The synthesis of novel S-, S,S-, S,S,S-, and N,S-substituted nitrodienes from polyhalonitrodienes and thiols

Article abstract of DOI:10.1080/10426507.2011.588297

The novel S-, S,S-, and S,S,S-substituted nitrobutadienes were synthesized from the reactions of 2-nitrobutadiene compounds with some thiols. The new N,S-substituted nitrobutadienes were obtained fromthe reaction of the mono-thiosubstituted butadienes wit

Full text of DOI:10.1080/10426507.2011.588297

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Phosphorus, Sulfur, and Silicon and the
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The Synthesis of Novel S-, S,S-, S,S,S-,
and N,S-Substituted Nitrodienes from
Polyhalonitrodienes and Thiols
a
Cemil Ibiş & Hatice Yıldırım a
a Department of Chemistry, Faculty of Engineering , Istanbul
University , Avcilar, Istanbul, Turkey
Published online: 31 Oct 2011.
To cite this article: Cemil Ibiş & Hatice Yıldırım (2011) The Synthesis of Novel S-, S,S-, S,S,S-, and
N,S-Substituted Nitrodienes from Polyhalonitrodienes and Thiols, Phosphorus, Sulfur, and Silicon and
the Related Elements, 186:11, 2236-2249, DOI: 10.1080/10426507.2011.588297
To link to this article: http://dx.doi.org/10.1080/10426507.2011.588297
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Phosphorus, Sulfur, and Silicon, 186:2236–2249, 2011
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426507.2011.588297
THE SYNTHESIS OF NOVEL S-, S,S-, S,S,S-,
AND N,S-SUBSTITUTED NITRODIENES FROM
POLYHALONITRODIENES AND THIOLS
Cemil Ibis¸ and Hatice Yıldırım
Department of Chemistry, Faculty of Engineering, Istanbul University, Avcilar,
Istanbul, Turkey
GRAPHICAL ABSTRACT
Abstract The novel S-, S,S-, and S,S,S-substituted nitrobutadienes were synthesized from the
reactions of 2-nitrobutadiene compounds with some thiols. The new N,S-substituted nitrobuta-
dienes were obtained from the reaction of the mono-thiosubstituted butadienes with morpholine,
thiomorpholine, homopiperazine, and piperazine derivatives. The structures of new compounds
were determined by spectroscopic techniques.
Keywords Mono(thio)substituted nitrodiene; bis(thio)substituted nitrodiene; tris(thio)
substituted nitrodiene; N,S-substituted nitrodiene; variable temperature 1H-NMR
INTRODUCTION
The polyhalogenated nitrobuta-1,3-dienes are known as valuable synthetic forerun-
ners to develop polyfunctionalized bioactive molecules.1–3 In previous studies, we have
reported mono-, bis-, tris-, and tetrakis(thio)substituted nitrobutadienes obtained from the
reaction of nitrobutadienes with a variety of thiols4–7 and also N,S-substituted nitrobutadi-
enes from the reaction of some mono(thio)substituted nitrobutadienes with thiomorpholine,
morpholine, and piperazine derivatives.8–11 It is known that piperazine derivatives have great
importance in clinical chemistry. In the literature, there are many studies reported on the
Received 13 March 2011; accepted 5 May 2011.
We thank the Research Fund of Istanbul University for financial support to this work.
Address correspondence to Cemil Ibis¸, Department of Chemistry, Faculty of Engineering, Istanbul
University, 34320 Avcilar, Istanbul, Turkey. E-mail: ibiscml@istanbul.edu.tr
2236

SYNTHESIS OF NOVEL S-, S,S-, S,S,S-, AND N,S-SUBSTITUTED NITRODIENES
2237
biodegradation of morpholine with strains of Mycobacterium or Arthrobacter and Gram-
negative bacteria.12–15 Thiomorpholine analogs have found applications in medicine and
agriculture.16 N-arylpiperazines, N-arylindoles, N-arylpyrroles, and substituted anilines are
important compounds, particularly, in pharmaceutical research and also as intermediates
of synthesis. The N-arylpiperazine subunit is embedded in several pharmacologically in-
teresting targets such as compounds related to the serotonine ligands, calcium blockers,
antipsychotic drugs, antihypertensive, and acetylcholinesterase inhibitory activity.17–21
The goal of this study was to synthesize the novel S-, S,S-, S,S,S-, and N,S-substituted-
2-nitrobutadienes and to characterize these new compounds by spectroscopic methods. We
have also investigated the behavior of some N,S-substituted nitrobutadienes with 1H-NMR
technique at higher temperatures.
RESULTS AND DISCUSSION
The nitrodiene compounds 1 and 2 were obtained from the direct nitration of the
corresponding dienes. 2-Nitropentachlorobuta-1,3-diene 1 was gained from the nitration
of 1,1,2,4,4-pentachlorobutadiene with concentrated HNO3 in ∼40% yield. The nitration
of a mixture of two geometric isomers of 1-bromo-1,2,4,4-tetrachlorobuta-1,3-diene with
concentrated HNO3 occurs at the dichlorovinyl group by electrophilic substitution of the H
atom by the nitro group with the formation of a mixture of E- and Z-isomers of 4-bromo-
1,1,3,4-tetrachloro-2-nitrobuta-1,3-diene in ∼40% yield.2,3
These nitrodienes as the starting compounds reacted with various thiols at room
temperature. It is expected that mono(thio)substituted nitrobutadienes yielded products
such as a mixture of E- and Z-isomers. However, in the XRD (X-Ray Diffraction) data of
substituted nitrodienes reported in previous studies, it was noted that mono(thio)substituted
nitrobutadienes were E-isomers and N,S-substituted nitrbutadienes were also E-isomers. As
a consequence, it might be thought that the derived new nitrodiene products were probably
E-isomers.22–26
The nitrodiene compound 1 was stirred, respectively, with 2-propyl mercaptan, 4-
(methylthio)thiophenol, and (4-methoxyphenyl)methanethiol to derive the new compounds
3a, 3e, 3f, 4f, and 7. The new compounds 5a, 5e, 5d, and 5f were obtained by the reactions of
nitrodiene 2 with 2-propyl mercaptan, benzyl mercaptan, (4-methoxyphenyl)methanethiol,
and 2-naphthyl mercaptan. However, the new S,S-bis(thio)substituted nitrodienes 4b and
6b were synthesized by combining 2-methyl-2-propanethiol and the compounds 1 and 2
in basic surroundings with ethanol. The reactions of nitrodienes with the thiols occurred
according to the addition–elimination mechanism as reported before (Scheme 1).27
The 1H-NMR spectrum of the S-mono(thio)subtituted butadienes 3a and 5a exhibited
the presence of methine proton as a multiplet at 3.7–3.8 ppm. Although the quaternary
carbons of the S,S-bis(thio)substituted butadiene 4b appeared at 51.9 and 51.0 ppm, the
13C-NMR spectrum of the S,S-bisthiosubstituted butadiene 6b showed four peaks at 52.3,
51.8, 51.1, and 51.0 ppm.
The mass spectrum of mono- and bis-thiosubstituted butadienes 3e and 4e confirmed
the assigned structures. In the 1H-NMR spectrums of 3e and 4e, there were singlet peaks
corresponding to the methyl protons at 2.46 ppm and 2.41, 2.39 ppm.
The reaction of nitrodiene compund 1 with one molar equivalent of (4-
methoxyphenyl)methanethiol gave mono(thio)substituted 3f and bis(thio)substituted
4f nitrodienes. Besides, bis(thio)substituted 4f and tris(thio)substituted 7 nitrodienes
were obtained from the reaction of nitrodiene compund 1 with three molar equivalents

