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Structure of 766-97-2 * Storage: {[proInfo.prStorage]}
* 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.
Reference:
[1] Journal of Organic Chemistry, 1990, vol. 55, # 13, p. 4086 - 4089
2
[ 766-97-2 ]
[ 619-41-0 ]
Reference:
[1] Green Chemistry, 2017, vol. 19, # 8, p. 1983 - 1989
[2] Journal of Organic Chemistry, 2013, vol. 78, # 18, p. 9190 - 9195
[3] European Journal of Organic Chemistry, 2016, vol. 2016, # 1, p. 116 - 121
[4] Tetrahedron, 2016, vol. 72, # 29, p. 4151 - 4158
3
[ 766-97-2 ]
[ 6746-94-7 ]
[ 1273578-50-9 ]
Reference:
[1] Angewandte Chemie - International Edition, 2016, vol. 55, # 38, p. 11485 - 11489[2] Angew. Chem., 2016, vol. 128, p. 11657 - 11661,5
4
[ 593-53-3 ]
[ 536-74-3 ]
[ 673-32-5 ]
[ 766-47-2 ]
[ 766-82-5 ]
[ 766-97-2 ]
Reference:
[1] Journal of the American Chemical Society, 1989, vol. 111, # 16, p. 6008 - 6014
5
[ 67-56-1 ]
[ 593-53-3 ]
[ 536-74-3 ]
[ 673-32-5 ]
[ 766-47-2 ]
[ 766-82-5 ]
[ 577-16-2 ]
[ 766-97-2 ]
Reference:
[1] Journal of the American Chemical Society, 1989, vol. 111, # 16, p. 6008 - 6014
6
[ 460-12-8 ]
[ 108-88-3 ]
[ 766-47-2 ]
[ 766-82-5 ]
[ 766-97-2 ]
Reference:
[1] Journal of Physical Chemistry A, 2000, vol. 104, # 45, p. 10312 - 10320
7
[ 591-31-1 ]
[ 766-97-2 ]
[ 6971-51-3 ]
Reference:
[1] Chemical Communications, 2014, vol. 51, # 3, p. 576 - 579
8
[ 766-97-2 ]
[ 274-07-7 ]
[ 72316-17-7 ]
Yield
Reaction Conditions
Operation in experiment
48%
Stage #1: for 18 h; Reflux Stage #2: at 20℃; for 4 h;
[00140] 1-Ethynyl-4-methylbenzene (0.50 mL, 3.94 mmol, 1.00 eq) and catecholborane (0.50 mL, 4.73 mmol, 1 .20 eq) were dissolved in THF (1 .5 mL) and the mixture was refluxed for 18h. The solvent was evaporated and then H20 (1 mL) was added. The suspension was vigorously stirred for 4 h at room temperature. The solid was filtered and recrystallized with water. (E)-5-phenylpent-1-en-1-ylboronic acid (309.4 mg, 1.90 mmol, 48percent) was then filtered and dried under vacuum.1H NMR (400 MHz, DMSO-d6) OH /ppm 7.73 (5, 2H), 7.36 (d, J= 7.9 Hz, 2H), 7.18 (d, J= 7.9 Hz, 2H), 6.05 (d, J= 18.3 Hz, 1H), 2.31 (5, 3H).13C NMR (101 MHz, DMSO) Oc /ppm: 146.2, 138.4, 135.4, 129.8 (20), 127.0 (20), 21 .3.
With copper(l) iodide; diisopropylamine;1,1'-bis(di-tertbutylphosphino)ferrocene; palladium dichloride; In tetrahydrofuran; for 2.25h;
a) 1-ethyl-2-(4-methylphenyl)-1H-pyrrolo[2,3-b]pyridin-5-amine To a solution of <strong>[15862-31-4]2-amino-3-bromo-5-nitropyridine</strong> (1.2 g, 5.5 mmol) in anhydrous THF (23 ml), PdCl2 (52 mg, 0.29 mmol), 1,1'-Bis(di-tert-butylphosphino)ferrocene (D-tBPF, 0.17 g, 0.39 mmol), diisopropylamine (0.81 g, 8.0 mmol), and CuI (22 mg, 0.11 mmol) were added while stirring. To this mixture 4-ethynyltoluene (1.0 ml, 7.9 mmol) was added dropwise over 2.25 hours. The mixture thus obtained was filtered under vacuum through Celite, the residue washed several times with EtOAc. After evaporation of the solvent, the residue was purified by column chromagraphy on silica gel (Et2O/n-hexane, Et2O 30percent-->60percent) to give 5-nitro-3-(phenylethynyl)pyridin-2-amine as yellow solid: 1H-NMR (CDCl3): 8.93 (d, J= 2.7 Hz, 1 H); 8.36 (d, J= 2.7 Hz, 1 H); 7.42 (AA' of AA'BB' system, 2H); 7.19 (BB' of AA'BB' system, 2H); 5.85 (bs, 2H); 2.39 (s, 3H).
