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Chemical Structure| 14309-60-5

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Product Details of [ 14309-60-5 ]

CAS No. :14309-60-5
Formula : C15H12
M.W : 192.26
SMILES Code : CC1=CC=CC=C1C#CC2=CC=CC=C2
MDL No. :MFCD01319652

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Application In Synthesis of [ 14309-60-5 ]

* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

  • Downstream synthetic route of [ 14309-60-5 ]

[ 14309-60-5 ] Synthesis Path-Downstream   1~2

  • 1
  • [ 615-37-2 ]
  • [ 536-74-3 ]
  • [ 14309-60-5 ]
YieldReaction ConditionsOperation in experiment
99% With C19H25CuN5(1+)*F6P(1-); potassium carbonate; In N,N-dimethyl-formamide; at 135 - 140℃;Sealed tube; General procedure: A 20mL scintillation vial was charged with a Teflon stir bar, copper complex (0.1mmol), 76 potassium carbonate (0.75mmol), aryl iodide (0.5mmol), 77 phenylacetylene (0.75mmol) in 5mL non-anhydrous DMF in air. The vial was sealed and placed in an oil bath with pre-adjusted temperature at 135-140C. After the allowed time, the reaction mixture was cooled down, diluted with 25-30mL ethyl acetate, and filtered through a pad of silica gel. The solvent was then removed under vacuum and the residue was purified by column chromatography using mixtures of hexane and ethyl acetate to obtain analytically pure product.
97% With C19H28Cl2N4O2Pd; potassium carbonate; In ethanol; at 80℃; for 1h; General procedure: K2CO3 (2.5 × 10-4 mol, 2.5 equiv), aryl iodide (1.0 × 10-4 mol, 1.0 equiv), and alkyne (1.5 × 10-4 mol, 1.5 equiv) were mixed in a 10-mL vial, followed by addition of a solution of the selected catalyst (1 × 10-8 mol) in EtOH (1 mL). The vial was placed in a preheated oil bath at 80 C and stirred for 1 h. After cooling to 20-25 C, the reaction mixture was evaporated to dryness under a stream of dinitrogen followed by addition of 1.0 equiv of 1,2-dimethoxyethane as NMR internal standard, and extraction of the reaction mixture with three 0.20-mL portions of CDCl3. All fractions were joined and analyzed by 1H NMR spectroscopy. The product peak assignments were based on the authentic samples or on published dat, whereas quantifications were performed upon integration of the selected peak of the product relatively to the peak of the standard.
96% With C20H29Cl2N5O2Pd; potassium carbonate; In ethanol; at 80℃; for 2h; General procedure: Avial was charged with an aryl halide (0.1 mmol), an aryl or alkylacetylene(0.11 mmol), K2CO3 (0.15 mmol), palladium catalyst (0.05 mol %), and EtOH(2 mL). The mixture was refluxed with stirring for 2 h. After this time, themixture was cooled and CH2Cl2-n-hexane (1:2, 2 mL) and H2O (2 mL) wereadded. The organic layer was separated, filtered through a small amount ofsilica gel and analyzed by GC-MS. The solvent was removed and the residueweighed and analyzed by 1H NMR.
96% With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); at 55℃; for 3h;Ionic liquid; Green chemistry; General procedure: In a 4 mL screw-cap vial, 0.5 mmol of corresponding iodoarenecompound, 1.5 equiv of phenylacetylene or propargyl alcohol,0.005 equiv PdCl2(PPh3)2, and 0.8 mL of ionic liquid weremixed and stirred at 55 C for 3 h. After cooling, the mixturewas partitioned between 5 mL of water and 5 mL of pentane.After separation, the aqueous phase was extracted subsequentlywith 2 × 5 mL of pentane. The combined organic phase waswashed with brine, dried over MgSO4, filtered, and the solventwas evaporated under reduced pressure (ca. 10 mmHg). Theoily residue was purified by chromatography on silica gel(Merck Silicagel 60 (0.063-0.200 mm) for column chromatography(70-230 mesh ASTM)) eluted with n-pentane/EtOAc.The purity of the isolated products was >98%. The detailed experimentalprocedure as well as the characterization of isolatedcompounds are provided in Supporting Information File 1.
