Journal of Molecular Liquids 216 (2016) 354359

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Journal of Molecular Liquids

journal homepage: www.elsevier.com/locate/molliq

Spectroscopy and kinetics evidence for the hydrogen-bond activating

effect of anion/cation of [Bmim]OAc on the hydrolysis of esters
Xinxin Yu, Miaomiao Wang, Xirong Huang
Key Laboratory of Colloid & Interface Chemistry of the Education Ministry of China, Shandong University, Jinan 250100, China

a r t i c l e i n f o a b s t r a c t

Article history: Experimental and theoretical studies on the hydrolysis of esters catalyzed by different ionic liquids (ILs) have
Received 30 August 2015 been made. It is found that the rate of the IL catalyzed hydrolysis of an ester depends not only on the structure
Received in revised form 3 December 2015 of the ester but also on the structure of the ions. For the hydrolysis of p-NPB catalyzed by [Bmim]OAc, spectros-
Accepted 14 January 2016
copy and kinetics studies complemented by DFT calculations indicate that the hydrogen bonding formed be-
Available online 26 January 2016
tween the cation/anion of [Bmim]OAc and the reactants (both ester and water) is well correlated with the
Keywords:
catalytic efciency of the IL. The anion OAc of the catalyst contributes more than its cation [Bmim]+ to the hy-
Ionic liquid drolysis of p-NPB. A joined catalytic effect of [Bmim]+ and OAc was observed especially in neat [Bmim]OAc. The
Ester hydrolysis new evidence provided by present studies helps to fully understand the activation mechanism of an IL toward the
Hydrogen bond hydrolysis of an ester.
Joined effect 2016 Elsevier B.V. All rights reserved.

1. Introduction In this report on the hydrolysis of esters catalyzed by [Bmim]OAc,

An ionic liquid (IL) is a molten salt consisting of organic/inorganic
ions. It has some unique physical and chemical properties, such as low
vapor pressure and high thermal stability. As a new medium, IL has
been widely used in various elds of chemistry [14]. For a specic or-
ganic reaction, IL may have catalytic activity, depending on its composi-
tion and the ion structure. To date, many reports have been released on
IL catalyzed organic reactions [59].
Ester hydrolysis is an important type of organic reaction in the in-
dustries of foods, cosmetics and pharmaceutical intermediates
[1012]. The hydrolysis of an ester catalyzed by acid or base has been
thoroughly studied and the mechanism is basically clear (it goes via
the nucleophilic attack of water on carbonyl carbon) [13,14]. The use
of an IL to catalyze the hydrolysis of esters has been tried in recent
years [1518], and some ILs, e.g. 1-butyl-3-methylimidazolium acetate
([Bmim]OAc) are proved to be effective. The understanding of the un-
derlying mechanism for the effectiveness is important to the real appli-
cation of an IL as catalyst. The catalytic activity of an IL usually originates
from the activating effect of its anion or/and cation on reactants [17,
1923]. Ferreira et al. have suggested that the acceleration of the hydro-
lysis of acylglycerol by cholinium hexanoate is due to the activation of
the nucleophile water via a hydrogen bond (H-bond) [17]. In order to
determine the reaction mechanism, they performed a density functional
theory (DFT) study; however, they paid less attention to the supporting
experimental evidence.
Corresponding author.
E-mail address: xrhuang@sdu.edu.cn (X. Huang).
some new experimental evidences (from both spectroscopy and kinet-
ics studies) complemented by DFT calculations are provided to demon-
strate that the activating effect of [Bmim]OAc on the hydrolysis of esters
is well correlated with the H-bond interaction between the IL and the
reactants.
2. Experimental
2.1. Materials
p-Nitrophenol butyrate (p-NPB, 98%) was purchased from Sigma-
Aldrich. 1-Naphthyl acetate (99%), 4-acetoxyacetophenone (98%), and
phenyl acetate (99%) were obtained from J&K Scientic Ltd. Ibuprofen iso-
propyl ester was synthesized according to the procedure reported
elsewhere [24]. Ethyl butyrate (99%), sodium acetate, acetonitrile
(HPLC grade), and N, N-dimethylformamide (DMF) were purchased
from Sinopharm Chemical Reagent Co. Ltd., China. 1-Ethyl-3-
methylimidazolium acetate ([Emim]OAc), 1-butyl-3-methylimidazolium
acetate ([Bmim]OAc), 1-hexyl-3-methylimidazolium acetate
([Hmim]OAc), 1-butyl-2,3-dimethylimidazole acetate ([Bdmim]OAc), 1-
butyl-3-methylimidazolium triuoromethanesulfonate ([Bmim]CF3SO3),
1-butyl-3-methylimidazolium tetrauoroborate ([Bmim]BF4), 1-butyl-3-
methylimidazolium chloride ([Bmim]Cl), tetramethylammonium acetate
([(CH3)4N]OAc) and Choline acetate ([Chol]OAc) were purchased from
Shanghai Chengjie Co. Ltd. Prior to use, all ionic liquids were dried
under vacuum. Ultra pure water (18.25 Mcm) was used throughout
the experiments.