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; diisopropylamine; In dimethyl sulfoxide; at 20℃;Inert atmosphere;
CuI (6.00 mg, 0.03 mmol), PdCl2(PPh3)2 (30.0 mg, 0.04 mmol), and i-Pr2NH (2 mL) were added to <strong>[25710-18-3]2,3-dichloropyrido[2,3-b]pyrazine</strong>refPreviewPlaceHolder21 (240 mg, 1.20 mmol) in dry DMSO (4 mL) under a slow stream of argon. After 20 min stirring under argon, p-tolylacetylene (348 mg, 3.00 mmol) in i-Pr2NH (2 mL) was added drop wise for 25 min. Stirring was continued for 6 h at room temperature. The reaction mixture was then filtered and solids over the filter were rinsed with hexane (5 mL) giving 5. This crude product 5 was purified by flash column chromatography on silica gel (3.x.30 cm) with CHCl3 as the eluent. The yield was 346 mg. The filtrate was evaporated to dryness under reduced pressure. The residue was mixed with silica gel and purified by flash column chromatography on silica gel (2.x.20 cm) with CHCl3 as the eluent. The yellowish fraction Rf (CHCl3) 0.3 gave 25.0 mg of 5. Compound 5 was obtained in 86percent total yield (371 mg) as pale yellow crystals, mp 219-221 °C (decomp., EtOH); 1H NMR (CDCl3, 250 MHz) delta ppm: 2.39 (br s, 6H, 2Me), 7.20 (m, 4H, p-Tol), 7.59 (m, 4H, p-Tol), 7.67 (dd, J=8.4, 4.3 Hz, 1H, H(7)), 8.38 (dd, J=8.4, 1.9 Hz, 1H, H(8)), 9.13 (dd, J=4.3, 1.9 Hz, 1H, H(6)); 13C NMR (CDCl3, 62.9 MHz) delta ppm: 22.1, 86.5, 86.7, 97.9, 98.6, 118.6, 118.8, 126.0, 129.8, 132.8, 132.9, 136.5, 137.9, 141.0, 141.1, 142.5, 144.5, 149.3, 155.1; IR, cm-1: 2207 (CC). MS m/z: 359 ([M]+, 30), 344 (33), 217 (49), 203 (15), 190 (30), 179 (30), 164 (11), 140 (100), 141 (52), 89 (14), 77 (64), 65 (13). Anal. Calcd for C25H17N3: C, 83.54; H, 4.77; N, 11.69. Found: C, 83.71; H, 4.56; N, 11.54.
With palladium diacetate; triethylamine; triphenylphosphine; In acetonitrile; at 80℃; for 3.5h;Inert atmosphere;
General procedure: A mixture of substituted <strong>[95104-21-5]2-chloroquinoline-3-carbonitrile</strong>s 1(a-h) (0.25mmol), phenylacetylene (0.26mmol), Pd(OAc)2 (5mol%)and PPh3 (10mol%) in CH3CN (2mL) and TEA (2equiv) were stirred under N2 at 80C, after completion of reaction (as monitored by TLC), solvent was evaporated and further Pd(OAc)2 (5mol%), PPh3 (10mol%), K2CO3 (1.5equiv) and 4mL of methanol were added under aerobic condition at 80C upto completion. The mixture was concentrated in vacuo and residue was purified by column chromatography on silica gel using EtOAc/hexane as eluent.
