
| 92% |
With potassium phosphate In N,N-dimethyl-formamide at 90℃; for 24h; |
|
| 92% |
With tetra(n-butyl)ammonium hydroxide; sodium hydroxide; palladium dichloride In water at 70℃; for 0.5h; |
|
| 92% |
With potassium hydroxide In N,N-dimethyl-formamide at 100℃; for 8h; Inert atmosphere; Green chemistry; |
|
| 89% |
With copper(l) iodide; 2-carbomethoxy-3-hydroxyquinoxaline-di-N-oxide; caesium carbonate In N,N-dimethyl-formamide at 100℃; for 12h; Inert atmosphere; |
|
| 89% |
With potassium carbonate In dimethyl sulfoxide at 80℃; for 12h; Sealed tube; Schlenk technique; |
|
| 89% |
With iron(III) chloride hexahydrate; tetrabutylammomium bromide; caesium carbonate; N,N`-dimethylethylenediamine In water at 130℃; for 36h; Green chemistry; |
|
| 88% |
With copper(l) iodide; 2,2',2''-triaminotriethylamine; caesium carbonate In 1,4-dioxane at 110℃; for 21h; |
|
| 84% |
With N-phenylpicolinamide; copper; caesium carbonate In acetonitrile at 82℃; for 24h; Inert atmosphere; |
General coupling procedure for diaryl ether synthesis:
General procedure: To a 50mL multi-necked round bottom flask, 1 mmol of aryl halide, 1.2 mmol of phenol, 20 mol% ligand, 20 mol% copper powder, 2.0 mmol of base, and 20 mL of acetonitrile were added. The mixture was stirred at 82 °C for 24 h. The reaction mixture was diluted with ethyl acetate and filtered through Celite in a fritted filter funnel to remove any inorganic salts. The solvent was then removed with the help of a rotary evaporator. The residue was purified by flash chromatography using hexane and ethyl acetate as an eluent to yield the product. |
| 82% |
With dimethyl sulfoxide; potassium hydroxide at 135℃; for 24h; Inert atmosphere; |
|
| 80% |
With 2,2,6,6-tetramethylheptane-3,5-dione; iron(III) chloride; caesium carbonate In N,N-dimethyl-formamide at 135℃; for 20h; |
|
| 72% |
With sodium dodecyl-sulfate; potassium carbonate In water at 100℃; for 11h; Green chemistry; chemoselective reaction; |
General procedure for O-arylation of phenols with aryl halides
General procedure: To a stirred suspension of appropriate aryl halide(2.0 mmol) and phenol (2.0 mmol) in 6 ml water, Ni-alumina (0.125g, 6 mol % ofnickel metal) was added followed by K2CO3 (0.28 g, 2mmol) and SDS (0.04 g, 8 mol%). The reaction mixture was stirred for therequired period of time at 80°C till the reaction was complete (monitored withTLC). Then the reaction mixture was cooled to room temperature, ethyl acetate(20 mL) was added to dissolve the product and the catalyst was separated simplyby filtration. The residue (recovered catalyst) was thoroughly washed withEtOAc (4×5 mL) followed by water (2×10 mL). The aqueous reaction mixture was repeatedly extracted with ethyl acetate (3×5 mL). The combined organic extractswere washed with water (3× 10 mL) and dried over anhydrous Na2SO4.The crude product was obtained by removal of the solvent under reduced pressure which was furtherpurified by filtration chromatography on a short column of silica gel using1-4% ethyl acetate-hexane as eluent. |
| 50% |
With sodium hydroxide In neat (no solvent) at 90℃; for 8h; Green chemistry; |
2.8 Typical Procedure for C-O Cross-Coupling Reaction
General procedure: A round bottom glass tube was charged by phenol (1mmol,0.094g), iodobenzene (1mmol, 0.203g), NaOH (3mmol,0.12g), and Fe3O4AMCA-MIL53(Al)-NH2-CoII NPs(VI)(1.08mol%, 0.04g). The reaction mixture was stirred at 90°C under solvent free conditions. Thin layer chromatography(TLC) or gas chromatography (GC) were used to monitor the progress of the reaction. After completion of the reaction (6h), the reaction mixture was quenched by additionof 2mL ethyl acetate. The nanostructured catalyst was separated using an external magnetic field, washed with ethanol and water before drying in an oven at 50°C overnight for the next run use. The obtained crude product was purified by thin layer chromatography using n-hexane/ethyl acetate(50:1) to aford the pure diphenyl ether (0.161g, 95% yield). |
|
With copper at 195℃; |
|
|
With tetraethylammonium tosylate 1.) DMF, electrolysis, 2.) DMF, room temperature; Yield given. Multistep reaction; |
|
| 93 % Chromat. |
With copper(l) iodide; 1-methyl-3-(n-butyl)imidazolium iodide; sodium t-butanolate at 130℃; for 30h; |
|
| 88 %Chromat. |
With potassium phosphate; copper(l) iodide In dimethyl sulfoxide at 90℃; for 24h; Inert atmosphere; Glovebox; |
|
| 99 %Chromat. |
With caesium carbonate In tetrahydrofuran at 150℃; for 3h; Inert atmosphere; Sealed tube; |
|
| 98 %Chromat. |
With potassium fluoride In dimethyl sulfoxide at 135℃; for 16h; Inert atmosphere; |
|
|
With potassium carbonate In N,N-dimethyl-formamide at 140℃; for 1h; |
|
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