RADICAL-INDUCED REACTION OF MONOIODO-PERFLUOROALKANES AND DIIODO-PERFLUOROALKANES WITH ALLYL ACETATE - TELOMER AND REARRANGED PRODUCTS, MASS-SPECTRAL DISTINGUISHING OF REGIOISOMERS

The radical reaction of monoiodoperfluoroalkanes R(F)I (R(F) = C4F9, C6F13, C8F17) and diiodoperfluoroalkanes I-Q-I (Q=C4F8, C6F12) with allyl acetate initiated by peroxidic initiators is described. Under the reaction conditions employed, the conversion of both R(F)I and IQI was complete in most cases. The reactions of R(F)I also yielded some 2:1 telomers which are new compounds which have been characterized. In certain cases, the telomers were isolated in preparative yield up to 34%. Both 1:1 adducts [R(F)CH(2)CHICH(2)OCOCH(3), (2a-c)] and 2:1 telomers (5a-c) underwent subsequent thermal rearrangement [formation of R(F)CH(2)CH(OCOCH3)CH2I, (3a-c), and telomers (6a-c), respectively] at elevated temperatures. In the reaction of diiodides IQI, monoadducts [CH(3)COOCH(2)CHICH(2)QI, (9a,b)] and diadducts [(CH3COOCH2CHICH2)(2)Q (10a,b)] were formed, but no telomeric and rearranged products were found under the reaction conditions employed, On the other hand, isolated mono- (9) and di-adducts (10) underwent a similar rearrangement to the compounds 2a-c and 5a-c at elevated temperatures. Regioisomeric primary and rearranged products could be distinguished by mass spectrometry in which characteristic signals for a series of compounds with different R(F) groups were found.