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; In N,N-dimethyl-formamide; at 80℃; for 16h;Inert atmosphere;
To a solution of <strong>[6942-39-8]2-bromo-5-fluoro-benzoic acid methyl ester</strong> (466 mg, 2.00 mmol) in DMF (4 ml) are added bis(triphenylphosphine)-palladium(ll)-chloride (104 mg, 0.20 mmol), copper(l) iodide (11.4 mg, 0.060 mmol), triethylamine (0.83 ml, 6.00 mmol) and 1-ethynyl-4-methyl-benzene (279 mg, 2.40 mmol). The resulting dark brown solution is flushed with nitrogen, heated to 80C and stirred in a closed reaction vial at this temperature for 16 hours. The reaction mixture is allowed to cool to room temperature and partitioned between water and dichloromethane. The organic phase is washed with 1 N HCI, dried over sodium sulfate and evaporated under vacuum. The residue is chromato- graphed on a silica gel column with cyclohexane/ethyl acetate as eluent to give 5-fluoro-2-p-tolylethynyl-benzoic acid methyl ester as brown oil; HPLC/MS 2.29 min (A), [M+H] 269.
α-[(4-methylphenyl)ethynyl]-N,N-bis(phenylmethyl)benzenemethanamine[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
50%
With indium(III) chloride; In toluene;Inert atmosphere; Reflux;
General procedure: Acetal (1.2 mmol), alkyne (1.2 mmol), dibenzylamine (0.192 mL,1.0 mmol), and InCl3 (10 molpercent) were added to a flask (25 mL), followedby the addition of toluene (2.0 mL) under argon. The mixture was stirredunder reflux and monitored by TLC. The solution was then cooled to r.t.,diluted with dichloromethane (5.0 mL), washed with brine. The aqueouslayer was extracted with CH2Cl2 (3 × 10 mL), the combined organic layer was dried over MgSO4, filtered, and evaporated under vacuum. Theresidue was purified by column chromatography on silica gel (petroleumether) to afford the desired product.
3-Cyano-2-(4-methylphenylethynyl)pyridine (28c). N,N-Diisopropylamine (5.0 mL) and tetrahydrofuran (5.0 mL) were added to <strong>[20577-26-8]2-bromo-3-cyanopyridine</strong> 2790 (184 mg, 1.0 mmol), copper(l) iodide (19.2 g, 0.1 mmol), sodium ascorbate (20 mg, 0.10 mmol) and bis(triphenylphosphine)palladium(ll) dichloride (35 mg, 0.05 mmol) under argon. The mixture was stirred at 40C for 30 min. 1-Ethynyl-4-methylbenzene (1 16 mg, 1.0 mmol) was added and the mixture was stirred at 40C for 36 h. Evaporation and chromatography (petroleum ether / ethyl acetate 5:1? 3:1 ) gave 3-cyano-2-(4-methyl- phenylethynyl)pyridine 28c (170 mg, 80%) as a pale buff powder: mp 175-178C; 1H NMR (CDCIs) delta 2.38 (3 H, s, Me), 7.32 (1 H, dd, J = 8.0, 4.9 Hz, 5-H), 7.40 (2 H, J = 8.2 Hz, Ph 3,5-H2), 7.58 (2 H, d, J = 8.1 Hz, Ph 2,6-H2), 7.95 (1 H, dd, J = 8.0, 1.8 Hz, 4-H), 8.77 (1 H, dd, J = 4.9, 1.7 Hz, 6-H); 13C NMR (HSQC) (CDCI3) delta 21.70 (Me), 112.66 (2- C), 121.73 (5-C), 129.32 (Ph 3,5-C2), 132.50 (Ph 2,6-C2), 139.84 (4-C), 140.61 (Ph 4- C), 152.8 (6-C); MS m/z 219.0905 (M + H)+ (C15HnN2 requires 219.0922).
80%
General procedure: Compound 24 (150 mg, 0.80 mmol) in THF (5 mL) was stirredwith CuI (15.2 mg, 80 lmol) and (Ph3P)2PdCl2 (28 mg, 40 lmol)in Pri2NH (5 mL) under Ar at 45 C for 30 min. Phenylethyne 21a(163 mg, 1.6 mmol) was added. The mixture was stirred at 40 Cfor 5 d. Evaporation and chromatography (petroleum ether/EtOAc3:1) gave 25a (80 mg, 50%) as a pale buff powder.
