J . Org. Chem. 1999, 64, 6479-6482
6479
Ta ble 1. Su lfon yla tion Rea ction s Ca ta lyzed by
Bism u th (III) Ch lor id e (1a )
Bism u th (III) Tr iflu or om eth a n esu lfon a te:
An Efficien t Ca ta lyst for th e Su lfon yla tion
of Ar en es
entry
reactiona,b
product and isomersc
yield (%)c
1
2
3
4
5
6
7
2 + PhSO2Cl
3 + PhSO2Cl
8 + PhSO2Cl
2 + TsCl
10 (43:7:50)d
12 (32:6:62)d
16
22
8
tr
60
50
8
Sigrid Re´pichet, Christophe Le Roux,
Pierre Hernandez, and J acques Dubac*
11 (45:0:55)e
18 (25:7:68)e
20
3 + TsCl
He´te´rochimie Fondamentale et Applique´e (UPRES(A) 5069
CNRS), Universite´ Paul-Sabatier, 118 route de Narbonne,
31062 Toulouse Cedex, France
8 + TsCl
3 + Ts2O
18 (30:4:66) e
50
a
See Table 2; experimental conditions: 120 °C, 5 h (entries
1,2,5-7) or 6 h (entries 3,4). b Catalyst: 1a (5 mol %). c Determined
by GC. d,e Various isomers: (o:m:p)d, (2,4′:3,4′:4,4′)e.
J ean-Roger Desmurs
Rhodia Organique Fine, Centre de Recherche de Lyon,
85 Avenue des Fre`res-Perret,
acylation.10 In a stoichiometric process from arylsulfonyl
bromides, silver triflate gives trifluoromethanesulfonic
arenesulfonic anhydrides (ArSO2OTf), which are strong
sulfonylating reagents.11 We present here a study of the
catalytic activity of 1a and 1b for the sulfonylation
reaction of arenes (eq 1), for which 1b proved to be a
metal triflate capable of realizing an outstanding catalytic
process.
69192 Saint-Fons Cedex, France
Received February 11, 1999
Sulfonylation reactions are one of the most important
groups of aromatic electrophilic substitutions.1 The sul-
fonyl group is a widely used synthon for synthetic organic
chemists,2 and sulfones have many industrial applica-
tions.3 In Friedel-Crafts (FC) acylation and sulfonyla-
tion, a consequence of the complexation of the Lewis acid
with the reaction product implies that a stoichiometric
amount of the activator is often required. However, some
metal halides such as iron(III) chloride,1 Bro¨nsted acids,
for example polyphosphoric acid4 or triflic acid,5 and
zeolites6,7 have been reported to catalyze the sulfonylation
of arenes.
Resu lts a n d Discu ssion
In recent years, rare earth trifluoromethanesulfonates
(triflates) have been reported for the catalysis of the FC
acylation8 but not for the catalysis of the FC sulfonyla-
tion. Also, our laboratory reported that bismuth(III)
chloride (1a ) and particularly bismuth(III) triflate (1b)
were catalysts for acylation reactions,9 especially for FC
Initially, we started this study by comparing the
catalytic activity of 1a and 1b on the sulfonylation of
anisole, toluene, and chlorobenzene. Compound 1a was
a moderate catalyst for the reactions between anisole or
toluene with TsCl (Table 1, entries 4,5), but its efficiency
decreased strongly for those involving PhSO2Cl, less
reactive than TsCl (entries 1,2), or the deactivated
chlorobenzene (entries 3,6). The activity of 1a was nearly
the same for the reactions of toluene with TsCl and Ts2O
(entries 5,7). For the same reactions, the catalytic activity
of 1b was much higher, in particular for the reactions
involving PhSO2Cl as the reagent (Table 1, entries 1-3
and Table 2, entries 1,2,6) and those with chlorobenzene
(Table 1, entries 3,8 and Table 2, entries 6,12).
(1) (a) J ensen, F. R.; Goldman, G. In Friedel-Crafts and Related
Reactions; Olah, G., Ed.; Wiley-Interscience: New York, 1964; Vol. III,
pp 1319-1367. (b) Taylor, R. In Comprehensive Chemical Kinetics;
Bamford, C. H., Tipper, C. F. H., Eds.; Elsevier: New York, 1972; pp
77-83.
(2) (a) Magnus, P. D. Tetrahedron 1977, 33, 2019. (b) Field, L.
Synthesis 1978, 713.
(3) Roy, K. M. In Ullmann’s Encyclopedia of Industrial Chemistry;
Gerhartz, W., Ed.; VCH: Weinheim (Germany), 1985; Vol. A25, pp 487-
501.
