Al2O3/MeSO3H (AMA) as a new reagent for the thia-Fries rearrangement of arylsulfonates to hydroxyaryl sulfones

Article abstract of DOI:10.1080/104265090929878

A new facile method for thia-Fries rearrangement of arylsulfonates has been developed. A variety of arylsulfonates rearrange in excellent yields in the presence of Al₂O₃/MeSO₃H as a new reagent without the use of any solve

Full text of DOI:10.1080/104265090929878

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Al2O3/MeSO3H (AMA) as a
New Reagent for the Thia-
Fries Rearrangement of
Arylsulfonates to Hydroxyaryl
Sulfones
Hashem Sharghi a & Zahra Shahsavari-Fard a
a Department of Chemistry , College of Sciences,
Shiraz University , Shiraz, Iran
Published online: 16 Aug 2006.
To cite this article: Hashem Sharghi & Zahra Shahsavari-Fard (2005) Al2O3/MeSO3H
(AMA) as a New Reagent for the Thia-Fries Rearrangement of Arylsulfonates to
Hydroxyaryl Sulfones, Phosphorus, Sulfur, and Silicon and the Related Elements,
180:11, 2491-2501, DOI: 10.1080/104265090929878
To link to this article: http://dx.doi.org/10.1080/104265090929878
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Phosphorus, Sulfur, and Silicon, 180:2491–2501, 2005
Copyright © Taylor & Francis Inc.
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/104265090929878
Al2O3/MeSO3H (AMA) as a New Reagent for the
Thia-Fries Rearrangement of Arylsulfonates
to Hydroxyaryl Sulfones
Hashem Sharghi
Zahra Shahsavari-Fard
Department of Chemistry, College of Sciences, Shiraz University,
Shiraz, Iran
A new facile method for thia-Fries rearrangement of arylsulfonates has been de-
veloped. A variety of arylsulfonates rearrange in excellent yields in the presence of
Al2O3/MeSO3H as a new reagent without the use of any solvent.
Keywords Al2O3; MeSO3H; arylsulfonates; hydroxyaryl sulfones
INTRODUCTION
Sulfones are useful intermediates in a wide range of fields such
as drug and agrochemical intermediates,1 thermographic materials,2
polymers,3 and effective antivirial agents.4 The sulfonyl group is a
widely used synthon for synthetic organic chemists5 and sulfones
have many industrial applications.6 The hydroxyaryl sulfones are well
known as antiseptics and also are useful as fungicides and bactricides.7
There are several methods for synthesizing aromatic sulfones,8 but
many of these either give low yields, have serious limitations, or require
special techniques. The practical method for preparing hydroxyaryl sul-
fones is the thia-Fries rearrangement of arylsulfonates, which provides
a useful route to these compounds.9 However, these rearrangements
require drastic reaction conditions (solvent free with more than stoi-
chiometric amounts of AlCl3 at 80–160◦C or in refluxing nitrobenzene)
and produce very low yields (generally <20%) of the desired products.10
Supported clays such as Lewis acids give better results but the method
Received August 1, 2004; accepted December 1, 2004.
We gratefully acknowledge the support of this work by the Shiraz University Research
Council.
Address correspondence to Hashem Sharghi, Shiraz University, Department of Chem-
istry, College of Sciences, Shiraz 71454, Iran. E-mail: shashem@chem.susc.ac.ir
2491

