Allyl vinyl sulphide

Thiolsulphonates are effective in sulphenylation reactions, having been used recently for the stereoselective synthesis of allyl vinyl sulphides from RCH=CH-AlBu jBu". Mild reaction conditions are called for in the sulphenylation of active-methylene compounds by (ArS02)2CHSS02Ph. ... 

The double Diels-Alder reaction of tetrachlorothiophen 1,1-dioxide and allyl vinyl sulphide proceeded with cheletropic loss of SOj to give the hetero-isotwistene (26). Various Diels-Alder reactions of 2//-thiopyran yielded e/irfo-adducts, such as (27).28... 

Raasch has extended his studies of the reactivity of bis(trifluoro-methyl)thioketen (141). Scheme 8 gives a survey of the reactions that have been carried out. Thus common nucleophilic agents such as alcohols, thiols, primary, and secondary amines, etc., react with (141) with conservation of the C=S double bond, whereas the C==C double bond remains in the products of the reactions of (141) with certain ethers, dimethylaniline, and hydrides of tin and silicon. Compound (141) reacted with a variety of olehnic substances in accordance with the general ene-reaction formalism, yielding allyl vinyl sulphides (148). The formation... 

Substituents X and Y based on sulphur are particularly interesting. We have already seen that vinyl sulphides are latent ketones, that allyl sulphides form useful anions and that their sulphoxides give allyl alcohols. Evans17 has used cyclic allyl sulphoxide anions in an allyl alcohol synthesis, and has used the sulphoxide 148 in a Diels-Alder synthesis88 of the hasubanan derivative 149. 

A tracer study of the mechanism of the rearrangement of thiolsulphinate with acetic anhydride using 13C and lsO has been carried out by Oae and coworkers194. A deuterium isotope effect study of the mechanism of the reactions of singlet oxygen with allylic and vinylic sulphides,... 

Recognition of the role of sulphoxides in the inhibition chain has resulted in several studies of the autoxidation of mono- and disulphides (see later). In addition to the work by Hargrave [84], Bateman et al. [88— 90] have studied the oxidation of monosulphides, unsaturated monosulphides and cyclo-hex-2-enyl methyl sulphide. Allylic and vinylic sulphides were found to be much more reactive than saturated sulphides, although the methylene group, rather than the allylic double bond, was suggested to be the primary reaction centre. Reactivities were compared for the percentage yield of sulphoxide (A) and for the yield of hydroperoxide (B), viz. 

A detailed paper on the thermal rearrangements of allyl perchloro-vinyl sulphides has now appeared. Heating (32) to 100-120°(S led to mixtures of (33) and (34) in proportions indicated in the figures. The products were isolated by column chromatography and preparative gas chromatography. Diasteromeric mixtures of (33) were obtained. Treatment of (33a,c,d) with potassium t-butdxide gave (35). 

Uses of Saturated Sulphides, Selenides, and Tellurldes in Synthesis.— These applications are mostly based on the C—C bond-forming reactions of sulphenyl carbanions the extensive uses of vinyl sulphides and their allyl and propargyl analogues are discussed in a later section. Some methods for C—S or C—Se bond cleavage, which are used to terminate a use in synthesis, have been discussed in an earlier section other methods, notably the conversion of the sulphide into a sulphoxide followed by pyrolytic elimination of the sulphenic acid, are covered in later sections. 

The Wittig rearrangement of allyl vinyl and benzyl vinyl ethers brought about by strong bases is not shown by benzyl vinyl sulphides. Base-catalysed rearrangement of bis(propargyl) sulphides involves first the formation of the... 

ETHYLENE GLYCOL ETHYL MERCAPTAN DIMETHYL SULPHIDE ETHYL AMINE DIMETHYL AMIDE MONOETHANOLAMINE ETHYLENEDIAMINE ACRYLONITRILE PROPADIENE METHYL ACETYLENE ACROLEIN ACRYLIC ACID VINYL FORMATE ALLYL CHLORIDE 1 2 3-TRICHLOROPROPANE PROPIONITRILE CYCLOPROPANE PROPYLENE 1 2-DICHLOROPROPANE ACETONE ALLYL ALCOHOL PROPIONALDEHYDE PROPYLENE OXIDE VINYL METHYL ETHER PROPIONIC ACID ETHYL FORMATE METHYL ACETATE PROPYL CHLORIDE ISOPROPYL CHLORIDE PROPANE... 

DeShong (Scheme 20). Thus, reaction of nitrones with vinyl silanes followed by reduction provides Peterson - type intermediates which can then be eliminated to either Z- or E-products. Homoallylic amines were also prepared using allylsilane in the initial cycloaddition. Substitution reactions of allylic nitro compounds have received considerable attention and some examples are outlined in Scheme 21. In each case, examination of the regiochemistry of the reaction was of paramount concern, the results using palladium being superior to the SnCl mediated process. Allylic sulphides constitute yet another group of... 

Sigmatropic rearrangements of allyl sulphonium allyl ylides (75) provide the basis of a repetitive one-pot ring-expansion sequence" for 2-vinyl thiocyclic compounds (Scheme 50). A paper" and a section in a review article" have described the utilization of allyl thiol dianions and allyl sulphide anions in carbonyl group umpolung . 

Thermolysis of the camphor derivative (239) in the gas phase yielded the ring-expanded compound (240 65 %) by ene retrogression followed by intramolecular aldol condensation and dehydration of the intermediate keto-aldehyde. Pyrolysis in the condensed phase, however, converted (239) into (241 100%) by dehydration (loss of tertiary OH) and [1,5] sigmatropic H-shift in the a-vinyl-enol intermediate. The retro-ene mechanism is also involved in the pyrolytic conversion of allyl sulphides, e.g. (242), into thiocarbonyl compounds, e.g. thiocamphor. The flash thermolysis of... 

Allylsilanes result from allyl sulphides which have siloxy subsdtuents with regio and stereochemically using allyl-lithium, from alkenyl Fischer carbene complexes with silanes through addition of Si-H to the carbene, and opdcally active y-silylallylamines result frnn a n-allylPd intermediate obtained from the carbonate using amines or azide, while allyldichlorosilane can be prepared by the direct method at 220 - 320 C as the main product. The protodesilyladon of allylsilanes provides a route to vinyl sulphones while silylmethyl allyl sulphones result from silylmethyl cuprates and sulphonylalka-1,2-dienes, and are used in the... 

The formation of a- and 9-allylated sulphides by the Pummerer-type reaction of vinylic sulphoxides with allylmagnesium bromide has been reported by Iwata et al. Monoallylation and diallylation can take place, depending on the bulkiness of the yS-substituent, and both acyclic and cyclic vinyl sulphoxides undergo the reaction. This method offers applicability to asymmetric synthesis using sulfinyl chirality. 

Arylthio-carbenes yield arylthiocyclopropanes with alkenes, and add to alkynes and to allyl sulphides. Scheme 5 illustrates a convenient route to vinyl(arylthio)carbenes and their uses in synthesis. 

---