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CAS No. : | 134-85-0 | MDL No. : | MFCD00000622 |
Formula : | C13H9ClO | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | UGVRJVHOJNYEHR-UHFFFAOYSA-N |
M.W : | 216.66 | Pubchem ID : | 8653 |
Synonyms : |
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Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H302-H315-H319-H335 | Packing Group: | N/A |
GHS Pictogram: |
* 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.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With formamide at 170 - 175℃; Inert atmosphere; | 1.1 Step 1. 34.41g of 4-chlorobenzophenone and 48.17g of formamide are reacted under nitrogen protection at 170~175°C until the raw material is less than 3% detected by TLC/GC. The reaction system is added to 200g of water and suction filtered. Wash the filter cake, dry the filter cake at 55 , add 59.89g 36% hydrochloric acid, 21.33g absolute ethanol and 81.2g water to the crude product and heat to 75~80 to reflux, detect the complete hydrolysis, reduce the temperature to 25 , suction filter, filter cake Add water to make a paste, add sodium hydroxide and water to adjust the pH to 10~11, add DCM for extraction, wash the organic phase with saturated brine, dry with sodium sulfate and concentrate to obtain the compound of formula (III), which can be calculated by GC detection as shown in the figure , Yield 80%, purity 98%, |
With ammonium formate und Erhitzen des Reaktionsprodukts mit wss.HCl; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With dicyclohexyl(2',4',6'-triisopropyl-5-methoxy-3,4,6-trimethyl-[1,1'-biphenyl]-2-yl)phosphine; C50H70NO4PPdS; C50H70NO4PPdS; dicyclohexyl(2',4',6'-triisopropyl-4-methoxy-3,5,6-trimethyl-[1,1'-biphenyl]-2-yl)phosphine; ammonia; sodium t-butanolate In 1,4-dioxane at 50℃; for 24h; Inert atmosphere; | |
80% | Stage #1: 4-chlorobenzophenone With bis(bis(trimethylsilyl)amido)zinc(II); tri-tert-butyl phosphine; lithium chloride In tetrahydrofuran at 90℃; for 12h; Stage #2: With hydrogenchloride In tetrahydrofuran; diethyl ether | |
80% | With ammonium sulfate; C39H45FeNNiP2; sodium t-butanolate In 2-methyltetrahydrofuran at 100℃; for 7h; Inert atmosphere; Glovebox; Autoclave; |
70% | With bis[chloro(1,2,3-trihapto-allylbenzene)palladium(II)]; N-[2-(di(1-adamantyl)phosphino)phenyl]morpholine; ammonia; sodium t-butanolate In 1,4-dioxane at 20℃; for 2h; Inert atmosphere; chemoselective reaction; | |
70% | Stage #1: 4-chlorobenzophenone With [(k2-P,N-di(1-adamantyl)-2-morpholinophenylphosphine)Pd(Ph)Cl]; sodium t-butanolate In 1,4-dioxane Inert atmosphere; Glovebox; Stage #2: With ammonia In 1,4-dioxane at 24℃; Inert atmosphere; Glovebox; | |
With copper(I) oxide; ammonium hydroxide at 220℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With tris(6,6'-diamino-2,2'-bipyridine); 4,4-diphenyl-1,3,5,7,8-pentamethyl-2,6-diethyl-4-bora-3a,4a-diaza-s-indacene; Br2Ni*3H2O; water; N-ethyl-N,N-diisopropylamine In N,N-dimethyl-formamide; acetonitrile at 20℃; for 24h; Glovebox; Irradiation; Inert atmosphere; | |
38% | With nickel(II) sulfate hexahydrate; 4,4'-Dimethoxy-2,2'-bipyridin; 8,9-bis((R)-2-acetoxypropyl)-7,10-dimethoxyperyleno[1,12-def][1,3]dioxepine-5,6,11,12-tetrayl tetraacetate; <SUP>18</SUP>O-labeled water; N-ethyl-N,N-diisopropylamine In N,N-dimethyl-formamide; acetonitrile at 20℃; for 24h; Schlenk technique; Irradiation; Inert atmosphere; | 2.6. Typical experimental procedure for the hydroxylation of arylhalides with water catalyzed by HARCP General procedure: In a 10 mL schlenk tube with magnetic stirring bar, aryl halide 1(0.2 mmol), HARCP (1.2 mol%), NiSO46H2O (10 mol%), 4,40-dimethoxy-2,20-bipyridine (10 mol%), DIPEA (1.5 equiv), H2O (40 equiv)were dissolved in the mix solvent (CH3CN: DMF = 1: 1, 2 mL). Thereaction mixtures were then irradiated with 23 W CFL (at approximately2 cm away from the light source) under nitrogen atmosphere.When the reaction finished, the reaction mixtures werequenched with water (5 mL) and extracted with ethyl acetate (3x10 mL). The organic phase was washed with brine (3x 30 mL), driedover Na2SO4 and then concentrated in vacuum. The resulting residuewas purified by silica gel column chromatography to afford thedesired product 5. |
With copper(II) oxide; sodium hydroxide at 200℃; for 3h; | 1 The 4-hydroxy-benzophenone synthetic method, comprising the following steps (1) the high-pressure reaction kettle with stirring in accordance with the mass ratio of 1 : 0.01: 0.005 : 2 the proportion of 4-chloro benzophenone, copper oxide, the quality of a phase-transfer catalyst and the concentration of 5% of sodium hydroxide solution, control the stirring speed is 40r/min, heating to 200 °C reaction 3 hours;(2) after the reaction by the high-pressure reactor is poured out of the material after cooling to room temperature, add quality as the total mass of the material after the reaction of 2 times that of the de-ionized water after diluting goes to the copper oxide pumping filtered, phase-transfer catalyst and the unreacted 4-chloro benzophenone, to obtain 4-hydroxy-benzophenone alkaline solution, wherein the copper oxide, the phase transfer catalyst and unreacted 4-chloro benzophenone can be recovered for the step (1);(3) in the 4-hydroxy-benzophenone alkaline solution by adding activated carbon, is heated to boiling, 5 min oil filtering off the active carbon, obtained after the decoloring 4-hydroxy-benzophenone alkaline solution, wherein the amount of activated carbon 4-hydroxy benzophenone the total weight of the alkaline solution of 1%;(4) after the decoloring 4-hydroxy-benzophenone alkaline solution dropping the mass concentration is 5% hydrochloric acid solution until the solution is pH 1, filtered and dried to obtain the 4-hydroxy-benzophenone. |
With copper(I) oxide; sodium hydroxide at 220℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With N-Bromosuccinimide; water; In chloroform; for 3h;Reflux; | General procedure: In around-bottom flask, diarylmethanes (1.0 mmol), NBS (889.9 mg, 5.0 mmol) andwater (0 or 5.0 mmol) were dissolved in CHCl3 (4.0 mL). After refluxingfor 3 h in the air, the reaction mixture was quenched withNa2S2O3·5H2O, cooled to roomtemperature, washed with 5mL CH2Cl2, dried with MgSO4,and filtered to get clear organic solution. The solvent was removed reducedpressure by a rotary evaporator, and the resulting residue was subjected tocolumn chromatography on silica gel using co-solvent(ethyl acetate / petroleum ether, v/v) as eluent to give the correspondingdiaryllketones. |
95% | With oxygen; sodium t-butanolate; In dimethyl sulfoxide; at 50℃; for 5h;Sealed tube; | General procedure: To a predried 5 mL round-bottom flask diarylmethane 1 (0.4 mmol), dry DMSO (1 mL), andt-BuONa (0.8 mmol) were subsequently added as soon as possible. The reaction system wassealed by a rubber septum with a needle connected to an O2 balloon, and then stirred at 50 oC for5 h. During this period, the reaction system suffered complex color changes. Then the reactionmixture was allowed to cool at room temperature, and diluted with 1 mol/L HCl to pH = 6-7,washed with ethyl acetate (20 mL × 3), dried over anhydrous Na2SO4, and filtered to get clearorganic solution. The solvent was removed reduced pressure by a rotary evaporator, and theresulting residue was subjected to column chromatography on silica gel using co-solvent (ethylacetate / petroleum ether = 1/20, v/v) as eluent to give the corresponding diarylketones. |
82% | With pyridine; dipotassium peroxodisulfate; oxygen; In acetonitrile; at 80℃; under 760.051 Torr; for 16h;Green chemistry; | General procedure: Ethylbenzene (3a) (0.0531 g, 0.5 mmol), K2S2O8 (0.2703 g, 1.0 mmol), pyridine (0.0158 g, 0.2 mmol) and CH3CN (1.0 mL) were added to an oven-dried pressure vessel with a magnetic stir bar. Then the pressure vessel was filled with dioxygen and the reaction mixture was stirred at 80 C for 16 hours (oil bath). After the completion of the reaction, the solvent was evaporated and the reaction mixture was purified with column chromatography (eluenet: ethyl acetate/PE = 1/10) to give acetophenone (4a) (0.0535 g yield 89%). |
65% | With tert.-butylnitrite; oxygen; acetic acid; 2,3-dicyano-5,6-dichloro-p-benzoquinone; In 1,1,2,2-tetrachloroethane; at 130℃; for 24h;Autoclave; | General procedure: A Teflon-lines 316 L stainless steel autoclave (300 mL) equipped with magnetic stirring bar was charged with substituted diarylmethanes 1 (2 mmol), 136.2 mg DDQ (0.6 mmol, 30 mol %), 41.2 mg TBN (0.4 mmol, 20 mol %), 480 mg acetic acid (8 mmol) and 20 mL TeCA. The autoclave was closed and charged with oxygen to 0.3 MPa. Then the autoclave was placed in an oil bath, which was preheated to 130 C. The mixture was then stirred for a certain time until the reaction was completed. The autoclave was taken out from the oil bath, cooled to room temperature and carefully depressurized. The mixture was concentrated under reduced pressure and purified by column chromatography to give the desired diarylketones. |