2492
H. Sharghi and Z. Shahsavari-Fard
has not been applied to a wide range of arylsulfonates.11 We recently
have reported that a mixture of Al2O3/MeSO3H (AMA) was an effec-
tive reagent for Fries rearrangement,12 Beckmann rearrangement,13
conversion of nitriles into amides,14 monoesterification of diols,15a and
direct conversion of aromatic aldehydes to glycol monoesters.15b
RESULTS AND DISCUSSION
We report herein that AMA also works as a good reagent for the
synthesis of hydroxyaryl sulfones. When heated with AMA, arenesul-
fonate rearranges to give the corresponding hydroxyaryl sulfones in a
higher yield and milder condition than previously reported procedures
(Scheme 1).
SCHEME 1
To exploit an effective reagent for the thia-Fries rearrange-
ment of arenesulfonates, the reaction of 4-chlorophenyl 4-methyl-1-
benzensulfonate (1) was chosen as a model and its behavior was stud-
1
ied under a variety of conditions via TLC and H-NMR spectroscopy
(Scheme 2). The results are summarized in Table I.
SCHEME 2
According to Table I, entry 3 gives 81% hydroxylsulfonate in 2 min,
but the reaction required at least stoichiometric quantities of a Lewis
acid, which, after quenching, afforded a lot of metal oxides. These draw-
backs set a severe limit to the industrial application of the reaction be-
cause the process requires the handling and use of amounts of Lewis
acids that are too large resulting in high production costs and causing

AMA as Reagent for Thia-Fries
2493
TABLE I Thia-Fries Rearrangement of 0.2 mmol of
Arylsulfonate (1) Under Various Conditions
Entry
Conditions
Time (h)
Yield%a
1
2
3
4
5
6
7
8
AlCl3, 150◦C6
PPA, 150◦C16
4
4
35
32b
81
—
—
—
AlCl3-ZnCl2/MW8f
0.033
Montmorilonit Clay, 120◦C11
Al2O3 (3 mmol), 150◦C
8
2
2
2
2
MeSO3H (15 mmol), 150◦C
Al2O3 (3 mmol), MeSO3H (15 mmol), 100◦C
Al2O3(3 mmol), MeSO3H (15 mmol), 150◦C
20
70
aIsolated yields.
b65% bis (4-methyl phenyl) sulfone was obtained (Jacobsen
rearrangement).17
great plant damage. The problem turned more and more worrisome
in recent times due to the increasingly stringent environmental legis-
lations in developed countries during the last decade, which aimed to
minimize the production of waste and pollutant materials.
The best results were obtained by a mixture of Al2O3 and MeSO3H
in a molar ratio 3 mmol: 15 mmol, when carried out at 150◦C for 2 h.
The experiments also show the importance of the use of both Al2O3 and
MeSO3H, respectively.
The results show that all hydroxyaryl sulfones are prepared without
a Jacobsen rearrangement.17 We have confirmed that in AMA media
(in accordance with PPA), arenesulfonates react without desulfonyla-
tion and transsulfonation reactions. Because of this initial observation,
it seemed advantageous to investigate this reagent as a new and bet-
ter reagent for a thia-Fries rearrangement. A typical procedure is as
follows: to a mixture of alumina (0.3 g) and methanesulfonic acid 98%
(1 mL, 15 mmol) at 150◦C was added arenesulfonates (2 mmol). The
mixture was stirred and heated in an oil bath at 150◦C for 2 h. After
an usual work up, hydroxyaryl sulfones were obtained in good yield.
Infrared analysis of the product showed two strong absorption bonds
at 1300–1350 and 1100–1150 cm−1, which are characteristic of the sul-
fone group and also are strong absorption bonds at 3000–3400 cm−1 for
a hydroxyl group.
To establish the generality and applicability of this method, vari-
ous arenesulfonates were subjected to the same reaction conditions to
furnish the corresponding hydroxyaryl sulfones in good yields. Thus,
arenesulfonates with both electron-donating and -withdrawing sub-
stituents were carried out in the presence of AMA (Table II).

