Sodium periodate catalyzed selective sulfonylation of aromatics

Article abstract of DOI:10.1246/cl.2002.1066

Sodium periodate catalyzed sulfonylation of aromatics with p-toluenesulfonyl chloride gives the corresponding sulfones in good yield under neutral conditions.

Full text of DOI:10.1246/cl.2002.1066

1
066
Chemistry Letters 2002
Sodium Periodate Catalyzed Selective Sulfonylation of Aromatics
ꢀ
B. P. Bandgar and V. T. Kamble
Organic Chemistry Research Laboratory, School of Chemical Sciences, Swami Ramanand Teerth Marathwada University,
Vishnupuri, Nanded 431 606, India
(Received March 11, 2002; CL-020232)
Sodium periodate catalyzed sulfonylation of aromatics with
p-toluenesulfonyl chloride gives the corresponding sulfones in
good yield under neutral conditions.
Table 2. NaIO4 catalyzed sulfonylation of aromatics
a,b
Time Yield
Entry
a
Arene
Product
/
h
%
O
S
CH3
7
75
As a useful intermediate, sulfones have received consider-
1
O
able attention in organic synthesis, as well as in industrial
2
O
S
application. A well known procedure for the preparation of
b
CH3
7
76
sulfones is the oxidation of sulfides and sulfoxides or by a
displacement reaction using sodium arenesulfinate. The former
method suffers by foul smelling of the starting material while the
sulfinate method requires longer reaction times, anhydrous
O
O
S
O
CH3
CH3
CH3
c
9
7
79
84
86
3
;4
conditions and moderate yield of sulfones. Other methods
such as aluminium(III)chloride 1a which relies on its stoichio-
metric use are associated with purification problems. Sulfones are
O
S
O
O
S
d
F
F
Cl
Br
5
also prepared by the catalytic use of zeolites, Fe(III)exchanged
6
7
montmorillonite clay and bismuth(III)triflate. For the sulfony-
lation of unactivated aromatics, the most effective reported
catalyst is bismuth(III)triflate but this is not commercially
e
Cl
Br
7
7
O
O
S
O
available and has to be prepared from triphenyl bismuth and triflic
acid. More recently, indium(III)triflate 8 have been reported to
f
CH3
CH3
83
catalyze the sulfonylation of activated and unactivated aromatics.
Although several methods are reported for the preparation of
O
S
O
O
S
O
O
S
g
I
7
3
5
83
89
82
I
H3CO
H3C
sulfones under acidic conditions1
{3;5{8
and basic conditions, the
4
synthesis of sulfones under neutral conditions has not been
reported so far in the literature. Therefore, synthesis of diaryl
sulfones using inexpensive and neutral reagent is highly
desirable. In this communication, we wish to disclose our
preliminary results on the synthesis of diaryl sulfones using
sodium periodate as a catalyst under neutral conditions (Scheme
h
i
H3CO
H3C
CH3
CH3
CH3
O
H3C
H3C
H3C
1
).
O
S
j
5
H3C
H3C
H3C
83
82
O
CH3
NaIO4
H3C
O
Ar-H
1
CH C H SO Cl
ArSO C H CH
2 6 4 3
3
6
4
2
H3C
H3C
k
l
S
CH3 4.5
2
3
O
Scheme 1.
CH3
CH3
H3C
O
4
82
S
CH3
O
H3C
Table 1. A catalytic study of NaIO4 during sulfonylation of anisole
10 ml)with p-toluenesulfonyl chloride (5 mmol)at reflux temperature
O
S
O
(
CH3
m
9
75
Entry
NaIO4/mol%
Time/h
Yield/%
S
S
1
2
3
4
5
6
7
—
5
3
3
3
3
3
3
3
—
55
60
65
89
85
85
a
b
Yields are of pure isolated products. Products are characterized
by their physical constants and spectral analysis.
10
15
20
25
30
The catalytic activity of the sodium periodate was then
investigated with respect to the loadings. After much studies on
sulfonylation of anisole (10 ml)with p-toluenesulfonyl chloride
5 mmol)under reflux conditions, we found that when less than
(
Copyright Ó 2002 The Chemical Society of Japan

Chemistry Letters 2002
0 mol% of sodium periodate was applied, it resulted in low yield
of the corresponding product (Table 1, entries 2–4), whereas use
of more than 20 mol% did not improve the yield (Table 1, entries
1067
refluxed for 3 h. On completion of the reaction (TLC), the reaction
mixture was cooled and anisole was removed under reduced pressure.
