Dess-Martin periodinane
1880262
226085089
2008-07-16T19:32:05Z
Rifleman 82
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/* Preparation */ +title
{{Chembox new
| Name = Dess-Martin periodinane
| ImageFile = Dess-Martin Periodinane Structure.png
<!-- | ImageSize = 150px -->
| ImageName = Chemical structure of the Dess-Martin periodinane
| ImageFile1 = Dess-Martin-periodinane-3D-balls.png
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| ImageName1 = Ball-and-stick model of the Dess-Martin periodinane
| IUPACName = 1,1,1-Triacetoxy-1,1-dihydro-<br />1,2-benziodoxol-3(1H)-one
| OtherNames = Dess-Martin periodinane
| Section1 = {{Chembox Identifiers
| SMILES = O=C2C1=CC=CC=C1I<br />(OC(C)=O)(OC(C)=O)<br />(OC(C)=O)O2
| CASNo = 87413-09-0
}}
| Section2 = {{Chembox Properties
| Formula = C<sub>13</sub>H<sub>13</sub>IO<sub>8</sub>
| MolarMass = 424.14 g/mol
| Appearance = white powder, chips,<br />crystals or crystalline<br />powder and/or chunks
| Density = 1.362 g/cm<sup>3</sup> solid
| Solubility =
| MeltingPt = 103 - 133 °C
}}
| Section7 = {{Chembox Hazards
| ExternalMSDS =
| MainHazards =
}}
| Section8 = {{Chembox Related
| OtherCpds = [[2-Iodoxybenzoic acid]]
}}
}}
'''Dess-Martin periodinane''' is a [[chemical reagent]] used to [[oxidation|oxidize]] primary [[alcohol]]s to [[aldehyde]]s and secondary [[alcohol]]s to [[ketone]]s.<ref>{{cite journal | author = Dess, D. B.; Martin, J. C. | title = Readily accessible 12-I-5 oxidant for the conversion of primary and secondary alcohols to aldehydes and ketones | journal = [[J. Org. Chem.]] | year = 1983 | volume = 48 | pages = 4155 | doi = 10.1021/jo00170a070}}</ref><ref>Boeckman, R. J. In "''Encyclopedia of Reagents for Organic Synthesis''"; Paquette, L. A., Ed.; Wiley: Chichester, UK, 1995, Vol. 7, pp. 4982-4987. (Review)</ref> This [[periodinane]] has several advantages over [[chromium]]- and [[dimethyl sulfoxide|DMSO]]-based oxidants that include milder conditions, shorter reaction times, higher yields, and simplified workups. It is named after the American chemists [[Daniel Benjamin Dess]] and [[James Cullen Martin]].
==Preparation==
2-Iodobenzoic acid is [[oxidize]]d preferably by [[Oxone]], or by KBrO<sub>3</sub> to [[2-iodoxybenzoic acid]]. (Caution: 2-Iodoxybenzoic acid has been found to be impact and heat sensitive, decomposing explosively.) <ref>{{OrgSynth |title = The Dess-Martin Periodinane | 1,1,1-Triacetoxy-1,1-dihydro-1,2-benziodoxol-3(1H)-one | author = Boeckman, Jr., R. K.; Shao, P.; Mullins, J. J. | collvol = 10 | collvolpages = 696 | year = 2004 | prep = v77p0141}}</ref> The 2-Iodoxybenzoic acid is then treated with a mixture of [[acetic anhydride]], [[acetic acid]] and [[P-Toluenesulfonic acid|''p''-toluenesulfonic acid]] at 80-100 °C for 40 min. The resulted solids can be obtained via [[filtration]] and washing with [[diethyl ether|ether]].
To avoid the explosive nature of 2-iodoxybenzoic acid, other methods of preparation<ref>{{cite journal | author = Ireland, R. E.; Liu, L. | title = An improved procedure for the preparation of the Dess-Martin periodinane | journal = [[J. Org. Chem.]] | year = 1993 | volume = 58 | pages = 2899 | doi = 10.1021/jo00062a040}}</ref><ref>{{cite journal | author = Meyer, S. D.; Schreiber, S. L. | title = Acceleration of the Dess-Martin Oxidation by Water | journal = [[J. Org. Chem.]] | year = 1994 | volume = 59 | pages = 7549 | doi = 10.1021/jo00103a067}}</ref> as well as other periodinanes<ref>{{cite journal | author = Dess, D. B.; Martin, J. C. | title = A useful 12-I-5 triacetoxyperiodinane (the Dess-Martin periodinane) for the selective oxidation of primary or secondary alcohols and a variety of related 12-I-5 species | journal = [[J. Am. Chem. Soc.]] | year = 1991 | volume = 113 | pages = 7277 | doi = 10.1021/ja00019a027}}</ref> have been described.
==Properties and uses==
Dess-Martin periodinane is mainly used as an [[oxidant]] for complex, sensitive and multifunctional [[alcohol]]s. One of the reasons for its effectiveness is its high selectivity towards complexation of the [[hydroxide|hydroxylic]] group, which allows alcohols to rapidly perform [[ligand]] exchange; the first step in the oxidation reaction.
Its effectiveness as an oxidant is also due to its versatility; having a broad scope of being able to convert alcohols to [[carbonyl]] derivatives. Its reactions and yield are also known to be clean and high respectively. Work up is also clean and simple. Byproducts from the reaction can be removed easily by precipitation, filtration or [[chromatography]].
==References==
{{Reflist}}
==See also==
* [[Pyridinium chlorochromate]]
[[Category:Oxidizing agents]]
[[Category:Periodates]]
[[Category:Periodinanes]]
[[de:Dess-Martin-Periodinan]]
[[nl:Dess-Martin periodinaan]]
[[ja:デス・マーチン酸化]]
[[Category:Name reactions]]