Selective and highly efficient synthesis of xanthenedione or tetraketone derivatives catalyzed by ZnO nanorod-decorated graphene oxide

Article abstract of DOI:10.1039/c8nj01053f

ZnO nanorod-decorated graphene oxide (GO/ZnO), containing Lewis and Bronsted acid centers, was introduced as a selective, highly efficient and recoverable nanocatalyst for the pseudo three-component synthesis of diverse tetraketone or xanthenedione derivatives via condensation of aromatic aldehydes with 1,3-dicarbonyl compounds in short reaction times and good to excellent yields in H₂O under refluxing and solvent-free conditions, respectively. Moreover, the GO/ZnO nanocomposite was recovered and reused at least four times without a significant decrease in its activity. Low loading of the catalyst, high to excellent yields, the elimination of any toxic heavy metals or corrosive reagents for modification of the catalyst, simple separation and purification of the products, and the reusability of the catalyst are the most significant advantages of this green protocol. The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2018.

Full text of DOI:10.1039/c8nj01053f

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ISSN 1144-0546
PAPER
Jason B. Benedict et al.
The role of atropisomers on the photo-reactivity and fatigue of
diarylethene-based metal–organic frameworks
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Selective and highly efficient synthesis of xanthenedione or
tetraketone derivatives catalyzed by ZnO nanorods decorated
graphene oxide
Received 00th January 20xx,
Accepted 00th January 20xx
*
Sepideh Hasanzadeh Banakar, Mohammad G. Dekamin and Amene Yaghoubi
DOI: 10.1039/x0xx00000x
www.rsc.org/
ZnO nanorods decorated graphene oxide (GO/ZnO), having Bronsted and Lewis acid centers, was introduced
as a selective, highly efficient and recoverable nanocatalyst for the pesudo threeꢀcomponent synthesis of
diverse tetraketone or xanthenedione derivatives via condensation of aromatic aldehydes with 1,3ꢀdicarbonyl
2
compounds in short reaction times and good to excellent yields in H O under refluxing and solventꢀfree
conditions, respectively. Moreover, the GO/ZnO nanocomposite was recovered and reused at least four times
without significant decrease in its activity. Low loading of the catalyst, high to excellent yields, eliminating of
any toxic heavy metals or corrosive reagents for modification of the catalyst, simple separation and
purification of the products, and reusability of the catalyst are the most significant advantages of this green
protocol.
Graphene oxide (GO) contains a range of reactive oxygen functional
3
Introduction
groups. GO consists of intact graphitic regions interspersed with sp ꢀ
hybridized carbons containing functional groups such as carboxyl,
hydroxyl, and epoxide on the edge, top, and bottom of surface of
Furthermore, owing to its unique properties such as
thermal, chemical and mechanical stability, high specific surface
In recent years, nanoscience has emerged as an attractive and
important research area among chemistry, material, physics,
medicinal, biology, mechanic and other sciences because of its
novel, extensive and unique applications in various fields. Hence, a
lot of studies have been focused onto nanoparticles. Their reactivity,
toughness and other properties are also dependent on their unique
size, shape and structure. Indeed, nanoparticle chemistry is a new
branch of chemical research. For more than a century, transition
metal particles were widely used as heterogeneous catalysts. Today,
nanoscience appears to be essential and important in catalysis of
various reactions, especially in organic chemistry. Nanocatalysts
have been used in various reactions especially multicomponent
reactions to enhance the yield of products in shorter reaction times
and easier separation and recovery. Therefore, development of ecoꢀ
friendly methods for the preparation of nanoparticles is an important
7
ꢀ10
each sheet.
1
1
area and strong interactions with metal clusters,
potential
applications of graphene and GO have been actively pursued in the
different fields. For example, biological applications for cellular
imaging, drug delivery, and bio sensing, nano electronics as well
1
12
13
1
4
2
as nanocomposites
Furthermore, GO is
applications.
have been reported in recent years.
promising material for the catalytic
a
1
5
Catalysts are an important issue in the synthesis of fine
chemicals, production of bulk chemicals and environmental
3
16
industries. Therefore, utilization of catalysts with appropriate
properties including ease of preparation, recoverability, recyclability,
and higher yields of the desired products is the most important aims
in the catalystꢀdesign science. Zinc oxide (ZnO) is an inexpensive,
airꢀ and moisture stable, reusable, commercially available and
4
, 5
branch of nanotechnology.
