Use of sulphamic acid for the synthesis of isobenzofuran-1(3H)-ones from 2-carboxybenzaldehyde and substituted cyclic as well as non-cyclic ketones in good yield has been demonstrated. Sulphamic acid proved to be an excellent catalyst for this condensation reaction. Reaction has been carried out by both conventional and microwave methods

Devanand B. Shinde

Jaiprakash N. Sangshetti

Samruddhi S. Zambre

Sunil N. Darandale

Arabian Journal of Chemistry

AbstractUse of sulphamic acid for the synthesis of isobenzofuran-1(3H)-ones from 2-carboxybenzaldehyde and substituted cyclic as well as non-cyclic ketones in good yield has been demonstrated. Sulphamic acid proved to be an excellent catalyst for this condensation reaction. Reaction has been carried out by both conventional and microwave methods

Zambre, Samruddhi S.

Darandale, Sunil N.

Sangshetti, Jaiprakash N.

Shinde, Devanand B.

Elsevier - Publisher Connector 

Microwave-assisted solvent-free one pot synthesis of isobenzofuran-1(3H)-ones using sulphamic acid catalyst 

Arabian Journal of Chemistry (2016) 9, S1416–S1419King Saud University
Arabian Journal of Chemistry
www.ksu.edu.sa
www.sciencedirect.comORIGINAL ARTICLEMicrowave-assisted solvent-free one pot synthesis
of isobenzofuran-1(3H)-ones using sulphamic acid
catalyst* Corresponding author.
E-mail address: dbsjaiprakash05@rediffmail.com (D.B. Shinde).
Peer review under responsibility of King Saud University.
Production and hosting by Elsevier
http://dx.doi.org/10.1016/j.arabjc.2012.03.006
1878-5352 ª 2012 Production and hosting by Elsevier B.V. on behalf of King Saud University.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/3.0/).Samruddhi S. Zambre, Sunil N. Darandale, Jaiprakash N. Sangshetti,
Devanand B. Shinde *Department of Chemical Technology, Dr. Babasaheb Ambedkar Marathwada University, Aurangabad 431 004, MS, IndiaReceived 23 July 2010; accepted 14 March 2012
Available online 23 March 2012KEYWORDS
Isobenzofuran-1(3H)-ones;
Sulphamic acid catalyst 2-
carboxybenzaldehydeAbstract Use of sulphamic acid for the synthesis of isobenzofuran-1(3H)-ones from 2-carboxy-
benzaldehyde and substituted cyclic as well as non-cyclic ketones in good yield has been demon-
strated. Sulphamic acid proved to be an excellent catalyst for this condensation reaction.
Reaction has been carried out by both conventional and microwave methods.
ª 2012 Production and hosting by Elsevier B.V. on behalf of King Saud University. This is an open access
article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/3.0/).1. Introduction
Isobenzofuran-1(3H)-ones forms important class of natural
products possessing signiﬁcant biological properties like anti-
bacterial, anti-convulsant, anti-HIV, anti-asthmatic, antitu-
mor, anti-platelet activities, and anaesthesia (Pedrosa et al.,
2006; Zhu et al., 2004; Safari et al., 2007). In particular, 3-
substituted phthalides are vital heterocyclic motifs in many bio-
active compounds such as iso-coumarins, anthraquinones,
anthracyclines, and several alkaloids (Paradkar et al., 1998).
3-Substituted phthalides are easily converted into (a) 3-phena-
cylidene phthalides, known for their plant growth regulatory
activity (Bousquet et al., 2008; Houbin and Dayawan, 1981),(b) 3-alkylidene phthalides, known for their biological impor-
tance (Mali et al., 1990) and (c) 3-styryl phthalides which are
used as colour formers for heat and pressure-sensitive recording
materials importance (Mali and Massey, 1997). The literature
survey revealed that 3-phenacylphthalides are synthesized by
reacting 2-bromobenzaldehyde with 1,3 dicarbonyl compounds
under catalytic conditions in the presence of alkali importance
(Lee et al., 1997; Chatterjee et al., 1974). Recently it has been
reported that the reaction of phthalaldehydic acid with various
aromatic methyl ethers in the presence of TFA provided 3-aryl
phthalides in good yields (Paradkar et al., 1998). This observa-
tion led us to explore the reaction of 2-carboxybenzaldehyde
with acetophenone which gave 3-phenacylphthalide in good
yield. Substituted acetophenones and 2-carboxybenzaldehyde
gave products which were fully characterized by 1H NMR.
Solid acid catalyst has become one of the most important
tools for synthesis and development of sustainable chemical
production. These catalysts are economic, active and selective.
The combination of solid acid catalyst with microwave irradi-
ation provides more benign processes, very short reaction time,
and high product purity with no secondary reactions.
Microwave-assisted solvent-free one pot synthesis S1417In continuation of our ongoing research for the develop-
ment of simple and efﬁcient methods for the synthesis of
various heterocyclic compounds (Kokare et al., 2007;
Kotharkar et al., 2005; Bahekar and Shinde, 2004; Zambre
et al., 2009) herein we have presented a novel, mild and efﬁ-
cient method for the synthesis of isobenzofuran-1(3H)-ones
using microwave-assisted and conventional method in the
presence of sulphamic acid catalyst.2. Results and discussion
Synthesis of isobenzofuran-1(3H)-ones was achieved using
Methods A and B. Method A comprises of conventional heat-
ing and Method B is microwave-assisted synthesis. Microwave
used in the study is Microsynth Lab station of Ethusi Mile-
stone with temperature control (see Scheme 1).
