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Green Chemistry Letters and Reviews


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Recent advances in ionic liquids: green unconventional solvents of this century: part I
Suresh & Jagir S. Sandhu
a a a

Department of Chemistry , Punjabi University , Patiala, 147002, Punjab, India Published online: 19 May 2011.

To cite this article: Suresh & Jagir S. Sandhu (2011) Recent advances in ionic liquids: green unconventional solvents of this century: part I, Green Chemistry Letters and Reviews, 4:4, 289-310, DOI: 10.1080/17518253.2011.572294 To link to this article: http://dx.doi.org/10.1080/17518253.2011.572294

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Green Chemistry Letters and Reviews Vol. 4, No. 4, December 2011, 289310

RESEARCH REVIEW Recent advances in ionic liquids: green unconventional solvents of this century: part I
Suresh and Jagir S. Sandhu*
Department of Chemistry, Punjabi University, Patiala 147002, Punjab, India (Received 23 October 2009; final version received 11 March 2011) The present overview describes ionic liquids as alternate, attractive solvents of today and tomorrow in organic synthesis. Since this subject is too wide and developments have been too fast, only a recent account is presented on indispensable carbon-carbon bond forming named reactions such as Knoevenagel, Michael Aldol, Biginelli Reaction, and so on, which has never been done before exclusively.

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Keywords: ionic liquids; Aldol reaction; Knoevenagel reaction; Michael reaction; Biginelli reaction; green chemistry

Introduction There have been fast developments in all spheres of our society and these are interwoven with problems related to environmental pollution. Certainly, access to advanced materials and their preparation processes were great contributions to these developments (1). A good amount of contributions to these problems come from chemical/material developments. Thus, overall alarming environmental pollution prompted the government of the United States (2, 3) to issue an act (Pollution Prevention Act, 1990). This provided an impetus to other countries and arose worldwide concern and in the scientists playing a significant role in developing pollution-free methodologies/processes (4, 5). Significant approaches are listed below:
. . . . . . Supercritical liquids Biodegradable materials Catalysts selection/developments Biological process Ionic liquids Last but not least avoiding organic solvents

All the above areas contributed significantly to the development (633) of green chemistry. Twelve principles of Green Chemistry were laid down by Paul Anastas and John Warner (34) as follows:
(1) Prevention: It is better to prevent waste than to treat or clean up waste after it has been created. (2) Atom economy: Synthetic methods should be designed to maximize the incorporation of all materials used in the process into the final product.

(3) Less hazardous chemical syntheses: Wherever practicable, synthetic methods should be designed to use and generate substances that possess little or no toxicity to human health and the environment. (4) Designing safer chemicals: Chemical products should be designed to effect their desired function while minimizing their toxicity. (5) Safer solvents and auxiliaries: The use of auxiliary substances (e.g. solvents, separation agents, etc.) should be made unnecessary wherever possible and innocuous when used. (6) Design for energy efficiency: Energy requirements of chemical processes should be recognized for their environmental and economic impacts and should be minimized. If possible, synthetic methods should be conducted at ambient temperature and pressure. (7) Use of renewable feedstocks: A raw material or feedstock should be renewable rather than depleting whenever technically and economically practicable. (8) Reduce derivatives: Unnecessary derivatization (use of blocking groups, protection/deprotection, temporary modification of physical/chemical processes) should be minimized or avoided if possible, because such steps require additional reagents and can generate waste. (9) Catalysis: Catalytic reagents (as selective as possible) are superior to stoichiometric reagents. (10) Design for degradation: Chemical products should be designed so that at the end of their function they break down into innocuous degradation products and do not persist in the environment. (11) Real-time analysis for pollution prevention: Analytical methodologies need to be further developed to allow for real-time, in-process monitoring and control prior to the formation of hazardous substances.

