934-72-5

Usage

Uses

Used in Catalyst Applications:
1-METHYL-4-(METHYLSULFINYL)BENZENE is used as a catalyst in the preparation of homoallylic alcohols by the allylation of aldehydes with allyltrichlorosilane. It facilitates the reaction by lowering the activation energy and enhancing the reaction rate, leading to the formation of the desired product.
Used in Ligand Applications:
1-METHYL-4-(METHYLSULFINYL)BENZENE is used as a ligand in the synthesis of molybdenum chlorocomplexes. As a ligand, it plays a crucial role in stabilizing the metal center and influencing the properties and reactivity of the resulting complex. This application is particularly relevant in coordination chemistry and the development of new catalysts and materials.

Synthesis Reference(s)

Chemistry Letters, 15, p. 967, 1986Synthetic Communications, 19, p. 1569, 1989 DOI: 10.1080/00397918908051052Tetrahedron Letters, 19, p. 3415, 1978

InChI:InChI=1S/C8H10OS/c1-7-3-5-8(6-4-7)10(2)9/h3-6H,1-2H3

Upstream product

• 623-13-2 4-methylphenyl methylsulfide 
• 144-86-5 N-chloro-4-methylbenzenesulfonamide 
• 75-16-1 methylmagnesium bromide 
• 91378-37-9 S,S-diphenyl-(N-p-tolylfulfinyl)sulfoximine 
• 126218-83-5 1-bromo-2-(methylsulfinyl)benzene 
• 4294-57-9 para-methylphenylmagnesium bromide 
• 127-65-1 chloroamine-T 
• 74-88-4 methyl iodide 
• 942305-11-5 C₂₂H₂₁NO₃S₂ 
• 917-54-4 methyllithium 
• 39538-86-8 silver p-toluenesulfonate 
• 1519-39-7 (R)-(+)-methyl p-tolyl sulfoxide 
• 439585-11-2 N-[[[(benzyloxy)carbonyl]azanide]sulfonyl]-N,N-diethylethylammonium 
• 109-72-8 n-butyllithium 

Downstream Products

• 1600-44-8 1-oxothiolane 
• 623-13-2 4-methylphenyl methylsulfide 
• 67-68-5 dimethyl sulfoxide 
• 2211-89-4 diisopropyl sulfoxide 
• 2168-93-6 butyl sulfoxide 
• 13153-06-5 di-sec-butyl sulfoxide 
• 71899-71-3 (R)-(+)-3,3-dimethyl-1-(4-methylphenylsulfinyl)-2-butanone 
• 78687-06-6 2-((R)-Toluene-4-sulfinyl)-1-p-tolyl-ethanone 
• 52154-24-2 (R)-p-tolylsulfinylacetophenone 
• 68326-61-4 1-Cyclohexyl-2-((S)-toluene-4-sulfinyl)-ethanone 
• 700-58-3 2-Adamantanone 
• 29186-07-0 bisadamantylidene epoxide 
• 3185-99-7 Methyl p-tolyl sulfone 
• 131137-82-1 1-(2-Methoxyphenyl)-2-<(4-methylphenyl)sulphinyl>ethanone 

Relevant academic research and scientific papers

Unexpected nucleophilic participation and rearrangement of DBU in reactions with saccharin derivatives

DBU attacks saccharin derivatives with subsequent rearrangement to give rise to 3-[3′-(1″-azepin-2″-onyl)propylamino]-1, 2-benzisothiazole-1,1-dioxide 2 after work-up.

