TY - JOUR
T1 - Electrochemical Oxidation of Polyfluoroalkyl Iodides
T2 - Direct Anodic Transformation of C8F17CH2CH2I to Amides, Esters, and Etherst
AU - Becker, James Y.
AU - Smart, Bruce E.
AU - Fukunaga, Tadamichi
PY - 1988/11/1
Y1 - 1988/11/1
N2 - The cyclic voltammetry of polyfluoroalkyl iodides of the type RfCH2CH2I (Rf = n-C6F13, n-C8F17, n-C10F21) and RfI (Rf = n-C4F9, n-C6F13, n-C8F17, n-C10F21) was investigated in nonaqueous media. All the iodides exhibited one distinctive oxidation peak, but only C8F17CH2CH2I was suitable for surveying preparative-scale electrosynthetic reactions because the other iodides either had poor solubility or caused severe filming of the anode. The direct anodic transformations of the iodide to the corresponding amides (C8F17CH2CH2NHCOR; R = CH3, CH=CH2, C(Me)=CH2), esters (C8F17CH2CH2OCOR; R = CH3, CF3, CH=CH2, C(Me)=CH2, C6H5), ethers (mainly C8F17CH2CH2OCH2CF3), and alcohol (C8F17CH2CH2OH) were observed and a general mechanistic scheme involving a hypervalent iodanyl radical intermediate is proposed.
AB - The cyclic voltammetry of polyfluoroalkyl iodides of the type RfCH2CH2I (Rf = n-C6F13, n-C8F17, n-C10F21) and RfI (Rf = n-C4F9, n-C6F13, n-C8F17, n-C10F21) was investigated in nonaqueous media. All the iodides exhibited one distinctive oxidation peak, but only C8F17CH2CH2I was suitable for surveying preparative-scale electrosynthetic reactions because the other iodides either had poor solubility or caused severe filming of the anode. The direct anodic transformations of the iodide to the corresponding amides (C8F17CH2CH2NHCOR; R = CH3, CH=CH2, C(Me)=CH2), esters (C8F17CH2CH2OCOR; R = CH3, CF3, CH=CH2, C(Me)=CH2, C6H5), ethers (mainly C8F17CH2CH2OCH2CF3), and alcohol (C8F17CH2CH2OH) were observed and a general mechanistic scheme involving a hypervalent iodanyl radical intermediate is proposed.
UR - http://www.scopus.com/inward/record.url?scp=0001284152&partnerID=8YFLogxK
U2 - 10.1021/jo00259a020
DO - 10.1021/jo00259a020
M3 - Article
AN - SCOPUS:0001284152
VL - 53
SP - 5714
EP - 5720
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
SN - 0022-3263
IS - 24
ER -