An efficient and novel method for the synthesis of β-aroylpropionic acids under solvent-free conditions

Article abstract of DOI:10.1081/SCC-120023423

A simple and rapid reaction of succinic anhydride with aromatic hydrocarbons is described. The reaction is conducted under Friedel-Crafts conditions in the absence of solvent at room temperature using aluminium chloride as catalyst.

Full text of DOI:10.1081/SCC-120023423

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An Efficient and Novel Method for the Synthesis of β-
Aroylpropionic Acids Under Solvent-Free Conditions
K. Mogilaiah a , N. Vasudeva Reddy a & G. Randheer Reddy a
a Department of Chemistry, Kakatiya University, Warangal, India
Version of record first published: 17 Aug 2006.
To cite this article: K. Mogilaiah, N. Vasudeva Reddy & G. Randheer Reddy (2003): An Efficient and Novel Method for the
Synthesis of β-Aroylpropionic Acids Under Solvent-Free Conditions, Synthetic Communications: An International Journal for
Rapid Communication of Synthetic Organic Chemistry, 33:18, 3109-3113
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SYNTHETIC COMMUNICATIONSÕ
Vol. 33, No. 18, pp. 3109–3113, 2003
An Efficient and Novel Method for the
Synthesis of b-Aroylpropionic Acids
Under Solvent-Free Conditions
*
K. Mogilaiah, N. Vasudeva Reddy, and G. Randheer Reddy
Department of Chemistry,
Kakatiya University, Warangal, India
ABSTRACT
A simple and rapid reaction of succinic anhydride with aromatic
hydrocarbons is described. The reaction is conducted under Friedel–
Crafts conditions in the absence of solvent at roomtemperature
using aluminium chloride as catalyst.
Key Words:
Correspondence: K. Mogilaiah, Department of Chemistry, Kakatiya University,
Warangal 506 009, India; E-mail: mogilaiah_k@yahoo.com.
3109
DOI: 10.1081/SCC-120023423
Copyright & 2003 by Marcel Dekker, Inc.
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3110
Mogilaiah, Reddy, and Reddy
In recent years solvent-free organic reactions have been attracting the
synthetic organic chemists because of their simplicity and synthetic
value.[1–4] Further more, the solvent-free reaction has many advantages:
reduced pollution, low costs, enhanced reaction rates, cleaner products,
and simplicity in process and handling. These factors are especially
important in industry. b-Aroylpropionic acids have been widely investi-
gated due to their synthetic potential. The most practical laboratory
method of preparing b-aroylpropionicacids is the Friedel–Crafts method
employing succinic anhydride, aromatic hydrocarbon, and aluminium
chloride as catalyst under refluxing conditions.[5–8] However, these meth-
ods suffer fromdrawbacks such as long reaction time, higher reaction
temperature, low yields, and tedious work-up procedure Therefore,
development and introduction of convenient, milder, and efficient
method for the preparation of b-aryolpropionic acids is of practical
importance and is still in demand. For one of our ongoing projects, we
required b-aroylpropionic acids as the starting materials. In view of this
and in continuation of our work on solvent-free organic reactions,[9–12] in
this report, we describe a mild, efficient, and high yielding protocol for
the synthesis of b-aroylpropionic acids under solvent-free conditions at
roomtemperature.
Friedel–Crafts succinoylation of aromatic hydrocarbons with
succinic anhydride in the presence of anhyd. AlCl3 under solvent-free
conditions at roomtepmerature furnished the corresponding
b-aroylpropionic acids in good yields. The reaction is fairly general,
facile, and efficient and is devoid of any side products. The process is
environmentally benign. The reactions proceeded smoothly at ambient
temperature to afford b-aroylpropionic acids in high yields. The mild
reaction conditions, experimental simplicity, cleaner reaction products,
and short reaction times are the main advantages of this procedure.
In a typical procedure, a mixture of succinic anhydride and anhyd.
AlCl3 was ground with a pestle in the mortar for 1 min, then benzene was
added to the reaction mixture. The reaction mixture was ground for
20 min at room temperature and treated with crushed ice –HCl. After
O
O
AlCl3
Ar
H
+
O
Ar
COOH
O
Scheme 1.

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b-Aroylpropionic Acids
3111
usual work-up b-benzoylpropionic acid was obtained in 80% yield.
Similarly, several aromatic hydrocarbons were efficiently converted into
the corresponding b-aroylpropionic acids in the presence of anhyd. AlCl3
at roomtemperature. All the products were characterized by 1H NMR,
IR spectral data and also by comparison with authentic compounds.[5–8]
To the best of our knowledge this is the first report on solvent-free
roomtemperature synthesis of b-aroyl propionic acids.
Table 1. Friedel–Crafts reaction of succinic anhydride with aromatic
hydrocarbons in the presence of anhyd. AlCl3 under solvent-free conditions at
roomtemperature.
Time Yield M.p.
(ꢀC)
M.p. ref
(ꢀC) lit.
Entry Substrate
1
Product
(min)
(%)
115[6]
O
20
80
115
COOH
O
2
10
15
86
82
125
146
124–126[8]
COOH
COOH
146[7]
O
OCH3
3
H3CO
128–130[5]
O
Cl
4
25
75
129
COOH
Cl
Br
O
Br
5
22
12
70
78
146
112
145–148[8]
112–114[8]
COOH
COOH
O
6
7
O
18
72
154
154–155[8]
COOH

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3112
Mogilaiah, Reddy, and Reddy
In conclusion, we have demonstrated a new and highly efficient pro-
tocol for the preparation of b-aroylpropionic acids under solvent-free
conditions fromaromatic hydrocarbons and succinic anhydride in the
presence of anhyd. AlCl3 at room temperature. This method is superior
in terms of mildness of the procedure, experimental simplicity, economic
viability, short reaction times, and high yields of products to the reported
methods. In this methodology the products are pure and do not need any
purification.
EXPERIMENTAL SECTION
Melting points were determined on a Cintex apparatus and are
uncorrected. Infrared spectra were recorded in KBr on a Perkin-Elmer
spectrumBX series FT-IR spectrophotometer. 1H NMR spectra were
determined on a Varian Gemini 200 MHz instrument using TMS as
internal standard. TLC was performed on 0.25 mm E. Merk precoated
silica gel plates (60F–254).
General Procedure for the Synthesis
of b-Aroylpropionic Acids
A mortar was charged with the succinic anhydride (0.01 mol), and
powdered anhyd. aluminium chloride (0.02 mol) under efficient hood.
The reaction mixture was ground with a pestle in the mortar for 1 min,
then aromatic hydrocarbon (0.01 mol) was added to the reaction mixture.
The mixture was ground for the time indicated in Table 1. The progress
of the reaction was monitored by TLC. After completion of the reaction,
the mixture was treated with crushed ice-HCl. The solid formed was
collected and washed with water to give pure products.
ACKNOWLEDGMENT
NVR thank CSIR, New Delhi for the award of fellowship.
REFERENCES
1. Toda, F. Synlett (Account) 1993, 303.
2. Singh, N.B.; Singh, R.J.; Singh, N.P. Tetrahedron 1994, 50, 6441.

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b-Aroylpropionic Acids
3113
3. Desiraju, G.R. Solid State Ionics 1997, 101, 839.
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Commun. in press.
Received in the USA November 12, 2002

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