The fabrication of graphene oxideꢀbased nanocomposite
materials have been performed by different methods or techniques
such as hydrothermal, electrochemical deposition, in situ
polymerization, solꢀgel, sonochemical, electrospinning, microwave
and photocatalysis. However, finding a more appropriate way to
prepare this type of nanocomposites is still a great challenge.
environmentally
benign
piezoelectric,
Many nanostructures of ZnO have been prepared
under specific growth conditions, such as nanocombs, nanorings,
nanohelixes/nanosprings, nanobows, nanobelts, nanowires,
nanocages, nanocolumnar and nanrods. Hence, ZnO is probably
the richest family of nanostructures among all materials which has
material.
ZnO
demonstrates
semiconducting,
properties.
and
pyroelectric
multiple
1
7ꢀ21
6
2
2ꢀ25
Pharmaceutical and Heterocyclic Compounds Research Laboratory, Department of
Chemistry, Iran University of Science and Technology, Tehran, 16846-13114, Iran.
Email: mdekamin@iust.ac.ir
22, 26ꢀ30
been used as catalyst.
Indeed, ZnO nanoparticles decorated
graphene oxide (GO/ZnO) provide combination of ZnO and GO
properties in which the catalytic activity of each part has been
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See improved. However, only a few metal oxide or metal nanoparticlesꢀ
DOI: 10.1039/x0xx00000x
graphene (or graphene oxide) hybrids have been reported and fewer
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studies have investigated their potent applications in different fields. which are not recoverable, and production of byꢀproducts. In
Some recently applications of GO/ZnO, as a stable nanocomposite, continuation of our interest to develop mild, green and efficient
3
1
63ꢀ73
include synthesis of 5ꢀsubstitutedꢀ1Hꢀtetrazoles, chemical gas heterogeneous catalysts for different MCRs,
we wish herein
3
2
33
34
sensors, photocatalytic activities, photovoltaic cells, tunable to report the catalytic activity of the graphene oxide/ZnO
fluorescence and simultaneous detection and degradation of nanocomposite (GO/ZnO,
35
1, Fig. 2), as a green, novel,
3
6
harmful organic contaminants from aqueous solution.
Tetraketones (2,2′ꢀarylmethylene bis(3ꢀhydroxyꢀ5,5ꢀdimethylꢀ2ꢀ
cyclohexeneꢀ1ꢀone) and xanthenediones (1,8ꢀdioxoꢀ
octahydroxanthene) derivatives are important classes of oxygenꢀ
containing organic compounds that have gained much attention due
to their numerous applications in pharmacy, biology and material
science. Tetraketone derivatives demonstrate biological and
therapeutic properties such as lipoxygenase inhibitory (compound
recoverable and highly efficient heterogeneous nanocatalyst for
the oneꢀpot pseudo threeꢀcomponent synthesis of different
tetraketones in water, as a green solvent, as well as preparation
of xanthenedione derivatives under solventꢀfree conditions
(
Scheme 1).
3
7
38, 39
A
(
), tyrosinase inhibitory (compound
B)
and antiꢀtubercular
activities as well as selective estrogen receptor
modulators treatment of breast cancer (compound
4
0
compound
C)
4
1
D) (Fig. 1).
Furthermore, they are important synthetic intermediates that can
serve as versatile precursors in the synthesis of xanthenes and
4
2
polyhydroacridine derivatives. On the other hand, xantheneꢀ
based compounds are organic fluorophores and demonstrate
4
3
fluorescence properties such as fluorescein and rhodamine.
Fig. 2 A schematic structure of the ZnO nanorods decorated
graphene oxide (GO/ZnO) nanocomposite (1).
Scheme
arylmethylene bis(3ꢀhydroxyꢀ5,5ꢀdimethylꢀ2ꢀcyclohexeneꢀ1ꢀone)s (4aꢀ
) and 1,8ꢀdioxoꢀoctahydroxanthenes (5aꢀj) catalyzed by GO/ZnO ( ).
1. Oneꢀpot pseudo threeꢀcomponent synthesis of 2,2′ꢀ
Fig.1 Selected examples of 2,2′ꢀarylmethylene bis(3ꢀhydroxyꢀ5,5ꢀdimethylꢀ
ꢀcyclohexeneꢀ1ꢀone) and 1,8ꢀdioxoꢀoctahydroxanthene derivatives
demonstrating biological and pharmacological activity.
2
z
1
Recently, various homogeneous and heterogeneous catalysts
have been used in expanding and improving of reaction
Results and discussion
conditions for the synthesis of tetraketone and xanthenedione
derivatives. Some recent catalytic systems are nickel reported procedures in literature with a slight modification.
