A novel organic-inorganic hybrid material: Production, characterization and catalytic performance for the reaction of arylaldehydes, dimedone and 6-amino-1,3-dimethyluracil

Article abstract of DOI:10.1039/c9nj06393e

A novel silica-based organic-inorganic hybrid material namely N,N,N′,N′-tetramethyl-N-(silica-n-propyl)-N′-sulfonic acid-ethylenediaminium chloride/mesylate ([TSSECM]) was prepared, and characterized by EDS (energy-dispersive X-ray spectroscopy), FE-SEM (

Full text of DOI:10.1039/c9nj06393e

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DOI: 10.1039/C9NJ06393E
A novel organic-inorganic hybrid material: production,
characterization and catalytic performance for the reaction of
arylaldehydes, dimedone and 6-amino-1,3-dimethyluracil
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Abdolkarim Zare,*a Manije Dianata and Mohammad Mehdi Eskandarib
a Department of Chemistry, Payame Noor University, PO Box 19395-3697, Tehran, Iran. E-
mail: abdolkarimzare@pnu.ac.ir; abdolkarimzare@yahoo.com
b Nanotechnology Research Center, Research Institute of Petroleum Industry (RIPI), PO Box
1485733111, Tehran, Iran
† Electronic supplementary information (ESI) available: Selected spectral data and original
spectrums of the synthesized pyrimido[4,5-b]quinolines, and the FT-IR, XRD, TGA and
adsorption/desorption porosimetry diagrams of the catalyst. See DOI: …
A novel silica-based organic-inorganic hybrid material namely N,N,N′,N′-tetramethyl-N-
(silica-n-propyl)-N′-sulfonic acid-ethylenediaminium chloride/mesylate ([TSSECM]) was
prepared, and characterized by EDS (energy-dispersive X-ray spectroscopy), FE-SEM (field
emission scanning electron microscopy), FT-IR, XRD (X-ray diffraction), TGA (thermal
gravimetric analysis) and adsorption/desorption porosimetry analyses. The sizes of most
particles of [TSSECM] were less than 100 nm (i.e. they were nanomaterials), and some
particles had sizes more than 100 nm (up to 185 nm). The hybrid material was applied as a
highly efficacious, recyclable and dual-functional catalyst for the one-pot multi-component
reaction of arylaldehydes, dimedone and 6-amino-1,3-dimethyluracil under solvent-free
conditions to give pyrimido[4,5-b]quinolines.
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DOI: 10.1039/C9NJ06393E
1. Introduction
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In recent years, application of organic-inorganic hybrid materials as catalysts for organic
reactions has been intensely increased; because they have several advantages, such as
effectuality, easy separation from reaction medium, capacity to design (and functionalize) for
different catalytic applications, recyclability and environmentally-friendly nature.1-12 Among
the different inorganic material used for synthesis of this class of catalysts, silica is usually
preferable, due to possessing unique properties, including safety, eco-friendly nature, low
cost, suitable thermal and chemical stability, non‐corrosiveness, easy functionalization, and
simple isolation from reaction mixture.6-12
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Multi-component reactions,13-16 and solvent-free conditions17-20 are well-known,
practical and highly effective techniques which have been used in organic synthesis; the
various profits of them have been mentioned in the literature.13-20
The compounds containing pyrimidine, quinoline or pyrimido-quinoline moieties
exhibit a wide range of biological and medicinal activities. Pyrimidine-bearing compounds
have been used as inhibitors of AbI kinase and PTP1B,21,22 and as antimicrobial agent.23
Quinoline moiety is present in structure of many bioactive compounds, such as antitumor,24
DNA binding,25 DNA intercalating carrier,26 antihistaminic,27 and anti-inflammatory28 agents.