2238
C. IBIS¸ AND H. YILDIRIM
3, 4, 5, 6
R
Cl
Cl
Cl
Cl
Cl
Cl
Cl
SR
a
Cl
RSH
Cl
Cl
Cl
Cl
CH(CH3)2
Cl
Cl
SR
SR
SR
SR
b
C(CH3)3
Cl
NO2
Cl
Br
NO2
Cl
Br
NO2
1
3
c
4
d
CH2
Cl
Cl
Cl
SR
RSH
Cl
e
f
SCH3
Br
NO2
NO2
NO2
CH2
OCH3
2
5
6
OCH3
OCH3
OCH3
Cl
Cl
Cl
S
S
S
3 HSH
2
C
OCH3
Cl
Cl
Cl
Cl
S
S
Cl
NO2
Cl
NO2
Cl
NO2
1
4
f
7
OCH3
OCH3
Scheme 1
of (4-methoxyphenyl)methanethiol. It is well known that the reactions of 2-nitrodiene
with some thiols follow a classical SNVin process. The 2-nitrodiene initially reacts at the
terminal C-1 carbon atom to yield the product of mono(thio)substituted-2-nitrobutadienes
or 1,1-bis(thio)substituted-2-nitrobutadienes. Under more rigid conditions, a subsequent
substitution of chlorine atom on C-3 carbon atom is possible.2,28 When the XRD data
of tris(thio)substituted nitrodienes were investigated, it was shown that the third thiolate
anion was replaced with the chlorine atom on C-3 carbon atom.29,30 The peaks of
methilene carbons appeared at δ 40.9 ppm in the spectrum of 3f, at δ 40.7 and 39.5
ppm in the spectrum of 4f, and at δ 39.5, 38.7, and 36.1 ppm in the spectrum of 7. It
is clear that we synthesized mono-, bis-, and tris(thio)substituted nitrobutadienes with
(4-methoxyphenyl)methanethiol.
The N,S-substituted nitrodienes 8(k–n), 9, and 10 were achieved from the reactions of
mono(thio)substituted nitrodienes 3e and 3f with morpholine, 4-fluoroaniline, 1-(4-fluoro
phenyl)piperazine, 1-(2-fluorophenyl)piperazine, and 1-(4-hydroxyphenyl)piperazine, one
by one. In the same way, 13(k–o), 14, and 15 were synthesized from the reactions of
mono(thio)substituted nitrodienes 5c, 5d, and 5f with thiomorpholine, morpholine, 1-
(4-fluorophenyl)piperazine, 1-(2-fluorophenyl)piperazine, and 1-(4-hydroxyphenyl)pipera
zine. These substitution reactions proceed by addition–elimination reaction mechanism
(Scheme 2).27
The FTIR spectra of 8m showed a characteristic –OH band at 3305 cm−1 and there
1
was a singlet peak corresponding to –OH proton at 8.9 ppm in the H-NMR spectrum.
The 1H-NMR spectrum of 10 showed a singlet peak corresponding to the –NH– proton at
11.43 ppm.
The compound 12 was obtained from the reaction of mono(thio)subtituted diene 11
with homopiperazine. Although we obtained just the disubstituted homopiperazine com-
pound in this reaction, it was reported that the monosubstituted homopiperazine compound

SYNTHESIS OF NOVEL S-, S,S-, S,S,S-, AND N,S-SUBSTITUTED NITRODIENES
2239
Cl
Cl
Cl
SR
NH
Cl
SR
1
H2N
F
HN
NR
Cl
Cl
Cl
SR
N
NR1
Cl
NO2
Cl
NO2
10
Cl
NO2
3
8
F
1
SCH3
R=
8
R
R
Cl
SR
HN
O
SCH3
k
F
Cl
N
F
O
Cl
NO2
SCH3
SCH3
l
9
OH
F
m
n
SCH3
R=
CH2
OCH3
Br
Cl
S
Cl
Cl
Cl
HN
NH
Cl
N
S
NO2
Cl
NO2
Br
N
Cl
NO2
Cl
Cl
Br
S
Cl
11
12
Cl
SR
Cl
Cl
Cl
SR
N
1
HN
S
HN
NR
Cl
Cl
Cl
N
SR
S
NR1
Br
NO2
15
Br
NO2
Br
NO2
13
5
1
R
13
R
CH2
R=
Cl
SR
k
F
F
HN
O
Cl
N
CH2
l
O
Br
NO2
F
14
m
CH2
CH2
CH2
R=
OH
F
n
o
CH2
OC H3
Scheme 2
had got by the reaction of monothiosubstituted nitrodienes and homopiperazine.24 In the
ESI-MS spectrum of 12, the molecular ion peak was at m/z 874.37.
The mass spectrum analysis by electrospray ionization (ESI) method showed the
molecular ion peak at m/z 548.21 for the compound 13l. The mass spectrum of 13n showed
the molecular ion peak at m/z 545.84.
We had realized that there were some broad peaks corresponding to the methi-
lene protons of piperazine derivatives when we characterized the new N,S-substituted
nitodienes via the NMR technique. The piperazine protons are changing from axial to

2240
C. IBIS¸ AND H. YILDIRIM
Figure 1 1H-NMR spectra of 8l at 40 ◦C, 60 ◦C, 80 ◦C, and 100 ◦C (DMSO).
Figure 2 1H-NMR spectra of 8m at 40 ◦C, 60 ◦C, 80 ◦C, and 100 ◦C (DMSO).

SYNTHESIS OF NOVEL S-, S,S-, S,S,S-, AND N,S-SUBSTITUTED NITRODIENES
2241
Figure 3 1H-NMR spectra of 12 at 40 ◦C, 60 ◦C, 80 ◦C, and 100 ◦C (DMSO).
equatorial. This movement slows down at lower temperatures and picks up at higher
temperatures. At the room temperature, there were broad peaks corresponding to the
1
piperazine protons in the H-NMR. We reported in the previous study the proton peaks
of some N,S-substituted nitrobutadienes that formed from S-substituted nitrobutadienes
1
with thiomorpholine and N-diphenylmethyl piperazine were split in the H-NMR spec-
1
trum at higher temperatures.23 In this study, we analyzed the H-NMR of some new
compounds that formed monothiosubstituted-2-nitrobutadienes with homopiperazine, 1-
(4-fluorophenyl)piperazine, and 1-(2-fluorophenyl)piperazine at high temperatures.
We measured 1H-NMR of compounds 8l, 8m, and 12 at different temperatures such
◦
◦
◦
◦
as 40 C, 60 C, 80 C, and 100 C (Figures 1–3). We saw that the peaks of piperazine
–CH2– groups were broad bands at room temperature and when the temperatures increased
they were getting sharpened. In the previous study, the broad peaks were triplet peaks at
higher temperatures. However, in this case, it was shown that the peaks of protons were not
split, but got more sharpened at higher temperatures. It is thought that the nonsplit peaks
corresponding to –CH2– protons of piperazine ring may result from the effects of neighbor
groups and ring isomerism.
At 40 ◦C, the peaks of piperazine protons were as broad at 2.76 and 3.56 ppm. When
the temperature was increased, these broad bands changed to singlet peaks in the 1H-NMR
of 8l.
In the 1H-NMR of 8m, there were two broad peaks of piperazine protons at 2.72 and
3.54 ppm at 40 ◦C. When the sample warmed up, these peaks changed to singlet peaks.

