| Revision as of 21:23, 4 November 2011 editDweix (talk | contribs)84 edits Added references for explosiveness and bromate which were labeled as "reference needed"← Previous edit | Revision as of 21:30, 9 December 2011 edit undoChristian75 (talk | contribs)Extended confirmed users, New page reviewers, Pending changes reviewers, Rollbackers114,924 edits clean up using AWB (7794)Next edit → | ||
| Line 45: | Line 45: | ||
| }} | }} | ||
| '''IBX acid''' or '''2-iodoxybenzoic acid''' is an ] used in ] as an ]. This ] is especially suited to ] ]s to ]s. The IBX acid is prepared from 2-iodobenzoic acid, ] and ].<ref>{{cite journal | title = Dess-Martin periodinane: 1,1,1-Triacetoxy-1,1-dihydro-1,2-benziodoxol-3(1''H'')-one [1,2-Benziodoxol-3(1''H'')-one, 1,1,1-tris(acetyloxy)-1,1-dihydro-] | author = Robert K. Boeckman, Jr., Pengcheng Shao, and Joseph J. Mullins | journal = ] | volume = 77 | pages = 141 | |
'''IBX acid''' or '''2-iodoxybenzoic acid''' is an ] used in ] as an ]. This ] is especially suited to ] ]s to ]s. The IBX acid is prepared from 2-iodobenzoic acid, ] and ].<ref>{{cite journal | title = Dess-Martin periodinane: 1,1,1-Triacetoxy-1,1-dihydro-1,2-benziodoxol-3(1''H'')-one [1,2-Benziodoxol-3(1''H'')-one, 1,1,1-tris(acetyloxy)-1,1-dihydro-] | author = Robert K. Boeckman, Jr., Pengcheng Shao, and Joseph J. Mullins | journal = ] | volume = 77 | pages = 141 | year = 2000 | url = http://www.orgsyn.org/orgsyn/prep.asp?prep=v77p0141 }} ''(also in the (PDF)).''</ref> Frigerio and co-workers have also demonstrated, in ] that potassium bromate may be replaced by commercially available ].<ref name="Santagostino">{{cite journal | title = A User-Friendly Entry to 2-Iodoxybenzoic Acid (IBX) | author = Marco Frigerio, Marco Santagostino, and Simona Sputore | journal = ] | year = 1999 | volume = 64 | issue = 12 | pages = 4537–4538 | doi = 10.1021/jo9824596 | url = http://pubs.acs.org/doi/abs/10.1021/jo9824596 | format = abstract }}</ref> One of the main drawbacks of IBX is its limited solubility; IBX is insoluble in many common organic solvents. In the past, it was believed that IBX was ], but it was later proposed that samples of IBX were shock sensitive due to the residual potassium bromate left from its preparation.<ref name="Santagostino" /><ref name="DMP">{{citation | author=Dess, D. B.; Martin, J. C.|journal=]|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|year=1991|volume=113|pages=7277|doi=10.1021/ja00019a027}}</ref> Commercial IBX is stabilized by ]s such as ] and ]. | ||
| ==Reaction mechanism== | ==Reaction mechanism== | ||
| ] during conversion of ] to ]: a) ligand exchange reaction (] 9.1 ]/] (38 ]/mol), b) hypervalent twist 12.1 kcal/mol (51 kJ/mol), c) elimination 4.7 kcal/mol (20 kJ/mol)). There is steric repulsion between protons in red.]] | ] during conversion of ] to ]: a) ligand exchange reaction (] 9.1 ]/] (38 ]/mol), b) hypervalent twist 12.1 kcal/mol (51 kJ/mol), c) elimination 4.7 kcal/mol (20 kJ/mol)). There is steric repulsion between protons in red.]] | ||
| The ] for an oxidation of an ] to an ] according the so-called ]<ref>{{cite journal | title = Enhancing 2-Iodoxybenzoic Acid Reactivity by Exploiting a Hypervalent Twist | author = Julius T. Su and William A. Goddard III | journal = ] | |
