One-step synthesis of substituted isobenzofuran-1(3H)-ones and isobenzofuran-1,3-diones from indane derivatives in subcritical media

Article abstract of DOI:10.1007/s00706-013-0928-4

Molecular oxygen is one of the most attractive oxidants in organic synthesis because it is highly soluble in subcritical water. In this study, indane derivatives were oxidized to the corresponding isobenzofuran-1(3H)-one with molecular oxygen and isobenzofuran-1,3-dione with a mixture of molecular oxygen and H₂O₂ in subcritical water. This paper describes a simple, economic, environmentally benign,and general procedure that can be used for the synthesis of substituted isobenzofuran-1(3H)-ones and isobenzofuran-1,3-diones in only one step and without catalyst.

Full text of DOI:10.1007/s00706-013-0928-4

Monatsh Chem (2013) 144:1183–1186
DOI 10.1007/s00706-013-0928-4
ORIGINAL PAPER
One-step synthesis of substituted isobenzofuran-1(3H)-ones
and isobenzofuran-1,3-diones from indane derivatives
in subcritical media
Nermin Sımsek Kus
Received: 25 June 2012 / Accepted: 12 January 2013 / Published online: 28 February 2013
Ó Springer-Verlag Wien 2013
Abstract Molecular oxygen is one of the most attractive
oxidants in organic synthesis because it is highly soluble in
subcritical water. In this study, indane derivatives were oxi-
dized to the corresponding isobenzofuran-1(3H)-one with
molecular oxygen and isobenzofuran-1,3-dione with a mix-
ture of molecular oxygen and H2O2 in subcritical water. This
paper describes a simple, economic, environmentally benig-
n,and general procedure that can be used for the synthesis of
substitutedisobenzofuran-1(3H)-onesandisobenzofuran-1,3-
diones in only one step and without catalyst.
reactions, and cleaning [1]. The present work describes
an environmentally benign procedure for the synthesis
of isobenzofuran-1(3H)-ones and isobenzofuran-1,3-diones
(Scheme 1), employing molecular oxygen as an oxidant in
subcritical water as a reaction medium.
Results and discussion
In this study, indane derivatives were oxidized without
catalyst in subcritical water under oxygen pressure.
Indane derivatives were surprisingly transformed into iso-
benzofuran-1(3H)-one (1). A plausible reaction mechanism
based on classical reactions is presented in Scheme 2. First,
oxygen probably attacks the a-carbon atom to form a
hydroperoxide, which is readily decomposed to a carbonyl
group via the well-known Kornblum–DeLaMare reaction
[3–6]. The diketone can be attacked by hydrogen peroxide
formed during this reaction to form a lactone via the
Baeyer–Villiger reaction. Removal of 1 mol carbon mon-
oxide results in the formation of 1.
Keywords Oxidation Á Subcritical water Á
Isobenzofuran-1,3-dione Á Isobenzofuran-1(3H)-one
Introduction
Subcritical water is liquid water under pressure at tempera-
tures between the usual boiling point (100 °C) and the critical
temperature (374 °C) (Fig. 1) [1, 2]. Many of the anomalous
properties of water are due to very strong hydrogen bonding.
Above the subcritical temperature range, the extensive
hydrogen bonds break down, changing the properties more
than usually expected by increasing the temperature alone [2].
Water effectively becomes less polar and behaves more like
an organic solvent such as methanol or ethanol and the water
itself can act as a solvent, reagent, and catalyst in industrial
and analytical applications, including extraction, chemical
In the first part of this study, the experiments were
performed only with molecular oxygen in subcritical water.
In these experiments, 2,3-dihydro-1H-inden-1-one (3) and
1,2-dibromo-2,3-dihydro-1H-indene (4) were oxidized to
isobenzofuran-1(3H)-ones [7] (1) in high yields within
approximately 5 h. Unexpectedly, 2-bromo-2,3-dihydro-
1H-inden-1-one (5) also gave isobenzofuran-1(3H)-one [7]
(1) in poor yield within 8 h (Scheme 3).
2-Methyl-2,3-dihydro-1H-inden-1-one (6), 3-methyl-2,3-
dihydro-1H-inden-1-one (7), and 2,2-dibromo-1H-indene-
1,3(2H)-dione (8) did not react with molecular oxygen in
subcritical water (Scheme 4). 1,1,2,3-Tetrabromo-1H-indene
(9) gave 2,2-dibromo-1H-indene-1,3(2H)-dione (10) [8, 9] in
90 % yield (Scheme 5).
Dedicated to prof. Dr. Metin Balci on the occasion of 65th birthday.
N. Sımsek Kus (&)
Department of Chemistry, Mersin University,
33343 Mersin, Turkey
e-mail: nsimsek2000@yahoo.com
123

