Sulfides rearrangement

The isomerization reactions of pentafluorophcnyl and heptafluoro-2-naphthyl propargyl sulfides have been studied under a variety of conditions.38 For example, the naphthyl sulfide rearranges to the fluoromethyl derivative 46 in 81 % yield when distilled at 360 C in vacuo through a glass tube packed with quartz wool. 

Similar reactions are known of compounds in which the carbon-nitrogen bond is part of a heterocyclic nucleus.17 18 The oxygen atom of the reactive system may be replaced by a sulfur atom, with, however, some reduction in the tendency toward rearrangement. Allyl p-tolyl sulfide rearranges (XI —> XII) to the extent of 27% (50% based on sulfide not recovered) when subjected to refluxing at 228-264° for four hours.19... 

The application of nitro-sulfide rearrangements in heterocycle synthesis has been more recently reported [75]. 

Dialkylarsine sulfides rearrange to alkyl(alkylthio)arylarsine up>on heating (equation 167 ). 

Hydroxy sulfides rearrange to ketones under a variety of conditions. In aqueous acid it is the carbon bearing the sulfur group which ultimately becomes the carbonyl carbon. The rearrangement proceeds via protonation of the hydroxy group (Scheme 1, path b), and appears to be restricted to the expansion of... 

When exposed to soft electrophiles such as dichlorocarbene (generated in situ), 2-hydroxy sulfides rearrange wiA loss of the sulfur group and ketone formation at the hydroxy-bearing carbon, - as in the synthesis of cuparenone (23 equation 27). ... 

As compared to thioaldehydes, these compounds are somewhat easier to isolate, their reactivity in solution or towards the oxygen in air being more moderate. The first evidence is due to Ojima and Kondo [55], who studied a simple allyl vinyl sulfide rearrangement (Scheme9.11) at ambient temperature. By NMR, they detected an unsaturated thioketone, which was stable under a nitrogen atmosphere, but further converted to the corresponding ketone just by standing in air. 

Two efficient syntheses of strained cyclophanes indicate the synthetic potential of allyl or benzyl sulfide intermediates, in which the combined nucleophilicity and redox activity of the sulfur atom can be used. The dibenzylic sulfides from xylylene dihalides and -dithiols can be methylated with dimethoxycarbenium tetrafiuoroborate (H. Meerwein, 1960 R.F. Borch, 1968, 1969 from trimethyl orthoformate and BFj, 3 4). The sulfonium salts are deprotonated and rearrange to methyl sulfides (Stevens rearrangement). Repeated methylation and Hofmann elimination yields double bonds (R.H. Mitchell, 1974). 

Various S-nucleophiles are allylated. Allylic acetates or carbonates react with thiols or trimethylsilyl sulfide (353) to give the allylic sulfide 354[222], Allyl sulfides are prepared by Pd-catalyzed allylic rearrangement of the dithio-carbonate 355 with elimination of COS under mild conditions. The benzyl alkyl sulfide 357 can be prepared from the dithiocarbonate 356 at 65 C[223,224], The allyl aryl sufide 359 is prepared by the reaction of an allylic carbonate with the aromatic thiol 358 by use of dppb under neutral condi-tions[225]. The O-allyl phosphoro- or phosphonothionate 360 undergoes the thiono thiolo allylic rearrangement (from 0-allyl to S -allyl rearrangement) to afford 361 and 362 at 130 C[226],... 

Chemical Properties. Ammonium thiocyanate rearranges upon heating to an equiHbrium mixture with thiourea 30.3 wt % thiourea at 150°C, 25.3 wt % thiourea at 180°C (373,375). At 190—200°C, dry ammonium thiocyanate decomposes to hydrogen sulfide, ammonia, and carbon disulfide, leaving guanidine thiocyanate [56960-89-5] as a residue. Aqueous solutions of ammonium thiocyanate are weakly acidic a 5 wt % solution has a pH of 4—6. 

Besides displacement reactions, oxidations, rearrangements and cleavage of the sulfide linkage, the most important reactions take place at the sulfur atom. 

Electrophilic attack on the sulfur atom of thiiranes by alkyl halides does not give thiiranium salts but rather products derived from attack of the halide ion on the intermediate cyclic salt (B-81MI50602). Treatment of a s-2,3-dimethylthiirane with methyl iodide yields cis-2-butene by two possible mechanisms (Scheme 31). A stereoselective isomerization of alkenes is accomplished by conversion to a thiirane of opposite stereochemistry followed by desulfurization by methyl iodide (75TL2709). Treatment of thiiranes with alkyl chlorides and bromides gives 2-chloro- or 2-bromo-ethyl sulfides (Scheme 32). Intramolecular alkylation of the sulfur atom of a thiirane may occur if the geometry is favorable the intermediate sulfonium ions are unstable to nucleophilic attack and rearrangement may occur (Scheme 33). 

Nucleophiles like alcohols [2, S], hydrogen sulfide [2], thiols [2,10], ammonia, amines, hydrazines, hydroxylamines [2 11, 12, 13, 14, 75], azides [2], other pseudohalides [2], phosphonates [2,16,17,18,19, 20], and phosphanes [2,19] add rapidly across the CO or CN double bond to yield stable adducts The phosphonate adduets undergo a subsequent aleohol—lester rearrangement [19, 20] (equation 2)... 

Sharpless and Masumune have applied the AE reaction on chiral allylic alcohols to prepare all 8 of the L-hexoses. ° AE reaction on allylic alcohol 52 provides the epoxy alcohol 53 in 92% yield and in >95% ee. Base catalyze Payne rearrangement followed by ring opening with phenyl thiolate provides diol 54. Protection of the diol is followed by oxidation of the sulfide to the sulfoxide via m-CPBA, Pummerer rearrangement to give the gm-acetoxy sulfide intermediate and finally reduction using Dibal to yield the desired aldehyde 56. Homer-Emmons olefination followed by reduction sets up the second substrate for the AE reaction. The AE reaction on optically active 57 is reagent... 

The mechanism of the indolization of aniline 5 with methylthio-2-propanone 6 is illustrated below. Aniline 5 reacts with f-BuOCl to provide A-chloroaniline 9. This chloroaniline 9 reacts with sulfide 6 to yield azasulfonium salt 10. Deprotonation of the carbon atom adjacent to the sulfur provides the ylide 11. Intramolecular attack of the nucleophilic portion of the ylide 11 in a Sommelet-Hauser type rearrangement produces 12. Proton transfer and re-aromatization leads to 13 after which intramolecular addition of the amine to the carbonyl function generates the carbinolamine 14. Dehydration of 14 by prototropic rearrangement eventually furnishes the indole 8. 

---