Synthesis, characterization and application of nano-N,N,N′,N′-tetramethyl-N-(silica-n-propyl)-N′-sulfo-ethane-1,2-diaminium chloride as a highly efficient catalyst for the preparation of N,N′-alkylidene bisamides

Article abstract of DOI:10.1007/s11164-019-03775-7

Abstract: A novel mesoporous nanomaterial, namely nano-N,N,N′,N′-tetramethyl-N-(silica-n-propyl)-N′-sulfo-ethane-1,2-diaminium chloride (nano-[TSPSED][Cl]₂), was prepared, and characterized using Fourier-transform infrared spectroscopy (FT-IR), energy-dispersive X-ray spectroscopy (EDS), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), adsorption/desorption porosimetry (BET, Langmuir, BJH and adsorption/desorption isotherm), thermal gravimetric (TG), differential thermal gravimetric (DTG) and X-ray diffraction (XRD) analyses. Afterward, nano-[TSPSED][Cl]₂ was used as a highly efficient and recyclable nanocatalyst for the condensation reaction of primary amides (2 eq.) with arylaldehydes (1 eq.) under solvent-free conditions to afford N,N′-alkylidene bisamides in high yields and in short times. Graphical abstract: [Figure not available: see fulltext.].

Full text of DOI:10.1007/s11164-019-03775-7

Research on Chemical Intermediates
https://doi.org/10.1007/s11164-019-03775-7
Synthesis, characterization and application of
nano‑N,N,N′,N′‑tetramethyl‑N‑(silica‑n‑propyl)‑N′‑sulfo‑
ethane‑1,2‑diaminium chloride as a highly efcient catalyst
for the preparation of N,N′‑alkylidene bisamides
Abdolkarim Zare1 · Masoud Sadeghi‑Takallo1 · Mostafa Karami1 ·
Alireza Kohzadian1
Received: 17 November 2018 / Accepted: 12 February 2019
© Springer Nature B.V. 2019
Abstract
A novel mesoporous nanomaterial, namely nano-N,N,N′,N′-tetramethyl-N-(silica-
n-propyl)-N′-sulfo-ethane-1,2-diaminium chloride (nano-[TSPSED][Cl]2), was
prepared, and characterized using Fourier-transform infrared spectroscopy (FT-
IR), energy-dispersive X-ray spectroscopy (EDS), feld emission scanning electron
microscopy (FE-SEM), transmission electron microscopy (TEM), adsorption/des-
orption porosimetry (BET, Langmuir, BJH and adsorption/desorption isotherm),
thermal gravimetric (TG), diferential thermal gravimetric (DTG) and X-ray difrac-
tion (XRD) analyses. Afterward, nano-[TSPSED][Cl]2 was used as a highly efcient
and recyclable nanocatalyst for the condensation reaction of primary amides (2 eq.)
with arylaldehydes (1 eq.) under solvent-free conditions to aford N,N′-alkylidene
bisamides in high yields and in short times.
Electronic supplementary material The online version of this article (https://doi.org/10.1007/s1116
4-019-03775-7) contains supplementary material, which is available to authorized users.
*
Abdolkarim Zare
abdolkarimzare@pnu.ac.ir; abdolkarimzare@yahoo.com
1
Department of Chemistry, Payame Noor University, PO Box 19395-3697, Tehran, Iran
Vol.:(0123456789)
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A. Zare et al.
Graphical abstract
Keywords Mesoporous nanocatalyst · Silica-based nanocatalyst · Nano-N,N,N′,N′-
tetramethyl-N-(silica-n-propyl)-N′-sulfo-ethane-1,2-diaminium chloride (nano-
[TSPSED][Cl]2) · N,N′-alkylidene bisamide · Solvent-free
Introduction
In recent years, application of nanoparticles as catalysts for organic transformations
has been dramatically increased, because of possessing a large surface-to-volume
ratio compared to bulk materials (and consequently enhanced activity and ef-
ciency), capability to functionalize for diferent catalytic uses, low density and an
eco-friendly nature [1–12]. There are several kinds of nanocatalysts; an important
group of them is solid-supported ones [2–12]. Among the solid-supported nano-
catalysts, silica-based ones are usually preferred, since they have various inimitable
properties, including low cost, green nature, high surface area, safety, non-corro-
siveness, reasonable thermal and chemical stability, simple preparation and func-
tionalization, tunability of nano-sizes, and easy separation from the reaction mixture
[6–12].