To the residue chloroform (10 ml)and water (10 ml)was added. The
aqueous layer was washed with chloroform (3 Â 5 ml). The combined
organic layer was dried with anhydrous Na2SO4 and removal of the
solvent under vacuum furnished crude product which was further
2
6–7). When attempts were made to carry out sulfonylation of
anisole (10 ml)with p-toluenesulfonyl chloride (5 mmol)in the
absence of catalyst, sodium periodate, it resulted in almost
quantitative recovery of the substrate (Table 1, entry 1). The
sulfonylation of anisole in the presence of 20 mol% of sodium
purified
by
column
chromatography
(petroleum ether :
ethyl acetate ¼ 8 : 2). In case of solid substrates, nitrobenzene
(
10 ml)was used as
ꢁ
a
ꢁ
solvent.
12
3a: (Phenyl)-p-tolyl sulfone:
À1
mp ¼ 126 C (lit. 127 C); IR (KBr, cm ): 1153, 1303, 1500,
ꢁ
periodate under mild conditions (25 C)was failed even after
1
1
604; H NMR (300 MHz, CDCl3): ꢂ 2.4 (s, 3H, Ar-CH3), 7.2(d, 2H,
stirring the reaction mixture for 15 h. A plausible mechanism may
involve the formation of p-toluenesulfonyl periodate when
sodium periodate is used as a catalyst.
J ¼ 7:8 Hz, Ar-H), 7.4–7.8 (m, 5H, Ar-H), 8.01 (d, 2H, J ¼ 7:8 Hz, Ar-
ꢁ
À1
H). 3b: (Biphenyl)-p-tolyl sulfone: mp 155 C; IR (KBr, cm )1160,
1
1
7
312, 1512, 1601; H NMR (300 MHz, CDCl3): ꢂ 2.36 (s, 3H, Ar-CH3),
.11–7.24 (m, 5H, Ar-H), 7.75 (d, 2H, J ¼ 8:2 Hz, Ar-H), 7.89 (d, 2H,
9
The sulfonylation of various aromatics were carried out and
J ¼ 7:9 Hz, Ar-H), 8.1 (d, 2H, J ¼ 7:9 Hz, Ar-H), 8.3 (d, 2H,
the results are summarized in Table 2. It was observed that for the
sulfonylation of activated aromatics less reaction time was
required (Table 2, entries h–l)as compared to the unactivated and
heterocyclic aromatics (Table 2, entries a–g and m). It is
important to note that the selectivity of the reaction is impressive
in the reported examples wherein exclusively para isomers of
diaryl sulfones are obtained in good yields without detection or
ꢁ
J ¼ 8:2 Hz, Ar-H). 3c: (ꢀ-Naphthyl)-p-tolyl sulfone: mp ¼ 164 C;
À1
1
IR (KBr, cm ): 1155, 1305, 1509, 1607; H NMR (300 MHz, CDCl ):
3
ꢂ2.33 (s, 3H, Ar-CH3)7.06–7.15 (m, 4H, Ar-H), 7.7 (d, 2H, J ¼ 7:7 Hz,
Ar-H), 7.8 (d, 1H, J ¼ 8:1 Hz, Ar-H), 8.1 (dd, 1H, J ¼ 1:3 Hz, 8.1 Hz,
Ar-H), 8.2 (d, 1H, J ¼ 1:3 Hz, Ar-H), 8.3 (d, 2H, J ¼ 7:7 Hz, Ar-H). 3d:
ꢁ
ꢁ
12
(
cm ): 629, 775, 816, 880, 1050, 1110, 1175, 1355, 1590, 3390,; H
4-Fluorophenyl)-p-tolyl-sulfone: mp ¼ 93 C; (lit. 95 C); IR (KBr,
À
1
1
NMR (300 MHz, CDCl ): ꢂ 2.42 (s, 3H, Ar-CH ), 7.20 (m, 2H, Ar-H),
3
3
isolation of ortho/meta isomers in trace amounts. On the other
hand, recently reported indium(III)triflate 8 catalyzed sulfonyla-
tion of activated aromtics (e.g. anisole, toluene)yields a mixture
