Application of SiO 2 nanoparticles as an efficient catalyst to develop syntheses of perimidines and tetraketones

Article abstract of DOI:10.1007/s12039-019-1607-8

Abstract: In this paper, we explore the catalytic activity of SiO ₂ nanoparticles (NPs) as an eco-friendly, efficient and reusable catalyst in the synthesis of 2,3-dihydro-1H-perimidines as well as tetraketones. For tetraketones syntheses, a si

Full text of DOI:10.1007/s12039-019-1607-8

J. Chem. Sci.
(2019) 131:34
© Indian Academy of Sciences
https://doi.org/10.1007/s12039-019-1607-8
REGULAR ARTICLE
Application of SiO2 nanoparticles as an efficient catalyst to develop
syntheses of perimidines and tetraketones
HESHMATOLLAH ALINEZHAD∗, ARMIN AHMADI and PARVIN HAJIABBASI
Department of Organic Chemistry, Faculty of Chemistry, University of Mazandaran, Babolsar, Iran
E-mail: heshmat@umz.ac.ir
MS received 6 July 2018; revised 5 February 2019; accepted 14 February 2019
Abstract. In this paper, we explore the catalytic activity of SiO2 nanoparticles (NPs) as an eco-friendly,
efficient and reusable catalyst in the synthesis of 2,3-dihydro-1H-perimidines as well as tetraketones. For
tetraketones syntheses, a simple tandem Knoevenagel condensation following Michael addition procedure is
performed by the reaction between benzaldehydes and 5,5-dimethyl-1,3-cyclohexanediones under solvent-free
condition using SiO2 NPs as an efficient solid catalyst. In addition, for 2,3-dihydro-1H-perimidines syntheses,
cyclocondensation of various aldehydes with 1,8-diaminonaphthalene is achieved under solvent-free condition
using SiO2 NPs as a catalyst at room temperature. The results showed catalytic enhancement in both synthetic
procedures. In this work, 4-(2,3-dihydro-1H-perimidin-2-yl)benzonitrile and 2-(pyridin-4-yl)-2,3-dihydro-1H-
perimidine are synthesized as new compounds. Also, reusability study of SiO2 NPs was done to ensure its
applicability as a recycled catalyst in this work.
Keywords. 2,3-Dihydro-1H-perimidines; green synthesis; nano-SiO2; solid catalyst; solvent-free; tetraketone
derivatives.
1. Introduction
Perimidine derivatives are attractive either for their
biological activities such as antifungal, antimicrobial,
antiulcer and antitumor agents10 or for their application
as intermediates in organic synthesis.11,12 In addition,
tetraketones are also extensively used as important pre-
cursors for the synthesis of various acridinediones as
laser dyes,13,14 DNA intercalator,15 electron donors and
acceptors16–18 of the photoinitiated polymerization of
acrylates and methacrylates,19 and synthesis of some
heterocyclic compounds.20–23
Due to our interest in developing a new synthe-
sis in the field of catalyst applications,24–27 herein,
we explore the catalytic activity of SiO2 NPs as an
eco-friendly, efficient and reusable catalyst in the syn-
thesis of 2,3-dihydro-1H-perimidines as well as tetrake-
tones. In this work 4-(2,3-dihydro-1H-perimidin-2-
yl)benzonitrile and 2-(pyridin-4-yl)-2,3-dihydro-1H-
perimidine are synthesized as new compounds.
Although several approaches for the synthesis of both
skeletons have been reported,28–35 development of sim-
ple and convenient synthetic procedures is attractive for
research in synthetic organic chemistry.
Nanoparticles are particles that exist on a nanometre
range (i.e., below 100 nm in at least one dimension).
They can possess physical properties such as unifor-
mity, conductanceorspecialopticalpropertiesthatmake
them desirable in materials science and biology. Inor-
ganic nanoparticles such as SiO2 nanoparticles (NPs)
have attracted considerable attention because of their
potential importance in technological applications (e.g.,
catalysts, filler for polymers, pigments, pharmacy, elec-
tronics and thin film substrates, electronic and thermal
insulators, and humidity sensors and so on).1–3 More-
over, homogeneous catalysts have many deficiencies in
industrial and laboratory processes such as handling,
corrosiveness, difficult separation and toxicity of waste.
Indeed, most novel solid catalysts are based on silica
due to their excellent stability (chemical and thermal),
high surface area, and good accessibility of reactive cen-
ters.4–9
*
For correspondence
Electronic supplementary material: The online version of this article (https://doi.org/10.1007/s12039-019-1607-8) contains
supplementary material, which is available to authorized users.
0123456789().: V,-vol

