Acetone azine
| Acetone azine | |
|---|---|
| |
| IUPAC name | acetone azine diisopropylidenehydrazine |
| Other names | dimethyl ketazine |
| Identifiers | |
| InChI | InChI=1/C6H12N2/c1-5(2)7-8-6(3)4/h1-4H3 |
| InChIKey | PFLUPZGCTVGDLV-UHFFFAOYAR |
| Standard InChI | InChI=1S/C6H12N2/c1-5(2)7-8-6(3)4/h1-4H3 |
| Standard InChIKey | PFLUPZGCTVGDLV-UHFFFAOYSA-N |
| CAS number | [] |
| EC number | |
| ChemSpider | |
| SMILES | |
| Properties[1] | |
| Chemical formula | C6H12N2 |
| Molar mass | 112.17 g mol−1 |
| Appearance | colourless liquid |
| Density | 0.8390 g cm−3 |
| Melting point |
−12.5 °C |
| Boiling point |
133 °C |
| Refractive index (nD) | 1.4535 |
| Except where noted otherwise, data are given for materials in their standard state (at 25 °C, 100 kPa) | |
Acetone azine, Me2C=N–N=CMe2, is the condensation product of two equivalents of acetone with one equivalent of hydrazine. It is an intermediate in the industrial production of hydrazine by the Atofina–PCUK process[2][3] and by the Bayer hydrazine process.[4]
Contents
Laboratory preparation and use
On a laboratory scale, acetone azine is prepared by the direct reaction of acetone with hydrazine hydrate, with water being removed from the product by stirring with solid potassium hydroxide:[5][6] it is also commercially available. It is a useful precursor to acetone hydrazone[6][7] and hence to 2-diazopropane,[7][8][9] both of which must be prepared immediately before use and cannot be stored.[6][9]
As well as its use as an intermediate in organic synthesis, the coordination chemistry of acetone azine (as a ligand) has also been studied.[10][11][12] Acetone is also 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[13] and pharmaceuticals.[14]
Production of hydrazine
Atofina–PCUK process
The industrial preparation of acetone azine[2] might, at first sight, appear to be the reverse of the laboratory procedure: the azine is produced from acetone hydrazone, and then hydrolyzed to give hydrazine hydrate and acetone. The interest in preparing the azine is that it can be removed from the initial reaction mixture as an azeotrope with water:[3] in both laboratory practice and the Atofina–PCUK process, the aim is to avoid directly handling the unstable acetone hydrazone.
Bayer hydrazine process
The Bayer hydrazine process is a modification of the Raschig process, that is the oxidation of ammonia with sodium hypochlorite to produce hydrazine. The addition of acetone to the reaction mixture allows the separation and purification of acetone azine before its hydrolysis to hydrazine hydrate.[4]
References
- ↑ CRC Handbook of Chemistry and Physics, 62nd ed.; Weast, Robert C., Ed.; CRC Press: Boca Raton, FL, 1981; p C-74. ISBN 0-8493-0462-8.
- ↑ 2.0 2.1 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.
- ↑ 3.0 3.1 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.
- ↑ 4.0 4.1 Holleman, A. F.; Wiberg, E. Inorganic Chemistry; Academic Press: San Diego, 2001; p 619. ISBN 0-12-352651-5.
- ↑ Curtius, T.; Thun, K. Einwirkung von Hydrazinhydrat auf Monoketone und Orthodiketone. J. Prakt. Chem. (2. Ser.) 1891, 44, 161–86. DOI: 10.1002/prac.18910440121.
- ↑ 6.0 6.1 6.2 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.
- ↑ 7.0 7.1 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.
- ↑ 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.
- ↑ 9.0 9.1 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.
- ↑ 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.
- ↑ 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.
- ↑ 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.
- ↑ 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.
- ↑ 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.
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