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CAS No. : | 831-91-4 | MDL No. : | MFCD00003066 |
Formula : | C13H12S | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | LKMCJXXOBRCATQ-UHFFFAOYSA-N |
M.W : | 200.30 | Pubchem ID : | 13255 |
Synonyms : |
|
Num. heavy atoms : | 14 |
Num. arom. heavy atoms : | 12 |
Fraction Csp3 : | 0.08 |
Num. rotatable bonds : | 3 |
Num. H-bond acceptors : | 0.0 |
Num. H-bond donors : | 0.0 |
Molar Refractivity : | 62.65 |
TPSA : | 25.3 Ų |
GI absorption : | High |
BBB permeant : | Yes |
P-gp substrate : | No |
CYP1A2 inhibitor : | Yes |
CYP2C19 inhibitor : | Yes |
CYP2C9 inhibitor : | Yes |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -4.73 cm/s |
Log Po/w (iLOGP) : | 2.53 |
Log Po/w (XLOGP3) : | 3.93 |
Log Po/w (WLOGP) : | 3.83 |
Log Po/w (MLOGP) : | 4.42 |
Log Po/w (SILICOS-IT) : | 3.99 |
Consensus Log Po/w : | 3.74 |
Lipinski : | 1.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 1.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -3.99 |
Solubility : | 0.0203 mg/ml ; 0.000101 mol/l |
Class : | Soluble |
Log S (Ali) : | -4.16 |
Solubility : | 0.0138 mg/ml ; 0.0000691 mol/l |
Class : | Moderately soluble |
Log S (SILICOS-IT) : | -5.43 |
Solubility : | 0.000737 mg/ml ; 0.00000368 mol/l |
Class : | Moderately soluble |
PAINS : | 0.0 alert |
Brenk : | 0.0 alert |
Leadlikeness : | 2.0 |
Synthetic accessibility : | 2.15 |
Signal Word: | Danger | Class: | 9 |
Precautionary Statements: | P280-P301+P312+P330-P305+P351+P338+P310 | UN#: | 3335 |
Hazard Statements: | H302-H318 | Packing Group: | Ⅲ |
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 |
---|---|---|
100% | With [Hydroxy(tosyloxy)iodo]benzene In dichloromethane for 0.166667h; Ambient temperature; | |
100% | With tetranitromethane In acetonitrile at 40℃; for 2h; Irradiation; | |
100% | With tert.-butylhydroperoxide In acetonitrile at 50℃; for 2.75h; solid phase reaction; |
100% | With 12-molybdophosphoric acid; urea hydrogen peroxide addition compound In methanol at 20℃; for 0.283333h; chemoselective reaction; | |
99% | With (Bu4N)2S2O8 In dichloromethane for 1.5h; Ambient temperature; | |
99% | With dinitrogen tertoxide; iron nitrate (III) Ambient temperature; | |
99% | With iron(III) chloride; orthoperiodic acid In acetonitrile at 20℃; for 0.0333333h; | |
99% | With dihydrogen peroxide; tantalum pentachloride In <i>tert</i>-butyl alcohol at 45℃; for 3h; | |
99% | With dihydrogen peroxide; tantalum pentachloride In <i>tert</i>-butyl alcohol at 45℃; for 3h; chemoselective reaction; | |
99% | With aluminum hydrogen sulfate; mesoporous silica; sodium bromide; NaNO2 In water monomer; acetonitrile at 20℃; for 0.416667h; | |
99% | With 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine; dihydrogen peroxide at 25℃; for 0.0833333h; Neat (no solvent); chemoselective reaction; | |
99% | With dihydrogen peroxide In water monomer at 20℃; for 2.5h; | |
99% | With Nitroharnstoff; silica sulfuric acid; ammonium bromide In dichloromethane at 20℃; for 0.75h; | |
99% | With dihydrogen peroxide In ethanol at 35℃; for 5h; Green chemistry; chemoselective reaction; | |
99% | With phthaloyl peroxide In dichloromethane at 25℃; for 8h; Schlenk technique; chemoselective reaction; | |
99% | With palladium; dihydrogen peroxide In methanol at 60℃; for 15h; Green chemistry; chemoselective reaction; | |
99% | With 1,3-dimethylhexahydro-2,4,5,6-pyrimidinetetraone; dihydrogen peroxide; magnesium(II) sulfate In dichloromethane at 25℃; for 0.5h; | |
99% | With selenium(IV) dioxide; dihydrogen peroxide In water monomer; ethyl acetate chemoselective reaction; | 3.1. Synthesis of Sulfoxides 2a-f General procedure: In a 2 mL volumetric ask, ethyl acetate was added to suldes 1a±c,e±g (1.0 mmoL) or sulde1d (0.5 mmoL) to make up the required volume. (Solution A: 0.5 M (1a-c,e-g). In the case of 1d theconcentration was optimized at 0.25 M.) Into a 2 mL volumetric flask, 0.1 mmoL of SeO2 (11 mg) andH2O2 30 wt. % (2 mmoL, 205 L) were poured, and then water was added until the desired volumewas reached. (Solution B: 0.05 M (SeO2) and 1 M (H2O2). In the case of 1d, a dierent concentrationwas optimized at 0.025 M (SeO2) and 1.25 M (H2O2)).Solutions A and B were fluxed at the same flow rate through a multi-syringe pump apparatus(Chemyx Fusion 100, Staord, TX, USA) equipped with two syringes (2 mL), and they were mixed in aY-junction and flowed at 0.100 mL/min through a tubularPTFE reactor coil with internal diameter of1 mm and internal volume of 2 mL (Bohlender GmbH, Grünsfeld, Germany) at room temperature.The system was washed with 4 mL of ethyl acetate, and the aqueous and organic layers were collectedin a flask, quenched with an aqueous solution of Na2S2O3 10% (w/v) and extracted with ethyl acetate(5 mL 3). The combined organic layers were dried over sodium sulfate and concentrated underreduce pressure, aording the target sulfoxides. When required, the unreacted starting material wasremoved under vacuum, and in the case of 2d, it was separated from the corresponding sulfone (3d)by flash chromatography on a silica gel column using EtOAc/petroleum ether (2:98) as eluent. |
98% | With potassium peroxomonosulfate; aluminium chloride anhydrous for 0.5h; Heating; | |
98% | With cerium(III) sulphate; barium bromate In water monomer; acetonitrile at 20℃; for 2h; | |
98% | With iodosylbenzene; 3,5-disubstituted Cr(salen) In dichloromethane at 20℃; for 3h; | |
98% | With N-Bromosuccinimide; water monomer; mesoporous silica In dichloromethane at 20℃; for 0.583333h; | |
98% | With aluminium(III) nitrate nonahydrate; sulfuric acid; mesoporous silica; mesoporous silica; sodium bromide In dichloromethane; water monomer at 20℃; for 0.75h; chemoselective reaction; | |
98% | With water monomer; mesoporous silica; zirconium tetrachloride; potassium bromide; NaNO2 In acetonitrile at 20℃; for 3.83333h; chemoselective reaction; | |
98% | With aluminium(III) nitrate nonahydrate; water monomer; mesoporous silica; citric acid; potassium bromide In dichloromethane at 20℃; for 0.75h; | |
98% | With chloro-trimethyl-silane; dihydrogen peroxide In water monomer; acetonitrile at 25℃; for 0.0333333h; chemoselective reaction; | |
98% | With water monomer; ammonium bromide In dichloromethane at 20℃; for 0.833333h; chemoselective reaction; | |
98% | With water monomer; trimethylphenylammonium perbromide In ethyl acetate at 20℃; for 1h; chemoselective reaction; | |
98% | With dihydrogen peroxide In methanol at 20℃; for 0.416667h; | |
98% | With ammonium bromide In water monomer; acetonitrile at 20℃; for 2.83333h; | |
98% | With dihydrogen peroxide In methanol; water monomer at 20℃; for 1.5h; Green chemistry; chemoselective reaction; | |
98% | With dihydrogen peroxide In acetonitrile at 20℃; for 0.0833333h; chemoselective reaction; | |
98% | With salen complex of Cu(II) immobilized on Fe3O4 nanoparticles; dihydrogen peroxide In ethanol at 60℃; for 6h; | 2.5 General procedure for the oxidation of sulfides to sulfoxides General procedure: To a solution of sulfide (1mmol) and 33% H2O2 (0.5mL) in ethanol (10mL), Fe3O4/salen of Cu(II) as catalyst (0.05g) was added and the mixture was stirred at 60°C for the specified time. After completion of the reaction, the catalyst was separated by an external magnet. The product was extracted with CH2Cl2, washed with water (5mL) and dried over anhydrous Na2SO4. Finally, the excess of solvent was removed under reduced pressure to give the corresponding pure sulfoxide. |
98% | With 1-methyl-4-(trifluoromethyl)pyrimidinium trifluoromethanesulfonate; dihydrogen peroxide In methanol; water monomer at 25℃; for 6.5h; | |
98% | With dihydrogen peroxide In methanol at 20℃; for 2.5h; | 3.3 General procedure for catalytic oxidation of sulfides to sulfoxides General procedure: In a typical reaction, organic substrate (5 mmol) was added to a solution of catalyst [PAMo (3.44 mg) or PSMo (4.9 mg), containing 0.005 mmol of Mo] and 30% H2O2 (2.26 mL, 20 mmol) in 5 mL of water. The molar ratio of substrate: H2O2 and that of catalyst (Mo): substrate was maintained at 1: 4 and 1: 1000, respectively. The reaction was conducted at room temperature under magnetic stirring. The reaction progress was monitored by thin layer chromatography (TLC) and GC. After completion, the product and unreacted organic substrates were extracted with diethyl ether, dried over anhydrous sodium sulfate and distilled under reduced pressure to remove excess solvent. The crude product obtained was purified by column chromatography on silica gel with ethyl acetate- hexane (1: 9 v/v) as the eluent. |
98% | With dihydrogen peroxide In ethanol; water monomer at 25℃; for 0.0333333h; Green chemistry; chemoselective reaction; | |
98% | With dihydrogen peroxide In neat (no solvent) at 20℃; for 2h; chemoselective reaction; | |
98% | With dihydrogen peroxide In neat (no solvent) at 20℃; for 12h; Green chemistry; | 2.4. Typical procedure for the synthesis of sulfoxides General procedure: A mixture of sulfide (1 mmol) and H2O2 (1.5 mmol, 30% w/w) werestirred in presence of the biogenic nanocatalyst (2 mg) at room temperaturefor requisite time. After completion (by TLC, 10% EtOAc/nhexane),the reaction mixture was diluted with 5 mL Et2O and thecatalyst was recovered from the system by centrifugation. The reactionfiltrate was dried over anhydrous Na2SO4 and concentrated underreduced pressure to obtain the pure products in 80-98% yields, beingdetermined in NMR. |
98% | With water monomer; 1-(chloromethyl)-4-fluoro-1,4-diazoniabicyclo-[2.2.2]octane bis(tetrafluoroborate) In acetonitrile at 20℃; for 0.166667h; | Sulfoxides 2; 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 (177 mg, 0.5 mmol). Then the contents of the vial were stirred at rt in air for the indicated time (Table 2). The reaction could be monitored by TLC analysis. The reaction mixture was concentrated under reduced pressure and subjected to column chromatography using PE/EtOAc (from 4:1 to 1:1) as the eluent to afford the desired products 2. |
97% | With sodium bromite In 1,4-dioxane; water monomer for 0.25h; Ambient temperature; | |
97% | With benzyltriphenylphosphonium dichromate for 0.333333h; | |
97% | With benzyltriphenylphosphonium dichromate for 0.116667h; | |
97% | With [MoO(O2)2(Opyr)(H2O)] coated on SiO2 In methanol; acetonitrile at 20℃; for 13h; | |
97% | With [Mo(O)(O2)2(H2O)(pyrazole)] In methanol; acetonitrile at 20℃; for 6h; | |
97% | With dihydrogen peroxide; phenol at 25℃; for 0.075h; | |
97% | With benzyltriphenylphosphonium dichromate; mesoporous silica for 0.116667h; | |
97% | With water monomer; mesoporous silica; pyridinium hydrobromide perbromide In dichloromethane for 1h; | |
97% | With dihydrogen peroxide In ethanol at 50℃; for 0.25h; | |
97% | With trifluoromethylsulfonic anhydride; dihydrogen peroxide In ethanol at 20℃; for 0.116667h; | |
97% | With dihydrogen peroxide In methanol; water monomer at 20℃; chemoselective reaction; | |
97% | With 3H-2,1-benzoxaselenole Se-oxide; dihydrogen peroxide; magnesium(II) sulfate; trifluoroacetic acid In methanol; dichloromethane at 20℃; | |
97% | With dihydrogen peroxide; toluene-4-sulfonic acid In neat (no solvent) at 20℃; for 3.33333h; Green chemistry; chemoselective reaction; | |
97% | With calcium difluoride; dihydrogen peroxide In neat (no solvent) at 20℃; for 0.333333h; chemoselective reaction; | General Procedure for the Oxidation of Sulfides to Sulfoxides Using H2O2 Catalyzed by CaF2 General procedure: A mixture of sulfide (1 mmol), 30% H2O2 (3.6 meq, 0.4 gr) and CaF2 (0.25 mmol, 0.019 g) was stirred at room temperature for the time specified in Table 2. The progress was monitored by TLC or GC. Crude sulfoxide was obtained after treating the reaction mixture with H2O (5 mL) and Et2O(35 mL) and substantial separation, washing with brine (15mL), drying over anhydrous Na2SO4 and evaporation of organicphase. If the product had purity below 90%, purification was performed using short column chromatography with EtOAc/n-hexane (1/10). All the products are known and were characterized by IR and 1H NMR and by melting point in comparison with those of authentic samples [2, 4, 7, 15]. |
97% | With dihydrogen peroxide In ethanol at 20℃; for 5h; Green chemistry; | General procedure for oxidation of sulfides to sulfoxides General procedure: Dopamine sulfamic acid-functionalized magnetic Fe3O4 nanoparticles (DSA(at)MNPs) (0.02 g) were added to solution of sulfide (1 mmol) and 33 %H2O2 (0.5 mL) in ethanol (10 mL), the mixture was stirred at room temperature for the specified time, and the progress of the reaction was monitored by thin-layer chromatography (TLC). After completion of the reaction, the catalyst was separated using an external magnet. The product was extracted with CH2Cl2, washed with water (5 mL), and dried under vacuum at room temperature. |
97% | With tert.-butylhydroperoxide In water monomer at 60℃; for 3h; | |
97% | With dihydrogen peroxide In neat (no solvent) at 20℃; for 1.5h; Green chemistry; | |
97% | With dihydrogen peroxide In water monomer; acetone at 20℃; for 8h; | |
97% | With dihydrogen peroxide In neat (no solvent) at 20℃; for 0.75h; | 2.4. General procedure for the sulfoxides synthesis General procedure: In this step, to mixture of sulfide (1mmol) and H2O2 (0.4mL), SBA-15(at)serine(at)Pd catalyst (0.004g) was added and the reaction mixture was stirred at room temperature under solvent-free condition for appropriate time. Then, the completion of the reaction progress monitored by TLC with n-hexane solvent. Then, catalyst was filtered and washed with ethyl acetate to give the pure sulfoxides in good to high yields. |
97% | With dihydrogen peroxide In methanol at 20℃; for 2.91667h; Green chemistry; | 2.5. General procedure for catalytic oxidation of sulfides to sulfoxides General procedure: In a typical procedure, the sulfide oxidation reaction was carried out by placing organic substrate (5 mmol), catalyst containing 0.005 mmol of Ti [PATi (1.40 mg) or PMATi (1.88 mg)], 30% H2O2 (2.26 mL, 20 mmol) in 5 mL of water in a round bottom flask. The molar ratio of Ti: substrate was maintained at 1:1000 and substrate: H2O2 at 1:4. Reaction was conducted at ambient temperature under magnetic stirring. The progress of the reaction was monitored by thin layer chromatography (TLC) and GC. After completion of the reaction, the oxidized product along with unreacted organic substrate were extracted with diethyl ether, dried over anhydrous sodium sulfate and distilled under reduced pressure to remove excess diethyl ether. The product was then purified by column chromatography on silica gel with ethyl acetate-hexane (1: 9 v/v) as the eluent. The product obtained was characterized by IR, 1H NMR, 13C NMR spectroscopy and melting point determination (for solid products) [Text S1 (Supporting Information)]. |
97% | With dihydrogen peroxide In neat (no solvent) at 20℃; for 0.583333h; | 2.4 General Procedure for the Oxidation of sulfidesto sulfoxide General procedure: A mixture of sulfide (1 mmol), H2O2 (0.4 mL) and catalyst(0.01 g) at room temperature, was stirred under solventfreecondition for the certain period of time. The reactionwas monitored by thin-layer chromatography (TLC). Uponcompletion, the reaction mixture was decanted andextracted with dicoloromethan. The organic layer was driedover anhydrous Na2SO4 (1.5 g). Finally, the organic solventswere evaporated, and products were obtained in82-99 % yield. |
97% | With 1,6,8-trihydroxy-3-methyl-9,10-anthraquinone In methanol at 20℃; for 6h; Irradiation; | |
97% | With dihydrogen peroxide; WO(O<SUB>2</SUB>)L(CH<SUB>3</SUB>OH) In ethanol; water monomer for 0.5h; Reflux; | Oxidation of sulfides using hydrogen peroxide catalyzed by [WO(O2)L(CH3OH)] and [WO(O2)L(CH3OH)]/CM-PS General procedure: To an ethanolic solution (10 mL) of diphenyl sulfide(1 mmol) and the homogeneous (0.005 mmol) or heterogeneous(0.076 mmol) catalyst, 30% aqueous H2O2(2 mmol)was added and the reacting precursors were continuouslystirred under a refluxing environment for the stated periods of time as given in Table 3. TLC (eluent, n-hexane: ethylacetate, 5:2) was used to monitor the progress of the catalyticreaction, and GC analysis was used to quantify theyield of products. The products were purified using a 70:30combination of n-hexane and ethyl acetate as the eluent inchromatography over silica gel. All items were identified bycomparing their FT-IR and 1H NMR spectral data with theoriginal standard samples |
96% | With pyridine; trimethylphenylammonium perbromide for 2h; Ambient temperature; | |
96% | With phthalic anhydride; urea In acetonitrile for 1h; Ambient temperature; | |
96% | With iodosylbenzene; pyridinium 4-toluenesulfonate In acetonitrile for 1h; Ambient temperature; | |
96% | With CAN; mesoporous silica In dichloromethane for 0.75h; Ambient temperature; | |
96% | With 1-benzyl-4-aza-1-azoniabiyclo<2.2.2>octane peroxodisulfate In acetonitrile for 0.166667h; Heating; | |
96% | With Etamon; 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione In chloroform; water monomer at 20℃; for 36h; | |
96% | With boron trifluoride diethyl ether complex In acetonitrile for 0.0833333h; cooling; | |
96% | With dihydrogen peroxide; zirconium tetrachloride In methanol at 20℃; for 0.0333333h; | |
96% | With β,β-o-xylyl(ditriphenylphosphonium)dibromide In tetrahydrofuran; water monomer at 20℃; for 0.166667h; | |
96% | With NaBrO3; CAN; mesoporous silica In dichloromethane at 20℃; for 0.75h; | |
96% | With dihydrogen peroxide; nitric acid In ethanol at 25℃; for 0.116667h; chemoselective reaction; | |
96% | With 3-cyano-1-ethylpyrazinium tetrafluoroborate; dihydrogen peroxide In methanol; water monomer at 25℃; for 8h; chemoselective reaction; | |
96% | With dihydrogen peroxide; oxalic acid In methanol; water monomer at 20℃; for 1.5h; | |
96% | With dihydrogen peroxide In ethanol at 60℃; for 1.41667h; | General Procedure for the Oxidation ofSulfides to Sulfoxides General procedure: Fe3O4-SA-PPCA (0.04 g) was added to a mixture of sulfide (1 mmol) and H2O2 (0.5 mL) in EtOH at 60 °C and the mixture was stirred for the appropriate time. The progress was monitored by TLC. After completion of the reaction, the catalyst was separated by an external magnet and the combined organics were washed with water (5 mL) and dried over anhydrous Na2SO4. The evaporation of solvent under reduced pressure gave the pure products in excellent yields. |
96% | With ferric(III) chloride; urea hydrogen peroxide addition compound In acetonitrile at 20℃; for 2.5h; Green chemistry; | 2.2 General Procedure: Oxidation Reactions CatalyzedbyUHP/FeCl3 System inCH3CNasSolvent General procedure: In a 25 round-bottomed flask, to a solution a sulfide(1mmol) in CH3CN(10mL), UHP (1.5mmol) and FeCl3(1 mmol) were added successively and the mixture wasstirred magnetically at room temperature. The reaction progresswas followed by TLC (eluent: n-hexane/ethyl acetate:2:1). After completion of the reaction, the solvent wasremoved under vacuum and the residue was quenched byadding water (15mL), extracted with CH2Cl2(3 × 10mL).The combined organic layers were washed with water,dried over MgSO4and the solvent was removed in vacuum.The residue was purified by chromatography on silica gel(25-30 mesh), eluting with ethyl acetate/n-hexane to givepure sulfoxides. |
96% | With dihydrogen peroxide at 20℃; for 0.166667h; chemoselective reaction; | 2.4. General procedure to synthesize sulfoxides General procedure: To 1.0 mmol organic sulfide 1.5 mmol 30% (w/w) H2O2 was added at solvent-free condition in presence of 15 mg SBA-15/CCPy/Mn(OAc)2 (1 mol%) catalyst. The mixture was stirred for requisite time at ambient temperature. Progress of the reaction was monitored by thin layer chromatography. After completion of the reaction, the catalyst was isolated from the mixture by filtration and the products were extracted with Et2O and concentrated to afford the pure products. |
96% | With dihydrogen peroxide at 20℃; for 12h; chemoselective reaction; | 2.4. Typical experimental procedure for the preparation of sulfoxides General procedure: A mixture of sulfide (1 mmol), H 2 O 2 (1.5 mmol, 30% w/w) and Cu- Calendula Fe 3 O 4 nanocatalyst (20 mg, 1 mol%) was stirred in solvent-free conditions at room temperature for appropriate time. After completion (by TLC, EtOAc/n-hexane = 1/10), the catalyst was isolated from the reaction mixture by a magnet. The reaction filtrate was diluted with diethyl ether and dried over anhydrous Na 2 SO 4 . Finally, the total organic layer was evaporated under re- duced pressure to obtain the product in pure form (85-98% yields) without the requirement of chromatography |
96% | With oxygen In methanol; water monomer at 20℃; for 15h; Irradiation; Green chemistry; | |
95% | With sulfuric acid; nitric acid In nitromethane for 1.5h; Ambient temperature; | |
95% | With dihydrogen peroxide; acetic anhydride; mesoporous silica In dichloromethane for 16h; Ambient temperature; | |
95% | With periodate ion on Amberlite IRA-400 resin In ethanol for 35h; Heating; | |
95% | With 1-butyl-4-aza-1-azoniabicyclo[2.2.2]octane dichromate In acetonitrile for 1h; Heating; | |
95% | With anhydrous zinc chloride; 2-isopropyl-3-(pyridin-2-yl)oxaziridine In chloroform for 0.5h; | |
95% | With nitric acid; diphosphorus pentoxide; mesoporous silica In water monomer for 0.1h; | |
95% | With 1-iodyl-2-butoxybenzene In acetonitrile for 3h; Heating; | |
95% | With 1-(4-diacetoxyiodobenzyl)-3-methylimidazolium tetrafluoroborate; water monomer at 65℃; for 2h; | |
95% | With dihydrogen peroxide In methanol at 20℃; for 6.5h; | |
95% | With nitric acid; diphosphorus pentoxide; mesoporous silica for 0.1h; | |
95% | With tert.-butylhydroperoxide In methanol; dichloromethane at 20℃; | |
95% | With tert.-butylhydroperoxide In methanol; dichloromethane; water monomer at 20℃; | |
95% | With sodium hydrogen sulphate monohydrate; [bis(acetoxy)iodo]benzene In water monomer; acetonitrile for 0.0833333h; | |
95% | With sodium chlorine monoxide; sulfuric acid In ethanol; water monomer at 20℃; for 1h; chemoselective reaction; | |
95% | With sodium chlorine monoxide In ethanol; water monomer at 20℃; for 0.666667h; | |
95% | With 2-iodyl-3-propoxypyridine In acetonitrile for 2.5h; Reflux; Inert atmosphere; chemoselective reaction; | |
95% | With aminosulfonic acid; dihydrogen peroxide In neat (no solvent) at 20℃; for 0.25h; Green chemistry; chemoselective reaction; | |
95% | With dihydrogen peroxide In neat (no solvent) at 20℃; for 0.166667h; Green chemistry; chemoselective reaction; | General procedure for the oxidation of sulfides to sulfoxides General procedure: To a mixture of sulfide (1 mmol) and 30% H2O2 (0.5 g, 1.2 equiv.), MNPs-PSA (5 mg, 0.95 mol%) was added and the mixture was stirred at room temperature for the time specified. Completion of the reaction was indicated by TLC (n-hexane/ethylacetate 2:1). After completion of the reaction, Et2O (2× 5 mL) was added and the catalyst was separated by an external magnet. The combined organics were washed with brine (5 mL) and dried over anhydrous Na2SO4. The resulting solution was concentrated under reduced pressure to afford the essentially pure products in most cases. Further purification was achieved by short-column chromatography on silica gel with EtOAc/n-hexane as eluent. All the products are known and were characterized by IR, 1H NMR, 13C NMR and by melting point comparisons with those of authentic samples [12-14,25,27]. |
