JICS 6 4 Review 1

J. Iran. Chem. Soc., Vol. 6, No. 4, December 2009, pp. 647-678.
JOURNAL OF THE
Iranian
Chemical Society
Basic Ionic Liquids. A Short Review
A.R. Hajipoura,b,* and F. Rafieeb

a
Department of Pharmacology, University of Wisconsin, Medical School, 1300 University Avenue, Madison, WI,
53706-1532 USA
b
Pharmaceutical Research Laboratory, College of Chemistry, Isfahan University of Technology, Isfahan 84156,
Islamic Republic of Iran
(Received 17 September 2009, Accepted 14 October 2009)
Basic ionic liquids as environmental-friendly solvents and catalysts with high activity and selectivity and easily recovered
materials were used to replace traditional bases such as KOH, NaOH, K2CO3, NaHCO3, NaOAc, triethylamine, or
tetrabutylammonium acetate. Using the traditional bases generally suffered from disadvantages such as waste production,
corrosion and environmental problems. Basic ionic liquids offering a new possibility for developing environmentally friendly
basic catalysts due to the combination of the advantages of inorganic bases and ionic liquids. They are flexible, nonvolatile,
noncorrosive, and immiscible with many organic solvents. Basic ionic liquids (BILs) have been used in base-catalyzed processes
such as Michael addition, Markovnikov addition, Knoevenagel condensation, Henry reaction, Mannich reaction, oximation, Feist-
Benary reaction and etc. In this short review, we wish to present an overview of the types, properties, synthesis and applications
of basic ionic liquids.
Keywords: Basic ionic liquids, Task-specific ionic liquids, Lewis base ionic liquids, Condensation reactions
INTRODUCTION The use of ionic liquids as reactions medium may offer a

convenient solution to both the solvent emission and catalytic
Due to the increase in environmental consciousness in recycling problem [2]. Ionic liquids containing imidazolium
chemical research and industry, the challenge for a sustainable cations can be used as powerful media in some catalytic
environment calls for clean procedures that avoid the use of organic reactions not only for the facilitation of catalyst
harmful organic solvents. One of the most important principles recovery but also for the acceleration of the reaction rate and
of the green chemistry is the elimination of hazardous solvents improvement of selectivity [3]. Ionic liquids have been widely
in chemical synthesis and avoids using toxic solvent and the vaunted as greener solvents, suitable for a range of organic
generation of waste. Ionic liquids have received considerable reactions and providing possibilities such as control of product
attention due to their interesting chemical and physical distribution, enhanced rate and reactivity, ease of product
properties, such as wide liquid range with melting point recovery, catalyst immobilization, and recycling [4].
around room temperature, good stability in air and moisture, Numerous chemical reactions, such as esterification
high solubility including inorganic, organic, and even reaction [5-9], cleavages of ethers [10], aldol condensation
polymeric materials, and negligible vapor pressure [1]. [11], protection of carbonyls [12-16], Koch carbonylation
[17], polymerization [18], hydrogenation, regioselective
*Corresponding author. E-mail: [email protected] alkylation and Friedel-Crafts reactions [19-22], dimerization
Hajipour & Rafiee
[23-24], Diels-Alder reactions [25-26], Mannich reaction [27- solvents for the development of more efficient and sustainable
28], oximation [29], oxidation [30-32], Heck reaction [33], processes and products [46].
Knoevenagel reaction [34-36], Henry reactions [37], The acidity or basicity of reactive ionic liquids is governed
heterocyclic synthesis [38-41], cross-coupling reactions and by the strength of the cation, the anion, or by the combination
some enzyme reactions can be carried out in ionic liquids. of the cation and anion. The most common ionic liquids
These valuable solvents have also been referred to as comprise salts of tetraalkylphosphonium, tetraalkyl-
designer solvents regards that their physical and chemical ammonium, N-alkylpyridinium or N,N-dialkylimidazolium
properties could be adjusted by a careful choice of cation and cations. Common cations contain C1-18 alkyl groups, and
anion. Furthermore, they exhibit acidic or basic properties, include the ethyl, butyl and hexyl derivatives of N-alkyl-N-
therefore the combining of these unique properties emerging methylimidazolium and N-alkylpyridinium. Other cations
them as green reaction media [2]. include pyrrolidinium, pyridazinium, pyrimidinium,
Recently, the synthesis of functionalized ionic liquids or pyrazinium, pyrazolium, triazolium, thiazolium and
task-specific (TSILs) with special functions according to the oxazolium. A wide of anions can be matched with the cation
requirement of a specific reaction has become an attractive component of such ionic liquids for achieving a neutral ionic
field due to their tunable features for various targeted chemical liquid or one that possesses Lewis basicity. Commonly used
tasks and the advantages as reusable homogenous supports, anions include carboxylates, fluorinated carboxylates,
reagents, and catalysts with green credential. All these studies sulfonates, fluorinated sulfonates, imides, borates, phosphates,
offered us the possibility of designing suitable catalysts for the antimonates, halides, halometallates, etc. [47].
appointed reaction. The tasks specific ionic liquids often serve Room temperature ionic liquids include acidic, neutral and
the dual role of catalyst and reaction medium. Endowed with basic ionic liquids. The acidic and neutral ionic liquids have
catalytically active groups, functional ionic liquids have been been well recognized and successfully applied in many
developed and successfully applied as catalyze in a number of organic reactions. However, the related report about the basic
chemical transformations. These kinds of ionic liquids still ionic liquids was rare [48].
maintains the unique properties of ionic liquids, therefore can The most popular acidic ILs including either protonated
be easily recycled and reused as homogenous small molecular alkylimidazole salts or x-sulfonylalkylimidazolium salts are
catalysts. Up to now, functionalized ionic liquids catalysis has much less frequent basic ILs, for example 1,3-
been mainly focused on exploring acid or base mediated dialkylimidazolium hydroxide or monoalkylammonium salts
reactions. Considering the designer properties of ionic of diamines which are prepared from tertiary diamines by
liquids, there remains tremendous potential for FIL catalysis mono-quaternization [49].
[42-45]. Basic ionic liquids (BILs) used in some base-catalyzed
The acidity/basicity of the reaction media has a substantial processes offering a new possibility for developing
influence on the efficiency of many reactive processes; environmentally friendly basic catalysts due to the
therefore, a new class of acidic or basic ionic liquids is gaining combination of the advantages of inorganic bases, stability in
special attention due to the possibility of increasing the water and air, easy separation, high catalytic efficiency and
efficiency of many processes by a wise manipulation of their reusability. These strong BILs exhibited great potential for the
properties. Acidic or basic ionic liquids (ILs) represent new replacement of conventional basic catalysts because they are
classes of acids or bases. The study of the acidity/basicity of flexible, nonvolatile, noncorrosive, and immiscible with many
these task-specific ionic liquids is of great importance since organic solvents [1].
the efficiency of many processes depends on the Some of the reactions such as condensation reactions, that
acidity/basicity of the media or can be controlled by it. These catalyzed by a base, such as K2CO3, NaHCO3, NaOAc,
compounds aptness for the fine tuning of their properties triethylamine, or tetrabutylammonium acetate, etc., are of
through an endless combination of cations and anions, great importance for the synthesis of pharmaceutical and fine
cataloging them as designer solvents, allow the design of chemicals. Industrially, these reactions are indeed carried out
648
in the homogeneous phase with KOH or NaOH. Using these investigated; the relative acidity or basicity of the component
bases, however, have numerous disadvantages such as waste ions. Lewis base anions can exhibit a base catalysis
production, corrosion and no catalyst recovery. Thus it is an phenomenon, which can be utilized [52].
exciting challenge to find new Brnsted-type basic catalysts
with high activity and selectivity. Although the consumption Neutral Anions
of one equivalent of base is inevitable, a basic ionic liquid Typical ionic liquid anions are those that can be described
acting as both the solvent and base would make the procedure as neutral in the acid/base sense or very weakly basic; these
much easier to handle. This is essentially important for the exhibit only weak electrostatic interactions with the cation and
reactions where normally a large excess of organic base, e.g. thus impart advantageously low melting points and viscosities.
triethylamine, DBU, or piperidine, is required, which causes Included in this class are anions such as hexafluorophosphate,
an additional environmental burden [50]. bis(trifluoromethanesulfonyl)amide (TFSA, also known as
Basic ionic liquids have been successfully utilized to TFSI and (Tf)2N, tetrafluoroborate, methanesulfonate
catalyze the Michael addition, Heck reaction and (mesylate), thiocyanate, tricyanomethide and p-toluene-
Markovnikov addition [51]. sulfonate (tosylate) (Scheme 1). Ionic liquids formed from
these anions typically exhibit good thermal and
CLASSIFICATION OF IONIC LIQUIDS electrochemical stability and thus are often utilized as inert
ACCORDING TO ACIDITY/ BASICITY solvents in a wide range of applications [53-56].
There is significant interest in the development of task Acidic Cations and Anions
specific ionic liquids, where the anion and/or cation is The simplest examples of slightly acidic ionic liquids are
designed to impart specific properties to the ionic liquid, such those based on the protic ammonium, pyrrolidinium and
as chirality, or improved extraction or separation capabilities. imidazolium ions, of which many are known. The well known
The design and choice of ionic liquids commonly focuses AlCl3 based ionic liquids are Lewis acidic when they contain
on physical properties such as water-miscibility, conductivity, an excess of AlCl3 (Scheme 2) [57-67].
viscosity and solubility properties, although how the chemical
structure of the ionic liquid affects these various Basic Cations and Anions
characteristics is still poorly understood. However, there is There are a number of ionic liquid forming anions that can
another chemical property that imparts a variety of physical class as basic. These include the lactate, formate, acetate (and
characteristics to the ionic liquids that has been little carboxylates generally) and the dicyanamide (dca) anion. The
Anion Cation
R
F 3C N CF 3
SO2 SO 2 C R N R
N R
N
H3C SO 3-
R1
Neutral
S
N R3 R2
BF4- PF6- NO3-
H3C SO 3- S C N-
Scheme 1
649
Hajipour & Rafiee
Anion Cation
N N
R
COOH N N Cl
N N S
R
Acidic H 2PO4- HSO 4- O
N N N N
N N SO 3H S
O
Scheme 2
Anion Cation
N
N N N
N
Basic
R
O
HO O
H3C O-
O-
Scheme 3
dicyanamides, in particular, have become readily available salts to produce ionic liquids at room temperature. Familiar
because of their low viscosity, including as phosphonium salts. examples of such liquids are mixtures of aluminum chloride
Since the basicity of these anions imparts different, with 1-n-butylpyridinium chloride (BPC) or l-methyl-3-
advantageous properties to the ionic liquids, such as different ethylimidazolium chloride (MEIC). Both systems have been
solubilizing and catalytic properties, as discussed below, this found to be good solvents for electrochemistry and
category of ionic liquids is likely to grow considerably in the spectroscopy.
coming years. The Lewis acid-base properties of these ionic liquids can
An alternative to the design of ionic liquids utilizing a be varied by adjusting the ratio of AlCl3, to organic salt. Melts
basic anion is to incorporate a basic site into the cation. This in which the apparent mole fraction of AlCl3 exceeds 0.5 are
may afford more thermally stable ionic liquids than those acidic, owing to the presence of the heptachloroaluminate ion,
containing basic anions, which frequently exhibit relatively which is a chloride ion acceptor. Those melts with an A1C13
low decomposition temperatures (Scheme 3) [52]. mole fraction less than 0.5 are basic, since they contain
uncomplexed chloride ion [68-69].
Amphoteric Anions
There are a small number of ionic liquid anions that fall BASICITY CHARACTERIZATION OF BASIC
into the interesting class of amphoteric anions, with the IONIC LIQUIDS AND SYNTHESIS OF BASIC
potential to both accept and donate protons depending on the IONIC LIQUIDS
other substances present. The hydrogen sulfate (HSO4) and
dihydrogen phosphate (H2PO4) anions are simple examples of Basicity Characterization
such anions [52]. One of the important and very revealing properties of any
solvent is the way that it responds to the presence of an acidic
Lewis Base Aluminum Chloride Combined with or basic solute. The state of an acid or base compound, such as
Room Temperature Ionic Liquids acetic acid or ammonia, in an ionic liquid solvent is a strong
Aluminum chloride can be combined with certain organic function of the acidity/basicity of the ionic liquid itself.
650
In traditional solvents, acids and bases are categorized in chloride, and the mixture was stirred vigorously at room
terms of Brnsted acidity, which relates to the ability of the temperature for 10 h. The precipitated KBr was filtered off,
acid, HA, to donate a proton to a molecule of the solvent, S: and the filtrate was evaporated to leave the crude [bmim]OH
as a viscous liquid that was washed with ether and dried at 90
HA + S A - + HS+ C for 10 h to prepare the pure ionic liquid for use [70].
Also the basic ionic liquid [bmim]OH was prepared by
The equilibrium constant for this reaction, Ka, is a measure anion change of [bmim]Cl using 1 mol equivalent KOH. The
of the acidity of the acid, but it clearly also has a dependence ionic liquid was dried under vacuum for 24 h and stored in a
on the basicity of the solvent, S. The more general Lewis desiccator. This ionic liquid is highly stable under ambient
definition of acidity and basicity involves simply the ability of conditions and can be used in reactions without any difficulty.
the molecule to accept or donate electrons. The role of the The ionic liquid was firstly dried with anhydrous sodium
solvent can be to act as the predominant base and thereby to sulfate, and the filtrate was then dried under vacuum at 90 C
form HS+ (e.g., H3O+ in water). for 24 h to eliminate the residual water [48].
Some of the basic anions are more basic than water and
therefore can be expected to act as stronger proton acceptors Preparation of Supported Basic Ionic Liquid
than water. An acid dissolved in an ionic liquid containing A mixture of polystyrene resin and 1-methylimidazole in
such an anion may then exhibit a higher degree of dissociation toluene was refluxed for 24 h. After cooling to room
than in water. Thus the Brnsted acidity of a solute acid may temperature, the reaction mixture was filtered, and the
be higher (Ka larger) in such ionic liquids than in water. The supported ionic liquid 1 (SIL 1) was washed with toluene,
extent to which this is the case is a matter of the relative HCl, water and methanol, followed by drying under reduced
acceptor strength of the ionic liquid anion and the conjugate pressure to give SIL 1 (Scheme 4).
base of the solute acid. Such basic ionic liquids turn weak For preparation of supported basic ionic liquid 2 and 3
acids into stronger acids. This understanding can be solid potassium hydroxide or potassium hydrogen carbonate
investigated further by using acid solutes which have and SIL 1 (10.0 g) were added to water and the mixture was
spectroscopic signatures that are sensitive to their state of stirred vigorously at room temperature for 24 h. Then the
protonation; the measurement of the basicity scale of these mixture was filtrated and washed with water until neutral,
ionic liquids was conducted on UV-Vis spectrophotometer followed by drying under reduced pressure to give the
with an acidic indicator. supported basic ionic liquid 2 (SBIL 2) and supported basic
For example between ionic liquids contain acetate, ionic liquid 3 (SBIL 3) (Scheme 4) [51].
dicyanamide (dca), tricyanomethide (tcm), nitrate, PF6, TFSA
and BF4, emim acetate is able to act as a stronger acceptor for Synthesis of (3-Amino-propyl)-tributyl-phosphonium
protons than water. In contrast to the neutral ionic liquids this Glycine ([3a-C3P(C4)3][Gly])
ionic liquid can produce strongly dissociated solutions of the Equal molar amounts of tri-n-butylphosphine and 3-
solute acid. The anions S- in these ionic liquids thus act as bromopropylamine hydrobromate were added to a round-
Brnsted bases to promote the dissociation of the dissolved bottom flask containing acetonitrile as solvent. The mixture
acid [52]. was vigorously stirred for 8 h at 60 C, and then 48 h at 80 C.
The state of a base will be altered by the presence of water The solvent acetonitrile was removed by vacuum evaporation
in a neutral ionic liquid. Water will be at least partly at 70 C. Then, n-hexane was added to the flask to dissolve the
dissociated, producing OH- in a basic ionic liquid. remaining material with thorough stirring. After standing for
30 min, two phases were formed. The top phase, containing
Preparation of 1-Butyl-3-methylimidazolium Hydroxide unreacted starting material and n-hexane, was decanted. The
Solid potassium hydroxide was added to a solution of bottom phase was the product fraction. This washing process
[bmim]Br with equal molar amounts in dry methylene was repeated until no starting material exited in the top phase.
651
Hajipour & Rafiee
N
Cl
N Cl -
+ N N
Toluene
Ref lux (24 h)
SIL1
N OH -
KOH
N
N
Cl- SIL2
N
KHCO3 N
HCO3-
SIL3
Scheme 4
H
N
N
+ CH3COOH CH3COO-
N
N
Scheme 5
The obtained product, [3a-C3P(C4)3]Br, was dried in a vacuum undec-7-en-8-ium acetate ([DBU][Ac]) through the
oven at 70 C for 24 h. Then [3a-C3P(C4)3]Br was dissolved in neutralization reaction of equal molar amounts of DBU and
deionic water, and the solution was added to the pretreated acetic acid. To a three necked flask was added DBU. Acetic
ionic exchange resin column, resulting in the transformation of acid was then added dropwise at the temperature of 65 C
Br- into OH-. The obtained solution of [3a-C3P(C4)3][OH] was cooled by ice bath. After dropwise addition, the ice bath was
evaporated to remove most of the water. Equal molar amount removed and the reaction mixture was stirred at room
of glycine was added to the solution of [3a-C3P(C4)3][OH] temperature for 24 h. The oil residue was dried in vacuum at
with stirring for 24 h at room temperature. Then, water was 60 C for 24 h to afford [DBU][Ac] as a light yellow, viscous
removed by vacuum evaporation. The final product [3a- liquid (Scheme 5) [72].
C3P(C4)3][Gly] was dried in a vacuum oven at 70 C for 48 h
[71]. 1-(2'-Diisopropylamino)ethyl-3-methylimidazolium
Hexafluorophosphate (1) or Bis (trifluoromethane-
sulfonyl)amide (2)
Synthesis of (3-Amino-propyl)-tributyl-phosphonium
N-Methylimidazole was added to a solution of 2-
Alanine ([3a-C3P(C4)3][Ala])
(diisopropylamino)ethyl chloride hydrochloride in ethanol,
This synthesis followed the same procedure as for [3a-
and the mixture was heated at reflux for 12 h. After the
C3P(C4)3][Gly] described above, although alanine was used
reaction was complete, the solvent was removed under
instead of glycine [71].
reduced pressure, and the residue was washed with THF to
leave a white powder. The solid was dissolved in water and
Task-Specific Ionic Liquid, 1,8-Diazabicyclo[5.4.0]- NaOH was added. After stirring for 15 min, dichloromethane
undec-7-en-8-ium Acetate and KPF6 were added, stirred for a further 30 min, and the
Basic task-specified ionic liquid, 1,8-diazabicyclo[5.4.0]- aqueous phase was extracted with CH2Cl2. The combined
652
organic layer was dried with Na2SO4. After evaporation of the

