@article{a9920f104470496195dfcaf7b5767d18,
title = "Anodic fragmentation of branched alkanes",
abstract = "Branched alkanes produce acetamidated fragments when oxidized in CH 3CN-Et4N+,BF4- at -45°.",
author = "Siegel, {Theodore M.} and Miller, {Larry L.} and Becker, {James Y.}",
note = "Funding Information: It therefore seems likely that direct oxidation of substrate, not a process involving electrolyte oxidation4 is involved. The case of t-butyl-cyclohexane is particularly clear on this point since the oxidation can be performed at potentials well below back- ground and good yields of both fragments result. Our working hypothesis is that initial electron transfer is followed by fragmentation and further oxidation resulting in carbonium ions. There is clear precedent for carbonium ions as precursors of acetamides in acetonitrile3 and the products from 2,2,4-trimethylpentane and 2,3,4-trimethyl- pentane point to carbonium ion rearrangements. Within this scheme one might postulate that low tempera- tures favour processes with positive AS* such as uni-molecular decomposition of an initially formed cation radical. This overall scheme rationalizes all the data including the selectivity toward formation of highly sub- stituted fragments, but more evidence is clearly needed to understand the reaction. The analogy with mass spectro- scopy should, however, be noted. We thank the National Science Foundation for support. (Received, 28th December 1973; Corn. 1740.) 1 E. A. Mayeda, L. L. Miller, and J. F. Wolf, J. Amer. Chem. SOL, 1972, 94, 6812. 2 D. Clark, M. Fleischmann, and D. Pletcher, J.C.S. Perkin 11,1973, 1578. 3 V. R. Koch and L. L. Miller, J. Amer. Chem. Soc., in the press. 4 L. L.Miller and V. Ramachandran, J. Org. Chem., in the press.",
year = "1974",
month = jan,
day = "1",
doi = "10.1039/C39740000341",
language = "English",
pages = "341--342",
journal = "Chemical Communications",
issn = "0022-4936",
publisher = "Royal Society of Chemistry",
number = "9",
}