Reduction of nitro compounds

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The chemical reactions described as reduction of nitro compounds can be effected by many reagents and reaction conditions. Historically, the nitro group was one of the first functional groups to be reduced.

Alkyl and aryl nitro compounds behave differently. Thus, reduction conditions can be broadly classified by starting materials: aliphatic nitro compounds or aromatic nitro compounds. Secondary classifications are based upon reaction products.

Aliphatic nitro compounds[edit]

Reduction to hydrocarbons[edit]

Generalization of the reduction of a nitroalkane to an alkane

Hydrodenitration (replacement of a nitro group with hydrogen) is difficult to achieve but can be effected by catalytic hydrogenation over platinum on silica gel at high temperatures.[1]

Reduction to amines[edit]

Generalization of the reduction of a nitroalkane to an amine

Aliphatic nitro compounds can be reduced to aliphatic amines by several reagents:

α,β-Unsaturated nitro compounds can be reduced to saturated amines by:

Reduction to hydroxylamines[edit]

Aliphatic nitro compounds can be reduced to aliphatic hydroxylamines using diborane.[7]

Generalization of the reduction of a nitroalkane to a hydroxylamine

The reaction can also be carried out with zinc dust and ammonium chloride[citation needed]:

R-NO2 + 4 NH4Cl + 2 Zn → R-NH-OH + 2 ZnCl2 + 4 NH3 + H2O

Reduction to oximes[edit]

Generalization of the reduction of a nitroalkane to an oxime

Nitro compounds are typically reduced to oximes using metal salts, such as stannous chloride[8] or chromium(II) chloride.[9] Additionally, catalytic hydrogenation using a controlled amount of hydrogen can generate oximes.[10]

Aromatic nitro compounds[edit]

Reduction to anilines[edit]

Generalization of the reduction of a nitroarene to aniline

The reduction of nitroaromatics is conducted on an industrial scale.[11] Many methods for the production of anilines from aryl nitro compounds exist, such as:

Metal hydrides are typically not used to reduce aryl nitro compounds to anilines because they tend to produce azo compounds. (See below)

Reduction to hydroxylamines[edit]

Several methods for the production of aryl hydroxylamines from aryl nitro compounds exist:

Reduction to hydrazino compounds[edit]

See also: Hydrazine

Treatment of nitroarenes with excess zinc metal results in the formation of N,N'-diarylhydrazine.[23]

Reduction to azo compounds[edit]

Generalization of the reduction of a nitroarene to an azo compound

Treatment of aromatic nitro compounds with metal hydrides gives good yields of azo compounds. For example, one could use:

Reduction to azoxy compounds[edit]

Aromatic compounds are reduced to azoxy compounds by using:

Na3AsO3 or glucose or NaOH[25]
C6H5NO2

References[edit]