N N CH2 N N Bu
solvent, the desired product was obtained (Scheme 6) [50]. N
N
X-
NTf 2-
1-Butyl-3-(2-pyridinylmethyl)imidazolium Bis(tri-
1 X=PF6 3
fluoromethanesulfonyl) Amide (3) 2 X=NTf 2
To 2-(bromomethyl) pyridine hydrobromide dissolved in Scheme 6
methanol was added sodium hydrogen carbonate (1 equiv.) to
neutralize hydrobromide. After stirring for 30 min at room
temperature, 1-butylimidazole was added, and the solution
was stirred at 25 C for 12 h. Methanol was then evaporated
under reduced pressure, and the residue was dissolved in water N
N
and extracted several times with ether. To the aqueous phase
was added LiNTf2. The resulting oily product was washed
with water and dried in vacuum (Scheme 6) [50]. N(CF3SO2)2-
Scheme 7
(R)-(1-Phenylethyl)[2-diisopropylamino)ethyl]
dimethylammoniumbis(trifluoromethanesulfonyl)
imide NaOH solution and finally again with distilled water until the
2-(Diisopropylamino)ethyl chloride was added to (R)-N,N- pH of the washing water was neutral. A saturated solution of
dimethyl-1-phenylethanamine. The flask was flushed with 2-[2-(dimethylamino) ethoxy]ethyl-N,N-diisopropyl-
nitrogen, closed with a septum, and the mixture was stirred at ammonium bromide in distilled H2O was than applied to the
60 C for 4 days. A light-orange precipitate could be seen in top of the column, which was then washed with distilled
the solution. After cooling to room temperature n-hexane was water. The pH of the fractions was monitored and those with
added. The supernatant solution was decanted and the solid basic pH were collected. Into this basic solution was added,
was washed twice with n-hexane. The crude light-yellow under stirring, a solution of L-proline in distilled water. The
crystals were dried at room temperature at high vacuum to resulting mixture was then stirred at room temperature for 20
give the corresponding chloride. This was dissolved in h. Water was evaporated using a rotary evaporator and the
distilled water and the solution was washed with CH2Cl2. To residue was dried under high vacuum to obtain ionic liquid as
the water solution was then added, under stirring, in small a light brown very viscous liquid (Scheme 8) [49].
portions, a solution of LiN(SO2CF3)2 in distilled water. The
mixture was stirred at room temperature for 3 h, and the upper Synthesis of Choline Hydroxide
water layer was separated and washed with CH2Cl2. To the Methanol, choline chloride and KOH in term of molar ratio
bottom (ionic liquid) layer was added CH2Cl2, and the solution of 1:1 were charged in a three-neck flask fixed with a
was washed with distilled water. CH2Cl2 solutions were condenser and magnetic stirrer. The reactor was then heated to
combined and dried over MgSO4. After filtration to remove 60 C in water bath under stirring strongly for 12 h. After
the MgSO4, CH2Cl2 was evaporated. Product was obtained as cooling to room temperature, the mixture reaction solution
light-yellow oil (Scheme 7) [49]. was filtered to remove solid KCl and choline hydroxide
solution was obtained (Scheme 9) [73].
2-(2-(Diisopropylamino)ethoxy)-N-ethyl-N,N-di-
methylethanammonium(S)pyrrolidine-2-carboxylate Synthesis of 1-Ethyl-4-aza-1-azoniabicyclo[2.2.2]
Reaction was started by preparation of Annex AT in OH octane Iodide ([C2dabco]I)
mode. An Annex AT 0806 column was washed with distilled 1,4-Diazabicyclo[2.2.2]octane (dabco) was reacted with
water, which is five times the volume of Annex AT, then with less than equimolar amount of iodoethane in ethyl acetate for 2
653
Hajipour & Rafiee
N
N F3 C N CF3
O S S
N N - OOC
N O O O O
H
Scheme 10
Scheme 8
O
N
O-
OH
N Scheme 11
OH -
Scheme 9
N
N F3 C N CF3
h at room temperature. The white precipitate was collected by C8 H 17
S S
O
filtration, and was then dried in vacuum. The filtrate was O O O
recrystallized from isopropanol to give the compound as a