The graphene oxide (GO) was first prepared according to
7
4
4
4
45
nanoparticles, nanocrystalline TiO
2
,
copper nanoparticles After that, GO/ZnO nanocomposite (
1) was prepared by
4
6
47
supported onto silica,
[
n
ꢀPr
2
NH
2 4
][HSO ],
molybdate functionalizing of GO with Zn(OAc) .2H O analogous with
2
2
4
8
49
50
51
31
sulfonic acid, BiOCl, CsF, natural phosphate, Amano described procedure by Nasrollahzadeh and coworkers with a
5
2
53
lipase DF,
MCMꢀ41ꢀSO
Fe @SiO ꢀimidꢀPMA, aminoꢀappended
CoFe nanoparticles, ZnO particles,
urea under ultrasonication. Most of these synthetic strategies and Zn(OAc) .2H O. Subsequently, the obtained materials were
βꢀcyclodextrin grafted with butyl sulfonic acid,
slight modification. In the preliminary studies, various mass
5
4
55
56
H0.5PW12O
40,
3
H, [MNPꢀPImꢀSO
3
H]Cl, Cs2.5
–cyclodextrin,
ratios of GO to Zn(OAc) .2H O such as 1:3, 1:2 and 1:1 were
2
2
5
7
58
3
O
4
2
β
examined for the preparation of GO/ZnO nanocomposite (
1).
5
9
29, 60
61
2
O
4
3
GOꢀSO H
and Indeed, the best result was obtained by 1:1 mass ratio of GO
6
2
2
2
suffer from restrictions such as harsh reaction conditions, long characterized with several spectroscopic and techniques such as
reaction times, toxicity of solvents, often expensive catalysts Fourier transform infrared (FTIR) spectroscopy, field emission
2
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ꢀ1
scanning electron microscopy (FESEM), energy dispersive Xꢀray the range of < 500 cm such as observed signals at 414, 443
ꢀ1
spectroscopy (EDX) and thermogravimetric analysis (TGA) and cm are assigned to the stretching vibrations of the ZnꢀOꢀZn
7
5
powder Xꢀray diffraction (XRD). The reaction between GO and interactions. Interestingly, the characteristic carbonyl signal of
ꢀ
1
GO at 1724 cm has almost been disappeared in the GO/ZnO
nanocomposite. This observation as well as absence of a very
broad band of COOH functional groups in the region 3300ꢀ
ZnO nanoparticles under ultrasound and then formation of ZnO
nanoparticles (in the presence of OH ) on graphene oxide sheets
and preparation of GO/ZnO nanocomposite (1) are shown in
ꢀ
ꢀ1
2
400 cm confirm that ZnO nanoparticles are completely
) and bonded with the formed carboxylates at the edge of GO.
(
Fig. 2).
The FTIR spectra of the GO/ZnO nanocomposite (
1
GO are compared in Fig. 3. The observed changes are referred However, the observed broad characteristic bands at 3600ꢀ3300
to chemical interactions between functional groups of GO and are attributed to the stretching vibration of the OꢀH bonds of
ZnO. In the FTIR spectrum of GO, the appeared characteristic COH groups on the surface of GO/ZnO nanocomposite (
1
).
) shows the
and C–OH functional groups, respectively. Moreover, the presence of the ZnO characteristic bands and reduction in peak
ꢀ1
bands at 1724, 1616 and 1200 cm were assigned to C=O, C=C Indeed, FTIR spectrum of GO/ZnO nanomaterial (
1
ꢀ1
signals observed at 1053 and 835 cm are attributed to epoxy intensity of the band corresponding to carboxylic acid (2400ꢀ
ꢀ1
(
C–O–C) vibrations. On the other hand, in the FTIR spectrum 3600 cm ). All these findings confirm functionalization of GO
of GO/ZnO nanocomposite (
), the strong absorption bands in by ZnO (Figs. 2, 3).
1
Fig. 3 FTIR spectra of the graphene oxide (GO) sheets (down) and ZnO decorated graphene oxide (GO/ZnO) nanocomposite (1, up).
Furthermore, energy dispersive Xꢀray spectroscopy (EDX) nanocomposites
of GO/ZnO nanocomposite ( ) indicates the presence of C, O signal at 2Ɵ = 12.12 and other diffraction peaks in the structure of
and Zn elements in the nanomaterial composition. These GO/ZnO nanocomposite (1) which are similar to pure hexagonal
(1) are outlined in Figure 6. The Existence of GO
3
3
1
2
2, 31
observations, especially presence of Zn in the composition of phase of ZnO nanorods (JPCDS 36ꢀ1451)
the GO/ZnO nanomaterial illustrates the successful of this nanocomposite.
confirm construction
(1)
inclusion of expected ZnO in the material network (Fig. 4).
