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[ CAS No. 13141-38-3 ] {[proInfo.proName]}

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Chemical Structure| 13141-38-3
Chemical Structure| 13141-38-3
Structure of 13141-38-3 * Storage: {[proInfo.prStorage]}
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Product Details of [ 13141-38-3 ]

CAS No. :13141-38-3 MDL No. :MFCD00168849
Formula : C14H11N Boiling Point : -
Linear Structure Formula :- InChI Key :BZDTZZOSIAUOBS-UHFFFAOYSA-N
M.W : 193.24 Pubchem ID :1211370
Synonyms :

Calculated chemistry of [ 13141-38-3 ]

Physicochemical Properties

Num. heavy atoms : 15
Num. arom. heavy atoms : 12
Fraction Csp3 : 0.0
Num. rotatable bonds : 0
Num. H-bond acceptors : 0.0
Num. H-bond donors : 1.0
Molar Refractivity : 63.27
TPSA : 26.02 Ų

Pharmacokinetics

GI absorption : High
BBB permeant : Yes
P-gp substrate : No
CYP1A2 inhibitor : Yes
CYP2C19 inhibitor : Yes
CYP2C9 inhibitor : Yes
CYP2D6 inhibitor : No
CYP3A4 inhibitor : No
Log Kp (skin permeation) : -5.16 cm/s

Lipophilicity

Log Po/w (iLOGP) : 2.53
Log Po/w (XLOGP3) : 3.26
Log Po/w (WLOGP) : 2.76
Log Po/w (MLOGP) : 3.53
Log Po/w (SILICOS-IT) : 3.19
Consensus Log Po/w : 3.05

Druglikeness

Lipinski : 0.0
Ghose : None
Veber : 0.0
Egan : 0.0
Muegge : 2.0
Bioavailability Score : 0.55

Water Solubility

Log S (ESOL) : -3.68
Solubility : 0.04 mg/ml ; 0.000207 mol/l
Class : Soluble
Log S (Ali) : -3.48
Solubility : 0.0639 mg/ml ; 0.000331 mol/l
Class : Soluble
Log S (SILICOS-IT) : -4.64
Solubility : 0.00442 mg/ml ; 0.0000229 mol/l
Class : Moderately soluble

Medicinal Chemistry

PAINS : 0.0 alert
Brenk : 2.0 alert
Leadlikeness : 1.0
Synthetic accessibility : 2.15

Safety of [ 13141-38-3 ]

Signal Word:Warning Class:N/A
Precautionary Statements:P261-P305+P351+P338 UN#:N/A
Hazard Statements:H315-H319-H335 Packing Group:N/A
GHS Pictogram:

Application In Synthesis of [ 13141-38-3 ]

* 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 [ 13141-38-3 ]

[ 13141-38-3 ] Synthesis Path-Downstream   1~84

  • 1
  • [ 35010-17-4 ]
  • [ 13141-38-3 ]
YieldReaction ConditionsOperation in experiment
87% With indium(III) trichloride; indium powder; lithium hydroxide monohydrate In tetrahydrofuran at 50℃; for 5h;
70% With nickel In N,N-dimethyl-formamide for 0.5h; Ambient temperature;
56% With lithium hydroxide monohydrate; N-ethyl-N,N-diisopropylamine; bis[2-(diphenylphosphino)phenyl] ether; palladium (II) chloride; hexakis(oxomethylidene)molybdenum In tetrahydrofuran at 90℃; for 24h;
With hydrogenchloride; glacial acetic acid; stannous chloride
With stannous chloride In ethanol for 1h; Yield given;
With iron(0); ammonia hydrochloride In isopropanol

  • 2
  • [ 13141-38-3 ]
  • [ 948-65-2 ]
YieldReaction ConditionsOperation in experiment
100% In various solvent(s) at 100℃; for 0.166667h; microvawe irradiation;
99% With carbon monoxide In toluene at 100℃; for 5h;
99% With anhydrous zinc bromide In toluene at 130℃; for 24h; 4.4. General procedure for the synthesis of alkynylanilines 7 and indoles 8 General procedure: To a stirred solution of the corresponding 2-iodoaniline (6, 1 mmol) in toluene (3 mL) under argon atmosphere were added Pd/CuO-Fe3O4 (50 mg), NaOH (400 mg, 10 mmol), and the corresponding alkyne (2, 1.5 mmol). The resulting mixture was stirred at 130 °C until the end of reaction (see Table 6). 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 product was purified by chromatography on silica gel (hexane/ethyl acetate) to give the corresponding compounds 7. Yields are included in Table 6. Then, to a stirred solution of 7 (1 mmol) in toluene (4 mL) was added ZnBr2 (225 mg, 1 mmol). The resulting mixture was stirred at 130 °C during 24 h. The mixture was quenched with water and extracted with EtOAc. The organic phases were dried over MgSO4, followed by evaporation under reduced pressure to give the pure products 8 in quantitative yields. Physical and spectroscopic data for compounds 7 and 8, as well as literature for known compounds, follow.
99% With C16H23AuBClN2O2 In hexadeuterobenzene at 20℃; for 1h;
98% With gold(III) trichloride In ethanol at 70℃; for 4.5h;
98% With silver(I) nitrate In lithium hydroxide monohydrate at 130℃; Sealed tube; Sonication; Green chemistry; regioselective reaction; 2-Phenyl-1H-pyrrolo[2,3-b]pyridine (2a); Typical Procedure General procedure: To a sealed tube (10 mL) was added 3-(phenylethynyl)pyridin-2-amine (1a; 50 mg, 0.26 mmol), H2O (2 mL), and AgNO3 (8.7 mg, 0.052 mmol). After ultrasonic oscillation for 5 min, the mixture was stirred at 130 °C for about 16 h. The reaction product was filtered, washed with H2O, and dried to give a brown solid; yield: 48 mg (96%); mp 209-210 °C; HPLC purity 98%.
98% With Na(1+)*[AuCl4](1-)*99H2O=Na[AuCl4]*99H2O In dichloromethane at 50℃; for 6h;
98% With anhydrous zinc bromide In toluene at 110℃; for 24h;
96% With silica-supported palladium catalyst In N,N-dimethyl-formamide at 100℃; for 1h;
96% With (1,3-bis(2,6-diisopropylphenyl)-4,5,6,7-tetrahydro-1,3-diazepin-2-ylidene)AuCl; trifluoromethane sulfonic acid silver salt In ethanol at 20℃; for 45h; Inert atmosphere; Schlenk technique;
96% With Pt(II)-NaY zeolite In toluene at 110℃;
95% With indium(III) bromide In toluene for 1h; Heating;
95% With indium(III) bromide In toluene for 0.5h; Heating;
95% With (1-methyl-2-phenyl-4-tolyl-1,2,3-triazol-5-ylidenyl)gold(I) bis(trifluoromethanesulfonyl)imidate In acetonitrile at 34℃; for 24h; Inert atmosphere; Glovebox;
95% With sodium tetrachloridoaurate(III) dihydrate; oxygen In acetonitrile at 80℃; for 7h;
95% With anhydrous silver tetrafluoroborate; C41H40Au2I2N6O4 In toluene at 20℃; for 6h; Schlenk technique; Inert atmosphere;
93% In dichloromethane at 35℃; for 1h;
93% With gold nanoparticles supported on titanium dioxide (TiO<SUB>2</SUB>) In toluene at 120℃; for 1h; Microwave irradiation;
91% With anhydrous zinc bromide In toluene for 16h; Reflux;
90% With sodium tetrafluoroborate; bis[dichlorido(η5-1,2,3,4,5-pentamethyl-cyclopentadienyl)iridium(III)] In acetonitrile at 40℃; for 8h; Inert atmosphere; Schlenk technique; General procedure for the catalytic reactions In a typical reaction [Cp*IrCl2]2 (8 mg, 0.01 mmol), NaBF4 (2 mg, 0.02 mol) and 2-(phenylethynyl)aniline (97 mg, 0.5 mmol) were dissolved in dry acetonitrile (3 mL) in a Carius tube. The mixture was subjected to three cycles of freeze-pump-thaw and was then stirred at 40oC for 8 h, after which the reaction solvent was removed by rotary evaporation to give the crude product. Purification of the crude product by silica gel (60-120 mesh) column chromatography using ethylacetate/hexane (1:9, v/v) as eluent gave pure 2-phenylindole, 3a. Similar procedures were used with the other alkynylanilines to obtain 3b-s. The amount of reagents used, product formed (with yield) and HRMS for the products, are given in the Table 2.
90% With potassium-t-butoxide; copper (II) acetate; phenyl cyanide In dimethyl sulfoxide at 120℃; for 24h; Inert atmosphere;
89% With iron(III) chloride In 1,2-dichloro-ethane at 80℃; for 2h;
87% With anhydrous zinc bromide In toluene at 110℃; for 6h; Inert atmosphere;
86% With Au/Carbon G-60 catalyst In toluene at 90℃; for 24h; Inert atmosphere; Schlenk technique;
85% With tetrahydropyrrole In lithium hydroxide monohydrate at 200℃; for 1.5h; Microwave irradiation;
85% Stage #1: 2-(2-phenylethynyl)benzenamine With gold(I) chloride In acetonitrile at 20℃; for 24h; Inert atmosphere; Stage #2: In acetonitrile
84% With platinum tetrachloride In 1,2-dichloro-ethane Reflux; General procedure for PtCl4-catalyzed intramolecular hydroamination of N-acetyl-2-alkynylaniline substrates for the synthesis of N-acetyl-2-substituted indole derivatives (Procedure B) General procedure: A solution of N-(5-fluoro-2-(phenylethynyl)phenyl)acetamide (1k) (52.8mg, 0.2085mmol, 1.00equiv) in DCE (5.0mL) was added with PtCl4 (1.2mg, 0.0045mmol, 0.02equiv) in one portion. The resulting reaction mixture was equipped with a condenser and heated at reflux until the reaction was complete as monitored by TLC. Upon completion, the reaction mixture was filtered through a short plug of silica gel while rinsing with DCM to remove the catalyst. The filtrate solution was concentrated under reduced pressure to give 51.7 mg (98%) of analytically pure indole 2k.
83% With NaAuCl4; ethyl acrylate In ethanol at 30℃;
83% With XPhosAuCl; sodium tetrakis[(3,5-di-trifluoromethyl)phenyl]borate In 1,2-dichloro-ethane at 80℃; for 0.25h;
82% With palladium (II) chloride In acetonitrile for 3h; Inert atmosphere; Reflux;
82% With sodium chloride; anhydrous zinc bromide for 8h; Milling;
82% With Cu(OAc)2*H2O at 80℃; for 20h; Sealed tube; Inert atmosphere;
81% With sodium hydroxide In N,N-dimethyl acetamide at 170℃; for 0.333333h; Microwave irradiation;
81% With anhydrous silver tetrafluoroborate; 1,3-bis(2,6-di-isopropylphenyl)imidazole-2-ylidenegold(I) chloride In hexane at 40℃; for 3h; Inert atmosphere; Schlenk technique; general procedure for the gold(I)-catalyzed formation of indole derivatives General procedure: To a solution of aniline derivative in hexane ([substrate] = 0.125 mol/L) in a Schlenk tube equipped with a Teflon-coated magnetic stirring bar, (IPr)AuCl followed by AgBF4 were added. The reaction mixture was then stirred at 40 °C in an oil bath. At the end of the reaction (1H NMR or TLC monitoring), the solvent was removed in vacuo. The resulting crude product was directly purified by flash column chromatography on silica gel (n-hexane/ethyl acetate) to afford the corresponding indole.
80% With bis(acetonitrile)palladium(II) chloride In acetonitrile for 2h; Heating;
80% With sodium tetrachloridoaurate(III) dihydrate In ethanol at 40℃; for 8h;
79% With potassium-t-butoxide In 1-methyl-pyrrolidin-2-one at 25℃; for 4h;
79% With potassium-t-butoxide In 1-methyl-pyrrolidin-2-one at 20℃; for 4h;
79% With dibenzoic acid copper (II) In 1,2-dichloro-ethane for 48h; Heating;
78% With nanocomposite fibers consisting of crosslinked polyvinylpyrrolidone-supported gold nanoparticles In toluene at 0.12℃; for 48h; Sealed tube; 3.5. Catalysis Gold catalyzed cyclisation of 2-(phenylethynyl)aniline (1) to 2-phenyl-1H-indole (2): To a stirredsolution of 2-(phenylethynyl)aniline (1) (38.2 mg, 0.20 mmol) in dry PhMe (1 mL) at ca. 20 °C, was added the PVP/Au electrospun membrane (15.4 mg, 2% wt, 0.5 mol %, 0.0525 mmol Au/g of catalyst).The mixture was heated to ca. 120 °C in a sealed tube until complete consumption of the startingmaterial (TLC, 48 h). The mixture was then cooled to ca. 20 °C and the polymer filtered and washed with t-BuOMe (10 mL). The membrane was reused in subsequent reactions without further treatment.The organic washings were combined, adsorbed onto silica and chromatographed (n-hexane/DCM,60:40) to give 2-phenyl-1H-indole (2) (29.8 mg, 78%) as colorless plates, mp (hotstage) 183-185 °C(from n-hexane, lit. 186-187 °C [68]); Rf 0.50 (n-hexane/DCM, 60:40); νmax/cm-1 3443m (N-H), 3050w(C-H), 1605w, 1541w, 1493w, 1481m, 1456m, 1447m, 1404m, 1352m, 1339m, 1298m, 1242m, 1231m,1190m, 1115m, 1074w, 1049w, 1028w, 1009w, 932w, 907w, 797m, 762s, 743s; dH(500 MHz; CDCl3) 10.66(1H, s, NH), 7.86 (2H, d, J 7.5 Hz, Ar H), 7.57 (1H, d, J 7.9 Hz, Ar H), 7.45 (2H, dd, J 7.7, 7.7 Hz, Ar H),7.44 (1H, d, J 8.2 Hz, Ar H), 7.31 (1H, dd, J 7.4 Hz, Ar H), 7,10 (1H, dd, J 7.4, 7.4 Hz, Ar H), 7.02 (1H, d, J7.5 Hz, Ar H), 6.90 (1H, s, Ar H); dC(125 MHz; CDCl3) 138.8 (s), 138.4 (s), 133.6 (s), 130.2 (s), 129.8 (d),128.3 (d), 125.9 (d), 122.7 (d), 121.1 (d), 120.5 (d), 112.0 (d), 99.9 (d); m/z (MALDI-TOF) 193 (M+, 90%),165 (100), identical to that reported [68].
77% With palladium (II) chloride In acetonitrile for 3h; Reflux; Inert atmosphere; Synthesis of 2-phenylindoles I; general procedure General procedure: To a solution of A (0.5mmol) in MeCN (3mL), PdCl2 (24mg, 0.1mmol) was added, and the mixture was heated at reflux with stirring for 3h. The desired product was isolated by TLC.
70% With iron(III) trichloride hexahydrate In 1,2-dichloro-ethane; N,N-dimethyl-formamide at 80℃; Inductive heating;
69% With benzo[1,3,2]dioxaborole In (2)H8-toluene at 50 - 110℃; Inert atmosphere; Glovebox;
68% With copper(II) bis(trifluoromethanesulfonate) In toluene for 1.5h; Heating;
64% With potassium-t-butoxide In N,N-dimethyl-formamide
64% With glacial acetic acid In dichloromethane at 100℃; for 6h; Sealed tube; Inert atmosphere; regioselective reaction;
62% In tetrahydrofuran for 0.5h; Heating;
46% In lithium hydroxide monohydrate at 200℃; for 1.5h; Microwave irradiation;
41% With C21H25AuCl3N3O In chloroform at 50℃; for 24h;
29% With iodine In dichloromethane at 20℃; for 24h; Inert atmosphere;
25% With gold nanoparticles; mesoporous silica In ethanol at 20℃; for 35h; Inert atmosphere;
7% Stage #1: 2-(2-phenylethynyl)benzenamine With hydrogen fluoride In acetonitrile at 20℃; for 0.0833333h; Sealed tube; Stage #2: In acetonitrile at 65℃; for 3h; Sealed tube;
84 % Chromat. In ethanol at 20℃; for 5h;
99 % Spectr. With indium(III) bromide In toluene for 0.166667h; Heating;
Multi-step reaction with 2 steps 1: pyridine / CH2Cl2 / 0 - 20 °C 2: 10 percent / diethyl zinc / toluene / Heating
Multi-step reaction with 3 steps 1: 1) NaNO2, HCl, 2) NaN3 / y / 2) H2O, 40 min, RT 2: Bu3SnH, AIBN / fluorobenzene / 3 h / Heating 3: Bu4NF
Multi-step reaction with 2 steps 1: tetrahydrofuran / 0.25 h / 0 - 5 °C 2: Pd2(dba)3, tris<2,4,6-(MeO)3-C6H2>3P / tetrahydrofuran / 3 h / 60 °C
Multi-step reaction with 2 steps 1: tetrahydrofuran / 0.25 h / 0 - 5 °C 2: 34 percent / Pd2(dba)3, tris<2,4,6-(MeO)3-C6H2>3P / tetrahydrofuran / 3 h / 60 °C
> 95 %Spectr. With anhydrous silver tetrafluoroborate; [Rh(mesBIAN)(CO)Cl] In [(2)H6]acetone at 50℃; for 0.2h;
With {Rh[bis(1-pyrazolyl)methane](CO)2}{tetrakis[3.5-bis(trifluoromethyl)phenyl]borate} In hexadeuterobenzene at 100℃; for 0.08h; Inert atmosphere; Microwave irradiation;
73 %Chromat. With C40H50Cl2Ir2N4(2+)*2F6P(1-) In acetonitrile for 24h; Inert atmosphere; Reflux;
With sodium tetrachloroaurate(III) In isopropanol at 20℃; for 3h;
99 %Spectr. With [(C10H6CH(CH3)NMe2)Pd(MeCN)2](perchlorate) In 1,1-dichloroethane at 80℃; for 9h; Inert atmosphere;
With anhydrous silver tetrafluoroborate; C18H25ClIrN4(1+)*C24H20B(1-) In [(2)H6]acetone at 50℃; for 1.5h;
With palladium (II) chloride In acetonitrile at 80℃; for 4h;
71 %Spectr. With anhydrous silver carbonate In 1,4-dioxane at 60℃; for 12h;
Multi-step reaction with 3 steps 1: pyridine / 2 h / 0 - 25 °C 2: tetrakis-(triphenylphosphine)-palladium; Cs2CO3 / acetonitrile / 1 h / 100 °C 3: magnesium / methanol / 6 h / 50 °C
50 %Spectr. With CH6B11Br6(1-)*Li(1+) In toluene at 120℃; for 24h; Schlenk technique; Glovebox;
100 %Chromat. With anhydrous silver tetrafluoroborate In toluene at 50℃; for 0.2h; 4.6 General procedure for the catalytic experiments Catalytic experiments were performed under air in a Pyrex tube, using 0.3mmol of substrate, 2.4mL of solvent, catalyst (0.1-2.0mol%) and AgBF4 (6mol%), and heating at 50°C. Yields and conversions were determined by GC analysis using anisole as internal standard. Isolated yields were determined by 1H NMR spectroscopy using 1,3,5-trimethoxybenzene as the external standard.
98 %Chromat. With SiO2-700-supported Zn(II) In toluene at 90℃; for 24h; Glovebox; Schlenk technique;
With SiO2-700-supported Zn(II) In toluene at 90℃; for 24h; Glovebox; Schlenk technique;
With palladium (II) chloride In acetonitrile at 90℃; Inert atmosphere;
100 %Chromat. With Zn-UiO-67-BPY metal organic framework from ZrCl4, 2,2’-bipyridine-5,5’-dicarboxylic acid and Zn(BF4)2*xH2O In toluene at 100℃; for 24h; Schlenk technique; Inert atmosphere;
Multi-step reaction with 2 steps 1: pyridine / dichloromethane / 16 h / 20 °C 2: copper(I) tetrakis(acetonitrile)tetrafluoroborate; tripotassium phosphate tribasic / acetonitrile / 2.5 h / 80 °C
With palladium (II) chloride In tetrahydrofuran for 5h; Reflux;
Multi-step reaction with 2 steps 1: palladium diacetate / toluene / 6 h / 10 °C / Sealed tube 2: potassium-t-butoxide / tetrahydrofuran / 12 h / 20 °C / Inert atmosphere
In lithium hydroxide monohydrate; toluene at 50℃; 2.3. General procedure for the cyclisation of 2-alkynil anilines. General procedure: In a Pyrex tube and under air, 2-(phenylethynyl)aniline (1 eq.)water (2 eq.), catalyst and toluene (substrate concentration0.0625 M) were mixed. The reaction was stirred at 50 °C in an oilbath. Conversion of substrate was monitored by GC-FID using anisoleas an internal standard. When the reaction was completed thesolvent was removed and the yield of isolated product analyzed by1H and 13C NMR. Recycling experiments were carried out under thesame reaction conditions as described before. After completion ofeach run, the reaction mixture was allowed to reach room temperatureand the catalyst was isolated by decantation. The remainingsolid was washed thoroughly with MeOH, dried and reused in thefollowing run.

