The phase-vanishing (PV) method is based on spontaneous reaction controlled by diffusion of reagents into fluorous media, such as perfluorohexanes (FC-72) and polyperfluoroethers. Thus, the original PV reaction utilizes a triphasic test tube method composed of a bottom reagent phase, a middle fluorous phase, and a top substrate phase. In such a triphasic system, the fluorous phase acts as a liquid membrane to transport the bottom reagents to the top organic phase containing substrates. In the end, the bottom layer disappears and two phases remain. Since the first demonstration of the PV method by bromination of alkenes with molecular bromine, a number of applications have been developed thus far. These include halogenation of alcohols with SOBr 2 and PBr 3, demethylation of methoxyarenes with BBr 3, cyclopropanation of alkenes by CH 2I 2-AlEt 3, and Friedel-Crafts acylation of aromatic compounds with SnCl 4. A fluorous triphasic U-tube method is effective for chlorination of alcohols based on lighter (less dense) reagents such as SOCl 2 and PCl 3. A system using a solution containing reagents as a bottom phase is useful for oxidation with m-CPBA, which may be defined as a new category for the "extractive PV" method. Recent advances include a " quadraphasic" PV method, in which an aqueous "scavenger" phase is added to the original triphasic PV method to remove acidic by-products.