The reaction between diphenyliodonium iodide and disulfides in the presence of a Zn/AlCl3 system: A convenient method for the synthesis of organic sulfides

Article abstract of DOI:10.1080/104265090920796

A convenient method for the synthesis of alkyl aryl- and diaryl sulfides by the reaction of diphenyliodonium iodide and disulfides in the presence of Zn/AlCl₃ system in acetonitrile is reported. Copyright Taylor & Francis Inc.

Full text of DOI:10.1080/104265090920796

This article was downloaded by: [New York University]
On: 28 June 2015, At: 08:59
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954
Registered office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH,
UK
Phosphorus, Sulfur, and Silicon
and the Related Elements
Publication details, including instructions for
authors and subscription information:
http://www.tandfonline.com/loi/gpss20
The Reaction Between
Diphenyliodonium Iodide and
Disulfides in the Presence of a
Zn/AlCl System: A Convenient
3
Method for the Synthesis of
Organic Sulfides
a
a
Barahman Movassagh & Amir Mossadegh
a
Department of Chemistry, K. N. Toosi University of
Technology , Tehran, Iran
Published online: 22 Aug 2006.
To cite this article: Barahman Movassagh & Amir Mossadegh (2005) The Reaction
Between Diphenyliodonium Iodide and Disulfides in the Presence of a Zn/
AlCl System: A Convenient Method for the Synthesis of Organic Sulfides,
3
Phosphorus, Sulfur, and Silicon and the Related Elements, 180:10, 2275-2278, DOI:
10.1080/104265090920796
To link to this article: http://dx.doi.org/10.1080/104265090920796
PLEASE SCROLL DOWN FOR ARTICLE
Taylor & Francis makes every effort to ensure the accuracy of all the
information (the “Content”) contained in the publications on our platform.
However, Taylor & Francis, our agents, and our licensors make no
representations or warranties whatsoever as to the accuracy, completeness,
or suitability for any purpose of the Content. Any opinions and views
expressed in this publication are the opinions and views of the authors, and
are not the views of or endorsed by Taylor & Francis. The accuracy of the

Content should not be relied upon and should be independently verified with
primary sources of information. Taylor and Francis shall not be liable for any
losses, actions, claims, proceedings, demands, costs, expenses, damages,
and other liabilities whatsoever or howsoever caused arising directly or
indirectly in connection with, in relation to or arising out of the use of the
Content.
This article may be used for research, teaching, and private study purposes.
Any substantial or systematic reproduction, redistribution, reselling, loan,
sub-licensing, systematic supply, or distribution in any form to anyone is
expressly forbidden. Terms & Conditions of access and use can be found at
http://www.tandfonline.com/page/terms-and-conditions

Phosphorus, Sulfur, and Silicon, 180:2275–2278, 2005
Copyright © Taylor & Francis Inc.
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/104265090920796
The Reaction Between Diphenyliodonium Iodide
and Disulfides in the Presence of a Zn/AlCl System:
3
A Convenient Method for the Synthesis
of Organic Sulfides
Barahman Movassagh
Amir Mossadegh
Department of Chemistry, K. N. Toosi University of Technology,
Tehran, Iran
A convenient method for the synthesis of alkyl aryl- and diaryl sulfides by the reac-
tion of diphenyliodonium iodide and disulfides in the presence of Zn/AlCl system
3
in acetonitrile is reported.
Keywords Diphenyliodonium iodide; disulfides; sulfides; Zn/AlCl3 system; zinc
thiolate
INTRODUCTION
Organic disulfides are not conventional starting materials for the prepa-
ration of sulfides. However, heterolytic or homolytic cleavage of the S S
bond by carbanions or carbon free radicals, or the abstraction of the sul-
fur atoms by certain reagents, may be of use for the preparation of some
1
sulfides. Cleavage of disulfide bonds by carbanions is known to give sul-
2
3
fides in such reactions with phenyl lithium, lithium acetylides, and
4
benzyne. Benzyl sulfides also have been prepared via reaction of benzyl
bromide with disulfides promoted by a Sm/BiCl3 system in an aqueous
5
media. Recently we reported the synthesis of sulfides through a sim-
ple reaction of disulfides with alkyl or aryl halides using a Zn/AlCl3
6
system.
Received July 20, 2004; accepted October 13, 2004.
The authors are thankful to K.N. Toosi University of Technology Research Council for
partial support of this work.
Address correspondence to Barahman Movassagh, K.N. Toosi University of Technol-
ogy, Department of Chemistry, P.O. Box 15875-4416, Tehran, Iran. E-mail: bmovass1178@
yahoo.com
2275

