RESUMO
In order to elucidate the potential of substituted o-quinodimethanes as reagents for the trapping of nitric oxide (NO) in biological systems, the reaction of alkoxyl- and alkyl-substituted 7,8-diphenyl- and 7,7,8-triphenyl-o-quinodimethanes with nitric oxide in solution was investigated by ESR spectroscopic and UV/vis stopped-flow techniques. Photolytic decarbonylation of 1,3-diphenyl- and 1,1,3-triphenylindan-2-ones gave the corresponding phenyl-substituted benzocyclobutenes as the major products and low photostationary concentrations of o-quinodimethanes. During 266-nm laser flash photolysis (LFP) of 1,3-dimethoxy-1,3-diphenylindan-2-one and 1-methoxy-1,3,3-triphenylindan-2-one in acetonitrile, species absorbing in the 400-600 nm range were produced, which were attributed to configurational isomers of the corresponding 7,7,8,8-substituted o-quinodimethanes. The isomeric o-quinodimethanes decayed at significantly different rates, indicating a strong influence of the relative orientation of the terminal substituents on their stability. Reaction of the raw photolysates of the 2-indanones with NO produced strong ESR spectra of the corresponding cyclic nitroxide radicals, isoindolin-2-oxyls. The nitroxide radicals were generated in a two-phase process, the first, rapid phase being attributed to the reaction of NO with the photolytically formed o-quinodimethanes and the second, slow phase reflecting the reaction with small amounts of o-quinodimethanes, generated by thermal ring opening of the phenyl-substituted benzocyclobutenes and probably a direct reaction of NO with the benzocyclobutenes. The kinetics of both steps, as evaluated by stopped-flow UV/vis and ESR spectroscopy, revealed a strong dependence of the rate constants of the o-quinodimethane + NO reaction on the substitution pattern of the o-quinodimethanes, with rate constants spanning a range of 10-4000 M(-)(1) s(-)(1). The rate constants ((0.4-7.5) x 10(-)(4) s(-)(1)) for the reaction of NO with the 7,7,8,8-tetrasubstituted benzocyclobutenes are much less influenced by the substitution pattern. The utility of phenyl-substituted benzocyclobutenes as "reservoirs" for o-quinodimethane-type nitric oxide traps is discussed.
RESUMO
Laser flash photolysis has been used to determine the absolute rate constants for addition of several partially fluorinated n-alkyl radicals to three styrenes at 25 °C in Freon 113. Fluorination at the γ-position (RCF2CH2CH2â¢) gives radicals with essentially the same reactivity as non-fluorinated n-alkyls. The RCH2CF2CH2⢠and RCH2CH2CHF⢠radicals are both about three times as reactive as RCF2CH2CH2â¢, but the RCH2CH2CF2⢠radical is ca. five to six times rather than ca. three times as reactive as RCH2CH2CHFâ¢. Similarly, the perfluorinated radical CF3CF2CF2⢠is much more reactive than would be expected on the basis of the reactivities of the RCH2CF2CH2⢠and RCH2CH2CF2⢠radicals. Thus, perfluorinated n-alkyl radicals are very considerably more reactive than would be predicted from the individual effects of α-, ß-, and γ-fluorination.