Metal-based surface active ionic liquids: Self-assembling characteristics and C[sbnd]C bond functionalization of tertiary amines with TMSCN in aqueous micellar solutions

Article abstract of DOI:10.1016/j.molliq.2019.112157

Metal-based surface active ionic liquids (MSAILs), 1-alkyl-3-methyl imidazoliumtetrachloromanganate [C_nmim][MnCl₄]^{2 ?} (n= 8,10,12) have been synthesized and characterized for self-assembling behavior in aqueous

Full text of DOI:10.1016/j.molliq.2019.112157

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Metal-based surface active ionic liquids: Self-assembling
characteristics and C-C bond functionalization of tertiary amines
with TMSCN in aqueous micellar solutions
Akshay Kulshrestha, Gaurav Kumar, N.H. Khan, Arvind Kumar
PII:
S0167-7322(19)35335-8
DOI:
https://doi.org/10.1016/j.molliq.2019.112157
MOLLIQ 112157
Reference:
To appear in:
Journal of Molecular Liquids
Received date:
Revised date:
Accepted date:
25 September 2019
11 November 2019
16 November 2019
Please cite this article as: A. Kulshrestha, G. Kumar, N.H. Khan, et al., Metal-based
surface active ionic liquids: Self-assembling characteristics and C-C bond
functionalization of tertiary amines with TMSCN in aqueous micellar solutions, Journal
of Molecular Liquids(2019), https://doi.org/10.1016/j.molliq.2019.112157
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Metal-based Surface Active Ionic Liquids: Self-Assembling Characteristics and C-C Bond
Functionalization of Tertiary Amines with TMSCN in Aqueous Micellar Solutions
Akshay Kulshrestha,ab Gaurav Kumar ,ac N.H. Khan,ac and Arvind Kumara,b,
*
aAcademy of Scientific and Innovative Research (AcSIR)-Central Salt and Marine Chemicals Research
Institute, Council of Scientific and Industrial Research (CSIR), G. B. Marg, Bhavnagar, 364002, Gujarat
India.
bSalt and Marine Chemicals Division, CSIR-Central Salt and Marine Chemicals Research Institute,
Council of Scientific and Industrial Research, G. B. Marg, Bhavnagar, 364002, Gujarat India
cInorganic Materials and Catalysis Division, CSIR-Central Salt and Marine Chemicals Research
Institute, Council of Scientific and Industrial Research, G. B. Marg, Bhavnagar, 364002, Gujarat India
*To whom correspondence should be addressed: e-mail: mailme_arvind@yahoo.com;
arvind@csmcri.org; Tel: +91-278-2567039; Fax: +91-278-2567562.
Abstract
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Metal-based
surface
active
ionic
liquids
(MSAILs),
1-alkyl-3-methyl
imidazoliumtetrachloromanganate [Cnmim][MnCl4]2- (n=8,10,12) have been synthesized and
characterized for self-assembling behavior in aqueous solution using tensiometry, fluorescence,
conductivity, dynamic light scattering (DLS) and transmission electron microscopy (TEM) techniques.
MSAILs have exhibited 4 to 5 fold higher surface activity as compared to the non-metal based
surface active ionic liquids. MSAILs micellar solutions have been successfully used for C(sp3)-H
functionalized oxidative cyanation of the tertiary amines. Oxidative Strecker reaction was carried out
with different concentrations of the MSAILs, cyanide source (TMSCN) and substrate, and moderate
to very high yields (up to 95%) could be achieved in 3-4 h. Usually, cyanation of tertiary amines is
carried out in organic solvents under harsh conditions without recycling of the catalyst. Herein
aqueous MSAILs micellar solutions have been used as a solvent, catalyst as well as template with a
good recycling ability, thus making the approach simpler, greener, and sustainable.
Keywords: Metal-based surface active ionic liquids, micellar catalysis, cyanation, tertiary amines.