Synergistic cooperative effect of CF3SO2Na and bis(2-butoxyethyl)ether towards selective oxygenation of sulfides with molecular oxygen under visible-light irradiation

A safe, practical and eco-friendly method for the switchable synthesis of sulfoxides and sulfones through visible-light-initiated oxygenation of sulfides at ambient temperature under transition-metal-, additives-free and minimal solvent conditions. The synergistic catalytic efforts between CF3SO2Na and 2-butoxyethyl ether represents the key promoting factor for the reaction. This journal is

Niobium(V) oxido tris-carbamate as easily available and robust catalytic precursor for the selective sulfide to sulfone oxidation

The oxidation of the sulfide function promoted by a variety of vanadium compounds has been largely explored, whereas the use of homogeneous catalytic systems based on the heavier group 5 metals remains less explored. We report the use of easily available niobium and tantalum carbamates, i.e. [M(O2CNMe2)5] (M = Nb, 1; M = Ta, 2), [Nb(O2CNMe2)4], 3, [NbO(O2CNEt2)3], 4, and [NbCl3(O2CNEt2)2], 5, as effective catalysts for the conversion of a series of alkyl aryl and aromatic sulfides into the corresponding sulfones. NMR investigations on the performant niobium catalyst 4 unexpectedly revealed the substantial stability of this compound in the protic catalytic environment, and a plausible catalytic cycle was obtained by DFT studies. The two active catalytic species, i.e. 4 and its minor mono-methoxide derivative, presumably interconvert to each other exploiting the versatile coordination of the carbamato ligand.

Synthesis of a light-harvesting ruthenium porphyrin complex substituted with BODIPY units. Implications for visible light-promoted catalytic oxidations

A light-harvesting ruthenium porphyrin substituted covalently with four boron-dipyrrin (BODIPY) moieties has been synthesized and studied. The resulting complex showed an efficient decarbonylation reaction predominantly due to a photo-induced energy transfer process. Chemical oxidation of the ruthenium(ii) BODIPY-porphyrin afforded a high-energytrans-dioxoruthenium(vi) species that is one order of magnitude more reactive towards alkene oxidation than those analogues supported by conventional porphyrins. In the presence of visible light, the ruthenium(ii) BODIPY-porphyrin displayed remarkable catalytic activity toward sulfide oxidation and alkene epoxidation using iodobenzene diacetate [PhI(OAc)2] and 2,6-dichloropyridineN-oxide (Cl2pyNO) as terminal oxidants, respectively. The findings in this work highlight that porphyrin-BODIPY conjugated metal complexes are potentially useful for visible light-promoted catalytic oxidations.

Air atmospheric photocatalytic oxidation by ultrathin C,N-TiO2nanosheets

Herein, we demonstrate the highly efficient photocatalytic sulfide oxidation reaction under mild conditions,i.e.in air, at room temperature and in the absence of a sacrificial reagent, co-catalyst or redox mediator, by using ultrathin C,N-TiO2nanosheets as a photocatalyst.

Organocatalytic sulfoxidation

Treatment of a sulfide with a catalytic amount of a 1,3-diketone in the presence of silica sulfuric acid as a co-catalyst and hydrogen peroxide (50% aq) as the stoichiometric oxidant leads to the corresponding sulfoxide product. The reaction is effective for diaryl, aryl-alkyl and dialkyl sulfides and is tolerant of oxidisable and acid sensitive functional groups. Investigations have shown that the tris-peroxide 2, formed on reaction of pentane-2,4-dione with hydrogen peroxide under acidic reaction conditions, can oxidise two equivalents of sulfide using the exocyclic peroxide groups whereas the endocyclic peroxide remains intact. Calculations provide a mechanism consistent with experimental observations and suggest the reaction proceeds via an initial acid catalysed ring opening of a protonated tris-peroxide prior to oxygen transfer to a sulfur nucleophile.

Luminescent cis-Bis(bipyridyl)ruthenium(II) Complexes with 1,2-Azolylamidino Ligands: Photophysical, Electrochemical Studies, and Photocatalytic Oxidation of Thioethers

New 1,2-azolylamidino complexes cis-[Ru(bipy)2(NH=C(R)az*-κ2N,N)](OTf)2 (R = Me, Ph; az? = pz, indz, dmpz) are synthesized via chloride abstraction after a subsequent base-catalyzed coupling of a nitrile with the previously coordinated 1,2-azole. The synt