2494
H. Sharghi and Z. Shahsavari-Fard
TABLE II Thia-Fries Rearrangement of 0.2 mmol of
Arylsulfonates Using Al2O3 (3 mmol)/MeSO3H (15 mmol) at 150◦C
Yield (%)c,d
(ortho: para)
Entry
1
Substrate a,b
Time (h)
2
Products
80
(1:3)
2
3
2
2
75
(1:3)
88
(1:3)
4
2
75e
5
6
2
2
70
65
7
2
75

AMA as Reagent for Thia-Fries
2495
TABLE III Thia-Fries Rearrangement of 0.2 mmol of Arylsulfonates
Using Al2O3 (3 mmol)/MeSO3H (15 mmol) at 150◦C (Continued)
Yield (%)c,d
(ortho: para)
Entry
8
Substrate a,b
Time (h)
2
Products
68
9
2
2
65
(1:1)
10
78
—
11
12
No Reaction
12
13
12
12
No Reaction
No Reaction
—
—
14
2
85
(10:1)
aTs = Tosyl.
bRefrences 18, 19, and 20.
cAll yields refer to pure isolated products.
dThe ratio of the products were determined by 1H NMR analysis.
eThe IPSO rearrangement product also is produced (15%). The product is
3-methyl-4-[(methylphenyl)sulfonyl]phenol.

2496
H. Sharghi and Z. Shahsavari-Fard
According to Table II, activated sulfonates gave a mixture of two
isomers (ortho and para) hydroxyaryl sulfones in good yields (entries
1–4, 11). p-Chloro and bromo sulfonates selectively gave the ortho iso-
mer of hydroxyaryl sulfones in 70% and 65% yields, respectively (en-
tries 5, 6). In order to increase the yields of these hydroxyaryl sul-
fones, the time of the reaction was increased, but no changes were
observed. Special mention must be made of the rearrangement of o-
chloro and bromo sulfonates. The corresponding para isomer selec-
tively formed in 75% and 68% yields, respectively (entries 7, 8). In
particular, m-ditosyl benzene undergoes the reaction to produce the
corresponding sulfone in a 78% yield (entry 10) and only a monosul-
fonylated product has been formed. However, the reaction of p-ditosyl
benzene did not afford the corresponding sulfone (entry 12). With
more bulky naphthyl tosylate, the reaction is regioselective and the
2-isomer is the selective product (entry 14). Finally, nitro-substituted
sulfonates do not rearrange to produce the corresponding hydroxyaryl
sulfones. These results indicate that electrophilic substitution does not
occur because an electron-withdrawing group deactivates the aromatic
ring.
The relative reactivities of the aromatic substrates are consistent
with a mechanism involving an attack on the aromatic ring by an elec-
trophilic reagent. The attacking electrophile in this case must be weak
and demands an electron-rich ring. The reaction mechanism in the
formation of hydroxyaryl sulfones apparently involves the sulfonium
cation, ArSO2+, which is very similar to the mechanism involved in the
preparation of aromatic ketones (via the acyl cation, ArCO+)21 in PPA.
In conclusion, we have demonstrated that a readily available and in-
expensive reagent, AMA, is very effective for the thia-Fries rearrange-
ment of arylsulfonates. The simple procedure and work up, the lack of
solvent in the reaction step, and the good yields make this method a
useful addition to the present methodologies. Hence, we believe that
it will find wide application in organic synthesis as well as in the
industry.
EXPERIMENTAL
General
1H NMR and 13C NMR spectra were measured on Bruker Advance DPX
FT 250 and 62.9 MHz spectrometry with TMS as an internal standard.
IR spectra were obtained on Perkin-Elmer or FTIR-800 instruments.
Mass spectra were obtained on a Shimadzu GCMS0QP 1000EX at 20
and 70 ev, or both.

