Azine

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File:General structural formula of azines.svg
The generic formula of an azine. For an aldazine, R2, R4 = H.

Azines are a functional class of organic compounds with the connectivity Page Module:Chem2/styles.css has no content.RR′C=N−N=CRR′. These compounds are the product of the condensation of hydrazine with ketones and aldehydes, although in practice they are often made by alternative routes. Ketazines are azines derived from ketones.[1] For example, acetone azine is the simplest ketazine. Aldazines are azines derived from aldehydes.[2]

Preparation

The usual method of industrial production is the peroxide process, starting from the ketone, ammonia, and hydrogen peroxide.[3]

File:Pechiney-Ugine-Kuhlmann process.png

In the laboratory, azines are typically prepared by condensation of hydrazine with two equivalents of a carbonyl.[4]

Azines are also produced when chalcone reacts with a hydrazone to produce 3,5-diphenyl-1H-pyrazole,[5] in a conversion also carried out with hydrazine hydrate.[6][7]

File:Lasri condensation reaction.svg

Reactions

Azines characteristically undergo hydrolysis to hydrazines. The reaction proceeds by the intermediacy of a hydrazone:

Page Module:Chem2/styles.css has no content.R2C=N−N=CR2 + H2O → R2C=N−NH2 + R2C=O
Page Module:Chem2/styles.css has no content.R2C=N−NH2 + H2O → N2H4 + R2C=O

Azines have been used as precursors to hydrazones:[4][8]

Page Module:Chem2/styles.css has no content.R2C=N−N=CR2 + N2H4 → 2R2C=N−NH2

They are also precursors to diazo compounds.[9][8][10]

File:Acetone azine chem.png

The coordination chemistry of azines (as ligands) has also been studied.[11][12][13]

Acetone is used to derivatize hydrazine into acetone azine for analysis by gas chromatography. This method is used to determine trace levels of hydrazine in drinking water[14] and pharmaceuticals.[15]

Applications

Ketazines are also important intermediates in the industrial production of hydrazine hydrate by the peroxide process.[3] In the presence of an oxidant, ammonia and ketones react to give hydrazine via ketazine:

2 Me(Et)C=O + 2 NH3 + H2O2 → Me(Et)C=NN=C(Et)Me + 2 H2O

The ketazine can be hydrolyzed to the hydrazine and regenerate the ketone:

Me(Et)C=NN=C(Et)Me + 2 H2O → 2 Me(Et)C=O + N2H4

Ketazines have been also used as sources of hydrazine produced in situ, for example in the production of herbicide precursor 1,2,4-triazole.[16]

