Zinc-mediated fast sulfonylation of aromatics

Article abstract of DOI:10.1081/SCC-100103538

Zn dust-mediated Friedel-Crafts sulfonylation of aromatic compounds with p-toluenesulfonyl chloride was carried out to give corresponding sulfones in good yields. Isolation of pure products by simple filtration and evaporation is an important feature of this method.

Full text of DOI:10.1081/SCC-100103538

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ZINC-MEDIATED FAST
SULFONYLATION OF
AROMATICS
a
a
B. P. Bandgar & S. P. Kasture
a
School of Chemical Sciences, Swami Ramanand
Teerth Marathwada University, Organic Chemistry
Research Lab., Vishnupuri, Nanded, 431 606,
Maharashtra, India
Version of record first published: 09 Nov 2006.
To cite this article: B. P. Bandgar & S. P. Kasture (2001): ZINC-MEDIATED FAST
SULFONYLATION OF AROMATICS, Synthetic Communications: An International
Journal for Rapid Communication of Synthetic Organic Chemistry, 31:7, 1065-1068
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SYNTHETIC COMMUNICATIONS, 31(7), 1065–1068 (2001)
ZINC-MEDIATED FAST SULFONYLATION
OF AROMATICS
B. P. Bandgar* and S. P. Kasture
Organic Chemistry Research Lab.,
School of Chemical Sciences,
Swami Ramanand Teerth Marathwada University,
Vishnupuri, Nanded-431 606, Maharashtra, India
ABSTRACT
Zn dust-mediated Friedel-Crafts sulfonylation of aro-
matic compounds with p-toluenesulfonyl chloride was carried
out to give corresponding sulfones in good yields. Isolation of
pure products by simple filtration and evaporation is an
important feature of this method.
We report here the selective synthesis of diaryl sulfones using micro-
waves and zinc dust under solvent-free conditions, as well as using a
conventional heating mode. Results are summarized in the Table. Activated
as well as deactivated aromatics underwent smoother and faster sulfonyla-
tion under microwave irradiation than under conventional heating mode.
*
Corresponding author. Fax: 0091-2462-26119.
065
1
Copyright & 2001 by Marcel Dekker, Inc.
www.dekker.com

1
066
BANDGAR AND KASTURE
Table. Zinc-Mediated Sulfonylation of Aromatics
Reaction Time
Conv.Á M.W. Conv.Á M.W.
a,b
Yield
8
Sr. No.
1
Arene
Product
(min.) (sec.)
(%)
69
(%)
60
60
45
60
30
45
45
50
60
60
70
60
45
90
15
60
60
20
45
45
72
2
3
4
5
6
7
8
86
72
62
75
72
82
78
52
58
89
c
86
70
d
77
70
77
91
62
62
1
0
1
1
a
b
Yields are of isolated products; Products were characterized by their physical
8
1
c
d
constants IR, H NMR, and mass; ortho : para ¼ 1:3; ortho : para ¼ 1:4.

AROMATIC SULFONYLATION
1067
Zn-mediated sulfonylation using even conventional mode of heating is fast
30–60 min), compared with sufonylation using Fe(III)-exchanged mon-
(
6
tmorillonite (3–12 h). It is also important to note that the p-selectivity of
sulfonylation is impressive with this method. On the other hand, aluminium
chloride yields mixture of ortho : meta : para products. The synthesis of
0
diphenyl sulfone, an intermediate for DIPSONE (4,4 -diaminodiphenyl
7
sulfone) effective for leprosy treatment and synthesis of similar drug
intermediates using Zn dust offers a commerciably feasible route with
control of effluents. The products obtained by this method are in good
yields with essentially pure form.
In conclusion, we have developed novel method for the synthesis of
useful sulfone intermediates for drug industry. Isolation pure products by
simple filtration and evaporation is an important feature of this method.
EXPERIMENTAL
IR spectra were recorded on a Bomem MB104 FT-IR spectrometer,
1
whereas H NMR spectra were recorded on a Perkin-Elmer 90 MHz
spectrometer.
Typical Procedure for Sulfonylation of Toluene
A mixture of toluene (5 mmol), p-toluenesulfonyl chloride (5 mmol),
and Zn dust (5 mmol) was exposed to microwaves for 45 s or heated at
ꢀ
1
10 C for 60 min (Table). After completion of reaction (TLC), the product
was extracted with ether (3ꢁ10 mL). Removal of the solvent under reduced
pressure gave product in good yield and in pure form. In most of the cases,
the reaction works very well on 25 mmol scale.
ACKNOWLEDGMENTS
We thank UGC, New Delhi, for financial assistance.
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1
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BANDGAR AND KASTURE
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Accepted May 8, 2000