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Structure of 873-73-4 * 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, 2017, vol. 82, # 14, p. 7200 - 7214
[2] Journal of Organic Chemistry, 2017, vol. 82, # 14, p. 7200 - 7214
11
[ 873-73-4 ]
[ 615-43-0 ]
[ 221910-19-6 ]
Yield
Reaction Conditions
Operation in experiment
76%
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In tetrahydrofuran at 20℃; Inert atmosphere; Schlenk technique
General procedure: In a typical reaction, PdCl2(PPh3)2 (88 mg, 0.125 mmol), CuI (24 mg, 0.125 mmol) and THF (5 ml) were placed in an oven-dried, 2-neck RB flask. To this suspension, 2-iodoaniline (5.47 mg, 2.5 mmol) and triethylamine (702 μl, 5.0 mmol) were added. The reaction mixture was degassed by bubbling with argon for 15 min. Phenylacetylene (300 μl, 2.75 mmol) was then added, and the reaction mixture stirred at RT. After complete consumption of the 2-iodoanilines (~2 h, by TLC), the reaction mixture was filtered through celite, and the solvent rotary evaporated to obtain the crude product which was purified by silica gel (60-120 mesh) column chromatography using ethylacetate/ hexane (1:9, v/v) as eluent to give pure 2-phenylethynylaniline, 2a (400 mg, 83percent).
Reference：
[1] Dalton Transactions, 2017, vol. 46, # 5, p. 1539 - 1545
[2] Tetrahedron Letters, 2014, vol. 55, # 40, p. 5495 - 5498
[3] Tetrahedron, 2011, vol. 67, # 46, p. 8918 - 8924
[4] Journal of Organic Chemistry, 2012, vol. 77, # 1, p. 617 - 625
[5] Journal of Organic Chemistry, 2013, vol. 78, # 20, p. 10319 - 10328
[6] Organic Letters, 2013, vol. 15, # 23, p. 5940 - 5943
[7] Organic Letters, 2014, vol. 16, # 18, p. 4924 - 4927
[8] Journal of Organic Chemistry, 2016, vol. 81, # 10, p. 4412 - 4420
[9] Journal of Organic Chemistry, 2016, vol. 81, # 10, p. 3994 - 4001
[10] Advanced Synthesis and Catalysis, 2017, vol. 359, # 8, p. 1373 - 1378
[11] Chemical Communications, 2017, vol. 53, # 61, p. 8533 - 8536
[12] Chemical Communications, 2017, vol. 53, # 64, p. 8980 - 8983
[13] Organic Letters, 2017, vol. 19, # 15, p. 3982 - 3985
[14] Journal of Organic Chemistry, 2017, vol. 82, # 16, p. 8455 - 8463
[15] Journal of Organic Chemistry, 2017, vol. 82, # 23, p. 12386 - 12394
[16] Advanced Synthesis and Catalysis, 2018, vol. 360, # 18, p. 3460 - 3465
[17] Journal of Chemical Research, 2018, vol. 42, # 11, p. 558 - 563
12
[ 873-73-4 ]
[ 274-07-7 ]
[ 154230-29-2 ]
Yield
Reaction Conditions
Operation in experiment
99%
Stage #1: for 18 h; Reflux Stage #2: at 20℃; for 4 h;
[00142] 1-Chloro-4-ethynylbenzene (0.50 g, 3.66 mmol, 1.00 eq) and catecholborane (0.47 mL, 4.39 mmol, 1 .20 eq) were dissolved in THF (1 .4 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)-(4-chlorostyryl)boronic acid (652.9 mg, 3.62 mmol, 99percent) was then filtered and dried under vacuum. 1H NMR (400 MHz, DMSO-d6) OH /ppm 7.83 (s, 2H), 7.50 (d, J= 8.4 Hz, 2H), 7.45—7.39 (m,2H), 7.24 (d, J= 18.4 Hz, 1H), 6.14 (d, J= 18.3 Hz, 1H).13C NMR (101 MHz, DMSO) Oc /ppm: 145.7, 144.8, 137.0, 133.3, 129.2 (20), 128.7(20).
