4-(Methylthio)benzaldehyde

clear yellow liquid

General procedure: In a typical procedure, diphenyl sulfoxide (2.2 g, 0.01 mol) and brominated silica (18.18 g, 40 mmole Br/g silica) are mixed in an aprotic solvent, e.g. dichloromethane (2 mL) or carbon tetrachloride, at room temperature with exclusion of atmospheric moisture, for 5 min. Diphenyl sulfide is isolated in pure state by simple filtration and evaporation of the solvent (1.84, 99percent).General procedure: In a 10 mL round-bottom flask, to a solution of diphenylsulfoxide (202 mg, 1.0mmol) in CH3CN (4 mL), tantalum (IV) chloride (179 mg, 0.5 mmol) and sodium iodide (300 mg, 2.0 mmol) were added at room temperature. The mixture turned dark brown almost immediately and the progress of the reaction was followed by TLC. After completion of the reaction (3 min), the reaction mixture was diluted with water and then extracted with ethyl acetate. The combined organic extracts were washed successively with 10percent aq Na2S2O3 and H2O. The organic layer was separated and dried over anhydrous Na2SO4 and concentrated under reduced pressure. The resulting crude product was purified through silicagel column chromatography (hexane:ethyl acetate = 2:1) to afford diphenylsulfide (88 mg, 95percent).General procedure: Diphenylsulfoxide (101 mg, 0.5 mmol) and hafnium(IV) chloride (320 mg, 1.0 mmol) were mixed in CH3CN (5 mL) and zinc powder (131 mg, 2.0 mmol) was then added to this solution. The whole mixture was stirred for 3 h at room temperature and the progress of the reaction was followed by TLC. On completion, the solvent was removed under reduced pressure and the residue was extracted successively with ethyl acetate, washed with water and brine. The organic layer was separated, dried over anhydrous Na2SO4 and concentrated under reduced pressure. The crude product was purified by column chromatography on a silica gel (hexane:ethyl acetate = 2:1) to afford diphenylsulfide (88 mg, 95percent). All of the products were identified by comparison of their spectroscopic data with authentic samples.[34]General procedure: Indium powder (229 mg, 2.0 mmol) and tantalum(V) chloride(358mg, 1.0mmol)weremixed inCH3CN(5 mL). The resultingmixture was sonicated for 0.5 h to produce a solution of the lowvalenttantalum–indium complex. Diphenyl sulfoxide (101 mg, 0.5 mmol) was then added to this solution and the reactionmixturewas stirred for 3.0 h at room temperature. The progressof the reaction was followed by TLC. On completion, the solventwas removed under reduced pressure and the residue wasextracted successively with ethyl acetate, washed with water andbrine. The organic layerwas separated and dried over anhydrousNa2SO4. The crude product was purified by column chromatographyon silica gel (hexane:ethyl acetate=2:1) to afford diphenylsulfide (86mg, 92percent). All of the productswere identified by comparisonof their spectroscopic data with authentic samples.General procedure: A mixture of catalyst PS–PEG-TD2–Cu(OAc)2 (100 mg, 0.05mmol Cu), BnOH (1a, 27.0 mg, 0.25 mmol), and TEMPO (7.8 mg, 0.05 mmol) in heptane (2.0 mL) was stirred at 80 °C for 24 hunder air (1 atm). The mixture was then cooled and filtered, andthe resulting solid material was washed with Et2O (3 × 2 mL).The organic phases were combined, concentrated to a volume of2 mL, and the internal standard was added to determine the GCyield. The crude product was purified by column chromatography[silica gel, hexane–Et2O (99:1)]. In the formation of somebenzaldehydes, low isolated yields were observed because ofinstability of the benzaldehydes on silica gelGeneral procedure: To a 48 mL tube, were added Cu(II) or Cu(I) salt (0.05 mmol), PEG-PyTa (0.025 mmol) and HGeneral procedure: To a 10mL round bottom flask, the mixture of 12 benzylalcohol 1a (1.0mmol, 0.104mL) and CuGeneral procedure: A CHGeneral procedure: A mixture of p-methylbenzyl alcohol (1.0 mmol), N-phenylglycine(0.0076 g, 0.05 mmol), CuBr2 (0.0112 g, 0.05 mmol), Na2CO3 (0.1060 g, 1.0 mmol), TEMPO (0.0078 g, 0.05 mmol), H2O (3.0 mL) were added to a 100 mL Schlenk tube, which wasvigorously stirred in air under reflux for 0.5 h. After the reaction, the product was extracted with CH2Cl2 (3 × 2.0 mL). Thecombined organic phase was washed with H2O (3.0 mL) anddried over anhydrous MgSO4. After concentration undervacuum, the residue was purified by column chromatography toafford p-methylbenzaldehyde.Isolated yield: 0.1080 g (90percent).General procedure: In a 150 mL thick-walled pressure tube equipped