4-Cyano-3-(4-methylphenylethynyl)pyridine (98b). A mixture of 3-bromo-4- cyanopyridine 34 (91.5 mg, 0.5 mmol), tetrakis(triphenylphosphine)palladium(0) (30 mg, 0.025 mmol), copper(l) iodide (9.6 mg, 0.05 mmol) and sodium ascorbate (9.9 mg, 0.05 mmol) in tetrahydrofuran (5.0 mL) and diisopropylamine (5.0 mL) was stirred at 40C under argon for 30 min. 1-Ethynyl-4-methylbenzene 98a (available from Acros Organics - catalogue number 39256) (120 mg, 1.0 mmol) was added and the mixture was stirred at 40C under argon for 16 h. The mixture was cooled and the solvent was evaporated. The residue was purified by chromatography (petroleum ether / ethyl acetate 4: 1? 3: 1? 3:2) to give 4-cyano-3-(4-methylphenylethynyl)pyridine 98b (66 mg, 62%) as a buff powder: mp 94-96C; 1H NMR (CDCI3) delta 2.39 (3 H, s, Me), 7.20 (2 H, d, J = 8.4 Hz, Ph 3,5-H2), 7.51 (3 H, m, 5-H, Ph 2,6-H2), 8.65 (1 H, d, J = 5.0 Hz, 6- H), 8.90 (1 H, s, 2-H); 13C NMR (CDCI3) (HSQC / HMBC) delta 21.62 (Me), 100.01 (ethynyl 1-C), 1 13.20 (C=N), 114.90 (ethynyl 2-C), 119.50 (Ph 1 -C), 123.50 (4-C), 124.90 (5-C), 129.15 (Ph 4-C), 129.31 (Ph 3,5-C2), 132.03 (Ph 2,6-C2), , 140.50 (3-C), 148.15 (6-C), 152.02 (2-C); MS (ESI) m/z 219.0910 (M + H) (C^H^Nz requires 219.0922).
62%
General procedure: Compound 34 (91.5 mg, 0.5 mmol) was stirred with (PPh3)4Pd(30 mg, 25 lmol), CuI (9.6 mg, 50 lmol) and Na ascorbate (9.9 mg,50 lmol) in THF (5 mL) and Pri2NH (5 mL) at 40 C under Ar for30 min. PhC?CH 21a (102 mg, 1.0 mmol) was added and the mixturewas stirred at 40 C under Ar for 16 h. Cooling, evaporationand chromatography (petroleum ether/EtOAc 4:1?1:3) gave 35a(55 mg, 50%) as a pale buff powder.
With copper(l) iodide; 1,8-diazabicyclo[5.4.0]undec-7-ene; In toluene; at 25℃; for 0.0833333h;Inert atmosphere;
General procedure: To a stirred mixture of 1-benzyl-1H-indole-2,3-dione (1a, 0.25 g,1.05 mmol), CuI (0.01 g, 0.05 mmol, 0.05 equiv), and phenylacetylene (2a, 0.11 g, 1.11 mmol, 1.05 equiv) in anhyd toluene (2 mL), DBU (0.032 g, 0.21 mmol, 0.2 equiv) was added at 25 C under a N2 atmosphere. Stirring was continued at this temperature until the starting material was completely consumed (TLC monitoring). After completion, the mixture was quenched with sat. aq NH4Cl (2mL) and extracted with EtOAc (2 × 5 mL). The combined organic layers were dried (anhyd Na2SO4) and evaporated under reduced pressure to dryness. The crude product thus obtained was purified by column chromatography (activated silica gel, 60-120 mesh, hexane-EtOAc) to afford pure 3aa as a white solid; yield: 0.35 g (97%); mp 177-179 C.
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; In N,N-dimethyl-formamide; at 60℃; for 6h;Inert atmosphere;Catalytic behavior;
General procedure: In a 10 mL round-bottom flask under N2 atmosphere, 2-bromo-1,3,4-oxadiazole (0.7 mmol), alkyne (1.0 mmol), PdCl2(PPh3)2 (5 mol%), CuI (10 mol%), and Et3N (2.0 equiv) in anhydrous DMF (2.0 mL) were combined. The reaction mixture was stirred at 60 C for 6-16 h, and progress of reaction was monitored by TLC. Afterthe consumption of the starting materials, the reaction mixture wasallowed to cool, and subsequently extracted with Et2O (2 × 15 mL).The combined organic extracts were dried over anhydrous Na2SO4, filtered, and concentrated in vacuo followed by flash chromatographyon silica to afford the corresponding 2-alkynyl-1,3,4-oxadiazolein good yield.
