Hydrogen In Nitroarenes Research Articles

Oxidative nucleophilic substitution of hydrogen in nitroarenes with trifluoromethyl carbanions. Synthesis of trifluoromethyl phenols

Trifluoromethyl carbanions generated from the Ruppert reagent and TASF add to highly electron-deficient nitroarenes to produce σH adducts subsequently oxidized with dimethyldioxirane to substituted trifluoromethyl phenols.

Oxidative nucleophilic substitution of hydrogen in nitroarenes with trifluoromethyl carbanions. Synthesis of trifluoromethyl phenols

Trifluoromethyl carbanions generated from the Ruppert reagent and TASF add to highly electron-deficient nitroarenes to produce σ H adducts subsequently oxidized with dimethyldioxirane to substituted trifluoromethyl phenols.

Oxidative Nucleophilic Substitution of Hydrogen in Nitroarenes by Silyl Enol Ethers.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Oxidative nucleophilic substitution of hydrogen in nitroarenes by silyl enol ethers

Enolates generated by treatment of silyl ketene acetals and enol ethers with fluoride ion sources add to nitroarenes to produce σ H adducts that oxidize either with KMnO 4 to give substituted nitroarenes or with dimethyldioxirane to give substituted phenols. In the latter case the oxidation results in replacement of the nitro group with a hydroxy group. It was shown that high effectiveness of these reactions is not due to stabilization of the σ H adducts via O-silylation but due to the nature of the accompanying cation.

Electrochemical Synthesis of Nitroanilines

Alkylamines and amides are readily prepared by nucleophilic aromatic substitution of hydrogen in nitroarenes by electrochemical oxidation. Useful yields (15−85%) are achieved in a simple direct and regioselective amination process. The synthetic method has been examined in the absence and presence of external bases, used to promote the first step of the nucleophilic aromatic substitution reaction, i.e. the nucleophilic attack. In both cases, good results were obtained. The unreacted starting material can easily be recovered at the end of the electrochemical oxidation process. This new method represents an environmentally favourable route to amino- and amido-substituted nitroaromatic compounds.

Electrochemical Synthesis of Nitroaromatic Ketones

Nitroaromatic ketones are readily prepared by nucleophilic aromatic substitution of hydrogen in nitroarenes by electrochemical oxidation. Carbanions of various ketones were added to selected nitroarenes in DMF/ketone mixtures leading to formation of the σH complexes. The reaction was promoted using potassium tert-butoxide as a base. Useful yields were achieved (80−100%) in the C-arylation of ketones. In most cases, the process proceeded with high selectivity. This new method represents an environmentally favourable route for obtaining nitroaromatic ketones.

Synthesis of (p-Nitroaryl)diarylmethanes via Vicarious Nucleophilic Substitution of Hydrogen

(p-Nitroaryl)diarylmethanes are readily prepared via vicarious nucleophilic substitution of hydrogen in nitroarenes with carbanions of diarylmethyl p-chlorophenyl sulfide. These carbanions are efficient for introduction of diarylmethyl substituents in the para position of nitroarenes via the VNS reaction. The reaction does not proceed ortho to the nitro group due to steric hindrances on the addition step.

ChemInform Abstract: Oxidative Nucleophilic Substitution of Hydrogen in Nitroarenes with Phenylacetonitrile Derivatives.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Oxidative nucleophilic substitution of hydrogen in nitroarenes with phenylacetonitrile derivatives

Tertiary carbanions generated from α-substituted phenylacetonitriles in liquid ammonia add to nitro-benzenes in the para position to form the corresponding σ H-adducts which are transformed, depending on the starting nitriles and the reaction conditions, to products of oxidative nucleophilic substitution of hydrogen, ONSH or vicarious nucleophilic substitution, VNS.

Isotope effect in oxidative nucleophilic substitution of hydrogen in nitroarenes

In a series of competitive experiments with labelled nitrobenzenes carried out in liquid ammonia at −70 °C it was shown that the rate of oxidative substitution of hydrogen with the carbanion of 2-phenylpropionitrile is ca. 9.8 times faster than the analogous substitution of deuterium in 4-D-nitrobenzene and perdeuterionitrobenzene. Thus Carom.-H bond breaking is the rate limiting step of the oxidative process.

ChemInform Abstract: Reactions of Organic Anions. Part 198. Nucleophilic Substitution of Hydrogen in Nitroarenes with Carbanions of Benzodithiolane Sulfoxides via an Intramolecular Redox Process.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

ChemInform Abstract: Reactions of Organic Anions. Part 176. Vicarious Nucleophilic Substitution of Hydrogen in Nitroarenes by Carbanions of Alkyl Dichloroacetates. Some New Transformations of Chloro(nitroaryl)acetates.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Vicarious Nucleophilic Substitution of Hydrogen in Nitroarenes by Carbanions of Alkyl Dichloroacetates. Some New Transformations of Chloro(nitroaryl)acetates

Vicarious Nucleophilic Substitution of Hydrogen in nitroarenes by ethyl dichloroacetate anion provides ethyl chloro(nitroaryl)acetates, which can be transformed into ethyl imino(nitroaryl)acetates and ethyl oxo(nitroaryl)acetates by treatment with sodium azide.