The thermal stability of the GO/ZnO nanocomposite (1) was
On the other hand, the morphology and particle size of the
also investigated using thermogravimetric analysis (TGA)
technique (See ESI). This analysis illustrated higher thermal
stability of GO/ZnO nanocomposite (1) than GO. A weight loss
GO/ZnO nanocomposite (
scanning electron microscopy (FESEM). As it can be clearly
seen in Figure , the FESEM images show GO layers (Fig. 5b
1) was evaluated using field emission
5
)
at the temperature below 200 ˚C corresponding to the removal
of water. On the other hand, the second weight loss between
and immobilized ZnO nanoparticles on the surface or between
graphene oxide layers (Fig. 5a). The gray thin films are the GO
sheets and the white regions on the GO background
demonstrate the presence of ZnO nanorods. Moreover, Xꢀray
diffraction patterns (XRD) of GO, ZnO and GO/ZnO
2
00 and 400 ˚C is attributed to desorption of oxygenated carbon
groups located in the GO/ZnO nanocomposite (1) structure.
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Fig. 4. Energy dispersive spectroscopy (EDX) pattern of the ZnO decorated
graphene oxide (GO/ZnO) nanocomposite (1).
(a)
(b)
Fig. 5. Field emission scanning electron microscopy (FESEM) of the ZnO nanorodsꢀdecorated graphene oxide (GO/ZnO)
nanocomposite (a, b).
4
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Fig. 6. XꢀRay diffraction (XRD) pattern of the GO, ZnO nanorodsꢀdecorated graphene oxide (GO/ZnO) nanocomposite (1, b), ZnO
nanoparticles and the hexagonal phase of ZnO (JPCDS 36ꢀ1451).
To show the e
fficiency of the GO/ZnO nanomaterials (
1
), as amount of the catalyst to 15 mg catalyst loading, had no
a
catalyst, for the synthesis of tetraketones
4
and significant influence on the yield of the desired product (entry
xanthenediones 5
, the reaction of 4ꢀchlorobenzaldehyde (2a, 1 9). On the other hand, both bulk ZnO and GO were also
mmol), and dimedone (3a) was investigated as the model employed, as the catalyst, in the model reaction under similar
reaction. The reaction conditions were optimized with regard to reaction conditions. It was observed that the desired product 4a
appropriate catalyst loading, different solvents and temperature. was obtained in lower yields and longer reaction times
The results are summarized in Table
1.
compared to GO/ZnO nanomaterials (
and 11).
1) (Table 1, entries 10
It is noteworthy that the 2,2'ꢀ(4ꢀchlorophenyl)methylene
bis(3ꢀhydroxyꢀ5,5ꢀdimethylꢀ2ꢀcyclohexeneꢀ1ꢀone) 4a was
(
)
Furthermore, the model reaction afforded low yield of the
obtained in very low yields and longer reaction times in the desired product 4a under ultrasonic conditions at room
absence of any catalyst even at 90 ˚C (entries 1,2). temperature compared to reflux conditions (entry 12). Finally,
Interestingly, after addition of 10 mg of the catalyst (
yield of the desired tetraketone 4a in the presence of GO/ZnO the presence of GO/ZnO nanocomposite (
nanocomposite (
) was significantly improved in shorter and solventꢀfree conditions at 100˚C, only 30 % tetraketone 4a
1
), the when 4ꢀclorobenzaldehyde 2a was reacted with dimedone 3a in
1) under catalystꢀfree
1
reaction time in EtOH under reflux conditions compared to was obtained and no corresponding xanthenedione products 5a
catalystꢀfree conditions. In the next step, the effect of various was formed (entry 14). However, after adding of the catalyst to
solvents such as THF, CH Cl , CH CN and H
2 2 3 2
O on the yield the reaction mixture, only corresponding xanthenedione
and reaction time was studied. The best results, in terms of product 5a was obtained in excellent yield and shorter reaction
reaction time and yield of the desired product 4a, was obtained time under similar conditions (entry 15). Further increasing of
when the reaction was performed in protic solvents such as temperature had no remarkable effect on the yield of the desired
2 2
EtOH or H O (Table 1, entries 3ꢀ7). When H
O was used as the product 5a (entries 16 and 17). On the other hand, decreasing of
solvent, it afforded the corresponding tetraketone 4a in 99 % the amount of catalyst loading afforded product 5a in lower
yield and shorter reaction time compared to EtOH. Afterwards, yield and longer reaction time (entry 18). In contrast, increasing
the effect of catalyst loading on the completion of the reaction of the amount of catalyst to 15 mg catalyst loading had no
was examined in the next experiments.
significant effect on the yield and reaction time (entry 19).