Optimization of reaction in Method A was carried out
using different concentrations of sulphamic acid. Effect of dif-
ferent concentrations of sulphamic acid on the yield of ﬁnal
product was studied. From the data in Table 1 it is observed
that the use of 20 mol% sulphamic acid was more effective.
Also inMethod B optimization was carried out by using differ-
ent watts at different temperatures. It was observed that maintain-
ing temperature at 80 C at 1000 W was most favourable.
Using similar conditions different derivatives were synthe-
sized. The yields and time required for the reaction using
Methods A and B are summarized in Table 2.
The progress of the reaction was monitored by TLC [sol-
vent system: (ethyl acetate):(hexane) = 1:4]. After completion
of the reaction, the reaction mixture was extracted with dichlo-
romethane:water. The pure products were obtained by recrys-
tallization using EtOH with 93–98% yields in Method A andOH
O
O
O
M
M
+
1 2a-2l
Scheme 1 Synthesis of isobenzofuran-1(3H)-ones using sulphamic a
Conventional synthesis: Sulphamic acid catalyst 20 mol%, 105–120 m
Sulphamic acid catalyst 20 mol%, 2 min, 80 C solvent free.
Table 1 Synthesis of different isobenzofuran-1(3H)-ones using sulp
sulphamic acid.
Sr. no. Sulphamic acid catalyst (mol%) Reaction tim
Conventiona
1 50 100
2 40 100
3 30 105
4 20 105
5 10 13094–99% in Method B. All the synthesized compounds were
characterized by 1H NMR, mass spectrometry (ES-MS).
In conclusion novel and highly efﬁcient methodology for the
synthesis of isobenzofuran-1(3H)-ones by one pot condensation
reaction of acetophenones, phthalaldehydic acid catalysed by
sulphamic acid has been established. This method offers several
signiﬁcant advantages such as, high conversions, easy handling,
clean reaction proﬁle and shorter reaction times, which makes it
a useful and attractive process for the rapid synthesis of substi-
tuted isobenzofuran-1(3H)-ones.
2.1. Method A
2.1.1. General procedure for conventional synthesis of
isobenzofuran-1(3H)-ones (3a–3l)
A mixture of 2-carboxybenzaldehyde (10 mmol), ketone
(12 mmol) and sulphamic acid (2 mmol) was treated at 120 C
(the reaction mixture turns to liquid) under solvent-free condi-
tion for the appropriate time as indicated in Table 1. The pro-
gress of the reaction was monitored by TLC [solvent system:
(ethyl acetate):(hexane) = 1:4]. After completion of the
reaction, the reaction mixture was extracted with dichlorometh-
ane:water. The pure products were obtained by recrystallization
using EtOH in 93–98% yields. All the synthesized compounds
were characterized by 1H NMR, mass spectrometry (ES-MS).
2.2. Method B
2.2.1. General procedure for microwave-assisted synthesis of
isobenzofuran-1(3H)-ones (3a–3l)
A mixture of 2-carboxybenzaldehyde (10 mmol), ketone
(12 mmol) and sulphamic acid (2 mmol) was treated at 80 CO
O
Oethod A
ethod B
3a-3l
cid as a novel catalyst under solvent-free condition. Method A:
in, 120 C, solvent free. Method B: Microwave-assisted synthesis:
hamic acid under solvent-free condition using various mol% of
e (min) Yield (%)
l Microwave Conventional Microwave
2 98 99
2 98 99
2 98 99
2 98 99
2 92 94
Table 2 Synthesis of different isobenzofuran-1(3H)-ones using sulphamic acid under solvent-free condition.
Sr. no. Reactants Time (min) Melting point (C) Yield (%)
Conventional Microwave Observed Reference Conventional Microwave
3a 105 2 145 145 98 99
3b 120 2 146 146 95 97
3c 105 2 220 219 93 95
3d 120 2 209 210 94 95
3e 120 2 134 135 93 95
3f 110 2 149 149 94 96
3g 110 2 154 154 95 96
3h 120 2 170 170 96 96
3i 105 2 104 104 94 94
(continued on next page)
S1418 S.S. Zambre et al.
Table 2 (continued)
Sr. no. Reactants Time (min) Melting point (C) Yield (%)
Conventional Microwave Observed Reference Conventional Microwave
3j 110 2 79 78 94 94
3k 115 2 220 220 97 98
3l 110 2 Oil Oil 97 98
Microwave-assisted solvent-free one pot synthesis S1419(the reaction mixture turns to liquid) under solvent-free condi-
tion for the appropriate time as indicated in Table 1. The pro-
gress of the reaction was monitored by TLC [solvent system:
(ethyl acetate):(hexane) = 1:4]. After completion of the
reaction, the reaction mixture was extracted with dichlorometh-
ane:water. The pure products were obtained by recrystalliza-
tion using EtOH in 94–99% yields. All the synthesized
compounds were characterized by 1HNMR,mass spectrometry
(ES-MS).
The representative analytical data for 3-(2-oxo-2-phenyl-
ethyl) isobenzofuran-1(3H)-ones (3a):
1HNMR (CDCl3 – 200 MHz): 8.00–7.66 (m,9H), 6.123–
6.043 (t,1H, J= 6.5), 3.864–3.808 (d,1H, J= 17.5),
3.755–3.691 (d,1H, J= 18.1).
ES-MS m/z (%): 252(M+ H).
Anal. Calcd for C16H12NO3: C, 76.18; H, 4.79; Found: C,
76.21; H, 4.81.Acknowledgement
The authors are thankful to the Head of the Department of
Chemical Technology, Dr. Babasaheb Ambedkar Marathw-
ada University, Aurangabad 431 004 (MS), India, for provid-
ing the laboratory facility.References
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Microwave-assisted solvent-free one pot synthesis of isobenzofuran-1(3H)-ones using sulphamic acid catalyst

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Microwave-assisted solvent-free one pot synthesis of isobenzofuran-1(3H)-ones using sulphamic acid catalyst

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