N-[3-(4-Chlorophenyl)propargyl]-N-methyl-(1-naphthylmethyl)amine[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With paraformaldehyde;Zinc chloride; In 1,4-dioxane;
(a) N-[3-(4-Chlorophenyl)propargyl]-N-methyl-(1-naphthylmethyl)amine 15 g of methyl-(1-naphthylmethyl)amine, 12 g of p-chlorophenylacetylene, 2.61 g of paraformaldehyde and 1.1 g of zinc chloride are refluxed in absolute dioxane, in the absence of water, for 3 hours. The mixture is then evaporated and the residue is divided between saturated aqueous NaHCO3 solution and chloroform. The organic phase is dried and evaporated and the crude product is recrystallized from ethanol, m.p. 74-75.
With triethylamine;dichlorobis(triphenylphosphine)palladium[II]; In dichloromethane;
EXAMPLE 3 Preparation of 4-chloro-5-(4-chlorophenylethynyl)pyrimidine A mixture of 0.6 g of 1-chloro-4-ethynylbenzene, 1.44 g of <strong>[63558-65-6]4-chloro-5-iodopyrimidine</strong> (J. Chem. Soc. Perkins Trans. I, 1977,621, Allen et al), 7.0 cc of triethylamine, 58 mg of copper iodide and 108 mg of dichlorobis(triphenylphosphine)palladium II was stirred at room temperature under nitrogen for 18 hours. The reaction mixture was evaporated in vacuo. The resulting tan solid was partitioned between water and dichloromethane and the organic extracts washed twice with water, dried over sodium sulfate and evaporated to give a dark brown solid, 1.57 g. The solid was redissolved in dichloromethane and hexanes added to give 120 mg of a beige powder after filtration. The filtrate was purified by column chromatography on silica gel using 1:1 ethyl acetate/dichloromethane as the eluant. The middle rf spot fractions (silica gel TLC in 1:1) were pooled and evaporated to give 0.8 g of a yellow solid, 4-chloro-5-(4-chlorophenylethynyl)-pyrimidine
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; at 50℃; for 12h;Inert atmosphere;
General procedure: Under nitrogen conditions, 2-bromobenzaldehyde(10 mmol), phenylacetylene (12 mmol), Pd(PPh3)2Cl2(0.2 mmol) and CuI (0.1 mmol) were successively introducedinto a 100-mL two-neck flask equipped with Et3N(40 mL). The resulting mixture was stirred at 50 C for 12 hand monitored with TLC. After completion, the crude mixturewas filtered through celite and Et3Nwas removed undervacuum. The residue was diluted with EtOAc (60 mL) andwashed with water (2 × 50 mL). The organic layer was driedover Na2SO4,which was further purified via column chromatographyon silica gel (the mixture of petroleum ether andEtOAc was used as elute) to give 2-(phenylethynyl)benzaldehyde(1.83 g) in 89% yield. 2-(phenylethynyl)benzaldehyde was dissolved in methanol(30 mL), and the resulting mixture was cooled to 0 C. NaBH4 (5 mmol) was added in portions, and the solutionwas stirred for additional 20 min. The reaction was quenchedwith saturated ammonium chloride solution (30 mL).Methanol was removed under vacuum, and the residue wasextracted by EtOAc (2 × 30 mL). The combined organic layerwas dried over anhydrous Na2SO4.After the solvent wasremoved under reduced pressure, (2-(phenylethynyl)phenyl)methanol 1a was obtained (1.76 g) in 95% yield, which wasused directly for the next cyclization without purification.
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; In tetrahydrofuran; at 20℃;Inert atmosphere; Schlenk technique;
General procedure: In a typical reaction, PdCl2(PPh3)2 (88 mg, 0.125 mmol), CuI (24 mg, 0.125 mmol) and THF (5 ml) were placed in an oven-dried, 2-neck RB flask. To this suspension, 2-iodoaniline (5.47 mg, 2.5 mmol) and triethylamine (702 mul, 5.0 mmol) were added. The reaction mixture was degassed by bubbling with argon for 15 min. Phenylacetylene (300 mul, 2.75 mmol) was then added, and the reaction mixture stirred at RT. After complete consumption of the 2-iodoanilines (~2 h, by TLC), the reaction mixture was filtered through celite, and the solvent rotary evaporated to obtain the crude product which was purified by silica gel (60-120 mesh) column chromatography using ethylacetate/ hexane (1:9, v/v) as eluent to give pure 2-phenylethynylaniline, 2a (400 mg, 83%).