AMA as Reagent for Thia-Fries
2497
All starting materials, p-toluenesulfonic acid and phenols, were pur-
chased from Fluka or Merck. Alumina (Al2O3) type 5016A, (pH 0.9)
and methanesulfonic acid 98% were purchased from Fluka.
Typical Procedure
General Procedure for Thia-Fries Rearrangement
of Arylsulfonates
To a mixture of alumina (3 g) and methansulfonic acid (10 mL) at 150◦C,
arylsulfonate (20 mmol) was added and stirred for 2 h. Then the mixture
was poured into water, extracted with chloroform (2 × 25 mL), washed
with 5% sodium hydrogen carbonate solution (2 × 25 mL), dried over
anhydrous CaCl2, and evaporated. The crude product was isolated in
a pure state by silica gel column with n-hexane/ethyl acetate. The pro-
duced hydroxyaryl sulfones were known. Specific detailed data for each
of the compounds are given below:
(a) 2-[(4-Methylphenyl)sulfonyl]phenol 8f
White crystal, m.p.: 124–125◦C (Lit.8f 126◦C); IR (neat): 3292, 159,
1361, 1145 cm−1;1H NMR (CDCl3, 250 MHz) δ 2.42 (s, 3H), 7.00 (m,
2H), 7.30 (d, 2H), 7.45 (d, 1H), 7.65 (d, 1H), 7.84 (d, 2H), 9.26 (s, 1H);
MS (m/e) = 248 (M+, 59.6), 172 (23.5), 94 (58.2), 65 (100, base peak).
(b) 4-[(4-Methylphenyl)sulfonyl]phenol 8f
White crystal, m.p.: 143–144◦C (Lit.8 f 143◦C); IR (neat): 3375, 1585,
1
1284, 1144 cm−1; H NMR (CDCl3, 250 MHz) δ 2.38 (s, 3H), 6.30 (s,
1H), 6.90 (d, 2H), 7.37 (d, 2H), 7.79 (d, 4H); MS (m/e) 249(M+, 100, base
peak), 141 (45.8), 108 (43.4), 91 (32.6), 65 (66.2), 43 (54.7).
(c) 2-Methyl-6-[(4-methylphenyl)sulfonyl]phenol 22
White crystal, m.p.: 130–131◦C (Lit.22 130–132◦C); IR (neat): 3330,
1593, 1284, 1144 cm−1; 1H NMR (CDCl3, 250 MHz) δ 2.45 (s, 3H), 2.58
(s, 3H), 6.80 (t, 1H), 7.35 (d, 3H), 7.85 (d, 2H), 9.30 (s, 1H); MS (m/e)
262 (M+, 100, base peak), 195 (17.6), 155 (64.6), 107 (93.0), 65 (41.3),
43 (68.5).
(d) 2-Methyl-4-[(4-methylphenyl)sulfonyl]phenol 22
White crystal, m.p.: 117–119◦C (Lit.22 120◦C); IR (neat): 3367, 1590,
1
1283, 1147 cm−1; H NMR (CDCl3, 250 MHz) δ 2.25 (s, 3H), 2.38 (s,
3H), 5.40 (s, 1H), 6.80 (d, 1H), 7.25 (d, 2H), 7.66 (d, 2H), 7.78 (d, 2H);
MS (m/e) 262 (M+, 0.2), 247 (98.2), 155 (11.0), 139 (100, base peak), 107
(11.1), 91 (32.7), 65 (35.9), 43 (15.1).