94% With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine; di-O-methyl-1,4:3,6-dianhydro-D-glucitol; at 25℃; for 1h;Microwave irradiation; Inert atmosphere; General procedure: To an oven-dried 5 mL microwave vessel was addedPd(PPh3)2Cl2 (2 mol%), aryl halide (1 equiv.), and alkyne couplingpartner (1.05 equiv.). The vessel was capped and purgedwith N2 before addition of DMI (0.5 mL, 0.5 M), and Et3N (1.1equiv.). The reaction mixture was maintained at room temperature(25 C) with stirring for 1 h before the vessel was ventedand decapped. The solution was then diluted with EtOAc (10mL) and washed with water (2 × 20 mL) and brine (2 × 20 mL).The organics were then passed through a hydrophobic frit andconcentrated under reduced pressure to give a residue, whichwas purified by flash chromatography (silica gel) to afford theproduct.
94% With dimethylammonium chloride; potassium carbonate; In glycerol; at 120℃; for 12h; General procedure: A mixture of phenylacetylene (1.2 mmol), aryl halide (1 mmol), K2CO3 (2 mmol), and GO-Fe3O4-Cellulose-Pd (1 mol%, 0.024 g) in 3 mL of DES (DMAC:Gly) was left under stirring at 120 C. After completing the reaction (monitored by TLC), the mixture was quenched with water (10 mL) and extracted with ethyl acetate (3 × 10 mL). The work-up procedure was performed similar to the Heck coupling reaction.
92% With copper oxide (I); Cs2CO3; In N,N-dimethyl-formamide; at 135℃; for 24h;Inert atmosphere; General procedure: A sealable vial equipped with a magnetic stir bar wascharged with Cs2CO3 (652 mg, 2.0 mmol) and Cu2O (7.0 mg,0.05 mmol) under a nitrogen atmosphere. The aperture of thevial was then covered with a rubber septum. Under a nitrogen atmosphere, aryl alkyne 1 (1.5 mmol), aryl iodide 2 (1.0 mmol), and DMF (0.5 mL) were added by syringe. The septum was then replaced by a screw cap containing a Teflon-coated septum, and the reaction vessel was placed at 135 C. After stirring at this temperature for 24 h, the heterogeneous mixture was cooled to r.t. and diluted with EtOAc (20 mL). The resulting solution was filtered through a pad of silica gel, then washed with EtOAc (20 mL), and concentrated to give the crude material which was then purified by column chromatography on silica gel to yield alkyne 3.
92% With sodium hydroxide; palladium (II) chloride; at 20 - 80℃; for 0.416667h;Green chemistry; General procedure: A round-bottom flask was charged with phenylacetylene(1.5 mmol, 0.16 mL), NaOH (1.5 mmol, 100 mg), PEG200(2 mL), and aryl halide (1.0 mmol). To this mixture,3.0 mol% of PdCl2 and 8.0 mol% of DPPPEG200 wereadded. The reaction mixture was placed in an 80 C oilbath and stirred to complete. The completion of the reactionwas monitored by TLC. After completion of reaction,the mixture was cooled to room temperature, and the catalystwas removed by addition of Et2O and then centrifugated.The isolated catalyst was dried and reused. Thefiltered solution was evaporated reduced pressure, and theexpected product was purified by column chromatographyover silica gel [60 Merck (230-240 mesh)] using petroleumether/ethyl acetate (5:1) as eluent to afford the product withhigh purity in 58-95 % yield.
90% With copper (I) iodide; potassium carbonate; In ethanol; water monomer; at 90℃; for 8h;Green chemistry; General procedure: A mixture of arylhalide (1 mmol), phenylacetylene (1 mmol), CuI(2 mol%), K2CO3(1 mmol), and nano Pd/ZnO (0.009 g) in H2O (1 mL)was stirred at 90C for the appropriate time. In the case of the sub-strates which are insoluble in water, a mixture of H2O/EtOH (1:1)was used as solvent. The progress of the reaction was monitored byTLC or GC. The separation of the catalyst from the reaction mixture and the work-up process is similar to the section 2.3.All compounds were known and characterized by comparison of their physical and spectroscopic data with the data already described in the literature.
