Synthesis of some novel S-and N, S-substituted chlorobutadienes

Article abstract of DOI:10.1080/10426507.2012.657313

Mono(thio)substituted nitrodienes were synthesized by reactions of 2-nitro-pentachloro-1,3-butadiene with some thiols [(tert-butylbenzyl)thio- and 2,3,5,6-tetra-fluorophenylthio-] either directly or in ethanol in the presence of sodium hydroxide. N,S-Subs

Full text of DOI:10.1080/10426507.2012.657313

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Phosphorus, Sulfur, and Silicon and the
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Synthesis of Some Novel S- and N,S-
Substituted Chlorobutadienes
a
Cemil İbiş , Zeliha Gökmen a & Zerrin Çetin a
a Division of Organic Chemistry, Department of Chemistry, Faculty of
Engineering, Istanbul University, Istanbul, Turkey
Accepted author version posted online: 23 Jan 2012.Version of
record first published: 07 Jun 2012.
To cite this article: Cemil İbiş , Zeliha Gökmen & Zerrin Çetin (2012): Synthesis of Some Novel S- and
N,S-Substituted Chlorobutadienes, Phosphorus, Sulfur, and Silicon and the Related Elements, 187:8,
965-975
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Phosphorus, Sulfur, and Silicon, 187:965–975, 2012
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426507.2012.657313
SYNTHESIS OF SOME NOVEL S- AND
N,S-SUBSTITUTED CHLOROBUTADIENES
˙
Cemil Ibis¸, Zeliha Go¨kmen, and Zerrin C¸ etin
Division of Organic Chemistry, Department of Chemistry, Faculty of Engineering,
Istanbul University, Istanbul, Turkey
GRAPHICAL ABSTRACT
Cl
SR1
N
Cl
Cl
Cl
Cl
HN NR2
R1_SH
Cl
Cl
Cl
SR1
NR2
Cl
Cl
NO2
Cl
NO2
Cl
NO2
Abstract Mono(thio)substituted nitrodienes were synthesized by reactions of 2-nitro-
pentachloro-1,3-butadiene with some thiols [(tert-butylbenzyl)thio- and 2,3,5,6-tetra-
fluorophenylthio-] either directly or in ethanol in the presence of sodium hydroxide.
N,S-Substituted 1,3-butadienes were obtained from the reaction of the mono(thio)substituted
nitrodienes with morpholine and some piperazine derivatives in dichloromethane. Also
mono- and di(thio)substituted perchlorobutadienes were synthesized from the reactions of
hexachloro-1,3-butadiene with o-aminothiophenol in ethanol in the presence of sodium
hydroxide. The structures of the new compounds were characterized by microanalysis and
spectroscopic data.
Keywords Morpholine; N,S-substituted nitrodiene; piperazine derivatives; polychloro-1,3-
butadiene; thioether
INTRODUCTION
It has been reported previously that some mono-, bis-, tris-, tetrakis, and pen-
takis(thio)substituted diene compounds can be prepared from hexachloro-1,3-butadiene.1–8
We have obtained the novel N,S-substituted nitrobutadienes by reaction of some
mono(thio)substituted nitrobutadienes with morpholine and piperazine derivatives.9–16
Substituted piperazine compounds are important for clinical chemistry17 and also have
been subjected to medicinal applications and gene transfer studies due to their interesting
biological activity and chemical effects.18 Substituted morpholines enhanced the activity
against Gram-positive bacteria.19
Nitro-1,3-butadienes, especially their halogen derivatives have proved to be useful
precursors for synthesizing new complex polyfunctional derivatives of different compound
classes and various functional heterocyclic compounds showing antibacterial, antiviral,
antihelmintic activity as well as antiarrhytmic, antihypoxic, and antitumor activity.20
Received 16 November 2011; accepted 10 January 2012.
This work was funded by the Research Fund of Istanbul University, Istanbul, Turkey.
˙
Address correspondence to Cemil Ibis¸, Division of Organic Chemistry, Department of Chemistry, Faculty
of Engineering, Istanbul University 34320, Avcilar, Istanbul, Turkey. E-mail: ibiscml@istanbul.edu.tr
965

˙
966
C. IBIS¸ ET AL.
The aim of this work was to synthesize novel S-, S,S-, S,S,S-, N,S-substituted
chlorobutadienes by carrying out reactions of hexachlorobutadiene and 2-nitro-pentachloro-
1,3-butadiene with some thiols and N-nucleophiles and to characterize the structure of these
novel compounds.
RESULT AND DISCUSSION
The mono(thio)substituted compounds 3a and 3b were obtained from the reactions of
1 with 2a and 2b. The tris(thio)substituted compound 4a was prepared by the reaction be-
tween 1 and 2a in the presence of NaOH in EtOH. The mono(thio)substituted compounds 3a
and 3b were treated with some piperazine derivatives and morpholine in dichloromethane.
