New perchlorobutadienyl sulfanes

Article abstract of DOI:10.1080/10426500802073175

Hexachlorobutadiene 1 reacts with 3-mercapto-1-hexanol in water-ethanol mixture in the presence of sodium hydroxide to give the new monosubstituted thioether 3-(perchlorobuta-1,3-dienyl-thio)-hexan-1-ol 3a and the disubstituted thioether 3,3′-(perchlorobu

Full text of DOI:10.1080/10426500802073175

This article was downloaded by: [Heriot-Watt University]
On: 28 December 2014, At: 04:01
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
New Perchlorobutadienyl
Sulfanes
a
Zeliha Gökmen a & Cemil İbiş
a Istanbul University, Faculty of Engineering,
Department of Chemistry , Avcılar , Istanbul ,
Turkey
Published online: 19 Dec 2008.
To cite this article: Zeliha Gökmen & Cemil İbiş (2008) New Perchlorobutadienyl
Sulfanes, Phosphorus, Sulfur, and Silicon and the Related Elements, 184:1, 1-9, DOI:
10.1080/10426500802073175
To link to this article: http://dx.doi.org/10.1080/10426500802073175
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, 184:1–9, 2009
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500802073175
New Perchlorobutadienyl Sulfanes
.
¨
Zeliha Gokmen and Cemil Ibis¸
Istanbul University, Faculty of Engineering, Department of Chemistry,
Avcılar-Istanbul, Turkey
Hexachlorobutadiene
1 reacts with 3-mercapto-1-hexanol in water-ethanol
mixture in the presence of sodium hydroxide to give the new monosubstituted
thioether 3-(perchlorobuta-1,3-dienyl-thio)-hexan-1-ol 3a and the disubstituted
thioether 3,3ꢀ-(perchlorobuta-1,3-diene-1,4-diyl) bis(sulfane-diyl)-dihexan-1-ol
4a. 1-Chlorohexan-3-yl-pentachlorobutadienyl-sulfide 5a, 2-chloroethyl-penta-
chlorobutadienyl-sulfide 5b, 2-chloropropyl-pentachlorobutadienyl-sulfide 5c and
1,2,3,4-tetra-chlorobuta-1,4-bis(2-chloroethylsulfanyl)-buta-1,3-diene 6b were
obtained from the reaction of 3a–c and 4b with SOCl2 in pyridine. The derivatives
8b–k and 9a were synthesized from the reaction of componds 5b and 5c in
water-ethanol mixture in the presence of sodium hydroxide with the corresponding
thiol, respectively.
Keywords Hexachloro-1,3-butadiene; (perchlorobuta-1,3-dienyl)sulfanes; thioalcohols;
thioethers
INTRODUCTION
Thioethers are involved in the synthesis of specific classes of com-
pounds including agricultural chemicals,1–3 pharmacological drugs,4–5
chemical-resistant polymers,6–7 and rubber antioxidants.8–9 Alkyl and
heterocyclic sulfides exhibit pharmacological activity, e.g., germicidal
properties;10 some unsymmetrical sulfides exhibit antioxidant activity
(AOA).11
The occurance of sulfur as a donor atom for transition metals is
well-known. Sulfur acts as a very good ligating atom in the form of
the sulfide ion (S−2) or as a mercaptide ion (RS−), while complexes of
thioethers (R-S-R) are much less common.12
Received 10 March 2008; accepted 23 March 2008.
We thank the Research Fund of the University of Istanbul for financial support of
this work.
.
Address correspondence to Cemil Ibis¸, Istanbul Universitesi, Mu¨hendislik Faku¨ltesi,
Kimya Bo¨lu¨mu¨, Avcilar, Istanbul, Turkey. E-mail: ıbıscml@istanbul.edu.tr
1