1. Introduction
Ionic liquids (ILs) are molten organic salts with wide liquidus range (up to 100oC). Due to negligible
vapor pressure and other suitable physicochemical properties, ILs are considered as comparatively
greener solvents.[1,2] Recently, ILs have been widely used in colloidal science as medium or
surfactants because of their tunable properties and insignificant vapor pressure, which avoids the
environment pollution.[3] ILs which exhibit surface active properties are synthesized by introducing
the amphiphilic character into the ILs and have been termed as surface active ionic liquids (SAILs).
Many of such SAILs have some superior surface activity in solvent media as compared to the
conventional surfactants.[4] The self-assembly of SAILs leads to the formation of micelles, worm-
shaped micelles, vesicles, rod-like micelles, reverse vesicles, reverse micelles.[5-10] ILs have also
found applications in several organic transformations as both catalyst and solvent. Due to the
multiple advantages of the ILs, we performed organic transformations via micellar route by using ILs
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as a catalyst and an emulsifying agent. Literature survey on SAILs has shown a variety of applications
such as drug screening,[11] micellar catalysis,[12] micellar extraction,[13] biochemical reaction,
detergents, pharmaceutical and their biochemical demand like gene transfection, DNA binding, drug
delivery, interaction with biomolecules.[14-16]
The use of surfactants under micellar conditions represents one of the simplest methods to achieve
catalysis in water. Micellar Catalysis has been used to perform the synthesis of the organic
molecules, and conventional materials in the surfactant aggregate.[17] The micellar solution
provides the hydrophobic and ionic environment to perform the reaction, and the product can be
separated by an aqueous biphasic system.[18-20] ILs can dissolve the series of the transition
metals.[21] Therefore, the metal-based ionic liquids can be used as a catalyst as well as solvent in
organic transformations in an eco-friendly way. Previously, conventional surfactants (SDS, Triton X-
100, Brij-36) have been used for organic transformation.[22-29] The micellar aqueous solutions have
been used in the dehydration reaction,[22] C-C bond forming reaction,[23]Oxidation reaction,[24]
metal catalyzed reaction,[25,26]cross-coupling reaction (Suzuki, Sonoghasira, Negishi)[27-29] or
Carbon–heteroatom coupling reaction[30] with the better yield and selectivity. In another case, the
metal nanoparticle can be stabilized in the micelles, which can be cross contact between the micellar
and heterogeneous catalysis.[10,31 ]Many groups have rooted their work on the micellar catalysis by
SAILs, to increase the rate of the reaction and to perform the reactions in aqueous media. The work
of Bica and co-workers,[32-34 ]shows the enhancement in the rate of the Diels Alder Reaction by the
micellar solution of the 1-dodecyl-3- methyl imidazolium chloride and replacement of traditional
organic solvent with water. Effect of the nucleophile (Cl, Br, I, OTs, OTf, Ms) on the rate of the
reaction for the degradation of the organophosphorus compounds and palladium catalyzed micellar
catalysis with [Cnmim][X] for the cross-coupling reaction has also been investigated. Xie et al.