With palladium/copper catalyst;Inert atmosphere;
General procedure: All reagents were used as received without further purification.2-Alkynylanilines 1a-i were prepared by palladium/copper-catalysedSonogashira coupling reactions of 2-iodoanilines with terminalalkynes according to a literature method.31 The Fe3O4SiO2-bipy-AuCl3 complex was prepared according to our previous procedure.42The gold content was determined to be 0.62 mmol g-1. All reactionswere carried out under Ar in oven-dried glassware with magneticstirring. 1H NMR spectra were recorded on a Bruker Avance 400 (at400 MHz) spectrometer with TMS as an internal standard using CDCl3as the solvent. 13C NMR spectra were recorded on a Bruker Avance 400(at 100 MHz) spectrometer using CDCl3 as the solvent. HRMS spectrawere recorded on a quadrupole-time of flight Bruker MicroTOF-QII mass spectrometer equipped with an ESI and APCI source. Goldcontent was determined using ICP-AES on an Atomscan16 instrument(TJA Corporation).
With copper(l) iodide; In water; dimethyl sulfoxide; at 20℃;
General procedure: N-(2,4-dimethoxybenzyl)-N-methyl-3-phenylprop-2-yn-1-amine (5a). CuI (20 mg, 0.10 mmol) was added to a solution of phenylacetylene(510.6 mg, 5.0 mmol), HCHO (36% aq., 2 mL),<strong>[102503-23-1]N-methyl(2,4-dimethoxybenzyl)amine</strong> (1.09 g, 6.0 mmol) in DMSO (10.0mL). The resulting yellow green solution was stirred at room temperatureovernight and then diluted with H2O (10 mL), extracted with Et2O (15 mL x 3). The combined extractswas washed with H2O (2 x), brine (2 x) respectively, dried over Na2SO4, filtered, concentrated. Theresultant yellow oil was purified through flash column chromatography (silica gel, EtOAc/Hex = 1:6 to1:3) to give the product (5a, 1.14 g, 96%).
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.
25%
2- (4-Chlorophenylethynyl)-3-cyanopyridine (28d). N,N-Diisopropylamine (10 mL) and tetrahydrofuran (10 mL) were added to <strong>[20577-26-8]2-bromo-3-cyanopyridine</strong> 2790 (400 mg, 2.2 mmol), bis(triphenylphosphine)palladium(ll) dichloride (76 mg, 0. 1 mmol), copper(l) iodide (40 mg, 0.22 mmol) and sodium ascorbate (25 mg, 0.12 mmol) under argon. The mixture was stirred at 40C for 30 min. 4-Chlorophenylethyne (2.2 mmol) was added and the mixture was stirred at 40C for 12 h. Evaporation and chromatography (petroleum ether / ethyl acetate 5:1? 1 :3) gave 2-(4-chlorophenylethynyl)-3- cyanopyridine 28d (1 3 mg, 25%) as a pale amber powder: mp 84-86C; 1H NMR (CDCI3)? NMR (CDCI%) as J = 4.8, 2.4 Hz, 5-H), 7.37 (2 H, d, J = 8.7 Hz, Ph 3,5-H2), 7.61 (2 H, d, J = 6.7 Hz, Ph 2,6-H2), 7.98 (1 H, dd, J = 7.9, 1.7 Hz, 4-H), 8.79 (1 H, dd, J = 5.0, 1.7 Hz, 6-H); 3C NMR (CDCI3) (HSQC / HMBC) delta 86.38 (ethyne 2-C), 94.80 (ethyne 1 -C), 112.87 (3-C), 1 15.82 (C?N), 119.43 (Ph 1-C), 122.31 (5-C), 128.92 (Ph 3,5-C2), 133.63 (Ph 2,6-C2), 136.30 (Ph 4-C), 139.77 (4-C), 145.75 (2-C), 152.85 (6-C); MS m/z 239.0353 (M + H)+ (C14H835CIN2H requires 239.0376).
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; In N,N-dimethyl-formamide; at 60℃; for 10h;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.
ethyl 3-(4-chlorophenyl)indolizine-1-carboxylate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
87%
With potassium acetate; silver carbonate; In N,N-dimethyl-formamide; at 110℃; for 12h;
General procedure: A mixture of phenylacetylene 1a(1 equiv.), ethyl-2-pyridylacetate 2a(2 equiv.), Ag2CO3 (2 equiv.), and KOAc (2 equiv.) in DMF was stirred at 110 C for 12 h. The completion of the reaction was monitored by TLC, the mixture was quenched with diluted hydrochloride (3 mL, 2M), and the reaction mixture was filtered with sintered funnel and washed with ethyl acetate. The filtrate was poured into water and extracted with ethyl acetate 3 times. The organic layers were combined, and dried over sodium sulfate. The pure product was obtained by column chromatography on silica gel to afford 3a in 86% yield.
