Synthesis of novel thioethers from polyhalobutadienes and thiols

Article abstract of DOI:10.1080/10426507.2011.583615

Substituted perchlorobutadienes were synthesized from the reactions of hexachloro-1,3-butadiene with some thiols in ethanol in the presence of sodium hydroxide. The oxidation products were obtained from the reactions of thioethers with m-chloroperbenzoic acid. The structures of the new compounds were characterized by microanalysis and spectroscopic data. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/10426507.2011.583615

This article was downloaded by: [Korea University]
On: 02 January 2015, At: 03:07
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
Synthesis of Novel Thioethers from
Polyhalobutadienes and Thiols
Nihal Onul a , Wafaa M. Dib Brimo a & Cemil Ibis a
a Division of Organic Chemistry, Department of Chemistry, Faculty of
Engineering , Istanbul University , 34320, Avcilar, Istanbul, Turkey
Published online: 31 Oct 2011.
To cite this article: Nihal Onul , Wafaa M. Dib Brimo & Cemil Ibis (2011) Synthesis of Novel Thioethers
from Polyhalobutadienes and Thiols, Phosphorus, Sulfur, and Silicon and the Related Elements,
186:11, 2180-2188, DOI: 10.1080/10426507.2011.583615
To link to this article: http://dx.doi.org/10.1080/10426507.2011.583615
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, 186:2180–2188, 2011
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426507.2011.583615
SYNTHESIS OF NOVEL THIOETHERS FROM
POLYHALOBUTADIENES AND THIOLS
Nihal Onul, Wafaa M. Dib Brimo, and Cemil Ibis
Division of Organic Chemistry, Department of Chemistry, Faculty of Engineering,
Istanbul University, 34320 Avcilar, Istanbul, Turkey
GRAPHICAL ABSTRACT
SR
Cl
Cl
SR
Cl
Cl
Cl
Cl
Cl
RSH
Cl
Cl
Cl
RS
Cl
EtOH/NaOH
Cl
Cl
Cl
Cl
m--Cl--PBA
CHCl3, 0 oC
O
O
R
S
S
R
Cl
Cl
O
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Abstract Substituted perchlorobutadienes were synthesized from the reactions of hexachloro-
1,3-butadiene with some thiols in ethanol in the presence of sodium hydroxide. The oxidation
products were obtained from the reactions of thioethers with m-chloroperbenzoic acid. The
structures of the new compounds were characterized by microanalysis and spectroscopic data.
Keywords Hexachloro-1,3-butadiene; thiols; thioethers; sulphones; sulphoxides
INTRODUCTION
In our previous studies, we have carried out the reaction of hexachlorobutadiene with
thiols and dithiols in various solvents such as DMSO, DMF, and EtOH.1–11 The treatment
of hexachlorobutadiene with thiols and dithiols yielded mono(thio) substituted, bis(thio)
substituted halogenobutadiene compounds, and cyclic or acylic thioethers.12–14
Recently, significant attention was paid to compounds with high sulfur content such as
thioethers, as they play some key roles in biochemistry, nanochemistry, polymer chemistry,
supramolecular chemistry, and material chemistry.15–18 Additionally, it was reported in
Received 8 February 2011; accepted 19 April 2011.
Address correspondence to Cemil Ibis, Department of Chemistry, Faculty of Engineering, Istanbul Univer-
sity, 34320 Avcilar, Istanbul, Turkey. E-mail: ibiscml@istanbul.edu.tr
2180

SYNTHESIS OF NOVEL THIOETHERS FROM POLYHALOBUTADIENES AND THIOLS 2181
some patents issued in the United States that thio-substituted butadiene compounds exhibit
biological activities as interesting molecules in the field of pharmacology.19
As for halogenobutadienes, they are suitable for dielectrics, refrigerants, and heat
transfer agents, and they can be used as aerosols, lubricants, and floatation agents. Many
halogenobutadienes exhibit high antitumor activities.20–22
The aim of this work was to synthesize novel S- and S,S- substituted halogenobuta-
diene compounds by carrying out reactions of hexachlorobutadiene with some thiols, and
to characterize the structure of these novel compounds.
RESULTS AND DISCUSSION
As shown in Scheme 1, novel compounds were obtained by reactions of hexachloro-
1,3-butadiene (1) with acyclic, cyclic, and aromatic thiols 2a–l in ethanol in the presence
of sodium hydroxide.