*Corresponding author. Email: j_sandhu2002@yahoo.com


ISSN 1751-8253 print/ISSN 1751-7192 online # 2011 Taylor & Francis http://dx.doi.org/10.1080/17518253.2011.572294 http://www.tandfonline.com

290

Suresh and J.S. Sandhu Because of these attractive properties, ILs are employed in a broad area of applications listed below (4671):
(1) Solvent extraction (46); (2) Physico-chemical processes (47); (3) ILs as media for nucleophilic substitution reactions (47); (4) As mobile phase modifier in HPLC (48); (5) Electrodeposition of metals and semiconductors in ILs (49); (6) Chemical analysis (50); (7) Dye-sensitized solar cells (51, 52); (8) ILs for the nuclear fuel cycle: electrodeposition and extraction (53); (9) Nuclear-based separations (54); (10) Oil shale processing (55); (11) Separation of petrochemical relevance (56); (12) Synthesis of functional nanoparticles and other inorganic nanostructures (57); (13) ILs as solvents for electrochemistry (58); (14) ILs as solvents for polymerization processes (59); (15) Chemical and biochemical transformations (60); (16) materials chemistry (61); (17) Biocatalysts in ILs (6271).

(12) Inherently safer chemistry for accident prevention: Substances and the form of a substance used in a chemical process should be chosen to minimize the potential for chemical accidents including releases, explosions, and fires.

Ionic liquids fulfill all conditions of green chemistry required of green solvents; prominently, they are not volatile and several of them are recyclable and do not leave any hazardous wastes on work-up. Ionic liquids (ILs) background

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Keeping in mind the above principles of green chemistry, ILs have attracted much attention in the scientific community (chemists, biologists, and other related workers) during the past two decades or so. Here, in this mini review we are presenting recent developments (e.g. 1999 to 2009 also if scanty work is there deviations are made) in selected carbon-carbon bond forming reactions such as Knoevenagel, Michael Aldol, Biginelli Reaction, and so on. Before we proceed further, we provide some background information about these new solvents promoted as future green solvents of the present century. Historically, ILs are mentioned as molten salts and this dates back to 1914 or even before (35), when the first ionic liquid was reported. However, its earliest use was as a propellant in warfare specifically ethylammonium nitrate. Though there are no hard and fast rules layed down, there are considered to be ionic salts substances having a melting point up to 1008C. They are certainly advocated to have the following properties, which have generated a voluminous body of research (3645):
(1) Unlike conventional solvents, they are not volatile and do not have any vapor pressure; (2) They are stable over a long temperature range; (3) They can be called universal solvents, as they can dissolve a range of organic compounds; (4) They can dissolve even gases like H2, CO, O2, and CO2. They can be used even under supercritical CO2; (5) In ILs, the solubility determining factors are cations and anions of which these are composed; (6) They do not participate in co-ordination with metal complexes, macrocycles like enzymes, etc; (7) Mainly, the ionic character of ILs accelerates the rate of reaction even under MW irradiations; (8) They are stable and can be stored without decomposition for a long time; (9) ILs have found extensive use in the control of stereoselectivity. (10) The viscosity of ILs derived form imidazoles can be manipulated by variations in branching.

There are many types of ILs available commercially and some of these that are conveniently available and used in organic synthesis. The following selected classes are given below as a reference for the readers and some of these are often used in the reactions presented in this paper. Ionic liquids classification Ionic Liquids-Anions A) Borate: I. Tetracyanoborate TCB: [B(CN)4]  II. Tetrafluoroborate TFB: [BF4]  III. Oxalatoborate BOB: [B(C2O4)2]  B) Dicyanamide DCN: [N(CN)2] C) Halide: Br , Cl , F, I  I. Bromide: Br II. Chloride: Cl  III. Fluoride: F IV. Iodide: I  D) Bis(trifluoromethylsulfonyl)imide NTF: [N(SO2CF3)2] E) Nonaflate NON: [C4H9SO3]  F) Phosphate I. Alkylphosphate II. Fluoroalkylphosphate FAP: [(C2F5)3PF3]  III. Hexafluorophosphate HFP: [PF6]  G) Sulfate HSO4: [HSO4] , and Alkylsulfate: [RSO4] 

Green Chemistry Letters and Reviews H) Sulfonate I. Methanesulfonate MSO: [CH3SO3] II. Tosylate TOS: [CH3C6H4SO3] III. Trifluoromethanesulfonate OTF: [CF3SO3]  I) Thiocyanate SCN: [SCN] J) Tricyanomethide TCC: [C(CN)3]  http://www.merck-chemicals.com/1-butyl-3methylimidazolium-tricyanomethane/MDA_ CHEM-490330/p_Klmb.s1OrfMAAAEj0Fg LFwSw F) Piperidines MOEMPIP:
CH3 + N O CH3

291

G) Pyridiniums PYR:

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Ionic Liquids-Cations A) Ammoniums N(R,R1,R2,R3):