With potassium acetate; silver carbonate; In N,N-dimethyl-formamide; at 110℃; for 12h;
General procedure: A mixture of phenylacetylene 1a(1 equiv.), ethyl-2-pyridylacetate 2a(2 equiv.), Ag2CO3 (2 equiv.), and KOAc (2 equiv.) in DMF was stirred at 110 C for 12 h. The completion of the reaction was monitored by TLC, the mixture was quenched with diluted hydrochloride (3 mL, 2M), and the reaction mixture was filtered with sintered funnel and washed with ethyl acetate. The filtrate was poured into water and extracted with ethyl acetate 3 times. The organic layers were combined, and dried over sodium sulfate. The pure product was obtained by column chromatography on silica gel to afford 3a in 86% yield.
4-(4-chlorophenylethynyl)-3-cyanopyridine[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
59%
General procedure: 4-Bromo-3-cyanopyridine 27 (92 mg, 0.5 mmol) in THF (5 mL)was added to CuI (9.6 mg, 50 lmol), (Ph3P)4Pd (29 mg, 25 lmol)and Na ascorbate (9.9 mg, 50 lmol) in Et3N (5 mL) under Ar. Themixture was stirred at 40 C for 30 min. Phenylethyne 21a(76.5 mg, 0.75 mmol) was added and the mixture was stirred at40 C for 10 h. Evaporation and chromatography (petroleumether/EtOAc 3:1) gave 28a (80 mg, 78%) as an off-white powder.
3-(4-chlorophenylethynyl)-4-cyanopyridine[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
41%
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 diacetate; triethylamine; In 1,4-dioxane; at 110℃; for 24h;
A mixture of di-2-pyridinone(55 mg, 0.3 mmol), 4-chlorophenylacetylene (82 mg, 0.6 mmol), copper acetate (5.4 mg,0.03 mmol), and triethylamine (60 mg, 0.6 mmol) were dissolved in 1,4-dioxane (2 mL). The resulting mixture is obtainedWas heated to 110 , 24 hours after the reaction TLC monitoring reaction has been complete. The reaction was stopped, filtered and the crude product was passed through a silica gel columnChromatography (100-200 mesh, n-hexane: ethyl acetate = 3: 1) to give 89 mg of the desired product in 93% yield.
4-bromo-2-(4-chlorophenylethynyl)pyridine[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
77%
With copper(l) iodide; palladium(II) trifluoroacetate; diisopropylamine; triphenylphosphine; In acetonitrile; for 24h;Reflux; Inert atmosphere;
General procedure: <strong>[58530-53-3]2,4-dibromopyridine</strong> (237 mg, 1.0 mmol), phenylacetylene (51 mg, 0.5 mmol), i-Pr2NH (101 mg, 1.0 mmol), Pd(CF3COO)2 (16.6 mg, 5 mol%), PPh3 (26 mg, 10 mol%), and CuI (9.5 mg, 5 mol%) were dissolved in CH3CN (5 mL). The reaction mixture was stirred at reflux under nitrogen atmosphere for 24 h and then cooled. The solid was filtered off and the filtrate was concentrated. The crude product was then dissolved in CH2Cl2 (10mL) and the solution was washed with brine (10 mL), and dried over sodium sulfate. Upon evaporation, the resulting residue was subjected to column chromatography (petroleum ether/AcOEt, 200:1) to give 3a (108 mg, 84%) as a colorless liquid.
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).
2-(4-chlorophenyl)-3-(phenylthio)benzofuran-6-carboxylic acid[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
80%
With copper(l) iodide; dimethylaminoacetic acid; caesium carbonate; In N,N-dimethyl-formamide; at 100℃; for 20h;Inert atmosphere;
In a 25 ml three-mouth flask, add D-2 (268 mg, 1mmol), (264 mg, 1mmol), then add Cs2CO3(652 mg, 2mmol), diphenyl disulfide (109 mg, 0 . 5mmol), vitamin B16 (30.9 mg, 0 . 3mmol), cuprous iodide (19 mg, 0 . 1mmol), p-chlorophenylacetylene (132 mg, 1mmol), 5mL DMF. Under the protection of nitrogen, in a 100 C oil bath react for 20h, cool, add 5 ml water, for each time 5 ml ethyl acetate extraction, after repeated four times, extraction the fluid uses full and salt water washing, dry anhydrous sodium sulfate, after filtration the liquid reduced pressure distillation, a silica gel column to separate distillate (showering liquid is petroleum ether: ethyl acetate = 50:1), to obtain strawcoloured viscous liquid 304.6 mg, yield is 80%.