performed Ugi-type reaction by the copper-catalyzed in surfactant medium[35] whereas Klumphu et
al. showed the cycloisomerization conversion of the allenes into the heterocyclic product in the
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presence of gold (ppm) in micellar media.[36] The Nitrile group is an essential and handy purposeful
assembly in organic synthesis. It is also a needy backbone for various drug compounds[37 ]as it is
easily converted to further valuable functional groups.[38] Consequently, the cyano group as a
primer into an organic framework at C1 position has been well studied.[39] Amongst the wide-
ranging bioactive molecules and synthetic intermediates of alpha-amino carbonyl compounds and
1,2-diamines, alpha-amino nitrile derivatives are the primary representative of substructure.[40] The
most legendary Strecker reaction is the reliable paramount method for synthesis of alpha-amino
nitrile derivatives, i.e., the addition of a cyanide anion to an imine.[41]
In new existences, C−C bond formations are always high in demand, and it can be readily synthesized
via C−H bond activation, which is a most favorable synthetic tool.*42+ The oxidative cyanation
reaction is leading age route C−C bond formations through C−H bond activation, which is considered
to be an environmentally sustainable and atom-efficient procedure for a sustainable development
perspective. Oxidative cyanation of tertiary amines compounds has been actively examined in many
reports. Since 2003, many groups like as Murahashi,*43+ Li’s,*44+ and others reported the
groundbreaking work of C–H cyanation of N, N dialkyl aniline.[45]Also, other recipes of oxidants and
cyanide cradles were similarly relevant to oxidative C–H cyanation.[46] Contemporary advancement
of photo-redox catalysis assists direct C–H bonds functionalization.[47-48] Commonly, oxidative
cyanation reactions are dependent on the use of transition metal catalysts like ruthenium,[43]
manganese[49] and iron[50] besides various oxidants, such as H2O2,[51] O2,[52] tert-
butylhydroperoxide,[53] and 2,3-dichloro-5,6-dicyanobenzoquinone(DDQ).[54]
In this report, we have synthesized a series of manganese-based SAILs using the 1-alkyl-3-
imidazolium chloride and Manganese Chloride and characterized using Raman Spectra, UV spectra,
and EPR spectra. The thermal behavior has been analyzed using TGA, and DTG Micellar solutions of
imidazolium-type of amphiphilic ILs have been reported to increase the solubility organic
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compounds,[55]therefore, we have utilized the synthesized MSAILs micellar solutions as a solvent
system and catalyst for the chemical transformation of tertiary amine to the cyanated product.
2. Materials and methods
2.1 Material: Methyl imidazole (>98% purity), 1-Chlorodecane (>98% purity), 1-Chlorododecane
(>98% purity) were purchased from TCI Chemical (India) Pvt. Ltd. 1-Octyl-3-methyl imidazolium
chloride (>97% purity), manganese (II) chloride tetrahydrate and TBHP were purchased from Sigma-
Aldrich. N, N-dimethyl aniline, TMSCN was obtained from Spectrochem. The Hydrogen Peroxide
solution 50% was purchased from Qualigens fine chem. Ltd. The solvent-like methanol, ethyl acetate,
and n-hexane of AR grade were purchased from Loba Chemie Ltd., India.
Scheme 1. Chemical structure of investigated MSAILs
2.2 Synthesis and Characterization: Details of synthesis and characterization of MSAILs are
provided in supporting information (ESI†). In brief, 1- Chlorododecane and 1-chlorodecane was
added (1.1: 1 mole eq.) dropwise in a solution of 1-methylimidazole in the acetonitrile at 90oC under
reflux conditions for 48 h. *Cnmim+Cl (n =8,10,12) and manganese(II) chloride tetrahydrate were
taken in methanol solvent, and reaction mixtures were kept for reflux for 24 hours. The product was
washed with ethyl acetate and hexane, dried and stored in a desiccator. Synthetic scheme is shown in
Figure S1, and the molecular structures of synthesized MSAILs are shown in Scheme 1. Materials
1
were characterized using H NMR, Raman, UV, and EPR spectra. Confirmation of Mn-Cl bond and
tetrahedral manganese complex formation in the (MnCl4)2-counterion of MSAILs was obtained from
Raman and UV spectra (Figure S2) whereas the oxidation number of Mn(II) in (MnCl4)2-of the MSAILs
was obtained from EPR spectra (Figure S3). C, H, N, and ICP measurements were done for elemental
analysis (Table S1). Thermal stability of the MSAILs was investigated by the thermogravimetric
analysis (TGA) experiment (Figure S4).
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2.3 Methods:
2.3.1. Spectroscopy. LabRAM HR Evolution Horiba Jobin, Yvon Raman spectrometer, was used to
identify the characteristic peak of Mn-Cl bond of the complex [MnCl4]2-at 298.15 K of the sample. UV
spectra of MSAILs solutions prepared in acetonitrile were recorded by the JobinYvon UV−VIS
spectrophotometer. For EPR spectra of the investigated MSAILs solutions were prepared in
acetonitrile solvent, and the spectra were recorded by using EPR benchtop instrument (Freiberg
Instruments, Germany). Characteristic parameters were: magnetic field range 300 to 400 mT,
frequency 100 kHz, sweep time 60s, and the modulation 0.20 mT.
