Phase-transfer catalysis of a new cationic gemini surfactant with ester groups for nucleophilic substitution reaction

Article abstract of DOI:10.1016/j.cclet.2014.04.006

A highly effective phase transfer of a quaternary ammonium gemini surfactant with ester groups ((diethylhexanedioate) diyl-α,ω-bis(dimethyl dodecyl ammonium bromide) referred to as 12-10-12) was synthesized with high yield and characterized by infrared spectroscopy, elemental analysis and ¹H-NMR. Then, 12-10-12 was used as a phase transfer catalyst to study the catalytic effect on the reaction of anhydrous sodium acetate and 4-methylbenzyl chloride. The possible catalytic mechanism and the influence of surfactant concentration, temperature and type are also discussed. The experimental results showed that the catalysis efficiency was more active than the traditional, single-chained surfactant, tetrabutyl ammonium bromide. It also revealed that the reaction was first-order with respect to the concentration of 4-methylbenzyl chloride. The concentration of 4-methylbenzyl chloride grew linearly with the concentration of 12-10-12 and as the reaction temperature increased. The optimum reaction time was 7 h.

Full text of DOI:10.1016/j.cclet.2014.04.006

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CCLET-2943; No. of Pages 5
Chinese Chemical Letters xxx (2014) xxx–xxx
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Chinese Chemical Letters
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Original article
Phase-transfer catalysis of a new cationic gemini surfactant with ester
groups for nucleophilic substitution reaction
Dong-Qing Xu a, Zhong-Wen Pan b,
*
a Center of Analysis and Measurement, Anhui Science and Technology University, Fengyang 233100, China
b School of Chemistry and Chemical Engineering, Anhui University, Hefei 230039, China
A R T I C L E I N F O
A B S T R A C T
Article history:
A highly effective phase transfer of a quaternary ammonium gemini surfactant with ester groups
Received 22 November 2013
Received in revised form 21 March 2014
Accepted 24 March 2014
Available online xxx
((diethylhexanedioate) diyl-a,v-bis(dimethyl dodecyl ammonium bromide) referred to as 12-10-12)
was synthesized with high yield and characterized by infrared spectroscopy, elemental analysis and 1H-
NMR. Then, 12-10-12 was used as a phase transfer catalyst to study the catalytic effect on the reaction of
anhydrous sodium acetate and 4-methylbenzyl chloride. The possible catalytic mechanism and the
influence of surfactant concentration, temperature and type are also discussed. The experimental results
showed that the catalysis efficiency was more active than the traditional, single-chained surfactant,
tetrabutyl ammonium bromide. It also revealed that the reaction was first-order with respect to the
concentration of 4-methylbenzyl chloride. The concentration of 4-methylbenzyl chloride grew linearly
with the concentration of 12-10-12 and as the reaction temperature increased. The optimum reaction
time was 7 h.
Keywords:
Gemini surfactant
Phase-transfer catalyst
Kinetic model
ß 2014 Zhong-Wen Pan. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights
reserved.
1. Introduction
great deviation from the pseudophase ion-exchange model at
high concentration. Also some studies examined aqueous/organic
Rapid development in the field of catalysis has directed
increasing attention on the catalyst. Phase-transfer catalysis and
micellar phase-transfer catalysis are two well-known methods of
promoting organic reactions, but surfactants are among the most
important catalysts. Traditional single-chained surfactants have
been widely studied [1–3]. In 1991, Menger et al. synthesized, for
the first time, reported on a series of three, two-chained
surfactants with lower critical micell concentration (CMC) than
traditional, single-chained surfactants and named them gemini
surfactants. In recent years, more and more investigators are
studying these new structural surfactants and their phase-
transfer catalytic effects [4–11]. However, a few researchers have
studied the micellar catalysis of gemini surfactants [12–17]. For
example, Qiu et al. [13] studied micellar-catalyzed alkaline
hydrolysis of 2,4-dinitrochlorobenzene (DNCB) in the presence
of the cationic gemini surfactant, 1,2-ethane bis(dimethyldodecyl
ammonium bromide), and found that this system had a relatively
low second-order rate constant in micellar pseudophase and a
two-phase reactions [18,19] or focused on studying their
elemental characteristics, for example, since they can be more
easily adsorbed in the interface between water and air at lower
critical micelle concentrations [4], provide greater efficiency in
reducing the surface tension and lowering the Krafft temperature,
and better solubilization in comparison with conventional
surfactants [20–24].
