- Nucleophile-induced intramolecular dipole 1,5-transfer and 1,6-cyclization: Experimental and ab initio studies of formation, thermolysis, and molecular and electronic structures of 3,6-diphenyl-1-propanesulfenimido-1,2,4,5-tetrazine
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Reaction of dichlorobenzaldazine (2) with sodium azide followed by 1-propanethiol/Et3N furnished tetrazine ylide 1 as the main product. The structure of this unprecedented ylide was confirmed with single-crystal X-ray analysis [C17H17N5S, monoclinic P21/n a = 6.8294(4) A, b = 13.6781(9) A, c = 17.5898(12) A, β = 90.666(1)°, Z = 4] and favorably compared with the results of ab initio calculations. The mechanisms of formation of the ylide and its thermal decomposition to 2,5-diphenyltetrazine (5) were investigated using ab initio methods and correlated with the experimental observations. The results suggest that formation of 1 involves intramolecular cyclization of a nitrile imine and thermolysis of 1 might generate a sulfenylnitrene. The formation of 1 is considered to be the first example of a potentially more general reaction.
- Kaszynski, Piotr,Young Jr., Victor G.
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- A coordination network that catalyzes O2-based oxidations
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Reaction of Tb(III) and two bridging ligands, a redox-active benzoic acid-terminated hexavandate ([V6O13{(OCH2)3C(4-CONHC6H4CO2H)}2]2- (1) and 4,4′-bis(pyridine-N-dioxide) (bpdo) produces a catalytically active open-framework pillared layer-type coordination polymer, Tb1. The network material catalyzes aerobic oxidation of PrSH to PrSSPr and the oxidation tetrahydrothiophene (THT) to tetrahydrothiophene oxide (THTO) by tert-butylhydroperoxide under ambient conditions. Tb(III) ions and bpdo units form two-dimensional (2D) coordination layers, and the 2D layers are connected by 1 to produce a three-dimensional coordination network. IR and powder X-ray diffraction of Tb1 before and after catalysis indicate the catalyst maintains an open framework structure during the catalytic reactions. Copyright
- Jong, Woo Han,Hill, Craig L.
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- Application of Bulky NHC-Rhodium Complexes in Efficient S-Si and S-S Bond Forming Reactions
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The efficient and straightforward syntheses of silylthioethers and disulfides are presented. The synthetic methodologies are based on new rhodium complexes containing bulky N-heterocyclic carbene (NHC) ligands that turned out to be efficient catalysts in thiol and thiol-silane coupling reactions. These green protocols, which use easily accessible reagents, allow obtaining compounds containing S-Si and S-S bonds in solvent-free conditions. Additionally, preliminary tests on coupling of mono- and octahydro-substituted spherosilicates with selected thiols have proved to be very promising and showed that these catalytic systems can be used for the synthesis of a novel class of functionalized silsesquioxane derivatives.
- Bo?t, Ma?gorzata,?ak, Patrycja
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supporting information
p. 17579 - 17585
(2021/11/18)
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- Substituted o-Aminophenols as Redox-Mediators in the Thiol Oxidation to Unsymmetrical Disulfides
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A number of substituted o-aminophenols has been investigated as redox mediators of the thiol oxidation to disulfides. The electrooxidation of o-aminophenols leads to the corresponding o-iminobenzoquinones. These compounds react with thiols in the solution with a formation of disulfides. It was established that the use of 4,6-di-tert-butyl-2-(tert-butylamino)phenol as a redox mediator can reduce the overpotential of the thiol oxidation by 0.2-1.4 V depending on the nature of the coupling thiols. The unsymmetrical disulfides with alkyl, aryl, and heteroaryl substituents were obtained as the result of the indirect electrosynthesis.
- Berberova, Nadezhda T.,Burmistrova, Daria A.,Galustyan, Andrey,Smolyaninov, Ivan V.