Finally, the optimized conditions worked very well for larger
scales (5 mmol) of the limiting reactants of both model
reactions to afford desired products 4a and 5a in high yields,
respectively (entries 13 and 20).
By reducing of the amount of the catalyst to 5 mg catalyst
loading, lower yield of the product 4a was obtained under
similar conditions (entry 8). In contrast, increasing of the
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Table 1. Optimization of the pseudo threeꢀcomponent reaction 4ꢀchlorobenzaldehyde (2a), dimedone (3a) under different
a
conditions
b
b
Yield 4a (%)
Yield 5a (%)
Catalyst
loading (mg)
Entry
Solvent
Temp. (°C)
Time (min)
1
2
3
4
5
ꢀ
H
2
O
O
r.t
600
210
20
40
50
95
70
54
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
H
2
90 ˚C
Reflux
Reflux
Reflux
10
10
10
EtOH
THF
130
180
CH
2
Cl
2
6
10
MeCN
Reflux
40
80
7
8
10
5
H
H
H
H
H
H
H
2
2
2
2
2
2
2
O
O
O
O
O
O
O
Reflux
Reflux
Reflux
Reflux
Reflux
r.t
10
10
99
93
99
60
65
60
95
30
ꢀ
ꢀ
ꢀ
9
15
10
10
10
50
ꢀ
10
ꢀ
c
10
11
12
240
180
60
ꢀ
d
e
f
ꢀ
ꢀ
13
Reflux
100
12
ꢀ
1
1
1
1
1
1
4
SolventꢀFree
SolventꢀFree
SolventꢀFree
SolventꢀFree
SolventꢀFree
SolventꢀFree
SolventꢀFree
100
30
ꢀ
5
6
7
8
9
10
10
10
5
100
99
99
99
89
99
93
110
30
ꢀ
120
25
ꢀ
100
30
ꢀ
15
50
100
30
ꢀ
f
20
100
35
ꢀ
a
b
c
Reaction conditions: 4ꢀchlorobenzaldehyde (2a, 1 mmol), dimedone (3a, 2 mmol) under different conditions. Isolated yields.
Catalysed by ZnO nanoparticles, Catalysed by GO, Under ultrasonic condition. 4ꢀChlorobenzaldehyde (2a, 5 mmol), dimedone (3a,
0 mmol).
d
e
f
1
After finding of optimal conditions, to evaluate the catalytic reactions is dependent on the substituent effect. In fact,
activity of GO/ZnO nanocomposite ( ), for the synthesis of substrates having an electronꢀwithdrawing group on the phenyl
tetraketone derivatives, the optimized conditions were further ring of aldehydes (Table 2, entries 1ꢀ14) produced higher yields
developed to other aromatic carbocyclic and heterocyclic of desired products or in same reaction times compared
aldehydes 2aꢀp. The results are outlined in Table . As it can be with ones having an electronꢀdonating substituent (Table 2,
seen, in all studied examples, good to excellent yields of the entries 17ꢀ23). Furthermore, heterocyclic aldehydes such as
desired products 4aꢀz were obtained under the optimal reaction cinamaldehyde 2n), furfural 2o and thiopheneꢀ2ꢀ
1
4
5
2
(
(
)
conditions within short reaction times. Furthermore, the carbaldehyde (2p), which are susceptible to polymerization
optimized conditions were also used for the synthesis of under acidic conditions, reacted under optimal reaction
xanthenedione derivatives which the results of this part of our conditions to afford the corresponding products (Table 2,
study are shown in Table
3. Both aromatic carbocyclic and entries 24ꢀ26).
heterocyclic aldehydes containing electronꢀwithdrawing and
electronꢀdonating groups involved in the optimized reaction
conditions. The obtained results indicated that the yield of the
A probable mechanistic pathway for the formation of
tetraketones
4
and 1,8ꢀdioxoꢀoctahydroxanthenes 5 is outlined in
6
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Scheme 2. According to the depicted mechanism, it can be proposed
that GO/ZnO nanocomposite (1) owing to having Lewis and
Table 4 compares the efficiency of GO/ZnO nanocomposite
1) with some of the previously introduced procedures to
(
Bronsted acidic sites acts as an acidic catalyst. Therefore, supported demonstrate its catalytic activity for the synthesis of different
Zn (II) species and OH groups on the surface of the catalyst (1) can tetraketones or 1,8ꢀdioxoꢀoctahydroxanthenes. Obviously,
activate the carbonyl group of aldehydes 2 to facilitate nucleophilic GO/ZnO nanocomposite shows higher catalytic activity in
addition of dimedone or cyclohexanedione (3aꢀb) on the aldehydes
to afford Knoevenagel intermediate (I) with elimination of a water
molecule. The catalyst can also activate carbonyl group of dimedone
or cyclohexanedione (3aꢀb) and is able to increase concentration of
the enol form of 1,3ꢀdicarbonyl compounds 3a'ꢀb'. After that, by
Michael addition of second molecule of 1,3ꢀdicarbonyl compounds
3a'ꢀb' in the second step, tetraketones 4aꢀz can be prepared.
