Ionic Liquids

A solidified ionic liquid1)

An ionic liquid is a salt in which the ions are poorly coordinated, which results in these
solvents being liquid below 100°C, or even at room temperature (room temperature ionic
liquids, RTIL's). At least one ion has a delocalized charge and one component is organic,
which prevents the formation of a stable crystal lattice.

The methylimidazolium and pyridinium ions have proven to be good starting points for the
development of ionic liquids:

Properties, such as melting point, viscosity, and solubility of starting materials and other
solvents, are determined by the substituents on the organic component and by the counterion.
Many ionic liquids have even been developed for specific synthetic problems. For this
reason, ionic liquids have been termed "designer solvents".

One of the first RTILs was a mixture of [emim]Cl with AlCl3 forming a series of equilibria
between [emim][AlCl4], [emim][Al2Cl7], and [emim][Al3Cl10]. This RTIL is not water stable.
The discovery of water-insoluble RTILs such as [bmim][PF6] allowed the development of
new work-up methods, including the separation of water-soluble byproducts by simple
extraction. Some transition metal catalysts that are soluble in ionic liquids may be recycled
together with the ionic liquid, after extraction with water and the non-polar organic solvent
used for product separation. The catalyst and ionic liquid may be recycled several times.

In addition, the following RTIL, derived from fructose (a renewable feedstock), is a

promising solvent for implementing fully "green chemistry" methods:

S. T. Handy, M. Okello, G. Dickenson, Org. Lett., 2003, 5, 2513-2515.

This ionic liquid was proven to be suitable for Heck Reactions:

S. T. Handy, M. Okello, G. Dickenson, Org. Lett., 2003, 5, 2513-2515.

The absence of volatility is one of the most important benefits of ionic liquids, offering a
much lower toxicity as compared to low-boiling-point solvents. Ionic liquids can also make
for safer microwave synthesis methods, because sudden pressure surges are not possible. The
dipole characteristics of ionic liquids translate into rapid excitation by microwaves, and
consequently faster reactions.

Reviews on Ionic Liquids

P. Wasserscheid, W. Keim, Angew. Chem. Int. Ed. Engl. 2000 , 39, 3772. DOI

Books on Ionic Liquids

Ionic Liquids in Synthesis

Peter Wasserscheid, Tom Welton
Hardcover, 364 Pages
First Edition, November 2002
ISBN: 3-527-30515-7 - Wiley-VCH
Chemistry in Alternative Reaction Media
D. J. Adams, P. J. Dyson, S. J. Taverner
Paperback, 268 Pages
First Edition, November 2003
ISBN: 0-471-49849-1 - Wiley

Recent Literature

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The Brønsted acidic ionic liquid [Dsim]Cl (1,3-disulfonic acid imidazolium chloride) enables
the sulfonation of aromatic compounds via in situ generation of sulfuric acid at 50°C under
mild aqueous conditions.
A. R. Moosavi-Zare, M. A. Zolfigol, E. Noroozizadeh, Synlett, 2016, 27, 1682-1684.

Use of the powerful Lewis acid, iron(III) triflimide, generated in situ from iron(III) chloride
and a readily available triflimide-based ionic liquid allowed activation of N-iodosuccinimide
(NIS) and efficient iodination of a wide range of arenes under mild conditions.
D. T. Racys, C. E. Warrilow, S. L. Pimlott, A. Sutherland, Org. Lett., 2015, 17, 4782-4785.

An 1,4-diazobicyclo[2.2.2]octane (DABCO) based ionic liquids were used as recyclable

catalysts for the aza-Michael addition at room temperature without any organic solvent. A
low loading of the very efficient [DABCO-PDO][OAc] catalyzed reactions of various amines
with a wide range of α,β-unsaturated amides to afford products in very good yields within
hours. Moreover, the catalyst could be reused up to eight times.
A. Ying, Z. Li, J. Yang, S. Liu, S. Xu, H. Yan, C. Wu, J. Org. Chem., 2014, 79, 6510-6516.

