Azine

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The generic formula of an azine. For an aldazine, R2 = H.

Azines are a functional class of organic compounds, formed from the condensation reaction of two equivalents of an aldehyde or ketone with one equivalent of hydrazine.[1][2] They may be further classified as aldazines or ketazines, depending on the nature of the carbonyl compound.[3][4]

Preparation

Azines may be prepared by the direct reaction of a carbonyl compound with hydrazine hydrate:[5] the reaction is exothermic.[6] The usual method of industrial production is the Pechiney-Ugine-Kuhlmann process, starting from the ketone, ammonia and hydrogen peroxide.[7][8]

Reactions and uses

Azines have been used as precursors to hydrazones[5][9] and diazo compounds.[9][10][11]

Acetone azine chem.png

Azines are also important intermediates in the industrial production of hydrazine hydrate by the Bayer hydrazine process[12][13] or the Pechiney-Ugine-Kuhlmann process.[7][8] They have been also used as sources of hydrazine produced in situ, for example in the production of herbicide precursor 1,2,4-triazole.[14]

The coordination chemistry of azines (as ligands) has also been studied.[15][16][17] Acetone is used to derivatize hydrazine, through formation of acetone azine, for analysis by gas chromatography: the method has been used to determine trace levels of hydrazine in drinking water[18] and pharmaceuticals.[19]

Nomenclature

Azines may be named by substitutive or functional class nomenclature.[20][21] In functional class nomenclature, the functional modifier "azine" is appended to the name of the carbonyl compound: hence, "acetone azine".[20] In older nomenclature, the functional class name "ketazine" has been used with the names of the hydrocarbyl substituents: e.g., "methyl ethyl ketazine". In substitutive nomenclature, azines are named as derivatives of hydrazine: hence, "diisopropylidenehydrazine".[20] In the presence of groups of higher seniority, the prefixes "hydrazinylidene" and "hydrazinediylidene" are used.[22]

Unsymmetrical azines, that is compounds of the type X=N–N=Y with X ≠ Y, are not named as azines: in the absence of other functional groups having higher seniority, they can be named as substituted hydrazones.[23]

