* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Reference：
[1] Advanced Synthesis and Catalysis, 2018, vol. 360, # 21, p. 4197 - 4204
[2] Journal of the Chemical Society, 1949, p. 1089,1096
[3] Journal of the Chemical Society, 1932, p. 696,703
[4] Journal of the American Chemical Society, 1948, vol. 70, p. 2310,2313
[5] Recueil des Travaux Chimiques des Pays-Bas, 1923, vol. 42, p. 522
[6] Phosphorus, Sulfur and Silicon and the Related Elements, 1990, vol. 53, # 1-4, p. 43 - 67
[7] Advanced Synthesis and Catalysis, 2004, vol. 346, # 7, p. 767 - 776
[8] Patent: US2001/23257, 2001, A1,
[9] Chimia, 2008, vol. 62, # 1-2, p. 23 - 28
2
[ 625-95-6 ]
[ 1256294-83-3 ]
[ 49617-83-6 ]
Reference：
[1] Bioorganic and Medicinal Chemistry, 2009, vol. 17, # 17, p. 6390 - 6401
3
[ 625-95-6 ]
[ 122-04-3 ]
[ 636-98-6 ]
[ 1711-06-4 ]
Reference：
[1] Journal of the American Chemical Society, 2018, vol. 140, # 32, p. 10140 - 10144
4
[ 625-95-6 ]
[ 100-20-9 ]
[ 1711-02-0 ]
[ 1711-06-4 ]
Reference：
[1] Journal of the American Chemical Society, 2018, vol. 140, # 32, p. 10140 - 10144
5
[ 625-95-6 ]
[ 618-51-9 ]
Reference：
[1] Synthetic Communications, 2010, vol. 40, # 19, p. 2922 - 2929
[2] Journal of Chemical Education, 1938, vol. 15, p. 217
[3] Journal of the Chinese Chemical Society (Peking), 1946, vol. 14, p. 24,29
6
[ 15226-74-1 ]
[ 625-95-6 ]
[ 6148-64-7 ]
[ 33166-79-9 ]
Yield
Reaction Conditions
Operation in experiment
73%
With 1H-imidazole; palladium diacetate; triethylamine; [5-(diphenylphosphanyl)-9,9-dimethyl-9H-xanthen-4-yl]diphenylphosphane; magnesium chloride In tetrahydrofuran at 90℃; for 0.5 h; Microwave irradiation
To a stirred mixture of aryl or heteroaryl halide(Br, I) (0.5 mmol), potassium mono ethyl malonate (0.75 mmol) in THF (10 mL) taken in a 30 mL microwave vial, was added Pd(OAc)2(5 molpercent), Xantphos (5 mol percent), MgCl2 (0.75), Et3N ( 0.75mmol), imidazole (1 mmol) followed by Co2(CO)8 (0.15mmol). The vial was sealed immediately and microwave irradiated at 90°C for 30min. The reaction mixture was concentrated and diluted with ethyl acetate and water. The ethyl acetate layer was separated, dried over sodium sulphate and concentrated. The crude product obtained was purified by column chromatography to get the pure compound.
