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 cycle]].<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>
 
'''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 cycle]].<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>
  
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==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]]:<ref>{{citation | first1 = T. | last1 = Curtius | first2 = K. | last2 = Thun | journal = J. Prakt. Chem. | volume = 44 | pages = 161 | year = 1891}}.</ref><ref name="OrgSynth">{{OrgSynth | first1 = A. C. | last1 = Day | first2 = M. C. | last2 = Whiting | title = Acetone hydrazone | collvol = 6 | collvolpages = 10 | volume = 50 | pages =3 | year = 1970 | prep = cv6p0010}}.</ref> it is also commercially available. It is a useful precursor to [[acetone hydrazone]]<ref name="OrgSynth"/><ref name="Ber">{{citation | first1 = H. | last1 = Staudinger | first2 = A. | last2 = Gaule | journal = Ber. Dtsch. Chem. Ges. | volume = 49 | pages = 1897 | year = 1916}}.</ref> and hence to [[2-diazopropane]],<ref name="Ber"/><ref>{{citation | first1 = A. C. | last1 = Day | first2 = P. | last2 = Raymond | first3 = R. M. | last3 = Southam | first4 = M. C. | last4 = Whiting | journal = J. Chem. Soc. C | pages = 467 | year = 1966}}.</ref><ref name="diazo">{{OrgSynth | first1 = S. D. | last1 = Andrews | first2 = A. C. | last2 = Day | first3 = P. | last3 = Raymond | first4 = M. C. | last4 = Whiting | title = 2-Diazopropane | collvol = 6 | collvolpages = 392 | volume = 50 | pages = 27 | year = 1970 | prep = cv6p0392}}.</ref> both of which must be prepared immediately before use and cannot be stored.<ref name="OrgSynth"/><ref name="diazo"/>
 
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]]:<ref>{{citation | first1 = T. | last1 = Curtius | first2 = K. | last2 = Thun | journal = J. Prakt. Chem. | volume = 44 | pages = 161 | year = 1891}}.</ref><ref name="OrgSynth">{{OrgSynth | first1 = A. C. | last1 = Day | first2 = M. C. | last2 = Whiting | title = Acetone hydrazone | collvol = 6 | collvolpages = 10 | volume = 50 | pages =3 | year = 1970 | prep = cv6p0010}}.</ref> it is also commercially available. It is a useful precursor to [[acetone hydrazone]]<ref name="OrgSynth"/><ref name="Ber">{{citation | first1 = H. | last1 = Staudinger | first2 = A. | last2 = Gaule | journal = Ber. Dtsch. Chem. Ges. | volume = 49 | pages = 1897 | year = 1916}}.</ref> and hence to [[2-diazopropane]],<ref name="Ber"/><ref>{{citation | first1 = A. C. | last1 = Day | first2 = P. | last2 = Raymond | first3 = R. M. | last3 = Southam | first4 = M. C. | last4 = Whiting | journal = J. Chem. Soc. C | pages = 467 | year = 1966}}.</ref><ref name="diazo">{{OrgSynth | first1 = S. D. | last1 = Andrews | first2 = A. C. | last2 = Day | first3 = P. | last3 = Raymond | first4 = M. C. | last4 = Whiting | title = 2-Diazopropane | collvol = 6 | collvolpages = 392 | volume = 50 | pages = 27 | year = 1970 | prep = cv6p0392}}.</ref> both of which must be prepared immediately before use and cannot be stored.<ref name="OrgSynth"/><ref name="diazo"/>
  
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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>
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==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 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.
 
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.
  
 
The Atofina–PCUK process produces acetone azine from acetone (2&nbsp;eq.), [[ammonia]] (2&nbsp;eq.) and [[hydrogen peroxide]] (1&nbsp;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)&nbsp;= 6).<ref name="Atochem"/>
 
The Atofina–PCUK process produces acetone azine from acetone (2&nbsp;eq.), [[ammonia]] (2&nbsp;eq.) and [[hydrogen peroxide]] (1&nbsp;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)&nbsp;= 6).<ref name="Atochem"/>
  
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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]].
+
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&nbsp;bar and temperatures of 130&nbsp;°C at the base of the column and 179&nbsp;°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"/>
  
 
==References==
 
==References==

Revision as of 10:31, 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 [627-70-3]
EC number 211-009-6
ChemSpider 71417
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 cycle.[2][3]

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:[4][5] it is also commercially available. It is a useful precursor to acetone hydrazone[5][6] and hence to 2-diazopropane,[6][7][8] both of which must be prepared immediately before use and cannot be stored.[5][8]

As well as its use as an intermediate in organic synthesis, the coordination chemistry of acetone azine (as a ligand) has also been studied.[9][10]

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 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,[11] 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]

References

  1. ↑ 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. ↑ 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. ↑ 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. ↑ Curtius, T.; Thun, K. J. Prakt. Chem. 1891, 44, 161.
  5. ↑ 5.0 5.1 5.2 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.
  6. ↑ 6.0 6.1 Staudinger, H.; Gaule, A. Ber. Dtsch. Chem. Ges. 1916, 49, 1897.
  7. ↑ Day, A. C.; Raymond, P.; Southam, R. M.; Whiting, M. C. J. Chem. Soc. C 1966, 467.
  8. ↑ 8.0 8.1 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.
  9. ↑ 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.
  10. ↑ 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.
  11. ↑ Gilbert, E. C. J. Am. Chem. Soc. 1929, 51, 3394–3409.
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