The N,S-substituted nitrodiene compounds 6a, 8a–c, 10a, and 12a were achieved from the
reactions of 3a with 5, 7a, 7b, 7c, 9, and 11, respectively. In the same way, 6b and 8d–f
were synthesized from the reactions of 3b with 5, 7a, 7b, and 7c, respectively. The new
N,S-substituted nitrodienes were obtained in good yields and are stable yellow solids. These
substitution reactions proceed via an addition-elimination reaction mechanism.9 The new
compounds were purified by column chromatography.
The mono- and bis(thio)substituted butadiene compounds 14 and 15 were prepared
by the reaction of hexachloro-1,3-butadiene 13 with o-aminothiophenol in the presence of
NaOH in EtOH (Scheme 1).
The structures of all products were determined by microanalysis and spectroscopic
1
data such as IR, H NMR, 13C NMR, and MS. The spectroscopic characterization of
all compounds is reported in the experimental section. All these new compounds gave
spectroscopic data in accordance with the proposed structures.
The mono(thio)substituted nitrobutadiene compound 3a gave 1H NMR methyl signals
at δ = 1.24 ppm and methyl 13C NMR signals at δ = 30.23 ppm. The mass spectrum of
the tris(thio)substituted nitrobutadiene 4a in the positive ion mode for ESI confirmed the
proposed structure; the molecular peak was identified at m/z: 701.78 [M]+. The molecular
peak of 4a was given in Figure 1.
The 1H NMR spectrum of 3b exhibits aromatic proton multiplets at δ = 7.23–7.33
ppm. In the 13C NMR spectra of compounds 6a, 8a, 8b, and 8c, which contain the morpho-
line and piperazine ring, the morpholine carbons were observed at δ = 52.55, 65.35 for 6a,
the piperazine carbons were observed at δ = 49.35, 52.32, δ = 49.45, 52.04, δ = 48.22,
49.70 ppm for 8a, 8b, and 8c, respectively.
In the IR spectra of 10a and 12a, no lines in the region 3200–3450 cm−1, region
attributable to the streching vibration of the bonded N-H group, were observed. So it was
obvious that the butadienyl groups were connected from both sides to piperazine ring to form
disubstituted butadienyl piperazine compounds. In the 1H NMR spectra of compounds 6b,
8d, 8e, and 8f, which contain the morpholine and piperazine ring, the morpholine protons
were observed as three broad singlet at δ = 3.85–3.28 ppm for 6a, the piperazine protons
were observed as three broad singlet at δ = 2.80–4.14, δ = 2.88–4.11, δ = 2.05–3.95 ppm
for 8d, 8e, and 8f, respectively. The IR specta of 14 and 15 showed a characteristic N-H
streching band for the NH2 group at ν = 3382, 3478 cm−1, and ν = 3379, 3475 cm−1
,
respectively.
The title compounds, C15H15Cl4NO2S and C20H13Cl3F5N3O2S, contain the expected
N,S-substituted butadienyl skeleton, phenly rings, and a piperazine ring for 8d. The bu-
tadiene unit was not completely planar as one would expect if the double bonds were
fully conjugated. The C C bond lengths of the butadiene chain are 1.311(2)Å, 1.475(3)Å,

SYNTHESIS OF SOME NOVEL S- AND N,S-SUBSTITUTED CHLOROBUTADIENES
967
Cl
Cl
R1
2,3,4,6,10,12
a
Cl
Cl
SR1
R1_SH
2
Cl
Cl
Cl
Cl
NO2
Cl
3
Cl
SR1 SR1
F
Cl
NO2
F
b
1
SR1
NO2
F
F
4
R2
7
a
SR1
N
HN
O
Cl
o_F_C6H4
_
Cl
Cl
Cl
5
O
p_F_C6H4
_
CH2Cl2
b
c
Cl
NO2
6
_
CH3
HN
NR2
Cl
Cl
SR1
N
NR2
7
R1
R2
CH2Cl2
Cl
Cl
NO2
8
8
p-ter.butyl_C6H4_CH2
o_F_C6H4
p_F_C6H4
H3C-
_
_
a
3
SR1
HN
NH
_
p-ter.butyl_C6H4_CH2
p-ter.butyl_C6H4_CH2
_
NO2 Cl
b
c
11
N
N
_
Cl
CH2Cl2
NO2
SR1 Cl
12
F
F
_
o_F_C6H4
CH3
d
CH3
N
HN
NH
F
F
F
F
Cl
SR1
N
p_F_C6H4
_
NO2 Cl
Cl
9
H3C
e
f
Cl
Cl
NO2
CH3
CH2Cl2
SR1 Cl
F
F
10
F
F
H3C-
F
F
SR3
Cl
Cl
SR3
Cl
Cl
Cl
Cl
R3_SH
2
EtOH / NaOH
R3 = o_H2N_C6H4
_
Cl
Cl
Cl
Cl
+
SR3 Cl
Cl
Cl
13
Cl
Cl
14
15
Scheme 1 Reaction of chlorobutadienes 1 and 13 with thiols and monothiosubstituted nitrodienes with derivatives
of amines.