Finally, ring closure and subsequent tautomerization of the obtained
tetraketones and elimination of second molecule of water, in the
presence of GO/ZnO nanocomposite (1) affords the desired
products 5aꢀj under solventꢀfree conditions (Scheme 2). Indeed,
effective catalytic activity of GO/ZnO nanocomposite (1) compared
to other catalysts containing GO structure can be attributed to active
Lewis acidic centers.
Another important aspect of this active, efficient, and ecoꢀ
friendly heterogeneous nanocatalyst is its recyclability. After
completion of the reaction, GO/ZnO nanocomposite (1) was
separated and washed by EtOH, EtOAc and acetone, respectively.
The recycled catalyst was then dried under vacuum and reused in
subsequent runs. The results are summarized in (Fig. 7). As a
part of our study, it has been presented that the GO/ZnO
nanocomposites (1) could be recovered and reused at least four
times in the subsequent runs for the model reaction using the same
recovered catalyst without a considerable loss of its catalytic
activity.
Fig. 7 Reusability of GO/ZnO nanocomposite (
and 5a
1) for the synthesis of
4a
.
comparison to several of the others in terms of catalyst loading,
product yield, avoiding the use of toxic transition metals, toxic
solvents and required reaction time.
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New J. Chem.
Table 2. GO/ZnO (
1
) catalyzed oneꢀpot pseudo threeꢀcomponet synthesis of 2,2′ꢀarylmethylene bis(3ꢀhydroxyꢀ5,5ꢀdimethylꢀ2ꢀcyclohexeneꢀ1ꢀone)
a
derivatives 4aꢀz from aldehydes 2aꢀp, cyclohexanediones 3aꢀb under the optimized conditions.
O
O
Ar
O
O
Ar
O
O
H + 2 R
Graphene oxide/ZnO nanocomposite (1)
Ar
R
R
R
O
R
R
H O, reflux
2
R
R
O O
R
R
OH
OH
R = CH , H
3
4
a-z
2
3
M.p (°C)
Found / Reported
Time
b
Entry
Aldehyde 2
R
Product 4
Yield (%)
(min)
7
6
1
CH
3
10
99
145/ 140-142
2
a
4
a
5
9
2
H
15
96
204/204-206
2
a
4
b
7
7
3
CH
3
10
95
200/ 205
2
b
4
c
5
9
4
H
15
94
227/229-231
2
b
4
d
7
8
5
CH
3
10
96
154/158-159
8
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ARTICLE
2
c
4e
7
4
8
9
9
0
6
H
CH
CH
15
90
96
97
243/240-241
204/201-203
192/188-190
2
c
4
f
7
3
10
2
d
4
g
8
3
10
2
e
4
h
8
1
9
H
15
95
217/218
2
e
4
i
7
7
1
0
CH
3
10
95
199/197-198
2
f
4
j
8
2
1
1
H
15
92
207/209-210
2
f
4
k
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New J. Chem.
5
8
1
2
CH
3
10
96
192/188-190
2
g
4
l
8
2
1
3
H
15
91
213/212-213
2
g
4
m
83
1
1
1
4
5
6
CH
CH
H
3
10
97
95
93
169-171/165-167
2
h
4
n
o
p
7
7
3
10
196 / 194-195
2
i
4
8
2
15
219/217-218
2
i
4
83
1
7
CH
3
10
94
188-190/188-190
2
j
4
q
1
0 | New J. Chem., 2018, 00, 1-17
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ARTICLE
5
9
1
8
H
15
92
196/192-194
2
j
4
r
8
4
1
9
CH
3
10
88
145/142-143
2
k
4s
5
7
8
9
7
0
2
2
2
0
1
2
H
CH
CH
15
10
10
87
89
85
197/193-195
185/187-188
130/126-128
2
k
4
t
3
2
l
4
u
3
2
m
4
v
8
5
2
3
H
20
82
193/190-191
2
m
4w
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ARTICLE
New J. Chem.