Until now, it was reported [1,25–28] that extensive micellar
catalytic reactions were generally carried out in solution with
conventional monomeric surfactants. However, still few studies
involved liquid-solid catalysis effects on inorganic/organic reac-
tions using monomeric surfactants, let alone gemini surfactants.
In this paper,
a new gemini surfactant connecting two
alkyldimethylammonium bromide moieties, namely 12-10-12,
was synthesized and mainly applied to catalysis reactions. Two
synthetic steps were designed to form the final product which had
a flexible spacer containing ten carbon atoms and two alkyl chains
with twelve carbon atoms (Scheme 1). Moreover, the catalysis
effect on the reaction of anhydrous sodium acetate and 4-
methylbenzyl chloride was also investigated, in contrast to the
traditional monomeric surfactants. The results show that 12-10-12
possesses better catalysis ability. Based on the related knowledge,
*
Corresponding author.
E-mail address: ahdxpzw@163.com (Z.-W. Pan).
http://dx.doi.org/10.1016/j.cclet.2014.04.006
1001-8417/ß 2014 Zhong-Wen Pan. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.
Please cite this article in press as: D.-Q. Xu, Z.-W. Pan, Phase-transfer catalysis of a new cationic gemini surfactant with ester groups for
nucleophilic substitution reaction, Chin. Chem. Lett. (2014), http://dx.doi.org/10.1016/j.cclet.2014.04.006

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collected at regular intervals for analysis using Agilent 7820 Gas-
Chromatograph equipped with a FID detector, and orthodichlor-
obenzene served as an internal standard. The 4-methylbenzyl
acetate was extracted by benzene.
The kinetic equations are expressed as follows:
Â
Ã
d½Crꢃ
rate ¼ ꢂ
¼ kobsd½Crꢃ ¼ ½Crꢃðk1k2 Nþ þ k0Þ
dt
¼ ½Crꢃð2k1k2½C12ꢃ þ k0Þ
Â
Ã
Nþ ¼ 2½C12ꢃ:kobsd ¼ 2k1k2½C12ꢃ þ k0
Scheme 1. Synthetic route for the gemini surfactant 12-10-12.
where kobsd is the apparent first-order rate constant for the
reaction, [Cr] is the concentration of 4-methylbenzyl chloride, [C12
]
a theoretical model was presented to explain why this gemini
surfactant could promote liquid-solid reactions.
is the concentration of 12-10-12, k0 is the first-order rate constant
without phase transfer catalyst, k1 is the equilibrium constant and
k2 is the second-order-rate constant with the phase transfer
catalyst, respectively. The above equations suggest: (1) The
reaction is first-order with respect to the concentration of 4-
methylbenzyl chloride and the plots of ln[Cr] vs. time should be
linear. (2) kobsd increases with the concentration of phase transfer
catalyst and the plots of kobsd vs. [C12] are linear lines.
2. Experimental
2.1. Materials and methods
Chemicals, reagents and solvents from commercial sources are
of analytical or spectroscopy grade and used as received without
further purification. 1H NMR spectra were recorded on an AVANCE-
400 NMR spectrometer. Elemental analyses were carried out on an
Elementar Vario EL-ꢀ. FT-IR spectra were measured on a Nicolet
NEXUS 870 spectrometer (KBr discs). Thermogravimetry analyses
(TGA) were carried out using a Pyris1 TGA (PE Corp., USA) at a
heating rate of 10 8C/min from 40 8C to 600 8C under a nitrogen
atmosphere.
3. Results and discussion
3.1. Thermal analysis
The TGA measurement of 12-10-12 was determined in the
range of 20–600 8C under nitrogen (Fig. 1). In order to study the
thermal stability of this compound, thermogravimetric analysis
(TGA) was performed on single crystal samples. TGA data show
that 12–10-12 is stable up to 205 8C, loses weight from 205 8C to
320 8C corresponding to decomposition of double alkyl chains, and
finally loses weight from 320 8C to 410 8C corresponding to the
losses of the flexible spacer.
2.2. Synthesis and characterization
Synthesis of compound A: Compound A was obtained by
refluxing dimethyl hexanedioate (8.70 g, 50.00 mmol) with
dimethylaminoethanol (26.70 g, 300.00 mmol) in the presence
of 1.50 g dibutyltin dilaurate catalyst at 100 8C for 6 h (Scheme 1).