Electrochemical oxygenation of sulfides with molecular oxygen or water: Switchable preparation of sulfoxides and sulfones

A practical and eco-friendly method for the controllable aerobic oxygenation of sulfides by electrochemical catalysis was developed. The switchable preparation of sulfoxides and sulfones was effectively controlled by reaction time, in which both molecular oxygen and water can be used as the oxygen source under catalyst and external oxidant-free conditions. The electrochemical protocol features a broad substrate scope and excellent site selectivity and is successfully applied to the modification of some sulfide-containing pharmaceuticals and their derivatives. This journal is

Selectivity switch in the aerobic oxygenation of sulfides photocatalysed by visible-light-responsive decavanadate

Nanometre-sized metal oxides are promising species for the development of visible-light-responsive photocatalysts for the selective transformation of organic functional groups. In this article, we report that decavanadate ([V10O28]6-, V10) behaved as an efficient visible-light-responsive photocatalyst in the product-selective oxygenation of sulfides achieved using O2 (1 atm) as the green oxidant. In particular, we revealed that visible-light-responsive photocatalysis of V10 showed remarkable activity for the oxygenation of structurally diverse sulfides to form the corresponding sulfones using O2 in methyl ethyl ketone (MEK). Furthermore, by simply adding water to the reaction mixture, the product selectivity of sulfide oxygenation can be significantly switched toward the production of sulfoxides, without concomitant loss of photocatalytic activity. Based on experimental evidence, we inferred the following mechanistic steps for this photocatalytic system: the aerobic oxygenation of sulfides to form the corresponding sulfoxides initiated by a visible-light-induced photoredox reaction of V10. As for the formation of sulfones, MEK-derived peroxide species as the co-catalysts are probably involved in the oxygenation of sulfoxides to sulfones. The selectivity switch of the V10-photocatalysed reaction brought about by water addition is most likely achieved by suppressing the formation of MEK-derived peroxide species. This journal is

Formation and kinetic studies of manganese(IV)-oxo porphyrins: Oxygen atom transfer mechanism of sulfide oxidations

Visible light irradiation of photo-labile porphyrin-manganese(III) chlorates or bromates (2) produced manganese(IV)-oxo porphyrins [MnIV(Por)(O)] (Por = porphyrin) (3) in three porphyrin ligands. The same oxo species 3 were also formed by chemical oxidation of the corresponding manganese(III) precursors (1) with iodobenzene diacetate, i.e. PhI(OAc)2. The systems under study include 5,10,15,20-tetra(pentafluorophenyl)porphyrin?manganese(IV)-oxo (3a), 5,10,15,20-tetra(2,6-difluorophenyl)porphyrin?manganese(IV)-oxo (3b), and 5,10,15,20-tetramesitylporphyrin?manganese(IV)-oxo (3c). As expected, complexes 3 reacted with thioanisoles to produce the corresponding sulfoxides and over-oxidized sulfones. The kinetics of oxygen atom transfer (OAT) reactions of these generated 3 with aryl sulfides were studied in CH3CN solutions. Second-order rate constants for sulfide oxidation reactions are comparable to those of alkene epoxidations and activated C[sbnd]H bond oxidations by the same oxo species 3. For a given substrate, the reactivity order for the manganese(IV)-oxo species was 3a > 3b > 3c, consistent with expectations on the basis of the electron-withdrawing capacity of the porphyrin macrocycles. Free-energy Hammett analyses gave near-linear correlations with σ values, indicating no significant positive charge developed at the sulfur during the oxidation process. The mechanistic results strongly suggest [MnIV(Por)(O)] reacts as a direct OAT agent towards sulfide substrates through a manganese(II) intermediate that was detected in this work. However, an alternative pathway that involves a disproportionation of 3 to form a higher oxidized manganese(V)-oxo species may be significant when less reactive substrates are present. The competition product studies with the Hammett correlation plot confirmed that the observed manganese(IV)-oxo species is not the true oxidant for the sulfide oxidations catalyzed by manganese(III) porphyrins with PhI(OAc)2.