Moreover, the heterocycles containing pyrimido-quinoline scaffold have been applied as anti-
allergic,29 anti-inflammatory,30 anticancer,31 antimalarial,32 and antimicrobial33 drugs. The
one-pot multi-component reaction of arylaldehydes, dimedone and 6-amino-1,3-
dimethyluracil has been utilized as a practical method for the production of pyrimido[4,5-
b]quinolines.34-42 Although the reaction of arylaldehydes, dimedone and 6-amino-1,3-
dimethyluracil is of great importance; it has not been comprehensively studied in the
literature.
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Considering the high importance of organic-inorganic hybrid catalysts, solventV-ifewreAerticle Online
DOI: 10.1039/C9NJ06393E
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conditions, and multi-component reactions, it is ideal to use them simultaneously in a
synthetic process. In this work, we have accomplished this process; i.e. we have prepared a
novel silica-based organic-inorganic hybrid material namely N,N,N′,N′-tetramethyl-N-(silica-
n-propyl)-N′-sulfonic acid-ethylenediaminium chloride/mesylate ([TSSECM]), and
characterized it by EDS (energy-dispersive X-ray spectroscopy), FE-SEM (field emission
scanning electron microscopy), FT-IR, XRD (X-ray diffraction), TG (thermal gravimetric),
DTG (derivative thermal gravimetric), DTA (differential thermal analysis) and
adsorption/desorption porosimetry (BET, Langmuir, t-plot, BJH and adsorption/desorption
isotherm) analyses. Then, we have utilized [TSSECM] as a highly efficacious, recyclable and
dual-functional catalyst for the one-pot multi-component reaction of arylaldehydes, dimedone
and 6-amino-1,3-dimethyluracil under solvent-free conditions to afford pyrimido[4,5-
b]quinolines.
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2. Experimental section
2.1. Materials and instruments
All chemicals were purchased from Fluka or Merk Chemical Companies. The nano-silica for
the synthesis of [TSSECM] was prepared by the reported procedure.43 All known compounds
were identified by comparison of their melting points and spectral data with those reported in
the literature. Progress of the reactions was monitored by thin layer chromatography (TLC)
using silica gel SIL G/UV 254 plates. The melting points were recorded on a Buchi B-545
device in open capillary tubes. FT-IR was run on Bruker apparatus (model: Tensor 27,
Germany). The 1H NMR (250, 400 or 500 MHz) and 13C NMR (62.5, 100 or 125 MHz) were
run on a Bruker Avance DPX FT-NMR spectrometer using TMS as internal standard and
DMSO-d6 as solvent (chemical shift in ppm). Mass spectra were recorded on a spectrometer
5975C VL MSD model triple-axis detector. Thermal gravimetric analysis (TGA) was
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accomplished using Linseis STA PT 1000 apparatus, at 50-600 ºC, with temperatDuOreI: 1i0n.1c0r39e/aCs9eNJ06393E
rate of 10 ºC.min−1 in argon atmosphere. The morphologies and sizes of particles were
characterized by field emission scanning electron microscopy (FE-SEM), model
MIRA3TESCAN-XMU. Energy dispersive X-ray spectroscopy (EDS) was performed by
SAMx-EDS (France system). The X-ray diffraction (XRD) analysis was performed using an
instrument model X'Pert PRO MPD, PANalytical, the Netherlands (Cu Kα radiation,
λ=1.5408).
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2.2. Procedure for the synthesis of [TSSECM] (Scheme 1)
A mixture of (3-chloropropyl)trimethoxysilane (0.99 g, 5 mmol) and N,N,N′,N′-
tetramethylethylenediamine (0.58 g, 5 mmol) in dry toluene (15 mL) was stirred and refluxed
for 12 h; thereafter, the toluene was evaporated under vacuum at 95 ºC to afford I.6 Nano-
silica gel (0.30 g, 5 mmol) and EtOAc (15 mL) was treated with I, stirred and refluxed for 8
h, centrifuged and decanted. The obtained precipitate was washed by EtOAc (2 × 5 mL), and
dried under vacuum at 80 ºC to give II.6 Subsequently, II was added gradually to a stirring
solution of chlorosulfonic acid (0.58 g, 5 mmol) in dry CH2Cl2 (10 mL) at 10 ºC, stirred for 2
h at room temperature, centrifuged and decanted; the residue was washed by CH2Cl2 (3 × 10
mL), and dried under vacuum at 80 ºC to give III.7 In the last step, a solution of
methanesulfonic acid (5 mmol) in dry CH2Cl2 (15 mL) was slowly added to intermediate III
at room temperature, and stirred for 10 h at this temperature. The solvent was removed by
centrifuging and decanting, and the resulting solid was washed by CH2Cl2 (2 × 5 mL), and
dried under vacuum at 80 ºC to give [TSSECM].
