36832-47-0

Basic information

• Product Name: Benzene, 1-(ethenylsulfinyl)-4-methyl-
• Synonyms: 4-methylphenyl vinyl sulfoxide;(+/-)-4-Vinylsulfin-toluol;p-tolyl vinyl sulfoxide;vinyl-4-tolylsulfoxide;p-tolyl-vinyl sulfoxide;p-Tolyl-vinyl-sulfoxid
• CAS NO: 36832-47-0
• Molecular Formula: C9H10OS
• Molecular Weight: 166.244
• Mol File: 36832-47-0.mol

Chemical Properties

• CAS DataBase Reference: Benzene, 1-(ethenylsulfinyl)-4-methyl-(CAS DataBase Reference)
• NIST Chemistry Reference: Benzene, 1-(ethenylsulfinyl)-4-methyl-(36832-47-0)
• EPA Substance Registry System: Benzene, 1-(ethenylsulfinyl)-4-methyl-(36832-47-0)

Safety Data

• Hazardous Substances Data: 36832-47-0(Hazardous Substances Data)

Upstream product

• 79-24-3 Nitroethane 
• 31536-21-7 isopropyl 4-methylbenzenesulfinate 
• 1826-67-1 vinyl magnesium bromide 
• 106-45-6 para-thiocresol 
• 216855-39-9 (S)-N-(p-tolylsulfinylimino)triphenylphosphorane 
• 188447-91-8 (S)-p-toluenesulfinimide 
• 1517-82-4 (1R,2S,5R,SS)-(-)-menthyl p-toluenesulfinate 
• 103-19-5 di(p-tolyl) disulfide 
• 1519-40-0 (+)-(R)-ethyl p-tolyl sulfoxide 
• 50635-73-9 (R_S,R)-1-(1-bromoethylsulfinyl)-4-methylbenzene 
• 98-80-6 phenylboronic acid 
• 10439-23-3 4-methylbenzenesulfinyl chloride 
• 16336-54-2 p-tolyl vinyl sulfide 

Downstream Products

• 108873-43-4 diethyl-[2-(toluene-4-sulfinyl)-ethyl]-amine 
• 77670-24-7 3-nitro-1-p-tolylsulphinylbutane 
• 27328-17-2 (+)-p-tolyl vinyl sulphoxide 
• 111849-28-6 5-<(tert-butyldimethylsilyl)oxy>-4,4-dimethylpentyl p-tolyl sulfoxide 
• 103-19-5 di(p-tolyl) disulfide 
• 405-31-2 bis(4-fluorophenyl)disulfide 
• 1519-40-0 (+)-(R)-ethyl p-tolyl sulfoxide 
• 27328-17-2 (S)-(-)-p-tolyl vinyl sulfoxide 
• 54828-68-1 (R)-p-tolyl vinyl sulfoxide 
• 62961-00-6 (S)-1-(ethylsulfinyl)-4-methylbenzene 
• 1315281-55-0 C₁₃H₁₈OSi 
• 86012-02-4 (C₆H₅)3SnCH₂CH₂S(O)C₆H₄CH₃ 
• 137603-97-5 1-(1-Allyl-pent-4-enylsulfanyl)-4-methyl-benzene 
• 28415-26-1 1-Methyl-4-(2-phenylsulfanyl-ethanesulfinyl)-benzene 

Relevant articles and documents

Gold(I)-Catalyzed Synthesis of Highly Substituted 1,4-Dicarbonyl Derivatives via Sulfonium [3,3]-Sigmatropic Rearrangement

An efficient and straightforward gold-catalyzed protocol for the synthesis of 2-substituted 4-oxo-4-arylbutanal derivatives from commercially available or easily accessible alkynes and vinylsulfoxide substrates has been developed. Extension of the methodology to the use of 1-cycloalkenyl sulfoxides allowed the facile synthesis of five-, six-, and seven-membered-ring cycloalkyl-1-one backbone. Subsequently, the tetrahydrocycloalkyl[b]pyrrole derivatives, which are found in many active pharmaceutical ingredients, were isolated in good yields. Mechanistic investigation highlighted a [3,3]-sigmatropic rearrangement of a sulfonium intermediate in this process.

Extended Pummerer fragmentation mediated by carbon dioxide and cyanide

Pummerer rearrangement reactions generate sulfur (II) oxidation state from sulfur (IV) starting materials in the presence of activating reagents. We found unprecedented transformation of vinyl sulfoxide; disulfide formation reactions mediated by atmospheric pressure of carbon dioxide in extended Pummerer rearrangement reactions. Only under CO2 atmosphere, we observed moderate to high yields of disulfide starting from sulfur (IV) starting materials. Investigations on the reaction mechanism revealed that the degradation of the starting materials and the products was significant in the absence of CO2. Further evidence for the suggested reaction mechanism was obtained by a cross-over experiment and a radical trapping reagent.

Hydrogenative Kinetic Resolution of Vinyl Sulfoxides

Enantiopure sulfoxides are valuable precursors of organosulfur compounds with broad application in organic and pharmaceutical chemistry. An unprecedented strategy for obtaining highly enantioenriched sulfoxides based on a hydrogenative kinetic resolution using Rh-complexes of phosphine-phosphite ligands as catalysts is reported. After optimization, highly efficient conditions for the kinetic resolution of racemic sulfoxides have been identified. This methodology has been applied to a set of racemic aralkyl or aryl vinyl sulfoxides and allowed the isolation of both recovered and reduced products in excellent yields and enantioselectivities (up to 99% and 97% ee, respectively; 16 examples).