90% With anhydrous potassium acetate; In N,N-dimethyl-formamide; at 100℃; for 2.5h; General procedure: Into a conical flask, a mixture of pectin supported Pd nanoparticles(0.05 g of the composite, contains 0.0028 mmol of Pd), aryl halide(1 mmol), terminal acetylene (2 mmol), KOAc (1.5 mmol) and DMF(2 mL) were stirred at 100 C under aerobic conditions. After completionof the reaction (monitored by TLC or GC), water (10 mL) andethylacetate (10 mL) was added to the reaction mixture anddecanted. The organic layer was dried over anhydrous Na2SO4. Afterevaporation of the solvent, the products were purified by columnchromatography. Finally, evaporation of the solvent gave the desiredpure products in good yields
90% With tetrabutylammonium bromide; triethylamine; In water monomer; at 70℃; for 6h; General procedure: An aryl halide (1.0 mmol) and a terminal alkyne (1.2 mmol)were added to a mixture of PS-tet-Pd(II) (0.04 g), Et3N (2.0 mmol),TBAB (1.0 mmol), and H2O (6 mL) in a glass flask under vigorousstirring. The mixture was stirred at 70 C for the appropriate timeunder aerobic conditions. After completion of the reaction, the catalystwas removed by filtration. The polymer was washed withH2O and MeCN, vacuum dried, and stored for a new run. AfterGC analysis, the solvent was removed under vacuum, and thenthe residue was subjected to column chromatography to affordthe pure product. The desired pure products were characterized by NMR, FT-IR, elemental analysis (CHN), and from their meltingpoints.
90% With potassium carbonate; for 4h;Heating; Green chemistry; General procedure: A round-bottom flask was charged with phenylacetylene (0.75 mmol, 0.08 mL), K2CO3 (0.75 mmol, 100 mg), PEG 200 (1 mL), and aryl halide (0.5 mmol). To this mixture, Pd(0) nano-catalyst supported on SDPP (1.5 mol-%, 3.0 mg) prepared according to our previous report [13] was added. In the case of aryl iodides and activated aryl bromides, the reaction mixture was placed in a 100 C oil bath; and in the case of the less active and deactivated aryl bromides and chlorides, the reaction mixture was placed in a 120 C oil bath. After completion of the reaction, the catalyst was removed by centrifugation and the remaining mixture was extracted with ethyl acetate (310 mL) and water several times and dried over anhydrous Na2SO4. The organic layer was evaporated under reduced pressure, and then purified by column chromatography over silica gel 60 (230-240 mesh; Merck) using petroleum ether/ethyl acetate (5 : 1) as eluent to afford the product with high purity in 51-95% yield. Note: This procedure can also be used, but the catalyst is prepared in situ by adding the appropriate amounts of SDPP and Pd(OAc)2.
90% With trimethyl-(2-hydroxyethyl)ammonium chloride; potassium carbonate; In glycerol; at 80℃; for 2.5h;Sealed tube; General procedure: The Sonogashira reaction was performed in a 10 mL screwcappedvial, phenylacetylene (1.1 mmol), aryl halide (1 mmol),K2CO3 (2 mmol), GO/Fe3O4G2/Co (1 mg, 0.4 mol%), and DES(ChCl:glycerol, 3 mL) was charged and stirred at 90 C for theproper time. The control of reaction, the separation of the catalyst,work-up process, and purification of the Sonogashira productswere analogous to that for the Suzuki reaction.
88% With triethylamine; In water monomer; at 90℃; for 0.75h; General procedure: A mixture of aryl iodide (1.0mmol), terminal alkyne (1.5mmol), Et3N (2.0mmol), H2O (2mL), and the catalyst (0.012mmol, 1.2mol% Pd) was stirred at 90C under aerial conditions. The progress of the reaction was monitored by TLC. After completion, H2O was evaporated, and CHCl3 (10mL) was added to the reaction mixture, and the catalyst was recovered with centrifugation. The organic layer was washed with H2O (2×5mL), dried over anhydrous MgSO4, filtered and concentrated in vacuum. The crude product was further purified by preparative TLC (silica gel) using n-hexane as eluent to afford the desired product. All the products were characterized by IR, 1H, and 13C NMR spectroscopy.