34 Page 2 of 10
J. Chem. Sci.
(2019) 131:34
2. Experimental
2.3c 2-(Pyridin-4-yl)-2,3-dihydro-1H-perimidine(3o):
◦
1
Light yellow powder. M.p.: 162–163 C. H NMR (400
MHz, DMSO-d6): δ 5.42 (s, 1H, N-CH-N), 6.50 (s, 2H,
NH), 6.98 (m, 2H, ArH), 7.14 (m, 2H, ArH), 7.54 (m, 2H,
ArH), 8.57 (m, 2H, ArH). 13C NMR (100 MHz, DMSO-
d6): δ 64.84, 105.01, 112.90, 115.96, 123.06, 127.40, 130.08,
134.74, 142.46, 150.10, 151.43.
2.1 General information
All chemicals were used without further purification and
purchased from commercial sources as follows: 1,8-diamino-
naphthalene (Sigma-Aldrich-99%), dimedone (Sigma-
Aldrich-97%),
benzaldehyde
(Sigma-Aldrich->99%),
Tetraethoxysilane (Sigma-Aldrich-98%). Other chemicals
and solvents were prepared commercially without further
purification. IR spectra were recorded from KBr disk using
an FT-IR Bruker Tensor 27 instrument. Melting points were
measured by using the capillary tube method with a thermal
scientific 1900 apparatus. The progress of reactions was mon-
itored by thin-layer chromatography (TLC) on 0.2 mm silica
gel F-252 (Merck) plates using n-hexane/ethyl acetate as elu-
ent. The 1H NMR (400 MHz) and 13C NMR (100 MHz) was
run on a Bruker DPX using TMS as an internal standard.
Scanning Electron Microscopy (SEM) analysis was recorded
on an electron microscope model Tescan Vega MV 2300T/40.
2.4 General procedure for the preparation of
tetraketone derivatives (9a–9p)
A mixture of dimedones (2 mmol), benzaldehydes (1 mmol)
and SiO2 NPs (2 mol%, 0.001 g) was heated at 110 C
◦
under solvent-free condition. After completion of the reac-
tion monitored by TLC, 5 mL THF was added to the
reaction mixture. Then after isolating the catalyst by cen-
trifuging, the solvent was evaporated to yield the crude
products 2,2ꢀ-arylmethylene bis(3-hydroxy-5,5-dimethyl-2-
cyclohexene-1,3-dione) (9a–9p).
2.4a 2,2ꢀ-(Phenylmethylene)bis(5,5-dimethylcyclohe-
xane-1,3-dione) (9a): M.p.: 194–195 ◦C. 1H NMR (400
MHz, CDCl3): δ 1.12 (s, 6H, Me), 1.26 (s, 6H, Me), 2.30–2.50
(m, 8H, CH2), 5.56 (s, 1H, CH), 7.11 (m, 2H, ArH), 7.19 (m,
1H, ArH), 7.21 (m, 1H, ArH), 7.29 (m, 1H, ArH), 11.93 (s,
1H, OH).13C NMR (100 MHz, CDCl3): δ 27.40, 29.60, 31.42,
32.73, 46.45, 47.06, 115.59, 125.85, 126.77, 128.22, 138.06,
189.41, 190.49.
2.2 Preparation of silica nanoparticles
Tetraethoxysilane (TEOS) and aqueous ammonia 25% were
separately dissolved in ethanol. Then, these two solutions
were mixed and stirred for 24 h to obtained white sus-
pension. The particles in the suspension were collected by
