The preparation and characterization of boehmite nanoparticles-TAPC: A tailored and reusable nanocatalyst for the synthesis of 12-aryl-8,9,10,12-tetrahydrobenzo[a]xanthen-11-ones

Article abstract of DOI:10.1039/c4nj01128g

A one-pot multi-component, green, and highly efficient protocol has been described for the synthesis of a wide range of 12-aryl-8,9,10,12-tetrahydrobenzo[a]xanthen-11-ones using TAPC supported on boehmite nanoparticles (BNPs-TAPC) as an eco-friendly and r

Full text of DOI:10.1039/c4nj01128g

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The preparation and characterization of Boehmite nanoparticles-TAPC:
A tailored and reusable nanocatalyst for the synthesis of 12-aryl-
8,9,10,12-tetrahydrobenzo[a]xanthen-11-ones
Kiumars Bahrami,*a,b Mohammad M. Khodaei,*a and Mohsen Roostaeia
5
Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
DOI: 10.1039/b000000x
be retained and it can be rendered suitable for recovery and
40 reuse.1
A one-pot multi-component, green, and highly efficient
protocol has been described for the synthesis of a wide range
of 12-aryl-8,9,10,12-tetrahydrobenzo[a]xanthen-11-ones using
Functionalization of nanoparticles with organic components is
currently an area of intense scientific interest for a wide variety of
goals.2 The good dispersability in organic media of such surface
modified nanoparticles by organic molecules offers many
45 possibilities in important areas of chemistry such as catalysis,
analytical chemistry and medical research.3
In recent years, boehmite with nanoscale dimensions and
morphological specificity has attracted enormous interest from
both fundamental and practical viewpoints.4
10 TAPC supported on boehmite nanoparticles (BNPs-TAPC) as
an eco-friendly and recyclable nanocatalyst in excellent yields
under solvent-free conditions. Short reaction time, easy and
quick isolation of the products, use of inexpensive
heterogeneous nanocatalyst, solvent-free process and
15 excellent chemoselectivity are other remarkable features of
this environmentally benign protocol. The BNP-TAPC was
characterized by transmission electron microscopy (TEM),
scanning electron microscopy (SEM), X-ray diffraction
(XRD) and FT-IR methods.
50 Moreover, boehmite (Fig. 1), which is an aluminum
oxyhydroxide (AlO(OH)), contains terminal groups that render
high reactivity to the surface and provide
a hydrophilic
environment improving the homogeneity of the medium being for
all these reasons a promising support.5
20 Introduction
55 On the other hand as a typical oxyhydroxy compound, boehmite
is also extensively used as an absorbents,6 catalysts,7 filler in
Heterogeneous catalysts provide numerous opportunities for
recovering and recycling catalysts from reaction environments.
These features can lead to improved processing steps, better
process economics, and environmentally friendly industrial
25 manufacturing. However, further efforts are necessary in the
design of new heterogeneous catalysts to reach activity and
selectivity values competitive with homogeneous ones.
Homogeneous catalysts are known for high activity and
selectivity but the major disadvantage of the homogeneous
30 catalysts is the need to separate off the reaction products and
recover the catalyst. This can be both complex and expensive.
Other disadvantages are that these catalysts are relatively easily
decomposed so temperatures must be well controlled, and that
they can be deactivated if poisonous byꢀproducts are formed.
35 Heterogeneous catalysts are not soluble like homogeneous and
hence can be recovered and even reused but lacks the activity and
selectivity of homogeneous catalysts. If a homogeneous catalyst
is anchored on to a solid support, its activity and selectivity can
membrane,8
optical
reinforcement material in ceramics.11
materials,9
coatings,10
composite
60
OH
Al
OH
Al
OH
Al
OH
O
O
O
O
O
O
O
Al
O
O
O
O
O
O
O
O
O
Al
Al
HO
Al
HO
Al
Al
65
O
O
HO
OH
Fig. 1 Boehmite Structure.