88% With potassium carbonate; at 85℃; for 24h;Inert atmosphere; Green chemistry; General procedure: To a mixture of the catalyst 3 (20mg containing 0.05mol% Pd for aryl iodides and 40mg containing 0.1mol% Pd for aryl bromides and chlorides), aryl halide (1mmol), alkyne (1.5mmol), and K2CO3 (1.5mmol, 207mg) was added PEG 200 (2mL) under argon atmosphere. The reaction mixture was stirred for the appropriate reaction time at 85 or 130C (see, Table 2). The progress of the reaction was monitored by using gas chromatography. After completion of the reaction, pure products were obtained by using column chromatography with hexane and ethyl acetate as eluents.
86% With copper (I) iodide; potassium carbonate; ethylene glycol; In N,N-dimethyl acetamide; at 110℃; for 24h; General procedure: Aromatic iodide (1.0mmol), alkyne (2.0mmol), K2CO3 (3.0mmol), glycol (0.2g) and CuI (0.02mmol) were added into a tubular reactor containing 15mgPdCPVC fiber mat and 3.2mL DMAc. The reaction was carried out at 110C with magnetic stirring. The post treatment was the same as that of PdCPVC catalyzed Heck reaction. The coupling products were confirmed by the 1H NMR spectra and mass spectra.
84% With triethylamine; In water monomer; at 60℃; for 10h;Inert atmosphere; General procedure: Aryl halide (1 mmol), phenylacetylene (1.5 mmol), and PNIPAM-co-PPAP/Pd catalyst (0.1 mol% Pd based on Aryl halide) were added into a 10 mL overpressure screw-capped vial equipped with a magnetically stirring bar, and then 1 mL deionized water was added. After the mixture was degassed under argon gas for 10 min, Et3N (3 mmol) was added in, and the solution was stirred at a given temperature for appropriate time. After the reaction was completed and cooled to room temperature, the solution was diluted with deionized water, and extracted with ethyl acetate (3 × 6 mL). The organic phase was washed with brine, dried with MgSO4, and then the solvent was evaporated under reduced pressure. The resulting residue was chromatographed on silica gel (hexane/ethyl acetate) to give pure product which was analyzed by 1H and 13C NMR, and the specific data were shown in Supporting Information.
84% With potassium carbonate; In ethanol; for 13h;Reflux; General procedure: in a typical procedure, the Sonogashira couplingreactions consist of aryl halide (0.5 mmol) in 3 mL of pure ethanol, phenylacetylene (0.75 mmol), K2CO3 (1 mmol) and 10 mg of the Pd-ZnFe2O4 catalyst(0.000764 mmol of Pd or 0.153 mol % of Pd). The reaction was carried outunder reflux condition for 11-14 h and was monitored by gas chromatography(GC). After completion, the reaction mixture was cooled to room temperatureand the catalyst (MNPs) was separated using an external magnet. The catalystwas then washed with ethanol, dried at 100 C for 3 h and preserved for nextcycle. The pure product was obtained using silica gel column chromatographyusing n-hexane-EtOAc as mobile phase.
84% With piperidine; In N,N-dimethyl-formamide; at 110℃; for 24h;Inert atmosphere; General procedure: To a stirred solution of 1.0 mmol of aryl halide in 4 mL of DMF,1.0 mmol of terminal alkyne, 1.5 mmol of piperidine and 0.2 mol%of Pd/Fe3O4NPs were added and the mixture was heated on anoil bath at 110C for 24 h under inert atmosphere (N2). After com-pletion of the reaction (as monitored by TLC), the reaction mixturewas cooled to room temperature and the catalyst was separatedusing a magnetic separator. The solvent was evaporated at reducedpressure, and the residue was subjected to gel permeation chro-matography to afford pure products. All the products are knowncompounds and the spectral data and melting points were identicalto those reported in the literature.