95% | With O40PW12(3-)*3C14H16NO3S(1+); dihydrogen peroxide In ethanol; water monomer at 60℃; for 0.75h; Green chemistry; | Oxidation of solid sulfur compounds General procedure: To a stirred suspension of the substrate (5 mmol), catalyst (0.2 g, 1.0 mol%) in H2O: EtOH (7:3v/v, 10 mL), 30% aq. H2O2 (1.1 mL, 10 mmol) was added in one portion. The slurry was stirred at 60 °C for 45 min. The reaction mixture was cooled to 10 °C, and the catalyst was separated by filtration. The corresponding sulfoxide product was extracted with Et2O from the reaction mixture. Evaporation of the solvent afforded the crude product. The crude product was purified by column chromatography on silica gel using EtOAc/hexane as eluent (method (c)). Similar method was utilized to produce sulfones. In this case 3.4 mL of 30% aq. H2O2 (30 mmol) was used for 60 min (method (d)). |
95% | With trimethyl-(2-hydroxyethyl)ammonium chloride; dihydrogen peroxide; toluene-4-sulfonic acid In ethanol at 40℃; for 1h; Green chemistry; chemoselective reaction; | Selective oxidation of sulfide 1a and the recovery of DES General procedure: A mixture of benzyl phenyl sulfide (0.2 g, 1 mmol), 30% H2O2 (2 mmol), ethanol (3 mL) and ChCl/p-TsOH (20 mol%, four drops) was stirred at 40°C for 1 h (monitored by TLC). After completion of the reaction, the reaction mixture was extracted with EtOAc (3×5 mL). The organic layer was concentrated and the resulting crude product was further purified by column chromatography on silica gel with petroleum ether/EtOAc as eluent, providing the sulfoxide 2a in 95% yield. The DES was then readily recovered via evaporation under vacuum at 80°C and reused for the next cycle. All the products are known compounds and fully characterised. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With potassium permanganate; iron(III) chloride In acetonitrile at 23℃; for 1.25h; | |
100% | With dihydrogen peroxide; titanium(IV) oxide In acetonitrile at 20℃; for 10h; | |
99% | With trifluoroacetyl peroxide In trifluoroacetic acid at 30℃; |
99% | With manganese(II) sulfate; dihydrogen peroxide; sodium hydrogencarbonate In water; acetonitrile at 20℃; for 0.25h; | |
99% | With aluminium trichloride; 3-carboxypyridinium chlorochromate In acetonitrile for 0.0166667h; microwave irradiation; | |
99% | With dihydrogen peroxide; tantalum pentaethoxide In methanol at 45℃; for 2.5h; | |
99% | With dihydrogen peroxide; tantalum pentaethoxide In methanol at 45℃; for 2.5h; chemoselective reaction; | |
99% | With 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine; dihydrogen peroxide at 25℃; for 0.216667h; Neat (no solvent); chemoselective reaction; | |
99% | With dihydrogen peroxide In water; acetonitrile at 20℃; for 3.16667h; Green chemistry; chemoselective reaction; | |
99% | With selenium(IV) oxide; dihydrogen peroxide In water; ethyl acetate chemoselective reaction; | 3.2. Synthesis of Sulfones 2a-g General procedure: In a 2 mL volumetric ask, ethyl acetate was added to suldes 1a±c,e±g (1.0 mmoL) or sulde1d, (0.5 mmoL) to make up the required volume. (Solution A: 0.5 M (1a-c,e-g). In the case of 1d, theconcentration was optimized at 0.25 M) In a 2 mL volumetric flask, 0.1 mmoL of SeO2 (11 mg) andH2O2 30 wt. % (10 mmoL, 1.025 mL) were poured, and then water was added until the desired volumewas reached. (Solution B: 0.05 M (SeO2) and 5 M (H2O2). In the case of 1d, a dierent concentrationwas optimized at 0.025 M (SeO2) and 2.5 M (H2O2)). |
99% | With dihydrogen peroxide In acetonitrile at 25℃; for 0.0833333h; | General procedure for the preparation of sulfones General procedure: To a mixture of sulfide (1 mmol) and AgCeO2 (0.05 g) in2 cm3acetonitrile, 0.3 cm330% H2O2(3 equiv.) was added,and the mixture was stirred at room temperature until thecomplete consumption of sulfide (monitored by TLC). Aftercompletion of the reaction, 10 cm3acetonitrile was addedto the reaction mixture and the mixture heated for 10 minat 50 °C. After that, the catalyst was separated from thereaction mixture by filtration and the organic residue wasextracted with 20 cm3EtOAc, washed with 10 cm3distilledwater, dried over MgSO4,and recrystallized in a mixture ofEtOH and H2Oto obtain the pure product. |
98% | With dihydrogen peroxide; zirconium(IV) chloride In methanol at 20℃; for 0.0333333h; | |
98% | With 30percent aq. H2O2 In methanol at 20℃; for 4h; | |
98% | With dihydrogen peroxide In ethanol at 50℃; for 0.666667h; | |
98% | With dihydrogen peroxide In nitromethane at 20℃; for 2.5h; | |
98% | With dihydrogen peroxide In ethanol at 50℃; for 0.166667h; Green chemistry; | |
97% | With Oxone; aluminium trichloride for 0.5h; Heating; | |
97% | With caro's acid; silica gel In acetonitrile for 5h; Heating; | |
97% | With chromium(VI) oxide; periodic acid In ethyl acetate; acetonitrile at -35℃; for 1.75h; | |
97% | With aluminium trichloride; butyltriphenylphosphonium dichromate In acetonitrile for 0.0416667h; microwave irradiation; | |
97% | With N-methylpyrrolidine-2-one hydrotribromide; dihydrogen peroxide In water; acetonitrile at 80℃; for 0.133333h; | |
97% | With N,N'-dibenzyl-N,N,N',N'-tetramethylethylenediammonium bis(permanganate); acetic acid In acetonitrile at 20℃; for 0.0333333h; | |
97% | With tert.-butylhydroperoxide In water; acetonitrile at 60℃; for 4.5h; Inert atmosphere; | |
97% | With borax; dihydrogen peroxide; sodium hydroxide In methanol; water at 20℃; for 3h; chemoselective reaction; | |
97% | With 1,3,5-trichloro-2,4,6-triazine; dihydrogen peroxide In water; acetonitrile at 20℃; for 0.283333h; chemoselective reaction; | General procedure for the preparation of sulfones General procedure: To a mixture of sulfide (1 mmol) and TCT (1 mmol, 0.184 g) in acetonitrile (5 mL) was added 30% H2O2 (2 mmol, 0.2 mL). The mixture was stirred at room temperature for the appropriate period of time until complete consumption of the starting material as observed by TLC. After completion of the reaction, H2O (10 mL) was added to the reaction mixture which was then extracted with EtOAc (4 × 5 mL) and the combined extracts were dried (MgSO4). The filtrate was evaporated and the corresponding sulfone was obtained as the only product (Table 1). |
97% | With dihydrogen peroxide In methanol at 60℃; for 8h; 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. |
96% | With 3-chloro-benzenecarboperoxoic acid In diethyl ether for 10h; Ambient temperature; | |
96% | With potassium permanganate at 20℃; for 1h; | |
96% | With dihydrogen peroxide In ethanol; water for 2h; Reflux; | |
96% | With niobium carbide; dihydrogen peroxide In ethanol; water at 60℃; for 4h; chemoselective reaction; | |
95% | With oxygen; isobutyraldehyde In 1,2-dichloro-ethane at 25 - 28℃; for 0.75h; | |
95% | With dihydrogen peroxide; urea; trifluoroacetic anhydride In acetonitrile for 1.5h; Ambient temperature; | |
95% | With potassium permanganate In acetonitrile at 20℃; for 55h; | |
95% | With 1H-imidazole; manganese(II) tetraphenylporphyrinate; tetra-n-butylammonium hydrogen monopersulfate In dichloromethane at 20℃; for 0.0166667h; | |
95% | With dihydrogen peroxide; titanium tetrachloride In acetonitrile at 25℃; for 0.0333333h; | |
95% | With aminosulfonic acid; dihydrogen peroxide In neat (no solvent) at 20℃; for 0.916667h; Green chemistry; chemoselective reaction; | |
95% | With tetra-n-butylammonium peroxomonosulfate In water at 25℃; for 0.75h; chemoselective reaction; | |
95% | With tetra-n-butylammonium hydrogen monopersulfate In water at 25℃; for 0.333333h; | |
94% | With silica gel; magnesium monoperoxyphthalate hexahydrate In dichloromethane for 1.25h; Heating; | |
94% | With formic acid; dihydrogen peroxide; urea for 2h; Ambient temperature; | |
94% | With dihydrogen peroxide In 1,2-dichloro-ethane for 0.3h; Reflux; | |
94% | With dihydrogen peroxide In methanol at 40℃; for 0.416667h; chemoselective reaction; | |
94% | With dihydrogen peroxide In water at 20℃; for 10h; | |
94% | With dihydrogen peroxide In ethanol; water at 50℃; for 0.166667h; Green chemistry; chemoselective reaction; | |
94% | With dihydrogen peroxide; C16H16N3O5V In ethanol; water for 0.333333h; Reflux; | 2.5 Generalized method for the selective oxidation of sulfides to sulfones catalyzed by [VO2(HL)] General procedure: A solution of methylphenyl sulfide (1mmol), 30% aqueous H2O2 (4mmol) and [VO2(HL)] complex (1mol%) in 5mL of EtOH, was refluxed with vigorous stirring. The catalytic conversion is continuously observed by employing thin layer chromatography by using a 70:30 mixture of n-hexane and diethyl ether as eluent. After that, the reaction mixture was cooled to room temperature and then the hot ethanol (3mL) was added up and the contents were stirred for 10min. At this stage, the catalyst is recovered by filtration and washed thrice with hot ethanol. From the filtrate the solvent was evaporated slowly to get the desired refined products. The products gained after the completion of the catalytic cycle were characterized spectroscopically and then the data was compared with the standard samples. |
93% | With dihydrogen peroxide In acetonitrile at 20℃; for 0.5h; | |
93% | With tert.-butylhydroperoxide; lanthanum(III) oxide In water; ethyl acetate at 150℃; for 5h; | |
92% | With L-alanin; silica gel; Chloro-hydroxy-dioxo-chromium In tetrachloromethane at 65℃; for 5h; | |
92% | With dihydrogen peroxide In acetonitrile at 20℃; for 1h; chemoselective reaction; | 2.4. Synthesis of sulfoxides and sulfones General procedure: To a stirred suspension of the selected sulfide (1 mmol) and the heterogeneous catalyst PW12(at)Al-MCF (3 mol%) in methanol (5 ml), H2O2 (8 mmol) was added in one portion. The slurry was stirred at room temperature for 20 min. The catalyst was filtered off and washed with methanol (5 ml). Ethyl acetate (5 ml) was added and resulting solution was dried with anhydrous sodium sulfate and evaporated in vacuo to afford the crude product which was purified by column chromatography on silica gel (10% EtOAc in hexane) to afford the pure sulfoxide. |
92% | With dihydrogen peroxide In water; acetonitrile at 50℃; for 3h; chemoselective reaction; | General procedure for the oxidation of sulfide to sulfone General procedure: A solution of sulfide (1 mmol) and catalyst (100 mg), in acetonitrile (9 mL), was added to H2O2 35% (w/v) (10 mmol). The mixture was stirred at 50 °C for a time period (see Tables 1 and 2). The solvent was evaporated and then H2O (5 mL) was added. The substrate was extracted with toluene (2 × mL) and dried with anhydrous Na2SO4; filtration and evaporation afforded the corresponding sulfoxides. The crude solids were purified by recrystallization to affordthe pure sulfones |
92% | With dihydrogen peroxide In water at 20℃; for 0.5h; chemoselective reaction; | General procedure for the oxidation of sulfides to sulfones General procedure: To a mixture of sulfide (1 mmol) and catalyst (0.04 g), H2O2 30%(v/v) (0.28 g, 2.5 equiv.) was added and stirred at room temperature for a specified time. After completion of the reaction, as indicated on thin-layer chromatography (TLC), ethyl acetate (20 mL) was added and the mixture was centrifuged to separate the catalyst. The filtrate was washed with brine and dried over anhydrous Na2SO4. Purification of the combined organics by preparative TLC (hexane-ethyl acetate, 10:1) provided pure products. The recycled catalyst was washed with ethyl acetate and acetone. After being dried at 60 °C, it can be reused without further purification. All of the products were known and identified by comparison of their melting points and spectral data with those reported in the literature 2.4. |
92% | With water; N-fluorobis(benzenesulfon)imide at 20℃; for 24h; chemoselective reaction; | |
91% | With dihydrogen peroxide In acetic acid | |
91% | With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; 4-methoxyisoquinoline; oxygen; copper(II) sulfate In methanol at 65℃; for 48h; Schlenk technique; Sealed tube; Green chemistry; | 12 Example 12: Preparation of phenyl p-toluenesulfonic acid from phenyl p-toluene sulfide TEMPO (3.9 mg, 0.025 mmol) was added to a 100 mL Schlenk reaction tube in turn. Methanol (1mL), CuSO4 (4.0mg, 0.025mmol), 4-methoxyisoquinoline (39.8 mg, 0.25 mmol), Phenyl p-toluene sulfide (100.2 mg, 0.5 mmol), Filled with 1 atm of oxygen, The sealed reaction tube was heated to 65 ° C for 48 h. After the reaction is completed, it is cooled to room temperature. Add the right amount of ethyl acetate, A blue solid precipitated in the reaction solution. Filtration, the filtrate is concentrated under reduced pressure, and purified by column chromatography to obtain The product has a yield of 91%. |
90% | With dihydrogen peroxide; boric acid at 20℃; for 0.5h; neat (no solvent); chemoselective reaction; | |
90% | With dihydrogen peroxide In water at 20℃; for 0.583333h; | |
90% | With O40PW12(3-)*3C14H16NO3S(1+); dihydrogen peroxide In ethanol; water at 60℃; for 1h; Green chemistry; | Oxidation of solid sulfur compounds General procedure: To a stirred suspension of the substrate (5 mmol), catalyst (0.2 g, 1.0 mol%) in H2O: EtOH (7:3v/v, 10 mL), 30% aq. H2O2 (1.1 mL, 10 mmol) was added in one portion. The slurry was stirred at 60 °C for 45 min. The reaction mixture was cooled to 10 °C, and the catalyst was separated by filtration. The corresponding sulfoxide product was extracted with Et2O from the reaction mixture. Evaporation of the solvent afforded the crude product. The crude product was purified by column chromatography on silica gel using EtOAc/hexane as eluent (method (c)). Similar method was utilized to produce sulfones. In this case 3.4 mL of 30% aq. H2O2 (30 mmol) was used for 60 min (method (d)). |
90% | With tetra-n-butylammonium hydrogen monopersulfate In water at 25℃; for 3h; | |
90% | With 2,2,2-Trifluoroacetophenone; dihydrogen peroxide; acetonitrile In <i>tert</i>-butyl alcohol at 20℃; for 1h; Green chemistry; | Organocatalytic Oxidation of Sulfides to Sulfones; General Procedure General procedure: Sulfide (1.00 mmol) was placed in a round-bottom flask, followed by t-BuOH (0.5 mL), 2,2,2-trifluoroacetophenone (34.8 mg, 0.20 mmol), aq buffer solution (0.5 mL, 0.6 M K2CO3/4 × 10-4 M EDTA disodium salt), MeCN (0.15 mL, 3.00 mmol) and 30% aq H2O2 (0.36 mL, 3.00 mmol). The reaction mixture was stirred for 1-5 h. The reaction was quenched with 1 M HCl (5 mL) and extracted with CHCl3 (3 × 10 mL). The combined organic layers were dried over Na2SO4, filtered and concentrated in vacuo to afford the desired product. |
90% | With dihydrogen peroxide at 20℃; for 0.166667h; Green chemistry; chemoselective reaction; | |
90% | With oxygen; epi-Cercosporin In methanol at 25℃; for 24h; Irradiation; | 1 Example 1 Catalytic Synthesis of Benzyl Phenyl Sulfone by Cercosporin Catalyst In a 10 mL reaction tube, cercosporin (0.005 mmol) and benzyl phenyl sulfide (0.5 mmol) were sequentially added.2mL of methanol, then oxygen protection, 15W white light irradiation, room temperature 25 ° C reaction for 24h.The reaction solution was evaporated to dryness by rotary evaporation, and then evaporated, and then evaporated, eluent, eluent, ethyl acetate/ petroleum ether (v: v = 1:5).The benzyl phenyl sulfone was obtained in a yield of 90%. |
89% | With 1,3,5-trichloro-2,4,6-triazine; dihydrogen peroxide In tetrahydrofuran at 20℃; for 0.416667h; | |
88% | With HOF* CH3CN; water In dichloromethane at -20℃; for 0.0833333h; | |
88% | With copper phthalocyanine; tetra-n-butylammonium hydrogen monopersulfate In water at 25℃; for 1h; chemoselective reaction; | |
87% | With sodium periodate; silica gel In dichloromethane for 0.0416667h; Irradiation; | |
87% | With potassium permanganate; Rexyn 101 H ion exchange resin In dichloromethane for 5.3h; Heating; | |
87% | With sodium hypochlorite; silica gel In dichloromethane; water for 0.15h; Microwave irradiation; chemoselective reaction; | |
87% | With sodium bromate In water at 80℃; for 0.5h; Ionic liquid; | Oxidation of sulfides, tellurides and phosphines; general procedure General procedure: A mixture of sodium bromate (3.12 mmol), and substrate 1 or 3 or 5(1.04 mmol) in 4 mL of [bmim]HSO4:H2O (3:1, v/v) was placed in a 50 mL round-bottomed flask mounted over a magnetic stirrerand fitted with an air condenser. The contents were heated in an oil-bath maintained at 80 °C for the time specified in Table 2 and 3.The progress of the reaction was monitored by TLC using ethylacetate:petroleum ether (50:50, v/v) as eluent. After completion ofthe reaction, the contents were allowed to cool to room temperature.A saturated solution of sodium thiosulfate (~5 mL) was added into thereaction mixture in order to remove excess unreacted bromine. Themixture was poured into a beaker containing ice cold water (~30 mL)and stirred well. The solid product was filtered under suction pumpand recrystallised. The products were characterised by its m.p., IR andNMR spectra. |
87% | With palladium; dihydrogen peroxide In methanol at 100℃; for 6h; Green chemistry; chemoselective reaction; | |
87% | With urea hydrogen peroxide adduct In ethanol at 20℃; for 0.5h; | 2.1. General procedure for catalytic oxidation of organic sulfides to sulfones Organic sulfide (1.0 mmol), UHP (5.0 mmol) and catalyst (0.05 mmol) were stirred in ethanol (5 mL) at room temperature and the progress of the reaction was monitored using thin layer chromatography (TLC). After completion of the reaction, precipitate formed was filtered off, washed with cold ethanol and dried to obtain the pure organic sulfone. In case of soluble organic sulfones, solvent was evaporated under reduced pressure; residue was triturated with dichloromethane (5 mL) and filtered to remove the insoluble urea and catalyst. The filtrate containing sulfone was dried and recrystallized from dichloromethane/hexane mixture. |
86% | With manganese(IV) oxide; potassium permanganate at 20℃; for 1.41667h; ultrasonic irradiation; | |
86% | With 3-oxo-1λ3-benzo[d][1,2]iodaoxol-1(3H)-yl 2,2,2-trifluoroacetate In acetonitrile for 16h; Reflux; | Procedure for the synthesis of sulfones 10a-h General procedure: The mixture of sulfide (0.5 mmol) and reagent 8 (413 mg, 2.4 equiv) in acetonitrile (3 mL) was heated atreflux temperature for 16-20 h. The course of reaction was monitored by TLC. After completion ofreaction, saturated solution of sodium bicarbonate (5 mL) was added to the reaction mixture andextracted with ethyl acetate (3 X 15 mL). The combined organic layer was dried over anhydrous sodiumsulphate and concentrated under vacuum. The crude products were purified by column chromatographyon silica gel using EtOAc-hexane (1:3) and isolated products were characterized as sulfones 10 byspectroscopic analysis. |
85% | With potassium permanganate; copper(II) sulfate at 20℃; for 12h; | |
82% | With potassium permanganate; N-benzyl-N,N,N-triethylammonium chloride; benzoic acid In dichloromethane; water for 3h; | |
82% | With 3-butyl-1-methyl-1H-imidazolium perrhenate; dihydrogen peroxide; 1-butyl-3-methylimidazolium Tetrafluoroborate In water at 60℃; for 5.5h; 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). |
82% | With urea-2,2-dihydroperoxypropane In tetrahydrofuran at 20℃; for 1.16667h; 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. |
81% | With N,N'-bis(salicylidene)-1,2-phenylene diaminocobalt(II); oxygen; isobutyraldehyde In acetonitrile at 70℃; for 6h; | |
81% | With phenanthroline hydrotribromide; dihydrogen peroxide In water; acetonitrile at 20℃; for 0.583333h; | Oxidation of benzyl phenyl sulfide General procedure: 30% hydrogen peroxide, 1.5 mL (10 mmol) was added drop wise to a stirred solution ofbenzyl phenyl sulfide, 2 g (10 mmol) and PhenHTB, 0.042 g (10 mol %) in acetonitrile-water mixture (10 mL, 1:1) at roomtemperature for an appropriate time. After completion of the reaction as monitored by TLC, the reaction mixture was poured inwater and the excess hydrogen peroxide was destroyed by the addition of aq. sodium bisulfite followed by the filtration through asmall Buckner funnel. After filtration the organic products were extracted with ether. The ether layer was washed with water (2mL) and dried over Na2SO4. The organic solvent was removed under reduced pressure to give the corresponding sulfoxide. Theproducts were further purified by column chromatography on silica gel using ethyl acetate/hexane (1:4) as eluent. Evaporation ofthe solvent yielded the corresponding benzyl phenyl sulfoxide (10, Table 1). The reaction time and yield of the products arepresented in the Table 1. |
81% | With 1,2-diphenyl-1,1,2,2-tetrahydroperoxyethane In tetrahydrofuran at 20℃; for 1.1h; 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. |
81% | With dihydrogen peroxide In water at 75℃; for 4h; | |
78% | With potassium permanganate supported on montmorillonite K10 at 20℃; for 2h; | |
78% | With oxygen at 100℃; for 20h; Schlenk technique; chemoselective reaction; | |
70% | With tetra-n-butylammonium hydrogen monopersulfate In water at 25℃; for 1h; chemoselective reaction; | |
8.2% | With dihydrogen peroxide; calcium(II) trifluoromethanesulfonate In acetonitrile at 29.84℃; for 6h; | |
8% | With dihydrogen peroxide In ethanol; n-heptane; water at 60℃; for 1h; | Oxidation of solid sulfides General procedure: Solid sulfides were oxidized to the corresponding sulfonesby stirring a solution of the sulfide (1 mmol) and the catalyst(0.15 g) in n-heptane-ethanol (v/v, 4:2). Then a certain amountof H2O2 (30% aq.) was added as the oxidant. The mixture wasstirred for a specified time at 60 °C, and the reaction was monitoredusing thin-layer chromatography. After completion ofthe reaction, the catalyst was separated from the reaction solutionusing an external magnet. The corresponding sulfoneproducts were separated from the reaction mixture. The solventwas evaporated to generate the crude product. The crude product was purified by column chromatography on silica gelusing hexane/ethyl acetate as the eluent (method b). |
With oxygen; isobutyraldehyde In 1,2-dichloro-ethane for 1.25h; various reaction conditions; | ||
With dihydrogen peroxide; acetic acid | ||
With 3-chloro-benzenecarboperoxoic acid | ||
With chromium(VI) oxide In acetic acid at 90 - 100℃; for 0.5h; | ||
With phthalic anhydride; urea In acetonitrile for 1.5h; Ambient temperature; | ||
With dihydrogen peroxide In acetic acid | ||
With tetrabutylammonium polychromiumphosphotungstate trihydrate; dihydrogen peroxide In water; acetonitrile at 25℃; for 0.166667h; Green chemistry; chemoselective reaction; | Typical procedure for the catalytic oxidation of sulfides to sulfones General procedure: PWCr catalyst (0.0245 mmol), CH3CN (3 mL), sulfide (1 mmol), and hydrogenperoxide (4 mmol, 30% aq solution) were added to a glass tube as the reaction vessel. The reaction was carried out at 298 K. The mixture was sampled periodically and analyzed by GC. After completion of the reaction, the product was extracted with CH2Cl2 and the combined organic layers were dried over anhydrous Na2SO4. The solvent was removed under reduced pressure to give the corresponding pure sulfone. The products were identified by comparison of their 1H NMR and 13C NMR signals with the literature data (see Supplementary Data, Figures S5-S18). | |
80 %Chromat. | With potassium permanganate In o-xylene at 20℃; for 11h; Green chemistry; | |
With 4C16H36N(1+)*PW11CrO39(4-)*3H2O; dihydrogen peroxide In water at 25℃; for 0.5h; Green chemistry; | General procedure for the oxidation of sulfides to sulfones: The sulfide (1mmol) was added to a solution of 30% H2O2 (6.5 equiv) and TBAPWCr (16.5μmol), and the mixture was stirred at room temperature for the time specified in Table2. The progress of reactions was monitored by TLC and GC. After completion of the reaction, the product was extracted with ethyl acetate. Further purification was achieved by short-column chromatography on silica gel with EtOAc/n-hexane (1/10) as eluent. All of the products were known and characterized by 1HNMR and 13CNMR (see Supplementary data, Figs. S3-S15) [38-41]. | |