R + N R1 R3
H2N C H2N

H) Pyrrolidines MPL:
H3C R N
+

R2
+

B) Guanidiniums GUA:
NH2

I) Sulfones
CH3 S H3C
+

C) Imidazoles MIM: I. Disubstituted Imidazoles


H3C N
+

CH3

II. Trisubstituted Imidazoles


CH3 H3C N
+

D) Morpholines MOEMMO:
CH3 + N O O CH3

Apart from the areas mentioned in the forgoing pages there are special reviews and even journals devoted to developments in organic synthesis (72 85). The authors are presenting the latest developments using ILs in the following named reactions of organic chemistry, which has never been done by previous reviewers exclusively. This paper also includes the authors own work in the area of green chemistry
Aldol reaction Knoevenagel reaction Michael reaction Biginellli and Hanstzch reaction (combination of Knoevenagel and Michael) . Other related ones like Doebnor modification . . . .

E) Phosphoniums PH3T:
H3C [ ]4 + [ ]4 CH3

Aldol reaction Among carbon-carbon bond forming reactions in organic chemistry, the Aldol reaction (Scheme 1) is the most popular for this process; it was discovered by Charles-Adolphe Wurtz and A. P. Borodin
O O OH IL Me Me R Me O

H3 C

[ ]12

[ ]4 CH3

R H

R = Ph, 4-O2NC6H4, 2-O2NC6H4, 4-BrC6H4, 4-MeC6H4, i-Pr, 3-O2NC6H4.

Scheme 1. Simple Aldol reaction using Ils.

292

Suresh and J.S. Sandhu


EWG1 EWG2 R1 Cat. -H2O RHC R2

RCHO

was used, though less studied but there are a few cases such as this reaction, being carried (142) in ionic liquids [Bmim]BF4 and [Bpyr]BF4 (I & II) to synthesize ab-unsaturated carboxylic acid. Michael reaction The discovery of this reaction dates back to 1883; it was generalized by and named after Arthur Michael (143145). The reaction is very similar to the Knoevenagel reaction and in conventional chemistry, in both the reactions, similar solvents and catalysts have been employed and volumous research work reported and both seem complementary to each other. Precisely, Knoevenagel is 1-2 and Michael is 1-4 conjugate addition (Scheme 5) on to carbonyl and electron deficient alkenes, respectively. In pursuit of green chemistry, here also the authors made considerable contributions in developing some environmentally benign protocols using non-polluting catalysts and replacing volatile organic solvents (VOCs) under solvent-free conditions. Already reported by the authors are catalysts like BiCl3, Cu(II), alumina, and so on (146151), efforts to obtain solvent-free mild catalyst are much reported by the authors. ILs being solvents of the present, their recent progress is given here. Biginelli and Hanztsch reactions Development of environmental benign protocols can be briefly characterized as time saving, pollution free, and reducing reaction steps (novel nomenclature for these is multi-component reactions MCRs); clearly these are prominent steps toward green chemistry. These two reactions are selected since they are now three well-developed component reactions and also they are a combination of previously discussed two reactions, viz., Knoevenagel followed by Michael so both are tandem/cascade reactions (Scheme 6). The following scheme presenting a plausible reaction scheme for the Biginelli reaction is accepted today. Here, urea, acetoacetic ester, and aldehydes are employed (see Scheme 7) as a three component one

Scheme 2. Acid catalyzed Knoevenagel reaction.

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independently in 1872 and thus have a long history (8688). Aldol, when dehydrates, yields ab-unsaturated ketones called chalcones and is known as the ClaisenSchmidt reaction. In both these reactions the present authors, while looking for greener procedures/processes, have developed the use of Al(III) and Bi(III) (89). However, the use of ILs in this reaction is of latest interest and is discussed below. Knoevenagel reaction This reaction represents an efficient way of producing carbon-carbon double bonds and was discovered back in 1894 by Knoevenagel (101103). The conventional Knoevenagel reaction (Scheme 2) has been reported in several reviews and monographs; however, the use of ILs in this reaction is recent. In the pursuit of developing green chemistry we did make considerable efforts for solvent free and also milder Lewis acids catalysts developments such as LiBr, CdI2, BiCl3, KI, Alum (104108), and so on. Evidently, these were milder processes than the earlier reported ones employing strong Lewis acids or strong organic bases. No doubt that ILs are of current interest for use in this reaction and developments are given below. Doebner condensation/modification Doebner condensation is a modified version of Knoevenagel reaction and pyridine or piperidine type catalysts have always been used to produce unsaturated acid from aldehydes and malonic acids (Scheme 3 and 4). Evidently, these catalysts are harmful to humans. In pursuit of green processes, the present authors used BiCl3 as a mild catalyst (141). In IL this reaction

O OH H Cat. H R1 R2 R3

+
OH O

OH

R1 R2

R3

Scheme 3. Base or acid catalyzed Doebner modication.