An efficient cross-coupling reaction of aryl/het-aryl/benzyl halides with stable and easily

workable sulfonyl hydrazides as thiol substitutes delivers unsymmetrical sulfides in the
presence [DBU][HOAc] and CuI under microwave irradiation.
N. Singh, R. Singh, D. S. Raghuvanshi, K. N. Singh, Org. Lett., 2013, 15, 5874-5877.

A convenient and practical method for the one-pot, three-component synthesis of terminal
vinylphosphonates from aldehydes, nitromethane and trialkylphosphites through a tandem
Henry-Michael reaction followed by nitro elimination in the presence of 5-
hydroxypentylammonium acetate (5-HPAA) as a task-specific ionic liquid offers good yields
of the products under mild reaction conditions.
S. Sobhani, M. Honarmand, Synlett, 2013, 24, 236-240.

Ionic liquids [bmim][X] (X = Cl, Br, I, OAc, SCN) are highly efficient reagents for
nucleophilic substitution reactions of sulfonate esters derived from primary and secondary
alcohols. The newly developed protocol is very environmentally attractive because the
reactions use stoichiometric amounts of ionic liquids as sole reagents without additional
solvents and activating reagents. Moreover, these ionic liquids can be readily recycled.
Y. Liu, Y. Xu, S. H. Jung, J. Chae, Synlett, 2012, 23, 2663-2666.

Triflyl nitrate (TfONO2) and trifluoroacetyl nitrate (CF3CO2NO2), generated via metathesis in
the readily available ethylammonium nitrate (EAN) ionic liquid as solvent, are powerful
electrophilic nitrating reagents for a wide variety of aromatic and heteroaromatic compounds.
Comparative nitration experiments indicate that EAN/Tf2O is superior to EAN/TFAA for
nitration of strongly deactivated systems.
G. Aridoss, K. K. Laali, J. Org. Chem., 2011, 76, 8088-8094.
A straightforward and efficient Yb(OTf)3 catalyzed three-component reaction of aldehydes,
alkynes, and amines under microwave irradiation in an ionic liquid provides 2,4-disubstituted
quinolines in excellent yield under mild reaction condition. The catalyst can be recycled up to
four times.
A. Kumar, V. K. Rao, Synlett, 2011, 2157-2162.

1-Alkyl-3-methylimidazolium cation based ionic liquids efficiently catalyze N-tert-

butyloxycarbonylation of amines with excellent chemoselectivity. The catalytic role of the
ionic liquid is envisaged as electrophilic activation of di-tert-butyl dicarbonate (Boc2O)
through bifurcated hydrogen bond formation with the C-2 hydrogen of the 1-alkyl-3-
methylimidazolium cation.
A. Sarkar, S. R. Roy, N. Parikh, A. K. Chakraborti, J. Org. Chem., 2011, 76, 7132-7140.

In a method for the Friedel-Crafts-type insertion reaction of acetylene with acid chlorides in
chloroaluminate ionic liquids, the use of ionic liquids not only serves to avoid the use of
carbon tetrachloride or 1,2-dichloroethane but also suppresses side reactions, and enables a
simpler purification procedure, giving a range of aromatic and aliphatic β-chlorovinyl ketones
in high yield and purity.
D. J. M. Snelders, P. J. Dyson, Org. Lett., 2011, 13, 4048-4051.

A strategy for the asymmetric Michael addition of aldehydes to nitroolefins with a catalytic
system of an organocatalyst in combination with ionic-liquid-supported benzoic acid gives
excellent diastereo- and enantioselectivities. A notable feature of this organocatalytic system
is that the catalyst can be recycled more than 12 times without significant loss of
enantioselectivity.
D. Sarkar, R. Bhattarai, A. D. Headley, B. Ni, Synthesis, 2011, 1993-1997.
2-Hydroxyethylammonium formate as a cost-effective and task-specific ionic liquid
efficiently promotes the condensation of nitroalkanes with various aldehydes to produce β-
nitrostyrenes in very good yields at room temperature. This reaction does not involve any
hazardous organic solvent and toxic catalyst. The ionic liquid can be recovered and recycled
for subsequent reactions.
A. Alizadeh, M. M. Khodaei, A. Eshgi, J. Org. Chem., 2010, 75, 8295-8298.