A useful and practical technique in synthetic organic chemistry, which is in
accordance with green chemistry protocols, is solvent-free conditions. It has been
extensively utilized during the last decades, and possesses various advantages com-
pared to the classical solution conditions. These benefts include production of target
compounds in higher yield and shorter reaction time with higher selectivity, saving
1 3

Synthesis, characterization and application of…
energy, reducing or preventing synthesis of waste/by-products, and easier work-up
and purifcation of product [13–17].
Amide and bisamide moieties are of importance, as they are present in scafolds
of many chemical, industrial, biological and pharmacological compounds [18–25].
Bisamides are essential components to introduce gem-diaminoalkyl fragments in
retro-inverse pseudo-peptide derivatives [21, 22]. Furthermore, these compounds
are applied in the preparation of peptidomimetic compounds [23, 24]. Bisamides are
also utilized as ligands in an Ullmann reaction leading to potential drugs [25]. The
common approach for the preparation of N,N′-alkylidene bisamides is the condensa-
tion reaction of primary amides (2 eq.) with arylaldehydes (1 eq.) using diferent
catalysts, such as heteropoly-11-tungsto-1-vanadophosphoric acid supported on nat-
ural clay [26], NiFe2O4@KIT-6@ZnO [27], montmorillonite K10 [28], NiFe2O4@
SiO2-PPA [29], H14[NaP5W29MoO110] [30], nano-SnCl4.SiO2 [31], hydroxyapatite
[32], 3D-network polymer supported Bronsted acid ionic liquid based on calix [4]—
resorcinarene [33], p-toluene sulfonic acid [34], boric acid [35], and Silzic [36].
In this work, we have aggregated the advantages of nanocatalysts, silica-based
catalysts and solvent-free technique to achieve a useful organic transformation. In
this regard, we have reported synthesis of a novel mesoporous silica-based nano-
catalyst, namely nano-N,N,N′,N′-tetramethyl-N-(silica-n-propyl)-N′-sulfo-ethane-
1,2-diaminium chloride (nano-[TSPSED][Cl]2), and its characterization using FT-IR
(Fourier-transform infrared spectroscopy), EDS (energy-dispersive X-ray spectros-
copy), FE-SEM (feld emission scanning electron microscopy), TEM (transmission
electron microscopy), adsorption/desorption porosimetry (BET, Langmuir, BJH
and adsorption/desorption isotherm), TG (thermal gravimetric), DTG (diferential
thermal gravimetric) and XRD (X-ray difraction) analyses. Subsequently, we have
applied nano-[TSPSED][Cl]2 as a Brønsted acidic nanocatalyst for the preparation
of N,N′-alkylidene bisamides from primary amides and arylaldehyde under solvent-
free conditions.
Experimental
Materials and instruments
All starting materials and solvents were purchased from Merck or Fluka Chemical
Companies. Identifcation of the products was achieved by comparison of their melt-
ing points and/or spectral data with the reported data in the literature. The nano-
silica gel for the synthesis of nano-[TSPSED][Cl]2 was prepared by the reported
procedure [37]. Progress of the reactions was monitored by TLC using silica gel
SIL G/UV 254 plates. The 1H NMR (500 MHz) and 13C NMR (125 MHz) were run
on a Bruker Avance DPX FT-NMR spectrometer (δ in ppm). Melting points were
recorded on a Buchi B-545 apparatus in open capillary tubes. FT-IR spectrums were
run using Shimadzu IR-60 apparatus. Thermal gravimetric analysis (TGA) was done
using Bahr STA 504 (Germany) apparatus, at 25–600 °C, with temperature increase
rate of 10 °C.min−1 in argon atmosphere. Adsorption/desorption porosimetry analy-
ses were acquired on a BELSORP-mini II Surface Area Analyzer. A transmission
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A. Zare et al.
electron microscope, model Zeiss EM900, 80 keV, was used to measure the size
and shape of particles. The morphologies and particles sizes of samples were char-
acterized by feld emission scanning electron microscopy, model MIRA3TESCAN-
XMU. Energy dispersive X-ray spectroscopy (EDS) was performed by SAMx-EDS
(France system). The X-ray difraction (XRD) analysis was performed using Cu Kα
radiation (λ=1.5408, model: X’Pert PRO MPD, PANalytical, the Netherlands).
