1669-98-3Relevant academic research and scientific papers
Tert-Butyl Nitrite Mediated Expeditious Methylsulfoxidation of Tetrazole-amines with DMSO: Metal-free Synthesis of Antifungal Active Methylsulfinyl-1H-tetrazole Derivatives
Dai, Peng,Luo, Kai,Yu, Xiang,Yang, Wen-Chao,Wu, Lei,Zhang, Wei-Hua
, p. 468 - 473 (2018)
A tert-butyl nitrite mediated methyl-sulfoxidation of tetrazole-amines in neat DMSO or methyl-sulfinyl derivatives is revealed for the first time. The reaction exhibits good group tolerance, as well as highly selectivity to sulfinyl substitutions. This new protocol provides an expeditious and operationally simple procedure for C?S(O) bond construction. Preliminary bioactivity evaluation on selected products shows promising antifungal activities. (Figure presented.).
Stereospecific Reductive Desulfinylation of 1-Aryl-2-(methylsulfinyl)-2-(methylthio)ethenes with Grignard Reagents
Ogura, Katsuyuki,Arai, Kazutaka,Tsuchihashi, Gen-ichi
, p. 3669 - 3670 (1982)
(E)-1-Aryl-2-(methylsulfinyl)-2-(methylthio)ethene, obtained by the Knoevenagel-type condensation of methyl (methylthio)methyl sulfoxide with the corresponding aromatic aldehyde, was found to react with ethylmagnesium chloride to give (Z)-1-aryl-2-(methylthio)ethene predominantly.Since the reaction of (Z)-1-(methylsulfinyl)-1-(methylthio)-2-phenylethene afforded (E)-1-(methylthio)-2-phenylethene, the present reaction appeared to be stereospecific.
Calix[4]arene-based (hemi)carcerands and carceplexes: Synthesis, functionalization, and molecular modeling study
Van Wageningen, Andre M. A.,Timmerman, Peter,Van Duynhoven, John P. M.,Verboom, Willem,Van Veggel, Frank C. J. M.,Reinhoudt, David N.
, p. 639 - 654 (1997)
The synthesis of 11 calix[4]arene-based carceplexes obtained by solvent or doped inclusion is reported. Carceplexes with amides, for example, DMF, NMP, and 1,5-dimethyl-2-pyrrolidinone, and sulfoxides, for example, DMSO and thiolane-1-oxide, were obtained by solvent inclusion. In these cases the yield of the carceplex decreases with increasing guest size. Potential guests that do not form carceplexes by solvent inclusion, such as 2-butanone and 3-sulfolene, could be incarcerated by doped inclusion with 1.5-dimethyl-2-pyrrolidinone as a solvent 'doped' with 5-15 vol% of potential guest. The amide bridges of the carceplexes were converted into thioamide bridges in essentially quantitative yield by means of Lawesson's reagent in refluxing xylene. The dynamic properties of the incarcerated guests were examined by 2D NMR spectroscopy. Whereas for most guests a preference for one orientation inside the calix[4]arene-based (thia)carcerands was observed, for DMA, NMP, and ethyl methyl sulfoxide inside calix[4]arene-based (thia)carcerands two different orientations were present. The energy barriers for interconversion between the various orientations of DMA, NMP, and ethyl methylsulfoxide inside calix[4]arene-based (thia)-carcerands were determined with 2D EXSY NMR. The energy barriers are higher for the thiacarcerands than for the corresponding careerands with amide bridges. This may be due to the stronger hydrogen-bond-donating character of the thioamide group. Furthermore, molecular modeling simulations indicate that in case of the thiacarcerand the cavity is smaller as a result of a smaller diametrical distance between the NH atoms. Our results demonstrate that molecular modeling can be used to estimate the energy barriers for interconversion; the calculated activation energies showed good quantitative agreement with the experimental values.
Poly(ethylene) glycol as a green and reusable solvent in the oxidation of sulfides to sulfoxides using NaClO
Amoozadeh, Ali,Nemati, Firouzeh
, p. 1381 - 1385 (2010)
This article describes selective oxidation of a range of sulfides to the corresponding sulfoxides in good yields by NaClO in poly(ethylene) glycol as a green and reusable solvent using sulfuric acid as an efficient acid catalyst. The new method compares favorably with previous methods in literature. A separable mixture of two new diastereoisomers is reported. Copyright Taylor & Francis Group, LLC.