http://dx.doi.org/10.1016/j.molliq.2016.01.049
0167-7322/ 2016 Elsevier B.V. All rights reserved.
 X. Yu et al. / Journal of Molecular Liquids 216 (2016) 354359
2.2. Typical procedure for hydrolysis of esters in [Bmim]OAc
Esters (2.5 105 mol) and water (2.5 104 mol) were added into
500 L [Bmim]OAc, and the resulting mixture was stirred at 35 C for
2.5 h. Then an aliquot of the nal mixture as sample was taken out
and diluted with acetonitrile. The sample was analyzed on an HPLC
equipped with a Shimadzu LC-20AT high-pressure pump, SPD-20A
UVvisible detector, SIL-10AF autosampler and VP-ODS column
(250 mm 4.6 mm). The separation and detection conditions for a spe-
cic ester are as follows: CH3CN:H2O = 7.5:2.5, 1.0 mL min1, and =
270 nm for p-NPB; CH3CN:H2O = 6.5:3.5, 0.8 mL min1 and =
247 nm for 4-acetoxyacetophenone, or 277 nm for phenyl acetate or
254 nm for 1-naphthyl acetate; CH3CN:H2O = 6.0:4.0 (NaOAc/HOAc
buffer, 20 mM, pH = 3.5), 0.8 mL min1, and = 254 nm for ibuprofen
isopropyl ester & ethyl benzoate or 210 nm for ethyl butyrate.
2.3. Typical procedure for hydrolysis of p-NPB in DMF by different ILs
Ester (2.0 mmol), water (10 mmol), and IL (0.4 mmol) as catalyst
were added into 3 mL DMF, respectively (for [(CH3)4N]OAc, it mixed
rst with water, then its aqueous solution was added into DMF). The
resulting mixture was reuxed at 85 C for a certain time. Then an
aliquot of the nal mixture as sample was taken out and diluted with
CH3CN. The sample was analyzed with HPLC (its chromatographic
conditions were the same as in Section 2.2).
2.4. 1H NMR characterization of the imidazolium C2-H
[Bmim]OAc (0.024 mmol) and equivalent p-NPB were dissolved in
600 L acetonitrile-d3. After a certain period of incubation, the spectrum
of the mixture was recorded on a Bruker AV300 NM. The 1H NMR spec-
trum of [Bmim]OAc without p-NPB was set as the control.
2.5. FTIR characterization of the H-bond between the anion of IL and water
The FTIR spectra of different samples (liquid lm membrane) were
collected on a VERTEX-70 infrared spectrometer (Bruker Co.) after mul-
tiple accumulations.
2.6. Kinetic procedures
The hydrolysis of p-NPB was carried out under pseudo-rst order
conditions (excess water, np-NPB:nwater = 1:10). In a typical kinetic ex-
periment, p-NPB (2.0 mmol), water (20 mmol), and IL (40 mmol) as cat-
alyst were added into 3 mL DMF, respectively. The mixed solution was
kept into a water bath at 55 C. After a period of time, an aliquot of the
resulting mixture as sample was taken out and diluted with DMF (con-
taining TrisHCl buffer, 50 mM, pH = 8.0). The absorbance of the dilut-
ed sample at 415 nm was measured on a Shimadzu 2550 UVVis
Spectrophotometer. The kinetic data were analyzed using the following
equations:
 