Procedure for the synthesis of nano‑N,N,N′,N′‑tetramethyl‑N‑(silica‑n‑propyl)‑N′‑s
ulfo‑ethane‑1,2‑diaminium chloride (nano‑[TSPSED][Cl]2) (Scheme 1)
A mixture of N,N,N′,N′-tetramethylethane-1,2-diamine (0.58 g, 5 mmol) and (3-chlo-
ropropyl) trimethoxysilane (0.99 g, 5 mmol) in toluene (15 mL) was stirred under
refux conditions for 12 h; then, the solvent (toluene) was evaporated under vacuum
at 95 °C to give I [12]. Intermediate I was reacted with nano-silica gel (0.30 g,
5 mmol) in EtOAc (15 mL) under refux conditions for 8 h. The produced precipi-
tate was separated by centrifuging and decanting, washed by EtOAc (2×5 mL), and
dried under vacuum at 80 °C to aford II [12]. Afterward, the obtained intermedi-
ate (II) was added gradually to a stirring solution of chlorosulfonic acid (0.58 g,
5 mmol) in CH2Cl2 (10 mL) at 10 °C, and stirred for 2 h at room temperature. The
solvent was removed by centrifuging and decanting, and the residue was triturated
with dichloromethane (3×10 mL), and dried under vacuum at 80 °C to give nano-
[TSPSED][Cl]2 as a pale yellow powder.
General procedure for the synthesis of N,N’‑alkylidene bisamide derivatives
A mixture of aromatic aldehyde (1 mmol), amide (2 mmol) and nano-[TSPSED]
[Cl]2 (0.03 g, 4 mol %) was frstly stirred in an oil bath at 90 °C, and after solidi-
fcation of the reaction mixture, it was stirred by a small rod at the same tempera-
ture. The reaction progress was monitored by TLC. After completion of the reaction,
the mixture was cooled to room temperature, EtOAc (10 mL) was added, stirred
Cl
Toluene
Reflux,12 h
(H3C)2N
N(CH3)2
+
Cl
(H3CO)3Si
N(CH3)2
(H3CO)3Si
N(CH3)2
N
H3C CH3
(I)
Cl
O
Nano-silica
ClSO3H
CH2Cl2
O
Si
N
H3C CH3
(II)
Ethyl acetate, Reflux, 8 h
O
_
3CH3OH
Cl
N
H3C
CH3
SO3H
Cl
N
O
O
O
Si
H3C CH3
(Nano-[TSPSED][Cl]2)
Scheme 1 The preparation of nano-[TSPSED][Cl]2
1 3

Synthesis, characterization and application of…
for 2 min in refux conditions, followed by centrifugation and decanting to separate
the insoluble nanocatalyst (the catalyst was washed by EtOAc (2×3 mL), dried and
used for next run). The EtOAc resulting from the decanting was evaporated, and the
solid residue was recrystallized from EtOH (95%) to aford the pure bisamide.
Results and discussion
Characterization of nano‑[TSPSED][Cl]2
The reactions related to the preparation of nano-N,N,N′,N′-tetramethyl-N-(silica-
n-propyl)-N′-sulfo-ethane-1,2-diaminium chloride (nano-[TSPSED][Cl]2) are dis-
played in Scheme 1 (“Experimental” Section). The nanomaterial was characterized
by FT-IR, EDS, FE-SEM, TEM, adsorption/desorption porosimetry (BET, Lang-
muir, BJH and ads**orption/desorption isotherm), TG, DTG and XRD methods.
The FT-IR spectrum of nano-[TSPSED][Cl]2 is shown in Fig. 1, and the obtained
data are summarized in Table 1. As Fig. 1 and Table 1 indicate, the expected func-
tional groups and bonds were observed in the spectrum; the results are in accordance
to the literature [38–47]. The FT-IR data of intermediate II (Scheme 1) are displayed
in Table 2. When the data of Table 1 were compared with those of Table 2, the peaks
related to bonding of SO3H to N(CH3)2 group of II were observed in the IR spec-
trum of nano-[TSPSED][Cl]2, i.e. 577, 675, 888, 1111, 1180 and 2400-3650 cm−1.
The elemental composition of nano-[TSPSED][Cl]2 was determined by energy-
dispersive X-ray spectroscopy (Fig. 2). The EDS spectrum showed that there are C,
N, O, Si, S and Cl elements in the nanocatalyst structure (as expected).