1.357(2) Å for compound 3a and 1.287(5) Å, 1.471(4) Å, 1.390(4) Å, respectively, for
C1-C2, C2-C3 and C3-C4 .The observed values in 3a and 8d are consistent with the cor-
responding values in similar compounds.21 The phenyl ring is planar with a maximum
deviations of 0.0075 Å (plane 1: C6-C7-C8-C9-C10-C11) in compound 3a. In the com-
pound 8d, the piperazine ring adopts a chair conformation and planar with a maximum
deviation of 0.0174(1) Å. The distances of two chair atoms in the para positions (N2 and
N3) from the plane of the other four atoms of the six-membered piperazine ring are 0.631
(1) Å and −0.672(1) Å, respectively. The two phenyl rings of compound 8d are planar with
maximum deviations of 0.0043 Å (plane 1: C5-C6-C7-C8-C9-C10) and 0.0028 Å (plane

˙
968
C. IBIS¸ ET AL.
Figure 1 Full-MS spectrum of compound 4a in the positive mode of ESI.
2: C15-C16-C17-C18-C19-C20). The dihedral angles are 19.0(1)◦, 37.7(1)◦ between the
planes of the phenyl rings (plane 1 and plane 2) and piperazine ring, respectively. Yellow
single crystals of 3a and orange single crystals of 8d crystallized from ethanol and were
unambiguously characterized by means of X-ray experiments (see Figures 2. and 3 and
Supplemental Materials; Tables 1 and 2).
EXPERIMENTAL
Melting points were measured on a Bu¨chi B-540 capillary apparatus and were uncor-
rected. IR spectra (ν/cm−1) were recorded on an FTIR spectrometer Shimadzu IR Prestige
Figure 2 The molecular structure of the 3a compound. Displacement ellipsoids are drawn at the 50% probability
level.

SYNTHESIS OF SOME NOVEL S- AND N,S-SUBSTITUTED CHLOROBUTADIENES
Table 1 Crystal data and refinement parameters
969
Compound 3a
Compound 8d
CCDC 851960
C20H13Cl3F5N3O2S
Orange, block
560.75
CCDC number
Empirical formula
Crystal color, habit
Formula weight
Temperature
CCDC 852475
15H15Cl4NO2S
Yellow, block
415.16
C
293.1 K
293.1 K
Wavelength
0.71070 Å
0.71070 Å
Crystal system
Space group
Monoclinic
P21/n
Monoclinic
P21/n
Cell dimensions
a = 9.5473(3) Å
b = 16.5512(5)Å
c = 12.3094(4) Å
β = 106.700(2) Å
1863.09(10) Å3
4
a = 7.3342(2) Å
b = 20.3489(6)Å
c = 15.0409(5) Å
β = 91.438(2) Å
2244.04(12) Å3
4
Volume
Z
Density (calculated)
F000
1.480 g/cm3
848.00
1.660 g/cm3
1128.00
Crystal size
Index ranges
0.7 × 0.6 × 0.4 mm
−13 ≤ h ≤ 13
−23 ≤ k ≤ 23
−17 ≤ l ≤ 17
110734
0.5 × 0.4 × 0.2 mm
−8 ≤ h ≤ 8
−24 ≤ k ≤ 24
−17 ≤ l ≤ 17
84162
Reflections collected
Independent reflections
Goodness of fit indicator
Final R indices [I>3σ(I)]
Largest diff. peak and hole
5653[Rint = 0.025]
4128 [Rint = 0.101]
1.231
1.184
R1 = 0.073, wR2 = 0.033
0.61 and −0.47 eÅ−3
R1 = 0.043, wR2 = 0.042
0.24 and −0.28 eÅ−3
1
21 model Diamond, ATR method. H and 13C NMR spectra were recorded on a Var-
1
ian Unity Inova spectrometer at 499.83 MHz for H 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
Table 2 Selected geometric parameters of 3a and 8d compounds (Å,◦). H atoms were treated as riding, with
C—H = 0.95 (6) Å and Uiso(H) = 1.2Ueq(C).
Compounds
3a
8d
Bond lengths (Å)
S1—C5
C3—C4
C3—C2
C1—C2
Bond angles(o)
C4—C3—C2
1.824 (2)
1.357 (2)
1.475 (3)
1.311 (2)
1.775(3)
1.390(4)
1.471(4)
1.287(5)
123.6 (2)
121.7 (2)
122.9 (3)
124.0 (3)
C3—C2—C1
Torsion angels(o)
C4—S1—C5—C6
N1—C3—C2—Cl3
C4—C3—C2—C1
N3—C12—C11—N2
N3—C13—C14—N2
−177.7(9)
87.6(2)
88.0 (2)
—
−53.6(3)
−81.1 (3)
−92.4(4)
−59.5 (4)
54.3 (4)
—

˙
C. IBIS¸ ET AL.
970
Figure 3 The molecular structure of the 8d compound. Displacement ellipsoids are drawn at the 50% probability
level.
