Graphite/methanesulfonic acid (GMA) as a new reagent for sulfonylation of phenols and thia-Fries rearrangement of aryl sulfonates to sulfonylphenols

Article abstract of DOI:10.1002/hlca.200490295

A new facile method for direct sulfonylation of phenols was developed. Graphite in methanesulfonic acid (GMA) was used to prepare sulfonylphenols by sulfonylation of phenol and naphthalene derivatives with p-toluenesulfonic acid (=4-methylbenzenesulfonic acid) (Table 1) and the thia-Fries rearrangement of aryl sulfonates (Table 4). Mechanistic studies showed that the sulfonylation reaction of phenols in GMA occurred through an initial sulfonate formation followed by a thia-Fries rearrangement of the aryl sulfonate by an intermolecular mechanism (Scheme 3).

Full text of DOI:10.1002/hlca.200490295

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Helvetica Chimica Acta ± Vol. 88 (2005)
Graphite/Methanesulfonic Acid (GMA) as a New Reagent for Sulfonylation
of Phenols and Thia-Fries Rearrangement of Aryl Sulfonates to
Sulfonylphenols
by Hashem Sharghi* and Zahra Shahsavari-Fard
Chemistry Department, College of Sciences, Shiraz University, Shiraz 71454, I.R. Iran
(phone: 0098711 2284822; fax: 0098711 2280926; e-mail: shashem@chem.susc.ac.ir)
A new facile method for direct sulfonylation of phenols was developed. Graphite in methanesulfonic acid
(GMA) was used to prepare sulfonylphenols by sulfonylation of phenol and naphthalene derivatives with p-
toluenesulfonic acid (ˆ4-methylbenzenesulfonic acid) (Table 1) and the thia-Fries rearrangement of aryl
sulfonates (Table 4). Mechanistic studies showed that the sulfonylation reaction of phenols in GMA occurred
through an initial sulfonate formation followed by a thia-Fries rearrangement of the aryl sulfonate by an
intermolecular mechanism (Scheme 3).
Introduction. ± Sulfones are useful intermediates in a wide range of fields such as
drug and agrochemical intermediates [1], thermographic materials [2], polymers [3],
antiviral agents [4], and antiseptics, and they are also useful as fungicides and
bactericides [5].
The exceptional ability of graphite to adsorb organic molecules [6] and to act as a
carrier of intercalated reagents is well-known [6b]. Diels ± Alder and ene reactions [7],
Friedel ± Crafts acylations [7a], decarboxylations [7a], decompositions [8], rearrange-
ments [7a][9], ketocarboxylations [10], oxidation of propan-2-ol [11], thermolyses of
esters [12], thermal reactions in heterocyclic syntheses [13], decompositions of metal
complexes [14], pyrolysis of urea [15], acylations of aromatic compounds [16],
acylative cleavage of ethers [17], and conversions of aldehydes to nitriles were effected
under such conditions [18]. Because graphite has a large surface area, it is a good heat
conductor, and the reactions can be carried out under milder conditions [7].
We report herein that graphite in methanesulfonic acid (GMA) works as a good
coupling reagent for the synthesis of sulfonylphenols from p-toluenesulfonic acid (ˆ4-
methylbenzenesulfonic acid) and phenols (Scheme 1).
Scheme 1
ꢀ 2005 Verlag Helvetica Chimica Acta AG, Zürich

Helvetica Chimica Acta ± Vol. 88 (2005)
43
Results and Discussion. ± To exploit an effective reagent for the arylsulfonylation of
phenols, the reaction of p-toluenesulfonic acid (1) with m-cresol (ˆ 3-methylphenol; 2)
was chosen as a model, and its behavior was studied under a variety of conditions by
1
TLC and H-NMRspectroscopy ( Scheme 2). It was found that phenol 2 was not
sulfonylated with p-toluenesulfonyl chloride (or 1) in the presence of AlCl3 [19], ZnCl2
[20], FeCl3 [21], SnCl4 [21], SbCl5 [22], montmorillonite clay (Fe3‡) [21], or triflic acid
(ˆtrifluoromethanesulfonic acid) [23]. In the case of triflic acid, 3-methylphenyl 4-
methylbenzenesulfonate (4) was obtained in 60% yield (Scheme 2). However, the
target sulfonylphenol 3 could be prepared in 40% yield in the presence of
polyphosphoric acid (PPA), while bis(4-methylphenyl) sulfone (Jacobsen rearrange-
ment product [24]) was obtained as a by-product in 40% yield.