85%Chromat. | With dihydrogen peroxide; trifluoroacetic acid; zinc dibromide; In 1,4-dioxane; water; at 100℃; for 16h; | General procedure: In a 25 mL pressure tube, ZnBr2 (10 mol %) and a stirring bar were added. After the addition of diphenylmethane (1 mmol), trifluoroacetic acid (0.2 mL) and 1,4-dioxane (2 mL) by syringe, H2O2 (4 mmol; 30% aqueous) was added in one pot to the solution and the final solution was kept at 100 C for 16 h. Then hexadecane (100 mg) and ethyl acetate (3 mL) were injected, a part of solution was taken for GC and GC-MS analysis after properly mixed. All the products are commercially available. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97.2% | With oxygen at 110℃; for 8h; Sealed tube; | 15 Example 15: Synthesis of 4-chlorobenzophenone Add 0.5mmol of 1-chloro-4-(1-phenylvinyl)benzene and 1mL polyethylene glycol dimethyl ether (MW=250) as a solvent to a test tube, seal the test tube, perform oxygen replacement, and insert the refill The balloon with pure oxygen was placed at 110°C for 8 hours and the yield was 97.2%. |
97% | With oxygen at 110℃; for 8h; Schlenk technique; Green chemistry; | |
94% | With iron(III) chloride; potassium sulfide; oxygen In N,N-dimethyl-formamide at 80℃; for 14h; |
83% | With 3-chloro-benzenecarboperoxoic acid In dichloromethane at -78 - 20℃; for 1.33333h; Inert atmosphere; | |
82% | With cerium(III) chloride; 1,1,1-trichloroethanol In acetonitrile at 25℃; for 40h; Irradiation; | |
80% | With tetrahydrofuran; oxygen In water at 20℃; for 18h; Irradiation; Green chemistry; | |
78% | With 2,2'-azobis(isobutyronitrile); oxygen In nitromethane at 60℃; for 12h; Schlenk technique; | |
78% | With oxygen; rose bengal; acetic acid In water at 20℃; for 48h; Irradiation; Schlenk technique; | 1.7 General procedure for synthesis of products (taking 2a as an example) General procedure: A mixture of 1,1-diphenylethylene 1a (36 mg, 0.20 mmol), Acid Red 94 (10 mg, 0.01 mmol), AcOH (6 mg, 0.1 mmol)and H2O (2.0 mL) were added to a 25 mL Schlenk tube. The reaction tube was flushed with O2 for 1.0 minute and then equipped with a O2 balloon. The reaction was stirred for 48 h under 18 W blue LEDs irradiation. Then the resulting mixture was extracted with EtOAc (3×10 mL). The combined organic phase was dried over anhydrous MgSO4, filtered, and all the volatiles were evaporated under reduced pressure. The resultant residue was purified by silica gel column chromatography (eluent: PE (60-90°C) / EtOAc = 20:1) to afford the desired product 2a in 95% yield. |
77% | With sodium tetrafluoroborate; [Cu(salicylate)2(NCMe)]2; tetrabutyl-ammonium chloride; oxygen In tetrahydrofuran at 60℃; for 12h; | |
72% | With dibutyl diselenide; dihydrogen peroxide In ethanol; water at 80℃; for 96h; Green chemistry; | |
71% | With tetrafluoroboric acid; iodobenzene; 1,1,1,3',3',3'-hexafluoro-propanol; 3-chloro-benzenecarboperoxoic acid In water; toluene at 35℃; for 4h; Sealed tube; | 4.2 General procedure for the syntheses of 4 and 6 General procedure: To a 10 mL sealed tube styrenes (0.2 mmol) and m-CPBA (89.15 mg, 2.2 equiv.) were added. Then PhI (5 μL, 20 mol%), HBF4 (28 μL, 2.2 equiv.), toluene (1.2 mL), H2O (0.4 mL) and HFIP (0.2 mL) were added. The vessel was sealed with a teflon-lined cap, and the reaction mixture was stirred at 35 oC. The progress of reaction was monitored by TLC. After completion, the mixture was diluted with ethyl acetate (10 mL) and washed with a saturated aqueous NaHCO3 solution (3 x 5 mL). The combined organic layer was washed with brine solution and dried over anhydrous Na2SO4. Solvent was removed under reduced pressure to get crude products. After that crude products were purified by flash chromatography (Petroleum ether : EtOAc). |
70% | With 18-crown-6 ether; tetrakis(tetrabutylammonium)decatungstate(VI) In water at 25℃; for 24h; Irradiation; Green chemistry; | |
With 2,2,2-trifluoroethanol; oxygen; titanium(IV) oxide In acetonitrile Irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 11% 2: 37% | With dichloro-acetic acid; oxygen In acetonitrile at 13℃; Irradiation; Further byproducts given. Title compound not separated from byproducts; | |
1: 11% 2: 17% | With dichloro-acetic acid; oxygen In acetonitrile at 13℃; Irradiation; Further byproducts given. Title compound not separated from byproducts; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 11% 2: 37% | With dichloro-acetic acid; oxygen In acetonitrile at 13℃; Irradiation; Further byproducts given; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With potassium phosphate monohydrate; 1-methyl-2-(2-(dicyclohexylphosphino)phenyl)-1H-benzoimidazole; palladium diacetate In 1,4-dioxane at 135℃; for 24h; Inert atmosphere; | |
98% | With 2-chloro-1,3-[di-(2,6-diisopropyl)phenyl]-1,3,2-diazaphospholidine; tris-(dibenzylideneacetone)dipalladium(0); cesium fluoride In 1,4-dioxane at 80℃; for 19h; Inert atmosphere; | |
93% | With {N,N-bis((3,5-dimethylpyrazol-1-yl)methyl)benzylamine}PdCl2; tetrabutylammomium bromide; caesium carbonate In water; N,N-dimethyl-formamide at 120℃; for 5h; |
90% | With potassium carbonate In water; N,N-dimethyl-formamide at 100℃; for 12h; | |
88% | With potassium phosphate; lithium bromide In 1,4-dioxane at 135℃; for 18h; | |
85% | With trans-bis([1-N-(2,6-diisopropylphenyl)-2-acetamido]-3,5-dimethylpyrazole)Pd(II) dichloride; tetrabutylammomium bromide; caesium carbonate In water; N,N-dimethyl-formamide at 120℃; for 5h; in air; | |
84% | With trans-chloro(9-phenanthrenyl)bis(triphenylphosphine)nickel(II); potassium carbonate; triphenylphosphine In toluene at 110℃; for 18h; Inert atmosphere; | |
80% | With bis(tricyclohexylphosphine)nickel(II) dichloride; potassium carbonate In toluene at 180℃; for 0.166667h; Microwave irradiation; Inert atmosphere; | |
74% | With potassium <i>tert</i>-butylate In tetrahydrofuran at 60℃; for 24h; | |
72% | With 1,3-bis(2,6-diisopropylphenyl)-1,3,2-diazaphospholidine-2-oxide; potassium phosphate; chloro(1-naphthyl)bis(triphenylphosphine)nickel(II) In toluene at 110℃; for 18h; Schlenk technique; Inert atmosphere; | General procedure for the Suzuki cross-coupling reactions General procedure: Aryl chloride (1.0 mmol),arylboronic acid (1.2 mmol), precatalyst (0.05 mmol), preligand (0.05 mmol),and base (3.0 mmol) were added to a Schlenk tube equipped with a magnetic stirring bar, a septum, and a reflux condenser. After the tube was evacuated and refilled with nitrogen gas three times, degassed solvent (3 mL) was added via a syringe. The reaction mixture was heated to the described temperature for the required time. After the reaction cooled to room temperature, water (10 mL) was added tothe reaction mixture. The resulting mixture was extracted with CH2Cl2(3 x 10 mL). The combined organic layers were dried over anhydrous Na2SO4,filtered and concentrated to dryness. The remaining residue was analyzed by GC(Table 1) or purified by flash chromatogram phy on silica gel with ethylacetate-hexanes (0-20% ethyl acetate in hexanes) of as eluents. |
70% | With potassium phosphate; 1,2-bis(diphenylphosphino)ethane nickel(II) chloride; trisodium tris(3-sulfophenyl)phosphine; zinc In 1,4-dioxane; water at 50℃; | |
70% | With potassium carbonate In water at 100℃; for 6h; | 2.3. General procedure for the CoGO/Fe3O4/L-dopa catalyzed Suzukicross-coupling General procedure: A mixture of aryl halide (1 mmol), phenyl boronic acid (1.2 mmol),K2CO3 (1.2 eq.) and CoGO/Fe3O4/L-dopa (0.05 g, 1.84 mol% Co) in double distilled water (5 mL) was stirred in a round bottom flask (50 mL) at 100 °C till the completion of reaction (monitored by TLC) (Table 3). After that, the reaction mixture was cooled to room temperature.The catalyst was removed via external magnet and washed with EtOAc (3×5 mL) followed by deionized water (3×10 mL). It was dried under vacuum for 2 h. The organic fraction was washed with brine solution and dried over anhydrous Na2SO4. Finally, the product was obtained either by the exclusion of the solvent under reduced pressure or by passing through column of silica gel using EtOAc-pet.ether as eluting solvent. |
63% | With caesium carbonate In water; N,N-dimethyl-formamide at 100℃; for 24h; | Suzuki-Miyaura Reaction; General Procedure: General procedure: Arylhalide 19 or 22 (1.0 mmol), phenylboronic acid (20; 1.2mmol, 0.146 g), 18 (0.015 mmol, 0.002 g), Cs2CO3 (1.5mmol, 0.489 g), DMF (2.5 mL), and H2O (2.5 mL) wereplaced in a 25 mL round-bottomed flask equipped with amagnetic stirrer. The flask was immersed in an oil bathregulated at 80 or 100 °C for the reaction time indicated inTable 1 or Table 2. After the reaction mixture was cooled tor.t., Et2O (8 mL) and H2O (8 mL) were added to the flask.The resulting mixture was vigorously stirred for 5 min, andthen filtered. The solid 18 collected on the filter was washedwith H2O (10 mL) and Et2O (10 mL) and then dried. Thefiltrate was transferred to a separation funnel and the organicphase was separated and washed with H2O (5 × 25 mL) andbrine (10 mL), and then dried over MgSO4. The solvent wasremoved under reduced pressure and the resulting residuewas analyzed by 1H and 13C NMR spectroscopy. When arylchlorides were used as substrates, the crude products werepurified by silica gel column chromatography. |