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  • 3
  • [ 615-43-0 ]
  • [ 536-74-3 ]
  • [ 13141-38-3 ]
YieldReaction ConditionsOperation in experiment
100% With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide In triethylamine for 4h; Reflux;
100% With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine at 20℃; for 2h; Inert atmosphere;
99% Stage #1: 1-ethynylbenzene With piperidine; copper (I) iodide at 20℃; for 2.5h; Stage #2: 2-iodophenylamine With piperidine at 20℃; Further stages.;
99% With tetrakis(acetonitrile)copper(I) perchlorate; 2,5-bis(2-(diphenylphosphino)5-methoxyphenyl)-1,3,4-oxadiazole; potassium carbonate In 1,4-dioxane Reflux; Inert atmosphere; Schlenk technique;
99% With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine at 20℃; for 4h; Inert atmosphere; Schlenk technique;
98% Stage #1: 2-iodophenylamine With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine In tetrahydrofuran at 20℃; Inert atmosphere; Stage #2: 1-ethynylbenzene In tetrahydrofuran at 20℃; Inert atmosphere;
97% With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine at 0 - 20℃; Inert atmosphere;
97% With copper oxide (I); Cs2CO3; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene In 1,4-dioxane at 135℃; for 12h; Inert atmosphere;
97% With potassium carbonate; copper chloride (I) In methanol; acetonitrile at 25 - 30℃; for 4h; Inert atmosphere; Irradiation;
97% With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine at 20℃; for 5h; Inert atmosphere;
96% With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine In tetrahydrofuran at 20℃; for 2h;
96% With copper (I) iodide; triethylamine In tetrahydrofuran at 20℃;
96% With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide In triethylamine at 50℃; for 5h; Inert atmosphere;
96% With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine at 20 - 40℃; for 6h; Inert atmosphere; Schlenk technique;
96% With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine Inert atmosphere;
95% With triethylamine for 3h; Heating;
95% With tetrahydropyrrole at 100℃; for 0.5h; Microwave irradiation;
95%
95% With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine In tetrahydrofuran at 20℃; for 2h; Inert atmosphere;
95% With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine In tetrahydrofuran at 20℃; Inert atmosphere;
95% With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine at 20℃; for 11h; Schlenk technique; Inert atmosphere;
95% With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine at 20℃; for 3h; Inert atmosphere;
95% With tetrabutylammonium bromide; C32H26Cl2N8O4Pd2; potassium carbonate In methanol; lithium hydroxide monohydrate for 0.333333h; Reflux;
94% With copper (I) iodide In triethylamine at 40℃; for 19h;
94% With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; diethylamine In N,N-dimethyl-formamide at 50℃; Inert atmosphere;
94% With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine at 20℃; for 2h; Inert atmosphere; Schlenk technique;
94% With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine at 20℃; for 3h;
93% With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine for 2h; Heating;
93% With piperidine; tetrabutylammonium bromide; triphenylphosphine In tetrahydrofuran; lithium hydroxide monohydrate at 20℃;
93% With copper (I) iodide; trans-bis(triphenylphosphine)palladium(II) dichloride; triethylamine In tetrahydrofuran at 20℃; for 3h; Schlenk technique; Inert atmosphere;
93% With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine In triethylamine at 20℃; for 4h;
93% With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine In tetrahydrofuran at 20℃; for 24h; Inert atmosphere;
93% With copper (I) iodide; tetrakis-(triphenylphosphine)-palladium; triethylamine at 70℃; for 12h; Inert atmosphere;
92% for 8h;
92% With copper (I) iodide; tetrakis-(triphenylphosphine)-palladium; diethylamine In N,N-dimethyl-formamide at 20℃; Inert atmosphere;
92% With bis(µ-iodo)bis((-)-sparteine)dicopper(I); Cs2CO3 In N,N-dimethyl-formamide at 120℃; for 8h; Inert atmosphere; General procedure: The reaction vessel was charged with aryl halide (1 mmol), alkyne (1.1 mmol), Cs2CO3 (2 equiv) and the catalyst [Cu2I2(spa)2](1) (5 mol %) in N,N-dimethylformamide (3 mL). The reaction mixture was heated at 110-125 °C for the desired time (indicated in Table 2) and the progress of reaction was monitored by TLC. At the end of the reaction, the reaction mixture was cooled to room temperature and was diluted with EtOAc (20 mL), washed with 1 N aq HCl and water. The combined organic phase was dried over anhydrous Na2SO4. After removal of the solvent, the residue was subjected to column chromatography on silica gel using ethyl acetate and hexane to afford the desired product in high purity.
92% With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; diethylamine at 20℃; for 24h; Inert atmosphere;
91% With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide In triethylamine at 75℃;
91% With 2C2H3O2(1-)*Pd(2+)*3Na(1+)*C18H12O9PS3(3-); potassium-t-butoxide; propane-1,2,3-triol at 100℃; for 2h; Schlenk technique; Inert atmosphere; chemoselective reaction;
91% With copper (I) iodide; di-μ-chlorobis{hydrogen bis(diphenylphosphito)(1-)-P,P'}dipalladium; N-ethyl-N,N-diisopropylamine In toluene at 80℃; for 18h; Inert atmosphere;
91% With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine at 20℃; for 2h; Inert atmosphere;
90% Stage #1: 2-iodophenylamine With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine In acetonitrile at 20℃; for 0.5h; Inert atmosphere; Stage #2: 1-ethynylbenzene In acetonitrile at 20℃; Inert atmosphere; Representative procedure: Preparation of substrate 1a (R1 = Ph) 2-iodoaniline (500.2 mg, 2.28 mmol, 1.0 equiv) was dissolved in Et3N (4.5 mL). The resulting solution was added with PdCl2(PPh3)2 (32.1 mg, 0.046 mol, 0.02 equiv) and CuI (17.4 mg, 0.091mmol, 0.04 equiv). The orange-yellow solution was degassed by bubbling with a stream of argon into the solution at room temperature for 30 min. After degassing, phenylacetylene (0.30 mL,279.0 mg, 2.73 mmol, 1.2 equiv) was added as a neat liquid into the solution via syringe. The resulting dark brown solution was allowed to stir at room temperature under argon atmosphere overnight. The reaction was quenched by addition of sat. aq. NH4Cl. The separated aqueousphase was extracted with EtOAc (3x times). The combined organic phases were washed with sat. aq. NaCl, dried over anh. Na2SO4, filtered and concentrated to a crude product. The crudeproduct was purified by SiO2 column chromatography eluting with 0-10% EtOAc-hexane to give 398.2 mg (90%) of 2-(phenylethynyl)aniline as an orange solid.
90% With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine for 12h; Inert atmosphere; Preparation of sulfonamide raw materials: Take a 250mL reaction flask and add o-iodoaniline (2.19g, 10mmol), PdCl2(PPh3)2 (0.14g, 0.2mmol), CuI (0.076g, 0.4mmol) to it, Add 30mL of anhydrous triethylamine and phenylacetylene under nitrogen protection (1.3 mL, 12 mmol), after reacting for 12 h, after concentrating under reduced pressure to remove the solvent, the product was separated by column chromatography (petroleum ether/ethyl acetate=10:1) to obtain a white solid product (1.7 g, 90%).
89% With 1,4-diaza-bicyclo[2.2.2]octane; Cs2CO3 In N,N-dimethyl-formamide at 135 - 140℃; for 8h;
89% With ferric(III) chloride; Cs2CO3; methyl[2-(methylamino)ethyl]amine In toluene at 135℃; for 72h; Inert atmosphere;
89% With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine In acetonitrile at 60℃; for 3h; Schlenk technique; Inert atmosphere; Synthesis of phenylethynylanilines A; general procedure General procedure: To a solution of 2,3,4-trifluoro-6-iodoaniline [or o-iodoaniline] (1mmol) and ethynylbenzene (150 mg, 1.5 mmol) in dry MeCN (10mL) in a Schlenk flask under argon Pd(PPh3)2Cl2 (28 mg, 0.04 mmol), CuI (17 mg, 0.09 mmol) and Et3N (3 mL) were added. The reaction mixture was stirred at 60°C for 3h. Then, the mixture was allowed to cool down to r.t., and CH2Cl2 (10 mL) was added. The mixture was poured into H2O (20 mL) and extracted with CH2Cl2 (3×50mL). The combined organic layers were washed with H2O (20 mL) and dried (MgSO4). After evaporation of the solvent in vacuo, the crude product was purified by preparative TLC to obtain the target product.
88% With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); ammonium hydroxide; copper (I) iodide In tetrahydrofuran at 20℃; for 3.5h;
88% With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine at 20℃; for 16h; Inert atmosphere;
88% With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine In tetrahydrofuran at 20℃; Inert atmosphere; Step 1: 2-(phenylethynyl)aniline (20). To a solution of 2-iodoaniline42 (500 mg, 2.28 mmol) in anhydrous THF (8 mL) was added bis(triphenylphosphine)palladium(II) dichloride (48 mg, 0.07 mmol, 0.03equiv), copper(I) iodide (22 mg, 0.12 mmol, 0.05 equiv), TEA (2 mL)and phenylacetylene (376 μL, 3.42 mmol, 1.5 equiv) under N2 atmosphere.The resulting mixture was stirred at room temperature overnight.Upon completion, the reaction mixture was extracted with EA (20mL × 3). The organic layers were combined, washed with brine, dried over Na2SO4, filtered, and concentrated under reduced pressure. Thepure product was obtained as a white solid (360 mg, 91%) by flashchromatography (Hexane:EA = 15:1, v/v). 1H NMR (400 MHz, CDCl3) δ7.62 - 7.49 (m, 2H), 7.43 - 7.31 (m, 4H), 7.17 (td, J = 7.7, 1.6 Hz, 1H),6.75 (t, J = 7.4 Hz, 2H), 4.30 (s, 2H).
88% With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine In tetrahydrofuran at 20℃; Inert atmosphere; Step 1: 2-(phenylethynyl)aniline (20). To a solution of 2-iodoaniline42 (500 mg, 2.28 mmol) in anhydrous THF (8 mL) was added bis(triphenylphosphine)palladium(II) dichloride (48 mg, 0.07 mmol, 0.03equiv), copper(I) iodide (22 mg, 0.12 mmol, 0.05 equiv), TEA (2 mL)and phenylacetylene (376 μL, 3.42 mmol, 1.5 equiv) under N2 atmosphere.The resulting mixture was stirred at room temperature overnight.Upon completion, the reaction mixture was extracted with EA (20mL × 3). The organic layers were combined, washed with brine, dried over Na2SO4, filtered, and concentrated under reduced pressure. Thepure product was obtained as a white solid (360 mg, 91%) by flashchromatography (Hexane:EA = 15:1, v/v). 1H NMR (400 MHz, CDCl3) δ7.62 - 7.49 (m, 2H), 7.43 - 7.31 (m, 4H), 7.17 (td, J = 7.7, 1.6 Hz, 1H),6.75 (t, J = 7.4 Hz, 2H), 4.30 (s, 2H).
87% Stage #1: 2-iodophenylamine With copper (I) iodide; N,N-diisopropylamine In N,N-dimethyl-formamide Stage #2: 1-ethynylbenzene In N,N-dimethyl-formamide at 0 - 20℃; for 1.5h;
87% With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine at 20℃; Inert atmosphere;
86% With aluminum(III) oxide; potassium fluoride; triphenylphosphine for 0.0416667h; Irradiation; in 1000 W microwave oven;
85% With N,N-diisopropylamine; trilithium salt of 3,3',3''-phosphanotriylbenzenecarboxylic acid In lithium hydroxide monohydrate; acetonitrile at 60℃; for 20h;
85% With copper (I) iodide; tetrakis-(triphenylphosphine)-palladium; triethylamine for 3h; Inert atmosphere;
85% With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine In tetrahydrofuran at 20℃; Inert atmosphere;
84% With sodium tetrachloropalladium (II); sodium lauryl sulfate; sodium hydroxide In lithium hydroxide monohydrate at 20℃; for 11h;
84% With copper (I) iodide; trans-bis(triphenylphosphine)palladium(II) dichloride; triethylamine In tetrahydrofuran at 20℃; Inert atmosphere;
84% With potassium hydroxide In N,N-dimethyl-formamide at 120℃; for 8h; General procedure for the Sonogashira reaction in the presence of the Ni/Cu-MCM-41 General procedure: A mixture of phenylacetylene (1.2 mmol), aryl halide (1 mmol), KOH (2 mmol), DMF (5 mL) and Ni/Cu-MCM-41 (20 mg) are added into a 25 mL flask. The resulting mixture is stirred at 120 oC for appropriate reaction time. Progress of reactions is monitored by TLC. After completion of the reaction, the catalyst is separated by centrifugation. Then, the reaction mixture is extracted with ethyl acetate and water. The organic phase is dried by addition of MgSO4 and concentrated under reduced pressure. The residue is purified by column chromatography.
84% Stage #1: 2-iodophenylamine With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine at 20℃; for 0.0833333h; Inert atmosphere; Schlenk technique; Stage #2: 1-ethynylbenzene at 20℃; for 3h; Inert atmosphere; Schlenk technique;
83% With copper (I) iodide; palladium(0); triphenylphosphine for 0.05h; microwave irradiation (100 percent power);
83% With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine In tetrahydrofuran at 20℃; Inert atmosphere; Schlenk technique; General procedure for the preparation of the alkynylanilines 2 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, 83%).
80% With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; diethylamine In N,N-dimethyl-formamide at 20℃; for 0.25h;
80% With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; N,N-diisopropylamine at 20℃; for 1h; Inert atmosphere;
80% With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine at 80℃; Sealed tube; Inert atmosphere;
79% With C38H35ClCuN4P; potassium carbonate In toluene at 110 - 120℃; for 20h; Inert atmosphere; 4.5. Catalytic studies General procedure: In a round bottom flask, 8 mol% of catalyst, K2CO3 (2.0 mmol),phenylacetylene (2.5 mmol), aryl halide (2.0 mmol), and 20 mltoluene was taken. The whole solution was heated with stirring at110-120° C for 20 h under N2 atmosphere. The solutionwas cooledto room temperature and filtered to remove insoluble impurities.Filtrate was evaporated and the solid was then passed throughcolumn. The desired compound was characterized by 1H NMR and13C NMR.
78% With copper (I) iodide; 8-quinolinol; Cs2CO3 In N,N-dimethyl-formamide at 130℃; for 30h; Inert atmosphere; Combinatorial reaction / High throughput screening (HTS);
76% With Cs2CO3; 2‐hydroxybenzoic acid; copper chloride (II) In N,N-dimethyl-formamide at 130℃; for 36h; Inert atmosphere;
75% With tetrahydropyrrole In lithium hydroxide monohydrate at 100℃; for 24h;
75% With potassium carbonate In dimethyl sulfoxide at 120℃; for 12h;
74% With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine In tetrahydrofuran at 120℃; for 6h;
72% With copper (I) iodide; tetrakis-(triphenylphosphine)-palladium; triethylamine In tetrahydrofuran at 20℃; Inert atmosphere; Schlenk technique;
70% With copper (I) iodide; bis(acetato)bis(triphenylphosphine)palladium(0); triethylamine at 20℃; Inert atmosphere;
68% With sodium hydroxide In toluene at 130℃; for 72h; 4.4. General procedure for the synthesis of alkynylanilines 7 and indoles 8 General procedure: To a stirred solution of the corresponding 2-iodoaniline (6, 1 mmol) in toluene (3 mL) under argon atmosphere were added Pd/CuO-Fe3O4 (50 mg), NaOH (400 mg, 10 mmol), and the corresponding alkyne (2, 1.5 mmol). The resulting mixture was stirred at 130 °C until the end of reaction (see Table 6). 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 product was purified by chromatography on silica gel (hexane/ethyl acetate) to give the corresponding compounds 7. Yields are included in Table 6. Then, to a stirred solution of 7 (1 mmol) in toluene (4 mL) was added ZnBr2 (225 mg, 1 mmol). The resulting mixture was stirred at 130 °C during 24 h. The mixture was quenched with water and extracted with EtOAc. The organic phases were dried over MgSO4, followed by evaporation under reduced pressure to give the pure products 8 in quantitative yields. Physical and spectroscopic data for compounds 7 and 8, as well as literature for known compounds, follow.
66% Stage #1: 2-iodophenylamine With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine at 20℃; for 0.0833333h; Inert atmosphere; Stage #2: 1-ethynylbenzene for 12h; Inert atmosphere;
64% With 4-(pyridin-2-yl)pyrimidin-2-aminepaladium(II) chloride; anhydrous Sodium acetate In propane-1,2,3-triol at 60℃; for 16h; Green chemistry;
63% With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine at 50℃; for 2h; Inert atmosphere; general procedure for the synthesis of 2-alkynylanilines General procedure: Under argon gas, a mixture of 2-iodoaniline (1 eq), alkyne (1.1-1.3 eq), CuI (3 mol%), PdCl2(PPh3)2 and Et3N ([substrate] = 0.45 mol/L) as solvent was stirred for 2h at 50 °C . The reaction mixture was next diluted in water and extracted with CH2Cl2. The organic phase was dried over MgSO4 and the solvent was evaporated under reduce pressure. The crude product was purified by chromatography on silica gel with n-hexane/ethyl acetate as the eluent to afford the expected 2 -ethynylanilines.
60% With piperidine; silica-supported palladium catalyst at 70℃; for 0.5h;
50% With tetrabutylammonium bromide; potassium carbonate; triphenylphosphine at 135 - 140℃; for 24h;
44% With D-glucose; palladium diacetate; triethylamine In lithium hydroxide monohydrate; acetonitrile at 100℃; for 16h; Sealed tube;
33% With bis(cyclohexylisocyanide)palladium(II) chloride; potassium carbonate; benzoic acid hydrazide In ethanol at 80℃; for 2h; Sonogashira reaction (general procedure). General procedure: A solution of comple 1 in ethanol with a required concentrationwas added with stirring to a mixture of iodoarene2a-2g (0.3 mmol), phenylacetylene (3, 0.5 mmol),potassium carbonate (0.7 mmol), and ethanol (2 mL). The mixture was heated for 2 h on an oil bath at a bathtemperature of 80°C. After cooling to room temperature,the mixture was diluted with 10 mL of waterand extracted with hexane-methylene chloride (5 : 1,2 × 5 mL), and the combined extracts were dried overanhydrous sodium sulfate and analyzed by GC/MS.The solvent was evaporated, and the product wasisolated by silica gel column chromatography usingn-hexane as eluent.The properties of the isolated compounds were inagreement with the data given in [23-27].
With copper (I) iodide; {Pd(OAc)2(PPh3)2}; diethylamine In N,N-dimethyl-formamide for 3h; Ambient temperature;
With piperidine; tetrakis-(triphenylphosphine)-palladium for 6h; Ambient temperature;
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine In N,N-dimethyl-formamide at 20℃;
99 % Spectr. Stage #1: 1-ethynylbenzene With piperidine; indium(III) bromide at 20℃; for 2.5h; Stage #2: 2-iodophenylamine With piperidine; [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) at 20℃; for 1h;
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine In tetrahydrofuran at 20℃;
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine In tetrahydrofuran at 20℃;
With copper (I) iodide; triethylamine In tetrahydrofuran
With copper (I) iodide; tetrakis-(triphenylphosphine)-palladium In diethylamine
With copper (I) iodide; triethylamine at 20℃;
With diethylamine In N,N-dimethyl-formamide at 20℃;
Inert atmosphere;
With copper (I) iodide; tetrakis-(triphenylphosphine)-palladium; triethylamine In N,N-dimethyl-formamide at 20℃;
With copper (I) iodide; bis(triphenylphosphine)palladium(II) dichloride; diethylamine In N,N-dimethyl-formamide at 20℃; Inert atmosphere;
With copper (I) iodide; N,N-diisopropylamine In acetonitrile at 60℃; for 12h; Inert atmosphere;
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; diethylamine In N,N-dimethyl-formamide at 20 - 60℃; Inert atmosphere;
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine at 20℃;
With tetrakis-(triphenylphosphine)-palladium In lithium hydroxide monohydrate