2
276
B. Movassagh and A. Mossadegh
While most alkyl aryl sulfides are generally prepared by the re-
1
action of alkali metal salts of thiols with alkyl halides, methods
for the preparation of aryl sulfides suffers from limited applica-
bility in that activated reactants, severe reaction conditions, com-
plicated procedures, or a combination of these requirements are
1
,7
involved.
RESULTS AND DISCUSSION
In the course of our study to explore an alternative route for the prepa-
ration of alkyl aryl- and diarylsulfides from disulfides, we found that
diaryliodonium salts are efficient electrophilic arylating agents for this
purpose. These tricoordinate iodine species are, in general, ionic sub-
stances; chlorides, bromides, and iodides possess some covalent char-
8
acters in a manner similar to that in the aryliodo dichlorides. These
salts are more susceptible to nucleophilic displacement because their
positive charges should facilitate polar fission of the bonds to the aro-
8
matic systems. There are strong indications that the reactions of
diphenyliodonium salts with bases proceeded by nucleophilic rather
than by radical attack on the 1-carbons of the diphenyliodonium salts
8
b
to give iodobenzene and the phenyl derivatives of the bases. Here
we introduce a convenient route for the preparation of various alkyl
aryl- and diaryl sulfides via reaction of diphenyliodonium iodide salt
and disulfides promoted by a Zn/AlCl3 system. Simple stirring of
disulfides with metallic zinc dust in the presence of anhydrous alu-
◦
minum chloride in acetonitrile at 80 C produced the zinc thiolate.
This was followed by the addition of diphenyliodonium iodide which
gave, after workup, the desired sulfides (Scheme 1) in 75–90% yield
as shown in Table I. As indicated in Table I, relatively shorter reac-
tion times and higher yields are obtained for aryl, compared to alkyl,
disulfides.
In summary, the present work shows a new general, simple, mild, and
superior procedure for the synthesis of various alkyl aryl- and diaryl
sulfides, and the range of useful applications of diaryliodonium salts
as highly electrophilic arylating reagents in organic synthesis has been
extended.
SCHEME 1

Diphenyliodonium Iodide and Disulfides
2277
TABLE I Synthesis of Alkyl Aryl- and Diaryl Sulfides From Disulfides
and Diphenyliodonium Iodide in the Presence of Zn/AlCl
3
◦
◦
m.p. ( C)/b.p. ( C)/Torr
Reaction
time (h)
Yield
(%)
a
Reportedb
Run
R
Found
9
1
2
3
4
5
6
7
8
9
Ph
3
3.5
4
4.5
3
4
4
3
5
7
80
84
82
83
90
82
80
88
78
77
75
Oil
Oil
Oil
Oil
75–77
Semi solid
Oil
49–51
41–42
Oil
145/8
1
0
4-ClC6H4
4-MeC6H4
2-ClC6H4
2-NO2C6H4
4-BrC6H4
4-FC6H4
2-Naphthyl
PhCH2
141/2
170–175/18
1
1
1
3
1
0
132/1
1
2
76
9
25
147–148/15
1
4
51
1
5
41–42
1
6
7
1
1
0
1
n-C4H9
n-C8H17
117/15
147/18
1
8.5
Oil
a
b
Yields of pure isolated products.
References for physical data of products.
EXPERIMENTAL
General
Diphenyliodonium iodide was prepared by standard procedure.8b All
products were characterized by comparison of their spectral and phys-
1
ical data with those of known samples. H NMR were recorded using a
Jeol JNM-EX90A NMR spectrometer. IR spectra were obtained using a
Shimadzu IR-408 spectrophotometer. Melting points were obtained by
an Electrothermal 9100 apparatus and are uncorrected.
General Procedure for the Preparation of Alkyl Aryl-
and Diaryl Sulfides
A mixture of the disulfide (0.5 mmol), anhydrous aluminum chloride (1
◦
mmol), zinc dust (2 mmol), and acetonitrile (10 mL) was stirred at 80 C
for 2 h until the zinc powder had almost disappeared; diphenyliodo-
nium iodide (1 mmol) and water (2 mL) were then added at once to the
solution and stirring was continued at that temperature for 3–7 h in
an air atmosphere. After completion of the reaction, the solution was
filtered and washed with diethyl ether. The combined Et2O/CH3CN so-
lution was then washed with 5% sodium hydroxide solution (30 mL)
and water (2 × 20 mL). After drying with anhydrous magnesium sul-
fate, the solvent was evaporated in vacuo. The crude sulfide was ei-
ther recrystallized from ethanol or purified by preparative thin layer