The by-products of methanol and residual dimethylaminoethanol
were removed by vacuum from the reaction mixture and the crude
product was purified by column chromatography. Yield: 9.00 g
3.2. The catalytic mechanisms of gemini surfactant
According to previous knowledge [13,24], a model to explain
the liquid–solid phase transfer catalysis reaction mechanism has
been proposed for the nucleophilic substitution reaction of
anhydrous sodium acetate and 4-methylbenzyl chloride with
the phase transfer catalyst of 12-10-12 (Scheme 2). It is noted that
the solubility of anhydrous sodium acetate in DMF is poor at 60 8C.
(62.50%). 1H NMR (400 MHz, CDCl3):
d 1.66–1.73 (m, 4H,
CCH2CH2C), 2.33–2.56 (m, 4H, 2 ꢁ COCH2), 3.48 (s, 12H,
4 ꢁ CH3), 4.14–4.17 (t, 4H, J = 7.2 Hz, 2 ꢁ NCH2), 4.46–4.72 (m,
4H, OCH2). IR (KBr, cmꢂ1): 2947, 2822, 1736, 1460, 1383, 1172,
1041 [15].
Synthesis of 12-12-12: A solution of compound A (5.00 g, 17.40
mmol) and n-C12H25Br (13.00 g, 52.50 mmol) in acetone was
refluxed for 24 h. The precipitate was recrystallized from acetone
to afford white crystals 12.50 g. Yield: 91.60%. 1H NMR (400 MHz,
100
12-10-12
CDCl3):
d
0.86–0.88 (t, 6H, J = 6.8 Hz, 2 ꢁ CH3), 1.25–1.36 (m, 36H,
80
60
40
20
0
2 ꢁ (CH2)9), 1.71–1.77 (m, 8H, 2 ꢁ CH2, CCH2CH2C), 2.33–2.56 (m,
4H, 2 ꢁ CH2COO), 3.48 (s, 12H, 2 ꢁ (CH3)2), 3.62–3.66 (t, 4H,
J = 7.6 Hz, 2 ꢁ 2CH2), 4.14–4.17 (t, 4H, J = 7.2 Hz, 2 ꢁ CH2N+), 4.47–
4.73 (m, 4H, 2 ꢁ CH2) [29]. Anal. calcd. for C38H78Br2N2O4: C, 57.98;
H, 9.92; N, 3.56. Found: C, 57.37; H, 9.94; N, 3.53. IR (KBr, cmꢂ1):
2921, 2851, 1723, 1472, 1382, 1274, 1153.
2.3. Kinetic measurements
Anhydrous sodium acetate, 3.50 g (42.70 mmol, 0.9163
mmol/L),
4-methylbenzyl
chloride
5.00 g
(35.60 mmol,
0
100
200
300
400
500
600
Temperature( oC)
0.764 mol/L) and a certain amount of 12-10-12 were added to
40 mL DMF. The mixture was stirred at required speed and desired
temperature. The reaction continued for 7 h. The samples were
Fig. 1. TGA curve of 12-10-12.
Please cite this article in press as: D.-Q. Xu, Z.-W. Pan, Phase-transfer catalysis of a new cationic gemini surfactant with ester groups for
nucleophilic substitution reaction, Chin. Chem. Lett. (2014), http://dx.doi.org/10.1016/j.cclet.2014.04.006

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H3C H3C
3
k1
N
NaX(s)
(1)
(org)
(intermediate, org)
CH3COONa (s)
N
CH3COO
H3C
X
H3C
H3C
N
H3C
k2
CH3COO
(org) (2)
N
(org)
CH2COOCH3
H3C
k0
(org)
H3C
CH2Cl
X
H3C
H3C
(intermediate, org)
(s)
(3)
H3C
CH2COOCH3
NaCl
CH3COONa (s)
H3C
CH2Cl
(org)
Scheme 2. Model of solid–liquid phase transfer catalysis reaction mechanism (k0 is the first-order rate constant without phase transfer catalyst, k1 is the equilibrium constant
and k2 is the second-order-rate constant with the phase transfer catalyst, respectively).
Table 1
Some kinetic and thermodynamic parameters to better understand
Catalysis parameters of gemini surfactant at various concentrations at 50 oC.
the catalytic mechanism were obtained. The reaction of 4-
methylbenzyl chloride and anhydrous sodium acetate with the
participation of 12-10-12 can be supposed to take place in the
liquid–solid interface.