Scheme 2
The best yield (85%) of 3 was obtained from 1 and 2 in the presence of a mixture of
graphite and MeSO3H (ˆGMA; ratio 0.3 g/1 ml), at 1208 after 2 h, and this without
Jacobsen rearrangement desulfonylation, and trans-sulfonation reactions (for a typical
procedure, see Exper. Part). In the absence of MeSO3H or graphite, attempted
phenylsulfonylation did not afford 3.
To establish the generality and applicability of this GMA sulfonylation method,
various phenols with both electron-donating and -withdrawing substituents were
subjected to the same reaction conditions as 2 to furnish the corresponding
sulfonylphenols in good yield (Table 1).
Activated phenols gave mixtures of two isomeric (ortho (o) and para (p))
sulfonylphenols in good yields (Entries 1 ± 4). The p-chloro- and p-bromophenols
selectively furnished the o-sulfonylphenols in 75 and 70% yields, respectively (Entries 5
and 6). To increase further these yields, longer reaction periods were applied but no
changes in the yields occurred (see also below). It should be noted that the
sulfonylation of o-chloro- and o-bromophenol gave the corresponding p-sulfonyl
isomer selectively in 73 and 70% yield, respectively (Entries 7 and 8). Benzene-1,3-diol
underwent the reaction to produce only the corresponding monosulfonylated product
in 80% yield (Entry 10). However, benzene-1,4-diol did not react with 1 in the presence
of GMA (Entry 11). In the case of the bulkier naphthalenol, the reaction was
regioselective and produced essentially the 2-sulfonylated isomer (Entry 14). Nitro-
substituted phenols did not react with 1 in the presence of GMA indicating that
electrophilic substitution does not occur when an electron-withdrawing group
deactivates the aromatic ring.
The relative reactivity of the aromatic substrates in the GMA sulfonylation is
consistent with a mechanism involving attack at the aromatic ring by a weak
electrophilic reagent that requires an electron-rich ring. Apparently, the sulfonylium

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Helvetica Chimica Acta ± Vol. 88 (2005)
Table 1. Sulfonylation of Phenols with 1 in the Presence of a Mixture of Graphite and MeSO3H (GMA) at 1208
Entry
1
Phenols
Time [h]
2
Productsa)
Yield [%]b) (ortho/para)c)
75 (1 : 2)
2
3
4
2
2
2
75 (1 : 5)
85 (1 : 2)
65d)
5
6
7
8
9
2
2
2
2
2
75
70
73
70
74 (1 : 1)

Helvetica Chimica Acta ± Vol. 88 (2005)
45
Table 1 (cont.)
Entry
10
Phenols
Time [h]
2
Productsa)
Yield [%]b) (ortho/para)c)
80
11
12
no reaction
±
12
13
12
12
no reaction
no reaction
±
±
14
2
80 (10 : 1)
a) Ts ˆ tosyl ˆ 4-MeC6H4SO2. b) Isolated yield. c) The ratio of the products was determined by 1H-NMR
analysis. d) The ipso rearrangement product was also produced (13%); the product was 3-methyl-4-[(4-
methylphenyl)sulfonyl]phenol.
‡
cation, MeC6H4SO2 is involved, which is very similar to the occurrence of the acyl
‡
cation ArCO in the mechanism proposed for the formation of aromatic ketones in
PPA [25].
The sulfonylation of p-chlorophenol (5) with p-toluensulfonic acid (1) in the
presence of GMA (Scheme 3) was monitored by 1H-NMRspectroscopy under
different reaction conditions. The results (Table 2) clearly established that, in all cases,
first aryl sulfonate 6 was formed, which then decomposed to give the final product 7, the
rate of its formation increasing with increasing temperature (Scheme 3).
The intermediacy of the aryl sulfonate was confirmed by exposing sulfonate 6 for
1 h to GMA at 1208, which gave sulfonylphenol 7 in 95% yield.
