| 100% |
With sodium (meta)periodate; ruthenium on carbon In lithium hydroxide monohydrate at 20℃; for 2h; |
7
Add 0.01 g of Ru / C catalyst and 235 mg (1.1 mmol) of sodium periodate to the reaction flask, and then add 3 mL of water, and then add 154 mg (1 mmol) of 4-methoxyanisole sulfide I-7 to In a reaction flask, react at room temperature for 2 h. The reaction of 4-methoxyanisole sulfide was detected by TLC, and the reaction was stopped. The reaction solution was filtered, the filter cake was washed with dichloromethane (10 mL × 2) (recyclable after treatment), and the filtrate and washing solution were combined. It was washed twice with saturated sodium chloride solution, and water was removed with anhydrous sodium sulfate. The solvent was distilled off and dried to obtain high-quality compound II-7, with a yield of 100%. The filter cake is placed in a muffle furnace for drying and recycling and can be reused. |
| 99% |
With potassium peroxomonosulfate; kaolin In dichloromethane for 3h; Ambient temperature; |
|
| 99% |
With sodium (meta)periodate In dichloromethane; lithium hydroxide monohydrate; acetonitrile at 75℃; for 1h; |
|
| 99% |
With dihydrogen peroxide; Cu2H4O40Te2W8(12-)*(x)H2O*12Na(1+) In acetonitrile at 20℃; for 6h; Sealed tube; |
|
| 99% |
With lithium hydroxide monohydrate; 1-(chloromethyl)-4-fluoro-1,4-diazoniabicyclo-[2.2.2]octane bis(tetrafluoroborate) In acetonitrile at 20℃; for 6h; |
Sulfones 3; General Procedure
General procedure: In air, to a vial containing a magnetic stirring bar were added 1 (0.5 mmol), MeCN (2 mL), H2O (18 L, 1.0 mmol), and Selectfluor (354 mg,1.0 mmol). Then the contents of the vial were stirred in air at rt for the indicated time (Table 2). The reaction could be monitored by TLC analysis. The reaction mixture was concentrated under reduced pressureand subjected to column chromatography using PE/EtOAc (from 5:1 to 2:1) as eluent to afford the desired products 3. |
| 98% |
With tert.-butylhydroperoxide In lithium hydroxide monohydrate; acetonitrile at 60℃; for 2.75h; Inert atmosphere; |
|
| 98% |
With niobium carbide; dihydrogen peroxide In ethanol; lithium hydroxide monohydrate at 60℃; for 5h; chemoselective reaction; |
|
| 98% |
With C68H108N4O4*4H(1+)*Mo8O26(4-); dihydrogen peroxide In lithium hydroxide monohydrate; acetonitrile at 50℃; for 1h; |
|
| 98% |
With n-octanoic acid; dihydrogen peroxide In acetonitrile at 50℃; for 0.5h; Schlenk technique; Green chemistry; |
2.3 General Procedure for Oxidation of Sulfideto Sulfone Compounds (Table 4)
General procedure: An oven-dried Schlenk flask was allowed to cool toroom temperature and charged sequentially with sulfide(1.0 mmol), MeCN (3.0 mL) and caprylic acid (20 mol%).The reaction was then activated by the addition of 30%H2O2 (2.4 equiv.) and stirred at 50 °C for the required timeas given in Table 4. The progress of reaction was monitoredby GC. After completion of the reaction, the reaction to the reaction mixture. Then the product was extractedwith CH2Cl2 (30 mL) and then washed with distilled water(10 mL). The organic extract dried over Na2SO4 and thesolvent removed under reduced pressure. The resultantproduct was purified (if necessary) by column chromatographyusing silica gel (60-120 mesh) with n-hexaneand ethyl acetate as solvent to get the pure product. Thestructure of the product was confirmed by GC-MS, M.P./B.P. and 1H NMR spectroscopic techniques. |
| 98% |