C12 (mol/L)
Kobsd
Linear correlation
coefficients
0
0.071
0.14
0.17
0.21
0.24
0.30
0.999
0.999
0.999
0.999
0.999
0.999
0.004
0.008
0.012
0.016
0.020
As represented by the reaction mechanism of the micellar
catalysis in Scheme 2, the hydrophilic group of gemini
surfactant initially unites with CH3COOꢂ group, and then reacts
with 4-methylbenzyl chloride through the nucleophilic
substitution reaction. While the increasing of aggregation
number and the micelle size may significantly influence the
reaction rate between the reactants at the micelle surface
region. So when the concentration of 12-10-12 approaches the
value of CMC, the molecules of the gemini surfactant began to
form micelles (molecular agglomerates), and the number of
micelles will increase with the concentration of 12-10-12. By
this stage, the cationic gemini surfactants can bind with more
and more CH3COOꢂ groups at the micelle surface region. This
is to the benefit of the process of the nucleophilic substitution
reaction, and thus leads to the increasing of the reaction
rate.
The apparent first-order rate constants (kobsd
) and linear
correlation coefficients were evaluated from the linear plots
of ln(1/Cr) vs. time. The data are summarized in Table 1. Clearly,
the values of linear correlation coefficients were close to one,
which indicated that the association between ln(1/Cr) and
reaction time is coincident with a linear relationship and the
experimental results were reliable. Then, Fig. 3 was obtained by
using the values of the concentrations of 12-10-12 (C12) and the
apparent first-order rate constants (kobsd) in Table 1 as the X and
Y axes, respectively. The relationship between the apparent
first-order rate constants (kobsd) and the concentrations of 12-
10-12 (C12) was also close to a linear relationship, and its slope
and intercept were estimated to be 10.6 and 0.071, respectively.
Finally, the linear equation between the surfactant concentra-
tion (C12) and the apparent-first-order rate constants (kobsd) is
deduced as follows:
3.3. Influence of surfactant concentration
Firstly, in order to investigate the effect of surfactant
concentration for the apparent-first-order rate constants (kobsd),
a series of nucleophilic reactions was carried out in the presence
of 12-10-12 with various concentrations at 50 8C. As shown by
the ꢂlnCr vs. time characteristics in Fig. 2, all the kinetic results
fit the first-order rate equation very well: ln(1/Cr) = kobsd t + A.
kobsd ¼ 10:6½C12ꢃ þ 0:071
2.5
0.30
0.25
0.20
0.15
0.10
0.05
0 mol/L
0.004 mol/L
0.008 mol/L
0.012 mol/L
0.016 mol/L
0.020 mol/L
2.0
1.5
1.0
0.5
0.000
0.005
0.010
0.015
0.020
Concentration (mol/L)
1
2
3
4
5
6
7
Time (h)
Fig. 3. Plot of kobsd vs. concentration of 12-10-12 for the phase transfer catalysis by
12-10-12 at 50 8C. [4-Methylbenzyl chloride] = 0.764 mol/L, [sodium
acetate] = 0.9163 mol/L.
Fig. 2. Plot of ꢂlnCr vs. time for the phase transfer catalysis by 12-10-12 at 50 8C. [4-
Methylbenzyl chloride] = 0.764 mol/L, [sodium acetate] = 0.9163 mol/L.
Please cite this article in press as: D.-Q. Xu, Z.-W. Pan, Phase-transfer catalysis of a new cationic gemini surfactant with ester groups for
nucleophilic substitution reaction, Chin. Chem. Lett. (2014), http://dx.doi.org/10.1016/j.cclet.2014.04.006

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1.8
40 oC
45 oC
50 oC
55 oC
60 oC
3.6
3.0
2.4
1.8
1.2
0.6
12-10-12
1.6
1.4
1.2
1.0
0.8
0.6
0.4
Tetrabutyl ammonium bromide
CTAB
1
2
3
4
5
6
7
1
2
3
4
5
6
7
Time (h)
Time (h)
Fig. 4. Plot of ꢂlnCr vs. time for phase transfer catalysis by 12-10-12 at different
temperatures. [4-Methylbenzyl chloride] = 0.764 mol/L, [sodium acetate] =
0.9163 mol/L.