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  • 4
  • [ 13141-38-3 ]
  • [ 199277-23-1 ]
YieldReaction ConditionsOperation in experiment
93% Stage #1: 2-phenylethynylaniline With sulfuric acid; sodium nitrite In water; N,N-dimethyl-formamide; acetonitrile at 0℃; for 0.5h; Stage #2: With sodium azide In water; N,N-dimethyl-formamide; acetonitrile at 0 - 20℃; for 2h; General procedure 2: Preparation of 2-alkynyl azidoarenes 1a-1x General procedure: To a solution of 2-alkynyl aminobenzene a-x (3 mmol) in CH3CN (18 mL), DMF (3 mL),and 10% H2SO4 (18 mL) at 0 oC was slowly added a solution of NaNO2 (3.6 mmol) in H2O(1.5 mL). The resulting mixture was stirred at 0 oC for 30 minutes followed by the slowaddition of NaN3 (3.6 mmol) in H2O (1.5 mL). The reaction was warmed to roomtemperature and stirred for 2 h. The reaction was diluted with H2O (20 mL), and thenextracted with EtOAc (3 x 20 mL). The combined organic layers were washed with water(15 mL), brine (15 mL), dried over anhydrous MgSO4, filtered, and concentrated (aspirator). Crude product was purified by flash column chromatography on silica gel(SiO2, ethyl acetate/hexanes) to provide the corresponding 2-alkynyl azidoarenes 1a-1x.
With hydrogenchloride; sodium azide; sodium nitrite 2) H2O, 40 min, RT; Yield given. Multistep reaction;
Stage #1: 2-phenylethynylaniline With hydrogenchloride; sodium nitrite In water at 0℃; for 0.5h; Inert atmosphere; Stage #2: With sodium azide In water at 20℃; for 2h; Inert atmosphere;
  • 5
  • [ 13141-38-3 ]
  • [ 124-63-0 ]
  • [ 125345-25-7 ]
YieldReaction ConditionsOperation in experiment
96% With pyridine at 20℃; for 19h;
92% With pyridine; dmap In tetrahydrofuran at 20℃; Inert atmosphere;
91% With pyridine In dichloromethane at 0 - 20℃; Inert atmosphere;
85% With pyridine In dichloromethane at 0 - 20℃; for 24h; 3.2 General procedure and characterization data for 2-alkynylanilides (1a-1t) General procedure: RCl (R = Ts, Ms, or Ac, 0.60 mmol) was added to a solution of 2-alkynylanilines (0.50 mmol) and pyridine (0.08 mL, 1.00 mmol) in CH2Cl2 (10 mL) at 0 oC. And then the solution was warmed to room temperature and stirred for 24 h. The reaction was monitored by TLC. After completion, H2O (10 mL) was added to quench the reaction and extracted with ethyl acetate (3 × 10 mL). The combined organic solution was washed with brine, dried over anhydrous MgSO4, concentrated under reduced pressure. The crude product was purified by column chromatography to give 2-alkynylanilides (1a-1t).
58% With pyridine In dichloromethane at 20℃; for 8h; Preparation of 2-Alkynylaniline Derivatives. General procedure: Therequisite 2-alkynylaniline derivatives were prepared from 2-iodoanilines or2-bromoanilines reacted with alkynes following the modified method reported byZhao and co-workers.1To a solution of 2-alkynylaniline (1.00 mmol) inCH2Cl2 (8 mL) were added pyridine (5.00 mmol) and TsCl (1.20mmol) respectively. The resulting reaction mixture was stirred at rt for 8 h.After which the reaction mixture was quenched by H2O (10 mL), andthe aqueous layer was extracted with CH2Cl2 (3×15 mL).The combined organic layers were dried over Na2SO4,filtered, and concentrated under reduced pressure. The crude product waspurified by silica gel flash column chromatography to obtain corresponding product.
With pyridine In tetrahydrofuran for 24h; Ambient temperature; Yield given;
With pyridine In dichloromethane at 0 - 20℃;
Inert atmosphere;
With pyridine In dichloromethane at 0 - 20℃; Inert atmosphere; Schlenk technique; Synthesis of 2p: In a 2-neck RB flask, 2a (150 mg, 0.78 mmol) was dissolved in DCM (5 mL) under an argon atmosphere. To this solution, pyridine (120 μL, 0.56 mmol) and methanesulfonyl chloride (72 μL, 0.93 mmol) were added at 0oC. The reaction mixture was warmed to ambient temperature and allowed to stir. The reaction was monitored by TLC. After completion of the reaction, water (5 mL) was added and extracted with diethylether(3×10 mL). The combined organic solution was washed with NaCl solution, dried over MgSO4, and then concentrated under reduced pressure. The crude product obtained was purified by silica gel (60-120 mesh) column chromatography using ethylacetate/ hexane (1:9, v/v) as eluent to give pure 2p
With pyridine In dichloromethane at 20℃; for 12h; Inert atmosphere;
244.2 mg With pyridine In dichloromethane at 0 - 20℃; for 20.25h; Inert atmosphere;
With pyridine In dichloromethane at 20℃;
With pyridine at 50℃; for 2h;

Reference: [1]Hiroya, Kou; Itoh, Shin; Sakamoto, Takao [Journal of Organic Chemistry, 2004, vol. 69, # 4, p. 1126 - 1136]
[2]Shen, Zengming; Lu, Xiyan [Advanced Synthesis and Catalysis, 2009, vol. 351, # 18, p. 3107 - 3112]
[3]Liu, Jun; Xie, Xin; Liu, Yuanhong [Chemical Communications, 2013, vol. 49, # 100, p. 11794 - 11796]
[4]Zhang, Sheng-Yan; Sun, Shan-Gang; Guo, Yu-Shuang; Lu, Xiao-Fan; Guo, Dian-Shun [Tetrahedron Letters, 2018, vol. 59, # 41, p. 3719 - 3723]
[5]Li, Yin-Long; Li, Jian; Yu, Sheng-Nan; Wang, Ji-Bo; Yu, Yan-Min; Deng, Jun [Tetrahedron, 2015, vol. 71, # 43, p. 8271 - 8277]
[6]Yasuhara, Akito; Kanamori, Yuichi; Kaneko, Masashi; Numata, Atsushi; Kondo, Yoshinori; Sakamoto, Takao [Journal of the Chemical Society. Perkin transactions I, 1999, # 4, p. 529 - 534]
[7]Yin, Yan; Ma, Wenying; Chai, Zhuo; Zhao, Gang [Journal of Organic Chemistry, 2007, vol. 72, # 15, p. 5731 - 5736]
[8]Matsuda, Naoki; Hirano, Koji; Satoh, Tetsuya; Miura, Masahiro [Journal of Organic Chemistry, 2012, vol. 77, # 1, p. 617 - 625]
[9]Kumaran, Elumalai; Leong, Weng Kee [Tetrahedron Letters, 2014, vol. 55, # 40, p. 5495 - 5498]
[10]Yu, Liu-Zhu; Wei, Yin; Shi, Min [Chemical Communications, 2017, vol. 53, # 64, p. 8980 - 8983]
[11]Lv, Jiahang; Zhao, Binlin; Liu, Li; Han, Ying; Yuan, Yu; Shi, Zhuangzhi [Advanced Synthesis and Catalysis, 2018, vol. 360, # 21, p. 4054 - 4059]
[12]Zhu, Bo-Han; Wang, Cai-Ming; Su, Hong-Yu; Ye, Long-Wu [Chinese Journal of Chemistry, 2019, vol. 37, # 1, p. 58 - 62]
[13]He, Yu-Ping; Cao, Jian; Wu, Hua; Wang, Qian; Zhu, Jieping [Angewandte Chemie - International Edition, 2021, vol. 60, # 13, p. 7093 - 7097][Angew. Chem., 2021, vol. 133, # 13, p. 7169 - 7173,5]
  • 6
  • [ 13141-38-3 ]
  • [ 75-36-5 ]
  • [ 26385-33-1 ]
YieldReaction ConditionsOperation in experiment
98% With pyridine In dichloromethane at 0 - 20℃; for 24h; 3.2 General procedure and characterization data for 2-alkynylanilides (1a-1t) General procedure: RCl (R = Ts, Ms, or Ac, 0.60 mmol) was added to a solution of 2-alkynylanilines (0.50 mmol) and pyridine (0.08 mL, 1.00 mmol) in CH2Cl2 (10 mL) at 0 oC. And then the solution was warmed to room temperature and stirred for 24 h. The reaction was monitored by TLC. After completion, H2O (10 mL) was added to quench the reaction and extracted with ethyl acetate (3 × 10 mL). The combined organic solution was washed with brine, dried over anhydrous MgSO4, concentrated under reduced pressure. The crude product was purified by column chromatography to give 2-alkynylanilides (1a-1t).
97% With triethylamine In dichloromethane at 0 - 20℃; for 8h;
96% With triethylamine In dichloromethane at 0 - 20℃; Representative procedure: Preparation of substrate 1a (R1 = Ph) 2-(phenylethynyl)aniline (302.8 mg, 1.57 mmol, 1.0 equiv) was dissolved in DCM (5.0 mL) and cooled to 0 °C. The solution was then added with Et3N (0.24 mL, 174.1 mg, 1.72 mmol, 1.1equiv), followed by acetyl chloride (0.18 mL, 198.0 mg, 2.52 mmol, 1.6 equiv). The resulting reaction mixture was allowed to stir at 0 °C while slowly warming to room temperature over 5 h,at which point the reaction was complete as indicated by TLC. The reaction mixture was byaddition of water. The separated aqueous phase was extracted with DCM (3x times). The combined organic phases were washed with sat. aq. NaCl, dried over anh. Na2SO4, filtered and concentrated to a crude solid. The crude solid product was purified by SiO2 column chromatography eluting with 20% EtOAc-hexane to give 354.4 mg (96%) of compound 1a as awhite solid.
88% With pyridine In dichloromethane at 0 - 20℃; for 2h; Inert atmosphere;
75% With pyridine In dichloromethane at 20℃; for 8h; Preparation of 2-Alkynylaniline Derivatives. General procedure: Therequisite 2-alkynylaniline derivatives were prepared from 2-iodoanilines or2-bromoanilines reacted with alkynes following the modified method reported byZhao and co-workers.1To a solution of 2-alkynylaniline (1.00 mmol) inCH2Cl2 (8 mL) were added pyridine (5.00 mmol) and TsCl (1.20mmol) respectively. The resulting reaction mixture was stirred at rt for 8 h.After which the reaction mixture was quenched by H2O (10 mL), andthe aqueous layer was extracted with CH2Cl2 (3×15 mL).The combined organic layers were dried over Na2SO4,filtered, and concentrated under reduced pressure. The crude product waspurified by silica gel flash column chromatography to obtain corresponding product.
With pyridine In tetrahydrofuran for 24h; Ambient temperature; Yield given;
With pyridine In dichloromethane at 0 - 20℃;
In tetrahydrofuran at 20℃;

  • 7
  • [ 13141-38-3 ]
  • [ 98-59-9 ]
  • [ 442155-91-1 ]
YieldReaction ConditionsOperation in experiment
100% With pyridine; dmap In tetrahydrofuran at 20℃; Inert atmosphere;
100% With pyridine In dichloromethane at 0 - 20℃; for 12h;
96% With pyridine In tetrahydrofuran at 20℃; for 24h; Inert atmosphere;
96% With pyridine In dichloromethane at 20℃; for 8h; Preparation of 2-Alkynylaniline Derivatives. General procedure: Therequisite 2-alkynylaniline derivatives were prepared from 2-iodoanilines or2-bromoanilines reacted with alkynes following the modified method reported byZhao and co-workers.1To a solution of 2-alkynylaniline (1.00 mmol) inCH2Cl2 (8 mL) were added pyridine (5.00 mmol) and TsCl (1.20mmol) respectively. The resulting reaction mixture was stirred at rt for 8 h.After which the reaction mixture was quenched by H2O (10 mL), andthe aqueous layer was extracted with CH2Cl2 (3×15 mL).The combined organic layers were dried over Na2SO4,filtered, and concentrated under reduced pressure. The crude product waspurified by silica gel flash column chromatography to obtain corresponding product.
96% With pyridine In dichloromethane at 0 - 20℃; for 24h; 3.2 General procedure and characterization data for 2-alkynylanilides (1a-1t) General procedure: RCl (R = Ts, Ms, or Ac, 0.60 mmol) was added to a solution of 2-alkynylanilines (0.50 mmol) and pyridine (0.08 mL, 1.00 mmol) in CH2Cl2 (10 mL) at 0 oC. And then the solution was warmed to room temperature and stirred for 24 h. The reaction was monitored by TLC. After completion, H2O (10 mL) was added to quench the reaction and extracted with ethyl acetate (3 × 10 mL). The combined organic solution was washed with brine, dried over anhydrous MgSO4, concentrated under reduced pressure. The crude product was purified by column chromatography to give 2-alkynylanilides (1a-1t).
95% With pyridine In dichloromethane at 0 - 20℃;
93% With pyridine In dichloromethane at 20℃; for 16h;
92% With pyridine at 20℃; for 11h;
90% With pyridine In dichloromethane at 0 - 20℃; Inert atmosphere;
90% With pyridine In dichloromethane at 20℃; for 16h;
89% With pyridine In dichloromethane at 20℃; for 2h; Add the obtained product to a 250mL reaction flask, add TsCl (2.1g, 10.8mmol), add 20mL of dichloromethane and pyridine (1mL, 11.7mmol), react at room temperature for 2h, add saturated ammonium chloride solution to remove the pyridine After extraction with dichloromethane and concentration under reduced pressure, the product was separated by column chromatography (petroleum ether/ethyl acetate=10:1) to obtain a white solid product (2.8 g, 89%).
79% With pyridine In dichloromethane Inert atmosphere;
68% With pyridine In dichloromethane at 0 - 20℃; Preparation of compound 1a-Bz, 1a-Ts, 1a-Boc 2-(phenylethynyl)aniline (63.6 mg, 0.33 mmol, 1.0 equiv) was dissolved in DCM (6.6 mL) and cooled to 0 °C. The solution was added with p-TsCl (81.6 mg, 0.43 mmol, 1.3 equiv) followed by pyridine (80 μL, 78.1 mg, 0.99 mmol, 3.0 equiv). The resulting reaction mixture was allowedto stir at 0 °C while slowly warming to room temperature overnight. After completion, asindicated by TLC, the reaction mixture was added with water and the separated aqueous phasewas extracted with DCM (3x times). The combined organic phases were washed with aq. HCl (1M) and sat. aq. NaCl, dried over anh. Na2SO4, filtered and concentrated to a crude oil which waspurified by SiO2 column chromatography eluting with 2% EtOAc-hexane to give 74.7 mg (68%) of compound 1a-Ts as a yellow oil.
63% With pyridine In dichloromethane at 20℃;
61% With pyridine for 16h; Reflux;
With pyridine In tetrahydrofuran
With pyridine In dichloromethane at 0 - 20℃;
With pyridine In dichloromethane
With pyridine at 0 - 25℃; for 2h;
With pyridine at 0 - 25℃; for 2h;
With pyridine Inert atmosphere;
2.9 g With pyridine In dichloromethane at 0 - 20℃; for 6h; Inert atmosphere;
With pyridine In dichloromethane at 0 - 20℃; for 12.25h;
With pyridine In dichloromethane at 20℃; for 12h; Inert atmosphere;
3.19 g With pyridine In dichloromethane at 0 - 20℃; for 20.25h; Inert atmosphere;
With pyridine In dichloromethane at 20℃;
With pyridine In dichloromethane at 20℃; for 12h;
With pyridine In chloroform at 20℃;
3.19 g With pyridine In dichloromethane at 0 - 20℃; for 20.25h; Inert atmosphere; General procedure for the synthesis of N-Sulfonyl anilines from 2-(phenylethynyl)anilines. General procedure: Then the obtained 2-(phenylethynyl)anilines compounds taken in dry dichloromethane (0.05M) was added with pyridine (2 equiv) followed by tosyl chloride or Methanesulfonyl chloride (1.3 eq) at 0°C over a period of 15 min. After addition completes, reaction stirred at RT for 20 hours. After reaction completed (monitored by TLC and GC-MS), reaction mass quenched with ice-cold water and extracted into DCM. The combined organic layer was washed with 2N HCl and brine solution, dried and evaporated to give crude residue. The obtained crude material passed through flash column chromatography to give pure products in quantitative yield.
With pyridine at 50℃; for 2h;
With pyridine In dichloromethane at 20℃; for 12h; Inert atmosphere;