2242
C. IBIS¸ AND H. YILDIRIM
It appeared that just two broad peaks of the >N–CH2 protons changed to singlet
peaks but the peak of other CH2 protons of homopiperazine did not change when 12 was
warmed up.
EXPERIMENTAL
Melting points were measured on a Bu¨chi SMP 20 (B-540) capillary apparatus and
were uncorrected. IR-spectra were recorded on a Perkin Elmer Precisely Spectrum One
FTIR instrument. NMR spectra were obtained with a Varian Unity Inova 500 MHz instru-
1
ment (499.8 MHz for H, 125.7 MHz for 13C). Mass spectra were obtained on a Thermo
Finnigan LCQ Advantage MAX LC/MS/MS spectrometer using the ESI probe. UV spectra
were recorded with a UV-VIS spectrophotometer TU-1901; positions of the absorption
maxima λmax are given in nm. Microanalyses were obtained using a Termo Finnigan Flash
EA 1112 Series element analyzer. Thin-layer chromatography (TLC): silica gel 60 F254
foils (Merck), detection with ultraviolet light (254 nm). Column chromatography: silica gel
60 (particle size 0.063–0.20 mm, Merck).
General Procedure
Synthesis of Thiosubstituted Nitrodienes. A: Polyhalo-2-nitrodiene (1 and 2)
and some thiols were mixed directly and stirred between 12–48 h at room temperature. The
yields of reaction were extracted with chloroform and dried with sodium sulfate (Na2SO4).
The residues were purified by column chromatography on silica gel.
B: Polyhalo-2-nitrodiene (1 and 2) and some thiols were dissolved in ethanol
(25 mL) and added to the solution of sodium hydroxide in ethanol and stirred every 2
h at room temperature. The yields of reaction were extracted with chloroform and dried
with sodium sulfate (Na2SO4). The residues were purified by column chromatography on
silica gel.
Synthesis of N,S-Substituted Nitrodienes. C: S-monothiosu¨bstituted-2-
nitro-1,3-butadiene (3 and 5) and thiomorpholine, morpholine, and some piperazine
derivates were dissolved in chloroform (25 mL) and stirred between 12 and 48 h at room
temperature. The products were extracted with chloroform and dried over sodium sulfate
(Na2SO4). The residues were purified by column chromatography on silica gel.
2-Nitro-1,3,4,4-tetrachloro-1-(2-propylthio)-1,3-butadiene (3a) was synthesized
from nitrobutadiene compound 1 (1 g, 3.68 mmol) and 2-propyl mercaptan (0.28 g, 3.68
mmol) according to the general procedure A.
Yield: 0.75 g (65%); mp: 66.5 ◦C–67.1 ◦C. IR(KBr, cm−1): υ 1524, 1316 (NO2), 1604
(C C), 2965, 2930, 2870 (C–H). 1H-NMR (499.83 MHz, CDCl3, ppm): δ 3.80–3.70 (m,
J: 6.8 Hz, 1H, CH), 1.40 (d, J: 6.8 Hz, 6H, CH3); 13C-NMR (125.68 MHz, CDCl3, ppm):
δ 156.7, 128.9, 125.8, 121.8 (Cq), 41.6 (CH), 23.2 (CH3). UV (CHCl3): λmax (logꢀ) 348
(4.0), 246 (3.8). MS (+ESI): m/z 311.73 [M]+; C7H7Cl4NO2S (311.01): Calcd. C 27.03, H
2.27, N 4.50, S 10.31; Found C 27.51, H 2.44, N 4.36, S 10.58.
4-Bromo-2-nitro-1,3,4-trichloro-1-(2-propylthio)-1,3-butadiene (5a) was synthe-
sized from nitrobutadiene compound 2 (1 g, 3.17 mmol) and 2-propyl mercaptan (0.24 g,
3.17 mmol) according to the general p◦rocedure ◦A.
Yield: 0.54 g (51%); mp: 69.4 C–72.1 C. IR(KBr, cm−1): υ 1528, 1370 (NO2),
1
1596 (C C), 2976, 2954, 2925, 2865 (C–H). H-NMR (499.83 MHz, CDCl3, ppm): δ
3.83–3.70 (m, J: 6.8 Hz, 1H, CH), 1.41 (d, J: 6.8 Hz, 6H, CH3); 13C-NMR (125.68
MHz, CDCl3, ppm): δ 155.3, 154.9, 124.0, 122.1, 115.1, 113.9 (Cq), 40.3 (CH), 22.0

SYNTHESIS OF NOVEL S-, S,S-, S,S,S-, AND N,S-SUBSTITUTED NITRODIENES
2243
(CH3). UV (CHCl3): λmax (logꢀ) 349 (4.3), 248 (4.1). GC-MS: m/z 355.0 [M]+, 266.9
[M–(2Cl+CH3)]+. C7H7BrCl3NO2S (355.46): Calcd. C 23.65, H 1.98, N 3.94, S 9.02;
Found C 23.64, H 2.11, N 3.74, S 9.16.
1,1-Bis(2-methyl-2-propylthio)-2-nitro-3,4,4-trichloro-1,3-butadiene (4b) was
synthesized from nitrobutadiene compound 1 (2 g, 7 mmol) and 2-methyl-2-propylthiol
(0.67 g, 7 mmol) according to the general procedure B.
◦
◦
Yield: 0.63 g (44%); mp: 82.3 C–83.9 C. IR(KBr): υ 1541, 1365 (NO2), 2965,
1
2923, 2898 (C–H). H-NMR (499.83 MHz, CDCl3, ppm): δ 1.41, 1.42 (s, 18H, CH3).
13C-NMR (125.68 MHz, CDCl3, ppm): δ 152.1, 140.1, 128.3, 119.7 (Cbutadiene), 51.9, 51.0
(Cq), 31.1, 31.0 (CH3). UV (CHCl3): λmax (logꢀ) 247 (3.87). MS (–ESI): m/z 379.37 [M]−,
MS2 (–ESI): m/z 341.49 [M–Cl]− C12H18Cl3NO2S2 (378.77): Calcd. C 38.05, H 4.79, N
3.70, S 16.93; Found C 37.96, H 4.19, N 3.39, S 15.20.
1,1-Bis(2-methyl-2-propylthio)-4-bromo-3,4-dichloro-2-nitro-1,3-butadiene
(6b) was synthesized from nitrobutadiene compound 2 (2g, 6 mmol) and 2-methyl-2-
propylthiol (0.57 g, 6 mmol) according to the general procedure B.
Yield: 0.53 g (40%). IR (KBr, cm−1): υ 1541, 1365 (NO2), 2964, 2923 (C–H). 1H-
NMR (499.83 MHz, CDCl3, ppm): δ 1.40, 1.41, 1.42, 1.43 (s, 18H, CH3). 13C-NMR (125.68
MHz, CDCl3, ppm): δ 152.8, 151.9, 140.0, 139.6, 122.9, 121.1, 115.8, 114.6 (Cbutadiene),
52.3, 51.8, 51.1, 51.0 (Cq), 31.2, 31.1, 31.0, 30.9 (CH3). UV (CHCl3): λmax (logꢀ)
249 (4.22). MS (–ESI): m/z 422.39 [M–H]−, 397.80 [M–(2CH3)]−. C12H18BrCl2NO2S2
(423.22): Calcd. C 34.06, H 4.29, N 3.31, S 15.15; Found C 35.56, H 3.30, N 3.25, S 8.40.
4-Bromo-1-(2-naphthylthio)-2-nitro-1,3,4-trichloro-1,3-butadiene (5c) was syn-
thesized from nitrobutadiene compound 2 (2 g, 6 mmol) and 2-naphthyl mercaptan (1.02
g, 6 mmol) according to the general procedure A.
Yield: 0.56 g (20%); mp: 129.7 ◦C–132.0 ◦C. IR(KBr, cm−1): υ 1521, 1342 (NO2),
1581 (C C), 2963 (Ar–H). 1H-NMR (499.83 MHz, CDCl3, ppm): δ 8.12 (s, 1H, Arom-H),
7.95–7.86 (q, J: 8.3Hz, 3H, Arom-H), 7.66–7.57 (m, 2H, Arom-H), 7.53 (d, J: 8.3 Hz, 1H,
Arom-H). APT-NMR (125.68 MHz, CDCl3, ppm): δ 156.5, 156.1, 133.1, 132.3, 124.7,
123.6, 121.7, 115.3, 114.1 (Cq), 135.5, 130.3, 128.5, 127.4, 127.3, 126.9, 126.3 (CHarom).
UV (CHCl3): λmax (logꢀ) 344 (5.0), 247 (5.04). MS (–ESI): m/z 440.23 [M]−, 418.38
[M–O]−, 197.97 [M–(Cl+Br+naphthyl)]−. C14H7BrCl3NO2S (439.54): Calcd. C 38.26, H
1.61, N 3.19, S 7.30; Found C 38.49, H 1.98, N 3.03, S 5.01.
1-Benzylthio-4-bromo-2-nitro-1,3,4-trichloro-1,3-butadiene (5d) was synthesized
from nitrobutadiene compound 2 (1 g, 3.2 mmol) and benzyl mercaptan (0.39 g, 3.2 mmol)
according to the general procedure A.
Yield: 0.47 g (37%); mp: 101.1 ◦C–102.2 ◦C. IR(KBr, cm−1): υ 1526, 1298 (NO2),
1593 (C C), 2963, 2925, 2852 (C–H), 3062, 3028 (Ar–H). 1H-NMR (499.83 MHz, CDCl3,
ppm): δ 7.40–7.20 (m, 5H, Arom-H), 4.30 (s, 2H, CH2). 13C-NMR (125.68 MHz, CDCl3,
ppm): δ 155.5, 155.1, 131.7, 123.7, 121.7, 115.3, 114.2 (Cq), 128.5, 128.2, 127.6 (CHarom),
40 (CH2). UV (CHCl3): λmax (logꢀ) 349 (4.23), 248 (4.07). MS (+ESI): m/z 332.32
[M–(2Cl)]+; MS2: m/z 240.18 [M–(2Cl+CH2+Ph)]+. C11H7BrCl3NO2S (403.51): Calcd.
C 32.74, H 1.75, N 3.47, S 7.95; Found C 32.66, H 1.61, N 2.63, S 7.59.
1-[(4-Methylthiophenyl)thio]-2-nitro-1,3,4,4-tetrachloro-1,3-butadiene (3e) and
1,1-Bis[(4-methylthiophenyl)thio]-2-nitro-3,4,4-trichloro-1,3-butadiene (4e) were syn-
thesized from nitrobutadiene compound 1 (1 g, 3.7 mmol) and 4-(methylthio)thiophenol
(0.58 g, 3.7 mmol) according to the general procedure A.
3e: Yield: 1.03 g (72%); mp: 78.5 ◦C–79.8 ◦C. IR(KBr, cm−1): υ 1535, 1392 (NO2),
1601, 1575 (C C), 2922, 2851 (C–H), 3059 (Ar–H). 1H NMR (499.83 MHz, CDCl3, ppm):