Fig. 1 The FT-IR spectrum of nano-[TSPSED][Cl]2
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A. Zare et al.
Table 1 The FT-IR data of nano-[TSPSED][Cl]2
Absorption (cm−1
)
Assignments
Ref.
475
577
675
Rocking of Si–O
Bending of –SO2–
Stretching of S–O
[38, 39]
[40, 41]
[42]
851
888
Bending of Si–O–Si
Stretching of N–S
[43]
[44]
1011
1070
1111
1180
1284
1322
1484
1630
Stretching of Si–C
[45]
[39]
[42, 46]
[42, 46]
[47]
[48]
[48]
[38]
Stretching of Si–O–Si
Symmetric stretching of –SO2–
Asymmetric stretching of –SO2–
Stretching of Si–C
Stretching of C–N
Bending of C–H
Bending of O–H group of molecular water
adsorbed on silica gel
2945
Symmetric stretching of C–H
[48]
2400–3650
Stretching of OH group of the SO3H and OH
[46, 47,
groups on silica surface
49]
Table 2 The FT-IR data of intermediate II
Absorption (cm−1
)
Assignments
Ref.
467
799
Rocking of Si–O
Bending of OH (silanol)
[38, 39]
[38]
969
Stretching of Si–OH
[38]
1093
1399
1486
1640
2933
3025
3483
Stretching of Si–O–Si
[38]
[48]
[48]
[38]
[48]
[48]
[46, 47]
Stretching of C–N+
Bending of C–H
Bending of O–H group of molecular water adsorbed on silica gel
Symmetric stretching of C–H
Asymmetric stretching of C–H
Hydrogen-bonding of OH groups on silica surface
As the FE-SEM micrographs of nano-[TSPSED][Cl]2 indicate (Fig. 3), the par-
ticles sizes were in nano-scale (about 15–27 nm). The FE-SEM images of the used
nano-silica for the preparation of nano-[TSPSED][Cl]2 are shown in Fig. 4; size
range of the silica nanoparticles was about 18-31 nm. As it can be seen in Figs. 3
and 4, in the nanocatalyst, the particles have aggregated more than the nano-silica.
Furthermore, most of the particles in nano-[TSPSED][Cl]2 and the nano-silica were
observed in amorphous form.
The TEM micrograph of nano-[TSPSED][Cl]2 is shown in Fig. 5; we observe
agglomerates or amorphous cases from the micrograph.
1 3

Synthesis, characterization and application of…
Fig. 2 The EDS spectrum of nano-[TSPSED][Cl]2
Fig. 3 The FE-SEM images of nano-[TSPSED][Cl]2
As the BET plot shows (Fig. 6), the specifc surface area (SBET), total pore volume
and mean pore diameter of the nanocatalyst were 128.24 m2 g−1, 0.1883 cm3 g−1
and 5.8738 nm, respectively. Furthermore, according to the BET model [50], SBET
was calculated as 128.33 m2 g−1 (Eq. 1). It should be mentioned that SBET, total pore
volume and mean pore diameter of the applied nano-silica for the synthesis of nano-
[TSPSED][Cl]2 were found to be 418.02 m2 g−1, 0.8128 cm3 g−1 and 7.7776 nm,
correspondingly (see Fig. S1, Supplementary material).
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A. Zare et al.
Fig. 4 The FE-SEM micrographs of the nano-silica
Fig. 5 The TEM image of nano-
[TSPSED][Cl]2
0.001 × Vm
SBET
SBET
=
=
× N × A(N2)
22.4
0.001 × 29.465 cm3 g−1
× 6.022 × 1023 mol−1 × 0.162 × 10−18 m2 = 128.33 m2 g−1
22.4 cm3 mol−1
(1)
The specifc surface area (as,Lang) of nano-[TSPSED][Cl]2, according to the Lang-
muir plot (Fig. 7), was 146.15 m2 g−1. The as,Lang of the nano-silica was 535.26 m2 g−1
(see its Langmuir curve in Fig. S2, Supplementary material).