2.3.2.Tensiometry, Conductivity, and Fluorimetry.Attention Force Sigma 700 tensiometer with Du
Nouy ring method was used for the surface tension measurements. Triplicate measurements were
done, and the average value was considered as surface tension value. CMC and other surface
parameters were determined from measured surface tension values. Conductivity measurement
was done on digital Eutech auto temperature conductivity meter model PC 2700 assembled with a
conductivity cell and temperature probe. Solution temperature was maintained by using a Julabo
thermostat at 25oC (with  0.1oC). The conductivity was measured after each addition of the MSAILs
in the solution. Conductivity value was used to find out the CMC, degree of counterion binding (β),
and standard free energy of micellization. The Fluorescence of pyrene was measured at different
concentrations of MSAILs by Fluorolog (Horiba Jobin Yvon) spectrometer. The excitation/emission
wavelength is 334/365nm (slit width 1.2nm). Measurements were done in a quartz cuvette of 1 cm
path length.
2.3.3. Transmission electron microscopy and Dynamic Light Scattering (DLS). TEM images were
recorded by JEOL JEM-2100 electron microscope at aworking voltage of 80kv. The MSAILs samples
were prepared by putting a drop of MSAIL solutions on the carbon-coated copper grid (300 mesh),
and the samples were dried under vacuum desiccator. Dynamic light scattering measurements were
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performed at a 90o angle with a He-Ne laser (660-670 nm, 4mW) by using NaBiTec Spectro-Size300
light scattering apparatus (NaBiTec, Germany).
2.3.4. Gas chromatography (GC). Gas chromatography was carried out on the Shimadzu GC-
2010. The column oven temperature was at 110oC, FID 200oC, and the pressure of GC was 110kPa.
All the samples were prepared in methanol, and dodecane as a standard solution was used.
3. Result and discussion
3.1. Surface tension: The surface activity of the investigated MSAILs was determined by surface
tension measurements. The adsorption isotherms determined from surface tension (γ)
measurements at 298.15 K are shown in Figure 1A. The surface tension of aqueous-MSAILs solutions
decreased in a polynomial manner with the logarithm of concentration because of adsorption of
MSAILs molecules at the air/water interface and attained a critical micelle concentration (cmc) value,
above which a nearly constant value of surface tension (γcmc) is observed. The cmc values decreased
with increase in the length of the alkyl chain of MSAIL i.e. [C8mim]2[MnCl4] (51.18 mM),
[C10mim]2[MnCl4] (5.6 mM) and [C12mim]2[MnCl4] (2.05mM). The cmc values of the are 4 to 5 folds
lower than the previously reported cmc values for the SAILs, [Cnmim][X],[56] [CnPy][X][57,58] (where
n = 8,10,12; X = Br and Cl), or functionalized SAILs.[59] Lower cmc values are due to higher
hydrophobicity of tetrahedral [MnCl4]2- metal counterion.
The surface activity and related parameters at air/solution interface, i.e. adsorption
efficiency (πcmc), effectiveness reduction in surface tension (pC20), surface excess concentration
(Γmax), covered area by single-molecule (Amin) and packing parameter (P) were derived from
documented equations [60] and are provided in Table 1. The Amin value of the MSAILs is higher than
the conventional surfactants. The Amin follows the order: [C8mim]2[MnCl4] < [C10mim]2[MnCl4] <
[C12mim]2[MnCl4+ whereas Γmax values follow a reverse order indicating that the molecules are
assembling more compactly at air-water interface with the increase in the chain length.