2244
C. IBIS¸ AND H. YILDIRIM
δ 7.37 (d, J: 8.8 Hz, 2H, Arom-H), 7.22 (d, J: 8.8 Hz, 2H, Arom-H), 2.46 (s, 3H, S–CH3).
13C-NMR (125.68 MHz, CDCl3, ppm): δ 157.0, 143.3, 127.8, 122.9, 120.3 (Cq), 135.1,
125.4 (CHarom), 13.9 (S–CH3). UV (CHCl3): λmax (logꢀ) 395 (3.8), 245 (4.5). MS (–ESI):
m/z 372.12 [M–O]−; C11H7Cl4NO2S2 (391.12): Calcd. C 33.78, H 1.80, N 3.58, S 16.40;
Found C 35.62, H 1.83, N 3.57, S 16.66.
4e: Yield: 0.094 g (5%); mp: 94.6 ◦C–96.0 ◦C. IR(KBr, cm−1): υ 1509, 1392 (NO2),
1
1573 (C C), 2920, 2852 (C–H), 3056 (Ar–H). H NMR (499.83 MHz, CDCl3, ppm): δ
6.96–6.92 (m, 6H, Arom-H), 6.81–6.76 (m, 2H, Arom-H), 2.41 and 2.39 (s, 6H, S–CH3);
13C-NMR (125.68 MHz, CDCl3, ppm): δ 160.2, 141.1, 139.8, 138.5, 127.3, 121.4 (Cq),
133.7, 130.9, 125.4, 124.7 (CHarom), 14.4, 14.1 (S–CH3). UV (CHCl3): λmax (logꢀ) 397
(4.1), 283 (4.6). MS (+ESI): m/z 511.91 [M+H]+, 533.91 [M+Na]+; C18H14Cl3NO2S4
(510.93): Calcd. C 42.31, H 2.76, N 2.74, S 25.10; Found C 42.5, H 3.01, N 2.57, S 23.37.
4-Bromo-1-(4-methoxybenzylthio)-2-nitro-1,3,4-trichloro-1,3-butadiene
(5f) was synthesized from nitrobutadiene compound 2 (1 g, 3.17 mmol) and (4-
methoxyphenyl)methanethiol (0.49 g, 3.17 mmol) according to the general procedure A.
Yield: 0.47 g (34%); mp: 76.9 ◦C–78.3 ◦C. IR(KBr, cm−1): υ 1512 (NO2), 1608, 1585
(C C), 2948, 2929, 2906, 2831 (C–H), 3013 (Ar–H). 1H NMR (499.83 MHz, CDCl3, ppm):
δ 7.22 (d, J: 8.8 Hz, 2H, Arom-H), 6.83 (d, J: 8.3 Hz, 2H, Arom-H), 4.28 (s, 2H, S–CH2),
3.74 (s, 3H, O–CH3). APT-NMR (125.68 MHz, CDCl3, ppm): δ 160.1, 156.9, 156.5, 124.9,
124.3, 123.0, 116.5, 115.3 (Cq), 131.1, 114.9 (CHarom), 40.9 (CH2), 55.6 (O–CH3). UV
(CHCl3): λmax (logꢀ) 351 (4.3), 247 (4.2). MS (–ESI): m/z 354.55 [M–Br]−; MS2: m/z
317.92 [M–(Br+Cl)]−; C12H9BrCl3NO3S (433.54): Calcd. C 33.59, H 2.67, N 3.51 S 7.29;
Found C 33.25, H 2.09, N 3.23, S 7.40.
1-(4-Methoxybenzylthio)-2-nitro-1,3,4,4-tetrachloro-1,3-butadiene (3f) and 1,1-
Bis(4-methoxybenzylthio)-2-nitro-3,4,4-trichloro-1,3-butadiene (4f) were synthesized
from nitrobutadiene compound 1 (1 g, 3.69 mmol) and (4-methoxyphenyl)methanethiol
(0.57 g, 3.69 mmol) according to the general procedure A.
◦
◦
3f: Yield: 0.72 g (50%); mp: 112.2 C–114.2 C. IR(KBr, cm−1): υ 1518, 1305
(NO2), 1609, 1585 (C C), 2949, 2928, 2850, 2831 (C–H), 3013 (Ar–H). 1H NMR (499.83
MHz, CDCl3, ppm): δ 7.20 (d, J: 8.3 Hz, 2H, Arom-H), 6.81 (d, J: 8.8 Hz, 2H, Arom-H),
4.26 (s, 2H, S–CH2), 3.72 (s, 3H, O–CH3). APT-NMR (125.68 MHz, CDCl3, ppm): δ
160.1, 157.2, 138.7, 129.0, 124.3, 121.6 (Cq), 131.1, 114.9 (CHarom), 40.9 (S–CH2), 55.6
(O–CH3). UV (CHCl3): λmax (logꢀ) 351 (4.3), 247 (4.3). MS (+ESI): m/z 316.67 [M–2Cl]+,
288.72 [M–(Cl+3O+CH3)]+, 256.72 [M–(CH3+2Cl+NO2)]+; C12H9Cl4NO3S (389.08):
Calcd. C 37.04, H 2.33, N 3.60, S 8.24; Found C 40.26, H 2.23, N 3.94, S 10.78.
4f: Yield: 0.22 g (24%); mp: 99.3 ◦C–101.2 ◦C. IR(KBr, cm−1): υ 1523, 1511, 1303
(NO2), 1609, 1583 (C C), 2959, 2934, 2833 (C–H), 3013, 2991 (Ar–H). 1H NMR (499.83
MHz, CDCl3, ppm): δ 7.16 (d, J: 8.8 Hz, 2H, Arom-H), 7.11 (d, J: 8.8 Hz, 2H, Arom-H),
6.80 (d, J: 8.8 Hz, 2H, Arom-H), 6.76 (d, J: 8.8 Hz, 2H, Arom-H), 4.14 (s, 2H, S–CH2),
4.09 (s, 2H, S–CH2), 3.72 (s, 3H, O–CH3), 3.71 (s, 3H, O–CH3). APT-NMR (125.68 MHz,
CDCl3, ppm): δ 158.7, 158.5, 158.2, 140.2, 126.9, 126.0, 125.4, 121.8 (Cq), 129.6, 129.4,
113.4, 113.3 (CHarom), 40.7, 39.5 (S–CH2), 54.4, 54.3 (O–CH3). UV (CHCl3): λmax (logꢀ)
369 (4.1), 242 (4.6). MS (+ESI): m/z 530.10 [M+Na]+; C20H18Cl3NO4S2 (506.85): Calcd.
C 47.39, H 3.58, N 2.76, S 12.65; Found C 47.93, H 3.47, N 2.13, S 11.02.
1,1-Bis(4-methoxybenzylthio)-2-nitro-3,4,4-trichloro-1,3-butadiene (4f) and 4,4-
Dichloro-2-nitro-1,1,3-tris(4-methoxybenzylthio)-1,3-butadiene (7) were synthesized
from nitrobutadiene compound 1 (1 g, 3.69 mmol) and (4-methoxyphenyl)methanethiol
(1.71 g, 11.06 mmol) according to the general procedure A.