Synthesis and characterization of 3-[N,N′-bis-3-(salicylidenamino) ethyltriamine] Mo(vi)O2@SBA-15: A highly stable and reusable catalyst for epoxidation and sulfoxidation reactions
Lazar, Anish,Thiel, Werner R.,Singh
, p. 14063 - 14073 (2014)
The efficient and reusable oxidation catalyst 3-[N,N′-bis-3- (salicylidenamino)ethyltriamine] Mo(vi)O2@SBA-15 has been synthesized by the anchoring of the 3-[N,N-bis-3-(salicylidenamino)ethyltriamine] ligand (L or Salpr) on the inner surfaces of organofunctionalized SBA-15 and subsequent complexation with Mo(vi)O2(acac)2. The physico-chemical properties of the functionalized catalysts were analyzed by elemental analysis, ICP-OES, XRD, N2-sorption measurements, TG & DTA, solid state 13C, 29Si NMR spectroscopy, FT-IR, Raman spectroscopy, XPS, DRS UV-Vis spectroscopy, SEM and TEM. XRD and N2 sorption analyses helped to find out the morphological and textural properties of the synthesized catalysts and confirm that an ordered mesoporous channel structure was retained even after the multistep synthetic procedures. The (100), (110) and (200) reflections in SBA-15 provide hints of a good structural stability, the existence of long range ordering and a high pore wall thickness. TG and DTA results reveal that the thermal stability of (L)Mo(vi)O2@SBA-15 was maintained up to 300°C. The organic moieties anchored over the surface of the SBA-15 support were determined by solid state 13C NMR and FT-IR spectroscopy. Further, solid state 29Si NMR spectroscopy provides the information about the degree of functionalization of the surface silanol groups with the organic moiety. The electronic environment and the oxidation state of the molybdenum site in (L)Mo(vi)O2@SBA-15 were monitored by Raman spectroscopy, XPS and DRS UV-Vis techniques. Moreover, the morphology and topographic information of the synthesized catalysts were confirmed by SEM and TEM imaging. The synthesized catalysts were evaluated in epoxidation and sulfoxidation reactions, and the results show that (L)Mo(vi)O2@SBA-15 exhibits high conversion and selectivity towards epoxidation and sulfoxidation reactions in combination with high stability. The anchored solid catalysts can be recycled effectively and reused several times without major loss in activity. In addition, Sheldon's hot filtration test was also carried out.
Sulphoxidation of ethyl methyl sulphide, 4-chlorophenyl methyl sulphide and diphenyl sulphide by purified pig liver flavin-containing monooxygenase
Nnane, Ivo P.,Damani
, p. 83 - 91 (2003)
1. The biotransformation of ethyl methyl sulphide (EMS), 4-chlorophenyl methyl sulphide (CPMS) and diphenyl sulphide (DPS) to their corresponding sulphoxides by purified flavin-containing monooxygenase (FMO) is described. 2. Purified pig liver flavin-containing monooxygenase catalysed the sulphoxidation of EMS, CPMS and DPS to their corresponding sulphoxides and the reactions followed single enzyme Michelis-Menten kinetics. 3. The apparent Km and Vmax for the sulphoxidation of EMS were 1.38 ± 0.05 mM and 78.74 ± 3.9 nmoles mg-1 protein min-1, respectively. The apparent Km and Vmax for the sulphoxidation of CPMS were 0.185 ± 0.03 mM and 103 ± 5.0 nmoles mg-1 protein min-1, respectively. The apparent Km and Vmax for the sulphoxidation of DPS were 0.068 ± 0.002 mM and 49.26 ± 2.05 nmoles mg-1 protein min-1, respectively. 4. A significant reduction of the sulphoxidation of these simple sulphides was observed with addition of 1-naphthylthiourea in the incubation medium. On the other hand, incorporation of catalase and superoxide dismutase into the incubation media produced no appreciable inhibition of the observed sulphoxidation of the sulphides. 5. These results suggest that FMO is responsible, at least in part, for the sulphoxidation of nucleophilic sulphides as well as for the oxidation of sulphur atoms that reside within or adjacent to aromatic systems.
A Tricopper(I) Complex Competent for O Atom Transfer, C-H Bond Activation, and Multiple O2 Activation Steps
Cook, Brian J.,Di Francesco, Gianna N.,Kieber-Emmons, Matthew T.,Murray, Leslie J.