Green Chemistry Letters and Reviews

293

Scheme 4. IL catalyzed Doebner condensation.

I & II

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O X R

O Y

H2C

EWG

IL/Catalyst X YOC

R EWG

Scheme 5. Michael reaction employing a variety of catalysts.

pot synthesis. For detailed accounts of both these reactions see the most recent accounts (161, 162). Though conventional Biginelli involves aldehydes, urea, and active methylene compounds, authors demonstrated that even ketones can participate in this reaction affording unconventional Biginelli compounds in excellent yields (163).

As usual, organic reactions are named after their discoverers. In conventional preparative methods of Biginelli compounds and Hanstzch pyridines, hundreds of papers have been published employing green, mild Lewis acids. The authors made considerable efforts in developing green process/procedures for these reactions as well. As such, the authors made significant contribution for finding green reactions/ protocols and demonstrated the efficacy of LiBr, Cu, Ni, Ga(III), lactic acid, and their salts in solvent-free conditions too (164168). Certainly, these were milder Lewis acids than the ones used conventionally earlier, as there were no corrosive side products or waste formed during aqueous work-up so these were

R R CH N H 8 R H3C NH HO H3C N H 10 O -H2O H3C N H 2 O R'O2C NH R 9


+

R'O2C NH OR'

+
NH2 H3C O H2N O

Scheme 6. A plausible reaction pathway of Biginelli reaction.

O CHO O

CH3

+
R

H2N

NH2

Catalysts Solvents N H

NH

Scheme 7. Ketone instead of 1,3-dicarbonyl employed Biginelli reaction.

294

Suresh and J.S. Sandhu


NO2

greener protocols. The use of ILs in combination with mild Lewis acids is a fertile area of research and systematic developments are given below. Hantzsch reactions Historically 1, 4-dihydropyridine 1 preparation is described by Arthur Hantzsch more than a century ago (190, 191). Exploration of these pyridines initially were quite slow, later it picked up very fast because of their structural resemblance to reduced nicotinamide adenine dinucleotide (NADH) 2, which is an established hydrogen transferring agent in biological processes (192). Clearly, the Hantzsch pyridines are a subset of the co-enzyme 2.
CONH2 O
O R O Me N H Me
1

O H3C H3CO2C O CH3

CH3 N

H3C

N H

CH3

. HCl

(Bec/Sapresta, Maruko Seiyaku, Japan, 1996)

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NH2 N O O P OH H OH H O H O CH2 O H H H OH N N O P OH N

O OR
1

N H

H2C H

OH HO

These pyridines are commonly called Hantzsch pyridines and the reaction is called Hantzsch reaction. The original synthesis reported by Hantzsch is three components coupling reaction in refluxing ethanol, which involved acetoacetic ester, benzaldehyde, and ammonia (Scheme 8). Evidently, the first step is Knoevenagel followed by Michael, and later on cyclization incorporating in the ring system (Scheme 9). For a detailed account and mechanism see (193). Since these molecules had great significance to biologists, they are taken to be privileged molecule of chemistry (possessing more than one activity) and their use in clinical practice attracted much attention of chemists to develop greener production process. Present authors also made effective contribution in this direction (194, 195). Some selected examples of these molecules in clinical use are presented below. As such there are more than two dozen drug molecules in clinical use from this family. Needless to say, a similar number is under development stage as anti-hypertensive agents (196, 197). For a selection see below: Lercanidipine (Lerdip, Recordati, Italy, 1997) Aranidipine

O H3C O O H3C N H

NO 2 CO 2CH3

CH3

Cilnidipine (Cinalong or Siscard, Fujirebio, Japan, 1995)


NO2

O MeO O

H3C

N H

CH3

Efonidipine Hydrochloride Ethanol (Landel, Nissan chemical, Japan, 1994)