SYNTHESIS OF NOVEL S-, S,S-, S,S,S-, AND N,S-SUBSTITUTED NITRODIENES
2245
4f: Yield: 0.75 g (37%); mp: 99.3 ◦C–101.2 ◦C.
7: Yield: 0.4 g (21%); mp: 161.6 ◦C–162.4 ◦C. IR (KBr, cm−1): υ 1512, 1302 (NO2),
1
1609, 1583 (C C), 2917, 2836 (C–H), 3000 (Ar–H). H-NMR (499.83 MHz, CDCl3,
ppm): δ 7.18 (d, J: 8.8 Hz, 2H, Arom-H), 7.14 (d, J: 8.8 Hz, 2H, Arom-H), 7.03 (d, J:
8.8 Hz, 2H, Arom-H), 6.78–6.70 (m, 6H, Arom-H), 4.06 (sb, 4H, S–CH2), 3.73–3.70 (b,
2H, S–CH2), 3.69 (s, 3H, O–CH3), 3.63 (s, 3H, O–CH3), 3.62 (s, 3H, O–CH3). APT-NMR
(125.68 MHz, CDCl3, ppm): δ 158.5, 158.3, 158.2, 150.6, 143.3, 127.8, 126.7, 126.3, 126.2,
123.8 (Cq), 129.5, 129.4, 113.4, 113.2, 113.1 (CHarom), 39.5, 38.7, 36.1 (S–CH2), 54.3,
54.2 (O–CH3). UV-vis (CHCl3): λmax (logꢀ) 252 (5.3). MS (+ESI): m/z 645.85 [M+Na]+;
C28H27Cl2NO5S3 (624.62): Calcd. C 53.84, H 4.36, N 2.24, S 15.40; Found C 54.76, H
4.70, N 2.55, S 15.81.
1-[(4-Fluorophenyl)piperazinyl)-1-[(4-methylthiophenyl)thio]-2-nitro-3,4,4-
trichloro-1,3-butadiene (8k) was synthesized from 1-[(4-methylthiophenyl)thio]-2-nitro-
1,3,4,4-tetrachloro-1,3-butadiene (3e) (0.1 g, 0.26 mmol) and 1-(4-fluorophenyl)piperazine
(0.046 g, 0.26 mmol) according to the general procedure C.
Yield: 0.128 g (93%); mp: 188.0 ◦C–189.7 ◦C. IR(KBr, cm−1): υ 1510, 1393 (NO2),
1
1572, 1605 (C C), 2917, 2849 (C–H), 3075 (Ar–H). H NMR (499.83 MHz, CDCl3,
ppm): δ 7.30 (d, J: 8.3 Hz, 2H, Arom-H), 7.20 (d, J: 8.3 Hz, 2H, Arom-H), 6.90–6.85
(m, 2H, Arom-H), 6.72–6.68 (m, 2H, Arom-H), 3.80–3.30 (bs, 4H, N–CH2), 2.90–2.60
(bs, 4H, N–CH2), 2.39 (s, 3H, S–CH3). 13C-NMR (125.68 MHz, CDCl3, ppm): δ 164.6,
157.8, 155.9, 145.7, 141.1, 125.7, 125.2, 124.4 (Cq), 132.2, 126.4, 117.8, 117.7, 114.9,
114.7 (CHarom), 51.9, 48.5 (N–CH2), 14.3 (S–CH3). UV (CHCl3): λmax (logꢀ) 389 (4.0),
278 (4.2), 245 (4.1). MS (+ESI): m/z 535.96 [M]+; C21H19Cl3FN3O2S2 (534.88): Calcd.
C 47.16, H 3.58, N 7.86, S 11.99; Found C 45.55, H 3.89, N 7.53, S 9.18.
1-[(2-Fluorophenyl)piperazinyl]-1-[(4-methylthiophenyl)thio]-2-nitro-3,4,4-
trichloro-1,3-butadiene (8l) was synthesized from 1-[(4-methylthiophenyl)thio]-2-nitro-
1,3,4,4-tetrachloro-1,3-butadiene (3e) (0.1 g, 0.26 mmol) and 1-(2-fluorophenyl)piperazine
(0.05 g, 0.26 mmol) according to the general procedure C.
Yield: 0.13 g (94%); mp: 181.1 ◦C–183.3 ◦C. IR (KBr, cm−1): υ 1522, 1504, 1355
1
(NO2), 1611, 1573 (C C), 2959, ◦2913, 2848, 2822 (C–H), 3069, 3050 (Ar–H). H-
NMR (499.83 MHz, DMSO, 100 C, ppm): δ 7.48 (d, J: 8.4 Hz, 2H, Arom-H), 7.40
(d, J: 8.4 Hz, 2H, Arom-H), 7.16–7.04 (m, 2H, Arom-H), 7.03–6.95 (t, 1H, Arom-
H), 6.91–6.83 (t, 1H, Arom-H), 3.58 (s, 4H, CH2), 2.82 (s, 4H, CH2), 2.47 (s, 3H,
S–CH3). 13C-NMR (125.68 MHz, DMSO, ppm): δ 156.5, 154.6, 142.2, 139.2, 127.5,
126.0 (Cq), 133.9, 129.8, 127.9, 127.3, 125.5, 120.1, 116.9, 116.7 (CHarom), 53.8, 49.3
(N–CH2), 15.1 (S–CH3). UV (CHCl3): λmax (logꢀ) 389 (4.3), 278 (4.5). MS (+ESI): m/z
536.24 [M+H]+, 558.10 [M+Na]+; MS2: m/z 517.84 [M–O]+, 488.02 [M–NO2]+, 362.98
[M–(O+2S+CH3+Ph)]+. C21H19Cl3FN3O2S2 (534.88): Calcd. C 47.16, H 3.58, N 7.86,
S 11.99; Found C 47.31, H 3.39, N 7.85, S 9.24.
1-[(4-Hydroxyphenyl)piperazinyl]-1-[(4-methylthiohenyl)thio]-2-nitro-3,4,4-
trichloro-1,3-butadiene (8m) was synthesized from 1-[(4-methylthiophenyl)thio]-2-
nitro-1,3,4,4-tetrachloro-1,3-butadiene (3e) (0.1 g, 0.26 mmol) and 1-(4-hydroxyphenyl)
piperazine (0.05 g, 0.26 mmol) according to the general procedure C.
Yield: 0.10 g (74%); mp: 208.3 ◦C–210.0 ◦C. IR (KBr, cm−1): υ 3305 (OH), 1537,
1512, 1349 (NO2), 1595 (C C), 2921, 2823 (C–H). 1H-NMR (499.83 MHz, DMSO, ppm):
δ 8.90 (s,1H, OH); 7.45 (d, J: 8.5 Hz, 2H, Arom-H), 7.38 (d, J: 8.5 Hz, 2H, Arom-H), 6.67
(d, J: 8.9 Hz, 2H, Arom-H), 6.62 (d, J: 8.9 Hz, 2H, Arom-H), 3.70–3.40 (bs, 4H, CH2),
2.90–2.55 (bs, 4H, CH2), 2.45 (s, 3H, S–CH3). 13C-NMR (125.68 MHz, DMSO, ppm): δ