84% With piperidine; In N,N-dimethyl-formamide; at 110℃; for 24h;Inert atmosphere; Green chemistry; General procedure: To a stirred solution of 1.0 mmol of aryl halide in 4 mL of DMF,1.0 mmol of terminal alkyne, 1.5 mmol of piperidine and 0.2 mol%of Pd/Fe3O4NPs were added and the mixture was heated on anoil bath at 110C for 24 h under inert atmosphere (N2). After com-pletion of the reaction (as monitored by TLC), the reaction mixturewas cooled to room temperature and the catalyst was separatedusing a magnetic separator. The solvent was evaporated at reducedpressure, and the residue was subjected to gel permeation chro-matography to afford pure products. All the products are knowncompounds and the spectral data and melting points were identicalto those reported in the literature
83% With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine; at 30℃; for 24h;Inert atmosphere; Sealed tube; General procedure: For example, synthesis of 1,2-diphenylethyne, 3a. To an oven-dried 5 mL microwave vessel was added Pd(PPh3)2Cl2 (3.5 mg, 0.005 mmol, 2 mol %) and CuI (1.9 mg, 0.01 mmol, 4 mol %). The vessel was then capped and purged with N2 before addition of Cyrene (0.5 mL, 0.5 M), Et3N (38 µL, 0.275 mmol, 1.1 equiv), iodobenzene (27.9 µL, 0.25 mmol, 1 equiv), and phenylacetylene (28.8 µL, 0.263 mmol, 1.05 equiv). The reaction mixture was heated to 30 C and maintained at this temperature with stirring for 1 h before the vessel was vented, and decapped. The solution was then diluted with EtOAc (10 mL), and washed with water (2× 20 mL) and brine (2 × 20 mL). The organics were then passed through a hydrophobic frit and concentrated under reduced pressure to give a yellow oil, which was purified by flash chromatography (silica gel, 0-5% Et2O in petroleum ether) to afford the title compound as a white solid (44.5 mg, quant.).
83% With Cu(II)IL/Schiff base complex decorated on γ-Fe2O3; In dimethyl sulfoxide; at 90℃; for 4h; General procedure: In a typical run, 4-iodotoluene (1.0 mmol) and phenylacetylene(1.2 mmol) were dissolved in 2.0 mL DMSO.The catalyst (80 mg, 0.4 mol%) was added to the mixture,and the resultant mixture was stirred at 90 C under aerobic conditions. The reaction progress was monitored byTLC. Upon the reaction completion, the magnetic catalystwas separated using an external magnetic field, and then,water (5 mL) and dichloromethane (5 mL) were addedto the reaction mixture. The organic layer was separated,and the aqueous layer was extracted with further DCM.The organic layers were combined, dried over MgSO4,andthen, the solvent was removed under reduced pressure. The products were purified by silica gel column chromatography.The products were identified by 1HNMR and 13CNMRand comparison with the corresponding authentic samples
83% With 1,4-diaza-bicyclo[2.2.2]octane; In N,N-dimethyl-formamide; at 80℃; for 17h;Inert atmosphere;Catalytic behavior; General procedure: To a flask containing the aryl halide (0.5mmol) and phenylacetylene (0.75mmol, 0.08mL), DABCO (0.75mmol, 0.08g) and DMF (2mL), MWCNTIL-Pd nanocatalyst (25mg containing 0.5 mol% Pd) were added. The mixture was stirred at 80C for aryl iodides and 100C for aryl bromides under an argon atmosphere. After completion of the reaction (monitored by GC), deionized water (2mL) was added to the reaction mixture and the crude product was extracted with ethyl acetate (3×5mL). For further purification, the organic solvent was removed under vacuum and the resulting residue was purified by column chromatography on silica gel using hexane and ethyl acetate as eluents.
83% With 1,4-diaza-bicyclo[2.2.2]octane; In N,N-dimethyl-formamide; at 80℃; for 17h;Inert atmosphere;Catalytic behavior; General procedure: To a flask containing the aryl halide (0.5mmol) and phenylacetylene (0.75mmol, 0.08mL), DABCO (0.75mmol, 0.08g) and DMF (2mL), MWCNTIL-Pd nanocatalyst (25mg containing 0.5 mol% Pd) were added. The mixture was stirred at 80C for aryl iodides and 100C for aryl bromides under an argon atmosphere. After completion of the reaction (monitored by GC), deionized water (2mL) was added to the reaction mixture and the crude product was extracted with ethyl acetate (3×5mL). For further purification, the organic solvent was removed under vacuum and the resulting residue was purified by column chromatography on silica gel using hexane and ethyl acetate as eluents.