1-(4-fluoro-3-methylphenyl)-4-(p-tolyl)-1H-1,2,3-triazole[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
84%
With sodium azide; In water; at 20℃; for 5h;Green chemistry;
General procedure: Aryl boronic acid(1 mmol), phenyl acetylene (1 mmol) and NaN3 (1.2 mmol) in H2O (2 mL) wereplaced in a 10 ml RB flask to which 10 mol % chitosanCuSO4 catalyst wasadded. The reaction mixture was stirred at room temperature and monitoredby TLC until total conversion of the starting materials. After completion of thereaction, water (20 mL) was added to the resulting reaction mixture followedby extraction with EtOAc (4 10 mL). Catalyst was separated by simpledecantation and dried for 3 h at 60 C temperature. The recovered catalyst wasused directly in the next cycle. The organic phase was washed with water anddried with Na2SO4. Solvent was removed under vacuum and the crude productwas purified by column chromatography to obtain the corresponding triazolecompound.
With trifluorormethanesulfonic acid; silver trifluoromethanesulfonate; lithium bromide; In water; toluene; at 40℃; for 8h;Green chemistry;
General procedure: A test tube (25 mL) wascharged with 2-aminobenzyl alcohol 1 (0.5 mmol, 1equiv), alkynes 2 (0.75 mmol, 1.5 equiv), AgOTf (0.025 mmol, 5 mol %), HOTf (0.05mmol, 10 mol%), LiBr (0.05 mmol, 10mol%), H2O (0.2 mL), and toluene (3 mL) were added. Themixture was stirred at 40 oC in air for 8 hours, the reaction wascooled down to room temperature, the mixture was quenched by sat. aq. NaHCO3,and diluted with 10 mL dichloromethane and washed with 10 mL H2O.The aqueous layer was extracted twice with dichloromethane (10 mL) and thecombined organic phase was dried over Na2SO4. Afterevaporation of the solvents, the residue was purified by silica gelchromatography (hexane/AcOEt = 30:1).
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; copper(l) iodide; triethylamine; In toluene; for 24h;Reflux;
General procedure: 2-(Methylthio)benzoxazoles or 2-(methylthio)benzothiazoles 1 (0.5 mmoles) were dissolved in 3 mL toluene. To the resulted solution were added the corresponding alkyne 2 (3 eq.), triethylamine (3 eq.), CuI (20 mol%) and Pd(dppf)Cl2 (10 mol%) and the mixture was stirred to reflux in air for 24 hours.The solvent was removed in vacuo and the residue was column cromatographed using various solvent mixtures to yield pure products 3.
With copper(l) iodide; bis(triphenylphosphine)palladium(II) chloride; triethylamine; In tetrahydrofuran;Inert atmosphere; Reflux;
General procedure: (1) intermediate compound 3a-3i synthesis:Taking 1mmol compound 1a-1c, compound 1mmol 2a-2c, 0 . 1mmol CuI of, 0.03mmol the Pd (PPh3)2Cl2and 2mmol triethylamine dissolved in 5 ml of tetrahydrofuran, under the protection of nitrogen, heating to reflux, TLC monitoring of the reaction process, the reaction is complete, the reactant is cooled to room temperature, by adding a proper amount of water, and then divide the liquid extraction, drying, then column chromatography, to obtain compound 3a-3i (the 1 to 2-bromophenylacetic formaldehyde or 2-bromo-5-methyl-phenyl-formaldehyde or 2-bromo-5-chlorobenzene formaldehyde, 2 for phenylacetylene or the methyl acetylene or to paradichlorbenzene acetylene, thus 1a-1c and 2a-2c intermediate obtained by reaction of a compound 9 a).
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; In tetrahydrofuran;Reflux;
Taking 1mmol compound 1a-1c, compound 1mmol 2a-2c, 0 . 1mmol CuI of, 0.03mmol the Pd (PPh 3) 2 Cl 2 and 2mmol triethylamine dissolved in 5 ml of tetrahydrofuran, under the protection of nitrogen, heating to reflux, TLC monitoring of the reaction process, the reaction is complete, the reactant is cooled to room temperature, by adding a proper amount of water, and then divide the liquid extraction, drying, then column chromatography, to obtain compound 3a-3e.
methyl 7-methoxy-1-(4-methylbenzoyl)-3-(trifluoromethyl)pyrrolo[2,1-a]isoquinoline-2-carboxylate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
In a round bottom flask4-methoxyisoquinoline (80-104 mg, 0.5-0.65 mmol) was added,P-methylphenylacetylene (58 mg, 0.5 mmol),Trifluoromethylpropiolate (114 mg, 0.75 mmol),Cuprous bromide (7.2 mg, 10 mol%),Toluene (5 mL) as solvent,Pumping nitrogen protection,Reacting at room temperature for 16-24 hours;Then copper bromide (11.2 mg, 10 mol%) was added as a catalyst,Pyridine (40 mg, 0.5 mmol),Heating to 100 ~ 120 C reaction 18 to 24 hours later,Cooled to room temperature,Diluted with saturated saline,Ethyl acetate extraction three times,The combined organic layers were dried over anhydrous Na2SO4,The product was purified by column chromatography.Light yellow solid.
