Oxime sulfenates

Imino-l-sulfenic acids Oxathiol-2-ylidenimmonium salts Oxime sulfenates Sulfenyliminoesters Sulfinyl cyanides N-Sulfinylimines Thiohydroximic acids and esters... 

The attack by the thiolate anion on the N-oxide oxygen of 62 produces the intermediate sulfenic acid derivative 65, which, in the presence of thiols, further reacts with the thiolate anion, to give the oxime 66, which has been isolated among the reaction products. By contrast, spontaneous loss of the halide anion from 65 affords the ni-troso intermediate 67 that, by losing NO and the thiyl radical directly, or through 68, produces the a-nitrosoolefm 69. By a Michael type reaction with water this last product immediately yields the final oxime 70, which has been isolated among the reaction products. 

An interesting variation to cycloadditions involving sulfenes is a reaction carried out with a-amino ketoximes, by which thietane dioxides are produced. The authors suggested a two-step mechanism via the intermediate cyanoenamine 83. Higher yields were obtained when the oximes were... 

Oximes are readily sulfonylated by sulfenes to yield the O-sulfonyl oximes (53)91,134-136 (equation 45). Aldoxime sulfonates (53, R = H) are easily converted to the nitriles, RC=N134, while the benzophenone derivative (53, R,R = Ph) undergoes the Beckmann rearrangement to benzanilide91. Attempts to observe cycloaddition of sulfenes and nitrile oxides led to a-chloroaldoxime sulfonic esters (53, R = Q)134 136,145. It is not known if the... 

Alkylthio-l-oximes S-Aminosulfoxonium ylids 1-Imino-l-sulfenic acids Thiohydroxamic acid esters Thiohydroxamic acids Thiolcarbamic acid esters Thiolurethans Thionocarbamic acid esters... 

Heteroatom Oxidation Drugs and other chemicals that contain heteroatoms (mostly N and S) with hydrogen attached form the corresponding hydroxylamines and sulfenic acids. This oxidation is most commonly observed when the heteroatom is eonnected to an aromatic ring. Tertiary amines or heteroaromatic amines and sulfur ethers form N-oxides and sulfoxides, respectively, whereas imines ean form oximes or nitrones. 

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