Radical-induced reaction of monoiodo- and diiodo-perfluoroalkanes with allyl acetate

What is it about?

The radical reaction of monoiodoperfluoroalkanes RFI (RF = 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 RFI and IQI was complete in most cases. The reactions of RFI 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 [RFCH2CHICH2OCOCH3, (2a-c)] and 2:1 telomers (5a-c) underwent subsequent thermal rearrangement [formation of RFCH2CH(OCOCH3)CH2I, (3a-c), and telomers (6a-c), respectively] at elevated temperatures. In the reaction of diiodides IQI, monoadducts [CH3COOCH2CHICH2QI, (9a,b)] and diadducts [(CH3COOCH2CHICH2)2Q (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 RF groups were found.

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Why is it important?

The radical reaction of monoiodoperfluoroalkanes RFI (RF = 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 RFI and IQI was complete in most cases. The reactions of RFI 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 [RFCH2CHICH2OCOCH3, (2a-c)] and 2:1 telomers (5a-c) underwent subsequent thermal rearrangement [formation of RFCH2CH(OCOCH3)CH2I, (3a-c), and telomers (6a-c), respectively] at elevated temperatures. In the reaction of diiodides IQI, monoadducts [CH3COOCH2CHICH2QI, (9a,b)] and diadducts [(CH3COOCH2CHICH2)2Q (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 RF groups were found.

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