47% | With tris-imidazolium-stabilized palladium; potassium carbonate In water; toluene at 110℃; for 16h; | |
45% | With potassium carbonate In water; N,N-dimethyl-formamide at 80℃; for 4h; Schlenk technique; | 19. General procedure for the Suzuki-Miyaura reaction: General procedure: An oven-dried Schlenk flask, equipped with a magnetic stir bar, septum, and a condenser was charged with aryl halide (1.0 mmol), arylboronic acid (1.2 mmol), K2CO3 (2 mmol), 4 (0.143 g, 1 mol %), and 5 mL of solvent. The flask was immersed in an oil bath and stirred at 80 °C. Upon complete consumption of starting materials as determined by TLC analysis, the reaction mass was filtered and the solid washed with water (2Χ5 mL), and extracted with diethyl ether (3Χ5 mL). The combined organic layers were collected, dried over anhydrous Na2SO4, and concentrated in vacuum to afford product which was purified by silica gel column chromatography (n-hexane/EtOAc = 9:1) |
41% | With potassium carbonate In ethanol at 80℃; for 9h; Schlenk technique; | 4.4 Typical experimental procedure for the Suzuki-Miyaura reaction General procedure: In a typical procedure 50mL Schlenk tube containing magnetic stirring bar and equipped with reflux condenser was charged aryl bromide (1.0mmol), arylboronic acid (1.2mmol), K2CO3 (2.0mmol), and 0.009g catalyst (0.02mol%) in ethanol (5mL). The reaction mixture was vigorously stirred at 80°C. After completion of the reaction as monitored by TLC, the catalyst was separated out by filtration, followed by washing with water and diethyl ether. The filtrate was extracted with diethyl ether (3×10mL). The combined organic layers were collected, dried over anhydrous Na2SO4 and concentrated in vacuum to afford crude product, which was purified by silica gel column chromatography (n-hexane:EtOAc=9:1). |
36% | With potassium carbonate In ethanol at 80℃; for 12h; Green chemistry; | |
20% | With potassium carbonate In ethanol at 80℃; for 14h; Schlenk technique; | |
20% | Stage #1: 4-chlorobenzophenone; phenylboronic acid With p-xylene-2-sulphonic acid sodium salt In water at 28℃; for 0.0833333h; Stage #2: With palladium 10% on activated carbon; potassium carbonate In water at 28℃; for 12h; | |
100 % Chromat. | With potassium phosphate; bis(1-n-butyl-3-methylimidazolium) tetrachloronickelate(II); triphenylphosphine In 1,4-dioxane at 79.85℃; for 2h; | |
With palladium diacetate; potassium phosphate; 2-diphenylphosphino-2'-methylbiphenyl In water; toluene for 1h; | ||
With potassium fluoride; potassium phosphate; p-(MeOPEG2000-OCH2)C6H4CH2P(1-adamantyl)2*HBr In dimethyl sulfoxide at 80℃; for 18h; | ||
With PdCl(2-HO-C6H4-CH(Ph)-NH-(CH2)3-SeC6H5); potassium carbonate In water; N,N-dimethyl-formamide Heating; | ||
99 %Chromat. | With [Pd2(μ-1,1′-bis(diphenylphosphino)ferrocene)(4-methoxy-N′-(mesitylidene)benzohydrazide)2]; tetrabutylammomium bromide; potassium carbonate In water; N,N-dimethyl-formamide at 90℃; for 10h; | General procedure General procedure: An oven-dried round bottom flask (10 ml) was charged with 0.1ml dimethylformamide solution of complex IV (0.1 mol % for aryl bromides and 0.2 mol % for aryl chlorides), aryl boronic acid (1.2 mmol), aryl halide (1.0 mmol), K2CO3 (1.5 mmol), TBAB (1.0 mmol) and 2 ml water. The reaction mixture was then heated (to 70 °C for aryl bromides and 90 °C for aryl chlorides) with stirring under aerobic conditions for the required time. At the end of the reaction, the reaction mixture was cooled to room temperature and extracted with ethyl acetate (2×5 ml). The combined extract was washed with water (2×10 ml), dried over anhydrous sodium sulfate and then subjected to GC-MS analysis for identification and yield determination (from the areas under the peaks) of the products. In the case of reactions with 2-naphthylboronic acid, the combined extract was evaporated to dryness under reduced pressure and the residue was purified by column chromatography (silica gel, ethyl acetate/n-hexane) to afford the coupling products. The products were identified by 1H and 13C NMR and HR-MS analysis. |
With C42H26Cl2N2PdS2; potassium carbonate at 90℃; for 12h; | ||
With C25H22Cl2NPPd; potassium carbonate In water; N,N-dimethyl-formamide at 105℃; for 10h; | 2.5.1. Suzuki coupling (i.e., C-C coupling) reaction General procedure: A 100 mL round bottom flask (equipped with a refluxing con- denser) was charged with aryl halide (1.0 mmol), phenylboronic acid (1.1 mmol, 0.133 g), K 2 CO 3 (2.0 mmol, 0.276 g), Pd(II) complex (0.01 or 0.001 mol%) and aqueous DMF (5.0 mL). The reaction mix- ture was refluxed at 105 °C for 10 h and the progress of catalytic reaction was monitored using thin layer chromatography (TLC). Af- ter completion of ten hours, the resultant mixture was cooled to room temperature and water was added to it. Thereafter, the ex- traction of cross-coupled product was carried out using diethyl ether. The organic layer was dried over anhydrous Na 2 SO 4 and the solvent was evaporated using rotary evaporator to obtain the prod- uct. The % conversion was estimated using 1 H NMR and GC stud- ies. Thereafter, the product was subjected to silica gel column chro- matography for purification using ethyl acetate and n -hexane mix- ture as an eluent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With [Pd(eta(5)-C5H5)Fe(eta(5)-C5H3-C(CH3)=N-C6H4-4-CH3)Cl(P(C6H5)3)]; potassium carbonate; In 1,4-dioxane; at 110℃; for 12h;Inert atmosphere; | General procedure: A reaction vessel was charged with a mixture of phenylboronic acid (0.5 mmol), K2CO3 (1.0 mmol), catalyst 2 (0.5 mol %) in toluene (2.0 mL), and stirred for about 20 min under nitrogen atmosphere. Then benzoic anhydride or benzoyl chloride was then added. The mixture was heated to 60 C and incubated in an oil bath at 60 C for 12 h under nitrogen atmosphere. After the completion of the reaction, the mixture was quenched by 5 mL water and then extracted with ethyl acetate (3×10 mL). The combined organic layer was dried over MgSO4. After removal of the solvent in vacuo, the product was obtained by purifying on preparative TLC, eluting with ethyl acetate/petroleum ether and the yield was calculated based on the phenylboronic acid (the purified products were identified by NMR spectra and comparison of the melting points with the literature data). In the recycle experiment, the residue was subjected to a second run of the acylation reaction by charging with the same substrates (benzoic anhydride or benzoyl chloride, phenylboronic acid, dioxane, and K2CO3) without further addition of cyclopalladated catalyst 2. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With tris(dibenzylideneacetone)dipalladium (0); 2,8,9-tribenzyl-2,3,8,9-tetraaza-1-phosphabicyclo[3,3,3]undecane; cesium fluoride In 1,4-dioxane at 60℃; for 28h; | |
93% | With P(i-BuNCH2CH2)3N; cesium fluoride In 1,4-dioxane at 100℃; for 30h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | In water; N,N-dimethyl-formamide at 150℃; for 0.5h; microwave irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
61% | With sodium hydroxide; tetrabutylammomium bromide In water at 120℃; for 0.416667h; microwave irradiation (40-45 W); | |
61% | With sodium hydroxide In water at 120℃; for 0.416667h; microwave irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With 3-(dicyclohexylphosphino)-2-(2-methoxyphenyl)-1-methyl-1-H-indole; tetrabutyl ammonium fluoride; palladium diacetate In toluene at 110℃; for 3h; Schlenk technique; Inert atmosphere; Sealed tube; | |
65% | With tetrabutyl ammonium fluoride In 1,4-dioxane at 80℃; for 17h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | Stage #1: bromobenzene With lithium Stage #2: With zinc(II) chloride Stage #3: 4-chlorobenzophenone In tetrahydrofuran; 1-methyl-pyrrolidin-2-one at 70℃; for 6h; Further stages.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogenchloride; sodium hydroxide; lithium; In tetrahydrofuran; diethyl ether; water; acetic acid; | EXAMPLE IV Preparation of alpha-(p-chlorophenyl)-alpha-phenylimidazole-2-methanol. To 5.6 g. of lithium in 150 ml. of anhydrous diethyl ether in a nitrogen atmosphere 44.5 g. of butyl bromide in 100 ml. of diethyl ether were added drop-wise at a temperature of -10 C. Upon completion of the reaction after 2 hours, the solution was filtered and added drop-wise to 55.5 g. of 1-(toluene-p-sulphonyl)imidazole dissolved in 450 ml. of anhydrous tetrahydrofuran and 225 ml. of anhydrous diethyl ether at a temperature of -30 C. After 1 hour, 58.6 g. of 4-chlorobenzophenone, dissolved in 300 ml. of anhydrous tetrahydrofuran and 150 ml. of anhydrous diethyl ether, were added drop-wise at -30 C. The mixture was kept at a temperature of -40 to -50 C. for 3 hours, allowed to return to ambient temperature and washed twice with water. The organic solvents layer was concentrated and 500 ml. of glacial acetic acid, 50 ml. of 36% hydrochloric acid solution and 50 ml. of water were added. The mixture was boiled under reflux for 1.5 hours. Glacial acetic acid was removed as completely as possible and water and diethyl ether were added. The ether layer containing unreacted ketone and the aqueous oily layer containing the desired compound as the hydrochloride salt were separated. The aqueous layer was made alkaline by addition of 2 N sodium hydroxide solution and extracted with diethyl ether. The ether layer was acidified with 36% hydrochloric acid solution and extracted with water. The aqueous layer was treated with activated charcoal, made alkaline with 2 N sodium hydroxide solution and again extracted with diethyl ether. The diethyl ether layer was dried and concentrated and the solid obtained crystallized from isopropyl alcohol. Melting point of the product was 162-165 C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With C21H18N8Ni2O(2+)*2F6P(1-) In tetrahydrofuran; 1-methyl-pyrrolidin-2-one at 20 - 80℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With potassium phosphate; palladium(II) trifluoroacetate In water; acetonitrile at 50℃; for 6h; Inert atmosphere; Sealed tube; | |