Scheme 12
brilliant white powder [74].
Synthesis of 1-Ethyl-4-aza-1-azoniabicyclo[2.2.2] 1-Octyl-4-aza-1-azonia-bicyclo[2.2.2]octane Bis(tri-

octane bis(trifluoromethane sulfonyl)amide fluoromethanesulfonyl)amide ([C8dabco]TFSA)
([C2dabco]TFSA) The bromide salt and LiTFSA in molar ratio of 1:1 yielded
The iodide derivative was dissolved in distilled water and [C8dabco]TFSA as a colorless oil [75] (Scheme 12).
slightly excess LiTFSA aqueous solution was added. Since the
TFSA derivative is water soluble, the desired material was APPLICATION OF BASIC IONIC LIQUIDS
extracted from aqueous solution by means of dichloromethane IN ORGANIC REACTIONS
and the solvent was evaporated in vacuum. Acetone and
activated charcoal were added to the residue and the solution Knoevenagel Condensation
was stirred with charcoal at room temperature for 2 h. The Within the family of base catalyzed reactions for fine
mixture was filtered through an activated alumina column. chemical synthesis, the Knoevenagel condensation is widely
The solvent was removed by rotary evaporator and the residue employed to synthesize intermediates of fine chemicals. The
was dried in vacuum for 2 days at 90 C (Scheme 10) [74]. Knoevenagel condensation is a very useful reaction and has
been widely employed for carbon-carbon bond formation in
N-Butyl-N-methylpyrrolidinium Acetate organic synthesis from carbonyl compounds and active
N-n-Butyl-N-methylpyrrolidinium iodide was dissolved in methylene groups. This reaction is usually catalyzed by a base,
distilled water and added to a column loaded with acetate an acid, or a heterogeneous neutral support. A wide range of
anions. (The first step in the use of the ion exchange resin bases can be employed for this condensation; however, alkali
involves loading with the desired anion. A 20 wt% NaOAc metal hydroxides and pyridine as well as other amines such as
solution was flushed through a column containing 1 kg of ethylenediamine and piperidine are the most studied. A wide
resin. The above solution was required to achieve complete range of solid catalysts and solid-supported catalysts have also
substitution of the chloride ions. Then, flushing the column been applied to this reaction such as anion-exchange resins,
with an aqueous solution of the iodide salt of the desired KF, magnesium and aluminum oxides, alkali-exchanged and
cation resulted in rapid displacement of the target anion by the alkali-encapsulated zeolites, hydrotalcites, amino group-
iodide. After the reaction was complete, the aqueous solution immobilized silica materials, clays, alkali and alkaline earth
containing the new IL was concentrated and the IL isolated carbonates, nitridated aluminosilicates and
and dried (Scheme 11) [75]. aluminophosphates, and porous silicate quaternary ammonium
654
composites [76-79]. [bmim]OH

R1 E1 (20 mol %) R1 E1
The basic ionic liquid 1-butyl-3-methylimidazolium O +
r.t.
hydroxide, [bmim]OH, efficiently catalyzed Knoevenagel R2 E2 R2 E2
condensation without requirement of any organic solvent. A

wide range of aliphatic and aromatic aldehydes and ketones R1, R2= alkyl, aryl, H
easily undergo condensations with diethyl malonate, E1, E2= CN, COMe, COOMe, COOEt, COOH
malononitrile, ethyl cyanoacetate, malonic acid and ethyl
Scheme 13
acetoacetate (Scheme 13). The reactions proceed at room
temperature and are very fast. The significant advantages
CHO EWG
EWG
offered by this methodology were: (a) general applicability to [bmim]OH
+
a large number of substrates with very facile reaction of R OH CO2 Et r.t. O O
R
aliphatic aldehydes with diethyl malonate, which was difficult
to achieve by other methods, (b) mild reaction conditions Scheme 14
(room temperature), (c) clean and fast (7-40 min) reaction, (d)
high isolated yields of products and (e) reusability of catalyst CN
and cost-effectiveness. Another attractive feature of this R1

Y
HO
R1 CN - H2O
R1 CN
methodology was the use of ionic liquid as catalyst as well as O Y

R2 BIL R2 H R2 Y
reaction medium primarily avoiding hazardous organic solvent
in the whole procedure in contrast to the reported procedures
R1, R2=H, alkyl, aryl
using ionic liquids together with additional catalysts and Y=CO2H, CO2R, COR, CN
organic solvents in the process [80].
When an aromatic o-hydroxy aldehyde was condensed
N O N
with diethyl malonate or ethyl acetoacetate by this procedure, N N
the corresponding coumarin was obtained in one pot in very

high yields (Scheme 14) [80]. BIL1 BIL2
Task specific basic ionic liquids had been shown to
facilitate the Knoevenagel condensation reaction of a range of
O N
carbonyl molecules with methylene nucleophiles (Scheme 15). N O
Using the basic ionic liquid without solvent produced a

BIL3
homogeneous reaction system and showed high initial activity
and overall conversion. However, on recycle, degradation of
Scheme 15
the IL was observed and it was difficult to remove the entire
product by solvent extraction due to the reaction mixture
solidifying which results in loss of activity on subsequent magnetism. The basic magnetic nanoparticles were used as
reactions. Supporting the basic ionic liquid in an immiscible efficient heterogeneous catalysts for the Knoevenagel
solvent or on a silica support reduces the initial activity, in condensation reaction of several aldehydes with malononitrile
general; however, in both cases, excellent recyclability was under mild conditions (Scheme 16). The cooperation between
found with the reaction repeated over five times without the basic magnetic nanoparticles carrier and supported basic
leaching of the ionic liquid into the extractant phase or ionic liquids resulted in a significant rise of catalytic activity.
reduction in activity [81]. The basic magnetic catalyst could be facilely isolated from the
Hydroxyapatite-encapsulated -Fe2O3 nanoparticles reaction mixture by simple magnetic decantation using a
functionalized with aliphatic amine basic ionic liquids leaded permanent magnet and it could be reused four times without
to creation of surface basic sites as well as increase of significant degradation in activity [82].
655
Hajipour & Rafiee
R1 R1
RCHO +
Cat.
RHC
temperature, 2% of [bmim]Im showed good catalytic
R2 - H 2O R2 properties for Knoevenagel condensations between aromatic
aldehyde and active methylene compounds with 86%-95%
yield and 100% selectivity for ylidenemalononitriles. This
O
OEt
N N N kind of imidazolide ionic liquid also has better recycle ability
Si
O [84].
PF6-
Cat:
Henry Reaction
N
The Henry reaction is one of the most useful carbon-
N N
carbon bond forming reactions and has wide synthetic
PF6-
applications in organic synthesis by which 2-nitroalcohols are
Scheme 16
formed on treatment of nitroalkanes and carbonyl derivatives
with a basic catalyst. Nitroalcohols are useful intermediates in
CHO CN CN the preparation of nitroalkenes, -nitroketones, and -
Cat.
+ aminoalcohols derivatives, such as ephedrine and
R
R - H 2O
norephedrine. Henry reactions can be catalyzed by organic and
inorganic bases. For example 1,1,3,3-tetramethyl guanidine
(TMG) and its cyclic analogs were utilized as efficient
OEt N
O
Si
N N catalysts [37].
O
OH - An efficient protocol for Henry reaction using basic ionic
Cat: liquid [bmim]OH as catalyst and reaction medium was
reported (Scheme 18) [85].
N N N
OH- Michael Reaction

Scheme 17 N-Substituted imidazoles, triazoles, pyrazoles,
pyrimidines, purines and their derivatives obtained through
A series of basic ionic liquids functionalized Michael addition are usually pharmacologically active and
hydroxyapatite-encapsulated -Fe2O3 magnetic nanoparticles may be applied as potential therapeutic alternatives. Generally
were used as efficient heterogeneous catalysts for aqueous these reactions require strong bases or Lewis acids to activate
Knoevenagel condensation under mild condition and excellent nucleophiles or Michael acceptors. These would lead to
results for extended substrates were obtained (Scheme 17). In environmentally hazardous residues and undesirable side-
comparison with the control experiments, the high activity products. To avoid typical disadvantages resulting from the
isascribed to the cooperatives between the base sites generated presence of such a catalyst, a large number of alternative
by framework hydroxyapatite and supported basic ionic strategies have been developed in the past few years using
liquids. Separation of the catalyst from the reaction mixture basic clays, KF/Al2O3, guanidine, microwave irradiation and
was readily achieved by simple magnetic decantation and the enzyme. Unfortunately, many of these procedures require long
catalyst could be easily recycled without appreciable loss of reaction times (several days), rigorous reaction conditions or
catalytic activity [83]. highly dangerous chemicals. Moreover, the use of solvents
A novel basic ionic liquid paired by 1-butyl-3- such as DMSO or DMF is inevitable for some N-heterocycles
methylimidazolium cation and imidazolide anion ([bmim]Im) such as pyrimidines and purines. Generally the catalyst could
was synthesized and its basicity was investigated. The basicity not be recycled. Thus, development of a fast and facile
of [bmim]Im approaches to that of [bmim]OH and is much protocol that could be performed at ambient temperature for
stronger than that of [bmim]OAc. In aqueous solution at room the Michael addition of N-heterocycles to ,-unsaturated
656
Me
CH3NO2 HO NO 2 HO Me HO Me
NO2
RCHO +
[bmim]OH R [bmim]OH R NO 2 R NO 2
Scheme 18
R2 R1 R2
[bmim]OH
Nu-H +
R1 EWG
r.t.
Nu EWG
EWG = CN, COMe, CO2Me
Scheme 19
R2
W=COR
R1
W [bmim]OH R1 W
+
R2
W=CN R1 W
CO 2Me
R2 W
O O
[bmim]OH SR
Ar
RSH Ar SR
R1 R1 R1
[bmim]OH
+ R3X or
R2 R2 R3 R2 R3
R3
Scheme 20
compounds becomes particularly fascinating and remains a carboxylic esters and nitriles. It further catalyzes the addition
great challenge [48]. of thiols to ,-acetylenic ketones and alkylation of 1,3-
A fast and green protocol for the Michael addition of N- dicarbonyl and -dicyano compounds (Scheme 20). The
heterocycles to ,-unsaturated compounds at room Michael addition to ,-unsaturated ketones proceeded in the
temperature was developed using a basic ionic liquid, 1- usual way, giving the monoaddition products, whereas
methyl-3-butylimidazolium hydroxide, [bmim]OH, as a addition to ,-unsaturated esters and nitriles leaded
catalyst and a reaction medium (Scheme 19). The reactions exclusively to the bis-addition products. The ,-acetylenic
were performed at room temperature with good yields in short ketones undergo double conjugate addition with thiols
reaction times (0.5-3 h). This strategy is quite general and it produced -keto 1,3-dithio-derivatives. In the alkylation
works with a broad range of N-heterocycles, including five- reaction the acyclic 1,3-diketones were monoalkylated,
membered N-heterocycles, pyrimidines and purines. The whereas cyclic ketones undergo dialkylation under identical
recovered ionic liquid could be reused for several cycles with conditions. This method offered marked improvements with
consistent activity. regard to operational simplicity, reaction time, high isolated
The basic ionic liquid 1-methyl-3-butylimidazolium yields of products, greenness of the procedure, avoiding
hydroxide, [bmim]OH, catalyzed the Michael addition of hazardous organic solvents and toxic catalysts. The ionic
active methylene compounds to conjugated ketones, liquid was also recycled [86].
657
Hajipour & Rafiee
The aza-Michael reaction is an important reaction in R2

