Benzotrifluoride (BTF, trifluoromethylbenzene,a,a,a-trifluorotoluene, C 6 H 5 CF 3 ) and related

compounds are introduced as new solvents for traditional organic synthesis and for fluorous

synthesis. BTFismoreenvironmentallyfriendlythanmanyotherorganicsolventsandis

available in large quantities. BTF is relatively inert and is suitable for use as a solvent for a wide

rangeof chemistryincludingionic, transition-metalcatalyzedandthermalreactions. Itis

especially useful for radical reactions, where it may replace benzene as the current solvent of

choice for many common transformations. BTF and related solvents are also crucial compo-

nentsoffluoroussynthesissincetheycandissolvebothstandardorganicmoleculesand

highly fluorinated molecules. This chapter provides an overview of the reactivity and toxico-

logicalpropertiesofBTFandanalogsandthensummarizestheirrecentusesasreaction

solvents in both traditional organic and new fluorous synthesis.