A facile procedure for preparation of carboxylic sulfonic anhydrides under solvent-free conditions

Article abstract of DOI:10.1080/10426500307785

A manipulatively one-pot and rapid method for the synthesis of carboxylic sulfonic anhydride from acid chloride or sulfonyl chloride and potassium salt of carboxylic or sulfonic acid under solvent-free conditions is reported. The reaction has been carried out in excellent yield and short reaction time in the presence of DABCO under solvent-free conditions.

Full text of DOI:10.1080/10426500307785

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Phosphorus, Sulfur, and Silicon and the Related
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A Facile Procedure for Preparation of Carboxylic
Sulfonic Anhydrides Under Solvent-Free Conditions
A. R. Hajipour a & Gh. Mazloumi a
a Isfahan University of Technology , Isfahan, Iran
Published online: 27 Oct 2010.
To cite this article: A. R. Hajipour & Gh. Mazloumi (2003) A Facile Procedure for Preparation of Carboxylic Sulfonic
Anhydrides Under Solvent-Free Conditions, Phosphorus, Sulfur, and Silicon and the Related Elements, 178:1, 137-141, DOI:
10.1080/10426500307785
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Phosphorus, Sulfur and Silicon, 2003, Vol. 178:137–141
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Copyright 2003 Taylor & Francis
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DOI: 10.1080/10426500390170273
A FACILE PROCEDURE FOR PREPARATION
OF CARBOXYLIC SULFONIC ANHYDRIDES
UNDER SOLVENT-FREE CONDITIONS
A. R. Hajipour and Gh. Mazloumi
Isfahan University of Technology, Isfahan, Iran
(Received January 27, 2002; accepted June 14, 2002)
A manipulatively one-pot and rapid method for the synthesis of car-
boxylic sulfonic anhydride from acid chloride or sulfonyl chloride and
potassium salt of carboxylic or sulfonic acid under solvent-free condi-
tions is reported. The reaction has been carried out in excellent yield
and short reaction time in the presence of DABCO under solvent-free
conditions.
Keywords: Carboxylic sulfonic anhydride; DABCO; solid-state; sul-
fonyl chloride
INTRODUCTION
Acid anhydrides are among the most important class of reagents used
in organic synthesis. They are the preferred reactive acid derivatives
for the preparation of amides, esters, and peptides.1,2 Further, the use
of acid anhydrides does not require any acid scavengers unlike in the
case of acid chloride. This article presents a general method that may
be applied to the preparation of anhydride unlikely or difficult to obtain
by the other known methods, exclusively.
Heterogeneous reaction under solvent-free conditions have received
attention in recent years.3–7 The advantage of these methods over
conventional homogenous reactions is that they provide greater se-
lectivity, enhanced reaction rates, cleaner products, and manipulative
simplicity.7
Financial support of this work by the Graduate School (IUT) and the Research Affairs
Division of Isfahan University of Technology (IUT) is acknowledged.
Address correspondence to A. R. Hajipour, Pharmaceutical Research Laboratory,
College of Chemistry, Isfahan University of Technology, Isfahan, 84156, IR, Iran. E-mail:
haji@cc.iut.ac.ir
137

138
A. R. Hajipour and Gh. Mazloumi
RESULTS AND DISCUSSION
In connection with our ongoing program to develop environmentally
benign methods using solid supports,7 herein we wish to report an ex-
tremely convenient method for preparation of different anhydride with
different potassium salt of acid and acid chloride in the presence of
DABCO under solvent-free conditions (Scheme 1). The process in its
entirety involves a simple mixing of carboxylic acid chloride or sulfonyl
chloride and potassium salt of carboxylic or sulfonic acid in the presence
of DABCO in a mortar and grinding the mixture for the time specified in
Table I at room temperature. This method is very fast and purification
of product is very easy (Scheme 1).
SCHEME 1
We believe that the effect of DABCO is to react with acid chloride
or sulfonyl chloride to produce 1-aza-acyl-4-azoniabycyclo[2.2.2]ocatane
chloride 3a or 1-aza-sulfonyl-4-azoniabycyclo[2.2.2]ocatane chloride 3b.
These salts then react with potassium salt of carboxylic or sulfonic acids
to produce corresponding carboxylic sulfonic anhydride, the probably
mechanism is shown in Scheme 1.
The carboxylic sulfonic anhydrides have been identified by 1H NMR,
IR, and CHN analysis. The IR of carboxylic sulfonic anhydride obtained
in this work showed two very strong and sharp absorption bands in
the region 1800–1720 cm 1, arising due to symmetric and asymmetric
carbonyl stretching vibrations and two very strong and sharp absorp-
tion bands in the region 145–1100 cm 1, arising due to symmetric and
asymmetric sulfonyl stretching vibrations, characteristic of carboxylic
sulfonic anhydride. The results of these efforts are presented in Table I.
The desired product was usually isolated in excellent yield (Table I). As
shown in Table I, a series of acid chlorides were reacted with potassium
salt of acid in the presence of DABCO under solvent-free conditions.
Potassium salt of acid could be easily reacted with different sulfonyl