1 3

Synthesis, characterization and application of…
Fig. 6 The BET plot of nano-[TSPSED][Cl]2
The BJH plot (Fig. 8) showed that specifc pore volume (Vp), pore radius (rp), and
pore area (ap) of the nanocatalyst were 0.2174 cm3 g−1, 1.93 nm and 186.16 m2 g−1,
respectively. This result (pore radius: 1.93 nm, and consequently pore diameter:
3.86 nm), confrmed that the nanocatalyst was mesoporous. The Vp, rp and ap of the
nano-silica were 0.8446 cm3 g−1, 2.38 nm and 564.46 m2 g−1, correspondingly; it
was also mesoporous (see Fig. S3, Supplementary material).
The N2 adsorption–desorption isotherm of nano-[TSPSED][Cl]2 indicated as
characteristic of a type IV curve, according to the IUPAC classifcation (mesoporous
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A. Zare et al.
Fig. 7 The Langmuir plot of nano-[TSPSED][Cl]2
structure) (Fig. 9). The silica nanoparticles were also mesoporous (type IV) (see Fig.
S4, Supplementary material).
The TG and DTG curves of nano-[TSPSED][Cl]2 are presented in Fig. 10; as
it can be seen in this Figure, weight losses of the catalyst occurred in three steps.
The frst step of weight loss (below 155 °C) seems to be due to removing the
adsorbed solvents (or water) on the silica surface. The second weight loss, which
was observed at a range of about 155–300 °C, can be attributed to decompos-
ing the organically moieties on the silica surface. The third weight loss (about
300–600 °C) can related to condensation of the silanol groups. These explana-
tions are in accordance to the literature [51–53].
1 3

Synthesis, characterization and application of…
Fig. 8 The BJH plot of nano-[TSPSED][Cl]2
The XRD spectrum of nano-[TSPSED][Cl]2 in a domain of 2θ ≈ 2°–70°
is shown in Fig. 11. The spectrum indicated two broad peaks: the frst at
2θ ≈ 4.5°–14° with the equivalent Bragg angle at 2θ ≈ 7.3°, and the second at
2θ ≈ 18-28° with the equivalent Bragg angle at 2θ ≈ 22.4°. Moreover, several dif-
fraction lines were observed at 2θ ≈ 25.6°, 31.4°, 38.7°, 41.0°, 43.3°, 45.3°, 46.9°,
48.8°, 52.2°, 55.9° and 62.2°. These results proved that the nanomaterial is in
both amorphous and crystalline forms; the literature data verifed this topic [54].
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A. Zare et al.
Fig. 9 The adsorption–desorption isotherm plot of nano-[TSPSED][Cl]2
To determine loading of the catalytic species on the silica surface, the acidic
nanocatalyst was titrated with a NaOH solution; the results showed that the loading
of the catalytic species to be 1.32 mmol/g.
Examining catalytic activity of nano‑[TSPSED][Cl]2 for the synthesis
of N,N’‑alkylidene bisamides
To obtain the optimal reaction conditions, as a model reaction, the condensation of
benzamide (2 mmol) with 3-nitrobenzaldehyde (1 mmol) was studied in the pres-
ence of 0.01–0.04 g (1.3–5.3 mol %) of nano-[TSPSED][Cl]2 at range of 80–95 °C
under solvent-free conditions (Scheme 2). The best results were obtained when
0.03 g (4 mol %) of the nanocatalyst was used at 90 °C (yield: 98%; time: 18 min).
To recognize generality and scope of the catalyst, the reaction of diverse arylalde-
hydes (bearing electron-withdrawing, halogen and electron-releasing substituents on
para, meta and ortho positions) with benzamide (or acetemide) was examined under
1 3

Synthesis, characterization and application of…
Fig. 10 The TG and DTG analyses of nano-[TSPSED][Cl]2
the optimal conditions. The respective results are exhibited in Table 3. As it can be
seen in Table 3, all N,N′-alkylidene bisamides were produced in good to excellent
yields and in relatively short times. The obtained results proved generality and high
efcacy of nano-[TSPSED][Cl]2 for this synthesis.
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A. Zare et al.
Fig. 11 The XRD patterns of the nanocatalyst
NO2
O
O2N
CHO
O
Nano-[TSPSED][Cl]2
+
N
H
N
H
Solvent-free
Different conditions
NH2
O
H2N
O
Scheme 2 The model reaction
A plausible mechanism for the preparation of N,N’-alkylidene bisamides using
the acidic nanocatalyst is displayed in Scheme 3; the mechanism is supported by
the literature [29, 33]. At frst, the acidic hydrogen of nano-[TSPSED][Cl]2 acti-
vates aldehyde; then, nucleophilic attack of amide to the activated aldehyde provides
intermediate III. Removing a H2O molecule from III using the catalyst gives inter-
mediate IV. Lastly, another molecule of amide adds to the activated IV by the nano-
catalyst, and bisamide is produced.