centrifugation and dried in vacuum for 12 h to produce silica
nanoparticles as the literature reported.38
2.4b 2,2ꢀ-((4-Chlorophenyl)methylene)bis(5,5-dimet-
2.3 General procedure for the preparation of 2,3-
dihydro-1H-perimidine derivatives (3a–3p)
◦
1
hylcyclohexane-1,3-dione) (9c): M.p.: 136–138 C. H
NMR (400 MHz, CDCl3): δ 1.12 (s, 6H, Me), 1.23 (s, 6H,
Me), 2.19 (m, 4H, CH2), 2.35 (m, 4H, CH2), 5.49 (s, 1H,
CH), 7.02 (d, J = 7.6 Hz, 2H, ArH), 7.23 (m, 2H, ArH),
11.89 (s, 1H, OH).13C NMR (100 MHz, CDCl3): δ 27.41,
29.68, 31.42, 32.40, 46.42, 47.04, 115.33, 128.19, 128.34,
129.77, 130.01, 131.58, 136.70, 189.43, 190.63.
The mixture of 1,8-diaminonaphthalene (1.0 mmol), carbonyl
compound (1.0 mmol) and SiO2 NPs (0.001 g, 2 mol%) was
ground by mortar and pestle at room temperature for an appro-
priate time. After completion of the reaction as monitored
by TLC, the mixture was dissolved in ethyl acetate; then the
catalystwasisolatedbycentrifugingandthesolventwasevap-
orated to yield the crude product (3a–3p).
2.4c 2,2ꢀ-((2-Nitrophenyl)methylene)bis(5,5-dimethy-
◦
1
lcyclohexane-1,3-dione) (9o): M.p.: 204–206 C. H
NMR (400 MHz, CDCl3): δ 1.02 (s, 6H, Me), 1.12 (s, 6H,
Me), 2.26–2.35 (m, 4H, CH2), 2.43-2.54 (m, 4H, CH2), 6.05
(s, 1H, CH), 7.26 (s, 1H, ArH), 7.32 (m, 1H, ArH), 7.48 (d,
J = 7.6 Hz, 1H, ArH), 7.51 (d, J = 7.8 Hz, 1H, ArH), 11.60
(s, 1H, OH).13C NMR (100 MHz, CDCl3): δ 28.14, 28.63,
30.06, 31.90, 46.31, 46.84, 114.64, 124.33, 127.17, 129.57,
131.36, 132.10, 149.73, 189.41, 191.20.
2.3a 4-(2,3-Dihydro-1H-perimidin-2-yl)benzonitrile
◦
1
(3j): Brown powder. M.p.: 177–179 C. H NMR (400
MHz, DMSO-d6): δ 5.48 (s, 1H, N-CH-N), 6.49 (s, 2H, NH),
6.94–7.00 (m, 4H, ArH), 7.14 (t, 2H, ArH), 7.75 (d, J = 8.0
Hz, 2H, ArH), 7.87 (d, J = 8.4 Hz, 2H, ArH).13C NMR (100
MHz, DMSO-d6): δ 60.22, 104.96, 111.40, 112.82, 115.96,
119.23, 127.39, 129.19, 132.70, 134.74, 142.64, 148.27.
2.3b
2-(Thiophen-2-yl)-2,3-dihydro-1H-perimidine
◦
1
3. Results and Discussion
(3n): Light yellow powder. M.p.: 115–117 C. H NMR
(400 MHz, DMSO-d6): δ 5.49 (s, 1H, N-CH-N), 6.48 (s,
2H, NH), 6.78 (m, 2H, ArH), 6.95 (d, J = 7.6 Hz, 2H,
ArH), 7.12 (m, 2H, ArH), 7.28 (m, 1H, ArH), 7.52 (m, 1H,
ArH), 7.54 (m, 1H, ArH). 13C NMR (100 MHz, DMSO-
d6): δ 62.46, 104.85, 113.04, 115.70, 124.05, 126.68, 127.32,
127.50, 134.82, 143.17, 144.44.
3.1 SiO2NPs as an efficient catalyst to improve the
synthetic procedure of 2,3-dihydro-1H-perimidines
We wish to report our results in the synthesis of
2,3-dihydro-1H-perimidines (3a–3p) by the reaction