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- Copper-catalyzedortho-selective direct sulfenylation ofN-aryl-7-azaindoles with disulfides
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A copper-catalyzed direct C-H chalcogenation ofN-aryl-azaindoles with disulfides is described. This transformation was performed using Earth abundant Cu(OAc)2as a catalyst, benzoic acid as an additive, air as a terminal oxidant, and readily available diaryl and dialkyldisulfides (or diselenide) as chalcogenation reagents. High functional group tolerance and excellent regioselectivity are demonstrated by the efficient preparation of a wide range ofortho-sulfenylation-7-azaindoles.
- Ru-Jian, Yu,Chun-Yan, Zhang,Xiang, Zhou,Xiong, Yan-Shi,Duan, Xue-Min
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supporting information
p. 2901 - 2906
(2021/04/14)
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- METHOD FOR OXIDATION OF SULFUR-CONTAINING COMPOUNDS
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Various embodiments disclosed relate to a method of oxidizing sulfur-containing compounds. The method involves contacting a sulfur-containing compound with a helmet phthalocyaninato-type catalyst in the presence of an oxidant. The present invention also provides a method of removing undesired sulfur-containing compounds from a fluid, such as natural gas, crude oil or an aqueous waste stream.
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Paragraph 0141-0142
(2021/10/30)
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- Transformation of arylboronic acids with sodium thiosulfate into organodisulfides catalyzed by a recyclable polyoxometalate-based Cr(iii) catalyst
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Organo disulfides represent an abundant class of compounds in chemical biology, pharmaceutical fields, and industry. They are traditionally synthesized by the oxidation of mercaptan in the presence of an organic ligand supported metal catalyst or toxic oxidants under harsh conditions. Here, we disclose a highly-efficient pathway in which disulfide is synthesized by organic boric acid and Na2S2O3 using the catalyst (NH4)3[CrMo6O18(OH)6], demonstrating a high activity and excellent selectivity. Various boric acid derivatives have been successfully transformed into the corresponding disulfides. Mechanistic insights have been furnished based on the observation of intermediate and control experiments.
- Chang, Yalin,Li, Huiyi,Tao, Chaofu,Wang, Aiping,Wei, Yongge,Xie, Ya,Yu, Han,Yu, Shunming
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supporting information
p. 6059 - 6064
(2021/08/23)
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- Directed oxidative coupling of thiols in the synthesis of unsymmetrical disulfides
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Oxidative coupling of two different thiols bearing aliphatic, alicyclic, aromatic, and hetero-aromatic moieties promoted by mild oxidizing agents, viz., sterically hindered o-benzo(imino)-quinones, carried out in N-methylpyrrolidone at room temperature led to unsymmetrical disulfides. Among the studied oxidizers, the most active was 3,6-di-tert-butyl-o-benzoquinone, which, in contrast to 3,5-di-tert-butyl-o-benzoquinone, was not involved in the Michael addition. Under the optimal reaction conditions, the yields of the target unsymmetrical disulfides reach 81%.
- Berberova, N. T.,Burmistrova, D. A.,Smolyaninov, I. V.
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p. 990 - 995
(2020/06/17)
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- Key Odor-Active Compounds in Raw Green and Red Toona sinensis (A. Juss.) Roem. And Their Changes during Blanching
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Application of aroma extract dilution analysis and headspace aroma dilution analysis revealed 51 odorants in raw green Toona sinensis and 54 odorants in raw red T. sinensis in the flavor dilution factor range of 8-4096. (E,E)-2,4-Decadienal, nonanal, 2,3,5-trimethylpyrazine, (E,Z)- and (Z,Z)-di-1-propenyl trisulfide, 2-methoxyphenol, and 4-ethylphenol were first identified as key odorants of T. sinensis. Clear differences between green and red T. sinensis in aroma profiles, flavor dilution factors, quantitative data, and odor activity values verified that (E,E)-, (E,Z)-, and (Z,Z)-di-1-propenyl disulfide, (E,E)-, (E,Z)- and (Z,Z)-di-1-propenyl trisulfide, cis- and trans-2-mercapto-3,4-dimethyl-2,3-dihydrothiophene, and dimethyl sulfide caused the distinct sulfury odor note of each variety. Further, hexanal, (E)-2-hexenal, (E)-2-hexen-1-ol, and (E,Z)-2,6-nonadienal led to the green odor note in green T. sinensis, while 2-methoxyphenol and 4-ethylphenol contributed to the intense phenolic aroma note in red T. sinensis. Quantitation experiments and triangle tests in blanched T. sinensis verified that the quick loss of the abovementioned sulfur-containing compounds, aldehydes, the alcohol (E)-2-hexen-1-ol, and phenols was responsible for the changes in the overall aroma profile during blanching.