Organic syntheses involving greener process and under solventꢀ
free conditions have been investigated world wide due to
70 stringent environment and economic regulations.12
Xanthenes and benzoxanthenes are important classes of
biologically active heterocyclic compounds that are known to
possess great biological activities such as antiplasmodial,13 antiꢀ
inflammatory,14 antiviral,15 antibacterial16 and also have been
75 used as antagonists for drugꢀresistant leukemia lines.17
A number of xanthene based compounds are also available from
natural sources.18 Santalin pigments, as they are popularlyknown,
have been isolated from a number of plant species.18
a Department of Organic Chemistry, Faculty of Chemistry, Razi
University, Kermanshah 67149ꢀ67346, Iran.
b Nanoscience and Nanotechnology Research Center (NNRC), Razi
University, Kermanshah, 67149ꢀ67346, Iran. Eꢀmail:
kbahrami2@hotmail.com; Fax: +98(831)4274559; Tel:
+98(831)4274559.
† Electronic Supplementary Information (ESI) available: Experimental
details, including 1H NMR spectra for for some products. See
DOI: 10.1039/b000000x/
Various literature procedures are available to synthesize
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xanthenes and benzoxanthenes, including silica supported
NaHSO4.SiO2,19 triflate20
strontium pꢀtoluenesulfonic
acid(pTSA)/ionic liquid([bmim]BF4),21 InCl3/P2O5,22 iodine,23
tetra(nꢀbutyl)ammonium fluoride24 and proline triflate.25
Even though various procedures are reported, disadvantages
including low yields, prolonged reaction times, use of an excess
of reagents/catalysts and use of toxic organic solvents necessitate
the development of an alternative route for the synthesis of
xanthene derivatives.
10 Multicomponent reactions (MCRs) have attracted considerable
attention due to significant advantages such as simplicity of
operation, reduction of isolation and purification steps, and
minimization of costs, time and waste production26 (Fig. 2). Thus,
MCRs are accepted as green chemical processes.
15
60
65
70
5
Stepwise reaction:
Scheme 2 The route for the preparation of BNPsꢀTAPC.
20
75 The route for the preparation of BNPsꢀTAPC is shown in Scheme
2. This Catalyst was synthesized by the reaction of boehmite
nanoparticle with 1,3,5ꢀtriazoꢀ2,4,6ꢀtriphosphorineꢀ2,2,4,4,6,6ꢀ
hexachloride (TAPC) due to the inherent affinity of phosphorus
toward oxygen and the presence of hydroxyl groups in boehmite
80 structure. The BNPꢀTAPC was characterized by transmission
electron microscopy (TEM), scanning electron microscopy
(SEM), Xꢀray diffraction (XRD) and FTꢀIR methods.
Multicomponent reaction:
25
Fig. 2 Stepwise reaction versus multicomponent reaction.
30 Due to our interest in the multicomponent syntheses27 and in
continuation of our work on the development of new synthetic
methodologies,28 in the present work we report the preparation,
characterization and investigation of catalytic activity of TAPC
supported on boehmite nanoparticles (BNPsꢀTAPC) for the
35 preparation of 12ꢀarylꢀ8,9,10,12ꢀtetrahydrobenzo[a]xanthenꢀ11ꢀ
one derivatives (Scheme 1). As far as we know, our report
constitutes the first example of boehmite nanoparticles as support
for hexachlorocyclotriphosphazene (TAPC) in heterogeneous
catalysis.
85
90
95
40
45
100
Scheme 1 The condensation reaction of βꢀnaphthol, a variety of
aldehydes, and dimedone.
Results and discussion
105
50 1,3,5ꢀTriazoꢀ2,4,6ꢀtriphosphorineꢀ2,2,4,4,6,6ꢀhexachloride
(TAPC), usually called hexachlorocyclotriphosphazene or
trimeric phosphonitrilic chloride were widely used in organic
synthesis,29 but one major problem, which has been associated
with this homogeneous catalyst, is the recovery of catalyst from
55 reaction medium, therefore, one way to overcome this problem is
to immobilize it on solid supports. In other words, the reusability
of a supported catalyst is of great importance from economical
and synthetic points of view.
Fig. 3 FTꢀIR spectra (KBr disk) of TAPC, BNPs, and BNPsꢀ
TAPC.
The most informative evidence, which confirmed the anchoring
110 of TAPC on the boehmite nanoparticles was obtained by
comparison of the FTꢀIR spectra of TAPC, boehmite
nanoparticles (BNPs) and BNPsꢀTAPC (Fig. 3). In the BNPsꢀ
TAPC spectrum, the stretching vibration of (PꢀO) due to
2
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HCl. The in situ generated HCl acts as a protic acid to activate the
carbonyl oxygen. The reaction proceeds through the intermediate
50 orthoꢀquinone methides (oꢀQMs), which is formed by the
nucleophilic addition of βꢀnaphthol 2 to aldehyde 1 catalyzed by
H+. Subsequent Michaelꢀtype addition of the enolic form of
dimedone 3 to the oꢀQMs gives the intermediate 6, followed by
cyclization to afford the corresponding product 4, accompanied
55 by loss of H2O.