7
7
2
4
CH
3
30
60
219/215-217
2
n
4x
4y
4z
86
2
5
CH
3
15
88
208ꢀ210/207ꢀ209
2
o
8
7
2
6
CH
3
15
89
218/216ꢀ217
2
p
a
Reaction conditions: 4ꢀChlorobenzaldehyde (2a, 1 mmol), dimedone (3a, 2 mmol) or1,3ꢀcyclohexanedione (3b, 2mmol) in the presence of 10 mg of the catalyst (1) under
b
2
H O reflux conditions at 100 C̊ . Isolated Yields.
1
2 | New J. Chem., 2018, 00, 1-17
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ARTICLE
Table 3. GO/ZnO (
1
) catalyzed oneꢀpot pseudo threeꢀcomponet synthesis of 1,8ꢀdioxoꢀoctahydroxanthenes 5a from aldehydes
2
, dimedone (3a
)
a
under the optimized conditions.
M.p (°C)
Time
min)
b
Entry
Aldehyde 2
Product 5
Yield (%)
(
Found / Reported
8
8
1
30
99
89
90
231ꢀ233/ 230ꢀ233
2
a
5
a
8
9
2
40
223ꢀ225/226ꢀ228
2
b
5
b
90
3
30
240ꢀ242/ 242ꢀ244
2
c
5
c
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New J. Chem.
90
4
30
92
228/224ꢀ226
2
e
5
d
9
0
5
40
90
167ꢀ169/164ꢀ166
2
f
5
e
91
6
40
90
256/258ꢀ262
2
g
5
f
90
92
93
7
8
9
30
45
40
95
91
92
224/220ꢀ222
200/199ꢀ200
246/241ꢀ243
2
h
5
g
2
i
5
h
2
k
5
i
1
4 | New J. Chem., 2018, 00, 1-17
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ARTICLE
89
1
0
30
99
225/222ꢀ224
2
m
5
j
a
Reaction conditions: 4ꢀchlorobenzaldehyde (2a, 1 mmol), dimedone (3a, 2 mmol) in the presence of 10 mg of the catalyst (1) under solventꢀfree conditions at
00 C̊ . Isolated Yields.
b
1
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Scheme 2. Proposed mechanism for the synthesis of tetraketones 4 and 1,8ꢀdioxoꢀoctahydroxanthenes 5 catalyzed by GO/ZnO nanocomposite (1).
1
6 | New J. Chem., 2018, 00, 1-17
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ARTICLE
Table 4. Comparative synthesis of compounds 4a and 5a using the reported methods versus the present method.
Catalyst
Temp (˚C)
Time (min) Yield (%) 4a Yield (%) 5a
Ref.
Entry
Catalyst
GꢀSO
Solvent
Loading
20 mg
6
6
1
1
3
H
H
2
O
O
80
80
120
120
ꢀ
ꢀ
90
81
1
2
GO
20 mg
H
2
Nanocrystalline
TiO
4
5
5
5
1
1
1
0 mg
Neat
80
rt
23
ꢀ
98
ꢀ
95
ꢀ
3
4
5
2
Natural phosphate
Natural phosphate
500 mg
2
H O
120
390
EtOH
(90%)
1500 mg
78
90
3 4 2
Fe O @SiO ꢀ
ImidꢀPMA
5
4
3
6
3
0 mg
EtOH
EtOH
78
80
60
60
ꢀ
91
ꢀ
6
7
Copper (0)
nanoparticles onto
silica
100 mg
93
CoFe
nanoparticles
2
O
4
H
2
O : EtOH
(1 : 1)
5
9
9
4
1
1.7 mg
60
rt
4
89
83
ꢀ
ꢀ
8
9
Fe
3
O
4
@SiO
2
ꢀ
1
0 mg
2
H O
80
SO
3
H
Nano Fe/NaY
zeolite
95
10
2.5 mg
EtOH
78
70
98
ꢀ
1
2
3
GO/ZnO
GO/ZnO
10 mg
10 mg
H
2
O
100
100
10
30
99
ꢀ
ꢀ
This Work
This Work
1
Neat
99
mL) for 120 min in an oil bath at 65 ˚C. Then KMnO (3 g) was
4
gradually added while keeping the temperature <20 ºC. The
mixture was then stirred at 35ꢀ40 ˚C for 30 min and at 65ꢀ80 ˚C
for 45 min, respectively. Next, distilled water (46 mL) was
added and the mixture heated at 98ꢀ105 ˚C for 30 min. The
reaction was terminated by addition of distilled water (140 mL)
Experimental
General
All chemicals were purchased from Merck or Aldrich
companies and were used as received. Field emission scanning
electron microscopy (FESEM) images and Energy dispersive
spectroscopy (EDX) patterns was obtained using MIRA III
instrument of TESCAN Company, Czech Republic. Thermal
gravimetric analysis (TGA) was performed by means of
Netzsch ꢀTGA 209 F1 instrument. XꢀRay diffraction patterns
and 30% H O2 solution (10 mL). The obtained solid was
2
washed by repeated centrifugation and filtration, first with 5%
HCl aqueous solution, and then distilled water. Water (160 mL)
was added to the final product and dried at 70˚C in an oven for
2
days.