[bmim]OH R1 R2
NH +
organic chemistry, especially for the synthesis of C-N R1 EWG r.t. R1 N EWG
heterocycles containing the -aminocarbonyl functionality, R2
which not only constitutes a component of biologically active EWG=CN, COMe, CO2Me
natural products but also serves as an essential intermediate in
the synthesis of -amino ketones, -amino acids and -lactam Scheme 21
antibiotics. Such aza-Michael reactions have generally been
promoted by harsh bases or strong acids, which give rise to O O
environmentally hazardous residues and undesirable by-
R1 Cat, ionic liquid
products. With the goal of avoiding the typical disadvantages + ArNH2
R1
r.t.
resulting from the presence of such catalysts, a large number R2
ArHN R2
of alternative procedures have been developed in the past few
years. Unfortunately, though, many of these procedures
require long reaction times, rigorous reaction conditions, large O O
excesses of reagents, and/or highly damaging chemicals. In Cat, ionic liquid

many cases the catalyst and excess reagents have not been + ArNH 2
r.t. Ar
N
recoverable, which has strongly limited industrial applications. n n H
The development of an environmentally benign and simple
procedure for aza-Michael addition has thus become Scheme 23
particularly fascinating and remains a great challenge.
A highly efficient [bmim]OH catalyzed the aza-Michael
The basic ionic liquid [bmim]OH provided a convenient,
reaction of aromatic amines and N-heterocycles to ,-
clean, efficient, and recyclable catalytic medium for Michael
unsaturated cyclic and acyclic ketones under solvent-free
addition reactions between various amines and ,-unsaturated
conditions to produce the desired Michael adducts smoothly
compounds, thus substituting for volatile organic solvents and
(Scheme 23). The process was simple and generated a diverse
toxic catalysts (Scheme 21). Furthermore, the products were
range of aromatic amino carbonyl derivatives in excellent
distilled directly from the ionic liquid in large-scale reactions,
yields. Furthermore, it was remarkable that the use of an easily
thus totally avoiding the use of any organic solvent. The ionic
accessible and recyclable basic ionic liquid make this
liquid was reused for at least eight runs without loss of
procedure as a quite simple, more convenient and
activity, thanks to which it exhibited industrial potential.
environmentally benign [88].
Furthermore, the ionic liquid was stable during the reaction
By performing density functional theory calculations, the
process [87].
Michael addition of acetylacetone to methyl vinyl ketone in
A task-specific ionic liquid, 1,8-diazabicyclo[5.4.0]-undec-
the absence and presence of the ionic liquid 1-butyl-3-
7-en-8-ium acetate had been successfully used as a catalyst for
methylimidazolium hydroxide ([bmim]OH) had investigated.
aza-conjugate addition of aliphatic or aromatic amines to
In the absence of ionic liquids, acetylacetone was firstly
various electron deficient alkenes under solvent-free
tautomerized to enol form and then take place Michael
conditions and at room temperature (Scheme 22). The catalyst
addition to methyl vinyl ketone. As in the catalyzed Michael
was reused for six times without noticeable loss of activity
addition reaction, a [bmim]+OH- ion pair was introduced into
[72].
O
O
R2
R2
NH 2 + [DBU][Ac] NH
R3
R1 R3
r.t.
R1
Scheme 22
658
the reaction system to model the effect of the ionic liquid [bmim]OH, TMSCN NC NO2
environment on the reactivity. The calculated results showed Ar H

that the anion enhanced nucleophilic ability of acetylacetone Ar-CHO + CH3NO 2
[bmim]OH, NH4SCN
since the OH- anion captures a proton to form an acetylacetone NCS NO2
anion-H2O complex, and the cation improved the electrophilic

Ar H
ability of methyl vinyl ketone by forming intermolecular Scheme 24
hydrogen-bonds. Both the remarkable effects of the cation and
anion on the reactivity of reactants promoted this reaction, of nitromethane, aromatic aldehydes and trimethylsilyl
which take place more easily compared with uncatalyzed cyanide (TMSCN) or ammonium thiocyanate had been
reaction. The calculated results showed that the main product developed for an expeditious synthesis of -nitrocarbonitriles
of the Michael addition was in its ketone form [89]. or -nitrothiocyanates, respectively, via C-C and C-S bond-
Modern synthetic design demands high efficiency in terms forming reactions (Scheme 24). The synthetic protocol
of minimization of synthetic steps together with maximization strategically involved a one-pot sequential Henry reaction and
of complexity. One of the ways to fulfill these goals is the a Michael addition efficiently promoted by the same ionic
development and use of multicomponent reactions (MCRs) liquid [bmim]OH. The main advantages of the present
which consist of several simultaneous bond-forming reactions approach included the use of inexpensive simple substrates
and allow a highly efficient synthesis of complex molecules and an ionic liquid as an efficient reaction promoter for the
starting from simple substrates in a one-pot procedure. mild synthesis in a one-pot procedure [90].
The importance of nitroalkanes in organic synthesis is tied
up to their propensity to undergo facile a-alkylation reactions Markovnikov Addition
and interconversions to other important organic functional Markovnikov-type addition is among the most useful
groups. Aliphatic nitro compounds have proven to be valuable carbon-carbon, oxygen-carbon, or nitrogen-carbon bond-
intermediates, and are powerful synthetic tools because they forming reactions. It is especially important to synthesize
facilitate the carbon-carbon bond-forming processes. Most bioactive N-heterocycles derivatives with a nitrogen-carbon
importantly, the nitro group can be converted to a carbonyl linkage, which could be achieved by an addition reaction. This
compound using the Nef reaction. An efficient nitroalkane- reaction was traditionally promoted by harsh bases, strong
mediated cyclopropanation is a key step in the synthesis of - acid, or high temperature, which would lead to
amino acid analogues of Pregabalin and Gabapentin that target environmentally hazardous residues and unwanted byproducts.
the 2- protein. Hydrocyanation or hydrothiocyanation of A lot of effort has been made in view of green synthesis [91].
nitroalkenes affords straightforward access to nitroalkanes The basic ionic liquid 1-butyl-3-methyl imidazolium
bearing a nitrile or thiocyanate functionality of considerable hydroxide ([bmim]OH) provided an efficient and convenient
synthetic utility. The diverse transformations in which nitriles protocol for Markovnikov addition of N-heterocycles to vinyl
participate place them among the most versatile intermediates esters without the requirement of any other catalyst and
in organic chemistry. Furthermore, organic thiocyanates have organic solvent (Scheme 25). This strategy was quite general
gained considerable importance in various areas of and it worked with a broad range of N-heterocycles as addition
organosulfur chemistry and are useful scaffolds for the substrates, including five-membered N-heterocycles,
synthesis of various heterocycles, some of which are pyrimidines, and purines. Furthermore, this method exhibited
associated with herbicidal and other important biological a simple and green procedure, mild conditions, and general
activity. Moreover, the thiocyanato group occurs as an applicability and avoids hazardous organic solvent and toxic
important functionality in certain anticancer natural products catalysts [92].
formed by deglycosylation of glucosinolates derived from
cruciferous vegetables. Mannich-Type Reaction
A novel and convenient three-component coupling reaction The Mannich-type reactions are very important carbon-
659
Hajipour & Rafiee
R2 R2
O
N N
[bmim]OH
R1 + O R3 R1
N N O
H
O R3
Scheme 25
carbon bond-forming reactions in organic synthesis and have O O Ar 1