With oxygen; isobutyraldehyde In acetonitrile at 20℃; for 1.5h; Green chemistry; | ||
With dihydrogen peroxide In acetonitrile at 25℃; for 0.5h; Reflux; | ||
With (n-Bu4N)6(Mo7O24); dihydrogen peroxide In acetonitrile at 22℃; for 1h; | ||
With dihydrogen peroxide In acetonitrile at 20℃; for 0.5h; | ||
With oxygen; LmbC oxygenase; glycerol; NADPH; flavin adenine dinucleotide; sodium chloride In 1,4-dioxane at 24℃; for 24h; Enzymatic reaction; | ||
With dihydrogen peroxide; C17H19MoN3O7 In ethanol; water Reflux; Green chemistry; | 2.3. Generalized method for the catalytic selective oxidation of sulfides by MoO 2 L(CH 3 OH) complex General procedure: A solution of methylphenyl sulfide (1 mmol), 30% aqueous H 2 O 2 (4 mmol), MoO 2 L(CH 3 OH) complex (1 mol%) and chlorobenzene (1 mmol) as internal standard in 5 mL of EtOH, was refluxed with vigorous stirring. The catalytic conversion is continuously observed by employing thin layer chromatography by using a 70:30 mixture of n -hexane and diethyl ether as eluent. After that, the reaction mixture was cooled to room temperature and then the hot ethanol (3 mL) was added up and the contents were stirred for 10 minutes. On complete conversion, the resultant mixture was filtered offand then the solvent was evaporated slowly to get the desired refined products. The products gained after the completion of the catalytic cycle were characterized spectroscopically and then the data was compared with the standard samples. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With mildly basic modified zeolite catalyst In 2,2,4-trimethylpentane at 110℃; for 4h; | |
95% | With C40H30Cl2N2NiO2S2; sodium hydroxide In N,N-dimethyl-formamide at 70℃; for 1h; | 4.1.8. Phenyl benzyl sulfide (3l) A mixture of benzyl chloride (127 mg, 1 mmol), thiophenol (110 mg, 1 mmol), NaOH (60 mg, 1.5 mmol) and 5 mol % NiL2 (38 mg) in DMF was stirred at 70 °C for 1 h. The reaction mixture was filtered and the solvent evaporated in vacuo to give the crude product, which was purified by column chromatography (hexane/ethyl acetate=4/1) to give the title compound 3l (190 mg, 95%) as a colourless oil; [Found: C, 77.90; H, 6.21. C13H12S requires C, 77.95; H, 6.04%]; Rf=0.4 (hexane/ethyl acetate=4/1). 1H NMR (400 MHz, CDCl3): δ 7.36-7.30 (m, 10H), 4.06 (s, 2H), 13C NMR (100 MHz, CDCl3): δ 139.4, 138.8, 129.9, 128.4, 128.3, 127.2, 126.9, 39.3. |
93% | Stage #1: thiophenol In acetonitrile for 0.333333h; Heating; Stage #2: benzyl chloride In acetonitrile for 1.5h; Heating; |
91% | With triethylamine at 80℃; for 24h; Inert atmosphere; | |
90% | With 1-pentyl-3-methylimidazolium bromide at 25 - 30℃; for 0.416667h; | |
90% | With silica gel at 20℃; for 5h; | |
75% | With montmorillonite-3-aminopropyltriethoxysilane at 95℃; for 0.0833333h; | |
75% | With potassium fluoride on alumina at 50℃; for 0.216667h; Microwave irradiation; | 3.2.2. S-alkylation of thiols into corresponding thioethers by KF/Al2O3 undersolvent-free reaction conditions assisted by microwave irradiation (Method B) General procedure: Asuitable quantity of alkyl halides (1.5mmol) and KF/Al2O3 (0.6 g) was added to a specifictest tube (h = 9 cm, d = 1.5 cm) containing the thiol (1.5mmol). The test tube was placedinto a Discover CEM microwave oven. For each of the thiols, an irradiation program wasfixed to operate at power of oven (4W), reaction temperature (50°C) and reaction time(minutes), see Table 1. After cooling, the reaction mixture was worked up as described inmethod A. |
With lithium methanolate In methanol at 20℃; other temperatures; | ||
With sodium hydroxide | ||
With ethanol; sodium ethanolate | ||
With potassium <i>tert</i>-butylate In N,N-dimethyl-formamide at 25℃; for 0.5h; | ||
With sodium hydroxide; cetyltrimethylammonim bromide In water; benzene at 20℃; | ||
With potassium carbonate In acetone Reflux; | ||
With potassium carbonate In acetone at 60℃; for 4h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With sodium hydroxide; sodium tris(acetoxy)borohydride In tetrahydrofuran for 2.5h; Heating; | |
95% | With borohydride exchange resin In methanol for 3h; Ambient temperature; | |
95% | With zinc In acetonitrile for 12h; Ambient temperature; |
92% | With hydrogenchloride; zinc In water at 20℃; for 0.25h; Ionic liquid; Inert atmosphere; | General procedure for the synthesis of diorganyl selenides and sulfides: commercially available Zn dust (33 mg, 0.5 mmol) and PhSeSePh/PhSSPh (0.5 mmol) and 15 μL of HCl 1N were added to BMIM-BF4 (0.5 mL) at room temperature under nitrogen. The mixture was allowed to stir for 2-3 min. Then corresponding organic halides (1 mmol) was slowly added. The reaction mixture was allowed to stir until the color change (monitored by TLC and assisted by visual observation). The mixture was then extracted with ether (3×15 mL), and the combined ether extract was washed with brine, dried (MgSO4), and evaporated to leave the crude product. Purification by column chromatography over silica gel (hexane/ethyl acetate 98:2) furnished the corresponding products. |
85% | With tin(ll) chloride; copper(ll) bromide at 20℃; for 0.5h; Inert atmosphere; Ionic liquid; | General Procedure for the synthesis of diorganyl selenide and sulfides General procedure: In a schlenk tube, under argon atmosphere, diaryl dichalcogenide (0.5 mmol) SnCl2 (1.2 mmol) and CuBr2 (0.1 mmol) were added to BMIM-BF4 (0.5 mL) at room temperature. Then organic halide (1.1 mmol) was slowly added. The reaction mixture was stirred 60 min to afford the corresponding diorganyl selenide whereas 30 minute reaction time was used for the synthesis of diorganyl sulfide. After completion of the reaction, (monitored by TLC) the mixture was then extracted with diethylether (5x 10 mL), and the combined ether extract was washed with brine, dried (MgSO4) and evaporated to leave the crude products which were purified by column chromatography. |
80% | Stage #1: diphenyldisulfane With zirconium(IV) chloride; zinc In tetrahydrofuran at 40℃; for 5h; Stage #2: benzyl chloride In tetrahydrofuran | |
80% | With triphenylphosphine; 1-pentyl-3-methylimidazolium bromide at 75℃; for 2.5h; | Representative procedure for the synthesis of benzyl phenyl sulfide (Table 2, entry 2a). General procedure: A mixture of benzyl bromide (171 mg, 1 mmol), diphenyl disulfide (131 mg, 0.6 mmol), PPh3 (184 mg, 0.7 mmol), and [pmIm]Br21 (94 mg, 0.4 mmol) was stirred at 75 °C for 1.5 h (TLC). The reaction mixture was extracted with Et2O, and the organic layer was washed with brine (2 × 5 mL) and dried (Na2SO4). Evaporation of solvent left the crude product which was purified by column chromatography over silica gel (hexane) to afford the pure product, benzyl phenyl sulfide (168 mg, 84%) as a colorless liquid; IR (neat) 3058, 3028, 2923, 1581, 1495, 1479, 1452, 1438, 1238, 1090, 1068, 1024 cm-1; 1H NMR (300 MHz, CDCl3) δ 4.21 (s, 2H), 7.32-7.41 (m, 10H); 13C NMR (75 MHz, CDCl3) δ 39.5, 127.6, 128.0, 129.0 (2C), 129.3 (2C), 129.5 (2C), 130.3 (2C), 136.9, 137.9. The spectroscopic (FT-IR, 1H NMR and 13C NMR) data are in good agreement with the reported values.9b The remaining ionic liquid was washed with ether, dried under vacuum, and reused five times without appreciable loss of catalytic activity. |
75% | With indium iodide In dichloromethane at 20℃; for 3h; | |
With sodium hydroxide | ||
80 %Chromat. | With indium In dichloromethane for 3h; Reflux; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | In acetonitrile at 20℃; for 16h; | |
In water Heating; | ||
In acetonitrile |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | Stage #1: Benzyl phenyl sulfide With n-butyllithium In tetrahydrofuran; hexane at 0℃; for 1h; Stage #2: chloro-trimethyl-silane In tetrahydrofuran; hexane at 20℃; for 0.5h; | |
89% | With n-butyllithium In tetrahydrofuran; hexane at 0 - 20℃; | |
80% | With n-butyllithium In tetrahydrofuran; hexane for 2h; Ambient temperature; |
With n-butyllithium; N,N,N,N,-tetramethylethylenediamine 1) THF, -78 deg C; Yield given. Multistep reaction; | ||
Stage #1: Benzyl phenyl sulfide With n-butyllithium In tetrahydrofuran at -78℃; Stage #2: chloro-trimethyl-silane In tetrahydrofuran at -78 - 20℃; | ||
With lithium diisopropyl amide In tetrahydrofuran at -78℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
58% | With MoO(O2)2(H2O); C15H24N2O4; dihydrogen peroxide; tetraphenylphosphonium bromide In chloroform; lithium hydroxide monohydrate at 0℃; for 1h; enantioselective reaction; | 3.5. General Procedure for Enantioselective Mo-Catalyzed Oxidation of Sulfides in the Presence of HLR General procedure: The reactor (a 50 mL vial equipped with a Young valve and containing a stirrer flea) was charged with [Mo(O)(O2)2(H2O)n] (100 μL, 0.25 M aqueous solution, 0.025 mmol), HLR (0.0125 mmol), [PPh4]Br as specified (typically 0.05 mmol), the reaction solvent (1 mL), the oxidant (30% aqueous H2O2; 1 mmolper sulfide substrate, see details above) and the sulfide substrate (1 mmol), in the aforementioned order.The reactor was sealed and maintained at the working temperature, with constant stirring (600 rpm)in a thermostatted bath for the duration of the reaction. Upon completion, the reaction mixture wastreated with diethyl ether (10 mL) and then filtered with 0.45 μm nylon syringe filter. The resultingsolution was analyzed by GC (by adding 50 μL of dodecane as the internal standard). Afterwards thesolution was evaporated to dryness by using a rotavap. The resulting residue was then analyzed by HPLC (by adding 20 mL of ethyl acetate). |
46% | Stage #1: Benzyl phenyl sulfide With titanium isopropoxide; (1S,2S)-(-)-1,2-diphenyl-1,2-ethanediol In hexane at 20℃; for 0.5h; Inert atmosphere; Stage #2: With Cumene hydroperoxide In hexane for 21h; enantioselective reaction; | |
With potassium peroxomonosulfate; bovine serum albumine In lithium hydroxide monohydrate at 4℃; Yield given; |
With (DHQD)2Pyr; dihydrogen peroxide; tungsten(VI) oxide In tetrahydrofuran at 0℃; for 24h; Title compound not separated from byproducts; | ||
With (2R)-3,3-di(pyridin-2-yl)-2-[(S)-α-methylbenzyl]oxaziridine; anhydrous zinc chloride In chloroform Title compound not separated from byproducts; | ||
With (S)-2-(N-3',5'-diiodosalicylidene)-amino-3,3-dimethyl-1-butanol; dihydrogen peroxide; 4-methoxybenzoic acid In dichloromethane; lithium hydroxide monohydrate at 20℃; for 16h; Title compound not separated from byproducts; | ||
With vanadyl(IV) acetylacetonate; (R,R)-N,N'-bis(salicylidene)-1,2-cyclohexanediamine; dihydrogen peroxide In chloroform; lithium hydroxide monohydrate at 0℃; for 16h; | ||
With dihydrogen peroxide In dichloromethane at 0℃; for 4h; Title compound not separated from byproducts; | ||
With sodium (meta)periodate In methanol; lithium hydroxide monohydrate at 25℃; Yield given. Yields of byproduct given; | ||
With 6-aza-5β,6β-epoxy-cholestane-based tetrafluoroborate salt In dichloromethane at -70 - 20℃; for 3h; Title compound not separated from byproducts.; | ||
With dihydrogen peroxide; 3-butyl-1-methyl-1H-imidazol-3-ium hexafluorophosphate In Carbon tetrachloride at 20℃; for 16h; Title compound not separated from byproducts.; | ||
With dihydrogen peroxide In dichloromethane at 20℃; for 16h; Title compound not separated from byproducts.; | ||
With titanium isopropoxide; Cumene hydroperoxide; (1S,2R,4S,5R)-2,5-diisopropylcyclohexane-1,4-diol In Carbon tetrachloride at 0℃; for 36h; Molecular sieve; optical yield given as %ee; enantioselective reaction; | ||
Stage #1: Benzyl phenyl sulfide With titanium isopropoxide; diethyl (2S,3S)-tartrate; lithium hydroxide monohydrate In toluene at 50℃; for 0.75h; Stage #2: With Cumene hydroperoxide; N-ethyl-N,N-diisopropylamine In toluene at -20℃; for 1h; optical yield given as %ee; | ||
With Cumene hydroperoxide In dichloromethane at 0℃; for 1.33333h; | ||
With iodosylbenzene; C75H102Cl3Fe3N6O6 In dichloromethane at 20℃; for 15h; optical yield given as %ee; enantioselective reaction; | ||
With vanadyl(IV) acetylacetonate; 2,4-bis(1,1-dimethylethyl)-6-([(1S)-1-hydroxymethyl-2,2-dimethylpropyl]imino}methyl)phenol; dihydrogen peroxide In dichloromethane at 0℃; for 20h; optical yield given as %ee; enantioselective reaction; | ||
With tert.-butylhydroperoxide; Fe2(SO4)3; (R,R)-N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediamine In lithium hydroxide monohydrate for 2.3h; Reflux; optical yield given as %ee; enantioselective reaction; | ||
Stage #1: Benzyl phenyl sulfide With copper(II) bis(2,4-pentanedionate); (S)-2-(N-3',5'-dichlorosalicylidene)-amino-3,3-dimethyl-1-butanol In methanol; hexane at 20℃; for 0.0833333h; Stage #2: With dihydrogen peroxide In methanol; hexane at 20℃; for 16h; optical yield given as %ee; enantioselective reaction; | ||
Stage #1: Benzyl phenyl sulfide With (R)-(3,3'-bis(1-naphthyl)-1,1'-binaphthanele-2,2'-yl)phosphoric acid In chloroform at -40℃; for 0.5h; Stage #2: With dihydrogen peroxide In chloroform; lithium hydroxide monohydrate at -40℃; for 88h; optical yield given as %ee; enantioselective reaction; | ||
With sodium phosphite; phosphite dehydrogenase; [Thermobifida fusca phenylacetone monooxygenase]-[ABE(054)F01497] chimera; tris(hydroxymethyl)methylamine hydrochloride; NADPH In dimethyl sulfoxide at 20℃; Enzymatic reaction; optical yield given as %ee; enantioselective reaction; | ||
With sodium phosphite; phosphite dehydrogenase; [Thermobifida fusca phenylacetone monooxygenase]-[Acinetobacter sp. cyclohexanone monooxygenase] chimera; tris(hydroxymethyl)methylamine hydrochloride; NADPH In dimethyl sulfoxide at 20℃; Enzymatic reaction; optical yield given as %ee; enantioselective reaction; | ||
With vanadyl(IV) acetylacetonate; 2,4-di(tert-butyl)-6-[(1S,2S,3R,5S)-3-hydroxymethyl-2,6,6-trimethylbicyclo[3.1.1]hept-2-ylimino]methyl}phenol; dihydrogen peroxide In dichloromethane; lithium hydroxide monohydrate at 20℃; for 3h; optical yield given as %ee; enantioselective reaction; | ||
16 % ee | With μ-oxido-bis({(1R,2S)-(-)-2-[(1-oxido-1-phenylpropyl)iminomethyl]-4-bromophenolato-κ3N,O,O'}oxidovanadium(V)); dihydrogen peroxide In methanol; dichloromethane; lithium hydroxide monohydrate at 20℃; for 0.5h; Overall yield = 86 %Spectr.; enantioselective reaction; | 2.4. Complexes General procedure: In typical procedure, to a solution of vanadium(V) complex (0.010 mmol) in 3 ml of CH2Cl2/MeOH solution (7:3, v/v), sulfide (1.00 mmol) was added at room temperature or -20 °C, together with 1,3,5-trimethoxybenzene as internal standard. Aqueous 30% H2O2 or cumene hydroperoxide (CHP) as oxidant was added (1.10 mmol) by small portions and the resulting mixture was stirred. After the appropriate reaction time, the solution was quenched with 2 ml of sodium sulfite solution (0.1 M) and extracted with CH2Cl2 (3 × 5 ml). The combined organic layers were evaporated to dryness. The solid product dissolved in CDCl3 was analyzed (yield and ee - enantiomeric excess value) by 1H NMR spectra in the presence of chiral shift reagent Eu(hfc)3 (where Hhfc is 3-(heptafluoropropylhydroxymethylene)-(+)-camphoric acid) [22]. |
18 % ee | With μ-oxido-bis({R(-)-2-[(2-oxidopropyl)iminomethyl]-4-methylphenolato-κ3N,O,O'}oxidovanadium(V)); dihydrogen peroxide In methanol; dichloromethane; lithium hydroxide monohydrate at 20℃; for 0.5h; Overall yield = 73 mg; enantioselective reaction; | 2.2.1. Sulfoxidation General procedure: 3 ml of CH2Cl2/MeOH solution (7:3, v/v), sulfide (1.00 mmol)was added at room temperature or -20 ◦C, together with 1,3,5-trimethoxybenzene as internal standard. Aqueous 30% H2O2 or cumene hydroperoxide (CHP) as oxidant was added (1.10 mmol) by small portions and the resulting mixture was stirred. After the appropriate reaction time, the solution was quenched with 2 ml of sodium sulfite solution (0.1 M) and extracted with CH2Cl2 (3×5 ml). The combined organic layers were evaporated to dryness. The solid product dissolved in CDCl3 was analyzed (yield and ee value) by 1H NMR spectra in the presence of chiral shift reagent Eu(hfc)3 (where Hhfc is 3-(heptafluoropropylhydroxymethylene)-(+)-camphoric acid) [22]. |
79 % ee | With copper(II) bis(2,4-pentanedionate); (S)-2-(N-3',5'-dichlorosalicylidene)-amino-3,3-dimethyl-1-butanol; dihydrogen peroxide In methanol; hexane; lithium hydroxide monohydrate at 20℃; for 16h; Overall yield = 90 %; enantioselective reaction; | Experimental procedure for asymmetric sulfide oxidation General procedure: Copper (II) acetylacetonate (5.2mg, 2.0mol%) was added to a round-bottomed flask containing Schiff base ligand 4 (11.6mg, 4.0mol%), and 9:1 hexane/MeOH (1mL). The resulting solution was stirred at room temperature for 5min, and then a solution of sulfide (1mmol) in 9:1 hexane/MeOH (1mL) was added. After 5min stirring at room temperature. H2O2 (0.130mL, 30%, 1.1mmol) was added in one portion, dropwise to the solution. The reaction mixture was stirred at room temperature for a further 16h. Then H2O (1mL) and CH2Cl2 (1mL) were added and the phases separated; the organic layer was washed with water (2×5mL) and brine (5mL), dried and concentrated under reduced pressure to give the crude product. The ratio of sulfide-sulfoxide-sulfone in the crude product was determined by 1H NMR. The product was purified by column chromatography on silica gel (6:4 hexane/ethyl acetate). Schiff base ligand can be recovered after chromatography and can be re-used. |
29 % ee | With μ-oxido-bis({S-(+)-2-[(1-oxido-3-methylpentyl)iminomethyl]-6-methoxyphenolato-κ3N,O,O'}oxidovanadium(V)); dihydrogen peroxide In lithium hydroxide monohydrate at 20℃; for 0.5h; Overall yield = 76 %; enantioselective reaction; | 2.3.1 Sulfoxidation General procedure: In typical procedure, to a solution of catalyst (0.010mmol) in 3ml of CH2Cl2/MeOH solution (7:3, v/v), sulfide (1.00mmol) was added at room temperature or -20°C, together with 1,3,5-trimethoxybenzene as internal standard. Aqueous 30% H2O2 was added (1.10mmol) by small portions and the resulting mixture was stirred. After the appropriate reaction time, the solution was quenched with 2ml of sodium sulfite solution (0.1M) and extracted with CH2Cl2 (3×5ml). The combined organic layers were evaporated to dryness. The solid product dissolved in CDCl3 was analysed (yield and ee value) by 1H NMR spectra in the presence of chiral shift reagent Eu(hfc)3 (where Hhfc is 3-(heptafluoropropylhydroxymethylene)-(+)-camphoric acid) [28]. |
51 % ee | With μ-oxido-bis({1S,2R(+)-2-[(1-oxido-1,2-diphenylethyl)iminomethyl]naphtholato-κ3N,O,O'}oxidovanadium(V)); dihydrogen peroxide In methanol; dichloromethane at 20℃; for 0.5h; Overall yield = 84 %; | 2.3.1.Sulfoxidation General procedure: In typical procedure, to a solution of catalyst (0.010 mmol)in 3 ml of CH2Cl2/MeOH solution (7:3, v/v), sulfide (1.00 mmol)was added at room temperature or -20C, together with 1,3,5-trimethoxybenzene as internal standard. Aqueous 30% H2O2wasadded (1.10 mmol) by small portions and the resulting mixturewas stirred. After the appropriate reaction time, the solutionwas quenched with 2 ml of sodium sulphite solution (0.1 M)and extracted with CH2Cl2(3 × 5 ml). The combined organic lay-ers were evaporated to dryness. The solid product dissolved inCDCl3was analyzed (yield and ee value) by1H NMR spectra inthe presence of chiral shift reagent Eu(hfc)3(where Hhfc is 3-(heptafluoropropylhydroxymethylene)-(+)-camphoric acid) [30]. |
5 % ee | With C21H19N2O4V; dihydrogen peroxide for 48h; Overall yield = 82 %; enantioselective reaction; | |
12 % ee | With dihydrogen peroxide at 20℃; for 0.166667h; Overall yield = 97 %; | General procedure for the oxidation of sulfides to sulfoxides The sulfide (1 mmol) was added to a mixture of 30% H2O2(1 g,2.4 equiv) and VO(pseudoephedrine)MNPs (40 mg, 1.4 mol%), andthen the mixture was stirred at room temperature for the time spec-ified. The progress was monitored by TLC (EtOAc/n-hexane, 1/2).After completion of the reaction, the catalyst was separated fromthe product by an external magnet (within 5 s), washed with Et2O(2 × 5 mL) and decanted. The combined organics were washed withbrine (5 mL) and dried over anhydrous Na2SO4.The evaporation of Et2O under reduced pressure gave the pure products in 80-97%yields and 9-15% ee. |
With (R,R)-[iron(III)chloride(C6H10(NCHC6H2(tBu)2O)2)]; iodosylbenzene In methanol at 20℃; for 4h; Optical yield = 74 %ee; | ||
6 % ee | With 1,2,3-trimethoxybenzene; {S(+)-2-[(2-oxidopropyl)iminomethyl]-6-methoxyphenolato-κ3N,O,O'}dioxidomolybdenum(VI); dihydrogen peroxide In methanol; dichloromethane; lithium hydroxide monohydrate at 20℃; for 0.75h; Overall yield = 84 %; enantioselective reaction; | 2.2.1. Sulfoxidation General procedure: To a solution of catalyst (0.010 mmol) in 3 ml of CH2Cl2/MeOHmixture (7:3), thioanisole or benzyl phenyl sulfide (1.00 mmol)was added at 20 °C or room temperature, with 1,3,5-trimethoxybenzeneas an internal standard. Aqueous 30% H2O2 was added(1.10 mmol) in small portions and the resulting mixture was stirred.After the appropriate reaction time, the solution was quenchedwith 3 ml of sodium sulfite solution (0.1 M) and extracted withethyl acetate (3 3 ml). The combined organic layers were evaporatedto dryness. The solid product, dissolved in CDCl3, was analyzed(yield and ee value) by 1H NMR spectra in the presence ofthe chiral shift reagent Eu(hfc)3 [21]. |
With human telomeric 5'-(G<SUB>3</SUB>T<SUB>2</SUB>A)<SUB>3</SUB>G<SUB>3</SUB>-3'; Cu(4,4'-bimethyl-2,2'-bipyridine); potassium chloride; dihydrogen peroxide In aq. buffer at 15℃; for 5h; Optical yield = 32 %ee; enantioselective reaction; | ||
61 % ee | With dihydrogen peroxide; glacial acetic acid In methanol; lithium hydroxide monohydrate at 0℃; for 12h; Overall yield = 77 %; enantioselective reaction; | 2.3. Catalytic oxidation of sulfides to sulfoxides General procedure: The appropriate catalyst 5 (10 mol%) and sulfide (1.0 mmol) were dissolved in CH3OH/H2O (1:1) (5 mL) and this solution was cooled to 0 °C. Subsequently the additive HOAc (2.0 mmol) and the oxidant hydrogen peroxide (1.5 mmol, 30%, w/w) were added. The mixture was stirred for 12 h and then was treated with 10 mL of saturated ammonium chloridesolution and extracted with ethyl acetate. The organic layer was dried (MgSO4), filtered and concentrated to give pure sulfoxides through flash column chromatography on silica gel (hexane/ethyl acetate(10:1)). All the products in the paper are known compounds that exhibited spectroscopic data identical to those reported in the literature [34]. The ee was determined by HPLC on chiral column (Daicel,Chiralpak, OD-H). The configuration of sulfoxides product from these reactions was proven to be (S) by comparing the specific rotation with the literature values [35]. |
With tert.-butylhydroperoxide; C78H60NO10V In dichloromethane at 0℃; for 1.5h; Overall yield = 78 %Chromat.; Optical yield = 19 %ee; enantioselective reaction; | ||