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Cl
DOI: 10.1039/C9NJ06393E
PhMe
NMe2
NMe2
+
(MeO)3Si
Cl
Me2N
(MeO)3Si
N
Reflux,12h
Me Me
(I)
Cl
N
Me
Cl
Me
Cl
O
O
ClSO3H
NMe2
Nano-silica
O
Si
Si
N
O
Si
N
SO3H
CH2Cl2
EtOAc, Reflux, 8h
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Me Me
(III)
Me Me
O
O
_
MeOH
(II)
MeSO3
Me
Cl
N
Me
Me
Me
MeSO3
Cl
N
O
O
MeSO3H
N
or
O
O
N
Si
SO3H
SO3H
Me Me
Me Me
O
O
([TSSECM])
Scheme 1 The production of [TSSECM].
2.3. General procedure for the preparation of pyrimido[4,5-b]quinoline derivatives
A mixture of compounds consisting of aldehyde (1 mmol), dimedone (0.140 g, 1 mmol), 6-
amino-1,3-dimethyluracil (0.155 g, 1 mmol) and [TSSECM] (0.024 g) was stirred vigorously
by a small rod at 125 ºC. After the reaction was completed, as monitored by TLC, the
reaction mixture was cooled to room temperature, EtOAc (20 mL) was added, stirred for 1
min under reflux conditions, centrifuged and decanted to separate the insoluble catalyst (this
action was performed again). The solvent of the solution obtained from the decanting was
evaporated, and the residue was recrystallized from EtOH/H2O (95/5) to give the pure
product.
3. Results and discussion
3.1. Characterization of [TSSECM]
The reactions pertaining to the synthesis of N,N,N′,N′-tetramethyl-N-(silica-n-propyl)-N′-
sulfonic acid-ethylenediaminium chloride/mesylate ([TSSECM]) are shown in Scheme 1
(Experimental section). It was characterized by EDS, FE-SEM, FT-IR, XRD, TG, DTG,
DTA and adsorption/desorption porosimetry (BET, Langmuir, t-plot, BJH and
adsorption/desorption isotherm) methods.
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To determine elemental composition of [TSSECM], EDS spectrum was used (Fig. 1).
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As expected, carbon, nitrogen, oxygen, silicon, sulfur and chlorine were seen in the spectrum.
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Fig. 1 The EDS spectrum of [TSSECM].
According to the FE-SEM micrographs of [TSSECM] (Fig. 2), the sizes of most
particles were about 20-90 nm (i.e. they were nanomaterials), and some particles had sizes
more than 100 nm (up to 185 nm).
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Fig. 2 The FE-SEM images of [TSSECM].