Table 1 The condensation reaction of benzaldehyde, βꢀnaphthol
and 5,5ꢀdimethylcyclohexaneꢀ1,3ꢀdione
conditions
under different
Yielda
(%)
Entry
Conditions/Amount of catalystref.
Time
1
TCT,solventꢀfree, 80 ºC30/ 5 mol%
50 min
5 h
5 h
1.2 h
1 h
10 min
5 min
2 min
90
85
79
89
0
93
92
95
2
3
4
5
6
7
8
Sr(OTf)2, ClCH2CH2Cl, 80 ºC20/10 mol%
Proline Triflate, H2O, reflux25/10 mol%
HClO4ꢀSiO2, solventꢀfree, 80 ºC32/
Table 2 BoehmiteꢀTAPC Catalyzed Synthesis of 12ꢀArylꢀ
8,9,10,12ꢀ tetrahydrobenzo[a]xanthenꢀ11ꢀonesa
BNPsꢀTAPC, solventꢀfree, 80 ºC/ 0 g
BNPsꢀTAPC, solventꢀfree, 80 ºC/0.01 g
BNPsꢀTAPC, solventꢀfree, 80 ºC/0.02 g
BNPsꢀTAPC, solventꢀfree, 80 ºC/0.03 g
Entry
Aldehyde/(Product)
Yield (%)b
Mp (mp)ref
a Isolated yields.
/Time (min)
C6H5CHO
(4a)
1
2
93 (10)
99 (8)
150ꢀ152 (151ꢀ153)22
173ꢀ176 (175ꢀ176)30
206ꢀ208 (207ꢀ208)30
199ꢀ202 (201ꢀ204)31
222ꢀ224 (223ꢀ225)22
238ꢀ240 (240ꢀ241)22
230ꢀ232 (227ꢀ228)32
180ꢀ182 (180ꢀ182)22
174ꢀ178 (178ꢀ180)22
223ꢀ225 (223ꢀ225)22
179ꢀ180 (168ꢀ170)22
307ꢀ310 (310ꢀ311)30
aromatic ring did not show strongly obvious effects in terms of
yields under the reaction conditions. The threeꢀcomponent
cyclocondensation reaction proceeded smoothly under solventꢀ
free conditios and was completed in 8ꢀ15 min. Benzaldehyde and
other aromatic aldehydes containing electronꢀwithdrawing groups
or electronꢀdonating were employed and reacted well to give the
10 desired products in excellent yields with high purity. It is
noteworthy that the reaction proceeded without the protection of
acidic hydroxyl substituents (Table 2, entries 5ꢀ7). This reaction
is also compatible with other functional groups such as halo,
nitro, and ether (Table 2). This reaction was further explored for
15 the synthesis of bisꢀbenzo[a]xanthenꢀ11ꢀone compound (Table 2,
entry 12) in excellent yields by the reaction of terephthalaldehyde
with 2 equiv. βꢀnaphthol and 5,5ꢀdimethylꢀ1,3ꢀcyclohexanedione
under similar conditions (Scheme 3).
5
4ꢀMeC6H4CHO
(4b)
4ꢀMeOC6H4CHO
(4c)
3
99 (10)
99 (10)
95 (10)
95 (15)
99 (10)
99 (10)
95 (8)
3,4ꢀ(MeO)2C6H3CHO
(4d)
4
4ꢀHOC6H4CHO
(4e)
5
3ꢀHOC6H4CHO
(4f)
6
2ꢀHOC6H4CHO
(4g)
7
4ꢀClC6H4CHO
(4h)
8
2,4ꢀCl2C6H3CHO
(4i)
9
20
2ꢀO2NC6H5CHO
(4j)
10
11
12
99 (12)
95 (12)
95 (12)
3ꢀNOC6H5ꢀCHO
(4k)
4ꢀOHCC6H5CHO
(4l)
25
aThe purified products were characterized by mp and 1H and 13C NMR
spectroscopy. bYield refers to pure isolated product.
Scheme
3
The condensation reaction of βꢀnaphthol,
terephthalaldehyde, and dimedone.