In another study for illustrating the efectiveness of nano-[TSPSED][Cl]2 for the
preparation of N,N′-alkylidene bisamides, it was compared with the reported cata-
lysts in terms of yield, temperature, the reaction time, TOF and the reaction media;
this comparison is shown in Table 4. As the Table indicates, nano-[TSPSED][Cl]2
gave better results with respect to the other catalysts in terms of one or more of these
1 3

Synthesis, characterization and application of…
Table 3 The preparation of N,N′-alkylidene bisamide derivatives using nano-[TSPSED][Cl]2
O
Ar
H
O
Ar
O
Nano-[TSPSED][Cl]2 (4 mol%)
Solvent-free, 90 °C
+
NH2
O
H2N
O
R
N
H
N
H
R
R
R
Product No.
R
Ar
Time (min) Yielda (%) TON TOF (min−1
)
M.p. °C (Lit.)
1a
1b
1c
1d
1e
1f
C6H5 C6H5
CH3 C6H5
20
35
93
86
98
98
98
98
97
92
89
90
95
23.25 1.16
21.50 0.61
24.50 1.44
24.50 1.22
24.50 1.36
24.50 1.11
24.25 1.21
23.00 1.53
22.25 0.56
22.50 1.50
23.75 1.58
212–214 (214–216)
[31]
232–234 (233–236)
[33]
C6H5 4-O2NC6H4 17
CH3 4-O2NC6H4 20
C6H5 3-O2NC6H4 18
CH3 3-O2NC6H4 22
C6H5 2-O2NC6H4 20
265–267 (265–267)
[32]
273–275 (271–273)
[32]
233–235 (230–232)
[27]
228–230 (230–232)
[29]
1 g
1 h
1i
255–257 (257–259)
[28]
C6H5 4-ClC6H4
CH3 4-ClC6H4
15
40
252–254 (252–254)
[30]
253–255 (254–257)
[33]
1j
C6H5 2,4-Cl2C6H3 15
197–199 (198–200)
[29]
1 k
C6H5 4-BrC6H4
15
251–253 (254–256)
[29]
1 l
1 m
C6H5 4-MeC6H4
CH3 4-MeC6H4
25
55
91
83
22.75 0.91
20.75 0.38
238–240 (240) [35]
267–269 (270–273)
[33]
1n
CH3 4-MeOC6H4 55
86
21.50 0.39
215–217 (216–219)
[33]
aIsolated yield
factors: yield, temperature, time, TOF and the reaction media. TOF of our catalyst
was better than entries 8-13. Only, TOF of entry 6 was higher than nano-[TSPSED]
[Cl]2; nevertheless, the advantages of our work with respect to it, include: (1) higher
yields, (2) shorter reaction times, and (3) greener reaction media (in the work tabu-
lated in entry 6, a toxic solvent (methanol) has been used).
Recyclability and reusability of nano-[TSPSED][Cl]2 were also checked, and the
relevant results are displayed in Table 5 (the nanocatalyst was recycled according to
the procedure mentioned in “General procedure for the synthesis of N,N′-alkylidene
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A. Zare et al.
O
R
H
O
O
Ar
Nano-[TSPSED][Cl]2
Nano-[TSPSED][Cl]2
NH2
Ar
O
O
S O
O
Ar
R
N
H
OH
O
H
H
(III)
O
S
O
O
R
H
O
O
Ar
O
Nano-[TSPSED][Cl]2
NH2
_
R
N
Ar
R
N
OH
R
N
(IV)
Ar
H2O
H
H
O
S
O
O
O
Ar
O
Nano-[TSPSED][Cl]2
+
R
N
H
N
R
H
(Bisamide)
Scheme 3 The proposed mechanism for the synthesis of bisamides
Table 4 Comparing nano-[TSPSED][Cl]2 with the reported catalysts for the synthesis of N,N′-alkylidene
bisamides
Entry Catalyst
Conditions
Time (min) Yield (%) TOF (min−1
)
Ref.