Green Chemistry Letters and Reviews


NO2

295

Cl
CH3 O H3C P O O H3C N H CH3 O N O

O H3C O

Cl O O CH3

.HCl. EtOH
Nilvadipine
NO 2

H3C

N H

CH3

(Plendil, Astra, Sweden, 1988)

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CH3

O CH3

Nifedipine (1977)
O

H3C

H (Nivadil, Fujisawa, Japan, 1989) Isradipine (Prescal, Sandoz, Switzerland, 1989)

H3C

CN

NO2 H3COOC COOCH3

N O CH3 H3C O O N O CH3 O

H3C

N H

CH3

H3C

N H

CH3

Naturally, because of commercial significance of Hantzsch 1,4-dihydropyridine (DHP), ILs are used

Felodipine
Ar O H5C2O
H3C

CHO

O OC2H5 O CH3 H5C2O

Ar

O OC2H5

+
O NH4OH

H3C

N H

CH3

Scheme 8. Synthesis of Hantzsch pyridine.


O O CH3 ArCH OC2H5 O 4 H3C OO 3 CH3 H3C OC2H5 H5C2O OC2H5 NH3 H5C2O H3C H2N OH O 7 OC2H5 CH3 O O Ar O O Ar O

- H 2O

O H5C2O H3C

Ar

O OC2H5 H5C2O

Ar

O OC2H5

N H 1

CH3

H3C - H2O

NH2 O 8

CH3

Scheme 9. A plausible reaction pathway of Hantzsch 1,4-dihydropyridine.

296

Suresh and J.S. Sandhu

in this important reaction and these developments are given in Table 1: Table 1. ILs used in DHP as catalysts or/and solvents.
Catalyst used Without catalyst Reaction conditions 1,1,3,3-N,N,N?,N?-tetramethylguanidinium trifluoroacetate, ultrasound irradiation, r.t., 1.452.30 h
CH3 H3C N
+

References (198)

N H2 CF3COOH3C N CH3

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3,4,5-Trifluorobenzeneboronic acid/ InCl3

1-butyl-3-methylimidazolium chloride, r.t.


ClH3C N
+

(199)

C4H10

Without catalyst

1-n-butyl-3-methylimidazolium hexafluorophosphate or 1-n-butyl-3-methylimidazolium tetrafluoroborate, r.t., 4.512 h


PF6 H3C
-

(200)

C4H10

or
BF4 H3C
-

C4H10

Without catalyst

1-methylimidazolium trifluoroacetate, r.t.


CF 3COOH3C N
+

(201)

NH

1-Butyl-3-methylimidazolium hydroxide
OHH3C N
+

solvent-free, r.t., 0.51.5 h

(202)

C4H10

1-Butyl-3-methylimidazolium hydroxide
OHH3C N
+

solvent-free, r.t., 0.54.0 h

(203)

C4H10

Without catalyst

1-n-butyl-3-methylimidazolium tetrafluoroborate
BF4 H3C
-

(204)

C4H10

Green Chemistry Letters and Reviews


Table 1. (Continued) Catalyst used Without catalyst Reaction conditions 1-n-butyl-3-methylimidazolium saccharinate
O

297

References (205)

H3C

NC4 H 9 O S O

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Table 2. ILs used in Aldol reaction act as catalyst or solvent or both catalyst and solvent. Catalyst used 1-methyl-3-{2-[(2S)-pyrrolidine-2-carbonyloxy]ethyl}-1H-imidazol-3-ium trifluoroacetate
+

Reaction conditions Solvent-free, r.t. 25 h

References (90)

N N H3C

O Pro-H

CF3COO-

1(R),2(R)-bis((S)-prolinamido)cyclohexane or (Rax)-2,2?-bis((S)-prolinamido)-1,1?-binaphtyl
O O NH NH 1 2 NH HN O N H O NH or NH N H

(1-butyl-3-methylimidazolium) tetrafluoroborate-water (1:1 v/v), 08C or 268C; 410 h or 2025 h


BF4H3C N
+

(91)

C4H10 . H O 2

Imidazolium bis(trifluoromethylsulfonyl)imidesubstituted proline and butyldimethylammonium bis(trifluoromethylsulfonyl) imide-substituted praline

1-butyl-3-methylimidazolium Bis(trifluoromethylsulfonyl) imide, r.t. 24 h


N(SO 2CF 3) 2H3C N
+

(92)

C4H10

(93) Piperidine 1-butyl-2,3-dimethylimidazolium tetrafluroborate, r.t.