Reference: [1]Shen, Zengming; Lu, Xiyan [Advanced Synthesis and Catalysis, 2009, vol. 351, # 18, p. 3107 - 3112]
[2]Boominathan, Siva Senthil Kumar; Senadi, Gopal Chandru; Vandavasi, Jaya Kishore; Chen, Jeff Yi-Fu; Wang, Jeh-Jeng [Chemistry - A European Journal, 2015, vol. 21, # 8, p. 3193 - 3197]
[3]Shi, Wei; Coleman, Robert S.; Lowary, Todd L. [Organic and Biomolecular Chemistry, 2009, vol. 7, # 18, p. 3709 - 3722]
[4]Li, Yin-Long; Li, Jian; Yu, Sheng-Nan; Wang, Ji-Bo; Yu, Yan-Min; Deng, Jun [Tetrahedron, 2015, vol. 71, # 43, p. 8271 - 8277]
[5]Zhang, Sheng-Yan; Sun, Shan-Gang; Guo, Yu-Shuang; Lu, Xiao-Fan; Guo, Dian-Shun [Tetrahedron Letters, 2018, vol. 59, # 41, p. 3719 - 3723]
[6]Swamy, Nalivela Kumara; Yazici, Arife; Pyne, Stephen G. [Journal of Organic Chemistry, 2010, vol. 75, # 10, p. 3412 - 3419]
[7]Tussing, Sebastian; Ohland, Miriam; Wicker, Garrit; Flörke, Ulrich; Paradies, Jan [Dalton Transactions, 2017, vol. 46, # 5, p. 1539 - 1545]
[8]Hiroya, Kou; Itoh, Shin; Sakamoto, Takao [Journal of Organic Chemistry, 2004, vol. 69, # 4, p. 1126 - 1136]
[9]Liu, Jun; Xie, Xin; Liu, Yuanhong [Chemical Communications, 2013, vol. 49, # 100, p. 11794 - 11796]
[10]Zelenay, Benjamin; Munton, Peter; Tian, Xiaojie; Díez-González, Silvia [European Journal of Organic Chemistry, 2019, vol. 2019, # 29, p. 4725 - 4730]
[11]Current Patent Assignee: HANGZHOU NORMAL UNIVERSITY - CN112321481, 2021, A Location in patent: Paragraph 0051; 0053
[12]Nair, Reji N.; Lee, Paul J.; Rheingold, Arnold L.; Grotjahn, Douglas B. [Chemistry - A European Journal, 2010, vol. 16, # 27, p. 7992 - 7995]
[13]Chaisan, Nattawadee; Kaewsri, Wilailak; Thongsornkleeb, Charnsak; Tummatorn, Jumreang; Ruchirawat, Somsak [Tetrahedron Letters, 2018, p. 675 - 680]
[14]Chong, Eugene; Blum, Suzanne A. [Journal of the American Chemical Society, 2015, vol. 137, # 32, p. 10144 - 10147]
[15]Gonzalez-Gomez, Alvaro; Dominguez, Gema; Perez-Castells, Javier [European Journal of Organic Chemistry, 2009, # 29, p. 5057 - 5062]
[16]Witulski, Bernhard; Alayrac, Carole [Angewandte Chemie - International Edition, 2002, vol. 41, # 17, p. 3281 - 3284] Martinez-Esperon, Maria Fernanda; Rodriguez, David; Castedo, Luis; Saa, Carlos [Organic Letters, 2005, vol. 7, # 11, p. 2213 - 2216] Martínez-Esperón, María Fernanda; Rodríguez, David; Castedo, Luis; Saá, Carlos [Tetrahedron, 2006, vol. 62, # 16, p. 3843 - 3855]
[17]Yin, Yan; Ma, Wenying; Chai, Zhuo; Zhao, Gang [Journal of Organic Chemistry, 2007, vol. 72, # 15, p. 5731 - 5736]
[18]McNulty, James; Keskar, Kunal [European Journal of Organic Chemistry, 2014, vol. 2014, # 8, p. 1622 - 1629] McNulty, James; Keskar, Kunal [European Journal of Organic Chemistry, 2014, vol. 2014, # 8, p. 1622 - 1629]
[19]Jang, Young Ho; Youn, So Won [Organic Letters, 2014, vol. 16, # 14, p. 3720 - 3723]
[20]Youn, So Won; Lee, So Ra [Organic and Biomolecular Chemistry, 2015, vol. 13, # 16, p. 4652 - 4656]
[21]Zhao, Yingying; Hu, Yancheng; Wang, Haolong; Li, Xincheng; Wan, Boshun [Journal of Organic Chemistry, 2016, vol. 81, # 10, p. 4412 - 4420]
[22]Obata, Tomoyuki; Suzuki, Sho; Nakagawa, Asuka; Kajihara, Ryota; Noguchi, Keiichi; Saito, Akio [Organic Letters, 2016, vol. 18, # 16, p. 4136 - 4139]
[23]Boominathan, Siva Senthil Kumar; Wang, Jeh-Jeng [Advanced Synthesis and Catalysis, 2017, vol. 359, # 11, p. 1844 - 1848]
[24]Yu, Liu-Zhu; Wei, Yin; Shi, Min [Chemical Communications, 2017, vol. 53, # 64, p. 8980 - 8983]
[25]Lv, Jiahang; Zhao, Binlin; Liu, Li; Han, Ying; Yuan, Yu; Shi, Zhuangzhi [Advanced Synthesis and Catalysis, 2018, vol. 360, # 21, p. 4054 - 4059]
[26]Zhu, Bo-Han; Wang, Cai-Ming; Su, Hong-Yu; Ye, Long-Wu [Chinese Journal of Chemistry, 2019, vol. 37, # 1, p. 58 - 62]
[27]Correia, José Tiago Menezes; Piva da Silva, Gustavo; André, Elias; Paixão, Márcio Weber [Advanced Synthesis and Catalysis, 2019, vol. 361, # 24, p. 5558 - 5564]
[28]Li, Yongqiang; Liu, Yuxiu; Qu, Yi; Song, Hongjian; Wang, Qingmin; Xu, Wentao; Zhang, Jingjing [Journal of Organic Chemistry, 2020, vol. 85, # 8, p. 5379 - 5389]
[29]Lv, Jiahang; Zhao, Binlin; Han, Ying; Yuan, Yu; Shi, Zhuangzhi [Chinese Chemical Letters, 2021, vol. 32, # 2, p. 691 - 694]
[30]He, Yu-Ping; Cao, Jian; Wu, Hua; Wang, Qian; Zhu, Jieping [Angewandte Chemie - International Edition, 2021, vol. 60, # 13, p. 7093 - 7097][Angew. Chem., 2021, vol. 133, # 13, p. 7169 - 7173,5]
[31]Arisawa, Mitsuhiro; Matsuzaki, Tsuyoshi; Murai, Kenichi; Ohno, Shohei; Qiu, Jiawei; Sako, Makoto; Suzuki, Takeyuki; Takehara, Tsunayoshi; Tanaka, Tomoyuki [Organic Letters, 2021, vol. 23, # 11, p. 4284 - 4288]
  • 8
  • [ 13141-38-3 ]
  • [ 51234-11-8 ]
YieldReaction ConditionsOperation in experiment
75% With tetrafluoroboric acid; [bis(pyridine)iodine]+ tetrafluoroborate In dichloromethane at -80℃; for 8h;
Multi-step reaction with 2 steps 1: 84 percent Chromat. / NaAuCl4*2H2O / aq. ethanol / 5 h / 20 °C 2: I2; KOH / ethanol / 20 °C
  • 9
  • [ 536-74-3 ]
  • [ 615-36-1 ]
  • [ 13141-38-3 ]
YieldReaction ConditionsOperation in experiment
80% With copper(l) iodide; di-μ-chlorobis{hydrogen bis(diphenylphosphito)(1-)-P,P'}dipalladium; N-ethyl-N,N-diisopropylamine In toluene at 80℃; for 18h; Inert atmosphere;
72% With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; ethanolamine In tetrahydrofuran at 60℃; for 19h;
62% With bis-triphenylphosphine-palladium(II) chloride; (triphenylphosphine)gold(I) chloride; triethylamine In N,N-dimethyl-formamide at 80℃; for 4h; Inert atmosphere;
62% With (triphenylphosphine)gold(I) chloride; bis(triphenylphosphine)palladium(II) chloride; triethylamine In N,N-dimethyl-formamide at 80℃; for 4h; Inert atmosphere;
52% With tetrahydrofuran; iron(III) chloride; TPGS-750-M; methylmagnesium bromide; palladium diacetate; triethylamine; XPhos In water at 20 - 45℃; Inert atmosphere;
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide In triethylamine; N,N-dimethyl-formamide at 100℃; for 2h;

  • 10
  • [ 13141-38-3 ]
  • [ 78-94-4 ]
  • [ 95275-68-6 ]
YieldReaction ConditionsOperation in experiment
88% Stage #1: 2-phenylethynylaniline With sodium tetrachloroaurate dihydrate In various solvent(s) at 50℃; for 24h; Stage #2: methyl vinyl ketone In various solvent(s) at 80℃; for 24h; Further stages.;
74% With sodium tetrachloroaurate dihydrate In ethanol at 30℃; for 5h;
74% With palladium dichloride In acetonitrile at 60℃; for 4h; Inert atmosphere; 3.1 General experimental procedure for the synthesis of 2,3-disubstituted indoles General procedure: The substituted 2-alkynylaniline (1.0 mmol) was dissolved in acetonitrile (5.0 mL) and stirred until the solution became homogeneous. To this solution, methyl vinyl ketone (1.5 mmol) followed by 20 mol % of PdCl2 (59-60%, 35 mg) was added under a nitrogen atmosphere, then heated to 60 °C and monitored by TLC. After completion of the reaction, the mixture was cooled to room temperature and the acetonitrile was removed by vacuum evaporation. The resulting crude product was purified by column chromatography to afford the desired 2,3-disubstituted indoles. (2-Phenyl-1H-indol-3-yl)butan-2-one (3a) Yield: (184 mg, 70%); White solid; mp: 114-116 °C. FT-IR (KBr) (ν/cm-1): 3343, 1708. 1H NMR (400 MHz, CDCl3) δH (ppm): 8.12 (br s, 1H), 7.61 (d, J=7.92 Hz, 1H), 7.55-7.52 (m, 2H), 7.49-7.45 (m, 2H), 7.40-7.63 (m, 2H), 7.25-7.21 (m, 1H), 7.18-7.14 (m, 1H), 3.22-3.18 (m, 2H), 2.84-2.80 (m, 2H), 2.11 (s, 3H). 13C NMR (100 MHz, CDCl3) δC (ppm): 208.8, 136.0, 134.6, 133.2, 129.1, 128.9, 128.1, 127.9, 122.5, 119.8, 119.0, 111.9, 111.1, 44.6, 30.1, 18.9. LRMS (EI) (m/z) (relative intensity): 263 (M+, 50), 221.4 (100), 205.5 (90), 179.1 (25); HRMS calcd for C18H17O1N1 (M+): 263.1310, found 263.1314.
  • 11
  • [ 13141-38-3 ]
  • [ 1896-62-4 ]
  • 4-phenyl-4-(2-phenyl-1H-indol-3-yl)butan-2-one [ No CAS ]
YieldReaction ConditionsOperation in experiment
88% With sodium tetrachloroaurate dihydrate In ethanol at 30℃; for 2.5h;
75% With palladium dichloride In acetonitrile at 60℃; for 48h; Inert atmosphere; 3.18 General experimental procedure for the synthesis of 2,3-disubstituted indoles General procedure: The substituted 2-alkynylaniline (1.0 mmol) was dissolved in acetonitrile (5.0 mL) and stirred until the solution became homogeneous. To this solution, methyl vinyl ketone (1.5 mmol) followed by 20 mol % of PdCl2 (59-60%, 35 mg) was added under a nitrogen atmosphere, then heated to 60 °C and monitored by TLC. After completion of the reaction, the mixture was cooled to room temperature and the acetonitrile was removed by vacuum evaporation. The resulting crude product was purified by column chromatography to afford the desired 2,3-disubstituted indoles. 4-Phenyl-4-(2-phenyl-1H-indol-3-yl)butan-2-one (3r) Colorless solid; Yield: (237 mg, 75%); mp: 123-125 °C; FT-IR (KBr): ν/cm-1 3401, 1680; 1H NMR (400 MHz, CDCl3) δH (ppm): 8.14 (br s, 1H), 7.61 (d, J=8 Hz, 1H), 7.54-7.52 (m, 2H), 7.47-7.33 (m, 6H), 7.29-7.26 (m, 2H), 7.21-7.17 (m, 2H), 7.12-7.09 (m, 1H), 5.08 (t, J=7.3 Hz, 1H), 3.49-3.34 (m, 2H),1.97 (s, 3H). 13C NMR (100 MHz, CDCl3) δC (ppm): 207.7, 144.6, 136.4, 135.9, 133.1, 129.0, 128.9, 128.6, 128.3, 127.8, 127.6, 126.2, 122.2, 120.8, 119.9, 114.1, 111.4, 49.5, 37.2, 30.5. LRMS (EI) (m/z) (relative intensity): 339 (M+, 50), 282 (100), 204 (85), 78 (80); HRMS calcd for C24H21O1N1 (M+): 339.1614, found 339.1623.
  • 12
  • [ 13141-38-3 ]
  • [ 614-47-1 ]
  • [ 557785-79-2 ]
YieldReaction ConditionsOperation in experiment
82% With sodium tetrachloroaurate dihydrate In ethanol at 30℃; for 9h;
70% With palladium dichloride In acetonitrile at 60℃; for 48h; Inert atmosphere; 3.19 General experimental procedure for the synthesis of 2,3-disubstituted indoles General procedure: The substituted 2-alkynylaniline (1.0 mmol) was dissolved in acetonitrile (5.0 mL) and stirred until the solution became homogeneous. To this solution, methyl vinyl ketone (1.5 mmol) followed by 20 mol % of PdCl2 (59-60%, 35 mg) was added under a nitrogen atmosphere, then heated to 60 °C and monitored by TLC. After completion of the reaction, the mixture was cooled to room temperature and the acetonitrile was removed by vacuum evaporation. The resulting crude product was purified by column chromatography to afford the desired 2,3-disubstituted indoles. 1,3-Diphenyl-3-(2-phenyl-1H-indol-3-yl)propan-1-one (3s) Colorless solid; Yield: (307 mg, 70%); mp 98-100 °C; FT-IR (KBr): ν/cm-1 3387, 1675; 1H NMR (400 MHz, CDCl3) δH (ppm): 8.05 (br s, 1H), 7.83-7.81 (m, 2H), 7.61 (d, J=7.96 Hz, 1H) 7.52-7.50 (m, 3H), 7.48-7.41 (m, 2H), 7.40-7.33 (m, 6H), 7.27-7.24 (m, 2H), 7.21-7.15 (m, 2H), 7.11-7.07 (m, 1H), 5.32 (t, J=6.94 Hz, 1H), 4.01-3.87 (m, 2H). 13C NMR (100 MHz, CDCl3) δC (ppm): 198.8, 144.7, 137.2, 136.4, 135.7, 133.2, 133.0, 129.0, 128.9, 128.6, 128.5, 128.3, 128.2, 128.0, 127.8, 126.1, 122.2, 120.8, 119.9, 114.9, 111.3, 44.6, 37.0, LRMS (EI) (m/z) (relative intensity): 401 (M+, 35), 282 (100), 105 (100), 77 (87); HRMS calcd for C29H23O1N1 (M+): 401.1788, found 401.1780.
  • 13
  • [ 766-98-3 ]
  • [ 13141-38-3 ]
  • 1-(1-(4-fluorophenyl)vinyl)-2-phenyl-1H-indole [ No CAS ]
YieldReaction ConditionsOperation in experiment
75% at 20℃; for 3h;
69% With silver trifluoromethanesulfonate In neat (no solvent) at 20℃; for 4h; Inert atmosphere; Green chemistry; Synthesis of 2-phenyl-1-(1-phenylvinyl)-1H-indole (3a); generalprocedure 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.
  • 14
  • [ 13141-38-3 ]
  • [ 536-74-3 ]
  • 2-phenyl-1-(1-phenylvinyl)-1H-indole [ No CAS ]
YieldReaction ConditionsOperation in experiment
82% at 20℃; for 3h;
81% With silver trifluoromethanesulfonate In neat (no solvent) at 20℃; for 4h; Inert atmosphere; Green chemistry; Synthesis of 2-phenyl-1-(1-phenylvinyl)-1H-indole (3a); generalprocedure 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.2-Phenyl-1-(1-phenylvinyl)-1H-indole (3a):31 Oil; 1H NMR (400MHz, CDCl3): δ 7.67 (d, J = 7.6 Hz, 1H), 7.48 (d, J = 7.2 Hz, 2H),7.28-7.20 (m, 6H), 7.19-7.11 (m, 5H), 6.77 (s, 1H), 5.89 (s, 1H), 5.25 (s,1H); 13C NMR (100 MHz, CDCl3): δ 143.6, 141.3, 139.1, 137.3, 132.8,128.8, 128.6, 128.4, 128.3, 128.1, 127.5, 125.9, 122.3, 120.7, 120.5,113.8, 111.5, 103.7.
  • 15
  • [ 13141-38-3 ]
  • [ 768-60-5 ]
  • 1-(1-(4-methoxyphenyl)vinyl)-2-phenyl-1H-indole [ No CAS ]
YieldReaction ConditionsOperation in experiment
70% With silver trifluoromethanesulfonate In neat (no solvent) at 20℃; for 4h; Inert atmosphere; Green chemistry; Synthesis of 2-phenyl-1-(1-phenylvinyl)-1H-indole (3a); generalprocedure 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.
69% at 20℃; for 3h;
  • 16
  • [ 13141-38-3 ]
  • [ 766-97-2 ]
  • 2-phenyl-1-(1-(p-tolyl)vinyl)-1H-indole [ No CAS ]
YieldReaction ConditionsOperation in experiment
79% at 20℃; for 3h;
78% With silver trifluoromethanesulfonate In neat (no solvent) at 20℃; for 4h; Inert atmosphere; Green chemistry; Synthesis of 2-phenyl-1-(1-phenylvinyl)-1H-indole (3a); generalprocedure 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.
  • 17
  • [ 477585-38-9 ]
  • [ 13141-38-3 ]
  • C20H17N3O3 [ No CAS ]
YieldReaction ConditionsOperation in experiment
80% With N-ethyl-N,N-diisopropylamine; HATU In N,N-dimethyl-formamide at 20℃; for 18h; 4.A Example 4:; Part A:; To a solution of monoacid (3, 6, or 5-hydantoinacetic acid) (0.12 mmol) and HATU (68 mg, 0.18 mmol) in DMF (2 mL) was added amine building block (1.2 equivalents) and diisopropylethylamine (69 μL, 0.40 mmol). The reaction mixture was stirred at room temperature for 18 hours. LC-MS analysis of the reaction indicated that the reaction was complete. The volatiles were removed in vacuo, ethyl acetate was added, and the organic solution washed successively with saturated NaHCO3 (x1), water (x1), brine (x1 ), dried over magnesium sulfate and concentrated. Purification by Prep.LC afforded compounds 32 - 47 (80 - 90 % yield).
  • 18
  • [ 13141-38-3 ]
  • [ 78-94-4 ]
  • [ 849359-76-8 ]
YieldReaction ConditionsOperation in experiment
90% In various solvent(s) at 50℃;
65% With palladium diacetate; lithium chloride In tetrahydrofuran at 60℃; for 24h; Inert atmosphere; 3.24 Phenyl(2-phenyl-1H-indol-1-yl)methanone (4c) The substituted 2-alkynylaniline (1.0 mmol) was dissolved in acetonitrile (5.0 mL) and stirred until the solution became homogeneous. To this solution, methyl vinyl ketone (1.5 mmol) followed by 20 mol % of PdCl2 (59-60%, 35 mg) was added under a nitrogen atmosphere, then heated to 60 °C and monitored by TLC. After completion of the reaction, the mixture was cooled to room temperature and the acetonitrile was removed by vacuum evaporation. The resulting crude product was purified by column chromatography to afford the desired 2,3-disubstituted indoles. 4-((2-(Phenylethynyl)phenyl)amino)butan-2-one (5a) Yield: (170 mg, 65%); Yellow Liquid. FT-IR (KBr) (ν/cm-1): 3348, 1710. 1H NMR (400 MHz, CDCl3) δH (ppm): 7.54 (dd, J=7.78 Hz, 2H), 7.38-7.31 (m, 4H), 7.23-7.19 (m, 1H), 6.68-6.62 (m, 2H), 5.0 (br s, 1H), 3.52 (t, J=6.32 Hz, 2H), 2.79 (t, J=6.30 Hz, 2H), 2.18 (s, 3H). 13C NMR (100 MHz, CDCl3) δC (ppm): 207.7, 148.5, 132.4, 131.6, 130.1, 128.5, 128.3, 123.5, 116.8, 109.6, 108.2, 95.4, 85.9, 42.9, 38.2, 30.5. LRMS (EI) (m/z) (relative intensity): 263 (M+, 58), 206.2 (100), 193 (25); HRMS calcd for C20H21O1N1 (M+): 263.1310, found 263.1316.
  • 19
  • [ 13141-38-3 ]
  • [ 98-74-8 ]
  • [ 946161-96-2 ]
YieldReaction ConditionsOperation in experiment
42% With pyridine In dichloromethane at 20℃; for 8h; Preparation of 2-Alkynylaniline Derivatives. General procedure: Therequisite 2-alkynylaniline derivatives were prepared from 2-iodoanilines or2-bromoanilines reacted with alkynes following the modified method reported byZhao and co-workers.1To a solution of 2-alkynylaniline (1.00 mmol) inCH2Cl2 (8 mL) were added pyridine (5.00 mmol) and TsCl (1.20mmol) respectively. The resulting reaction mixture was stirred at rt for 8 h.After which the reaction mixture was quenched by H2O (10 mL), andthe aqueous layer was extracted with CH2Cl2 (3×15 mL).The combined organic layers were dried over Na2SO4,filtered, and concentrated under reduced pressure. The crude product waspurified by silica gel flash column chromatography to obtain corresponding product.
With pyridine In dichloromethane at 0 - 20℃;
  • 20
  • [ 13141-38-3 ]
  • [ 98-09-9 ]
  • [ 215997-61-8 ]
YieldReaction ConditionsOperation in experiment
83% With pyridine In dichloromethane at 20℃; for 8h; Preparation of 2-Alkynylaniline Derivatives. General procedure: Therequisite 2-alkynylaniline derivatives were prepared from 2-iodoanilines or2-bromoanilines reacted with alkynes following the modified method reported byZhao and co-workers.1To a solution of 2-alkynylaniline (1.00 mmol) inCH2Cl2 (8 mL) were added pyridine (5.00 mmol) and TsCl (1.20mmol) respectively. The resulting reaction mixture was stirred at rt for 8 h.After which the reaction mixture was quenched by H2O (10 mL), andthe aqueous layer was extracted with CH2Cl2 (3×15 mL).The combined organic layers were dried over Na2SO4,filtered, and concentrated under reduced pressure. The crude product waspurified by silica gel flash column chromatography to obtain corresponding product.
With pyridine In dichloromethane at 0 - 20℃;
With pyridine In chloroform at 20℃;
  • 21
  • [ 13141-38-3 ]
  • [ 98-88-4 ]
  • [ 104682-98-6 ]
YieldReaction ConditionsOperation in experiment
97% With triethylamine In dichloromethane at 20℃; Preparation of compound 1a-Bz, 1a-Ts, 1a-Boc 2-(phenylethynyl)aniline (187.7 mg, 0.97 mmol, 1.0 equiv) was dissolved in DCM (5.0 mL).The solution was added with BzCl (0.12 mL, 145.2 mg, 1.03 mmol, 1.1 equiv) followed by Et3N (0.15 mL, 108.8 mg, 1.08 mmol, 1.1 equiv). The resulting reaction mixture was allowed to stir at room temperature overnight. After completion, as indicated by TLC, the reaction mixture wasadded with water and the separated aqueous phase was extracted with DCM (3x times). Thecombined organic phases were washed with aq. HCl (1 M) and sat. aq. NaCl, dried over anh. Na2SO4, filtered and concentrated to a crude solid which was purified by SiO2 column chromatography eluting with 2-10% EtOAc-hexane to give 280.8 mg (97%) of compound 1a-Bzas a light yellow solid.
94% With triethylamine In tetrahydrofuran at 20℃; for 16h; Inert atmosphere;
91% With triethylamine In dichloromethane at 0 - 20℃; for 8h;
89% With pyridine In dichloromethane at 0 - 20℃; Inert atmosphere;
With pyridine In dichloromethane at 0 - 20℃;
In tetrahydrofuran at 20℃;
In dichloromethane at 20℃; Schlenk technique; Inert atmosphere; regioselective reaction;