88% | With potassium carbonate at 95℃; for 2h; Sealed tube; Inert atmosphere; | |
81% | With palladium diacetate; potassium carbonate In methoxybenzene at 140℃; for 12h; |
76% | With C35H20F34NO3(1-)*Pd(2+)*Cl(1-); N-ethyl-N,N-diisopropylamine In water at 140℃; for 0.333333h; Microwave irradiation; | 6 Carbonylative Suzuki-Miyaura coupling of aryl halideand arylboronic acid: general procedure General procedure: A mixture of the aryl halide (0.6 mmol), arylboronic acid (2.5 equiv), Mo(CO)6 (1.5 equiv), DIPEA (3.0 equiv), palladacycle 1 (1 mol % Pd), and water (1.0 mL) was heated in a pressure tube at 140 °C under microwave irradiation. The reaction was monitored by TLC. When the reaction has completed, the reaction mixturewas cooled to room temperature, poured into EtOAc (20 mL) and washed successively with water (310 mL). The organic layer was dried over anhydrous MgSO4, filtered and concentrated. The crude product was then purified by column chromatography to give pure 4. |
81 %Chromat. | With potassium carbonate In N,N-dimethyl-formamide at 100℃; for 24h; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: diethyl iodomethanephosphonate With potassium hexamethylsilazane In tetrahydrofuran at -78℃; for 2h; Inert atmosphere; Stage #2: 4-chlorobenzophenone In tetrahydrofuran at -78 - 0℃; Inert atmosphere; | General procedure for gem-diiodoalkene derivatives General Procedure: An Ar-purged two-necked flask containing a solution of KHMDS (499 mg, 2.50 mmol) in THF (10 mL) was cooled to -78 °C and then a solution of (iodomethyl)phosphonic acid diethyl ester (1.39 g, 5.00 mmol) in THF (2 mL) was added. After steering at this temperature for 2 h, a solution of the ketone (2.00 mmol) in THF (1 mL) was added to the reaction mixture at -78 °C. The reaction mixture was wormed up to 0 °C and monitored by TLC or GC. When the reaction was complete, the reaction mixture was carefully diluted with water. The resulting mixture was extracted several times with EtOAc and the organic fraction was then washed with brine and dried over MgSO4. After removal of the solvent under reduced pressure, the residue was purified by chromatography on SiO2 to give the corresponding gem-diiodoalkene derivative. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With potassium carbonate for 1h; Autoclave; Reflux; | |
96% | With potassium carbonate for 0.5h; Autoclave; Reflux; | |
95% | With potassium phosphate; palladium diacetate at 20℃; for 20h; |
93% | With potassium carbonate at 90℃; for 8h; Autoclave; | 2.5. Procedure of carbonylative Suzuki-Miyaura cross couplingcatalysed by Pd(PS-SAL) General procedure: In a 100 mL, autoclave equipped with magnetic stirrer (Fig. 1),phenyl boronic acid (1 mmol), iodobenzene (1 mmol), potassiumcarbonate (3 equiv.), anisole (5 mL) and Pd(PS-SAL) catalyst (15 mg,0.01 mmol based on Pd active centre) were added. Then it waspurged three times with carbon monoxide (65 psi) and after closingthe autoclave tightly, it was heated at 90 °C. The reaction wascontinued for 8 h, cooled at room temperature then Pd(PS-SAL)catalyst was removed from the reaction system and washeddown with methanol. The organic content was dried out absolutelywith sodium sulfate after work up it with ethyl acetate (3 x 10 mL)followed by water. The unstable components were allowed toevaporate through a rotary evaporator. The solid product wasanalyzed by 1H NMR spectroscopy (supporting information). |
92% | With cesiumhydroxide monohydrate; sodium carbonate; sodium iodide; iron(II) chloride; Trimethylacetic acid at 120℃; for 12h; Green chemistry; chemoselective reaction; | |
90% | With iron(III) chloride; sodium hydrogencarbonate; iron(II) chloride at 100℃; for 24h; Schlenk technique; | |
89% | With potassium fluoride; potassium phosphate; copper; Trimethylacetic acid at 100℃; for 12h; | |
89% | With potassium fluoride; potassium phosphate; copper; Trimethylacetic acid at 100℃; for 12h; | 2 General procedure: A 25 mL reaction flask was charged with copper nanoparticles (0.1 mmol)Aryl diiodonium (0.5 mmol),Benzene boronic acid (1.5 mmol),Potassium phosphate (1.0 mmol),Potassium fluoride (0.5 mmol), pivalic acid (0.5 mmol) and polyethylene glycol-400 (2.0 g)And the introduction of an atmospheric carbon monoxide.The reaction mixture was reacted at 100 ° C until the reaction was complete and cooled to room temperature,The product was isolated by column chromatography after evaporation of the solvent under reduced pressure. |
85% | With potassium phosphate; nickel dichloride; Trimethylacetic acid at 80℃; for 4h; | |
85% | With palladium diacetate; sodium carbonate In water at 100℃; for 8h; Sealed tube; Autoclave; Green chemistry; | General procedure for the carbonylative Suzuki coupling reaction General procedure: A 75 mL autoclave equipped with a Teflon liner and a magnetic stirrer bar was charged with Pd(OAc)2 (4.48 mg, 2.0 × 10-2 mmol), L (46.7 mg, 4.0 × 10-2 mmol) and H2O (6 mL) and the mixture was stirred at room temperatures for 0.5 h under N2. Then iodobenzene (113 μL, 1 mmol), phenylboronic acid (134 mg, 1.1 mmol), Na2CO3(106 mg, 1 mmol), and n-decane (0.1 mL, GC internal standard) were added. Once sealed, the autoclave was purged three times with CO, and pressurized to 1 atm of CO. The reaction mixture was stirred at 100 °C for 2 h. After reaction, the mixture was extracted with diethyl ether (3 × 5 mL). The combined organic layer was concentrated in vacuo and the product was purified by column chromatography. In the recycling experiment, the aqueous phase containing the catalyst was subjected to a second run by charging it with the same substrates as mentioned above, and the reaction performed under the same conditions. |
85% | With potassium phosphate; nickel dichloride; Trimethylacetic acid at 80℃; for 4h; Green chemistry; | 1 Example 1 General procedure: Into a 25 ml reaction flask was successively added nickel chloride (0.01 mmol), substituted or non-substituted aryliodide (table 1) (0.5 mmol), phenylboronic acid (0.75 mmol), potassium phosphate (1.0 mmol), pivalic acid (0.25 mmol) and polyethylene glycol 400 (2.0 g), and introduce one atmospheric pressure carbon monoxide. The reaction mixture at 80 °C react until starting material reaction complete and cool to room temperature, pressure reducing evaporate the solvent column chromatography separation to obtain the product. The experimental results are set out in table 1. |
81% | With tris-(dibenzylideneacetone)dipalladium(0); potassium carbonate In methoxybenzene at 100℃; for 20h; chemoselective reaction; | |
With potassium carbonate at 100℃; for 8h; Autoclave; | Carbonylative Suzuki coupling reactions Carbonylative Suzuki coupling reactions All of the carbonylative Suzuki coupling reactions were conducted in a sealed stainless steel reaction kettle. Arylboronic acid (1.5 mmol), aryl iodide (1.0 mmol), base (3.0 mmol), 3 wt% Pd/SiC and anisole (10 mL) were added to the reaction kettle, and the resulting mixture was placed under a certain pressure of CO. All of the reactions were conducted over several hours at certain temperatures. The products of the reactions were analyzed by GC-MS on a Bruker SCION SQ 456 GC-MS system (Karlsruhe, Germany). | |
56 %Chromat. | With potassium carbonate; triphenylphosphine; palladium dichloride at 80℃; for 18h; | |
89 %Chromat. | With potassium carbonate at 80℃; for 6h; Autoclave; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With [Ph2P(ferrocene-1,1′-diyl)ONHCH2CH2NHC(NH2)NH2]Cl*0.4chloroform; palladium diacetate; anhydrous sodium carbonate In water monomer; toluene at 50℃; for 1h; Schlenk technique; Inert atmosphere; | |
95% | With trans-(Et3NH)2[PdCl2(Ph2Pferrocene-1,1′-diylSO3-κP)2]; sodium salt of phosphorous acid In water monomer; toluene at 50℃; for 3h; Inert atmosphere; Schlenk technique; Sealed tube; | |
93% | With palladium 10% on activated carbon; anhydrous sodium carbonate In water monomer; acetone at 60℃; Green chemistry; |