The following mechanism of the sulfonylation reaction is thus suggested: the phenol
is first converted to the aryl sulfonate by reaction with p-toluenesulfonic acid (1). The
aryl sulfonate subsequently undergoes rapid intermolecular decomposition in the

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Helvetica Chimica Acta ± Vol. 88 (2005)
Scheme 3
Table 2. Sulfonylation of p-Chlorophenol (5) with p-Toluenesulfonic Acid (1) in the Presence of GMA
Entry
Time [h]
Temp. [8]
Yield [%]a)b)
6
7
1
2
3
4
5
6
7
8
9
8
0.5
2
4
8
12
1
2
4
0.5
1
50
80
80
80
80
±
±
17
35.4
40
32.7
29
36
34.6
15
12
±
±
±
±
21.7
42.3
±
26.4
42
±
80
100
100
100
120
120
120
10
11
12
45
75
2
5
b
a) Isolated yield. ) The ratio of the products was determined by H-NMRanalysis.
1
presence of GMA (thia-Fries rearrangement) to produce the sulfonylium cation
‡
MeC6H4SO2 and the phenol, which combine to form the sulfonylphenols (Scheme 3)
To establish the intermediacy of a free sulfonylium cation in the sulfonation
reaction in the presence of CMA (Scheme 3), the trapping of the cation by a
sulfonylium acceptor should afford the same products as those obtained from the
normal thia-Fries rearrangement. Thus, we first tested if m-xylene (8) would be an
appropriate competitive acceptor by exposing it at 1208 for 2 h to 1 in the presence of
GMA; this was the case, since sulfonylxylene 9 was isolated in 70% yield (Scheme 4).
We then treated a mixture of sulfonate 6 and 2.5 equiv. of m-xylene (8) with GMA at
1208 (Scheme 4). After 1 h, no thia-Fries rearrangement product 7 was formed, and
only compound 9 was obtained (see Table 3). Extending the reaction time to 4 h
resulted in an equilibrium mixture containing only 14% of 7, which was rather poor but
reasonable because the aromatic ring of p-chlorophenol (5) also is reactive such as that

Helvetica Chimica Acta ± Vol. 88 (2005)
47
Scheme 4
Table 3. Progress of the Thia-Fries Rearrangement of Aryl Sulfonate 6 in the Presence of m-Xylene
Time [h]
Temp. [8]
Yield [%]
6
7
9
0.5
1
2
3
4
120
120
120
120
120
65
55
45
30
11
±
±
5
10
14
35
45
50
60
75
of m-xylene (8). Considering these results, it can be safely concluded that the formation
of sulfonylphenols by a thia-Fries rearrangement of the aryl sulfonate 6 occurs via an
intermolecular mechanism.
The application of the new reagent to the thia-Fries rearrangement of other aryl
sulfonates was also successful (see Table 4). Thus, GMA rearranged the aryl sulfonates
to the same sulfonylphenols as those obtained in the sulfonylations of the correspond-
ing phenols (cf. Tables).
In conclusion, we have demonstrated that the readily available and inexpensive
reagent graphite/MeSO3H (GMA) is very effective for the direct sulfonylation of
phenol and naphthalenol derivatives with p-toluenesulfonic acid (1) and for the thia-
Fries rearrangement of aryl sulfonates. The simple procedure and workup, the lack of
solvent in the reaction step, and the high 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 industry.
We gratefully acknowledge the support of this work by the Shiraz University Research Council.

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Helvetica Chimica Acta ± Vol. 88 (2005)
Table 4. Thia-Fries Rearrangement of Aryl Sulfonates by Using a Mixture of Graphite and MeSO3H (GMA) at
1208
Aryl sulfonate
Time [h]
1
Productsa)
Yield [%]b) (ortho/para)c)
85 (1 : 2)
1
1
1
80 (1 : 3)
90 (1 : 2)
90d)
1
1
1
1
1
95
90
85
80
75 (1 : 1)

Helvetica Chimica Acta ± Vol. 88 (2005)
49
Table 4 (cont.)
Aryl sulfonate
Time [h]
Productsa)
Yield [%]b) (ortho/para)c)
1
85
12
no reaction
±
12
12
no reaction
no reaction
±
±
1
90 (10 : 1)
c
a) Ts ˆ tosyl ˆ 4-MeC6H4SO2. b) Isolated yield. ) The ratio of the products was estimated by 1H-NMRanalysis.
d) The ipso rearrangement product was also produced (10%); the product was 3-methyl-4-[(4-methylphenyl)-
sulfonyl]phenol.
