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CAS No. : | 5335-84-2 | MDL No. : | MFCD00017832 |
Formula : | C12H8Br2S2 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | N/A |
M.W : | 376.13 g/mol | Pubchem ID : | - |
Synonyms : |
|
Signal Word: | Danger | Class: | 8 |
Precautionary Statements: | P261-P264-P271-P280-P302+P352-P304+P340-P305+P351+P338-P310-P332+P313-P362-P403+P233-P405-P501-P273-P391 | UN#: | 1759 |
Hazard Statements: | H315-H318-H335-H410 | Packing Group: | Ⅲ |
GHS Pictogram: |
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Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With tert.-butylnitrite; ascorbic acid In acetonitrile at 20℃; for 4 h; Schlenk technique; Inert atmosphere | General procedure: For solid disulfide: A 10-mL Schlenk tube with a magnetic stirring bar was charged with aniline(0.2 mmol) and disulfide (0.2 mmol). The tube was evacuated and backfilled with dry nitrogen (this operation was repeated three times). Acetonitrile (1 mL) was added by syringe, followed by L-ascorbicacid (0.5 equiv., 20 mg) dissolved in 0.1 mL DMSO. For liquid disulfide: A 10-mL Schlenk tube with a magnetic stirring bar was charged with aniline(0.2 mmol). The tube was evacuated and backfilled with dry nitrogen (this operation was repeated three times). Acetonitrile (1 mL) was added by syringe, followed by disulfide (0.2 mmol or 0.4mmol) and L-ascorbic acid (0.5 equiv., 20 mg) dissolved in 0.1 mL DMSO.The mixture was stirred vigorously for 1 minute before t-BuONO (0.3 mmol, 36 μL) was added via syringe. After the resulting mixture was stirred at 20 °C for 4 hours, the solvent was removed under reduced pressure. Purification of the crude product was achieved by column chromatography |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With iodine In ethanol for 0.166667h; Reflux; | |
100% | With iodine Schlenk technique; Inert atmosphere; | |
100% | With Cs2CO3 In N,N-dimethyl-formamide at 20℃; |
99% | With 1-n-butyl-3-methylimidazolium methylselenite at 100℃; for 3h; | General procedure for the oxidation of thiols with [bmim][SeO2(OCH3)]: Method A: In a Schlenk tube under open atmosphere and at room temperature, the corresponding thiol (1.0 mmol) was added to [bmim][SeO2(OCH3)]10 (1.0 mL). The reaction mixture was allowed to stir at 60 °C for the time indicated in Table 1. The progress of the reaction was monitored by TLC. Method B: In a 10 mL glass vial equipped with a small magnetic stirring bar, containing 1.0 mL of [bmim][SeO2(OCH3)] was added the thiol (1.0 mmol). The vial was tightly sealed with an aluminum/Teflon crimp top. The mixture was then irradiated in a microwave reactor (CEM Explorer) for the time indicated in Table 2 at 30 °C (temperature was measured with an IR sensor on the outer surface of the reaction vial), using an irradiation power of 100 W and pressure of 150 psi. After the reaction was complete, the product was extracted by successive washings with petroleum ether (3 × 5 mL), dried over MgSO4, and concentrated in vacuum. The residue was purified by column chromatography on silica gel using ethyl acetate/hexanes as the eluent. |
99% | With poly(4-vinylpyridinium nitrate) I In acetonitrile at 20℃; for 2.5h; | |
99% | With poly(4-vinylpyridinium tribromide) In dichloromethane at 20℃; for 0.666667h; | |
99% | With silica sulfuric acid; potassium iodide at 20℃; for 0.25h; | General procedure for the oxidative coupling of thiols using PVPP-H2O2/SiO2-OSO3H/KI General procedure: To a suspension of polyvinylpolypyrrolidone-supported hydrogen peroxide (0.175 g),silica sulfuric acid (0.1 g) and potassium iodide (0.02 mmol) in dichloromethane or ethylacetate (5 mL) was added a thiol (1 mmol), and the mixture was stirred at room temperaturefor the specified time (Table I). The progress of the reaction was monitored by TLC. Aftercompletion of the reaction, the reaction mixture was filtered and the residue washed withCH2Cl2 (20 mL), (the residue of entry 5 was washed with ethanol). Finally, the organicsolvent was evaporated and pure product was obtained as judged by TLC and 1H-NMRspectroscopy. |
99% | With polyvinylpolypyrrolidonium tribromide In ethanol at 20℃; for 0.133333h; Green chemistry; | General procedure: A 25 mL round-bottom flask was charged with thiol (1 mmol), polyvinylpolypyrrolidoniume tribromide (1.2 gr), and EtOH(5 mL) as solvent. The reaction mixture was stirred at room temperature, and the progressof the reaction was monitored by TLC. After completion of the reaction, corresponding disulfides easily obtained by passing of reaction mixture through a short column using dichlromethane and acetone (95:5) as eluent. |
99% | With dihydrogen peroxide In lithium hydroxide monohydrate; acetonitrile at 20℃; for 0.25h; Green chemistry; chemoselective reaction; | 2.3. Typical procedure for selective oxidation of thiols to disulfides General procedure: In a typical oxidative coupling reaction, 2 mmol thiophenol was dissolved in acetonitril (3 mL). Then 0.03 g (0.02 mmol) catalyst and 0.25 g hydrogenperoxide (30% aqueous) were added. The reaction mixture was stirred for the various reaction times as indicated in Table 2. After the completion of the reaction (determined by TLC), which is associated with precipitation of disulfide and elimination of thiol odor. The catalyst was separated by filtration, washed with ethyl acetate and heated at 60 °C prior to its reuse in the next reaction. The combined organic filtrates were then washed with water and the organic layer separated and dried over magnesium sulfate. The product was obtained after removal of the solvent. The conversion was determined by isolated yield and compounds were characterized by 1H and 13C NMR. In most cases, the products could be isolated in their pure forms by simple filtration and evaporation of the solvent. |
99% | With salen complex of Cu(II) immobilized on Fe3O4 nanoparticles; dihydrogen peroxide In ethanol at 20℃; for 2h; | 2.6 General procedure for the oxidative coupling of thiols General procedure: A 25mL round-bottom flask was charged with thiol (1mmol), H2O2 33% (0.5mL), and catalyst (0.01g) in ethanol as solvent. The reaction mixture was stirred at room temperature, and the progress of the reaction was monitored by TLC. After completion of the reaction, the catalyst was separated by an external magnet and the product was extracted with CH2Cl2. The combined organics were washed with water (5mL) and dried over anhydrous Na2SO4. Finally, the solvent was removed to give the corresponding pure disulfides |
99% | With Eosin In ethanol for 16h; Irradiation; | |
99% | With dihydrogen peroxide In ethanol at 20℃; for 0.5h; Green chemistry; chemoselective reaction; | 2.5. General procedure for the oxidative coupling of thiols into disulfides using H2O2 in the presence of M-Salen-MNPs General procedure: M-Salen-MNPs (0.01 g) was added to a mixture of thiol (1 mmol) and H2O2 (0.4 mL) in ethanol (5 mL). Then the mixture was stirred for the appropriate time at room temperature. The progress was monitored by TLC. After completion of the reaction, the catalyst was separated by an external magnet and the mixture was washed with ethyl acetate. The product was extracted with ethylacetate. The organic layer was dried over anhydrous Na2SO4 (1.5 g). In some cases, the product was recrystallized from ethanol for further purification and products were obtained in good to high yield. |
99% | With dihydrogen peroxide In dichloromethane at 20℃; for 1.66667h; | |
99% | With (S)-tetrahydrotellurophen-3-amine hydrochloride; dihydrogen peroxide In dichloromethane at 25℃; Flow reactor; | |
98% | With calcium hypochlorite; Montmorillonite K10 In hexane at 20℃; for 0.5h; | |
98% | With aluminum(III) oxide; dimethyl sulfoxide at 40℃; for 0.5h; | |
98% | With tungstate sulfuric acid; NaNO2 In dichloromethane at 20℃; for 0.116667h; | |
98% | With trimethylphenylammonium perbromide In ethyl acetate at 20℃; for 0.0833333h; | |
98% | With aluminum(III) oxide In neat (no solvent) for 0.333333h; Milling; chemoselective reaction; | |
98% | With potassium bromate; hexaammonium heptamolybdate tetrahydrate In lithium hydroxide monohydrate; acetonitrile at 20℃; for 0.0833333h; | Typical Procedure General procedure: 4-chlorothiophenol (0.145 g, 1 mmol) was added to a heterogeneous mixture of KBrO3 (0.167 g, 1 mmol), (NH4)6Mo7O24·4H2O (0.124 g, 10 mmol%), and CH3CN/H2O (7:3) (5 mL) and the mixture was stirred under a hood for 4 min at ambient atmosphere and room temperature. The progress of the reaction was monitored by TLC (eluent: EtOAc/n-C6H14, 1/13). After completion, CH2Cl2 (20 mL) was added and the reaction mixture was filtered. The filtrate was washed with 5% NaOH, water, and dried over anhydrous MgSO4. Finally, evaporation of the solvent gave the product with sufficient purity formost purposes |
98% | With Cu(NO<SUB>3</SUB>)<SUB>2</SUB>3H<SUB>2</SUB>O In lithium hydroxide monohydrate; ethyl acetate at 20℃; for 0.3h; Green chemistry; | |
98% | With dihydrogen peroxide In ethanol at 20℃; for 2h; | |
98% | With dihydrogen peroxide In ethanol at 20℃; for 2h; | |
98% | With titanium(IV) dioxide; oxygen In acetonitrile for 0.0833333h; Irradiation; | |
97% | With oxygen In 5,5-dimethyl-1,3-cyclohexadiene at 120℃; for 4h; | |
97% | With dihydrogen peroxide In neat (no solvent) at 20℃; for 0.25h; chemoselective reaction; | |
97% | With dihydrogen peroxide In ethanol at 20℃; for 3h; Green chemistry; | General procedure for oxidative coupling of thiols General procedure: Dopamine sulfamic acid-functionalized magnetic Fe3O4 nanoparticles (DSA(at)MNPs) (0.004 g) were added to solution of thiol (1 mmol) and H2O2 33 % (0.5 mL) in ethanol (10 mL). The reaction mixture was stirred at room temperature, and the progress of the reaction was monitored by TLC. After completion of the reaction, the catalyst was separated using an external magnet, and the product was extracted with CH2Cl2 and dried over anhydrous Na2SO4. Finally, the solvent was removed by simple evaporation to give the corresponding pure disulfides. |
97% | With dihydrogen peroxide In ethanol at 20℃; for 0.333333h; Green chemistry; | General procedure for the oxidative coupling of thiols to the disulfides General procedure: A mixture of thiol (1 mmol), hydrogen peroxide (0.5 mL) and the catalyst (0.005 g) in ethanol (2 mL) was stirred at ambient temperature. Reaction progress was monitored by TLC (acetone: n-hexane, 2:8). After completion of the reaction, catalyst was separated by an external magnet and washed with ethyl acetate; next, the product was extracted with ethyl acetate (5 mL 9 4). The organic layer was dried over anhydrous Na2SO4 (1.5 g). Finally, the organic solvents were evaporated, and the corresponding disulfides were obtained in high to excellent yields (88-98%). |
97% | With dihydrogen peroxide In acetonitrile at 20℃; for 0.583333h; Green chemistry; | |
97% | With iron phthalocyanine In tetrahydrofuran at 20℃; for 0.333333h; | |
97% | With dihydrogen peroxide In ethanol; lithium hydroxide monohydrate at 20℃; for 0.333333h; Green chemistry; | General procedure for the oxidative coupling of thiols into disulfides General procedure: Fe3O4MCM-41Ni-P2C (10 mg) was added to a mixture of thiol (1 mmol) and 33% H2O2 (0.4 mL) in ethanol (3 mL). The resulting reaction mixture was stirred for the specified time at room temperature (the progress of reaction was monitored by TLC). After completion of the reaction, the catalyst was separated by an external magnet and the product was washed with ethyl acetate. Then organic layer was dried over anhydrous Na2SO4 (1.5 g). Finally, the organic solvent was removed by simple evaporation and disulfides were obtained in very high isolated yields. |
97% | With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; oxygen In ethanol for 1.75h; Sealed tube; Irradiation; chemoselective reaction; | 3.2 Procedure for the oxidation of thiols to disulfides General procedure: 0.6 mmol of thiol 1 and 90 μL (1/3 mol/L) TEMPO/EtOH (and 1.8 mmol of thiol 3) were combined in a 10 mL Pyrex vessel with 1 mL of EtOH dissolved. Subsequently, O2 was injected into the sealed vessel to reach 0.1 MPa of pressure. Then the reaction mixture was magnetically stirred at 1500 rpm and simultaneously illuminated with 3 W blue LEDs until it came to an end monitored by thin layer chromatography (TLC). The reaction pressure was released and the crude products were purified with column chromatograph (petroleum ether: ethyl acetate = 80:1). Then the target product was obtained. |
96% | With dimethyl sulfoxide at 90℃; for 6h; | |
96% | With potassium permanganate supported on montmorillonite K10 In dichloromethane at 20℃; for 0.5h; | |
96% | With nickel(II) ferrite; dihydrogen peroxide In acetonitrile at 20℃; for 0.0833333h; Green chemistry; chemoselective reaction; | |
96% | With dihydrogen peroxide In ethanol at 20℃; for 2h; Green chemistry; | |
96% | With dihydrogen peroxide In ethyl acetate at 20℃; for 2.66667h; | General procedure for the oxidative coupling of thiols General procedure: Boehmite-SSA (0.002 g) was added to a mixture of thiol(1 mmol) and H2O2 (0.4 mL) in ethyl acetate (2 mL). Then,the mixture was stirred for the appropriate time at room temperature. The progress of reaction was monitored byTLC. After completion of the reaction, the catalyst was separated by filtration and the mixture was washed with ethyl acetate. The product was extracted with ethyl acetate.The organic layer was dried over anhydrous Na2SO4(1.5 g). The products were obtained in good to high yield. |
96% | With dihydrogen peroxide In ethanol at 20℃; for 0.5h; Green chemistry; | |
96% | With dihydrogen peroxide In ethanol at 20℃; for 0.416667h; | General procedure for the oxidative coupling of thiols to thedisulfdes: General procedure: A mixture of thiol (1 mmol), hydrogen peroxide (0.5 mL)and Fe3O4 MNPs-DETA/Benzyl-Br3 (12.5 × 10-3 mol%) inethanol (2 mL) was stirred at ambient temperature. Reactionprogress was monitored by TLC (acetone: n-hexane, 2:8). Aftercompletion of the reaction, catalyst was separated by externalmagnet and washed with ethyl acetate, and next, the productwas extracted with ethyl acetate (4 × 5 mL). The organic layerwas dried over anhydrous Na2SO4 (1.5 g). Finally, the organic solvents were evaporated, and the corresponding disulfdeswere obtained in high to excellent yields (89-98%).All the products are known compounds and were characterized by comparison of their IR and NMR spectraldata and physical properties with those reported in theliterature. |
95% | With aluminum(III) oxide; sodium periodate In hexane at 20℃; for 0.5h; | |
95% | With 1,4-diazabicyclo[2.2.2]octane N,N′-dioxide In acetonitrile for 1h; Heating; | |
95% | With maleic anhydride; urea-hydrogen peroxide In methanol at 0℃; for 0.166667h; | |
95% | With 1H-imidazole; [N,N'-bis(salicylidene)-o-phenylenediaminato]manganese(III) chloride; urea hydrogen peroxide In methanol at 0℃; for 0.166667h; | |
95% | With rosolic acid In methanol at 20℃; for 1h; | |
95% | With 2,3-dicyano-5,6-dichloro-p-benzoquinone In dichloromethane at 0℃; for 0.0833333h; | 4.2. General procedure for the synthesis of disulfides Procedure for symmetrical molecules: DDQ (0.5 mmol) was added to an ice-cooled solution of thiol (1 mmol) in dichloromethane (3.0 mL). The reaction mixture stirred for 5 min at 0 °C and monitored by TLC analysis. The reaction mixture was concentrated under reduced pressure and directly purified by column chromatography by gradient elution of ethyl acetate in hexanes to give the title compounds. |
95% | With dihydrogen peroxide; trichlorophosphate In diethyl ether; lithium hydroxide monohydrate at 0℃; for 0.0833333h; | |
95% | With dihydrogen peroxide In ethanol; lithium hydroxide monohydrate at 20℃; for 2h; | |
95% | With silica gel-supported iodine monochloride In chloroform at 20℃; for 0.666667h; | |
95% | With dihydrogen peroxide; N,N,N-tributyl-1-butanaminium iodide In lithium hydroxide monohydrate at 20℃; for 1.08333h; Large scale reaction; | |
95% | With urea hydrogen peroxide addition compound In ethanol at 20℃; for 0.433333h; | Typical procedure for the synthesis of disulfides catalyzed by Co(at)MCM-41 or Fe(at)MCM-41: as a typical procedure General procedure: A mixture of thiols (1 mmol), UHP (5 mmol), and Co orFeMCM-41 (20 mg) was stirred at room temperature inethanol and the progress of the reaction was monitored by TLC.After completion of the reaction, the catalyst was removed andthe products were extracted with CH2Cl2 (3 × 10 mL). Theresults are shown in Table 7. |
95% | With magnetic ion exchanged Montmorillonite-k10 In tetrahydrofuran at 50℃; for 1h; Green chemistry; | |
95% | With iodine In ethanol at 20℃; for 18h; | |
95% | With dihydrogen peroxide In neat (no solvent) at 20℃; for 1.33333h; Green chemistry; | |
95% | With dihydrogen peroxide In ethanol; lithium hydroxide monohydrate at 20℃; for 0.333333h; | General procedure for the oxidative coupling of thiols into disulfides General procedure: A mixture of thiol (1 mmol), 33 % H2O2 (0.4 mL) and Fe3O4MCM-41VO-SPATB (10 mg) in ethanol (3 mL) was stirred for the specified time at ambient temperature (the progress of reaction was monitored by TLC). After completion of the reaction, the catalyst was separated by applying an external magnet and the product was washed with ethyl acetate, and then dried over anhydrous Na2SO4 (1.5 g). Finally, Evaporation of the solvent gave the disulfides invery high isolated yields |
95% | With dihydrogen peroxide In ethanol at 20℃; for 1.33333h; Green chemistry; | |
94% | With butyltriphenylphosphonium dichromate In acetonitrile for 0.025h; Microwave irradiation; | |
94% | With γ-picolinium chlorochromate In dichloromethane at 20℃; for 0.6h; | |
94% | With graphite oxide In chloroform at 100℃; for 0.166667h; | |
94% | With air In ethanol at 20℃; for 4h; | Thiol coupling reactions for the synthesis of disulfides General procedure: General procedure (1mM scale): In a 25 mL round bottom flask, a thiol(1; 1.0 mmol) was dissolved in EtOH (1 mL) and the mixture was stirredin the open atmosphere for 4 h (completion of reaction was confirmedby TLC). Then the mixture in the flask was evaporated in vacuo. Theresidue was either directly dried to give pure products 2a-i or subjectedto silica gel column chromatography using petroleum ether as eluent togive pure products 2j-l (see Table 2).General procedure (10 mM scale): In a 50 mL round bottom flask,a thiol (1a, 1b or 1d; 10.0 mmol) was dissolved in EtOH (10 mL) andthe mixture was stirred in the open atmosphere for 6 h (progress ofreaction was followed by TLC). Evaporation of solvent provided thecorresponding pure disulfides 2a, 2b and 2d. |
94% | With dihydrogen peroxide In ethanol at 20℃; for 0.75h; Green chemistry; | |
94% | With dihydrogen peroxide In ethanol at 20℃; for 0.833333h; | General procedure for the oxidative coupling of thiols General procedure: To the mixture of the thiol (1 mmol) and Fe3O4*MCM-41Zn-Arg (15 mg) in ethanol (3 mL), H2O2 (0.4 mL) was added and stirred at room temperature. After completion ofthe reaction (monitored by TLC), the catalyst was separated from the mixture by an external magnet and the product was extracted with ethyl acetate and the solvent was removed by simple evaporation to give pure disulfides. |
93% | With sodium (meta)periodate In lithium hydroxide monohydrate at 20℃; for 0.0333333h; | |
93% | With nicotinic acid hydrobromide perbromide at 20℃; for 0.0833333h; Neat (no solvent); | |
93% | With [Mn(III)(BHBPDI)Cl]; oxygen In ethanol at 20℃; for 1h; | |
93% | With hydrogen bromide; dimethyl sulfoxide In chloroform at 20℃; for 6h; Inert atmosphere; Schlenk technique; | General procedure for the synthesis of symmetrical disulfides: General procedure: A mixture of thiols(1.0 mmol) and HX (0.2 mmol) in DMSO-CHCl3 (5 mL, 1:1, v/v) was stirred atroom temperature for respective time (Table 3). After the completion of thereaction, as monitored by TLC, the reaction mixture was diluted with 10 mL ofwater and extracted with CHCl3 (3 15 mL). The combined organic layerswere washed with brine (2 10 mL), dried over anhydrous Na2SO4, andevaporated in a rotary evaporator under reduced pressure. A reasonably pureproduct obtained was further purified by recrystallization using hexane-CHCl3mixture. The purity of the compound was confirmed by melting point andNMR measurements. |
93% | With potassium carbonate; copper chloride (II) In methanol | |
93% | With H5PV2Mo10O40; oxygen In ethanol; lithium hydroxide monohydrate at 90℃; for 5.5h; Green chemistry; | |
92% | With calcium hypochlorite; lithium hydroxide monohydrate; mesoporous silica In hexane at 20℃; for 0.333333h; | |
92% | With air In hexane at 30℃; for 2h; | |
92% | With ethylenebis(N-methylimidazolium) chlorochromate In acetonitrile at 20℃; for 0.0833333h; | |
92% | With 1,3-dibromo-5,5-dimethylhydantoin In chloroform at 20℃; for 1h; Inert atmosphere; | |
92% | With tert.-butylnitrite; oxygen In 1,2-dichloro-ethane at 50℃; for 2h; Sealed tube; Green chemistry; | Typical procedure for disulfides (2a) General procedure: A sealed tube (90 mL) equipped with a magnetic stirring bar and an O2 balloon was charged with dichloroethane (DCE, 20 mL), thiophenol (1a, 4 mmol, 0.44 g) and TBN (0.16 mmol, 4 mol%, 19.2 mL). Then the tube was placed in an oil bath, which was preheated to 50°C. The mixture was stirred for 1 h until starting material was completely consumed as monitored by GC and TLC. After removing the solvent, the residue was purified by column chromatography on silica gel to give the desired diphenyl disulfide (2a, 90%, 0.394 g) as a white solid. |
92% | With urea hydrogen peroxide addition compound In ethanol at 20℃; for 0.3h; | General procedure for oxidative coupling of thiols to disulfides with UHP catalyzed by Cr-MCM-41 and Mn-MCM-41 General procedure: Thiols ((1 mmol), 5 mmol UHP, and 4 mL acetone as solvent along with 25 mg catalyst were added to a 10-mL two-necked flask equipped with a stirrer. The progress of the reaction was monitored by TLC. After completion of the reaction, the catalyst was removed and the pure products were extracted with CH2Cl2(3 9 10 mL). The results are presented in Table 6. |
91% | With urea hydrogen peroxide addition compound In acetonitrile at 20℃; for 0.333333h; | |
91% | With dihydrogen peroxide In ethanol at 20℃; for 0.916667h; Green chemistry; chemoselective reaction; | |
91% | With trimethylphenylammonium perbromide In tetrahydrofuran at 30℃; for 4h; | General experimental procedure (C) for the synthesis of disulfane: General procedure: To a well stirred solution of Thiols (1equiv.) in THF Phenyl Trimethyl ammonium Tribromide (PTAB) (0.5 equiv) was added and the reaction was stirred at room tempearature for 4-8 hrs. After completion of the reaction which was monitored by TLC, The reaction mixture was quenched with distilled water and extracted with ethyl acetate (3X3ml). The organic fraction was washed with saturated brine solution and dried over oven dried anhydrous sodium sulphate. The solvent was evaporated under reduced pressure. The residual crude mass was subjected to a short silica gel column filtration (petroleum ether/ethyl acetate) afforded the desired disulfane as the pure product. |
91% | With dihydrogen peroxide In ethanol at 20℃; for 0.25h; | 2.5 General Procedure for the Oxidation of Thiolsto Disulfides General procedure: General experimental procedure for the oxidative couplingof thiols is as following: MCM-41(at)Tryptophan-M (Cd orHg) (0.005) was added to a mixture of thiol (1 mmol) andH2O2(0.5 mL) in ethanol (3 mL). Then the mixture wasmagnetically stirred for the appropriate time at room temperature.The progress of reaction was monitored by TLC.After completion of the reaction, the catalyst was removedby filtration and the mixture was washed with ethyl acetate.The product was extracted with ethyl acetate. After the evaporationof ethyl acetate, the pure product was obtained bycrystallization from ethanol (Scheme 3). |
90% | With p-nitro-α-oxo-benzeneacetaldehyde; glacial acetic acid for 0.333333h; Reflux; | |
90% | With guanidinium nitrate In dichloromethane at 20℃; for 0.283333h; chemoselective reaction; | |
90% | With dihydrogen peroxide In lithium hydroxide monohydrate; ethyl acetate at 20℃; for 0.5h; Green chemistry; | General procedure for the oxidation of thiols to disulfides General procedure: In another study, a mixture of the VO-AMPD(at)SBA-15 (0.004 g), thiol (1 mmol) and H2O2 (0.4 mL) was stirred at room temperature in ethyl acetate (2 mL). The progress was monitored by TLC. After completion of the reaction, VO-AMPD(at)SBA-15 catalyst was separated from the mixture by filtration. Then products were extracted with ethyl acetate and dried, and the solvent was removed to give the pure disulfides. |
90% | With dihydrogen peroxide In neat (no solvent) at 20℃; for 0.5h; Green chemistry; chemoselective reaction; | |
90% | With urea hydrogen peroxide addition compound In ethanol at 20℃; for 0.75h; | |
89% | With 10 wtpercent cubic Ag2O nanoparticle incorporated mesoporous silica; air In lithium hydroxide monohydrate for 5h; Reflux; Green chemistry; chemoselective reaction; | |
89% | With TiO2/MoS2 (10:1 molar ratio of Ti to Mo) nanocomposite; air In ethanol at 20℃; Irradiation; Green chemistry; | General procedure for the synthesis of disulfides General procedure: TiO2/MoS2 (10:1 molar ratio, 10 mg) was added to a solution of thiol 1 (1 mmol) in ethanol (1 mL). The reaction mixture was stirred under a 14W CFL irradiation at a distance of 10 cm at room temperature for a certain time. After reaction (monitored by thin-layer chromatography, TLC), ethyl acetate was added, and the solid catalyst was recovered by centrifugation. The reaction mixture was extracted with ethyl acetate and washed with water. The combined organic phase was then dried over Na2SO4 and concentrated under reduced pressure to give the crude residue, which was purified by column chromatography with petroleum ether-ethyl acetate to afford the pure product 2. The recovered catalyst was then washed with ethanol and deionized water, dried under vacuum, and reused for the next run. |
89% | With dihydrogen peroxide In neat (no solvent) at 20℃; for 0.916667h; Green chemistry; | |
89% | With dihydrogen peroxide In neat (no solvent) at 20℃; for 0.916667h; | 2.4. General procedure for the oxidative coupling of thiols to thedisulfides General procedure: 0.005 g Fe3O4-AMPD-Pd was added to a mixture including1 mmol thiol, 0.4 mL H2O2 33% and free solvent were stirred atroom temperature. The reaction was followed by TLC after completion.The nanocatalyst was isolated by a simple magnet. |
89% | With titanosilicate molecular sieve In cyclohexane at 120℃; for 5h; Inert atmosphere; | 5 Weigh 30 mg of ETS-10 catalyst into a reaction tube, then add 0.22 mmol of p-bromothiophenol and 1 mL of cyclohexane.In a nitrogen atmosphere, the reaction was carried out in a heater at 120 °C for 5 h, and after the experiment was completed, centrifugation was performed.The solid phase product obtained was separated by flash column chromatography (the elution reagent was pure cyclohexane) to obtain a white solid.The product yield can reach 89% |
88% | With urea hydrogen peroxide addition compound In methanol; dichloromethane at 20℃; for 2h; | General conditions for catalytic oxidation of thiols General procedure: A typical reaction using the Fe3O4(at)SiO2-NH2Mn(III) nanoparticles as catalyst and thiols as substrate is described as follows. To a solution of thiol (1 mM) and catalyst (0.01 g,containing 0.0002 mM of manganese complex) in a (1 : 1) mixture of CH3OH-CH2Cl2 (2 mL) was added UHP (0.093 g, 1 mM) as the oxidant. The mixture was stirred at room temperature for 2 h. The catalyst particles were then collected at the bottom of the test tube using a magnet, the supernatant was carefully decanted, and the completion of oxidation reaction was followed by TLC (petroleum ether/ethyl acetate, 4 : 1). After the separation of catalyst nanoparticles, the solvent supernatant was removed under vacuum and the remaining was purified by column chromatography using petroleum ether/ethyl acetate, 4 : 1. Isolated products were weighted and also analyzed by 1H NMR. Washing several timeswith methanol and dichloromethane, the catalyst particles were dried in vacuum and could be reused. |
