Zinin reaction

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Zinin reaction
Named after Nikolay Zinin
Reaction type Organic redox reaction

Zinin reaction or Zinin reduction involves reduction of nitro aromatic compounds to the amines using sodium sulfide. [1] It is used to convert nitrobenzenes to anilines. [2] [3] The reaction selectively reduces nitro groups in the presence of other easily reduced functional groups (e.g., aryl halides and C=C bonds) are present in the molecule.

Contents

Reaction mechanism and example

The reaction requires water, with thiosulfate being formed as a by-product. A possible stoichiometry for the reaction is:

4 ArNO2  +   6 S2-  + 7 H2O → 4  ArNH2  +   3 S2O32- + 6 OH-

Mechanistic studies have implicated a role for disulfide that is generated in situ. Nitrosobenzenes (ArNO) and phenylhydroxylamine (ArNHOH) are probable intermediates. [4]

Dinitrobenzenes can often be reduced selectively to the nitroaniline, [5] for example in the synthesis of 3-nitroaniline from 1,3-dinitrobenzene

History

The reaction was discovered by a Russian organic chemist Nikolay Zinin (Russian: Николай Николаевич Зинин) (25 August 1812, Shusha – 18 February 1880, Saint Petersburg).

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<span class="mw-page-title-main">Nikolay Zinin</span>

Nikolay Nikolaevich Zinin was a Russian organic chemist.

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<span class="mw-page-title-main">Thioquinanthrene</span> Chemical compound

Thioquinanthrene, also known as thiochinathren, is an aromatic organic chemical compound. It has the chemical formula C18H10N2S2 and reacts with alcoholates or alkoxides. One of the key uses is to act as a catalyst poison in the Rosenmund reduction. It has the IUPAC name of 2,13-dithia-10,21-diazapentacyclo[12.8.0.03,12.04,9.015,20]docosa-1(14),3(12),4,6,8,10,15,17,19,21-decaene.

References

  1. Porter, H. K. (1973). "The Zinin Reduction of Nitroarenes". Organic Reactions . 20 (4): 455–481. doi:10.1002/0471264180.or020.04. ISBN   0471264180.
  2. Zinin, N. (1842). "Beschreibung einiger neuer organischer Basen, dargestellt durch die Einwirkung des Schwefelwasserstoffes auf Verbindungen der Kohlenwasserstoffe mit Untersalpetersäure" [Description of some new organic bases, represented by the action of hydrogen sulphide on hydrocarbons with sub-nitric acid]. Journal für Praktische Chemie (in German). 27 (1): 140–153. doi:10.1002/prac.18420270125.
  3. Richard Willstätter, Heinrich Kubli (1908). "Über die Reduktion von Nitroverbindungen nach der Methode von Zinin" [On the reduction of nitro compounds by the method of Zinin]. Berichte der deutschen chemischen Gesellschaft (in German). 41 (2): 1936–1940. doi:10.1002/cber.19080410273.
  4. Porter, H. K. (2011), "The Zinin Reduction of Nitroarenes", Organic Reactions, John Wiley & Sons, Ltd, pp. 455–481, doi:10.1002/0471264180.or020.04, ISBN   978-0-471-26418-7 , retrieved 2022-02-01
  5. Sebla Dincer (2002). "The preferential reduction of 4,6 (5,7)-dinitro and 5,6-dinitrobenzimidazoles". Dyes and Pigments. 53 (3): 263–266. doi:10.1016/S0143-7208(02)00018-9.