H
O
Leaching of active species was not observed and the catalyst was
recovered by decantation leaving the solid with hot ethanol. The
60 reaction was repeated five times without significant loss of
activity or selectivity. Thus, after the first run, which gave the
corresponding product in 99% yield, after recovery the catalyst
was subjected to a second reaction from which it gave the desired
+
-H2O
H
Ar
OH
H
H
1
30
35
40
O
O
OH
Ar
O
Ar
2
5
o-QMs
H
O
O
O
Ar
H
OH
O
O
3
65
Ar
O
6
o-QMs
OH
O
OH
O
O
70
H
-H2O
Ar
O
Ar
O
Ar
O
4
6
7
Scheme 4 Tentative mechanism for the formation of 12ꢀarylꢀ
45 8,9,10,12ꢀtetrahydrobenzo[a]xanthenꢀ11ꢀone derivatives.
Fig. 7 Recyclability of BNPꢀTAPC for the preparation of 9,9ꢀ
dimethylꢀ12ꢀpꢀtolylꢀ9,10ꢀdihydroꢀ8Hꢀbenzo[a]xanthenꢀ11(12H)ꢀ
75 one.
A possible mechanism for the formation of product 4 is shown in
Scheme 4. Adventitious entry of moisture leads to the release of
4
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product in 96% yield; the average chemical yield for 5 55 methodology for the synthesis of 12ꢀarylꢀ8,9,10,12ꢀ
consecutive runs was 95%, which clearly demonstrates the
practical recyclability of the BNPsꢀTAPC nanocatalyst (Fig. 7).
FTꢀIR spectra of BNPꢀTAPC nanocatalyst after 1 and 5 catalytic
cycles are presented in Fig. 8. These spectra look quite similar
and this definitely indicates that the active component catalyst did 60 variety of aromatic aldehydes bearing different types of
not loss from the solid catalyst.
tetrahydrobenzo[a]xanthenꢀ11ꢀone derivatives using BNPsꢀ
TAPC as an environmentally benign and recoverable
nanocatalyst under solventꢀfree conditions. The novel
heterogeneous nanocatalyst was efficiently applicable to a wide
5
10
15
20
25
substituents, affording the desired products in excellent yields.
This catalyst can be reused five times without significant loss in
catalytic activity. This methodology also overcomes the
formation of unwanted byꢀproducts, slow reaction times and
65 hazardous solvents. thus, we believe this will find significant
application in the field of organic synthesis and could be an
important addition to the existing methodologies.
Acknowledgements
The authors acknowledge the Razi University Research Council
70 for support of this work.
Notes and references
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Fig. 8 The comparative FTꢀIR spectra for BNPsꢀTAPC after 1
and 5 catalytic cycles.
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30 General procedure for the preparation of BNPs-TAPC
85
In a 100 ml roundꢀbottom flask equipped and a magnetic stirrer
bar, boehmite naoparticles (50 mg), TAPC (50 mg) and CH2Cl2
(20 mL) were mixed and sonicated for 1 h at 30° C and then the
reaction mixture was refluxed at 40 °C for 12 h. Then, the solids
35 were collected by filtration, washed thoroughly with CH2Cl2 and
dried at room temperature to afford a cream powder as the
product.
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40 TAPC
95
To a mixture of aldehyde (1.0 mmol), βꢀnaphthol (1 mmol, 0.144
g), and 5,5ꢀdimethylcyclohexaneꢀ1,3ꢀdione (1.0 mmol), was
added BNPsꢀTAPC (10 mg) and heated at 80 ºC for an
appropriate time (Table 3). The reaction was monitored by TLC.
45 After completion of the reaction, ethanol was added the reaction
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Page 7 of 7
New Journal of Chemistry
View Article Online
DOI: 10.1039/C4NJ01128G
Graphical Abstract
A one-pot multi-component, green, and highly efficient protocol has been described for the synthesis of a wide range of 12-aryl-
8,9,10,12-tetrahydrobenzo[a]xanthen-11-ones using TAPC supported on boehmite nanoparticles (BNPs-TAPC) as an eco-
friendly and recyclable nanocatalyst in excellent yields under solvent-free conditions.
Ar
CHO
O
O
BNPs-TAPC
O
Solvent-Free, 80 °C
O
Ar
OH
Cl
Cl
N
N
P
O
P
BNPs-TAPC =
N
Cl
P
Cl
Cl
= Boehmite nanoparticles (BNPs)