2246
C. IBIS¸ AND H. YILDIRIM
152.4, 143.5, 142.2, 127.6, 126.1, 124.9 (Cq), 133.9, 127.9, 119.2, 116.2 (CHarom), 53.8,
49.7 (N–CH2), 15.1 (S–CH3). UV (CHCl3): λmax (logꢀ) 389 (4.4), 277 (4.6), 246 (4.7).
MS (+ESI): m/z 534.11 [M+H]+, 556.67 [M+Na]+; MS2: m/z 451.86 [M–(NO2+Cl)]+,
361.01 [M–(OH+2S+CH3+Ph)]+. C21H20Cl3N3O3S2 (532.89): Calcd. C 47.33, H 3.78,
N 7.89, S 12.03; Found C 46.94, H 4.22, N 7.39, S 11.48.
1-[(4-Fluorophenyl)piperazinyl]-1-(4-methoxybenzylthio)-2-nitro-3,4,4-
trichloro-1,3-butadiene (8n) was synthesized from 1-[(4-methylthiophenyl)thio]-2-
nitro-1,3,4,4-tetrachloro-1,3-butadiene (3e) (0.57 g, 1.47 mmol) and 1-(4-fluorophenyl)
piperazine (0.26 g, 1.47 mmol) according to the general procedure C.
Yield: 0.51 g (71%); mp: 165.0 ◦C–166.4 ◦C. IR (KBr, cm−1): υ 1539, 1511, 1389,
1370 (NO2), 1607, 1582 (C C), 2955, 2915, 2833 (C–H), 3072, 3002 (Ar–H). 1H-NMR
(499.83 MHz, CDCl3, ppm): δ 7.12 (d, J: 8.3 Hz, 2H, Arom-H), 6.94–6.87 (t, 2H, Arom-H),
6.82–6.76 (m, 4H, Arom-H), 4.10 (bs, 2H, S–CH2), 3.87–3.30 (b, 4H, N–CH2), 3.12 (bs,
4H, N–CH2), 3.72 (s, 3H, O–CH3). 13C-NMR (125.68 MHz, CDCl3, ppm): δ 166.7, 158.6,
157.9, 155.9, 145.7, 126.3, 125.8, 124.1 (Cq), 129.2, 117.7, 117.6, 114.9, 114.8, 113.6
(CHarom), 52.1, 49.4, 38.9 (CH2), 54.3 (O–CH3). UV (CHCl3): λmax (logꢀ) 397 (4.1), 287
(4.1), 248 (4.2). MS(+ESI): m/z 556.25 [M+Na]+; 534.06 [M+H]+. C22H21Cl3FN3O3S
(532.84): Calcd. C 49.59, H 3.97, N 7.89, S 6.02; Found C 51.38, H 3.78, N 8.83, S 8.13.
1-[(4-Methylthiophenyl)thio]-1-morpholinyl-2-nitro-3,4,4-trichloro-1,3-
butadiene (9) was synthesized from 1-[(4-methylthiophenyl)thio]-2-nitro-1,3,4,4-
tetrachloro-1,3-butadiene (3e) (0.32 g, 0.81 mmol) and morpholine (0.07 g, 0.81 mmol)
according to the general procedure C.
Yield: 0.28 g (78%); mp: 142.3 ◦C–143.8 ◦C. IR (KBr, cm−1): υ 1533, 1385 (NO2),
1
1552 (C C), 2963, 2917, 2864 (C–H), 3000 (Ar–H). H-NMR (499.83 MHz, CDCl3,
ppm): δ 7.30 (d, J: 8.8 Hz, 2H, Arom-H), 7.20 (d, J: 8.3 Hz, 2H, Arom-H), 3.62–3.18 (bs,
8H, CH2), 2.41 (s, 3H, S–CH3). 13C-NMR (125.68 MHz, CDCl3, ppm): δ 164.3, 141.2,
125.6, 125.1, 124.5, 118.8 (Cq), 132.1, 126.3 (CHarom), 64.4 (O–CH2), 52.3 (N–CH2), 14.2
(S–CH3). UV (CHCl3): λmax (logꢀ) 390 (4.3), 279 (4.5). MS (+ESI): m/z 442.92 [M]+;
MS2: m/z 424.91 [M–O]+, 406.94 [M–Cl]+. C15H15Cl3N2O3S2 (441.78): Calcd. C 40.78,
H 3.42, N 6.34, S 14.52; Found C 41.13, H 3.32, N 6.31, S 15.02.
1-(4-Fluoroanilinyl)-1-[(4-methylthiophenyl)thio]-2-nitro-3,4,4-trichloro-1,3-
butadiene (10) was synthesized from 1-[(4-methylthiophenyl)thio]-2-nitro-1,3,4,4-
tetrachloro-1,3-butadiene (3e) (0.1 g, 0.26 mmol) and 4-fluoroaniline (0.03 g, 0.26 mmol)
according to the general procedure C.
Yield: 0.11 g (92%); mp: 125.4 ◦C–127.3 ◦C. IR (KBr, cm−1): υ 1558, 1547, 1346
1
(NO2), 1606 (C C), 2962, 2919 (C–H), 3059 (Ar–H). H-NMR (499.83 MHz, CDCl3,
ppm): δ 11.43 (s, 1H, NH), 6.90–6.76 (m, 8H, Arom-H), 2.35 (s, 3H, S–CH3). 13C-NMR
(125.68 MHz, CDCl3, ppm): δ 161.5, 159.5, 158.8, 140.6, 132.1, 127.2, 122.8, 122.7,
120.4 (Cq), 132.2, 126.7, 126.6, 125.5, 114.9, 114.7 (CHarom), 14.3 (S–CH3). UV (CHCl3):
λmax (logꢀ) 379 (4.4), 281 (4.4). MS(–ESI): m/z 465.08 [M]−; MS2: m/z 428.91 [M–Cl]−;
C17H12Cl3FN2O2S2 (465.78): Calcd. C 43.84, H 2.60, N 6.01, S 13.77; Found C 44.51, H
2.63, N 5.99, S 11.27.
1,4-Bis[1-(4-bromophenylthio)-3,4,4-trichloro-2-nitrobuta-1,3-dienyl]-1,4-
diazepane (12) was synthesized from 1-(4-bromophenylthio)-2-nitro-1,3,4,4-tetrachloro-
1,3-butadiene (11) (0.2 g, 0.47 mmol) and homopiperazine (0.047 g, 0.47 mmol) according
to the general procedure C.
Yield: 0.12 g (58%); mp: 217.9 ◦C–218.4 ◦C. IR(KBr, cm−1): υ 1523, 1389 (NO2),
1
1562 (C C), 2925 (C–H), 3086 (Ar–H). H NMR (499.83 MHz, DMSO, ppm): δ 7.68