J. Chem. Sci.
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Page 3 of 10
34
Table 1. Syntheses of 2,3-dihydro-1H-perimidine derivatives catalyzed by SiO2 NPs.
Entry
1
Reagent 5
Product
Time (min)
Yield (%)
M.p. (ºC)
103-10428
30
95
2
3
45
35
90
91
117-11828
144-14628
4
60
15
20
97
95
97
158-16036
191-19328
200-20128
5
6
7
20
88
131-13328

34 Page 4 of 10
Table 1. (contd.)
J. Chem. Sci.
(2019) 131:34
Entry
Reagent 5
Product
Time (min)
Yield (%)
M.p. (ºC)
8
30
92
160-16228
9
20
35
90
92
166-16728
10
new
11
12
35
27
85
90
49-5236
138-14029
13
14
10
96
182-18328
15
10
90
95
115-11723
15
16
new
15
90
165-16736

J. Chem. Sci.
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Page 5 of 10
34
Table 2. Optimization of the reaction condition in the syn- of 1,8-diaminonaphthalene 1 and various aldehydes 2
thesis of compound 3a.
using SiO2 as a nano heterogeneous catalyst (Table 1).
To study the effect of solvent and temperature in the
reaction of benzaldehyde and 1,8-diaminonaphthalene
was chosen as a model reaction (Table 2). Among the
exa◦mined conditions, grinding in a neat condition at
25 C was found to be the most effective situation to
produce excellent yields of products (entry 6). Also,
in the optimization procedure, 2 mol% of catalyst was
the appropriate amount of the reaction. Lesser amount
gave a low yield and bigger amounts could not cause
the obvious increase in the production of 3a (Table 3).
Finally, the recovered catalyst could be reused without
Entry Solvent Temperature (◦C) Time (min) Yield (%)
1
2
3
4
5
6
7
8
H2O
EtOH
CH3CN
CH2Cl2
THF
Neat
Neat
25
25
25
25
25
25
50
90
30
30
30
30
30
30
15
15
trace
50
35
32
44
95a
90
Neat
50
a
The best condition
Table 3. Optimization of the amount of SiO2 NPs as a cat- anynoticeablelossinitsreactivity. Thenewstructuresof
products were characterized by spectral data (1H NMR
and C NMR). Other structures were characterized in
comparison to their authentic samples.
alyst in the synthesis of compound 3a.
13
Entry
Catalyst (mol%)
Time (min)
Yield (%)
A plausible mechanism and the crucial role of SiO2
NPs in activating the carbonyl group of the alde-
hyde is shown in Scheme 1. Aldehyde 2 and 1,8-
diaminonaphthalene 1 was condensed by releasing one
water molecule to form imine intermediate 6. After
1
2
3
4
5
-
1
2
5
10
60
60
30
25
20
trace
75
95a
95
95
a
The best condition
o
i
S
2
O
NP
R
H
o
i
S
2
2
NP
o
i
S
H
+
2
O
H
O
NP
δ
R
H
R
4
N
o
H2N
i
S
2
o
i
S
2
H
H2N
H2N
NP
NP
H
N
6
O
1
R
H2N
5
H
H
N
R
H
R
N
HN
NH
7
a-
3
3
p
Scheme 1. A plausible mechanism for the synthesis of 2,3-dihydro-1H-perimidine derivatives.