78 % ee | Stage #1: Benzyl phenyl sulfide With titanium isopropoxide; lithium hydroxide monohydrate; (R)-6,6'-dibromo-[1,1'-binaphthyl]-2,2'-diol In toluene at 25℃; for 1h; Stage #2: With tert.-butylhydroperoxide In lithium hydroxide monohydrate; toluene at 0 - 30℃; for 14h; Overall yield = 76 percent; Overall yield = 1.63 g; enantioselective reaction; | General Procedure for the Catalytic Oxidation of Sulfides (1a-1f) General procedure: To a solution of (R)-6,6'-dibromo-BINOL(0.72g, 1.62 mmol) in toluene (20 mL) were added Ti(OiPr)4(0.22 mL, 0.81 mmol), water (0.14 mL, 8 mmol) and stirred for 30 min at room temperature. To the resulting homogeneous solution was added methyl phenyl sulfide (2.0 g, 16.0 mmol), and the mixture was stirred at room temperature for 60 min. The solution was then cooled to 0-5°C, 70% aqueous TBHP solution (4.4 mL, 32 mmol) was added slowly and stirred at 0-5°C for 5 h. Increased the temperature to 25-30°C and stirred for 9 h. The reaction mixture was concentrated under reduced pressure to obtain the crude product. This was further purified by column chromatography (ethyl acetate, cyclohexane 1:1) to get 1.80 g, (80% yield), of (R)-methyl phenyl sulfoxide (1a).[α]20D = +136 (c=1.7 in acetone); lit: [α]D = +130 (c = 1.7 in acetone) for (R), 89% ee;1 1b to 1f were prepared in the same manner. |
57 % ee | Stage #1: Benzyl phenyl sulfide With (S)-2-(N-3',5'-dichlorosalicylidene)-amino-3,3-dimethyl-1-butanol; copper(II) acetylacetonate In methanol; hexane at 20℃; for 0.0833333h; Stage #2: With dihydrogen peroxide In methanol; hexane at 20℃; for 16h; Overall yield = 75 percent; Overall yield = 162 mg; | |
With hydroxy(phenyl)-λ3-iodanyl ((1S,4R)-7,7-dimethyl-2-oxobicyclo[2.2.1]heptan-1-yl)methanesulfonate In propan-2-one at -78℃; Overall yield = 89 percent; Optical yield = 1 percent ee; | ||
85 % ee | With (R)-DTP-COF-QA; air In lithium hydroxide monohydrate at 15℃; for 16h; Irradiation; Overall yield = 81 percent; enantioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With triethylamine tris(hydrogen fluoride) In acetonitrile at 20℃; electrolysis at 1.6 V anodic potential (platinum anode and cathode); | |
91% | In acetonitrile at 20℃; electrolysis: platinum anode and cathode, Et3N*3HF as a supporting electrolyte, anodic potential 1.6 V, charge passed 2.2 F/mol; | |
With oxygen; N-methylquinolinium tetrafluoroborate salt In acetonitrile Photolysis; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With hydrogenchloride; iodosylbenzene for 0.0833333h; | |
96% | With hydrogenchloride; iodosylbenzene for 0.0833333h; | |
90% | With 1,3-dichloro-5,5-dimethylhydantoin; acetic acid In dichloromethane; water at 0 - 5℃; Inert atmosphere; |
62% | With N-chloro-succinimide In dichloromethane; benzyl alcohol for 18h; Ambient temperature; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With 4-cyclohexen-1-ylmorpholine; phosphorus pentachloride In dichloromethane at 0℃; for 1h; | |
99% | With magnesium; mercury dichloride In methanol at -43℃; for 5h; | |
99% | With 2,4-diphenyl-1,3-diselenadiphosphetane-2,4-diselenide In toluene for 20h; Heating; |
98% | With boron trifluoride diethyl etherate; sodium iodide In acetonitrile for 0.666667h; | |
98% | With N,N-dimethylthioformamide; sulfuric acid In acetone at 30℃; for 3h; | |
98% | With 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine; potassium iodide for 0.0166667h; Neat (no solvent); chemoselective reaction; | |
98% | With silica bromide In dichloromethane at 20℃; for 0.0833333h; Inert atmosphere; | Deoxygenation of diphenyl sulfoxide to diphenylsulfide 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, 99%). |
97% | With tris(2-carboxyethyl)phosphine; iodine In 1,4-dioxane for 1h; Heating; | |
97% | With bromine; triphenylphosphine; copper(I) bromide In acetonitrile for 30h; Heating; | |
97% | With trifluoromethylsulfonic anhydride; potassium iodide In acetonitrile at 20℃; for 0.05h; | |
97% | With 1,3,5-trichloro-2,4,6-triazine; potassium iodide In acetonitrile at 20℃; for 0.166667h; chemoselective reaction; | General procedure for the preparation of sulfides General procedure: To a flask containing a stirred mixture of sulfoxide (1 mmol) in acetonitrile (5 mL), TCT (1 mmol, 0.184 g) and KI (2.5 mmol, 0.42 g) were added. The mixture was stirred at room temperature and monitored by TLC. On completion of the reaction, H2O (10 mL) was added to the reaction mixture which was then extracted with EtOAc (4 × 5 mL) and the combined extracts were dried (MgSO4). The filtrate was evaporated and the corresponding sulfide was obtained as the sole product (Table 2). |
96% | With molybdenum(V) chloride; sodium iodide In acetonitrile at 20℃; for 0.166667h; | |
96% | With indium; pivaloyl chloride In isopropyl alcohol at 20℃; for 2h; | |
95% | With thexylchloroborane*methyl sulfide In dichloromethane at 0℃; for 0.166667h; | |
95% | With titanium tetrachloride; sodium iodide In acetonitrile for 0.0833333h; Ambient temperature; | |
95% | With tungsten(VI) chloride; sodium iodide In acetonitrile for 0.333333h; Ambient temperature; | |
95% | With ziconium(IV) oxychloride octahydrate; sodium iodide In water at 90℃; for 5h; chemoselective reaction; | |
94% | With titanium(IV) iodide In acetonitrile at 0℃; for 0.166667h; | |
94% | With Silphos; iodine In acetonitrile for 0.25h; Heating; | |
94% | With ReOBr<SUB>2</SUB>(hmpbta)(PPh<SUB>3</SUB>); phenylsilane In tetrahydrofuran for 0.25h; Reflux; chemoselective reaction; | |
94% | With N,N,N’,N’-tetrabromobenzene-1,3-disulfonamide; triphenylphosphine In dichloromethane at 20℃; for 0.0166667h; | 2.1 General procedure for synthesis of pyrimidine General procedure: To a mixture of TBBDA (0.4 mmol) and PPh3 (2.5 mmol)in CH2Cl2 (5 mL), sulfoxide (1 mmol) was added at roomtemperature. The progress of the reaction was monitoredby TLC. After completion of the reaction (Table 2), thesolvent was evaporated. The crude product was purified byshort column chromatography (packed with silica gel,using n-hexane/ethyl acetate (8:2) as the eluent) toachieve the desired sulfide with good to excellent yields |
94% | With hafnium tetrachloride; zinc In acetonitrile at 20℃; for 3.5h; | 4.2. General procedure 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, 95%). All of the products were identified by comparison of their spectroscopic data with authentic samples.[34] |
94% | With ReOBr<SUB>2</SUB>(2-(2-hydroxy-5-methylphenyl)benzotriazole-(H))(PPh<SUB>3</SUB>); 4,4,5,5-tetramethyl-[1,3,2]-dioxaboralane In tetrahydrofuran for 0.5h; Reflux; | |
94% | With tantalum pentachloride; sodium iodide In acetonitrile at 20℃; for 0.05h; chemoselective reaction; | 4.2. General procedure 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 10% 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, 95%). |
93% | With boron trifluoride diethyl etherate; sodium iodide In acetone for 0.25h; | |
93% | With indium; titanium tetrachloride In tetrahydrofuran at 20℃; for 0.166667h; | |
93% | With sodium tetrahydroborate; iodine In tetrahydrofuran at 20℃; for 0.2h; | |
93% | With chloro-trimethyl-silane; 3-mercaptopropionic acid In acetonitrile at 20℃; for 0.5h; | |
93% | With indium; niobium pentachloride In tetrahydrofuran at 20℃; for 3.5h; | |
93% | With sodium iodide at 20℃; for 1.5h; Green chemistry; | 4.1. General procedure General procedure: To a solution of a sulfoxide (1 mmol) in PEG-200 (1 ml), silica sulfuric acid (374 mg, equal to 2.2 mmol H+) and NaI (2.2 mmol) were added. The mixture was stirred magnetically at room temperature and the progress of the reaction was monitored by TLC or GC until the starting sulfoxide was completely consumed. The reaction mixture was then neutralized using NaOH solution (0.5 M, 1 ml), and subsequently the enough well-powdered Na2S2O3 · 5H2O was added to mixture with stirring to react with iodine. The mixture was then extracted with EtOAc (5 × 1 ml). The organic layers were decanted, combined, dried over Na2SO4, filtered and concentrated. The crude product was further purified by silica gel chromatography using n-hexane as eluent to provide the desired product in excellent yields. |
93% | With MoO<SUB>2</SUB>Cl<SUB>2</SUB>(dmf)<SUB>2</SUB> In toluene at 140℃; for 0.166667h; Microwave irradiation; | |
92% | With N-Bromosuccinimide; 3-mercaptopropionic acid In acetonitrile at 20℃; for 1.66667h; | |
92% | With [ReOCl3(PPh3)2] In chloroform for 17h; Reflux; | 4.2. General procedure for the reduction of sulfoxides catalyzed by ReOCl3(PPh3)2 General procedure: To a solution of ReOCl3(PPh3)2 (10.0 mol %) in CHCl3 (3 mL) was added the sulfoxide (1.0 mmol). The reaction mixture was heated at reflux temperature under air atmosphere (the reaction times are indicated in the Table 1, Table 2 and Table 3) and the progress of the reaction was monitored by TLC or 1H NMR. Upon completion, the reaction mixture was evaporated and purified by silica gel column chromatography with n-hexane to afford sulfides and sulfones, which are all known compounds. |
92% | With bis(N,N-dimethylformamide)dichloridodioxidomolybdenum(VI); glycerol In toluene at 230℃; for 0.0833333h; Microwave irradiation; Green chemistry; chemoselective reaction; | |
92% | With indium; tantalum pentachloride In acetonitrile at 20℃; for 2h; Sonication; chemoselective reaction; | General procedure for the deoxygenation of sulfoxides 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, 92%). All of the productswere identified by comparisonof their spectroscopic data with authentic samples. |
91% | With 1,3 dithiane; N-Bromosuccinimide In chloroform at 20℃; for 0.333333h; | |
91% | With gallium; bis(cyclopentadienyl)titanium dichloride In tetrahydrofuran at 20℃; for 0.5h; chemoselective reaction; | |
91% | With 2,3-dimethyl-2,3-butane diol; [MoO2Cl2(dmf)2] at 90℃; for 4h; Neat (no solvent); | |
90% | With triphenyl phosphite In acetonitrile for 2h; Heating; | |
90% | With iodine; tiolacetic acid In acetonitrile at 20℃; for 2.33333h; | |
90% | With hydrogen In 1,4-dioxane at 80℃; for 12h; chemoselective reaction; | |
90% | With sodium iodide In ethanol at 20℃; for 1.33333h; Green chemistry; | General Experimental Procedure for the Deoxygenation of Sulfoxides General procedure: A mixture of diphenyl sulfide (1 mmol), NaI (2.5 mmol), and CSA (0.45 g equalto 2.2 mmol H+) and ethanol (5 mL) was stirred at r.t. for 210 min. The progress of the reaction was monitored by TLC. When the starting sulfoxide had completely disappeared,the mixture was neutralized by adding NaOH solution. The product was extracted withEtOAc (3× 5 mL). The combined extracts were washed with 10% aq Na2S2O3. Theorganic layer dried over MgSO4. The filtrate was evaporated, and then residue was purifiedby column chromatography on silica gel. |
90% | With iodine; sodium hydrogensulfite In chloroform at 20℃; for 4h; | General procedure: General procedure: A mixture of a sulfoxide (1 mmol), NaHSO3 (1.1 mmol), and I2 (0.025-0.1 mmol) in CHCl3 (1 mL) was stirred at room temperature or at 50 °C. The progress of the reaction was monitored by TLC. After completion, the solution was decanted from the residue, washed with EtOAc (2 x 1 mL). The combined organic layers were concentrated and the residue purified by chromatography on silica gel using n-hexane as eluent. |
89% | With niobium pentachloride; sodium iodide In acetonitrile at 20℃; for 0.0833333h; | |
89% | With hydrogen; triethyl phosphite In isopropyl alcohol at 100℃; for 12h; Glovebox; chemoselective reaction; | |
87% | With indium; molybdenum(V) chloride In tetrahydrofuran at 20℃; for 0.0833333h; | |
87% | With indium; tungsten(VI) chloride In tetrahydrofuran at 20℃; for 0.0833333h; | |
85% | With bis(cyclopentadienyl)titanium dichloride; indium In tetrahydrofuran at 20℃; for 0.166667h; | |
84% | With aluminium; nickel dichloride In tetrahydrofuran at 20℃; for 0.75h; | |
81% | With Tebbe reagent In tetrahydrofuran at -40 - 0℃; for 3h; | |
80% | With samarium; titanium tetrachloride In tetrahydrofuran for 0.5h; Ambient temperature; | |
80% | With hydrogenchloride; N-Bromosuccinimide In 1,4-dioxane at 120℃; for 10h; Schlenk technique; Sealed tube; | 2 General procedure for synthesis of compounds 2 General procedure: Under an air atmosphere,a 10 mL of Schlenk tube equipped with a stir bar was charged with sulfoxide(0.2 mmol), NBS (0.2 equiv), HCl (2.0 equiv, 12 M) and 1,4-dioxane(2.0 mL). The tube was sealed with a Teflon lined cap. The reaction mixturewas stirred at 120 °C for 10 h in oil bath. After the completion ofthe reaction, saturated NaOH (2 mL) was added to the mixture, and extractedwith ethyl acetate (4 mL × 3). The combined organic extracts were dried over anhydrous Na2SO4. Subsequently, the solvent was filtered and evaporated under reduced pressure, and theresidue was purified by flash column chromatography on silica gel withpetroleum as the eluent to give the desired products. |
75% | With iodine; magnesium In methanol at 20℃; for 2h; | |
72% | With sodium tetrahydroborate; nickel dichloride In tetrahydrofuran at 0 - 5℃; for 1.5h; | |
72% | With tris(pentafluorophenyl)borate; phenylsilane In toluene at 60℃; for 8h; Inert atmosphere; Schlenk technique; Green chemistry; | |
70% | at 140℃; similar reaction with NaBr and TsOH as catalyst; | |
69% | With aluminum oxide; sodium hypophosphite; iron(II) sulfate for 0.0777778h; microwave irradiation; | |
45% | With silica-gel-supported sulfuric acid; 1-benzyl-1-aza-4-azoniabicyclo<2.2.2>octane bromide at 20℃; for 0.166667h; Grounding; | |
With iodine; sodium iodide; triethyl phosphite 1.) acetonitrile, -10 deg C, 5 h, 2.) room temperature; reflux, 1 h; Yield given. Multistep reaction; | ||
94 %Chromat. | With hydrogen In toluene at 140℃; for 12h; Autoclave; Molecular sieve; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
77% | With triethylsilane In dichloromethane Ambient temperature; | |
77% | With triethylsilane In dichloromethane Ambient temperature; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 75% 2: 8% | With diphenyldisulfane In benzene Irradiation (UV/VIS); nitrogen atmosphere; mercurial and PhSSPh (2.5 equiv) in deoxygenated solvent irradiated (250-W sunlamp, 40 °C, 6h);; filtration; solvent removed (vacuum); PhCH2CH2Ph and PhCH2SPh analysed by (1)H NMR, GLC and GCMS;; | |
1: 8 % Spectr. 2: 72 % Spectr. | With diphenyldisulfane In benzene at 45℃; for 6h; Irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With sodium hydroxide; tetra-(n-butyl)ammonium iodide In water; benzene for 24h; | |
98% | With aluminum oxide; potassium carbonate for 0.0833333h; microwave irradiation; | |
97.5% | With sodium hydroxide at 100℃; for 6h; |
96% | With N-benzyl-trimethylammonium hydroxide at 20℃; Neat (no solvent); | |
96% | at 100℃; for 16h; Neat (no solvent); | |
95% | With potassium carbonate In N,N-dimethyl-formamide at 110℃; for 5h; | |
94% | With n-butyllithium In tetrahydrofuran; hexane for 0.333333h; Ambient temperature; | |
92% | In hexane for 12h; Heating; | |
92% | With 1-pentyl-3-methylimidazolium bromide at 25 - 30℃; for 0.333333h; | |
91% | Stage #1: thiophenol In acetonitrile for 0.333333h; Heating; Stage #2: benzyl bromide In acetonitrile for 1.5h; Heating; | |
85% | With cesium fluoride In acetonitrile at 82℃; | |
85% | With silica gel In water at 20℃; for 2h; | |
81% | With ethanol; sodium at 20℃; for 16h; | Procedure for the synthesis of arylalkyl sulfides 9d-h General procedure: Thiophenol derivative (1.0 mmol) was addedto freshly prepared sodium ethoxide solution by dissolving sodium metal (34 mg, 1.5 equiv) in ethanol(5.0 mL). The resulted mixture was stirred for 15 min at room temperature and then alkyl halide (2.0equiv) was added at the same temperature. The reaction mixture was allowed to stir at roomtemperature for 16 h. The progress of reaction was monitored using TLC. After completion of reaction,water (10 mL) was added to reaction mixture and then extracted with dichloromethane (3 X 10 mL). Thecombined organic layer was washed with 2M NaOH solution followed by brine solution (10 mL). Theorganic layer was dried over anhydrous sodium sulphate evaporated under vacuum. The crude productswere purified by column chromatography on silica gel using EtOAc-hexane (1:4) as eluent and isolatedproducts were characterized as sulfides 9d-h spectroscopic analysis. |
53% | With potassium carbonate In N,N-dimethyl-formamide at 20℃; for 4h; | |
With potassium hydroxide In ethanol for 5h; Ambient temperature; | ||
With potassium carbonate In acetone | ||
With pyridine In dichloromethane | ||
With potassium carbonate In N,N-dimethyl-formamide at 20℃; for 4h; Inert atmosphere; | ||
Stage #1: thiophenol With sodium hydride In tetrahydrofuran at 0℃; for 0.0833333h; Stage #2: benzyl bromide In tetrahydrofuran at 0℃; for 4h; | ||
With potassium carbonate In N,N-dimethyl-formamide at 20℃; for 4h; | A Step A: Benzyl bromide (10.Ommol), thiophenol was added to a 50 mL flask under a room temperature air atmosphere.(10.Ommol) and K2C03 (1 · 52g, 1 .Ommol) in DMF (10.OmL), the mixture is maintained at this temperature Continue stirring reaction for 4h. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With borohydride exchange resin In methanol for 3h; Ambient temperature; | |
96% | With hydrogenchloride; zinc In water at 20℃; for 0.166667h; Ionic liquid; Inert atmosphere; | General procedure for the synthesis of diorganyl selenides and sulfides: commercially available Zn dust (33 mg, 0.5 mmol) and PhSeSePh/PhSSPh (0.5 mmol) and 15 μL of HCl 1N were added to BMIM-BF4 (0.5 mL) at room temperature under nitrogen. The mixture was allowed to stir for 2-3 min. Then corresponding organic halides (1 mmol) was slowly added. The reaction mixture was allowed to stir until the color change (monitored by TLC and assisted by visual observation). The mixture was then extracted with ether (3×15 mL), and the combined ether extract was washed with brine, dried (MgSO4), and evaporated to leave the crude product. Purification by column chromatography over silica gel (hexane/ethyl acetate 98:2) furnished the corresponding products. |
94% | With sodium hydroxide; Aminoiminomethanesulfinic acid In tetrahydrofuran; water for 4.5h; Heating; |
90% | Stage #1: diphenyldisulfane With aluminium trichloride; zinc In water; N,N-dimethyl-formamide at 65℃; Stage #2: benzyl bromide In water; N,N-dimethyl-formamide at 65℃; for 13h; | |
90% | With aluminium trichloride; zinc In water; N,N-dimethyl-formamide at 65℃; for 13h; | |
90% | With samarium In methanol at 20℃; for 0.5h; | |
90% | Stage #1: diphenyldisulfane With indium In 1,2-dichloro-ethane for 0.166667h; Sonication; Stage #2: In 1,2-dichloro-ethane Reflux; Stage #3: benzyl bromide In 1,2-dichloro-ethane at 25℃; for 0.05h; | |
86% | Stage #1: diphenyldisulfane With zinc In N,N-dimethyl-formamide at 110℃; for 11h; Stage #2: benzyl bromide In N,N-dimethyl-formamide at 20℃; | |
86% | With indium In dichloromethane for 3h; Reflux; Inert atmosphere; | |
84% | With triphenylphosphine; 1-pentyl-3-methylimidazolium bromide at 75℃; for 1.5h; | Representative procedure for the synthesis of benzyl phenyl sulfide (Table 2, entry 2a). A mixture of benzyl bromide (171 mg, 1 mmol), diphenyl disulfide (131 mg, 0.6 mmol), PPh3 (184 mg, 0.7 mmol), and [pmIm]Br21 (94 mg, 0.4 mmol) was stirred at 75 °C for 1.5 h (TLC). The reaction mixture was extracted with Et2O, and the organic layer was washed with brine (2 × 5 mL) and dried (Na2SO4). Evaporation of solvent left the crude product which was purified by column chromatography over silica gel (hexane) to afford the pure product, benzyl phenyl sulfide (168 mg, 84%) as a colorless liquid; IR (neat) 3058, 3028, 2923, 1581, 1495, 1479, 1452, 1438, 1238, 1090, 1068, 1024 cm-1; 1H NMR (300 MHz, CDCl3) δ 4.21 (s, 2H), 7.32-7.41 (m, 10H); 13C NMR (75 MHz, CDCl3) δ 39.5, 127.6, 128.0, 129.0 (2C), 129.3 (2C), 129.5 (2C), 130.3 (2C), 136.9, 137.9. The spectroscopic (FT-IR, 1H NMR and 13C NMR) data are in good agreement with the reported values.9b The remaining ionic liquid was washed with ether, dried under vacuum, and reused five times without appreciable loss of catalytic activity. |
80% | With indium iodide In dichloromethane at 20℃; for 2.5h; | |
75% | With bismuth(III) chloride; samarium In water; N,N-dimethyl-formamide at 60℃; for 5h; | |
70% | With indium In tetrahydrofuran; water at 25℃; for 24h; | |
With bis(triphenylstannyl)tellurium; cesium fluoride 1) CH3CN, r.t., 5 h; Yield given. Multistep reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With nanolayered cobalt-molybdenum sulphide with Co/(Mo+Co) mole ratio 0.83 In Hexadecane; toluene at 180℃; for 10h; Inert atmosphere; Autoclave; chemoselective reaction; | |
95% | With bis(2,2,2-trifluoroethoxy)triphenylphosphorane | |
92% | Stage #1: benzyl alcohol With t-butyl bromide; 1-pentyl-3-methylimidazolium bromide at 60℃; for 1.5h; Stage #2: thiophenol With 1-pentyl-3-methylimidazolium bromide at 60℃; for 0.333333h; |
92% | With 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine at 50℃; for 0.0333333h; Neat (no solvent); | |
90% | With zinc(II) iodide In 1,2-dichloro-ethane for 1.5h; Heating; | |
90% | With silica gel; zirconium(IV) chloride at 50℃; for 0.25h; | |
82% | In dodecane at 180℃; for 24h; Inert atmosphere; | |
43% | With 2-butyl-1,3-diphenyl-1,3,2-diazaphospholidine; 1,1'-azodicarbonyl-dipiperidine In 1,2-dichloro-ethane at 40℃; for 36h; | |
32% | With zirconocene bis(triflate) tetrahydrofuran complex at 100℃; for 24h; | |
0.35 g | Stage #1: benzyl alcohol With iodine; 1-butyl-3-methylimidazolium Tetrafluoroborate at 20℃; for 0.5h; Stage #2: thiophenol at 20℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | Stage #1: bromobenzene With 1,2,3-Benzotriazole; copper(l) iodide In dimethyl sulfoxide for 0.166667h; Stage #2: phenylmethanethiol With potassium <i>tert</i>-butylate In dimethyl sulfoxide at 80℃; Further stages.; | |
97% | Stage #1: phenylmethanethiol With potassium carbonate In xylene at 0 - 20℃; Stage #2: bromobenzene With tris(dibenzylideneacetone)dipalladium (0); 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene In xylene at 140℃; for 0.4h; | |
92% | With N-ethyl-N,N-diisopropylamine; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene In 1,4-dioxane for 8h; Heating; |
92% | With N-ethyl-N,N-diisopropylamine In 1,4-dioxane for 8h; Heating / reflux; | |
92% | With potassium hydroxide In dimethyl sulfoxide at 80℃; for 4h; | 2.6. General procedure for the S-arylation coupling reaction Thiol General procedure: Thiol (1.2 mmol), aryl halide (1 mmol), KOH (1.5 mmol) and the supported palladium catalyst (Fe3O4SiO2C22-Pd(II), 0.5 mol%)in DMSO (2 mL) were stirred at 80 °C for an appropriate time. The progress of the reaction was monitored by TLC, using n-hexane as eluent. After the completion and magnetic separation of the catalyst, the reaction mixture was treated with ethyl acetate (10 mL) and water (3 mL). The organic layer was separated and the aqueous layer was extracted with ethyl acetate (3 × 5 mL). The combined organic solution was washed with brine (3 × 5 mL). Drying(Na2SO4) and evaporation of the solvent provided a residue which was purified on preparative TLC (silica gel), using hexane. All of the products have been previously reported, and their identities have been confirmed by comparing their1H and13C NMR spectral data with the values of the authentic samples. |
89% | With (SIPr)Pd(Py)Cl2; potassium <i>tert</i>-butylate In toluene at 100℃; for 16h; Inert atmosphere; | |
84% | With potassium carbonate In water; N,N-dimethyl-formamide at 90℃; for 20h; | 1.3.General procedure for the S-arylation coupling reaction General procedure: Aryl halide (1.0 mmol), thiol (1.2 mmol), K2CO3 (2.0 mmol) and catalyst (0.4 mol% Cu) in DMF/H2O (v/v = 2:1, 1.5 mL) were stirred at 90 C for the appropriate time. The progress of the reaction was monitored by TLC using n-hexane-EtOAc (30:1) as eluent. After completion of the reaction, EtOAc (5 mL) was added to the mixture and filtered. The organic phase was separated and the aqueous layer was extracted with ethyl acetate (3 × 5 mL). The organic layer drying (MgSO4) and evaporation of the solvent provided a residue which was purified on preparative TLC (silica gel). All the products have been previously reported, and their identities were confirmed by comparison of their 1H and 13C NMR spectral data with the values of authentic samples. |