QTRAP was operated in the triple quadruple mass spectrometer mode using an electrospray
ionization (ESI) source in the experiments presented here. Elemental analyses (C, H, S)
were conducted using the Thermo Finnigan Flash EA 1112 elemental analyzer; their re-
sults 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 chromatogra-
phy (TLC). All chemicals were reagent grade and were used without further purification.
Moisture was excluded from the glass apparatus using CaCl2 drying tubes.
X-Ray Structure Data Collection and Refinement
All measurements were made on a Rigaku R-Axis Rapid-S imaging plate area detector
with graphite monochromated Mo-Kα radiation (λ = 0.71070 Å). The data were collected at
room temperature to a maximum θ value of 30.2◦. Experimental conditions are summarized
in Table 1. The structure was solved by SIR9222 and refined with CRYSTALS.23 H atoms
were treated as riding, with C–H = 0.95 (6) Å and Uiso(H) = 1.2Ueq(C). Drawings were
performed with the program ORTEP-III24 with 30% probability displacement ellipsoids in
Figures 2 and 3. Crystallographic data (excluding structure factors) for the structure reported
in this paper have been deposited with the Cambridge Crystallographic Data Centre as sup-
plementary publication no. CCDC-852475 and CCDC-851960. The data and any further in-
formation can be obtained free of charge at http://www.ccdccam.ac.uk/const/retrieving.html
or from the Cambridge Crystallographic Data Centre (CCDC), 12 Union Road, Cambridge
CB2 1EZ, UK; fax:+44-1223-336033 or e-mail: deposit@ccdc.cam.ac.uk
General Procedure 1
Equimolar amounts of 2-nitro-pentachloro-1,3-butadiene (1) and thiol were stirred
directly for 12–24 h at room temperature. The end of the reactions was checked by TLC.

SYNTHESIS OF SOME NOVEL S- AND N,S-SUBSTITUTED CHLOROBUTADIENES
971
Chloroform was added to the reaction mixture to separate the organic layer. Then, the
organic layer was washed with water (4 × 30 mL) and dried with Na2SO4 or MgSO4. After
filtering, the solvent was evaporated and the residue was purified by column chromatography
on silica gel or by crystallization.
General Procedure 2
Equimolar amounts of the mono(thio)substituted nitrodienes 3a, 3b, and N-
nucleophiles (morpholine, piperazine, and their derivatives) were stirred for 2 to 4 h at
room temperature in CH2Cl2. The end of the reactions was checked by TLC. CHCl3 was
added to the reaction mixture to separate the organic layer. Then, the organic layer was
washed with water (4 × 30 mL) and dried with Na2SO4 or MgSO4. After filtering, the
solvent was evaporated and the residue was purified by column chromatography on silica
gel or crystallization.
2-Nitro-1-[(4-tert-butylbenzyl)thio]-1,3,4,4-tetrachloro-1,3-butadiene
(3a):
Compound 3a was synthesized from 1 (1.0 g, 3.72 mmol) and 2a (0.67 g, 3.72 mmol)
according to the general procedure 1. Yellow single crystals of 3a suitable for X-ray
analysis were obtained by slow evaporation of an ethanol solution. Yield: 1.46 g (95%).
M.p.: 110.2–111.0 ◦C. Rf 0.6 (PET/CHCl3 2:1). IR: 3058 (C-Harom.), 2866, 2964
1
(C-Haliph.), 1601 (C C), 1525, 1293 (NO2). H NMR: 1.24 (s, 9H, CH3), 4.29 (s, 2H,
SCH2), 7.21–7.23 (d, J = 8.3 Hz, 2H, Harom.), 7.31–7.33 (d, J = 8.3 Hz, 2H, Harom.). 13
C
NMR: 30.2 (CH3), 33.6 (Cq-t-butyl), 39.7 (SCH2), 120.3, 127.9, 137.4, 156.0 (Cbutadien).
C15H15Cl4NO2S (415.16), calcd. C, 43.40; H, 3.64; S, 7.72; N, 3.37; found C, 43.77; H,
3.69; S, 7.03; N, 3.00.
2-Nitro-1-(2,3,5,6-tetrafluorophenylthio)-1,3,4,4-tetrachloro-1,3-butadiene (3b):
Compound 3b was synthesized from 1 (1.92g, 7.14 mmol) and 2b (1.3 g, 7.14 mmol)
according to the general procedure 1. Yellow crystals. Yield: 2.03 g (89%). M.p.: 78.0–79.0
1
◦C. Rf 0.57 (PET/CHCl3 2:1). IR: 3084 (C-Harom.), 1607 (C C), 1304, 1544 (NO2). H
NMR: 7.23–7.33 (m, 1H, Harom.).13C NMR: 109.7–110.1 (m, CHarom.), 110.7–111.20 (t,
S-Carom.), 120.1, 130.2, 141.2,152.8 (Cbutadien). C10HCl4F4NO2S (416.84), calcd. C, 28.80;
H, 0.24; S, 7.69; N, 3.36; found C, 29.49; H, 0.56; S, 7.83; N, 2.95.
