The Course of the Willgerodt-Kindler Reaction of Alkyl Aryl Ketones

Ketones react with sulfur and NH3 or amines at room temperature to produce Δ3‐thiazolines, 5‐alkylidene‐Δ3‐thiazolines, Δ3‐imidazoline‐5‐thiones, hexathiacycloheptane derivatives, α,α′‐dioxodisulfides, bis‐(1‐aralk‐1‐yl) disulfides, or thiocarboxamides, depending on the coreactant and on the reaction conditions. It was recognized that the formation of all of these numerous types of compounds can be explained basically by primary thiolations and geminal dithiolations, which in conjunction with their reverse reaction (desulfurization) and the assumption of a thioreductone equilibrium permit a new interpretation of the course of the Willgerodt‐Kindler reaction of alkyl aryl ketones.