34 Page 6 of 10
J. Chem. Sci.
(2019) 131:34
Scheme 2. The Crucial role of catalyst in limiting the reaction to yield products 9.
imine formation 6, it might be possible to interact with Table 4. Optimization of the reaction condition in the syn-
thesis of compound 9a.
SiO2 nanoparticle by hydrogen bonding which has an
intramolecular react with a second amine group to form
intermediate 7. Finally, 1,3-proton transfer gives the cor-
responding 2,3-dihydro-1H-perimidines (3a–3p).
Entry Solvent Temperature (◦C) Time (h) Yield (%)
1
2
3
4
5
6
7
H2O
EtOH
Toluene
THF
Neat
Neat
70
70
70
70
70
90
110
1
1
1
1
1
30
35
50
47
62
80
92a
3.2 SiO2NPs as an efficient catalyst to improve the
synthetic procedure of tetraketone derivatives
30 min
15 min
Neat
In continuation of our work, we examined SiO2 as a
nano heterogeneous catalyst in the condensation of ben-
zaldehydes 2 with 5,5-dimethyl-1,3-cyclohexanediones
8. As illustrated in Scheme 2, the crucial role of
catalyst in limiting the reaction to yield products
9 or 10 is evident.37 Surprisingly, only intermedi-
ate 2,2ꢀ-phenylmethylene bis(3-hydroxy-5,5-dimethyl-
2-cyclohexene-1,3-dione) (9a) obtained in 92% yield
and cyclized product 10 did not form.
Initially, the optimization of reaction condition was
studied in a model reaction of benzaldehyde and dime-
done in preparing compound 9a (Table 4). It was
found that solvent-free condition can afford the prod-
uct in good yield even better than other organic sol-
vents (Entries 1–5). In addition, it ◦was found that
increasing the temperature to 110 C leads to the
higher yields (Entries 6 and 7). Entry 7 was the most
desired condition among the various reaction condi-
tions used in Table 1. In addition, in the optimiza-
tion procedure, 2 mol% of catalyst was the appro-
priate amount for the reaction as shown in Table 5.
The fewer amount gave a low yield and the more
amounts could not cause the apparent increase in the
production of 2,2ꢀ-phenylmethylenebis(5,5-dimethyl-2-
cyclohexene-1,3-dione) (9a). Therefore, a mixture of
dimedones, various benzaldehydes bearing electron-
withdrawing and electron-donating substitu◦ents and
SiO2 NPs as a catalyst were heated at 110 C under
solvent-free condition to prepare crude products 2,2ꢀ-
arylmethylene bis(3-hydroxy-5,5-dimethyl-2-cyclo-
hexene-1,3-diones) (9a–9p) in high to excellent yields
a
The best condition
Table 5. Optimization of the amount of nano-SiO2 as a cat-
alyst in the synthesis of compound 9a.
Entry
Catalyst (mol%)
Time (min)
Yield (%)
1
2
3
4
5
-
60
30
15
8
trace
76
1
2
5
7
92a
95
5
95
a
The best condition
13
NMR and C NMR analysis and by comparison with
their authentic samples.
The mechanism seems to proceed via sequential Kno-
evenagel condensation-Michael addition reaction. The
crucial role of SiO2 NPs is shown in Scheme 3 by form-
ing a complex and thus activating the carbonyl group of
benzaldehydes for nucleophilic addition. In this proto-
col, intermediate alcohol 11 is formed by the attack of
activated dimedone 8. After the Knoevenagel conden-
sation reaction, intermediate 12 which undergoes the
nucleophilic attacking of another dimedone by Michael
addition is transformed into the desired products (9a–
9p).
3.3 Catalyst
(Table 6). The resulting solid products were dissolved in Moreover, mesoscopic structure of silica with 50 nm
hot ethanol to crystallize; then were characterized by 1H particles is established in the SEM image (Figure 1) of

J. Chem. Sci.
(2019) 131:34
Page 7 of 10
34
Table 6. Syntheses of tetraketone derivatives 9a–9p catalyzed by SiO2 NPs.
Entry
-X
R
Product
Time (min)
Yield (%)
M.p. (◦C)
1
2
3
4
5
6
7
8
H
4-OH
4-Cl
4-NO2
4-OMe
4-Me
H
4-OH
4-Cl
2-NO2
4-NO2
4-OMe
3-Br
4-Me
2-NO2
3-Br
Me
Me
Me
Me
Me
Me
H
H
H
H
H
H
H
H
Me
H
9a
9b
9c
9d
9e
9f
9g
9h
9i
9j
9k
9l
9m
9n
9o
9p
15
30
15
10
15
20
10
30
20
8
92
74
95
97
90
92
95
80
93
95
96
90
96
92
93
92
194-19532
187-18932
136-13831
177-17931
136-13931
123-12631
208-21031
197-19931
202-20431
204-20632
210-21232
190-19132
206-20832
190-19131
204-20632
206-20831
9
10
11
12
13
14
15
16
5
20
10
15
10
7
o
i
S
2
NP
o
o
2
i
i
S
S
2
NP
NP
O
H
H
O
O
X
H
O
O
O
O
2
O
R
11
o
i
S
2
NP
8
8
-
H
2O
o
i
S
2
NP
H
O
O
O
O
O
O
O
H
2O
O
X
12
X
a-
9 9
p
Scheme 3. Proposed mechanism for syntheses of tetraketone derivatives.