91% | With C35H35ClFeN3O2PPd; Sodium hydrogenocarbonate In water monomer; toluene at 50℃; Inert atmosphere; | |
91% | With C16H16Cl2N2O2Pd2; potassium carbonate In 2-methyltetrahydrofuran at 80℃; for 6h; | |
90% | With [Pd(η(5)-C5H5)Fe(η(5)-C5H3-C(CH3)=N-C6H4-4-CH3)Cl(P(C6H5)3)]; potassium carbonate In toluene at 60℃; for 12h; Inert atmosphere; | 4.2. General procedure for the acylation reaction General procedure: A reaction vessel was charged with a mixture of phenylboronic acid (0.5 mmol), K2CO3 (1.0 mmol), catalyst 2 (0.5 mol %) in toluene (2.0 mL), and stirred for about 20 min under nitrogen atmosphere. Then benzoic anhydride or benzoyl chloride was then added. The mixture was heated to 60 °C and incubated in an oil bath at 60 °C for 12 h under nitrogen atmosphere. After the completion of the reaction, the mixture was quenched by 5 mL water and then extracted with ethyl acetate (3×10 mL). The combined organic layer was dried over MgSO4. After removal of the solvent in vacuo, the product was obtained by purifying on preparative TLC, eluting with ethyl acetate/petroleum ether and the yield was calculated based on the phenylboronic acid (the purified products were identified by NMR spectra and comparison of the melting points with the literature data). In the recycle experiment, the residue was subjected to a second run of the acylation reaction by charging with the same substrates (benzoic anhydride or benzoyl chloride, phenylboronic acid, dioxane, and K2CO3) without further addition of cyclopalladated catalyst 2. |
89% | With sodium hydroxide In toluene at 100℃; for 2h; Schlenk technique; | 2. General Procedure for the Preparation of Dissymmetric Ketones General procedure: An oven-dried Schlenk flask, equipped with a magnetic stir bar, septum and a condenser was charged with acyl chloride (1.0 mmol), arylboronic acid (1.0 mmol), NaOH (4 mmol) and 5.0 mL of toluene. The flask was immersed and stirred in an oil bath at 100 °C. Upon complete consumption of starting materials as determined by GC analysis, the water (10.0 mL) was added. The reaction mixture was extracted with diethyl ether (3 × 5.0 mL). The combined organic layer was collected, dried over anhydrous Na2SO4 and concentrated in vacuum to afford product which was purified by silica gel column chromatography (eluent: n-hexane/ethyl acetate = 9:1 or 8:2). |
89% | With C32H28N6Pd(2+)*2Br(1-); potassium carbonate In toluene at 60℃; for 6h; Inert atmosphere; Schlenk technique; | |
80% | With tripotassium phosphate tribasic; palladium diacetate; tricyclohexylphosphine tetrafluorohydroborate for 0.166667h; Milling; Sealed tube; chemoselective reaction; | |
75% | With C42H36ClFeN2O4PPdS*C6H15N; anhydrous sodium carbonate In water monomer; toluene at 50℃; for 1h; Inert atmosphere; Schlenk technique; Sealed tube; | |
73% | With 2C60H80NaO12(2+)*Cl6Pd2(2-); potassium carbonate; triphenylphosphine In toluene at 70℃; for 12h; | General procedure for the acylodeboronation reaction of arylboronic acids with benzoylchloride. General procedure: A 5 mL flask charged with benzoyl chloride (1.0 mmol), arylboronic acid (0.5 mmol),K2CO3 (1.0 mmol), complex 1 (0.5 mol%, 3.1 mg), PPh3 (0.01 mmol, 1.3 mg) and toluene (2.0mL) was put into a preheated 70 oC oil bath for an appropriate period of time under air. After thereaction was finished, the reaction mixture was cooled to room temperature, filtered through ashort silica column and washed with ethyl acetate. Then the combined filtrates were concentratedin vacuo and the residue was purified by flash chromatography (eluent: ethylacetate/petroleumether). All the products were known compounds and characterized by comparing mp, 1H NMRand 13C NMR spectra with literature. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With potassium phosphate monohydrate; 1-methyl-2-(2-(dicyclohexylphosphino)phenyl)-1H-benzoimidazole; palladium diacetate In 1,4-dioxane; 1,3,5-trimethyl-benzene at 135℃; for 24h; Inert atmosphere; | |
93% | With potassium phosphate; 3-(dicyclohexylphosphino)-2-(2,6-dimethoxyphenyl)-1-methyl-1H-indole; palladium diacetate In 1,4-dioxane at 100℃; for 2h; Schlenk technique; Sealed tube; Inert atmosphere; | |
85% | With C42H36Cl2N2Pd; potassium carbonate In water; toluene at 140℃; for 24h; Inert atmosphere; Sealed tube; | General procedure for Pd-catalyzed Suzukicross-coupling reactions General procedure: To a Young tube, aryl chlorides (5.0 mmol), K2CO3 (1.5 g,11 mmol), arylboric acid (6 mmol), complex Pd2 (37.5 mg,1 mol %), toluene (10 mL) and H2O (2 mL) were added. Themixture was degassed for 2 min. Then, the sealed Young tubewas set into the pre-heated 140 °C oil bath. After stirring for24 hours, the Young tube was allowed to cool to room temperature. After filtration and extraction with toluene (50 mL), theresulted solution was concentrated under vacuum and thedesired biaryl was isolated by column chromatography. |
With potassium phosphate; (dppf)Ni(o-tol)Cl; benzaldehyde In water; toluene at 85℃; for 2h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogenchloride; oxygen In aq. phosphate buffer at 37℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
45% | With hydrogenchloride; borane-ammonia complex In aq. phosphate buffer at 37℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: hydrogenchloride; borane-ammonia complex / aq. phosphate buffer / 37 °C / pH 7.8 2: hydrogenchloride; oxygen / aq. phosphate buffer / 37 °C / 760.05 Torr / pH 7.8 | ||
Multi-step reaction with 2 steps 1: dichloromethane / 0.17 h / 0 - 20 °C 2: 2,4,6-triphenylpyrylium tetrafluoroborate / 10 h / 35 °C / Irradiation |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
58% | Stage #1: 2H-1,4-benzothiazin-3-one With tris-(dibenzylideneacetone)dipalladium(0); 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene; lithium hexamethyldisilazane In tetrahydrofuran; m-xylene at 20℃; for 0.166667h; Inert atmosphere; Stage #2: 4-chlorobenzophenone In tetrahydrofuran; m-xylene at 150℃; for 1h; Inert atmosphere; Microwave irradiation; | General procedure for C-arylation of 1,4-benzothiazin-3-one (Table 3) General procedure: In a microwavable tube were placed benzothiazin-3-one (1 mmol), Pd2(dba)3 (0.05 mmol), and xantphos (0.1 mmol). This mixture was carefully purged with N2 before the tube was capped. Under stirring, anhydrous xylene (2.5 mL) and a 1.0 M solution of LiHMDS in THF (2.5 mL) were sequentially added. The resulting mixture was stirred at rt for 10 min before aryl halides (pre-degassed with N2) was added. This mixture was subjected to microwave irradiation at 150 °C for 1 h. After cooling to rt, filtration was carried out. The combined filtrates were concentrated on rotavap and the residue was subjected to silica gel column chromatograph purification (20-30% ethyl acetate in heptane), furnishing desired products as yellowish solids |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | Stage #1: 4-chlorobenzophenone With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; palladium diacetate In tetrahydrofuran; toluene Inert atmosphere; Sealed tube; Stage #2: phenylmagnesium bromide In tetrahydrofuran; toluene at 20℃; for 2h; Inert atmosphere; Sealed tube; chemoselective reaction; | |
21% | Stage #1: phenylmagnesium bromide With titanium(IV) tetraethanolate In tetrahydrofuran at 20℃; for 0.5h; Inert atmosphere; Stage #2: 4-chlorobenzophenone With tributylphosphine; cobalt(II) chloride In tetrahydrofuran at 20℃; for 8h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With trifuran-2-yl-phosphane; palladium dichloride; In chloroform; at 60℃; for 2h;Inert atmosphere; | General procedure: After the reaction of arylboronic acid (1 mmol) with tributyltin methoxide (0.321 g, 1 mmol) at 100 C for 1 h under solvent-free conditions, chloroform (4 mL) was added to the reaction mixture at room temperature. Either Pd(OAc)2 (0.0022 g, 0.01 mmol) or PdCl2 (0.0017 g, 0.01 mmol) and tri(2-furyl)phosphine (0.0046 g,0.02 mmol) were added under an argon gas stream, followed by addition of aroyl chloride (1 mmol) at room temperature. The resulting mixture was heated in a heating block with stirring at 60 C for 2 h. The reaction mixture was filtered through a Celite pad, and the solvent was removed under reduced pressure. After addition of THF (5 mL) and 3 M NaOH (1 mL) to the residue, the mixture was stirred for 0.5 h at room temperature and then diluted with H2O (4 mL). The aqueous phase was extracted with EtOAc (35 mL) and organic layers were washed with brine (5 mL) dried over Na2SO4, filtered, and then concentrated in vacuo. The residue was purified by column chromatography on silica gel to give pure diaryl ketone. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With copper(l) iodide; tris(triphenylphosphine)rhodium(l) chloride; potassium carbonate; In 5,5-dimethyl-1,3-cyclohexadiene; at 120℃; for 2h; | General procedure: A reaction vessel was charged with a mixture of a benzoic anhydride (or an aryl carboxylic anhydride) (0.30 mmol), potassium aryltrifluoroborate (or potassium phenyltrifluoroborate) (0.60 mmol), K2CO3 (0.60 mmol), CuI (0.30 mmol), RhCl(PPh3)3 (0.003 mmol, 1.0 mol %) and xylene (1.5 mL). The mixture was heated to 120 C and stirred for 2 h. After the completion of the reaction, the mixture was quenched with 5 mL of water, and then extracted with ethyl acetate (3×10 mL). The combined organic layers were dried over magnesium sulfate. After removal of the solvent in vacuo, the product was isolated by column chromatography. Ethyl acetate/petroleum ether was used for elution and the yield was calculated based on the amount of aryl benzoic anhydride (the purified products were identified by NMR spectra). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With potassium carbonate; nickel dibromide; In N,N-dimethyl-formamide; at 100℃; for 2.8h; | General procedure: 4-Iodotoluene (1.0 mmol, 0.21 g) was added to a flask equipped with Ph3SnCl (0.4 mmol, 0.15 g), NiBr2 (16.0 mol%, 0.034 g), K2CO3 (3.0 mmol, 0.29 g), and Cr(CO)6 (1.0 mmol, 0.22 g) in DMF (3.0 mL) and the resulting mixture was heated in an oil bath at 100 C and stirred for 2.7 h. Progress of the reaction was monitored by TLC. After completion, the reaction mixture was cooled to room temperature, then H2O (10 mL) was added and the mixture was transferred to a separatory funnel. The aqueous phase was further washed with EtOAc (3×10 mL) and the combined organic phases were dried over anhydrous Na2SO4 and then filtered. Column chromatography of the obtained residue on silica gel (n-hexane/EtOAc=20:1) gave the desired ketone in 89% yield (0.11 g) (Table4, entry 2). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With potassium carbonate; nickel dibromide; In N,N-dimethyl-formamide; at 100℃; for 3h; | General procedure: 4-Iodotoluene (1.0 mmol, 0.21 g) was added to a flask equipped with Ph3SnCl (0.4 mmol, 0.15 g), NiBr2 (16.0 mol%, 0.034 g), K2CO3 (3.0 mmol, 0.29 g), and Cr(CO)6 (1.0 mmol, 0.22 g) in DMF (3.0 mL) and the resulting mixture was heated in an oil bath at 100 C and stirred for 2.7h. Progress of the reaction was monitored by TLC. After completion, the reaction mixture was cooled to room temperature, then H2O (10 mL) was added and the mixture was transferred to a separatory funnel. The aqueous phase was further washed with EtOAc (3×10 mL) and the combined organic phases were dried over anhydrous Na2SO4 and then filtered. Column chromatography of the obtained residue on silica gel (n-hexane/EtOAc=20:1) gave the desired ketone in 89% yield (0.11 g) (Table4, entry 2). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With dichloro bis(acetonitrile) palladium(II); cesium fluoride In 1-methyl-pyrrolidin-2-one at 80℃; for 6h; | Typical procedure for carbonylative coupling with aryl iodines: General procedure: A mixture of aryl silane (0.5 mmol), aryl iodines (0.5 mmol), PdCl2(MeCN)2 (5 mol%), and CsF (0.5 mmol) was stirred at 80oC for 6 h in NMP (5 mL) under CO (1atm). Afterwards, 2 mL water was added to the reaction solution and then filtered through a filter paper and the solution was extracted by Et2O (2 mL) for three times. The organic phase was combined and evaporated under reduced pressure. The residue was purified on a SiO2 column to afford the desired product (ethyl acetate/hexane). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With dichloro bis(acetonitrile) palladium(II); cesium fluoride In 1-methyl-pyrrolidin-2-one at 100℃; for 6h; | Typical procedure for carbonylative coupling with aryl bromides: General procedure: A mixture of aryl silane (0.5 mmol), aryl bromides (0.5 mmol), PdCl2(MeCN)2 (5 mol%), and CsF (0.5 mmol) was stirred at 100oC for 6 h in NMP under CO (1atm) (5 mL). Afterwards, 2 mL water was added to the reaction solution and then filtered through a filter paper and the solution was extracted by Et2O (2 mL) for three times. The organic phase was combined and evaporated under reduced pressure. The residue was purified on a SiO2 column to afford the desired product(ethyl acetate/hexane). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; palladium(II) trifluoroacetate In tert-butyl methyl ether at 80℃; for 6h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | Stage #1: Methyltriphenylphosphonium bromide With potassium <i>tert</i>-butylate In tetrahydrofuran at 20℃; for 1h; Stage #2: 4-chlorobenzophenone In tetrahydrofuran at 50℃; for 1h; | |
73% | Stage #1: Methyltriphenylphosphonium bromide With potassium <i>tert</i>-butylate In tetrahydrofuran at 0℃; for 0.5h; Stage #2: 4-chlorobenzophenone In tetrahydrofuran at 0 - 20℃; | |
69% | Stage #1: Methyltriphenylphosphonium bromide With n-butyllithium In tetrahydrofuran at 0 - 20℃; for 0.5h; Inert atmosphere; Stage #2: 4-chlorobenzophenone In tetrahydrofuran at 20℃; Inert atmosphere; Cooling; | Typical procedure for the synthesis of 5a-i and 5k-5p General procedure: Ph3PCH3Br (1.20 equiv) was added to a flame-dried round-bottom flask, evacuated, backfilled with N2 three times, and suspended in THF (0.25 M) at 0°C. To this vigorously stirring heterogeneous solution was added nBuLi (1.20 equiv) dropwise, and the reaction was allowed to stirred at room temperature for 30 min until a bright yellow heterogeneous mixture was achieved. Then commercially available 1,1-diarylmethanone (1.00 equiv) was added slowly. Upon complete addition, the cooling bath was removed and the reaction was allowed to stir overnight. Then, the solution was washed by brine and extracted with EtOAc (3×10 mL). The combined organic layers were dried over MgSO4, and concentrated under vacuum. The residue was purified by silica gel flash chromatography (PE:EA = 100:1) to afford the corresponding 1,1-diarylethene 5 and NMR spectra was compared to known literatures values. |
Stage #1: Methyltriphenylphosphonium bromide With potassium <i>tert</i>-butylate In tetrahydrofuran at 0℃; for 0.75h; Stage #2: 4-chlorobenzophenone In tetrahydrofuran at 0 - 20℃; for 16h; | ||
Stage #1: Methyltriphenylphosphonium bromide With n-butyllithium In tetrahydrofuran at 0℃; for 0.25h; Inert atmosphere; Stage #2: 4-chlorobenzophenone In tetrahydrofuran at 0 - 20℃; for 48h; Inert atmosphere; | ||
Stage #1: Methyltriphenylphosphonium bromide With potassium <i>tert</i>-butylate In tetrahydrofuran at 20℃; for 1h; Inert atmosphere; Stage #2: 4-chlorobenzophenone In tetrahydrofuran at 20℃; Inert atmosphere; | ||
Stage #1: Methyltriphenylphosphonium bromide With potassium <i>tert</i>-butylate In tetrahydrofuran at 20℃; for 1h; Inert atmosphere; Stage #2: 4-chlorobenzophenone In tetrahydrofuran at 20℃; Inert atmosphere; | Step 1: General procedure: In an oven dried flask, was added methyl triphenylphosphonium bromide (1.2 equiv) followed by THF (2.5 mL/mmol). Then t-BuOK (1.2 equiv) was added and the resulting yellow suspension was stirred at room temperature for 60 min. To this suspension, a solution of ketone or aldehyde (1.0 equiv) was added in one portion and the resulting mixture was further stirred at room temperature overnight. Water and DCM were added to the reaction mixture, and the aqueous phase was extracted with DCM (3 × 50 mL). The combined organic phases were washed with saturated NaCl solution, dried over Na2SO4 and the solvent removed under reduced pressure. The reaction mixture was purified by column chromatography over silica gel (200-300 mesh) using hexanes as eluent afforded S1. | |
With potassium <i>tert</i>-butylate In tetrahydrofuran at 0 - 50℃; for 2.5h; | ||
With potassium <i>tert</i>-butylate In tetrahydrofuran at 20℃; for 3h; | ||
Stage #1: Methyltriphenylphosphonium bromide With potassium <i>tert</i>-butylate In tetrahydrofuran at 0℃; for 0.75h; Stage #2: 4-chlorobenzophenone In tetrahydrofuran at 0 - 20℃; for 16h; | ||
Stage #1: Methyltriphenylphosphonium bromide With potassium <i>tert</i>-butylate In tetrahydrofuran at 20℃; for 1h; Schlenk technique; Inert atmosphere; Stage #2: 4-chlorobenzophenone In tetrahydrofuran at 20℃; for 12h; Schlenk technique; Inert atmosphere; | ||
Stage #1: Methyltriphenylphosphonium bromide With potassium <i>tert</i>-butylate In tetrahydrofuran at 0℃; for 0.5h; Inert atmosphere; Stage #2: 4-chlorobenzophenone In tetrahydrofuran at 20℃; Inert atmosphere; | ||
Stage #1: Methyltriphenylphosphonium bromide With potassium <i>tert</i>-butylate In diethyl ether at 20℃; Inert atmosphere; Stage #2: 4-chlorobenzophenone In diethyl ether at 0 - 20℃; Inert atmosphere; | ||
Stage #1: Methyltriphenylphosphonium bromide With potassium <i>tert</i>-butylate In tetrahydrofuran at 20℃; for 1h; Inert atmosphere; Stage #2: 4-chlorobenzophenone In tetrahydrofuran at 20℃; Inert atmosphere; | ||