1 c0
kobs ln
t ct
At
ct c0 2
b
where kobs is the observed pseudo-rst order rate constant, At is the
absorbance of p-nitrophenolate at time t, and c0 and ct are the concen-
trations of p-NPB at t = 0 and t = t, respectively. The molar extinction
coefcient () of p-nitrophenolate in DMF (pH = 8.0) was
26,000 L mol1 cm 1. kobs was obtained from the plot of ln(c0/ct)
versus t.
355
2.7. Computational method
All calculations were performed with the Gaussian 09 program
package [25] employing the DFT with the hybrid functional M06 and
6-31G(d,p) basis set. The starting model is based on the optimized
geometry of reactants and ionic liquid. Frequency calculations at the
6-31G(d,p) theory level were carried out to identify all of the stationary
points as minima (zero imaginary frequency) or transition states (one
imaginary frequency). All bond lengths are given in angstrom ().
3. Results and discussion
3.1. Structural effect of substrate and catalyst on the hydrolysis of ester in
neat ionic liquids
[Bmim]OAc has been proved to be effective for the hydrolysis of
ester polymer [15]. So, in the present study, [Bmim]OAc was selected
as a catalyst for the hydrolysis of esters (small nonglyceride molecule).
The hydrolytic conversion of esters of various structures (see Fig. 1) in
neat [Bmim]OAc (as both solvent and catalyst) was studied. As can be
seen from Fig. 2, [Bmim]OAc has a catalytic effect on the hydrolysis of
the selected esters. The catalytic efciency of the IL depends on the
structure of esters. Among the esters studied, the conversion of p-NPB
is the highest (97.3%) while that of ethyl benzoate is the lowest
(5.2%). Fig. 1 also indicates that the conversion of phenol esters 14 is
higher than that of alcohol esters 57. Obviously, the difference in con-
version is caused by the substituent on esters.
For the hydrolysis of p-NPB, the catalytic efciency of several ILs was
also investigated (see Entries 14 in Table 1, all ILs are liquid at room
temperature). The conversion of p-NPB is signicantly reduced when
[Bmim]OAc is replaced by [Bdmim]OAc, which indicates that C2-H on
[Bmim]+ is involved in the hydrolytic process. When [Bmim]+ is
combined with different anions, the resulting ILs also display different
catalytic activities (decreased in the order of
[Bmim]OAc N [Bmim]CF3SO3 N [Bmim]BF4). It follows that the catalytic
efciency of [Bmim]OAc depends not only on its cation ([Bmim]+),
but also on the anion (OAc).
3.2. Effect of cation on the hydrolysis of p-NPB catalyzed by [Bmim]OAc in
DMF
To extensively investigate the IL composition dependent hydrolytic
conversion of an ester, as well as to avoid some inconvenience caused
by neat IL medium (e.g. high viscosity), the hydrolysis of p-NPB cata-
lyzed by ILs was carried out in DMF. To facilitate the comparison of
the catalytic performance of different ILs, the reaction conditions were
appropriately optimized (results see Fig. S1). In the following experi-
ments, the hydrolysis parameters were set at T = 85 C, t = 6.5 h, np-
NPB:nwater = 1:5, and nIL = 20 mol% for temperature, reaction time,
the molar ratio of ester to water, and the amount of catalyst,
respectively.
The effect of the cation of [Bmim]OAc (OAc as counter-anion) as
catalyst on the hydrolysis of p-NPB was rstly explored (Entries 510
1 in Table 1). Based on the conversion, these cations could be divided
Fig. 1. Structure of different esters.
356 X. Yu et al. / Journal of Molecular Liquids 216 (2016) 354359