1
2
3
4
5
6
7
8
Nano-[TSPSED][Cl]2
HPVAC-20a
Solvent-free, 90 °C
15–55
83–98
85–96
75–97
71–85
52–93
74–95
69–94
87–95
79–92
85–99
35–85
38–92
73–89
0.38–1.58
–
b
Solvent-free, 110 °C 25–45
NiFe2O4@KIT-6@ZnO Solvent-free, 60 °C 10
Solvent-free, 100 °C 27–180
–
[26]
[27]
[28]
[29]
[30]
[31]
[32]
[33]
[34]
[35]
b
–
b
Montmorillonite K10
NiFe2O4@SiO2-PPA
H14[NaP5W29MoO110
Nano-SnCl4.SiO2
–
b
CH3OH, refux
CH3OH, refux
n-hexane, refux
CH3CN, refux
Toluene, refux
40–130
50–150
49–390
180
–
]
0.56–3.80
b
–
Hydroxyapatite
0.10–0.11
0.22–0.46
0.14–0.17
0.09–0.28
0.001–0.006 [35]
0.09–0.17 [36]
9
Polymer-supported ILc
20–50
10
11
12
13
p-Toluene sulfonic acid Solvent-free, 100 °C 60
Boric acid
Boric acid
Silzic
CH2Cl2, microwave 20–40
Toluene, refux 16–70 h
Solvent-free, 100 °C 25–40
aHeteropoly-11-tungsto-1-vanadophosphoric acid supported on natural clay
bIn this work, the amount of the active site of the catalyst has not been calculated; thus, calculation of
TOF was not possible
c3D-network polymer supported Bronsted acid ionic liquid based on calix [4]—resorcinarene
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Synthesis, characterization and application of…
Table 5 Results on reusability
Recycling
Time (min)
Yielda (%)
of nano-[TSPSED][Cl]2 for
the reaction of benzamide with
Fresh catalyst
18
25
35
40
50
98
94
91
83
77
3-nitrobenzaldehyde
1
2
3
4
aIsolated yield
Fig. 12 The FT-IR spectrum of recycled nano-[TSPSED][Cl]2
Fig. 13 The XRD spectrum of the recycled nanocatalyst
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A. Zare et al.
Fig. 14 The FE-SEM micrographs of recycled nano-[TSPSED][Cl]2
bisamide derivatives” Section). As Table 5 illustrates, no signifcant loss of its
catalytic activity was observed after 1 time recycling; however, the yield slightly
decreased, and the reaction time increased in a second recycling. In a third recycling,
the results were almost good. Catalytic activity of nano-[TSPSED][Cl]2 considera-
bly decreased in a fourth recycling; it was characterized by FT-IR, XRD and SEM in
this step (Figs. 12, 13, 14). In the FT-IR spectrum of the recycled nano-[TSPSED]
[Cl]2 (in fourth recycling), the peaks related to SO3H group (577, 675, 888, 1111,
1180 and 2400–3650 cm−1) were not observed (the peak at about 3000–3700 cm−1
belongs to OH groups on a silica surface); i.e., this acidic group has been taken from
the catalyst during recycling and reusing; nevertheless, the other organic moieties
immobilized on the silica surface were retained. Decreasing the number of sharp
difraction lines in the XRD spectrum (Fig. 13) can be related to enhancement of the
amorphous form and decreasing the crystalline form of nano-[TSPSED][Cl]2 during
recycling. According to the SEM result (Fig. 14), nanoparticles have slightly aggre-
gated during recycling and reusing, and their sizes have slightly increased. Dimin-
ishing catalytic activity of nano-[TSPSED][Cl]2 in a fourth recycling can be attrib-
uted to leaving the SO3H group (as main moiety to catalyze the reaction) from the
catalyst, and aggregating the nanoparticles.
Conclusions
Briefy, we have prepared nano-N,N,N′,N′-tetramethyl-N-(silica-n-propyl)-N′-sulfo-
ethane-1,2-diaminium chloride as a novel mesoporous nanocatalyst for the synthe-
sis of N,N′-alkylidene bisamides. The benefts of this work consist of efcacy and
generality of the catalyst, using few amounts of the catalyst in the reaction, pro-
ducing the products in high yields and in relatively short reaction times, excellent
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Synthesis, characterization and application of…
competition with the reported catalysts, utilization of solvent-free conditions, and
good application with green chemistry protocols.
Acknowledgements The authors gratefully acknowledge support of this work by Payame Noor
University.
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