SR
Cl
Cl
2,3,4,5,6
a
R
Cl
CH3 (CH2)4
CH3 (CH2)7
Cl
Cl
RSH
2
Cl
Cl
b
c
Cl
Cl
3
CH3 (CH2)8
(CH3)2CH
(CH3)3C
EtOH/NaOH
Cl
Cl
1
d
SR
Cl
Cl
e
f
Cl
RS
Cl
g
4
h
O
S
R
SR
Cl
Cl
Cl
F
i
m-Cl-PBA
Cl
Cl
Cl
Br
j
CHCl3, 0oC
Cl
Cl
5a,d
Cl
Cl
H2
N
k
l
3a,d
CH2
O
O
O
R
S
S
R
Cl
SR
Cl
Cl
Cl
O
Cl
m-Cl-PBA
Cl
Cl
Cl
Cl
+
CHCl3, 0oC
Cl
Cl
Cl
Cl
5f
Cl
Cl
3f
6f
O
O
S CH2 CH CH2
Cl
Cl
S CH2 CH CH2
S CH2 CH CH2
O
Cl
Cl
m-Cl-PBA
CHCl3, 0oC
Cl
Cl
Cl
Cl
+
Cl
Cl
Cl
Cl
Cl
Cl
Cl
7
8
9
Scheme 1

2182
N. ONUL ET AL.
Oxidation of sulfide compounds 3a, 3d, 3f, and 78 was carried out using one equivalent
of metachloroperbenzoic acid (m-CPBA) at 0 ◦C to yield the sulfoxides 5a, 5d, 5f, 8, and
the sulfones 6f and 9.
The 1H NMR spectra of 3a–c and 4a–c exhibit signals at about δ 2.5–2.9 ppm due to
the SCH2 protons. Studies on bis-thiosubstituted butadienes have shown that substitution
occurs at positions 1 and 4.1,6,13 The 13C NMR spectra of 3a–h show four signals due to the
butadiene skeleton. As expected, two signals for the symmetric carbons of butadiene were
observed in the 13C NMR spectra of 4a–h. The 13C NMR shifts of the C-4 carbon atoms of
butadiene in compounds 3a–h appeared around 125 ppm. On the other hand, C-4 and C-1
carbon atoms of butadiene in compounds 4a–h appeared around 131 ppm in the 13C NMR
spectra. The quaternary carbons of 3e and 4e appeared at δ 52 and 49 ppm in the 13C NMR
spectra. The 1H NMR spectra of 3g and 4g showed triplet signals corresponding to S–CH2
proton at about δ 2.9 ppm and a multiplet for aromatic protons at about δ 7.1–7.4 ppm.
In multiple reaction monitoring (MRM), a precursor mass ion is selected for each
compound in the first quadrupole (Q1) and then fragmented in the collision cell (Q2) to
yield a diagnostic product ion monitored by the third quadrupole (Q3). A signal is detected
only if the selected precursor ion from Q1 yields a selected product ion in Q3, so in the
MRM mode each ionized compound gives distinct precursor-to-product ion transitions that
are diagnostic for the presence of that particular compound.
Two MRM transitions were monitored for each compound. Q3 detects a selected
mass of product ions generated by collision-induced dissociation of the precursor ions
selected in Q1. The precursor ion (Q1) mass spectrum of 4f is given in Figure 1 and the
product ion mass spectrum is given in Figure 2.
The precursor ion peak [M+H]+ was detected at m/z 549.2 with strong abundance.
Fragmentation of m/z 549.2 is shown in Figure 2. The peak of compound 4f was caused
by successive losses of chloro substituents. The transitions of the precursor ions to the
productions m/z 549.2 → 514.2, m/z 549.2 → 478.1 and m/z 549.2 → 443.2 were monitored
for 4f.
Figure 1 The precursor ion mass spectrum of 4f.

SYNTHESIS OF NOVEL THIOETHERS FROM POLYHALOBUTADIENES AND THIOLS 2183
Figure 2 The product ion mass spectrum of 4f.
Aromatic protons of 3i, 3j, 3k, and 4j appeared at about δ 6.5–7.5 in the 1H NMR
spectrum. Also, these compounds showed characteristic absorptions of aromatic C–H at
around 3000 cm−1 in the IR spectrum.
The IR spectrum of compounds 3l and 4l showed characteristic C–O–C absorption
at around 1080–1160 cm−1
.
The bands at 1070, 1035, and 1060 cm−1 in the IR spectrum of 5a, 5d, 5f, and
8 were assigned to S O stretching vibration, respectively. SO2 group of 5f and 9 were
observed in the spectrum at 1150, 1300, and 1350 cm−1. Those oxidation products were
also characterized by mass spectrometry.
All of the compounds provided data conclusive to the proposed chemical structures.
EXPERIMENTAL
Melting points were measured on Bu¨chi B-540 capillary apparatus and were uncor-
rected. IR spectra (cm−1) were recorded on an FTIR spectrometer Shimadzu IR Prestige
1
21 model Diamond, ATR method. H and 13C NMR spectra were recorded on a Varian
Unity Inova spectrometer at 499.83 MHz for 1H and 125.48 MHz for 13C by using CDCl3
as solvent and TMS as internal standard. Mass spectra were obtained on a hybrid triple
quadrupole linear ion trap mass spectrometer (4000 QTRAP, ABSciex). The 4000 QTRAP
was operated in the triple quadruple mass spectrometer mode using an electrospray ion-
ization (ESI) source in the experiments presented here. Elemental analyses (C, H, S) were
conducted using the Thermo Finnigan Flash EA 1112 elemental analyzer; their results were
found to be in good agreement ( 0.2%) with the calculated values. Products were isolated
by column chromatography on silica gel (Fluka Silica gel 60, particle size 63–200 µm).
