* 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.
With dichloro bis(acetonitrile) palladium(II); cesium fluoride In 1-methyl-pyrrolidin-2-one at 80℃; for 6 h;
General procedure: A mixture of aryl silane (0.5 mmol), aryl iodines (0.5 mmol), PdCl2(MeCN)2 (5 molpercent), 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).
With dichloro bis(acetonitrile) palladium(II); cesium fluoride In 1-methyl-pyrrolidin-2-one at 100℃; for 6 h;
General procedure: A mixture of aryl silane (0.5 mmol), aryl bromides (0.5 mmol), PdCl2(MeCN)2 (5 molpercent), 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).
With oxygen; copper diacetate; potassium carbonate; aniline In dimethyl sulfoxide at 120℃; Schlenk technique; Sealed tube
General procedure: An oven-dried Schlenk tube was charged with a magnetic stir-bar, 1,2-diarylalkynes 1 (0.5mmol), aniline (0.6mmol), K2CO3 (0.5mmol), Cu(OAc)2 (0.075mmol), DMSO (3mL), The tube was sealed, and oxygen was purged through syringe. Reaction was stirred at 120°C for 16–18h. After the reaction was finished, the reaction mixture was diluted in 30mL ethyl acetate, filtered on Celite pad. The organic portion was washed with a saturated solution of brine (8mL), saturated NH4Cl (8mL), a saturated solution of brine (8mL), dried (Na2SO4) and concentrated in vacuum, and the resulting residue was purified by silica gel column chromatography (hexane/ethyl acetate) to afford the desired products 2.
With oxygen; sodium t-butanolate In dimethyl sulfoxide at 50℃; for 5 h; 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.
With palladium; hydrogen; In acetone; at 50℃; for 22h;
To a solvent of acetone (2 mL) with PdNPore (2.7 mg, 5 mol%) catalyst, 3,4-dimethylbenzophenone (105.1 mg, 0.5 mmol) as a substrate was added, and the mixture was placed on a magnetic stirrer at 50 C. After 22 hours of reaction, column chromatography (silica gel, 200-300 mesh; developing solvent, petroleum ether, ethyl acetate) gave 102.9 mg of 3,4-dimethylbenzyl alcohol with a yield of 97%.
With sulfuryl dichloride; dibenzoyl peroxide; In chlorobenzene;
A mixture of 3,4-dimethylbenzophenone (1.0 mole), benzoyl peroxide (5 grams), chlorobenzene (800 ml.) and 3.0 moles of sulfuryl chloride was heated at 90 C. for 3-1/2 hours. During the last 30 minutes of the reaction nitrogen was passed through the reactor to remove the excess sulfuryl chloride. The resultant mixture was cooled and 50 grams of carbon black was added and the mixture stirred for 30 minutes, after which the carbon black was removed by filtration. The product 3,4-bis(chloromethyl)benzophenone was isolated by stripping of the solvent. Analysis found: 62.1% C, 4.3% H, and 27.1% Cl. Theoretical: 64.5% C, 4.3% H, and 25.5% Cl.
Part (I)Synthesis of 4-CMe2Ph-o-xyleneThe 3, 4-dimethylbenzophenone (15.Og, 71.43mmol) was added to a 500ml schlenk flask, to this was added benzoic acid (150mg) . The solid was then dissolved in toluene (100ml) . To this was then added trimethyl aluminium (2.0M in toluene, 100ml, 200mmol) . The resultant solution was then heated to 125C for 60 hours. The solution was then allowed to cool to room temperature and was then quenched by the very slow addition of water (100ml) . This gave a white suspension, diethyl ether (150ml) was then added and the suspension filtered. The filtrate was then dried over sodium sulphate and filtered. The filtrate was then dried under vacuum, this gave a colourless oil, yield =13.4g, 84%.
With toluene-4-sulfonic acid; In ethanol; for 5h;Reflux;
General procedure: To a solution of benzophenone (7.28 g, 40 mmol) in EtOH (30 mL)were added TsNHNH2 (7.44 g, 40 mmol) and TsOH·H2O (76 mg, 0.4mmol, 1 mol%). The resulting mixture was refluxed for 5 h. After completionof the reaction, the mixture was cooled to r.t., the precipitatewas collected by filtration, and washed with PE. The precipitate wasdried in a desiccator under vacuum to afford the pure product 5a(13.12 g, 94%). The yields for other tosylhydrazones 5b-k were about75-95%. The reactions were usually carried out overnight and weremonitored by TLC.
With oxygen; copper diacetate; potassium carbonate; aniline; In dimethyl sulfoxide; at 120℃;Schlenk technique; Sealed tube;
General procedure: An oven-dried Schlenk tube was charged with a magnetic stir-bar, 1,2-diarylalkynes 1 (0.5mmol), aniline (0.6mmol), K2CO3 (0.5mmol), Cu(OAc)2 (0.075mmol), DMSO (3mL), The tube was sealed, and oxygen was purged through syringe. Reaction was stirred at 120C for 16-18h. After the reaction was finished, the reaction mixture was diluted in 30mL ethyl acetate, filtered on Celite pad. The organic portion was washed with a saturated solution of brine (8mL), saturated NH4Cl (8mL), a saturated solution of brine (8mL), dried (Na2SO4) and concentrated in vacuum, and the resulting residue was purified by silica gel column chromatography (hexane/ethyl acetate) to afford the desired products 2.
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 0C. 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.
With dichloro bis(acetonitrile) palladium(II); cesium fluoride; In 1-methyl-pyrrolidin-2-one; at 80℃; under 760.051 Torr; for 6h;
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).
With dichloro bis(acetonitrile) palladium(II); cesium fluoride; In 1-methyl-pyrrolidin-2-one; at 100℃; under 760.051 Torr; for 6h;
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).
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.
In tetrahydrofuran; at 20℃;Inert atmosphere; Cooling with ice;
General procedure: To a two-necked flask under argon atmosphere loaded with a solution of ketone (5mmol) in anhydrous THF (5mL) then under vigorous stirring Grignard reagent (1.0M in THF, 5.5mL, 5.5mmol, 1.1 equiv.) was dropwise added via syringe in ice-bath. The mixture was stirred for 0.5h in ice bath, then warmed to room temperature and stirred for 2-5h. After detected by TLC, aqueous NH4Cl (6mL) was added to quench the reaction, then the mixture was extracted with EtOAc (5mL×3). The combined organic layers were dried over anhydrous magnesium. The solvent was removed in vacuo by ratory evaporator. And the crude was purified by chromatography on silica gel to obtain desired allylic alcohols.
With tetrakis(triphenylphosphine) palladium(0); potassium acetate; silver fluoride; triphenylphosphine; In hexane; at 140℃; for 20h;Sealed tube; Inert atmosphere;
(1) Adding 3,4-dimethylbenzophenone 0.0420 g (0.2 mmol) and tetratriphenylphosphine palladium to the reaction tube0.0116 g (0.01 mmol), potassium acetate 0.0786 g (0.8 mmol), triphenylphosphine 0.0157 g (0.06 mmol), silver fluoride 0.0077 g (0.06 mmol), ethyl bromodifluoroacetate 0.0203 g (1.00 mmol) and 0.25 mL of n-hexane, filled with argon gas, and reacted at 140 C for 20 hours;(2) TLC tracks the reaction until it is completely over;(3) The crude product obtained after the completion of the reaction was separated by column chromatography (petroleum ether: ethyl acetate = 15:1) to obtain a target.Product (yield 54%).