The acquired FT-IR data of [TSSECM] are briefed in Table 1, and the FT-IR spectrum
is given in supplementary information (Fig. S1). The expected peaks related to the bonds and
functional groups in the catalyst structure were observed in the spectrum (Table 1). The
results are in accordance with the literature.7
Table 1 The FT-IR data of [TSSECM]
Absorption (cm−1)
464
Related bond or group
Rocking of Si–O
589
Bending of –SO2–
698
Stretching of S–O
855
Bending of Si–O–Si
882
Stretching of N–S
1055
Stretching of Si–C
1085
Stretching of Si–O–Si
1111
Symmetric stretching of –SO2–
Asymmetric stretching of –SO2–
Bending of C–H
1168
1478
1644
Bending of O–H groups of H2O molecules adsorbed on SiO2 surface
Symmetric stretching of C–H
Stretching of OH group of the SO3H, and OH groups on silica surface
2964
2650-3750
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The XRD spectrum of [TSSECM] was run in a domain of 2θ ≈ 10–80° (supplementary
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information, Fig. S2). In the spectrum, two broad peaks were observed: (i) the peak at 2θ ≈
12.5–23.7°, and (ii) the peak at 2θ ≈ 23.7-37°. Furthermore, some diffraction lines were seen
at 2θ ≈ 27.1, 29.5, 35.8, 38.5, 43.0, 45.5, 52.1, 55.1, 56.8, 62.8, 64.2 and 72.4°. According to
the results, [TSSECM] is in both amorphous and crystalline forms; the literature proved this
subject.7,44
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Considering the TG, DTG and DTA curves of the organic-inorganic hybrid material
(supplementary information, Fig. S3), weight losses were occurred in two steps: (i) the
weight loss below 150 °C, which can attribute to removal of the adsorbed solvents (or water)
on the silica surface, and (ii) the weight loss at range of about 150-600 °C, which can relate to
decomposition of the organic groups immobilized on the silica surface, and condensation of
the silanol groups. These interpretations were confirmed by the literature.45-47
According to the adsorption/desorption porosimetry results (supplementary information,
Fig. S4-S8), BET surface area, Langmuir surface area and t-plot external surface area of the
hybrid material were 189, 263 and 179 m2.g−1, respectively. The BJH results showed that
pore volume and average pore diameter of [TSSECM] were 0.36 cm3.g−1 and 6.5 nm,
correspondingly. Considering the BJH pore diameter (6.5 nm), the hybrid material was
mesoporous. The N2 adsorption-desorption isotherm of [TSSECM] showed characteristic of
type IV curve, according to the IUPAC classification (mesoporous structure). The average
particle size was also 31.7 nm.
3.2. Examining catalytic activity of [TSSECM] for the reaction of arylaldehydes,
dimedone and 6-amino-1,3-dimethyluracil
The synthesis of pyrimido[4,5-b]quinoline 1c via the reaction of 4-chlorobenzaldehyde (1
mmol), dimedone (1 mmol) and 6-amino-1,3-dimethyluracil (1 mmol) was chosen as a
model, and examined in the presence of different amounts of [TSSECM] at a range of 110-
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130 ºC under solvent-free conditions (Scheme 2); the results are presented in Table 2. As it
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can be seen in Table 2, the best results were obtained when the reaction was performed using
0.024 g of the catalyst at 125 ºC (Table 2, entry 2). Although, increasing the catalyst amount
up to 0.030 and the temperature up to 130 ºC slightly decreased the reaction times, 0.024 g of
[TSSECM] and 125 ºC were selected as optimal conditions; because performing the reaction
using fewer amount of the catalyst at lower temperature is more compliance with green
chemistry protocols (Table 2, entries 3 and 5). In another study, the model reaction was
examined under catalyst-free conditions, and also in the presence of nano-silica, N,N,N′,N′-
tetramethyl-N-(silica-n-propyl)-N′-sulfonic acid-ethylenediaminium chloride ([TSSEC]) and
N,N,N′,N′-tetramethyl-N-(silica-n-propyl)-ethylenediaminium mesylate ([TSEM]) as catalysts
(Fig. 3). The reaction yield was low (29%) in the absence of catalyst (Table 2, entry 8).
Nano-silica afforded the product in 46% yield (Table 2, entry 9). When [TSSEC] (a catalyst
containing SO3H group, and without mesylate) was utilized, the product was obtained in 83%
yield (Table 2, entry 10). Furthermore, [TSEM] (a catalyst bearing mesylate, and without
SO3H group) gave the product in 70% yield (Table 2, entry 11). Comparing entries 2 and 8-
11 of Table 2 gave the following consequences: (i) nano-silica didn’t acted as only
immobilizing support, but also it had catalyst role, (ii) both acidic and weak basic moieties
(i.e. SO3H and mesylate) were necessary to carry out the reaction, and (iii) our program for
the production of [TSSECM] and collecting the inorganic and organic moieties (i.e. nano-
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silica, the SO3H-bearing chain and mesylate anion) in its structure were logical and efficient.