Kieselgel 60 F-254 plates (Merck) were used for thin layer chromatography (TLC). All

2184
N. ONUL ET AL.
chemicals were reagent grade and were used without further purification. Moisture was
excluded from the glass apparatus using CaCl2 drying tubes.
Preparation of S-Substituted Polyhalobutadienes
General Procedure I. Equimolar amounts of 1,1,2,3,4,4-hexachloro-1,3-butadiene
1 in 10 mL of ethanol and thiols in 10 mL EtOH were mixed and NaOH (1.2 g in 8 mL of
water) was added at room temperature. The mixture was stirred for 24 h until completion
of the reaction (TLC). CHCl3 (30 mL) was added to the reaction mixture and the organic
ˆ
layer was separated, washed with water (4 I 30 mL), and dried over anhydrous sodium
sulfate. The residue was subjected to a separation by column chromatography using hexane
as eluent. This afforded pure samples after evaporation of the solvents.
General Procedure II. Compounds 3a, 3d, 3f, and 7 (1 mol) in 30 mL of CHCl3
were mixed with m-cpba moles) in 30 mL of CHCl3 at 0 ◦C for 24 h; 2N NaOH (30 mL)
was added, and then CHCl3 (30 mL) was added to the reaction mixture. The organic layer
ˆ
was separated and washed with water (4 I 30 mL) and dried over anhydrous sodium sulfate.
The residue was subjected to a separation by column chromatography using chloroform as
eluent to afford pure samples after evaporation of the solvents.
1,1,2,3,4-Pentachloro-4-(pentylthio)-1,3-butadiene (3a) and 1,2,3,4-tetrachloro-
1,4-bis(pentylthio)-1,3-butadiene (4a): Compounds 3a and 4a were synthesized from
1,1,2,3,4,4-hexachloro-1,3-butadiene (1) (2.0 g, 7.66 mmol) and 1-pentanethiol (2a) (0.79
g, 7.66 mmol) according to General Procedure I.
3a: Oil, yield 1.6 g (64%). Rf: 0.91 (hexane). IR (film) ν = 2900, 2950 (CH), 1610
(C C). 1H NMR: δ = 0.83 (t, J = 6.83 Hz, 3H, CH3), 1.23–1.36 (m, 4H, CH2), 1.56–1.61
(m, 2H, CH2), 2.95 (t, J = 7.32 Hz, 2H, SCH2). 13C NMR: δ = 12.86 (CH3), 21.14, 28.46,
29.60, 32.93 (CH2), 119.89, 124.3, 125, 133.25 (Cbutadiene). MS (+ESI): m/z: 329 [M+H]+,
293 [M+H–Cl]+, 257 [M+H–2Cl]+; C9H11Cl5S (328.51). Calcd.%: C, 32.9; H, 3.38; S,
9.76. Found%: C, 32.55; H, 3.24; S, 9.77.
4a: Oil, yield 1.0 g (33%). Rf: 0.73 (hexane). IR (film) ν = 2930, 2970 (CH), 1600
(C C). 1H NMR: δ = 0.8–0.9 (m, 6H, 2 CH3), 1.23–1.36 (m, 8H, 4 CH2), 1.54–1.64 (m,
J = 7.32 Hz, 4H, 2 CH2), 2.6–2.9 (m, 4H, 2 SCH2). 13C NMR: δ = 12.93 (CH3), 21.29,
29.95, 31.77, 38.23 (CH2), 123.95, 131.88 (Cbutadiene). MS (+ESI): m/z: 397 [M+H]+, 362
[M+H–Cl]+, 327 [M+H–2Cl]+; C14H22Cl4S2 (396.27). Calcd.%: C, 42.43; H, 5.60; S,
16.18. Found%: C, 42.52; H, 5.80; S, 16.25.
1,1,2,3,4-Pentachloro-4-(octylthio)-1,3-butadiene (3b) and 1,2,3,4-tetrachloro-
1,4-bis(octylthio)-1,3-butadiene (4b): Compounds 3b and 4b were synthesized from
1,1,2,3,4,4-hexachloro-1,3-butadiene (1) (3.0 g, 11.49 mmol) and 1-octanethiol (2b) (1.68
g, 11.49 mmol) according to General Procedure I.
3b: Oil, yield 1.6 g (38%). Rf: 0.90 (hexane). IR (film) ν = 2900, 2920 (CH), 1600
1
(C C). H NMR: δ = 0.85 (t, J = 6.84 Hz, 3H, CH3), 1.2–1.6 (m, 12H, 6 CH2), 2.5 (t,
J = 7.32 Hz, 2H, SCH2). 13C NMR: δ = 14 (CH3), 23, 28.9, 29, 29.2, 29.4, 29.8, 30.2
(CH2), 120.9, 124.9, 126, 134.6 (Cbutadiene). MS (+ESI): m/z: 371 [M+H]+, 335 [M–Cl]+;
C12H17Cl5S (370.6). Calcd.%: C, 38.89; H, 4.62; S, 8.65. Found%: C, 38.95; H, 4.50; S,
8.70.