with a magnetic stirrer, In an air atmosphere, To the system was added benzyl alcohol (i.e., R1 in formula (I) H) 1.0 mmol (108.1 mg)Ammonia (1.6 x 10-2 mol / L) 5.0 mL, 5 molpercent (9.5 mg) of cuprous iodide, TEMPO 5 molpercent (7.8 mg), 100 & lt; 0 & gt; C for 12 h, After the reaction is over, The reaction solution was cooled to room temperature, And extracted with ethyl acetate (3 x 5.0 mL). The organic layers were combined and concentrated in vacuo to remove ethyl acetate to give the crude product. The crude product was purified by column chromatography(Petroleum ether: ethyl acetate = 10: 1) to give the pure desired product.The yield of 97.6 mg was 92percent.General procedure: To a solution of 1-(p-bromophenyl)ethanol I-23 (201 mg, 1.0 mmol) in DMF (2.0 mL) was added HIOGeneral procedure: To a screw tube in a glovebox was added In(Oi-Pr)3 (29.2 mg, 0.1 mmol). The tube was then sealed and removed from the glovebox, and CHCl3 (1 mL), alcohol (0.5 mmol), and pivalaldehyde (280 μL, 2.5 mmol) were added under N2 in this order. After stirring the mixture at r.t. for 3 h, H2O (1.0 mL) was added to the reaction mixture, which was then extracted with EtOAc. The organic phase was dried (Na2SO4), and evaporated under reduced pressure. The crude material was purified by silica gel column chromatography (Table 2 and Scheme 2).General procedure: A 30-mL Schlenk tube was evacuated and filled with OGeneral procedure: In a 5 ml glass flask, catalyst (10 mg, containing 0.2 molpercent Pd), alcohol(0.5 mmol), K2CO3 (104 mg, 0.75 mmol) and H2O or toluene(2 mL) were added and reaction mixture was stirred continuously at90 °C for the desired time under O2 atmosphere (from a balloon). Then, in the case of water as solvent, products were extracted with ethylacetate and the catalyst was recovered by an external magnet. Yields ofdesired products were determined by gas chromatography.General procedure: An oven dried pressure tube was chargedwith aryl bromide (1 mmol), CuI (1 mmol), DABCO (2 mmol) and dry DMSO (5 mL).Then the tube was sealed with a teflon cap and heated with stirring at 130 Cin NGeneral procedure: An oven dried pressure tube was charged with aryl halide (0.5mmol), CuI (10–25molpercent), anhydrous Zn(OAc)General procedure: To a round bottomed flask equipped with magnetic stir bar and reflux condenser were added: the aryl halide (2.0 mmol), dimethylsulfoxide (10 mL), N, N-diisopropylethylamine (0.35 mL, 2.0 mmol), and water (approximately 0.04 mL, 2.0 mmol). The reaction was heated to reflux temperature (189 °C) in a sand bath and stirred for the specified time. Reaction progress was monitored by TLC and/or In a 500 mL dry three-necked flask, add DMF (150 mL), thioanisole (100.0 g), and cool to -5°C -5°C.150.0 g of phosphorus oxychloride was slowly added dropwise. During the addition, the internal temperature was kept between -5°C and 5°C. After the dripping is completed, Slowly raise the reaction temperature between 35-45°C, stir the reaction for 7 hours, and check the reaction by TLC.After the reaction was completely completed, the reaction solution was cooled to room temperature, and the reaction solution was slowly added to 500 mL of ice water, keeping the temperature not higher than 35°C.After the completion of the transfer, and stirring at not more than 35 ° C for 10 minutes, add 200mL of dichloromethane, with 10percent sodium hydroxide to adjust the pH to 7-8, separate the organic phase, Continue to extract once with 200 mL of methylene chloride. Combine the organic phases and dry over anhydrous sodium sulfate.The organic solvent was distilled off, distillation was continued, and a fraction between 85-90°C was collected to obtain 109.4 g of a colorless transparent liquid in a yield of 89.2percent.General procedure: In a 5 ml glass flask, catalyst (10 mg, containing 0.2 molpercent Pd), alcohol(0.5 mmol), K2CO3 (104 mg, 0.75 mmol) and H2O or toluene(2 mL) were added and reaction mixture was stirred continuously at90 °C for the desired time under O2 atmosphere (from a balloon). Then, in the case of water as solvent, products were extracted with ethylacetate and the catalyst was recovered by an external magnet. Yields ofdesired products were determined by gas chromatography.

Molecular Weight:152.22
XLogP3:2
Hydrogen Bond Acceptor Count:2
Rotatable Bond Count:2
Exact Mass:152.02958605
Monoisotopic Mass:152.02958605
Topological Polar Surface Area:42.4
Heavy Atom Count:10
Complexity:106
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes