- Synthesis and Characterization of "atlas-Sphere" Copper Nanoclusters: New Insights into the Reaction of Cu2+ with Thiols
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Thiolates are a widely used ligand class for the stabilization of M(0)-containing gold and silver nanoclusters. Curiously, though, very few thiolate-stabilized Cu nanoclusters are known. Herein, we report an examination of the reactivity of RSH (R = CH2CH2Ph, n-Bu, n-C12H25) with Cu2+ under anhydrous conditions. These reactions result in the formation of fluorescent "Atlas-sphere"-type copper thiolate nanoclusters, including [Cu12(SR′)6Cl12][(Cu(R′SH))6] (2, R′ = nBu) and [H(THF)2]2[Cu17(SR′′)6Cl13(THF)2(R′′SH)3] (3, R′′ = CH2CH2Ph), which were characterized by X-ray crystallography, electrospray ionization mass spectrometry, NMR spectroscopy, as well as X-ray absorption near-edge structure and extended X-ray absorption fine structure (EXAFS) spectroscopies. Consistent with our X-ray crystallographic results, the edge energies of 2 and 3 suggest they are constructed exclusively with Cu(I) ions. Similarly, EXAFS of 2 and 3 reveals long Cu-Cu pathlengths, which is also consistent with their X-ray crystal structures. Given these results, as well as past work on Cu2+/thiol reactivity, we suggest that Cu(0) is unlikely to be formed by the reaction of Cu2+ with a thiol and that previous reports of Cu(0)-containing nanoclusters synthesized by reaction of Cu2+ with thiols are likely erroneous.
- Cook, Andrew W.,Jones, Zachary R.,Wu, Guang,Teat, Simon J.,Scott, Susannah L.,Hayton, Trevor W.
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- METAL COMPLEXES OF TETRAPYRAZINOPORPHYRAZINES - EFFECTIVE CATALYSTS OF THE OXIDATION OF MERCAPTANS
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The catalytic activity of the tetrapyrazinoporphyrazine complexes of cobalt and iron have been studied in the oxidation of aliphatic mercaptans by molecular oxygen. n-Butyl mercaptan was used as the model compound.The metallotetrapyrazinoporphyrazines tested exhibited a considerably higher catalytic activity than cobalt phtalocyanine.
- Maizlish, V. E.,Korzhenevskii, A. B.,Klyuev, V. N.
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- Rearrangement of radicals with migration of the chlorine atom from sulfur to carbon during the reaction of thiols with vinylsulfonyl chloride
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1. A study was made of the reaction of n-butanethiol and thiophenol with vinylsulfonyl chloride at ~20° in an argon atmosphere. The reaction products are, respectively, β-chloroethyl butyl sulfide and β-chloroethyl phenyl sulfide (8-12% yields), and SO2 is liberated. The other reaction products are, respectively, the dibutyl and diphenyl disulfides (60-70% yields), HCl, and H2O. 2. Apparently, the formation of β-chloroethyl butyl sulfide and β-chloroethyl phenyl sulfide is associated with the addition of the thiyl radical to the double bond of vinylsulfonyl chloride and subsequent rearrangement of the RSCH2CHSO2Cl radicals, with the migration of chlorine from sulfur to the adjacent carbon atom.
- Kandror,Freidlina
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- Synergistic Effect of Iodine and Neighboring Amine Groups on Thioester Deacylation
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The synergistic effect of a Lewis acid (I2) and an intramolecular Lewis base facilitates the deacylation of thioesters.When iodine is added to aqueous slution of S-3-(dimethylamino)propylthioacetate (I), deacylation is accelerated by a factor of 103-104.A severafold acceleration is observed for S-2-(2-pyridyl)ethyl thioacetate (II), and no rate enhancement is observed in the reaction of S-n-butyl thioacetate (III).The rate of iodine consumption at invariant pH and thioseter and iodine concentrations is zero order in iodine when III reacts and the first order in iodine when I reacts.Both kinetic orders are observed when II reacts.The effect of pH and iodine concentration on the rates of I and II is explaned by an intramolecular interaction between an iodine-thioester complex and the neighboring amine.The product of the reaction of the unsubstituted thioester III is the disulfide.However, overoxidation is observed in the reactions of I and II, and the sulfonic acids were the isolated products.The product from the oxidation of I has been confirmed to be (CH3)2+NH(CH2)3SO3- (IV) by single-crystal X-ray crystallography.
- Doi, Joyce Takahashi,Carpenter, Tracy Louise,Olmstead, Marylin M.,Musker, W. Kenneth
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Read Online
- Visible-light-responsive lanthanide coordination polymers for highly efficient photocatalytic aerobic oxidation of amines and thiols
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Development of visible-light-induced photocatalytic reactions using molecular oxygen as the terminal oxidant is intriguing in view of the current environmental and energy issues. We report herein the synthesis and characterization of a series of novel pho
- An, Shuyi,Guo, Zhifen,Liu, Xin,Che, Yan,Xing, Hongzhu,Chen, Peng
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p. 15767 - 15775
(2021/09/22)
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- T BuOK-triggered bond formation reactions
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Recently, inexpensive and readily available tBuOK has seen widespread use in transition-metal-free reactions. Herein, we report the use of tBuOK for S-S, S-Se, NN and CN bond formations, which significantly extends the scope of tBuOK in chemical synthesis. Compared with traditional methods, we have realized mild and general methods for disulfide, azobenzenes imine etc. synthesis.
- Xu, Yulong,Shi, Xiaonan,Wu, Lipeng
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p. 24025 - 24029
(2019/08/13)
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- Trisulfides over disulfides: Highly selective synthetic strategies, anti-proliferative activities and sustained H2S release profiles
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Temperature-and solvent-induced selective synthesis of trisulfides and disulfides is demonstrated. A remarkable selectivity was achieved using Na2S as a sulfur-Transfer agent under mild, greener, catalyst-free and additive-free conditions. This study reveals trisulfides as a better model than disulfides in general for a sustained release of H2S and potent anti-cancer activities.
- Bhattacherjee, Debojit,Sufian, Abu,Mahato, Sulendar K.,Begum, Samiyara,Banerjee, Kaustav,De, Sharmistha,Srivastava, Hemant Kumar,Bhabak, Krishna P.
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supporting information
p. 13534 - 13537
(2019/11/14)
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- Laccase-catalyzed in situ generation and regeneration of N-phenyltriazolinedione for the aerobic oxidative homo-coupling of thiols to disulfides
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The first report on aerobic in situ generation and regeneration of N-phenyltriazolinedione, a valuable oxidizing agent, from a catalytic amount of N-phenyl urazole in the presence of a laccase enzyme is presented. The application of a 4-phenyl urazole/Laccase/O2 as a new cooperative catalytic oxidation system is reported for a transition-metal-free and halogen free oxidative homo-coupling reaction of structurally diverse thiols to their corresponding disulfides with good to excellent yields in a phosphate buffer solution under mild reaction conditions.
- Khaledian, Donya,Rostami, Amin,Zarei, Seyed Amir
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- A rapid, efficient and green procedure for transformation of alkyl halides/ tosylates to organochalcogens in water
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A one-pot and efficient synthesis of dialkyl dichalcogenides (S, Se) in aqueous media under catalyst-free conditions using benzylic, allylic and primary halides with elemental sulfur and selenium has been developed. Also, this procedure was extended to preparation of trisulfides and triselenides from secondary and tertiary halides in same condition. In all cases, products can be obtained in good to excellent yield in short reactions time.
- Soleiman-Beigi, Mohammad,Yavari, Issa,Sadeghizadeh, Fatemeh
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- Synthesis and in vitro biological evaluation of thiosulfinate derivatives for the treatment of human multidrug-resistant breast cancer
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Organosulfur compounds derived from Allium vegetables have long been recognized for various therapeutic effects, including anticancer activity. Allicin, one of the main biologically active components of garlic, shows promise as an anticancer agent; however, instability makes it unsuitable for clinical application. The aim of this study was to investigate the effect of stabilized allicin derivatives on human breast cancer cells in vitro. In this study, a total of 22 stabilized thiosulfinate derivatives were synthesized and screened for their in vitro antiproliferative activities against drug-sensitive (MCF-7) and multidrug-resistant (MCF-7/Dx) human adenocarcinoma breast cancer cells. Assays for cell death, apoptosis, cell cycle progression and mitochondrial bioenergetic function were performed. Seven compounds (4b, 7b, 8b, 13b, 14b, 15b and 18b) showed greater antiproliferative activity against MCF-7/Dx cells than allicin. These compounds were also selective towards multidrug-resistant (MDR) cells, a consequence attributed to collateral sensitivity. Among them, 13b exhibited the greatest anticancer activity in both MCF-7/Dx and MCF-7 cells, with IC50 values of 18.54±0.24 and 46.50±1.98 μmol/L, respectively. 13b altered cellular morphology and arrested the cell cycle at the G2/M phase. Additionally, 13b dose-dependently induced apoptosis, and inhibited cellular mitochondrial respiration in cells at rest and under stress. MDR presents a significant obstacle to the successful treatment of cancer clinically. These results demonstrate that thiosulfinate derivatives have potential as novel anticancer agents and may offer new therapeutic strategies for the treatment of chemoresistant cancers.
- Roseblade, Ariane,Ung, Alison,Bebawy, Mary
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p. 1353 - 1368
(2017/10/10)
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- Europhtal (8020) efficiently catalyzes the aerobic oxidation of in situ generated thiols to symmetric disulfides (disulfanes)
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Efficient, odorless and scalable synthetic protocols have been introduced for the preparation of symmetric alkyl disulfides by treatment of the corresponding organic halides with thiourea and NaHCO3in the presence of commercially available Europhtal catalyst (8020) in both H2O and poly ethylene glycol (PEG-200) media at 80–90 °C. Structurally diverse primary, secondary, allylic and benzylic halides were examined successfully whereas, the result with tert-butyl bromide was not satisfactory. Also, another procedure has been introduced for achieving symmetric aryl disulfides in high yields by reacting aryl halides, thiourea and NaHCO3in PEG-200 at 115–120 °C using CuI along with Europhtal catalysts. The results showed that the aerobic oxidation of in situ generated thiols proceeded efficiently in the presence of Europhtal catalyst giving the symmetric disulfide without contamination by symmetric sulfide side-product.
- Abbasi, Mohammad,Sabet, Askar,Sabet, Askar
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- Simple and green method for synthesis of symmetrical dialkyl disulfides and trisulfides from alkyl halides in water; PMOxT as a sulfur donor
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An environmentally new, mild and efficient method has been developed for the synthesis of dialkyl disulfides and dialkyl trisulfides in aqueous conditions by a reaction between alkyl halides (and tosylate) and potassium-5-methyl-1,3,4-oxadiazole-2-thiolate (PMOxT) as a sulfur transfer reagent. The advantages of this method are that it occurs under mild reaction conditions, it is base free, it uses water as the solvent and it occurs in high yields. A variety of dialkyl disulfides and dialkyl trisulfides can be obtained in good to excellent yields up to 98%.
- Soleiman-Beigi, Mohammad,Mohammadi, Fariba
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p. 134 - 141
(2017/03/07)
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- Conversion of organic halides to disulfanes using KCN and CS2
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A sulfur transfer reagent was produced in situ upon stirring a mixture of KCN and CS2 in DMF at r.t. for 15 min, which after heating with an alkyl halide or aryl halide and CuI gave the corresponding symmetric dialkyl or diaryl disulfide, respectively, in high to excellent yields.
- Abbasi, Mohammad,Nowrouzi, Najmeh,Borazjani, Saeedeh Ghassab
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p. 4251 - 4254
(2017/10/11)
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- Oxidative dimerization of thiols to disulfide using recyclable magnetic nanoparticles
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Abstract: Dimerization of thiol groups to disulfide is an important transformation in chemical processes. In this study, magnetic ion exchanged Montmorillonite-k10 was synthesized and characterized using FTIR, X-ray diffraction and scanning electron microscope techniques. Then, the application of the synthesized catalyst as an efficient oxidizing agent was evaluated in oxidative dimerization of different thiols to corresponding disulfides under optimal reaction conditions. The reaction was easily performed with aromatic, aliphatic and heterocyclic thiols. The magnetic catalyst was easily recovered by applying an external magnet and, further, was reused in successive reactions. Graphical Abstract: [Figure not available: see fulltext.]
- Masnabadi, Nasrin,Ghasemi, Mohammad Hadi,Beyki, Mostafa Hossein,Sadeghinia, Mohammad
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p. 1609 - 1618
(2017/02/15)
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- Tunable and Practical Synthesis of Thiosulfonates and Disulfides from Sulfonyl Chlorides in the Presence of Tetrabutylammonium Iodide
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A tunable and practical synthesis of electrophilic sulfenylating reagents, thiosulfonates and disulfides, from inexpensive and easily available sulfonyl chlorides, has been developed. By appropriate choice of solvents, the reaction of sulfonyl chlorides and tetrabutylammonium iodide gave the target products in good to excellent yields, respectively. These transformations probably proceed through a reducing–coupling pathway. (Figure presented.).
- Zheng, Yong,Qing, Feng-Ling,Huang, Yangen,Xu, Xiu-Hua
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supporting information
p. 3477 - 3481
(2016/11/13)
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- One-pot conversion of alkyl halides to organic disulfides (disulfanes) using thiourea and hexamethyldisilazane (HMDS) in DMSO
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A practical method to synthesize symmetric disulfides from alkyl halides has been developed. Using this procedure primary, secondary, benzylic and allylic disulfides were prepared by treating the corresponding alkyl halides with thiourea and HMDS in DMSO at 50 °C within 10-24 h in high yields.
- Abbasi, Mohammad,Jabbari, Arida
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- Synthesis of Disulfanes from Organic Thiocyanates Mediated by Sodium in Silica Gel
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We report an efficient procedure for the synthesis of symmetrical disulfanes from organic thiocyanates in the presence of sodium in silica gel at room temperature. By avoiding the use of foul-smelling thiols, the present protocol provides an attractive alternative to existing methods for the preparation of symmetrical disulfanes.
- Maurya, Chandra Kant,Mazumder, Avik,Kumar, Ajeet,Gupta, Pradeep Kumar
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p. 409 - 411
(2016/02/09)
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- The synthesis of symmetrical disulfides by reacting organic halides with Na2S2O3·5H2O in DMSO
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A one-pot, and scalable method to prepare symmetric disulfides from their corresponding primary, secondary, allylic, and benzylic halides has been developed. In this method, a disulfide is synthesized by reacting an alkyl halide with Na2S2O3·5H2O at 60-70 °C in DMSO.
- Abbasi, Mohammad,Mohammadizadeh, Mohammad Reza,Saeedi, Narges
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supporting information
p. 89 - 92
(2016/01/12)
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- One-Pot Intermolecular C–S Self-Coupling of Dimethyl Sulfoxide Promoted by Molybdenum Pentachloride
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The reactions between MoCl5and 1–2 equiv. of a selection of sulfoxides at room temperature in dichloromethane as solvent were studied. The 1:1 molar reaction between MoCl5and dimethyl sulfoxide (DMSO) afforded the C–S coupling product [Me2SCH2SMe][MoOCl4] (1), which was isolated in 46 % yield and characterized by analytical and spectroscopic methods and by X-ray diffraction. MoOCl3, SMe2and HCl were identified as side products. The reactions between MoCl5and tetrahydrothiophene 1-oxide, nBu2SO, MePhSO or (PhCH2)2SO yielded the corresponding sulfides and, in the cases of (PhCH2)2SO and MePhSO, also C–S activation compounds. According to DFT calculations, the unusual formation of 1 is the consequence of thermodynamically feasible Cl/O interchange between MoCl5and DMSO, this being a prerequisite for successive C–H bond activation.