Experimental Part
General. All starting materials, p-toluenesulfonic acid (1) and phenols, were used as purchased from Fluka
or Merck. Graphite (flake-type; Aldrich) and 98% methanesulfonic acid were purchased from Fluka. UV
Spectra: lmax (e) in nm. IRSpectra: n in cmÀ1. NMRSpectra: d in ppm. MS: in m/z (rel. %).
Direct Sulfonylation of Phenols: General Procedure. To a mixture of graphite (3 g) and methanesulfonic
acid (10 ml) at 1208, 1 (20 mmol) and a phenol derivative (20 mmol) were added, and the mixture was stirred for
2 h. Then the mixture was poured into H2O, and the graphite was filtered off. The filtrate was extracted with
CHCl3 (2 Â 25 ml), the extract washed with 5% NaHCO3 soln. (2 Â 20 ml), dried (CaCl2), and evaporated, and
the crude product purified by column chromatography (silica gel, hexane/AcOEt).
Thia-Fries Rearrangement of Aryl Sulfonates: General Procedure. To a mixture of graphite (3 g) and
methanesulfonic acid (10 ml) at 1208, the aryl sulfonate (20 mmol) was added and stirred for 1 h. Then the
mixture was poured into H2O and worked up as described above. The synthesized sulfonylphenols are known.
Specific detailed data are given below:
2-[(4-Methylphenyl)sulfonyl]phenol [26]: White crystals. M.p. 124 ± 1258 ([26]: 1268), IR(neat): 3292, 1590,
1361, 1145. 1H-NMR(CDCl 3, 250 MHz): 2.42 (s, 3 H); 7.00 (m, 2 H); 7.30 (d, 2 H); 7.45 (d, 1 H); 7.65 (d, 1 H);
‡
7.84 (d, 2 H); 9.26 (s, 1 H). MS: 248 (59.6, M ), 172 (23.5), 94 (58.2), 65 (100).

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Helvetica Chimica Acta ± Vol. 88 (2005)
4-[(4-Methylphenyl)sulfonyl]phenol [26]: White crystals. M.p. 143 ± 1448 ([26]: 1438). IR(neat): 3375, 1585,
1284, 1144. 1H-NMR(CDCl 3, 250 MHz): 2.38 (s, 3 H); 6.30 (s, 1 H); 6.90 (d, 2 H); 7.37 (d, 2 H); 7.79 (d, 4 H).
‡
MS: 249 (100, M ), 141 (45.8), 108 (43.4), 91 (32.6), 65 (66.2), 43 (54.7).
2-Methyl-6-[(4-methylphenyl)sulfonyl]phenol [27]: White crystals. M.p. 130 ± 1318 ([27]: 130 ± 1328). IR
1
(neat): 3330, 1593, 1284, 1144. H-NMR(CDCl 3, 250 MHz): 2.45 (s, 3 H); 2.58 (s, 3 H); 6.80 (t, 1 H); 7.35 (d,
‡
3 H); 7.85 (d, 2 H); 9.30 (s, 1 H). MS: 262 (100, M ), 195 (17.6), 155 (64.6), 107 (93.0), 65 (41.3), 43 (68.5).
2-Methyl-4-[(4-methylphenyl)sulfonyl]phenol [27]: White crystals. M.p. 117 ± 1198 ([27]: 1208). IR(neat):
3367, 1590, 1283, 1147. 1H-NMR(CDCl 3, 250 MHz) 2.25 (s, 3 H); 2.38(s, 3 H); 5.40 (s, 1 H); 6.80 (d, 1 H); 7.25
‡
(d, 2 H); 7.66 (d, 2 H); 7.78 (d, 2 H). MS: 262 (0.2, M ), 247 (98.2), 155 (11.0), 139 (100), 107 (11.1), 91 (32.7),
65 (35.9), 43 (15.1).
