Ozonides

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Ozonides are a rare class of unstable chemical compounds that result from the addition of ozone to a double or triple bond within an unsaturated chemical compound.

history

Ozonides were discovered in 1866 by Christian Friedrich Schönbein when ozone was passed through concentrated alkaline solutions and turned red. In 1868 Charles Adolphe Wurtz , who observed a characteristic discoloration of the reaction product during his experiments on the reaction of potassium hydroxide with ozone, a solid reaction product. The exact chemical composition of this yellow-brown compound, which immediately decomposed in the absence of ozone, remained unclear for a long time. For example, Baeyer and Villiger explained the compound as the salt of the hypothetical acid H 2 O 4 . It was not until 1949 that Isaak Abramovich Kazarnovskii recognized the correct composition MO 3 and coined the term “ozonide”. In the period from 1960 to 1970, ionic ozonides, in contrast to the covalent ozonides that are formed during the ozonolysis of unsaturated hydrocarbons , were examined primarily by Russian and American scientists with regard to their use as oxygen generators for space travel. However, the intrinsic instability of the ozonides on the one hand prevented technical application and on the other hand made it difficult, given the experimental possibilities at the time, the pure preparation and manageability. Therefore, interest in this class of substances declined after 1970. It was not until 1985 that alkali metal ozonides could be produced purely in grams using a process by Schnick and Jansen.

The organic ozonides were first investigated in 1898 by Marius-Paul Otto , who systematically studied the reactions of ozone with organic substances. 1904 then by Carl Harries the ozonolysis discovered and 1951, the three-step mechanism of ozonolysis by Rudolf Criegee elucidated.

Organic ozonides

In organic chemistry, ozonides are understood to be compounds with a trioxolane basic structure (cyclic, acetyl-like peroxides derived from aldehydes and ketones ), which are formed when alkenes or alkynes react with ozone. Here, 1,2,3-trioxolanes are referred to as primary ozonides or molozonides and the 1,2,4-trioxolanes which arise spontaneously at higher temperatures as secondary ozonides. A distinction is also made between monomeric and oligomeric ozonides. These are mostly more or less thick oils or colorless syrupy masses. Amorphous or crystalline compounds are also rare. As a rule, they are unstable and spontaneously decompose, although more stable compounds (such as those of citral ) are also known. Most organic ozonides are sparingly soluble in water or decompose on contact with water, but are soluble in organic solvents.

Formation of organic ozonides.

The stable ozonide Arterolan is being investigated as a potential antimalarial agent.

Inorganic ozonides

In inorganic chemistry , compounds MO 3 (M = alkali metal ) are referred to as ozonides. They contain a paramagnetic angled O 3 - ion with an OOO angle of about 113.5 ° (the angle varies somewhat depending on the cation), the unpaired electron of which is in the π * molecular orbital . Alkali metal ozonides are formed when ozone acts on the solid hyperoxides of metals (such as potassium , rubidium or cesium ), whereby the enthalpy of reaction has to be removed by cooling. The production and handling of inorganic ozonides is thus expensive and requires z. B. low temperatures below −10 ° C and an inert gas atmosphere.

The inorganic ozonides have a deep red color and are usually chemically unstable. They decompose to hyperoxides and oxygen at room temperature. Inorganic ozonides are known from all alkali metals with the exception of lithium and francium .

Tetramethylammonium ozonide N [CH 3 ] 4 O 3 , which also belongs to this group, is the most stable ionic ozonide and only decomposes above 75 ° C. It can be made by reacting tetramethylammonium hyperoxide with cesium ozonide or potassium ozonide in liquid ammonia .

Phosphitozonides (RO) 3 PO 3 have also been known since the early 1960s .