Reference：
[1] Journal of the American Chemical Society, 2002, vol. 124, # 10, p. 2245 - 2258
[2] Journal of the American Chemical Society, 2001, vol. 123, # 13, p. 3183 - 3185
[3] Journal of the Chemical Society, 1949, p. 1089,1096
8
[ 625-95-6 ]
[ 618-91-7 ]
Reference：
[1] Journal of the Chinese Chemical Society (Peking), 1946, vol. 14, p. 24,29
9
[ 625-95-6 ]
[ 766-82-5 ]
Reference：
[1] Patent: US2002/169200, 2002, A1,
[2] Bulletin of the Academy of Sciences of the USSR, Division of Chemical Science (English Translation), 1967, p. 460 - 461[3] Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, 1967, # 2, p. 466 - 467
[4] Journal of Organic Chemistry, 1977, vol. 42, # 15, p. 2626 - 2629
[5] Organic Letters, 2014, vol. 16, # 3, p. 948 - 951
[6] Synthesis (Germany), 2014, vol. 46, # 24, p. 3415 - 3422
[7] Chemistry - A European Journal, 2015, vol. 21, # 4, p. 1463 - 1467
[8] Organic Letters, 2015, vol. 17, # 10, p. 2522 - 2525
[9] Organic and Biomolecular Chemistry, 2015, vol. 13, # 35, p. 9186 - 9189
[10] Photochemical and Photobiological Sciences, 2017, vol. 16, # 10, p. 1495 - 1501
10
[ 625-95-6 ]
[ 74-86-2 ]
[ 766-82-5 ]
Reference：
[1] Chemical Science, 2017, vol. 8, # 5, p. 3623 - 3627
11
[ 201230-82-2 ]
[ 625-95-6 ]
[ 109-89-7 ]
[ 134-62-3 ]
Yield
Reaction Conditions
Operation in experiment
85%
With potassium carbonate In N,N-dimethyl-formamide at 120℃; for 2 h; Autoclave
General procedure: Catalytic reactions were carried out in a Teflon-linedstainless steel autoclave (50 mL) equipped with a magneticstirrer bar and an automatic temperature controller. In atypical experiment, 0.5 molpercent Pd, aryl iodide (1.0 mmol),amine (3.0 mmol) and K2CO3 (414.6 mg, 3.0 mmol) wereadded to DMF (4 mL) and allowed to react under COatmosphere (1 bar) at 120 C for 2–4 h. After the reaction,the reactor was cooled to room temperature. The reactionmixture was centrifuged at 5000 rpm for 10 min, and theclear supernatant, to which was added ethyl phenylacetateas an internal standard, was analyzed with GC. For the studyof substrate scope, after completion of the reaction, thecatalyst was centrifuged at 5000 rpm for 10 min and theclear supernatant was diluted with 20 percent HCl and extractedwith diethyl ether. The organic layer was washed withsaturated NaHCO3 and NaCl solutions, respectively, driedover anhydrous Na2SO4 and evaporated under vacuum afterfiltration. The residue obtained was purified by columnchromatography (silica gel, 200–300 meshes; petroleum–ethyl acetate, 20:1) to afford the pure products. All productswere confirmed by 1H and 13C NMR analyses. For therecycling experiment, the solid catalyst was separated bycentrifugation from the reaction mixture, washed threetimes with the reaction solvent (DMF) and then engaged ina new catalytic cycle under the same reaction conditions.All the synthesized amides are known products, and wehave reported recently [28].
84%
With triethylamine In N,N-dimethyl acetamide at 130℃; for 1.5 h; Autoclave; Green chemistry
General procedure: reactionThe catalytic reactions were carried out in a 150 ml stainlesssteel autoclave equipped with a mechanical stirrer. Palladium cat-alyst (0.07 mmol), aryl iodide (10 mmol), amine (20 mmol), base(30 mmol) and solvent (15 ml) were loaded into the reactor. Theautoclave was purged three times with CO and pressurized to1.5 MPa with CO at room temperature. The reaction was carriedout at 130C for appropriate time. After the reaction, the reactorwas cooled to room temperature and depressurized. The reac-tion mixture was centrifuged at 5000 rpm for 10 min and the clearsupernatant which was added naphthalene as an internal standardwas analyzed with GC. For the study of substrate scope, after com-pletion of the reaction, the catalyst was centrifuged at 5000 rpmfor 10 min and the clear supernatant was diluted with 20percent HCland extracted with diethyl ether. The organic layer was washedwith saturated NaHCO3and NaCl solutions, respectively, dried overanhydrous Na2SO4, and evaporated under vacuum after filtration.The residue obtained was purified by column chromatography (sil-ica gel, 200–300 mesh; petroleum-ethyl acetate, 20:1) to afford thepure products.
