Synthesis of polymeric diaryliodonium salts and its use in preparation of diaryl sulfides and diaryl ethers

Article abstract of DOI:10.1081/SCC-100105332

Polymeric diaryliodonium salts were synthesized and applied to the preparation of diaryl ethers and diaryl sulfides under mild conditions. The byproduct, polyiodostyrene, could be recycled and reused.

Full text of DOI:10.1081/SCC-100105332

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SYNTHESIS OF POLYMERIC DIARYLIODONIUM SALTS
AND ITS USE IN PREPARATION OF DIARYL SULFIDES
AND DIARYL ETHERS
Xian Huang a , Qing Zhu a & Yongxi Xu a
a Chemistry Department , Zhejiang University , Xixi Campus, Hangzhou, 310 028, P. R.
China
Published online: 15 Aug 2006.
To cite this article: Xian Huang , Qing Zhu & Yongxi Xu (2001) SYNTHESIS OF POLYMERIC DIARYLIODONIUM SALTS AND ITS
USE IN PREPARATION OF DIARYL SULFIDES AND DIARYL ETHERS, Synthetic Communications: An International Journal for
Rapid Communication of Synthetic Organic Chemistry, 31:18, 2823-2828, DOI: 10.1081/SCC-100105332
To link to this article: http://dx.doi.org/10.1081/SCC-100105332
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SYNTHETIC COMMUNICATIONS, 31(18), 2823–2828 (2001)
SYNTHESIS OF POLYMERIC
DIARYLIODONIUM SALTS AND ITS
USE IN PREPARATION OF DIARYL
SULFIDES AND DIARYL ETHERS
Xian Huang,* Qing Zhu, and Yongxi Xu
Chemistry Department, Xixi Campus,
Zhejiang University, Hangzhou, 310 028, P. R. China
ABSTRACT
Polymeric diaryliodonium salts were synthesized and applied
to the preparation of diaryl ethers and diaryl sulfides under
mild conditions. The byproduct, polyiodostyrene, could be
recycled and reused.
Recently much attention has been paid to hypervalent iodine (III)
compounds in organic synthesis.1 The most widely investigated species
were diaryliodonium salts, which are used today in imaging systems.2 As
arylating agents, they react with various organic substrates under mild con-
ditions. Typical examples of the conditions with anionic nucleophiles under
polar conditions include arylations of thiocarbamates,3 dialkyl phosphates,4
aryl selenides,5 o,o-dialkyl s-aryl phosphoro thiolates,6 etc. However, in
these reactions diaryliodonium salts are converted into iodobenzene,
which is difficult to remove from products and hard to reuse.
*Corresponding author.
2823
Copyright & 2001 by Marcel Dekker, Inc.
www.dekker.com

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HUANG, ZHU, AND XU
Polymeric diaryliodonium salts were widely used as photo and thermal
initiated cationic polymerization.7 No examples cited their synthetic utility
in organic synthesis. In this paper, we report polymeric diaryliodonium salts
were used as aryl transfer reagents to react with sodium phenyloxide or
sodium thiophenyloxide.
Poly[styrene (iodoso diacetate)] was prepared from commercially
available polystyrene (MW 250,000) by literature method.8 To a mixture
of poly[styrene (iodoso diacetate)] and arenes, concentrated sulfuric acid was
added dropwise at room temperature. After 1–3 days, the solution was
poured into cold water to afford polymeric diaryliodonium salts (Scheme
1). IR spectra showed that the characteristic peak of acetate disappeared
and that of bisulfate anion appeared. The exact capacity of functional group
was determined by elemental analysis of sulfur, which indicated that the
functional groups were 1.35–1.53 mmol/g (Table 1).
Scheme 1.
As electrophilic reagent, diaryliodonium salts are more reactive
than aryl halides. Diaryl ethers and diaryl sulfides could be obtained by
the reaction of aryl halides and phenols and thiophenols under critical con-
ditions, such as high temperature and pressure equipment.9 By using poly-
meric diaryliodonium salts, we synthesized the diaryl ether and diaryl sulfide
under comparative mild conditions. A mixture of sodium benzenethiolate or
sodium phenolate and polymeric diaryliodonium salts (3) in DMF was kept
at 100ꢀC for 10 or 24 h (Scheme 2). The arylated products (5) were obtained
in good yield (Table 2).
Table 1. Synthesis of Polymeric Diaryliodonium Salts
Time
(h)
Functional group
(mmol)
Resin
R1
3a
3b
3c
H
CH3
OCH3
72
24
24
1.35
1.48
1.53