Ar1-CHO, Ar2-NH2 Ar 2
been one of the most basic and useful methods for the N
H
preparation of -amino carbonyl compounds for its use in [bmim]OH
various pharmaceuticals, natural products, and versatile
synthetic intermediates. Mannich reactions have gained Scheme 26
popularity in synthetic chemistry over the past decades. The
most frequently used promoters like Lewis acid catalysts, the application of some of these methods is limited due to the
Brnsted acid catalysts, Lewis base catalysts, rare metal salt moderate yields of the products, longer reaction time and
catalysts, and organo catalysts have been reported to catalyze laborious workup procedure. Furthermore, some of these
the Mannich reaction. Most of these methods suffer from catalysts such as MgO can only catalyze the condensation
severe drawbacks including the use of large amount of reaction of aromatic aldehydes, malononitrile and -naphtol
catalysts, expensive reagents or catalysts, harsh reaction not -naphtol. The development of an environmentally benign
conditions and difficulty in product separation, sometimes and simple procedure for synthesis of 2-amino-2-chromenes
long reaction time, and low yield, etc. Hence, there is high has thus become particularly fascinating and remains a great
interest in developing new convenient methods for the challenge [96-98].
synthesis of -amino carbonyl compounds [93-95]. The basic ionic liquid 1-butyl-3-methyl imidazolium
The basic ionic liquid [bmim]OH catalyzed one-pot hydroxide ([bmim]OH), catalyzed three-component
Mannich-type reaction for three-component synthesis of - condensation reaction of aromatic aldehydes, malononitrile
amino carbonyl compounds (Scheme 26). The ionic liquid, and - or -naphthol proceeded rapidly in water at reflux to
which was environmentally friendly, was recycled at least 5 afford corresponding 2-amino-2-chromenes in high yields
times without significant loss of activity [95]. (Scheme 27). The attractive features of this protocol were
simple procedure, short reaction time, use of cheap and benign
Synthesis of Substituted 2-Amino-2-chromenes solvent, the reuse of the aqueous media, and its adaptability
2-Amino-2-chromenes are an important class of for synthesis of a diverse set of 2-amino-2-chromenes [2].
compounds found as the main components of many naturally A simple, clean, and environmentally benign three-
occurring products employed as cosmetics and pigments and component process to the synthesis of 2-amino-4Hchromenes
utilized as potential biodegradable agrochemicals. Thus the using N,N-dimethylaminoethylbenzyldimethyl ammonium
synthesis of 2-amino-2-chromenes is of much importance to chloride, [PhCH2Me2N+CH2CH2NMe2]Cl-, as an efficient
organic chemists. These compounds are generally prepared by catalyst under solvent-free condition was described (Scheme
reacting aldehydes, activated methylene compounds and 28). A wide range of aromatic aldehydes easily undergo
activated phenols in organic solvents (i.e., ethanol, condensations with -naphthol and malononitrile under
acetonitrile) and in the presence of organic bases like solvent-free condition to afford the desired products of good
piperidine, which are frequently utilized in stoichiometric purity in excellent yields. This procedure offered several
amounts. advantages including mild reaction conditions, cleaner
Recently, relatively benign catalysts such as reaction, and satisfactory yields of products, as well as a
cetyltrimethylammonium chloride (CTACl), montmorillonite simple experimental and isolated procedure, which make it a
KSF clay, KF/Al2O3, TiCl4, triethylamine, basic alumina, useful and attractive protocol for the synthesis of these
MgO and NaOH have been used in this reaction. However, compounds [99].
660
NH 2
CN
OH O
Ar
CN [bmim]OH
ArCHO + + or CN
CN Ar NH 2
OH
O
Scheme 27
Me
OH
Ph N CH 2CH2 NMe2]
CN Me Cl - O NH 2
ArCHO + +
CN CN
Ar
Scheme 28
Hydrolysis of Propylene Carbonate to 1,2-Propylene O
Glycol SBIL HO OH
O O + H 2O
1,2-Propylene glycol is chemicals of acknowledge
commercial importance. It can be used in many applications Scheme 29
areas such as antifreeze agents, brake fluids, intermediates in
the production of pharmaceuticals and fine chemicals, the diol 1,2-propylene glycol. The results show that the SBIL3 exhibits
component in the manufacture of polyurethanes and the the highest activity. Excellent selectivity (>99%) and yield
starting point for the manufacture of poly(propylene glycol)s. (>99%) of 1,2-propylene glycol was obtained in the presence
Therefore, a number of routes leading to the manufacture of of SBIL 3. The activity of SBIL 3 is higher than that of SBIL
1,2-propylene glycol, such as the addition of water to 1,2- 2 and a simple hydroxide containing ion exchange resin was
propylene oxide, the preparation from propene via 1,2- probably due to the reaction of OH-, CO2 and H2O (Scheme
diacetoxypropane followed by saponification thereof, the 30) [51].
single-stage hydrogenolysis of dihyfroxyacetone, the
hydrogenolysis of glycerol and the hydrolysis of propylene Synthesis of Oximes
carbonate. However, currently all these methods suffered from Numerous functional group transformations of oximes
low selectivity and/or yield of 1,2-propylene glycol, and high make them very important in synthetic organic chemistry.
pressure and high temperature are required. Development of a Among other synthesis applications, these compounds were
method for the manufacture of 1,2-propylene glycol with high successfully transformed into nitriles, amides, nitro
selectivity and yield under mild conditions still remains a compounds amines, etc. Therefore, synthetic organic chemists
challenge [100-104]. are interested in a facilitation of oxime synthesis. The classical
Hydrolysis of propylene carbonate to 1,2-propylene glycol method for preparing oximes is the reaction of an aldehyde or
was performed by using a supported basic ionic liquid (SBIL) ketone with hydroxylamine hydrochloride in an alcoholic
catalyst (Scheme 29). solution, under reflux temperature, and in the presence of
The activities of different supported ionic liquid were sodium acetate or pyridine. The latter method is the most used,
tested for the hydrolysis of propylene carbonate to produce especially for the oximation of hardly soluble ketones and
661
Hajipour & Rafiee
- H2O CO2
OH- + CO2 CO32- HCO3-
+ H2O
N N N
N Cl- N OH- N
HCO3-
SIL1 SIL2 SIL3
Scheme 30
R1 R1
steroidal ketones. However, pyridine presents some limitations [bmim]OH
O + NH2OH.HCl NOH
since this base is highly flammable, and harmful by inhalation u.s. r.t.
R2 R2
and in contact with skin. To avoid typical disadvantages Scheme 31
resulting from the presence of such a catalyst, a large number
of alternative strategies have been developed in the past few
OH -
years using alumina, silica gel coupled with microwave OH -
N N
irradiation, TiO2/SO42- without solvent, supported-POM and N N
Na2SO4. These methods all have their own merits and Scheme 32
shortcomings. Some methods are not very satisfactory due to
drawbacks such as low yields, high reaction temperature, long influences on their performances. Because the properties of
reaction time and effluent pollution. Recently, high yield of nano-materials depend on their size and shape, new synthetic
hydroxyiminocycloalkanes could be achieved by treatment of strategies in which the size and shape of nanostructures can be
the corresponding ketones with hydroxylamine or its salts in easily tailored are important. Wurtzite-type ZnO crystals are
ionic liquids and in the presence of additives, such as sodium used for a wide variety of industrial applications, such as
acetate. However, the substrate is limited on cyclohexanone varistors, semiconductors, catalysts, room-temperature UV
only [105-108]. lasers, light-emitting diodes, solar cells, and sensors. Several
The basic ionic liquid 1-butyl-3-methylimidazolium techniques are used for preparation of Wurtzite-type ZnO
hydroxide, [bmIm]OH, efficiently catalyzed the condensation crystals. Among them, hydrothermal synthesis is becoming
reaction of aldehydes and ketones with hydroxylamine popular for environmental reasons [110-111].
hydrochloride under ultrasound irradiation (Scheme 31). Flower-like ZnO morphology, with different shapes, had
Compared with conventional methods, the main advantages of been successfully synthesized via a novel and environment-
the present procedure were milder conditions, shorter reaction friendly hydrothermal method using zinc acetate and a task
time and higher yields [109]. specific dicationic dibasic ionic liquid, [mmpim]2[OH]2
(Scheme 32), which played an important role in fabrication of
Synthesis of Flower-Like ZnO ZnO structure [112].
ILs can act as morphology templates for the synthesis of
inorganic materials with novel or improved properties. Synthesis of Quinazoline-2,4(1H,3H)-diones
Various nano- or micro-structured materials, such as Bi2S3 Quinazoline-2,4(1H,3H)-diones are important
nanostructures, Bi2Se3 nanosheets, and hollow TiO2 micro- intermediates in the pharmaceutical industry as a key building
spheres have been recently synthesized in ILs. There have blocks in the synthesis of FK 366 (Zenarestat) and KF 31327
been few reports on the preparation of ZnO micro-flower in molecules. FK 366 (Zenarestat), which functions as an aldose
ILs. ZnO, a wide band gap semiconductor with large reductase inhibitor and also useful as a remedy for
excitation binding energy, possesses unique properties. The complication of diabetes mellitus. KF 31327 was developed as
size and morphology of ZnO nano-particles have great a remedial drug for heart disease and as an impotence
662
H
medicine. NH2
[bmim]OH
N O
R + CO 2
The 6,7-dimethoxyquinazoline-2,4(1H,3H)-dione R
NH
CN
derivatives are useful building blocks in the synthesis of alpha
O
adrenergic receptor antagonists such as Prazosin (Minipress1), Scheme 33
Bunazosin (Detantol1) and Doxazosin (Cardenalin1) and are
also useful as anti-hypertensive. Several synthetic hydroxydihydrofuran stage using a milder base, it is called the
methodologies exists for the preparation of quinazoline- Interrupted Feist-Benary (IFB) reaction. The IFB reaction is
2,4(1H,3H)-diones, i.e. via reaction of anthranilic acid with important for an easy access to substituted dihydrofurans
urea, anthranilamide with phosgene and anthranilic acid with which are constituents of many natural products arising from
potassium cyanate or chlorosulfonyl isocyanate. However, the plants and marine organisms with promising biological
scope of these methodologies for the preparation of activities. However, only a limited number of methods are
quinazoline-2,4(1H,3H)-diones are often limited by the available for FB and IFB reactions [114-115].
requirement for specialized reagents, and operational The basic ionic liquid, 1-butyl-3-methylimidazolium
complexity due to the use of either toxic or cumbersome hydroxide promoted the interrupted Feist-Benary reaction at
reagents like-phosgene. room temperature under organic solvent-free conditions to
Few efforts were made to replace toxic reagents using produce a variety of substituted hydroxydihydrofurans. The
incorporation of CO2 into quinazoline-2,4(1H,3H)-diones hydroxydihydrofurans were converted to furans (Feist-Benary
derivatives. However, most of these reports have drawbacks products) using the ionic liquid, 1-methyl-3-
like the high catalyst loading, lower substrate compatibility, pentylimidazolium bromide at 70-75 C (Scheme 34). The
use of organic solvents and the use of non-recyclable significant advantages offered by this procedure were room
homogeneous base, which limits their application. There was temperature operation, considerably fast reaction, high yields
sufficient scope for the development of an active and and excellent cis stereoselectivity for the IFB products [116].
recyclable base catalyst for this transformation (Scheme 33).
Hence, considering the economical value of the quinazoline- Glycolysis of Poly(ethylene terephthalate)
2,4(1H,3H)-diones derivatives still there was need to develop Poly(ethylene terephthalate) (PET) is a thermoplastic
a truly catalytic and environmentally viable protocol which polyester with excellent tensile and impact strength, chemical
can minimizes the number of unit operations and waste resistance, clarity, processability, transparency, and
streams [113]. appropriate thermal stability. Tremendous quantities of this
material are consumed in the manufacture of video and audio
Feist-Benary Reaction tapes, X-ray films, food packaging, and especially of soft-
The Feist-Benary (FB) reaction is a very useful reaction drink bottles. With the widespread use and increasing
for the construction of highly substituted furan derivatives via consumption of PET, the amount of waste PET is growing
condensation of -dicarbonyl compounds with -haloketones rapidly. Although this kind of polyester does not create a
in the presence of a base. If this reaction is stopped at the direct hazard to the environment, it does not decompose
Br O RO2 C OH
O O
[bmim]OH CO 2Et
+
R1 R2 R3 OEt r.t. R1 R3
O
O
[pmim]Br
RO2 C CO2 Et
R1 O R3
Scheme 34
663
Hajipour & Rafiee
O O
readily in nature. Thus, the effective recycling of PET wastes
O C C OCH2CH2
for the preservation of resources and protection of the HOCH2CH2OH
n
environment has received considerable attention. PET wastes
can be converted by mechanical methods into extruded or
molded articles, whose properties are inferior to those of the O O
original. PET decomposition and its conversion into reusable O C C OCH2CH2
chemical products becomes one of the important recycling m
strategies for this material.
Several processes for PET depolymerization have been put Oligomers
forward, such as alcoholysis process with methanol, glycolysis
with ethylene glycol or other glycol, and hydrolysis under the
promotion of acidic or basic conditions. Alcoholysis to Dimer
dimethyl terephthalate (DMT) with liquid or gaseous methanol
has the obvious disadvantage of volatilization of methanol.
O O
The glycolysis process involves the insertion of a diol into
HOCH2CH2 O C C OCH2CH2OH
PET chains to give bis(hydroxyethyl) terephthalate (BHET),
which is easily integrated into conventional PET products. The BHET
main drawback of this process is that the reaction products are
not discrete chemicals but BHET along with higher oligomers, Scheme 35
which are difficult to purify with conventional methods [117-
118]. conversion of PET was diminished. The catalytic effect of
Hydrolysis of PET under acidic or basic conditions gives basic ionic liquids was desirable and the conversion of PET
terephthalic acid (TPA), along with corrosion and pollution could reach 100%. However, this kind of ionic liquids was
problems. Since glycolysis of PET can produce the BHET quite complex to synthesize and price of the materials was
monomer, which has been widely used in the production of very high. Neutral ionic liquids, which also had good catalytic
unsaturated polyesters and rigid or flexible polyurethanes. effects and appropriate price, became the alternative [71].
Various kinds of catalysts, such as titanium-phosphate,
metal acetate, and solid super acids are required to facilitate Synthesis of Hydrofluoroether
the process. Although these catalysts are effective in the Hydrofluoroethers (HFEs) have been considered as the
glycolysis of PET, it is difficult to separate the catalysts from most promising candidates for refrigerants, cleaning solvents,
the products, as illustrated in the literature. Thus, the catalysts and blowing agents to replace chlorofluorocarbons (CFCs) and
could not be recycled and reused, and the purity as well as hydrochlorofluorocarbons (HCFCs), due to their zero ozone
application fields of the depolymerization products will be depleting potential, low global warming potential, and
seriously threatened. favorable physical and chemical properties including low
The glycolysis of PET was catalyzed by different kinds of surface tension, nonflammability, and excellent solvating
ionic liquids at atmospheric pressure (Scheme 35). Results ability. HFEs have also been regarded as an important class of
showed that basic ionic liquids (3-amino-propyl)-tributyl fluorinated organic compounds for many potential
phosphonium glycine ([3a-C3P(C4)3][Gly], (3-amino-propyl)- applications: heat transfermedia, particulate removal and
tributyl-phosphonium alanine [3a-C3P(C4)3][Ala]) and neutral carrier fluids, buffing abrasive agents, displacement drying
ionic liquids 1-butyl-3-methylimidazolium chloride agents, power cycle working fluids, and clinical usages [119-
([bmim]Cl, 1-butyl-3-methylimidazolium bromine [bmim]Br) 120].
accelerated the glycolysis process. But when acidic ionic Numerous methods have been reported to produce HFEs
liquids ([bmim]H2PO4, [bmim]HSO4) were used the including the fluorination of ether with F2 or metal fluoride,
664
CF3CH2OH + CF3CF=CF2 CF3CH2OCF2CHFCF3 3

