Comparison of 9-Phenylfluorenyl and Triphenylmethyl in the Decomposition of Azo Compounds^1a,b

Abstract

p-Nitrophenylazo-, o-nitrophenylazo-, and 2,4-dinitrophenylaso derivatives of 9-phenylfluorene and triphenylmethane have been prepared and the kinetics of their decomposition in toluene has been studied. In each case the phenylfluorenyl derivative decomposed more rapidly than the corresponding triphenylmethyl derivative, and with lower activation energy. This is ascribed to and cited as evidence for the greater resonance stabilization of phenylfluorenyl as compared with triphenylmethyl radical. The partially compensating energies and entropies of activation are discussed. The relevance of these results to the dissociation of the related hexaarylethanes is discussed. Attempts to prepare azo compounds as sources of 9-fluorenyl radical, for comparison with diphenylmethyl, are described.

Being the New York Times: The Political Behaviour of a Newspaper

“…The last two rows of Table 2 report the relative frequency of stories about those aggregates of topics which, in accord with the issue ownership dataset, I classify as Democratic and Republican ones 13 . The set of Democratic issues comprises Civil Rights, Health Care, Labor & Employment and Social Welfare; the set of Republican ones comprises Defense and Law & Crime.…”

“…The relative advantage of Republican issues over Democratic ones on the pages of the New York Times is around 6 percent for New York City stories, and around 5 percent for federal ones; it is less than one percent for TriState stories. 13 See section 4.4 below.…”

“…As vividly described by Cohen [1963], the press "[...]may not be successful much of the time in telling people what to think, but it is stunningly successful in telling its readers what to think about. The world will look di¤erent to di¤erent people depending on the map that is drawn for them by writers, editors, and publishers of the paper they read.…”

The Spin Doctor Meets the Rational Voter: Electoral Competition with Agenda-Setting Effects

“…G(0) = 1 2 , and G(y) = 1 G( y), for all y. One should note how in this model there is no aggregate uncertainty, as the factor determines an empirical distribution of votes for the two candidates, which is certain 15 .…”

“…Cohen [1963] systematically attached a higher ex post importance to the issue whose coverage had been increased.…”