Palladium-catalyzed suzuki-miyaura reaction involving a secondary sp 3 carbon: Studies of stereochemistry and scope of the reaction

Palladium-catalyzed C-C bond formation involving secondary sp 3-hybridized carbon is described. These reactions occur with secondary 1-bromoethyl arylsulfoxides and different arylboronic acids, to produce the corresponding arylated sulfoxides in moderate to high yields and with complete stereospecificity. Despite the presence of β hydrogens in the substrate, the competitive β-hydride elimination is not a significant side reaction when coordinating solvents are used. The reported cross-coupling involves secondary Csp3-Csp2 bond formation: this is the first time that a mechanistic study has been carried out with such substrates. The reaction proceeds with inversion of configuration at the stereogenic C sp3 carbon. The high stereospecificity of the coupling and the mildness of the reaction conditions allow for the preservation of the optical purities of reagents and products and the preparation of useful chiral targets.

Synthesis of functionalized asymmetric star polymers containing conductive polyacetylene segments by living anionic polymerization

Novel 3-arm ABC, 4-arm ABCD, and 5-arm ABCDE asymmetric star polymers comprising the conductive polyacetylene precursor, poly(4-methylphenyl vinyl sulfoxide) (PMePVSO), and other segments, such as polystyrene, poly(α-methylstyrene), poly(4-methoxystyrene)

Serial ligand catalysis: A highly selective allylic C-H oxidation

We are reporting a mild, chemo-, and highly regioselective Pd(II)-catalyzed allylic oxidation of α-olefins to furnish branched allylic esters that proceeds via a novel serial ligand catalysis mechanism in which two different ligands (i.e., vinyl sulfoxide 2 and BQ) interact sequentially with the metal to promote distinct steps of the catalytic cycle (i.e., C-H cleavage and π-allyl functionalization, respectively). Copyright

Vinyl sulfoxides as stereochemical controllers in intermolecular Pauson-Khand reactions: Applications to the enantioselective synthesis of natural cyclopentanoids

The use of sulfoxides as chiral auxiliaries in asymmetric intermolecular Pauson-Khand reactions is described. After screening a wide variety of substituents on the sulfur atom in α,β-unsaturated sulfoxides, the readily available o-(N,N-dimethylamino)phenyl vinyl sulfoxide (1i) has proved to be highly reactive with substituted terminal alkynes under N-oxide-promoted conditions (CH3CN, 0°C). In addition, these Pauson-Khand reactions occurred with complete regioselectivity and very high diastereoselectivity (de = 86→96%, (S,RS) diastereomer). Experimental studies suggest that the high reactivity exhibited by the vinyl sulfoxide 1i relies on the ability of the amine group to act as a soft ligand on the alkyne dicobalt complex prior to the generation of the cobaltacycle intermediate. On the other hand, both theoretical and experimental studies show that the high stereoselectivity of the process is due to the easy thermodynamic epimerization at the C5 center in the resulting 5-sulfinyl-2- cyclopentenone adducts. When it is taken into account that the known asymmetric intermolecular Pauson-Khand reactions are limited to the use of highly reactive bicyclic alkenes, mainly norbornene and norbornadiene, this novel procedure constitutes the first asymmetric version with unstrained acyclic alkenes. As a demonstration of the synthetic interest of this sulfoxide-based methodology in the enantioselective preparation of stereochemically complex cyclopentanoids, we have developed very short and efficient syntheses of the antibiotic (-)-pentenomycin I and the (-)-aminocyclopentitol moiety of a hopane triterpenoid.

Asymmetric Intermolecular Pauson-Khand Reactions of Unstrained Olefins: The (o-Dimethylamino)phenylsulfinyl Group as an Efficient Chiral Auxiliary

The first asymmetric version of intermolecular Pauson?Khand reactions of unstrained alkenes is described. Generally simple acyclic alkenes exhibit low reactivity and regioselectivity in intermolecular Pauson?Khand reactions; however, o-(dimethylamino)phen

Synthesis of nonracemic α-trifluoromethyl α-amino acids from sulfinimines of trifluoropyruvate

We describe a novel and useful method for the synthesis of nonracemic α-trifluoromethyl α-amino acids (α-Tfm-AAs). Key building blocks are the sulfinimines (S)-1a and (S)-1b, prepared by Staudinger reaction from trifluoropyruvate esters and the chiral N-sulfinyl iminophosphorane (S)-8, which were treated with benzyl, allyl, and alkylmagnesium halides. The resulting diastereomeric N-sulfinyl α-Tfm α-amino esters, 12 and 13, were produced with moderate to good stereoselectivity and yields. When alkyl Grignard reagents were used, stereocontrol became progressively higher with increasing steric bulk, while reversed, though poor, stereocontrol was achieved with benzyl/allyl Grignard reagents. An explanation for the observed stereochemical outcome is proposed, on the basis of the exclusive E geometry (N-sulfinyl and CF3 trans about the C=N bond) of the chiral sulfinimines 1. This assignment is the product of structural correlation and is supported by ab initio calculations and NOE experiments. Sulfinamides 12 and 13 were transformed into a series of nonracemic α-Tfm-AAs 16-22. The sulfinyl auxiliary can be regenerated and recycled.

Oxidation of aryl vinyl sulfides in the Butooh-Ti(OPri)4-(R,R)-diethyl tartrate system

Oxidation of aryl vinyl sulfides into aryl vinyl sulfoxides in the ButOOH-Ti(OPri)4-(R, R)-diethyl tartrate system was studied. The process afforded low optical yields (no more than 5%). A model of the oxidation was proposed that allows interpreting the dependence of the reaction enantioselectivity on the structure of a substrate.