Alkali zonides
Sodium ozonide Potassium ozonide Rubidium ozonide Cesium ozonide
formula NaO 3 KO 3 RbO 3 CsO 3
Appearance red dark red dark red dark red
decomposition below room temperature slowly at room temperature slowly at room temperature from 50 ° C
OOO angle 113.0 ° 113.5 ° 113.7 ° 114.6 °
Crystal structure Sodium nitrite structure (orthorhombic,
space group Im 2 m (space group no.44, position 3) ) Template: room group / 44.3		 tetragonal room
group I 4 / mcm ( room group no.140)Template: room group / 140 		monoclinic,
room group P 2 1 / c (room group no.14)Template: room group / 14 		Cesium chloride structure

Individual evidence

  1. ↑ a b J. Houben: Houben-Weyl Methods of Organic Chemistry Vol. III, 2nd Edition Oxygen, Sulfur, Halogen Compounds . Georg Thieme Verlag, 2014, ISBN 3-13-199222-0 , p. 292 ff . ( limited preview in Google Book search).
  2. ↑ a b c N. N. Greenwood, A. Earnshaw: Chemistry of the Elements . Elsevier, 2012, ISBN 978-0-08-050109-3 , pp. 610 ( limited preview in Google Book Search).
  3. ↑ a b Hannelore Nuss: Chemistry of Metastable Anions - Synthesis and Characterization of New Aurides and Ozonides Dissertation, University of Stuttgart, 2007 urn : nbn: de: bsz: 93-opus-35282 .
  4. ^ A b Mordecai B. Rubin: The History of Ozone. Part III - CD Harries and the Introduction of Ozone into Organic Chemistry , accessed July 24, 2015.
  5. ↑ Wilhelm J. Baader, Erick Leite Bastos, Daniel Bellus, Uwe Bergsträßer, Albrecht Berkessel, Marina Della Greca, Jens Hartung, Heinrich Heydt, Maria Rosaria Iesce, Ioannis Lykakis, Tamsyn Montagnon, Michael Orfanopoulos, Alessandro Scarso, Yian Shi, Ichiro Shinkai , Manolis Stratakis, Giorgio Strukul, Manolis Tzirakis, Georgios Vassilikogiannakis: Science of Synthesis: Houben-Weyl Methods of Molecular Transformations Vol. 38 Peroxides . Georg Thieme Verlag, 2014, ISBN 3-13-172151-0 , p. 380 ( limited preview in Google Book search).
  6. ↑ Anirudh Gautam, Tausif Ahmed, Pradeep Sharma, Brijesh Varshney, Monika Kothari, Nilanjan Saha, Arjun Roy, Joerg J. Moehrle, Jyoti Paliwal: Pharmacokinetics and Pharmacodynamics of Arterolane Maleate Following Multiple Oral Doses in Adult Patients With Malaria. In: The Journal of Clinical Pharmacology. 51, 2011, p. 1519, doi : 10.1177 / 0091270010385578 .
  7. ↑ a b Ralf Steudel: Chemistry of the non-metals with atomic structure, molecular geometry and bond theory . Walter de Gruyter, 1998, ISBN 978-3-11-012322-7 , p. 244 ( limited preview in Google Book search).
  8. ^ A b c Egon Wiberg, Nils Wiberg: Inorganic Chemistry . Academic Press, 2001, ISBN 978-0-12-352651-9 , pp. 1109 ( limited preview in Google Book search).
  9. ↑ Martin Jansen, Hanne Nuss: Ionic Ozonides. In: Journal of Inorganic and General Chemistry. 633, 2007, p. 1307, doi : 10.1002 / zaac.200700023 .
  10. ^ A b Bruno Pignataro: New Strategies in Chemical Synthesis and Catalysis . John Wiley & Sons, 2012, ISBN 978-3-527-33090-4 , pp. 83 ( limited preview in Google Book search).
  11. ^ Catherine E. Housecroft, AG Sharpe: Inorganic Chemistry . Pearson Education, 2005, ISBN 978-0-13-039913-7 , pp. 439 ( limited preview in Google Book search).
  12. ^ Wilhelm Klein, Martin Jansen: Representation and structural analysis of sodium ozone. In: Journal of Inorganic and General Chemistry. 626, 2000, p. 136, doi : 10.1002 / (SICI) 1521-3749 (200001) 626: 1 <136 :: AID-ZAAC136> 3.0.CO; 2-K .
  13. ↑ Schnick, Wolfgang; Jansen, Martin: Preparation, crystal structure, and thermal behavior of potassium ozonide. In: Revue de Chimie Minerale , 1987, 24, 446-456.
  14. ↑ W. Schnick, M. Jansen: Crystal Structures of Potassium Ozonide and Rubidium Ozonide. In: Angewandte Chemie , 24 , 1985 , pp. 54-55 doi : 10.1002 / anie.198500541 .