4,4-Dichloro-2-nitro-1,1,3-tris[(4-tert-butylbenzyl)thio]-1,3-butadiene
(4a):
Compound 4a was synthesized from 1 (1.0 g, 3.71 mmol) and 2a (1.34 g, 7.42 mmol)
at room temperature in the presence of NaOH in EtOH. Yellow crystals. Yield: 1.95 g
◦
(75%). M.p.: 91.1–92.0 C. Rf 0.56 (PET/CHCl3 1:1). IR: 3027, 3055 (C-Harom.), 2867,
1
2904, 2963 (C-Haliph.), 1573, 1611 (C C), 1310, 1535 (NO2). H NMR: 1.16 (s, 18H,
CH3), 1.21 (s, 9H, CH3), 4.05 (s, 2H, SCH2), 4.09 (s, 4H, SCH2), 7.05–7.26 ppm (m, 12H,
Harom.). 13C NMR: 30.2, 30.3 ppm (CH3), 33.5, 33.5 (Cq-t-butyl), 36.3, 38.9, 39.6 (SCH2),
124.0, 127.7, 143.4, 150.9 (Cbutadien). MS (+ESI): m/z 701.78 [M]+. C37H45Cl2NO2S3
(702.86), calcd. C, 63.23; H, 6.45; S, 13.69; N, 1.99; found C, 63.36; H, 6.62; S, 12.21; N,
2.88.
1-Morpholino-2-nitro-1-[(4-tert-butylbenzyl)thio]-3,4,4-trichloro-1,3-butadiene
(6a): Compound 6a was synthesized from 3a (0.1 g, 0.24 mmol) and 5 (0.022 g, 0.24
mmol) according to the general procedure 2. Yellow crystals. Yield: 0.036 g (32%). M.p.:
◦
154.0–155.0 C. Rf 0.35 (CH2Cl2). IR: 3054 (C-Harom.), 2870, 2965 (C-Haliph.), 1592
1
(C C), 1273, 1531 (NO2). H NMR: 1.24 (s, 9H, CH3), 3.33–3.63 (bs, 4H, CH2morph.),
3.69 (s, 4H, CH2morph.), 4.10 (s, 2H, SCH2), 7.11–7.13 (d, J = 8.3 Hz, 2H, Harom.),
7.28–7.30 (d, J = 8.3 Hz, 2H, Harom.). 13C NMR: 30.3 (CH3), 33.6 (Cq-t-butyl), 38.9

˙
C. IBIS¸ ET AL.
972
(SCH2), 52.6 (NCH2), 65.4 (OCH2), 108.8, 118.1, 124.2, 150.6 (Cbutadien). MS (+ESI):
m/z 489.84 [M+Na]+. C19H23Cl3N2O3S (465.82), calcd. C, 48.99; H, 4.98; S, 6.88; N,
6.01; found C, 49.12; H, 4.59; S, 6.59; N, 6.11.
1-Morpholino-2-nitro-1-(2,3,5,6-tetrafluorophenylthio)-3,4,4-trichloro-1,3-
butadiene (6b): Compound 6b was synthesized from 3b (0.1 g, 0.24 mmol) and 5 (0.021
g, 0.24 mmol) according to the general procedure 2. Yellow crystals. Yield: 0.097 g (86%).
M.p.: 172.0–173.0 ◦C. Rf 0.40 (CH2Cl2). IR: 3058 (C-Harom.), 2856, 2985 (C-Haliph.), 1587,
1621 (C C), 1276, 1537 (NO2). 1H NMR: 3.28–3.44 (bs, 2H, CH2morph.), 3.57–3.71 (bs,
4H, CH2morph.), 3.72–3.85 (bs, 2H, CH2morph.), 7.11–7.18 (m, 1H, Harom.). 13C NMR: 52.7
(NCH2), 65.2 (OCH2), 107.5–107.8 (t, CHarom.), 109.2–109.5 (t, SCarom.), 120.4, 123.9,
126.1, 161.3 (Cbutadien). MS (+ESI): m/z 490.80 [M+Na]+. C14H9Cl3F4N2O3S (467.65),
calcd. C, 35.96; H, 1.94; S, 6.86; N, 5.99; found C, 35.46; H, 1.86; S, 7.28; N, 5.96.