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POLYMERIC DIARYLIODONIUM SALTS
2825
Scheme 2.
Table 2. Preparation of Diaryl Ethers and Diaryl Sulfides
Time
(h)
Purity
(%)
Yields
(%)a
Products
Resin
R2
X
5a
5b
5c
5d
5e
5f
5g
5h
5i
3a
3b
3c
3a
3b
3c
3a
3b
3c
3a
3b
3c
3a
3b
3c
3a
3a
H
H
H
CH3
CH3
CH3
NO2
NO2
NO2
H
H
H
CH3
CH3
CH3
Cl
24
24
24
24
24
24
24
24
24
10
10
10
10
10
10
10
24
O
O
O
O
O
O
O
O
O
S
S
S
S
S
S
S
O
90
90
95
85
80
87
85
92
80
84
90
95
88
88
85
90
85
48
58
52
52
65
56
46
62
55
67
76
74
65
88
81
76
46b
5j
5k
5l
5m
5n
5o
5p
5a
H
aIsolated yield.
bBy using polymeric diaryliodonium salt recycled for 3 times.
EXPERIMENTAL SECTION
1H-NMR spectra were recorded at 60 MHz on a Varian EM-300 spec-
trometer from a solution in CCl4 of the products. Infrared spectra were
recorded on a Perkin Elmer 683 spectrophotometer in KBr or film with
absorption in cmÀ1. Poly[styrene (iodoso diacetate)] was prepared according
to the literature method.8

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HUANG, ZHU, AND XU
Preparation of polymeric diaryliodonium salts: To a cold mixture
of 1.0 g poly[styrene (iodoso diacetate)], 10 mL arenes and 60 mL acetic
acid, 10 mL conc. sulfuric acid was added dropwise. The solution was kept
at room temperature for 24–72 h. The mixture was diluted with 100 mL of
ice water and the precipitate was washed with methanol (10 mL Â 3), water
(20 mL Â 5) and dried to give 0.6–0.8 g polymeric diaryliodonium salts. IR
(KBr) n (cmÀ1) 3450, 1180, 1040. Resin (3a): S 4.35%, functional group
1.35 mmol/g; Resin (3b): S 4.74%, functional group 1.48 mmol/g; Resin
(3c): S 4.89%, functional group 1.53 mmol/g.
Typical procedure of the preparation of diaryl sulfides: 1.5 mmol of
phenyl polymeric styryliodonium salts (3a) and 1 mmol sodium p-methyl
benzenethiolate were added to 10 mL of DMF. The temperature was kept
at 100ꢀC for 10 h. Then the solution was poured into 100 mL cold water
to precipitate the polymer. The aqueous layer was extracted with ether
(2 Â 10 mL) and chloroform (15 mL). The combined organic layer was
washed with water (20 mL Â 2) and dried over MgSO4. After evaporated
the solvent gave p-methylphenyl phenyl sulfide (5m).
5a: purity 90%; yield 48%; oil (lit.10a m.p. 25–27ꢀC); 1H-NMR
(CCl4) d: 6.65–7.40 (m, 10H); IR (film) n (cmÀ1): 3040, 1580, 1480, 1230,
1160, 1020.
5b: purity 90%; yield 58%; oil (lit.10a oil); 1H-NMR (CCl4) d:
6.70–7.60 (m, 9H), 2.37 (s, 3H); IR (film) n (cmÀ1): 2920, 1690, 1590,
1490, 1235, 1120, 1000, 870, 760, 690.
5c: purity 95%; yield 52%; oil (lit.10b oil); 1H-NMR (CCl4) d:
6.50–7.70 (m, 9H), 3.70 (s, 3H); IR (film) n (cmÀ1): 2920, 2820, 1690,
1595, 1480, 1460, 1230, 1030, 810, 790, 730.
5d: purity 85%; yield 52%; oil (lit.10a oil); 1H-NMR (CCl4) d:
6.70–7.60 (m, 9H), 2.27 (s, 3H); IR (film) n (cmÀ1): 2920, 1590, 1490,
1235, 1120, 1000, 870, 760, 690.
5e: purity 80%; yield 65%; white solid (recrystallized from hexane);
m.p. 49–50ꢀC (lit.10c m.p. 50ꢀC); 1H-NMR (CCl4) d: 6.57–7.06 (m, 8H), 2.26
(s, 6H); IR (KBr) n (cmÀ1): 2920, 1480, 1230, 1150, 1020, 820.
5f: purity 87%; yield 56%; white solid (recrystallized from hexane);
m.p. 45–46ꢀC (lit.10c m.p. 45–46ꢀC); H-NMR (CCl4) d: 6.45–7.40 (m, 8H),
1
3.72 (s, 3H), 2.40 (s, 3H); IR (KBr) n (cmÀ1): 2920, 2820, 1580, 1490, 1250,
1170, 1070, 1030, 820, 800.
5g: purity 85%; yield 46%; pale yellow solid (recrystallized from
hexane); m.p. 59–60ꢀC (lit.10c m.p. 61ꢀC); H-NMR (CCl4) d: 7.80–8.27
1
(m, 2H), 6.60–7.55 (m, 7H); IR (KBr) n (cmÀ1): 2920, 2820, 1590, 1490,
1435, 1340, 1245, 1110, 1000, 870, 810, 750.
5h: purity 92%; yield 62%; pale yellow solid (recrystallized from
hexane); m.p. 68–69ꢀC (lit.10c m.p. 69ꢀC); H-NMR (CCl4) d: 8.00–8.15
1