2
278
B. Movassagh and A. Mossadegh
chromatography (silica gel, eluent EtOAc: Pet. ether = 1:2) to afford the
desired product.
REFERENCES
[
[
1] S. Oae, Organic Chemistry of Sulfur, p. 57. New York: Plenum press (1977).
2] A. Sch o¨ nberg, A. Stephenson, H. Kaltschmidt, E. Petersen, and H. Schutten, Ber.
Dt. Chem. Ges. B, 66, 237 (1933).
[
[
[
[
3] J. R. Nooi and J. F. Arens, Rec. Trav. Chem. Pays-Bas, 80, 245 (1961).
4] I. Tabushi, K. Okazaki, and R. Oda, Tetrahedron Lett., 3591 and 3821 (1967).
5] G. Lu and Y. Zhang, Synth. Commun., 28, 4479 (1988).
6] (a) B. Movassagh, M. M. Lakouraj, and Z. Fadaei, J. Chem. Res. (S), 350 (2000);
(
b) M. M. Lakouraj, B. Movassagh, and Z. Fadaei, Synth. Commun., 32, 1237 (2002).
[
7] (a) J. F. Bunnett and W. D. Merritt, J. Am. Chem. Soc., 79, 5967 (1957); (b) R. Adams
and A. Ferretti, J. Am. Chem. Soc., 81, 4927 (1959); (c) C. Palomo, M. Oiarbide, R.
Lopez, and E. Gomez-Bengoa, Tetrahedron Lett., 41, 1283 (2000).
[
8] (a) D. F. Banks, Chem. Rev., 66, 243 (1966); (b) F. M. Beringer, A. Brierley, M. Drexler,
E. M. Gindler, and C. C. Lumpkin, J. Am. Chem. Soc., 75, 2705 and 2708 (1953).
9] S. Suwa, T. Sakamoto, and Y. Kikugawa, Chem. Pharm. Bull., 47, 980 (1999).
[
[
[
[
10] S. Oae and Y. H. Khim, Bull. Chem. Soc. Jap., 40, 1716 (1967).
11] H. Burton and W. A. Davy, J. Chem. Soc., 528 (1948).
12] E. D. Amstutz, I. M. Hunsberger, and J. J. Chessick, J. Am. Chem. Soc., 73, 1220
(
1951).
[
13] N. J. Leonard and L. E. Sutton, J. Am. Chem. Soc., 70, 1564 (1948).
[
14] F. M. Furman, J. H. Thelin, D. W. Hein, and W. B. Hardy, J. Am. Chem. Soc., 82,
1
450 (1960).
15] R. D. Rieke, S. J. Uhm, and P. M. Hudnall, J. Chem. Soc., Chem. Commun., 269
1973).
[
[
(
16] (a) T. Mukaiyama and M. Ueki, Tetrahedron Lett., 3429 (1967); (b) V. Horak, J.
Pecka, and J. Jurjev, Collect. Czech. Chem. Commun., 32, 3386 (1967); CA, 67, 85460f
(
1967).
[
17] V. Franzen, H. I. Joschek, and C. Mertz, Ann., 654, 82 (1962).