- Bortoluzzi, Marco,Ferretti, Eleonora,Hayatifar, Mohammad,Marchetti, Fabio,Pampaloni, Guido,Zacchini, Stefano
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p. 3838 - 3845
(2016/08/19)
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- Experimental study on deep desulfurization of MTBE by electrochemical oxidation and distillation
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With the increasing awareness of environmental protection, deep desulfurization of methyl tert-butyl ether (MTBE), which is the most important octane booster in gasoline, is extremely urgent. Herein, a new desulfurization method, involving the combination of electrochemical oxidation and distillation, is proposed to reduce the sulfur content in MTBE. Under optimum operating conditions, the sulfur content of real MTBE decreases from 132.5 μg g-1 to 2.3 μg g-1 and the desulfurization efficiency reaches 98.25%. The oxidation products with high boiling points can be separated by distillation. FTIR analyses prove that electrochemical oxidation has no influence on the main properties of MTBE. Moreover, GC/MS is used to study the conversion of model organic sulfides (dimethyl disulfide, diethyl sulfide and butyl mercaptan) in the electrochemical oxidative desulfurization process. Finally, the possible reaction mechanism of the electrochemical oxidative desulfurization of MTBE is proposed.
- Li, Jing-Jing,Zhou, Fei,Tang, Xiao-Dong,Hu, Tao,Cheng, Jin
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p. 4803 - 4809
(2016/01/29)
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- Cd(II)-MOF-IM: Post-synthesis functionalization of a Cd(II)-MOF as a triphase transfer catalyst
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A robust and porous Cd(ii)-MOF based on a bent imidazole-bridged ligand was synthesized and post-synthetically functionalized with linear alkyl chains to afford imidazolium salt (IM)-type triphase transfer catalysts for organic transformations. The imidazolium salt decorated Cd(ii)-MOF-IM exhibits typical solid phase transfer catalytic behavior for the azidation and thiolation of bromoalkane between aqueous/organic phases. Moreover, they can be easily recovered and reused under the PTC conditions. Cd(ii)-MOF-IM herein created a versatile family of solid phase transfer catalysts for promoting a broad scope of reactions carried out in a biphasic mixture of two immiscible solvents.
- Wang, Jian-Cheng,Ma, Jian-Ping,Liu, Qi-Kui,Hu, Yu-Hong,Dong, Yu-Bin
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supporting information
p. 6989 - 6992
(2016/06/09)
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- Ultrasound-Accelerated Synthesis of Asymmetrical Thiosulfonate S-Esters by Base-Promoted Reaction of Sulfonyl Chlorides with Thiols
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Amberlyst A-26, Mg-Al hydrotalcite, potassium fluoride absorbed on alumina, triethylamine and pyridine have been tested as base catalysts and reagents for the reaction of sulfonyl chlorides with thiols to prepare thiosulfonate S-esters. The reactions were performed under solvent-free conditions or with a minimum amount of solvent assisted by magnetic stirring, ultrasound irradiation and microwave irradiation. Ultrasound irradiation has good effects on the synthesis of sterically hindered thiosulfonate S-esters in solvent-free media as well as in a minimum amount of anhydrous diethyl ether.
- Pham, Hien Thi,Nguyen, Ngoc-Lan Thi,Duus, Fritz,Luu, Thi Xuan Thi
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p. 1934 - 1941
(2015/12/12)
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- Fast and efficient green synthesis of thiosulfonate S-esters by microwave-supported permanganate oxidation of symmetrical disulfides
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Potassium permanganate absorbed on copper(II) sulfate pentahydrate has been found to be an efficient, inexpensive, and green oxidation agent for the synthesis of "symmetrical" thiosulfonate S-esters by oxidation of the corresponding symmetrical disulfides. The oxidation reactions were carried out under solvent-free reaction conditions within 15 min under the influence of microwave irradiation, as well as (for comparison) supported by conventional heating, to afford yields of the thiosulfonate S-esters in the range of 60-83%. The oxidation reaction appears to proceed (at least partly) via an intermediate symmetrical vic-disulfoxide.
- Luu, Thi Xuan Thi,Nguyen, Thao-Tran Thi,Le, Thach Ngoc,Spanget-Larsen, Jens,Duus, Fritz
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p. 340 - 350
(2015/04/27)
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- Haloacid/dimethyl sulfoxide-catalyzed synthesis of symmetrical disulfides by oxidation of thiols
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A novel method is developed for the oxidation of thiols to the corresponding disulfides using 20 mol % haloacid (HBr or HI) in combination with dimethyl sulfoxide. A tentative mechanism is proposed for the oxidation. In addition to the advantages of cost-effectiveness, simple processes, and broad functional group tolerance, the exclusive formation of disulfides is the principle reward of this methodology while compared to known methods that further oxidize disulfides to S-oxides and other byproducts.
- Natarajan, Palani,Sharma, Himani,Kaur, Mandeep,Sharma, Pooja
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supporting information
p. 5578 - 5582
(2015/09/21)
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- 4,4'-Azopyridine as an easily prepared and recyclable oxidant for synthesis of symmetrical disulfides from thiols or alkyl halides(tosylates)/thiourea
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Heterocyclic azo compounds, prepared from corresponding amines in one step, are used as effective oxidants for the conversion of thiols into symmetrical disulfides in high yields. Among the studied azo compounds, 4,4'-azopyridine was found to be very efficient for the odorless conversion of alkyl halides into disulfides in the presence of thiourea. An attractive feature of this azo compound is that its obtained solid side product hydrazine is easily separated by filtration and can be recycled to its azo compound for further use.