Fig. 2. The hydrolytic conversion of different esters in [Bmim]OAc. An ester
(2.5 105 mol) was treated with 2.5 104 mol water in [Bmim]OAc at 35 C for 2.5 h.
into two categories: [Chol] + and 1-alkyl-3-methylimidazolium
cations ([C n mim] +, Entries 57) have higher catalytic activity,
while [(CH3)4N]+ and [Bdmim]+ have lower activity. As far as the
three imidazolium-based ILs ([Emim] + , [Bmim] + and [Hmim]+ )
are concerned, it is found that the longer the alkyl chain length of
the cations, the lower their catalytic effects would be. When the
structures of [Bmim]+ and [Bdmim]+ are correlated to their catalytic
activities, a conclusion that C2-H on [Bmim] + is involved in the
catalytic process can be drawn. Similarly, the higher catalytic activity
of [Chol]+ compared to that of [(CH3)4N]+ results from the hydroxyl
group on [Chol]+.
The above ndings imply that an H-bond between the C2-H on
[Bmim]+ and the carbonyl oxygen on p-NPB might activate the ester,
thereby facilitating the attack of water as a nucleophile toward the
ester [26]. To demonstrate the existence of the H-bonding, 1H NMR
spectroscopy was used to probe the interaction between [Bmim]OAc
and p-NPB [27]. Fig. 3 shows that the chemical shift of C2-H on
[Bmim]+ is located at 10.095 ppm, but it moves to 9.370 ppm after
2 h of incubation with equimolar p-NPB. With the extension of the incu-
bation time, it moves gradually to 9.048 ppm. This result may be related
to the competition between the H-bond acceptors (OAc and the car-
bonyl oxygen on p-NPB) for the H-bond donor (C2-H on [Bmim]+)
[20]. Addition of p-NPB results in a competition between p-NPB and
OAc for the H-bond donor (C2-H), which makes the resonance of
C2-H shift upeld [28]. The fact that the observed signal in the mixture
Table 1
The hydrolytic conversion of p-NPB catalyzed by various ILsa.
Entry IL
1 [Bmim]OAc
2 [Bmim]CF3SO3
3 [Bmim]BF4
4 [Bdmim]OAc
5 [Bmim]OAc
6 [Emim]OAc
7 [Hmim]OAc
8 [Chol]OAc
9 [Bdmim]OAc
10 [(CH3)4N]OAc
11 [Bmim]Cl
12 [Bmim]CF3SO3
13 [Bmim]BF4
14 Without IL
a
For Entries 14: p-NPB (2.5 105 mol), water (2.5 104 mol), 2.5 h in neat ILs at
35 C. For Entries 512: p-NPB (2.0 mmol), water (10 mmol), catalyst (0.4 mmol), 6.5 h in
DMF at 85 C.
b
Conversion was determined by HPLC.
Fig. 3. Chemical shift of the C2-H on [Bmim]+ () in the absence and presence of p-NPB. In
the mixture, varied with the incubation time.
changes with time is ascribed to the equilibrium established by the two
competitors (OAc and p-NPB) which is time dependent at comparable
concentrations of the two competitors. 1H NMR studies demonstrate
that there exists an H-bond between the C2-H on [Bmim]+ and the car-
bonyl oxygen on p-NPB. It is reported that the H-bond donor ability of
[Cnmim]+ is inversely proportional to the alkyl chain length, i.e., it de-
creases in the following order [Emim]+ N [Bmim]+ N [Hmim]+ [5,29]).
Interestingly, this order is found to be in accord with the sequence of
the conversions of p-NPB catalyzed by the imidazolium-based ILs of
different alkyl chain lengths. That is to say, the stronger the H-bonding
between the cation of the IL and p-NPB, the higher the conversion of
p-NPB would be. It follows that C2-H on [Bmim]+ can activate the
ester via H-bonding and promote the hydrolysis of esters.
3.3. Effect of anion on the hydrolysis of p-NPB catalyzed by [Bmim]OAc in
DMF
The effect of the anion of [Bmim]OAc ([Bmim]+ as counter-cation)
on the hydrolysis of p-NPB was also explored (see Entries 911 in
Table 1). As far as different anions are concerned, the catalytic activity
of OAc is the highest among the anions tested with the activity being
decreased in the order of OAc N Cl N CF3SO
3 N BF4 . This difference
may be related to the H-bond acceptor ability of anion [30]. A good
H-bond acceptor is easy to form an H-bond with water, thereby activat-
ing it as a nucleophile.
To verify the interaction between the anion of IL and water, the FTIR
spectra of IL/water binary systems were recorded. It is known that the
OH stretching vibration (OH) of water is very sensitive to the
H-bond [31]. For (OH), H-bond formation causes a red-shift of the ab-
sorption band and probably an increase in its bandwidth [32,33]. To
weaken the effect of solvent on water, CH3CN (relatively poor H-bond
Conversion (%)b
acceptor) was selected to replace DMF (Fig. S2). As can be seen from
97.3
Fig. 4, in the absence of IL the (OH) band of water in CH3CN is cen-
23.7
14.9 tered at ca. 3600 cm1. When [Bmim]OAc was added into the system,
31.7 the (OH) band moved to lower frequency with the main peak at
95.9 3424 cm1 and a shoulder peak at near 3558 cm1. This change indi-
97.4 cates that an H-bond is formed between [Bmim]OAc and water. Consid-
84.6
ering that the H-bond between [Bmim]+ and water (it is weaker than
87.2
46.5 that between anion and water [34]) may lead to the appearance of
43.8 low-frequency peaks, the FTIR spectra of [Bdmim]OAc were also
28.3 recorded. Fig. 5 shows that the presence of [Bdmim]OAc also makes
25.7