Stage #1: Methyltriphenylphosphonium bromide With potassium <i>tert</i>-butylate In tetrahydrofuran at 0 - 20℃; Stage #2: 4-chlorobenzophenone In tetrahydrofuran at 0 - 20℃; | General procedure for the preparation of substituted olefin: General procedure: An oven-dried round-bottom flask was charged with CH3PPh3Br (1.5 equiv.) or CH3CH2PPh3Br (1.5equiv.) and THF (carbonyl substrate concentration = 0.2 M). tBuOK (1.5 equiv.) was added to thesuspension at 0 °C. The resulting mixture was allowed to warm up to room temperature and stirred for 1h. The yellow suspension was cooled to 0 °C again followed by portion-wise addition of the carbonylsubstrate (1 equiv.). Subsequently, the mixture was further stirred at room temperature for 1-12 hours.After the completion of the reaction, the solvent was removed by evaporation, the resulting mixture wasdiluted with water (30 mL) and extract with dichloromethane (3 x 20 mL), and the combined organiclayer was dried with anhydrous Na2SO4. Concentration in vacuo followed by silica gel columnpurification with petroleum ether/ethyl acetate eluent gave the desired product in yields range from 50-95%. | |
Stage #1: Methyltriphenylphosphonium bromide With n-butyllithium In tetrahydrofuran at 0℃; for 1h; Inert atmosphere; Stage #2: 4-chlorobenzophenone In tetrahydrofuran at 0 - 20℃; for 2.5h; Inert atmosphere; | ||
Stage #1: Methyltriphenylphosphonium bromide With potassium <i>tert</i>-butylate In tetrahydrofuran at 20℃; for 1h; Inert atmosphere; Stage #2: 4-chlorobenzophenone In tetrahydrofuran at 20℃; for 1h; Inert atmosphere; | 2.2 One typical example for the preparation of alkenes. General procedure: To a suspension of tBuOK (12 mmol, 1.2 equiv.) in anhydrous THF (20 mL) was added MePPh3Br (12 mmol, 1.2 equiv.) under argon atmosphere. The suspension was stirred at room temperature for 1 h. Then corresponding ketone (10 mmol, 1.0 equiv.) was added and the reaction mixture was stirred at the same temperature for 1 h . Then the mixture was filtered through a short pad of silica gel, which was subsequently washed with ethyl acetate (200 mL). After evaporation of the organic solvent, the residue was purified by silica gel column chromatography to provide alkene 1i (1.31g, 90%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
> 99 % ee | With pyridoxal 5'-phosphate; transaminase-3; piruvate In dimethyl sulfoxide at 30℃; Enzymatic reaction; enantioselective reaction; | Determination of activity in kinetic resolution mode. General procedure: The activity measurements were performed in a TECAN Infinite 200 PRO reader, and all measurements were performed at least in triplicate. A direct photometric assay was used28, in which the enzymatic reaction took place in CHES buffer (50 mM, pH 9.0) at 30 °C in a total volume of 200 μl. 1 mM racemic amine (1a-4a) and 2 mM pyruvate were added to the buffer (final concentrations) containing the TA of interest. Due to the preparation of the amine stock solution in organic solvent, 5% (vol/vol) 2-propanol or dimethylsulfoxide (DMSO, 0.1% for compounds 5-7) was present in the final reaction medium. The kinetic resolution was initiated by the addition of the amine acceptor (pyruvate). The final concentration of the enzyme varied between 2 and 800 μg ml-1, depending on the specific activity towards the substrates under examination. The production of the corresponding ketones (1b-7b) was monitored at the optimum wavelength for each compound (1b, 16,562M-1 cm-1 at 264 nm; 2b, 9,646 M-1 cm-1at 245 nm; 3b, 5,714 M-1 cm-1 at 340 nm; 4b, 6,115 M-1 cm-1 at 245 nm (ref. 27);5b and 6b, 6,530 M-1 cm-1 at 242 nm (ref. 15); and 7b, 7,098 M-1 cm-1at 252 nm (ref. 14)). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With sodium hydrogencarbonate In N,N-dimethyl-formamide at 120℃; Sealed tube; | 4.1. The process of Pd-Pt NDs catalyzed ligand-free carbonylative Suzukicross-coupling General procedure: General procedure: a 50 mL ask equipped with a magnetic stir bar was charged with aryboronic acid (1 mmol, 1 equiv), aromatic halides (1.2 mmol, 1.2 equiv), catalyst (2 mol%), base (2 mmol, 2 equiv), DMF (5 mL) solution under CO (1 atm) atmosphere, along with sealed the reaction flask by a rubber stopper and CO was injected into it with a stainless steel gas flowmeter. The mixture was then stirred at 120 °C forthe indicated time (SI, Fig. S1). After being allowed to cool to roomtemperature, the reaction mixture was diluted with 5 mL water and extracted with diethyl ether (3 × 5 mL). The organic phases werecombined, and the volatile components were evaporated in a rotaryevaporator. The residue was puried by column chromatography onsilica gel. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: 1-bromo-2-(2-naphthyl)benzene With n-butyllithium In tetrahydrofuran at -78℃; for 2h; Stage #2: 4-chlorobenzophenone In tetrahydrofuran for 2h; | 4.2 Preparation of Chemical Formula 4B Chemical Formula 4A (50.0 g, 176.57 mmol) was put into 500 ml of anhydrous tetrahydrofuran, and cooled to -78° C. Thereafter, n-butyl lithium (91.8 mL, 229.54 mmol) was slowly added dropwise thereto over 60 minutes while the mixture was being stirred, and then the resulting mixture was reacted for 1 hour. Thereafter, (4-chlorophenyl) (phenyl)methanone was introduced thereinto in a solid state, the temperature was slowly increased to normal temperature, and the resulting mixture was reacted for 2 hours. After the reaction, the reaction was terminated by pouring water thereto, and then the aqueous layer and the organic layer were separated, and then the organic layer was distilled under reduced pressure to obtain a solid. The solid was again put into 500 ml of acetic acid while the mixture was being stirred, and one or two drops of sulfuric acid was(were) introduced thereinto as a catalyst, and then the resulting mixture was refluxed. After the mixture was reacted for 2 hours, the produced solid was filtered, and the filtered material was again dissolved in chloroform, and then was neutralized and extracted by using water saturated with calcium carbonate, and then the organic layer was dried by using magnesium sulfate. Thereafter, the organic layer was distilled under reduced pressure, and then recrystallized by using ethanol. The produced solid was filtered and then dried to prepare Chemical Formula 4B (45.5 g, 64%). n-butyl lithium and (4-chlorophenyl) (phenyl)methanone were purchased from Aldrich Inc., and TCI Co., Ltd., respectively. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91 % ee | With pyridoxal 5'-phosphate; amine transaminase from Ruegeria sp. TM1040 variant Y59W-Y87F-Y152F-T231A-W59L-R420A; isopropylamine In dimethyl sulfoxide at 30℃; for 20h; Enzymatic reaction; | |
Multi-step reaction with 2 steps 1: formamide / 170 - 175 °C / Inert atmosphere 2: L-Tartaric acid / 30 - 90 °C / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80 % ee | With pyridoxal 5'-phosphate; amine transaminase from Ruegeria sp. TM1040 variant Y59W-Y87F-Y152F-T231A-W59L-R420W; isopropylamine In dimethyl sulfoxide at 30℃; for 20h; Enzymatic reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With sodium carbonate In water; N,N-dimethyl-formamide at 120℃; for 10h; | 3.12. 4-benzoylbenzonitrile (2m) 6 A round-bottomed flask (10 mL) was charged with 4-chlorobenzophenone (1.5 mmol, 0.324 g), Na2CO3 (1.8 mmol, 0.190 g), the catalyst (0.0075 g, 1.7 mol%) and 1:1 (V/V) DMF/H2O (5 mL). The reaction mixture was heated to 120 °C and K4[Fe(CN)6].3H2O (0.60 mmol, 0.253 g) was then added. The final mixture was stirred for 10 h. at 120 °C. After allowing the mixture to cool to room temperature, the catalyst was filtrated.Then H2O (15 mL) was added to the mixture and the product was extracted with ethyl acetate (3 10 mL). The organic extracts were collective and dried over anhydrous Na2SO4. Evaporation of the solvent afforded the crude desired product, which was purified by column chromatography using hexane/EtOAc 20:5 (v/v) as the eluents, to afford the title compound. Yield: 85%. Light yellow solid. M.p. 109-112 oC.1H-NMR (250 MHz, CDCl3/TMS) δ (ppm): 7.43-7.49 (m, 2H), 7.54-7.60 (m, 1H), 7.69-7.74 (m, 4H), 7.81 (d, J = 8.2 Hz, 2H). IR (KBr, cm-1): 2846, 2229, 1743, 1650, 1550, 1535, 1519, 1458, 1311, 1280, 1110, 933, 856, 794, 694, 594, 586. Anal.Calcd.for C14H9NO (207.48): C, 81.14; H, 4. 38; N, 6.76. Found: C, 81.09; H, 4.31; N, 6.69. |
85% | Stage #1: potassiumhexacyanoferrate(II) trihydrate; 4-chlorobenzophenone With sodium 2'‐(dicyclohexylphosphaneyl)‐2,6‐diisopropyl‐[1,1'‐biphenyl]‐4‐sulfonate; palladium diacetate; potassium carbonate In water at 120℃; for 12h; Inert atmosphere; Sealed tube; Stage #2: potassiumhexacyanoferrate(II) trihydrate; 4-chlorobenzophenone With potassium acetate In water at 100℃; for 12h; Inert atmosphere; Sealed tube; | 2.3 General Procedure forPalladium-CatalyzedCyanation ofAryl ChlorideswithK4[Fe(CN)6]·3H2O inPEG-400/H2O General procedure: A pressure tube equipped with a magnetic stir bar wascharged with Pd(OAc)2 (4.5mg, 0.02mmol), XPhos-SO3Na(20.9 mg, 0.04 mmol), K4[Fe(CN)6]·3H2O (105.6 mg,0.25mmol), K2CO3(35mg, 0.25mmol) and PEG-400(1.0mL). The reaction tube was evacuated and backfilledwith argon (this sequence was carried out three times) andthen aryl chloride (1.0mmol, if liquid) and water (1.0mL)were added by syringe (aryl chlorides that were solids atroom temperature were added with the palladium catalystand ligand). The reaction tube was sealed and the reactionmixture was stirred for 12h at the indicated temperature.After being cooled to room temperature, the mixture wasextracted with cyclohexane (3 × 10mL). The combinedcyclohexane phase was concentrated under reduced pressure,and the residue was purified by flash column chromatographyon silica gel (light petroleum ether-ethyl acetate)to afford the desired aryl nitrile 2.The residue of the extraction was heated to 50C invacuo for 30min to remove the residual cyclohexane, andthen subjected to a second cycle of the cyanation reactionby charging with the same substrates (aryl chloride,K4[Fe(CN)6]·3H2O and K2CO3)under the same conditionswithout further addition of Pd(OAc)2 and Xphos-SO3Na. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