- Khalili, Dariush,Iranpoor, Nasser,Firouzabadi, Habib
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p. 544 - 555
(2015/10/19)
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- Cubic Ag2O nanoparticle incorporated mesoporous silica with large bottle-neck like mesopores for the aerobic oxidative synthesis of disulfide
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Highly stable, environmentally benign cubic Ag2O nanoparticles dispersed on mesoporous silica with large bottle-neck like mesopores were synthesized and characterized by BET surface area analysis, HR TEM, EDX, FTIR and powder XRD studies. The Ag2O nanoparticles were homogeneously distributed having an average size of 20-40 nm. The activity of the catalyst was probed through an efficient aerobic chemoselective oxidation of thiols to disulfides in water under atmospheric oxygen as the cheapest oxidant. Alkyl, aryl and imine containing symmetrical disulfides can be easily obtained in high yields under mild reaction conditions with no over oxidized product. The efficiency of the catalyst was further demonstrated as the highly sensitive imine bond was well sustained under these mild reaction conditions. Moreover, unlike the other literature precedents, in this present work, single crystal structures of both simple symmetrical disulphide as well as imine containing disulphides are reported for the first time. The catalyst is very much water compatible and can be recycled and reused for at least five cycles. The standard leaching experiment proved that the reaction was heterogeneous with this recyclable catalyst.
- Das, Paramita,Ray, Suman,Bhaumik, Asim,Banerjee, Biplab,Mukhopadhyay, Chhanda
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p. 6323 - 6331
(2015/02/19)
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- Graphene Oxide-Assisted One-Pot and Odorless Synthesis of Symmetrical Disulfides Using Primary and Secondary Alkyl Halides (Tosylates) and Thiourea as Sulfur Source Reagent
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Graphene oxide is described as a heterogeneous oxidant for the synthesis of symmetrical disulfides through the in situ generation of thiols from primary and secondary alkyl halides (tosylates) and thiourea in wet acetonitrile. A variety of alkyl halides and alkyl tosylates can be converted to corresponding disulfides in good to excellent yields. This strategy is free of foul-smelling thiols.
- Khalili, Dariush
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p. 1727 - 1734
(2015/12/12)
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- One-pot synthesis of organic disulfides (disulfanes) from alkyl halides using sodium sulfide trihydrate and hexachloroethane or carbon tetrachloride in the poly(ethylene glycol) (PEG-200)
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Abstract Symmetric disulfides are produced by treating their corresponding organic halides including benzylic, allylic, primary and secondary halides with Na2S·3H2O and C2Cl6 or CCl4 in PEG-200 at room temperature in high yields.
- Abbasi, Mohammad,Mohammadizadeh, Mohammad Reza,Moosavi, Hekmat,Saeedi, Narges
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p. 1185 - 1190
(2015/03/31)
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- Effect of irradiation intensity on rate and selectivity of photosensitized oxidation of dibutyl sulfide over C70 fullerene
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Photoinitiated oxidation of dibutyl sulfide (DBS) with air oxygen in a toluene solution of C70 fullerene during irradiation with visible light at a wavelength of 500-700 nm results in the formation of dibutyl sulfone as a main detected product, dibutyl sulfoxide, and butanal. A change in the intensity of radiation incident on the reaction mixture from 2.2 to 44 mW/cm2 insignificantly increases the quantum efficiency of the DBS consumption from 4.5 to 5.9%. The selectivity for sulfoxide increases during the process, while selectivity for sulfone decreases.
- Arsentyev,Vorontsov,Parmon
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p. 167 - 172
(2015/05/20)
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- Equilibrium shift induced by chiral nanoparticle precipitation in rhodium-catalyzed disulfide exchange reaction
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Chiral silica (P)-nanoparticles grafted with (P)-helicene recognize the molecular structure of a chiral diol disulfide in the presence of monool disulfide and dibutyl disulfide. The (P)-nanoparticles selectively adsorb the diol disulfide, aggregate, and precipitate from solution. Under rhodium-catalyzed equilibrium among three disulfides, the diol disulfide is removed from solution by precipitation, which induces an equilibrium shift in the solution. By conducting the precipitation experiment twice, we obtained the diol disulfide in 37% yield from a statistical 1:2:1 equilibrium mixture of three disulfides. The method is applied to a racemic monool disulfide, and an optically active diol disulfide is obtained via kinetic resolution and equilibrium shift.
- Miyagawa, Masamichi,Arisawa, Mieko,Yamaguchi, Masahiko
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p. 4920 - 4926
(2015/06/23)
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- A mild radical method for the dimerization of dithiocarbamates
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A general, practical, and efficient method for the dimerization of dithiocarbamates has been developed that can be used to prepare the corresponding bis(1-arylimino-1-alkyl/ arylthiomethyl) disulfides with dilauroyl peroxide (DLP) as mild oxidant. Notably, a lauroyl radical, rather than an undecyl radical, was established as the radical hydrogen-ab- stractor during the dimerization process. The amount of DLP impacts the dimerization yield, with 50 mol-% DLP giving the disulfides in the highest yields. The use of an excess of DLP generates the undecyl radical, which decomposes the disulfides rapidly to the corresponding isothiocyanates.