- Granvogl, Michael,Zhai, Xiaoting
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p. 7169 - 7183
(2020/07/21)
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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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- Ni/NHC-catalyzed cross-coupling of methyl sulfinates and amines for direct access to sulfinamides
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It was reported to develop a simple and convenient method for the Ni/NHC-catalyzed cross-coupling of methyl sulfinates and amines without an acid/base to afford secondary or tertiary sulfinamides in moderate to good yields. The method can provide the desired products with broad substrate scope, good chemoselectivity and good functional group compatibility. The presented approach may enrich the Ni/NHC catalyst system and promote the applications of methyl sulfinates in the organic sulfur chemistry.
- Li, Gang-Jian,Pan, You-Lu,Liu, Yan-Ling,Xu, Hai-Feng,Chen, Jian-Zhong
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supporting information
(2019/10/28)
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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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- Thermal conversion of primary alcohols to disulfides: Via xanthate intermediates: An extension to the Chugaev elimination
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Primary alcohols are converted into dialkyl disulfides via heating in situ generated O-alkyl S-difluoro(ethoxycarbonyl)methyl xanthates from ethyl bromodifluoroacetate and potassium xanthates, prepared from primary alcohols and carbon disulfide in the presence of KOH. The reaction mechanism is suggested as an alkyl C[1,3] shift followed by a radical mechanism. This extends to the Chugaev elimination which yields olefins. The current research provides easy access to dialkyl disulfides from commercially available primary alkanols.
- He, Wei,Ding, Yong,Tu, Jianzhuo,Que, Chuqiang,Yang, Zhanhui,Xu, Jiaxi
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p. 1659 - 1666
(2018/03/21)
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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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- 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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- Solvent- and metal-free selective oxidation of thiols to disulfides using I2/DMSO catalytic system
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We describe herein a simple, fast and inexpensive protocol for the oxidative coupling of thiols employing a stoichiometric amount of DMSO and iodine as the catalyst. Various aromatic disulfides were obtained in good to excellent yields in short reaction times at room temperature, while aliphatic disulfides were achieved in good yields when the reactions were conducted under microwave irradiation.
- Bettanin, Luana,Saba, Sumbal,Galetto, Fábio Z.,Mike, Gustavo A.,Rafique, Jamal,Braga, Antonio L.
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supporting information
p. 4713 - 4716
(2017/11/21)
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- Dicationic Thiolate-Bridged Diruthenium Complexes for Catalytic Oxidation of Molecular Dihydrogen
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Dicationic thiolate-bridged diruthenium complexes bearing sterically bulky alkane substituents on the thiolate ligands such as [Cp?Ru(μ-SiPr)2Ru(OH2)Cp?](OTf)2 have been found to work as effective catalysts toward oxidation of molecular dihydrogen into protons and electrons in protic solvents such as water and methanol. DFT calculations indicate that the sterically bulky alkane substituent in the complex plays an important role in facilitating the reaction step of the coordination of molecular dihydrogen.
- Yuki, Masahiro,Sakata, Ken,Nakajima, Kazunari,Kikuchi, Syoma,Sekine, Shinobu,Kawai, Hiroyuki,Nishibayashi, Yoshiaki
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supporting information
p. 4499 - 4506
(2017/12/05)
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- Polyoxometalate-based gelating networks for entrapment and catalytic decontamination
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We report the synthesis and characterization of a new class of organic/inorganic hybrid polymers composed of covalently-bound 1,3,5-benzenetricarboxamide linkers and anionic polyoxovanadate clusters with varying counter-cations. These materials form gels within seconds upon contact with polar aprotic organic liquids and catalyze the degradation of odorants and toxic molecules under mild conditions including aerobic oxidation of thiols, hydrogen peroxide-catalyzed oxidation of sulfides, and hydrolysis of organophosphate chemical warfare agent analogues.