Reference：
[1] Transition Metal Chemistry, 2016, vol. 41, # 1, p. 1 - 7
[2] Applied Catalysis A: General, 2014, vol. 475, p. 40 - 47
12
[ 625-95-6 ]
[ 17933-03-8 ]
Reference：
[1] Journal of the American Chemical Society, 2010, vol. 132, # 40, p. 14006 - 14008
13
[ 625-95-6 ]
[ 637-04-7 ]
Reference：
[1] Chinese Journal of Chemistry, 2018, vol. 36, # 11, p. 1003 - 1006
14
[ 625-95-6 ]
[ 531-91-9 ]
[ 65181-78-4 ]
Reference：
[1] Journal of Physical Chemistry, 1984, vol. 88, # 20, p. 4707 - 4714
15
[ 625-95-6 ]
[ 75903-62-7 ]
[ 72811-73-5 ]
Yield
Reaction Conditions
Operation in experiment
53.1%
With copper; potassium carbonate In butan-1-ol
EXAMPLE 1 Preparation of 3-Sulfonamido-4-(3'-methylphenyl)aminopyridine (formula I: R1=3'-Methyl; R2=H). Method A. To an oven dried flask equipped with magnetic stirrer, condenser and thermometer and cooled under nitrogen was added 3-sulfonamido-4-amino pyridine (2.0 g, 11.5 mmol), 3-iodotoluene (3.77 g, 17.2 mmol), potassium carbonate (4.0 g, 28.9 mmol), and n-butanol (20 mL) and the suspension was stirred for 10 minutes, at which point copper (2.94 g, 46.2 mmol) was added. The mixture was heated to 118° C. and stirring was continued for about 24 h. The reaction mixture was cooled to 45-50° C. and a mixture of methanol-water (70:30 v/v) was added. The reaction mixture was filtered through a pad of Celite.(TM).. The solution was evaporated under vacuum to 9 mL, then water (10 mL) was added and the mixture was evaporated to 9 mL. Another portion of water (10 mL) was added and the mixture was evaporated again to 9 mL. Water (12 mL) and a saturated sodium thiosulfate solution (5 mL) was added and the mixture was stirred for 45 minutes. The mixture was extracted twice with dichloromethane (24 mL total) and the organic phase was evaporated to dryness under vacuum. Water (12 mL) was added and the solution was acidified to pH=6 with glacial acetic acid (1 mL). The mixture was evaporated to dryness under vacuum. Ethanol (15 mL) was added and the mixture evaporated to dryness under vacuum. The crude mixture was chromatographed on silica gel (initially 4percent methanol in dichloromethane, then polarity increased to 9percent methanol in dichloromethane), to give 3-sulfonamido-4-(3'-methylphenyl) aminopyridine as a white powder (1.61 g, 53.1percent yield). Mass spectral data: Direct electron impact: 264 (M+1, 100percent). 1H NMR (DMSO-d6) δ: 8.65 (s, 1H), 8.24 (d, 1H, J=5.5 Hz), 8.05 (s, 1H, D2O exchangeable), 7.76 (s, 2H, D2O exchangeable), 7.33 (dd, 1H, J=7.54, 7.51 Hz), 7.12-7.04 (m, 3H), 6.98 (d, 1H, J=5.5 Hz), 2.33 (s, 3H). 13C NMR (DMSO-d6) δ: 152.69, 149.04, 147.30, 139.20, 138.58, 138.08, 129.42, 126.03, 124.11, 122.98, 120.59, 107.83, 20.89.
Reference：
[1] Patent: US6593475, 2003, B1,
16
[ 625-95-6 ]
[ 87199-17-5 ]
[ 400744-83-4 ]
Yield
Reaction Conditions
Operation in experiment
71.3%
With bis-triphenylphosphine-palladium(II) chloride; potassium carbonate In water; acetonitrile at 20℃;
3-Iodotoluene (0.87 g, 4 mmol), 4-formylphenylboronicacid (0.72 g, 4.8 mmol), K2CO3 (2.0 g, 14.4 mmol)and [P(Ph)3]2PdCl2 (85 mg, 0.121 mmol) weretaken in 100 mL single neck round bottom flask, added 10:10 mLwater-acetonitrile. The reaction mixture was stirred at room temperature overnight.And the reaction was monitored by thin-layer chromatography (TLC). After thereaction completed, the reaction mixture was filtered. The filtrate wasextracted with EtOAc (15 mL x 3). Thecombined organic layer was dried on anhydrous Na2SO4 and concentrated;the crude product was purified by column chromatography over silica gel toafford target product with high yield of 71.3percent.