With copper(I) bromide; In toluene; at 20℃; for 24h;Inert atmosphere;
General procedure: The mixture of isoquinoline 1 (1.3 mmol), terminal alkyne 2 (1.0 mmol), methylperfluoroalk-2-ynoates 3 (1.5 mmol), and CuBr (0.1 mmol) was stirred in toluene (5 mL) under N2. After stirring at room temperature for 24 h, CuBr2 (0.2 mmol), pyridine (1.0 equiv) were added. The mixture was stirred at 100 C under air for an additional 16 h. Then, the reaction was quenched with water and extracted with ethyl acetate (3×5 mL). The combined extracts were washed with brine, dried over anhydrous Na2SO4, and filtered. The filtrate was concentrated. The crude product was purified by flash chromatography on a silica gel (eluent: petroleum ether /ethylacetate) to give pure 5a-5q.
2-((4-(p-tolyl)-1H-1,2,3-triazol-1-yl)methyl)quinoline[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
82%
With copper(l) iodide; sodium azide; sodium carbonate; In methanol; water; at 50℃; for 20h;
General procedure: <strong>[3747-74-8]2-(Chloromethyl)quinoline hydrochloride</strong> (428 mg, 2 mmol), Na2CO3 (210 mg, 2 mmol), NaN3(143 mg, 2.4 mmol), alkyne (4 mmol) and CuI (23 mg, 0.12 mmol) were placed in a reaction tubecontaining a mixed solvent of CH3OH/H2O (1:1 v:v, 4 mL). Each reaction was stirred at 50 C for 20 hon a MultiMax reactor. The alkynes, 3,3-diethoxy-1-propyne, 3-ethynyltoluene and 4-ethynyltoluenewere used for the synthesis of 1-3, respectively. (Scheme 2) On completion, each mixture wasextracted with ethyl acetate three times. The combined organic extract was washed with brine,concentrated and purified by column chromatography on silica.
(E)-1-(1-iodo-2-((4-methoxyphenyl)sulfonyl)vinyl)-4-methylbenzene[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
84%
With potassium iodide; dibenzoyl peroxide; In dimethyl sulfoxide; at 20℃; for 12h;
General procedure: A 25 mL round-bottom ask was charged with alkynes 1 (0.2 mmol), sulfonylhydrazides 2 (0.3 mmol), KI(0.2 mmol), BPO (0.2 mmol, benzoyl peroxide), and DMSO(2 mL). Then the mixture was stirred at room temperature in air over night. Upon completion (TLC), the reaction mixture was mixed with water (10 mL), and the resulting suspension was extracted with ethyl acetate (3 × 10 mL). The combined organic phase was dried over anhydrous Na2SO4 and fltrated.The solution was evaporated under reduced pressure to remove the solvent. Purifcation of the residue by ash silica column chromatography using ethyl acetate (EA)/and petroleum ether(PET) mixtures as eluent (VEA: VPET = 1: 15) afforded pure product. NMR Spectra were measured in CDCl3 at 400 MHz (1H) and 100 MHz (13C). The Supplemental Materials file contains sample 1H and 13C NMR of the products 3 (FiguresS2-S33). (E)-1-(2-Iodo-2-phenylvinylsulfonyl)-4-methylbenzene(3a).17 White solid; m.p. 69 C; 1H NMR: delta 7.44 (d, J = 8.0 Hz,2 H), 7.36 (s, 1 H), 7.31-7.25 (m, 3 H), 7.22 (d, J = 6.0 Hz, 2 H),7.17 (d, J = 7.6 Hz, 2 H), 2.37 (s, 3 H); 13C NMR: 144.6, 141.3,139.7, 137.2, 129.8, 129.7, 127.95, 127.88, 127.7, 114.3, 21.7.