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POLYMERIC DIARYLIODONIUM SALTS
2827
(m, 2H), 6.70–7.30 (m, 6H), 2.30 (s, 3H); IR (KBr) n (cmÀ1): 2920, 1590,
1520, 1490, 1345, 1240, 1115, 870, 850.
5i: purity 80%; yield 55%; pale yellow solid (recrystallized from
hexane); m.p. 110–111ꢀC (lit.10d m.p. 110–111ꢀC); 1H-NMR (CCl4) d:
7.93–8.05 (m, 2H), 6.50–7.05 (m, 6H), 3.65 (s, 3H); IR (KBr) n (cmÀ1):
2920, 2820, 1580, 1505, 1490, 1440, 1350, 1250, 1110, 820.
5j: purity 84%; yield 67%; oil (lit.10e oil); 1H-NMR (CCl4) d: 7.02–7.74
(m, 10H); IR (film) n (cmÀ1): 3060, 1580, 1470, 1440, 1080, 1030.
5k: purity 90%; yield 76%; oil (lit.10e oil); 1H-NMR (CCl4) d:
6.80–7.80 (m, 9H), 2.37 (s, 3H); IR (film) n (cmÀ1): 3040, 2930, 1590,
1485, 1080, 1010, 800, 750, 700.
5l: purity 95%; yield 74%; oil (lit.10e oil); 1H-NMR (CCl4) d: 6.56–7.56
(m, 9H), 3.70 (s, 3H); IR (film) n (cmÀ1): 3020, 2920, 2820, 1585, 1490, 1070,
1030, 1000, 810, 755, 690.
5m: purity 88%; yield 65%; oil (lit.10e oil); 1H-NMR (CCl4)
d: 6.80–7.80 (m, 9H), 2.37 (s, 3H); IR (film) n (cmÀ1): 3040, 2930, 1590,
1485, 1080, 1010, 800, 750, 700.
5n: purity 88%; yield 88%; pale yellow solid (recrystallized from
hexane); m.p. 56–57ꢀC (lit.10f m.p. 56–57ꢀC); H-NMR (CCl4) d: 6.73–7.65
1
(m,8H),2.24(s,3H);IR(KBr)n(cmÀ1):3040,2920,1595,1485,1080,1005,790.
5o: purity 85%; yield 81%; pale yellow solid (recrystallized from
hexane); m.p. 45–46ꢀC (lit.10g m.p. 45–46ꢀC); H-NMR (CCl4) d: 6.55–7.53
1
(m, 78H), 3.68 (s, 3H), 2.25 (s, 3H); IR (KBr) n (cmÀ1): 2920, 2820, 1595,
1490, 1065, 800.
1
5p: purity 90%; yield 76%; oil (lit.10h oil); H-NMR (CCl4) d: 7.20–
7.55 (m, 9H); IR (film) n (cmÀ1): 1685, 1590, 1480, 1090, 1010, 820, 740, 690.
5a (by using recycled resin): purity 85%; yield 46%; oil (lit.10am.p.
25–27ꢀC); 1H-NMR (CCl4) d: 6.65–7.40 (m, 10H); IR (film) n (cmÀ1):
3040, 1580, 1480, 1230, 1160, 1020.
Regeneration and reuse of polymeric diaryliodonium salts:: After the
reaction, polyiodostyrene was recovered simply by filtration, and was oxi-
dized to poly[styrene (iodoso diacetate)] with peracetic acid according the
known method.8 After treatment with arenes and conc. sulfuric acid, poly-
meric diaryliodonium salts were regenerated. Resin 3a: S 4.32%, functional
group 1.34 mmol/g; Resin 3b: S 4.40%, functional group 1.38 mmol/g; Resin
3c: S 4.70%, functional group 1.47 mmol/g.
ACKNOWLEDGMENT
The project 29932020 was supported by the National Natural
Foundation of China.

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HUANG, ZHU, AND XU
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Received in the USA November 21, 2000

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