- Sullivan, Kevin P.,Neiwert, Wade A.,Zeng, Huadong,Mehta, Anil K.,Yin, Qiushi,Hillesheim, Daniel A.,Vivek, Skanda,Yin, Panchao,Collins-Wildman, Daniel L.,Weeks, Eric R.,Liu, Tianbo,Hill, Craig L.
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supporting information
p. 11480 - 11483
(2017/10/23)
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- Thiol Reactivity toward Atomic Oxygen Generated during the Photodeoxygenation of Dibenzothiophene S-Oxide
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Aromatic heterocyclic oxides, such as dibenzothiophene S-oxide (DBTO), have been suggested to release ground state atomic oxygen [O(3P)] upon irradiation, and as such, they have been used to create a condensed phase reactivity profile for O(3P). However, thiols, which are highly reactive with O(3P) in the gas phase, were not previously investigated. An earlier study of O(3P) with proteins in solution indicated a preference for thiols. A further investigation of the apparent thiophilicity provided the subject for this study. DBTO was employed as a putative O(3P)-precursor. However, the effective rate of O(3P) formation was found to be dependent on reactant concentrations in certain cases. All reactants were found to increase the rate of deoxygenation to some extent, but in the presence of reactants containing an alcohol linked to a reactive functional group, deoxygenation occurred substantially more rapidly. The rate enhancement was quantified and attributed to the reaction of activated O atom within the solvent cage prior to escape into the bulk solution. Through competition experiments, the relative rate constants of O(3P) with thiols and other functional groups were found. A small preference for primary thiols was observed over other thiols, sulfides, and alkenes. A much larger preference was observed for thiols, sulfides, and alkenes over aromatic groups. In summary, DBTO was successfully used as an O(3P)-precursor, and the thiophilicity of O(3P) was confirmed and quantified.
- Omlid, Sara M.,Zhang, Miao,Isor, Ankita,McCulla, Ryan D.
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p. 13333 - 13341
(2017/12/15)
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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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- 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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- A two in one approach: Renewable support and enhanced catalysis for sweetening using chicken feather bound cobalt(II) phthalocyanine under alkali free environment
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Poultry waste chicken feathers, an inexpensive and abundantly available material has been used as a renewable support for immobilizing a cobalt phthalocyanine catalyst. The synthesized heterogeneous cobalt(ii) phthalocyanine catalyst was used for the aerobic oxidation of mercaptans to the corresponding disulfides using ultrasonic irradiation under alkali free conditions. The significantly higher catalytic activity of the heterogeneous catalyst as compared to a homogeneous one can be attributed to the synergistic effect of the support matrix. In addition, the catalyst could easily be recovered and recycled for several runs without loss of activity, which makes the process greener and more cost-effective.
- Chauhan, Deepak K.,Patnam, Padma L.,Ganguly, Sudip K.,Jain, Suman L.
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p. 51983 - 51988
(2016/06/13)
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- Visible-light-mediated facile synthesis of disulfides using reusable TiO2/MoS2nanocomposite photocatalyst
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A nontoxic and inexpensive TiO2/MoS2nanocomposite was prepared and employed as an efficient photocatalyst for the synthesis of symmetrical disulfides under visible light irradiation at room temperature. Both aryl and alkyl thiols survived the reaction conditions, affording the corresponding disulfides in good to excellent yields. The photocatalyst could be easily recovered by simple centrifugation and filtration and reused several times without significant loss in its activity.