5-Methyl-2-[(4-methylphenyl)sulfonyl]phenol [28]: White crystals. M.p. 144-1458 ([28]: 145 ± 1478). IR
1
(neat): 3315, 1594, 1300, 1149. H-NMR(CDCl 3, 250 MHz): 2.30 (s, 3 H); 2.38 (s, 3 H); 6.65 (s, 1 H); 6.78 (d,
‡
1 H); 7.31 (d, 2 H); 7.47 (d, 2 H); 7.77 (d, 2 H); 9.16 (s, 1 H). MS: 262 (45.4, M ), 246 (33.4), 228 (25.7), 180
(37.9), 139 (100), 107 (21.5), 91 (91.4), 65 (83.1).
3-Methyl-4-[(4-methylphenyl)sulfonyl]phenol [28]: White crystals. M.p. 150-1518 ([28] 151 ± 1528). IR
1
(neat): 3366, 1595, 1317, 1153. H-NMR(CDCl 3, 250 MHz): 2.32 (s, 3 H); 2.40 (s, 3 H); 6.41 (s, 1 H); 6.65 (s,
‡
1 H); 6.79 (d, 1 H); 7.26 (d, 2 H); 7.69 (d, 2 H); 8.04 (d, 1 H). MS: 262 (24.7, M ), 244 (25.0), 227 (12.1), 196
(100), 153 (50.0), 107 (26.4), 77 (99.8).
4-Methyl-2-[(4-methylphenyl)sulfonyl]phenol [26]: White crystals. M.p. 133 ± 1348 ([26] 1358). IR(neat):
3319, 1595, 1367, 1147. 1H-NMR(CDCl 3, 250 MHz): 2.26 (s, 3 H); 2.4 (s, 3 H); 6.9 (d, 1 H); 7.25 (d, 3 H); 7.34 (s,
‡
1 H); 7.83 (d, 2 H); 9.08 (s, 1 H). MS: 262 (26.0, M ), 186 (51.9), 107 (100), 77 (73.8), 51 (22.5).
4-Chloro-2-[(4-methylphenyl)sulfonyl]phenol [28]: White needles. M.p. 127 ± 1288 ([28]: 1278). IR(neat):
3386, 1596, 1290, 1141, 817. 1H-NMR(CDCl 3, 250 MHz): 2.32 (s, 3 H); 6.68 (d, 1 H); 7.13 (d, 2 H); 7.24 (s, 1 H);
‡
7.73 (d, 2 H); 9.10 (s, 1 H). MS: 282 (63.5, M ), 215 (26.1), 126 (14.5), 108 (15.8), 92 (100), 65 (54.9), 41 (23.4).
2-Chloro-4-[(4-methylphenyl)sulfonyl]phenol [26]: White cubic crystals. M.p. 174 ± 1758 ([26]: 1768). IR
(neat): 3327, 1584, 1303, 1132, 737. 1H-NMR(CDCl 3, 250 MHz): 2.33 (s, 3 H); 6.07 (s, 1 H); 7.02 (d, 1 H); 7.23 (d,
‡
2 H); 7.69 (d, 3 H); 7.85 (s, 1 H). MS: 282 (82.3, M ), 175 (40.7), 139 (77.1), 108 (91.7), 9 (100), 65 (98.6), 41
(53.7).
5-Fluoro-2-[(4-methylphenyl)sulfonyl]phenol [29]: White crystals. M.p. 128 ± 1308. IR(neat): 3345, 1591,
1
1279, 1148, 1090. H-NMR(CDCl 3, 250 MHz): 2.35 (s, 3 H); 6.60 (d, 1 H); 7.19 (s, 1 H); 7.24 (d, 2 H); 7.58 (t,
‡
1 H); 7.72 (d, 2 H); 9.35 (s, 1 H). MS: 266 (98.4, M ), 202 (20.1), 155 (22.6), 139 (22.2), 108 (47.1), 91 (100), 65
(65.6).
3-Fluoro-4-[(4-methylphenyl)sulfonyl]phenol [29]: White crystals. M.p. 124 ± 1268. IR(neat): 3405, 1609,
1
1319, 1140, 1248. H-NMR(CDCl 3, 250 MHz): 2.34 (s, 3 H); 6.50 (d, 1 H); 6.68 (s, 1 H); 7.07 (s, 1 H); 7.26 (d,