BF 4
+

CH3 N C4H10

N H

H 3C

(94) Choline hydroxide Solvent-free, r.t.

298

Suresh and J.S. Sandhu

Table 2 (Continued) Catalyst used N-methyl-3-aminopropylated silica (NHMeSiO2) Reaction conditions 1-butyl-3-methylimidazolium hexafluorophosphate, r.t.
PF6 H3C
-

References (95)

C4H10

1-butyl-3-methylimidazolium tetrafluoroborate
BF4 H3C
-

Solvent-free, r.t.

(96)

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C4H10

L-proline
H OH N H O

1-butyl-3-methylimidazolium tetrafluoroborate
BF4 H3C
-

(97)

C4H10

Morpholine
O N H

1-butyl-3-methylimidazolium tetrafluoroborate, 808C, 820 h


BF 4 H3 C
-

(98)

C4H10

NaOH 1-butyl-3-methylimidazolium hexafluorophosphate, 408C


PF6 H3C
-

(99)

C4H10

Hydrotalcites

1-butyl-3-methylimidazolium hexafluorophosphate and 1-butyl-3-methylimidazolium tetrafluoroborate, 608C


PF6 H3C
-

(100)

BF4
+

C4H10

or

H3C

C4H10

Table 3. ILs used in Knoevenagel reaction act as catalyst or solvent or both catalyst and solvent. Catalyst used Reaction conditions References (109) (110)

Hydroxyapatite-encapsulated g-Fe2O3 nanoparticles Water, 308C, 1h N-(3-propyltrimethoxysilane)imidazole 1,3-dimethylimidazolium methyl sulfate, r.t., 100 min glycine
O OH

[CH3SO4]N
+

NH2

[H3NCH2CH2OH][CH3COO_]

Solvent-free, r.t. 1 h

(111)

Green Chemistry Letters and Reviews


Table 3 (Continued) Catalyst used 1-butyl-3-methylimidazolium imidazolide
N N
+

299

Reaction conditions Water, r.t. 20 min

References (112)

_ N N

Tri-(2-hydroxyethyl)ammonium acetate
OO

Tri-(2-hydroxyethyl) ammonium acetate, 808C, h

(113)

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N HO

OH OH

1-butyl-3-methylimidazolium hexafluorophosphate with alkali metal hydroxide


PF6 H3C
-

Ethanol, r.t. 6 h

(114)

C4H10 .

KOH or NaOH

Methoxyl propylamine acetate 1-butyl-3-methyl imidazolium hydroxide


HO
H3C
+

Solvent-free, 508C, 38 h Water, r.t.

(115) (116)

C4H10

Metal carbonate

1-butyl-3-methylimidazolium hexafluorophosphate or 1-butyl-3-methylimidazolium bromide- benzene


PF 6 H3C
-

(117)

C4H10

or

H3C

Br

C4H10

.C6H6

Hexadecyltrimethyl ammonium chloride and ethylmethyl imidazolium chloride


H3C ClH3C N
+

Tetrahydrofuran, 808C, 12 h

(118)

CH3 C10H25 H3C

ClN
+

CH3

1-butyl-3-methylimidazolium hexafluorophosphate and (119) 1-butyl-3-methylimidazolium tetrafluoroborate, r.t.


PF6 H3C
-

Hydrotalcites or without this catalyst

BF4
+

C4H10

or

H3C

C4H10

Glycine
O OH NH2

see IL, 45558C, 22 h

(120)

300

Suresh and J.S. Sandhu

Table 3 (Continued) Catalyst used 1-butyl-3-methyl imidazolium hydroxide


HO
H3C
+

Reaction conditions CH3CN, r.t. 1015 h

References (121)

C4H10

1-butyl-3-methyl imidazolium hydroxide


HO
H3C
+

Solvent-free r.t.

(122)

C4H10

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Hunigs base tethered ammonium ionic liquids


H3C N CH3 H3C N H3C CH3 O n
+

Solvent-free, 30 min. r.t.

