Difference between revisions of "Acetone azine"
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| − | '''Acetone azine''', Me<sub>2</sub>C=N–N=CMe<sub>2</sub>, is the [[Condensation reaction|condensation product]] of two [[equivalent (chemistry)|equivalent]]s of [[acetone]] with one equivalent of [[hydrazine]]. It is an intermediate in the industrial production of hydrazine by the [[Atofina–PCUK process]]<ref name="PCUK">{{citation | inventor1-first = Jean-Pierre | inventor1-last = Schirmann | inventor2-first = Jean | inventor2-last = Combroux | inventor3-first = Serge Yvon | inventor3-last = Delavarenne | assignee = Produits Chimiques Ugine Kuhlmann | country-code = US | patent-number = 3972878 | title = Method for preparing azines and hydrazones | issue-date = 1976-08-03}}. {{citation | inventor1-first = Jean-Pierre | inventor1-last = Schirmann | inventor2-first = Pierre | inventor2-last = Tellier | inventor3-first = Henri | inventor3-last = Mathais | inventor4-first = Francis | inventor4-last = Weiss | assignee = Produits Chimiques Ugine Kuhlmann | country-code = US | patent-number = 3978049 | title = Process for the preparation of hydrazine compounds | issue-date = 1976-08-31}}.</ref><ref name="Atochem">{{citation | inventor1-first = Jean-Pierre | inventor1-last = Schirmann | inventor2-first = Jean | inventor2-last = Combroux | inventor3-first = Serge Y. | inventor3-last = Delavarenne | assignee = Atochem | country-code = US | patent-number = 4724133 | title = Preparation of a concentrated aqueous solution of hydrazine hydrate | issue-date = 1988-02-09}}.</ref> and by the [[Bayer hydrazine process]].<ref>{{Holleman&Wiberg|page=619}}.</ref> | + | '''Acetone azine''', Me<sub>2</sub>C=N–N=CMe<sub>2</sub>, is the [[Condensation reaction|condensation product]] of two [[equivalent (chemistry)|equivalent]]s of [[acetone]] with one equivalent of [[hydrazine]]. It is an intermediate in the industrial production of hydrazine by the [[Atofina–PCUK process]]<ref name="PCUK">{{citation | inventor1-first = Jean-Pierre | inventor1-last = Schirmann | inventor2-first = Jean | inventor2-last = Combroux | inventor3-first = Serge Yvon | inventor3-last = Delavarenne | assignee = Produits Chimiques Ugine Kuhlmann | country-code = US | patent-number = 3972878 | title = Method for preparing azines and hydrazones | issue-date = 1976-08-03}}. {{citation | inventor1-first = Jean-Pierre | inventor1-last = Schirmann | inventor2-first = Pierre | inventor2-last = Tellier | inventor3-first = Henri | inventor3-last = Mathais | inventor4-first = Francis | inventor4-last = Weiss | assignee = Produits Chimiques Ugine Kuhlmann | country-code = US | patent-number = 3978049 | title = Process for the preparation of hydrazine compounds | issue-date = 1976-08-31}}.</ref><ref name="Atochem">{{citation | inventor1-first = Jean-Pierre | inventor1-last = Schirmann | inventor2-first = Jean | inventor2-last = Combroux | inventor3-first = Serge Y. | inventor3-last = Delavarenne | assignee = Atochem | country-code = US | patent-number = 4724133 | title = Preparation of a concentrated aqueous solution of hydrazine hydrate | issue-date = 1988-02-09}}.</ref> and by the [[Bayer hydrazine process]].<ref name="H&W">{{Holleman&Wiberg|page=619}}.</ref> |
==Laboratory preparation and use== | ==Laboratory preparation and use== | ||
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As well as its use as an intermediate in [[organic synthesis]], the [[coordination chemistry]] of acetone azine (as a [[ligand]]) has also been studied.<ref>{{citation | first1 = A. S. | last1 = Gudkova | first2 = O. A. | last2 = Reutov | first3 = M. Ya. | last3 = Aleinikova | journal = Izv. Akad. Nauk SSSR, Otdel. Khim. Nauk | year = 1962 | issue = 8 | pages = 1382–87}}; {{citation | title = Reactions of hydrazones and azines with metal salts 4. Reactions of azines of aldehydes and ketones with cupric salts | journal = Russ. Chem. Bull. (Transl.) | year = 1962 | volume = 11 | issue = 8 | pages = 1298–1302 | doi = 10.1007/BF00907973}}.</ref><ref>{{citation | first1 = Fiona | last1 = King | first2 = David | last2 = Nicholls | title = Complex of titanium halides with acetone azine and its isomer 3,5,5-trimethyl-pyrazoline | journal = Inorg. Chim. Acta | volume = 28 | year = 1978 | pages = 55–58 | doi = 10.1016/S0020-1693(00)87413-7}}.</ref> | As well as its use as an intermediate in [[organic synthesis]], the [[coordination chemistry]] of acetone azine (as a [[ligand]]) has also been studied.<ref>{{citation | first1 = A. S. | last1 = Gudkova | first2 = O. A. | last2 = Reutov | first3 = M. Ya. | last3 = Aleinikova | journal = Izv. Akad. Nauk SSSR, Otdel. Khim. Nauk | year = 1962 | issue = 8 | pages = 1382–87}}; {{citation | title = Reactions of hydrazones and azines with metal salts 4. Reactions of azines of aldehydes and ketones with cupric salts | journal = Russ. Chem. Bull. (Transl.) | year = 1962 | volume = 11 | issue = 8 | pages = 1298–1302 | doi = 10.1007/BF00907973}}.</ref><ref>{{citation | first1 = Fiona | last1 = King | first2 = David | last2 = Nicholls | title = Complex of titanium halides with acetone azine and its isomer 3,5,5-trimethyl-pyrazoline | journal = Inorg. Chim. Acta | volume = 28 | year = 1978 | pages = 55–58 | doi = 10.1016/S0020-1693(00)87413-7}}.</ref> | ||
| − | ==Atofina–PCUK process== | + | ==Production of hydrazine== |