With dihydrogen peroxide In lithium hydroxide monohydrate at 80℃; for 3.08333h; Green chemistry; |
2.6. General procedure for catalytic oxidation of sulfides to sulfones
General procedure: To a stirred solution of 5 mmol sulfide in 5 mL water, 0.01 mmol of Ti containing catalyst [PATi (2.81 mg) or PMATi (3.77 mg)] was added, followed by addition of 50% H2O2 (1.36 mL, 20 mmol) in a round bottom flask. The Ti: substrate molar ratio was maintained at 1 : 500 and the substrate: H2O2 molar ratio at 1 : 4. The reaction was conducted at 80 °C temperature. The reaction was monitored by thin-layer chromatography (TLC) and GC. After completion of the reaction, the system was allowed to cool to room temperature. The sulfone obtained was then isolated, purified and characterized by following similar procedure as mentioned under above section. |
| 97% |
With anhydrous potassium sulfate; sulfuric acid potassium salt; potassium peroxomonosulfate; wet-montmorillonite In dichloromethane for 1.5h; Ambient temperature; |
|
| 97% |
With sodium (meta)periodate; ammonium acetate; C24H28ClN4O2Ru(1+)*F6P(1-) In dichloromethane; lithium hydroxide monohydrate; acetonitrile at 25℃; for 0.333333h; |
|
| 96% |
With sodium chlorine monoxide In lithium hydroxide monohydrate; toluene at 20℃; for 1h; |
8
(Example 8) 1-methoxy-4-(methylthio)benzene (1.00 g, 6.48 mmol) and cyanuric acid (84 mg, 0.65 mmol) were mixed with toluene (20 mL). 10% aqueous solution of sodium hypochlorite (11.1 g, 14.9 mmol) was added to the mixture at room temperature, and it was stirred for 1 hour. After that, sodium sulfite (408 mg, 3.24 mmol) and water (10 mL) were added to the reaction mixture, and it was extracted with ethyl acetate (10 mL). An organic layer was concentrated under reduced pressure, and the obtained residue was subjected to purification by means of a silica gel column to obtain 1-methoxy-4-(methylsulfonyl)benzene (1.16 g, yield: 96%). 1H-NMR (300MHz, CDCl3) δ 3.03 (3H, s), 3.89 (3H, s), 7.00-7.05 (2H, m), 7.84-7.90 (2H, m) |
| 96% |
With sodium chlorine monoxide; lithium hydroxide monohydrate; isocyanuric acid In toluene at 20℃; for 1h; Inert atmosphere; |
|
| 95% |
With mesoporous silica; magnesium monoperoxyphthalate hexahydrate In dichloromethane for 0.333333h; Heating; |
|
| 95% |
With oxygen In phosphate buffer; <i>tert</i>-butyl alcohol at 55℃; for 5h; |
|
| 95% |
With vanadium pentoxide; 1-methyl-3-dodecylimidazolium hydrogen sulfate; dihydrogen peroxide In lithium hydroxide monohydrate at 20℃; for 4h; |
|
| 95% |
With C2MoO9(2-)*H2O*2C19H42N(1+); dihydrogen peroxide In lithium hydroxide monohydrate at 20℃; for 0.5h; chemoselective reaction; |
|
| 95% |
With nonanebis(peroxoic acid) In lithium hydroxide monohydrate at 50 - 55℃; for 0.416667h; |
|
| 95% |
With dihydrogen peroxide In lithium hydroxide monohydrate at 75℃; for 1.5h; |
|
| 94% |
With 1-butyl-3-methylimidazolium perrhenate; dihydrogen peroxide; 1-n-butyl-3-methylimidazolium tetrafluoroborate In lithium hydroxide monohydrate at 60℃; for 2h; Schlenk technique; Inert atmosphere; Green chemistry; |
2.3 Catalytic oxidation of sulfides