the (OH) band of water red-shift (3426 cm1 and 3555 cm 1);
20.2
6.0 moreover, with the increase of [Bdmim]OAc concentration, the area
normalized v(OH) band of water at low frequency (3250 cm1) be-
comes stronger, i.e., the H-bond becomes stronger [32]. All these results
indicate that there exists an H-bond between OAc. A similar protocol
was used to characterize the H-bond acceptor ability of other anions
 X. Yu et al. / Journal of Molecular Liquids 216 (2016) 354359
Fig. 4. FTIR spectra in the v(OH) region of H2O in the absence (solid line) and presence of
[Bmim]OAc (dash line) or [Bdmim]OAc (dot line) in CH3CN. The molar concentration of
the two ILs was equal.
(Fig. 6). The H-bond acceptor ability of the tested anions decreases in
the following order: OAc N Cl N CF3SO
3 N BF4 (the more obvious
1
the peak at 3240 cm , the stronger the H-bond [35,36]). This order is
found to be in good agreement with the sequence of the conversions
of p-NPB catalyzed by the corresponding ILs, i.e., a strong H-bond accep-
tor favors the hydrolysis of the ester. The above studies demonstrate
that the anion of [Bmim]OAc can activate the nucleophile water via
H-bonding to enhance the hydrolysis of p-NPB.
3.4. Kinetics studies on the hydrolysis of p-NPB catalyzed by [Bmim]OAc in
DMF
Kinetics effect can reect the specic ILreactant/activated complex/
product interaction [37,38]. For further understanding of the role of
[Bmim]OAc in ester hydrolysis, the kinetics of the hydrolysis of p-NPB
catalyzed by different ILs in DMF was investigated. In the present kinet-
ics studies, all the experiments were carried out at 55 C and under
pseudo-rst order conditions (using an excess of water). Table 2
shows the kobs for the hydrolysis of p-NPB catalyzed by different ILs.
As can be seen, [Bmim]OAc results in the largest kobs among the ILs test-
ed. The comparison of kobs under [Bmim]OAc with that under
[Bdmim]OAc indicates an obvious activating effect of C2-H on
[Bmim]+, and by similar comparison it can be concluded that the cata-
lytic effect of OAc is the most pronounced among the tested anions.
Fig. 5. The normalized OH stretching band of H2O in CH3CN in the presence of different
values of [Bdmim]OAc. The molar concentration of the IL was set at 0 M (solid line),
0.5 M (dash line), 0.75 M (dot line), and 1.0 M (dash dot line).
357
Fig. 6. The normalized OH stretching band of H2O in CH3CN in the absence (solid line)
and presence of different ILs ([Bmim]BF4, dash line; [Bmim]CF3SO3, dot line; [Bmim]Cl,
dash-dot line; [Bmim]OAc, dash-dot-dot line) at a xed IL concentration.
Table 2 also shows that kobs under [Bmim]OAc is ca. 10 times as high
as that under [Bdmim]OAc, while the former is 131 times and 214
times higher than kobs under [Bmim]Cl and kobs under [Bmim]BF4, re-
spectively. This result indicates that the contribution of the anion
OAc in [Bmim]OAc was higher than that of the cation [Bmim]+ to
the hydrolysis of p-NPB. The same conclusion could be drawn from
the corresponding conversions under [Bmim]OAc, [Bmim]BF4,
[(CH3)4N]OAc and [Bdmim]OAc (see Table 1). It follows that both kobs
and conversion have similar dependence on anion/cation of ILs.
3.5. Joined effect of anion/cation of [Bmim]OAc on the hydrolysis of p-NPB
The preceding studies have demonstrated the activating effects of
both [Bmim]+ and OAc on the hydrolysis of p-NPB. Further analysis
on the available data also indicates that there is a joined effect be-
tween the anion and the cation during the catalysis. As [Bdmim]+ and
[(CH3)4N]+ are not involved in the H-bonding, the catalytic effect of
[Bdmim]OAc or [(CH3)4N]OAc results from the anion (OAc). Similarly,
the catalytic effect of [Bmim]BF4 originates mainly from the cation
[Bmim]+ due to the weak H-bond acceptor ability of BF 4 . The compar-
ison of the sum of the catalytic effects of both [Bdmim]OAc/
[(CH3)4N]OAc and [Bmim]BF4 with the catalytic effect of [Bmim]OAc is
helpful to the better understanding of the joined effect. The kobs-
5 1
[Bmim]OAc for the hydrolysis of p-NPB (78.6 10 s ) is found to be
higher than the sum of kobs-[Bdmim]OAc and kobs-[Bmim]BF4
(8.09 10 5 s 1) (see Table 2); i.e., the cation and the anion of
[Bmim]OAc have a joined effect on the hydrolysis of p-NPB. From the
conversion data, a similar effect is also observed. The conversion of p-
NPB catalyzed by [Bmim]OAc (95.7%) is higher than the sum of that
by [Bdmim]OAc and [Bmim]BF4 (66.7%) in DMF. A similar comparison
between the conversion by [Bmim]OAc and those by both
[(CH3)4N]OAc and [Bmim]BF4 further demonstrates the joined effect.
The electrostatic interaction between the cation and anion of an IL
should be responsible for the joined effect [22,39,40].
Table 2
kobs for the hydrolysis of p-NPB catalyzed by different ILsa.
IL kobs 105 (s1)
[Bmim]OAc 78.6 5.3
[Bdmim]OAc 7.73 0.65
[Bmim]Cl 0.591 0.031
[Bmim]BF4 0.364 0.021
a
Reaction conditions: p-NPB (2.0 mmol), water (20 mmol),
catalyst (40 mmol) in DMF at 55 C.
358 X. Yu et al. / Journal of Molecular Liquids 216 (2016) 354359