References

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  1. ^ IUPAC, Compendium of Chemical Terminology, 5th ed. (the "Gold Book") (2025). Online version: (2006–) "ketazines". Script error: No such module "CS1 identifiers".
  2. ^ IUPAC, Compendium of Chemical Terminology, 5th ed. (the "Gold Book") (2025). Online version: (2006–) "aldazines". Script error: No such module "CS1 identifiers".
  3. ^ a b Jean-Pierre Schirmann, Paul Bourdauducq "Hydrazine" in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, 2002. Script error: No such module "CS1 identifiers"..
  4. ^ a b Page Module:Citation/CS1/styles.css has no content.Day, A. C.; Whiting, M. C. (1970). "Acetone Hydrazone". Organic Syntheses. 50: 3. doi:10.15227/orgsyn.050.0003.
  5. ^ Page Module:Citation/CS1/styles.css has no content.Lasri, Jamal; Ismail, Ali I. (2018). "Metal-free and FeCl3-catalyzed synthesis of azines and 3,5-diphenyl-1H-pyrazole from hydrazones and/or ketones monitored by high resolution ESI+-MS". Indian Journal of Chemistry, Section B. 57B (3): 362–373.
  6. ^ Page Module:Citation/CS1/styles.css has no content.Outirite, Moha; Lebrini, Mounim; Lagrenée, Michel; Bentiss, Fouad (2008). "New one step synthesis of 3,5-disubstituted pyrazoles under microwave irradiation and classical heating". Journal of Heterocyclic Chemistry. 45 (2): 503–505. doi:10.1002/jhet.5570450231.
  7. ^ Page Module:Citation/CS1/styles.css has no content.Zhang, Ze; Tan, Ya-Jun; Wang, Chun-Shan; Wu, Hao-Hao (2014). "One-pot synthesis of 3,5-diphenyl-1H-pyrazoles from chalcones and hydrazine under mechanochemical ball milling". Heterocycles. 89 (1): 103–112. doi:10.3987/COM-13-12867.
  8. ^ a b Page Module:Citation/CS1/styles.css has no content.Staudinger, H.; Gaule, Alice (July 1916). "Vergleich der Stickstoff-Abspaltung bei verschiedenen aliphatischen Diazoverbindungen". Berichte der Deutschen Chemischen Gesellschaft. 49 (2): 1897–1918. doi:10.1002/cber.19160490245.
  9. ^ Page Module:Citation/CS1/styles.css has no content.Day, A. C.; Raymond, P.; Southam, R. M.; Whiting, M. C. (1966). "The preparation of secondary aliphatic diazo-compounds from hydrazones". Journal of the Chemical Society C: Organic: 467. doi:10.1039/J39660000467.
  10. ^ Page Module:Citation/CS1/styles.css has no content.Andrews, S. D.; Day, A. C.; Raymond, P.; Whiting, M. C. (1970). "2-Diazopropane". Organic Syntheses. 50: 27; Page Module:Citation/CS1/styles.css has no content.Collected Volumes, vol. 6, p. 392..
  11. ^ Page Module:Citation/CS1/styles.css has no content.Gudkova, A. S.; Reutov, O. A.; Aleinikova, M. Ya. (August 1962). "Reactions of hydrazones and azines with metal salts". Bulletin of the Academy of Sciences of the USSR Division of Chemical Science. 11 (8): 1298–1302. doi:10.1007/BF00907973.
  12. ^ Page Module:Citation/CS1/styles.css has no content.Gudkova, A. S.; Aleinikova, M. Ya.; Reutov, O. A. (May 1966). "Reactions of hydrazones and azines with metal salts Communication 5. Reactions of hydrazones and azines with mercuric halides". Bulletin of the Academy of Sciences, USSR Division of Chemical Science. 15 (5): 807–811. doi:10.1007/BF00849376.
  13. ^ Page Module:Citation/CS1/styles.css has no content.King, Fiona; Nicholls, David (January 1978). "Complex of titanium halides with acetone azine and its isomer 3, 5, 5-trimethyl-pyrazoline". Inorganica Chimica Acta. 28: 55–58. doi:10.1016/S0020-1693(00)87413-7.
  14. ^ Page Module:Citation/CS1/styles.css has no content.Davis, II, William E.; Li, Yongtao (July 2008). "Analysis of Hydrazine in Drinking Water by Isotope Dilution Gas Chromatography/Tandem Mass Spectrometry with Derivatization and Liquid−Liquid Extraction". Analytical Chemistry. 80 (14): 5449–5453. Bibcode:2008AnaCh..80.5449D. doi:10.1021/ac702536d. PMID 18564853.
  15. ^ Page Module:Citation/CS1/styles.css has no content.Sun, Mingjiang; Bai, Lin; Liu, David Q. (February 2009). "A generic approach for the determination of trace hydrazine in drug substances using in situ derivatization-headspace GC–MS". Journal of Pharmaceutical and Biomedical Analysis. 49 (2): 529–533. doi:10.1016/j.jpba.2008.11.009. PMID 19097722.
  16. ^ Page Template:Citation/styles.css has no content.US 6002015, Nagata, Nobuhiro; Nishizawa, Chiharu & Kurai, Toshikiyo, "Method of producing 1,2,4-triazole", published Script error: No such module "auto date formatter"., assigned to Mitsubishi Gas Chemical Co. .

Further reading

  • Page Module:Citation/CS1/styles.css has no content.Gilbert, E. C. (1929). "Studies on Hydrazine. The Hydrolysis of Dimethylketazine and the Equilibrium between Hydrazine and Acetone". J. Am. Chem. Soc. 51 (11): 3394–3409. Bibcode:1929JAChS..51.3394G. doi:10.1021/ja01386a032.
  • Page Template:Citation/styles.css has no content.US 3965097, Eichenhofer, Kurt-Wilhelm & Schliebs, Reinhard, "Production of ketazines", published Script error: No such module "auto date formatter"., assigned to Bayer .
  • Page Template:Citation/styles.css has no content.US 3972878, Schirmann, Jean-Pierre; Combroux, Jean & Delavarenne, Serge Yvon, "Method for preparing azines and hydrazones", published Script error: No such module "auto date formatter"., assigned to Produits Chimiques Ugine Kuhlmann .
  • Page Template:Citation/styles.css has no content.US 3978049, Schirmann, Jean-Pierre; Tellier, Pierre & Mathais, Henri et al., "Process for the preparation of hydrazine compounds", published Script error: No such module "auto date formatter"., assigned to Produits Chimiques Ugine Kuhlmann .
  • Page Template:Citation/styles.css has no content.US 4093656, Schirmann, Jean-Pierre; Combroux, Jean & Delavarenne, Serge Yvon, "Method for making azines", published Script error: No such module "auto date formatter"., assigned to Produits Chimiques Ugine Kuhlmann .
  • Page Template:Citation/styles.css has no content.US 4724133, Schirmann, Jean-Pierre; Combroux, Jean & Delavarenne, Serge Y., "Preparation of a concentrated aqueous solution of hydrazine hydrate", published Script error: No such module "auto date formatter"., assigned to Atochem .
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