3-[2-(4-chlorophenyl)ethynyl]-5-nitro-pyridine[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
200 mg
With palladium diacetate; caesium carbonate; 4,5-bis(diphenylphos4,5-bis(diphenylphosphino)-9,9-dimethylxanthenephino)-9,9-dimethylxanthene; In tetrahydrofuran; at 70℃; for 16.0h;Inert atmosphere;
To a flask was added <strong>[15862-30-3]3-bromo-5-nitropyridine</strong> (203 mg, 1 mmol), 1-chloro-4-ethynylbenzene (164 mg, 1.2 mmol), Pd(OAc)2 (11.2 mg, 50 mumol), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (57.9 mg, 100 mumol), Cs2CO3 (652 mg, 2 mmol) and THF (4 mL). A pale brown suspension was formed. Then it was bubbled with N2 for 5 min and heated to reflux (70 C. oil bath) for about 16 hours. The mixture was filtered through celite and the filtrate was concentrated to give a dark oil. The oil was purified via combiflash (eluting with EA/PE=0?20%?30%). About 200 mg 3-[2-(4-chlorophenyl)ethynyl]-5-nitro-pyridine (Compound 69A) was obtained as yellow solid. MS: calc'd 259 (M+H)+, measured 259 (M+H)+.
methyl 1-(4-chlorobenzoyl)-7-nitro-3-(trifluoromethyl)pyrrolo[2,1-a]isoquinoline-2-carboxylate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
In a round bottom flask4-Nitroisoquinoline (95-119 mg, 0.5-0.65 mmol) was added,P-Chlorophenylacetylene (68 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.
[00142] 1-Chloro-4-ethynylbenzene (0.50 g, 3.66 mmol, 1.00 eq) and catecholborane (0.47 mL, 4.39 mmol, 1 .20 eq) were dissolved in THF (1 .4 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)-(4-chlorostyryl)boronic acid (652.9 mg, 3.62 mmol, 99%) was then filtered and dried under vacuum. 1H NMR (400 MHz, DMSO-d6) OH /ppm 7.83 (s, 2H), 7.50 (d, J= 8.4 Hz, 2H), 7.45-7.39 (m,2H), 7.24 (d, J= 18.4 Hz, 1H), 6.14 (d, J= 18.3 Hz, 1H).13C NMR (101 MHz, DMSO) Oc /ppm: 145.7, 144.8, 137.0, 133.3, 129.2 (20), 128.7(20).
4-(4-chlorophenyl)-6-(2,4-dimethylphenyl)-2-phenylpyrimidine[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
57%
With potassium tert-butylate; In dimethyl sulfoxide; at 120℃; for 12h;Inert atmosphere;
0.20 mmol of benzamidine hydrochloride, 0.25 mmol of 4-chlorophenylacetylene, 0.25 mmol<strong>[15764-16-6]2,4-dimethylbenzaldehyde</strong>, 0.4 mmol of potassium tert-butoxide, 1 ml of dimethyl sulfoxide,Under the nitrogen protection strip,Stir at 120 CMix reaction for 12 hours,Stop heating and stirring,Cool to room temperature.Ethyl acetate extraction reaction solution,The solvent was removed by distillation under reduced pressure,And then purified by column chromatography,Get the target product,The column chromatography eluent used was in a volume ratio of 500: 1Of the petroleum ether: BEthyl acetate mixed solvent,The yield was 57%.
With copper(l) iodide; L-proline; sodium hydroxide; In dimethyl sulfoxide; at 80℃; for 12h;Inert atmosphere; Sealed tube;
General procedure: A sealable reaction tube equipped with a magnetic stirrer bar was charged with 2-iodophenols 1 (1 mmol), alkynes 2 (1 mmol), NaOH (2 mmol), CuI (0.1 mmol), proline (0.3 mmol) and DMSO (5 mL), and the reaction vessel placed in an oil bath at 80 C under N2 . After stirring the mixture at this temperature for 12 h, it was cooled to room temperature and diluted with ethyl acetate, washed with water and brine, dried over by MgSO4. After the solvent was removed under reduced pressure, the residue was purified by column chromatography on silica gel to afford the corresponding product.