2 +
1
CF3CH2OCF=CFCF3 4, 5 (cis and trans)
+
CF3CH2OCF2CF=CF2 6
4, 5 + CF3CH2OH CF3CH2OCF2CHFCF2OCH2CF3 7
6 + CF3CH2OH (CF3CH2O)2CFCHFCF3 8
Scheme 36
the electrochemical fluorination of ether, and the alkylation of imidazolium acetate, 1-butyl-3-methylimidazolium
acyl halides using a sulfonic acid ester as an alkylating agent bicarbonate, or 1-butyl-3-methylimidazolium carbonate.
in the presence of anhydrous KF. However, these methods Structures of the products from the hydroalkoxylation of HFP
suffer from either the low product selectivity or the difficulty with TFE are shown in (Scheme 36) [121].
in handling the hazardous and reactive raw materials. HFEs N-Heterocyclic Carbomethoxylation
can also be obtained from the hydroalkoxylation reaction of Carbamates are very important materials in the fields of
commercially available fluorinated olefins (tetrafluoroethylene medicine and agriculture. They are also frequently used as
and hexafluoropropylene) in the presence of a base catalyst or protecting groups in organic synthesis. Conventionally,
free radical initiator, but these methods either require long carbamates are mostly synthesized using phosgene or its
reaction time or produce relatively large amounts of derivatives and catalyzed by stoichiometric strong bases.
unsaturated HFEs were always co-produced, which are However, phosgene or its derivatives are extremely toxic
difficult to remove by distillation due to the closeness in reagents. Obviously, these procedures are not environmentally
boiling points between saturated and unsaturated HFEs. benign. On the other hand, strong bases restrict the use of
Ionic liquids such as 1-ethyl-3-methylimidazolium substrates containing certain functional groups, and are
tetrafluoroborate ([Emim]BF4) and 1-ethyl-3- difficult to be recycled. To avoid these drawbacks, numerous
methylimidazolium hexafluorophosphate ([Emim]PF6) were studies on carbamates synthesis have been investigated [122].
also employed as catalysts and reaction media for the Many efforts are currently being turned to the utilization of
hydroalkoxylation of fluoroolefins, but the yields of HFEs dimethyl carbonate (DMC) as a carbomethoxylating reagent
were not high even at elevated temperatures and long reaction DMC is considered as a safe, nontoxic and eco-friendly
time, possibly due to the lack of basicity of [Emim]BF4 and reagent. DMC molecule contains several active basic groups,
[Emim]PF6. Since base catalysts such as NaOH and KF are such as CH3-, CH3O-CO-, -CO- group; therefore, it has been
known to be highly active for the hydroalkoxylation of used in carbonylation, carbomethoxylation and methylation
fluoroolefins, it is easily conceivable that a basic ionic liquid reactions to substitute phosgene, methyl halides, etc. [123-
could proceed the hydroalkoxylation more effectively than the 126].
neutral ionic liquids, [Emim]BF4 and [Emim]PF6. It is also A procedure for the synthesis of N-heterocyclic
expected that the unique properties of ionic liquids could carbamates from N-heterocycles and dimethyl carbonate
suppress the formation of olefinic side products. catalyzed by ionic liquids was investigated (Scheme 37).
A hydrofluoroether, one of the third generation These ionic liquids had high catalytic activities under mild
chlorofluorocarbon (CFC) alternatives, CF3CH2OCF2CHFCF3 reaction conditions. Furthermore, ionic liquids was recycled
was obtained in high yield and selectivity from the by simple extraction and reused at least four times without any
hydroalkoxylation reaction of hexafluoropropylene and 2,2,2- loss of activity. The activation of carbonyl group of DMC
trifluoroethanol conducted in the presence of an imidazolium- taken by the hydrogen bond interaction between imidazolium
based ionic liquid catalyst such as 1-butyl-3-methyl- cation and the carbonyl oxygen played a dominating role in
665
Hajipour & Rafiee
[bmim]OH
Therefore, the development of facile and environmentally
N DMC N benign methods for synthesis of pyrroles is a necessary part of
H
O organic synthesis [129-130].
O
Scheme 37 Synthesis of tetrasubstituted pyrroles by the three
component condensation reaction of acid chlorides, dialkyl
acetylenedicarboxylates, and amino acids in the presence of
[bmim]OH
O various room-temperature ionic liquids (RTILs) as catalysts in
2RNH2 + CO2 R R + H2O
HN NH water was reported. Among the ionic liquids used, the basic
R= Alkyl, Cyclohexyl, Benzyl
functionalized ionic liquid, butyl methyl imidazolium
hydroxide [bmim]OH, was the most effective catalyst. The
Scheme 38 [bmim]OH/H2O catalyst system was reused for at least five
recycles without appreciable loss of efficiency. The attractive
catalyzing the reaction of indole and DMC [127]. features of this protocol were: simple procedure, short reaction
time, use of cheap and environmentally benign solvent, and
Synthesis of Substituted Ureas reuse of the aqueous media [131].
The synthesis of disubstituted ureas from amines and CO2
were carried out using a basic ionic liquid (IL) 1-n-butyl-3- Synthesis of Highly Functionalized Pyrroles
methyl imidazolium hydroxide ([bmim]OH) as the catalyst Task-specific basic ionic liquid was used as a reusable and
(Scheme 38). The effects of reaction time, amount of green catalyst for one-pot synthesis of highly functionalized
[bmim]OH, reaction temperature, pressure, and solvent on pyrroles in aqueous media (Scheme 39) [132].
yields of the products were investigated. The results indicated
that aliphatic amines, cyclohexylamine, and benzylamine were Synthesis of 4H-Benzo[b]pyran
converted to the corresponding ureas selectively in moderate In recent years, 4H-benzo[b]pyran compounds have
yields under solvent-free conditions without using any attracted much attention due to their wide range of biological
dehydrating regent. The ionic liquid was reused after a simple and pharmacological activities. It has been reported that
separation procedure [128]. benzo[b]pyran derivatives have diverse pharmacological
activities such as anticoagulant, anticancer, spasmolytic,
Syntheses of Heterocyclic Compounds and Tetra- antiancaphylactia, etc. In addition, 4H-benzo[b]pyrans also
substituted Pyrroles constitute the structural unit of a series of natural products.
Pyrrole is one of the most important heterocyclic Considering the importance of these compounds, many
compounds, having become increasingly important in methods for the synthesis of 4Hbenzo[b]pyran derivatives
medicinal chemistry and organic synthesis. Consequently, have been reported successively. The conventional synthesis
numerous procedures have been developed for the involves the condensation of 5,5-dimethylcyclohexane-1,3-
construction of pyrroles. However, some of these methods dione (dimedone) with aromatic aldehyde and malononitrile
often suffer from certain drawbacks such as hazardous organic under refluxing DMF or acetic acid. However, these solvents
solvents, high cost, long reaction time, use of stoichiometric make the workup procedure complicated, lead to poor yields
and even excess amounts of acids because they can be trapped of products, and pollute the environment. The use of
by amine in this condensation, and drastic reaction conditions. microwave and ultrasound irradiation is also reported for the
O O E E
[bmim]OH
R + + E C C E
OH Ar Cl
R N Ar
NH2
H
Scheme 39
666
synthesis of pyrans. benzo[b]pyran derivatives (Scheme 41). The ionic liquid acted
Recently, many methods had been reported for the both as catalyst and reaction medium and was reusable up to
preparation of 4H-benzo-[b]pyrans through two-component or five times without loss of activity [136].
three-component condensation including the use of 4-
dodecylbenzenesulfonic acid, rare earth perfluorooctanoate Hydrogen-Transfer Reduction
(RE(PFO)3), (NH4)2HPO4, NaBr, tetramethyl ammonium Asymmetric transfer hydrogenation of prochiral ketones
hydroxide N-methylimidazole, (S)-proline, etc., as catalysts and imines is an effective method for preparation of optically
had been introduced for the synthesis of 4Hbenzo[b]pyrans. In active alcohols or amines. The most famous catalysts for
spite of the merits of these procedures, each of them suffered asymmetric hydrogen-transfer reaction are Ru(arene)(diamine)
at least from one of the following limitations: low yields, complexes with chiral ligands. In particular, a ruthenium
unavailability of the reagents, long reaction times, effluent catalyst with a chiral ligand such as mono N-tosylated
pollution, harsh reaction conditions, and tedious workup diphenylethylenediamine (TsDPEN; Noyoris catalyst) has
procedures [133-134]. been well studied on a variety of substrates [137-139].
A simple, clean, and environmentally benign three- Attempts to improve the handling and separation of the
component process for the synthesis of 4H-benzo[b]pyran catalyst from the reaction product, and its recycling, have led
derivatives using basic ionic liquid N,N-dimethyl to immobilization of this catalytic system on a variety of
aminoethylbenzyldimethylammonium chloride supports, either inorganic or organic. Noyoris catalyst has
+ -
([PhCH2Me2N CH2CH2NMe2]Cl ) as an efficient catalyst been immobilized on supports such as dendritic polymers,
under solvent-free condition was described (Scheme 40). A silica, polystyrene, or, with hydrophilic function, for biphasic
wide range of aromatic aldehydes easily undergoes catalysis. Noyoris ligand can be immobilized on an ionic
condensation with malononitrile and 5,5- liquid moiety by introduction of imidazolium tags either at the
dimethylcyclohexane-1,3-dione (dimedone) under solvent-free complexed arene or at the tosyl group.
condition to afford the desired products of good purity in Although application of ILs in organic synthesis and
excellent yields. Taking into account environmental and catalysis is a very active area of chemistry, few papers report
economical considerations, the protocol presented here had the use of ILs for hydrogen-transfer reactions.
merits of environmentally benign, simple operation, Several achiral and chiral basic ionic liquids (ILs) were
convenient workup, and good yields [135]. prepared and tested as the medium for Ru-catalyzed hydrogen-
transfer reduction of different aromatic ketones (Scheme 42).
Synthesis of Tetrahydrobenzo[b]pyran Derivatives Hydrogen-transfer reduction of ketones proceeded well in
The task specific basic ionic liquid, [bmim]OH promoted achiral basic ILs using chiral catalysts. The interesting
efficient, green and one-pot synthesis of tetrahydro- observation was made that raising the reaction temperature did
O Ar
O
O CN
CN [PhCH 2Me2N +CH 2CH 2NMe2]Cl-
+ +
Ar H
CN O NH 2
O
Scheme 40
O O R
CN [bmim]OH CN
Me + RCHO + Me
O CN
Me O NH 2
Me
Scheme 41
667
Hajipour & Rafiee
O OH
RuCl2(p-cymene)2/TsDPEN
HCOOH/IL
Br Br
N
ILs: N N N
O
N(SO2CF3)2- N(SO2CF3)2-
Scheme 42
not have a negative effect on enantioselectivity of the reaction. OH

Ru-CHNAP-MgO
O
On the other hand no reaction was observed in chiral ILs. R1 R2 Toluene, O2 R1 R2