  1. ^ M. J. Guttieri & W. F. Maier (1984). "Selective cleavage of carbon-nitrogen bonds with platinum". J. Org. Chem. 49 (16): 2875–2880. doi:10.1021/jo00190a006. 
  2. ^ A. T. Nielsen (1962). "The Isomeric Dinitrocyclohexanes. II. Stereochemistry". J. Org. Chem. 27 (6): 1998–2001. doi:10.1021/jo01053a019. 
  3. ^ Dauben, Jr., H. J.; Ringold, H. J.; Wade, R. H.; Pearson, D. L.; Anderson, Jr., A. G. (1963). "Cycloheptanone". Org. Synth.  ; Coll. Vol., 4, p. 221 
  4. ^ Senkus, M. (1948). "Ind. Eng. Chem.". 40: 506. 
  5. ^ A. S. Kende & J. S. Mendoza (1991). "Controlled reduction of nitroalkanes to alkyl hydroxylamines or amines by samarium diiodide". Tetrahedron Letters. 32 (14): 1699–1702. doi:10.1016/S0040-4039(00)74307-3. 
  6. ^ A. Burger, M. L. Stein and J. B. Clements (1957). "Some Pyridylnitroalkenes, Nitroalkanols, and Alkylamines". J. Org. Chem. 22 (2): 143–144. doi:10.1021/jo01353a010. 
  7. ^ H. Feuer, R. S. Bartlett, B. F. Vincent and R. S. Anderson (1965). "Diborane Reduction of Nitro Salts. A New Synthesis of N-Monosubstituted Hydroxylamines". J. Org. Chem. 30 (9): 2880–2882. doi:10.1021/jo01020a002. 
  8. ^ Braun, V. J.; Sobecki, W. (1911). "Über primäre Dinitro-, Nitronitrit- und Dialdoxim-Verbindungen der Fettreihe". Ber. 44 (3): 2526–2534. doi:10.1002/cber.19110440377. 
  9. ^ J. R. Hanson & E. Premuzic (1967). "Applications of chromous chloride--II : The reduction of some steroidal nitro-compounds". Tetrahedron. 23 (10): 4105–4110. doi:10.1016/S0040-4020(01)97921-9. 
  10. ^ C. Grundmann (1950). "Über die partielle Reduktion von Nitro-cyclohexan". Angewandte Chemie. 62 (23-24): 558–560. doi:10.1002/ange.19500622304. 
  11. ^ Gerald Booth (2007). "Nitro Compounds, Aromatic". In: Ullmann's Encyclopedia of Industrial Chemistry. John Wiley & Sons: New York. doi:10.1002/14356007.a17_411
  12. ^ Mazaheri O., Javad Kalbasi R. "Preparation and characterization of Ni/mZSM-5 zeolite with a hierarchical pore structure by using KIT-6 as silica template: an efficient bi-functional catalyst for the reduction of nitro aromatic compounds". Org. Synth. doi:10.1039/C5RA02349A. 
  13. ^ Bavin, P. M. G. (1973). "2-Aminofluorene". Org. Synth. ; Coll. Vol., 5, p. 30 
  14. ^ Allen, C. F. H.; VanAllan, J. (1955). "2-Amino-p-cymene". Org. Synth.  ; Coll. Vol., 3, p. 63 
  15. ^ Fox, B. A.; Threlfall, T. L. (1973). "2,3-Diaminopyridine". Org. Synth.  ; Coll. Vol., 5, p. 346 
  16. ^ Redemann, C. T.; Redemann, C. E. (1955). "5-Amino-2,3-dihydro-1,4-phthalazinedione". Org. Synth.  ; Coll. Vol., 3, p. 69 
  17. ^ Hartman, W. W.; Silloway, H. L. (1955). "2-Amino-4-nitrophenol". Org. Synth.  ; Coll. Vol., 3, p. 82 
  18. ^ Faul, Margaret M.; Thiel, Oliver R. (2005). "Tin(II) Chloride". Encyclopedia of Reagents for Organic Synthesis. Encyclopedia of Reagents for Organic Synthesis. doi:10.1002/047084289X.rt112.pub2. ISBN 9780470842898. 
  19. ^ Basu, M. K. (2000). "Ultrasound-promoted highly efficient reduction of aromatic nitro compounds to the aromatic amines by samarium/ammonium chloride". Tet. Lett. 41 (30): 5603. doi:10.1016/S0040-4039(00)00917-5. 
  20. ^ Ayyangar, N. R.; Brahme, K. C.; Kalkote, U. R.; Srinivasan, K. V. (1984). "Facile Transfer-Reduction of Nitroarenes to N Arylhydroxylamines with Hydrazine in the Presence of Raney Nickel". Synthesis. 1984 (11): 938. doi:10.1055/s-1984-31027. 
  21. ^ Harman, R. E. (1963). "Chloro-p-benzoquinone". Org. Synth. ; Coll. Vol., 4, p. 148 
  22. ^ Kamm, O. (1941). "β-Phenylhydroxylamine". Org. Synth. ; Coll. Vol., 1, p. 445 
  23. ^ a b Bigelow, H. E.; Robinson, D. B. (1955). "Azobenzene". Org. Synth.  ; Coll. Vol., 3, p. 103 
  24. ^ R. F. Nystrom & W. G. Brown (1948). "Reduction of Organic Compounds by Lithium Aluminum Hydride. III. Halides, Quinones, Miscellaneous Nitrogen Compounds". J. Am. Chem. Soc. 70 (11): 3738–3740. doi:10.1021/ja01191a057. PMID 18102934. 
  25. ^ O.P.Tandon