General procedure: To a stirred solution of sulfide (10mmol) and [C4mim][ReO4] (0.1955g, 5 mol%) in [C4mim][BF4] (2mL), an aqueous solution of hydrogen peroxide (35% in water) (3.5mL, 40mmol) is added in 2-3 portions at 60°C. The progress of the reaction is followed by TLC. The reaction mixture is extracted with diethyl ether (5×10mL) and the extract is dried over anhydrous MgSO4. The yield and selectivity of methyl phenyl sulfone are calculated from calibration curves (r2>0.999) recorded using 3-methylanisole and 1,4-diacetylbenzene as internal standard. The crude product is obtained by rolling evaporation and purified by column chromatography separation (silica gel using hexane/ethyl acetate 90:10 v/v). The RTIL phase is diluted with CH2Cl2 and then treated with MnO2 to destroy the excess peroxide. The obtained liquid is first dried over anhydrous MgSO4 and then for 4h in vacuo at 50°C to remove CH2Cl2. Fresh substrate and hydrogen peroxide are then added for a new reaction cycle. All products are characterized by melting point, 1H NMR, 13C NMR and IR spectroscopy (see Supporting information). |
| 94% |
With diethylene glycol dibutyl ether; oxygen; sodium trifluoro-methanesulfinate at 20℃; for 24h; Irradiation; |
|
| 93% |
With oxygen at 100℃; for 20h; Schlenk technique; chemoselective reaction; |
|
| 93% |
With diethylene glycol dibutyl ether; oxygen at 100℃; for 20h; Green chemistry; |
|
| 93% |
With diethylene glycol dibutyl ether; oxygen at 100℃; for 20h; |
|
| 92% |
With dihydrogen peroxide In acetonitrile at 20℃; for 0.5h; |
|
| 92% |
With urea-2,2-dihydroperoxypropane In tetrahydrofuran at 20℃; for 0.916667h; Green chemistry; chemoselective reaction; |
Typical Procedure for Selective Oxidation of Methyl(phenyl)sulfide Sulfides to (methylsulfinyl)benzene and(methylsulfonyl)benzene
General procedure: To a stirred solution of sulfide (1 mmol, 0.124 g) and THF (4 mL), urea-2,2-dihdroperoxypropane (2 or 6 mmol, 0.336-1.00 g pending to products) was added and the mixture was stirred at room temperature for an appropriate time. After completion of the reaction as monitored by TLC, saturated aqueous solution of Na2SO3 (2 mL of 1 M solution) was added to quench the excessive oxidant remaining in the mixture. Then water (10 mL) was added to the mixture and extracted using chloroform (3 × 5 mL) and dried over anhydrous MgSO4. After evaporation of solvent under reduced pressure, chromatography on silica gel was used to give pure products. |
| 92% |
With 4O4S(2-)*8Na(1+)*2H2O2*NaCl; glacial acetic acid at 75℃; for 6h; Green chemistry; |
|
| 91% |
With tetra-n-butylammonium tetrafluoroborate; lithium hydroxide monohydrate In dichloromethane at 20℃; for 9h; Electrochemical reaction; Green chemistry; |
|
| 90% |
With 1,1,2,2-tetrahydroperoxy-1,2-diphenylethane In tetrahydrofuran at 20℃; for 0.833333h; Green chemistry; chemoselective reaction; |
General procedures for selective oxidation of sulfdes tosulfoxides or sulfones
General procedure: To a stirred solution of sulfde (1 mmol) and THF (4 mL),THPDPE (1 up to 5.5 mmol (0.310 up to 1.70 g) dependingon the substrates and products) was added and the mixture wasstirred at room temperature for an appropriate time. After completion of the reaction, as monitored by TLC, a saturated aqueous solution of Na2SO3 (2 mL of 1 M solution) was added toquench the excessive oxidant that was remained in the mixture.Water (10 mL) was added to the mixture and extracted usingchloroform (3 × 5 mL) and dried over anhydrous MgSO4. Afterevaporation of solvent under reduced pressure chromatographyon silica gel was used to give pure products. |
| 89% |
With (pyridinium)H3PMo11VO40; dihydrogen peroxide In lithium hydroxide monohydrate; acetonitrile at 40℃; for 3h; |
