関: 1,2,4-trioxane

WordNet

any of a class of unstable chemical compounds resulting from the addition of ozone to a double bond in an unsaturated compound

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出典(authority):フリー百科事典『ウィキペディア（Wikipedia）』「2015/10/27 03:23:02」(JST)

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Ozonide is an unstable, reactive polyatomic anion O₃⁻, derived from ozone, or an organic compound similar to organic peroxide formed by a reaction of ozone with an unsaturated compound^{[clarification needed]}.

Inorganic ozonides

Inorganic ozonides^[1] are dark red ionic compounds containing the reactive O₃⁻ anion. The anion has the V shape of the ozone molecule.

Inorganic ozonides are formed by burning potassium or heavier alkali metals in ozone, or by treating the alkali metal hydroxide with ozone; if potassium is left undisturbed in air for years it accumulates a covering of superoxide and ozonide. They are very sensitive explosives that have to be handled at low temperatures in an atmosphere consisting of an inert gas. Lithium and sodium ozonide are extremely unstable and must be prepared by low-temperature ion exchange starting from CsO₃. Sodium ozonide, NaO
3, which is prone to decomposition into NaOH and NaO
2, was previously thought to be impossible to obtain in pure form.^[2] However, with the help of cryptands and methylamine, pure NaO
3 may be obtained as red crystals isostructural to NaNO
2.^[3]

Inorganic ozonides are being investigated as promising sources of oxygen in chemical oxygen generators, as tetramethylammonium ozonide, which can be made by a metathesis reaction with caesium ozonide in liquid ammonia, is stable up to 348K:

CsO₃ + [(CH₃)₄N][O₂] → CsO₂ + [(CH₃)₄N][O₃]

Phosphite ozonides, (RO)₃PO₃, are used in the production of singlet oxygen, which is made by ozonizing a phosphite ester in dichloromethane at low temperatures.^[4]

Molozonides

Organic ozonides are called molozonides and are typically formed by the addition reaction between ozone and alkenes. They are more explosive cousins of the organic peroxides and as such are rarely isolated during the course of the ozonolysis reaction sequence. Molozonides are unstable and rapidly convert to the trioxolane ring structure with a five-membered C-O-O-C-O ring.^[5]^[6] They usually appear in the form of foul-smelling oily liquids, and rapidly decompose in the presence of water to carbonyl compounds: aldehydes, ketones, peroxides.

Formation of an organic ozonide. The second arrow represents several steps as shown in ozonolysis.

References

^ F. A. Cotton and G. Wilkinson "Advanced Inorganic Chemistry", 5th edition (1988), p.462
^ Korber, N.; Jansen, M. (1996). "Ionic Ozonides of Lithium and Sodium: Circumventive Synthesis by Cation Exchange in Liquid Ammonia and Complexation by Cryptands". Chemische Berichte 129 (7): 773–777. doi:10.1002/cber.19961290707.
^ Klein, W.; Armbruster, K.; Jansen, M. (1998). "Synthesis and crystal structure determination of sodium ozonide". Chemical Communications (6): 707–708. doi:10.1039/a708570b.
^ Catherine E. Housecroft; Alan G. Sharpe (2008). "Chapter 16: The group 16 elements". Inorganic Chemistry, 3rd Edition. Pearson. p. 496. ISBN 978-0-13-175553-6.
^ Criegee, Rudolf. "Mechanism of Ozonolysis". Angewandte Chemie International Edition in English 14 (11): 745–752. doi:10.1002/anie.197507451.
^ http://www.organic-chemistry.org/namedreactions/ozonolysis-criegee-mechanism.shtm Ozonolysis mechanism on Organic Chemistry Portal site

External links

Matrix reactions of alkali metal atoms with ozone: Infrared spectra of the alkali metal ozonide molecules

English Journal

Matrix Isolation Study of the Ozonolysis of 1,3- and 1,4-Cyclohexadiene: Identification of Novel Reaction Pathways.