Reference：
[1] Bioorganic and Medicinal Chemistry Letters, 2017, vol. 27, # 24, p. 5429 - 5435
With N-Bromosuccinimide; dibenzoyl peroxide; In chlorobenzene;
a 1 -bromomethyl-3-iodobenzene 4.4 g of 3-iodotoluene were dissolved in 10 ml of chlorobenzene and, at 132 C., mixed a little at a time with a mixture of 3.6 g of N-bromo-succinimide and 100 mg of dibenzoyl peroxide. The mixture was stirred at 132 C. for another hour and, after cooling, diluted with 100 ml of EA and then washed, first with 100 ml of a saturated aqueous Na2SO3 solution and then with 100 ml of a saturated aqueous Na2CO3 solution. The organic phase was dried over MgSO4 and the solvent was removed under reduced pressure. This gave 5.3 g of a pale yellow oil. Rf(EA/HEP 1:8)=0.44; MS (ES+): 298 (M+H)+
5,11-di-m-tolyl-5,11-dihydroindolo[3,2-b]carbazole[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With potassium carbonate; In water; toluene;
Preparation of 5,11-di-m-tolyl-<strong>[6336-32-9]5,11-dihydro<strong>[6336-32-9]indolo[3,2-b]carbazole</strong></strong>: A 200-milliliter 3-necked round bottom flask equipped with a mechanical stirrer, reflux condenser, and argon inlet was purged with argon and then charged with <strong>[6336-32-9]5,11-dihydro<strong>[6336-32-9]indolo[3,2-b]carbazole</strong></strong> (5.1 grams, 0.02 mol), 3-iodotoluene (8.69 grams, 0.04 mol), copper sulfate pentahydrate (0.25 gram, 1.0 mmol), potassium carbonate (5.52 grams, 0.04 mol), and n-tridecane (5.0 milliliters). Under an argon atmosphere, the reaction mixture was heated to about 250°C with a heating mantle and allowed to proceed at this temperature to completion in about 6 hours. The mixture was cooled to about 100°C, and 100 milliliters of toluene and 15 milliliters of water were then added with vigorous stirring. The resulting two phase mixture was transferred into a separatory funnel and the layers separated. The organic phase, which contained the desired product, was washed with water, and treated with 25 grams of alumina under an argon atmosphere, and filtered.
With copper(I) oxide; caesium carbonate; imidazole-4-carboxylic acid; In acetonitrile; at 80℃; for 24h;
General procedure: To a screw-capped vial (4-mL) were added Cs2CO3 (1.0 mmol, 325 mg), Cu2O (0.005 mmol, 0.7 mg), 1H-imidazole-4-carboxylic acid (0.01 mmol, 1.1 mg) and acetonitrile (0.25 mL). The vial was sealed with septum and allowed to stir for a while; the iodoarene (0.5 mmol) and phenol (0.6 mmol) were then injected into the reaction mixture via a syringe. The septum was removed, and the vial was sealed with a screw cap. The reaction mixture was stirred at 80 oC for 24 h. The crude reaction mixture was diluted with CH2Cl2, filtered through a thin Celite pad, and concentrated in vacuo. The residue was isolated through a column chromatography by using hexane and ethyl acetate as eluent to give the pure product. Products 3a-v were obtained according to this procedure. The known structures were characterized by the 1H NMR and 13C NMR of reported literatures.1-3 Spectral data, 1H NMR and 13C NMR spectra for all the new compounds are listed below.
83%
With caesium carbonate; In tetrahydrofuran; at 150℃; for 3h;Inert atmosphere;Catalytic behavior;
General procedure: The catalytic O-arylation reactions were conducted in asealed stainless-steel reactor. A phenol (14 mmol), aryl halide(14 mmol), Cs2CO3 (14 mmol), tetrahydrofuran (THF, 10 mL),and the Cu2O/SiC catalyst (10 mg) were placed in the reactor.The reaction was performed under Ar at 150 C for 3 h. Afterthe reaction, the suspension was collected and centrifuged. Thesupernatant was analyzed using gas chromatography-massspectrometry (Bruker SCION SQ 456GC-MS, Germany). Theyields and TOFs were calculated based on the aryl halide usingthe following equations:Yield = Conversion (%) selectivity (%)= (1 - na/nb) x ntp/(ntp + nbp) x 100%TOF = Amount of aryl halides (mol) x conversion (%)x selectivity (%)/(mass of Cu2O/SiC (g) x Cu2O loading (%) xreaction time (h)/M[Cu2O] (g/mol))where na is the moles of aryl halide after reaction, nb is themoles of aryl halide before reaction, ntp is the moles of targetproduct after reaction, and nbp is the moles of byproduct afterreaction.