General procedure: The oxidation of methyl phenyl sulfide to methyl phenyl sulfoxide or methyl phenyl sulfone (Scheme 1) was typically carried out bystirring a solution of 0.7 mmol of the substrate and 0.01 mmol of the catalyst in 5 mL of acetonitrile, at 20 or 40 °C, respectively. Theoxidant used was H2O2 35% in aqueous solution (2 or 20 mmol,respectively). The sample was collected from the reaction mixtureduring the reaction at time intervals. About 20 μL of the reactionmixture was taken for each sample, which was then diluted in amixture of water-dichloromethane (2 mL). The dichloromethanelayer was dried with anhydrous sodium sulfate and filtered. GC/MSanalyses were performed on an HP 5971 mass detector coupled to anHP gas chromatograph fitted with a 30 m×0.25 mm DB5 capillarycolumn. The percentages of each compound in the reaction mixturewere directly estimated from the corresponding chromatographicpeak areas. The yield (%) of pure sulfoxide or sulfone, the turnovernumber (TON: product mol×catalyst mol-1) and turnover frequency(TOF: product mol×catalyst mol-1×h-1) were also calculated. Under these optimum conditions and using M11PV1Py1 ascatalyst, different sulfides were oxidized to sulfoxides (for 30 min)and to sulfones (for 2.5 and 3.5 h) depending on the substrate. |
| 87% |
With thio-xanthene-9-one; oxygen In butanone at 35 - 40℃; for 24h; Schlenk technique; UV-irradiation; Green chemistry; |
4.1. A typical procedure for the visible-light-promoted aerobic oxidation of sulfides 3 or sulfoxides1 in a ketone solvent
General procedure: To a dried Schlenk tube equipped with a stirrer bar which wasevacuated and backfilled with oxygen, were added thioxanthone(10.6 mg, 0.05 mmol, 5.0% mol) and sulfide3 or sulfoxide 1(1.0 mmol), then 5 mL of DEK or MEK was added into the reactiontube via a syringe. The mixture was irradiated by a purple LED lampat 35e40C under oxygen atmosphere (1 atm). After 24 h, thesolvent was removed and the residue was purified by flash column chromatography on silica gel to give the corresponding sulfone2. |
| 86% |
With phenanthroline hydrotribromide; dihydrogen peroxide In lithium hydroxide monohydrate; acetonitrile at 20℃; for 0.616667h; |
Oxidation of 4-methoxyphenyl methyl sulfide:
General procedure: 30% Hydrogen peroxide of 1.5 mL (10 mmol) was added drop wise to a stirredsolution of 4-methoxyphenyl methyl sulfide, 1.54 g (10 mmol) and PhenHTB, 0.042 g (10 mol %) in acetonitrile-water (10 mL,1:1) at room temperature for an appropriate time. After completion of the reaction as monitored by TLC, the reaction mixture waspoured in water and the excess hydrogen peroxide was destroyed by the addition of aq. sodium bisulfite followed by the filtrationthrough a small Buckner funnel. After filtration the organic products were extracted with ether. The ether layer was washed with water (2 mL) and dried over Na2SO4. The organic solvent was removed under reduced pressure to give the corresponding 4-methoxyphenyl methyl sulfoxide. The products were further purified by column chromatography on silica gel using ethylacetate/hexane (1:4) as eluent. Evaporation of the solvent yielded the corresponding sulfoxide (2, Table 1). The reaction time andyield of the products are presented in Table 1. |
| 85% |
With tert.-butylhydroperoxide In decane; dichloromethane at 20℃; for 1h; |
|
| 85% |
With Ti(η5-C5H4SiMe2OPh7Si7O11-κ2O2)Cl; dihydrogen peroxide In methanol; lithium hydroxide monohydrate at 50℃; for 3h; chemoselective reaction; |
|
| 85% |
