Zinin reaction

Zinin reaction
Named after	Nikolay Zinin
Reaction type	Organic redox reaction

Short description: Conversion of nitro aromates like nitrobenzene to amines by reduction with sodium sulfides

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.

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 S^2- + 7 H₂O → 4 ArNH₂ + 3 S₂O₃^2- + 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).

References

↑ Porter, H. K. (1973). "The Zinin Reduction of Nitroarenes". Organic Reactions 20 (4): 455–481. doi:10.1002/0471264180.or020.04. ISBN 0471264180.
↑ "Beschreibung einiger neuer organischer Basen, dargestellt durch die Einwirkung des Schwefelwasserstoffes auf Verbindungen der Kohlenwasserstoffe mit Untersalpetersäure" (in German). Journal für Praktische Chemie 27 (1): 140–153. 1842. doi:10.1002/prac.18420270125. https://zenodo.org/record/1427792.
↑ Richard Willstätter, Heinrich Kubli (1908). "Über die Reduktion von Nitroverbindungen nach der Methode von Zinin" (in German). Berichte der deutschen chemischen Gesellschaft 41 (2): 1936–1940. doi:10.1002/cber.19080410273. https://zenodo.org/record/1426301.
↑ Porter, H. K. (2011), "The Zinin Reduction of Nitroarenes" (in en), Organic Reactions (John Wiley & Sons, Ltd): pp. 455–481, doi:10.1002/0471264180.or020.04, ISBN 978-0-471-26418-7, https://onlinelibrary.wiley.com/doi/abs/10.1002/0471264180.or020.04, retrieved 2022-02-01
↑ 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.

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[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] "Beschreibung einiger neuer organischer Basen, dargestellt durch die Einwirkung des Schwefelwasserstoffes auf Verbindungen der Kohlenwasserstoffe mit Untersalpetersäure" (in German). Journal für Praktische Chemie 27 (1): 140–153. 1842. doi:10.1002/prac.18420270125. https://zenodo.org/record/1427792.

[3] Richard Willstätter, Heinrich Kubli (1908). "Über die Reduktion von Nitroverbindungen nach der Methode von Zinin" (in German). Berichte der deutschen chemischen Gesellschaft 41 (2): 1936–1940. doi:10.1002/cber.19080410273. https://zenodo.org/record/1426301.

[4] Porter, H. K. (2011), "The Zinin Reduction of Nitroarenes" (in en), Organic Reactions (John Wiley & Sons, Ltd): pp. 455–481, doi:10.1002/0471264180.or020.04, ISBN 978-0-471-26418-7, https://onlinelibrary.wiley.com/doi/abs/10.1002/0471264180.or020.04, 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.

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Zinin reaction

Topic: Chemistry

Reaction mechanism and example

History

References