- Chen, Ning,Zhong, Xin,Li, Pingfan,Xu, Jiaxi
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p. 802 - 809
(2015/02/19)
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- Imidazole Promoted Highly Efficient Large-Scale Thiol-Free Synthesis of Symmetrical Disulfides in Aqueous Media
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A highly efficient and environmentally friendly method for the imidazole promoted preparation of symmetrical organic disulfides from Bunte salts is described. This thiol-free procedure produces the desired disulfides even on a large scale by reaction of Bunte salts with imidazole in good to high yields in aqueous media.
- Mokhtari, Babak,Kiasat, Ali Reza,Monjezi, Javid
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p. 1573 - 1579
(2015/09/15)
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- Nickel ferrite nanoparticles-hydrogen peroxide: A green catalyst-oxidant combination in chemoselective oxidation of thiols to disulfides and sulfides to sulfoxides
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Nickel ferrite nanoparticles-hydrogen peroxide has been demonstrated for the first time as a green and efficient catalyst-oxidant combination in the chemoselective oxidation of thiols to disulfides and sulfides to sulfoxides. This magnetically separable catalyst was found to be reusable for five consecutive runs without appreciable change in the activity, as well as composition of the catalyst. The mechanism for the oxidation of thiols and sulfides has also been proposed. the Partner Organisations 2014.
- Kulkarni, Aparna M.,Desai, Uday V.,Pandit, Kapil S.,Kulkarni, Makarand A.,Wadgaonkar, Prakash P.
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p. 36702 - 36707
(2014/12/10)
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- Organocatalyzed anodic oxidation of aldehydes to thioesters
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A method has been developed for the direct conversion of aldehydes to thioesters via integration of organocatalysis and electrosynthesis. The thiazolium precatalyst was found to facilitate oxidation of thiolate anions, leading to deleterious formation of disulfide byproducts. By circumventing this competing reaction, thioesters were obtained in good-to-excellent yields for a broad range of aldehyde and thiol substrates. This approach provides an atom-efficient thioesterification that circumvents the need for stoichiometric exogenous oxidants, high cell potentials, or redox mediators.
- Ogawa, Kelli A.,Boydston, Andrew J.
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supporting information
p. 1928 - 1931
(2014/05/06)
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- (NH 4) 6Mo 7O 34·4H 2O as an efficient, selective, and reusable catalyst for the oxidation of thiols to disulfides using potassium bromate
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Ammonium molybdate, (NH 4) 6Mo 7O 34·4H 2O, is found to be an efficient and selective catalyst for the oxidation of thiols to corresponding disulfides using potassium bromate in aqueous acetonitrile as the solvent. Among various solvents tested, CH3CN/H2O showed better results in terms of the reaction yield and rate. In the absence of (NH4)6Mo 7O24·4H2O, the oxidation reaction is not selective for the formation of disulfides. The catalyst can be easily recovered after completion of the reaction and reused without any significant loss of its activity. [Supplementary materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfer, and Silicon and the Related Elements for the following free supplemental files: Additional text and figures.]
- Bayraq, Samad Shoghpour,Nikseresht, Ahmad,Khosravi, Iman
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supporting information
p. 1236 - 1243
(2013/09/23)
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- One-pot efficient synthesis of disulfides from alkyl halides and alkyl tosylates using thiourea and elemental sulfur without contamination by higher polysulfides
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An efficient and odorless synthesis of disulfides from alkyl halides using thiourea and elemental sulfur in the presence of sodium carbonate in wet polyethylene glycol (PEG 200) at 40 C without contamination by higher polysulfides has been developed. This procedure was then extended to preparation of disulfides from alkyl tosylates at 70 C.
- Abbasi, Mohammad,Mohammadizadeh, Mohammad Reza,Taghavi, Zeinab Khatoon
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p. 201 - 205
(2013/07/26)
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- Polyoxometalate-catalyzed insertion of oxygen from O2 into tin-alkyl bonds
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The polyoxometalate H5PV2Mo10O 40 mediates the insertion of an oxygen atom from H5PV 2Mo10O40 into the tin-carbon bond of n-Bu 4Sn through its activation by
- Khenkin, Alexander M.,Efremenko, Irena,Martin, Jan M. L.,Neumann, Ronny
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supporting information
p. 19304 - 19310
(2014/01/17)
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- Switching the activity of a photoredox catalyst through reversible encapsulation and release
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Reversible encapsulation of [Ru(bpy)3]2+ within a self-assembled hexameric resorcin[4]arene capsule turns off the photocatalytic aerobic oxidation of an aliphatic sulfide. Upon addition of a competitive cationic guest, the Ru(ii) catalyst is released into solution where its catalytic activity is restored.