4b: Oil, yield 1 g (18%). Rf: 0.71 (hexane). IR (film) ν = 2920, 2970 (CH), 1600
1
(C C). H NMR: δ = 0.85 (t, J = 6.84 Hz, 6H, 2 CH3), 1.2–1.4 (m, 24H, 12 CH2), 2.7
(t, J = 7.32 Hz, 4H, 2 SCH2). 13C NMR: δ = 13.5 (CH3), 21.6, 28.1, 28.5, 28.9, 29.4,
30.7, 30.9 (CH2), 122, 134 (Cbutadiene). MS (+ESI): m/z: 481 [M+H]+, 444 [M+H–Cl]+;

SYNTHESIS OF NOVEL THIOETHERS FROM POLYHALOBUTADIENES AND THIOLS 2185
C20H34Cl4S2 (480.4). Calcd.%: C, 50.0; H, 7.13; S, 13.35. Found%: C, 49.7; H, 7.22; S,
13.43.
1,1,2,3,4-Pentachloro-4-(nonylthio)-1,3-butadiene (3c) and 1,2,3,4-tetrachloro-
1,4-bis(nonylthio)-1,3-butadiene (4c): Compounds 3c and 4c were synthesized from
1,1,2,3,4,4-hexachloro-1,3-butadiene (1) (3.0 g, 11.49 mmol) and 1-nonanethiol (2c) (1.84
g, 11.49 mmol) according to General Procedure I.
3c: Oil, yield 1.4 g (32%). Rf: 0.90 (hexane). IR (film) ν = 2900, 2970 (CH), 1600
(C C). 1H NMR: δ = 0.7 (t, J = 6.84 Hz, 3H, CH3), 1.06–1.61 (m, 14H, 7 CH2), 2.85 (t,
J = 7.32 Hz, 2H, SCH2). 13C NMR: δ = 14.3 (CH3), 22.8, 28.6, 29.2, 29.4, 29.6, 29.9, 30,
32.2 (CH2), 121, 125, 125.6, 134.5 (Cbutadiene). MS (+ESI) m/z: 385 [M+H]+; C13H19Cl5S
(384.6). Calcd.%: C, 40.6; H, 4.98; S, 8.34. Found%: C, 40.5; H, 4.89; S, 8.3.
4c: Oil, yield 0.9 g (16%). Rf: 0.80 (hexane). IR (film) ν = 2900, 2930 (CH), 1600
(C C). 1H NMR: δ = 0.85–0.88 (m, 6H, 2 CH3), 1.2–1.6 (m, 28H, 14 CH2), 2.75–2.85 (m,
4H, 2 SCH2). 13C NMR: δ = 13.5 (CH3), 21.6, 27.4, 28, 28.1, 28.3, 28.7, 30.8, 32.9 (CH2),
119.9, 133.3 (Cbutadiene). MS (+ESI) m/z: 509 [M+H]+, 473 [M+H–Cl]+; C22H38Cl4S2
(508.5). Calcd.%: C, 51.97; H, 7.53; S, 12.61. Found%: C, 52.11; H, 7.55; S, 12.59.
1,1,2,3,4-Pentachloro-4-(2-propylthio)-1,3-butadiene (3d) and 1,2,3,4-tetrachloro-
1,4-bis(2-propylthio)-1,3-butadiene (4d): Compounds 3d and 4d were synthesized from
1,1,2,3,4,4-hexachloro-1,3-butadiene (1) (3.0 g, 11.49 mmol) and 2-propanethiol (2d) (0.86
g, 11.49 mmol) according to General Procedure I.
3d: Oil, yield 1.14 g (33%). Rf: 0.82 (hexane). IR (film) ν = 2950, 2970 (CH), 1610
(C C). 1H NMR: δ = 1.32 (d, J = 6.84 Hz, 6H, 2 CH3), 3.54–3.62 (m, J = 6.84 Hz, H,
CH). 13C NMR: δ = 22.3 (CH3), 38.4 (CH), 121, 124, 125, 132.9 (Cbutadiene). MS (+ESI)
m/z: 301 [M+H]+, 265 [M+H–Cl]+; C7H7Cl5S (300.5). Calcd.%: C, 27.98; H, 2.35; S,
10.67. Found%: C, 27.78; H, 2.19; S, 10.71.
4d: Oil, yield 0.78 g (20%). Rf: 0.62 (hexane). IR (film) ν = 2900, 2930 (CH), 1600
1
(C C). H NMR: δ = 1.55 (d, J = 6.84 Hz, 12H, 4 CH3), 3.2–3.3 (m, J = 6.84 Hz, H,
CH), 3.4–3.5 (m, J = 6.84 Hz, H, CH). 13C NMR: δ = 23.3 (CH3), 37.3 (CH), 123.8,
131.2 (Cbutadiene). MS (+ESI) m/z: 341 [M+H]+, 305.3 [M+H–Cl]+, 269 [M+H–2Cl]+,
234 [M+H–3Cl]+; C10H14Cl4S2 (340.2). Calcd.%: C, 35.31; H, 4.15; S, 18.85. Found%:
C, 35.28; H, 4.11; S, 18.71.