63% | With manganese; 4,4'-Dimethoxy-2,2'-bipyridin; magnesium chloride; nickel dibromide; In 1-methyl-pyrrolidin-2-one; at 80℃; for 24h;Inert atmosphere; Sealed tube; | Under a nitrogen atmosphere, nickel bromide (4.4 mg, 0.02 mmol),4,4'-dimethoxy-2,2'-bipyridine (4.3 mg, 0.02 mmol), magnesium chloride (28.6 mg, 0.3 mmol), manganese powder (43.95 mg, 0.8 mmol), and a solvent NMP (0.5 mL) was added )And stir well. Weigh 4-chlorobenzophenone (43.33mg, 0.2mmol)Dissolve in NMP (0.5mL), add <strong>[762-51-6]1-fluoro-2-iodoethane</strong> (26muL, 0.3mmol) after dissolutionAnd mix well, the solution is transferred to the sealed tube. After sealing, stir the reaction in an oil bath at 80 C. 24Hour, cool the reaction to room temperature, ether (5mL)Add an equal volume of saturated ammonium chloride solution to the diluted reaction solution.Filter through a diatomaceous sand core funnel, rinse with a small amount of ether, and collect the filtrate.The filtrate was extracted three times with diethyl ether, and the organic phases were combined (add internal standard dodecane,GC-MS determined crude yield). Dry over anhydrous sodium sulfate, filter, and remove the solvent by distillation under reduced pressure.After the residue was separated by silica gel column chromatography, the product was weighed.The calculated yield was 63%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With sodium t-butanolate; In N,N-dimethyl acetamide; at 80℃; for 0.25h; | General procedure: Aryl halide (1.0 mmol), arylboronic acid (1.1 mmol),t-BuONa (2.0 mmol), SBA-16/DFMP-Pd (0.0026 g,0.2 mol%), and Cr(CO)6 (0.5 mmol, 0.11 g) in DMA(3.0mL) was stirred in a flask at 80C. The reaction progress was monitored by thin layer chromatography (TLC).Upon the reaction’s completion, the mixture was allowed to cool down to room temperature and then filtered and washed with H2Oand ethyl acetate. The organic fraction was separated,dried over anhydrous Na2SO4 and then the solvent was removed using a rotary evaporator. Further purification was performed on silica gel column chromatography to afford the pure products. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With 2-(2,6-dimethoxyphenyl)-1-methyl-3-(diphenylphosphino)-1H-indole; palladium diacetate; lithium tert-butoxide In 1,4-dioxane at 100℃; for 1h; Schlenk technique; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With palladium diacetate; 2-(2-(di-tert-butylphosphanyl)phenyl)-1-methyl-1H-indole; lithium tert-butoxide In 1,4-dioxane at 100℃; for 18h; Schlenk technique; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With bis(1,5-cyclooctadiene)nickel (0); 7,9-bis(2,6-diisopropylphenyl)-7H-acenaphtho[1,2-d]imidazol-9-ium chloride; potassium <i>tert</i>-butylate In water; toluene at 35℃; for 24h; Glovebox; Sealed tube; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With bis(1,5-cyclooctadiene)nickel (0); CyPAd-DalPhos; sodium 2,2,2-trifluoroacetate; 1,8-diazabicyclo[5.4.0]undec-7-ene In toluene at 110℃; for 18h; Inert atmosphere; Sealed tube; Glovebox; | N-Arylation of Amides with Aryl Electrophiles (Figures 3 and4); General Procedure General procedure: In a N2-filled glovebox, a screw-capped vial containing a magneticstirrer bar was charged with Ni(COD)2 (5 mol%), CyPAd-DalPhos (5 mol%), the appropriate aryl (pseudo)halide (0.45mmol, 1.0 equiv, 0.12 M), DBU (2.0 equiv), NaTFA (2.0 equiv),and the appropriate amide (1.1 equiv), followed by the additionof toluene (3.75 mL). The vial was sealed with a cap containing aPTFE septum, removed from the glovebox, and placed in a temperature-controlled aluminum heating block set to 100 °C for 18h, with magnetic stirring. The vial was then removed from theheating block and left to cool to rt. The crude reaction mixturewas filtered through a short plug of Celite and silica gel (3:1v/v), eluting with EtOAc. The volatile materials were evaporatedin vacuo, and the crude product was purified by flash-columnchromatography. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
45% | With potassium <i>tert</i>-butylate; cobalt(II) chloride; 1,3-bis[2,6-diisopropylphenyl]imidazolium chloride In tetrahydrofuran at 60℃; for 24h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With (S,E)-3-methyl-N-phenyl-2-((pyridin-2-ylmethylene)amino)butanamide-UiO-Fe metal-organic framework In tetrahydrofuran at 25℃; for 2h; Inert atmosphere; Glovebox; enantioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94.1% | With iron(III) oxide at 120℃; for 8h; | 6 Under stirring, benzene (13.3mol), p-chlorobenzoic acid (1.338mol),Fe2O3 (0.12mol) and p-chlorotrichlorotoluene (1.472mol) were added to the reactor in turn,Use jacket steam to heat, after adding p-chlorotrichlorotoluene, at 120,The reaction was stirred at 0.2MPa for 8 hours until no hydrogen chloride gas was discharged. During the reaction, the discharged gas was recovered through the water circulation condensation system, and the organic components were recompressed back into the reactor, and the discharged hydrogen chloride gas was absorbed with water to make 30% industrial hydrochloric acid. After the reaction, a brown reaction mixture is obtained. The brown reaction mixture is filtered and washed with pressure. The resulting organic layer is subjected to atmospheric pressure and reduced pressure (pressure of 1000 Pa) at 85°C to recover chlorobenzene to obtain crude 4-chlorodibenzene. Methyl ketone; place the crude 4-chlorobenzophenone in a rectification kettle, heat and rectify under reduced pressure, when the pressure is less than 500Pa, collect the fractions with a temperature of 140150 to obtain purified 4-chlorobenzophenone The ketone is 544.6 g, the purity is 98.42%, and the yield is 94.1%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With tris(dibenzylideneacetone)dipalladium(0) chloroform complex; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene In N,N-dimethyl-formamide at 140℃; for 24h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: 1-bromo-2-(methoxymethyl)benzene With iodine; magnesium In tetrahydrofuran at 60℃; for 2h; Inert atmosphere; Stage #2: 4-chlorobenzophenone In tetrahydrofuran at 60℃; for 6.33333h; |
Tags: 134-85-0 synthesis path| 134-85-0 SDS| 134-85-0 COA| 134-85-0 purity| 134-85-0 application| 134-85-0 NMR| 134-85-0 COA| 134-85-0 structure
[ 1016-78-0 ]
(3-Chlorophenyl)(phenyl)methanone
Similarity: 0.98
[ 25017-08-7 ]
1-(4-Chlorophenyl)pentan-1-one
Similarity: 0.95
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H303 | May be harmful if swallowed |
H304 | May be fatal if swallowed and enters airways |
H305 | May be harmful if swallowed and enters airways |
H310 | Fatal in contact with skin |
H311 | Toxic in contact with skin |
H312 | Harmful in contact with skin |
H313 | May be harmful in contact with skin |
H314 | Causes severe skin burns and eye damage |
H315 | Causes skin irritation |
H316 | Causes mild skin irritation |
H317 | May cause an allergic skin reaction |
H318 | Causes serious eye damage |
H319 | Causes serious eye irritation |
H320 | Causes eye irritation |
H330 | Fatal if inhaled |
H331 | Toxic if inhaled |
H332 | Harmful if inhaled |
H333 | May be harmful if inhaled |
H334 | May cause allergy or asthma symptoms or breathing difficulties if inhaled |
H335 | May cause respiratory irritation |
H336 | May cause drowsiness or dizziness |
H340 | May cause genetic defects |
H341 | Suspected of causing genetic defects |
H350 | May cause cancer |
H351 | Suspected of causing cancer |
H360 | May damage fertility or the unborn child |
H361 | Suspected of damaging fertility or the unborn child |
H361d | Suspected of damaging the unborn child |
H362 | May cause harm to breast-fed children |
H370 | Causes damage to organs |
H371 | May cause damage to organs |
H372 | Causes damage to organs through prolonged or repeated exposure |
H373 | May cause damage to organs through prolonged or repeated exposure |
Environmental hazards | |
Code | Phrase |
H400 | Very toxic to aquatic life |
H401 | Toxic to aquatic life |
H402 | Harmful to aquatic life |
H410 | Very toxic to aquatic life with long-lasting effects |
H411 | Toxic to aquatic life with long-lasting effects |
H412 | Harmful to aquatic life with long-lasting effects |
H413 | May cause long-lasting harmful effects to aquatic life |
H420 | Harms public health and the environment by destroying ozone in the upper atmosphere |
Sorry,this product has been discontinued.
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