34 Page 8 of 10
J. Chem. Sci.
(2019) 131:34
was completed four times without any noticeable loss
of reactivity (Table 7).
We have compared the efficiency of SiO2 NPs with
various conditions in the synthesis of 2,3-dihydro-
1H-perimidines as shown in Table 8. In addition, we
have also compared the efficiency of various catalysts
in the synthesis of tetraketones (Table 9). The high
yield of products and short reaction times demonstrated
that SiO2 NPs acts as an efficient catalyst in these
reactions.
4. Conclusions
Figure 1. SEM image of SiO2 NPs.
In conclusion, we have developed a simple strategy
for the synthesis of a series of organic compounds
using the catalytic amount of SiO2 nanoparticles under
mild condition. The advantages of this method are
solvent-free conditions, broad scope, easy handling,
and high to excellent yields. Further, some different
selectivities of SiO2 NPs catalytic system is observed
which is the formation of 2,2ꢀ-arylmethylene bis(3-
hydroxy-5,5-dimethyl-2-cyclohexene-1-one) and not its
corresponding cyclized compound.
Table 7. Reusability of SiO2 NPs as catalyst.
Run
1
2
3
4
Yield of compound 3a
Yield of compound 9a
95%
92%
93%
91%
90%
89%
88%
86%
these nanoparticles which were prepared according to
the literature.38
Supplementary Information (SI)
To check the reusability, the recovered catalyst could
be washed with diluted aqueous Et3N solution, water
and acetone sequentially. After a period of drying, the
catalyst could be reused in the synthesis of compound
1H NMR and 13C NMR of some compounds (Figure S2–
S21), list of 2,3-dihydro-1H-perimidine derivatives, list of
2,3-dihydro-1H-perimidine derivatives, some data about cat-
alyst (Tables S1–S9, Scheme S1–S3 and Figures S1) are
9a and 3a as a model reaction. The process of recycling available at www.ias.ac.in/chemsci.
Table 8. Comparison of various catalysts in the synthesis of 2,3-dihydro-1H-perimidines in recent years.
Entry
Catalyst
Solvent
Condition
Time
Yield (%)
Year
1
2
3
4
NaY zeolite
NSSA
CMK-5-SO3H
Ethanol
Ethanol
Ethanol
Ethanol
Stir. at rt.
Stir. at rt.
Stir. at rt.
Stir. at rt.
45–50 h
50 min
5 min
70
84
91
84
200936
201028
201339
201329
I2
40 min
Comparing the current work with previous works
SiO2NPs Neat
5
Grinding
10-60 min
85–97
This work
Table 9. Comparison of various conditions in the synthesis of tetraketones in recent years.
Entry
Catalyst
Solvent
Condition
Time
Yield (%)
Ref.
1
2
3
-
DMF
Neat
H2O
Stir. at 80 ◦C
Grinding
Stir. at rt.
1 h
2–5 min
1–4 h
65–86
73–88
64–99
200030
201131
201032
Yb(OTf)3-SiO2
-
Comparing the current work with previous works
SiO2NPs Neat
4
Heating at 110 ◦C
5–30 min
74–97
This work

J. Chem. Sci.
(2019) 131:34
Page 9 of 10
34
Acknowledgements
14. Shanmugasundram P, Murugan P, Ramakrishnan V
T, Srividya N and Ramamurthy P 1996 Synthesis
of acridinedione derivatives as laser dyes Heteroatom
Chem. 7 17
We gratefully acknowledge the financial support from the
Research Council of the University of Mazandaran.
15. Sivaraman K, Subramanian K, Ganesan S and Ramakr-
ishnan V T 1995 Spectroscopic studies on the interaction
of three partially hydrogenated acridine dyes with calf
thymus DNA and their structural comparison J. Biomol.
Struct. Dyn. 13 119
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