1184
N. Sımsek Kus
Fig. 1 Phase diagram for a pure
substance; the regions of
supercritical and subcritical
water are marked [1]
Solid
(ice)
Liquid
(Water)
22
Critical
point
Saturated Vapor
Pressure Curve
0.1
6.1ꢀ10-4
Gas
(Stream)
0
100
374
Temperature/°C
Scheme 1
Scheme 4
O
O
O
O
O
O
O
r
B
O
H
C
3
r
B
O
H
C
7
8
1
2
6
3
Scheme 5
Scheme 2
r
B
O
r
B
O
O
O
r
r
20 bar O2
H2 120 o
2 h 90
,
%
B
H
O O
O O
r
B
+
2H
2O
O
O
C
,
B
H
H
O
2
r
B
O
10
3
1
9
-
- -
H
H
O O
H
O
O
O
O
O
H
-
H
2O
O
O
O
-
CO
Scheme 6
r
B
O
r
B
20 bar O2
H2 120 o
Scheme 3
O
C
,
r
B
O
2 h 80
,
%
N
O2
N
O2
O
r
B
O
20 bar O2
20 bar O2
r
B
11
12
O
H2 120 o
H2 120 o
O
,
C
O
,
C
4
3
1
5 h 69
,
%
5 h 85
,
%
-
e
i ld
40 75
%
y
1,1,3-Tribromo-4-nitro-2,3-dihydro-1H-indene (11) was
oxidized to 4-nitro-1H-indene-1,3(2H)-dione [7] (12) in
70 % yield (Scheme 6). 1,1,2,3-Tetrabromo-5-methoxy-
1H-indene (13) was converted to 2,3-dibromo-5-methoxy-
1H-inden-1-one (14) [10] with both molecular oxygen (at
2 MPa) and a mixture of molecular oxygen (at 2 MPa) and
30 % H2O2 in subcritical water (Scheme 7).
20 bar O2
H2 120 o
O
,
C
8 h 50
,
%
O
r
B
B
r
5
123

One-step synthesis of some substituted isobenzofuran-1(3H)-ones and isobenzofuran-1,3-diones
1185
Scheme 7
20 bar O2
,
r
r
O
r
B
B
r
B
r
B
B
r
B
r
20 bar O2
,
H
2O2
H2 120 o
r
r
r
B
H2 120 o
O
,
C
O
,
C
e
M O
e
M
e
M
O
O
B
B
2 h 85
B
,
%
2 h 85
,
%
14
13
13
Scheme 8
O
r
B
r
B
5
H
20 bar O2 2O2
,
H2 120 o
O
,
C
8 h 95
,
%
O
O
r
B
O
20 bar O2, H2O2
H2 120 o
ar
20 b
H
O2 2O2
,
r
B
H2 120 o
O
,
C
O
,
C
2
O
4
5 h 73
7
0
,
%
5 h
%
,
3
H
20 bar O2 2O2
,
H2 120 o
O
,
C
8 h 90
,
%
r
B
r
B
r
B
r
B
9
In the second part of this study, the experiments were
performed with both molecular oxygen (at 2 MPa) and
30 % H2O2 in subcritical water. 2,3-Dihydro-1H-inden-1-
one (3), 1,2-dibromo-2,3-dihydro-1H-indene (4), 2,2-
dibromo-2,3-dihydro-1H-inden-1-one (5),and 1,1,2,3-tet-
rabromo-1H-indene (9) were oxidized to isobenzofuran-
1,3-dione [7] (2) (Scheme 8). 1,1,3-Tribromo-4-nitro-2,3-
dihydro-1H-indene (11) was similarly oxidized to the
corresponding isobenzofuran-1,3-dione (15) (Scheme 9).
The structures of all products obtained in the synthesis
of substituted isobenzofuran-1(3H)-one and isobenzofuran-
1,3-dione from substituted indane derivatives were identi-
Scheme 9
r
B
O
O
O
r
B
H
20 bar O2 2O2
,
H2 120 o
O
,
C
2 h 85
,
%
r
B
N
O2
N
O2
11
15
Conclusions
1
fied by H and 13C NMR analyses. The amount of oxygen
This paper describes the synthesis of substituted iso-
benzofuran-1(3H)-ones and isobenzofuran-1,3-diones from
indane derivatives in subcritical water in the absence of an
organic solvent and metal salts/complexes; this method is
indeed very green chemistry. Indane derivatives were oxi-
dized without catalyst in a single step via the well-known
Kornblum–DeLaMare reaction [3–6] in subcritical water
under oxygen pressure. Substituted isobenzofuran-1(3H)-
ones and isobenzofuran-1,3-diones are important molecules
was regulated by the oxygen pressure, and the amount of
dissolved oxygen in water (2.4 mmol at 2 MPa and
120 °C) was determined according to Henry’s law [11]. All
oxidation reactions were performed with one equivalent of
substrate and 2.4 equivalents of oxygen in 50 cm3 of water.
Furthermore, it was observed that a greater increase in
oxygen pressure led to decomposition of the starting
materials to afford uncharacterized tars.
123

