Oxidation of sulfides to sulfoxides. Part 2: Oxidation by hydrogen peroxide

Kaczorowska, Katarzyna; Kolarska, Zofia; Mitka, Katarzyna; Kowalski, Piotr

doi:10.1016/j.tet.2005.05.044

Cited by 385 publications

(145 citation statements)

References 91 publications

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“…The interest specifically stemsfromthe potentialapplication of suchsulfurcontaining entitiesinthe process of preparingcompounds of biologicalimportance [1] as well as from potential applications in the desulfurization of crudeoil in industrial-scale petrochemicalindustry processes [ 2].Ap romising pathway in this contexti s researchdone on the field of polymer-bound oxidovanadium species [3][4][5][6][7]. In the wake of testing the effectiveness of one of our catalysts with oxidizing methylphenylsulfide, the title compound wasobtained.Toascertainthe chemicalcomposition of the productand confirm the effected mono-oxidation, its crystal structure wasdetermined.…”

Section: Discussionmentioning

confidence: 99%

Crystal structure of methylphenylsulfoxide, C7H8OS

Hosten

Tshentu

Betz

2014

Zeitschrift Für Kristallographie - New Crystal Structures

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Source of materialThec ompoundw as obtained in analogy to the procedures describedinreferences [3-7]. Crystals suitable for the diffraction studywereobtaineduponcooling thereaction productto0°C. Experimental detailsCarbon-boundHatoms were placed in calculated positions(C-H 0.95 Å) andwereincludedinthe refinement in the riding model approximation, with U iso (H) setto1.2U eq (C). The Hatoms of the methyl group were allowed to rotate with afixed angle around the C-C bond to best fit the experimental electron density (HFIX 137 in the SHELX program suite [11]), with U iso (H) setto1.5U eq (C). DiscussionThe development and synthesis of powerful and targeted oxygenation catalysts to convert organic sulfides into sulfoxides and sulfonesh as been af ocus of research in chemistry. The interest specifically stemsfromthe potentialapplication of suchsulfurcontaining entitiesinthe process of preparingcompounds of biologicalimportance[1] as well as from potential applications in the desulfurization of crudeoil in industrial-scale petrochemicalindustry processes [ 2].Ap romising pathway in this contexti s researchdone on the field of polymer-bound oxidovanadium species [3][4][5][6][7]. In the wake of testing the effectiveness of one of our catalysts with oxidizing methylphenylsulfide, the title compound wasobtained.Toascertainthe chemicalcomposition of the productand confirm the effected mono-oxidation, its crystal structure wasdetermined. Thecompound is an asymmetric sulfoxidefeaturing amethyl andaphenyl group bonded to the sulfur atom. The S-O bond length of 1.4938(12) Åisingood agreement-although slightlytowards smallervalues-withothervaluesreported for organic sulfoxides whose structural data wasdeposited with the Cambridge Structural Database [8].The angles aroundthe sulfur atom spanarangeof97.40 (7)-107.18 (7)°with the smallest angle foundinbetween the two organic substituentsand the largest angle apparent in betweenthe oxygen atom and the phenyl group. Theleast-squares planes as defined by the non-hydrogen atomsof the phenyl moiety on the one hand and the O=S-C ar entity on the otherhand intersect at an angle of 16.49(9)°only.Inthe crystal, intermolecularC -H×××Oc ontacts can be observed whose range falls invariably by more than 0.1 Åb elow the sum of van-derWaals radii of the atoms participatinginthem. These are exclusively supported by hydrogen atomso ft he methyl group. The oxygen atom serves as two-fold acceptor but could be discussed to be the end point of athird C-H×××Ocontact, the latter one being an intramolecular onestemming from ahydrogen atom in ortho position on the aromatic substituent. This could explain the small torsional angle as mentioned above for the intersection of the least-suqaresp lanes. In total, them olecules are connected to planes perpendiculart ot he crystallographic c axis.I nt erms of graph-seta nalysis[ 9, 10],t he descriptor for these contacts is S(5)C 1 1 (4)C 1 1 (4) on the unary level. The shortest intercentroid distance between two centers of gravity was found at 4.9447(10) Åruling ...

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Section: Discussionmentioning

confidence: 99%

Crystal structure of methylphenylsulfoxide, C7H8OS

Hosten

Tshentu

Betz

2014

Zeitschrift Für Kristallographie - New Crystal Structures

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“…By addition of absolute ether to the reaction mixture, a initial crop (25-28%) of the corresponding chlorides precipitated and after standing one more day, from the filtrate an additional 24-26% (total 49-54%) of the salt deposited. Some other attempts were conducted in the presence of weak oxidant reagents, which are reported in literature to afford only sulfoxide, without over-oxidation, such as sodium periodate supported on wet silica gel, 15 hydrogen peroxide and N-hydroxysuccinimide, 16 The new glycosides 7e-i were also prepared in moderate yield (54-60%) within a research program directed to the synthesis of thiophenes derivatives with polyhydroxylated alkyl side chains in position 2. Having a number of useful properties, which include chirality, rigidity, lipophilicity, hydrophilicity, and flexibility in one system, polyhydroxyalkyl thiophenes are quite interesting scaffolds to utilize in the synthesis of a variety of biologically interesting molecules.…”

Section: Methodsmentioning

confidence: 99%

Synthesis of new 2-substituted 3-amino-4-hydroxymethylthiophenes through intramolecular nitrile oxide cycloaddition processes and N,O-bond cleavage

Pistarà¹,

Corsaro²,

Chiacchio³

et al. 2011

Arkivoc

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A synthesis of new 2-substituted 3-amino-4-hydroxymethylthiophenes 7 is reported as a useful alternative to the long known oximation of oxothiophenes 8, followed by treatment with gaseous hydrochloric acid in a polar solvent. The synthesis consists of an INOC process of unsaturated sulfide nitrile oxides, obtained from the condensation of corresponding nitroalkenes and allylmercaptan and then dehydration, which leads to tetrahydrothieno [3,4-c]

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“…There are a lot of reagents available for the oxidation of dialkyl, alkylaryl and diaryl sulfides to sulfoxides. 10 Most of them cause over oxidation to sulfones. Therefore, the condition of the reaction, that is time, temperature and relative amounts of oxidants have to be controlled to avoid side product formation.…”

Section: Scheme 1 N-methylthiomethylation Of Benzimidazolesmentioning

confidence: 99%

N-Methylthiomethylation of benzimidazoles with DMSO and their chemoselective oxidation to sulfoxides with NaBiO3

Mukhopadhyay¹,

Tapaswi²,

Sarkar³

et al. 2011

Arkivoc

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A straightforward one-step method for the N-methylthiomethylation of benzimidazoles has been developed employing DMSO as a solvent and as a reagent. This methodology has been applied for the synthesis of diverse N-methylthiomethyl derivatives of benzimidazoles. The products can be chemoselectively oxidized to the corresponding sulfoxides with NaBiO3 in acetic acid. Both the N-methylthiomethyl derivatives of benzimidazoles and their corresponding sulfoxides are important medicinal scaffolds.

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Oxidation of sulfides to sulfoxides. Part 2: Oxidation by hydrogen peroxide

Cited by 385 publications

References 91 publications

Crystal structure of methylphenylsulfoxide, C7H8OS

Crystal structure of methylphenylsulfoxide, C7H8OS

Synthesis of new 2-substituted 3-amino-4-hydroxymethylthiophenes through intramolecular nitrile oxide cycloaddition processes and N,O-bond cleavage

N-Methylthiomethylation of benzimidazoles with DMSO and their chemoselective oxidation to sulfoxides with NaBiO3

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