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Ionic Liquid

Presented by :Xin Huang

Green Chemistry Presentation

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Development

0 200 400 600 800 1000

No of publications

1995

1997

1999

2001

2003

Year

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Outline

Definition

Conclusion

Examples

Ionic liquid in synthesis

Advantage

Applications

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What are Ionic Liquids

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Common Definition

Ionic Liquids (ILs) is the generic term for a class of materials, consistingentirely of ions and being liquid below 100C.

If they are liquid at room temperature, we call them room temperatureionic liquids (RTILs).

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Typical Cation and Anion

Typical IL Cations

N

R

N N

R1 R2

* [PF6]-for moisture stable, water immiscible IL

* [BF4]-for moisture stable, but water miscible IL

* [AlCl4-] (or other Lewis acids) decomposes in water

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Discovery and History * The description of a low melting point salt -

1914 Ethyl ammonium nitrate

* The first room temperature ionic liquid - 1951 N-ethylpyridinium bromide- aluminium chloride melt

* The most stable and conductive salts -1982

1,3-dialkylimidazolium salts * The hydrophobic ionic liquids -

1992 1-ethyl-3-methylimidazolium tetrafluoroborate

Paul Walden

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Advantage Easy separation

Very low vapor pressure

Non-flammable substance

High thermally stable

High mechanically stable

Electrochemically stable Low toxicity

Non-volatility

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Application

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Comparison of organic solvents with ionic liquids

Plechkova, N. V.; Seddon K. R. Chem. Soc. Rev. 2008, 37, 123150

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Ionic Liquids in Organic Synthesis Catalytic

Hydrogenetions

Hydroformylations

Heck reactions

Suzuki coupling

Stille Coupling

FriedelCrafts

Alkoxycarbonylation

Olefin dimerization

Diels-Alder

Oxidations

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Diels-Alder reaction

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Heck Reaction

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Wittig reaction

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Suzuki-Miyaura coupling reaction

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Stille reaction

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Friedel-Crafts reaction

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Hydrogenation

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Fluorination

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Journal of Fluorine ChemistryA novel pyrrolidinium ionic liquid with 1,1,2,2 tetrafluoro

2 (1,1,2,2-tetrafluoroethoxy) ethanesulfonate anion as arecyclable reaction medium and efficient catalyst forFriedelCrafts alkylations of indoles with nitroalkenes

Jin-Hong Lin, Cheng-Pan Zhang, Zhi-Qiang Zhu, Qing-Yun Chen, Ji-

Chang Xiao *

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Preparation of pyrrolidinium salts

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Reaction

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Flow chart

NH

+ H2O

HNO365~68%

r.t.

60,stirred overnight washed with diethyl ether 50ml*3

concentratedyellow solid

TM.

+ CH3OHH(CF2)4O(CF2)2SO3Na/MeOH stirred, 12h

filtration

r.t.

filtrateconcentrated

pale yellow liquid

HN

N+

O

-O

+

50, stir red extracted

toluene (3 ml*3)

upper-layer concentrated purified

(flash chromatography)

AlCl3

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Green Aspects The yeild for preparing Ionic liquid is as high 99%. (Principle 2)

Seperation of Ionic liquid is easy , just by filtration.

Reaction condition is mild .(Principle 12)

No byproducts in the preparation .(Principle 8)

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Green Aspects The high concentration of highly acidic species that can be immobilized

in ionic liquids and that leads to a highly reactive catalytic phaseallowing for fast reactions under mild conditions. In fact, acidic ionic

liquids catalyze all reactions that are conventionally catalyzed by AlCl3,but without suffering the disadvantage of the low solubility of AlCl3 inmany solvents.(Principle #3,5,9)

The liquid nature of the catalytic phase eliminates the heat and masstransfer problems frequently encountered with heterogeneous Friedel

Crafts-catalysts and make the reaction get high yield .(Principle 2)

The miscibility gap of most ionic liquids with alkylated aromatics allowsfor product isolation by simple decantation.(Principle #1,7)

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Green Aspects Ionic liquid also act as solvent in this

reaction ,it prevents the waste of solvent.

(Principle 1)

Ionic liquid can be used directly for the next

run after removing the solvent. Principle 7

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Conclusion Ionic liquids ,as the new materials of multifunction , are widely

used in various of fields.

Environmently-friendly reaction process have vigorously beenstudied from the standpoint of green chemistry and based onthe properities of easy separation , low toxicity , selectivemiscibility , ILS play an important role in organic synthesis asthe green alternative solvent.

Withe the development of multifunctional ILS , we can expectIlS would apply in more fields .

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