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3.2. Conductivity: The conductivity measurements are used for the determination of the cmc as well
as the degree of counterion binding (β). The specific conductivity (κ, m.Scm-1) was measured as a
function of MSAILs concentration (mmol.L-1) in the aqueous solution. Figure 5 shows κ vs. C profile of
a representative MSAIL, [C12mim]2[MnCl4] (profiles for other MSAILs are provided in supporting
information, Figure S5). The κ vs. C profiles were used to determine cmc values. Similar to the
surface tension behavior, the observed cmc value of MSAILs from conductivity measurements follow
the order is [C8mim]2[MnCl4] > [C10mim]2[MnCl4] > [C12mim]2[MnCl4](Fig. S5,ESI†). The β value is
obtained from the formula (β =1-α) where the α is the degree of counterion dissociation which is
obtained by the ratio of the slope post micellar region and the pre micellar region (S2/S1) were used
to derive the value of standard free energy of micellization from the equation:[61]
Gmoic  (1 )RT ln Xcmc
Where Xcmc is the cmc in mole fraction, T is the temperature in Kelvin (K), and R is the gas
constant. The negative value of the standard free energy of micellization shows the spontaneous
formation of the micelles. The standard free energy of micellization and β values is provided in Table
1.
3.3. Steady State Fluorescence measurement: Fluorescent probe pyrene is very sensitive to the
polarity of the cybotactic region and used to identify the cmc of amphiphilic molecules in the
aqueous solution.[61,62] The pyrene fluorescent probe shows the five emission bands. The first
vibronic peak I1 is sensitive to the polarity, which shows a decrease in the intensity with the addition
of the amphiphilic molecules, whereas the third vibronic peak I3 is not sensitive to the polarity.
Therefore, the ratio I1/I3 is a good indicator of pyrene environment in the solution and can be used
for determination of cmc. The plot of I1/I3 vs. concentration of a representative MSAIL,
[C12mim]2[MnCl4] is provided in Fig. 1C. (profiles for other MSAILs are provided in supporting
information, Fig. S6 ESI†). The observed order of cmc of MSAILs by fluorescence measurements is
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similar to that determined from the surface tension and conductivity measurements,
i.e.[C8mim]2[MnCl4]>[C10mim]2[MnCl4]> [C12mim]2[MnCl4+ (Fig. S6, ESI†).
Fig. 1 (a) The surface tension vs. concentration plot of the various
MSAILs, (b, c) Conductivity plot andI1/I3 intensity ratio of a representative
MSAIL, *C12mim+2*MnCl4+, and (d)Intensity vs. λ graph on increasing the
concentration,Cq of *C12mim+2*MnCl4+.
3.4. Size and shape of the aggregates: DLS and TEM imaging were performed to determine the size
and the shape of the aggregated structure of MSAILs in the aqueous solution. Fig. 2A shows the
graph between the hydrodynamic diameter (nm) and the intensity count per second distribution
profile of the micellar aqueous solution of the MSAILs. The autocorrelation diagram is provided in
supporting information (Fig. S7, ESI†). The DLS profiles of [C8mim]2[MnCl4] and [C10mim]2[MnCl4]
show two peaks centered at around 3 nm and 10 nm indicating co-existence of smaller size micelles
along with bigger aggregates. DLS profiles of [C12mim]2[MnCl4] shows only a single peak around 3 nm
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indicating the formation only smaller micelles. TEM images (Fig. 2b-d) also confirms formation of
micellar structures of similar sizes by MSAILs.
Fig. 2 (a) DLS plot of MSAILs with different alkyl chain length. (b-d)
shows the TEM images of *C12mim+2*MnCl4+, *C10mim+2*MnCl4+, and
*C8mim+2*MnCl4+ MSAILs.
3.5. Micellar Catalysis
Functionalized Oxidative Cyanation using MSAILs micellar solutions: Insights into the influence of
structural features of metal-based surface active ionic liquids on the oxidative cyanation of tertiary
amines with trimethylsilyl cyanide have been obtained as per Scheme 2.
Scheme 2. Cyanation of tertiary amines in micellar solutions
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Preliminary trials on the oxidative cyanation reaction were accomplished by using 100 mM
concentration of various MSAILs, which is quite higher than the cmc of MSAILs in aqueous solution.