Scheme 1. Suggested mechanism for the hydrolysis of ester catalyzed by [Bmim]OAc.

3.6. H-bond based DFT calculations for a possible pathway
For the hydrolysis of p-NPB catalyzed by [Bmim]OAc, a DFT calcula-
tion was performed to propose an H-bond involved reaction pathway
(see Scheme 1). The optimized reactant complex (Rcs) shows a 2.03
long H-bond between the C2-H on [Bmim]+ and the carbonyl oxygen
on p-NPB (Fig. 7) in addition to an H-bond formed between the oxygen
atom on OAc and the hydrogen atom on water. The electrostatic po-
tential of Rcs (Rcs-ESP) intuitively displays the electrostatic interaction
between [Bmim]+ and OAc [41,42]. Obviously, the electrostatic inter-
action makes the activated carbonyl be easily attacked by the activated
water. Going through transition state TS-1, intermediate (Int) and tran-
sition state TS-2, the reactants transform into the products (Ps). During
the transformation, the bond length of (C2-HO_C) varies (it is 2.03,
1.82, 1.68, 1.70 and 2.09 for the initial state, TS-1, Int, TS-2, and the
nal state, respectively). It follows that the H-bonding can not only ac-
tivate the reactions, but also stabilize the intermediate and transition
states.
4. Conclusions
The hydrolysis of different esters in [Bmim]OAc and the catalytic ef-
fects of different ILs on the conversion of p-NPB were investigated. It is
found that the IL catalyzed conversion of an ester depends not only on
the structure of the ester but also on the structure of the IL. For the hy-
drolysis of p-NPB catalyzed by [Bmim]OAc, the catalytic activities of
both the cation and the anion are well correlated with the H-bonding
between the IL and p-NPB and/or water. The spectroscopy studies

Fig. 7. Optimized geometries of reactant complex (Rcs) and its electrostatic potential on the 0.001 e/bohr3 isodensity surface (Rcs-ESP), transition states (TS), intermediate (Int), and
product (Ps) of the hydrolysis of p-NPB by [Bmim]OAc.
 X. Yu et al. / Journal of Molecular Liquids 216 (2016) 354359
complemented by DFT calculations indicate that [Bmim]+ could acti-
vate an ester via H-bonding between C2-H and the carbonyl oxygen
on ester; the OAc, as an H-bond acceptor, could also activate the nucle-
ophile (water) via H-bonding. The kinetics studies indicate that for
[Bmim]OAc as catalyst, its anion OAc contributes more than its cation
[Bmim]+ to the hydrolysis of p-NPB, and the anion/cation has a joined
effect on the hydrolysis. The new evidence provided by the present
study helps to fully understand the activation mechanism of an IL
toward the hydrolysis of esters.
Acknowledgments
We are grateful for the nancial support from the Fundamental Re-
search Funds of Shandong University (2015CJ005), the Provincial Key
R & D Project of Shandong (2015GSF121035) and the National Natural
Science Foundation of China (20973103 and 21173133).
Appendix A. Supplementary data
Supplementary data to this article can be found online at http://dx.
doi.org/10.1016/j.molliq.2016.01.049.
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