Vinyl Sulphones Research Articles

Addition of phenyl areneselenosulphonates to acetylenes:a route to acetylenic sulphones

Treatment of phenyl areneselenosulplonates (1) with terminal acetylenes resulted in the formation of β-(phenylseleno)vinyl sulphones (2), which on treatment with excess of hydrogen peroxide in tetrahydrofuran at room temperature gave acetylenic sulphones (3) in good yields.

Reaction of vinyl sulphone with α-metallated nitriles

Vinyl sulphones (1) were subjected to nucleophilic addition by α-lithionitriles (2) and gave cyclized products, 3-oxothian 1,1-dioxides (3) or cyclopropane derivatives (4), in satisfactory yields according to the substituents on the reagents. The cyclopropanation reactions could be extended to the formation of cyclopropyl sulphides (12)–(16) in good yields.

Base catalysed addition of phenols to aryl vinyl sulphones

The addition of some phenols to aryl vinyl sulphones was studied in 1:1 (v/v) aqueous ethanol at 25°C in the presence of a basic catalyst. The reaction follows second-order kinetics, being first order in the sulphone and first order in the phenolate ion, the only active nucleophile. The Hammett and Bronsted equations were used to correlate the effects of substituents in the aromatic ring of the substrate and of the nucleophile. These both indicate that while there is a large accumulation of negative charge on the carbon α to the sulphonyl group in the transition state, the degree of formation of the C–O bond depends on the substituent in the ring of the sulphone. The reactivity of the phenolates, despite their greater basicity, is lower by a factor of some 4 × 104 than that of the arenethiolates studied previously. The following order of reactivity has been estabilished: PhO– < OH– < EtO– PhS–; this indicates that polarizability and/or solvation are more important than Bronsted basicity in determining the reactivity in the addition of anionic nucleophiles to aryl vinyl sulphones.

Aryl versus alkyl and vinyl migration in the mass spectra of sulphone derivatives

AbstractThe 2‐acetoxyethyl aryl sulphones were found to be unsuitable for a comparative study with the corresponding chlorides and alcohols as their predominant fragmentation involved cleavage of the aliphatic carbon‐sulphur bond with charge retention on the aliphatic part of the molecule The expected McLafferty rearrangement to yield an intermediate vinyl species was only a minor fragmentation path.Indirect evidence for alkyl migration in the molecular ion was found in the spectrum of 2‐acetoxyethyl 1‐paranitro phenyl sulphone. The spectra of the aryl vinyl sulphones revealed intense [Aryl SO]+ ions resulting from preferred migration of the vinyl group from sulphur to oxygen.

Kinetics of the nucleophilic addition of some aromatic thiols to aryl vinyl sulphones

Download options Please wait... Article information DOI https://doi.org/10.1039/J29710002335 Article type Paper Download Citation J. Chem. Soc. B, 1971, 2335-2338 BibTex EndNote MEDLINE ProCite ReferenceManager RefWorks RIS Permissions Request permissions Kinetics of the nucleophilic addition of some aromatic thiols to aryl vinyl sulphones P. De Maria and A. Fini, J. Chem. Soc. B, 1971, 2335 DOI: 10.1039/J29710002335 To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page. If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given. If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page. Read more about how to correctly acknowledge RSC content. Search articles by author P. De Maria A. Fini

Elimination–addition. Part XI. Electronic effects upon the reactivity of aryl vinyl sulphones towards amines

Rates of addition of t-butylamine to a series of nuclear-substituted aryl vinyl sulphones have been measured for reactions in ethanol at 25°. The results are well correlated by the Hammett σρ relationship, the value of ρ=+1·59 being obtained with substituents possessing σ constants in the range –0·268 to +0·778. The reaction is compared with others which proceed via a carbanionic transition state.

42—NEW REACTIONS IN REDUCED WOOL FIBRES

The ·SH-groups in reduced wool react quickly and smoothly with vinyl sulphones as occurs with cysteine in model experiments. From this, an analytical method is developed for determining the extent of reduction in wool. Bifunctional divinyl sulphone leads to an extensive network formation in the fibres. Dimethyl maleate and N-p-phenetyl maleinimide also react quickly with ·SH-wool. These alkylating agenls replace the labile ·S·S·bonds in wool by stable thioether bonds. The ease of reaction of vinyl sulphones also allows the recognition of ·SH groups formed by the action of KCN and of NaOH on wool. ·SH-wool has also been treated with thiosulphinic acid esters, whereby unsymmetrically substituted ·S·S· bonds can be produced in wool. Cyclic thiosulphinic acid sters lead to a network formation in the fibre. It is thus possible for the first time to introduce additional ·S·S· bonds into wool with an increase in the total S content. Unsymmetrical disulphides and bis-disuiphides are recognised in the wool hydroly...