Fluorous chemistry: Difference between revisions
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{{main|Fluorocarbon|Organofluorine chemistry}} |
{{main|Fluorocarbon|Organofluorine chemistry}} |
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'''Fluorous chemistry''' involves the use of [[perfluorinated compounds]] or perfluorinated substituents to facilitate recovery of a [[catalyst]] or reaction product. [[Organofluorine chemistry#Fluorous phases|Perfluorinated groups]] impart unique physical properties including high solubility in perfluorinated solvents. This property can be useful in [[organic synthesis]] and separation methods such as [[solid phase extraction]].<ref name=Horvath>István T. Horváth (Ed.) Topics in Current Chemistry 2011 "Fluorous Chemistry" {{ |
'''Fluorous chemistry''' involves the use of [[perfluorinated compounds]] or perfluorinated substituents to facilitate recovery of a [[catalyst]] or reaction product. [[Organofluorine chemistry#Fluorous phases|Perfluorinated groups]] impart unique physical properties including high solubility in perfluorinated solvents. This property can be useful in [[organic synthesis]] and separation methods such as [[solid phase extraction]].<ref name=Horvath>István T. Horváth (Ed.) Topics in Current Chemistry 2011 "Fluorous Chemistry" {{doi|10.1007/128_2011_282}}</ref> In practice, a perfluorinated [[alkyl group]] is incorporated into an otherwise conventional organic reagent as an [[Affinity chromatography|affinity tag]]. These reagents can then be separated from organic solvents by extraction with fluorinated solvents such as perfluorohexane. |
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==Applications== |
==Applications== |
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The utility of fluorous chemistry hinges on the [[Partition coefficient|partitioning]] modality distinct from [[Chemical polarity|polar]]/[[non-polar]] or [[hydrophilic]]/[[hydrophobic]]. A major application of fluorous chemistry involves the use of [[fluorosurfactant]] [[perfluorooctanoic acid]] (PFOA) to facilitate the production of [[Teflon]]. The technology is controversial because of the slow rates of biodegradation of such compounds.<ref name=Prevedouros2006>{{cite journal |
The utility of fluorous chemistry hinges on the [[Partition coefficient|partitioning]] modality distinct from [[Chemical polarity|polar]]/[[non-polar]] or [[hydrophilic]]/[[hydrophobic]]. A major application of fluorous chemistry involves the use of [[fluorosurfactant]] [[perfluorooctanoic acid]] (PFOA) to facilitate the production of [[Teflon]]. The technology is controversial because of the slow rates of biodegradation of such compounds.<ref name=Prevedouros2006>{{cite journal |
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|vauthors=Prevedouros K, Cousins IT, Buck RC, Korzeniowski SH |
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|title=Sources, fate and transport of perfluorocarboxylates |
|title=Sources, fate and transport of perfluorocarboxylates |
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|journal=Environ. Sci. Technol. |
|journal=Environ. Sci. Technol. |
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|volume=40 |issue=1 |pages=32–44 | |
|volume=40 |issue=1 |pages=32–44 |date=December 2006 |
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|doi=10.1021/es0512475 |pmid=16433330}}</ref> |
|doi=10.1021/es0512475 |pmid=16433330|bibcode=2006EnST...40...32P}}</ref> |
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===Ponytails=== |
===Ponytails=== |
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In compounds exploited in academic fluorous chemistry, molecules comprise both nonfluorous and fluorous domains. The fluorous domain is often a substituent intended to confer solubility in the fluorocarbon medium. Such perfluorosubstituents are often introduced in what |
In compounds exploited in academic fluorous chemistry, molecules comprise both nonfluorous and fluorous domains. The fluorous domain is often a substituent intended to confer solubility in the fluorocarbon medium. Such perfluorosubstituents are often introduced in what are called ponytails. Typical fluorous ponytails have the formula CF<sub>3</sub>(CF<sub>2</sub>)<sub>n</sub>(CH<sub>2</sub>)<sub>m</sub>- where n is about 10 and m is about 3.<ref name=Horvath/> |
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Through the use of high affinity of fluorous tags (ponytails) for fluorous phases or fluorous-derivatized solid phases allows for near complete recovery of the tagged reagent (i.e., near complete reduction in a chemical waste stream), making the use of fluorous chemistry techniques a popular topic in [[green chemistry]].<ref>E.G. Hope, A.P. Abbott, D.L. Davies, G.A. Solan and A.M. Stuart |
Through the use of high affinity of fluorous tags (ponytails) for fluorous phases or fluorous-derivatized solid phases allows for near complete recovery of the tagged reagent (i.e., near complete reduction in a chemical waste stream), making the use of fluorous chemistry techniques a popular topic in [[green chemistry]].<ref>E.G. Hope, A.P. Abbott, D.L. Davies, G.A. Solan and A.M. Stuart "Green Organometallic Chemistry" in Comprehensive Organometallic Chemistry III, 2007, Volume 12, Pages 837-864. {{doi|10.1016/B0-08-045047-4/00182-5}}</ref> |
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==Partition coefficients== |
==Partition coefficients== |
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The fluorous character of a molecule can be assessed by its [[partition coefficient]] between a perfluorocarbon and a hydrocarbon. In the following table, the data are for perfluoromethylcyclohexane:toluene.<ref name=Horvath/> |