(123)

CH3 CH3

Potassium carbonate KCO3

1-n-butyl-3-methylimidazolium bromide, MWI


H3C

(124)

Br

C4H10

1-methyl-3-(3-triethoxysilylpropyl imidazolium chloride 1-butyl-3-methylimidazolium hydroxide


HO
H3C
+

Solvent-free, r.t. h; 1208C Solvent-free, r.t. 1030 min

(125) (126)

C4H10

L-proline
H OH N H O

1-n-butyl-3-methylimidazolium tetrafluoroborate, 1248 h, 508C

(127)

1-n-butyl-3-methylimidazolium tetrafluoroborate
BF4 H3C
-

Solvent-free, MWI/grinding, r.t.

(128)

C4H10

1-aminoethyl-3-methylimidazolium hexafluorophosphate
PF 6 H3C
-

Water, r.t.

(129)

NH2

Green Chemistry Letters and Reviews


Table 3 (Continued) Catalyst used Piperidine Reaction conditions 1-ethyl-3-methylimidazolium tetrafluoroborate, CH3COOH, r.t.
BF 4
N H
-

301

References (130)

H3C

Without catalyst

1-methylimidazolium trifluoroacetate, r.t. 430 min


CF3COO-

(131)

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H3C

NH

Without catalyst

Ethylammonium nitrate, r.t.

(132)

Piperidine

1-butyl-3-methylimidazolium tetrafluoroborate, r.t.


BF4
-

(133)

N H

H3C

C4H10

1-hexyl-3-methylimidazolium tetrafluoroacetate
CF3COOH3C N
+

Solvent-free

(134)

C6H15

2-hydroxyethylammonium acetate
H N H
+

Solvent-free, r.t.

(135)

H CH3COOOH

Without catalyst

Ethylammonium nitrate, r.t.

(136)

Without catalyst

EAN, 1-butyl-3-methylimidazolium hexafluoropho(137) sphate and 1-butyl-3-methylimidazolium tetrafluoroborate, r.t.


PF6 H3C
-

BF4
+

C4H10

&

H3C

C4H10

1,1,3,3-tetramethylguanidium lactate
H3C N H3C H3C H3C N N H2 Lac+

Solvent-free

(138)

302

Suresh and J.S. Sandhu

Table 3 (Continued) Catalyst used NaOMe Reaction conditions 1-butyl-3-methylimidazolium hexafluorophosphate, 34.5 h 958C
PF6 H3C
-

References (139)

C4H10

GaCl3

Triethylammonium acetate (TEAA), 658C, 3045 min

(140)

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Table 4. ILs used in Michael reaction act as catalyst, solvent, or both. Catalyst used (S)-pyrrolidine sulfonamide
O CH3 NH N H S O N H3C N
+

Reaction conditions Isopropyl alcohol, r.t.

References (152)

BF 4 -

Copper nanoparticles

1-H-tetrazole-5-acetic acid, r.t., 515 min


OH

(153)

NC

N N N

Br -

CH3

Triethylammonium acetate (TEAA)

Solvent-free, 258C, 120 min

(154)

Piperidine

Ionic liquid, r.t. 2 h


ETSO 4-

(155)

N H

H3C

C2 H5

N-methylimidazole
N N CH3

Imidazolium-based ILs, r.t.

(156)

Green Chemistry Letters and Reviews


Table 4 (Continued) Catalyst used Pyrrolidine-based functionalized chiral ionic liquids
NTf 2 H3C N N
+

303

Reaction conditions Methanol, r.t. 3 days

References (157)

O S O NH N H

Pyrrolidine-based chiral pyridinium ionic liquids

Solvent-free, 1648 h, 48C

(158)

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XN N H X = BF 4, PF 6, NTf 2
+

1-methyl-3-butylimidazolium hydroxide
+

Solvent-free

(159)

HO
H3C

C4H10

Metal carbonate

1-butyl-3-methylimidazolium hexafluorophosphate and (160) 1-butyl-3-methylimidazolium bromide benzene


PF 6 H3C
-

C4H10

&

H3C

Br

C4H10

.C6H6

Table 5. ILs used in Biginelli reaction act as catalyst, solvent, or both. Catalyst used 1-butyl-3-methylimidazolium FeCl4
FeCl 4H3C N
+

Reaction conditions Solvent-free, 908C, 23 h

References (169)

C4H10

L-prolinium sulfate
H OH N H
+

Tetrahydrofuran, r.t. 2130 h

(170)