1186
N. Sımsek Kus
in many areas. The syntheses in subcritical water media
outlined here have potentially abundant applications, and it
is hoped that this paper will motivate such efforts.
were the same as those described above. Only 3 cm3 30 %
H2O2 with 47 cm3 H2O was put into the reaction medium.
Isobenzofuran-1(3H)-one (1) [7]
Yield 50–85 %; colorless crystals; m.p.: 69–71 °C.
Experimental
Isobenzofuran-1,3-dione (2) [7]
Yield 70–95 %; colorless crystals; m.p.: 129–131 °C.
All chemical reagents were commercially available. The
substrates were purified (distilled or crystallized) before
2,2-Dibromo-1H-indene-1,3(2H)-dione (10) [8, 9]
Yield 90 %; colorless crystals; m.p.: 183–185 °C.
1
application in the reaction. H and 13C NMR spectra were
recorded on a Bruker 400 MHz spectrometer. Infrared
spectra were obtained as films on NaCl plates for liquid and
KBr pellets for solids on a Win FirstÒSatellite infrared
recording spectrophotometer. All column chromatography
was performed on silica gel (60-mesh, Merck).
4-Nitro-1H-indene-1,3(2H)-dione (12) [7]
Yield 70 %; colorless crystals; m.p.: 127–129 °C.
2,3-Dibromo-5-methoxy-1H-inden-1-one (14) [10]
Yield 85 %; yellow crystals; m.p.: 151–152 °C.
4-Nitroisobenzofuran-1,3-dione (15) [7]
Yield 85 %; colorless crystals; m.p.: 158–161 °C.
General procedure for oxidation reactions with O2
Oxidation reactions were carried out at 120 °C in a
150-cm3 stainless steel reactor. A Teflon vessel was
inserted into the reactor and the oxidation occurred without
contact with the stainless steel reactor surface in order to
avoid the catalytic effect of steel and corrosion. The
oxidation was performed by adding 50 cm3 of water and
1 mmol of substrate to a high pressure reaction vessel
under nitrogen. The vessel was pressurized with 2 MPa
(2.4 mmol) oxygen and placed in a tube furnace preheated
to 120 °C. The internal operating pressure of this vessel is
4 MPa at its maximum operating conditions. After the
reaction was completed, the mixture was cooled to room
temperature and filtered, and the residue was washed with
CHCl3 (3 9 40 cm3). After drying over MgSO4, the
solvents were evaporated in vacuo and the products were
purified by column chromatography on silica gel (60-mesh,
Merck with 50-cm glass column, eluent CCl4/Et2O). The
products were characterized by 1H and 13C NMR, GC/MS,
and IR spectroscopy.
Acknowledgments I am grateful to Professor Dr. Metin Balci and
Professor Dr. Hasan Secen for their help during this work, as well as
TUBITAK (The Scientific and Technical Council of Turkey) (grant
no. TBAG-2144-102T043) and Mersin University (BAP-FEF KB
(NS¸K) 2010-3 A) for their financial support of this work.
References
1. Kus NS (2012) Tetrahedron 68:949
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1st edn. Akademie-Verlag, Berlin
3. Zagorski MG, Salomon RG (1980) J Am Chem Soc 102:2501
4. Zagorski MG, Salomon RG (1982) J Am Chem Soc 104:3498
5. Zagorski MG, Salomon RG (1984) J Am Chem Soc 106:1750
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7. Lide DR (2008) Handbook of chemistry and physics, 88th edn.
CRC/Taylor & Francis, Boca Raton
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38:1333
11. Tromans D (2000) Ind Eng Chem Res 39:805
General procedure for oxidation reactions with both O2
and H2O2
The oxidation reactions were carried out at 120 °C in a
150-cm3 stainless steel reactor. The reaction conditions
123