‡
2 H); 7.76 (d, 3 H). MS: 266 (44.7, M ), 159 (26.8), 139 (37.4), 108 (65.8), 91 (57.5), 65 (50.1), 43(100).
2-[(4-Methylphenyl)sulfonyl]naphthalen-1-ol [26]: White crystals. M.p. 128 ± 1308 ([26]: 1298). IR(neat):
3150, 1570, 1120, 1350. 1H-NMR(CDCl 3, 250 MHz): 2.37 (s, 3 H); 7.30 (d, 2 H); 7.60 (m, 4 H); 7.65 (d, 1 H); 7.85
‡
(d, 2 H); 8.40 (d, 1 H); 10.46 (s, 1 H, OH). MS: 298 (91.9, M ), 191 (19.8), 162 (10.4), 139 (57.9), 115 (50.2), 91
(42.6), 59 (47.5), 43 (100).
4-[(4-Methylphenyl)sulfonyl]-1-naphthalen-1-ol [26]: White crystals. M.p. 1608 ([26]: 1638). IR(neat):
3200, 1600, 1110, 1360. 1H-NMR(CDCl 3, 250 MHz): 2.38 (s, 3 H); 6.93 (m, 4 H); 7.26 (d, 2 H); 7.85 (d, 1 H); 7.90
‡
(d, 2 H); 8.10 (s, 1 H); 8.21 (d, 1 H). MS: 298 (100, M ); 265 (11.5), 234 (23.1), 206 (22.7), 142 (73.2), 114 (64.6),
91 (47.4), 65 (48.2), 43 (43.5).
4-[(4-Methylphenyl)sulfonyl]benzene-1,3-diol [30]: White crystals. M.p. 160 ± 1628 ([30]: 155 ± 1578): UV
(CHCl3): 308.4 (1993). IR(neat): 3358, 1595, 1334, 1136. 1H-NMR(CDCl 3, 250 MHz): 2.33 (s, 3 H); 5.62 (s,
1 H); 6.37 (d, 2 H); 7.20 (d, 2 H); 7.43 (d, 1 H); 7.71 (d, 2 H); 9.20 (s, 1 H). 13C-NMR(CDCl 3, 62.9 MHz): 22.01;
‡
105.02; 109.34; 126.95; 127.25; 130.42; 131.49; 132.82; 149.50; 154.32. MS: 264 (100, M ), 199 (21.1), 157 (22.1),
125 (14.31), 108 (33.8), 91 (60.0), 65 (57.3).
4-Bromo-2-[(4-methylphenyl)sulfonyl]phenol [31]: White needles. M.p. 145 ± 1468. UV (CHCl3): 251
(2909), 307.7 (1180). IR(neat): 3388, 1469, 1290, 1141, 131. 1H-NMR(CDCl 3, 250 MHz): 2.43 (s, 3 H); 6.89 (d,
1 H); 7.34 (d, 2 H); 7.51 (d, 1 H); 7.73 (s, 1 H); 7.81 (d, 2 H); 9.37 (s, 1 H). 13C-NMR(CDCl 3, 62.9 MHz): 22.05;
‡
121.12; 125.47; 125.95; 127.42; 129.81; 130.67; 134.80; 138.33; 145.83; 145.66. MS: 328 (46.9, M ), 261 (12.2), 181
(10.5), 139 (28.0), 108 (16.4), 92 (100), 65 (58.4), 43 (47.6).
2-Bromo-4-[(4-methylphenyl)sulfonyl]phenol [31]: White crystals. M.p. 170 ± 1728. UV (CHCl3): 257.6
(2801), 301.3 (1778). IR(neat): 3327, 1593, 1299, 1110, 723. 1H-NMR(CDCl 3, 250 MHz): 2.41 (s, 3 H); 6.85 (t,
1 H); 7.31 (d, 2 H); 7.64 (d, 2 H); 7.82 (d, 2 H); 9.56 (s, 1 H). 13C-NMR(CDCl 3, 62.9 MHz): 21.96; 111.06; 117.07;

Helvetica Chimica Acta ± Vol. 88 (2005)
51
‡
127.89; 129.38; 130.42; 132.31; 135.30; 138.93; 144.75; 156.82. MS: 326 (6.4, M ), 155 (38.5), 108 (12.4), 91
(82.0), 69 (42.3), 43 (100).
