Synthesis of isobenzofuran-1(3h)-ones with the aid of silica-supported preyssler nanoparticles

Article abstract of DOI:10.1080/00397910902883751

Silica-supported Preyssler nanoparticles appear to be a new and efficient solid acid catalyst for an economical, and environmentally benign one-pot synthesis of 3-substituted phthalides.

Full text of DOI:10.1080/00397910902883751

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Synthesis of
Isobenzofuran-1(3H)-ones with
the Aid of Silica-Supported
Preyssler Nanoparticles
Majid M. Heravi a , Vahideh Rasmi a , Fatemeh F.
Bamoharram b , Sodeh Sadjadi a , Lida Fotouhi a ,
Samahe Sadjadi a & Mehdi Bakavoli c
a Department of Chemistry, School of Sciences,
Azzahra University, Tehran, Iran
b Department of Chemistry, Islamic Azad University,
Mashhad Branch, Mashhad, Iran
c Department of Chemistry, School of Sciences,
Ferdowsi University of Mashhad, Mashhad, Iran
Version of record first published: 16 Oct 2009.
To cite this article: Majid M. Heravi, Vahideh Rasmi, Fatemeh F. Bamoharram,
Sodeh Sadjadi, Lida Fotouhi, Samahe Sadjadi & Mehdi Bakavoli (2009): Synthesis of
Isobenzofuran-1(3H)-ones with the Aid of Silica-Supported Preyssler Nanoparticles,
Synthetic Communications: An International Journal for Rapid Communication of
Synthetic Organic Chemistry, 39:22, 4109-4116
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Synthetic Communications1, 39: 4109–4116, 2009
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print=1532-2432 online
DOI: 10.1080/00397910902883751
Synthesis of Isobenzofuran-1(3H)-ones with the
Aid of Silica-Supported Preyssler Nanoparticles
Majid M. Heravi,1 Vahideh Rasmi,1 Fatemeh F. Bamoharram,2
Sodeh Sadjadi,1 Lida Fotouhi,1 Samahe Sadjadi,1 and
Mehdi Bakavoli3
1Department of Chemistry, School of Sciences,
Azzahra University, Tehran, Iran
2Department of Chemistry, Islamic Azad University,
Mashhad Branch, Mashhad, Iran
3Department of Chemistry, School of Sciences, Ferdowsi University of
Mashhad, Mashhad, Iran
Abstract: Silica-supported Preyssler nanoparticles appear to be a new and
efficient solid acid catalyst for an economical, and environmentally benign
one-pot synthesis of 3-substituted phthalides.
Keywords: Isobenzofuran-1(3H)-ones, one-pot synthesis, phthalaldehydic acid,
silica-supported Preyssler nanoparticles, solvent-free condition
INTRODUCTION
Isobenzofuran and phthalides [isobenzofuran-1(3H)-ones] are integral
parts of many naturally occurring substances. Isobenzofuran-1(3H)-
ones possess a wide range of medicinal properties.[1] In particular,
3-substituted phthalides are vital heterocyclic motifs in many bioactive
compounds such as isocoumarins, anthraquinones, anthracyclines, and
several alkaloids.[2]
Received January 15, 2009.
Address correspondence to Majid M. Heravi, Department of Chemistry,
School of Sciences, Azzahra University, P. O. Box 1993891176, Tehran, Iran.
E-mail: mmh1331@yahoo.com
4109

