Acetone azine is the simplest ketazine. It is an intermediate in some hydrazine manufacturing processes.
Synthesis
Acetone azine can be prepared from acetone and hydrazine:[3]
- 2 (CH3)2CO + N2H4 → 2 H2O + [(CH3)2C=N]2
It can also be produced from acetone (2 eq.), ammonia (2 eq.) and hydrogen peroxide (1 eq.).[4] The first step is the formation of acetone imine, Me2C=NH; this is then oxidized by hydrogen peroxide through a complex mechanism to give 3,3-dimethyloxaziridine, which reacts with a further molecule of ammonia to produce acetone hydrazone. The hydrazone then condenses with a further molecule of acetone to produce the azine. The acetone azine product is distilled out of the reaction mixture as a 1:6 azeotrope with water.[5]
Reactions
Acetone azine can be used to prepare acetone hydrazone[3] and 2-diazopropane.[6]
Hydrazine can be produced through acid-catalysed hydrolysis of acetone azine:[7]
- 2 H2O + [(CH3)2C=N]2 → 2 (CH3)2CO + N2H4
References
- ^ "Acetone azine MSDS (Santa Cruz Biotechnology)" (PDF).
- ^ "Acetone azine MSDS (Sigma Aldrich)".
- ^ a b Day, A. C.; Whiting, M. C. (1970). "Acetone Hydrazone". Organic Syntheses: 3; Collected Volumes, vol. 6, 1988, p. 10.
- ^ US 3972878, Schirmann, Jean-Pierre; Combroux, Jean & Delavarenne, Serge Yvon, "Method for preparing azines and hydrazones", issued 1976-08-03, assigned to Produits Chimiques Ugine Kuhlmann.US 3978049, Schirmann, Jean-Pierre; Tellier, Pierre & Mathais, Henri et al., "Process for the preparation of hydrazine compounds", issued 1976-08-31, assigned to Produits Chimiques Ugine Kuhlmann
- ^ US 4724133, Schirmann, Jean-Pierre; Combroux, Jean & Delavarenne, Serge Y., "Preparation of a concentrated aqueous solution of hydrazine hydrate", issued 1988-02-09, assigned to Atochem
- ^ Andrews, S. D.; Day, A. C.; Raymond, P.; Whiting, M. C. (1970). "2-Diazopropane". Organic Syntheses: 27; Collected Volumes, vol. 6, 1988, p. 392.
- ^ 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, doi:10.1021/ja01386a032.