The novel 1,3-dialkyl-1,2,3-triazolium ionic liquids [bmTr][PF6] and [bmTr][NTf2] are

chemically inert under basic conditions and more suitable media for reactions involving bases
than common 1,3-dialkylimidazolium ionic liquids such as [bmim][PF6]. [bmTr][PF6] and
[bmTr][NTf2] were efficient reaction media for the Baylis-Hillman reaction.
Y. Jeong, J.-S. Ryu, J. Org. Chem., 2010, 75, 4183-4191.

A highly efficient and selective palladium-catalyzed ligand-free cyclocarbonylation reaction

of o-iodophenols with terminal acetylenes under atmospheric CO pressure affords diversified
chromones in very good yields. The use of a phosphonium salt ionic liquid as the reaction
medium enhances the efficiency of the cyclocarbonylation reaction.
Q. Yang, H. Alper, J. Org. Chem., 2010, 75, 948-950.

An efficient intermolecular hydroamination of unactivated alkenes with anilines catalyzed by

lanthanide salts gives Markovnikov products in good yields.
P. Yin, T.-P. Loh, Org. Lett., 2009, 11, 3791-3793.

A rapid and convenient free-radical-based synthesis of functionalized quinazolines relies on

microwave-promoted reactions of O-phenyl oximes with aldehydes in the presence of ZnCl2.
The method worked well with alkyl, aryl, and heterocyclic aldehydes and for a variety of
substituents in the benzenic part of the molecule.
F. Portela-Cubillo, J. S. Scott, J. C. Walton, J. Org. Chem., 2009, 74, 4934-4942.

Lanthanide triflates are efficient catalysts for the intramolecular Markovnikov-type

hydroalkoxylation/cyclization of primary/secondary and aliphatic/aromatic hydroxyalkenes in
room temperature ionic liquids (RTILs) to give five- and six-membered oxygen heterocycles
in very good yields.
A. Dzudza, T. J. Marks, Org. Lett., 2009, 11, 1523-1526.

An improved one-pot van Leusen oxazole synthesis using tosylmethyl isocyanide (TosMIC),
aliphatic halides and various aldehydes in ionic liquids allows the preparation of 4,5-
disubstituted oxazoles in high yields. The recovered ionic liquids could be reused as solvent
for six runs without significant loss of yields.
B. Wu, J. Wen, J. Zhang, J. Li, Y.-Z. Xiang, X.-Q. Yu, Synlett, 2009, 500-504.

Urea-hydrogen peroxide in the presence of a catalytic amount of magnesium bromide

efficiently oxidizes primary and secondary benzylic alcohols into the corresponding aromatic
aldehydes and ketones.
H. J. Park, J. C. Lee, Synlett, 2009, 79-80.

The application of the 1-butyl-3-methylimidazolium-based ionic liquid [BMIM][NTf2] as

solvent enabled clean α-methylenations of carbonyl compounds in a short time and good
yields. This ionic liquid was reused without affecting the reaction rates or yields over seven
runs.
J. A. Vale, D. F. Zanchetta, P. J. S. Moran, J. A. R. Rodrigues, Synlett, 2009, 75-78.

An eco-friendly method allows the synthesis of 2,4-disubstituted quinolines via Meyer-

Schuster rearrangement of 2-aminoaryl ketones and phenylacetylenes in the presence of a
catalytic amount of zinc trifluoromethanesulfonate in the ionic liquid [hmim]PF6. The ionic
liquid can be recycled.
R. Sarma, D. Prajapati, Synlett, 2008, 3001-3005.