2,4-Dimethyl-1-[(4-methylphenyl)sulfonyl]benzene (9) [23]: White crystals. M.p. 508 ([23]: 498). IR(neat):
1155, 1310 (OˆSˆO). 1H-NMR(CDCl 3, 250 MHz): 2.27 (s, 1 Me); 2.31 (s, 2 Me); 6.71 (s, 1 H); 7.08 (d, 1 H);
‡
7.14 (d, 2 H); 7.76 (d, 2 H); 8.01 (d, 1 H). MS: 276 (M ), 228 (41.0), 180 (6.6 ), 103 (12.5), 91 (83.0), 77 (100), 51
(43.0).
Aryl Sulfonate Derivatives: General Procedure [32]. A phenol (0.05 mol) and p-toluenesulfonyl chloride
(0.05 mol) were dissolved in acetone (50 ml) and the mixture was stirred at r.t. with a mechanical stirrer. Then
25% K2CO3 soln. (40 ml) was added gradually within 30 min. The sulfonate was filtered and treated with 10%
aq. NaOH soln. The product was again filtered and crystallized from EtOH.
The produced aryl sulfonates are known. Specific detailed data are given below:
3-Methylphenyl 4-Methylbenzenesulfonate (4) [32]: White crystals. M.p. 63 ± 648 ([321]: 62 ± 638). IR(neat):
1529, 1363, 1179. 1H-NMR(CDCl 3, 250 MHz): 2.31 (s, 3 H); 2.46 (s, 3 H); 6.74 (d, 2 H); 6.88 (s, 1 H); 6.95 (d,
‡
2 H); 7.04 (d, 1 H). MS: 262 (17.2, M ), 155 (45.2), 91 (100), 77 (25.1), 65 (35.2), 51 (14.7).
4-Methylphenyl 4-Methylbenzenesulfonate [32]: White needles. M.p. 70 ± 728 ([32]: 67 ± 688). IR(neat):
1595, 1376, 1175. 1H-NMR(CDCl 3, 250 MHz): 2.21 (s, 3 H); 6.75 (d, 2 H); 6.97 (d, 2 H); 7.22 (d, 2 H); 7.61 (d,
‡
2 H). MS: 262 (22.5, M ), 153 (43.7), 107 (20.1), 91 (100), 77 (45.7), 65 (45.7), 51 (23.4).
2-Methylphenyl 4-Methylbenzenesufonate [32]: White crystals. M.p. 52 ± 538 ([32]: 518). IR(neat): 1596,
1375, 1192. 1H-NMR(CDCl 3, 250 MHz): 2.01 (s, 3 H); 2.50 (s, 3 H); 6.78 (d, 1 H); 7.25 (m, 3 H); 7.35 (d, 3 H);
‡
7.72 (d, 3 H). MS: 262 (18.7, M ), 155 (43.9), 91 (100), 77 (44.7), 65 (45.7), 51 (23.4).
Phenyl 4-Methylbenzenesulfonate [32]: White crystals. M.p. 100 ± 1028 ([32]: 96 ± 988). IR(neat): 1595,
‡
1382, 1176. 1H-NMR(CDCl 3, 250 MHz): 2.47 (s, 3 H); 7.00 (d, 2 H); 7.70 (d, 2 H). MS: 248 (20.3, M ), 155
(44.9), 91 (100), 65 (58.1).
4-Chlorophenyl 4-Methylbenzenesulfoate (6) [32]: White crystals. M.p. 78 ± 798 ([32], 79 ± 818). IR(neat):
1596, 1379, 1174, 754. 1H-NMR(CDCl 3, 250 MHz): 2.38 (s, 3 H); 6.82 (d, 2 H); 7.15 (d, 2 H); 7.24 (d, 2 H); 7.24
‡
(d, 2 H); 7.95 (d, 2 H). MS: 282 (17.1, M ), 155 (59.71), 91 (100), 65 (27.9).
4-Bromophenyl 4-Methylbenzenesulfonate [33]: White crystals. M.p. 92 ± 938 ([33]: 93 ± 958). IR(neat):
1596, 1377, 1172 , 748. 1H-NMR(CDCl 3, 250 MHz): 2.47 (s, 3 H); 6.88 (d, 2 H); 7.29 (d, 2 H); 7.41 (d, 2 H); 7.71
‡
(d, 2 H). MS: 326 (14.6, M ), 155 (71.3), 91 (100), 65 (29.4).