.
2
Z. Go¨kmen and C. Ibis¸
The reaction of hexachloro-1,3-butadiene 1 with some thiols in
DMF, DMSO and EtOH has been reported.13−21 Some thioethers
were obtained from the reaction of hexachloro-1,3-butadiene with
methanethiol in EtOH. In a US Patent, it is reported that these com-
pounds exhibit biological activity.22
Previously, we described the synthesis of cyclic and open-chain
thioethers from the reactions of hexachlorobutadiene with some
thiols.23 The aim of this work was to synthesize new unsaturated sul-
fanes and to determine their structures.
RESULTS AND DISCUSSION
Hexachlorobutadiene reacted with 3-mercapto-1-hexanol in water-
ethanol mixture in the presence of sodium hydroxide to give the new
mono(thio)substituted thioether 3-(pentachlorobuta-1,3-dienyl-thio)-
hexan-1-ol 3a and di(thio)substituted thioether 3,3ꢀ-(perchlorobuta-
1,3-diene-1,4-diyl-bis(sulfanediyl)-dihexan-1-ol 4a, respectively. The IR
spectrum of 3a and 4a showed a band characteristic for the OH groups.
The 13C NMR spectrum of compounds 3a and 4a showed signals for
the hydroxy carbon atoms at δ = 59.4 ppm. The 13C NMR spectrum of
compound 4a showed signals for diene carbon atoms at δ = 136.1 (C-1
and C-4) and 120.1 (C-2 and C-3) ppm.
The hydroxy derivatives 3a, 3b20, 3c,21 and 4b20 were converted
to chlorides 5a–5c with SOCl2 in pyridine.24 The OH band was not
observed in the IR spectra of compounds 5a–c and 6b. (Scheme 1).
We synthesized compounds 8b–k from the reaction of compound
5b with some aliphatic and aromatic thiols in water-ethanol mix-
ture in the presence of sodium hydroxide. 1-(2-pentachlorobuta-1,3-
dienylsulfanyl-propylsulfanyl)-decane 9a was synthesized from the re-
action of compound 5c with decanethiol. The IR spectrum of 8b showed
a band characteristic for OH group. The mass spectrum of compound
1
8b confirms its molecular mass (362.55) MS: m/z = 362.57. The H
NMR spectra of compounds 8c–h, 8j, and 8k showed signals at δ =
6.57−7.81 ppm characteristic for the protons of the aromatic group.
The 1H NMR spectrum of compound 8i showed signals for the protons
of the vinyl group at δ = 5.09−5.58 (CH2 CH ) and 6.01 (CH2 CH )
ppm (Scheme 2).
Compounds 8b–k, 9a are new aliphatic and aromatic perchloro-buta-
1,3-dienylsulfanes. They are stable colorless oils. All compounds were
isolated in good yield and fully characterized. Their structures result
from the spectroscopic data and are supported by microanalysis.

New Perchlorobutadienyl Sulfanes
3
SCHEME 1
SCHEME 2

4

5

.
6
Z. Go¨kmen and C. Ibis¸
TABLE I 1H NMR and 13C NMR Spectroscopic Data of the New
Perchlorbuta-1,3-dienylsulfanes
1H/13C- NMR (CDCl3)
1H
δ(ppm)
3a
4a
5a
4.38 (s, 1H, OH), 1.48−3.8 (m, 8H,
CH2), 0.90 (s, 3H, CH3), 2.52 (s, 1H,
CH)
13.7, 31.4, 32.3, 35.4, 39.6, 59.4, 119.0,
124.3, 126.6, 136.1
4.38 (s, 2H, OH), 1.90–3.80 (m, 16H,
CH2), 0.90 (s, 6H, CH3), 2.52 (s, 2H,
CH)
13.7, 31.5, 32.2, 35.4, 39.6, 59.4, 120.1,
136.1
13C
1H
13C
1H
1.57−3.74 (m, 8H, CH2), 0.90 (s, 3H,
CH3), 2.52 (s, 1H, CH)
13C
13.7, 31.4, 33.3, 34.6, 39.4, 41.5, 120.1,
124.3, 126.6, 136.0
5b
5c
1H
13C
1H
3.15−4.05 (m, 4H, CH2)
30.4, 42.5, 120.1, 124.2, 126.7, 136.0
2.98−3.23 (m, 2H, CH2), 1.60 (s, 3H,
CH3), 3.92 (s, 1H, CH)
13C
24.4, 39.4, 52.0, 120.1, 124.2, 126.7,
136.0
6b
8b
1H
13C
1H
3.15−4.05 (m, 8H, CH2)
30.4, 42.5, 120.1, 136.0
4.78 (s, 1H, OH), 2.56−3.33 (m, 8H,
CH2)
13C
1H
28.6, 33.4, 34.0, 61.5, 120.1, 124.2,
126.7, 136.0
8c
8d
8e
7.26−7.39 (m, 4H, arom-H), 3.11−4.06
(m, 4H, CH2)
13C
1H
25.2, 34.6, 120.9, 124.7, 126.4, 129.5,
130.9, 131.7, 133.2, 135.7
7.20−7.51 (m, 5H, arom-H), 3.09−4.05
(m, 4H, CH2)
32.2, 39.3, 119.8, 124.8, 125.4, 126.1,
128.2, 129.7, 130.7, 136.1
6.57−7.26 (m, 4H, arom-H), 2.11−2.76
( m, 3H, CH3), 3.23−3.99 (m, 4H,
CH2)
21.3, 28.2, 36.2, 120.9, 124.8, 126.5,
128.6, 129.4, 133.4, 136.0, 137.5
6.57−7.26 (m, 3H, arom-H), 3.33−4.07
(m, 4H, CH2)
28.2, 36.8, 120.9, 124.2, 126.5, 128.6,
131.3, 135.2, 136.0, 141.4
(Continued on next page)
13C
1H
13C
1H
8f
13C