- Liu, Wenjie,Wang, Cancan,Huang, Yibo,Chen, Qun,Wang, Liang,He, Mingyang
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supporting information
p. 1268 - 1274
(2016/08/16)
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- The cytotoxicity of garlic-related disulphides and thiosulfonates in WHCO1 oesophageal cancer cells is dependent on S-thiolation and not production of ROS
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Background Garlic has been used for centuries in folk medicine for its health promoting and cancer preventative properties. The bioactive principles in crushed garlic are allyl sulphur compounds which are proposed to chemically react through (i) protein S-thiolation and (ii) production of ROS. Methods A collection of R-propyl disulphide and R-thiosulfonate compounds were synthesised to probe the importance of thiolysis and ROS generation in the cytotoxicity of garlic-related compounds in WHCO1 oesophageal cancer cells. Results A significant correlation (R2 = 0.78, Fcrit (7,1) α = 0.005) was found between the cytotoxicity IC50 and the leaving group pKa of the R-propyl disulphides and thiosulfonates, supporting a mechanism that relies on the thermodynamics of a mixed disulphide exchange reaction. Disulphide (1) and thiosulfonate (11) were further evaluated mechanistically and found to induce G2/M cell-cycle arrest and apoptosis, inhibit cell proliferation, and generate ROS. When the ROS produced by 1 and 11 were quenched with Trolox, ascorbic acid or N-acetyl cysteine (NAC), only NAC was found to counter the cytotoxicity of both compounds. However, NAC was found to chemically react with 11 through mixed disulphide formation, providing an explanation for this apparent inhibitory result. Conclusion Cellular S-thiolation by garlic related disulphides appears to be the cause of cytotoxicity in WHCO1 cells. Generation of ROS appears to only play a secondary role. General significance Our findings do not support ROS production causing the cytotoxicity of garlic-related disulphides in WHCO1 cells. Importantly, it was found that the popular ROS inhibitor NAC interferes with the assay.
- Smith, Muneerah,Hunter, Roger,Stellenboom, Nashia,Kusza, Daniel A.,Parker, M. Iqbal,Hammouda, Ahmed N.H.,Jackson, Graham,Kaschula, Catherine H.
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p. 1439 - 1449
(2016/05/09)
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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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- 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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- 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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- Magnetic Fe3O4@MgAl-LDH composite grafted with cobalt phthalocyanine as an efficient heterogeneous catalyst for the oxidation of mercaptans
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Magnetically separable layered double hydroxide MgAl-LDH@Fe3O4 composite supported cobalt phthalocyanine catalyst was synthesized and used for the aerobic oxidation of mercaptans to corresponding disulfides under alkali free conditions. The catalyst exhibited excellent activity for the oxidation of mercaptans using molecular oxygen as an oxidant which can be effectively recovered by using an external magnetic field. In addition, the covalent immobilization of cobalt phthalocyanine to MgAl-LDH@Fe3O4 support prevents the leaching of the catalyst and improves its activity and stability.
- Kumar, Pawan,Gill, Kareena,Kumar, Sunil,Ganguly, Sudip K.,Jain, Suman L.
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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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- Deep eutectic mixture catalysed the synthesis of disulfides using Bunte salts as thiol surrogates
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Bunte salts, easily prepared from odourless sodium thiosulfates and various alkyl and aryl halides, acted as thiol surrogates for preparation of disulfides in the presence of hydrogen peroxide and a Bronsted-acidic deep eutectic mixture. The reaction proceeded smoothly to give the corresponding disulfide products in moderate to good yields, leaving odourless sodium bisulfite and water as the by-products. Moreover, this catalytic system could be readily recovered and reused several times without significant loss in activity.
- Zhou, Yongsheng
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p. 332 - 335
(2015/08/18)
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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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- Direct synthesis of disulfides from alkyl halides using thiourea and CCl4 in glycerol
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Abstract Dialkyl disulfides were obtained on the basis of the reaction of alkyl halides and thiourea in the presence of CCl4 and Et3N. This procedure enables the odorless and one-pot synthesis of disulfides by employing cheap, easy-to-handle and readily available reagents and substrates in wet glycerol.