83% | With copper(l) iodide; 1-Hydroxymethyl-1H-benzotriazole; potassium <i>tert</i>-butylate In dimethyl sulfoxide at 80℃; | Synthesis of Compound 3 and 4 General procedure: To a solution of 1.0 mmol of aryl halide 1 in 2.0 mL of DMSO, was added 1.2 equiv. benzenethiol 2, 1.4 equiv. of KO t-Bu followed by the addition of CuI (0.5 mol %) and L2 (1.0 mol %). The reaction mixture was allowed to stir at 80° to 100°C for 4-6 h. The disappearance of the starting material was determinedby TLC. The reaction mixture was then washed with brine solution and was extracted with ethyl acetate (2 x 10 mL). The combined organic fractions were dried over anhydrous Na2SO4 and concentrated under vacuum to yield the crude product. The crude product was purified by column chromatography on neutralalumina/silica gel using hexane/ethyl acetate as the eluent. |
82% | With 1,3-bis(2,6-diisopropylphenyl)imidazolium chloride; potassium <i>tert</i>-butylate; nickel diacetate In N,N-dimethyl-formamide at 110℃; for 6h; Glovebox; Inert atmosphere; | General procedure for the coupling reaction of aryl halides with phenyl sulfide ; Benzyl phenyl sulfide General procedure: In a typical run, a 5 mL vial equipped with a magnetic bar was charged with a mixture of aryl halide (1 mmol), thiol (1 mmol), Ni(OAc)2 (0.1 mmol), NHC (0.05 mmol) and KOtBu (1.5 mmol) in glove box, 2 mL of DMF was injected, the mixture was stirred at 70 °C for 12 h. After cooling to room temperature, brine was added to the reaction mixture, and the aqueous phase was extracted with dichloromethane for three times. The combined organic layers were dried with Mg2SO4 and the solvent was removed under reduced pressure. The residue was purified by column chromatography on silica gel to afford the desired products. |
81% | Stage #1: phenylmethanethiol With sodium methylate In methanol at -10℃; for 0.166667h; Stage #2: bromobenzene In methanol at 20℃; | |
78% | With 1,3-bis(2,6-diisopropylphenyl)imidazolium chloride; potassium <i>tert</i>-butylate; nickel diacetate In N,N-dimethyl-formamide at 110℃; for 6h; Glovebox; Inert atmosphere; | General procedure for the coupling reaction of aryl halides with phenyl sulfide ; Benzyl phenyl sulfide General procedure: In a typical run, a 5 mL vial equipped with a magnetic bar was charged with a mixture of aryl halide (1 mmol), thiol (1 mmol), Ni(OAc)2 (0.1 mmol), NHC (0.05 mmol) and KOtBu (1.5 mmol) in glove box, 2 mL of DMF was injected, the mixture was stirred at 70 °C for 12 h. After cooling to room temperature, brine was added to the reaction mixture, and the aqueous phase was extracted with dichloromethane for three times. The combined organic layers were dried with Mg2SO4 and the solvent was removed under reduced pressure. The residue was purified by column chromatography on silica gel to afford the desired products. |
70% | With cesium hydroxide In dimethyl sulfoxide at 120℃; for 0.0833333h; | |
60% | With C24H22N6Ni; sodium t-butanolate In N,N-dimethyl-formamide; acetonitrile at 50℃; Inert atmosphere; Schlenk technique; | |
32% | With potassium hydroxide; tetrabutylammomium bromide In water at 80℃; for 19h; | |
89 % Chromat. | With potassium hydroxide; trans-bromo(phenyl)bis(triphenylphosphine)palladium(II); cetyltributylphosphonium bromide; triphenylphosphine In toluene at 100℃; for 15h; | |
With i-Pr2NEt | 14 Production of benzyl phenyl sulfide: Example 14 Production of benzyl phenyl sulfide: Heating and refluxing time: 8 hours. Aryl halide and its amount used: Bromobenzene (211 μL, 2 mmol). Thiol compound and its amount used: Benzylmercaptan (235 μL, 2 mmol). Amount of Pd2(dba)3 used: 46 mg, 0.05 mmol. Amount of Xantphos used: 58 mg, 0.1 mmol. Base and its amount used: i-Pr2NEt (700 μl, 4 mmol). Amount of 1,4-dioxane used: 4.2 mL. Property, yield and yield percentage of benzyl phenyl sulfide: Yellow solid; yield 368 mg; yield percentage 92 %. Development solvent in flash column chromatography: Hexane/ethyl acetate = 15/1. Melting point: 40°C-41°C. 1H NMR (CDCl3, 500 MHz) δ ppm: 7.16-7.31 (m, 10H), 4.10 (s, 2H). 13C NMR (CDCl3, 500 MHz) δ ppm: 137.89, 136.80, 130.26, 129.25, 128.90, 127.59, 126.76, 39.48. | |
< 5 %Spectr. | With C25H29Cl2N2PPd; potassium <i>tert</i>-butylate In toluene at 20℃; for 8.16667h; Inert atmosphere; Reflux; | |
With triethylamine In tetrahydrofuran at 0 - 20℃; for 0.5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
(i) nBuLi, (ii) /BRN= 1238185/; Multistep reaction; | ||
3.5 g | Stage #1: Benzyl phenyl sulfide With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1h; Stage #2: benzophenone In tetrahydrofuran; hexane at -30℃; for 7h; | 3 Synthesis Example 3: Compound 3 Into a two-necked flask with a volume of 50 mE were introduced benzyl(phenyl)sulfane (2.0 g, 10.0 mmol) and THF (12.0 mE), and the mixture was cooled to -78° C. To this solution was added n-butyllithium (1.56 M hexane solution, 6.82 mE, 10.5 mmol) and the mixture was stirred for 1 hour. To the resulting solution was thrther added a solution of benzophenone (1.82 g, 10.0 mmol) in THF (18.0 mE) and the mixture was stirred for 7 hours. During the reaction, the reaction temperature gradually increased to-30° C. The resulting reaction solution was poured into ice water and extracted with diethyl ether three times. The resulting diethyl ether solution was washed with water. Further, magnesium sulfate was added to remove water in the solution. Then, the magnesium sulfate was removed by filtration. The filtrate was concentrated and subjected to silica gel column chromatography (hexane: ethyl acetate=20: 1) to separate an intermediate 2 (3.50 g) shown below. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | In acetonitrile at 25℃; for 48h; | |
82% | With copper(I) triflate In acetonitrile at 25℃; for 48h; | |
82% | With copper(I) triflate In acetonitrile at 25℃; |
65% | With iodine In dichloromethane at 20℃; for 24h; Inert atmosphere; | 4.2. General Procedure for Imination of Sulfides 1 with Imino-phenyl-l3-iodane 2 in the Presence of I2 General procedure: Imino-3-iodane 2 (0.12-0.24 mmol) was added at room temperature to a stirred mixture of sulfide1 (0.10-0.20 mmol) and I2 (0.002-0.004 mmol) in dichloromethane (1.0-2.0 mL). The reaction wasstirred at room temperature for 24 h. After the reaction, 5% aqueous Na2S2O3 (2.5-5.0 mL) was addedto the mixture and the solution was extracted with ethyl acetate. The organic layer was dried overanhydrous Na2SO4 and concentrated under reduced pressure. The residue was separated by columnchromatography using the Hexane-EtOAc (1:1 to 0:100) to afford the pure product 3. |
99 %Spectr. | With C45H55BCuN6PS3 In acetonitrile at 20℃; for 0.5h; Inert atmosphere; | |
88 %Spectr. | With PPh4[CoIII(TAMLred)] In dichloromethane at 25℃; for 0.5h; Sealed tube; chemoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82.6% | With C64H64N4O6Ti2; dihydrogen peroxide In dichloromethane; water at -20℃; for 48h; optical yield given as %ee; enantioselective reaction; | |
1: 69.4% 2: 12.6% | With C68H72N4O6Ti2; dihydrogen peroxide In dichloromethane; water at 0℃; for 16h; optical yield given as %ee; enantioselective reaction; | |
22% | With (R,R)-[iron(III)chloride(C6H10(NCHC6H2(tBu)2O)2)]; iodosylbenzene In dichloromethane at 20℃; for 15h; optical yield given as %ee; enantioselective reaction; |
15% | With iodosylbenzene In dichloromethane at 20℃; for 5h; | |
1: 53 % ee 2: 11% | Stage #1: Benzyl phenyl sulfide With 2C2H7N*3Cd(2+)*3C14H8O4(2-)*19H2O*2H(1+)*C114H132N12O12Ti4(2-) In dichloromethane at 20℃; for 0.333333h; Stage #2: With dihydrogen peroxide In dichloromethane; water for 72h; | |
With titanium(IV) isopropylate; Cumene hydroperoxide; (+)-(2R,2'R,2''R)-triphenylethan-2-olamine In 1,2-dichloro-ethane at 0℃; Yield given. Yields of byproduct given; | ||
With titanium(IV) isopropylate; Cumene hydroperoxide; (+)-(2R,2'R,2''R)-triphenylethan-2-olamine In 1,2-dichloro-ethane at 0℃; Yield given. Yields of byproduct given. Title compound not separated from byproducts; | ||
With (S)-(-)-2-(N-3,5-diiodosalicylidene)amino-3,3-dimethyl-1-butanol; dihydrogen peroxide; 4-methoxybenzoic acid In dichloromethane at 20℃; for 16h; Title compound not separated from byproducts; | ||
With (S)-(-)-2-(N-3,5-diiodosalicylidene)amino-3,3-dimethyl-1-butanol; dihydrogen peroxide In dichloromethane at 20℃; for 0.5h; Title compound not separated from byproducts; | ||
With titanium(IV) isopropylate; tert.-butylhydroperoxide; (4S,5R)-4,5-dihydro-4,5-diphenyl-2-(2'-hydroxy-3'-tert-butylphenyl)-oxazoline In tetrachloromethane; dichloromethane at 0℃; for 24h; | ||
With Cumene hydroperoxide In 1,2-dichloro-ethane at 0℃; for 6h; Title compound not separated from byproducts; | ||
With Cumene hydroperoxide; (R,R,R)-titanatrane In 1,2-dichloro-ethane at 0℃; for 4h; Title compound not separated from byproducts; | ||
With (S)-C13H17I2NO2; vanadyl acetylacetonate; dihydrogen peroxide In dichloromethane; water at 20℃; for 16h; Title compound not separated from byproducts; | ||
With iodosylbenzene In acetonitrile at 0℃; for 2h; Title compound not separated from byproducts.; | ||
With iodosylmesitylene In acetonitrile at 20℃; for 2h; Title compound not separated from byproducts.; | ||
47.6 %Spectr. | With di-μ-oxo-titanium-(N,N-bis(salicylidene)-ethylenediamine(cyclohexane); dihydrogen peroxide In dichloromethane; water at 25℃; for 3h; optical yield given as %ee; enantioselective reaction; | |
19.0 %Spectr. | With C64H64N4O6Ti2; dihydrogen peroxide In dichloromethane; water at 25℃; for 2h; optical yield given as %ee; enantioselective reaction; | |
With Cumene hydroperoxide; C47H68F3NO6STi In toluene at -30℃; for 36h; Inert atmosphere; optical yield given as %ee; enantioselective reaction; | ||
With Cumene hydroperoxide; C49H75NO4Ti In dichloromethane at -78℃; for 24h; Inert atmosphere; optical yield given as %ee; enantioselective reaction; | ||
With bis(acetylacetonate)oxovanadium; 2-[(1S,2S,3R,5S)-3-hydroxymethyl-2,6,6-trimethylbicyclo[3.1.1]hept-2-ylimino]methyl}phenol; dihydrogen peroxide In dichloromethane; water at 20℃; for 3h; optical yield given as %ee; enantioselective reaction; | ||
With titanium(IV) isopropylate; tert.-butylhydroperoxide; 2-benzyl-1,3-diphenylpropane-1,3-diol In toluene at -20℃; for 36h; Molecular sieve; optical yield given as %ee; enantioselective reaction; | Typical experimental procedure for the synthesis of chiral sulfoxides General procedure: To a solution 1,3-diol (16 mg, 0.05 mmol) containing MS4Å (70 mg) was added Ti(O-iPr)4 (7.4 μL, 0.025 mmol) in toluene (1 mL). The mixture was stirred for 2 h at rt and then methyl(p-tolyl)sulfane (68 μL, 0.5 mmol) was added. The mixture was cooled to -20 °C and t-butylhydroperoxide (0.16 mL, 0.8 mmol)18 was added. After stirring for 36 h at the same temperature, the reaction was quenched with 10% aqueous solution of sodium sulfite. The aqueous layer was extracted with ethyl acetate (3 × 15 mL) and organic layer was dried (Na2SO4). The solvent was evaporated under reduced pressure to leave the crude product, which was separated by preparative TLC (3:2; hexane/ethyl acetate) to give 8g (46 mg, 60%). The product was characterised by spectroscopic analysis and the analyses were consistent with the literature. Enantiomeric excess was determined by chiral HPLC on a Chiralcel OD-H (250 × 4.6 mm) column eluting with a hexane/isopropanol (9:1) mixture (1 mL/min, λ = 250 nm). | |
7 % ee | With 1H-imidazole; C84H72ClMnN4O12S4(4-)*4Na(1+); dihydrogen peroxide In methanol; aq. phosphate buffer at 25℃; for 2h; Inert atmosphere; Overall yield = 57 %Chromat.; | 2.3. General procedure for asymmetric sulfoxidation General procedure: Methyl phenyl sulfoxide. Manganese porphyrin complex 1 (1.6 mg, 1 μmol) and imidazole (1.7 mg, 25 μmol) were placed in a test tube under argon. The solvent (375 μL MeOH + 125 μL PBS, pH 7) was then added via syringe, followed by the sulfide (5 μL, 42.3 μmol). Finally, hydrogen peroxide (1.8 μL, 21.2 μmol) was added in one portion to the solution. The reaction was followed by gas chromatography (GC). From GC we knew that the reaction was over after 2 h with a 100% yield containing 1% sulfone. The solution was extracted with dichloromethane three times and then dried over MgSO4. The ee was then determined by HPLC to be 33%. |
55 % ee | With C42H52N4O6Ti2; dihydrogen peroxide In dichloromethane; water at -10℃; for 16h; enantioselective reaction; | |
83 % ee | With C40H46Cl2N4O6Ti2; dihydrogen peroxide In dichloromethane; water at -10℃; for 40h; enantioselective reaction; | |
51 % ee | Stage #1: Benzyl phenyl sulfide With 2C2H7N*3Cd(2+)*3C14H8O4(2-)*19H2O*2H(1+)*C114H132N12O12Ti4(2-) In dichloromethane at 20℃; for 0.333333h; Stage #2: With dihydrogen peroxide In dichloromethane; water for 72h; | |
48 % ee | With 3Cd(2+)*HO(1-)*Br(1-)*2O(2-)*4Ti(4+)*4CH3O(1-)*3C3H7NO*H2O*4C34H42N3O4(3-); dihydrogen peroxide In acetone at 0 - 25℃; for 16.3333h; enantioselective reaction; | |
51 % ee | With dihydrogen peroxide In chloroform at 0℃; for 12h; enantioselective reaction; | |
With C29H44FeN2O5; dihydrogen peroxide; 4-methoxybenzoic acid In dichloromethane; water at 15℃; for 12h; Optical yield = 75 %ee; enantioselective reaction; | ||
79 % ee | Stage #1: Benzyl phenyl sulfide With titanium(IV) isopropylate; C51H54N2O4 In methanol; dichloromethane; water at 20℃; for 0.333333h; Inert atmosphere; Stage #2: With dihydrogen peroxide In methanol; dichloromethane; water at 0℃; for 1.5h; Inert atmosphere; enantioselective reaction; | |
1: 38% ee 2: 21 %Chromat. | With (S,S)-1-(1-carboxy-2-methylpropyl)-3-(1-carboxylate-2-methylpropyl)imidazolium; (x)H2O*MoO(4+)*2O2(2-); dihydrogen peroxide; tetraphenylphosphonium bromide In chloroform; water at 0℃; for 1h; | |
84 % ee | With dihydrogen peroxide; 6,6′-bis[(S)-4-isopropyloxazolin-2-y1]-2,2′-bipyridine; iron(II) chloride In tetrahydrofuran; water at -25℃; for 1h; enantioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 95% 2: 1 % Spectr. | With chloro-trimethyl-silane In acetonitrile at -15℃; for 10h; | |
1: 94% 2: 3% | With dihydrogen peroxide In methanol at 0℃; for 1h; | |
1: 90% 2: 5% | With Oxone In water at 25℃; for 4h; Green chemistry; |
1: 90% 2: 5% | With dihydrogen peroxide In ethanol; hexane; water at 80℃; for 1h; | 2.5.3. Oxidation of solid sulfur compounds to sulfones General procedure: A mixture of 0.03 g of the catalyst and 30% H2O2 (10 mmol)aq. was added to a solution of the sulfide (1 mmol) in a mixedsolvent of EtOH and hexane (1:1; 2 mL), and the resulting mixture was stirred at 80 °C. The reaction mixture was cooled toroom temperature and the catalyst was separated using anexternal magnetic field. The corresponding sulfones were extractedwith EtOH from the reaction mixture (Method c, Table2, entries 8-11). |
1: 90% 2: 10% | With dihydrogen peroxide; C14H11ClN3O4V In ethanol; water for 0.25h; Reflux; | 4.5. Catalysis experiments General procedure: In a typical experiment, to a 1 millimolar solution of diphenyl sulfide and VOL (0.004 mmol) or MoO2L (0.006 mmol) in EtOH (10 mL), 30% aqueous H2O2 (2 mmol) was mixed with the reacting stuff and refluxed along with vigorous stirring for a definite period of time and the results are given in Table 1. The monitoring of the catalytic cycle was ensured by TLC (eluent, n-hexane:ethyl acetate, 5:2) while the percentage yield was determined with the help of gas chromatography. The products were then purified with the help of liquid chromatography by using silica gel as a stationary phase and a mixture of n-hexane and ethyl acetate (70:30) as amobile phase. The spectroscopic data of the purified products were then compared with the available data bank of standard samples for their characterization. |
1: 10% 2: 85% | With dihydrogen peroxide In water; N,N-dimethyl-formamide at 20℃; for 0.0333333h; Green chemistry; chemoselective reaction; | |
1: 84% 2: 8% | With iodosylbenzene; C75H102Cl3Fe3N6O6 In dichloromethane at 20℃; for 15h; chemoselective reaction; | |
84% | With Ti(OCH(CH3)2)N(CH2C6H3C(CH3)3O)3; dihydrogen peroxide In methanol; water at 28℃; chemoselective reaction; | |
1: 5% 2: 80% | With 3-chloro-benzenecarboperoxoic acid In dichloromethane 1.) 0 deg C, 2 h, 2.) RT, 12 h; | |
74% | With oxygen; isobutyraldehyde In 1,2-dichloro-ethane at 25 - 28℃; for 2.5h; | |
1: 60% 2: 30% | With C19H13N3O4V; dihydrogen peroxide In methanol; dichloromethane at 0 - 4℃; for 2.5h; | Catalytic oxygenation of thioethers General procedure: To a solution of PhSMe (465 mg, 3.75 mmol) in methanol-dichloromethane (10:90 v/v), the catalyst [(L1)VO] (6.0 mg,0.015 mmol) and 50% H2O2 (1 mL) were added at 0 °C. The mixture was stirred for 2.5 h keeping the temperature at 0-4 °C. The solution was then dried in a vacuum. The products were isolated by thin layer chromatography (TLC). The solid PhSOMe and PhSO2Me were isolated as the third and second fractions, respectively, with yields of 187 mg and 222 mg, respectively. The products were characterised by IR spectroscopy. The results of the conversions of other thioethers to sulfoxides and sulfones are given in Table 2. |
1: 53% 2: 23% | With (Bu4N)2[{MoO(O2)2}2(μ-O)]; dihydrogen peroxide In acetonitrile for 3h; | Encouraged by the proficiency of 1 in the oxygenation of MPS,the catalytic performance of 1 was examined with additional substrateslisted in Chart 1 under the same conditions as those for theMPS reaction, and the results are collected in Table 1. Using oneequiv of H2O2, the reaction of BPS produced 53% sulfoxide and23% sulfone at 3 h, which indicates both a 100% utility of H2O2and lack of selectivity for sulfoxide. With 2.0 equiv of H2O2, BPSwas converted to the corresponding sulfone at 24 h. Compared tothe reactions of MPS and BPS, the reaction with PPS is significantlyslower, yielding 50% sulfoxide and 30% sulfone at 4 h. The reactionwith 4BT was slightly faster than that of MPS and resulted in 81%sulfoxide and 5% sulfone in 0.5 h (TOF: 910 h1). Lastly, PTEproceeded to 66% sulfoxide and 9% sulfone in 0.5 h for a TOF of660 h1. At 24 h, the reaction with PTE still contained 10% sulfoxidealong with 86% sulfone. This is possibly due to the conversionof PTE to the corresponding aldehyde as a minor side product |
1: 50% 2: 35% | With C36H27CuN8O2; dihydrogen peroxide In methanol; dichloromethane at 0℃; for 10h; | 2.8. General procedure for oxidation of organic thioethers General procedure: All the catalytic reactions were performed by a similar procedure.To a solution of 3 mmol of sulfide and 5 mL of 30% H2O2 in methanol-dichloromethane (1:9), 0.0120 mmol of catalyst 4a wasadded at 0 °C. The reaction mixture was stirred for 10 h. The solution was concentrated in a vacuum. The products were separatedby preparative TLC using benzene-acetonitrile (95:5) mixed solvent. Yields were determined by weighing the isolated products,which were characterized by 1H NMR and IR spectroscopy (Table 4). |
1: 21.7% 2: 50.4% | With dichloro(4,10-dimethyl-1,4,7,10-tetrazabicyclo[5.5.2]tetradecane)manganese(II); dihydrogen peroxide; calcium(II) trifluoromethanesulfonate In acetonitrile at 29.84℃; for 6h; | |
1: 30% 2: 48% | With C35H32ClCu2N2O7S2(1+)*ClO4(1-)*H2O; dihydrogen peroxide In methanol; dichloromethane at 0℃; for 2h; | 2.4 General procedure for the catalytic oxygenation of thioethers General procedure: Two catalytic reactions were performed by a similar procedure. To a solution of the catalyst [Cu2(L)(μ-OH)](ClO4)2 (0.0125 mmol) in methanol-dichloromethane (1:9) mixed solvent, 2.8 mmol of sulfide and 1mL of 50% H2O2 were added at 0 °C. The reaction mixture was stirred for 2 h. The solution was then dried in vacuum. The products were separated and purified by preparative TLC using benzene-acetonitrile (95:5) mixed solvent. The products were characterized by IR and 1H NMR spectra. |
1: 45% 2: 35% | With C19H15N3O4V; dihydrogen peroxide In methanol; dichloromethane; water at 0 - 4℃; for 0.5h; | |
1: 32% 2: 45% | With C19H14CuN4O; dihydrogen peroxide In methanol; dichloromethane at 0℃; for 6h; | 2.4. General procedure for catalytic oxygenation of thioethers General procedure: To the catalyst Cu(L) (0.014 mmol) dissolved in 10 mL dichloromethane-methanol (8:2) mixed solvent, 3 mmol of sulfide and 1.5mL of 50% H2O2 were all inserted in a 25 mL round-bottom flask at 0C. The mixture was stirred for 6 h. After the completion of the reaction the mixture was evaporated to dryness, water was addedand the product was extracted with dichloromethane. The organic layer was washed with brine, dried over Na2SO4, filtered. The products were separated and purified by preparative TLC using hexane-ethyl acetate (2:1) mixed solvent. The yields of the products obtained from all the reactions were determined after isolation,and characterized by1H NMR and IR spectra |
1: 35% 2: 8% | With cercosporin; oxygen In methanol at 20℃; Schlenk technique; Irradiation; Green chemistry; chemoselective reaction; | |
1: 15% 2: 5% | With Ir(ppy)<SUB>2</SUB>bpy; oxygen In methanol at 20℃; Irradiation; | 20 Example 1 Preparation of benzyl phenyl sulfoxide In a dry Shrek reaction tube,Add benzyl phenyl sulfide (0.25 mmol) sulfide in methanol (2.0 mL)PDI (0.5 mol%), PDI is a compound of formula A.Next, fill a balloon with oxygen and fix it on top of the Shrek reaction tube.The reaction was carried out at room temperature with a 15 W white CFL irradiation under a normal pressure of oxygen.After the reaction was completed, brine was added to the reaction.The aqueous phase was re-extracted with ethyl acetate.The synthesized organic extract was dried over Na 2 SO 4 and concentrated in vacuo.The residue obtained was separated by silica gel column chromatography ( petroleum ether: ethyl acetate = 10:1).Purification gave a white viscous solid (yield: 95%; selectivity: 100%). |
1: 1% 2: 93 % Spectr. | With dihydrogen peroxide In methanol; water at 25℃; for 24h; Title compound not separated from byproducts; | |
With urea-hydrogen peroxide In acetone at 20℃; for 2h; various catalysts, temp. and times; | ||
With buffer (pH 7.2-7.8); 3,3-dimethyldioxirane; bovine serum albumin at 4℃; for 3h; Yields of byproduct given; | ||
With buffer (pH 7.2-7.8); 3,3-dimethyldioxirane; bovine serum albumin at 4℃; for 3h; Yield given. Yields of byproduct given; | ||
With immobilized tungstate(IV) thermolysin; dihydrogen peroxide In <i>tert</i>-butyl alcohol at 40℃; for 24h; | ||
With iodosylbenzene In acetonitrile at 20℃; for 4h; Title compound not separated from byproducts.; | ||
1: 30.0 %Spectr. 2: 4.5 %Spectr. | With C68H72N4O6Ti2; dihydrogen peroxide In dichloromethane; water at 25℃; for 4.5h; enantioselective reaction; | |
With nitric acid In acetonitrile at 20℃; for 45h; chemoselective reaction; | ||
With C38H26N6NiS2(2+)*2NO3(1-); dihydrogen peroxide In water; acetonitrile at 20℃; | ||
With chloro-trimethyl-silane; dihydrogen peroxide In water; acetonitrile at 50℃; chemoselective reaction; | ||
With 1H-imidazole; urea hydrogen peroxide adduct In methanol; dichloromethane at 20℃; for 1h; | ||
With dihydrogen peroxide In water at 20℃; | ||
With bis(acetylacetonate)oxovanadium; 2-{2-[2,2-dimethylcyclopent-3-enyl]-2-hydroxypropylideneamino}phenol; dihydrogen peroxide In dichloromethane; water at 20℃; for 2h; | ||
With (η5-C5H5)Mo(CO)3C2Ph; dihydrogen peroxide In acetonitrile at 60℃; for 2h; Inert atmosphere; Schlenk technique; | ||