1-[(2-Fluorophenyl)piperazinyl]-2-nitro-1-[(4-tert-butylbenzyl)thio]-3,4,4-
trichloro-1,3-butadiene (8a): Compound 8a was synthesized from 3a (0.1 g, 0.24 mmol)
and 7a (0.04 g, 0.24 mmol) according to the general procedure 2. Yellow crystals. Yield:
0.113 g (83%). M.p.: 160.0–160.3 ◦C. Rf 0.53 (CH2Cl2). IR: 3054 (C-Harom), 2862, 2961
1
(C-Haliph.), 1586, 1611 (C C), 1275, 1540 (NO2). H NMR: 1.24 (s, 9H, CH3), 3.12 (s,
4H, CH2piper), 3.45–3.92 (bs, 4H, CH2piper), 4.12 (s, 2H, SCH2), 6.82–6.86 (t, 1H, Harom),
6.91-7.02 (m, 3H, Harom.), 7.13–7.15 (d, J = 8.3 Hz, 2H, Harom.), 7.28–7.31 ppm (d, J =
8.3 Hz, 2H, Harom.), 2). 13C NMR: 30.2 (CH3), 33.6 (Cq-t-butyl), 38.9 (SCH2), 49.4, 52.3
(NCH2), 115.4, 115.5, 124.1, 150.5 (Cbutad.), 153.7, 155.7 (F-Carom.). MS (+ESI): m/z
582.63 [M+Na]+. C25H27Cl3FN3O2S (558.92), calcd. C, 53.72; H, 4.87; S, 5.74; N, 7.52;
found C, 53.34; H, 4.80; S, 6.12; N, 7.99.
1-[(4-Fluorophenyl)piperazinyl]-2-nitro-1-[(4-tert-butylbenzyl)thio]-3,4,4-
trichloro-1,3-butadiene (8b): Compound 8b was synthesized from 3a (0.1 g, 0.24 mmol)
and 7b (0.04 g, 0.24 mmol) according to the general procedure 2. Red crystals. Yield:
0.115 g (86%). M.p.: 176.4–177.0 ◦C. Rf 0.50 (CH2Cl2). IR: 3028, 3063 (C-Harom.), 2868,
2966 (C-Haliph.), 1588, 1607 (C C), 1269, 1538 (NO2). 1H NMR: 1.24 (s, 9H, CH3), 3.12
(s, 4H, CH2piper.), 3.48–3.79 (bs, 4H, CH2piper.), 4.12 (s, 2H, SCH2), 6.78–6.81 (m, 2H,
Harom.), 6.89–6.93 (t, 2H, Harom.), 7.13–7.15 (d, J = 8.3 Hz, 2H, Harom.), 7.29–7.30 (d, J
= 8.3 Hz, 2H, Harom.). 13C NMR: 30.3 (CH3), 33.6 (Cq-t-butyl), 38.9 (SCH2), 49.5, 52.0
(NCH2), 124.2, 128.1, 145.6, 150.6 (Cbutadien), 157.9, 156.0 (F-Carom.). MS (+ESI): m/z
582.48 [M+Na]+. C25H27Cl3FN3O2S (558.92), calcd. C, 53.72; H, 4.87; S, 5.74; N, 7.52;
found C, 53.98; H, 5.00; S, 7.45; N, 7.39.
1-(N-Methylpiperazinyl)-2-nitro-1-[(4-tert-butylbenzyl)thio]-3,4,4-trichloro-1,
3-butadiene (8c): Compound 8c was synthesized from 3a (0.1 g, 0.24 mmol) and 7c
(0.024 g, 0.24 mmol) according to the general procedure 2. Yellow crystals. Yield: 0.08
g (69%). M.p.: 125.4–126.3 ◦C. Rf 0.60 (MeOH). IR: 3026, 3054 C-Harom.), 2801, 2870,
1
2966 (C-Haliph.), 1591 (C C), 1275, 1534 (NO2). H NMR: 1.24 (s, 9H, CH3), 2.25 (s,
3H, NCH3), 2.44 (s, 4H, CH2 piperazine), 3.36–3.68 (bs, 4H, CH2piper.), 4.09 (s, 2H, SCH2),
7.12–7.13 (d, J = 8.3 Hz, 2H, Harom.), 7.28–7.29 ppm (d, J = 8.3 Hz, 2H, Harom.). 13C
NMR: 26.2, 26.4 ppm (CH3), 29.7 (NCH3), 34.9 (Cq-t-butyl), 40.6, 40.7 (SCH2), 48.2,
49.7 (NCH2), 113.8, 119.94, 146.5, 162.9 (Cbutadiene). MS (+ESI): m/z 478.35 [M]+.
C20H26Cl3N3O2S (478.86), calcd. C, 50.16; H, 5.47; S, 6.70; N, 8.77; found C, 50.22; H,
5.11; S, 7.22; N, 8.46.