The reaction of N, N-dimethyl aniline and TMSCN using the micellar solution was achieved at 40oC
(Table 2). At 100 mM MSAILs concentration moderate yields were obtained (Table 2, entry 1-3).
Further investigations revealed a marked influence of concentration of the surface-active ionic
liquids. Therefore, to further enhance the yield of the products we carried out reactions at different
concentrations of MSAILs, i.e. 70, 25, 15, 5 mM, apart from varying other parameters. (Table 2, entry
4-15). An exceptional behavior was seen when the concentration was decreased to 25 mM. In the
case of *C12mim+ 2*MnCl4+, the yield increased to 95% (Table 2, entry 7). Similar behavior was also
observed for other MSAILs, albeit with lesser yield as compared to *C12mim+2*MnCl4+. Higher yields
with longer alkyl chain length MAIL, i.e. *C12mim+2*MnCl4+ is likely due to the formation of compact
micellar structure, which is providing more surface area for substrates to react. Further, by varying
the other parameters like as oxidant, cyanide source, with optimized *C12mim+2*MnCl4+ concentration
i.e., 25 mM, there was no further improvement of the yield of the desired products even by using
nascent oxygen or TBHP as an oxidant (Table 2, entry 16, 17). We also checked the reaction
parameters by without using oxidant wherein no reaction was observed (Table 2, entry 18). Oxidant
hydrogen peroxide was also optimized for the reaction. Finally, we varied the cyanide source (Table 2,
entry 19 and 20) and used sodium cyanide and potassium cyanide. Conventional non-metal ionic
liquid and manganese chloride were also tested (Table 2, entry 21, 22). The consequences give a
clear path that conventional ionic liquid as well MnCl2 are not sufficient separately to effectively
catalyze the reaction. Therefore, the use of MSAILs provides an effective procedure for C-H
functionalization of tertiary amines under aerobic conditions as a consequence of the hydrophobic
and ionic environment. Under optimized conditions of *C12mim+2*MnCl4+ (25 mM) cyanation of
1
various tertiary amines was carried out efficiently (Table 3). The H and 13C NMR spectra of the
cyanation products are provided in supporting information (ESI†).
Reaction mechanism: A conceivable reaction pathway has been projected for the sp3 C-H oxidative
cyanation of tertiary amines in the self-assembled structure of MSAIL in water with TMSCN. As
shown in Scheme 3, primarily Mn(II) containing micellar aqueous solution, reacts with H2O2 leading
to the formation of reactive oxo-complex species, which consequently reacts with the amine to give
an iminium ion. A conceivable reaction pathway has been projected for the sp3 C-H oxidative
cyanation of tertiary amines where the reaction trails an oxidative and reductive path. This
intermediate reacts with in-situ generated -CN and delivers the corresponding α-aminonitrile
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(Scheme 3). The detailed reaction mechanism of the reaction has been provided in supplementary
Information (Figure S8).
Scheme3. Plausible reaction mechanism for the Manganese
based surface active ionic liquids (MSAILs) catalyzed C-H
activation of tertiary amines with hydrogen peroxide.
4. Conclusion
The manganese-based imidazolium type surface active ionic liquids with varying chain length have
been synthesized and characterized for their thermal stability and surface activity. MSAILs have been
found more stable than the conventional imidazolium SAILs and form well organized self-assembled
micellar structures spontaneously in aqueous medium as suggested by various techniques viz.
tensiometry, fluorometry, and conductivity. The formation of micelles is confirmed using TEM
images and DLS profiles. The various surface parameters indicate that MSAILs are more surface
active than the conventional SAILs due to the incorporation of hydrophobic metal counterion. The
micellar solutions of MSAILs have been successfully used as catalyst, template as well solvent for
cyanation of tertiary amines using TMSCN as cyanide source in the presence of hydrogen peroxide as
the oxidant. Longer chain MSAILs have been found more efficient for catalytic activity due to the
formation of compact micellar structures, and yield as high as 95% could be achieved under
optimized conditions. The devised methodology of C-C bond functionalization of tertiary amines
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with TMSCN in aqueous MSAILs micellar solutions is more eco-friendly and follows more simple
protocols, and can be generalized for other chemical transformations in water.