With dihydrogen peroxide In methanol; water for 1h; | 2.4 Oxidation of benzyl phenyl sulfide to benzyl phenyl sulfoxide General procedure: A mixture of benzyl phenyl sulfide (1 g, 5.0 mmol), silica vanadic acid (5 mg, 0.039 mmol of V) and H2O2 30% (6 mmol) in CH3CN (3 mL) was stirred for 10 min. After completion of the reaction, solvent was evaporated and the product was extracted with ether (2× 10 mL), dried with anhydrous Na2SO4, filtered and evaporated to afford the crude sulfoxide product. Finally, the product was purified by column chromatography using ethyl acetate/hexane (1.5:8.5) as eluent to give benzyl phenyl sulfoxide as a white solid in 93% yield. | |
1: 87 %Spectr. 2: 13 %Spectr. | With C44Cl8F20N4Pd; oxygen In acetonitrile for 4h; UV-irradiation; | |
With 1H-imidazole; [(2-(2'-hydroxyphenyl)-5,6-dihydro-1,3-oxazine)2Mn(OAc)]; urea hydrogen peroxide adduct In methanol; dichloromethane at 20℃; for 0.0833333h; | 2.3. General procedure for sulfide oxidation General procedure: To a solution of sulfide (0.2 mmol), imidazole(ImH) (0.2 mmol) as axial ligand, chlorobenzene (0.2mmol) as internal standard, and [(N-O)2Mn(OAc)] (0.01 mmol) in a 1 : 1 mixture of CH3OH/CH2Cl2 (1 mL) was added 0.4 mmol UHP as oxidant. The mixture was stirred at room temperature and the reaction progress monitored by GC. Assignments of products were made by comparison with authentic samples. | |
Stage #1: Benzyl phenyl sulfide In methanol; dichloromethane at 20℃; for 0.166667h; Stage #2: With urea hydrogen peroxide adduct In methanol; dichloromethane at 20℃; for 2h; Overall yield = 66 %Chromat.; | 2.3.2. General procedure for oxidation of sulfides. A mixture of MPS (3mM), polymeric MoO2Salen complexes (0.005 mM) and (1 : 1) mixture of CH3OH/CH2Cl2 (2 mL) was stirred in a 5-mL tube for 10 min at room temperature. The oxidant UHP (3.75 mM) was then added, and the system was stirred at room temperature for approximately 2 h, and the reaction progress, was monitored by GC. Assignments of products were made bycomparison with authentic samples. All reactions were run at least in duplicate. | |
With dihydrogen peroxide In acetonitrile at 20℃; for 6h; | 2.5 General procedure for oxidation reaction General procedure: The liquid phase oxidation reactions were carried out in a two-necked round bottom flask fitted with a water condenser and placed in an oil bath at different temperatures under vigorous stirring for a certain period of time. Substrates (5 mmol) were taken in CH3CN solvent (5 mL) for different sets of reactions together with 2.5 × 10-2 mmol catalyst in which 10 mmol of H2O2 (30% in aq.) was added. Product analysis was performed using Varian 3400 gas chromatograph equipped with a 30 m CP-SIL8CB capillary column and a Flame Ionization Detector. All reaction products were identified by using Trace DSQ II GC-MS. | |
With [Fe(2-(2'-hydroxyphenyl)-2-thiazoline)2Cl]; urea hydrogen peroxide adduct In methanol; dichloromethane at 20℃; for 0.25h; Overall yield = 95 %Chromat.; | ||
With C10H10MoNO7; urea hydrogen peroxide adduct In methanol; dichloromethane at 20℃; for 0.333333h; | 2.3. General procedure for sulfide oxidation General procedure: To a solution of sulfide (0.2 mM), chlorobenzene (0.2 mM) as internal standard and [MoO(O2)2(phox)] (0.015 mM) in a 1 : 1 mixture of CH3OH/CH2Cl2 (1 mL), 0.4mM UHP was added as the oxidant. The mixture was stirred at room temperature and the reaction progress was monitored by GC. Assignments of products were made by comparison with authentic samples. | |
With [Fe(phox)2Cl]; urea hydrogen peroxide adduct In methanol; dichloromethane at 20℃; | General procedure for sulfide oxidation General procedure: To a solution of sulfide (0.2mmol), chlorobenzene (0.2mmol) as internal standard and [Fe(phox)2Cl] (0.01mmol) in a 1:1 mixture of CH3OH/CH2Cl2 (1mL) was added 0.4mmol UHP as a oxidant. The mixture was stirred at room temperature and the reaction progress was monitored by GC. Assignments of products were made by comparison with authentic samples. | |
With Ru<SUB>2</SUB>(3-hydroxybenzoate)<SUB>4</SUB>Cl; dihydrogen peroxide In 1,2-dichloro-benzene; acetonitrile for 2h; | General procedure: To a solution of 1.25mmol of methyl phenyl sulfide in 25mL CH3CN, 1% catalyst A, B, or C was dissolved along with 1.0mmol 1,2 dichlorobenzene for internal standard. Initiating the reaction with 8.0equivalents of hydrogen peroxide was carried out by adding the hydrogen peroxide drop wise over about 30s. Samples were taken at the indicated times by removing 300μL of reaction mixture and quenching the hydrogen peroxide with about 5mg of MnO2. From this sample, 2μL of solution was injected into GC for analysis under the conditions described above. For catalyst D, the reactions were completed in the same fashion, except that water: acetone (3:2, v/v) was used as solvent. Reactions with other sulfides were carried out at the same concentrations as the MPS reactions above. However these reactions were scaled down to 10mL MeCN, 0.50mmol sulfide, 0.4mmol 1,2-dichlorobenzene, and 8equiv hydrogen peroxide. The reactions were sampled at the indicated times by quenching the unreacted hydrogen peroxide with MnO2 as above. Samples were analyzed via gas chromatography and percentages determined via standard curves for purchased sulfides and synthesized sulfoxides and sulfones. | |
With dihydrogen peroxide In acetonitrile at 20℃; for 0.25h; | ||
With 1-methyl-1H-imidazole; (S,S)-chloro[2,2'-[1,2-cyclohexanediylbis(nitrilomethylidyne)]bis-[4,6-bis(1,1-dimethylethyl)phenolato]](2-)-N,N',O,O'-manganese; dihydrogen peroxide In methanol at 20℃; for 0.333333h; | General procedure: Catalytic experiments were carried out as follows: the sulfide, the additive, and H2O2were added in this order to a solution of the catalyst in 1 mL of MeOH. The relative amountsare reported in the footnotes of the Tables. After the chosen time, the reaction was quenchedwith a saturated aqueous Na2SO3 solution (1 mL). The mixture was extracted with diethylether (4 × 5 mL) and the organic phase was dried over anhydrous Na2SO4. The solventwas removed under vacuum and the sample dissolved in CDCl3 for the 1H-NMR analysis. | |
With H3N*12H(1+)*[Mo36(NO)4O108(H2O)16](12-)*30.84H2O; urea hydrogen peroxide adduct In methanol; dichloromethane at 20℃; for 0.5h; Green chemistry; | ||
With [iron(III)(acetylacetonato)(2-(2'-hydroxyphenyl)oxazoline)2]; urea hydrogen peroxide adduct In methanol; dichloromethane at 20℃; for 0.25h; | General procedure for sulfide oxidation General procedure: The following standard procedure was used for sulfide oxidation experiments. To a solution of sulfide (0.2 mmol), chlorobenzene (0.2 mmol) as internal standard and [Fe(phox)2(acac)] (0.01 mmol) in a 1:1 mixture of CH3OH/CH2Cl2 (1 mL), was added UHP (0.4 mmol). The mixture was stirred at room temperature, and the reaction progress was monitored by GC. Products were identified by comparison with authentic samples. | |
With dihydrogen peroxide In water; acetonitrile at 70℃; | General test for the oxidation General procedure: Sulfide oxidation studies were performed with dibenzylsulfide as the model reagent and with 35% w/v aq. H2O2as oxidant in the selected solvent, in a batch reactor under magnetic stirring at different temperatures, using the bulk and synthesized catalyst in homogeneous or heterogeneous conditions, respectively. The oxidation of dibenzylsulfide was typically carried out by heating asolution of 1 mmol (214 mg) of the substrate and 1 mmol% of bulkor supported catalyst in 5 mL of solvent, at the experiment temperatures (see tables). A variable amount of aqueous H2O235%w/v was used. The sample was collected from the mixture at time intervals. About 20 L of the reaction mixture was taken for each sample, which was then diluted in a mixture of H2O-CH2Cl2(2 mL).The CH2Cl2 layer was shaken with anhydrous Na2SO4. The reaction products were analyzed by gas chromatography using a Shimadzu 2010. The percentages of each compound in the reaction mixture were directly estimated from the corresponding chromatographic peak areas. The products were all known compounds and were identified by GC-MS using PerkinElmer equipment | |
With 1,5-diaminopentane tetrachloro mangenate; dihydrogen peroxide In water; acetonitrile at 40℃; for 5h; Green chemistry; | ||
With dihydrogen peroxide In methanol at 65℃; | ||
With C42H30Fe2N6O6*C2H6O; urea hydrogen peroxide adduct In acetonitrile at 20℃; for 0.25h; | 2.3. Catalytic sulfoxidation General procedure: 0.2 mmol UHP as an oxidant was added slowly to a stirringsolution of 1 ml of CH3CN containing the complex [Fe2(salcyn)3],a substrate (0.2 mmol) and chlorobenzene (0.2 mmol) as an internalstandard. Stirring was continued for 15 min at room temperaturein a closed system. The reaction progress was monitored by GC. Assignments of the products were made by comparison with authentic samples. | |
1: 90 %Chromat. 2: 10 %Chromat. | With dihydrogen peroxide In water at 25℃; for 0.5h; | 2.3. Procedure for oxidation of sulfides using MoO(O2)2Bipy-PMO-IL General procedure: In a typical experiment, methyl phenyl sulfide (0.2 mmol), H2O2(0.8 mmol), were added to 300 μL water in a reaction flask. Afterwards,the catalytic reaction was conducted by adding of MoO(O2)2Bipy-PMO-IL as the catalyst to the reaction mixture, then it was kept for vigorousstirring at room temperature for 30 min. After completion of thereaction, the catalyst filtered by centrifuge (3000 rpm, washed withmethanol and dichloromethane many times for next runs) and theproduct was extracted and identified by GC. |
With oxygen; methylene blue In ethanol at 20℃; for 0.0166667h; Irradiation; Flow reactor; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79% | With tetra-(n-butyl)ammonium iodide; potassium hydrogencarbonate In 1,4-dioxane at 100℃; for 11h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With bis(acetylacetonate)oxovanadium; (R,R)-Schiff-base ligand; dihydrogen peroxide In dichloromethane; water at 0℃; for 24h; | |
85% | With tert.-butylhydroperoxide; (S)-[1,1']-binaphthalenyl-2,2'-diol; bismuth(III) oxide In water; ethyl acetate at 20℃; for 22h; Green chemistry; enantioselective reaction; | |
78% | With chiral Schiff base derived from (R)-BINOL and (S)-t-leucinol; dihydrogen peroxide In dichloromethane at 0℃; for 24h; |
75% | Stage #1: Benzyl phenyl sulfide With iron(III) trifluoromethanesulfonate; C59H88N4O4 In tetrahydrofuran at 35℃; for 0.5h; Inert atmosphere; Stage #2: With dihydrogen peroxide In tetrahydrofuran; water at 0℃; for 24h; Inert atmosphere; enantioselective reaction; | |
73% | With titanium(IV) isopropylate; tert.-butylhydroperoxide; (R,R)-hydroxybenzoin; water In tetrachloromethane at 0℃; for 2h; | |
With titanium(IV) isopropylate; tert.-butylhydroperoxide; (R,R)-hydroxybenzoin In tetrachloromethane; water at 0℃; for 2h; Yield given; | ||
With titanium(IV) isopropylate; tert.-butylhydroperoxide; (R,R)-hydroxybenzoin In tetrachloromethane at 0℃; for 2h; | ||
With Acinetobacter baylyi ADP1; oxygen; NADH In ethanol at 30℃; Sealed tube; Enzymatic reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With sodium carbonate In tetrahydrofuran at 20℃; for 1h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With potassium phosphate; 4-tert-Butyl-2,6-diphenylphenol; 1-hydroxy-4-(2-chloroacetamido)-2,2,6,6-tetramethylpiperidine In dimethyl sulfoxide for 16h; Irradiation; | 21 Example 21: The benzyl-protected thiophenol (0.30 mmol), phenol catalyst 2,6-diphenyl-4-tert-butylphenol (4.0% of the molar amount of the substrate), hydrogen source 1-hydroxy-4-(2-chloroacetamido)-2,2,6,6-tetramethylpiperidine (0.40 mmol), alkali potassium phosphate (0.60 mmol) is dissolved in the solvent dimethyl sulfoxide (3.0 ml), after the addition, the reactant was irradiated under 515nm light for 16 hours, the reaction was quenched by adding water, and the aqueous phase was extracted three times with ethyl acetate (15 ml×3), the organic phases were combined, washed with water and saturated brine in turn, dried over anhydrous sodium sulfate, concentrated, and column chromatographed to obtain a protected product (95% yield). |
55% | With titanium(III) chloride; lithium In tetrahydrofuran at 25℃; for 16h; | |
89 - 90 %Chromat. | With potassium <i>tert</i>-butylate In 1-methyl-pyrrolidin-2-one for 2 - 3h; |
93 %Chromat. | With potassium <i>tert</i>-butylate In dimethyl sulfoxide for 2h; | |
85 %Chromat. | With potassium <i>tert</i>-butylate In diethylene glycol dimethyl ether for 3h; | |
88 %Chromat. | With potassium <i>tert</i>-butylate In desipramine for 2h; | |
0.4 %Chromat. | With dibutylmagnesium In hexane; diethylene glycol dimethyl ether at 50℃; for 5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | Stage #1: benzyl methyl ether With t-butyl bromide; 1-pentyl-3-methylimidazolium bromide at 60℃; Stage #2: thiophenol With 1-pentyl-3-methylimidazolium bromide at 60℃; | |
69% | With indium(III) chloride; silica gel for 0.25h; microwave irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With aluminium trichloride; zinc In water; acetonitrile at 65℃; for 4h; | |
94% | Stage #1: diphenyldisulfane With aluminium trichloride; zinc In acetonitrile at 65℃; for 2h; Stage #2: benzyl tosylate In water; acetonitrile at 65℃; for 4h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With 1,4-diaza-bicyclo[2.2.2]octane; copper(l) iodide; potassium carbonate In 1,2-dimethoxyethane at 120℃; for 12h; Sealed tube; Inert atmosphere; chemoselective reaction; | 2. General reaction procedure General procedure: A mixture of thiol (0.5 mmol), aryl halide (0.6 mmol), CuI (5 mol%, 4 mg), DABCO (10 mol%, 5.6 mg) K2CO3 (2 equiv., 138 mg) and DME (3 ml) were added to an oven-dried sealed tube equipped with a stirring bar under nitrogen. The above mixture was taken in a sealed tube and was stirred in a preheated oil bath at 120 oC for 12 h. It is then cooled to room temperature. The cooled mixture was diluted with ethyl acetate (30 ml) and washed with saturated aqueous NaCl solution (3 x 15 ml). Any moisture content if present was removed by drying with anhydrous Na2SO4. The dried mixture is filtered and the solvent was removed under vacuum. The crude residue was purified by column chromatography on silica gel using ethyl acetate/hexanes as the eluent to give the desired sulphides. |
98% | With caesium carbonate In N,N-dimethyl-formamide at 90℃; for 24h; | |
98% | With potassium hydroxide; copper(II) oxide In dimethyl sulfoxide at 80℃; for 11h; |
97% | With tetra(n-butyl)ammonium hydroxide In water at 50℃; for 24h; Inert atmosphere; Sealed tube; chemoselective reaction; | |
97% | With 1,4-diaza-bicyclo[2.2.2]octane; copper(l) iodide; potassium carbonate In 1,2-dimethoxyethane at 120℃; for 12h; Sealed tube; Inert atmosphere; chemoselective reaction; | General procedure General procedure: A mixture of thiol (0.5 mmol), aryl halide (0.6mmol), CuI (5 mol%, 4 mg), DABCO (10 mol%, 5.6 mg) K2CO3(2 equiv, 138 mg) and DME (3 ml) were added to an oven-dried sealed tube equipped with a stirring bar under nitrogen. The sealed tube was stirred in a preheated oil bath at 120 oC for 12 h. After being cooled to room temperature, the mixture was diluted with ethyl acetate(30 ml) and washed with saturated aqueous NaCl solution (3 x 15 ml).The organic phase was dried with anhydrous Na2SO4,filtered, and the solvent was removed under vacuum. The crude residue was purified by column chromatography on silica gel using ethyl acetate/hexanes as the eluent to give the desired sulphides. |
96% | With copper(l) iodide; potassium phosphate tribasic trihydrate at 110℃; for 12h; | |
94% | With trans-9,10-dihydro-9,10-ethanoanthracene-11,12-dimethanol; caesium carbonate; copper(I) bromide In acetonitrile at 82℃; for 15h; Inert atmosphere; Sealed tube; | |
94% | With tetra(n-butyl)ammonium hydroxide; sodium hydroxide; palladium dichloride In water at 70℃; for 0.8h; | |
92% | With caesium carbonate In dimethyl sulfoxide at 60℃; for 22h; | |
92% | With potassium hydroxide; tetrabutylammomium bromide at 110℃; for 12h; | |
92% | With copper(l) iodide; potassium fluoride on basic alumina In N,N-dimethyl-formamide at 110℃; for 8h; Inert atmosphere; Combinatorial reaction / High throughput screening (HTS); | |
91% | With sodium hydride In tetrahydrofuran; N,N-dimethyl-formamide for 8h; Heating; | |
91% | With potassium hydroxide; tetrabutylammomium bromide In water at 80℃; for 11h; | |
91% | With 1,2,3,4-tetrahydroquinolin-8-ol; potassium carbonate; copper(I) bromide In dimethyl sulfoxide at 80℃; for 24h; Inert atmosphere; | |
89% | With copper(I) oxide; caesium carbonate; ethyl 2-oxocyclohexane carboxylate In dimethyl sulfoxide at 80℃; for 20h; | |
86% | With copper(II) ferrite; potassium <i>tert</i>-butylate In 1,4-dioxane for 24h; Reflux; Inert atmosphere; | |
85% | With copper(I) oxide; potassium hydroxide; water In dimethyl sulfoxide at 80℃; for 24h; Inert atmosphere; | |
83% | With 1,3-bis(2,6-diisopropylphenyl)imidazolium chloride; potassium <i>tert</i>-butylate; nickel diacetate In N,N-dimethyl-formamide at 110℃; for 6h; Glovebox; Inert atmosphere; | General procedure for the coupling reaction of aryl halides with phenyl sulfide ; Benzyl phenyl sulfide General procedure: In a typical run, a 5 mL vial equipped with a magnetic bar was charged with a mixture of aryl halide (1 mmol), thiol (1 mmol), Ni(OAc)2 (0.1 mmol), NHC (0.05 mmol) and KOtBu (1.5 mmol) in glove box, 2 mL of DMF was injected, the mixture was stirred at 70 °C for 12 h. After cooling to room temperature, brine was added to the reaction mixture, and the aqueous phase was extracted with dichloromethane for three times. The combined organic layers were dried with Mg2SO4 and the solvent was removed under reduced pressure. The residue was purified by column chromatography on silica gel to afford the desired products. |
78% | With cesium hydroxide In dimethyl sulfoxide at 120℃; for 0.0833333h; | |
75% | With iron(III) chloride; potassium <i>tert</i>-butylate; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene In 1,4-dioxane at 135℃; for 24h; Inert atmosphere; | |
71% | With 1,10-Phenanthroline; potassium <i>tert</i>-butylate; copper(II) oxide In water at 120℃; for 0.5h; Microwave irradiation; Inert atmosphere; | Benzyl Phenyl Sulfide (3s) General procedure: A 4-mL sealable vial equipped with a magnetic stirrer bar wascharged with KOt-Bu (85.7 mg, 0.75 mmol), CuO (1.99 mg, 0.025mmol), ligand L1 (0.025 mmol), and the appropriate aryl iodide (0.6mmol) under N2. The vial was sealed with a cap containing a PTFEseptum, and the thiol (0.5 mmol) and H2O (0.5 mL) were added by syringe.The mixture was heated at 120 °C by microwave irradiationwith stirring for 30 min, then cooled to r.t. and diluted with EtOAc (20mL). The resulting solution was filtered through a pad of silica gel thatwas washed with EtOAc (20 mL). The organic phase was concentratedto give a crude material that was purified by column chromatography(silica gel, hexane). |
66% | With C24H22N6Ni; sodium t-butanolate In N,N-dimethyl-formamide; acetonitrile at 20℃; for 24h; Inert atmosphere; Schlenk technique; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | Stage #1: dibenzyl disulphide With aluminium trichloride; zinc In acetonitrile at 80℃; for 2h; Stage #2: diphenyliodonium iodide In water; acetonitrile at 80℃; for 5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | Stage #1: Benzyl phenyl sulfide With manganese(II) triflate; N1,N2-bis(2-((R)-4-isopropyl-4,5-dihydrooxazol-2-yl)phenyl)benzene-1,2-diamine In acetonitrile at 20℃; for 6h; Inert atmosphere; Green chemistry; Stage #2: With 1-Adamantanecarboxylic acid; dihydrogen peroxide In isopropyl alcohol; acetonitrile at -20℃; for 2h; Inert atmosphere; Green chemistry; enantioselective reaction; | |
87% | Stage #1: Benzyl phenyl sulfide With titanium(IV) isopropylate; (S,S)-hydrobenzoin In hexane for 0.5h; Inert atmosphere; Stage #2: With tert.-butylhydroperoxide; di-tert-butyl peroxide In hexane; water at 20℃; for 48h; enantioselective reaction; | 4.10. Enantioselective oxidation of aryl benzyl sulfide. Representative procedure General procedure: A solution of Ti(O-i-Pr)4 (0.014 g, 0.05 mmol) in 4 mL of n-hexane was added to a solution of (S,S)-hydrobenzoin (0.021 g,0.1 mmol) in 8 mL of n-hexane under a nitrogen atmosphere. The mixture was stirred for 1 h at room temperature. A solution of arylbenzyl sulfide (1 mmol) (as an alternative, a suspension of low soluble sulfides) in 8 mL of n-hexane was added at this stage, and the mixture was stirred for 30 min. After this time, 0.14 mL of a commercial 80% solution of tert-butyl hydroperoxide (in di-tertbutylperoxide/water 3:2) (1.1 mmol) was added and the stirring was continued for 2 days at room temperature. Finally, the solvent was removed in vacuo and the residue was subjected to column chromatography (petroleum ether/ethyl acetate 4:1). |
85% | With manganese(II) triflate; 1-Adamantanecarboxylic acid; C30H34N4O2; dihydrogen peroxide In water; isopropyl alcohol; acetonitrile at 20℃; for 0.0166667h; Flow reactor; enantioselective reaction; |
84% | With bis(acetylacetonate)oxovanadium; (R,S)-Schiff-base ligand; dihydrogen peroxide In dichloromethane; water at 0℃; for 24h; | |
84% | With manganese(II) triflate; C30H34N4O2; dihydrogen peroxide; acetic acid In dichloromethane; water at 0℃; for 1h; Inert atmosphere; enantioselective reaction; | |
With titanium(IV) isopropylate; tert.-butylhydroperoxide; (S,S)-hydrobenzoin enantioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With hydrogenchloride; zinc In water at 20℃; for 0.166667h; Ionic liquid; Inert atmosphere; | General procedure for the synthesis of diorganyl selenides and sulfides: commercially available Zn dust (33 mg, 0.5 mmol) and PhSeSePh/PhSSPh (0.5 mmol) and 15 μL of HCl 1N were added to BMIM-BF4 (0.5 mL) at room temperature under nitrogen. The mixture was allowed to stir for 2-3 min. Then corresponding organic halides (1 mmol) was slowly added. The reaction mixture was allowed to stir until the color change (monitored by TLC and assisted by visual observation). The mixture was then extracted with ether (3×15 mL), and the combined ether extract was washed with brine, dried (MgSO4), and evaporated to leave the crude product. Purification by column chromatography over silica gel (hexane/ethyl acetate 98:2) furnished the corresponding products. |
88% | With triphenylphosphine; 1-pentyl-3-methylimidazolium bromide at 75℃; for 1.5h; | Representative procedure for the synthesis of benzyl phenyl sulfide (Table 2, entry 2a). General procedure: A mixture of benzyl bromide (171 mg, 1 mmol), diphenyl disulfide (131 mg, 0.6 mmol), PPh3 (184 mg, 0.7 mmol), and [pmIm]Br21 (94 mg, 0.4 mmol) was stirred at 75 °C for 1.5 h (TLC). The reaction mixture was extracted with Et2O, and the organic layer was washed with brine (2 × 5 mL) and dried (Na2SO4). Evaporation of solvent left the crude product which was purified by column chromatography over silica gel (hexane) to afford the pure product, benzyl phenyl sulfide (168 mg, 84%) as a colorless liquid; IR (neat) 3058, 3028, 2923, 1581, 1495, 1479, 1452, 1438, 1238, 1090, 1068, 1024 cm-1; 1H NMR (300 MHz, CDCl3) δ 4.21 (s, 2H), 7.32-7.41 (m, 10H); 13C NMR (75 MHz, CDCl3) δ 39.5, 127.6, 128.0, 129.0 (2C), 129.3 (2C), 129.5 (2C), 130.3 (2C), 136.9, 137.9. The spectroscopic (FT-IR, 1H NMR and 13C NMR) data are in good agreement with the reported values.9b The remaining ionic liquid was washed with ether, dried under vacuum, and reused five times without appreciable loss of catalytic activity. |
85% | With iodine In 1-methyl-pyrrolidin-2-one at 130℃; Microwave irradiation; |