SYNTHESIS OF NOVEL S-, S,S-, S,S,S-, AND N,S-SUBSTITUTED NITRODIENES
2247
(d, J: 8.5 Hz, 4H, Arom-H), 7.35 (d, J: 8.5 Hz, 4H, Arom-H), 4.40–3.51 (b, 8H, N–CH2),
2.10–1.80 (b, 2H, N–CH2). 13C-NMR (125.68 MHz, DMSO, ppm): δ 129.9, 127.5, 124.6,
124.2, 119.0 (Cq), 134.7, 133.8 (CHarom), 55.0, 54.8 (N–CH2), 29.7 (CH2). UV (CHCl3):
λmax (logꢀ) 394 (4.6), 251 (4.9). MS (+ESI): m/z 874.37 [M]+; C25H18Br2Cl6N4O4S2
(875.09): Calcd. C 34.31, H 2.07, N 6.40, S 7.33; Found C 35.14, H 2.15, N 5.52, S 7.89.
4-Bromo-3,4-dichloro-1-[(4-fluorophenyl)piperazinyl]-1-(2-naphtylthio)-2-
nitro-1,3-butadiene (13k) was synthesized from 4-bromo-1-(2-naphtylthio)-2-nitro-1,3,4-
trichloro-1,3-butadiene 5c (0.036 g, 0.08 mmol) and 1-(4-fluorophenyl)piperazine (0.014
g, 0.08 mmol) according to the general procedure C.
Yield: 0.042 g (89%); mp: 178.3 ◦C–179.0 ◦C. IR(KBr, cm−1): υ 1510, 1380 (NO2),
1
1600 (C C), 2926, 2841 (C–H), 3054 (Ar–H). H NMR (499.83 MHz, CDCl3, ppm): δ
7.95 (d, J: 10.1 Hz, 1H, Arom-H), 7.83–7.79 (dd, J: 8.6, 1.5 Hz, 1H, Arom-H), 7.79–7.72
(m, 2H, Arom-H), 7.52–7.46 (m, 2H, Arom-H), 7.45–7.38 (dd, J: 19.2, 8.6 Hz, 1H, Arom-
H), 6.83–6.76 (td, J: 8.6, 3.5 Hz, 2H, Arom-H), 6.58–6.49 (td, J: 8.4, 4.5 Hz, 2H, Arom-H),
3.80–3.60 (bs, 2H, CH2piper.), 3.60–3.40 (bs, 2H, CH2piper.), 2.80–2.60 (bs, 4H, CH2piper.);
APT-NMR (125.68 MHz, CDCl3, ppm): δ 165.3, 159.1, 157.1, 146.8, 134.0, 133.3, 128.0,
113.2, 112.6 (Cq), 132.9, 130.3, 129.1, 129.0, 128.2, 128.0, 127.9, 127.7, 119.0, 118.9,
116.1, 115.9 (CHarom), 53.2, 49.7 (CH2). UV (CHCl3): λmax (logꢀ) 389 (4.59), 250 (4.95).
MS (+ESI): m/z 584.08 [M+H]+, 605.98 [M+Na]+; MS2: m/z 536.03 [M–(NO2)]+, 501.87
[M–(Cl+NO2)]+; C24H19BrCl2FN3O2S (583.30): Calcd. C 49.42, H 3.28, N 7.20, S 5.50;
Found C 50.07, H 2.74, N 6.93, S 5.81.
1-Benzylthio-4-bromo-3,4-dichloro-1-[(4-fluorophenyl)piperazinyl]-2-nitro-1,3-
butadiene (13l) was synthesized from 1-benzylthio-4-bromo-2-nitro-1,3,4-trichloro-1,3-
butadiene (5d) (0.273 g, 0.68 mmol) and 1-(4-fluorophenyl)piperazine (0.11 g, 0.68 mmol)
according to the general procedure C. ◦
◦
Yield: 0.3 g (81%); mp: 166.9 C–167.8 C. IR(KBr, cm−1): υ 1538, 1509, 1371
1
(NO2), 1580 (C C), 2915, 2866 (C–H), 3065, 3034 (Ar–H). H NMR (499.83 MHz,
CDCl3, ppm): δ 7.30–7.18 (m, 5H, Arom-H), 6.94–6.87 (t, J: 8.3 Hz, 2H, Arom-H),
6.82–6.77 (dd, J: 4.4, 2.4 Hz, 2H, Arom-H), 4.13 (s, 2H, Ar-CH2), 3.95–3.30 (bs, 4H,
CH2piper.), 3.21–3.04 (s, 4H, CH2piper.); 13C-NMR (125.68 MHz, CDCl3, ppm): δ 166.3,
165.9, 157.9, 155.9, 145.6, 134.5, 134.4, 129.1, 127.1, 111.7, 111.1 (Cq), 128.2, 127.9,
127.8, 127.3, 117.7, 117.6, 114.9, 114.8 (CHarom), 39.2 (S–CH2), 52.1; 49.4; 49.3 (CH2);
UV (CHCl3): λmax (logꢀ) 394(4.08), 293(4.04), 248(4.14). MS (+ESI): m/z 548.21 [M]+;
MS2: m/z 499.91 [M–NO2]+, 465.94 [M–(NO2+Cl)]+. C21H19BrCl2FN3O2S (547.27):
Calcd. C 46.09, H 3.50, N 7.68, S 5.86; Found C 46.21, H 2.25, N 7.63, S 6.01.
1-Benzylthio-4-bromo-3,4-dichloro-1-[(2-fluorophenyl)piperazinyl]-2-nitro-1,3-
butadiene (13m) was synthesized from 1-benzylthio-4-bromo-2-nitro-1,3,4-trichloro-1,3-
butadiene (5d) (0.1 g, 0.25 mmol) and 1-(2-fluorophenyl)piperazine (0.045 g, 0.25 mmol)
according to the general procedure C.
Yield: 0.10 g (73%); mp: 163.7 ◦C–165.2 ◦C. IR(KBr, cm−1): υ 1530, 1331 (NO2),
1610, 1574 (C C), 2951, 2928, 2838 (C–H), 3000, 2994 (Ar–H). 1H NMR (499.83 MHz,
CDCl3, ppm): δ 7.32–7.20 (m, 5H, Arom-H), 7.04–6.89 (m, 3H, Arom-H), 6.87–6.80 (t,
J: 8.5 Hz, 1H, Arom-H), 4.20 (s, 2H, S–CH2), 4.01–3.25 (b, 4H, CH2), 3.10 (s, 4H, CH2).
APT-NMR (125.68 MHz, CDCl3, ppm): δ 155.7,153.8, 137.5, 134.5, 129.1, 127.2, 111.6,
110.9 (Cq), 128.1, 127.9, 127.3, 123.6, 122.7, 118.3, 115.5, 115.4 (CHarom), 39.2 (S–CH2),
52.3, 49.4 (N–CH2); UV (CHCl3): λmax (logꢀ) 394 (4.1), 282 (4.1), 247 (4.2). MS (+ESI):
m/z 569.96 [M+Na]+, 547.99 [M]+; MS2: m/z 529.73 [M–O]+, 499.82 [M–NO2]+, 330.98
[M–(Cl+piperazine group)]+. C21H19BrCl2FN3O2S (547.27): Calcd. C 46.09, H 3.50, N
7.68, S 5.86; Found C 45.77, H 4.11, N 7.14, S 5.33.

2248
C. IBIS¸ AND H. YILDIRIM
1-Benzylthio-4-bromo-3,4-dichloro-1-[(4-hidroxyphenyl)piperazinyl]-2-nitro-
1,3-butadiene (13n) was synthesized from 1-benzylthio-4-bromo-2-nitro-1,3,4-trichloro-
1,3-butadiene (5d) (0.115 g, 0.28 mmol) and 1-(4-hydroxyphenyl)piperazine (0.051 g,
0.28 mmol) according to the general procedure C.
Yield: 0.09 g (58%). IR(KBr, cm−1): υ 3356 cm−1 (OH), 1513, 1386 (NO2), 2919,
1
2822 (C–H), 3027 (Ar–H). H NMR (499.83 MHz, CDCl3, ppm): δ 7.30–7.16 (m, 5H,
Arom-H), 6.76–6.68 (m, 4H, Arom-H), 4.15 (s, 2H, S–CH2), 3.80–3.40 (bs, 4H, CH2),
3.07 (s, 4H, CH2). 13C-NMR (125.68 MHz, CDCl3, ppm): δ 168.2, 167.8, 151.5, 143.9,
135.6, 130.3, 128.3, 120.8, 118.8, 112.9, 112.3 (Cq), 129.4, 129.2, 129.1, 128.6, 119.5,
116.4 (CHarom), 40.5 (S–CH2), 53.5, 51.3, 51.2 (N–CH2). UV (CHCl3): λmax (logꢀ) 395
(3.8), 245 (4.5); MS (+ESI): m/z 568.25 [M+Na]+, 545.94 [M]+, 452.12 [M–(CH2+Ph)]+,
372.26 [M–(Br+OH+Ph)]+; C21H20BrCl2N3O3S (M, 545.28): Calcd. C 46.26, H 3.70, N
7.7, S 5.88; Found C 47.31, H 4.61, N 6.29, S 5.61.
4-Bromo-3,4-dichloro-1-[(4-fluorophenyl)piperazinyl]-1-(4-methoxybenzylthio)-
2-nitro-1,3-butadiene (13o) was synthesized from 4-bromo-1-(4-methoxybenzylthio)-2-
nitro-1,3,4-trichloro-1,3-butadiene (5f)(0.1 g, 0.23 mmol) and 1-(4-fluorophenyl)piperazine
(0.04 g, 0.23 mmol) according to the gene◦ral procedure C.
◦
Yield: 0.095 g (71%); mp: 161.6 C–162.4 C. IR (KBr, cm−1): υ 1538, 1510,
1370 (NO2), 1607, 1582 (C C), 2954, 2931, 2913, 2820 (C–H), 3072, 3050 (Ar–H).
1H-NMR (499.83 MHz, CDCl3, ppm): δ 7.13 (d, J: 8.3 Hz, 2H, Arom-H), 6.95–6.87
(m, 2H, Arom-H), 6.83–6.76 (m, 4H, Arom-H), 4.11 (s, 2H, S–CH2), 4.00–3.30 (b, 4H,
N–CH2), 3.13 (bs, 4H, N–CH2), 3.73 (s, 3H, O–CH3). APT-NMR (125.68 MHz, CDCl3,
ppm): δ 158.6, 157.9, 156.0, 145.6, 127.2, 126.3, 126.2, 111.6, 110.9 (Cq), 129.2, 129.1,
117.8, 117.7, 115.0, 114.8, 113.5 (CHarom), 52.0, 49.5, 49.4 (N–CH2), 38.9 (S–CH2), 54.3
(O–CH3), UV (CHCl3): λmax (logꢀ) 396 (4.2), 387 (4.2), 247 (4.4). MS (+ESI): m/z 600.12
[M+Na]+; MS2: m/z 541.60 [M–Cl]+, 495.88 [M–Br]+, 443.91 [M–(2Cl+NO2+CH3)]+.
C22H21Cl2BrFN3O3S (577.30): Calcd. C 45.77, H 3.67, N 7.28, S 5.55; Found C 46.97, H
4.10, N 7.15, S 5.86.
1-Benzylthio-4-bromo-3,4-dichloro-1-morpholinyl-2-nitro-1,3-butadiene (14)
was synthesized from 1-benzylthio-4-bromo-2-nitro-1,3,4-trichloro-1,3-butadiene (5d)
(0.158 g, 0.39 mmol) and morpholine (0.034 g, 0.39 mmol) according to the general
procedure C.
Yield: 0.16 g (90%); mp: 147.5 ◦C–149.1 ◦C. IR(KBr, cm−1): υ 1530, 1357 (NO2),
1585 (C C), 2921, 2855 (C–H), 3000, 2988 (Ar–H). 1H NMR (499.83 MHz, CDCl3, ppm):
δ 7.30–7.21 (m, 3H, Arom-H), 7.21–7.17 (d, J: 7.3 Hz, 2H, Arom-H), 4.10 (s, 2H, S–CH2),
3.80–3.62 (bs, 4H, CH2), 3.60–3.20 (b, 4H, CH2). 13C-NMR (125.68 MHz, CDCl3, ppm):
δ 166.2, 165.9, 134.5, 134.4, 129.3, 127.1, 111.8, 111.1 (Cq), 128.2, 127.9, 127.3, 127.1
(CHarom), 39.2 (S–CH2), 65.4; 52.6 (CH2). UV (CHCl3): λmax (logꢀ) 397(4.8), 295(4.7). MS
(+ESI): m/z 454.87 [M+H]+; MS2: m/z 436.80 [M–O]+, 316.93 [M–(NO2+CH2+Ph)]+;
C15H15BrCl2N2O3S (454.17): Calcd. C 39.67, H 3.33, N 6.17, S 7.06; Found C 38.87, H
3.20, N 6.68, S 7.61.
1-Benzylthio-4-bromo-3,4-dichloro-1-thiomorpholinyl-2-nitro-1,3-butadiene
(15) was synthesized from 1-benzylthio-4-bromo-2-nitro-1,3,4-trichloro-1,3-butadiene
(5d) (0.15 g, 0.37 mmol) and thiomorpholine (0.038 g, 0.37 mmol) according to the
general procedure C.
Yield: 0.14 g (80%); mp: 159.6 ◦C–162.7 ◦C. IR(KBr, cm−1): υ 1521, 1379 (NO2),
1
1583 (C C), 2924, 2850 (C–H), 3000 (Ar–H). H NMR (499.83 MHz, CDCl3, ppm):
δ 7.35–7.15 (m, 5H, Arom-H), 4.11 (s, 2H, S–CH2), 4.03–3.40 (bs, 4H, CH2), 2.66 (s,
4H, CH2). 13C-NMR (125.68 MHz, CDCl3, ppm): δ 167.7, 167.4, 134.4, 134.3, 128.6,