1,1,2,3,4-Pentachloro-4-(tert-butylthio)-1,3-butadiene (3e)23 and 1,2,3,4-tetra-
chloro-1,4-bis(tert-butylthio)-1,3-butadiene (4e): Compounds 3e and 4e were synthesized
from 1,1,2,3,4,4-hexachloro-1,3-butadiene (1) (3.0 g, 11.49 mmol) and 2-methylpropane-
2-thiol (2e) (1.04 g, 11.49 mmol) according to General Procedure I.
3e: Oil, yield 1.5 g (42%). Rf: 0.68 (hexane). IR (film) ν = 2900, 2920 (CH), 1600
(C C). 1H NMR: δ = 1.2–1.6 (m, 9H, 3 CH3). 13C NMR: δ = 31.7 (CH3), 52 (Ctert), 124,
125, 131, 134 (Cbutadiene). MS (+ESI) m/z: 315 [M+H]+; C8H9Cl5S (314.5). Calcd.%: C,
30.55; H, 2.88; S, 10.20. Found%: C, 30.45; H, 2.78; S, 10.3.
4e: Oil, yield 1 g (24%). Rf: 0.48 (hexane). IR (film) ν = 2900, 2920 (CH), 1600
(C C). 1H NMR: δ = 1.3–1.4 (m, 18H, 6 CH3). 13C NMR: δ = 30.6 (CH3), 49 (Ctert.), 129,
132 (Cbutadiene). MS (+ESI) m/z: 369 [M+H]+; C12H18Cl4S2 (368.2). Calcd.%: C, 39.19;
H, 4.93; S, 17.42. Found%: C, 39.44; H, 4.87; S, 17.31.
1,1,2,3,4-Pentachloro-4-(4-tert-butylbenzylthio)-1,3-butadiene (3f) and 1,2,3,4-
tetrachloro-1,4-bis(4-tert-butylbenzylthio)-1,3-butadiene (4f): Compounds 3f and 4f
were synthesized from 1,1,2,3,4,4-hexachloro-1,3-butadiene (1) (3.0 g, 11.49 mmol)
and 4-(tert-butylphenyl)methanethiol (2f) (2.1 g, 11.49 mmol) according to General
Procedure I.

2186
N. ONUL ET AL.
3f: Oil, yield 1.47 g (32%). Rf: 0.58 (hexane). IR (film) ν = 3050 (CHarom), 2900,
2870 (CH), 1590 (C C). 1H NMR: δ = 1.0–1.3 (m, 9H, 3 CH3), 3.9–4.1 (m, 2H, SCH2),
7.1–7.3 (m, J = 8.32 Hz, 4H, Harom). 13C NMR: δ = 31.5 (CH3), 38 (CH2), 38.9 (Ctert),
133.9, 151 (Carom.), 125, 127 (CHarom), 120.9, 124.9, 126, 126.8 (Cbutadiene). MS (+ESI)
m/z: 405 [M+H]+, 369 [M+H–Cl]+, 334 [M+H–2Cl]+; C15H15Cl5S (404.6). Calcd.%: C,
44.53; H, 3.74; S, 7.92. Found%: C, 44.50; H, 3.85; S, 7.44.
4f: Oil, yield 1 g (16%). Rf: 0.76 (CCl4). IR (film) ν = 3050 (CHarom.), 2900, 2890
1
(CH), 1600 (C C). H NMR: δ = 0.9–1.2 (m, J = 7.32 Hz, 18H, 6 CH3), 3.4–4.1 (m,
4H, 2 SCH2), 7.0–7.3 (m, J = 8.32 Hz, 8H, Harom). 13C NMR: δ = 30.3 (CH3), 37 (CH2),
38.9 (Ctert), 133.2, 149 (Carom.), 127.8, 128 (CHarom), 119.9, 127 (Cbutadiene). MS (+ESI)
m/z: 549 [M+H]+, 514 [M+H–Cl]+, 478 [M+H–2Cl]+, 443 [M+H–3Cl]+; C26H30Cl4S2
(548.5). Calcd.%: C, 56.94; H, 5.51; S, 11.69. Found%: C, 56.95; H, 5.55; S, 11.73.
1,1,2,3,4-Pentachloro-4-(2-phenylethanethio)-1,3-butadiene (3g) and 1,2,3,4-tetra-
chloro-1,4-bis(2-phenylethanethio)-1,3-butadiene (4g): Compounds 3g and 4g were
synthesized from 1,1,2,3,4,4-hexachloro-1,3-butadiene (1) (3.0 g, 11.49 mmol) and
2-phenylethanethiol (2g) (1.59 g, 11.49 mmol) according to General Procedure I.
3g: Oil, yield 1.97 g (48%). Rf: 0.51 (hexane). IR (film) ν = 3040 (CHarom), 2900, 2960
(CH), 1600 (C C). 1H NMR: δ = 2.9 (t, J = 7.32 Hz, 2H, SCH2), 3.1–3.3 (m, 2H, CH2),
7.1–7.3 (m, 5H, Harom). 13C NMR: δ = 30 (SCH2), 38 (CH2), 125, 127, 128 (CHarom), 120.4,
124.1, 125.8, 132 (Cbutadiene), 138.1 (Carom). MS (+ESI) m/z: 363 [M+H]+, 327 [M–Cl]+,
290 [M–2Cl]+; C12H9Cl5S (362.5). Calcd.%: C, 39.76; H, 2.50; S, 8.84. Found%: C, 39.89;
H, 2.60; S, 8.50.