Hydrogen-transfer reductions of acetophenones in basic ILs
proceed with comparable enantioselectivity as in neutral or OH
IL: N
acidic ILs, but with lower reaction rate. This means the only
OH -
advantage of basic ILs as the reaction medium in this reaction
was that no external base had to be used, which was beneficial Scheme 43
environmentally [49].
Synthesis of Dimethyl Carbonate
Oxidation Dimethyl carbonate (DMC) is a green chemical that has
The selective oxidation of alcohols to carbonyl compounds been paid too much attention in recent years. It can be
is the foundation of many important industrial and fine- effectively used as an environmentally benign substitute for
chemical processes. Many stoichiometric oxidants are known highly toxic phosgene and dimethyl sulfate in carbonylation
for the oxidation of alcohols such as chromates, hypochlorites, and methylation reaction, as monomer for several types of
permanganates, and others, however many of these oxidants polymers and an intermediate in the synthesis of
are toxicand produce large amounts of wastes [140-141]. pharmaceutical and agricultural chemicals. Also, DMC can be
Much attention is being directed to newer and selective used as a promising octane booster due to its high oxygen
methods of oxidations. Catalytic oxidation with molecular content. Currently, DMC is produced by phosgene and non-
oxygen or air is particularly attractive from economical and phosgene route, but phosgene route is limited for the use of
environmental points of view. toxic phosgene. For the non-phosgene route, DMC is mainly
The design of nanobuilding units consisting of functional prepared by the oxidative carbonylation of methanol and the
metals generates a new class of high performance materials two-step transesterification from epoxide, methanol and CO2
with potential applications in the electronics, space, chemical in the bulk production. However, the oxidative carbonylation
and energy sectors. of methanol suffers from the low production rate, the need for
The selective oxidation of various alcohols into their corrosion resistant reactors, the toxicity and potential
corresponding aldehydes and ketones was achieved by explosion of carbon monoxide.
ruthenium species stabilized on the nanocrystalline Several catalysts, such as inorganic base composites and/or
magnesium oxide (NAP-MgO) by the incorporation of choline basic metal oxide, Re(CO)5Cl/K2CO3, KOH/4A molecular
hydroxide, a basic ionic liquid, in excellent yields (Scheme sieve, n-Bu4NBr/n-Bu3N, [bmim]/BF4, Mg containing.
43). The procedure was simple, efficient and environmentally Smectite, heterogeneous anion exchange resins and inorganic
benign. The catalyst was used for four cycles with almost base/phosphonium halide functionalized polyethylene glycol
consistent activity [142]. etc. have been employed for the one-pot synthesis of DMC.
668
O
O O
IL/MgO OH
CO2 + + CH3OH + O O + OH
O O
(DMC) (PE)
(PC)
Scheme 44
But, most of these systems suffer from several drawbacks such DBU, or piperidine, is required, which causes an additional
as lower activity and selectivity to DMC, difficult recycle of environmental burden. Moreover, ionic liquids have been
these catalysts and rigorous reaction conditions from a proven to be excellent media for syntheses of nanoparticles,
practical point of view. nanorods, and nanowires, whose preparation include chemical
The basic ionic liquid choline hydroxide, supported on reduction of transition-metal salts with various reagents, e.g.,
MgO to form Choline hydroxide/MgO material used as a hydrogen, hydrazine, borohydrides, or alcohols, in the
catalyst in one-pot synthesis of dimethyl carbonate from presence of stabilizers, such as special ligands, polymers, or
propylene oxide, methanol and carbon dioxide (Scheme 44). A surfactants of the type R4N+X-. There are few reports where
good catalytic performance was obtained with 98% conversion amines are used as reducing agents.
of epoxide and selectivity of above 90% to DMC + PC over Basic ionic liquid serve as both the solvent and base for
the composite catalyst. However, the catalyst was reused three Heck, copper-free Sonogashira reactions, and for
times without a significant change in its catalytic activity [73]. homocoupling reactions of terminal alkynes. The ionic liquids
with tertiary aliphatic amines are effective solvents for these
Carbon-Carbon Bond Formation Reactions reactions. Under reflux conditions, eight equivalent basic ionic
The Heck reaction has been studied extensively in ionic liquids and Pd(OAc)2 in THF or acetone produced palladium
liquids, where PdII complexes or Pd0 nanoparticles act as colloids with diameters of (2.6 0.3) or (3.7 0.5) nm,
catalysts. Catalytic cycle of palladium colloids described in respectively.
Heck reactions: a palladium precursor can act as a reservoir The Heck reaction of iodobenzene and butyl acrylate was
for a catalytically active Pd0 species (Pd colloids or highly conducted in ionic liquids 1-8 at 110 C with the use of 1 mol-
active forms of low coordinated Pd0 species) that undergoes % palladium acetate as the catalyst (Scheme 45). After eight
oxidative addition of the aryl halide on the surface with hours, almost quantitative conversions and selectivity were
subsequent detachment to generate a homogeneous PdII found when ionic liquids 1, 2, and 3 were used as solvents.
species. The main catalytic cycle is initiated by oxidative The reaction became much slower with the use of 5 or 7,
addition of iodobenzene to the Pd0 species, which is followed whereas no reaction occurred in 4, 6, or 8, where the nitrogen
by the reversible coordination of the olefin to the oxidative base was weaker. These results indicated that for Heck
addition product. The Pd0 formed in the main catalytic cycle, reactions the ionic liquids having aliphatic tertiary amine
after hydride and reductive elimination steps, can either pendants were superior to the ones substituted with pyridine
continue in the catalytic cycle or fall back to the nanoparticles functionality. The catalytic system described above was
reservoir [143]. readily recovered for further use simply by washing with a
In these cases, a base, such as K2CO3, NaHCO3, NaOAc, NaHCO3 solution. After five recycles, no obvious loss in
triethylamine, or tetrabutylammonium acetate, etc., must be catalytic activity was observed. By using 3 and 5, owing to
added. Although the consumption of one equivalent of base is their strong affinity for the product, a lengthy procedure was
inevitable, a basic ionic liquid acting as both the solvent and required to extract the product totally from the ionic liquid
base would make the procedure much easier to handle. This is phase. Because 2 was a liquid with low viscosity at room
essentially important for Sonogashira reactions where temperature, it was chosen as the solvent for C-C bond
normally a large excess of organic base, e.g. triethylamine, formation reactions, e.g. Heck and Sonogashira reactions, and
669
Hajipour & Rafiee
O
O
IL, Pd(OAc) 2
I + OBu
OBu
ILs: N N
N N N N
N N N Bu
X- N
NTf 2- NTf 2-
1 X=PF6 3 4
2 X=NTf 2
N N
CH 2 N N Bu N N 2 NTf 2- N N
N
N N - N NTf 2-
NTf 2
NTf 2- N N
5 6 8
7
Scheme 45
Knoevenagel condensations [50]. hydroxide hydrate and an alcohol. Chemical warfare agents
and simulants show in Scheme 46.
Decontamination Reactions The decontamination reactions occurred rapidly resulting
Despite the greatly reduced threat of Cold War superpower in alcoholysis, hydrolysis, and dehydrohalogenation processes.
confrontation, the threat of chemical, biological, radiological, These preliminary results suggested that alcoholic solutions of
and nuclear attack remains serious and credible. There is now tetraalkylammonium hydroxide hydrates in ionic liquids was
renewed interest to develop biological and chemical reaction provide a multipurpose chemical warfare agent
systems to neutralize a variety of chemical warfare agents decontamination reaction matrix that was very effective, did
(CWAs). These interests center on establishing rapid and not involve aqueous systems, and produced reaction products
reliable decontamination processes for the nerve agents Sarin that was isolated from the environmental Base-catalyzed
(GD) and VX and for the blister agent sulfur mustard (HD). dehydrohalogenation of CEPS show in Scheme 47 [145].
Established criteria asserted that, for a
decontamination/neutralization process to be effective, it must O-Acetylation of Alcohols and Carbohydrates
be rapid, generate nontoxic reaction products, and be Hydroxy group O-acetylation is used extensively in
contained in a medium that is environmentally safe [144]. carbohydrate chemistry as a protection strategy, and for the
Increased acts of international terrorism called for the isolation and identification of sugars. The standard O-
development of rapid and reliable chemical agent acetylation reaction uses acetic anhydride as the primary
decontamination reactions to minimize human exposure and reagent and a wide range of solvents and catalysts. Pyridine is
material loss. Even though many chemical reaction processes the most widely used solvent/catalyst for the acetylation of
had been reported, most remain unattractive for various saccharides even though it is known to have acute toxicity.
reasons. The chemical warfare agent simulants Derivatives of pyridine such as 4-(dimethylamino)pyridine
diisopropylfluorophosphate (DFP), bis(2-ethylhexyl) and 4-(1-pyrrolidino)pyridine also catalyze the acetylation, in
phosphate (BEHP), and CEPS were readily decontaminated in some cases faster than pyridine. Sodium acetate is also
a single reaction matrix comprising a binary ionic liquid commonly used as a catalyst in the acetylation of D-glucose it
solvent composed of 1,2-dimethyl-3-propylimidazolium yields exclusively the diacetylated product. Other reagents that
bis(trifluoromethylsulfonyl) amide and a tetraalkylammonium have been shown to catalyze acetylation of saccharides by
670
O O O
S
O P O P O N P
F F OCH 2CH3
GB (sarin) DFP (sarin simulant)