88% | With dihydrogen peroxide In ethanol at 20℃; for 1.5h; | |
87% | With dihydrogen peroxide In lithium hydroxide monohydrate at 20℃; for 0.416667h; Green chemistry; | The typical procedure for oxidative couplingof thiols to disulfides with H2O2 General procedure: 1 mmol thiol, 20 mg of γ-Fe2O3 /CuHPECGs, and H2O2(0.4 mL, 3.92 mmol) were stirred at room temperaturein 2 mL of H2Ofor the specified time shown in Table 1.The reaction progress was monitored by TLC (n-hexane/ethyl acetate: 1:4). After completion of the reaction, the heterogeneous catalyst was magnetically separated from themixture and the product was extracted using ethyl acetate.The obtained products dried over anhydrous Na2SO4andorganic solvent evaporation were afforded pure product. |
86% | With oxygen at 60℃; for 12h; Green chemistry; | |
86% | With 2,2'-(((diselanediylbis(2,1-phenylene))bis(azanediyl))bis(methylene))diphenol In acetonitrile at 20℃; for 7h; | |
86% | With oxygen; 1-n-hexyl-3-methylimidazol-1-ium bromide at 50℃; for 1.33333h; Green chemistry; | |
86% | With dihydrogen peroxide In ethanol at 25℃; for 1h; | |
85% | With sodium hydrogen sulphite; orthoperiodic acid In lithium hydroxide monohydrate at 20℃; for 1h; | |
85% | With ferric(III) chloride; sodium iodide In acetonitrile for 4h; | |
85% | With Bromotrichloromethane In tetrahydrofuran at 20℃; for 12h; Schlenk technique; Irradiation; | 9 Example 9 Add 75.6mg (0.4mmol) of p-bromothiophenol and 237.9mg (1.2mmol) of bromotrichloromethane into a 10mL Schlenk container, and then add 2mL of tetrahydrofuran with a syringe, and react for 12h under the irradiation of a 23W energy-saving lamp at room temperature. After the reaction is complete After concentrating to remove the solvent, the crude product was separated by silica gel column chromatography (eluent: petroleum ether) to obtain a colorless liquid: 63.8 mg, yield: 85%. |
84% | With bis(trichloromethyl) carbonate; triethylamine; Triphenylphosphine oxide In chloroform for 8h; Heating; | |
84% | With tris(2-phenylpyridinato-C<SUP>2</SUP>,N)iridium(III) In propan-2-one at 20℃; for 5h; Inert atmosphere; Sealed tube; Irradiation; Green chemistry; | |
84% | With Porcine Pancreas Lipase In lithium hydroxide monohydrate at 20℃; for 30h; Green chemistry; Enzymatic reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With trichloroisocyanuric acid; silica gel at 20℃; grinding; neat (no solvent); chemoselective reaction; | |
97% | With ammonium cerium (IV) nitrate; iodine; oxygen In poly(ethylene glycol) 400; water at 60℃; for 1.25h; chemoselective reaction; | |
93% | With Oxone; potassium bromide In water; acetonitrile at 20℃; for 0.283333h; | General procedure for synthesis of thiosulfonates from disulfides: General procedure: oxone(2.0 mmol) was added to a well-stirred solution of MX (KBr, KCl, NaBr andNaCl, 0.5 mmol) in aqueous acetonitrile (50:50, v/v), followed by substrate(1.0 mmol) was added. Resulting mixture was stirred for the appropriateperiod of time (Table 3) at room temperature. After complete consumption ofthe starting material as observed by TLC, water (50 mL) was added and themixture was extracted with ethyl acetate. The extract was washed with brine,dried over anhydrous sodium sulfate and evaporated to afford thecorresponding thiosulfonate as the sole product. It was further recrystallizedusing mixture of ethyl acetate and petroleum ether to remove color impurities.All of the products are known compounds and were characterized bycomparison with authentic samples (NMR spectra and melting points). |
73% | With bis-[(trifluoroacetoxy)iodo]benzene In dichloromethane for 0.25h; Ambient temperature; | |
73% | With tert.-butylhydroperoxide In chloroform at 90℃; for 10h; | 6 Example 6 Add in 100mL single-mouth bottlesDi-p-bromophenyl disulfide (20 mmol, 7.52 g),70% t-butyl hydroperoxide (200 mmol, 25.72 g) and 40 mL chloroform,The reaction was carried out at 90 ° C for 10 h. After the reaction is(TLC monitoring), the heating is stopped.After cooling to room temperature, 100 mL of water was added and extracted with dichloromethane (3 x 100 mL).The organic layers were combined, dried and concentrated under reduced pressure. Column chromatography (developing solvent: petroleum ether: ethyl acetate = 20:1) gave white title product.The yield was 73% (5.96 g). |
With sulfuric acid; dihydrogen peroxide; acetic acid |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | Stage #1: bis(4-bromophenyl)disulfide With aluminium trichloride; zinc In acetonitrile at 80℃; for 2h; Stage #2: diphenyliodonium iodide In water; acetonitrile at 80℃; for 4h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With ferric(III) bromide In N,N-dimethyl-formamide at 145℃; for 48h; | |
62% | With copper(l) iodide; oxygen In N,N-dimethyl-formamide at 120℃; for 24h; | |
62% | With tetrabutylammonium tetrafluoroborate In acetonitrile at 20℃; for 6h; Electrochemical reaction; | Electrosynthesis of phenyl (2,4,6-trimethoxyphenyl)sulfane. General procedure: To a reaction undivided cell was added 1,3,5-trimethoxybenzene(0.2 mmol), ArSSAr (0.2 mmol), n-Bu4NBF4 (0.1 mmol) and 10 mlMeCN under air atmosphere. The electrolytic cell was equippedwith a platinum plate electrode (5 mm × 5 mm × 0.1 mm) as theanode and a nickel plate (15 mm × 10 mm × 0.5 mm) as the cathode(Fig. S1 available online at stacks.iop.org/JES/168/015501/mmedia).The mixture was stirred at room temperature for 6 h. After thereaction was finished, the solvent was evaporated under reducedpressure. The crude product was purified by flash chromatographyon silica gel using petroleum ether and ethyl acetate as the eluent(100:0-100:5). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With copper(l) iodide; caesium carbonate; In dimethyl sulfoxide; at 80℃; | A mixture of 2-alkynylaniline 1a-1e (0.2 mmol), dichalcogenide 2a-2e (0.15 mmol), CuI (0.02 mmol), and Cs2CO3 (0.2 mmol) in DMSO (2 mL) was stirred at 80 C under an air atmosphere. After completion of the reaction that was monitored by GC-MS or TLC, 25 mL water was added, and the mixture was extracted with ethyl acetate, the combined organic layers were washed with water (10 mL x 3), dried over anhydrous Na2SO4. After filtration and removal of solvents in vacuum, the residue was purified by silica gel column chromatography to afford the corresponding products. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79% | With copper(l) iodide; caesium carbonate In dimethyl sulfoxide at 80℃; chemoselective reaction; | General procedure for synthesis of 3-chalcogenylindoles: A mixture of 2-alkynylaniline 1a-1e (0.2 mmol), dichalcogenide 2a-2e (0.15 mmol), CuI (0.02 mmol), and Cs2CO3 (0.2 mmol) in DMSO (2 mL) was stirred at 80 °C under an air atmosphere. After completion of the reaction that was monitored by GC-MS or TLC, 25 mL water was added, and the mixture was extracted with ethyl acetate, the combined organic layers were washed with water (10 mL x 3), dried over anhydrous Na2SO4. After filtration and removal of solvents in vacuum, the residue was purified by silica gel column chromatography to afford the corresponding products. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With copper(l) iodide; caesium carbonate; In dimethyl sulfoxide; at 80℃; | A mixture of 2-alkynylaniline 1a-1e (0.2 mmol), dichalcogenide 2a-2e (0.15 mmol), CuI (0.02 mmol), and Cs2CO3 (0.2 mmol) in DMSO (2 mL) was stirred at 80 C under an air atmosphere. After completion of the reaction that was monitored by GC-MS or TLC, 25 mL water was added, and the mixture was extracted with ethyl acetate, the combined organic layers were washed with water (10 mL x 3), dried over anhydrous Na2SO4. After filtration and removal of solvents in vacuum, the residue was purified by silica gel column chromatography to afford the corresponding products. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With copper(l) iodide; oxygen In dimethyl sulfoxide at 110℃; regioselective reaction; | 4.2. General procedure for chalcogenylation of azaheterocycles with dichalcogenides General procedure: A mixture of azaheterocycles 1 or 4 (0.20 mmol), dichalcogenides 2 (0.10 mmol), and CuI (0.020 mmol, 10 mol %) in DMSO (2.0 mL) was stirred at 110 °C under air atmosphere for 10-18 h until complete consumption of staring material as monitored by TLC. The solution was then cooled to room temperature, diluted with ethyl acetate (10 mL), washed with H2O (3×10 mL), dried over Na2SO4, filtered, and evaporated under vacuum. The crude product was purified by column chromatography on silica gel (eluting with PE/EA=25/1 to 4/1) to afford the desired products 3 or 5. |
93% | With ammonium iodide; water; acetic acid; dimethyl sulfoxide at 110℃; for 6h; Green chemistry; regioselective reaction; | 15 4.2.1. General procedure for synthesis General procedure: N-heteroarene (0.25 mmol), diorganyl dichalcogenide (0.125 mmol) NH4I (0.025 mmol, 10 mol%, 3.6 mg), acetic acid (1 eq.) and the mixture of DMSO/H2O (2.5:2.5 eq.) were placed into a round-bottom flask. The reaction was stirred at 110 °C in an oil bath for appropriate time (Tables 3-6). After the completion of the reaction, the mixture was cooled to room temperature, quenched with water and the aqueous layer was extracted with EtOAc. The organic phase was dried over MgSO4, filtered, and the volatiles were completely removed under vacuum to give the crude product. Purification by flash chromatography on silica with a mixture of Hexane/EtOAc as eluent furnished the desired chalcogenated product. |
90% | With 1-benzyl-3-butyl-2-ethylimidazolium tetrafluoroborate; caesium carbonate at 80℃; for 15h; Green chemistry; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With iodine; dimethyl sulfoxide In carbonic acid dimethyl ester at 40℃; for 6h; | |
85% | With oxygen; acetic acid; potassium iodide; sodium nitrite In acetonitrile at 60℃; for 2h; Sealed tube; Green chemistry; regioselective reaction; | 3-[(3-Methoxyphenyl)thio]-1H-indole (3aa):Typical Procedure General procedure: A 15 mL tube equipped with a magnetic stirring bar wascharged with 1H-indole (0.5 mmol), sodium S-(3-methoxyphenyl)thiosulfate (0.6 mmol), KI (20 mol%), and NaNO2 (10 mol%).The tube was then sealed with a rubber plug, and MeCN (3 mL)and HOAc (0.5 mL) were injected into the tube. The air in thetube was replaced by charging with oxygen, and the mixturewas stirred under an oxygen atmosphere (balloon) at 80 °Cuntil the reaction was complete (GC). The mixture was cooledto r.t. and the solvent was removed under vacuum. The residuewas washed with 10% aq Na2S2O3 (30 mL) and extracted withCH2Cl2 (4 × 20 mL). The organic layer was then dried (Na2SO4)and concentrated under vacuum. The residue was further purifiedby flash column chromatography (silica gel, PE-Et2O) togive a light-yellow solid; yield: 92 mg (72%); mp 87.6-88.4 °C. |
85% | With oxygen; acetic acid; potassium iodide; sodium nitrite In acetonitrile at 60℃; for 2h; | 12 Example 12: Preparation of 3-p-bromophenylthio-1H-indole (Formula 4) In a 15 mL glass tube, add 5 mL of acetonitrile, 1 mmol of 1H-hydrazine,0.5 mmol of bis(4-bromophenyl)disulfide, 0.2 mmol of KI and 0.1 mmol of NaNO2, replacing the air in the reaction tube with oxygen, sealing the bottle with a rubber stopper, inserting an oxygen balloon, and then using a syringe into the reaction tube Add 1 mL of HOAc,The reaction tube was placed in an oil bath previously heated to 60 ° C, and reacted for 2 hours with stirring.The reaction solution was stirred with a sodium thiosulfate solution, and then extracted with dichloromethane to separate an organic layer.The solvent was evaporated under reduced pressure, and then subjected to column chromatography, and the mixture of diethyl ether/petroleum ether ratio of 1:5 was used as an eluent to collect an eluent containing the target compound.Evaporating the solvent yields 3-p-bromophenylthio-1H-indole,The isolated yield was 85%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With potassium 5-methyl-1,3,4-oxadiazole-2-thiolate; basolite C300 In water; N,N-dimethyl-formamide at 130℃; for 3.25h; Green chemistry; chemoselective reaction; | 2.2 Symmetrical Diaryl Disulfides Synthesis; Typical Experimental Procedure General procedure: A mixture of iodobenzene (2.0 mmol), potassium 5-methyl-1,3,4-oxadiazole-2-thiolate (1) (3.0 mmol), MOF-199 (8 mg, 10 % mol) were added to a flask containing 2 mL DMF/H2O (20:1), The reaction continued at 130 °C under atmospheric conditions until completion. Thereaction progress was controlled by thin-layer chromatography. The reaction mixture was then filtered. The filtrate was evaporated under vacuum, CH2Cl2 (20 ml) was addedand the mixture was washed with H2O (2 x 15 ml). Theorganic layer was dried over anhydrous Na2SO4. The solvent was evaporated to give the crude diaryl disulfide, which was purified by plate chromatography (silica gel,n-hexane-ethyl acetate, 20:1). All spectra of the diaryl disulfides are mentioned in the electronic supplementary material. |
96% | With sulfur; potassium hydroxide In water at 130℃; for 5h; Green chemistry; | |
88% | With carbon disulfide; cycl-isopropylidene malonate; triethylamine; copper(l) chloride In N,N-dimethyl-formamide at 100℃; for 4h; Inert atmosphere; | Conversion of aryl iodides into diaryl disulfides using Meldrum’s acid dithioate General procedure: A mixture of Meldrum’s acid (1 mmol) and Et3N (2 mmol) in DMF was stirred for 15 min at r.t. Then, CS2 (1 mmol) was added and stirred for 15 min. Then, the obtained mixture was added to a stirred solution of aryl halide (1 mmol) and CuCl (0.1 mmol) in DMF (2 ml), and heated at 100 C for 4h. When the reaction was completed (TLC), the mixture was extracted with CH2Cl2 (3 3ml) and H2O (3ml). The organic layer was separated and dried (Na2SO4) and the solvent was evaporated in vacuo to give the diaryl disulfide. The product was purified by column chromatography on silica gel (EtOAc / Petroleum ether, 1:4). |
80% | With potassium sulfide; nickel(II) chloride hexahydrate; acetylacetone; potassium hydroxide In water; N,N-dimethyl-formamide at 110℃; for 24h; | General procedure for the synthesis of diaryl(dialkyl) disulfides General procedure: To a stirred mixture of aryl (primary alkyl) halide (2.0 mmol), 0.33 g potassium sulfide (3.0 mmol) and acac (20 mol%) in 2 cm3 DMF (containing a few drops water),NiCl2.6H2O (10 mol%) and then 1.0 g KOH (18.0 mmol) were added and the whole reaction mixture was heated at 110 °C under atmospheric conditions until completion. The progress of the reaction was monitored by TLC. Upon completion of the reaction, the mixture was cooled to room temperature. Then, the pH of mixture was adjusted to 7 with 5 % HCl and filtered. The filtrate was evaporated under vacuum, 20 cm3 ethyl acetate was added and the mixture was washed with H2O (2 x 15 cm3). The combined organic layer was dried over Na2SO4 and filtered to afford the crude diaryldisulfide and dialkyldisulfide, which was purified by preparative chromatography (silica gel, n-hexane:ethyl acetate 20:1; in the case of Table 3, entries 12-15 was 4:1). |
78% | With potassium 5-methyl-1,3,4-oxadiazole-2-thiolate; nickel(II) chloride hexahydrate; ethylene glycol; potassium hydroxide In water; N,N-dimethyl-formamide at 130℃; for 4.5h; | Symmetrical Organic Disulfide Synthesis; Typical ExperimentalProcedure General procedure: A mixture of iodobenzene (2.0 mmol), potassium 5-methyl-1,3,4-oxadiazole-2-thiolate (1, 0.462 g, 3.0 mmol), NiCl2·6H2O (10 mol%) and KOH (1.0 g, 18 mmol) were added to a flask containing DMF-H2O (2 mL, 20:1) and EG (0.11 mL, 2 mmol). The reaction mixture was heated at 130 °C under atmospheric conditions until completion, monitored by TLC. The reaction mixture was then filtered, the filtrate was evaporated under reduced pressure, CH2Cl2 (20 mL) was added, and the mixture was washed with H2O (2 × 15 mL). The organic layer was dried over anhydrous Na2SO4, filtered, and the solvent was evaporated to give the crude diaryl/alkyl disulfide, which was purified by preparative TLC (silica gel; n-hexane-EtOAc, 20:1). |
55% | Stage #1: 1,4-bromoiodobenzene With potassium 5-methyl-1,3,4-oxadiazole-2-thiolate In N,N-dimethyl-formamide at 20℃; for 0.333333h; Stage #2: With copper(l) chloride In N,N-dimethyl-formamide at 130℃; for 6h; | Symmetrical organic disulfides synthesis; typical experimental procedure General procedure: A mixture of iodobenzene (2.0 mmol), potassium 5-methyl-1,3,4-oxadiazole-2-thiolate(2) (3.0 mmol), and DMF (4 mL) was stirred at room temperature for 20 min until the potassium salt had completely dissolved. CuCl (0.6 mmol, 61 mg) was then added to the solution and stirring was continued at 130 °C for the appropriate time (Table 3) under air. After completion of the reaction, the DMF was evaporated, CH2Cl2 (15 mL) was added, and the mixture washed with H2O (3 × 10 mL). The organic layer was dried over anhydrous Na2SO4. The solvent was evaporated in vacuo to give diphenyl disulfide which was purified by preparative TLC (silica gel, eluent n-hexane: EtOAc = 50:1). |
52% | With 1H-imidazole; copper(l) iodide; sodium thiosulfate pentahydrate; potassium carbonate In water; dimethyl sulfoxide at 130℃; for 24h; Green chemistry; | Symmetrical Organic Disulfides Synthesis General procedure: A mixture of iodobenzene (1.0 mmol, 0.115 mL),Na2S2O3•5H2O (3 mmol, 248.21 mg), using CuI (0.7 mmol,190.45 mg) catalyst in the presence of K2CO3(2mmol,138.21 mg) and in the presence imidazole (1.6 mmol, 68.08mg) in DMSO/H2O (2 mL) at 130°C for 21 h under normal atmospheric conditions until completion. The reaction progresswas controlled by thin-layer chromatography. Also itcan be controlled by color change of litmus paper [38]. Thereaction mixture was then filtered. The filtrate was evaporatedunder vacuum, CH2Cl2 (20 mL) was added and themixture was washed with H2O (2 × 15 mL). The organiclayer was dried over anhydrous Na2SO4. The solvent wasevaporated to give the crude diaryl/alkyl disulfide, whichwas purified by plate chromatography (silica gel, n-hexane-ethyl acetate, 20:1) |
Multi-step reaction with 2 steps 1: sodium thiosulfate; copper(l) iodide; N,N`-dimethylethylenediamine / dimethyl sulfoxide / 4 - 12 h / 80 °C 2: dihydrogen peroxide; choline chloride; toluene-4-sulfonic acid / water / 6 h / 60 °C | ||
With nickel(II) chloride hexahydrate; morpholinium morpholine-1-carbodithioate; potassium hydroxide In water; ethylene glycol; N,N-dimethyl-formamide at 130℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | With sodium dithionite; water; potassium carbonate; In dimethyl sulfoxide; at 60℃; for 1.5h; | General procedure: A mixture of isatoic anhydride 1 (0.6 mmol), disulfide 2 (0.2 mmol), and Na2S2O4 (0.9 mmol) in undried DMSO (2 mL) was stirred at 60 C for respective time in Table 2 and Scheme 2. After the completion of the reaction, as monitored by TLC and GC-MS analysis, the reaction mixture washed with brine and extracted with ethyl acetate. The organic phase was separated and dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated and the resulting residue was purified by column chromatography on silica gel (300-400 mesh) with petroleum ether-EtOAc as eluent to provide the desired product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With di-tert-butyl peroxide at 120℃; for 12h; Inert atmosphere; | |
75% | With tert.-butylhydroperoxide In water at 120℃; for 12h; Molecular sieve; Inert atmosphere; Schlenk technique; | Typical Experimental Procedure for TBHP-Mediated OxidativeCross-Coupling of Disulfides with Ethers General procedure: To a Schlenk tube were added disulfide 1 (0.2 mmol), TBHP (2 equiv), 4-Amolecular sieve (100 mg), and ether 2 (2 mL). Then the tube was charged with argonand stirred at 120 C (oil bath temperature) for the indicated time until completeconsumption of starting material as monitored by thin-layer chromatography(TLC) and GC-MS analysis. After the reaction was finished, the reaction mixturewas cooled to room temperature, diluted in ethyl acetate (5 mL), and washed withbrine (31 mL). The aqueous phase was extracted with ethyl acetate (32 mL).The combined organic extracts were dried over Na2SO4 and concentrated invacuo, and the resulting residue was purified by silica-gel column chromatography(hexane=ethyl acetate20:1) to afford product 3. |