1-[(2-Fluorophenyl)piperazinyl]-2-nitro-1-(2,3,5,6-tetrafluorophenylthio)-3,4,4-
trichloro-1,3-butadien (8d): Compound 8d was synthesized from 3b (0.1 g, 0.24 mmol)
and 7a (0.04 g, 0.24 mmol) according to the general procedure 2. Orange single crystals

SYNTHESIS OF SOME NOVEL S- AND N,S-SUBSTITUTED CHLOROBUTADIENES
973
of 8d suitable for X-ray analysis were obtained by slow evaporation of an ethanol
solution. Yield: 0.06 g (44%). M.p.: 176.4–177.0 ◦C. Rf 0.56 (CHCl3). IR: 3054 C-Harom.),
1
2862, 2963 (C-Haliph.), 1590, 1627 (C C), 1267, 1537 (NO2). H NMR: 2.80–3.26 (bs,
4H, CH2 piperazine.), 3.39–3.65 (bs, 2H, CH2 piperazine.), 3.76–4.14 (bs, 2H, CH2 piperazine.),
6.80–6.86 (t, 1H, Harom.), 6.91–7.04 (m, 3H, Harom.), 7.08–7.17 (m, 1H, Harom.). 13C NMR:
49.3, 52.5 (NCH2), 108.5–109.0 (t, CHarom.), 110.0 (SCarom.), 118.5 (d, CHarom.), 121.8,
124.0, 126.1, 162.2 (Cbutadiene). MS (+ESI): m/z 584.28 [M+Na]+. C20H13Cl3F5N3O2S
(560.75), calcd. C,42.84; H, 2.34; S, 5.72; N, 7.49; found C, 42.51; H, 2.12; S, 6.28; N,
7.63.
1-[(4-Fluorophenyl)piperazinyl]-2-nitro-1-(2,3,5,6-tetrafluorophenylthio)-3,4,4-
trichloro-1,3-butadiene (8e): Compound 8e was synthesized from 3b (0.1 g, 0.24 mmol)
and 7b (0.04 g, 0.24 mmol) according to the general procedure 2. Orange crystals.
Yield: 0.072 g (53%). M.p.: 177.1–178.0 ◦C. Rf 0.5(CHCl3). IR: 3056 (C-Harom.),
1
2840, 2919 (C-Haliph.), 1595, 1631 (C C), 1279, 1559 (NO2). H NMR: 2.88–3.24 (bs,
4H, CH2 piperazine.), 3.37–3.63 (bs, 2H, CH2 piperazine.), 3.80–4.11 (bs, 2H, CH2 piperazine.),
6.76–6.84 (m, 2H, Harom.), 6.90–6.97 (m, 2H, Harom.), 7.08–7.17 (m, 1H, Harom.). 13C NMR:
49.5, 52.3 (NCH2), 107.3–107.8 (t, CHarom.), 109.4 (SCarom.), 114.9, 115.0 (CHarom.),
117.8–117.9 (d, CHarom.), 120.8, 123.9, 126.1, 161.3 (Cbutadiene). MS (+ESI): m/z 560.09
[M]+. C20H13Cl3F5N3O2S (560.75), calcd. C, 42.84; H, 2.34; S, 5.72; N, 7.49; found C,
42.63; H, 2.37; S, 5.74; N, 7.61.
1-(N-Methylpiperazinyl)-2-nitro-1-(2,3,5,6-tetrafluorophenylthio)-3,4,4-
trichloro-1,3-butadiene (8f): Compound 8f was synthesized from 3b (0.1 g, 0.24
mmol) and 7c (0.024 g, 0.24 mmol) according to the general procedure 2. Yellow
◦
crystals. Yield: 0.71 g (61%). M.p.: 119.2–120.0 C. Rf 0.40 (CH2Cl2/EtAc 1:1). IR:
3052 (C-Harom.), 2812, 2962 (C-Haliph.), 1585, 1629 (C C), 1274, 1539 (NO2). 1H NMR:
2.05–2.60 (bs, 4H, CH2piper.), 2.26 (s, 3H, CH3), 3.23–3.51 (bs, 2H, CH2piper.), 3.64–3.95
(bs, 2H, CH2piper.), 7.09–7.16 (m, 1H, Harom.). 13C NMR: 44.6 (NCH3), 52.3, 53.5 (NCH2),
107.3–107.6 (t, CHarom.), 109.5 (SCarom.), 120.2, 124.1, 125.9, 161.3 (Cbutadiene). MS
(+ESI): m/z 503.86 [M+Na]+. C15H12Cl3F4N3O2S (480.69), calcd. C, 37.48; H, 2.52; S,
6.67; N, 8.74; found C, 37.27; H, 2.48; S, 6.67; N, 8.61.