O
O
Ar
O
N
Ar
H
O
N
O
[TSSECM]
N
+
Solvent-free, 125°C
N
N
H
O
H2N
O
O
Scheme 2 The reaction of arylaldehydes, dimedone and 6-amino-1,3-dimethyluracil.
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Table 2 Studying influence of the catalyst amount and temperature on the reaction of 4-
chlorobenzaldehyde, dimedone and 6-amino-1,3-dimethyluracil
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8
9
Entry
Catalyst
Catalyst amount (g)
Temp. (ºC)
125
Time (min)
Yielda (%)
1
[TSSECM]
[TSSECM]
[TSSECM]
[TSSECM]
[TSSECM]
[TSSECM]
[TSSECM]
-
0.020
0.024
0.030
0.024
0.024
0.030
0.030
-
50
40
35
40
35
40
60
60
60
40
40
90
92
92
89
92
91
78
29
46
83
70
2
125
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3
125
4
120
5
130
6
120
7
110
8
125
9
Nano-silicab
[TSSEC]
[TSEM]
0.024
0.024
0.024
125
10
125
11
125
a Isolated yield.
b The nano-silica which was used for the preparation of [TSSECM].
Cl
MeSO3
NHMe2
Me
Me
Cl
N
Cl
O
O
N
O
O
Si
Si
N
SO3H
Me Me
Me Me
O
O
([TSSEC])
([TSEM)
Fig. 3 The structures of [TSSEC] and [TSEM].
To produce different derivatives of pyrimido[4,5-b]quinolines, various arylaldehydes
were reacted with dimedone and 6-amino-1,3-dimethyluracil using [TSSECM] under the
optimal conditions; the products structures, the melting points of the products, the reaction
times and yields are illustrated in Table 3. As the Table data indicate, all arylaldehydes
(benzaldehyde, aldehydes bearing halogens, electron-withdrawing and electron-donating
substituents on different positions of the aromatic rings, and aldehydes possessing two
substituents) afforded the relevant pyrimido[4,5-b]quinolines in high yields and relatively
short reaction times. So, [TSSECM] was general and highly efficient for the reaction.
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Table 3 The preparation of pyrimido[4,5-b]quinolines catalyzed by [TSSECM] (Scheme 2)
Product
No.
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6
Product
Time (min)
Yielda (%)
M.p. °C (Lit.)
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9
O
O
O
O
N
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40
93
271-273 (268-270)40
1a
N
N
N
N
H
O
O
O
Br
O
N
30
86
92
93
229-231 (227-230)36
1b
1c
1d
N
H
Cl
O
N
40
286-288 (287-290)35
N
H
Cl
Cl
O
O
30
>300 (>300)38
N
N
H
N
O
Cl
O
O
30
91
84
>300 (>300)38
1e
N
N
H
N
O
NO2
O
O
60
290-292 (287-290)36
1f
N
N
H
N
O
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NO2
O
O
O
O
30
92
292-294 (287-290)36
1g
N
N
H
N
O
10
11
12
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CH3
O
N
60
94
>300 (>300)38
1h
N
N
H
O
OCH3
OCH3
O
N
N
30
35
30
93
83
95
298-300 (294-296)38
1i
N
H
O
H3CO
O
OCH3
O
208-210
1j
N
N
N
H
O
OCH3
O
O
N
N
301-303 (>300)39
1k
N
H
O
OH
O
O
N
N
30
91
>300 (>300)39
1l
N
H
O
a Isolated yield.