82% With potassium carbonate; In N,N-dimethyl-formamide; at 120℃; for 5h; General procedure: A suspension of aryl halide (1.0mmol), K2CO3 (2.0mmol), Pd complex (0.3mol%) and DMF (5mL) were mixed in a reaction flask and phenylacetylene (1.2mmol) was added. The reaction mixture was stirred at 120C for an appropriate time. After completion of the reaction, the procedure was followed as outlined in Section 2.6.
79% With nickel(II) chloride hexahydrate; tetrabutylammonium bromide; sodium hydroxide; In ethylene glycol; at 120℃; for 24h; Reaction conditions: aryl halide (1.0 mmol), phenylacetylene (2.0 mmol), n-Bub4 INsBorla(t0e.d5 ymiemldo.l), NiCl26H2O (10 mol %), NaOH (2.0 mmol), EG (2 mL), 120 C. 3.2.16. 1-Methyl-2-(2-phenylethynyl)benzene (Table 3, entry 4).47 dH(250 MHz, CDCl3) 2.44 (3H, s, Me), 7.07e7.16 (3H, m, Ph), 7.25e7.27(3H, m, Ph), 7.40e7.48 (3H, m, Ph); dC (62.9 MHz, CDCl3) 20.7, 88.3,93.3, 123.0, 123.5, 125.5, 128.1, 128.30, 128.35, 129.4, 131.5, 131.8,140.1
78% With piperidine; In N,N-dimethyl-formamide; at 110℃; for 24h; General procedure: Degassed solvent (DMF), arylhalide (1.0 mmol), phenyl acetylene (1.0 mmol), base (1.5 mmol), and thenanocrystal catalyst (1.0 mol %) were added to a round-bottom flask, whichwas backfilled with argon. The reaction mixture was stirred for 24 h at 110 C.After the reaction, the mixture was cooled to room temperature and thecatalyst was separated using a magnet. The mixture containing products waspartitioned between methylene chloride and water, and the organic layer wasconcentrated and purified through flash chromatography using hexane andethyl acetate (20:1 v/v) as an eluent. The separated nanocrystal catalyst waswashed several times with hexane, methylene chloride, ethanol and then driedfor recycling experiment.
78% With C10H24Cl2N2Pd2Se2; triethylamine; In 1,4-dioxane; at 100℃; for 12h;Schlenk technique; General procedure: Inan oven dried 25 ml Schlenk tube add a mixture of aryl halide (1mmol),arylacetylene (1.2 mmol), Pd catalyst 1d (3mol%), triethyl amine (2mmol) in 4ml dioxane. The reaction mixture was heated in an oil bath at 100oCfor 12 h with continuous stirring. After 12 h the reaction mixture was cooledto room temperature and the product was extracted with ethyl acetate (3 x10ml). After drying over Na2SO4, the solvent was removedunder vacuum, and the resulting crude product was purified by columnchromatography on silica gel. The product was eluted with petroleum ether:ethyl acetate (10.0:0.0 to 9.5:0.5) solvent system.
71% With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); N,N,N-trimethyl-2-hydroxyethyl-ammonium hydroxide; at 40℃; for 2h;Green chemistry; General procedure: To a 25 mL round-bottom flask equipped with a magnetic bar, phenylacetylene (4.5 mmol), aryl halide (3.0 mmol), Pd(PPh3)2Cl2 ( 2.0 mol%) and ChOH (4.0 mL) were added. Then, the mixture was stirred at 40C. After being stirred, the reaction mixture was filtered. Then, the filtrate was acidified with 3M HCl aqueous solution, and the aqueous layer was extracted with diethyl ether (3 X 10 mL). The combined organic layers were washed with brine, dried with anhydrous Na2SO4, and evaporated under reduced pressure. The crude mixture was purified by column chromatography on silica gel (hexanes/ ethyl acetate).