Acknowledgement
The authors are grateful for the financial support from the Department of Science and
Technology, India(EMR/2016/004747).Authors thank Krishnaiah Damarla and P.S. Gehlot
for the helpful suggestions. We also thank the centralized Instrumental Facility of our
Institute for assistance.
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Table 1: Critical aggregation concentration (CAC), surface tension at CMC with ±0.1mN.m-1 accuracy (
), effective surface

tension reduction with ±0.1mN.m-1 accuracy (
), adsorption efficiency (
), maximum surfaceCeAxCcess concentration (
CMC
pC20
tot
max

), and minimum area occupied by a single molecule at the air-water interface (
), degree of counterion binding (β) and
Amin
o
standard free energy of micellization
of MSAILs in aqueous medium at 298.15K.
Gm
MSAILs
cmc
Surface parameter from ST and conductivity measurements
ST
Cond.
(mM)
50.8
flr.
γcmc
πcmc
pC20
Γmax
Amin
β
(kJ mol-1)
(mM)
52.8
4.46
1.94
(mM)
45.5
4.72
1.70
(mNm-1) (mNm-1)
(µmolm-2)
1.19
(Å2)
[C8mim]2[MnCl4]
[C10mim]2[MnCl4]
[C12mim]2[MnCl4]
30.51
26.12
30.59
38.85
43.12
40.07
2.69
4.22
3.67
139.8
153.9
165.7
0.32 -22.90
0.16 -27.08
0.20 -30.60
5.44
1.08
2.40
1.00
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Table 2: Optimization of reaction conditions for Effect of MSAILs concentration with manganese catalysed
oxidative cyanation of tertiary amines with cyanide source.
Entry
1
Surfactant
Conc. (mM)
Oxidant
H2O2
H2O2
H2O2
H2O2
H2O2
H2O2
H2O2
H2O2
H2O2
H2O2
H2O2
H2O2
H2O2
H2O2
H2O2
O2
Yield (%)
75
[C12mim]2[MnCl4]
[C10mim]2[MnCl4]
[C8mim]2[MnCl4]
[C12mim]2[MnCl4]
[C10mim]2[MnCl4]
[C8mim]2[MnCl4]
[C12mim]2[MnCl4]
[C10mim]2[MnCl4]
[C8mim]2[MnCl4]
[C12mim]2[MnCl4]
[C10mim]2[MnCl4]
[C8mim]2[MnCl4]
[C12mim]2[MnCl4]
[C10mim]2[MnCl4]
[C8mim]2[MnCl4]
[C12mim]2[MnCl4]
[C12mim]2[MnCl4]
[C12mim]2[MnCl4]
[C12mim]2[MnCl4]
[C12mim]2[MnCl4]
MnCl2
100
100
100
70
70
70
25
25
25
15
15
15
5
2
65
3
60
4
78
5
65
6
60
7
95
8
90
9
85
10
11
12
13
14
15
16
17
18
19b
20c
21d
22e
50
45
40
34
5
32
5
30
25
25
25
25
25
-
70
TBHP
-
88
N.R.
80
H2O2
H2O2
H2O2
H2O2
85
55
IL, [ C8mim][Cl]
-
10
a Reaction conditions: 1 equivalent mmol of N, N-dimethyl aniline, 1.5 equivalent of TMSCN, 1.5 equivalent
of H2O2 in 0.5 ml of MSAIL for 4 h. bNaCN 1.5 equivalent and cKCN 1.5 equivalent, dusing 10 mol % in water,
0.5 ml of IL,[ C8mim][Cl] was used.
e
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Table 3: Substrate Scope for the oxidative cyanation of tertiary
amines in micellar solution.a
21

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22

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Table of contents
Graphical abstract
Highlights
-based surface active ionic liquids.
surface activity than conventional surfactants.
23

Figure 1

Figure 2