SYNTHESIS OF NOVEL S-, S,S-, S,S,S-, AND N,S-SUBSTITUTED NITRODIENES
2249
127.5, 120.7, 118.8, 111.8, 111.1 (Cq), 128.2, 127.9, 127.8, 127.3 (CHarom), 39.1 (Ph-
CH2), 54.9, 26.9 (CH2). UV (CHCl3): λmax (logꢀ) 398 (3.9), 293 (3.9), 254 (3.9). MS
(+ESI): m/z 470.78 [M]+; MS2: m/z 452.74 [M–O]+, 332.80 [M–(NO2+CH2+Ph)]+.
C15H15BrCl2N2O2S2 (470.23): Calcd. C 38.31, H 3.22, N 5.96, S 13.64; Found C 40.05, H
3.98, N 5.38, S 13.23.
REFERENCES
1. Zapol’skii, V. A.; Namyslo, J. C.; Gjikaj, M.; Kaufmann, D. E. Arkivoc 2007, i, 76–93.
2. Kaberdin, R. V.; Potkin, V. I.; Zapol’skii, V. A. Russ. Chem. Rev. 1997, 66(10), 827–842.
3. Kaberdin, R. V.; Potkin, V. I.; Zapol’skii, V. A. Russ. Chem. Rev. 1999, 68(9), 765–779.
4. Ibis, C.; Goksel, F. S. Phosphorus Sulfur Silicon Relat. Elem. 1994, 97, 165–171.
5. Ibis, C. Phosphorus Sulfur Silicon Relat. Elem. 1996, 118, 49–60.
6. Ibis, C.; Yılmaz Bozkurt, N. Phosphorus Sulfur Silicon Relat. Elem. 2002, 177, 695–701.
7. Ibis, C.; Onul, M. Phosphorus Sulfur Silicon Relat. Elem. 2003, 178, 1881–1889.
8. Ibis¸, C.; Onul, N. Phosphorus Sulfur Silicon Relat. Elem. 2005, 180, 2787–2792.
9. Ibis¸, C.; Aydınlı, G. Phosphorus Sulfur Silicon Relat. Elem. 2007, 182, 1427–1436.
10. Ibis¸, C.; Yilmaz Onul, N. R. Roımaine Chim. 2007, 52(10), 953–956.
11. Ibis¸, C.; Tuyun, A. F.; Aydinli, G. Asian J. Chem. 2010, 22(2), 1360–1368.
12. Knapp, J. S.; Brown, V. R. Int. Biodeterior. 1988, 25, 299–306.
13. Knapp, J. S.; Emtiazi, G.; Yusoff, S.; Heron, S. T. Lett. Appl. Microbiol. 1996, 23, 334–338.
14. Dmitrenko, G. N.; Gvozdyak, P. I.; Udod, V. M. Khimiya i Teknologiya Vody 1987, 9, 442–445.
15. Cech, J. S.; Hartman, P.; Slosare, M.; Chudoba, J. Appl. Environ. Microbiol. 1988, 54, 619–621.
16. Barbachyn, M. R.; Hutchinson, D. K.; Brickner, S. J.; Cynamon, M. H.; Kilburn, J. O.; Klemens,
S. P.; Glickman, S. E.; Grega, K. C.; Hendges, S. K.; Toops, D. S.; Ford, C. W.; Zurenko, G. E.
J. Med. Chem. 1996, 39, 680–685.
17. Romero, M.; Harrak, Y.; Basset, J.; Ginet, L.; Constant, P.; Pujol, M. D. Tetrahedron 2006, 62,
9010–9016.
18. Lopez-Rodriguez, M. L.; Benhamu, B.; Morcillo, M. J.; Tejada, I.; Avila, D.; Marco, I.; Schiap-
parelli, L.; Frechilla, D.; Del Rio, J. Bioorg. Med. Chem. Lett. 2003, 13, 3177–3180.
19. Lopez-Rodriguez, M. L.; Ayala, D.; Benhamu, B.; Morcillo, M. J.; Viso, A. Curr. Med. Chem.
2002, 9, 443–469.
20. Gonzalez-Gomez, J. C.; Santana, L.; Uriarte, E.; Brea, J.; Villason, M.; Loza, M. I.; De Luca, M.;
Rivas, M. E.; Montenegro, G. Y.; Fontenia, J. A. Bioorg. Med. Chem. Lett. 2003, 13, 175–178.
21. Cappelli, A.; Gallelli, A.; Manini, M.; Anzini, M.; Memnuni, L.; Makovec, F.; Menziani, M. C.;
Alcaro, S.; Ortuso, F.; Vomero, S. J. Med. Chem. 2005, 48, 3564–3575.
22. Ibis¸, C.; C¸ . Sayıl; Deniz, N. G. Acta Cryst. 2006, E62, o800–o801.
23. Ibis¸, C.; Yıldırım, H. Phosphorus Sulfur Silicon Relat. Elem. 2009, 184, 369–378.
24. Ibis¸, C.; C¸ . Sayıl; Ozkok, F. Z. Naturforsch 2006, 61b, 1174–1179.
25. Ibis¸, C.; Deniz, N. G.; Tuyun, A. F. J. Chem. Crystallogr. 2010, 40, 353–356.
26. Aydınlı, G.; C¸ . Sayıl; Ibis¸, C. Spectrosc. Lett. 2010, 43, 44–50.
27. Ol’dekop, Yu. A.; Kaberdin, R. V.; Potkin, V. I. Zh. Org. Khim. 1980, 16, 543–547.
28. Fischer, R.; Jescheke, P.; Erdelen, C.; Lubos-Erdelen, A.; Losel, P.; Reckmann, U.; Kaufmann,
D. E.; Zapol’skii, V. A.; U.S. Patent, 7.332.512 B2 (2008).
29. Ibis¸, C.; Deniz, N. G. Acta Crystallogr. 2007, E63, O3058–U2187.
30. Aydınlı, G.; C¸ . Sayıl; Ibis¸, C. Acta Crystallogr. 2009, E65, O272–U1715.