7.35 (d, 2H, J ¼ 8:4 Hz, Ar-H)7.85 (d, 2H, J ¼ 8:4 Hz, Ar-H), 7.91–
7.98 (m, 2H, Ar-H). 3e: (4-Chlorophenyl)-p-tolyl sulfone:
mp ¼ 124 C; (lit-123 C); IR (KBr, cm ): 626, 772, 885, 816,
ꢁ
ꢁ
11
À1
1
9
90, 1040, 1100, 1175, 1353, 1599, 3397; H NMR (300 MHz, CDCl3):
of isomers with the composition of ortho : meta : para ¼
ꢂ 2.38 (s, 3H, Ar-CH3), 7.34 (d, 2H, J ¼ 7:7 Hz, Ar-H), 7.43–7.52 (m,
3
8 : 0 : 62. Also aluminium(III)chloride 10 gives mixtures of
2H, Ar-H), 7.82 (d, 2H, J ¼ 9:0 Hz, Ar-H), 7.86-7.92 (m, 2H, Ar-H). 3f:
ꢁ
isomers (e.g. ditolyl sulfones)with the composition of ortho :
meta : para ¼ 29 : 7 : 65 and it generates an enormous amount of
(4-Bromophenyl)-p-tolyl sulfone: mp ¼ 136–137 C; (lit. 135–
ꢁ 12 À1
1
36 C); IR (KBr, cm ): 626, 772, 816, 895, 1030, 1120, 1175,
1
7
1360, 1580, 3410; H NMR (300 MHz, CDCl3): ꢂ 2.49 (s, 3H, Ar-CH3),
solid waste. Similarly bismuth(III)triflate gives a mixture of
7
.48 (d, 2H, J ¼ 8:5 Hz, Ar-H), 7.76–7.91 (m, 4H, 4 Â Ar-H), 7.98 (d,
isomers (e.g. ditolyl sulfones)with the composition of
ortho : meta : para ¼ 29 : 5 : 66. In this regard the present
method is superior because it gives selectively p-ditolyl sulfones
in good yield (Table 2, entry i). Further, the improvement in
regioselectivity is also observed using sodium periodate in
sulfonylation of naphthalene with p-toluenesulfonyl chloride
giving only ꢀ-isomer without formation of ꢁ-isomer in trace
amounts. On the other hand sulfonylation of naphthalene using
ꢁ
2H, J ¼ 8:5 Hz, Ar-H). 3g: (4-Iodophenyl)-p-tolyl sulfone: mp 140 C;
IR (KBr, cm ): 621, 778, 801, 904, 1050, 1107, 1160, 1355, 1518,
1600; H NMR (300 MHz, CDCl3): ꢂ 2.4 (s, 3H, Ar-CH3), 7.76 (d, 2H,
À1
1
J ¼ 7:7 Hz, Ar-H), 7.72 (d, 2H, J ¼ 8:4 Hz, Ar-H), 8.1 (d, 2H,
J ¼ 8:4 Hz, Ar-H), 8.21 (d, 2H, J ¼ 7:7 Hz, Ar-H). 3h: (4-Meth-
ꢁ
ꢁ
11
oxyphenyl)-p-tolyl sulfone: mp ¼ 105 C; (lit. 104 C); IR (KBr,
À1
1
cm ): 683, 838, 1007, 1360, 1599, 2910, 3300; H NMR (300 MHz,
CDCl ): ꢂ 2.36 (s, 3H, CH ), 3.81 (s, 3H, OCH ), 6.95 (d, 2H,
3
3
3
J ¼ 7:2 Hz, Ar-H), 7.91 (d, 2H, J ¼ 7:2 Hz, Ar-H), 7.15(d, 2H,
J ¼ 8:8 Hz, Ar-H), 8.14 (d, 2H, J ¼ 8:8 Hz, Ar-H). 3i: Di-p-tolyl
6
the Fe(III)exchanged montmorillonite clay catalyst gave a
mixture of ꢁ- and ꢀ-isomers.
ꢁ
ꢁ
11
À1
sulfone: mp ¼ 156 C; (lit. 156 C) IR (KBr, cm ): 630, 765, 816,
1
9
90, 1035, 1100, 1180, 1360, 1460, 1500, 1600, 3421; H NMR
300 MHz, CDCl3): ꢂ 2.39 (s, 6H, 2 Â Ar-CH3), 7.27 (d, 4H, J ¼ 5 Hz,
 Ar-H), 7.80 (d, 4H, J ¼ 5 Hz, 4  Ar-H). 3j: (3,4-Dimethylphe-
In summary, we have described a novel and highly selective
procedure for the sulfonylation of activated and unactivated
aromatics using sodium periodate under almost neutral condi-
tions.
