of easy recovery and the lack of a metal-containing waste
stream, this approach should prove attractive for sulfonylation
reactions of simple aromatics.
of this work, and Zeolyst International for gifts of zeolites.
G. A. El-Hiti thanks the Royal Society of Chemistry for an
international author grant.
Experimental
References
A Hewlett Packard HP 5890 (Series II) or PU 4400 gas
chromatograph, fitted with a Carbowax capillary column
(30 m, 0.32 mm ID) was used to analyse reaction mixtures. The
GC conditions used for analysis were: the initial temperature
was 100 °C followed by a ramp rate at 20 °C min−1 to 220 °C
with helium as the carrier gas and nitrogen as a make-up gas.
The injector temperature was 300 °C and the flame ionisation
detector temperature was 350 °C. Further to GC analysis the
isomer distributions were verified by 1H NMR, which was car-
ried out on a Bruker AC 400 MHz instrument. All samples were
dissolved in CDCl3 and TMS was the standard.
1 N. S. Simpkins, Sulfones in Organic Synthesis, Pergamon Press,
Oxford, 1993.
2 W. J. Michaely and G. W. Kraatz, US Pat., 4,780,127, 1988 (Chem.
Abstr., 1989, 111, 129017a).
3 S. M. Mackinnon and J. Y. Wang, Macromolecules, 1998, 31, 7970.
4 F. Paolo, M. Giorgio, M. Patrizia, P. Concetto and S. Filippo, Mac-
romol. Chem. Phys., 1996, 197, 1007.
5 R. L. Robsein, J. J. Straw and D. R. Fahey, US Pat., 5,260,489, 1993
(Chem. Abstr., 1994, 120, 165200z).
6 K. M. Roy, in Ullmann’s Encyclopedia of Industrial Chemistry,
W. Gerhartz, ed., VCH, Weinheim (Germany), 1985, vol. A25, pp.
487–501.
7 Electrophilic Aromatic Substitution, R. Taylor, ed., John Wiley and
Sons, Chichester, 1990, pp. 334–337.
8 R. Taylor, in Comprehensive Chemical Kinetics, C. H. Banford and
C. F. H. Tipper, ed., Elsevier, New York, 1972, pp. 77–83; F. R.
Jensen and G. Goldman, in Friedel–Crafts and Related Reactions,
G. A. Olah, ed., Wiley-Interscience, New York, 1964, vol. III, pp.
1319–1367.
9 F. R. Jensen and H. C. Brown, J. Am. Chem. Soc., 1958, 80, 4046.
10 G. A. Olah, S. Kobayashi and J. Nishimura, J. Am. Chem. Soc.,
1973, 95, 564.
Chemicals
Methanesulfonic anhydride (98%) was obtained from Lancaster
Research Chemicals. Other chemicals were obtained from
Aldrich Chemical Company and were used directly without
further purification. Toluene was distilled and stored over 3 Å
molecular sieves.
11 S. Daley, K. A. Trevor, K. R. Randles and B. D. Gott, PCT Int.
Appl.WO93 18,000, 1993 (Chem. Abstr., 1994, 120, 54320u).
12 H. J. Sipe Jr., D. W. Clary and S. B. White, Synthesis, 1984, 283.
13 M. Ueda, K. Uchiyama and T. Kano, Synthesis, 1984, 323.
14 P. Laidlaw, D. Bethell, S. M. Brown, G. Watson, D. J. Willock and
G. J. Huchings, J. Mol. Catal. A, 2002, 178, 205.
Zeolites
Commercial zeolites were purchased from Aldrich Chemical
Company or provided as gifts by Zeolyst International. Zeolites
and Synclyst were freshly calcined at 400 °C and clays at 110 °C
for a minimum of 6 h prior to use.
15 B. M. Choudary, N. S. Chowdari, M. L. Kantam and R. Kannan,
Tetrahedron Lett., 1999, 40, 2859.
16 B. M. Choudary, N. S. Chowdari and M. L. Kantam, J. Chem. Soc.,
Perkin Trans. 1, 2000, 2689.
