Reduction and substitution in the reaction of 4-chloronitrobenzene with alkoxides

Bassani, Alberto; Prato, Maurizio; RAMPAZZO, P.; Quintily, U.; Scorrano, Gianfranco

doi:10.1021/jo01299a048

Cited by 17 publications

(13 citation statements)

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“…Additional evidence against both Schemes 5 and 6 comes from the observation that also t-BuOK in tert-butyl alcohol brings about reduction of nitrobenzenes with the same general features of the 2-PrOK/2-PrOH reaction, although more slowly. 2 We have shown that reduction of the substrate radical anion to the corresponding dianion is rate-limiting in these processes. Therefore, one reasonable reduction route to arrive at the nitrosobenzene compound involves bimolecular dismutation of the radical anion to nitrobenzene and dianion, followed by fast proton transfer and HO -elimination.…”

Section: A Scheme For the Nitro To Nitroso Reductionmentioning

confidence: 94%

“…The decay of 4c becomes much faster under oxygen-free conditions (t 1/2 ) 15 min) and leads exclusively to products of nitro reduction. 2 The investigation was extended to all twelve halonitrobenzenes. 4 o-and p-fluoronitrobenzene are highly activated for the S N Ar reaction and undergo fast and quantitative alkoxydehalogenation, regardless of the presence of oxygen.…”

Section: Reactions Of Nitrobenzenes With Alkoxidesmentioning

confidence: 99%

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

Paradisi

Scorrano

1999

Acc. Chem. Res.

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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.

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Section: A Scheme For the Nitro To Nitroso Reductionmentioning

confidence: 94%

Section: Reactions Of Nitrobenzenes With Alkoxidesmentioning

confidence: 99%

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

Paradisi

Scorrano

1999

Acc. Chem. Res.

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“…The common method reported for the preparation of nitro aryl ethers are the nucleophilic aromatic substitution of chloro nitro benzenes with alkoxides. [15] Basani et al [16] reported the reaction of 4-chloro nitro benzene with various alkoxides in the parent alcohols, a substantial yield of substitution product obtained only with ethoxide, where as dichloro azoxybenzene, dichloro azobenzene, and chloro anilines are the main products in 2-propanol and tertiory butanol. Paradisi et al [17] achieved the substitution products and inhibited the formation of reduced products by using the phase-transfer catalysts.…”

Section: A Facile and Convenient Methods For The Synthesis Of Nitro Phmentioning

confidence: 99%

A Facile and Convenient Method for the Synthesis of Nitro Phenols and Chloropyridinols

Raju

Neelakantan

Bhalerao

2004

Synthetic Communications

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“…[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 .…”

Section: Kinetic Studies In 60 % 14-dioxane/h 2 Omentioning

confidence: 99%

“…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 .…”

Section: Kinetic Studies In 60 % 14-dioxane/h 2 Omentioning

confidence: 99%

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

2007

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The kinetics of the reaction of N‐butyl‐2,4,6‐trinitroaniline (3) with NaOH have been studied in 10 and 60 % 1,4‐dioxane/H2O at 25 °C. In both cases, several processes were observed. In 10 % 1,4‐dioxane/H2O the only product formed was 2,4,6‐trinitrophenol (4), whereas in 60 % 1,4‐dioxane/H2O a mixture of 4 and 5,7‐dinitro‐2‐propyl‐1H‐benzimidazole 3‐oxide (5) was observed in ratios that depend on the HO– concentration. A mechanism involving the formation of σ complexes through the addition of one or two HO– anions to unsubstituted ring positions is proposed for 2,4,6‐trinitrophenol formation. The presence of these complexes was confirmed by NMR studies in 60 % [D8]1,4‐dioxane/D2O. The mechanism suggested for the formation of the N‐oxide includes the cyclization of an N‐alkylidene‐2‐nitrosoaniline‐type intermediate as the rate‐determining step. The decrease in solvent polarity produces a decrease in the observed rate constant for the formation of 4 of about one order of magnitude making the cyclization reaction a competitive pathway. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

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Reduction and substitution in the reaction of 4-chloronitrobenzene with alkoxides

Cited by 17 publications

References 0 publications

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

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

A Facile and Convenient Method for the Synthesis of Nitro Phenols and Chloropyridinols

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

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