4g: Oil, yield 1.49 g (28%). Rf: 0.19 (hexane). IR (film) ν = 3020 (CHarom), 2950,
2900 (CH), 1600 (C C). 1H NMR: δ = 2.7–2.9 (m, 4H, 2 SCH2), 3.0–3.2 (m, 4H, 2 CH2),
7.1–7.4 (m, 10H, Harom). 13C NMR: δ = 32 (SCH2), 39 (CH2), 125.7, 127.6, 130.3 (CHarom),
120.1, 138 (Cbutadiene), 139 (Carom.). MS (+ESI) m/z: 465 [M+H]+, 430 [M+H–Cl]+, 359
[M+H–3Cl]+; C20H18Cl4S2 (464.3). Calcd.%: C, 51.74; H, 3.91; S, 13.81. Found%: C,
51.91; H, 3.37; S, 13.39.
1,1,2,3,4-Pentachloro-4-(cyclopentylthio)-1,3-butadiene (3h) and 1,2,3,4-tetra-
chloro-1,4-bis(cyclopentylthio)-1,3-butadiene (4h): Compounds 3h and 4h were
synthesized from 1,1,2,3,4,4-hexachloro-1,3-butadiene (1) (2.0 g, 7.66 mmol) and
cyclopentanethiol (2h) (0.78 g, 7.66 mmol) according to General Procedure I.
3h: Oil, yield 1.53 g (61%). Rf: 0.83 (hexane). IR (film) ν = 2900, 2950 (CH), 1620
1
(C C). H NMR: δ = 1.53–1.77 (m, 4H, 2 CH2), 1.9–2.1 (m, 4H, 2 CH2), 3.6–3.7 (m,
H, CH). 13C NMR: δ = 23.8, 32.3 (CH2), 45 (CH), 120, 124, 125, 134 (Cbutadiene). MS
(+ESI) m/z: 325 [M–H]+, 289 [M–H–Cl]+, 183 [M–H–Cl]+; C9H9Cl5S (326.5). Calcd.%:
C, 33.11; H, 2.78; S, 9.82. Found%: C, 32.01; H, 2.79; S, 9.84.
4h: Oil, yield 0.9 g (30%). Rf: 0.6571 (hexane). IR (film) ν = 2900, 2930 (CH), 1610
(C C). 1H NMR: δ = 1.4–1.7 (m, 8H, 4 CH2), 1.8–2.1 (m, 8H, 4 CH2), 3.3–3.7 (m, 2H, 2
CH). 13C NMR: δ = 32, 34 (CH2), 46.1 (CH), 121.2, 131.9 (Cbutadiene). MS (+ESI) m/z: 393
[M+H]+, 357 [M+H–Cl]+, 322 [M+H–2Cl]+; C14H18Cl4S2 (392.2). Calcd.%: C, 42.87;
H, 4.63; S, 16.35. Found%: C, 42.58; H, 4.64; S, 16.50.
1,1,2,3,4-Pentachloro-4-(4-fluorophenylthio)-1,3-butadiene (3i): Compound 3i was
synthesized from 1,1,2,3,4,4-hexachloro-1,3-butadiene (1) (3.0 g, 11.49 mmol) and 4-
fluorobenzenethiol (2i) (1.63 g, 11.49 mmol) according to General Procedure I.
3i: Oil, yield 1.27 g (31%). Rf: 0.75 (hexane). IR (film) ν = 3050 (CHarom), 1595
(C C). 1H NMR: δ = 6.9–7.8 (m, 4H, Harom). C10H4Cl5FS (352.47). Calcd.%: C, 34.07;
H, 1.14; S, 9.09. Found%: C 34.06; H 1.26; S 9.54.

SYNTHESIS OF NOVEL THIOETHERS FROM POLYHALOBUTADIENES AND THIOLS 2187
1,1,2,3,4-Pentachloro-4-(4-bromophenylthio)-1,3-butadiene (3j and 1,2,3,4-
tetrachloro-1,4-bis(4-bromophenylthio)-1,3-butadiene (4j): Compounds 3j and 4j were
synthesized from 1,1,2,3,4,4-hexachloro-1,3-butadiene (1) (3.0 g, 11.49 mmol) and
4-bromobenzenethiol (2j) (2.33 g, 11.49 mmol) according to General Procedure I.
3j: Oil, yield 1.6 g (34%). Rf: 0.78 (hexane). IR (film) ν = 3050 (CHarom), 1600
(C C). 1H NMR: δ = 7.1–7.8 (m, 4H, Harom). C10H4Cl5BrS (413.37). Calcd.%: C, 29.05;
H, 0.97; S, 7.75. Found%: C, 29.07; H, 0.93; S, 7.38.
4j: Yellow crystals, mp: 95 ◦C–97 ◦C, yield 1.8 g (28%). Rf: 0.57 (hexane). IR (KBr)
ν = 3020 (CHarom), 1600 (C C). 1H NMR: δ = 7.3–7.6 (m, 8H, Harom). C16H8Cl4Br2S2
(565.99). Calcd.%: C, 33.95; H, 1.42; S, 11.33. Found%: C, 33.56; H, 1.58; S, 11.58.