  • 22
  • [ 201230-82-2 ]
  • [ 13141-38-3 ]
  • 3-(1-chloro-1-phenyl-methylidene)indolin-2-one [ No CAS ]
YieldReaction ConditionsOperation in experiment
66% With copper dichloride In tetrahydrofuran; benzene at 20℃; for 12h;
  • 23
  • [ 52670-38-9 ]
  • [ 591-50-4 ]
  • [ 13141-38-3 ]
YieldReaction ConditionsOperation in experiment
99% With pyrrolidine at 85℃; for 0.5h;
92% With copper(l) iodide; diisopropylamine In acetonitrile at 60℃; for 12h; Inert atmosphere;
82% With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; diisopropylamine; triphenylphosphine at 20℃; for 16h; Schlenk technique; Sealed tube; Inert atmosphere; 4.2.1 Synthesis of alkyne-substituted aromatic amines via Sonogashira coupling General procedure: The syntheses of alkyne-substituted aromatic amines (15-18) followed the general Scheme 1. A 50 mL Schlenk flask was charged with aryl iodide (2mmol, 1.0 eq.), bis-(triphenylphosphine) palladium dichloride (70mg, 0.05 eq.), cuprous iodide (10mg, 0.05 eq.), triphenylphosphine (13mg, 0.025 eq.), and a stir bar and sealed with rubber septum [33]. The flask was evacuated and refilled three times with Argon. Ethynylaniline (1.1 eq.) was added to 10mL of distilled dry iPr2NH and degassed together in a separated round bottom flask for 15min and then transferred to the Schlenk flask through cannula. The mixture was stirred for 16hat room temperature (65°C in the case of aryl bromide). After completion of the reaction, the mixture was diluted with ethyl acetate (50mL) and the slurry was filtered through a pad of Celite in a sintered glass funnel (medium frit). The tan solids were additionally washed with ethyl acetate until the filtrate was nearly colorless. The filtrate was washed with H2O and brine and dried over magnesium sulfate. The combined organic fraction filtrates were concentrated in vacuum, yielding a black solid. The residue was further purified by flash column chromatography on silica gel using ethyl acetate/hexane mixture as eluent.
80% With piperidine; silica-supported palladium catalyst at 70℃; for 0.5h;
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In N,N-dimethyl-formamide at 50℃;
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In N,N-dimethyl-formamide at 50℃;

  • 24
  • [ 35010-17-4 ]
  • [ 948-65-2 ]
  • [ 62058-64-4 ]
  • [ 13141-38-3 ]
YieldReaction ConditionsOperation in experiment
1: 87% 2: 5% 3: 3% With 5% Au/Fe2O3; hydrogen In toluene at 60 - 120℃; for 2h; Autoclave; chemoselective reaction;
1: 32.2% 2: 50.7% 3: 1% With 5% Au/Fe2O3; hydrogen In toluene at 60℃; Autoclave; chemoselective reaction;
  • 25
  • [ 1142-19-4 ]
  • [ 13141-38-3 ]
  • [ 1170720-88-3 ]
YieldReaction ConditionsOperation in experiment
95% With iodine In toluene at 110℃; for 8h; Schlenk technique;
92% With air; palladium dichloride In dimethyl sulfoxide at 80℃; for 24h;
82% With copper(l) iodide; caesium carbonate In dimethyl sulfoxide at 80℃; chemoselective reaction; General procedure for synthesis of 3-chalcogenylindoles: A mixture of 2-alkynylaniline 1a-1e (0.2 mmol), dichalcogenide 2a-2e (0.15 mmol), CuI (0.02 mmol), and Cs2CO3 (0.2 mmol) in DMSO (2 mL) was stirred at 80 °C under an air atmosphere. After completion of the reaction that was monitored by GC-MS or TLC, 25 mL water was added, and the mixture was extracted with ethyl acetate, the combined organic layers were washed with water (10 mL x 3), dried over anhydrous Na2SO4. After filtration and removal of solvents in vacuum, the residue was purified by silica gel column chromatography to afford the corresponding products.
  • 26
  • [ 13141-38-3 ]
  • [ 882-33-7 ]
  • [ 106345-32-8 ]
YieldReaction ConditionsOperation in experiment
94% With iodine In toluene at 110℃; for 8h; Schlenk technique;
92% With air; copper dichloride; palladium dichloride In dimethyl sulfoxide at 80℃; for 24h;
72% With copper(l) iodide; caesium carbonate In dimethyl sulfoxide at 80℃; chemoselective reaction; General procedure for synthesis of 3-chalcogenylindoles: A mixture of 2-alkynylaniline 1a-1e (0.2 mmol), dichalcogenide 2a-2e (0.15 mmol), CuI (0.02 mmol), and Cs2CO3 (0.2 mmol) in DMSO (2 mL) was stirred at 80 °C under an air atmosphere. After completion of the reaction that was monitored by GC-MS or TLC, 25 mL water was added, and the mixture was extracted with ethyl acetate, the combined organic layers were washed with water (10 mL x 3), dried over anhydrous Na2SO4. After filtration and removal of solvents in vacuum, the residue was purified by silica gel column chromatography to afford the corresponding products.
  • 27
  • [ 536-74-3 ]
  • [ 95-51-2 ]
  • [ 13141-38-3 ]
YieldReaction ConditionsOperation in experiment
85% With Cu(II)IL/Schiff base complex decorated on γ-Fe2O3 In dimethyl sulfoxide at 90℃; for 6h; General procedure for Sonogashira cross-couplingreaction 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 piperidine; tetrabutylammomium bromide In water at 60℃; for 6h;
69% With sodium hydroxide In water at 60℃; for 2.5h; Green chemistry;
65% With (Fe3O4 nanoparticles)(at)PEG/Cu-Co In water at 80℃; for 5.5h; Green chemistry;

  • 28
  • [ 13141-38-3 ]
  • [ 7624-95-5 ]
YieldReaction ConditionsOperation in experiment
92% With hydrogenchloride; sodium nitrite In water at 0 - 20℃; for 0.166667h; 15 General experimental procedure: representative procedure for the synthesis of 3-phenyl-1H-cinnolin-4-one: General procedure: To 2 N acidic suspension (2 mL) of 2-phenylethynyl-phenylamine (193 mg, 1 mmol), NaNO2 (103 mg, 1.5 mmol) was added in portions at 0-5 °C. The reaction mixture was stirred at 0-5 °C for 5 min followed by further 5 min at room temperature. The reaction mixture was extracted with EtOAc (2 × 5 mL), dried, concentrated and was left at room temperature to give 3-phenyl-1H-cinnolin-4-one as a pale yellow solid (204 mg, 92%), IR (KBr) 756, 1305, 1477, 1546, 2860, 2929 cm-1; 1H NMR (DMSO-d6, 300 MHz) δ 7.36-7.46 (m, 4H), 7.63 (d, J = 8.4 Hz, 1H), 7.77 (t, J = 7 Hz, 1H), 8.09-8.17 (m, 3H), 13.70 (s, 1H); 13C NMR (DMSO-d6, 75 MHz) δ 117.0, 124.0, 125.2, 125.3, 128.4 (2C), 128.8 (2C), 134.1, 135.5, 141.3, 146.0, 169.8; HRMS Calcd for C14H10N2O (M++H): 223.0871. Found: 223.0868.
92% With hydrogenchloride; water; sodium nitrite at 0 - 20℃; for 0.166667h; 4.2. General experimental procedure for the synthesis of 4(1H)-cinnolones. Representative procedure for 3-phenyl-1H-cinnolin-4-one (entry 1, Table 1) To 2 N-acidic suspension (2 mL) of 2-phenylethynyl-phenylamine (193 mg, 1 mmol), NaNO2 (103 mg, 1.5 mmol) was added in portions at 0-5 °C. The reaction mixture was stirred at 0-5 °C for 5 min followed by further 5 min at room temperature. The reaction mixture was extracted with EtOAc (2×5 mL), dried, concentrated and was left at room temperature to give 3-phenyl-1H-cinnolin-4-one as a pale yellow solid (204 mg, 92%), IR (KBr): 756, 1305, 1477, 1546, 2860, 2929 cm-1; 1H NMR (DMSO-d6, 300 MHz) δ 7.36-7.46 (m, 4H), 7.63 (d, J=8.4 Hz, 1H), 7.77 (t, J=7 Hz, 1H), 8.09-8.17 (m, 3H), 13.70 (s, 1H); 13C NMR (DMSO-d6, 75 MHz) δ 117.0, 124.0, 125.2, 125.3, 128.4 (2C), 128.8 (2C), 134.1, 135.5, 141.3, 146.0, 169.8; HRMS calcd for C14H10N2O (M++H): 223.0871, Found: 223.0868.
80% With sulfuric acid; sodium nitrite In water; N,N-dimethyl-formamide at 0℃; for 21.5h;
With hydrogenchloride; sodium nitrite In water at 0 - 20℃; for 50h;