O HSO 3-

304

Suresh and J.S. Sandhu

Table 5 (Continued) Catalyst used 1-hexyl-3-methylimidazolium HSO4


CH3 N

Reaction conditions Solvent-free, r.t. 1555 min

References (171)

Task-specific ionic liquids


R N
+

Solvent-free, 908C, 1015 min

(172)

R A-

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R SO3H

1-butyl-3-methyl-imidazolium hydrogen sulfate


HSO 4H3C N
+

Solvent-free, MWI, 1408C, 4.48 min

(173)

C4H10

1-butyl-3-methylimidazolium tetrafluoroborate immobilized Cu(acac)2


BF4 H3C
-

Solvent-free, 508C

(174)

C4H10 .

Cu(acac)2

1-n-butyl-3-methylimidazolium saccharinate
O

Solvent-free, r.t.

(175)

H3C

NC4 H 9 O S O

Alkylammonium and alkylimidazolium perhaloborates, phosphates, and aluminates


AH3C N
+

Solvent-free, 1208C, 1h

(176)

CH3 N I Bu H C 3 AN
+

N II

Bu AIII

NET3

Et3NH AIV Bu4N PF 6 V


+

A = BF 4 -, PF 6 -, AlCl 4, Al 2Cl7

1-butyl-3-methylimidazolium tetrafluoroborate
BF4 H3C
-

Solvent-free

(177)

C4H10

1-methylimidazolium hydrogen sulfate, 1-methylimidazolium trifluoroacetate


HSO 4H N
+

Solvent-free, 4090 min, 508C

(178)

CF 3COON CH3, H

CH3

Green Chemistry Letters and Reviews


Table 5 (Continued) Catalyst used 1-butyl-3-methyl-imidazolium hydrogen sulfate
HSO 4H3C N
+

305

Reaction conditions Solvent-free, r.t.

References (179)

C4H10

Polymer-supported IL
H3C N
+

Acid Acetic, 24 h 1008C (180)


X-

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n . X = BF 4 -, PF 6 .

1-butyl-3-methylimidazolium hexafluorophosphate and 1-butyl-3-methylimidazolium tetrafluoroborate


PF6 H3C
-

Solvent-free, r.t.

(181)

BF4
+

C4H10 , H3C

C4H10

1-butyl-3-methylimidazolium chloride 2AlCl3


ClH3C N
+

Solvent-free, r.t.

(182)

C4H10 .2AlCl3

Ultrasound, 4090 min, 308C

(183)

1-n-butylimidazolium tetrafluoroborate
BF 4 H
-

C4H10

1-butyl-3-methylimidazolium hexafluorophosphate and 1-butyl-3-methylimidazolium tetrafluoroborate


PF6 H3C
-

Solvent-free

(184)

BF4
+

C4H10 , H3C

C4H10

1-n-butyl-3-methylimidazolium saccharinate
O

Solvent-free, r.t.

(185)

H3C

NC4 H 9 O S O

1-n-butyl-3-methylimidazolium saccharinate
O

Solvent-free

(186)

H3C

NC4 H 9 O S O

306

Suresh and J.S. Sandhu

Table Table 5 5( (Continued Continued) ) Catalyst used n-butyl pyridinium tetrafluoroborate Reaction conditions Solvent-free, r.t. References (187)

1-butyl-3-methylimidazolium tetrafluoroborate

Solvent-free, MWI

(188)

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BF4 H3C

C4H10

tri-(2-hydroxyethyl) ammonium acetate


HO OH

908C, 58 h or MWI, 200 W, 48 min

(189)

CH3COO-

HO

Conclusions Ionic liquids are well-known alternative solvents replacing VOCs, but still some questions remain to be satisfactorily answered by readers and actual practioners. Are these really non-toxic recyclable and economically viable alternatives to VOCs used specifically in industrial processes? The future of these solvents seems to be very bright in view of human health and climate change. Certainly, much more is needed to be done to see them as really viable alternatives, in spite of a large number of research studies being published. ILs hold a very bright future in various fields of sciences. In this presentation, the authors have made every effort to be precise and if in this attempt, unknowingly, any authors fruitful work is left out, this is sincerely regretted.

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Acknowledgements
Authors wish to thank the Council of Scientic and Industrial Research (CSIR), New Delhi, India and Indian National Science Academy (INSA), New Delhi, India for nancial support for this research project.

Green Chemistry Letters and Reviews


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