70% | With tert.-butylhydroperoxide; sodium carbonate In water at 120℃; for 24h; Inert atmosphere; | Typical experimental procedure for TBHP-mediated thiolation of tetrahydrofuran with disulfides General procedure: Disulfide 1 (0.5 mmol), TBHP (2 equiv.), Na2CO3 (0.1 equiv.) and tetrahydrofuran 2 (1 mL) were added to a Schlenk tube. Then the tube was stirred at 120 °C (oil bath temperature) under an argon atmosphere for the indicated time until complete consumption of starting materialas monitored by TLC or GC-MS analysis. After the reaction was finished, the reaction mixture was cooled to room temperature, diluted in ethyl acetate (5 mL), and washed with brine (3 × 1 mL). The aqueous phase was extracted with ethyl acetate (3 × 2 mL). The combined organic layers were dried with anhydrous Na2SO4 and concentrated under reduced pressure and the resulting residue was purified by column chromatography on silica gel (hexane/ethyl acetate = 20 : 1) to afford the desired products 3a-h. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With tert.-butylhydroperoxide; potassium carbonate In water at 100℃; for 2h; | 2.3. Catalytic testing General procedure: In a typical run, a mixture of diphenyl disulfide (0.2 mmol), p-tolualdehyde (2.0 mmol), K2CO3(0.4 mmol), tert-butyl hydroper-oxide (TBHP) (0.6 mmol), catalyst (40 mg), H2O (2.0 mL) was stirredat desired temperature for 2 h. After the reaction was completed,the mixture was cooled down to room temperature and thenextracted with ethyl acetate. The organic phase was analyzed on anAgilent 7890A GC equipped with a FID detector and mass spectrom-eter. The product was purified by column chromatography on silicagel (200-300 mesh) (eluent: petroleum ether and ethyl acetate).The obtained product was identified by NMR spectra using a Bruker500 MHz spectrometer instrument. The1H NMR (500 MHz) and13CNMR (125 MHz) were recorded with spectrometers at 20C usingCDCl3as the solvent. Chemical shifts are given in parts per millionrelative to TMS as the internal standard at room temperature. Thespectra data were consistent with authentic compounds. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With sodium tetrafluoroborate; potassium iodide In acetonitrile at 60℃; for 6h; Electrolysis; | Electrosynthesis of 3-sulfenylindoles General procedure: The electrochemical experiment was performed on 263A Potentiostat/Galvanostat (PrincetonApplied Research, USA) in a 25 mL undivided cell. Two graphite rods(6mmin diameter, 1 cm in length) were employed as the working electrode and the counter electrode respectively. The reference electrode was Ag/Ag+ electrode (0.1 mol/L AgNO3 in CH3CN). 2-Methylindole(1a, 1.0 mmol), diphenyl disulfide (2a, 0.5 mmol) and KI (0.05 mmol) were added into 0.1 mol/L of NaBF4/CH3CN solution (15 mL)with stirring at 60°C. The electrolysis reactions were operated at 0.4V. After completion of the reaction (monitored by GC or TLC), the resulting mixture was concentrated under reduced pressure and purified by column chromatography on silica gel using hexanes/EtOAc(100:1) as eluent to afford 2-methyl-3-(phenylthio)-indole (3aa) as a white solid in 94% yield. |
97% | With sodium tetrafluoroborate; potassium iodide In acetonitrile at 60℃; for 6h; Electrochemical reaction; | 20 Example 20: Preparation of 2-methyl-3-p-bromophenylthio-1H-indole (Formula 5) Add in a 30ml beaker 0.1 mol/L sodium tetrafluoroborate in acetonitrile (15 mL), 2-methyl-1H-indole (1 mmol), di(p-bromophenyl)disulfide (0.5 mmol) and potassium iodide (0.05 mmol). Constant potential electrolysis at 60 ° C, 0.4 V, and the reaction was completed after 6 h. The solvent is distilled off under reduced pressure, and then subjected to column chromatography, and the mixture of ethyl acetate/n-hexane volume ratio of 1:100 is used as an eluent, and the eluent containing the target compound is collected, and the solvent is distilled off to obtain the product 2- Methyl-3-p-bromophenylthio-1H-indoleHey. The isolated yield was 97%. |
80% | With sodium iodide In acetonitrile at 20℃; for 18h; Irradiation; | Preparation of the benzothiazole 3a General procedure: To a 20 mL glass tube with a stir bar was charged 2-methyl-1H-indole 1a (39.35 mg, 0.3 mmol), diphenyldisulfide 2a (65.50 mg, 0.3 mmol), NaI (0.06 mmol, 9 mg) and MeCN (2 mL). The solution was stirred at room temperature with the irradiation of a 12 W blue LED for 18 h. The solvent was removed under vacuum. The residue was purified by column chromatography over silica gel (petroleum ether/ethyl acetate = 15/1) to give the product 3a (60 mg, 83%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
62% | With rhodium(III) chloride trihydrate; copper diacetate; tris(2,6-dimethoxyphenyl)phosphine In N,N-dimethyl-formamide at 120℃; for 6h; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | With potassium cyanide; carbon dioxide In dimethyl sulfoxide at 50℃; for 19h; | 1,2-bis(4-bromophenyl)disulfane (2i) In an 8 ml vial, a mixture of 1i (138.7 mg, 0.6 mmol), and 2 equivalent of potassium cyanide was stirred in DMSO (3 ml), under a carbon dioxide atmosphere (1 atm) at 50 °C for 19 h. The reaction was diluted with water, and extracted with diethyl ether three times. Combined organic phases was washed with water, dried over MgSO4, and concentrated under vacuum. The crude product was dissolved in n-heptane, and filtered through a silica plug. The n-heptane was concentrated under pressure, to give the corresponding disulfide in 65% isolated yield (73.5 mg). |
Yield | Reaction Conditions | Operation in experiment |
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58% | With dipotassium hydrogenphosphate; (4s,6s)-2,4,5,6-tetra(9H-carbazol-9-yl)isophthalonitrile; In dimethyl sulfoxide; at 20.0℃; for 24.0h;Inert atmosphere; Irradiation; | General procedure: Under argon, 4CzIPN (2 mol %) and <strong>[719-98-2]N-(trifluoromethylthio)phthalimide</strong> (3, 1.5 equiv),1a (0.2 mmol, 1 equiv), 2a (0.2 mmol, 1 equiv), and K2HPO4 (10 mol %) were dissolvedin dried DMSO (2 mL) at room temperature. After that, the tube was exposed to 10 Wblue LEDs and the mixture was stirred at room temperature for about 24 h until thereaction was completed as monitored by TLC analysis. Then, the reaction solution waspoured into 10 mL of water. The aqueous phase was extracted with EA (3 × 15 mL). Thecombined organic phases were washed with 15 mL of water and 15 mL of brine. Afterdrying over Na2SO4 and removal of the solvent in vacuo, the crude products were directlypurified by flash chromatography on silica gel to give the desired product. |
Tags: 5335-84-2 synthesis path| 5335-84-2 SDS| 5335-84-2 COA| 5335-84-2 purity| 5335-84-2 application| 5335-84-2 NMR| 5335-84-2 COA| 5335-84-2 structure
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Code | Phrase |
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Code | Phrase |
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P378 | |
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Disposal | |
Code | Phrase |
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Code | Phrase |
H200 | Unstable explosive |
H201 | Explosive; mass explosion hazard |
H202 | Explosive; severe projection hazard |
H203 | Explosive; fire, blast or projection hazard |
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H221 | Flammable gas |
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H223 | Flammable aerosol |
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H231 | May react explosively even in the absence of air at elevated pressure and/or temperature |
H240 | Heating may cause an explosion |
H241 | Heating may cause a fire or explosion |
H242 | Heating may cause a fire |
H250 | Catches fire spontaneously if exposed to air |
H251 | Self-heating; may catch fire |
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 |
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H272 | May intensify fire; oxidizer |
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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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