79% | With indium iodide In dichloromethane at 20℃; for 2.5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | Stage #1: Benzyl phenyl sulfide With anthracene; magnesium; ethylene dibromide In tetrahydrofuran Stage #2: With water In tetrahydrofuran at 0℃; Further stages.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | Stage #1: Benzyl phenyl sulfide With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.166667h; Stage #2: With N,N,N,N,-tetramethylethylenediamine In tetrahydrofuran; hexane for 0.166667h; Stage #3: diphenyl diselenide In tetrahydrofuran; hexane for 0.25h; Further stages.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With hydrogen In neat (no solvent) at 120℃; for 40h; | |
83% | With iodine; magnesium In methanol at 20℃; for 3h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 26% 2: 53.9% 3: 11% | With sodium hypochlorite In water; toluene at 20℃; for 3h; | 7 (Example 7); (Benzylthio)benzene (500 mg, 2.50 mmol) and cyanuric acid (32 mg, 0.25 mmol) were mixed with toluene (10 mL). 10% aqueous solution of sodium hypochlorite (5.57 g, 7.49 mmol) was added dropwise to the mixture at room temperature, and it was stirred for 3 hours. After that, sodium sulfite (315 mg, 2.50 mmol) and water (10 mL) were added to the reaction mixture, and it was extracted with ethyl acetate (10 mL). An organic layer was washed with water (5 mL) twice. The organic layer was concentrated under reduced pressure, and the obtained residue was subjected to purification by means of a silica gel column to obtain (benzylsulfinyl)benzene (138 mg, yield: 26%), [chloro(phenyl)methyl]sulfinyl}benzene (337 mg, yield: 53.9%) and (benzylsulfonyl)benzene (64 mg, yield: 11%). (Benzylsulfinyl)benzene: 1H-NMR (300MHz, CDCl3) δ 3.95-4.13 (2H, m), 6.95-7.01 (2H, m), 7.22-7.50 (8H, m) [Chloro(phenyl)methyl]sulfinyl}benzene: 1H-NMR (300MHz, CDCl3) δ 5.48 (1H, s), 6.89-7.50 (10H, m) (Benzylsulfonyl)benzene: 1H-NMR (300MHz, CDCl3) δ 4.31 (2H, s), 7.03-7.68 (10H, m) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With palladium diacetate; potassium carbonate; thiourea; XPhos In water at 20℃; for 4h; Inert atmosphere; | |
92% | With potassium carbonate; thiourea In water at 100℃; for 1.25h; Green chemistry; | 2.3 General Procedure for the Thioetherificationof Aryl Halides General procedure: To a mixture of aryl halide (1 mmol), benzyl bromide(1.1 mmol), K2CO3 (2 mmol), thiourea (1.2 mmol) and ASS-Cu(acac)2 (0.2g, 3.5 mol % Cu) in a round bottom flask (25 mL), water (5 mL) was added and the reaction mixture was stirred at 100 °C for an appropriate time (Scheme 2). After completion of the reaction (monitored by TLC), the reaction mixture was diluted with ethyl acetate and filtered. The residue was treated with hot ethyl acetate (3x10 mL) and the organic layer was washed with water (100 mL) and dried over anhyd. Na2SO4. Finally, the product was obtained after removal of the solvent under reduced pressure followed by purification using flash chromatography on silica gel (EtOAc-Petroleum ether). |
86% | With potassium carbonate; thiourea In water at 100℃; for 7.5h; Green chemistry; | 2.8. General procedure for the Pd(0)-EDA/SC-2 catalyzedthioetherification of aryl halides General procedure: To a mixture of aryl halide (1 mmol), benzyl bromide (1.1 mmol),K2CO3(0.50 mmol), thiourea (1.2 mmol) and Pd(0)-EDA/SC-2 (0.2 g,2.5 mol% Pd) in a round-bottom flask (25 mL), water (5 mL) wasadded and the reaction mixture was stirred at 100C for an appro-priate time (Scheme 4). After completion of the reaction (monitoredby TLC), the reaction mixture was diluted with ethyl acetate andfiltered. The organic layer was washed with water (100 mL) anddried over anhydrus Na2SO4. Finally, the product was obtainedafter removal of the solvent under reduced pressure followed bycrystallization or column chromatography on silica gel (EtOAc-pet.ether). The catalyst was washed with EtOAc (3 × 5 mL), double dis-tilled water (3 × 10 mL), respectively, and dried under vaccum for1 h at 100C for further use. |
85% | With potassium carbonate; thiourea In water at 140℃; for 0.2h; Microwave irradiation; Further stages; | |
82% | With potassium carbonate; thiourea In water at 99.84℃; for 12h; | |
82% | With potassium carbonate; thiourea In water at 100℃; | |
82% | With copper(II) ferrite; potassium carbonate; thiourea In water at 80 - 100℃; for 20h; | 2.2. General procedure for thioarylation reactions General procedure: In a 5 mL flask, aryl halide (1 mmol), alkyl halide (1.1 mmol),thiourea (91 mg, 1.2 mmol), CuFe2O4(12 mg, 5 mol%), K2CO3(552 mg, 4.0 mmol), H2O (0.3 mL), and PEG (2 mL) were added and stirred at 80-100°C for the appropriate reaction time. After completion of reaction, the mixture was cooled to room temperature and washed with 5 mL H2O and 10 mL EtOAc. Then,after separation and evaporation of organic solvent, the crude thioethers, were purified by flash column chromatography on silica gel eluted with the appropriate mixture of (EtOAc/n-hexane). |
80% | With copper(l) iodide; potassium carbonate; thiourea In water at 100℃; for 24h; Inert atmosphere; | |
80% | With potassium carbonate; thiourea In water for 10h; Green chemistry; | |
79% | With thiourea; potassium hydroxide In water at 100℃; for 10h; Green chemistry; | |
77% | With potassium carbonate; thiourea In water at 140℃; for 0.25h; Microwave irradiation; | 2.6. C-S coupling reaction over Cu-MPIOS General procedure: For a typical experiment, C-S cross coupling reaction has beenperformed under microwave irradiation by changing substrate, sol-vent and temperature in the presence of catalyst. 20 mg catalyst andabove mentioned three different reactant components were taken in 10 ml MW glass vial containing 5 ml H2O. We have performedthe coupling reaction using 4-bromoanisole (1.1 mmol, 188 mg);thiourea (1.2 mmol, 91 mg) and benzyl bromide (1 mmol, 187 mg)in the presence of the Cu-catalyst. A small magnetic needle wasinserted in the sealed glass vial to make homogeneous mixtureduring progression of reaction (15 min). Then the loaded tube wasplaced in the microwave reactor pre-set at desired temperature.After completion of reaction the glass tube was cooled down toroom temperature and transferred the solution to a separating fun-nel. The product was extracted using ethyl acetate and washedthoroughly with deionised water. Finally the oily pale yellow col-ored product was obtained after solvent evaporation using rotaryevaporator, and characterized through1H and13C NMR analysesusing CDCl3as solvent (Scheme 2). |
75% | With potassium carbonate; thiourea In water at 99.84℃; for 12h; | |
71% | With thiourea In water for 20h; Reflux; Green chemistry; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With thiourea In water for 10h; Reflux; Green chemistry; | |
92% | With copper(II) ferrite; potassium carbonate; thiourea In water at 80 - 100℃; for 12h; | 2.2. General procedure for thioarylation reactions General procedure: In a 5 mL flask, aryl halide (1 mmol), alkyl halide (1.1 mmol),thiourea (91 mg, 1.2 mmol), CuFe2O4(12 mg, 5 mol%), K2CO3(552 mg, 4.0 mmol), H2O (0.3 mL), and PEG (2 mL) were added and stirred at 80-100°C for the appropriate reaction time. After completion of reaction, the mixture was cooled to room temperature and washed with 5 mL H2O and 10 mL EtOAc. Then,after separation and evaporation of organic solvent, the crude thioethers, were purified by flash column chromatography on silica gel eluted with the appropriate mixture of (EtOAc/n-hexane). |
84% | Stage #1: iodobenzene With 1,1'-binaphthalene-2,2'-diamine; copper diacetate; potassium ethyl xanthogenate In N,N-dimethyl-formamide at 105℃; for 24h; Inert atmosphere; Stage #2: With potassium hydroxide In N,N-dimethyl-formamide at 105℃; for 3h; Inert atmosphere; Stage #3: benzyl bromide In N,N-dimethyl-formamide at 20℃; for 1h; Inert atmosphere; |
80% | With copper(l) iodide; potassium carbonate; thiourea In water at 80℃; for 24h; Inert atmosphere; | |
67% | Stage #1: iodobenzene With carbon disulfide; copper(l) iodide; diethylamine; sodium hydroxide In water for 15h; Inert atmosphere; Schlenk technique; Reflux; Green chemistry; Stage #2: With potassium hydroxide In water at 110℃; for 4h; Inert atmosphere; Schlenk technique; Green chemistry; Stage #3: benzyl bromide In water at 20℃; for 1h; Inert atmosphere; Schlenk technique; Green chemistry; | Synthesis by Method A (See Scheme 1) [9] General procedure: A solution of CS2 (0.92 g, 12 mmol), NaOH (10% aq. solution,10 mL) and diethylamine (1.2 mL, 12 mmol) were stirred for 1 h at room temperature. CuI (0.19 g, 0.99 mmol,10% mol), iodobenzene (2.0 g, 10 mmol) and PEG400 (20 mL) were added, and the reaction mixture was stirred at reflux. After 15 h, KOH (2.2 g, 40 mmol) was added and the mixture was stirred at 110 °C for 4 h. After cooling, (1-bromoethyl)benzene (2.8 g, 15 mmol) was added to the solution, which was stirred at room temperature for 1 h, and the reaction solution was diluted with water (20 mL) and further extracted with ethyl acetate (10 mL × 2). The solvent was removed in vacuo, and the residue was washed by cool diethyl ether (8 mL × 3). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | Stage #1: iodobenzene With basolite C300; thiourea; potassium hydroxide In water at 130℃; for 3h; Inert atmosphere; Stage #2: benzyl chloride In water at 130℃; for 1.5h; | Unsymmetrical sulfides synthesis; typical experimental procedure General procedure: MOF-199 (4 mg) were added to solution of iodobenzene (1.0mmol), thiourea (0.228 g, 3.0mmol) and KOH (0.168 g, 3 mmol) in 2ml PEG/H2O (20:1). The reaction continued at 130°C under N2 conditions until production of thiolate salt as intermediate after 3. Then 1.1 mmol benzylchloride was added to mixed reaction and the reaction continued at 130°C under atmospheric conditions. After completion of the reaction [about 10 h; TLC (EtOAc/hexane, 1:20) monitoring. CH2Cl2 (20 ml) was added and the mixture was washed with H2O (2×15 ml). The combined organic fractions dried (Na2SO4) and concentrated under reduced pressure. The residue was purified by preparative chromatography [silicagel, hexane/EtOAc, 20:1] to give the product. |
82% | Stage #1: iodobenzene With 1,1'-binaphthalene-2,2'-diamine; copper diacetate; potassium ethyl xanthogenate In N,N-dimethyl-formamide at 105℃; for 24h; Inert atmosphere; Stage #2: With potassium hydroxide In N,N-dimethyl-formamide at 105℃; for 3h; Inert atmosphere; Stage #3: benzyl chloride In N,N-dimethyl-formamide at 20℃; for 1h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | Stage #1: phenylboronic acid With potassium ethyl xanthogenate; copper(l) chloride In methanol for 3h; Inert atmosphere; Reflux; Stage #2: benzyl chloride With potassium hydroxide In methanol for 3h; Inert atmosphere; Reflux; | |
90% | With sulfur; potassium hydroxide In N,N-dimethyl-formamide at 80℃; for 32h; | 2.2. General procedure for the synthesis of unsymmetrical sulfide usingphenylboronic acid, S8 and aryl/benzyl halide in the presence of CuI-ZSM5as a catalyst General procedure: A mixture of aryl/benzyl halides (1 mmol), phenylboronic acid(146 mg, 1.2 mmol), S8 (48 mg), CuI-ZSM5 (60 mg), KOH (366 mg,6 mmol) and DMF (2 mL) was magnetically stirred at 80 °C for thetime specified in Table 4. After completion of the reaction, the catalystwas separated by filtration. H2O (5 mL) was added and the productwas extracted with diethyl ether (3 × 5 mL). The combined organicphases was washed with brine (15 mL) and dried over anhydrousNa2SO4. Evaporation of the solvent and purification by column chromatographyon silica gel (n-hexane/EtOAc, 4:1) gave the desired phenylaryl/benzyl sulfide. |
80% | With sulfur; copper(II) ferrite; potassium hydroxide at 80℃; for 26h; |
72% | With sulfur; copper(l) iodide; sodium hydroxide at 40 - 60℃; for 11h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With indium (III) iodide In toluene at 20℃; for 3h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With indium(III) bromide; 1,1,3,3-Tetramethyldisiloxane In 1,2-dichloro-ethane at 80℃; for 20h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With iodine In 1-methyl-pyrrolidin-2-one at 130℃; for 0.666667h; Sealed tube; Microwave irradiation; | |
83% | With nanolayered cobalt-molybdenum sulphide with Co/(Mo+Co) mole ratio 0.83 In toluene at 180℃; for 18h; Inert atmosphere; Autoclave; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 50% 2: 40% | With sodium acetate; silica gel In acetone at 65℃; for 24h; | Typical procedure and data complex 2a General procedure: Preligand 1a (0.0214 mg, 0.155 mmol), Pd(OAc)2 (0.0328 mg, 0.146 mmol), SiO2 (0.0544 mg; 375 mg per 1 mmol of preligand; 100-230 mesh) and a stirring bar were added to a small round-bottom flask and the components were vigorously mixed using spatula for ca. 1 min. The flask was fitted with a rubber septum and a 1-mL syringe packed with CaCl2 and then was immersed in a preheated oil bath. After stirring at 50 °C for 168 h, the mixture was transferred onto a glass filter and washed with acetone (3×5 mL). LiCl (0.025 g, 0.60 mmol) was added to the filtrate, and the resulting mixture was stirred overnight. The crude product was purified using preparative TLC (silica gel, benzene). Complex 2a was isolated as a yellow solid in 81% yield along with 12% of complex 3a, which appeared as an orange solid.Mp 140 °C (decomp.); Rf 0.62 (10:1 benzene-acetone). 1H NMR (CDCl3, δ,ppm): 2.21 (s, 3H,), 3.92 (d, J=14.6 Hz, 1H, CHA), 4.28 (d, J=14.6 Hz, 1H,CHB), 6.91 (m, 1H, H3 arom), 6.98 (d, J=5.0 Hz, 2H, H4 and H5), 7.41 (d,J=5.0 Hz, 2H, H6). 13C NMR (CDCl3, δ, ppm): 23.4 (SCH3), 47.3 (CH2S), 123.6 C4 arom), 125.3 (C3 arom), 126.2 (C5 arom), 135.6 (C6 arom), 146.9 (C2 arom), 148.1 (C-Pd). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
56% | With silica gel; trifluoroacetic acid In neat (no solvent) at 80℃; for 24h; | General procedure: We found that benzyl phenyl sulfide 5 undergoes transcyclopalladation on silica gel using CPC 1a at 80 °C in the presence of equimolar amount of CF3CO2H furnishing CPC 6 in 56% (Scheme 2 and entry 1 in Table 2 ). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | In acetonitrile at 20℃; for 1.5h; Green chemistry; chemoselective reaction; | Synthesis of sulfoxides and sulfones General procedure: To a stirred suspension of the selected sulphide (10 mmol) andthe heterogeneous catalyst 4.2% VMIL(101) (0.1 g,∼2.5 mol%) inmethanol (10 ml), H2O2 (8 mmol) was added in one portion. Theslurry was stirred at room temperature for 20 min. The catalyst wasfiltered off and washed with methanol (10 ml). Ethyl acetate (10 ml)was added and resulting solution was dried with anhydrous sodiumsulphate and evaporated in vacuo to afford the crude product whichwas purified by column chromatography on silica gel (10% EtOAc inhexane) to afford the pure sulfoxide. Similar method was utilizedto produce sulfones. In this case 4 mol% of VMIL(101) in CH3CNwere utilized. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With copper diacetate; triethylamine at 20℃; for 30h; | Typical procedure for O-arylation of phenol with Ph3SnCl catalyzed by Cu(OAc)2 General procedure: To a flask containing a stirring mixture of triphenyltin chloride (0.5 mmol, 0.193 g) and phenol (1 mmol, 0.094 g) in triethylamine (10 equiv, 1.4 mL) at room temperature, copper acetate (40 mol%, 0.076 g) was added. Monitoring the reaction with TLC showed that the reaction was completed within 30 h. The reaction mixture was washed with HCl (1 N, 1 mL) to remove the excess of Et3N. Then, the catalyst was filtered and the aqueous solution was extracted with ethyl acetate (5×10 mL) and dried over anhydrous Na2SO4. The solvent was evaporated and column chromatography of the crude mixture on silica-gel using n-hexane/ethyl acetate (3/1) as eluent afforded biphenyl ether in 85% yield (0.130 g). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With silver tetrafluoroborate; bis[dichloro(pentamethylcyclopentadienyl)iridium(III)]; copper diacetate at 80℃; for 12h; | 50 Example 50 80 ° C air atmosphere,The structural formula is numbered as AU thioether 0. 4mmol,a mixture of 0. 8 mmol of acrylic acid vinegar, [Cp*IrCl 2 ] 2 0 006 mmol, AgBF 4 0 024 mol and Cu (OAc) 2 0.48 mmol, added with 2 mL of hexafluoroisopropanol.The reaction was stirred for 12 h, the reaction mixture was cooled to room temperature and filtered over Celite.Silica gel column chromatography (ethyl acetate / petroleum ether = 1:10, ν / ν) to give product, product as a monoalylated product a, yield 80%. |
67% | With copper diacetate; C27H25ClN3RuS(1+)*F6P(1-) In 1,2-dichloro-ethane for 12h; Heating; | |
36 %Spectr. | With [Ru(C5Me5)(MeCN)3](SbF6)2; silver(I) acetate; copper diacetate In methanol at 120℃; for 24h; Schlenk technique; Inert atmosphere; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | Stage #1: benzyl chloride With [2,2]bipyridinyl; copper(ll) sulfate pentahydrate; sodium thiosulfate pentahydrate In methanol; water at 80℃; for 2h; Schlenk technique; Stage #2: aniline With tert.-butylnitrite In methanol; water at 0 - 80℃; for 4.66667h; Schlenk technique; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | Stage #1: benzyl chloride With [2,2]bipyridinyl; copper(ll) sulfate pentahydrate; Sodium thiosulfate pentahydrate In water at 80℃; for 2h; Schlenk technique; Inert atmosphere; Stage #2: 1-phenyl-3,3-tetramethylenetriazene With boron trifluoride diethyl etherate In water at 20℃; for 24h; Schlenk technique; Inert atmosphere; | |
97% | Stage #1: benzyl chloride With [2,2]bipyridinyl; copper(ll) sulfate pentahydrate; Sodium thiosulfate pentahydrate In water at 80℃; for 2h; Green chemistry; Stage #2: 1-phenyl-3,3-tetramethylenetriazene In water at 0℃; for 0.25h; Green chemistry; Stage #3: With boron trifluoride diethyl etherate In water at 0 - 20℃; for 12h; Green chemistry; | 18 Example 18 Synthesis of Benzyl (4-fluorophenyl) sulfide: The catalyst CuSO4.5H2O (2.0 mg, 0.02 mmol), ligand bipyridine L1 (3.1 mg, 0.02 mmol), benzyl chloride (1 mmol, 5 equiv.) and Na2S2O3·5H2O (248 mg, 1 mmol, 5 equiv.) were added to the reaction. After the reaction solvent water (1 mL) was added to the tube, the mixture was stirred at a reaction temperature of 80 ° C for 2 hours. Then, the reaction system was cooled to 0 ° C in an ice bath, and triazene 5 (0.2 mmol, 1 equiv.) was added. After stirring at this temperature for 15 minutes, BF3·Et2O (0.2 mmol, 1 equiv.) was slowly added dropwise. Then, the mixture was stirred in an ice bath, and the reaction system was allowed to naturally return to room temperature to continue the reaction for 12 hours. After the reaction was monitored by thin layer chromatography, 5 mL of ethyl acetate was added to the reaction mixture, and anhydrous sodium sulfate and anhydrous magnesium sulfate were added under stirring, and the mixture was stirred for five minutes and then filtered, and the filter cake was washed with ethyl acetate (5 mL x 3). Finally, the filtrate was evaporated under reduced pressure and purified by column chromatography to afford product 6 (eluent: EtOAc:EtOAc:EtOAc Yield: 97%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With sulfur; potassium fluoride; potassium carbonate In N,N-dimethyl-formamide at 80℃; for 31h; | 2.1. General procedure for the preparation of sulfides from triphenyltinchloride, S8, and aryl/benzyl halide catalyzed by CuII-ZSM5 General procedure: A one-necked flask was charged with, aryl/benzyl halides (1mmol),triphenyltin chloride (128 mg, 0.33 mmol), S8 (48 mg), CuII-ZSM5(30 mg), KF (174 mg, 3 mmol), K2CO3 (540 mg, 4 mmol), and DMF(2 mL). The mixture was magnetically stirred and heated at 80 °C for the appropriate reaction time (Table 2). After completion of the reaction,the catalyst was separated by filtration. H2O (5 mL) was addedand the product was extracted with diethyl ether (3 × 5 mL). The combinedorganic phaseswaswashedwith brine (15mL) and dried over anhydrousNa2SO4. The solventwas removed under reduced pressure andpurification was achieved by column chromatography on silica gel (nhexane/EtOAc, 4:1). |
74% | With sulfur; potassium fluoride; copper diacetate; potassium carbonate at 80℃; for 5h; chemoselective reaction; | 1.2. General procedure for the synthesis of phenyl aryl/benzyl sulfides General procedure: A one-necked flask was charged with Cu(OAc)2 (20 mg, 0.1 mmol), potassium carbonate (276 mg, 2.0 mmol), S8 (48 mg, 1.5 mmol), KF (180 mg, 3 mmol), aryl halide (1 mmol), triphenyltin chloride (0.35 mmol) and PEG 200 (2 mL). The mixture was magnetically stirred and heated at 60-80 C for the appropriate reaction time (Table 2). After completion of the reaction, the reaction mixture was cooled to room temperature and H2O (4 mL) was added. The products was extracted with EtOAc (3×4 mL) and dried over anhydrous Na2SO4. Evaporation of the solvent and purification by flash column chromatography on silica gel (EtOAc/n-hexane) gave the desired phenyl aryl sulfides in 70-95% yields. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With copper(l) iodide; 2,6-bis(2'-pyridyl)-4-(p-methoxyphenyl)pyridine; potassium hydroxide In dimethyl sulfoxide at 110℃; for 16h; Inert atmosphere; chemoselective reaction; | General procedure for the preparation of diorgano chalcogenides General procedure: A flame-dried test tube containing a magnetic stirringbar was charged with diorgano dichalcogenide (0.5 mmol), arylhalide (1.0 mmol), KOH (1.0 mmol), and anhydrous DMSO (2mL) [for aryl bromides or chlorides, TBAB (1.0 mmol) was alsoadded]. Then, CuI (10 mol%) and Mtpy (10 mol%) were added tothe above mixture, and the reaction mixture was heated at110 °C under nitrogen. The progress of the reaction was monitoredby TLC. Upon completion of the reaction, the mixture wascooled to r.t., poured into H2O (10 mL), and extracted withEtOAc (3 × 8 mL). The combined organic layers were dried overMgSO4, filtered, and concentrated in vacuo to give the crudeproduct, which was further purified by preparative TLC (silicagel; n-hexane-EtOAc, 9:1). The identities of the products wereconfirmed by IR, 1H and 13C NMR spectroscopic analysis. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85%Spectr. | With indium (III) iodide; In 1,2-dichloro-ethane; at 80℃; for 2h; | General procedure: Typical Procedure: Silyl ether 1c (0.135 g, 0.6 mmol) was added to a suspended solution of thiosilane 2a (0.089 g, 0.5 mmol) and InI3 (0.026 g, 0.05 mmol) in dichloromethane (0.5 mL). The reaction mixture was stirred at room temperature for 2 h and was then quenched by a saturated aqueous solution of NaHCO3. The crude product was extracted with dichloromethane. The combined organic layer was dried over MgSO4, and concentrated under reduced pressure. The NMR yield was determined by 1H-NMR (1H-NMR spectra were recorded on a JMTC-400/54/SS instrument at 400MHz (JEOL Ltd., Tokyo, Japan), using 1,1,2,2-tetrachloroethane as an internal standard. The crude product was purified by flash chromatography (Hexane/EtOAc = 95:5, spherical silica gel 60 μm, 30 g,diameter 2.7 cm, Shoko Scientific Co., Ltd., Kanagawa, Japan) to afford the corresponding thioether 3ca (0.119 g, 95%) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With hexaethylphosphoric triamide In benzene for 0.166667h; Reflux; | 51 Synthesis of benzyl (phenyl) sulfide Sequentially 21 (46.5mg, 0.2mmol, 1.0equiv. ) Liuyi phosphite and amine (59.4mg, 0.24mmol, 1.2equiv. After) was added to the reaction tube, followed by addition of the reaction solvent such as benzene, under reflux for 10 minutes the reaction conditions, the raw material 21 to be exhausted, the reaction system was cooled, the solvent was removed under reduced pressure to give the product was purified by column chromatography 46 (polar eluent: petroleum ether). Yield: 70% |