2498
H. Sharghi and Z. Shahsavari-Fard
(e) 5-Methyl-2-[(4-methylphenyl)sulfonyl]phenol 23
White crystal, m.p.: 144–145◦C (Lit.23 145–147◦C); IR (neat): 3315,
1594, 1300, 1149 cm−1; 1H NMR (CDCl3, 250 MHz δ 2.30 (s, 3H), 2.38
(s, 3H), 6.65 (s, 1H), 6.78 (d, 1H), 7.31 (d, 2H), 7.47 (d, 2H), 7.77 (d, 2H),
9.16 (s, 1H); MS (m/e) 262 (M+, 45.4), 246 (33.4), 228 (25.7), 180 (37.9),
139 (100, base peak), 107 (21.5), 91 (91.4), 65 (83.1).
(f) 3-Methyl-4-[(4-methylphenyl)sulfonyl]phenol 23
White crystal, m.p.: 150–151◦C (Lit.23 151-2◦C); IR (neat): 3366,
1595, 1317, 1153 cm−1; 1H NMR (CDCl3, 250 MHz) δ 2.32 (s, 3H), 2.40
(s, 3H,), 6.41(s, 1H), 6.65 (s, 1H), 6.79 (d, 1H), 7.26 (d, 2H), 7.69 (d, 2H),
8.04 (d, 1H); MS (m/e) 262 (M+, 24.7), 244 (25.0), 227 (12.1), 196 (100,
base peak), 153 (50.0), 107 (26.4), 77 (99.8).
(g) 4-Methyl-2-[(4-methylphenyl)sulfonyl]phenol 23
White crystal, m.p.: 133–134◦C (Lit.23 135◦C); IR (neat): 3319, 1595,
1367, 1147 cm−1; 1H NMR (CDCl3, 250 MHz) δ 2.26 (s, 3H), 2.4 (s, 3H),
6.9 (d, 1H), 7.25 (d, 3H), 7.34 (s, 1H), 7.83 (d, 2H), 9.08 (S, 1H); MS (m/e)
262 (M+, 26.0), 186 (51.9), 107 (100, base peak), 77 (73.8), 51 (22.5).
(h) 4-Chloro-2-[(4-methylphenyl)sulfonyl]phenol 8f
White crystal (needle type), m.p.: 127–128◦C (Lit.8f 127◦C); IR (neat):
3386, 1596, 1290, 1141, 817 cm−1; 1H NMR (CDCl3, 250 MHz) δ 2.32 (s,
3H), 6.68 (d, 1H), 7.13 (d, 2H), 7.24 (s, 1H), 7.73 (d, 2H), 9.10 (s, 1H); MS
(m/e) 282 (M+2, 63.5), 215 (26.1), 126 (14.5), 108 (15.8), 92 (100, base
peak), 65 (54.9), 41 (23.4).
(i) 2-Chloro-4-[(4-methylphenyl)sulfonyl]phenol 23
White crystal (cubic type), m.p.: 174–175◦C (Lit.23 176◦C); IR (neat):
1
3327, 1584, 1303, 1132, 737 cm−1; H NMR (CDCl3, 250 MHz) δ 2.33
(s, 3H) 6.07 (s, 1H), 7.02 (d, 1H), 7.23 (d, 2H), 7.69 (d, 3H), 7.85 (s, 1H);
MS (m/e) 282 (M+2, 82.3), 175 (40.7), 139 (77.1), 108 (91.7), 9 (100, base
peak), 65 (98.6), 41 (53.7).
(j) 5-Flouro-2-[(4-methylphenyl)sulfonyl]phenol 24
White crystal m.p.: 128–130◦C; IR (neat): 3345, 1591, 1279, 1148,
1090 cm−1; 1H NMR (CDCl3, 250 MHz)δ 2.35 (s, 3H), 6.60 (d, 1H), 7.19
(s, 1H), 7.24 (d, 2H), 7.58 (t, 1H), 7.72 (d, 2H), 9.35 (s, 1H); MS (m/e)266
(M+, 98.4), 202 (20.1), 155 (22.6), 139 (22.2), 108 (47.1), 91 (100, base
peak), 65 (65.6).