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M. M. Heravi et al.
In view of their importance, various methods have been developed
for the synthesis of phthalides [isobenzofuran-1(3H)-ones].[1]
These methods include cyclization reactions catalyzed by strong acids
such as trifluoroacetic acid[3] and trifluoromethanesulfonic acid.[4] Strong
bases such as 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU),[5,6] sodium
hydroxide (NaOH),[7] and potassium hydroxide (KOH)[8] are also used
in the synthesis of 3-phenacylphthalides. However, these methods involve
strong, corrosive, and harmful acids and bases, and high temperatures for
the reactions are required. Thus, the development of a simple and effi-
cient method under green reaction conditions for constructing of these
heterocycles is still in demand.
Polyoxometalates (POMs) are metal-oxo anionic clusters whose che-
mical properties can be controlled by transition-metal substitution and
the countercation used. POMs have wide applications in many fields such
as catalysis, medicine, magnetic properties, materials, surface chemistry,
photochromism, and electrochromism, owing to their so-called ‘‘value-
adding properties.’’ These properties, combined with their ability to
donate and accept electrons and their stability over a wide range of con-
ditions, make them attractive candidates for catalysis. On the other hand,
they are economically and environmentally attractive in both academic
and industrial settings as useful acids and=or oxidation catalysts in var-
ious organic reactions because their catalytic features can be controlled
at a molecular level.[9]
In continuation of our efforts to explore the catalytic utility of
heteropolyacid supported on silica gel,[10–12] herein we report for the first
time a direct and efficient method for the preparation of substituted
isobenzofuran-1(3H)-ones from the reaction of phthalaldehydic acid,
substituted acetophenones, and cyclic ketones using silica-supported
Preyssler nanoparticles as a novel and efficient catalytic system
(Scheme 1).
To determine the most appropriate reaction conditions and evaluate
the catalytic efficiency of silica-supported Preyssler nanoparticles, the
synthesis of 3a (as model reaction) was carried out in various conditions.
First, we tried the reaction without catalyst. When a mixture of
Scheme 1.

Synthesis of Isobenzofuran-1(3H)-ones
4111
Table 1. Reaction of phthalaldehydic acid with acetophenone in the presence of a
catalytic amount of silica-supported Preyssler nanoparticles in different solvents
Entry
Solvent
Temperature (ꢀC)
Time (h)
Yield (%)a
1
2
3
4
5
6
Ethanol
Acetonitrile
CHCl3
THF
Water
—
78
82
61
88
100
110
10
10
10
10
8
68
75
58
67
79
96
6
aYields were analyzed by GC.
phthalaldehydic acid and acetophenone was stirred (oil bath, temperature
110ꢀC) for 18 h in the absence of silica-supported Preyssler nanoparticles,
no conversion was detected. This observation indicated that a catalyst is
necessary for this transformation.
To study the effect of solvent on the yield of this reaction, the model
reaction was carried out in various solvents and a solvent-free system
using 0.03 mmol of silica-supported Preyssler nanoparticles as the cata-
lyst. As shown in Table 1, the best results in terms of yield and time were
achieved in solvent-free conditions.
To investigate the effect of silica-supported Preyssler nanoparticles,
we carried out comparative experiments with some silica-gel-supported
heteropolyacids, and the comparative results are summarized in Table 2.
Comparison
of
silica-supported
Preyssler
nanoparticles,
H3[PMo12O40]=SiO2, H4[PMo11VO40]=SiO2, and H3[PW12O40]=SiO2
shows that silica-supported Preyssler nanoparticles led to greater yields.
This observation can be explained by considering the reaction mechan-
ism. As shown in Scheme 2, the first stage of the reaction is the activation
Table 2. Comparative study of various supported heteropolyacid catalysts for
the preparation of 3a at 110ꢀC
Amount of catalyst
(mmol)
Time Yield
(%)
Entry
1
Catalyst
(h)
H14[NaP5W30O110]=SiO2
nanoparticles
0.03
6
96
2
3
4
5
H14[NaP5W30O110]=SiO2
H3[PMo12O40]=SiO2
H4[PMo11VO40]=SiO2
H3[PW12O40],=SiO2
0.05
0.05
0.05
0.05
8
9
9
8
89
79
73
84