1,1,2,3,4-Pentachloro-4-(4-aminophenylthio)-1,3-butadiene (3k): Compound 3k
was synthesized from 1,1,2,3,4,4-hexachloro-1,3-butadiene (1) (3.0 g, 11.49 mmol) and
4-aminobenzenethiol (2k) (1.44 g, 11.49 mmol) according to General Procedure I.
3k: Oil, yield 1.74 g (44%). Rf: 0.81 (hexane). IR (film) ν = 3000 (CHarom), 1595
(C C). 1H NMR: δ = 3.7–4.3 (m, 2H, NH2), 6.5–7.6 (m, 4H, Harom). C10H6Cl5NS (349.49).
Calcd.%: C, 34.36; H, 1.73; N, 4.0; S, 9.17. Found%: C, 34.14; H, 1.85; N, 3.9; S, 9.55.
1,1,2,3,4-Pentachloro-4-(2-furfurylthio)-1,3-butadiene (3l) and 1,2,3,4-tetra-
chloro-1,4-bis(2-furfurylthio)-1,3-butadiene (4l): Compounds 3l and 4l were synthesized
from 1,1,2,3,4,4-hexachloro-1,3-butadiene (1) (3.0 g, 11.49 mmol) and 2-furfurylthiol (2l)
(1.31 g, 11.49 mmol) according to General Procedure I.
3l: Oil, yield 1.9 g (49%). Rf: 0.86 (hexane). IR (film) ν = 3020 (CHarom.), 2900,
2930 (CH), 1600 (C C), 1080, 1160 (C–O–C). 1H NMR: δ = 4.2 (s, 2H, CH2), 6.0–6.4
(m, 2H, 2 CH), 7.35 (s, H, CHO). C9H5Cl5SO (338.47). Calcd.%: C, 31.94; H, 1.49; S,
9.47. Found%: C, 31.56; H, 1.43; S, 9.70.
4l: Oil, yield 0.81 g (17%). Rf: 0.22 (hexane). IR (film) ν = 3050 (CHarom), 2900,
1
2930 (CH), 1600 (C C), 1085, 1150 (C–O–C). H NMR: δ = 3.5–4.4 (m, 4H, 2 CH2),
5.9–6.4 (m, 4H, 4 CH), 7.1–7.5 (m, 2H, 2 CHO). C14H10Cl4S2O2 (416.18). Calcd.%: C,
40.4; H, 2.59; S, 15.4. Found%: C, 40.14; H, 2.30; S, 15.3.
1,1,2,3,4-Pentachloro-4-(pentylsulfinyl)-1,3-butadiene (5a): Compound 5a was syn-
thesized from 1,1,2,3,4-pentachloro-4-pentylthio-1,3-butadiene (3a) (0.1 g, 0.304 mmol)
and mcpba (0.21 g, 1.218 mmol) according to General Procedure II.
5a: Oil, yield 0.05 g (48%). Rf: 0.73 (CHCl3). IR (film) ν = 2900, 2970 (CH), 1610
(C C), 1070 (S O). MS (+ESI) m/z: 345 [M+H]+; C9H11Cl5OS (344.5). Calcd.%: C,
31.38; H, 3.22; S, 9.31. Found%: C, 31.52; H, 3.42; S, 9.44.
1,1,2,3,4-Pentachloro-4-(2-propylsulfinyl)-1,3-butadiene (5d): Compound 5d was
synthesized from 1,1,2,3,4-pentachloro-4-(2-propylthio)-1,3-butadiene (3d) (0.3 g, 0.998
mmol) and mcpba (0.69 g, 3.992 mmol) according to General Procedure II.
5d: White crystals, mp: 67 ◦C–68 ◦C, yield 0.1 g (31%). Rf: 0.36 (CHCl3). IR (KBr)
ν = 2910, 2970 (CH), 1610 (C C), 1060, 1035 (S O). MS (+ESI) m/z: 317 [M+H]+;
C7H7Cl5OS (316.5). Calcd.%: C, 26.57; H, 2.23; S, 10.13. Found%: C, 26.62; H, 2.40; S,
10.10.
1,1,2,3,4-Pentachloro-4-(4-tert-butylbenzylsulfinyl)-1,3-butadiene (5f) and 1,1,2,3,
4-pentachloro-4-(4-tert-butylbenzylsulfonyl)-1,3-butadiene (6f): Compounds 5f and 6f
were synthesized from 1,1,2,3,4-pentachloro-4-(4-tert-butylbenzylthio)-1,3-butadiene (3f)
(0.1 g, 0.247 mmol) and mcpba (0.17 g, 0.989 mmol) according to General Procedure II.
5f: Oil, yield 0.05 g (50%). Rf: 0.29 (CHCl3). IR (film) ν = 3050 (CHarom), 2800,
2960 (CH), 1600 (C C), 1060 (S O). MS (+ESI) m/z 421.1 [M+H]+; C15H15Cl5OS
(420.6). Calcd.%: C, 42.83; H, 3.59; S, 7.62. Found%: C, 42.87; H, 3.61; S, 7.60.