New Perchlorobutadienyl Sulfanes
7
TABLE II 1H NMR and 13C NMR Spectroscopic Data of the
New Perchlorbuta-1,3-dienylsulfanes (Continued)
1H/13C- NMR (CDCl3)
1H
δ(ppm)
8g
8h
8i
6.58−7.26 (m, 4H, arom-H), 3.25−4.35
(m, 4H, CH2)
28.2, 36.8, 115.7, 120.9, 124.7, 126.4,
129.4, 131.7, 136.0, 158.5
13C
1H
7.43−7.81 (m, 4H, arom-H), 3.25−3.89
(m, 4H, CH2)
13C
1H
28.2, 36.8, 119.5, 120.9, 124.8, 126.5,
129.8, 131.7, 133.6, 136.0
6.01 (s, 1H, CH2 =CH-), 5.09−5.58 (m,
2H, CH2 =CH ), 3.11−3.29 (m,
6H, CH2)
13C
1H
29.7, 34.0, 35.2, 118.3, 120.8, 124.7,
126.5, 133.6, 135.9
8j
7.27−7.55 (m, 4H, arom-H), 2.34 ( s,
3H, CH3), 3.25−3.90 (m, 4H, CH2)
21.5, 28.2, 38.1, 120.8, 124.7, 125.5,
125.9, 126.0, 126.4, 130.9, 131.7,
135.8, 136.1
7.16−7.26 (m, 4H, arom-H), 3.83 ( s,
3H, OCH3), 3.21−3.89 (m, 4H,
CH2)
28.2, 36.8, 55.8, 114.5, 120.9, 125.3,
126.5, 128.2, 129.4, 137.9, 152.4
1.29−3.33 (m, 20H, CH2), 0.88−1.26
(s, 6H, CH3), 2.98 (s, 1H, CH)
14.1, 21.1, 22.7, 28.5, 28.9, 29.3, 29.6,
30.9, 31.8, 35.4, 36.5, 40.1, 120.1,
124.2, 126.7, 136.0
13C
8k
9a
1H
13C
1H
13C
EXPERIMENTAL
All chemicals and solvents were obtained commercially and used with-
out purification. TLC was performed on precoated aluminum plates
(Silicagel 60 F254, Merck). Elemental analyses were performed by Carlo
Erba 1106 Elemental analyzer. IR spectra were recorded in KBr pel-
lets or in Nujol mulls with a Shimadzu FTIR-8101 spectrophotometer.
1H and 13C NMR spectra were recorded with a VarianUNITY INOVA
instrument, operating at 500 MHz (1H) and at 125 MHz (13C). Mass
spectra were obtained using a Finnigan LCQ Advantage Max. LC/MS
instrument.