4112
M. M. Heravi et al.
Scheme 2.
of the carbonyl group by an acidic catalyst. According to previous
reports, the acidic property of the Preyssler type of heteropolyacids is
greater than the Keggins.[13]
The efficiency of H14[NaP5W30O110]=SiO2 as catalyst was also
studied for this reaction, but the model reaction (reaction of phthalalde-
hydic acid and acetophenone) did not go to completion in the presence of
these catalysts even after long reaction times (8 h) and more amounts of
catalyst (Table 2).
In H14[NaP5W30O110]=SiO2 nanoparticles, the catalyst is supported
into silica nano-particles. As the particle size decreases, the relative num-
ber of surface atoms increases, and thus activity increases. Moreover,
because of quantum size effects, nanometer-sized particles can exhibit
unique properties.
The scope and generality of this process were illustrated with respect
to various substituted acetophenones and cyclic ketones, and the results
are presented in Table 3.
For optimization of reaction time, the yield of reactions were com-
pared at various times (1, 2, 4, and 6 h). The results indicate that in each
reaction, increasing the reaction time from 4 h to 6 h increases the yield,
but longer reaction times had no effect on the yields of reactions. Thus
the reaction time was fixed at 6 h.
The insolubility of the catalyst in different organic solvents provided
an easy method for its separation from the product. The catalyst was
easily separated by filtration and reused with only a gradual decrease
in its activity. For example, the reaction of phthalaldehydic acid and acet-
ophenone afforded corresponding isobenzofuran-1(3H)-one derivative in
96, 94, and 89% yields over three successive runs.
In conclusion, we report a new and efficient method for the synthesis
of functionalized isobenzofuran-1(3H)-ones by the one-pot cascade reac-
tion of phthalaldehydic acid with substituted acetophenones and cyclic

Synthesis of Isobenzofuran-1(3H)-ones
4113
Table 3. Synthesis of substituted isobenzofuran-1(3H)-ones by nano-structured
Preyssler supported on silica-catalyzed cyclization of phthalaldehydic acid with
ketonesa
Yieldb
(%)
Mp
(ꢀC)
Ref. mp
(ꢀC)
Entry
a
Ketone
Product
96
98
144–145
145[3]
b
120[3]
119–120
c
93
95
210[3]
218–219
148
d
149[3]
e
98
Oil
Oil[16]
f
96
219–220[6]
219
aReaction conditions: phthalaldehydic acid (0.8 mmol), ketone (1 mmol),
nano-structured Preyssler supported on silica (0.03 mmol), 110ꢀC, 6h.
bGC yields, based on phthalaldehydic acid.
ketones. There are several advantages for the use of nano-structured
Preyssler supported on silica as catalyst for this transformation, which
include high conversions, lowcost, and reusability of the catalyst. In

4114
M. M. Heravi et al.
addition, the use of supported catalyst under heterogeneous conditions
facilitates ease of separation and recovery of the catalyst.
EXPERIMENTAL
Catalyst Preparation
Supported heteropolyacid catalyst was synthesized according to our pre-
vious report[14] using a support in powder form (SiO2) with an aqueous
solution of the heteropolyacids. After stirring the mixture, the solvent was
evaporated, dried at 120ꢀC and calcined at 250ꢀC in a furnace prior to use.
Silica-supported Preyssler nano-structures were obtained through the
microemulsion method.[15]
Synthesis of Isobenzofuran-1(3H)-ones: General Procedure
A mixture of phthalaldehydic acid 1 (0.8 mmol) and an appropriate
ketone 2 (1 mmol) was heated under reflux (oil bath, temperature
110ꢀC) with magnetic stirring until the mixture melted. Silica-supported
Preyssler nanoparticles (0.03 mmol) were added to this mixture and stir-
red at 110ꢀC for 6 h. The progress of the reaction was monitored by
thin-layer chromatography (TLC). At the end of the reaction, the mixture
was cooled, diluted with dichloromethane, and separated from the cata-
lyst by filtration. Pure products were obtained after the addition of water
to the organic layer. Two phases of solution were extracted and then the
solvent was evaporated to afford isobenzofuran-1(3H)-ones 3.
All compounds were known, and their physical and spectroscopic
data were compared with those of authentic samples and found to be
identical.[3,6,16]
Reusing the Catalyst
The reusability of the catalyst was also investigated. The synthesis of 3a
was selected as the model reaction (Scheme 1). After completion, the
catalyst was filtered off and washed three times with 10 ml of dichloro-
methane, dried at 80ꢀC under reduced pressure (2 h), and subjected to
the second run of the model reaction.
ACKNOWLEDGMENT
The authors are thankful to Azzahra Research Council for partial
financial support.

Synthesis of Isobenzofuran-1(3H)-ones
4115
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