The ] for an oxidation of an ] to an ] according the so-called ]<ref>{{cite journal | title = Enhancing 2-Iodoxybenzoic Acid Reactivity by Exploiting a Hypervalent Twist | author = Julius T. Su and William A. Goddard III | journal = ] | year = 2005 | volume = 127 | issue = 41 | pages = 14146–14147 | doi = 10.1021/ja054446x | url = http://pubs.acs.org/cgi-bin/abstract.cgi/jacsat/2005/127/i41/abs/ja054446x.html | format = abstract | pmid = 16218584 }}</ref> involves a ] replacing the hydroxyl group by the alcohol followed by a twist and a ]. The twist is a requirement because the iodine to oxygen ] is oriented out of plane with the ] group and the ] elimination would not be able to take place. This twist reaction is a rearrangement in which the oxygen atom is moved into a proper plane for a 5 membered cyclic ] in the elimination reaction and is calculated by ] to be the ] in the oxidation. The twist mechanism also explains why oxidation is faster for larger alcohols than for small alcohols. The twist is driven forward by the ] that exists between the ] hydrogen atom and the protons from the ] group and larger alkoxy groups create larger steric repulsion. The same computation predicts a much faster reacting IBX derivative with a 100 fold ] when this ortho hydrogen atom is replaced by a ] group thus facilitating the twist until the elimination reaction takes prevalence as the rate determining step. | ||
| IBX exists as two ]s one of which is the ]. The ] of IBX which has been determined in water (] 2.4) and ] (pKa 6.65)<ref name="gallen">{{cite journal | title = o-Iodoxybenzoic Acid (IBX): pK<sub>a</sub> and Proton-Affinity Analysis | author = Michael J. Gallen, Régis Goumont, Timothy Clark, François Terrier, Craig M. Williams | journal = ] | volume = 45 | issue = 18 | pages = 2929–2934 | |
IBX exists as two ]s one of which is the ]. The ] of IBX which has been determined in water (] 2.4) and ] (pKa 6.65)<ref name="gallen">{{cite journal | title = o-Iodoxybenzoic Acid (IBX): pK<sub>a</sub> and Proton-Affinity Analysis | author = Michael J. Gallen, Régis Goumont, Timothy Clark, François Terrier, Craig M. Williams | journal = ] | volume = 45 | issue = 18 | pages = 2929–2934 | year = 2006 | doi = 10.1002/anie.200504156 | pmid = 16566050}}</ref> is known to affect organic reactions, for instance acid-catalyzed ] accompanying oxidations. | ||
| ==Scope== | ==Scope== | ||
| Line 61: | Line 61: | ||
| ===Oxidative cleavage=== | ===Oxidative cleavage=== | ||
| IBX is notable for oxidizing vicinal diols (or glycols) to diketones without cleavage of the carbon-carbon bond,<ref name="diol oxidation">{{ |
IBX is notable for oxidizing vicinal diols (or glycols) to diketones without cleavage of the carbon-carbon bond,<ref name="diol oxidation">{{citation | author=Frigerio, M.; Santagostino, M.|journal=]|title=A mild oxidizing reagent for alcohols and 1,2-diols: o-iodoxybenzoic acid (IBX) in DMSO|year=1994|volume=35|pages=8019|doi=10.1016/0040-4039(94)80038-3}}</ref> but oxidative cleavage of glycols to dialdehydes or diketones can occur when modified conditions are used (elevated temperatures or trifluoroacetic acid solvent).<ref>{{cite journal |title=Oxidative cleavage of vicinal diols: IBX can do what Dess–Martin periodinane (DMP) can |journal=Org. Biomol. Chem. |year=2007 |volume=5 |pages=767–771 |doi=10.1039/b618135j |author=Jarugu Narasimha Moorthy, Nidhi Singhal and Kalyan Senapati |pmid=17315062 |issue=5}}</ref> | ||
| :] | :] | ||
| Line 70: | Line 70: | ||
| ===α-Hydroxylations=== | ===α-Hydroxylations=== | ||
| Kirsch and co-workers were able to hydroxylate keto compounds with IBX in |
Kirsch and co-workers were able to hydroxylate keto compounds with IBX in α-position under mild conditions.<ref>{{cite journal | journal= J. Org. Chem. | year=2005 | volume=70 | issue= 24 | pmid= 16292876 | pages=10210–10212 | doi=10.1021/jo051898j | author = Kirsch, S.F. | title=IBX-Mediated α-Hydroxylation of α-Alkynyl Carbonyl Systems. A Convenient Method for the Synthesis of Tertiary Alcohols}}</ref> This method could be extended to β-keto esters.<ref>{{cite journal | journal=Chem. Europ. J. | volume=15 | issue=41 | pages=10713–10717 | doi=10.1002/chem.200901867 | author=Kirsch, S.F.; Duschek, A. | title=Novel Oxygenations with IBX | year=2009}}</ref> | ||