70% | With hexaethylphosphoric triamide In benzene for 0.166667h; Reflux; | 87 Example 87 Synthesis of benzyl (phenyl) sulfide: Sequentially 3a (46.5mg, 0.2mmol, 1.0equiv.)And hexaethylphosphite (59.4 mg, 0.24 mmol, 1.2 equiv.) Were added to the reaction tube,And then adding the reaction solvent to benzene,The reaction was carried out under reflux conditions for 10 minutes,After the raw material 3a is depleted, the reaction system is cooled,The solvent was removed under reduced pressure,After column chromatography, product 10a (eluent polarity: petroleum ether) was obtained. Yield: 70% |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With ammonium hydroxide; [bis(acetoxy)iodo]benzene In methanol at 0℃; for 0.25h; Flow reactor; Green chemistry; | |
93% | With [bis(acetoxy)iodo]benzene; ammonium carbamate In methanol at 25℃; for 3h; chemoselective reaction; | |
93% | With [bis(acetoxy)iodo]benzene; ammonium carbamate In methanol at 25℃; for 3h; |
92% | With [bis(acetoxy)iodo]benzene; ammonium carbamate In methanol at 20℃; for 0.5h; | |
90% | With diacetoxyiodo-3,4,5-trifluorobenzene; water; ammonium carbonate at 25℃; for 16h; Green chemistry; | |
89% | With [bis(acetoxy)iodo]benzene; ammonium carbonate In methanol Inert atmosphere; Schlenk technique; | |
Multi-step reaction with 2 steps 1: acetic acid; dihydrogen peroxide / 1 h / 0 °C 2: [bis(acetoxy)iodo]benzene; ammonium hydroxide / methanol / 0.25 h / 0 °C / Flow reactor; Green chemistry | ||
With [bis(acetoxy)iodo]benzene; ammonium carbonate In methanol at 20℃; Inert atmosphere; | ||
With [bis(acetoxy)iodo]benzene; ammonium carbamate In methanol at 20℃; | ||
With ammonium carbonate; I,I-bis(acetoxy)iodobenzene In methanol at 20℃; for 0.166667h; | 3.2.1. General Procedure A for the Synthesis of Substrates 1a-1w General procedure: To a stirred solution of sulfide (1 mmol) in MeOH (10 mL) was added (NH4)2CO3 (1.5 equiv.).Subsequently, PhI(OAc)2 (2.3 equiv.) was added, and the solution was stirred at rt for 10 min.The solvent was removed under reduced pressure, and the crude product was purified by flash columnchromatography eluted with dichloromethane (DCM)/MeOH from 30:1 to 10:1 to give the desiredproduct 1. Compounds 1e, 1f, 1q, R-1a, and S-1a were purchased from commercial sources and usedwithout further purification. Compounds 1a-1c, 1g-1i, 1l-1p, 1r-1w are known compounds. | |
With ammonium carbamate; [bis(acetoxy)iodo]benzene In methanol at 20℃; for 0.5h; | ||
With [bis(acetoxy)iodo]benzene; ammonium carbamate In methanol at 20℃; for 0.5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | With cobalt ferrite; potassium acetate; thiourea In dimethyl sulfoxide at 80℃; for 1.5h; | 2.3. General procedure for the synthesis of unsymmetrical sulfides A glass tube was charged with nitroarene (1 mmol), alkyl halide (1.2 mmol), thiourea (1.3 mmol), KOAc (1.5 mmol), DMSO (1 mL) and CoFe2O4 (5 mol%). The reaction mixture was stirred at 80 °C for an appropriate amount of time. The progress of the reaction was monitored using TLC (n-hexane-EtOAc, 9:1). After completion of the reaction, the reaction mixture was allowed to cool to room temperature. The magnetic nanoparticles of the catalyst were collected using a magnet. Then, 10mL of water was added to the mixture and the product was extracted with ethyl acetate (3 × 10 mL). The organic phase was dried over CaCl2, concentrated under vacuum and purified by column chromatography on silica gel (n-hexane-EtOAc, 9:1). All products were known compounds and were identified by comparison of their 1H NMR spectra with those of authentic samples [25,26]. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With cobalt ferrite; potassium acetate; thiourea In dimethyl sulfoxide at 80℃; for 1.5h; | 2.3. General procedure for the synthesis of unsymmetrical sulfides A glass tube was charged with nitroarene (1 mmol), alkyl halide (1.2 mmol), thiourea (1.3 mmol), KOAc (1.5 mmol), DMSO (1 mL) and CoFe2O4 (5 mol%). The reaction mixture was stirred at 80 °C for an appropriate amount of time. The progress of the reaction was monitored using TLC (n-hexane-EtOAc, 9:1). After completion of the reaction, the reaction mixture was allowed to cool to room temperature. The magnetic nanoparticles of the catalyst were collected using a magnet. Then, 10mL of water was added to the mixture and the product was extracted with ethyl acetate (3 × 10 mL). The organic phase was dried over CaCl2, concentrated under vacuum and purified by column chromatography on silica gel (n-hexane-EtOAc, 9:1). All products were known compounds and were identified by comparison of their 1H NMR spectra with those of authentic samples [25,26]. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
58% | With tris(bipyridine)ruthenium(II) dichloride hexahydrate; potassium carbonate In water; dimethyl sulfoxide at 20℃; for 5h; Irradiation; Inert atmosphere; | 7 Example 7: Synthesis of benzyl phenyl sulfide In the evacuated reaction tube, Ru (bpy) 3Cl2 6H2O (3.1 mg, 4 * 10-3 mmol), substrate 9a (38.4 mg, 0.2 mmol), substrate 2 (225.8 mg, 1 mmol) , K2CO3 (55.4 mg, 0.4 mmol), DMSO (containing 50 eq H2O) (About 0.78 mL DMSO / 0.22 mL H2O) (1 mL) was added and the reaction was stirred at room temperature for 5 hours under irradiation with a 8 W compact energy-saving lamp to monitor the progress of the reaction. After completion of the reaction, ethyl acetate (10 mL) was added to the system at room temperature, dried over anhydrous magnesium sulfate Dried, filtered, concentrated and chromatographed to give pale yellow solid 9 (23.1 mg, 58%), |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | With zinc(II) acetate dihydrate; N-ethyl-N,N-diisopropylamine; eosin y In methanol for 24h; Irradiation; Inert atmosphere; | |
73% | With zinc(II) acetate dihydrate; N-ethyl-N,N-diisopropylamine; eosin y In methanol; acetonitrile for 24h; Irradiation; Inert atmosphere; | 35 Synthesis of phenyl (benzyl) sulfide 4f In 25mL reaction tube, a nitrogen exchange was evacuated, was added eosin the Y (the Y Eosin) (2.5mg,. 4 * 10-3mmol), substrate 1a (73.6mg, 0.2mmol), the substrate 2b (135.8mg, 0.6mmol ), zinc acetate [Zn (OAc)2· 2H2O] (4.3mg, 0.02mmol), diisopropylethyl amine (DIPEA) (66μL, 0.4mmol), methanol (MeOH) (0.5mL), stirred for 24 hours at 23 watt lamp spiral irradiation, the reaction is completed after filtered, and concentrated to give a colorless liquid separation 4f (29.2mg, 73%) by column chromatography (PE), Rf0.4(PE) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | Stage #1: racemic methyl phenyl sulfoxide With diisopropylaminomagnesium chloride lithium chloride In tetrahydrofuran at 0℃; for 1h; Inert atmosphere; Stage #2: phenylmagnesium bromide In tetrahydrofuran; diethyl ether at 65℃; for 14h; | I.1. Two-step synthesis of benzyl(phenyl)sulfide (1b) General procedure: Step 1: The preparation was adapted from the procedure reported by Kakarla and co-workers,[5] as follows: to a solution of thioanisole 1a (0.3 mmol, 1.0 equiv.), silica gel (0.99 mmol, 3.33 equiv) and acetic anhydride (0.36 mmol, 1.2 equiv.) in DCM (5 mL) stirred at r.t., hydrogen peroxide (0.33 mmol,30% w/w solution in water, 1.1 equiv.) was added. The resulting mixture was stirred at r.t. for 24 h,then filtered, diluted in water and extracted with DCM. The combined organic layers were washed with brine, dried over Na2SO4, filtered and concentrated in vacuo. The crude mixture could be purified by column chromatography (DCM, Rf = 0.15) to obtain pure 2a (39 mg, 92% yield) as acolorless oil whose characterization data were in accordance with reported literature.[6]Step 2: The previously reported procedure [4] was followed: to a solution of 2a (39 mg, 0.28 mmol, 1.0equiv.) in anhydrous THF (2.4 mL) stirred at 0°C under Ar, a solution of DIPAMgCl·LiCl (0.52 mL of a0.58 M solution in THF, 0.31 mmol, 1.1 equiv.) was added dropwise. The resulting pale yellow solution was stirred at 0 °C for 1 h, then phenylmagnesium bromide (0.15 mL of a 2 M solution inEt2O, 0.29 mmol, 1.05 equiv.) was added dropwise. The resulting dark yellow solution was heated to 65°C and stirred for 14 h. The reaction was quenched with saturated aqueous NH4Cl (1 mL). The crude mixture was extracted with Et2O (3 x 1 mL), and the combined organic layers were dried over Na2SO4, filtered and concentrated in vacuo, affording a crude mixture that was analyzed by 1H-NMR(using 1,1,2,2-tetrachloroethane as internal standard), detecting thioether 1b in 73% yield. |
71% | Stage #1: racemic methyl phenyl sulfoxide With diisopropylaminomagnesium chloride lithium chloride In tetrahydrofuran at 0℃; for 1h; Inert atmosphere; Stage #2: phenylmagnesium bromide In tetrahydrofuran; diethyl ether at 0 - 65℃; for 14h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With bis(tri-ortho-tolylphosphine)palladium(0) In para-xylene at 150℃; Molecular sieve; Glovebox; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
0.79 g | Into a two-necked flask with a volume of 20 mL were introduced benzyl(phenyl)sulfane (0.60 g, 3.0 mmol) and tetrahydrofuran (THF) (6.0 mL), and the mixture was cooled to -78 C. To this solution was added n-butyllithium (1.56 M hexane solution, 2.019 mL, 3.15 mmol) and the mixture was stirred for 1 hout To the resulting solution was thrther added a solution of 4-vinylbenzaldehyde (0.4 g, 3.0 mmol) in THF (9.0 mL) and the mixture was stirred for 3 hours. During the reaction, the reaction temperature gradually increased to -30 C. The resulting reaction solution was poured into ice water and extracted with diethyl ether three times. The resulting diethyl ether solution was washed with watet Further, magnesium sulfate was added to remove water in the solution. Then, the magnesium sulfate was removed by filtration. The filtrate was concentrated and subjected to silica gel colunm chromatography (hexane:ethyl acetate=1 0:1) to separate a compound 1(0.79 g) shown below. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With (phthalocyaninato)iron(II); sodium nitrite In chloroform; water at 40℃; for 14h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With potassium hexamethylsilazane In diethyl ether at 40℃; for 24h; Sealed tube; Schlenk technique; Inert atmosphere; chemoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With potassium hexamethylsilazane In diethyl ether at 40℃; for 24h; Sealed tube; Schlenk technique; Inert atmosphere; chemoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With potassium hexamethylsilazane In diethyl ether at 40℃; for 24h; Sealed tube; Schlenk technique; Inert atmosphere; chemoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With potassium hexamethylsilazane In diethyl ether at 40℃; for 24h; Sealed tube; Schlenk technique; Inert atmosphere; chemoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With potassium hexamethylsilazane In diethyl ether at 40℃; for 24h; Sealed tube; Schlenk technique; Inert atmosphere; chemoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With potassium hexamethylsilazane In diethyl ether at 40℃; for 24h; Sealed tube; Schlenk technique; Inert atmosphere; chemoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With potassium hexamethylsilazane In diethyl ether at 40℃; for 24h; Sealed tube; Schlenk technique; Inert atmosphere; chemoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 76% 2: 17% | With bis[dichloro(pentamethylcyclopentadienyl)iridium(III)]; copper diacetate at 80℃; for 12h; Sealed tube; | |
1: 50% 2: 44% | With bis[dichloro(pentamethylcyclopentadienyl)iridium(III)]; copper diacetate at 80℃; for 12h; Overall yield = 94 percent; | 51 Example 51 A mixture of 0.4 mmol of thioether of structure AU, 0.8 mmol of acetonitrile, 0.82 mmol of [Cp*IrCl2]2, and 0.48 mmol of Cu(OAc) 2 was added to 2 mL of hexafluoroisopropanol at 80 ° C in an air atmosphere. Stirring reaction in alcohol for 12h, The reaction mixture was cooled to room temperature and filtered through Celite.Acid ethyl ester / petroleum ether = 1:10, ν / ν), the product is obtained, the product includes the monoalkenylation product a and the di-alkenylation product b, aThe yield was 50% and the yield was 44%, and the sum of the two products was 94%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1.4%Chromat.; 79.1%Chromat. | Copper(I) cyanide (8.0 mg, 90 μmol) was placed in a 20-mL glassSchlenk tube equipped with a Teflon -coated stir bar. After vacuum-drying, solvent (4.8 mL) and a 1.6 M solution of phenyllithium (2) inBu 2 O (1.9 mL, 3.0 mmol) were added at -50 C under Ar. To thissolution, freshly distilled carbon disulfide (0.22 mL, 3.6 mmol) wasadded dropwise and the resulting solution was stirred for 0.5 h at -50 C, then cooling bath was removed. After the mixture was stirred for 0.5h at rt, DMF (2.0 mL) and benzyl bromide (0.43 mL, 3.6 mmol) wereadded, and the mixture was stirred for 4 h. To this solution, water (8.0mL) was added and the organic phase was analyzed by GC-MS. Eachproduct was detected in the following retention time: biphenyl (10.3min), benzyl phenyl sulfide( 4) (14.2 min), thiobenzophenone (15.4min), benzyl benzodithioate (3) (19.7 min). Each product was identi-fied with commercially available samples. Biphenyl: MS (EI): 154 [M] +(100), 153 [M-H] + (39.5), 152 [M-H-H] + (31.5), 76 [Ph-H] +(19.8). Benzyl phenyl sulfide(4): 1 H NMR (400 MHz, CDCl 3 ) δ: 7.36-7.22 (10H, m), 4.16 (2H, s); 13 C{ 1 H} NMR (101 MHz, CDCl 3 ) δ: 137.7(1C), 134.1 (1C), 131.5 (2C), 129.3 (2C), 128.6 (2C), 128.2 (2C), 127.2(1C), 127.0 (1C), 40.0 (1C); MS (EI): 200 [M] + (14.5), 91 [Bn] + (100),77 [Ph] + (1.8). Thiobenzophenone: MS (EI): 198 [M] + (62.4), 165 [M-S-H] + (100), 121 [M-Ph] + (91.1), 77 [Ph] + (42.5). Benzyl benzo-dithioate (3): 1 H NMR (400 MHz, CDCl 3 ) δ: 8.02-7.98 (2H, m), 7.52(1H, tt, J = 7.4, 1.2 Hz), 7.41-7.26 (7H, m), 4.60 (2H, s); 13 C{ 1 H} NMR(101 MHz, CDCl 3 ) δ: 227.5 (1C), 144.8 (1C), 135.1 (1C), 132.6 (1C),129.4 (2C), 128.9 (2C), 128.5 (2C), 127.9 (1C), 127.1 (2C), 42.4 (1C);MS (EI): 244 [M] + (19.0), 153 [M-Bn] + (2.1), 121 [M-SBn] + (91.8), 91[Bn] + (100), 77 [Ph] + (37.5). | |
50.2%Chromat.; 31.5%Chromat. | Copper(I) cyanide (8.0 mg, 90 μmol) was placed in a 20-mL glassSchlenk tube equipped with a Teflon -coated stir bar. After vacuum-drying, solvent (4.8 mL) and a 1.6 M solution of phenyllithium (2) inBu 2 O (1.9 mL, 3.0 mmol) were added at -50 C under Ar. To thissolution, freshly distilled carbon disulfide (0.22 mL, 3.6 mmol) wasadded dropwise and the resulting solution was stirred for 0.5 h at -50 C, then cooling bath was removed. After the mixture was stirred for 0.5h at rt, DMF (2.0 mL) and benzyl bromide (0.43 mL, 3.6 mmol) wereadded, and the mixture was stirred for 4 h. To this solution, water (8.0mL) was added and the organic phase was analyzed by GC-MS. Eachproduct was detected in the following retention time: biphenyl (10.3min), benzyl phenyl sulfide( 4) (14.2 min), thiobenzophenone (15.4min), benzyl benzodithioate (3) (19.7 min). Each product was identi-fied with commercially available samples. Biphenyl: MS (EI): 154 [M] +(100), 153 [M-H] + (39.5), 152 [M-H-H] + (31.5), 76 [Ph-H] +(19.8). Benzyl phenyl sulfide(4): 1 H NMR (400 MHz, CDCl 3 ) δ: 7.36-7.22 (10H, m), 4.16 (2H, s); 13 C{ 1 H} NMR (101 MHz, CDCl 3 ) δ: 137.7(1C), 134.1 (1C), 131.5 (2C), 129.3 (2C), 128.6 (2C), 128.2 (2C), 127.2(1C), 127.0 (1C), 40.0 (1C); MS (EI): 200 [M] + (14.5), 91 [Bn] + (100),77 [Ph] + (1.8). Thiobenzophenone: MS (EI): 198 [M] + (62.4), 165 [M-S-H] + (100), 121 [M-Ph] + (91.1), 77 [Ph] + (42.5). Benzyl benzo-dithioate (3): 1 H NMR (400 MHz, CDCl 3 ) δ: 8.02-7.98 (2H, m), 7.52(1H, tt, J = 7.4, 1.2 Hz), 7.41-7.26 (7H, m), 4.60 (2H, s); 13 C{ 1 H} NMR(101 MHz, CDCl 3 ) δ: 227.5 (1C), 144.8 (1C), 135.1 (1C), 132.6 (1C),129.4 (2C), 128.9 (2C), 128.5 (2C), 127.9 (1C), 127.1 (2C), 42.4 (1C);MS (EI): 244 [M] + (19.0), 153 [M-Bn] + (2.1), 121 [M-SBn] + (91.8), 91[Bn] + (100), 77 [Ph] + (37.5). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With tert.-butylhydroperoxide; caesium carbonate; potassium iodide In water at 20℃; for 20h; | (3-Methoxyphenyl)(phenyl)sulfane (3a); Typical Procedure General procedure: A vial equipped with a stir bar was charged with thiol 2 (0.2 mmol, 2equiv), arylhydrazine hydrochloride 1 (0.1 mmol, 1 equiv), Cs2CO3(0.1 mmol, 1 equiv), KI (50 mol%), and TBHP (0.4 mmol, 4 equiv). H2O (0.3 mL) was added and the vial was capped. The resulting mixture was stirred at rt for 20 h. Upon completion of the reaction, the resulting mixture was extracted with EtOAc. The combined organic layer was dried (anhyd Na2SO4). After the removal of the solvent under reduced pressure, the crude product was purified by column chromatography(silica gel, EtOAc/hexane gradient) to provide the desired product 3a as a pale yellow oil; yield: 19 mg (87%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 74% 2: 8% | With nanolayered cobalt-molybdenum sulphide with Co/(Mo+Co) mole ratio 0.83 In toluene at 180℃; for 10h; Inert atmosphere; Autoclave; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With tris(triphenylphosphine)ruthenium(II) chloride; Benzohydroxamic acid; silver(I) acetate In methanol at 30℃; for 0.166667h; Schlenk technique; | |
81% | With silver hexafluoroantimonate; tris(triphenylphosphine)ruthenium(II) chloride; benzamide In dichloromethane at 20℃; for 0.166667h; | 4 General procedure: In an air atmosphere, N-(alkanoyloxy)amide and disubstituted sulfide are used as raw materials, ruthenium complexes are used as catalysts, and in the presence of silver salt additives and ligands, the reaction is carried out in the reaction solvent. After the reaction, the N-substituted sulfimide compound is obtained through recrystallization. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With tris(triphenylphosphine)ruthenium(II) chloride; Benzohydroxamic acid; silver(I) acetate In methanol at 30℃; for 0.166667h; Schlenk technique; | |
81% | With silver hexafluoroantimonate; [ruthenium(II)(η6-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2; benzoic acid In 1,2-dichloro-ethane at 90℃; for 0.133333h; | 5 General procedure: In an air atmosphere, N-(alkanoyloxy)amide and disubstituted sulfide are used as raw materials, ruthenium complexes are used as catalysts, and in the presence of silver salt additives and ligands, the reaction is carried out in the reaction solvent. After the reaction, the N-substituted sulfimide compounds can be obtained through column chromatography separation. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With tris(triphenylphosphine)ruthenium(II) chloride; Benzohydroxamic acid; silver(I) acetate In methanol at 25℃; for 0.166667h; | 6 General procedure: In an air atmosphere, N-(alkanoyloxy)amide and disubstituted sulfide are used as raw materials, ruthenium complexes are used as catalysts, and in the presence of silver salt additives and ligands, the reaction is carried out in the reaction solvent. After the reaction, the N-substituted sulfimide compound is obtained through recrystallization. |
83% | With tris(triphenylphosphine)ruthenium(II) chloride; Benzohydroxamic acid; silver(I) acetate In methanol at 30℃; for 0.166667h; Schlenk technique; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With tris(triphenylphosphine)ruthenium(II) chloride; Benzohydroxamic acid; silver(I) acetate In methanol at 30℃; for 0.166667h; Schlenk technique; | |
91% | With tris(triphenylphosphine)ruthenium(II) chloride; Benzohydroxamic acid; silver(I) acetate In methanol at 25℃; for 0.166667h; | 1 General procedure: In an air atmosphere, N-(alkanoyloxy)amide and disubstituted sulfide are used as raw materials, ruthenium complexes are used as catalysts, and in the presence of silver salt additives and ligands, the reaction is carried out in the reaction solvent, after the reaction, the N-substituted sulfimide compounds can be obtained through column chromatography separation, |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With tris(triphenylphosphine)ruthenium(II) chloride; Benzohydroxamic acid; silver(I) acetate In methanol at 30℃; for 0.166667h; Schlenk technique; | |
60% | With ruthenium trichloride; triphenylphosphine; silver(I) chloride In ethanol at 0℃; for 5h; | 2 General procedure: In an air atmosphere, N-(alkanoyloxy)amide and disubstituted sulfide are used as raw materials, ruthenium complexes are used as catalysts, and in the presence of silver salt additives and ligands, the reaction is carried out in the reaction solvent. After the reaction, the N-substituted sulfimide compound is obtained through recrystallization. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With tris(triphenylphosphine)ruthenium(II) chloride; Benzohydroxamic acid; silver(I) acetate In methanol at 30℃; for 0.166667h; Schlenk technique; | |
88% | With ruthenium(II) chloride; silver nitrate In toluene at 100℃; for 0.0833333h; | 3 General procedure: In an air atmosphere, N-(alkanoyloxy)amide and disubstituted sulfide are used as raw materials, ruthenium complexes are used as catalysts, and in the presence of silver salt additives and ligands, the reaction is carried out in the reaction solvent. After the reaction, the N-substituted sulfimide compounds can be obtained through column chromatography separation. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
64% | With dipotassium hydrogenphosphate; benzophenone; 4,4'-di-tert-butyl-2,2'-bipyridine; nickel dichloride at 20℃; for 12h; Inert atmosphere; Irradiation; | 1 Example 1 Under the protection of nitrogen,Add N-(phenylthio)phthalamide (48.2mg),Benzophenone (7.9mg),NiCl2(2.2mg),4,4'-di-tert-butyl-2,2'-bipyridine (2.7mg),K2HPO4 (70mg) addedInto the Shrek reaction tube,Finally add toluene (5mL),Placed under two 23W CFL lights,Irradiate the reaction at room temperature for 12h,After the reaction,Add 10 mL of water to the reaction solution,Then extract with 3x15ml ethyl acetate,Dry the organic phase with anhydrous sodium sulfate,Desolventize (ie, remove the solvent by rotary evaporation),Column chromatography is used to separate the target product.The target product is a white solid,The yield was 64%.The column chromatography method is:Elute with the concentration of pure petroleum ether,Collect and combine the eluent containing the target compound,The solvent was removed by rotary evaporation and then dried.The post-processing operation steps of this embodiment are applicable to other embodiments. |
Tags: 831-91-4 synthesis path| 831-91-4 SDS| 831-91-4 COA| 831-91-4 purity| 831-91-4 application| 831-91-4 NMR| 831-91-4 COA| 831-91-4 structure
[ 6317-56-2 ]
(4-(Phenylthio)phenyl)methanol
Similarity: 0.77
[ 6317-56-2 ]
(4-(Phenylthio)phenyl)methanol
Similarity: 0.77
[ 1208-87-3 ]
(4-(Chloromethyl)phenyl)(phenyl)sulfane
Similarity: 0.72
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H252 | Self-heating in large quantities; may catch fire |
H260 | In contact with water releases flammable gases which may ignite spontaneously |
H261 | In contact with water releases flammable gas |
H270 | May cause or intensify fire; oxidizer |
H271 | May cause fire or explosion; strong oxidizer |
H272 | May intensify fire; oxidizer |
H280 | Contains gas under pressure; may explode if heated |
H281 | Contains refrigerated gas; may cause cryogenic burns or injury |
H290 | May be corrosive to metals |
Health hazards | |
Code | Phrase |
H300 | Fatal if swallowed |
H301 | Toxic if swallowed |
H302 | Harmful if swallowed |
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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