With palladium diacetate; caesium carbonate; bis[2-(diphenylphosphino)phenyl] ether; In N,N-dimethyl-formamide; at 100℃; for 2h;Sealed tube; Inert atmosphere;
General procedure: In a 15 mL sealed tube equipped with a magnetic stirring bar were added 1 (1 mmol),2 (0.8 mmol), tert-butyl isocyanide (1.2 mmol, 136 muL), Pd(OAc)2 (0.03 mmol, 7 mg),DPEPhos (0.06 mmol, 32 mg), Cs2CO3 (0.8 mmol, 261 mg), and anhydrous DMF (2.0mL). The tube was purged with argon, and the contents were stirred at 100 °C for 2 h.Then Na2S*9H2O (1.2 mmol, 240 mg) was added for 2 h. After reaction completion,the mixture was filtered through a pad of Celite, and DMF was removed by a vacuum.The combined filtrates were refluxed in THF (15 mL) and oxalic acid (1 M, 3 mL) for 8h. The solvents were removed under reduced pressure, then poured into brine (20mL) and extracted by ethyl acetate (3 × 30 mL). The combined organic layers weredried (Na2SO4) and evaporated. The residue was purified on a silica gel column usingpetroleum ether/ethyl acetate as the eluent to give the pure target product.
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; ethylenediamine; at 180℃; for 1.5h;Microwave irradiation; Inert atmosphere;
General procedure: Microwave Heating:To a flame dried 35 mL microwave vial with a teflon coated cap, 25 mL of ethylene diaminewas added via syringe and degassed with nitrogen for 20 minutes. To this vessel was added504 mg (1.5 mmol) of bis(2-bromophenyl)amine (3), 66 mg (0.30 mmol) of copper iodide,and 219 mg (0.30 mmol) of bis(triphenylphosphine)palladium dichloride sequentially whilestirring under nitrogen. Next 3.0 mmol of aryl acetylene was added dropwise via syringe.The reaction flask was heated for 1.5 hours at 180 C in a microwave reactor. Uponcompletion, the reaction was then poured over ice, extracted into dichloromethane (3 x 35mL) and the combined organic layers were washed with water three times before purifyingon an amine treated KP-NH silica flash column using hexanes and ethyl acetate as eluent.Fractions include primarily bis(tolan)amines (4a-f), 9-substituted acridines (5a-f), andcarbazole (6) depending on conditions.
5-chloro-2-phenyl-1-(1-p-tolylvinyl)-1H-indole[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
74%
With silver trifluoromethanesulfonate; In neat (no solvent); at 20℃; for 4h;Inert atmosphere; Green chemistry;
General procedure: Fe3O4SiO2-bipy-AuCl3 (16 mg, 0.01 mmol) and AgOTf (8 mg,0.03 mmol) were added to a mixture of 2-(phenylethynyl)aniline(0.2 mmol) and phenylacetylene (0.4 mmol) under Ar at roomtemperature. The reaction mixture was stirred at room temperature.During this procedure the reaction mixture became a deep blackliquid very quickly. After 4 h the resulting mixture was diluted withethyl acetate and the supported catalyst was magnetically separated.The reaction solution was evaporated and the residue was purifiedby column chromatography on silica gel (eluting with hexane/ethylacetate = 25:1) to give the desired product 3a. The recovered catalystwas washed with MeOH (2 × 2 mL) and air-dried. When appropriate itcould be used directly for the next run.
With sodium azide; sodium L-ascorbate; In ethanol; at 80℃; for 0.25h;Green chemistry;
General procedure: In a 50 mL round bottom flask alkyl/ aryl halide (1.0 mmol), sodium azide (1.2 mmol), alkyne (1.0 mmol), Cu-AcP-Am-Fe3O4(at)SiO2 (40 mg) and sodium ascorbate (29 mg, 0.15 mmol) were mixed and stirred in 5 mL ethanol. The reaction was allowed to proceed for 20 min at 80 C. Reactions were monitored by Thin Layer Chromatography (TLC) using aluminium backed silica gel 60 (F254) plates eluting with 20% ethyl acetate-petroleum ether (Rf = 0.46). After completion of the reaction, the catalyst was separated magnetically using bar magnet. Finally, the resulting solution was extracted with ethyl acetate and dried over anhydrous Na2SO4 the solvent was removed under reduced pressure then the product was purified by column chromatography over silica gel using EtOAc /Petroleum ether as eluent.