Reactions of perfluoroalkylcopper compounds. Part V. The preparation of some polyfluoroalkyl-substituted acids and alcohols

Abstract

Reaction of perfluoroheptylcopper(I) with (E)-1,2-di-iodoethylene gave (E)-1H,2H-1-iodopentadecafluoronon-1-ene (I) which with copper(I) cyanide in dimethylformamide yielded (E)-1H,2H-1-cyanopentadecafluoronon-1-ene (II). Hydrolysis of (II) with sulphuric acid under vigorous conditions afforded (E)-2H,3H-pentadecafluorodec-2-enoic acid (III) which was readily hydrogenated to 2H,2H,3H,3H-pentadecafluorodecanoic acid (IV). Reduction of (IV) with lithium aluminium hydride afforded 1H,1H,2H,2H,3H,3H-pentadecafluorodecanol (V). Mild hydrolysis of the nitrile (II) gave (E)-2H,3H-pentadecafluorodec-2-enamide (VI). Reaction of 1,3-di-iodohexafluoropropane with copper bronze and an excess of (E)-1,2-di-iodoethylene similarly afforded (1E,6E)-3,3,4,4,5,5-hexafluoro-1,7-di-iodohepta-1,6-diene (VII) and (1E,6E,11E)-3,3,4,4,5,5,8,8,9,9,10,10-dodecafluoro-1,12-di-iodododeca-1,6,11-triene (VIII). Treatment of (VII) with copper (I) cyanide and hydrolysis of the resulting dinitrile gave (2E,7E)-4,4,5,5,6,6-hexafluoronona-2,7-diene-1,9-dioic acid (IX). Hydrogenation of (IX) gave 4,4,5,5,6,6-hexafluorononane-1,9-dioic acid (X). Reaction of (E)-1,2-di-iodoethylene with copper(I) cyanide gave (E)-2-iodoacrylonitrile.