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Moller Plesset (MP2). O efeito conjunto aniline is still a subject of debate: two
dos substituintes conduz a estabilidades protonated isomers have been found ex-
relativas para as espécies protonadas de perimentally (2); computationally, coe-
acordo com a seguinte escala: grupo nitro xistence of two isomers with slight
> grupo amino > carbono orto > car- energy preference towards protonation
bono para > carbono meta > carbono on the para carbon to the amino group is
ipso (posições relativas ao grupo amino). predicted (3). Regarding paranitroanili-
ne, experimental studies suggest that the
Palavras-chave: afinidad protónica, preferred protonation sites are the oxy¬
reactividad do anel aromático, efeitos in- gens belonging to the nitro group (4,5).
dutivos competitivos, p-Nitroanilina.
The various inductive effects on anili-
INTRODUCTION ne, nitrobenzene and paranitroaniline are
depicted in Figures 1-4. Atom charges
In Organic Chemistry, substituent effects (Figure 1) were calculated under the
are traditionally described in a qualitative CHELPG fitting scheme to the electrosta-
fashion. Substituent inductive effects are tic potential (6), resonant structures for
helpful in predicting the behavior and aniline (Figure 2), nitrobenzene (Figure
reactivity of many molecules, but they are 3) and p-nitroaniline (Figure 4) are drawn
not enough for a complete description in considering -NH as an electron donor

the cases where multiple substitution with group and -NO as an electron withdra¬

opposite effects are present. For exam¬ wing group. Charge distribution on the
ple, relative basicity criteria establish that ring in paranitroaniline resembles the
aniline protonation is favored on the ni¬ charge distribution in aniline, which sug¬
trogen atom of the amino group, predic¬ gests a dominant effect from the amino
tions that are in agreement with liquid group. The significant negative charges
phase experimental results (1). On the ot¬ on the nitrogen and oxygen atoms and on
her hand, gas phase protonation sites of the ortho carbon on p-nitroaniline makes

Figure 1. CHELPG charges on aniline, nitrobenzene and p-nitroaniline calculated at the B3LYP/6-31G*