, p. 11361 - 11368 (2018)
Oxygenation of a tricopper(I) cyclophanate (1) affords reactive transients competent for C-H bond activation and O atom transfer to various substrates (including toluene, dihydroanthracene, and ethylmethylsulfide) based on 1H NMR, gas chromatography/mass spectrometry (MS), and electrospray ionization (ESI)/MS data. Low product yields (1H NMR, and density functional theory (DFT) results for reaction of 1 with O2 are consistent with transient peroxo- and di(oxo)-bridged intermediates. DFT calculations elucidate a concerted proton-coupled electron transfer from toluene to the di(μ-oxo) intermediate and subsequent radical rebound as the C-H activation mechanism. Our results support a multicopper oxidase-like mechanism for O2 activation by 1, traversing species similar to the coplanar Cu3O2 unit in the peroxy and native intermediates.
Eight-membered ring petal-shaped V8 cluster: An efficient heterogeneous catalyst for selective sulfur oxidation
Ping, Qing-Dong,Cao, Jia-Peng,Han, Ye-Min,Yang, Mu-Xiu,Hong, Ya-Lin,Li, Jia-Nian,Wang, Ji-Lei,Chen, Jia-Li,Mei, Hua,Xu, Yan
, (2020)
An eight-membered ring petal-shaped cluster [V8ⅣO8(CH3O)16(C2O4)](C6NH16)2(CH3OH)2 (V8) has been successfully designed and synthesized via hydrothermal method. Structure analysis revealed that each vanadium atom was in an octahedral geometrical configuration six-coordinated, two adjacent vanadium atoms were linked by oxygen atoms on oxalic acid to form a ring. The selective sulfur oxidation experiments reveal that V8 had good catalytic activity under mild conditions, and the removal rate of phenyl sulfide was >99% within 4 h at 40 °C. In addition, the open aperture Z-scan test of V8 was carried out and found that V8 also has latent application value as nonlinear optical (NLO) material.
Correlating the role of hydrophilic/hydrophobic nature of Rh(I) and Ru(II) supported organosilica/silica catalysts in organotransformation reactions
Lazar, Anish,George, Shoy C.,Jithesh,Vinod,Singh
, p. 138 - 146 (2016)
Highly reactive and hydrophobic triphenyl phosphine based rhodium(I) and ruthenium(II) organometallic complexes over benzene containing periodic mesoporous organosilica (PMOB) have been synthesized. This has been achieved by the immobilization of neat metal complexes like RhCl(PPh3)3 [Wilkinson catalyst], RuHCl(CO)(PPh3)3 and RuCl2(PPh3)3 over aminofunctionalized PMOB to get RhCl(PPh3)2-PrNH2PMOB, RuHCl(CO)(PPh3)2-PrNH2PMOB and RuCl2(PPh3)3-PrNH2PMOB, respectively. The physico-chemical properties of the functionalized catalysts were analyzed by elemental analysis, ICP-OES, XRD, N2 sorption analyses, FT-IR, solid state 13C and 29Si NMR spectra, XPS, SEM, TEM and contact angle measurements. The XRD and N2 sorption analyses showed excellent textural properties with ordered mesoporous channel structure of all synthesized catalysts. The organic moieties anchored in PMOB were confirmed by 13C CPMAS NMR and FT-IR spectroscopy with 29Si CPMAS NMR spectroscopy providing the information about the degree of functionalization of surface silanol groups with organic moiety. The Rh(I) and Ru(II) complexes supported on MCM-41/SBA-15/PMOE (ethane-PMO) were synthesized, and their catalytic activities in hydrogenation and sulfoxidation reactions were compared with Rh(I) and Ru(II) complexes supported on PMOB. The results show that PMOB based catalysts exhibit higher activities and selectivities than MCM-41/SBA-15/PMOE supported catalysts, neat homogeneous complexes and without catalyst. The better catalytic performance of PMOB based catalyst is attributed to the hydrophobic nature and high surface area of the PMOB support. The recycling studies of anchored catalysts show no major deactivation of the catalyst.
A clean, mild, and selective oxidation of sulfides to sulfoxides using NaClO/H2SO4 in Aqueous Media
Amoozadeh, Ali,Nemati, Firouzeh
, p. 2569 - 2575 (2009)
A range of sulfides can be selectively oxidized to the corresponding sulfoxides in good yields using NaClO/H2SO4 in both water and 50:50 water:EtOH as solvent. Two new compounds are reported that show a diastereoselective oxidation in 2-phenylthioalcohols with possible neighboring hydroxyl group participation with a logic proposed mechanism. Taylor & Francis Group, LLC.
