ISSN:
0894-3230
Keywords:
Organic Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
,
Physics
Notes:
The equilibrium acidities of phenylacetonitrile, and 20 of its m- and p-substituted derivatives have been measured in Me2SO solution. Their pKa′s plot linearly with those of the corresponding anilines. Combination of the pKa′s of these acids with their oxidation potentials, Eox(HA), and those of their conjugate bases, Eox(A-), provide an estimate of the acidities of the corresponding radical cations. The pKHA+ values for ArCH2CN+., where Ar is Ph, 1- and 2-naphthyl, and 9-anthryl, are -32, -18·5, -17·5, and -11, respectively, compared to 21·9, 20·85, 20·65, and 19·8 for the corresponding ArCH2CN acids. Acidities of PhCH(Me)CN+., Ph2CHCN+., 9-CN-FlH+., and 9-CN-XnH+. are -33, -35, -25, and -27, respectively, compared to 23·0, 17·5, 8·3, and 13·6 for the corresponding acids from which they were derived. The homolytic bond dissociation energies (BDEs) for the benzylic C—H bonds in these arylacetonitriles, estimated by combining pKHA with Eox(A-), fall in the range of 69 kcal/mol for 9-CN-XnH to 82 kcal/mol for PhCH2CN. For GC6H4CH2CN+. radical cations the acidities are decreased, relative to G=H, when G is an electron donor substituent and increased when G is an acceptor. The BDEs of the benzylic C—H bonds in GC6H4CH2CN are weakened by up to 4 kcal/mol by para donors and strengthened by up to 1·2 kcal/mol by m- or p-acceptors. The significance of these changes in BDEs with regard to the use of σ. scales and the ΔAOP method for estimating substituent effects on radical stabilities is discussed.
Additional Material:
5 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/poc.610010405
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