| ==References== | ==References== | ||
Revision as of 21:30, 9 December 2011
"IBX" redirects here. For other uses, see IBX (disambiguation). | |||
| |||
| Names | |||
|---|---|---|---|
| Other names
1-hydroxy-1λ,2-benziodoxol-1,3-dione 1-hydroxy-1λ,2-benziodoxol-3(1H)-one 1-oxide | |||
| Identifiers | |||
| CAS Number | |||
| 3D model (JSmol) | |||
| ChEBI | |||
| ChEMBL | |||
| ChemSpider | |||
| ECHA InfoCard | 100.157.592 
| ||
| PubChem CID | |||
| CompTox Dashboard (EPA) | |||
InChI
| |||
SMILES
| |||
| Properties | |||
| Chemical formula | C7H5IO4 | ||
| Molar mass | 280.02 g/mol | ||
Except where otherwise noted, data are given for materials in their standard state (at 25 °C , 100 kPa).
 Y verify (what is ?)
Infobox references
| |||
IBX acid or 2-iodoxybenzoic acid is an organic compound used in organic synthesis as an oxidizing agent. This Periodinane is especially suited to oxidize alcohols to aldehydes. The IBX acid is prepared from 2-iodobenzoic acid, potassium bromate and sulfuric acid. Frigerio and co-workers have also demonstrated, in 1999 that potassium bromate may be replaced by commercially available Oxone. One of the main drawbacks of IBX is its limited solubility; IBX is insoluble in many common organic solvents. In the past, it was believed that IBX was shock sensitive, but it was later proposed that samples of IBX were shock sensitive due to the residual potassium bromate left from its preparation. Commercial IBX is stabilized by carboxylic acids such as benzoic acid and isophthalic acid.
Reaction mechanism
The reaction mechanism for an oxidation of an alcohol to an aldehyde according the so-called hypervalent twisting mechanism involves a ligand exchange reaction replacing the hydroxyl group by the alcohol followed by a twist and a elimination reaction. The twist is a requirement because the iodine to oxygen double bond is oriented out of plane with the alkoxy group and the concerted elimination would not be able to take place. This twist reaction is a rearrangement in which the oxygen atom is moved into a proper plane for a 5 membered cyclic transition state in the elimination reaction and is calculated by Computational chemistry to be the rate-determining step in the oxidation. The twist mechanism also explains why oxidation is faster for larger alcohols than for small alcohols. The twist is driven forward by the steric hindrance that exists between the ortho hydrogen atom and the protons from the alkoxy group and larger alkoxy groups create larger steric repulsion. The same computation predicts a much faster reacting IBX derivative with a 100 fold reaction rate when this ortho hydrogen atom is replaced by a methyl group thus facilitating the twist until the elimination reaction takes prevalence as the rate determining step.
IBX exists as two tautomers one of which is the carboxylic acid. The acidity of IBX which has been determined in water (pKa 2.4) and DMSO (pKa 6.65) is known to affect organic reactions, for instance acid-catalyzed isomerization accompanying oxidations.
Scope
IBX is also available as silica gel or polystyrene bound IBX. In many application IBX acid is replaced by Dess-Martin periodinane which is more soluble in common organic solvents. A sample reaction is a IBX oxidation used in the total synthesis of eicosanoid:
.
In 2001, K.C. Nicolaou and co-workers published a series of papers in the Journal of the American Chemical Society demonstrating, among other transformations, the use of IBX to oxidize benzylic carbons to conjugated aromatic carbonyl compounds.