| − | The industrial preparation of acetone azine<ref name="PCUK"/> 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 and acetone. The interest in preparing the azine is that it can be removed from the initial reaction mixture as an [[azeotrope]] with water:<ref name="Atochem"/> in both laboratory practice and the Atofina–PCUK process, the aim is to avoid directly handling the unstable acetone hydrazone. | + | ===Atofina–PCUK process=== |
| + | The industrial preparation of acetone azine<ref name="PCUK"/> might, at first sight, appear to be the reverse of the laboratory procedure: the azine is produced from [[acetone hydrazone]], and then [[Hydrolysis|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:<ref name="Atochem"/> in both laboratory practice and the Atofina–PCUK process, the aim is to avoid directly handling the unstable acetone hydrazone. | ||
The Atofina–PCUK process produces acetone azine from acetone (2 eq.), [[ammonia]] (2 eq.) and [[hydrogen peroxide]] (1 eq.). The first step is the formation of [[acetone imine]], Me<sub>2</sub>C=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 [[Condensation reaction|condenses]] with a further molecule of acetone to produce the azine. The acetone azine product is distilled out of the reaction mixture as its azeotrope with water (''n''(H<sub>2</sub>O)/''n''(azine) = 6).<ref name="Atochem"/> | The Atofina–PCUK process produces acetone azine from acetone (2 eq.), [[ammonia]] (2 eq.) and [[hydrogen peroxide]] (1 eq.). The first step is the formation of [[acetone imine]], Me<sub>2</sub>C=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 [[Condensation reaction|condenses]] with a further molecule of acetone to produce the azine. The acetone azine product is distilled out of the reaction mixture as its azeotrope with water (''n''(H<sub>2</sub>O)/''n''(azine) = 6).<ref name="Atochem"/> | ||
| − | The hydrolysis of the azine is [[Acid catalysis|acid-catalyzed]], hence the need to isolate the azine from the initial ammonia-containing reaction mixture. It is also [[endothermic]],<ref>{{citation | first = E. C. | last = Gilbert | journal = J. Am. Chem. Soc. | year = 1929 | volume = 51 | pages = 3394–3409}}.</ref> and so requires an increase in temperature (and pressure) to shift the equilibrium in favour of the desired products: acetone (which is recycled) and | + | The [[hydrolysis]] of the azine is [[Acid catalysis|acid-catalyzed]], hence the need to isolate the azine from the initial ammonia-containing reaction mixture. It is also [[endothermic]],<ref>{{citation | first = E. C. | last = Gilbert | journal = J. Am. Chem. Soc. | year = 1929 | volume = 51 | pages = 3394–3409}}.</ref> and so requires an increase in temperature (and pressure) to shift the equilibrium in favour of the desired products: acetone (which is recycled) and hydrazine hydrate.<ref name="Atochem"/> The reaction is carried out by simple [[distillation]] of the azeotrope: typical conditions are a pressure of 8 bar and temperatures of 130 °C at the base of the column and 179 °C at the top of the column. The hydrazine hydrate (30–45% aqueous solution) is run off from the base of the column, while the acetone is distilled off from the top of the column and recycled.<ref name="Atochem"/> |
| + | |||
| + | ===Bayer hydrazine process=== | ||
| + | The [[Bayer hydrazine process]] is a modification of the [[Raschig/Olin 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]].<ref name="H&W"/> | ||
==References== | ==References== | ||
Revision as of 10:25, 29 June 2010
| Acetone azine | |
|---|---|
| IUPAC name | acetone azine diisopropylidenehydrazine |
| 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]
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.
The Atofina–PCUK process produces acetone azine from acetone (2 eq.), ammonia (2 eq.) and hydrogen peroxide (1 eq.). 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 its azeotrope with water (n(H2O)/n(azine) = 6).[3]
The hydrolysis of the azine is acid-catalyzed, hence the need to isolate the azine from the initial ammonia-containing reaction mixture. It is also endothermic,[12] and so requires an increase in temperature (and pressure) to shift the equilibrium in favour of the desired products: acetone (which is recycled) and hydrazine hydrate.[3] The reaction is carried out by simple distillation of the azeotrope: typical conditions are a pressure of 8 bar and temperatures of 130 °C at the base of the column and 179 °C at the top of the column. The hydrazine hydrate (30–45% aqueous solution) is run off from the base of the column, while the acetone is distilled off from the top of the column and recycled.[3]
Bayer hydrazine process
The Bayer hydrazine process is a modification of the Raschig/Olin 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 3.2 3.3 3.4 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. J. Prakt. Chem. 1891, 44, 161.
- ↑ 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, A. Ber. Dtsch. Chem. Ges. 1916, 49, 1897.
- ↑ Day, A. C.; Raymond, P.; Southam, R. M.; Whiting, M. C. J. Chem. Soc. C 1966, 467.
- ↑ 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.
- ↑ 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.
- ↑ Gilbert, E. C. J. Am. Chem. Soc. 1929, 51, 3394–3409.
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