Carboxylic Sulfonic Anhydrides
139
TABLE I Preparation of Carboxylic Sulfonic Anhydrides
Reaction
Found (%)
time Yield m.p.
Mol.
formula
(calcd.)
C, H
Product
R1
C6H5
R2
C6H5
(min) (%)a
C
1a
10
94
Semi C13H19O4S 59.40, 3.80
Solid
—
(59.53, 3.84)
—
2a
1b
C6H5
C6H5
C6H5
p-ClC6H5
12
11
96
—
99 198–200 C13H9O4SCl 52.62, 3.00
(52.62, 3.05)
1b
1c
p-ClC6H4
C6H5
C6H5
p-MeC6H4
14
10
97
—
—
—
94 108–111 C14H13O4S 60.80, 4.30
(59.53, 3.84)
1c
1d
p-MeC6H4
C6H5
C6H5
p-NO2C6H4
10
9
98
—
—
—
93 188–190 C13H9NO6S 50.80, 2.90
(50.81, 2.95)
1d
1e
p-NO2C6H4 C6H5
8
10
96
97
—
—
—
C6H5
m-MeOC6H4
60–61 C14H12O3S 57.40, 4.10
(57.52, 4.14)
1e
m-MeOC6H4 m-MeOC6H4
7
95
—
—
—
aIsolated yield after simple extraction.
chloride or carboxylic acid chlorides at room temperature. It is note-
worthy that DABCO could recovered easily by filtration and washing
with NaOH 10% and extraction with CH2Cl2 and could be reused again
without significant decrease in its activity.
In conclusion a simple and efficient method for synthesis of carboxylic
sulfonic anhydrides under solvent-free conditions at room temperature
has been developed. This work also is a rapid and very convenient
method for the synthesis of carboxylic sulfonic anhydrides in excellent
yields with high purity. By this method a variety of acid carboxylic sul-
fonic anhydrides can be readily prepared in short reaction time. This
methodology is superior to the reported method8 from point of view
of yield, short reaction time, and the straightforward work-up of the
product.
EXPERIMENTAL
General
Products were characterized by comparison with authentic samples (IR,
1H-NMR spectrum, CHN analysis, melting point, mixed melting point,
and co-TLC analysis) with those obtained by literature method8 and us-
ing alternative method of synthesis. The structure of all the carboxilic
sulfonic anhydrides that obtained in this work showed two very strong

140
A. R. Hajipour and Gh. Mazloumi
and sharp absorption bands in the region 1800–1720 cm 1, arising due
to symmetric and asymmetric carbonyl stretching, characteristic of acid
carboxilic sulfonic anhydrides. All m.p.s were taken on a Gallenkamp
melting apparatus and are uncorrected. 1H NMR spectra were recorded
on a Varian EM-390 NMR Spectrometer operating at 90 MHz. The spec-
tra were measured in CCl4 and CDCl3 relative to TMS (0.00 ppm). IR
spectra were recorded on a Shimadzu 435 IR spectrophotometer. Spec-
tra of solids were performed using KBr pellets. The Research Institute
of Petroleum Industry. Tehran, I.R. Iran performed elemental analysis.
General Procedure
A mortar was charged with acid chloride (1 mmol), DABCO (0.11 g,
1 mmol); the mixture was ground with a pestle for 1 min until the reac-
tion mixture solidified. Then potassium salts of carboxylic acid (1 mmol)
were added to the mixture. The reaction mixture was ground for the
time specified in Table I. Then the reaction mixture was poured into a
mixture of ether (20 ml) and H2O (5 ml). The ethereal layer was dried
(CaCl2), and evaporated to dryness using a rotary evaporator to give the
pure product (>95% base on TLC analysis). The products could be fur-
ther purified by column chromatography on silica gel using a mixture
of n-hexane:EtOAc (80:20).
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