  • 29
  • [ 103-19-5 ]
  • [ 13141-38-3 ]
  • [ 1213786-14-1 ]
YieldReaction ConditionsOperation in experiment
78% With copper(l) iodide; caesium carbonate In dimethyl sulfoxide at 80℃; for 4h; chemoselective reaction; General procedure for synthesis of 3-chalcogenylindoles: A mixture of 2-alkynylaniline 1a-1e (0.2 mmol), dichalcogenide 2a-2e (0.15 mmol), CuI (0.02 mmol), and Cs2CO3 (0.2 mmol) in DMSO (2 mL) was stirred at 80 °C under an air atmosphere. After completion of the reaction that was monitored by GC-MS or TLC, 25 mL water was added, and the mixture was extracted with ethyl acetate, the combined organic layers were washed with water (10 mL x 3), dried over anhydrous Na2SO4. After filtration and removal of solvents in vacuum, the residue was purified by silica gel column chromatography to afford the corresponding products.
59% With iodine In toluene at 110℃; for 10h; Schlenk technique;
  • 30
  • [ 5335-84-2 ]
  • [ 13141-38-3 ]
  • [ 1285494-73-6 ]
YieldReaction ConditionsOperation in experiment
79% With copper(l) iodide; caesium carbonate In dimethyl sulfoxide at 80℃; chemoselective reaction; General procedure for synthesis of 3-chalcogenylindoles: A mixture of 2-alkynylaniline 1a-1e (0.2 mmol), dichalcogenide 2a-2e (0.15 mmol), CuI (0.02 mmol), and Cs2CO3 (0.2 mmol) in DMSO (2 mL) was stirred at 80 °C under an air atmosphere. After completion of the reaction that was monitored by GC-MS or TLC, 25 mL water was added, and the mixture was extracted with ethyl acetate, the combined organic layers were washed with water (10 mL x 3), dried over anhydrous Na2SO4. After filtration and removal of solvents in vacuum, the residue was purified by silica gel column chromatography to afford the corresponding products.
  • 31
  • [ 1666-13-3 ]
  • [ 13141-38-3 ]
  • [ 1285494-74-7 ]
YieldReaction ConditionsOperation in experiment
72% With copper(l) iodide; caesium carbonate In dimethyl sulfoxide at 80℃; chemoselective reaction; General procedure for synthesis of 3-chalcogenylindoles: A mixture of 2-alkynylaniline 1a-1e (0.2 mmol), dichalcogenide 2a-2e (0.15 mmol), CuI (0.02 mmol), and Cs2CO3 (0.2 mmol) in DMSO (2 mL) was stirred at 80 °C under an air atmosphere. After completion of the reaction that was monitored by GC-MS or TLC, 25 mL water was added, and the mixture was extracted with ethyl acetate, the combined organic layers were washed with water (10 mL x 3), dried over anhydrous Na2SO4. After filtration and removal of solvents in vacuum, the residue was purified by silica gel column chromatography to afford the corresponding products.
  • 32
  • [ 13141-38-3 ]
  • [ 1192-40-1 ]
  • [ 106345-32-8 ]
YieldReaction ConditionsOperation in experiment
52% With caesium carbonate; potassium iodide In dimethyl sulfoxide at 80℃; for 4h; chemoselective reaction; General procedure for synthesis of 3-chalcogenylindoles: A mixture of 2-alkynylaniline 1a-1e (0.2 mmol), dichalcogenide 2a-2e (0.15 mmol), CuI (0.02 mmol), and Cs2CO3 (0.2 mmol) in DMSO (2 mL) was stirred at 80 °C under an air atmosphere. After completion of the reaction that was monitored by GC-MS or TLC, 25 mL water was added, and the mixture was extracted with ethyl acetate, the combined organic layers were washed with water (10 mL x 3), dried over anhydrous Na2SO4. After filtration and removal of solvents in vacuum, the residue was purified by silica gel column chromatography to afford the corresponding products.
  • 34
  • [ 829-35-6 ]
  • [ 13141-38-3 ]
  • [ 1354644-39-5 ]
  • 35
  • [ 75-15-0 ]
  • [ 13141-38-3 ]
  • (Z)-4-benzylidene-4H-benzo[d][1,3]thiazine-2-thiol [ No CAS ]
YieldReaction ConditionsOperation in experiment
95% With 1,4-diaza-bicyclo[2.2.2]octane; silver nitrate In N,N-dimethyl-formamide at 20℃; Inert atmosphere; regiospecific reaction; 3.1.1. 4-Benzylidene-4H-benzo[d][1,3]thiazine-2-thiol (2a) General experimental procedure for tandem addition-cyclization of 2-alkynylbenzenamines (1) with CS2: A solution of 2-alkynylbenzenamines 1 (0.30 mmol), CS2 (3.0 mmol, 10 equiv), AgNO3 (5 mol %), DABCO (1.2 equiv) in DMF (2.0 mL) was stirred at room temperature. After completion of reaction as indicated by TLC, the reaction was quenched with water (10 mL), extracted with EtOAc (2×10 mL), and dried by anhydrous Na2SO4. Evaporation of the solvent followed by purification on silica gel provided the corresponding 4-benzylidene-4H-benzo[d][1,3]thiazine 2a.
80% With sulfuric acid; 1,8-diazabicyclo[5.4.0]undec-7-ene In acetonitrile at 25℃; for 24h; Sealed tube; Inert atmosphere; General procedure for the synthesis of product 2 General procedure: A sealed tube was charged with the mixture of 2-alkynylaniline 1 (1 mmol), carbon disulfide (1.5 mmol), then stirred in a solution of DBUH+ in CH3CN (1.5 mL) at room temperature under nitrogen atmosphere for indicated time. After completion, then H2O (5 mL) was added and the mixture was extracted with EtOAc (5 mL x 3), dried by anhydrous Na2SO4. Evaporation of the solvent followed by purification on silica gel (petroleum ether/ethylacetate = 4/1) provided the corresponding product 2.
  • 36
  • [ 13141-38-3 ]
  • [ 762-42-5 ]
  • [ 1373169-75-5 ]
YieldReaction ConditionsOperation in experiment
83% With oxygen; copper(l) chloride In N,N-dimethyl acetamide at 100℃;
60% With tris(2,2'-bipyridyl)ruthenium dichloride; oxygen; copper dichloride In N,N-dimethyl-formamide at 20℃; for 24h; Irradiation; Schlenk technique;
57% With tert.-butylnitrite; tetrabutylammomium bromide; oxygen; trifluoroacetic acid at 60℃; for 0.5h; Green chemistry;
  • 37
  • [ 13141-38-3 ]
  • [ 62058-64-4 ]
YieldReaction ConditionsOperation in experiment
97% With C14H29BrMnNO2P2; potassium <i>tert</i>-butylate; hydrogen In n-heptane at 30℃; for 16h; stereoselective reaction;
94% With potassium <i>tert</i>-butylate; copper(II) acetate monohydrate; 1,3-bis[2,6-diisopropylphenyl]imidazolium chloride; <i>tert</i>-butyl alcohol In toluene at 50℃; for 20h; Inert atmosphere; diastereoselective reaction; General procedure for the copper-catalyzed semihydrogenation of alkynes: for solid substrates (1d, f, g, h, i, j, l, m, q, r, w, z, and CA-4) General procedure: In air, Cu(OAc)2·H2O (5.0mg, 5mol%), IPr·HCl (10.6mg, 5mol%), and solid substrates (0.5mmol) were placed in a screw-capped reaction vial. The vial was moved into a glove box and t-BuOK (5.6mg, 10mol%) and solvent (1.0ml) were added. The vial was moved out of the glove box and connected to an argon line through a needle. The mixture was raised to 50°C and stirred for 1h. The mixture was then treated in two different manners: (1) if reaction temperature ≥50°C (1d, i, j, q, r, w and CA-4), PMHS (131mg, 4.0equiv) was then added dropwise with a microsyringe at 50°C and the solution was stirred for an additional 30min. After t-BuOH (74mg, 2.0equiv) was added, the mixture was raised to required reaction temperature and stirred for a specified period of time; (2) if reaction temperature 1f, g, h, l, m, z), the mixture was first cooled to the required temperature and PMHS (131mg, 4.0equiv) was then added and the solution was stirred for an additional 30min. After t-BuOH (74mg, 2.0equiv) was added, the mixture was stirred for a specified period of time. The reaction mixture was subsequently hydrolyzed by adding 1M NaOH aqueous (2ml) (for substrates with no hydroxyl group) or 1M TBAF in THF (2ml) at 0°C (for substrates with a hydroxyl group) for several hours. The mixture was extracted with ether (2ml×3). Crude products were obtained after evaporation and purified by silica gel chromatography.
19 %Chromat. With hydrogen In 1,4-dioxane at 85℃; for 14h; chemoselective reaction;
  • 38
  • [ 24424-99-5 ]
  • [ 13141-38-3 ]
  • [ 221353-36-2 ]
YieldReaction ConditionsOperation in experiment
100% In tetrahydrofuran at 80℃; for 48h;
76% In tetrahydrofuran for 40h; Reflux;
63% With triethylamine In tetrahydrofuran at 20℃; for 2h; Preparation of compound 1a-Bz, 1a-Ts, 1a-Boc 2-(phenylethynyl)aniline (188.4 mg, 0.96 mmol, 1.0 equiv) was dissolved in THF (2.0 mL). Thesolution was added with Boc2O (0.25 mL, 237.5 mg, 1.09 mmol, 1.1 equiv) followed by Et3N(0.15 mL, 108.8 mg, 1.08 mmol, 1.1 equiv). The resulting reaction mixture was allowed to stir at room temperature for 2 h and the reaction mixture was added with water and the separated aqueous phase was extracted with EtOAc (3x times). The combined organic phases were washed with sat. aq. NaCl, dried over anh. Na2SO4, filtered and concentrated to a crude solid which was purified by SiO2 column chromatography eluting with 2% EtOAc-hexane to give 180.9 mg(63%) of compound 1a-Boc as a white solid, along with some recovered starting material.
  • 39
  • [ 1629-58-9 ]
  • [ 13141-38-3 ]
  • [ 1428020-30-7 ]
YieldReaction ConditionsOperation in experiment
78% With palladium diacetate; lithium chloride In tetrahydrofuran at 60℃; for 24h; Inert atmosphere; 3.27 General experimental procedure for the synthesis of 2,3-disubstituted indoles The substituted 2-alkynylaniline (1.0 mmol) was dissolved in acetonitrile (5.0 mL) and stirred until the solution became homogeneous. To this solution, methyl vinyl ketone (1.5 mmol) followed by 20 mol % of PdCl2 (59-60%, 35 mg) was added under a nitrogen atmosphere, then heated to 60 °C and monitored by TLC. After completion of the reaction, the mixture was cooled to room temperature and the acetonitrile was removed by vacuum evaporation. The resulting crude product was purified by column chromatography to afford the desired 2,3-disubstituted indoles. 1-((2-(Phenylethynyl)phenyl)amino)pentan-3-one (5d) Yield: (216 mg, 78%); Yellow gummy solid. FT-IR (KBr) (ν/cm-1): 3348, 1712. 1H NMR (400 MHz, CDCl3) δH (ppm): 7.57 (dd, J=7.72, 1.48 Hz, 2H), 7.39-7.34 (m, 4H), 7.24-7.20 (m, 1H), 6.69-6.64 (m, 2H), 4.99 (t, J=5.76 Hz, 1H), 3.54 (q, J=6.34 Hz, 2H), 2.77 (t, J=6.34 Hz, 2H), 2.44 (q, J=7.34 Hz, 2H), 1.08 (t, J=7.32 Hz, 3H). 13C NMR (100 MHz, CDCl3) δC (ppm): 210.4, 148.6, 132.4, 131.6, 130.1, 128.5, 128.3, 123.5, 116.7, 109.7, 108.2, 95.4, 85.9, 41.6, 38.3, 36.6, 7.8. LRMS (EI) (m/z) (relative intensity): 277 (M+, 45), 206 (100); HRMS calcd for C19H19O1N1 (M+): 277.1467, found 277.1462.
  • 40
  • [ 13141-38-3 ]
  • [ 768-03-6 ]
  • [ 1428020-82-9 ]
YieldReaction ConditionsOperation in experiment
75% With palladium dichloride In acetonitrile at 60℃; for 8h; Inert atmosphere; 3.15 General experimental procedure for the synthesis of 2,3-disubstituted indoles General procedure: The substituted 2-alkynylaniline (1.0 mmol) was dissolved in acetonitrile (5.0 mL) and stirred until the solution became homogeneous. To this solution, methyl vinyl ketone (1.5 mmol) followed by 20 mol % of PdCl2 (59-60%, 35 mg) was added under a nitrogen atmosphere, then heated to 60 °C and monitored by TLC. After completion of the reaction, the mixture was cooled to room temperature and the acetonitrile was removed by vacuum evaporation. The resulting crude product was purified by column chromatography to afford the desired 2,3-disubstituted indoles. 1-Phenyl-3-(2-phenyl-1H-indol-3-yl)propan-1-one (3o) Yield: (243 mg, 75%); Yellow Liquid. FT-IR (KBr) (ν/cm-1): 3340, 1716. 1H NMR (400 MHz, CDCl3) δH (ppm): 8.1 (br s, 1H), 7.92 (d, J=7.4 Hz, 1H), 7.64 (d, J=7.84 Hz, 1H), 7.58-7.52 (m, 3H), 7.49-7.36 (m, 6H) 7.23 (d, J=7.32 Hz, 1H), 7.17 (t, J=7.46 Hz, 1H), 3.37 (s, 4H). 13C NMR (100 MHz, CDCl3) δC (ppm): 200.0, 137.0, 136.1, 134.7, 133.2, 133.1, 129.1, 129.0, 128.7, 128.2, 128.1, 128.0, 122.6, 119.9, 119.1, 112.3, 111.1, 39.9, 19.4. LRMS (EI) (m/z) (relative intensity): 325 (M+, 40), 206 (100); HRMS calcd for C23H19O1N1 (M+): 325.1467, found 325.1469.
  • 41
  • [ 13141-38-3 ]
  • [ 768-03-6 ]
  • [ 1428020-31-8 ]
YieldReaction ConditionsOperation in experiment
62% With palladium diacetate; lithium chloride In tetrahydrofuran at 60℃; for 24h; Inert atmosphere; 3.28 General experimental procedure for the synthesis of 2,3-disubstituted indoles The substituted 2-alkynylaniline (1.0 mmol) was dissolved in acetonitrile (5.0 mL) and stirred until the solution became homogeneous. To this solution, methyl vinyl ketone (1.5 mmol) followed by 20 mol % of PdCl2 (59-60%, 35 mg) was added under a nitrogen atmosphere, then heated to 60 °C and monitored by TLC. After completion of the reaction, the mixture was cooled to room temperature and the acetonitrile was removed by vacuum evaporation. The resulting crude product was purified by column chromatography to afford the desired 2,3-disubstituted indoles. 1-Phenyl-3-((2-(phenylethynyl)phenyl)amino)propan-1-one (5e) Yield: (201 mg, 62%); Yellow Liquid. FT-IR (KBr) (ν/cm-1): 3350, 1705. 1H NMR (400 MHz, CDCl3) δH (ppm): 7.98-7.96 (m, 2H), 7.59-7.55 (m, 3H), 7.46 (t, J=7.6 Hz, 2H) 7.38-7.32 (m, 2H), 7.25-7.21 (m, 1H), 6.72-6.66 (m, 2H), 5.12 (br s, 1H), 3.74 (q, J=5.9 Hz, 2H), 3.34 (t, J=6.36 Hz, 2H). 13C NMR (100 MHz, CDCl3) δC (ppm): 199.1, 148.6, 136.9, 133.5, 132.4, 131.7130.1, 128.8, 128.5, 128.3, 128.2, 123.5, 116.7, 109.6, 108.2, 95.4, 86.0, 38.6, 38.1. LRMS (EI) (m/z) (relative intensity): 325 (M+, 52), 206 (100); HRMS calcd for C23H19O1N1 (M+): 325.1467, found 325.1468.
  • 42
  • [ 13141-38-3 ]
  • [ 107-13-1 ]
  • [ 948-65-2 ]
YieldReaction ConditionsOperation in experiment
77% With palladium dichloride In acetonitrile at 60℃; for 24h; Inert atmosphere; 3.22 General experimental procedure for the synthesis of 2,3-disubstituted indoles General procedure: The substituted 2-alkynylaniline (1.0 mmol) was dissolved in acetonitrile (5.0 mL) and stirred until the solution became homogeneous. To this solution, methyl vinyl ketone (1.5 mmol) followed by 20 mol % of PdCl2 (59-60%, 35 mg) was added under a nitrogen atmosphere, then heated to 60 °C and monitored by TLC. After completion of the reaction, the mixture was cooled to room temperature and the acetonitrile was removed by vacuum evaporation. The resulting crude product was purified by column chromatography to afford the desired 2,3-disubstituted indoles. 2-Phenyl-1H-indole (4b) White solid. Mp: 190-192 °C. FT-IR (KBr) (ν/cm-1): 3430, 1457. 1H NMR (400 MHz, CDCl3) δH (ppm): 8.31 (br s, 1H), 7.68-7.64 (m, 3H), 7.47-7.40 (m, 3H), 7.35-7.32 (m, 1H), 7.23-7.19 (m, 1H), 7.16-7.12 (m, 1H), 6.85 (d, J=1.9 Hz, 1H). 13C NMR (100 MHz CDCl3) δC (ppm): 138.1, 137.0, 132.6, 129.4, 129.2, 127.9, 125.3, 122.5, 120.8, 120.5, 111.1, 100.2. LRMS (EI) (m/z) (relative intensity): 193 (M+, 100), 165 (19); HRMS calcd for C14H11N1 (M+): 193.0891, found 193.0895.
  • 43
  • [ 13141-38-3 ]
  • [ 948-65-2 ]
  • [ 2415-33-0 ]
YieldReaction ConditionsOperation in experiment
86% With Au/Carbon G-60 catalyst In toluene at 90℃; for 48h; Inert atmosphere; Schlenk technique;
1: 50% 2: 15% With ferrocene; sodium tetrachloroaurate(III) dihyrate In ethanol at 40℃; for 8h; Inert atmosphere; 2.2.3. Synthesis of 2-phenylindole (2b) and diphenylbiindole (3b) 2-Phenylethynylaniline (1b) (39 mg, 0.2 mmol), ferrocene (19 mg, 0.1 mmol), andNaAuCl42H2O (5%) (4 mg, 0.01 mmol) were dissolved in ethanol (5 mL) and stirred at40 C for 8 h under air or 70 C for 24 h under oxygen. After the reaction was completed,the reaction mixture was extracted by dichloromethane. The organic solventwas removed in vacuo and the residues were subjected to chromatographic separationon a silica gel column (2.030 cm). Elution with a mixture of dichloromethane andhexane (1:3/V:V) gave the corresponding pure product 2b (in air) and 3b (in oxygen).The spectroscopic data were consistent with those reported previously [26].2-Phenylindole (2b): 1H NMR (500 MHz, CDCl3): d: 8.31 (s, 1H, NH), 7.67-7.62 (m, 3H,ArH), 7.45-7.39 (m, 3H, ArH), 7.32 (t, 1H, J6.5 Hz, ArH), 7.20 (t, 1H, J2.5 Hz, ArH),7.12 (t, 1H, J9 Hz, ArH), 6.83 (s, 1H, C-3H) ppm. 13C NMR (125 MHz, CDCl3): d: 137.9,132.4, 129.2, 127.7, 125.2, 122.4, 120.7, 120.3, 110.1, 100.0.Diphenylbiindole (3b): 1H NMR (500 MHz, DLM): d: 10.65 (s, 2H, NH), 7.55 (d, 4H,J7.5 Hz, ArH), 7.49 (d, 2H, J8 Hz, ArH), 7.15-7.03 (m, 10H, ArH), 6.87 (t, 2H,J7.5 Hz, ArH) ppm. 13C NMR (125 MHz, DLM): d: 137.6, 135.5, 133.9, 130.7, 129.2,127.7, 127.4, 122.5, 120.3, 119.6, 111.9, 107.5.
  • 44
  • [ 13141-38-3 ]
  • [ 109744-41-4 ]
YieldReaction ConditionsOperation in experiment
81% With toluene-4-sulfonic acid; potassium iodide; sodium nitrite In water; acetonitrile at 10 - 20℃; for 2.16667h;
78% Stage #1: 2-phenylethynylaniline With toluene-4-sulfonic acid In acetonitrile Schlenk technique; Stage #2: With potassium iodide; sodium nitrite In acetonitrile at 0℃; for 0.166667h; Schlenk technique;
76% With toluene-4-sulfonic acid; potassium iodide; sodium nitrite In water; acetonitrile at 10 - 20℃; for 2.16667h;
50% Stage #1: 2-phenylethynylaniline With toluene-4-sulfonic acid In acetonitrile Stage #2: With potassium iodide; sodium nitrite In acetonitrile at 0℃;
Stage #1: 2-phenylethynylaniline With toluene-4-sulfonic acid; sodium nitrite In acetonitrile Stage #2: With potassium iodide In acetonitrile at 15℃;
Stage #1: 2-phenylethynylaniline With toluene-4-sulfonic acid In acetonitrile at 10 - 15℃; Stage #2: With potassium iodide; sodium nitrite In water; acetonitrile at 10 - 20℃; for 2h;
Multi-step reaction with 2 steps 1: acetonitrile 2: sodium nitrite; potassium iodide / water; acetonitrile / 0 °C