2188
N. ONUL ET AL.
6f: Oil, yield 0.05 g (45%). Rf: 0.64 (CHCl3). IR (film) ν = 3020 (CHarom), 2800,
2960 (CH), 1600 (C C), 1150, 1300 (SO2). MS (+ESI) m/z: 436 [M+H]+; C15H15Cl5O2S
(436.6). Calcd.%: C, 41.26; H, 3.46; S, 7.34. Found%: C, 41.52; H, 3.43; S, 7.40.
1,1,2,3,4-Pentachloro-4-(allylsulfinyl)-1,3-butadiene (8) and 1,1,2,3,4-pent-
achloro-4-(allylsulfonyl)-1,3-butadiene (9): Compounds 8 and 9 were synthesized from
1,1,2,3,4-pentachloro-4-allylthio-1,3-butadiene (7) (0.1 g, 0.335 mmol) and mcpba (0.23
g, 1.34 mmol) according to General Procedure II.
8: Oil, yield 0.05 g (48%). Rf: 0.40 (CCl4). IR (film) ν = 2900, 2960 (CH), 1600
(C C), 1040, 1060 (S = O). MS (+ESI) m/z: 314.8 [M+H]+, 298.8 [M–O]+; C7H5Cl5OS
(314.4). Calcd.%: C, 26.74; H, 1.60; S, 10.20. Found%: C, 26.85; H, 1.51; S, 10.90.
9: Oil, yield 0.06 g (54%). Rf: 0.81 (CCl4). IR (film) ν = 2900, 2960 (CH), 1610
(C C), 1150, 1350 (SO2). MS (+ESI) m/z: 331 [M+H]+, 314 [M+H–O]+; C7H5Cl5O2S
(330.4). Calcd.%: C, 25.44; H, 1.53; S, 9.70. Found%: C, 25.95; H, 1.72; S, 9.92.
REFERENCES
1. Roedig, A.; Ibis¸, C.; Zaby, G. Chem. Ber. 1981, 114, 684–698.
2. Ibis¸, C. Chim. Acta Turc. 1983, 11, 253–258.
3. Ibis¸, C. Liebigs Ann. Chem. 1984, 1873–1877.
4. Ibis¸, C. Liebigs Ann. Chem. 1987, 1009–1011.
5. Ibis, C. Bull. Soc. Chim. Belg. 1996, 105, 317–320.
6. Ibis¸, C.; Goksel, F. S.; Sayil, C. Phosphorus, Sulfur, Silicon, Relat. Elem. 1995, 107, 227–233.
7. Ibis¸, C.; Yilmaz, N. Phosphorus, Sulfur, Silicon, Relat. Elem. 2004, 179, 2543–2548.
8. Ibis¸, C.; Gokmen, Z.; Yilmaz, N. Phosphorus, Sulfur, Silicon, Relat. Elem. 2002, 177, 2907–2914.
9. Ibis¸, C.; Beyazıt, N. Arkivoc 2010, xi, 244–256.
10. Ibis¸, C.; Sahin, A. Bull. Korean Chem. Soc. 2010, 31, 2255–2260.
11. Ibis¸, C.; Ayla, S. S. Phosphorus, Sulfur, Silicon, Relat. Elem. 2011, 186, 58–66.
12. Roedig, A.; Zaby, G.; Scharf, W. Chem. Ber. 1977, 110, 1484–1491.
13. Roedig, A.; Zaby, G. Chem. Ber. 1979, 112, 1614–1625.
14. Hegenberg, P.; Maahs, G. Angew. Chem. 1966, 78, 939–940.
15. Auger, S.; Me´rand, Y.; Pelletier, J. D.; Poirier, D.; Labrie, F. J. Steroid. Biochem. Mol. Biol.
1995, 52, 547–565.
16. Schmidt, A.; Rahimi, A.; Gjikaj, M. Synthesis 2009, 2371–2379.
17. Gingras, M.; Raimundo, J. M.; Chabre, Y. M. Angew. Chem. Int. Ed. 2006, 45, 1686–1712.
18. Hankp, R.; Hammond, M. D.; Fruchtmann, R.; Pfitzner, J.; Place, G. A. J. Med. Chem. 1990, 33,
1163–1170.
19. Diamond Alkali Company (Inv. Bluestone, H.); U.S. Patent, 3, 021, 370 (13 Feb. 1962); Chem.
Abstr. 1962, 57, 3293c.
20. U.S. Patent, 3, 907, 911; Chem. Abstr. 1976, 84, 18 472.
21. Kaberdin, R. V.; Potkin, V. I.; Zapol’skii, V. A. Russ. Chem. Rev. 1999, 68, 765–779.
22. Potkin, V. I., PhD Thesis in Chemical Sciences, Institute of Physical Organic Chemistry, Academy
of Sciences of Belorussia, Minsk, (1996).
23. Veltman, J. C.; Dekant, W.; Guengerich, F. P.; Anders, M. W. Chem. Res. Toxicol. 1988, 1, 35–40.