- Abbasi, Mohammad,Khalili, Dariush
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p. 1425 - 1430
(2015/06/22)
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- Marine bacteria from the Roseobacter clade produce sulfur volatiles via amino acid and dimethylsulfoniopropionate catabolism
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Dimethylsulfoniopropionate (DMSP) is a versatile sulfur source for the production of sulfur-containing secondary metabolites by marine bacteria from the Roseobacter clade. 34S-labelled DMSP and cysteine, and several DMSP derivatives with modified S-alkyl groups were synthesised and used in feeding experiments that gave insights into the biosynthesis of sulfur volatiles from these bacteria. the Partner Organisations 2014.
- Brock, Nelson L.,Menke, Markus,Klapschinski, Tim A.,Dickschat, Jeroen S.
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supporting information
p. 4318 - 4323
(2014/06/23)
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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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- Redox chemistry between graphene oxide and mercaptan
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We report here redox reactions between graphene oxide (GO) and mercaptans, which reduces GO to reduced graphene oxide (RGO) and oxidizes mercaptans into disulfides. The reduction processes of GO using various mercaptans as the reducing agents are investigated through XPS, TGA, FT-IR, Raman and EA analysis. The degree of reduction of RGO depends on molecular structure of mercaptans and is controlled by the reaction time. The redox reaction is also employed to oxidize mercaptans into disulfides in medium to high yields under moderate conditions. The mechanism of the redox reaction may involve nucleophilic ring opening of oxirane on GO by alkylthio moiety, followed by addition of another alkylthio group, leaving the resulting disulfide. The reduction of the hydroxy group could be more complex, involving both radical and anionic processes.
- Fan, Deqin,Zhang, Chao,He, Junpo,Hua, Rong,Zhang, Yang,Yang, Yuliang
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experimental part
p. 18564 - 18571
(2012/10/08)
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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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- Base-free oxidation of thiols to disulfides using selenium ionic liquid
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We present here the results on the use of 1-n-butyl-3-methylimidazolium methylselenite, [bmim][SeO2(OCH3)], in the synthesis of symmetrical disulfides starting from thiols. This efficient and improved method is general for aromatic, aliphatic, and functionalized thiols affording the disulfides in good to excellent yields after easy work up. The use of a microwave accelerates the reaction and the [bmim][SeO2(OCH 3)] was reused for further oxidation reactions.
- Thurow, Samuel,Pereira, Vanda A.,Martinez, Débora M.,Alves, Diego,Perin, Gelson,Jacob, Raquel G.,Lenard?o, Eder J.
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experimental part
p. 640 - 643
(2011/02/28)
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- A Multiunit catalyst with synergistic stability and reactivity: A polyoxometalate-metal organic framework for aerobic decontamination
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A combination of polyanion size and charge allows the Keggin-type polyoxometalate (POM), [CuPW11O39]5-, a catalyst for some air-based organic oxidations, to fit snuggly in the pores of MOF-199 (HKUST-1), a metal-organic framework (MOF) with the POM countercations residing in alternative pores. This close matching of POM diameter and MOF pore size in this POM-MOF material, [Cu3(C9H3O 6)2]4[{(CH3)4N} 4CuPW11O39H] (1), results in a substantial synergistic stabilization of both the MOF and the POM. In addition, this heretofore undocumented POM-MOF interaction results in a dramatic increase in the catalytic turnover rate of the POM for air-based oxidations. While 1 catalyzes the rapid chemo- and shape-selective oxidation of thiols to disulfides and, more significantly, the rapid and sustained removal of toxic H 2S via H2S + 1/2 O2 → 1/8 S8 + H2O (4000 turnovers in 20 h), the POM or the MOF alone is catalytically slow or inactive. Three arguments are consistent with the catalytic reactions taking place inside the pores. POM activation by encapsulation in the MOF likely involves electrostatic interactions between the two components resulting in a higher reduction potential of the POM.
- Song, Jie,Luo, Zhen,Britt, David K.,Furukawa, Hiroyasu,Yaghi, Omar M.,Hardcastle, Kenneth I.,Hill, Craig L.
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supporting information; experimental part
p. 16839 - 16846
(2011/12/14)
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- An improved method for the synthesis of disulfides by periodic acid and sodium hydrogen sulfite in water
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An improved method for the synthesis of disulfide in water by using periodic acid and sodium hydrogen sulfite was developed.