N,N-Bis[2-nitro-1-[(4-tert-butylbenzyl)thio]-3,4,4-trichloro-1,3-butadienyl]-2,5-
dimethylpiperazine (10a): Compound 10a was synthesized from 3a (0.1 g, 0.24 mmol)
and 9 (0.027 g, 0.24 mmol) according to the general procedure 2. Yellow crystals. Yield:
0.71 g (81%). M.p.: 226.0◦C. Rf 0.62 (CH2Cl2). IR: 3027, 3056 (C-Harom.), 2868, 2906,
1
2963 (C-Haliph.), 1587, 1663 (C C), 1272, 1516 (NO2). H NMR: 1.20 (s, 24H, CH3),
2.44–2.67 (bs, 2H, CHpiper.), 3.65–3.78 (bs, 2H, CH2piper.), 3.65–3.78 (bs, 2H, CH2piper),
4.19–4.38 (bs, 2H, SCH2), 4.43–4.63 (bs, 2H, SCH2), 7.09–7.10 (d, J = 8.3 Hz, 4H,
Harom.), 7.25–7.27 (d, J = 8.3 Hz, 4H, Harom.). MS (+ESI): m/z 893.00 [M+Na]+.
C36H42Cl6N4O4S2 (871.59), calcd. C, 49.61; H, 4.86; S, 7.36; N, 6.43; found C, 49.93; H,
4.53; S, 7.33; N, 6.29.
N,N-Bis[2-nitro-1-[(4-tert-butylbenzyl)thio]-3,4,4-trichloro-1,3-butadienyl]-
piperazine (12a): Compound 12a was synthesized from 3a (0.1 g, 0.24 mmol) and
11 (0.021 g, 0.24 mmol) according to the general procedure 2. Yellow crystals. Yield:
◦
0.093 g (46%). M.p.: 228.0–228.6 C. Rf 0.4 (CH2Cl2). IR: 3054 (C-Harom.), 2868, 2963
(C-Haliph.), 1601 (C C), 1278, 1537 (NO2). 1H NMR: 1.23 (s, 18H, CH3), 3.04–3.50 (bs,
4H, CH2 piperazine.), 3.51–3.85 (bs, 4H, CH2 piperazine.), 3.87–4.25 (bs, 4H, SCH2), 7.09–7.11
(d, J = 8.3 Hz, 4H, Harom.), 7.28–7.29 ppm (d, J = 8.3 Hz, 4H, Harom.), 13C NMR:
29.9, 31.5 (CH3), 34.9 (Cq-t-butyl), 40.3 (SCH2), 51.7 (NCH2), 110.0, 121.4, 126.2,

˙
C. IBIS¸ ET AL.
974
152.0 (Cbutadiene). MS (+ESI): m/z 864.86 [M+Na]+. C34H38Cl6N4O4S2 (843.54), calcd.
C,48.41; H, 4.54; S, 7.60; N, 6.64; found: C, 48.81; H, 4.53; S, 6.24; N, 6.70.
1-(2-Aminophenylthio)-1,2,3,4,4-pentachloro-1,3-butadiene (14): Compound 14
was synthesized from of 13 (2 g, 7.75 mmol) and o-aminothiophenol (1.94 g, 15.5 mmol)
at room temperature in the presence of NaOH in EtOH. Brown crystals. Yield: 0.66 g
◦
(24%). M.p.: 46.5–47.0 C. Rf 0.84 (PET/CHCl3 1:1). IR: 3020, 3068 (C-Harom.), 1545,
1610 (C C), 3382, 3478 (NH2). 1H NMR: 4.17 (s, 2H, NH2), 6.64–6.68 (m, 2H, Harom.),
7.15–7.20 (t, J = 7.32 Hz, 1H, Harom.), 7.29–7.31 (dd, J1 = 7.81 Hz, J2 = 1.47 Hz, 1H,
Harom). 13C NMR: 120.6, 125.2, 126.0, 134.4 (Cbutadiene.). MS (+ESI): m/z 349.86 [M+H]+,
MS/MS (+ESI): m/z 313.89 (M-Cl). C10H6Cl5N (349.49), calcd. C, 34.37; H, 1.73; S, 9.17;
N, 4.01; found C, 34.57; H, 1.93; S, 10.28; N, 3.94.
1,4-Bis(2-aminophenylthio)-1,2,3,4-tetrachloro-1,3-butadiene (15): Compound
15 was synthesized from 13 (2 g, 7.75 mmol) and o-aminothiophenol (1.94 g, 15.5 mmol)
at room temperature in the presence of NaOH in EtOH. Yellow Oil. Yield: 1.60 g (47%).
Rf 0.59 (PET/CHCl3 1:1). IR: 3019, 3064 (C-Harom.), 1533, 1609 (C C), 3379, 3475
(NH2). 1H NMR: 3.80–4.55 (bs, 4H, NH2), 6.54–6.70 (m, 4H, Harom.), 7.07–7.20 (m, 3H,
Harom.), 7.36–7.47 (dd, J1 = 7.81 Hz, J2 = 1,46 Hz, 1H, Harom.). MS (+ESI): m/z 439.26
[M+H]+, MS/MS (+ESI): m/z 402.88 (M-Cl). C16H12Cl4N2S2 (438.22), calcd. C, 43.85;
H, 2.76; S, 14.63; N, 6.39; found C, 43.99; H, 2.61; S, 12.88; N, 6.18.
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