  • 45
  • [ 13141-38-3 ]
  • [ 98-80-6 ]
  • [ 1075174-17-2 ]
YieldReaction ConditionsOperation in experiment
85% With 2,6-dimethylpyridine; nonanoic acid; copper diacetate In toluene at 20℃; for 10h; 26 PREPARATION EXAMPLE 26 The 0.2 dag of (phenyl acetylene) aniline 2 - [2 - (phenylethynyl) aniline] with the 4.2 milliliters of toluene mixed, LSI, adding 1.5 equivalent of phenyl boronic acid (benzeneboronic acid), 2, 6 - dimethyl pyridine 1.1 equivalent of (2, 6 - lutidine), 0.2 equivalent [...] (nonanoic acid) and 0.1 equivalent of cupric acetate [Cu (OAc)2]. AT ROOM TEMPERATURE AND AIR UNDER THE ENVIRONMENT OF 10 HOURS INSTEAD ON INVITATION. THEN, THE ADDITION OF WATER TO TERMINATE THE REACTION, AND THE USE OF ETHYL ACETATE EXTRACTION PROCESSING. The collected ethyl acetate with the salt water solution (brine) is mixed in order to wash processing, and once again achieved [...] acid and acetic acid. THE ACETIC ACID [...] AND SODIUM SULFATE MIXED IN ORDER TO WATER REMOVAL PROCESSING, LSI, FILTERING PROCESSING, TO OBTAIN A FILTRATE. THE FILTRATE USING A CONCENTRATOR CONCENTRATING UNDER REDUCED PRESSURE, TO OBTAIN A CONCENTRATE. THE CONCENTRATE BY COLUMN CHROMAGRAPHY TO CARRY OUT PURIFICATION PROCESS. THE PURIFICATION TREATMENT IS THE USE OF NORMAL HEXANE AS [...]. BY THIS AFTER THE PURIFICATION PROCESSING, OBTAIN A UNFILTERED. THE UNFILTERED CONCENTRATE PROCESSING, IN ORDER TO REMOVE THE HEXANE, TO OBTAIN [...] OBJECTS [THE FOLLOWING SYMMETRICAL (1 - 26) INDICATED BY THE 2 - ALKYNYL ANILINE COMPOUNDS], YIELD IS 85%.
81% With 2,6-dimethylpyridine; nonanoic acid; copper diacetate In toluene at 20℃; for 30h;
70% With 2,6-dimethylpyridine; 1-decanoic acid; copper diacetate In toluene at 20℃; for 24h; Schlenk technique; Sealed tube;
  • 46
  • [ 13141-38-3 ]
  • [ 134150-01-9 ]
  • 2-phenyl-1-(4-propylphenyl)-1H-indole [ No CAS ]
  • 47
  • [ 13141-38-3 ]
  • [ 98-58-8 ]
  • 4-bromo-N-(2-(phenylethynyl)phenyl)benzenesulfonamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
80% With pyridine In dichloromethane at 20℃; for 8h; Preparation of 2-Alkynylaniline Derivatives. General procedure: Therequisite 2-alkynylaniline derivatives were prepared from 2-iodoanilines or2-bromoanilines reacted with alkynes following the modified method reported byZhao and co-workers.1To a solution of 2-alkynylaniline (1.00 mmol) inCH2Cl2 (8 mL) were added pyridine (5.00 mmol) and TsCl (1.20mmol) respectively. The resulting reaction mixture was stirred at rt for 8 h.After which the reaction mixture was quenched by H2O (10 mL), andthe aqueous layer was extracted with CH2Cl2 (3×15 mL).The combined organic layers were dried over Na2SO4,filtered, and concentrated under reduced pressure. The crude product waspurified by silica gel flash column chromatography to obtain corresponding product.
With pyridine In dichloromethane at 0 - 20℃; for 12.25h;
  • 48
  • [ 13141-38-3 ]
  • [ 98-60-2 ]
  • 4-chloro-N-(2-(phenylethynyl)phenyl)benzenesulfonamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
74% With pyridine In dichloromethane at 20℃; for 8h; Preparation of 2-Alkynylaniline Derivatives. General procedure: Therequisite 2-alkynylaniline derivatives were prepared from 2-iodoanilines or2-bromoanilines reacted with alkynes following the modified method reported byZhao and co-workers.1To a solution of 2-alkynylaniline (1.00 mmol) inCH2Cl2 (8 mL) were added pyridine (5.00 mmol) and TsCl (1.20mmol) respectively. The resulting reaction mixture was stirred at rt for 8 h.After which the reaction mixture was quenched by H2O (10 mL), andthe aqueous layer was extracted with CH2Cl2 (3×15 mL).The combined organic layers were dried over Na2SO4,filtered, and concentrated under reduced pressure. The crude product waspurified by silica gel flash column chromatography to obtain corresponding product.
  • 49
  • [ 13141-38-3 ]
  • [ 579-93-1 ]
  • 50
  • [ 37517-81-0 ]
  • [ 13141-38-3 ]
  • 2-methoxycarbonyl-N-[2-(phenylethynyl)phenyl]acetamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
96% With dmap; triethylamine In chloroform at 0℃; for 0.25h; Typical procedure for the preparation of 2-methoxycarbonyl-N-[2-(phenylethynyl)phenyl]acetamide: General procedure: To a stirred solution of N-benzyl-4-methyl-2-(phenylethynyl)phenylamine (400 mg, 1.35 mmol), methyl malonyl chloride (277 mg, 2.03 mmol) and DMAP (17mg, 0.14 mmol) in chloroform (5 mL), triethylamine (205 mg, 2.03 mmol) in chloroform (2 mL) was added dropwise over a 5-min period at 0 oC. After stirred for another 10 min, the reaction mixture was then diluted with100 mL of ethyl acetate, washed with water (3 × 50 mL), dried (Na2SO4), and concentrated in vacuo. The residue was chromatographed over 20 g of silica gel (eluted with 20:1 hexane-ethyl acetate) to give 530 mg (99%) of 1b.
  • 51
  • [ 13141-38-3 ]
  • [ 2498-50-2 ]
  • (E)-4-(3-(2-(phenylethynyl)phenyl)triaz-1-enyl)benzimidamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
85% General procedure: The synthesis of DMZ analogues followed previously reported procedure [19a], see Scheme 2. <strong>[2498-50-2]4-Aminobenzamidine dihydrochloride</strong> (212mg, 1.0mmol) was added to a stirred solution of 12N HCl (0.27mL) and water (1.5mL) in a 10mL flask at 0C and stirring was continued for 15min. To the mixture was added (dropwise) cold (?0C) NaNO2 solution (76mg in 0.27mL water, 1.1 eq.) and stirring was continued for 15min before cold (?0C) NaOAc solution (328mg in 1.5mL water, 4.0 eq.) was added dropwise over 15min to adjust the pH to 6.0. Cold (?0C) aromatic amine solution (1.0mmol in 1.0mL methanol) was added dropwise to the above solution and stirring was continued for another 1-12hat 0C. After the reaction was completed, the solvent was removed under reduced pressure. Water (100mL) was added to the residue and the aqueous mixture was washed with dichloromethane (2×15mL). The aqueous layer was then basified with 2.5% NaOH solution to make the pH>10.0. The desired compound was then extracted from the aqueous layer with ethyl acetate (2×100mL). The organic layer was washed with brine and dried with sodium sulfate. Finally, the solvent was removed under reduced pressure and the final product was obtained with purity >95%.
  • 52
  • [ 84563-54-2 ]
  • [ 13141-38-3 ]
  • 1-(4-(tert-butyl)phenyl)-2-phenyl-1H-indole [ No CAS ]
  • 53
  • [ 84563-54-2 ]
  • [ 13141-38-3 ]
  • bis(1-(4-(tert-butyl)phenyl)-2-phenyl-1H-indol-3-yl)methane [ No CAS ]
  • 54
  • [ 13141-38-3 ]
  • [ 100-47-0 ]
  • N-(3-phenylcinnolin-4-yl)benzamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
77% With tert.-butylnitrite; saccharin at 20℃; for 6h; Green chemistry; Typical procedure for the synthesis of 4-amidocinnolines General procedure: 2-(Phenylethynyl)aniline (1a, 193 mg, 1.0 mmol) was added and stirred slowly to 36 mg Sac-H (0.2 mmol) in1.0 cm3 dry nitrile for 5 min at room temperature. Then 0.20 cm3 t-butyl nitrite (* 1.5 mmol) was added through a micropipette over 2 min and the flask was stoppered and stirring was continued at room temperature for 6 h. After the completion, 5 cm3 10% aq. solution of NaHCO3 was added to the reaction mixture and the resulting solution was extracted with EtOAc (5 9 5 cm3). The combined ethylacetate extractions were washed with water (2 9 5 cm3)and brine (2 9 5 cm3), dried over anhydrous Na2SO4, and concentrated using vacuum rotary. The purification was carried out by column chromatography on silica gel (hexane/ethyl acetate = 8/2-4/6) to afford the desired product.
71% With tert.-butylnitrite; boron trifluoride diethyl etherate at 25℃; for 10h; Sealed tube;
  • 55
  • [ 2046-18-6 ]
  • [ 13141-38-3 ]
  • 4-phenyl-N-(3-phenylcinnolin-4-yl)butanamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
80% With tert.-butylnitrite; saccharin at 20℃; for 6h; Green chemistry; Typical procedure for the synthesis of 4-amidocinnolines General procedure: 2-(Phenylethynyl)aniline (1a, 193 mg, 1.0 mmol) was added and stirred slowly to 36 mg Sac-H (0.2 mmol) in1.0 cm3 dry nitrile for 5 min at room temperature. Then 0.20 cm3 t-butyl nitrite (* 1.5 mmol) was added through a micropipette over 2 min and the flask was stoppered and stirring was continued at room temperature for 6 h. After the completion, 5 cm3 10% aq. solution of NaHCO3 was added to the reaction mixture and the resulting solution was extracted with EtOAc (5 9 5 cm3). The combined ethylacetate extractions were washed with water (2 9 5 cm3)and brine (2 9 5 cm3), dried over anhydrous Na2SO4, and concentrated using vacuum rotary. The purification was carried out by column chromatography on silica gel (hexane/ethyl acetate = 8/2-4/6) to afford the desired product.
72% With tert.-butylnitrite; boron trifluoride diethyl etherate at 25℃; for 12h; Sealed tube;
  • 56
  • [ 78-82-0 ]
  • [ 13141-38-3 ]
  • N-(3-phenylcinnolin-4-yl)isobutyramide [ No CAS ]
YieldReaction ConditionsOperation in experiment
84% With tert.-butylnitrite; saccharin at 20℃; for 6h; Green chemistry; Typical procedure for the synthesis of 4-amidocinnolines General procedure: 2-(Phenylethynyl)aniline (1a, 193 mg, 1.0 mmol) was added and stirred slowly to 36 mg Sac-H (0.2 mmol) in1.0 cm3 dry nitrile for 5 min at room temperature. Then 0.20 cm3 t-butyl nitrite (* 1.5 mmol) was added through a micropipette over 2 min and the flask was stoppered and stirring was continued at room temperature for 6 h. After the completion, 5 cm3 10% aq. solution of NaHCO3 was added to the reaction mixture and the resulting solution was extracted with EtOAc (5 9 5 cm3). The combined ethylacetate extractions were washed with water (2 9 5 cm3)and brine (2 9 5 cm3), dried over anhydrous Na2SO4, and concentrated using vacuum rotary. The purification was carried out by column chromatography on silica gel (hexane/ethyl acetate = 8/2-4/6) to afford the desired product.
75% With tert.-butylnitrite; boron trifluoride diethyl etherate at 25℃; for 12h; Sealed tube;
  • 57
  • [ 4360-47-8 ]
  • [ 13141-38-3 ]
  • N-(3-phenylcinnolin-4-yl)cinnamamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
82% With tert.-butylnitrite; boron trifluoride diethyl etherate at 25℃; for 14h; Sealed tube;
76% With tert.-butylnitrite; saccharin at 20℃; for 6h; Green chemistry; Typical procedure for the synthesis of 4-amidocinnolines General procedure: 2-(Phenylethynyl)aniline (1a, 193 mg, 1.0 mmol) was added and stirred slowly to 36 mg Sac-H (0.2 mmol) in1.0 cm3 dry nitrile for 5 min at room temperature. Then 0.20 cm3 t-butyl nitrite (* 1.5 mmol) was added through a micropipette over 2 min and the flask was stoppered and stirring was continued at room temperature for 6 h. After the completion, 5 cm3 10% aq. solution of NaHCO3 was added to the reaction mixture and the resulting solution was extracted with EtOAc (5 9 5 cm3). The combined ethylacetate extractions were washed with water (2 9 5 cm3)and brine (2 9 5 cm3), dried over anhydrous Na2SO4, and concentrated using vacuum rotary. The purification was carried out by column chromatography on silica gel (hexane/ethyl acetate = 8/2-4/6) to afford the desired product.
  • 58
  • [ 536-74-3 ]
  • [ 62926-91-4 ]
  • [ 13141-38-3 ]
  • 59
  • [ 13141-38-3 ]
  • [ 13066-19-8 ]
YieldReaction ConditionsOperation in experiment
85% With chloro(1,5-cyclooctadiene)rhodium(I) dimer; potassium carbonate; bis(pinacol)diborane In isopropyl alcohol; acetonitrile at 70℃; for 3h; Inert atmosphere; 10 Example 10O Aminoarylsulfonic olefin J Preparation: 25mLSchlenk to dry reaction tube was added o-hydroxy diphenyl acetylene compound (38.6mg, 0.2mmol), followed by bis (pinacolato) borate (60.9mg, 0.24mmol), [Rh (cod) Cl]2(4.0mg, 0.008mmol), potassium carbonate (82.8mg, 0.6mmol), under nitrogen, was added acetonitrile (0.8 mL of), isopropanol (444mg, 6mmol), 70 reaction 3h.After completion of the reaction, the solvent was removed under reduced pressure, column chromatography (petroleum ether / acetonitrile = 30/1, volume ratio) to give the desired product J.Experimental data of the compound: Whitesolid, isolatedyield85%,
  • 60
  • [ 7188-38-7 ]
  • [ 13141-38-3 ]
  • [ 106-49-0 ]
  • (E)-N-(1-(tert-butyl)-3-phenylpyrrolo[2,3-b]indol-2(1H)-ylidene)-4-methylaniline [ No CAS ]
YieldReaction ConditionsOperation in experiment
67% Stage #1: tert-butylisonitrile; 2-phenylethynylaniline; <i>p</i>-toluidine With silver trifluoromethanesulfonate; cobalt acetylacetonate In 1,4-dioxane at 120℃; for 24h; Inert atmosphere; Schlenk technique; Stage #2: In 1,4-dioxane at 20℃; for 5h; stereoselective reaction; Typical procedure for the synthesis of products 4b Under a nitrogen atmosphere, 2-(phenylethynyl)aniline (1b, 96.5 mg, 0.5 mmol), p-toluidine (3a, 64.2 mg, 0.6 mmol, 1.2 equiv), Co(acac)2 (12.8 mg, 0.05 mmol, 10 mol %) and AgOTf (12.8 mg, 0.05 mmol, 10 mol %) were introduced into a 25-mL Schlenk reaction flask, tert-butyl isocyanide (2, 99.6 mg, 1.2 mmol, 2.4 equiv) and 1,4-dioxane (4.0 mL) were then successively added into this reaction mixture. The reaction system was stirred at 120 °C for 24 h. After the completion of the reaction (monitored by TLC), the reaction mixture was continuously stirred at room temperature under air conditions for 5 h until the reaction solution turned red. Next, the solvent was removed under vacuum. The residue was separated by column chromatography on silica gel (eluent, petroleum ether/ethylacetate) to afford the pure red solid 4b. (E)-N-(1-(tert-Butyl)-3-phenylpyrrolo[2,3-b]indol-2(1H)-ylidene)-4-methylaniline (4b) Red solid, mp 149-150 °C. 1H NMR (400 MHz, CDCl3) δ = 7.19-6.95 (m, 8H, Ar-H), 6.71 (s, 1H, Ar-H), 6.68-6.43 (m, 4H, Ar-H), 2.10 (s, 3H, CH3), 1.84 (s, 9H, CH3). 13C NMR (100 MHz, CDCl3) δ = 172.4, 163.2, 156.3, 144.1, 142.5, 132.8, 132.3, 131.9, 128.4, 128.2, 128.2, 127.7, 127.3, 123.6, 123.4, 122.5, 121.2, 118.9, 58.8, 29.8, 20.6. HRMS (TOF-APCI): m/z calcd for: C27H25N3, 392.2127 [M+H]+; found: 392.2154.
  • 61
  • [ 614-20-0 ]
  • [ 13141-38-3 ]
  • 3-oxo-3-phenyl-N-(2-(phenylethynyl)phenyl)propanamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
95% With dicyclohexyl-carbodiimide In chloroform at 20℃; for 16h; Typical procedure for the preparation of 2-alkanoyl-N-[2-(phenylethynyl)phenyl]acetamide: General procedure: A solution of N-benzyl-4-methyl-2-(phenylethynyl)phenylamine (200 mg, 0.67 mmol), 2-benzoylacetic acid (133 mg, 0.81 mmol) and DCC (180 mg, 0.87 mmol) in chloroform (10 mL) was stirred at room temperature for 16 h. The reaction mixture was then diluted with 100 mL of ethyl acetate washed with water (3×50 mL), dried (Na2SO4), and concentrated in vacuo. The residue was chromatographed over 20 g of silica gel (eluted with 20:1 hexane-ethyl acetate) to give 294 mg (99%) of 4a.
  • 62
  • [ 1045821-71-3 ]
  • [ 13141-38-3 ]
  • C15H9F3O2S2 [ No CAS ]
YieldReaction ConditionsOperation in experiment
73% Stage #1: 2-phenylethynylaniline With tert.-butylnitrite; boron trifluoride diethyl etherate In acetonitrile Cooling with ice; Stage #2: N-[(trifluoromethyl)sulfanyl]aniline With 1-aminomorpholine; bismuth(III) chloride; 1,4-diazabicyclo [2.2.2] octane-1,4-diium-1,4-disulfinate In acetonitrile at 80 - 100℃; 5 Example 5 Air atmosphere,1.8 parts by weight of t-butyl nitrite was placed in an ice-water bathAnd 1.5 parts by weight of 2-phenylethynylaniline was added dropwiseAnd 1.8 parts by weight of boron trifluoride diethyl ether in acetonitrile,Magnetic stirrer for 2-3 minutes.then,To the reaction system0.6 part by weight of DABSO (DABCO · (SO2) 2) was added,1.0 part by weight of N-aminomorpholine,1.3 parts by weight of N-trifluoromethylthioanilineAnd 2.0 parts by weight of bismuth chloride.The temperature of the system was raised to 80-100 ,The reaction was continued for 6-12 hours,The reaction was monitored by TLC until complete reaction.The reaction solution was extracted with ethyl acetate at the time of post-Anhydrous Na2SO4 dry,The purified product aryl trifluoromethanesulfonate 2e was isolated by flash column chromatography on a decompressed, solvent-dried solvent.Isolated yield: 73%
  • 63
  • [ 19241-24-8 ]
  • [ 13141-38-3 ]
  • 2-(tert-butyl)-11-phenyl-6H-indolo[2,3-b]quinoline [ No CAS ]
YieldReaction ConditionsOperation in experiment
76% With silver carbonate In dimethyl sulfoxide at 130℃; for 0.5h; Microwave irradiation; Sealed tube;
  • 64
  • [ 13141-38-3 ]
  • [ 187344-92-9 ]
  • 9-(3,5-dimethylphenyl)-11,13-dimethyl-9H-tribenzo[b,e,g]phosphindole 9-oxide [ No CAS ]
  • 65
  • [ 13141-38-3 ]
  • [ 80-17-1 ]
  • [ 106345-32-8 ]
YieldReaction ConditionsOperation in experiment
80% With iodine; toluene-4-sulfonic acid In 1,4-dioxane at 110℃; for 0.25h; Microwave irradiation; General Procedure for the synthesis of compounds 3aa-3ga General procedure: To a microwave vial, a mixture of 2-alkynylaniline (1 equiv), sulfonyl hydrazide (1.5 equiv), I2 (10 mol%) and pTSA (50 mol%) was taken in 1,4-dioxane irradiated for 15 min at 110°C, 100W in CEM microwave synthesizer. The progress and completion of reaction is monitored by TLC using EtOAc/n-Hexane (1:10) as an eluent. The reaction mixture was then cooled to room temperature and extracted with ethyl acetate. The combined organic phase was washed with sodium thiosulphate (50 mL) and dried over Na2SO4. After filtration and evaporation of the solvents in vacuum, the mixture of products was separated by column chromatography on silica gel (EtOAc/n-hexane: 1:10) to yield the desired product 3.
56% With (3-phenylallyl)(chloro)-[1,3-bis(2,6-diisopropylphenyl)-4,5-dihydroimidazol-2-ylidene]palladium(II); sodium thiosulfate; 3-(2-hydroxyethyl)-1-methyl-1H-imidazol-3-ium chloride at 100℃; for 16h; Green chemistry;
  • 66
  • [ 13141-38-3 ]
  • [ 1576-35-8 ]
  • [ 1213786-14-1 ]
YieldReaction ConditionsOperation in experiment
85% With iodine; toluene-4-sulfonic acid In 1,4-dioxane at 110℃; for 0.25h; Microwave irradiation; General Procedure for the synthesis of compounds 3aa-3ga General procedure: To a microwave vial, a mixture of 2-alkynylaniline (1 equiv), sulfonyl hydrazide (1.5 equiv), I2 (10 mol%) and pTSA (50 mol%) was taken in 1,4-dioxane irradiated for 15 min at 110°C, 100W in CEM microwave synthesizer. The progress and completion of reaction is monitored by TLC using EtOAc/n-Hexane (1:10) as an eluent. The reaction mixture was then cooled to room temperature and extracted with ethyl acetate. The combined organic phase was washed with sodium thiosulphate (50 mL) and dried over Na2SO4. After filtration and evaporation of the solvents in vacuum, the mixture of products was separated by column chromatography on silica gel (EtOAc/n-hexane: 1:10) to yield the desired product 3.
  • 67
  • [ 1950-68-1 ]
  • [ 13141-38-3 ]
  • [ 116757-23-4 ]
YieldReaction ConditionsOperation in experiment
82% With iodine; toluene-4-sulfonic acid; In 1,4-dioxane; at 110℃; for 0.25h;Microwave irradiation; General procedure: To a microwave vial, a mixture of 2-alkynylaniline (1 equiv), sulfonyl hydrazide (1.5 equiv), I2 (10 mol%) and pTSA (50 mol%) was taken in 1,4-dioxane irradiated for 15 min at 110C, 100W in CEM microwave synthesizer. The progress and completion of reaction is monitored by TLC using EtOAc/n-Hexane (1:10) as an eluent. The reaction mixture was then cooled to room temperature and extracted with ethyl acetate. The combined organic phase was washed with sodium thiosulphate (50 mL) and dried over Na2SO4. After filtration and evaporation of the solvents in vacuum, the mixture of products was separated by column chromatography on silica gel (EtOAc/n-hexane: 1:10) to yield the desired product 3.
  • 68
  • [ 13141-38-3 ]
  • [ 2266-41-3 ]
  • [ 1213786-17-4 ]
YieldReaction ConditionsOperation in experiment
78% With iodine; toluene-4-sulfonic acid In 1,4-dioxane at 110℃; for 0.25h; Microwave irradiation; General Procedure for the synthesis of compounds 3aa-3ga General procedure: To a microwave vial, a mixture of 2-alkynylaniline (1 equiv), sulfonyl hydrazide (1.5 equiv), I2 (10 mol%) and pTSA (50 mol%) was taken in 1,4-dioxane irradiated for 15 min at 110°C, 100W in CEM microwave synthesizer. The progress and completion of reaction is monitored by TLC using EtOAc/n-Hexane (1:10) as an eluent. The reaction mixture was then cooled to room temperature and extracted with ethyl acetate. The combined organic phase was washed with sodium thiosulphate (50 mL) and dried over Na2SO4. After filtration and evaporation of the solvents in vacuum, the mixture of products was separated by column chromatography on silica gel (EtOAc/n-hexane: 1:10) to yield the desired product 3.
  • 69
  • [ 13141-38-3 ]
  • [ 2751-25-9 ]
  • [ 1170720-88-3 ]
YieldReaction ConditionsOperation in experiment
80% With iodine; toluene-4-sulfonic acid In 1,4-dioxane at 110℃; for 0.25h; Microwave irradiation; General Procedure for the synthesis of compounds 3aa-3ga General procedure: To a microwave vial, a mixture of 2-alkynylaniline (1 equiv), sulfonyl hydrazide (1.5 equiv), I2 (10 mol%) and pTSA (50 mol%) was taken in 1,4-dioxane irradiated for 15 min at 110°C, 100W in CEM microwave synthesizer. The progress and completion of reaction is monitored by TLC using EtOAc/n-Hexane (1:10) as an eluent. The reaction mixture was then cooled to room temperature and extracted with ethyl acetate. The combined organic phase was washed with sodium thiosulphate (50 mL) and dried over Na2SO4. After filtration and evaporation of the solvents in vacuum, the mixture of products was separated by column chromatography on silica gel (EtOAc/n-hexane: 1:10) to yield the desired product 3.
  • 70
  • [ 2297-64-5 ]
  • [ 13141-38-3 ]
  • [ 1285494-73-6 ]
YieldReaction ConditionsOperation in experiment
77% With iodine; toluene-4-sulfonic acid In 1,4-dioxane at 110℃; for 0.25h; Microwave irradiation; General Procedure for the synthesis of compounds 3aa-3ga General procedure: To a microwave vial, a mixture of 2-alkynylaniline (1 equiv), sulfonyl hydrazide (1.5 equiv), I2 (10 mol%) and pTSA (50 mol%) was taken in 1,4-dioxane irradiated for 15 min at 110°C, 100W in CEM microwave synthesizer. The progress and completion of reaction is monitored by TLC using EtOAc/n-Hexane (1:10) as an eluent. The reaction mixture was then cooled to room temperature and extracted with ethyl acetate. The combined organic phase was washed with sodium thiosulphate (50 mL) and dried over Na2SO4. After filtration and evaporation of the solvents in vacuum, the mixture of products was separated by column chromatography on silica gel (EtOAc/n-hexane: 1:10) to yield the desired product 3.
  • 71
  • [ 2751-27-1 ]
  • [ 13141-38-3 ]
  • 3-((4-iodophenyl)thio)-2-phenyl-1H-indole [ No CAS ]
YieldReaction ConditionsOperation in experiment
79% With iodine; toluene-4-sulfonic acid; In 1,4-dioxane; at 110℃; for 0.25h;Microwave irradiation; General procedure: To a microwave vial, a mixture of 2-alkynylaniline (1 equiv), sulfonyl hydrazide (1.5 equiv), I2 (10 mol%) and pTSA (50 mol%) was taken in 1,4-dioxane irradiated for 15 min at 110C, 100W in CEM microwave synthesizer. The progress and completion of reaction is monitored by TLC using EtOAc/n-Hexane (1:10) as an eluent. The reaction mixture was then cooled to room temperature and extracted with ethyl acetate. The combined organic phase was washed with sodium thiosulphate (50 mL) and dried over Na2SO4. After filtration and evaporation of the solvents in vacuum, the mixture of products was separated by column chromatography on silica gel (EtOAc/n-hexane: 1:10) to yield the desired product 3.
  • 72
  • [ 2937-05-5 ]
  • [ 13141-38-3 ]
  • [ 1213786-18-5 ]
YieldReaction ConditionsOperation in experiment
75% With iodine; toluene-4-sulfonic acid In 1,4-dioxane at 110℃; for 0.25h; Microwave irradiation; General Procedure for the synthesis of compounds 3aa-3ga General procedure: To a microwave vial, a mixture of 2-alkynylaniline (1 equiv), sulfonyl hydrazide (1.5 equiv), I2 (10 mol%) and pTSA (50 mol%) was taken in 1,4-dioxane irradiated for 15 min at 110°C, 100W in CEM microwave synthesizer. The progress and completion of reaction is monitored by TLC using EtOAc/n-Hexane (1:10) as an eluent. The reaction mixture was then cooled to room temperature and extracted with ethyl acetate. The combined organic phase was washed with sodium thiosulphate (50 mL) and dried over Na2SO4. After filtration and evaporation of the solvents in vacuum, the mixture of products was separated by column chromatography on silica gel (EtOAc/n-hexane: 1:10) to yield the desired product 3.
  • 73
  • [ 6775-66-2 ]
  • [ 13141-38-3 ]
  • 3-((2,5-dichlorophenyl)thio)-2-phenyl-1H-indole [ No CAS ]
YieldReaction ConditionsOperation in experiment
72% With iodine; toluene-4-sulfonic acid In 1,4-dioxane at 110℃; for 0.25h; Microwave irradiation; General Procedure for the synthesis of compounds 3aa-3ga General procedure: To a microwave vial, a mixture of 2-alkynylaniline (1 equiv), sulfonyl hydrazide (1.5 equiv), I2 (10 mol%) and pTSA (50 mol%) was taken in 1,4-dioxane irradiated for 15 min at 110°C, 100W in CEM microwave synthesizer. The progress and completion of reaction is monitored by TLC using EtOAc/n-Hexane (1:10) as an eluent. The reaction mixture was then cooled to room temperature and extracted with ethyl acetate. The combined organic phase was washed with sodium thiosulphate (50 mL) and dried over Na2SO4. After filtration and evaporation of the solvents in vacuum, the mixture of products was separated by column chromatography on silica gel (EtOAc/n-hexane: 1:10) to yield the desired product 3.
  • 74
  • [ 16182-15-3 ]
  • [ 13141-38-3 ]
  • 3-(mesitylthio)-2-phenyl-1H-indole [ No CAS ]
YieldReaction ConditionsOperation in experiment
76% With iodine; toluene-4-sulfonic acid; In 1,4-dioxane; at 110℃; for 0.25h;Microwave irradiation; General procedure: To a microwave vial, a mixture of 2-alkynylaniline (1 equiv), sulfonyl hydrazide (1.5 equiv), I2 (10 mol%) and pTSA (50 mol%) was taken in 1,4-dioxane irradiated for 15 min at 110C, 100W in CEM microwave synthesizer. The progress and completion of reaction is monitored by TLC using EtOAc/n-Hexane (1:10) as an eluent. The reaction mixture was then cooled to room temperature and extracted with ethyl acetate. The combined organic phase was washed with sodium thiosulphate (50 mL) and dried over Na2SO4. After filtration and evaporation of the solvents in vacuum, the mixture of products was separated by column chromatography on silica gel (EtOAc/n-hexane: 1:10) to yield the desired product 3.
  • 75
  • [ 36331-57-4 ]
  • [ 13141-38-3 ]
  • 3-(benzylthio)-2-phenyl-1H-indole [ No CAS ]
YieldReaction ConditionsOperation in experiment
70% With iodine; toluene-4-sulfonic acid; In 1,4-dioxane; at 110℃; for 0.25h;Microwave irradiation; General procedure: To a microwave vial, a mixture of 2-alkynylaniline (1 equiv), sulfonyl hydrazide (1.5 equiv), I2 (10 mol%) and pTSA (50 mol%) was taken in 1,4-dioxane irradiated for 15 min at 110C, 100W in CEM microwave synthesizer. The progress and completion of reaction is monitored by TLC using EtOAc/n-Hexane (1:10) as an eluent. The reaction mixture was then cooled to room temperature and extracted with ethyl acetate. The combined organic phase was washed with sodium thiosulphate (50 mL) and dried over Na2SO4. After filtration and evaporation of the solvents in vacuum, the mixture of products was separated by column chromatography on silica gel (EtOAc/n-hexane: 1:10) to yield the desired product 3.
  • 76
  • [ 52260-00-1 ]
  • [ 13141-38-3 ]
  • 2-phenyl-3-(thiophen-2-ylthio)-1H-indole [ No CAS ]
YieldReaction ConditionsOperation in experiment
70% With iodine; toluene-4-sulfonic acid In 1,4-dioxane at 110℃; for 0.25h; Microwave irradiation; General Procedure for the synthesis of compounds 3aa-3ga General procedure: To a microwave vial, a mixture of 2-alkynylaniline (1 equiv), sulfonyl hydrazide (1.5 equiv), I2 (10 mol%) and pTSA (50 mol%) was taken in 1,4-dioxane irradiated for 15 min at 110°C, 100W in CEM microwave synthesizer. The progress and completion of reaction is monitored by TLC using EtOAc/n-Hexane (1:10) as an eluent. The reaction mixture was then cooled to room temperature and extracted with ethyl acetate. The combined organic phase was washed with sodium thiosulphate (50 mL) and dried over Na2SO4. After filtration and evaporation of the solvents in vacuum, the mixture of products was separated by column chromatography on silica gel (EtOAc/n-hexane: 1:10) to yield the desired product 3.
  • 77
  • [ 65227-54-5 ]
  • [ 13141-38-3 ]
  • 3-(naphthalen-2-ylthio)-2-phenyl-1H-indole [ No CAS ]
YieldReaction ConditionsOperation in experiment
61% With iodine; toluene-4-sulfonic acid In 1,4-dioxane at 110℃; for 0.25h; Microwave irradiation; General Procedure for the synthesis of compounds 3aa-3ga General procedure: To a microwave vial, a mixture of 2-alkynylaniline (1 equiv), sulfonyl hydrazide (1.5 equiv), I2 (10 mol%) and pTSA (50 mol%) was taken in 1,4-dioxane irradiated for 15 min at 110°C, 100W in CEM microwave synthesizer. The progress and completion of reaction is monitored by TLC using EtOAc/n-Hexane (1:10) as an eluent. The reaction mixture was then cooled to room temperature and extracted with ethyl acetate. The combined organic phase was washed with sodium thiosulphate (50 mL) and dried over Na2SO4. After filtration and evaporation of the solvents in vacuum, the mixture of products was separated by column chromatography on silica gel (EtOAc/n-hexane: 1:10) to yield the desired product 3.
  • 78
  • (4-bromophenyl)(4'-methoxyphenyl)iodonium triflate [ No CAS ]
  • [ 124-38-9 ]
  • [ 13141-38-3 ]
  • C21H14BrNO2 [ No CAS ]
YieldReaction ConditionsOperation in experiment
88% With 1,4-diaza-bicyclo[2.2.2]octane; silver(I) acetate In dimethyl sulfoxide at 60℃; for 8h; Autoclave; 20 Example 20 Add in the autoclave0.20 mmol of 2- (phenylethynyl) aniline,0.24 mmol of 4-bromo-4'-methoxydiphenyliodonium triflate,0.04 mmol silver acetate, 0.02 mmolDiazabicyclo [2.2.2] octane (DABCO), 2 ml of DMSO,Charged with 1MPa of CO2, the reaction was stirred at 60 ° C for 8 hours,Stop heating and stirring, cool to room temperature, and slowly vent unreacted CO2.The reaction mixture was washed with 10 mL of water and extracted three times with ethyl acetate (10 mL each)The organic phases were combined and dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure,Then separated and purified by column chromatography to obtain the desired product.The column eluate used was a volume ratio of 2: 1 petroleum ether:Ethyl acetate mixed solvent, yield 88%.
  • 79
  • [ 124-38-9 ]
  • [ 13141-38-3 ]
  • (2-cyanophenyl)(4'-methoxyphenyl)iodonium triflate [ No CAS ]
  • C22H14N2O2 [ No CAS ]
YieldReaction ConditionsOperation in experiment
80% With 1,4-diaza-bicyclo[2.2.2]octane; silver(I) acetate In dimethyl sulfoxide at 60℃; for 8h; Autoclave; 21 Example 21 Add in the autoclave0.20 mmol of 2- (phenylethynyl) aniline,0.24 mmol of 2-cyano-4'-methoxydiphenyliodonium triflate,0.04 mmol silver acetate, 0.02 mmolDiazabicyclo [2.2.2] octane (DABCO), 2 ml of DMSO,Charged with 1MPa of CO2, the reaction was stirred at 60 ° C for 8 hours,Stop heating and stirring, cool to room temperature, and slowly vent unreacted CO2.The reaction mixture was washed with 10 mL of water and extracted three times with ethyl acetate (10 mL each)The organic phases were combined and dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure,Then separated and purified by column chromatography to obtain the desired product.The column eluate used was a volume ratio of 2: 1 petroleum ether:Ethyl acetate mixed solvent, yield 80%.
  • 80
  • [ 124-38-9 ]
  • [ 13141-38-3 ]
  • [ 139139-80-3 ]
  • 4-(mesityloxy)-3-phenylquinolin-2(1H)-one [ No CAS ]
YieldReaction ConditionsOperation in experiment
89% With 1,4-diaza-bicyclo[2.2.2]octane; silver(I) acetate In dimethyl sulfoxide at 60℃; for 8h; Autoclave; 12 Example 12 To the autoclave was added 0.20 mmol of 2- (phenylethynyl) aniline,0.24 mmol of bis (2,4,6-trimethylphenyl) iodonium triflate,0.04 mmol silver acetate, 0.02 mmolDiazabicyclo [2.2.2] octane (DABCO), 2 ml of DMSO,Charged with 6MPa of CO2, the reaction was stirred at 60 ° C for 8 hours, stop heating and stirring,Cool to room temperature and allow to vent slowly to unreacted CO2. The reaction solution was washed with 10mL water,Extract three times with ethyl acetate (10 mL each)The organic phases were combined and dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure,Then separated and purified by column chromatography to obtain the desired product.The column eluate used was a volume ratio of 2: 1 petroleum ether:Ethyl acetate mixed solvent, yield 89%.
  • 81
  • [ 13816-33-6 ]
  • [ 13141-38-3 ]
  • 2-(4-isopropylphenyl)-4-phenylquinazoline [ No CAS ]
YieldReaction ConditionsOperation in experiment
59% With potassium <i>tert</i>-butylate; oxygen; copper diacetate In dimethyl sulfoxide at 120℃; for 24h;
  • 82
  • [ 13141-38-3 ]
  • [ 4421-09-4 ]
  • [ 1229610-03-0 ]
YieldReaction ConditionsOperation in experiment
62% With potassium <i>tert</i>-butylate; oxygen; copper diacetate In dimethyl sulfoxide at 120℃; for 24h;
  • 83
  • [ 931-53-3 ]
  • [ 13141-38-3 ]
  • [ 108-94-1 ]
  • N-(1-(1-cyclohexyl)-1H-tetrazol-5-yl cyclohexyl)-2-(phenylethynyl)aniline [ No CAS ]
YieldReaction ConditionsOperation in experiment
75% Stage #1: 2-phenylethynylaniline; cyclohexanone In methanol at 20℃; for 2h; Stage #2: Cyclohexyl isocyanide With trimethylsilylazide In methanol for 24h; General Procedure for the Synthesis of Compounds 5a-i General procedure: 2-(Phenylethynyl)aniline in MeOH (5 ml) and cyclohexanone (1mmol) were stirred at room temperature for 2 h, then the requisiteisocyanide (1 mmol) and trimethylsilyl azide were added.The mixture was stirred for 24 h until the reaction was completed.Then, the desired product was either filtered off as awhite solid filtered for 5a-e (ketone derivatives) or purifiedusing column chromatography on silica gel (n-hexane/EtOAc,9:1) for 5f-i (aldehyde derivatives). The yields were in the rangeof 75-92%.
  • 84
  • [ 931-53-3 ]
  • [ 5441-51-0 ]
  • [ 13141-38-3 ]
  • N-(1-(1-cyclohexyl-1H-tetrazol-5-yl)-4- ethylcyclohexyl)-2(phenylethynyl)aniline [ No CAS ]
YieldReaction ConditionsOperation in experiment
72% Stage #1: 4-ethylcyclohexanone; 2-phenylethynylaniline In methanol at 20℃; for 2h; Stage #2: Cyclohexyl isocyanide With trimethylsilylazide In methanol for 24h; General Procedure for the Synthesis of Compounds 5a-i General procedure: 2-(Phenylethynyl)aniline in MeOH (5 ml) and cyclohexanone (1mmol) were stirred at room temperature for 2 h, then the requisiteisocyanide (1 mmol) and trimethylsilyl azide were added.The mixture was stirred for 24 h until the reaction was completed.Then, the desired product was either filtered off as awhite solid filtered for 5a-e (ketone derivatives) or purifiedusing column chromatography on silica gel (n-hexane/EtOAc,9:1) for 5f-i (aldehyde derivatives). The yields were in the rangeof 75-92%.
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Alkynes