47% With triethylamine; In ethanol; water monomer; at 25 - 30℃; for 3h;Green chemistry; General procedure: A mixture of aryl halid (0.125mmol), phenylacetylene(0.137mmol), NEt3(0.0625mmol) in 0.2ml H2O:EtOH(1:2) and catalyst (0.001g, 0.03mol%) was stirred at roomtemperature for the appropriate of time. The progress of thereaction was monitored by TLC. After completion the reaction,the catalyst was removed with an external magnet andwashed with EtOH, dried and used directly for a subsequentround of reaction without further purification. Then, desiredproduct (liquid phase) was extracted by plate chromatographyeluted with n-hexane/EtOAc (10:1).
44% With triethylamine; In water monomer; at 80℃; for 24h; General procedure: A 10 mL round-bottom flask was charged with iodobenzene (4a, 1 mmol, 1 eq.), phenylacetylene (7a, 1.5mmol, 1.5 eq.), triethylamine (3 mmol, 3 eq.), H2O (2 mL), and Pd catalyst (0.01 mmol). The flask was stirred at 80C in air. The reaction was monitored by TLC and GC. After the reaction was complete, the reaction mixture was cooled to room temperature and ethyl acetate (5mL) was added to the flask. Afterward, the catalyst was filtered and washed with water (10 mL) and ethyl acetate (10 mL). The aqueous phase was extracted three times with 30 mL EtOAc. The organic phases were collected together, dried over MgSO4, and filtered. The solvent was then evaporated under reduced pressure. The pure product was obtained via silica gel column chromatography with an eluent of EtOAc and hexane. The resulting product was analyzed by 1H NMR spectroscopy.
41% With copper (I) iodide; Pd(2+)*C27H26P2*2CF3O3S(1-)*C22H16N4*H2O; triethylamine; In water monomer; at 100℃; for 2h;Microwave irradiation; General procedure: A mixture of the aryl halide (1mmol), phenylacetylene (1mmol), copper(I) iodide (7mol%), compound 1 (5mol%), TEA (1.2mmol) and H2O (5mL) in a microwave reaction vial was heated under microwave conditions in air at 100C for 2h and then cooled to room temperature. The crude product was purified by column chromatography. All coupled products were treated by a similar workup (for the NMR spectra and melting points of the products, see the supporting information).
31% With 1,4-diaza-bicyclo[2.2.2]octane; manganese(III) triacetate dihydrate; at 70℃;Green chemistry; General procedure: In a 25 mL reaction tube, Mn(OAc)3.2H2O(10 mol%), DABCO (2.5 equiv.) and a stirring bar were added. Then iodobenzene(1 mmol), phenyl acetylene (1 mmol) and PEG-400 were injected by syringe. The reaction tube was closed and transferred to a 70 C oil bath for 19-24 hours. After the reaction completed, cool down the reaction mixture to room temperature. Water (2 mL) was added and the reaction mixture was extracted with ethyl acetate and then concentrated and purified by column chromatography.
92%Chromat. With piperidine; In water monomer; at 100℃; for 1h; General procedure: In a typical reaction, a mixture of aryl halides (1.0 mmol), phenylacetylene (1.5 mmol), piperidine (2.0 mmol), H2O (6 ml) and catalyst (0.5 mol% of Pd) was stirred at 100 C for appropriate time. Progress of the reaction was monitored by GC analysis at different time interval of the reaction. After the completion of the reaction, the mixture was cooled to room temperature, diluted with water, and extracted with CH2Cl2 for three times. The organic phase thuscollected was dried with Na2SO4 and concentrated. The crude product was purified by flash column chromatography on silica gel. The product was analyzed by GC/MS, 1H NMR and elemental analyses. All the products were known compounds and were identified by comparison of their physical and spectra data with those of authentic samples.