AMA as Reagent for Thia-Fries
2499
(k) 3-Flouro-4-[(4-methylphenyl)sulfonyl]phenol 24
White crystal, m.p.: 124–126◦C; IR (neat): 3405, 1609, 1319, 1140,
1
1248 cm−1; H NMR (CDCl3, 250 MHz) δ 2.34 (s, 3H, CH3), 6.50 (d,
1H), 6.68 (s, 1H), 7.07 (s, 1H), 7.26 (d, 2H), 7.76 (d, 3H); MS (m/e) 266
(M+, 44.7), 159 (26.8), 139 (37.4), 108 (65.8), 91 (57.5), 65 (50.1), 43 (100,
base peak).
(l) 2-[(4-Methylphenyl)sulfonyl]-1-naphthol 25
White crystal, m.p. 128–130◦C (Lit.25134◦C); IR (neat): 3150, 1570,
1120, 1350 cm−1; 1H NMR (CDCl3, 250 MHz) δ 2.37 (s, 3H), 7.30 (d, 2H),
7.60 (m, 4H), 7.65 (d, 1H), 7.85 (d, 2H), 8.40 (d, 1H), 10.46 (s, 1H, OH);
MS (m/e) 298 (M+, 91.9), 191 (19.8), 162 (10.4), 139 (57.9), 115 (50.2),
91 (42.6), 59 (47.5), 43 (100, base peak).
(m) 4-[(4-Methylphenyl)sulfonyl]-1-naphthol 8f
White crystal, m.p.: 160◦C (Lit.8f 163◦C); IR (neat): 3200, 1600, 1110,
1360 cm−1; 1H NMR (CDCl3, 250 MHz) δ 2.38 (s, 3H), 6.93 (m, 4H), 7.26
(d, 2H), 7.85 (d, 1H), 7.90 (d, 2H), 8.10 (s, 1H), 8.21 (d, 1H); MS (m/e)
298(M+, 100, base peak), 265 (11.5), 234 (23.1), 206 (22.7), 142 (73.2),
114 (64.6), 91 (47.4), 65 (48.2), 43 (43.5).
(n) 4-[(4-Methylphenyl)sulfonyl]-1,3-benzendiol 18
White crystal, m.p.: 160–162◦C (Lit.18 155–157◦C); IR (neat): 3358,
1595, 1334, 1136 cm−1; 1H NMR (CDCl3, 250 MHz) δ 2.33 (S, 3H), 5.62
(s, 1H), 6.37 (d, 2H), 7.20(d,2H), 7.43 (d, 1H), 7.71 (d, 2H), 9.20 (s, 1H);
13C NMR (CDCl3, 62.9 MHz) d 22.01, 105.02, 109.34, 126.95, 127.25,
130.42, 131.49, 132.82, 149.50, 154.32; MS (m/e) 264(M+, 100, base
peak) , 199 (21.1), 157(22.1), 125(14.31), 108 (33.8), 91 (60.0), 65 (57.3);
UV (CHCl3) λmax 308.4 (ε = 1993).
(o) 4-Bromo-2-[(4-methylphenyl)sulfonyl]phenol 26
White crystal (needle type), m.p.: 145–146◦C; IR (neat): 3388, 1469,
1
1290, 1141, 131 cm−1; H NMR (CDCl3, 250 MHz) δ 2.43 (s, 3H), 6.89
(d, 1H), 7.34 (d, 2H), 7.51 (d, 1H), 7.73 (s, 1H), 7.81 (d, 2H), 9.37 (s, 1H);
13C NMR (CDCl3, 62.9 MHz) d 22.05, 121.12, 125.47, 125.95, 127.42,
129.81, 130.67, 134.80, 138.33, 145.83, 145.66; MS (m/e) 328(M+2, 46.9),
261(12.2), 181(10.5), 139 (28.0), 108 (16.4), 92 (100, base peak), 65 (58.4),
43 (47.6); UV (CHCl3) λmax 251 (ε = 2909), 307.7 (ε = 1180).
(p) 2-Bromo-4-([4-methylphenyl)sulfonyl]phenol 26
White crystal, m.p.: 170–172◦C; IR (neat): 3327, 1593, 1299, 1110,
723 cm−1; 1H NMR (CDCl3, 250 MHz) δ 2.41(s, 3H), 6.85 (t, 1H), 7.31 (d,

2500
H. Sharghi and Z. Shahsavari-Fard
2H), 7.64 (d, 2H), 7.82 (d, 2H), 9.56 (s, 1H); 13C NMR (CDCl3, 62.9 MHz)
d 21.96, 111.06, 117.07, 127.89, 129.38, 130.42, 132.31, 135.30, 138.93,
144.75, 156.82; MS (m/e) 326 (M+2, 6.4), 155 (38.5), 108 (12.4), 91 (82.0),
69 (42.3), 43 (100, base peak); UV (CHCl3) λmax 257.6 (ε = 2801), 301.3
(ε = 1778).
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