With pyridine; cesium fluoride; In dimethyl sulfoxide; at 105℃; for 2h;Inert atmosphere; Schlenk technique;
General procedure: An oven-dried Schlenk tube, containing a Teflon-coated magnetic stir bar was charged with CsF (228 mg, 1.5 mmol, 3 equiv) and bispinacolatodiboron (254 mg, 1 mmol, 2 equiv). Under an argon atmosphere, freshly distilled DMSO (0.4 mL), the appropriate aryl iodide (0.5mmol), and pyridine (0.4 to 1 equiv) were added successively. The reaction mixture was heated to 105 C and stirred for 2 h under argon.
76%
With potassium acetate; In N,N-dimethyl-formamide; at 30℃; for 3h;Inert atmosphere; Irradiation;
General procedure: Unless specified otherwise, all reactions were conducted in ambient Ar atmosphere at 30 C. A mixture of aryl halides (1mmol), B2pin2 (1.2 mmol, 305 mg), base (1 mmol, 98 mg), andPd/SiC catalyst (40 mg) was suspended in 10 mL ofN,N-dimethylformamide (DMF) in an oven-dried 25 mL quartzvial equipped with a magnetic stirring bar. During the reaction,the mixture was stirred at 500 rpm using a magnetic stirrerand then exposed to a xenon lamp with a wavelength range of375 to 800 nm (the spectral output is shown in Fig. S1). Alow-pass optical filter was employed to block wavelengths below400 nm. The light intensity was maintained at 0.65 W/cm2.The effect of the light wavelength on the catalytic performancewas investigated using various light-emitting diode (LED)lamps with different wavelengths. After reaction, the mixture was diluted with dichloromethane(DCM, 10 mL). The organic phase was extracted andfiltered through a millipore filter (pore size: 0.22 mum). Then, 0.5mmol of n-dodecane was added as an internal standard. Theproduct yield was determined by gas chromatography-massspectrometry (GC-MS, Bruker Scion SQ 456) using n-dodecaneas the internal calibration standard. The reported values arethe average of two experiments. The yields were calculatedbased on the amount of aryl halide. The residue was purified bycolumn chromatography on silica gel (200-300 mesh; eluant:hexane/ethyl acetate) to isolate the desired product.
89%Chromat.
With copper(II) ferrite; potassium tert-butylate; In N,N-dimethyl-formamide; at 20℃; for 12h;Green chemistry;
General procedure: 4-Iodoanisole (0.813 mmol, 200 mg), bis(pinacolato)diboron (1.219 mmol, 309 mg) were dissolved in 3 mL of dmf followed by copper ferrite nanoparticles (5mol% with respect to 4-iodoanisole) and potassiumtert-butoxide (1.219 mmol, 137 mg) were added to a 10 mLcapped vial and stirred at RT for time indicated. After stirring, the mixture was diluted with diethyl ether and filtered through celite bed. The filtrate was extracted with water (3 times) and the organic phase was dried over anhydrous MgSO4. The crude product was subjected to analyze by GC-MS. The conversion yield is accurately measured based on the consumption of 4-iodoanisole and the side product formed due to protodeiodination.
With potassium carbonate; In N,N-dimethyl-formamide; at 120℃; for 20h;Inert atmosphere;
General procedure: To a 10 mL glass tube aryl halide (1 mmol), K4FeCN6(0.6 mmol,220 mg), K2CO3(1.5 mmol, 207 mg), catalyst (10 mg), and 2 mL DMFwere added and mixture was stirred for appropriate reaction timeat 120C under argon atmosphere. The progress of the reactionwas monitored by GC analysis. After completion of the reaction,reaction mixture was washed with 5 mL water and crude productwas isolated using dichloromethane (5× 1 mL). Organic extractswere combined together, evaporated and purified by flash chro-matography using hexane/EtOAc to give the desired aryl cyanideproducts.
93%
With sodium carbonate; In N,N-dimethyl-formamide; at 120℃; for 3h;Schlenk technique;
General procedure: Aryl halide (1.5 mmol), Na2CO3 (1.8 mmol), K4[Fe(CN)6](0.2 mmol), Pd NPsFe3O4/chitosan/pumice hybrid beads (0.01 mol%), and DMF (5 mL) were put into a Schlenk tube and heated at 120 Cfor 3 h. After the cyanation reaction was completed, the resultingmixture was filtered. The filtrate was extracted with diethyl ether:waterat three times, and the organic phase dried on MgSO4. Finally, thedesired nitriles were obtained by evaporation of solvent, and they weresent to GC/MS, 1H NMR and 13C NMR analyses for characterizationstudies.