References

  1. Glossary of class names of organic compounds and reactivity intermediates based on structure (IUPAC Recommendations 1995). Pure Appl. Chem. 1995, 67 (8-9), 1307–75 at 1321. DOI: 10.1351/pac199567081307.
  2. azines, <http://goldbook.iupac.org/A00557.html> (accessed 2 July 2010), Compendium of Chemical Terminology Internet edition; International Union of Pure and Applied Chemistry (IUPAC).
  3. Glossary of class names of organic compounds and reactivity intermediates based on structure (IUPAC Recommendations 1995). Pure Appl. Chem. 1995, 67 (8-9), 1307–75 at 1312, 1348. DOI: 10.1351/pac199567081307.
  4. aldazines, <http://goldbook.iupac.org/A00207.html> (accessed 2 July 2010), Compendium of Chemical Terminology Internet edition; International Union of Pure and Applied Chemistry (IUPAC). ketazines, <http://goldbook.iupac.org/K03377.html> (accessed 2 July 2010), Compendium of Chemical Terminology Internet edition; International Union of Pure and Applied Chemistry (IUPAC).
  5. 5.0 5.1 Day, A. C.; Whiting, M. C. Acetone hydrazone. Org. Synth. 1970, 50, 3, <http://www.orgsyn.org/orgsyn/orgsyn/prepContent.asp?prep=cv6p0010>; Coll. Vol., 6, 10.
  6. Gilbert, E. C. Studies on Hydrazine. The Hydrolysis of Dimethylketazine and the Equilibrium between Hydrazine and Acetone. J. Am. Chem. Soc. 1929, 51 (11), 3394–3409. DOI: 10.1021/ja01386a032.
  7. 7.0 7.1 Schirmann, Jean-Pierre; Combroux, Jean; Delavarenne, Serge Yvon (Produits Chimiques Ugine Kuhlmann) Method for preparing azines and hydrazones. US Patent 3972878, issued 3 August 1976. Schirmann, Jean-Pierre; Tellier, Pierre; Mathais, Henri, et al. (Produits Chimiques Ugine Kuhlmann) Process for the preparation of hydrazine compounds. US Patent 3978049, issued 31 August 1976. Schirmann, Jean-Pierre; Combroux, Jean; Delavarenne, Serge Yvon (Produits Chimiques Ugine Kuhlmann) Method for making azines. US Patent 4093656, issued 6 June 1978.
  8. 8.0 8.1 Schirmann, Jean-Pierre; Combroux, Jean; Delavarenne, Serge Y. (Atochem) Preparation of a concentrated aqueous solution of hydrazine hydrate. US Patent 4724133, issued 9 February 1988.
  9. 9.0 9.1 Staudinger, H.; Gaule, Alice Vergleich der Stickstoff-Abspaltung bei verschiedenen aliphatischen Diazoverbindungen. Ber. Dtsch. Chem. Ges. 1916, 49 (2), 1897–1918. DOI: 10.1002/cber.19160490245.
  10. Day, A. C.; Raymond, P.; Southam, R. M.; Whiting, M. C. The preparation of secondary aliphatic diazo-compounds from hydrazones. J. Chem. Soc. C 1966, 467–69. DOI: 10.1039/J39660000467.
  11. Andrews, S. D.; Day, A. C.; Raymond, P.; Whiting, M. C. 2-Diazopropane. Org. Synth. 1970, 50, 27, <http://www.orgsyn.org/orgsyn/orgsyn/prepContent.asp?prep=cv6p0392>; Coll. Vol., 6, 392.
  12. Eichenhofer, Kurt-Wilhelm; Schliebs, Reinhard (Bayer) Production of ketazines. US Patent 3965097, issued 22 June 1976.
  13. Holleman, A. F.; Wiberg, E. Inorganic Chemistry; Academic Press: San Diego, 2001; p 619. ISBN 0-12-352651-5.
  14. Nagata, Nobuhiro; Nishizawa, Chiharu; Kurai, Toshikiyo (Mitsubishi Gas Chemical Co.) Method of producing 1,2,4-triazole. US Patent 6002015, issued 14 December 1999.
  15. Gudkova, A. S.; Reutov, O. A.; Aleinikova, M. Ya. Izv. Akad. Nauk SSSR, Otdel. Khim. Nauk 1962 (8), 1382–87; Reactions of hydrazones and azines with metal salts 4. Reactions of azines of aldehydes and ketones with cupric salts. Russ. Chem. Bull. (Transl.) 1962, 11 (8), 1298–1302. DOI: 10.1007/BF00907973.
  16. Gudkova, A. S.; Aleinikova, M. Ya.; Reutov, O. A. Izv. Akad. Nauk SSSR, Ser. Khim. 1966 (5), 844–48; Reactions of hydrazones and azines with metal salts 5. Reactions of hydrazones and azines with mercuric halides. Russ. Chem. Bull. (Transl.) 1966, 15 (5), 807–11. DOI: 10.1007/BF00849376.
  17. King, Fiona; Nicholls, David Complex of titanium halides with acetone azine and its isomer 3,5,5-trimethyl-pyrazoline. Inorg. Chim. Acta 1978, 28, 55–58. DOI: 10.1016/S0020-1693(00)87413-7.
  18. Davis, William E., II; Li, Yongtao Analysis of hydrazine in drinking water by isotope dilution gas chromatography/tandem mass spectrometry with derivatization and liquid-liquid extraction. Anal. Chem. 2008, 80 (14), 5449–53. DOI: 10.1021/ac702536d.
  19. Sun, Mingjiang; Bai, Lin; Liu, David Q. A generic approach for the determination of trace hydrazine in drug substances using in situ derivatization-headspace GC–MS. J. Pharm. Biomed. Anal. 2009, 49 (2), 529–33. DOI: 10.1016/j.jpba.2008.11.009.
  20. 20.0 20.1 20.2 Rule R-5.6.6.3. In A Guide to IUPAC Nomenclature of Organic Compounds; IUPAC Recommendations 1993; Blackwell Science: Oxford, 1993; p 105. ISBN 0-632-03488-2, <http://www.acdlabs.com/iupac/nomenclature/93/r93_469.htm>.
  21. Draft Rule P-68.3.1.2.3. In Nomenclature of Organic Chemistry; IUPAC Provisional Recommendations 2004; IUPAC, 2004, <http://old.iupac.org/reports/provisional/abstract04/favre_310305.html>.
  22. Draft Rule P-53.6.2. In Nomenclature of Organic Chemistry; IUPAC Provisional Recommendations 2004; IUPAC, 2004, <http://old.iupac.org/reports/provisional/abstract04/favre_310305.html>.
  23. Rule C-923.2. In Nomenclature of Organic Chemistry, Sections A, B, C, D, E, F, and H; IUPAC Recommendations 1979; Pergamon: Oxford, 1979. ISBN 0-08022-369-9, <http://www.acdlabs.com/iupac/nomenclature/79/r79_623.htm>.
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