- Bianchini, Giulio,Scarso, Alessandro,Sorella, Giorgio La,Strukul, Giorgio
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supporting information
p. 12082 - 12084
(2013/01/16)
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- A simple and practical method for the oxidation of thiols to disulfides at mild conditions without solvents
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A green, straightforward, and novel method for the oxidation of thiols to the corresponding disulfides is reported using hydrogen peroxide catalyzed by tetrabutylammonium iodide (TBAI) without solvents at room temperature. The corresponding disulfides were obtained with excellent yields and short reaction times. Copyright
- He, Ying,Hang, Dongliang,Lu, Ming
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experimental part
p. 1118 - 1124
(2012/08/14)
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- Microwave-assisted one-pot synthesis of symmetrical diselenides, ditellurides and disulfides from organoyl iodides and elemental chalcogen catalyzed by CuO nanoparticles
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In this study CuO nanoparticles were applied as a catalyst for CSe, CTe, and CS bond formation. The reaction was performed with organoyl iodides and elemental selenium, tellurium or sulfur under microwave irradiation in the presence of a base and solvent at 80 °C. This novel protocol allowed the synthesis of a variety of diselenides, ditellurides and disulfides in good to excellent yields in a very short reaction time.
- Botteselle, Giancarlo V.,Godoi, Marcelo,Galetto, Fabio Z.,Bettanin, Luana,Singh, Devender,Rodrigues, Oscar E.D.,Braga, Antonio L.
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p. 186 - 193
(2013/01/14)
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- Heteroaromatic azo compounds as efficient and recyclable reagents for direct conversion of aliphatic alcohols into symmetrical disulfides
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4,4′-Azopyridine 1a and 5,5′-dimethyl-3,3′-azoisooxazole 1e are used for the efficient, direct, and selective conversion of aliphatic alcohols into their corresponding disulfides in high yields under Mitsunobu conditions in combination with PPh3/sub
- Iranpoor, Nasser,Firouzabadi, Habib,Khalili, Dariush
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p. 6913 - 6915
(2013/01/15)
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- Unexpected reaction of 2-chloro-1-propen-3-yl isothiuronium chloride with potassium ditelluride: the first example of vicinal elimination of chlorine and sulfur-bearing moieties
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2-Chloro-1-propen-3-yl isothiuronium chloride reacts with potassium ditelluride in hydrazine hydrate to afford elemental tellurium and allene. The latter is formed due to the vicinal elimination of chlorine and a sulfur-bearing moiety.
- Levanova, Ekaterina P.,Grabelnykh, Valentina A.,Elaev, Alexander V.,Albanov, Alexander I.,Klyba, Lyudmila V.,Russavskaya, Natalia V.,Tarasova, Olga A.,Rozentsveig, Igor B.,Korchevin, Nikolai A.
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p. 505 - 511,7
(2020/09/16)
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- Silica-supported ICl as a novel heterogeneous system for the rapid and selective oxidation of thiols to symmetrical disulfides
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ICl-SiO2 as a new reactive system was prepared by treatment of iodine monochloride with activated silica gel in chloroform. ICl-SiO2 in a heterogeneous system efficiently converted thiols to the corresponding disulfides under mild conditions in high yields at room temperature.[image omitted].
- Karami, Bahador,Farahi, Mahnaz,Montazerozohori, Morteza,Nasr-Esfahani, Masoud
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experimental part
p. 483 - 488
(2012/06/16)
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- Photocatalytic transformation of organic and water-soluble thiols into disulfides and hydrogen under aerobic conditions using Mn(CO)5Br
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The photolysis of Mn(CO)5Br with thiols under aerobic conditions at room temperature produces the corresponding disulfides in high yields, accompanied by the evolution of hydrogen as the only other product. This transformation is a greener route toward the synthesis of disulfides and exhibits 100% atom economy. The catalytic system possesses high chemoselectivity, as evidenced by high disulfide yields even in the presence of numerous functional groups. A mechanism has been proposed to involve free radical species and is based on fac-Mn(CO)3(RSH)2Br being an important catalytic intermediate. Mn(CO)5Br is also able to catalyze the conversion of naturally occurring water-soluble thiols such as cysteine and glutathione. Coupled with suitable enzymes that regenerate thiols from disulfides using proton sources, it is possible to envisage a combined catalytic cycle that is able to reduce protons to hydrogen efficiently.
- Tan, Kheng Yee Desmond,Teng, Guan Foo,Fan, Wai Yip
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experimental part
p. 4136 - 4143
(2011/10/03)
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- Graphite oxide: A selective and highly efficient oxidant of thiols and sulfides
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The selective oxidation of thiols to disulfides and sulfides to sulfoxides using graphite oxide (GO), a heterogeneous carbocatalyst obtained from low cost, commercial starting materials is described. The aforementioned oxidation reactions were found to proceed rapidly (as short as 10 min in some cases) and in good yield (51-100%) (19 examples). No over-oxidation of the substrates was observed, and GO's heterogeneous nature facilitated isolation and purification of the target products.
- Dreyer, Daniel R.,Jia, Hong-Peng,Todd, Alexander D.,Geng, Jianxin,Bielawski, Christopher W.
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supporting information; experimental part
p. 7292 - 7295
(2011/12/02)
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- Phosphorus oxychloride promoted hydrogen peroxide for selective oxidation of thiols to disulfides
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Oxidation of aliphatic and aromatic thiols to the corresponding symmetric disulfides was achieved by using POCl3/H2O2. A new procedure for the oxidation of thiols to disulfides without any over oxidation has been reported. It is noteworthy that the reacti
- Lakouraj,Hasantabar
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experimental part
p. 919 - 920
(2011/12/16)
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- Arylglyoxals: A novel and efficient reagent for the oxidation of thiols to homodisulfides
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The stoichiometric oxidation of thiols to their corresponding homodisulfides by arylglyoxals has been described. The process has several advantages: high yields, short reaction times, simple experimental and work-up procedures. Figure Presented.