44%
With 3% Pd/ZrO2; sodium acetate; In N,N-dimethyl-formamide; isopropyl alcohol; at 55℃; for 12h;Irradiation;
To a 25 mL screw test tube was added 0.25 mmol of 3-methyl iodobenzene, 0.1mmol of cyanoating agent K4 [Fe (CN) 6] Sodium acetate 0. 25 mmol, 100 mg 3 wt% Pd / Zr 0.2, and then 7 mL of N, N-dimethylformamide and lmL isopropanol mixed organic solvent into a test tube, 400 W visible light source under magnetic stirring reaction, control Visible light intensity of 0.44W / cm2, anti Should be the temperature of 55 C, 12 hours after the reaction to stop the reaction, take a small amount of reaction solution by microporous membrane filtration, methanol solvent dilution And the liquid sample to be tested, the sample to be tested with 3-methyl iodobenzene standard, 3-methyl benzonitrile standard for high-performance liquid chromatography The conversion of the reaction substrate was 48.5%, the selectivity of the target product was 100%, and the liquid product yield was 48.5%. Post-treatment method for the use of cloth funnel filter washing catalyst, drying for recycling use; reaction solution by dichloromethane and water After extraction, the organic layer was concentrated and the final product, 3-methylbenzonitrile, was obtained by column chromatography. The isolated yield was 44%.
95%Chromat.
With potassium carbonate; In N,N-dimethyl-formamide; at 120℃; for 20h;Inert atmosphere;
General procedure: To a 10 mL glass tube aryl halide (1 mmol), K4FeCN6(0.6 mmol,220 mg), K2CO3(1.5 mmol, 207 mg), catalyst (10 mg), and 2 mL DMFwere added and mixture was stirred for appropriate reaction timeat 120C under argon atmosphere. The progress of the reactionwas monitored by GC analysis. After completion of the reaction,reaction mixture was washed with 5 mL water and crude productwas isolated using dichloromethane (5× 1 mL). Organic extractswere combined together, evaporated and purified by flash chro-matography using hexane/EtOAc to give the desired aryl cyanideproducts.
With potassium carbonate; In N,N-dimethyl-formamide; at 120℃; under 750.075 Torr; for 2h;Autoclave;
General procedure: Catalytic reactions were carried out in a Teflon-linedstainless steel autoclave (50 mL) equipped with a magneticstirrer bar and an automatic temperature controller. In atypical experiment, 0.5 mol% Pd, aryl iodide (1.0 mmol),amine (3.0 mmol) and K2CO3 (414.6 mg, 3.0 mmol) wereadded to DMF (4 mL) and allowed to react under COatmosphere (1 bar) at 120 C for 2-4 h. After the reaction,the reactor was cooled to room temperature. The reactionmixture was centrifuged at 5000 rpm for 10 min, and theclear supernatant, to which was added ethyl phenylacetateas an internal standard, was analyzed with GC. For the studyof substrate scope, after completion of the reaction, thecatalyst was centrifuged at 5000 rpm for 10 min and theclear supernatant was diluted with 20 % HCl and extractedwith diethyl ether. The organic layer was washed withsaturated NaHCO3 and NaCl solutions, respectively, driedover anhydrous Na2SO4 and evaporated under vacuum afterfiltration. The residue obtained was purified by columnchromatography (silica gel, 200-300 meshes; petroleum-ethyl acetate, 20:1) to afford the pure products. All productswere confirmed by 1H and 13C NMR analyses. For therecycling experiment, the solid catalyst was separated bycentrifugation from the reaction mixture, washed threetimes with the reaction solvent (DMF) and then engaged ina new catalytic cycle under the same reaction conditions.All the synthesized amides are known products, and wehave reported recently [28].