Oxidative cleavage
IBX is notable for oxidizing vicinal diols (or glycols) to diketones without cleavage of the carbon-carbon bond, but oxidative cleavage of glycols to dialdehydes or diketones can occur when modified conditions are used (elevated temperatures or trifluoroacetic acid solvent).
The reaction mechanism for this glycol cleavage is based on initial formation of an adduct between 10-I-4 IBX and DMSO to an 12-I-5 intermediate 3 in which DMSO acts as a leaving group for incoming alcohol 4 to intermediate 5. One equivalent of water is split off forming 12-I-5 spirobicyclic periodinane 6 setting the stage for fragmentation to 7. With hydroxyl alpha protons presents oxidation to the acyloin competes. Trifluoroacetic acid is found to facilitate the overall reaction.
α-Hydroxylations
Kirsch and co-workers were able to hydroxylate keto compounds with IBX in α-position under mild conditions. This method could be extended to β-keto esters.
References
- Robert K. Boeckman, Jr., Pengcheng Shao, and Joseph J. Mullins (2000). "Dess-Martin periodinane: 1,1,1-Triacetoxy-1,1-dihydro-1,2-benziodoxol-3(1H)-one [1,2-Benziodoxol-3(1H)-one, 1,1,1-tris(acetyloxy)-1,1-dihydro-]". Organic Syntheses. 77: 141.
{{cite journal}}: CS1 maint: multiple names: authors list (link) (also in the Collective Volume (2004) 10:696 (PDF)). - ^ Marco Frigerio, Marco Santagostino, and Simona Sputore (1999). "A User-Friendly Entry to 2-Iodoxybenzoic Acid (IBX)" (abstract). J. Org. Chem. 64 (12): 4537–4538. doi:10.1021/jo9824596.
{{cite journal}}: CS1 maint: multiple names: authors list (link) - Dess, D. B.; Martin, J. C. (1991), "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", J. Am. Chem. Soc., 113: 7277, doi:10.1021/ja00019a027
{{citation}}: CS1 maint: multiple names: authors list (link) - Julius T. Su and William A. Goddard III (2005). "Enhancing 2-Iodoxybenzoic Acid Reactivity by Exploiting a Hypervalent Twist" (abstract). J. Am. Chem. Soc. 127 (41): 14146–14147. doi:10.1021/ja054446x. PMID 16218584.
- Michael J. Gallen, Régis Goumont, Timothy Clark, François Terrier, Craig M. Williams (2006). "o-Iodoxybenzoic Acid (IBX): pKa and Proton-Affinity Analysis". Angewandte Chemie International Edition. 45 (18): 2929–2934. doi:10.1002/anie.200504156. PMID 16566050.
{{cite journal}}: CS1 maint: multiple names: authors list (link) - Debendra K. Mohapatra and Gorakhanath S. Yellol. "Asymmetric total synthesis of eicosanoid". Arkivoc. 2005 (iii).
- Frigerio, M.; Santagostino, M. (1994), "A mild oxidizing reagent for alcohols and 1,2-diols: o-iodoxybenzoic acid (IBX) in DMSO", Tetrahedron Lett., 35: 8019, doi:10.1016/0040-4039(94)80038-3
{{citation}}: CS1 maint: multiple names: authors list (link) - Jarugu Narasimha Moorthy, Nidhi Singhal and Kalyan Senapati (2007). "Oxidative cleavage of vicinal diols: IBX can do what Dess–Martin periodinane (DMP) can". Org. Biomol. Chem. 5 (5): 767–771. doi:10.1039/b618135j. PMID 17315062.
- Kirsch, S.F. (2005). "IBX-Mediated α-Hydroxylation of α-Alkynyl Carbonyl Systems. A Convenient Method for the Synthesis of Tertiary Alcohols". J. Org. Chem. 70 (24): 10210–10212. doi:10.1021/jo051898j. PMID 16292876.
- Kirsch, S.F.; Duschek, A. (2009). "Novel Oxygenations with IBX". Chem. Europ. J. 15 (41): 10713–10717. doi:10.1002/chem.200901867.
{{cite journal}}: CS1 maint: multiple names: authors list (link)