MULTIPLE MULTICENTER REACTIONS OF PERFLUORO KETONES WITH OLEFINS

Hexafluoroacetone gives stepwise reactions with olefins [formula omitted] some of which, surprisingly, occur at 25°. Products in a 2:1 ratio are general, and 2-methylpropene also gives a 3:1 product. Terminal olefins are the most reactive with 2-methyl-1-alkenes giving faster rates than 1-alkenes. Otherwise, olefin reactivity is decreased with increased alkyl substitution of their unsaturated carbon atoms. With such tri- and tetrasubstituted olefins or 1:1 products, acid-catalyzed isomerizations (product fluoro alcohols are acidic) occur prior to further reaction with hexafluoroacetone. Reactions giving 2:1 products are stereospecific owing to steric effects. © 1968, American Chemical Society. All rights reserved.