.
8
Z. Go¨kmen and C. Ibis¸
Preparation of S- and S,S-Substituted Polyhalodienes—
General Procedure
2 g (7.66 mmol) of 1,1,2,3,4,4-hexachloro-1,3-butadiene 1 in 25 mL of
ethanol and 2.06 g (15.32 mmol) of 3-mercapto-1-hexanol 2a in 25 mL
of ethanol were mixed and 0.62 g NaOH in 8 mL of water was added at
room temperature. The mixture was stirred for 24 h. Then chloroform
(20 mL) was added to the reaction mixture. The organic layer was
separated, washed with water (4 × 30 mL) and dried with MgSO4.
The solvent was eveporated and the residue was purified by column
chromatography on silica gel with CHCl3 as eluent. Compounds 3a,4a,
8b–k, and 9a were synthesized in the same way.
Chlorination of Hydroxysulfides—General Procedure
To a solution of the compounds 3a–c and 4b (1 equiv.) in pyridine (1
equiv.) was added dropwise thionyl chloride (2 equiv.). The reaction
mixture was strirred at room temperature for 1 h and then refluxed for
an additional 1 h. After, cooling water (50 mL) was added. The reaction
mixture was then extracted with CHCl3 (100 mL). The organic layer
was washed with 35 mL of aqueous NaOH (5%), with water (4 × 30
mL), and then dried over MgSO4. The solvent was eveporated and
the residue was purified by column chromatography on silica gel with
hexane as eluent. Compounds 5a–c and 6b were synthesized in the
same way.
The characteristics of compounds 3a, 4a, 5a–c,6b, 8b–k, and 9a are
given in Tables I and II.
REFERENCES
[1] Siegfrieg Aktiengesellschaft, U.S. Patent 4131608 (1977).
[2] Bayer CropScience AG, U.S. Patent 6908937 (2005).
[3] Bayer CropScience AG, U.S. Patent 6710045 (2004).
[4] Ciba Geigy Corporation, U.S. Patent 4785004 (1988).
[5] William H. Rorer, Inc., U.S. Patent 4520025 (1985).
[6] Societe Nationale Elf Aquitaine, U.S. Patent 4766195 (1988).
[7] ARCO Chemical Technology, U.S. Patent 5801290 (1988).
[8] W. L. Hawkins, V. L. Lanza, B. B. Loeffler, W. Matreyek, and F. H. Winslow, J.
Polymer Sci., 28, 439 (1958).
[9] Ethyl Corporation, Richmond, Va., U.S. Patent 4892965 (1990).
[10] Lever Brothers Company, U.S. Patent 3988377 (1976).
[11] P. I. Pinko, E. I. Terakh, E. A. Gorokh, V. V. Nikulina, A. E. Prosenko, and I. A.
Grigor’ev, Russ. J. Apppl. Chem., 75, 1660 (2002).
[12] W. Rosen and D. H. Busch, J. Am. Chem. Soc., 91, 4694 (1969).
.
[13] A. Roedig, C.Ibis¸, and G. Zaby, Chem. Ber., 114, 684 (1981).

New Perchlorobutadienyl Sulfanes
9
[14] G. Maahs and P. Hegenberg, Angew. Chem., 78, 939 (1966).
.
[15] C.Ibis¸, Chim. Acta Turc., 11, 253 (1983).
[16] A. Roedig and P. Bernemann, Liebigs Ann. Chem., 600, 1 (1956).
[17] G. Maahs, Liebigs Ann. Chem., 686, 55 (1965).
.
.
.
[18] C.Ibis¸ and C¸ . Gu¨ru¨n, Phosphorus, Sulfur, and Silicon, 72, 225 (1992).
[19] C.Ibis¸, F. S. Go¨ksel, and C¸ . Sayıl, Phosphorus, Sulfur, and Silicon, 107, 227 (1995).
[20] C.Ibis¸, Z. Go¨kmen, and N. Y. Bozkurt, Phosphorus, Sulfur, and Silicon, 177, 2907
(2002).
.
[21] C. Ibis¸ and Z. Go¨kmen, Phosphorus, Sulfur, and Silicon, 181, 939 (2006).
[22] Diamond Alkali Company (Ert. H. Bluestone), U.S. Patent 3021370 (1962); Chem
Abstr., 57, 3293c (1962).
.
[23] C.Ibis¸ and N. Yılmaz, Phosphorus, Sulfur, and Silicon, 179, 2543 (2004).
[24] E. Magnier, M. Tordeux, R. Goumont, K. Magder, and C. Wakselman, J. Fluorine
Chem., 124, 55 (2003).