- Khan, Khalid M.,Taha, Muhammad,Rahim, Fazal,Ali, Muhammad,Jamil, Waqas,Perveen, Shahnaz,Iqbal Choudhary
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experimental part
p. 415 - 419
(2011/03/22)
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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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- Metal-free air oxidation of thiols in recyclable ionic liquid: A simple and efficient method for the synthesis of disulfides
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An efficient procedure for the oxidative coupling of alkyl, aryl and heteroaryl thiols with atmospheric oxygen is reported. The methodology utilizes BMIM-BF4 as a recyclable solvent and does not require support materials or metal salts. Symmetric disulfides are obtained in excellent yields.
- Singh, Devender,Galetto, Fabio Z.,Soares, Letiere C.,Rodrigues, Oscar E. Dorneles,Braga, Antonio Luiz
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experimental part
p. 2661 - 2665
(2010/07/18)
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- A one-pot, efficient, and odorless synthesis of symmetrical disulfides using organic halides and thiourea in the presence of manganese dioxide and wet polyethylene glycol (PEG-200)
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Primary, secondary, tertiary, allylic, and benzylic halides are converted efficiently into symmetric disulfides in high yields using thiourea as the sulfur atom source. The reactions are odorless and are performed at 30-35 °C in wet PEG-200 using MnO2 as an oxidant.
- Firouzabadi, Habib,Iranpoor, Nasser,Abbasi, Mohammad
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experimental part
p. 508 - 509
(2010/10/02)
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- Distinct catalytic effect of micellar solution of sodium dodecyl sulfate (sds) for one-pot conversion of alkyl halides to disulfides via an odourless process using thiourea and mno2
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A novel one-pot odourless synthesis of symmetrical disulfides from their corresponding halides in aqueous mediausing thiourea and MnO2 in the presence of NaHCO3 or Na2CO3 catalyzed by micellar solution of sodium dodecyl sulfate (SDS) is described. By this method, primary, allylic and benzylic halides were converted into their corresponding disulfides in high yields.
- Firouzabadi, Habib,Iranpoor, Nasser,Abbasi, Mohammad
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experimental part
p. 698 - 702
(2010/08/08)
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- Catalytic oxidation of thiols to disulfides using iodine and CeCl3·7H2O in graphite
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A very simple procedure for the efficient oxidation of thiols to disulfides catalyzed by I2/CeCl3·7H2O in graphite and ethyl acetate as the solvent, in an open system at room temperature is described. The reaction proceeds cleanly under mild conditions and was performed with aromatic, aliphatic, and heterocyclic thiols.
- Silveira, Claudio C.,Mendes, Samuel R.
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p. 7469 - 7471
(2008/03/14)
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- Cleavage of C=N derivatives and oxidation of thiols in water under neutral conditions with 1,4-dichloro-1,4-diazoniabicyclo[2,2,2]octane bischloride
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1,4-Diazabicyclo[2,2,2]octane (DABCO) is easily chlorinated and gives a complex which efficiently converts aliphatic and aromatic oximes, phenylhydrazones and semicarbazones to their corresponding carbonyl compounds in water at 50°C in high yield. This reagent can also be used for conversion of thiols to their compounding disulfide under the same reaction conditions. DABCO is quantitatively recovered which can be rechlorinated and reused several times.
- Tajbakhsh, Mahmood,Habibzadeh, Setareh
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p. 486 - 489
(2008/09/20)
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- H14[NaP5W30O110] as a heterogeneous recyclable catalyst for the air oxidation of thiols under solvent free conditions
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The catalytic oxidation of thiols to the corresponding disulfides using Preyssler's catalyst H14[NaP5W30O 110] has been studied. These highly selective oxidations gave good yields of the target disulfides.
- Hekmatshoar, Rahim,Sajadi, Sodeh,Heravi, Majid M.,Bamoharram, Fatemeh F.