73%
With copper(l) iodide; sarcosine; caesium carbonate; at 100℃; for 24h;Inert atmosphere;
In a 25mL three-vial bottle,B-3 (280 mg, 1.1 mmol) was added,Then it was added and then Cs2CO3 (652 mg, 2 mmol) was added.N-methyl glycine (26.7 mg, 0.3 mmol),Copper iodide (38mg, 0.2mmol),p-chlorophenylacetylene (137mg, 1mmol),2mL DMSO,Under the protection of nitrogen,React in an oil bath at 100C for 24 hours,After cooling, add dilute hydrochloric acid to a pH of 4,Then add 5mL of water,Each time it is extracted with 5 mL of ethyl acetate,After repeating four times,The extract was washed with saturated saline solution.Drying with anhydrous sodium sulfate,The filtered liquid is distilled under reduced pressure,The distillate was separated on a silica gel column (gradiently eluted with petroleum ether and petroleum ether:ethyl acetate=20:1, respectively).191.2 mg of a white solid was obtained with a yield of 73%.
2-(4-chlorophenyl)benzo[b]furan-6-carboxylic acid[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
83%
With copper(l) iodide; L-proline; sodium hydroxide; In dimethyl sulfoxide; at 80℃; for 12h;Inert atmosphere; Sealed tube;
General procedure: A sealable reaction tube equipped with a magnetic stirrer bar was charged with 2-iodophenols 1 (1 mmol), alkynes 2 (1 mmol), NaOH (2 mmol), CuI (0.1 mmol), proline (0.3 mmol) and DMSO (5 mL), and the reaction vessel placed in an oil bath at 80 C under N2 . After stirring the mixture at this temperature for 12 h, it was cooled to room temperature and diluted with ethyl acetate, washed with water and brine, dried over by MgSO4. After the solvent was removed under reduced pressure, the residue was purified by column chromatography on silica gel to afford the corresponding product.
2-(4-chlorophenyl)-1-[1-(4-chlorophenyl)vinyl]-1H-indole[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
66%
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.
1-((4-chlorophenyl)ethynyl)-2-phenoxybenzene[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
92%
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; for 10h;Inert atmosphere;
(1)To <strong>[34883-46-0]1-iodo-2-phenoxybenzene</strong> (2g, 6.8mmol)a solution of triethylamine (20 mL) added to 4-chlorophenylacetylene(1.1g, 8.1mmol),Pd(PPh3)2Cl2 (95 mg, 135 mumol), CuI (26 mg, 135 mumol).Under argon protection conditions,After the reaction was carried out for 10 hours,Triethylamine was removed under reduced pressure.The residue was extracted with ethyl acetate (20 mL×3).Then use water (10mL)Wash twice with saturated brine (10 mL) and dry over anhydrous sodium sulfate.Filter and remove the solvent under pressure.The residue was purified by silica gel column chromatography eluting elut1-((4-Chlorophenyl)ethynyl)-2-phenoxybenzene(1.9 g, 92% yield).
1-(naphthalen-1-yl)-3-(4-chlorophenyl)benzo[de]phosphanaphthalene-1-oxide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
82%
With tert-Butyl peroxybenzoate; copper dichloride; In N,N-dimethyl-formamide; at 100℃;
Add 4-chlorophenylacetylene (0.068 g, 0.5 mmol) to the reaction flask.Dinaphthylphosphorus (0.30 g, 1 mmol),CuCl2 (0.014 g, 0.1 mmol),Tert-butyl peroxybenzoate (0.29 g, 3 mmol),And N,N-dimethylformamide (2 mL),100oC reaction;TLC tracks the reaction until it is completely over;The crude product obtained after the completion of the reaction was separated by column chromatography (ethyl acetate: petroleum ether = 1:1) to give the desired product.(Yield 85%).