The fluorous character of a molecule can be assessed by its [[partition coefficient]] between a [[perfluorocarbon]] and a hydrocarbon. In the following table, the data are for perfluoromethylcyclohexane:toluene.<ref name=Horvath/> |
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{| name="partition coefficients" class="wikitable" |
{| name="partition coefficients" class="wikitable" |
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==Scientific Community== |
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The [[International Symposium on Fluorous Technologies]] (ISoFT) is a biennial meeting that brings together scientists working in the area of fluorous chemistry. |
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== References == |
== References == |
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==Representative journal articles== |
==Representative journal articles== |
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*{{cite journal |doi= 10.1021/ol051170p |author= Yu, M. S. |
*{{cite journal |doi= 10.1021/ol051170p |author= Yu, M. S. |author2= Curran, D. P. |author3= Nagashima, T. |
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|year= 2005 |
|year= 2005 |
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|journal= [[Organic Letters|Org. Lett.]] |
|journal= [[Organic Letters|Org. Lett.]] |
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|pages= 3677–3680 |
|pages= 3677–3680 |
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|title= Increasing Fluorous Partition Coefficients by Solvent Tuning |pmid= 16092848}} |
|title= Increasing Fluorous Partition Coefficients by Solvent Tuning |pmid= 16092848}} |
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*{{cite journal |doi= 10.1016/j.tet.2006.08.051 |author= Zhang, W. |
*{{cite journal |doi= 10.1016/j.tet.2006.08.051 |author= Zhang, W. |author2= Curran, D. P. |
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|year= 2006 |
|year= 2006 |
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|journal= [[Tetrahedron (journal)|Tetrahedron]] |
|journal= [[Tetrahedron (journal)|Tetrahedron]] |
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Latest revision as of 15:27, 25 July 2023
Fluorous chemistry involves the use of perfluorinated compounds or perfluorinated substituents to facilitate recovery of a catalyst or reaction product. Perfluorinated groups impart unique physical properties including high solubility in perfluorinated solvents. This property can be useful in organic synthesis and separation methods such as solid phase extraction.[1] In practice, a perfluorinated alkyl group is incorporated into an otherwise conventional organic reagent as an affinity tag. These reagents can then be separated from organic solvents by extraction with fluorinated solvents such as perfluorohexane.
Applications
[edit]The utility of fluorous chemistry hinges on the partitioning modality distinct from polar/non-polar or hydrophilic/hydrophobic. A major application of fluorous chemistry involves the use of fluorosurfactant perfluorooctanoic acid (PFOA) to facilitate the production of Teflon. The technology is controversial because of the slow rates of biodegradation of such compounds.[2]
Ponytails
[edit]In compounds exploited in academic fluorous chemistry, molecules comprise both nonfluorous and fluorous domains. The fluorous domain is often a substituent intended to confer solubility in the fluorocarbon medium. Such perfluorosubstituents are often introduced in what are called ponytails. Typical fluorous ponytails have the formula CF3(CF2)n(CH2)m- where n is about 10 and m is about 3.[1]
Through the use of high affinity of fluorous tags (ponytails) for fluorous phases or fluorous-derivatized solid phases allows for near complete recovery of the tagged reagent (i.e., near complete reduction in a chemical waste stream), making the use of fluorous chemistry techniques a popular topic in green chemistry.[3]
Partition coefficients
[edit]The fluorous character of a molecule can be assessed by its partition coefficient between a perfluorocarbon and a hydrocarbon. In the following table, the data are for perfluoromethylcyclohexane:toluene.[1]
| solute | partition coefficient for CF3C6F11:toluene |
| octane | 5.4:94.6 |
| CH3(CH2)13CH=CH2 | 0.9:99.1 |
| C6H6 | 6:94 |
| C6F6 | 28.0:72.0 |
| C10F22(CH2)3OH | 80.5:19.5 |
| C8F20(CH2)3C6H5 | 49.5:50.5 |
| C8F20C6H5 | 77.5:22.5 |
Scientific Community
[edit]The International Symposium on Fluorous Technologies (ISoFT) is a biennial meeting that brings together scientists working in the area of fluorous chemistry.
References
[edit]- ^ a b c István T. Horváth (Ed.) Topics in Current Chemistry 2011 "Fluorous Chemistry" doi:10.1007/128_2011_282
- ^ Prevedouros K, Cousins IT, Buck RC, Korzeniowski SH (December 2006). "Sources, fate and transport of perfluorocarboxylates". Environ. Sci. Technol. 40 (1): 32–44. Bibcode:2006EnST...40...32P. doi:10.1021/es0512475. PMID 16433330.
- ^ E.G. Hope, A.P. Abbott, D.L. Davies, G.A. Solan and A.M. Stuart "Green Organometallic Chemistry" in Comprehensive Organometallic Chemistry III, 2007, Volume 12, Pages 837-864. doi:10.1016/B0-08-045047-4/00182-5
Representative journal articles
[edit]- Yu, M. S.; Curran, D. P.; Nagashima, T. (2005). "Increasing Fluorous Partition Coefficients by Solvent Tuning". Org. Lett. 7 (17): 3677–3680. doi:10.1021/ol051170p. PMID 16092848.
- Zhang, W.; Curran, D. P. (2006). "Synthetic Applications of Fluorous Solid-Phase Extraction (F-SPE)". Tetrahedron. 62 (51): 11837–11865. doi:10.1016/j.tet.2006.08.051. PMC 2396515. PMID 18509513.