(
4
ꢁ
À1
nyl)-p-tolyl sulfone: mp 55 C; IR (KBr, cm ): 1017, 1123, 1342,
1
1
2
447, 1515, 1603; H NMR (300 MHz, CDCl3): ꢂ 2.3 (s, 3H, ArCH3),
.36 (s, 3H, Ar-CH3)2.43 (s, 3H, Ar-CH 3), 7.1 (d, 1H, J ¼ 7:5 Hz, Ar-
H), 7.8 (d, 1H, J ¼ 1:5 Hz, Ar-H), 8.0 (dd, 1H, J ¼ 1:5 Hz, 7.5 Hz, Ar-
H)7.5 (d, 2H, J ¼ 8:6 Hz, Ar-H), 8.1 (d, 2H, J ¼ 8:6 Hz, Ar-H). 3k:
References and Notes
ꢁ
ꢁ
11
1
a)F. R. Jensen and G. Goldman, in ‘‘Friedel–Crafts and Related
Reactions,’’ ed. by G. Olah, Wiley Interscience, New York (1964),
Vol. III, pp 1319–1367. b)N. S. Simpkins, ‘‘Sulfones in Organic
synthesis,’’ Pergamon Press, Oxford (1993), and references cited
therein.
(2,4-Dimethylphenyl)-p-tolyl sulfone: mp ¼ 49 C (lit. 48–49 C) IR
À
1
1
(KBr, cm ): 1028, 1110, 1175, 1355, 1455, 1505, 1610;
H
NMR(300 MHz, CDCl ): ꢂ 2.34 (s, 3H, Ar-CH ), 2.38 (s, 3H, Ar-
3
3
CH )2.41 (s, 3H, Ar-CH ), 7.01 (d, 1H, J ¼ 1:7 Hz, Ar-H), 7.16 (dd,
3
3
1H, J ¼ 1:7 Hz, 7.7 Hz, Ar-H), 7.25 (d, 2H, J ¼ 8:8 Hz, Ar-H), 7.77 (d,
2H, J ¼ 8:8 Hz, Ar-H), 8.08 (d, 1H, J ¼ 7:7 Hz, Ar-H). 3l: (2,4,6-
2
3
K. M. Roy, in ‘‘Ullmann’s Encyclopedia of Industrial Chemistry,’’ ed.
by W. Gerhartz, VCH, Weinhelm (1985), Vol. A25, pp 487–501 and
references cited therein.
C. M. Suter, ‘‘The Organic Chemistry of Sulfur,’’ John Wiley and Sons,
New York (1948), pp 568–773.
ꢁ
ꢁ
1
11
Trimethylphenyl)-p-tolyl sulfone: mp ¼ 122 C (lit. 123 C). IR
À1
(KBr, cm Þ: 810, 1011, 1150, 1350, 1460, 1522, 1611; H NMR
(300 MHz, CDCl ): ꢂ 2.32 (s, 3H, Ar-CH ), 2.35 (s, 3H, Ar-CH ), 2.45
3
3
3
(s, 6H, 2 Â Ar-CH ), 7.03 (s, 2H, Ar-H), 7.62 (d, 2H, J ¼ 8:4 Hz, Ar-H),
3
4
5
J. Smeek and J. S. Fowler, J. Org. Chem., 33, 3422 (1968).
K. Smith, G. M. Ewart, and K. R. Randles, J. Chem. Soc., Perkin Trans.
8.2 (d, 2H, J ¼ 8:4 Hz, Ar-H). 3m: (Thiophene)-3-p-tolyl sulfone: mp
ꢁ
À1
1
110 C IR (KBr, cm ): 1160, 1310, 1500, 1610; H NMR (300 MHz,
CDCl ): ꢂ 7.8 (d, 2H, J ¼ 8:1 Hz, Ar-H), 8.02 (d, 2H, J ¼ 8:1 Hz, Ar-
1, 1997, 1085.
3
6
B. M. Choudary, N. S. Chowdari, M. L. Kantam, and R. Kannan,
Tetrahedron Lett., 40, 2859 (1999).
H), 8.12–8.3 (m, 3H, Ar-H).
10 G. A. Olah, S. Kobayashi, and J. Nishimura, J. Am. Chem. Soc., 95, 564
(1973).
7
8
9
S. Repichet, C. Le Roux, and J. Dubac, J. Org. Chem., 64, 6479 (1999).
C. G. Frost, J. P. Hartley, and A. J. Whittle, Synlett, 6, 830 (2001).
Typical experimental procedure: A mixture of anisole (10 ml), p-
toluenesulfonyl chloride (5 mmol)and sodium periodate (1 mmol)was
11 M. Ueda, K. Uchiyama, and T. Kano, Synthesis, 1984, 323.
12 B. M. Choudary, N. S. Chowdary, and M. L. Kantam, J. Chem. Soc.,
Perkin Trans. 1, 2000, 2689.