Chemical Structure| 52670-38-9

[ 52670-38-9 ]

2-Ethynylaniline

Similarity: 0.92

Chemical Structure| 207226-02-6

[ 207226-02-6 ]

3-Ethynylaniline hydrochloride

Similarity: 0.79

Chemical Structure| 54060-30-9

[ 54060-30-9 ]

3-Ethynylaniline

Similarity: 0.79

Chemical Structure| 1173153-20-2

[ 1173153-20-2 ]

2-((4-Fluorophenyl)ethynyl)aniline

Similarity: 0.79

Chemical Structure| 221910-19-6

[ 221910-19-6 ]

2-((4-Chlorophenyl)ethynyl)aniline

Similarity: 0.78

Amines

Chemical Structure| 52670-38-9

[ 52670-38-9 ]

2-Ethynylaniline

Similarity: 0.92

Chemical Structure| 207226-02-6

[ 207226-02-6 ]

3-Ethynylaniline hydrochloride

Similarity: 0.79

Chemical Structure| 54060-30-9

[ 54060-30-9 ]

3-Ethynylaniline

Similarity: 0.79

Chemical Structure| 1173153-20-2

[ 1173153-20-2 ]

2-((4-Fluorophenyl)ethynyl)aniline

Similarity: 0.79

Chemical Structure| 221910-19-6

[ 221910-19-6 ]

2-((4-Chlorophenyl)ethynyl)aniline

Similarity: 0.78