84%
With triethylamine; In N,N-dimethyl acetamide; at 130℃; under 15001.5 Torr; for 1.5h;Autoclave; Green chemistry;
General procedure: reactionThe catalytic reactions were carried out in a 150 ml stainlesssteel autoclave equipped with a mechanical stirrer. Palladium cat-alyst (0.07 mmol), aryl iodide (10 mmol), amine (20 mmol), base(30 mmol) and solvent (15 ml) were loaded into the reactor. Theautoclave was purged three times with CO and pressurized to1.5 MPa with CO at room temperature. The reaction was carriedout at 130C for appropriate time. After the reaction, the reactorwas cooled to room temperature and depressurized. The reac-tion mixture was centrifuged at 5000 rpm for 10 min and the clearsupernatant which was added naphthalene as an internal standardwas analyzed with GC. For the study of substrate scope, after com-pletion of the reaction, the catalyst was centrifuged at 5000 rpmfor 10 min and the clear supernatant was diluted with 20% HCland extracted with diethyl ether. The organic layer was washedwith saturated NaHCO3and NaCl solutions, respectively, dried overanhydrous Na2SO4, and evaporated under vacuum after filtration.The residue obtained was purified by column chromatography (sil-ica gel, 200-300 mesh; petroleum-ethyl acetate, 20:1) to afford thepure products.
With 1H-imidazole; palladium diacetate; triethylamine; 4,5-bis(diphenylphos4,5-bis(diphenylphosphino)-9,9-dimethylxanthenephino)-9,9-dimethylxanthene; magnesium chloride; In tetrahydrofuran; at 90℃; for 0.5h;Microwave irradiation;
To a stirred mixture of aryl or heteroaryl halide(Br, I) (0.5 mmol), potassium mono ethyl malonate (0.75 mmol) in THF (10 mL) taken in a 30 mL microwave vial, was added Pd(OAc)2(5 mol%), Xantphos (5 mol %), MgCl2 (0.75), Et3N ( 0.75mmol), imidazole (1 mmol) followed by Co2(CO)8 (0.15mmol). The vial was sealed immediately and microwave irradiated at 90C for 30min. The reaction mixture was concentrated and diluted with ethyl acetate and water. The ethyl acetate layer was separated, dried over sodium sulphate and concentrated. The crude product obtained was purified by column chromatography to get the pure compound.
With palladium diacetate; potassium carbonate; triphenylphosphine; In N,N-dimethyl-formamide; at 20 - 90℃; under 750.075 Torr; for 16h;Inert atmosphere;
General procedure: A mixture of Pd(OAc)2 (4.5 mg, 0.02 mmol), PPh3 (11.2 mg, 0.04 mmol), iodobenzene (1a) (82 mg, 0.4mmol), <strong>[936-59-4]3-chloropropiophenone</strong> (2a) (87 mg, 0.5 mmol), and K2CO3 (166 mg, 1.2 mmol) in DMF (2.5 mL) was stirred under a N2 atmosphere at room temperature for 10 min, and then heated at 90 C for 16 h. The reaction was then cooled to ambient temperature and diluted with CH2Cl2 (10 mL) before being filtered through a short pad of silica gel. The silica pad was rinsed with DCM (5 mL), and the combined filtrates were washed with brine (15 mL), dried over anhydrous Na2SO4. The solvent was then removed under reduced pressure to give the crude product as a residue, which was purified by silica gel column chromatography eluting with a mixture of petroleum ether (60-90 C)/EtOAc (v/v = 30:1).
EXAMPLE 1 Preparation of 3-Sulfonamido-4-(3'-methylphenyl)aminopyridine (formula I: R1=3'-Methyl; R2=H). Method A. To an oven dried flask equipped with magnetic stirrer, condenser and thermometer and cooled under nitrogen was added 3-sulfonamido-4-amino pyridine (2.0 g, 11.5 mmol), 3-iodotoluene (3.77 g, 17.2 mmol), potassium carbonate (4.0 g, 28.9 mmol), and n-butanol (20 mL) and the suspension was stirred for 10 minutes, at which point copper (2.94 g, 46.2 mmol) was added. The mixture was heated to 118 C. and stirring was continued for about 24 h. The reaction mixture was cooled to 45-50 C. and a mixture of methanol-water (70:30 v/v) was added. The reaction mixture was filtered through a pad of Celite. The solution was evaporated under vacuum to 9 mL, then water (10 mL) was added and the mixture was evaporated to 9 mL. Another portion of water (10 mL) was added and the mixture was evaporated again to 9 mL. Water (12 mL) and a saturated sodium thiosulfate solution (5 mL) was added and the mixture was stirred for 45 minutes. The mixture was extracted twice with dichloromethane (24 mL total) and the organic phase was evaporated to dryness under vacuum. Water (12 mL) was added and the solution was acidified to pH=6 with glacial acetic acid (1 mL). The mixture was evaporated to dryness under vacuum. Ethanol (15 mL) was added and the mixture evaporated to dryness under vacuum. The crude mixture was chromatographed on silica gel (initially 4% methanol in dichloromethane, then polarity increased to 9% methanol in dichloromethane), to give 3-sulfonamido-4-(3'-methylphenyl) aminopyridine as a white powder (1.61 g, 53.1% yield). Mass spectral data: Direct electron impact: 264 (M+1, 100%). 1H NMR (DMSO-d6) delta: 8.65 (s, 1H), 8.24 (d, 1H, J=5.5 Hz), 8.05 (s, 1H, D2O exchangeable), 7.76 (s, 2H, D2O exchangeable), 7.33 (dd, 1H, J=7.54, 7.51 Hz), 7.12-7.04 (m, 3H), 6.98 (d, 1H, J=5.5 Hz), 2.33 (s, 3H). 13C NMR (DMSO-d6) delta: 152.69, 149.04, 147.30, 139.20, 138.58, 138.08, 129.42, 126.03, 124.11, 122.98, 120.59, 107.83, 20.89.