(
XRD) was obtained using PW1730 instrument of PHILIPS
General procedure for the preparation of GO/ZnO
nanocomposite (1)
Company. FTIR spectra were acquired as KBr pellets on a
Shimadzu FTIRꢀ8400S spectrometer. Melting points were
determined using an Electrothermal 9100 apparatus and are
1
GO/ZnO nanocomposite (1) was prepared with weight ratio
uncorrected. H NMR (500 MHz) spectra were recorded using a
of (1:1) between GO and ZnO. 1 g dried GO was dispersed in
INOVAꢀ500 spectrometer in CDCl , as solvent, at ambient
3
1
00 mL of water and sonicated for 1 h to achieve a well dispersed
temperature. Analytical thin layer chromatography (TLC) for
monitoring reactions was carried out using Merck 0.2 mm silica
gel 60 Fꢀ254 Alꢀplates using EtOAc and nꢀhexane as eluents.
suspension. Then, 1.1 g of zinc acetate (Zn(CH CO ) 2H O) was
3
2 2
2
dissolved in 20 mL deionized water and added to suspension. The
obtained mixture was sonicated for 10 min and then definite
amount of NaOH (1 M) was successively added slowly to the
above GO suspension until its pH reach 7.0 and subsequently
followed by sonication for 30 min. Then the mixture was stirred
at 70 ˚C for 12 h. Finally, the composite was centrifuged and
General procedure for the preparation of GO
Graphene oxide (GO) was made by a modified Hummers
7
4
method using graphite flake as starting material. Graphite
flake (1 g) was stirred with NaNO (0.5 g) in 98% H SO (23
3
2
4
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New J. Chem.
washed several times with deionized water and the obtained Notes and references
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General experimental procedure for the synthesis of 2,2′ꢀ
arylmethylene bis(3ꢀhydroxyꢀ5,5ꢀdimethylꢀ2ꢀcyclohexeneꢀ1ꢀone)
3
.
derivatives
(4aꢀz)
4
.
S. Hasan, A Review on Nanoparticles: Their Synthesis and Types,
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In a 5 mL roundꢀbottomed flask, aldehyde (
2
, 1 mmol), 1,3ꢀ
, 10 mg)
5
.
dicarbonyl compound ( , 2 mmol) and GO/ZnO (
3
1
7
were added to H O (5 mL). The obtained mixture was stirred
2
6
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under reflux conditions for times indicated in Table
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eluent: nꢀHexane:EtOAc, 10:1). After completion of the
2 to afford
(
7
.
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. The obtained products were characterized by measuring of 9.
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octahydroxanthenes (5aꢀj)
To a mixture of aromatic aldehyde
dicarbonyl compound , 2 mmol), 10 mg GO/ZnO was added and
then the reaction mixture was stirred at 100 ˚C. The progress of
(
2
, 1 mmol) and 1,3ꢀ 12.
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3
1
1
3.
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1
1
6.
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23.
efficient methodology for the synthesis of 2,2′ꢀarylmethylene
bis(3ꢀhydroxyꢀ5,5ꢀdimethylꢀ2ꢀcyclohexeneꢀ1ꢀone) and 1,8ꢀ
dioxoꢀ1,2,3,4,5,6,7,8ꢀoctahydroxanthene derivatives using
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24.
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26.
27.
28.
29.
products were produced in good to excellent yields and short
reaction times in the present protocol. High to excellent yields,
low loading of the catalyst, eliminating of any toxic solvent,
easy separation and purification of the products as well as
reusability of the catalyst are the most significant advantages of
this protocol.
2
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We are grateful for the financial support from The Research
Council of Iran University of Science and Technology (IUST),
Tehran, Iran (Grant No 160/347). We would also like to
acknowledge the support of The Iran Nanotechnology Initiative
Council (INIC), Iran.
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