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p. 2223 - 2228
(2008/02/11)
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- Iron (III) perchlorate adsorbed on silica gel: A reagent for organic functional group transformations
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Adsorption of Fe(ClO4)3(H2O)6 onto chromatographic-grade silica gel in the presence of organic solvents (S=water, acetonitrile, or lower fatty acids) produces a supported reagent, Fe(ClO4)3(S)6/SiO2. This reagent has been found to be effective for the rapid organic functional group transformations such as dimerization of alkynes, aromatic hydrocarbons, selective oxidation of thiols to disulfides, and transannular reactions in 1,5-cyclooctadienes on grinding using pestle and mortar in the solid state. Copyright Taylor & Francis Group, LLC.
- Parmar, Anupama,Kumar, Harish
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p. 2301 - 2308
(2008/02/10)
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- Simple method for the preparation of symmetrical alkyl and aryl disulfides with alkyl sulfonyl halides in nitrogenous base
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In the present study, the reaction of thiols with alkyl sulfonyl halides was carried out in a nitrogenous base to compare the reactivity of -SH with that of -OH, which, however, led to the formation of disulfides. The reaction achieved as a result offers the use of an inexpensive reagent, quantitative yields of the product, and simplicity for the formation of the S-S bond. Copyright Taylor & Francis Group, LLC.
- Ali, Firdous Imran,Hashmi, Imran Ali,Siddiqui, Bina S.,Rasheed, Munawwer
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p. 2461 - 2465
(2008/02/10)
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- Trifluoromethylthiolation of 1,3-dithiane
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With a view to synthesize 2-(trifluoromethylthio)-1,3-dithiane (1), 1,3-dithiane (2) was reacted in dry pentane at -78°C under dry N2 with trifluoromethylsulfenyl chloride (3) and was found to furnish the desired compound in poor yields along with ten other compounds. Under similar conditions, 2-lithio-1,3-dithiane on treatment with 2 and bis-(trifluoromethyl) disulfide (4) gave 8.0% and 10.0% yields of 1, respectively. In connection with this study, (cholromethyl) propyl sulfide and bis(propylthio)methane were synthesized. The reaction of the latter with 3 was also investigated. The characterization of the primary compound formed in the reaction of 2 with 3 using the 'INAPT'-NMR and GC-MS, the probable mechanism of the formation of the various compounds and their mass spectral identification are presented in this article. Copyright Taylor & Francis Group, LLC.
- Munavalli,Rohrbaugh,Szafraniec,Durst
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p. 305 - 324
(2008/02/04)
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- Inexpensive, one-pot synthesis of unsymmetrical disulfides using 1-chlorobenzotriazole
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A new synthesis of unsymmetrical disulfides is described. The reaction of a thiol R1SH with 1-chlorobenzotriazole (BtCl) at -78 °C in DCM affords a high-yielding conversion to R1SBt without appreciable formation of the symmetrical disulfide R1SSR1. R1SBt is then reacted with R2SH to form the unsymmetrical disulfide in a one-pot sequence with green character that avoids the use of toxic and harsh oxidizing agents. The methodology has been developed for synthesis of various types of disulfides.
- Hunter, Roger,Caira, Mino,Stellenboom, Nashia
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p. 8268 - 8271
(2007/10/03)
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- Potassium permanganate oxidation of organic compounds
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It has been discovered that potassium permanganate is an effective heterogeneous oxidant, even without resorting to the use of a solid support, if acetonitrile is employed as the solvent. Primary benzylic and secondary alcohols are converted to the corresponding aldehydes and ketones, alkyl arenes are oxidized to the corresponding α-ketones in good yields using this procedure, and both alkyl and aryl sulfides are smoothly converted to the corresponding sulfones, also in excellent yields. When methylene chloride is used as the solvent, instead of acetonitile, the yields of aldehydes, ketones, α-ketones, and sulfones are reduced. However, the oxidation of thiols to disulfides proceeds satisfactorily when methylene chloride is the solvent.
- Shaabani, Ahmad,Tavasoli-Rad, Farahnaz,Lee, Donald G.
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p. 571 - 580
(2007/10/03)
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