With 3,5-Lutidine; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; oxygen; copper(II) sulphate In methanol at 65℃; for 48h; Schlenk technique; Sealed tube; Green chemistry; |
21 Example 21: Preparation of 4-methoxyphenyl methyl sulfone from 4-methoxythioanisole
TEMPO (3.9 mg, 0.025 mmol) was added to a 100 mL Schlenk reaction tube in turn. Methanol (1 mL), CuSO4 (4.0 mg, 0.025 mmol), 3,5-lutidine (28.2 μL, 0.25 mmol), 4-methoxythioanisole(69.5 μL, 0.5 mmol), Filled with 1 atm of oxygen, The sealed reaction tube was heated to 65 ° C for 48 h. After completion of the reaction, the mixture was cooled to room temperature, and an appropriate amount of ethyl acetate was added, and a blue solid was precipitated from the reaction mixture, which was filtered, and the filtrate was concentrated under reduced pressure and purified by column chromatography. The product was obtained in a yield of 85%. |
| 84% |
With dihydrogen peroxide; potassium carbonate; glacial acetic acid In lithium hydroxide monohydrate for 0.5h; Reflux; |
|
| 80% |
With [bis(acetoxy)iodo]benzene; toluene-4-sulfonic acid In lithium hydroxide monohydrate at 80℃; for 20h; |
General Procedure for the Selective Oxidation of Sulfides
General procedure: To a 25mL glass tube, sulfide (0.2 mmol), PhI(OAc)2 (0.22mmol or 0.42 mmol), p-toluenesulfonicacid (3.4 mg, 0.02 mmol), H2O (1.5 mL) were added and the mixture wasstirred at room temperature or 80 oC for desired time. The mixture was cooled to roomtemperature and extracted by saturated NaHCO3(5 mL), ethyl acetate (25 mL × 4). After dryingwith anhydrous Na2SO4, the organic residue was analysedby GC and then purified by column chromatographyon silica gel (200-300 mesh) with ethyl acetate/petroleum ether to afford thedesired product. |
| 78% |
With lithium hydroxide monohydrate In acetonitrile at 20℃; Electrochemical reaction; Flow reactor; |
|
| 76% |
With anhydrous potassium sulfate; sulfuric acid potassium salt; potassium peroxomonosulfate In lithium hydroxide monohydrate; propan-2-one cooling; |
|
| 74% |
With tetra-n-butylammonium perchlorate; lithium hydroxide monohydrate; oxygen In acetonitrile at 20℃; for 3h; Electrochemical reaction; |
|
| 70% |
With manganese sulphate; dihydrogen peroxide; Sodium hydrogenocarbonate In lithium hydroxide monohydrate; N,N-dimethyl-formamide at 20℃; for 0.25h; |
|
| 60% |
With Benzo<c>thioxanthon; oxygen In acetonitrile at 20℃; Sealed tube; Irradiation; |
General procedure E to the synthesis of sulfones
General procedure: A solution of sulfides 1 (0.2 mmol, 1.0 equiv) or sulfoxides 2 (0.2 mmol, 1.0 equiv), photocatalyst (c, 5 mol%), and ACN (1 mL, 0.2 M) was sealed in an oven-dried reaction tube equipped with an oxygen balloon (gas-switch three times with oxygen balloon). The reaction was agitated under 18 W 405 nm LEDs at room temperature for 12 to 24 h. The progress of the reaction was monitored by GC-MS or/and TLC. After completion of the reaction, the solvent was removed under reduced pressure, and the crude product 3 was purified by flash silica chromatography using n-hexane and ethyl acetate as eluent (v/v, 80:20). |
| 58% |
With tetra-n-butylammonium tetrafluoroborate; lithium hydroxide monohydrate In methanol at 25℃; for 10h; Electrochemical reaction; |
|
|
With dihydrogen peroxide; glacial acetic acid |
|
|
With 3-chloro-benzenecarboperoxoic acid |
|
| 100 % Spectr. |
With oxygen; 2,2-dimethypropanal In dichloromethane at 20℃; for 4h; |
|
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