- Mosslemin, Mohammad Hossein,Anary-Abbasinejad, Mohammad,Movahhed, Abolfazl Eshghi,Hassanabadi, Alireza,Ghoroghchian, Saeedeh
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experimental part
p. 111 - 115
(2012/01/06)
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- CARBOCATALYSTS FOR CHEMICAL TRANSFORMATIONS
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The disclosure relates to catalytically active carbocatalysts, e.g., a graphene oxide or graphite oxide catalyst suitable for use in a variety of chemical transformations. In one embodiment, it relates to a method of catalyzing a chemical reaction of an organic molecule by reacting the organic molecule in the presence of a sufficient amount of graphene oxide or graphite oxide for a time and at a temperature sufficient to allow catalysis of a chemical reaction. According to other embodiments, the reaction may be an oxidation reaction, a hydration reaction, a dehydrogenation reaction, a condensation reaction, or a polymerization reaction. Some reactions may include auto-tandem reactions. The disclosure further provides reaction mixtures containing an organic molecule and graphene oxide or graphite oxide in an amount sufficient to catalyze a reaction of the organic molecule.
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Page/Page column 56-57
(2011/12/14)
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- The thermal and mass spectral fragmentation of N-butyl thiolo-, thiono-, and dithio-chloroformate
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Thermal decomposition of n-butyl thiolochloroformate at 150C follows a similar pattern to that reported previously for n-butyl chloroformate, to give butyl chloride which is largely rearranged to the s-butyl isomer. An ion-pair mechanism, involving 1,2-and 1,3-hydride shifts, is proposed. The less stable thiono-and dithio-chloroformates decompose to give lower yields of butyl chlorides (mainly without rearrangement) together with numerous other byproducts, indicating the operation of a more complex combination of reaction pathways. The mass spectra of all three thio compounds exhibit molecular ions; the most prominent fragment ions in their spectra are the n-butyl cation, and the radical cations COS+ and CS2+. Numerous chlorine-containing ions of low intensity are also observed, and their mode of formation is discussed. Copyright Taylor &Francis Group, LLC.
- Hudson, Harry R.,Koplick, Andrew J.
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experimental part
p. 1635 - 1649
(2011/10/08)
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- Ionic liquids - Promoted S-methylation of thiols utilizing dimethyl carbonate
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Convenient and efficient S-methylation of mercaptans or thiophenols occurs with dimethyl carbonate (DMC) in room temperature ionic liquids (RTILs) [Bmim]Cl. [Bmim]Cl can be recycled in four subsequent runs with only a gradual decrease in activity. A possible mechanism of this transformation is also discussed. Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file. Copyright Taylor & Francis Group, LLC.
- Xie, Jiangang,Wu, Chengyao,Christopher, Branford White,Quan, Jing,Zhu, Limin
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experimental part
p. 31 - 37
(2011/04/22)
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- Easy and rapid method for disulfide syntheses using nanophase-manganese (VII) oxide coated clay
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Disulfide bond formation by the oxidation of several thiol compounds using nanophase manganese (VII) oxide coated clay (NM7O coated clay) in chlorinated, nonchlorinated (toluene), and polar solvents (water) is described. During the process, nitro and methoxy groups remain unaffected. The NM7O coated clay is easily prepared, stable, and inexpensive to manufacture. Furthermore, this and other studies prove that NM7O coated clay properties, i.e., mineralogy, chemical, and reactivity, are different from KMnO4. This rapid and facile synthesis coupled with the use of the recyclable NM7O coated clay catalyst will save energy due to low temperature and rapid reaction times, as well as minimal disposal problems, thus decreasing production costs.
- Gondi, Sudershan R.,Son, David Y.,Biehl, Edward R.,Vempati, Rajan K.
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scheme or table
p. 34 - 39
(2010/05/02)
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- CpMn(CO)3-catalyzed photoconversion of thiols into disulfides and dihydrogen
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The UV photolysis of CpMn(CO)3 with thiols at room temperature effected the following catalytic transformation: 2 RSH → R 2S2 + H2. This reaction is a cleaner and greener way toward making disulfides, as it produces dihydrogen as the only side-product. The manganese system exhibits high chemoselectivity as the transformation proceeds efficiently even in the presence of numerous functional groups. A manganese dicarbonyl complex, CpMn(CO)2RSH, and cyclopentadiene have also been detected using FTIR and NMR spectroscopic techniques, respectively. Based on our experimental data, a mechanism has been proposed to account for the catalysis.
- Tan, Kheng Yee Desmond,Kee, Jun Wei,Fan, Wai Yip
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experimental part
p. 4459 - 4463
(2011/01/10)
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- An efficient and selective oxidation of sulfides and thiols with silica-supported 1,1,3,3-tetramethylguanidine/Br2 complex
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Silica-supported 1,1,3,3-tetramethylguanidine/Br2 complex is an efficient reagent for the selective oxidation of aliphatic and aromatic sulfides to the corresponding sulfoxides and the oxidative coupling of thiols to disulfides in aqueous solution at room temperature in a short reaction time.
- Shaabani, Ahmad,Farhangi, Elham,Rahmati, Abbas
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experimental part
p. 463 - 468
(2010/06/19)
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