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[TSSECM] is a dual-functional catalyst, since it has acidic and basic groups (the SO3H
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is acid, and the mesylate is weak base). So, [TSSECM] can particularly catalyze the reactions
which need both acidic and basic catalysts simultaneously; e.g., the synthesis of
pyrimido[4,5-b]quinolines. Based on dual-functionality of the catalyst and the
literature,15,35,36 an attractive mechanism is proposed for the reaction (Scheme 3). The acidic
hydrogen of the SO3H group has three tasks: (i) activation of carbonyl groups to accept
nucleophilic attacks (steps 1, 3 and 4), (ii) assistance for removing H2O (steps 2 and 5), and
(iii) tautomerization (step 6). The basic anion plays two roles: (i) assistance for removing
H2O (step 5), and (ii) activation of nucleophiles (steps 1, 3 and 4).
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O
S
Me
O
H
O
O
O
[TSSECM]
O
OH
O
O
Ar
O
O
O
[TSSECM]
Me
[TSSECM]
Ar
H
Ar
Step1
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11
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30
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60
H
H
O
S
O
O
Si
N
O
O
Me
O
MeSO3
O
O
H
Me
H
O
O
H
O
O
Si
O
S N
O
Me
O
Ar
[TSSECM]
Ar
_
H2O
O
O
Step2
O
Me
O
S
O
H
N
N
O
O
H
O
O
Ar
N
N
[TSSECM]
Ar
O
O
Step3
N
O
H
H2N
O
O
S
O
Me
O
Si
O
N
O
Me
O
O
H
Ar
N
O
N
O
O
Ar
N
[TSSECM]
N
Step4
O
O
N
O H
HN
O
O
S
H
H
O
S
O
Me
Me
O
Me
O
Si
N
O
O
O
O
O
Ar
O
O
Ar
O
N
[TSSECM]
N
N
_
H2O
Tautomerization
N
H
N
O
N
O
Step5
Step6
O
H
H
H
O
S
Pyrimido[4,5-b]quinolines
O
S
O
Me
Me
O
Me
O
Si
N
O
O
O
O
Scheme 3 The reaction mechanism.
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The results on recyclability and reusability of [TSSECM] to catalyze the reaction of 4-
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7
8
cholorobenzaldehyde, dimedone and 6-amino-1,3-dimethyluracil are displayed in Table 4. As
it can be seen in Table 4, [TSSECM] was recyclable for two times; no loss of the catalytic
activity was observed in first recycling; however, the reaction time was slightly enhanced,
and the yields was slightly decreased in second recycling. The results in third recycling were
not good.
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Table 4 Results on reusability of [TSSECM] for the reaction of 4-cholorobenzaldehyde, dimedone and 6-
amino-1,3-dimethyluracil
Recycling
Time (min)
Yielda (%)
Fresh catalyst
40
40
50
60
92
91
88
73
1
2
3
a Isolated yield.
4. Conclusions
In summary, we have introduced N,N,N′,N′-tetramethyl-N-(silica-n-propyl)-N′-sulfonic acid-
ethylenediaminium chloride/mesylate as a novel organic-inorganic hybrid catalyst for the
production of pyrimido[4,5-b]quinolines. The advantages of this work consist of
effectiveness and generality of the catalyst, application of a few amount of the catalyst in the
reaction, recyclability of the catalyst, utilization of solvent-free conditions, production of the
products in high yields and relatively short reaction times, and good appliance with green
chemistry protocols.
Conflicts of interest
There are no conflicts to declare.
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Acknowledgements
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The authors gratefully acknowledge support of this work by Payame Noor University.
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Table of Contents
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A novel silica-based organic-inorganic hybrid catalyst was prepared, characterized and
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applied for the synthesis of pyrimido[4,5-b]quinolines.
[TSSECM], Solvent-free, 125 °C
O
O
Ar
O
N
Ar
H
O
N
O
N
+
N
N
H
O
H2N
O
O
30-60 min
83-95%
MeSO3
Me
Cl
Me
Me
Me
MeSO3
N
Cl
O
O
N
N
or
[TSSECM] =
O
Si
O
Si
N
SO3H
SO3H
Me Me
Me Me
O
O