From Tars to Products:  How To Disentangle the Reactions of Nitrobenzenes with Nucleophiles

Abstract

Cristina Paradisi received a Laurea degree in industrial chemistry from the University of Padova (1974) and a Ph.D. in chemistry from the University of California at Santa Cruz (1980). Researcher of the Italian National Council of Research (CNR) and, since 1992, Associate Professor in chemistry at the University of Padova. Main research interests: reactivity and mechanisms in solution, gas-phase ion chemistry, and, most recently, decomposition of organic compounds in nonthermal plasmas and the role of ionic intermediates in such processes.Gianfranco Scorrano received a Laurea degree in industrial chemistry from the University of Bologna (1963). Professor of organic chemistry at the University of Padova since 1975 and, since 1996, Director of the CNR Center for Studies of Organic Reaction Mechanisms. After terms as President of the Italian Chemical Society (1990-92) and of the Organic Chemistry Division of IUPAC (1996-97), he is presently a member of the University National Council of Italy. Main research interests: studies of reaction mechanisms, recently focused on fullerene chemistry, solvation, and decomposition of organic compounds by corona discharges or catalyzed oxidations. Chart 1 aa The identities of X substituents are, in general, represented as in the family of compounds 2.

Medium Effect on the Reaction of N‐Butyl‐2,4,6‐trinitroaniline with NaOH

“…It has been reported that in the reaction of nitrobenzene derivatives [29,30] and o-nitroanilines [9,28,31] in basic media, azoxybenzene derivatives are formed. Therefore, it is possible that azoxybenzene compounds are formed in our reaction system under N 2 .…”

“…[6,9,28] The reduction of nitro to nitroso groups of benzene derivatives in basic solution is a well-documented reaction that depends on the oxygen content of the reaction media. [29,30] In addition, the yield of 7-nitro-2-propyl-5-(trifluoromethyl)-1H-benzimidazole 3-oxide obtained from N-butyl-2,6-dinitro-4-(trifluoromethyl)aniline increases when the reaction is carried out under N 2 . [8] Thus, we investigated the effect of N 2 on the kinetics and product distribution of the reaction of 3 with NaOH in 60 % 1,4-dioxane/H 2 O.…”

Direct thioalkylation of nitroquinolines with alkanethiolate anions via nucleophilic displacement of a ring hydrogen atom

“…1, 4 One recent article has mentioned briefly that 3-chloronitrobenzene reacts with the ethanethiolate anion so as to displace a hydrogen atom, leading to the formation of some thioalkylation products. 1 However, the amount of such products was too small to indicate the preparative potential of this substitution reaction. 5 This would probably be due to the high ability of thiolate anions to act as a reducing agent for the nitro group.…”

Investigation of Cation−Anion Interactions in 2-Propanol Solutions of Sodium Alkoxides and Thiolates by23Na-NMR Spectroscopy

“…The situation is more complex for systems involving competing reactions, which, under otherwise identical experimental conditions, can give different products depending only on the extent of cationϪanion association. [5] Ion association phenomena thus need to be properly understood and considered in the context of planning new synthetic procedures.…”