With palladium diacetate; potassium hydroxide; In water; at 100℃; for 24h;Inert atmosphere;
General procedure: The mixture of 1 (0.1g), 2/2'/2"(1.5 equivalent), Pd(OAc)2 (5 mol%), KOH (3 equivalent) in 4 mL of nitrogen purged deionised water were stirred at 100 C. The reaction was carried out under nitrogen atmosphere. The progress of reaction was monitored using TLC. Upon completion of the reaction, silica gel was added and the mixture was evaporated under vacuum. The resulted mixture was purified by column chromatography using EtOAc:Petroleum ether (0.4:0.6 to 0.8:0.2, EtOAc:Petroleum ether) to afford pure 3-aryl <strong>[274-76-0]imidazo[1,2-a]pyridine</strong>s 3 and 4.
With bis-triphenylphosphine-palladium(II) chloride; potassium carbonate; In water; acetonitrile; at 20℃;
3-Iodotoluene (0.87 g, 4 mmol), 4-formylphenylboronicacid (0.72 g, 4.8 mmol), K2CO3 (2.0 g, 14.4 mmol)and [P(Ph)3]2PdCl2 (85 mg, 0.121 mmol) weretaken in 100 mL single neck round bottom flask, added 10:10 mLwater-acetonitrile. The reaction mixture was stirred at room temperature overnight.And the reaction was monitored by thin-layer chromatography (TLC). After thereaction completed, the reaction mixture was filtered. The filtrate wasextracted with EtOAc (15 mL x 3). Thecombined organic layer was dried on anhydrous Na2SO4 and concentrated;the crude product was purified by column chromatography over silica gel toafford target product with high yield of 71.3%.
With sodium methylate; In 1,4-dioxane; at 75℃; for 36h;Schlenk technique;
Accurate weighing<strong>[6737-42-4]1,3-bis(diphenylphosphino)propan</strong>e (0.1237 g, 0.3 mmol), sodium methoxide (0.0569 g,1.05 mmol) was added to a 25 mL Schlenk reaction flask.3-methyliodobenzene (128 muL, 0.9 mmol) was added.The solvent was dioxane (2 mL) and the reaction was carried out at 75 C for 36 h.After the reaction was completed, it was extracted with ethyl acetate/water.The organic phase was dried over anhydrous sodium sulfate and the solvent was evaporated.Separation of silica gel column using petroleum ether/ethyl acetate as eluentThe yield of the product was 60%.
With Wilkinson?s catalyst; 1,3-bis-(diphenylphosphino)propane; water; In tetrahydrofuran; at 140℃; for 12h;Inert atmosphere; Sealed tube;
General procedure: Rh(PPh3)3Cl (2.5 mol%) and DPPP (0.04 mmol) were transferred into an oven-dried tube(15 mL), which was evacuated and backfilled with N2 (5x). THF(2 mL), H2O (1 mmol), aryl iodides (1.2 mmol), furfural (1 mmol)and amine (1.8 mmol) were added into the tube via syringe and sealed with Teflon plug. The reaction mixture was stirred at 140 C for 12 h. After the reaction was complete, the mixture was concentrated by rotary evaporation. The crude product was purified by column chromatography (EA/PE = 1/20) on a silica gel to afford the desired product.
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