Pinelo L, Gudmundsdottir AD, Ault BS.AbstractThe ozonolysis reactions of 1,3- and 1,4-cyclohexadiene have been studied using a combination of matrix isolation, infrared spectroscopy and theoretical calculations. Experimental and theoretical results demonstrate that these reactions predominantly do not follow the long-accepted Criegee mechanism. Rather, the reaction of O3 with 1,4-cyclohexadiene leads to the essentially barrierless formation of benzene, C6H6, and H2O3. These two species are then trapped in the same argon matrix cage and weakly interact to form a molecular complex. There is also evidence for the formation of a small amount of the primary ozonide as a minor product, formed through a transition state that is slightly higher in energy. The reaction of O3 with 1,3-cyclohexadiene follows two pathways, one of which is the Criegee mechanism through a low energy transition state leading to formation of the primary ozonide. In addition, with a similar barrier, ozone abstracts a single hydrogen from C5 while adding to C1, forming a hydroperoxy intermediate. This study presents two of the rare cases in which the Criegee mechanism is not the dominant pathway for the ozonolysis of an alkene as well as the first evidence for dehydrogenation of an alkene by ozone.
The journal of physical chemistry. A.J Phys Chem A.2013 May 2. [Epub ahead of print]
The ozonolysis reactions of 1,3- and 1,4-cyclohexadiene have been studied using a combination of matrix isolation, infrared spectroscopy and theoretical calculations. Experimental and theoretical results demonstrate that these reactions predominantly do not follow the long-accepted Criegee mechanism
PMID 23638640

Potent Antimalarial 1,2,4-Trioxanes through Perhydrolysis of Epoxides.

Hao HD, Wittlin S, Wu Y.SourceState Key Laboratory of Bioorganic and Natural Products Chemistry, Shanghai Institution of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032 (P.R. China), Fax: (+86) 21-64166128.
Chemistry (Weinheim an der Bergstrasse, Germany).Chemistry.2013 Apr 9. doi: 10.1002/chem.201300076. [Epub ahead of print]
Perhydrolysis of a sterically congested multifunctional epoxide was achieved in ethereal H2 O2 with the aid of a recently developed Mo catalyst. The resulting hydroperoxide cyclized to give a 1,2,4-trioxane, which could be readily elaborated into qinghaosu and a range of novel analogues. Some of the
PMID 23576327

Japanese Journal

Ozonolyses of isophorone and of 3-methyl-2-cyclohexen-1-one and subsequent reactions of the respective ozonides to afford di-, tri- and tetraozonides

Jung In Chan,Sheikh Sad Alam,Jon Byong-Mun [他]
Heterocycles 81(10), 2323-2334, 2010-10-01
NAID 40017284223

414 バイオ燃料のオゾン改質とディーゼル機関への適用 : 燃料改質とオゾンの吸気系混入(新エネルギー(2),環境保全型エネルギー技術)

齋藤岳優,森棟隆昭
環境工学総合シンポジウム講演論文集 2008(18), 356-359, 2008-07-09
… It is expected that the flammable ozonide is generated in double bond of fatty acid contained in BDF by fuel reforming. …
NAID 110007703653

Related Pictures

★リンクテーブル★

リンク元	「オゾニド」「オゾン化物」

「オゾニド」

Ozonide
Names
	IUPAC name Trioxidan-1-id-3-yl
Identifiers
ChemSpider	10140300
	InChI InChI=1S/HO3/c1-3-2/h1H/p-1; Key: WURFKUQACINBSI-UHFFFAOYSA-M ; InChI=1/HO3/c1-3-2/h1H/p-1; Key: WURFKUQACINBSI-REWHXWOFAH ;
Jmol-3D images	Image
PubChem	11966307
	SMILES [O-]O[O] ;
Properties
Chemical formula	O3
Molar mass	47.999
	Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
	Infobox references