With C33H34Cl2N4O2Pd; potassium carbonate; In ethanol; at 80℃; for 4h; General procedure: Selected base (1.5×10-4 mol, 1.5 equivs), aryl iodide (1.0×10-4 mol, 1.0 equiv) and terminal alkyne (1.0×10-4 mol, 1.0 equivs) were mixed in a 10-mL vial, followed by addition of a solution of the selected catalyst (1×10-8 mol) in EtOH (1 mL). The vial was placed in a pre heated oil bath at 80 C and stirred for 4 h. After cooling to ca. 25 C, the reaction mixture was evaporated to dryness under a stream of dinitrogen followed by addition of 1.0 equivof 1,2-dimethoxyethane (NMR internal standard), and extraction of the reaction mixture with three 0.20 mL portions of CDCl3. All fractions were joined and analyzed by 1H NMR spectroscopy. The product peak assignments were based on authentic samplesor on published data [56,62-68] (several sources were used for published compounds), while the structure of two new products,i.e. 3,4-dimethoxy-5-(phenylethynyl)benzaldehyde (derived from the coupling of 3-iodo-4,5-dimethoxybenzaldehyde with phenylacetylene) and 1-fluoro-2-[(2-methylphenyl)ethynyl]benzene (prepared from 2-fluorophenylacetylene and 2-iodotoluene were undoubtedly established using NMR spectroscopy, MS and elemental analyses (see Supplementary data). Quantifications were performed upon integration of the selected peak of the product in the 1H NMR relatively to the peak of the standard.
With anhydrous Sodium acetate; In dimethyl sulfoxide; at 120℃; General procedure: Iodobenzene (0.50mmol), phenylacetylene (0.55mmol), NaOAc (1mmol), and dimethyl sulfoxide (DMSO, 8mL) were mixed. Well-dispersed Pd/Fe3O4GO (0.4mol%) in DMSO (2mL) was added to the mixture with vigorous stirring. After the reaction, the catalyst was separated from the solution by centrifugation. The product was extracted three times with dichloromethane (20mL) and dried using MgSO4.
With anhydrous potassium acetate; In dimethylsulfoxide-d6; at 100℃; General procedure: A two-necked flask was charged with, the aryl halide(0.180 mmol), 1,3,5-trimethoxybenzene (0.180 mmol, 30.3 mg) and KOAc (0.270 mmol, 26.5 mg). A dispersion of Fe3O4/oleic acid/Pd nanoparticles was made in DMSO-d6 (1.00 mL, 2.00 mg/mL) and was added to the two-necked flask. The acetylene (1.80 mmol) was added and the mixture was stirred for 3 h under reflux at 100 C. After stirring, the nanoparticles were isolated from the mixture with a magnet. The conversion, with respect to the desired end product,was determined by 1H NMR of the crude reaction mixture, using 1,3,5-trimethoxybenzene as an internal standard.For more detailed information: see supplementary material.
80%Spectr. With potassium carbonate; In N,N-dimethyl acetamide; ethylene glycol; at 110℃; for 5h; General procedure: Pd(at)CS/PEO fiber mat (50 mg, palladium contentof 4.9 μmol) was added to the N,N-dimethylacetamide solution containing glycol (0.2 g), aromatic halide (0.7 mmol), phenylene acetylene (1.4 mmol) and K2CO3 (3.0 mmol). The reaction was carried out at 110C and monitored by TLC and GC-MS analysis. After completion, the reaction mixture was quenched with 10 mL H2O. The Pd(at)CS/PEO was recovered by simple filtration and the filtrate was extracted three times (3 × 20 mL) by ethyl acetate. The combined organic layer was concentrated to ∼5 mL and then purified by silica gel chromatography to afford the coupling product.
82%Chromat. With 1,4-diaza-bicyclo[2.2.2]octane; In N,N-dimethyl acetamide; at 30℃; for 24h;Inert atmosphere; General procedure: In a 5mL flask, ZIF-67PdCu (25mg) ArX (0.5mmol) and DABCO (0.75mmol) were well dispersed in 2mL of DMA under argon atmosphere. The aryl acetylene (0.75mmol) was added to the resulting mixture and stirred at 30C for ArI and 40C for ArBr for 24h. The progress of the reaction was monitored by TLC and GC. After completion of the reaction, the mixture was extracted with ethyl acetate (3×5mL) and water (10mL). The residue was purified by column and plate chromatography with hexane and ethyl acetate as eluents. All products were identified by 1HNMR and 13CNMR spectroscopy.

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  • 2
  • [ 14309-60-5 ]
  • [ 1137-96-8 ]
  • [ 3469-20-3 ]
  • 2-phenyl-3-(o-tolyl)-1H-indole [ No CAS ]
 

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