ISSN:
0894-3230
Keywords:
Organic Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
,
Physics
Notes:
The excellent linearity (R2 = 0·997) of a plot of pKa values for 17 m- and p-substituted benzyl phenyl sulfones, GC6H4CH2SO2Ph, vs. those for the corresponding arylacetonitrile, GC6H4CH2CN, demonstrates that substituent solvation and substituent solvation assisted resonance (SSAR) effects for p-CN, p-COPh, and p-SPh are nearly identical in these two substrates. The PhSO2 group in PhCH2SO2Ph increases the BDE of the α-C—H bond by 2 kcal/mol, relative to toluene. The α-C—H bonds in GC6H4CH2SO2Ph sulfones are stabilized by 1-2 kcal/mol by acceptor G′s (m-CN, p-CN, m-CF3, p-CF3), but weakened by 1 and 5 kcal/mol, respectively, by donors (p-OMe and p-NMe2). The GC6H4CH2SO2Ph+. radical cation with G = H has a pKHA+. = -25. Its acidity is increased when G is an acceptor by as much as 9 to 10 kcal/mol (G = 3-CN, 3-CF3, 4-CF3, 4-NO2), but is decreased when G is a donor by as much as 33 kcal/mol (G = NMe2). When G = 4-SPh the radical cation is stabilized, relative to G = H, by a larger amount (25 kcal/mol) than when G = 4-OMe (18 kcal/mol). Structural changes along the series PhCH2SO2Ph, 2-naphthyl-CH2SO2Ph, 9-anthryl CH2SO2Ph cause negligible changes in the acidities of these acids, but sizable decreases in the acidities of the corresponding radical cations. Introduction of a phenylsulfonyl group into the methyl group of 9-methylanthracene or the 9-position of fluorene or xanthene increase the BDEs by 3, 2, and 7 kcal/mol, respectively. These effects of PhSO2 groups are compared and contrasted with those of CN groups.
Additional Material:
3 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/poc.610010406
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