Fig. 6. Plot of ꢂlnCr vs. time for phase transfer catalysis by 12-10-12, tetrabutyl
ammonium bromide and CTAB, respectively. [4-Methylbenzyl
chloride] = 0.764 mol/L, [sodium acetate] = 0.9163 mol/L, [12-10-12] = 0.012
mol/L, [tetrabutyl ammonium bromide] = 0.012 mol/L, [CTAB] = 0.012 mol/L.
In addition, the effect of the concentration of 4-methylbenzyl
chloride on the reaction rate was also studied, and a series of
nucleophilic reactions was carried out in the presence of 12-10-12
at fixed concentrations at 50 8C. As shown in Fig. S1 (Supporting
information), although the concentration of 4-methylbenzyl
chloride is different, the ratios between the values of ꢂlnCr and
reaction time (h) are almost same, which indicates the concentra-
tion of 4-methylbenzyl chloride can influence the reaction rate,
and it does not impact the apparent first-order rate constants
(kobsd).
80
70
60
50
40
30
20
10
12-10-12
Tetrabutyl ammonium bromide
CTAB
3.4. Influence of reaction temperature
1
2
3
4
5
6
7
The nucleophilic substitution reaction was carried out at
various temperatures (at 40, 45, 50, 55 and 60 8C) when the
concentration of 12-10-12 was 8.00 mmol/L (Fig. 4). The influence
of temperature on ꢂlnCr was studied according to the Arrhenius
equation: lnkobsd = ꢂEa/RT + lnA. Fig. 5 gave the plot of lnkobsd vs. 1/
T. The apparent activation energy was 93.11 kJ/mol obtained by the
slope.
Time (h)
Fig. 7. Plot of percent conversion vs. time for phase transfer catalysis by 12-10-12
and tetra butyl ammonium bromide, respectively. [4-Methylbenzyl chloride] =
0.764 mol/L, [sodium acetate] = 0.9163 mol/L, [12-10-12] = 0.012 mol/L, [tetrabutyl
ammonium bromide] = 0.012 mol/L, [CTAB] = 0.012 mol/L.
hexadecyl trimethyl ammonium bromide (CTAB). It is evident from
Figs. 6 and 7 that the catalysis kinetic model of 12-10-12 was
similar to that of conventional quaternary ammonium salt catalyst
and the catalytic activity of 12-10-12 was more efficient than
tetrabutyl ammonium bromide and CTAB at the same concentra-
tion. The reaction rate with 12-10-12 was greater than those of
tetrabutyl ammonium bromide and CTAB, which can be explained
in view of unique molecular structure of the gemini surfactant with
two catalyst active sites (active site is meant to be the catalyst
cation N+) in one molecule.
3.5. Influence of different surfactants
The nucleophilic substitution reaction was studied at 50 8C
when the concentration of surfactants was 12.00 mmol/L. The
surfactants were 12-10-12, tetrabutyl ammonium bromide and
-0.5
-1.0
-1.5
-2.0
-2.5
-3.0
4. Conclusion
In summary, a gemini surfactant (12-10-12) with ester groups
was conveniently synthesized and an investigation of the liquid-
solid phase transfer reaction of anhydrous sodium acetate and 4-
methylbenzyl chloride in the presence of 12-10-12 has been
studied. It was found that the phase transfer catalyst of gemini
surfactant (12-10-12) was more effective than the traditional
surfactant phase transfer catalyst (such as tetrabutyl ammonium
bromide). A suitable kinetic model was proposed to explain the
observed experimental results and it was determined that the
experimental results fit the model very well.
0.00300
0.00305
0.00310
0.00315
0.00320
1/T (1/K)
Fig. 5. Plot of lnkobsd vs. 1/T for phase transfer catalysis by 12-10-12. [4-
Methylbenzyl chloride] = 0.764 mol/L, [sodium acetate] = 0.9163 mol/L.
Please cite this article in press as: D.-Q. Xu, Z.-W. Pan, Phase-transfer catalysis of a new cationic gemini surfactant with ester groups for
nucleophilic substitution reaction, Chin. Chem. Lett. (2014), http://dx.doi.org/10.1016/j.cclet.2014.04.006

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5
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Acknowledgment
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This work was supported by the Talent Foundation of Anhui
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Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at http://dx.doi.org/10.1016/j.cclet.2014.04.006.
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Please cite this article in press as: D.-Q. Xu, Z.-W. Pan, Phase-transfer catalysis of a new cationic gemini surfactant with ester groups for
nucleophilic substitution reaction, Chin. Chem. Lett. (2014), http://dx.doi.org/10.1016/j.cclet.2014.04.006