Then, we extended the examples toward a series of
arenes, in the presence of 1b using an arylsulfonyl
chloride as an electrophile. Compound 1b is capable of
catalyzing not only the sulfonylation of activated arenes
(Table 2, entries 1-4,8,9,14,16-18) but also that of non-
or weakly activated ones (entries 5,10,11). Noteworthy
results were observed for the sulfonylation of deactivated
chloro- and bromobenzene (entries 6,7,12,13,15). In the
(4) (a) Graybill, B. M. J . Org. Chem. 1967, 32, 2931. (b) Sipe, H. J .,
J r.; Clary, D. W.; White, S. B. Synthesis 1984, 283. (c) Ueda, M.;
Uchiyama, K.; Kano, T. Synthesis 1984, 323.
(5) (a) Effenberger, F.; Huthmacher, K. Chem. Ber. 1976, 109, 2315.
(b) Ono, M.; Nakamura, Y.; Sato, S.; Itoh, I. Chem. Lett. 1988, 395.
(6) (a) Daley, S.; Trevor, K. A.; Randles, K. R.; Gott, B. D. (Zeneca
Ltd.) PCT Int. Appl. WO 93 18,000 (GB Appl. 92/4, 529, 3 Mar 1992)
(Chem. Abstr. 1994, 120, 54320u). (b) Bradford, N. A. (Imperial
Chemical Industries PLC) Eur. Pat. Appl. EP 455,332 (GB Appl. 90/7,
577, 4 Apr 1990) (Chem. Abstr. 1992, 117, 48101).
(7) Smith, K.; Ewart, G. M.; Randles, K. R. J . Chem. Soc., Perkin
Trans. 1 1997, 1085.
(8) (a) Kawada, A.; Mitamura, S.; Kobayashi, S. J . Chem. Soc.,
Chem. Commun. 1993, 1157. (b) Kawada, A.; Mitamura, S.; Kobayashi,
S. Synlett 1994, 545. (c) Kobayashi, S. Synlett 1994, 689. (d) Kobayashi,
S.; Moriwaki, M.; Hachiya, I. J . Chem. Soc., Chem. Commun. 1995,
1527. (e) Kobayashi, S.; Moriwaki, M.; Hachiya, I. J . Chem. Soc. J pn.
1997, 70, 267.
(9) (a) Le Roux, C. Thesis, Universite´ Paul-Sabatier, 1993. (b) Dubac,
J . Xth Intern. Symp. Organosilicon Chem., August 15-20, 1993; Adam
Mickiewicz University Ed.: Poznan (Poland), I-33. (b) Dubac, J .; Le
Roux, C.; Gaspard-Iloughmane, H. In Progress in Organosilicon
Chemistry; Marciniec, B., Chojnowski, J ., Eds; Gordon and Breach:
Basel, 1995; pp 325-343. (c) Le Roux, C.; Mandrou, S.; Dubac, J . J .
Org. Chem. 1996, 61, 3885. (d) Le Roux, C.; Dubac, J . Organometallics
1996, 15, 4646.
(10) (a) Dubac, J .; Labrouille`re, M.; Laporterie, A.; Desmurs, J . R.
(Rhoˆne-Poulenc Chimie) Eur. Pat. Appl. EP 698,593 (FR Appl. 94/10,
523, 24 Aug 1994) (Chem. Abstr. 1996,124, 316758y). (b) Desmurs, J .
R.; Labrouille`re, M.; Dubac, J .; Laporterie, A.; Gaspard, H.; Metz, F.
Ind. Chem. Libr. 1996, 8 (The Roots of Organic Development); Desmurs,
J . R., Ratton, S., Eds.; Elsevier: Amsterdam; pp 15-28. (c) Dubac, J .;
Gaspard, H.; Labrouille`re, M.; Laporterie, A. Desmurs, J . R.; Le Roux,
C. (Rhoˆne-Poulenc Chimie) PCT Int. Appl. WO 97 11,930 (FR Appl.
95/11, 250, 25 Sep 1995) (Chem. Abstr. 1997, 126, 317246h). (d)
Desmurs, J . R.; Labrouille`re, M.; Le Roux, C.; Gaspard, H.; Laporterie,
A.; Dubac, J . Tetrahedron Lett. 1997, 38, 8871. (e) Re´pichet, S.; Le
Roux, C.; Dubac, J .; Desmurs, J . R. Eur. J . Org. Chem. 1998, 2743, 3.
(11) Effenberger, F.; Huthmacher, K. Angew. Chem., Int. Ed. Engl.
1974, 13, 409.
10.1021/jo9902603 CCC: $18.00 © 1999 American Chemical Society
Published on Web 08/04/1999