VX (V-agent0
S
S Cl
Cl Cl
Scheme 46
O O O O
S S ILs
Cl CH3OH O
+ ROH R +
O OH
TMAH/DMPITf 2N
Scheme 47 ILs: N N N N
N
N
acetic anhydride include: Lewis/Brnsted acids such as ZnCl2, C C N
C C
N
N N
HClO4, FeCl3, H2SO4, iodine, heterogeneous catalysts such as
tetrabutylammonium bromide-NaOH, anionic surfactants, Scheme 48
Montmorillonite K-10, H-beta zeolite, zirconium sulfophenyl
phosphonate and enzyme catalysts such as lipases. A variety ionic liquid and acetic anhydride, even in the absence of any
of other reagents used to catalyze O-acetylation of alcohols are other catalyst. Polyhydroxylated compounds such as N-
also known [146]. acetylneuraminic acid, sucrose and raffinose were also
Basic ionic liquids used as catalysts in the context of the completely acetylated within 24 h at room temperature. An
base catalyzed acetylation of alcohols including glucose. This increase in the reaction temperature is expected to speed up
was a widely used means of protecting alcohol groups which the reaction rate for the complex saccharides by increasing
is conventionally performed using acetic anhydride and a base their solubility in the ionic liquids [52].
catalyst in a traditional solvent. There were a wide range of
solvents and catalysts commonly utilized for the O-acetylation Absorption of Sour Gases
reaction of carbohydrates; for example pyridine was a From the wide range of applications envisioned for ionic
commonly used solvent/catalyst, despite considerable safety liquids, such as catalysts for acid-catalyzed organic reactions,
concerns. hydrosilation processes, lubricants, performance additives,
Dicyanamide-based ionic liquids behaved as effective media for metal-catalyzed reactions, their use as CO2-selective
solvents and also as active base catalysts in the O-acetylation separation media for capture/sequestration of sour gases like
reactions of alcohols and carbohydrates using acetic anhydride CO2, H2S and SO2 was one of the most exciting and of
(Ac2O), with no additional base catalyst in some cases increasing interest.
(Scheme 48). They were low-viscosity solvents that dissolve a The development of improved, highly efficient and
wider range of inorganic and organic compounds including economically viable separation and storage processes was
unprotected saccharides as compared to other imidazolium gaining a special interest both by academia and industry.
ionic liquids with bis(trifluoromethanesulphonyl)amide [Tfsa], Nonetheless, and despite of the promising properties of ionic
Cl-, PF6- and BF4- anions. liquids, further research was required in order to make this
A number of simple alcohols such as 2-naphthol and t- neoteric solvents feasible candidates for these applications.
butyl alcohol were readily acetylated using a dicyanamide Being a key parameter in the design of equilibrium stage-
671
Hajipour & Rafiee
and rate-based separations, reliable gas solubility data was of sulfonates, fluorinated sulfonates, imides, borates, chloride
great interest and a fundamental step towards the development [147].
of industrial applications, either by the data itself or by Ionic liquids comprising cations that contain Lewis basic
developing predictive and simulation tools to aid in such groups were also used in reference to storing gases having
applications development. The absorption of sour gases was Lewis acidity. Examples of Lewis basic cations included N,N-
one of the processes that were enhanced by the basic character dialkylimidazolium and other ring with multiple heteroatom.
of the ionic liquid [46]. A Lewis basic group was also part of a substituent on either
the anion or cation. Potentially useful Lewis basic substituent
Gas Storage groups included amine, phosphine, ether, carbonyl, nitrile,
Many processes in the semiconductor industry require a thioether, alcohol, thiol, etc. [47].
reliable source of process gases for a wide variety of
applications. Often these gases are stored in cylinders or Electrochemical Applications
vessels and then delivered to the process under controlled Oxidation of Sn(II)/Sn(V). Room temperature ionic
conditions from the cylinder. The semiconductor liquids are expected to be the alternative media for various
manufacturing industry, for example, used a number of practical electrochemical processes, because they possess wide
hazardous specialty gases such as phosphine (PH3), arsine electrochemical potential windows, acceptable ionic
(AsH3), and boron trifluoride (BH3) for doping, etching, and conductivity, high thermal stability and negligible vapor
thin-film deposition. These gases pose significant safety and pressure. In EmiCl-AlCl3 ionic liquids, the oxidation of Sn(II)
environmental challenges due to their high toxicity and to Sn(IV) was possible in a basic ionic liquid but not in an
pyrophoricity (spontaneous flammability in air). In addition to acidic one, probably because tetravalent species was stabilized
the toxicity factor, many of these gases are compressed and by the complex formation with chloride ions in the basic ionic
liquefied for storage in cylinders under high pressured. liquid [148].
Storage of toxic gases under high pressure in metal cylinders Lithium electrochemistry. One key area of research was
is often unacceptable because of the possibility of developing the development of IL-based electrolyte materials for lithium
a leak or catastrophic rupture of the cylinder. ion rechargeable batteries, fuel cells, capacitors, solar cells,
In order to mitigate some of these safety issues associated actuators, and so on. Since ionic liquids were composed only
with high pressure cylinders, on-site electrochemical of ions, they were realized high ionic conductivity, often over
generation of such gases has been used. Because of difficulties 10-2 S cm-1 at room temperature. In most cases, however, such
in the on-site synthesis of the gases, a more recent technique electrolyte applications needed target ion transport, for
of low pressure storage and delivery systems has been to instance, lithium ions in the case of lithium batteries, since the
adsorb these gases onto a solid support. These storage and IL component ions were inert to typical electrode processes.
delivery systems suffer from poor capacity and delivery Therefore, it was necessary to add these ionic species to the
limitations, poor thermal conductivity, and so forth. ILs. Unfortunately, the addition of target ions, especially the
Gases having Lewis basicity to be stored and delivered lithium ion, generally brings about a decrease of ionic
from Lewis acidic reactive liquids, e.g. ionic liquids, may conductivity and an increase in viscosity induced by the strong
comprise one or more of phosphine, arsine, stibine, ammonia, electrostatic interactions of the lithium ion.
hydrogen sulfide, hydrogen selenide, hydrogen telluride, basic In ILs based on aliphatic and alicyclic ammonium cations,
organic or organometallic compounds, etc. which were very stable electrochemically, dissolved lithium
With reference to Lewis basic ionic liquids, which are salts was reversibly deposit and strip lithium metal.
useful for chemically complexing Lewis acidic gases, the Furthermore, when a zwitterion was added to the IL/lithium
anion or cation component or both of such ionic liquids can be salt mixture as a salt dissociator, the coulombic efficiency of
Lewis base and in some cases, both the anion and cation are the electrolyte system was significantly improved. An IL
Lewis basic, such as carboxylates, fluorinated carboxylates, containing a cyano substituted cation used as a lithium battery
672
electrolyte. Interestingly, the cyano IL showed slightly higher kinetic or engineering data had been extended continuously,
ionic conductivity after the addition of LiTFSA. Thus only little data with regard to the toxicity and ecotoxicity of
according to these results, the incorporation of a functional ionic liquids have been available until now. The green
group that promoted dissociation of the lithium salt seems an character of ionic liquids has usually been justified with their
attractive way forward in the design of new ILs for lithium negligible vapor pressure, but even if ionic liquids will not
batteries. evaporate and will not contribute to air pollution most of them
Lewis-base ionic liquid (IL) based on mono-charged 1,4- are water soluble and might enter the environment by this path
diazabicyclo[2.2.2]octane (dabco) with bis(trifluoro- (e.g. accidental spills, effluents).
methanesulfonyl)amide (TFSA) anion showed a surprisingly Experimental studies have been helpful in establishing
wide electrochemical window of over 4 V and was able to general guidelines for the selection of ILs with low potential
deposit and strip lithium from a nickel substrate. Further for toxicity. However, relatively little is still known about the
exploration of Lewis-base ILs will open up new pathways for toxicity of these materials as a class, especially when
IL electrolytes to improve both the target ion transport and compared to conventional organic solvents. Several recent
electrochemical stability [74]. toxicity studies have documented IL effects on organisms and
Electrochemical study of transition-metal ions following results obtained.
chemistry in BILs. Transition-metal ions form very stable Polymeric materials with pyridinium functionality can
anionic chloro complexes in basic ionic liquids BPC (1-n- exhibit significant toxicity to bacteria. Antimicrobial activity
butylpyridinium chloride)-AlCl3 or basic EmiCl (l-methyl-3- increased as the alkyl chain length increased on pyridinium,
ethylimidazolium chloride)-AlCl3. imidazolium, and quaternary ammonium salts [151].
Basic ionic liquids BPC-AlCl3 or basic EmiCl-AlCl3 were Many ILs are similar to cationic surfactants, which are
excellent solvents in which to study the solution chemistry of known to induce polar narcosis due to their ability to be
transition-metal chloride complexes at room temperature since incorporated into biological membranes. Therefore, longer
the solvation and solvolysis reactions commonly associated alkyl chains may be incorporated into the polar head groups of
with these complexes in aqueous solution were absent in the the phospholipids bilayer, which are the major structural
melts. components of membranes. Narcosis then results because
Some of the factors that were believed to contribute to the membrane-bound proteins are disrupted by the toxicant.
unusual stability of these species in these ionic liquids relative Many of the imidazolium and pyridinium compounds were
to other solvents include the absence of both the solvation and more toxic than common high-volume solvents such as
solvolysis reactions encountered in molecular solvents and the acetonitrile, acetone and methanol. Some exceptions include
thermally promoted dissociation and disproportionation low alkyl chain length quaternary ammonium ILs and those
reactions associated with high-temperature molten salts. ILs containing choline as the cation, which were relatively
A number of first-row transition-metal chloride complexes nontoxic. The data suggest that choline or quaternary
had been investigated in room-temperature chloroaluminate ammonium solvents may be more environmentally friendly
melts, including cobalt(II), copper(I) and copper(II), iron(II) alternatives than both aromatic ILs and some traditional
and iron(III), nickel(II), and titanium(III) and titanium(IV), industrial solvents.
while studies with second- and third-row transition-metal ions Varying the anion has a minimal effect on the toxicity of
have been limited to silver(I), molybdenum(III) and pyridinium and imidazolium salts, which suggests that toxicity
molybdenum(IV), ruthenium(III) and ruthenium(IV), and is largely driven by the cation, although recent studies indicate
tungsten(III) through tungsten(V) [69,149-150]. that the anion can play a role in toxicity.
Toxicity was predicted to increase slightly with the number
TOXICITY OF IONIC LIQUIDS of nitrogen atoms having two aromatic bonds and one single
bond. Thus ammonium cations are less toxic than pyridinium
Although the information about physical, thermodynamic, cations, which are slightly less toxic than imidazolium cations.
673
Hajipour & Rafiee
If true, this would mean that triazolium-based ILs would be and etc.
even more toxic than imidazolium-based compounds. The IL Using bases such as NaOH, KOH, K2CO3 and etc. in base-
toxicity should decrease as the number of negatively charges catalyzed reactions have numerous disadvantages such as
atoms on the cation increases. waste production, corrosion and no catalyst recovery.
Although anions play a secondary role in determining However ionic liquids offering a new possibility for
toxicity, the results indicate that the presence of positively developing environmental friendly basic catalysts regard to the
charged atoms in the anion leads to higher toxicity than those combination of the advantages of inorganic bases and ionic
systems with a single negative anion atom. The correlations liquids. Therefore basic ionic liquids exhibited great potential
also indicate that methylating the aromatic ring of the cation for the replacement of conventional basic catalysts because
should reduce toxicity [152-154]. they are flexible, nonvolatile, noncorrosive, and immiscible
with many organic solvents.
COST AND LIFE CYCLE OF BASIC IONIC
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cost-effective, mild, easily separable, and reusable has long 3753.
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J. Iran. Chem. Soc., Vol. 6, No. 4, December 2009, pp. 647-678.

Basic Ionic Liquids. A Short Review

A.R. Hajipoura,b,* and F. Rafieeb

(Received 17 September 2009, Accepted 14 October 2009)

INTRODUCTION The use of ionic liquids as reactions medium may offer a

organic layer was dried with Na2SO4. After evaporation of the

recrystallized from isopropanol to give the compound as a

Synthesis of 1-Ethyl-4-aza-1-azoniabicyclo[2.2.2] 1-Octyl-4-aza-1-azonia-bicyclo[2.2.2]octane Bis(tri-

composites [76-79]. [bmim]OH

condensation without requirement of any organic solvent. A

and cost-effectiveness. Another attractive feature of this R1

methodology was the use of ionic liquid as catalyst as well as O Y

the corresponding coumarin was obtained in one pot in very

Using the basic ionic liquid without solvent produced a

OH- Michael Reaction

EWG = CN, COMe, CO2Me

The aza-Michael reaction is an important reaction in R2

excesses of reagents, and/or highly damaging chemicals. In Cat, ionic liquid

environment on the reactivity. The calculated results showed Ar H

anion-H2O complex, and the cation improved the electrophilic

carbon bond-forming reactions in organic synthesis and have O O Ar 1

Hydrolysis of Propylene Carbonate to 1,2-Propylene O

SIL1 SIL2 SIL3

CF3CH2OH + CF3CF=CF2 CF3CH2OCF2CHFCF3 3

not have a negative effect on enantioselectivity of the reaction. OH

On the other hand no reaction was observed in chiral ILs. R1 R2 Toluene, O2 R1 R2

GB (sarin) DFP (sarin simulant)

Dyson, Chem. Eur. J. 10 (2004) 4886. press (2009).

Res. (S) 228 (1999). Tetrahedron Lett. 45 (2004) 6787.

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