ChemInform Abstract: Reactions of Organic Anions. Part 156. A Simple and Efficient Synthesis of Alkyl (2‐Nitroaryl)acetates and Alkyl 2‐(2‐Nitroaryl)propanoates (III) via Vicarious Nucleophilic Substitution of Hydrogen in Nitroarenes (I) by Carbanions of Alkyl Chloroacetates or Alkyl 2‐Chloropropanoates (II).

ChemInform Abstract: Reactions of Organic Anions. Part 156. A Simple and Efficient Synthesis of Alkyl (2‐Nitroaryl)acetates and Alkyl 2‐(2‐Nitroaryl)propanoates (III) via Vicarious Nucleophilic Substitution of Hydrogen in Nitroarenes (I) by Carbanions of Alkyl Chloroacetates or Alkyl 2‐Chloropropanoates (II).

A Simple and Efficient Synthesis of Alkyl (2-Nitroaryl)acetates and Alkyl 2-(2-Nitroaryl)propanoates via Vicarious Nucleophilic Substitution of Hydrogen in Nitroarenes by Carbanions or Alkyl Chloroacetates of Alkyl 2-Chloropropanoates

A Simple and Efficient Synthesis of Alkyl (2-Nitroaryl)acetates and Alkyl 2-(2-Nitroaryl)propanoates via Vicarious Nucleophilic Substitution of Hydrogen in Nitroarenes by Carbanions or Alkyl Chloroacetates of Alkyl 2-Chloropropanoates

Reactions of organic anions. Part 110. Vicarious nucleophilic substitution of hydrogen in nitroarenes with .alpha.-substituted nitriles and esters. Direct .alpha.-cyanoalkylation and .alpha.-carbalkoxyalkylation of nitroarenes

Reactions of organic anions. Part 110. Vicarious nucleophilic substitution of hydrogen in nitroarenes with .alpha.-substituted nitriles and esters. Direct .alpha.-cyanoalkylation and .alpha.-carbalkoxyalkylation of nitroarenes

Reactions of organic anions. Part 109. Vicarious nucleophilic substitution of hydrogen in nitroarenes with carbanions of .alpha.-haloalkyl phenyl sulfones

Reactions of organic anions. Part 109. Vicarious nucleophilic substitution of hydrogen in nitroarenes with carbanions of .alpha.-haloalkyl phenyl sulfones

Reaction of organic anions. Part 108. On the mechanism of the vicarious nucleophilic substitution of hydrogen in nitroarenes

Reaction of organic anions. Part 108. On the mechanism of the vicarious nucleophilic substitution of hydrogen in nitroarenes

Vicarious Nucleophilic Substitution of Hydrogen in Nitroarenes using 1-Chloroalkanesulfonic Esters; A Simple Synthesis of 1-(Nitrophenyl)-alkanesulfonic and (Nitrophenyl)-methanesulfonic Esters

Vicarious Nucleophilic Substitution of Hydrogen in Nitroarenes using 1-Chloroalkanesulfonic Esters; A Simple Synthesis of 1-(Nitrophenyl)-alkanesulfonic and (Nitrophenyl)-methanesulfonic Esters

Nucleophilic Substitution of Hydrogen in Nitroarenes by Phosphorus‐Stabilized Carbanions having “Vicarious” Leaving Groups

Angewandte Chemie International Edition in EnglishVolume 21, Issue 6 p. 451-452 Communication Nucleophilic Substitution of Hydrogen in Nitroarenes by Phosphorus-Stabilized Carbanions having “Vicarious” Leaving Groups Prof. Dr. Mieczysław Ma̧kosza, Prof. Dr. Mieczysław Ma̧kosza Institute of Organic Chemistry Polish Academy of Sciences, PL-01-244 Warszawa, Kasprzaka 44/52 (Poland)Search for more papers by this authorDr. Jerzy Goliński, Dr. Jerzy Goliński Institute of Organic Chemistry Polish Academy of Sciences, PL-01-244 Warszawa, Kasprzaka 44/52 (Poland)Search for more papers by this author Prof. Dr. Mieczysław Ma̧kosza, Prof. Dr. Mieczysław Ma̧kosza Institute of Organic Chemistry Polish Academy of Sciences, PL-01-244 Warszawa, Kasprzaka 44/52 (Poland)Search for more papers by this authorDr. Jerzy Goliński, Dr. Jerzy Goliński Institute of Organic Chemistry Polish Academy of Sciences, PL-01-244 Warszawa, Kasprzaka 44/52 (Poland)Search for more papers by this author First published: June 1982 https://doi.org/10.1002/anie.198204511Citations: 18AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article.Citing Literature Volume21, Issue6June 1982Pages 451-452 RelatedInformation