2-Chlorophenyl 4-Methylbenzenesulfonate [32]: White crystals. M.p. 81 ± 828 ([32]: 81 ± 838). IR(neat):
1596, 1373,118, 765. 1H-NMR(CDCl 3, 250 MHz): 2.55 (s, 3 H); 7.30 (m, 4 H); 7.45 (d, 2 H); 7.82 (d, 2 H). MS:
‡
282 (23.4, M ), 155 (87.7), 91 (100), 65 (30.8).
2-Bromophenyl 4-Methylbenzenesulfonate [33]: White crystals. M.p. 78 ± 798 ([33]: 77 ± 798). IR(neat):
1595, 1301, 1176, 763. 1H-NMR(CDCl 3, 250 MHz): 2.46 (s, 3 H); 7.13 (d, 2 H); 7.3 (m, 3 H); 7.51 (d, 2 H); 7.81
‡
(d, 2 H). MS: 326 (18.0, M ), 155 (99.6), 91 (100), 65 (28.0).
3-Fluorophenyl 4-Methylbenzenesulfonate [33]: White solid. M.p. 56 ± 588 ([33]: 55 ± 578). IR(neat): 1483,
1
1379, 1178, 1093. H-NMR(CDCl 3, 250 MHz): 2.46 (s, 3 H); 6.78 (t, 2 H); 7.00 (d, 1 H); 7.23 (d, 2 H); 7.72 (d,
‡
2 H). MS: 266 (21.7, M ), 155 (68.1), 91 (100), 65 (34.3).
Benzene-1,3-diol Bis(4-methylbenzenesulfonate) [33]: White crystals. M.p. 62 ± 648 ([33]: 63 ± 658). IR
(neat): 1595, 1375, 1178. 1H-NMR(CDCl 3, 250 MHz): 2.38 (s, 6 H); 6.59 (s, 1 H); 6.85 (d, 2 H); 7.16 (t, 1 H); 7.26
‡
(d, 4 H); 7.64 (d, 4 H). MS: 418 (10.9, M ), 199 (14.0), 155 (65.7), 91 (100), 65 (30.5).
3-Nitrophenyl 4-Methylbenzenesulfonate [33]: White crystals. M.p. 112 ± 1148 ([33]: 114 ± 1158). IR(neat):
1593, 13001, 1527, 1350, 1149. 1H-NMR(CDCl 3, 250 MHz): 2.49 (s, 3 H); 7.28 (d, 2 H); 7.46 (t, 1 H); 7.75 (d,
‡
2 H); 7.8 (s, 1 H); 8.14 (d, 1 H). MS: 293 (9.03, M ), 155 (98.2), 91 (100), 65 (33.5).
4-Nitrophenyl 4-Methylbenzenesulfonate [33]: White crystals. M.p. 98 ± 1008 ([33]: 978). IR(neat): 1589,
1300, 1527, 1350, 1149. 1H-NMR(CDCl 3, 250 MHz): 2.50 (s, 3 H); 7.25 (d, 2 H); 7.35 (d, 2 H); 7.77 (d, 2 H); 8.55
‡
(d, 2 H). MS: 293 (12.0, M ), 155 (100.0), 91 (100), 65 (39.9).
Benzene-1,4-diol Bis(4-methylbenzenesulfonate) [33]: White solid. M.p. 1628 ([33]: 163 ± 1648). IR(neat):
1596, 1371, 1199. 1H-NMR(CDCl 3, 250 MHz): 2.50 (s, 6 H); 6.85 (s, 4 H); 7.55 (d, 4 H); 7.75 (d, 4 H). MS: 418
‡
(13.0, M ), 155 (100), 91 (79.3), 65 (24.0).
Naphthalen-1-ol-4-Methylbenzenesulfonate [32]: White crystals. M.p. 100 ± 1018 ([32]: 99 ± 1008). IR(neat):
1
1600, 1350, 1170. H-NMR(CDCl 3, 250 MHz): 2.4 (s, 3 H); 7.26 (m, 6 H); 7.42 (d, 2 H); 7.82 (d, 2 H); 7.90 (d,
‡
1 H). MS: 298 (47.6, M ), 143 (100), 115 (86.8), 91 (45.4), 65 (24.3).

52
Helvetica Chimica Acta ± Vol. 88 (2005)
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Received July 12, 2004