(py)Cu<SUP>III</SUP>(CF<SUB>3</SUB>)<SUB>3</SUB>[ No CAS ]
(Z)-1-(4-chlorophenyl)-3,3,3-trifluoroprop-1-en-1-yl(4R)-4-((8R,9S,10S,13R,14S,17R)-10,13-dimethyl-3,7,12-trioxohexadecahydro-1H-cyclopenta[a]phenanthren-17-yl)pentanoate[ No CAS ]
(E)-1-(4-chlorophenyl)-3,3,3-trifluoroprop-1-en-1-yl(4R)-4-((8R,9S,10S,13R,14S,17R)-10,13-dimethyl-3,7,12-trioxohexadecahydro-1H-cyclopenta[a]phenanthren-17-yl)pentanoate[ No CAS ]
With potassium fluoride; sodium azide; silver carbonate; In N,N-dimethyl-formamide; at 50℃; for 6h;
General procedure: to a solution of phenylacetylene (1a)(0.055 mL, 0.5 mmol), 2,6-di-tert-butyl-4-methylphenol(BHT) (2a) (133 mg, 0.6 mmol), NaN3 (39 mg, 0.6 mmol)and KF (58 mg, 1.0 mmol) in DMF (1 mL) at 50 C, Ag2CO3(41 mg, 0.15 mmol) was added. The reaction mixture wasthen stirred for 6 h when TLC conformed that substrate 1a was consumed. The resulting reaction mixture was cooled toroom temperature and extracted by dichloromethane(3×15 mL). The organic layer was washed with brine(3×40 mL), dried over MgSO4 and concentrated. Purificationof the crude product via flash column chromatography (silicagel; petroleum ether) and concentratinon in vacuo affordedthe desired product of 3a-N2/3a-N1 in 91% yield.
With potassium fluoride; sodium azide; silver carbonate; In N,N-dimethyl-formamide; at 50℃; for 6.0h;
General procedure: to a solution of phenylacetylene (1a)(0.055 mL, 0.5 mmol), 2,6-di-tert-butyl-4-methylphenol(BHT) (2a) (133 mg, 0.6 mmol), NaN3 (39 mg, 0.6 mmol)and KF (58 mg, 1.0 mmol) in DMF (1 mL) at 50 C, Ag2CO3(41 mg, 0.15 mmol) was added. The reaction mixture wasthen stirred for 6 h when TLC conformed that substrate 1a was consumed. The resulting reaction mixture was cooled toroom temperature and extracted by dichloromethane(3×15 mL). The organic layer was washed with brine(3×40 mL), dried over MgSO4 and concentrated. Purificationof the crude product via flash column chromatography (silicagel; petroleum ether) and concentratinon in vacuo affordedthe desired product of 3a-N2/3a-N1 in 91% yield.
(4-chlorophenyl)(5-(thien-2-yl)-1,2,4-oxadiazol-3-yl)methanone[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
58%
With Iron(III) nitrate nonahydrate; potassium chloride; In nitrobenzene; at 100℃; for 36h;Inert atmosphere;
Take 3mL of nitrobenzene in a reaction tube, and then add 60 muL (0.6mmol) of <strong>[1003-31-2]2-cyanothiophene</strong>,28 g (0.2 mmol) of 4-chlorophenylacetylene, 60 mg (0.3 mmol) of ferric nitrate and 34 mg (0.2 mmol) of potassium chloride,The reaction was stirred at 100 C for 36h under the protection of N2.After completion of the reaction, the mixture was subjected to distillation under reduced pressure and separated by column chromatography (solvent volume ratio was petroleum ether: ethyl acetate = 1: 1)The title compound was obtained as a pale yellow solid in 58% yield.
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; at 20℃;Inert atmosphere;
General procedure: To a stirred solution of 2-(methylthio)benzoic acid (1.5g, 8.92 mmol) in anhydrous CH2Cl2 (20 mL) was added DMF (3 drops), oxalyl dichloride (1.13 mL, 1.5 equiv.). The reaction mixture was stirred at room temperature for 4 h before CH2Cl2 was removed by rotary evaporation. To the residue was added Et3N (25 mL), Pd(PPh3)2Cl2 (125 mg, 0.02 equiv.), and CuI (34 mg, 0.02 equiv.). Then, the mixture was degassed and recharged with argon. Phenylacetylene (1.17 mL, 1.2 equiv.) was added by a syringe. The reaction was stirred overnight at room temperature under argon atmosphere before Et3N was removed by rotary evaporation. The remained mixture was extracted with ethyl acetate (EtOAc) (20 mL x 3), and the combined organic layers were washed with H2O and brine, respectively, dried over anhydrous Na2SO4, filtered and concentrated in vacuo. The residue was purified by column chromatography on a silica gel (PE/EtOAc = 20/1 -10/1) to provide product (1.75 g, 78% yield) as a yellow solid.
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