17 S. Répichet, C. Le Roux, P. Hernandez, J. Dubac and J.-R. Desmurs,
J. Org. Chem., 1999, 64, 6479.
Typical experimental procedure for methanesulfonylation of
toluene
Quantities arerecordedinthefootnotes of theappropriate tables.
All reactions were carried out in a 50 ml round bottomed flask
fitted with a magnetic bar and a condenser. Methanesulfonic
anhydride (98%; 1.22 g, 7 mmol) was weighed into a flame-
dried 50 ml round bottomed flask containing freshly calcined
solid catalyst. Dry toluene (15 ml) was added to the mixture
and then the reaction mixture was heated on an oil bath under
reflux conditions for 18 h. The hot reaction mixture was filtered
and the filtrate was immediately quenched with cold iced water
(25 ml). The layers were separated and an additional extraction
was carried out on the aqueous layer using toluene (15 ml). The
catalyst recovered from the filtration was refluxed with CH2Cl2
(25 ml) for 30 min and the solid was then filtered. The toluene
and dichloromethane extracts were combined and washed with
Na2CO3 solution (1 M, 25 ml), then water (25 ml) and dried
(MgSO4). The solvent was removed by rotary evaporation and
the residue was purified by Kugelrohr distillation (133–141 °C,
3 mm). The products were analysed by GC.
18 S. Répichet, C. Le Roux and J. Dubac, Tetrahedron Lett., 1999, 40,
9233.
19 J. Marquié, A. Laporterie, J. Dubac, N. Roques and J.-R. Desmurs,
J. Org. Chem., 2001, 66, 421.
20 J.-R. Desmurs, J. Dubac, A. Laporterie, C. Laporte and J. Marquié,
PCT Int. Appl. WO98 40,339, 1998 (Chem. Abstr., 1998, 129,
244928g).
21 C. Laporte, J. Marquié, A. Laporterie, J.-R. Desmurs and J. Dubac,
C. R. Acad. Sci., Ser. IIc, 1999, 2, 455.
22 K. Smith and G. A. El-Hiti, Curr. Org. Synth., 2004, 1, 253.
23 K. Smith, S. D. Roberts and G. A. El-Hiti, Org. Biomol. Chem.,
2003, 1, 1552.
24 K. Smith, G. A. El-Hiti, A. J. Jayne and M. Butters, Org. Biomol.
Chem., 2003, 1, 1560; K. Smith, G. A. El-Hiti, A. J. Jayne and
M. Butters, Org. Biomol. Chem., 2003, 1, 2321.
25 K. Smith and G. Pollaud, J. Chem. Soc., Perkin Trans. 1, 1994,
3519.
26 K. Smith, G. A. El-Hiti, M. E. W. Hammond, D. Bahzad, Z. Li and
C. Siquet, J. Chem. Soc., Perkin Trans. 1, 2000, 2745; K. Smith, P. He
and A. Taylor, Green Chem., 1999, 1, 35.
27 K. Smith, M. Butters and B. Nay, Synthesis, 1985, 1157; K. Smith,
M. Butters, W. E. Paget, D. Goubet, E. Fromentin and B. Nay,
Green Chem., 1999, 1, 83.
Acknowledgements
28 K. Smith, K. Fry, M. Butters and B. Nay, Tetrahedron Lett., 1989, 30,
5333; K. Smith, A. Musson and G. A. DeBoss, J. Org. Chem., 1998,
63, 8448; K. Smith, T. Gibbins, R. W. Millar and R. P. Claridge,
J. Chem. Soc., Perkin Trans. 1, 2000, 2753; K. Smith, S. Almeer,
S. J. Black and C. Peters, J. Mater. Chem., 2002, 12, 3285.
29 K. Smith, G. M. Ewart and K. R. Randles, J. Chem. Soc., Perkin
Trans. 1, 1997, 1085.
We thank Zeneca and the University of Wales Swansea for
financial support, and the EPSRC Mass Spectrometry Centre
at Swansea for mass spectra. We also thank the EPSRC, the
Higher Education Funding Council for Wales (ELWa-HEFCW)
and the University of Wales Swansea for grants that enabled the
purchase and upgrading of NMR equipment used in the course
3 1 5 4
O r g . B i o m o l . C h e m . , 2 0 0 4 , 2 , 3 1 5 0 – 3 1 5 4