THE VON RICHTER REACTION¹

Abstract

Victor von Richter in 1871-1875 reported (1, 2, 3) the reaction of p-nitrobromobenzene with alcoholic potassium cyanide to give m-bromobenzoic acid, together with some equally odd reactions of other nitrohalobenzenes with the same reagent. This paper presents experimental confirmation of some of these reports, improvements in the experimental procedure, and investigations of the behavior of additional aromatic nitro compounds with alcoholic potassium cyanide. We believe that we are dealing with a general reaction of aromatic nitro compounds, and present our ideas on its mechanism.It is remarkable that in the three-quarters of a century elapsed since von Richter's4 papers, only Holleman (4) has done further work on the same sort of reaction. In Table I Holleman's results are displayed along with von Richter's. COOH

Aromatic Nucleophilic Substitution Reactions.

“…The most familiar example of the von Richter reaction is the conversion of p-bromonitrobenzene to m-bromobenzoic acid (in 22 per cent yield). m-Bromonitrobenzene gives a mixture of o-and p-bromobenzoic acids, while o-bromonitrobenzene gives no acidic products (104,473,474,475,612). The chloronitrobenzenes and iodonitrobenzenes react quite analogously (473,474,475,476).…”

“…These include the carboxylation of pyrazines by ethanolic cyanide (340), and the formation of 2-methoxy-6-nitrobenzonitrile from m-dinitrobenzene in methanol (373, 380), of 5-cyano-6-methoxyquinoline from 6-nitroquinoline in methanol ( 293 amino-4-cyano-2-naphthol from 1 -nitroso-2-naphthol (89), and of purpuric acids from polynitrophenols ( 76), all under the action of an alkali cyanide. Bunnett, Cormack, and McKay (104) have given some consideration to the mechanisms of these reactions. The theoretical problem remains, however, largely unanswered.…”

Microdetermination of m-dinitro compounds with cyanide and silver electrodes

“…The nature and products of the reaction of m-dinitro aromatic compounds with various nucleophiles including the cyanide ion have not been exactly known. Formation of a quinoid adduct (I and II) (6, 7,16-18), substitution with the cyanide and replacement of one of the nitro groups by alkoxyl group to give III (10)(11)(12)(13)(14)19) work. The product of the reaction of m-dinitrobenzene with potassium cyanide in the presence of methyl alcohol was isolated by extraction with ether, crystallized, and identified.…”

Contribution À l'ÉTUDE De La Réaction De Von Richter: Iv. Commentaires Concernant La Réaction

“…Au moment dksirk, la rkaction est interrompue. Les pi-oduits sont isolks et purifiits seloil le illode opilratoire clkjA clkcrit ( 5 ) . Les rksultats sont pr6sentks au Tableau I.…”