Some new S-, S,S- and N,S-substituted 2-nitrodienes and butadienyl-substituted piperazines

Article abstract of DOI:10.1080/10426500490467101

Nitrodiene 1 reacted with 2a,b and gave the novel compounds 3a,b, 4a,b, and 5a. Monosubstituted diene compound 3a gave the compounds 9a with morpholine, 11a with piperidine, and 13a with homopiperazine. Compound 3a gives the thioether compound 15 by the reaction with the dithiol (HS-(CH₂) ₂-O-(CH₂)₂-SH) in ethanol containing sodium hydroxide.

Full text of DOI:10.1080/10426500490467101

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SOME NEW S-, S,S- AND N,S-SUBSTITUTED 2-
NITRODIENES AND BUTADIENYL-SUBSTITUTED
PIPERAZINES
a
a
a
Cemil İbiş , F. Gülay Kirbaşlar & Gökşin Aydinli
a
Istanbul University, Department of Chemistry, Avcilar , Istanbul, Turkey
Published online: 16 Aug 2010.
To cite this article: Cemil İbiş , F. Gülay Kirbaşlar & Gökşin Aydinli (2004) SOME NEW S-, S,S- AND N,S-SUBSTITUTED 2-
NITRODIENES AND BUTADIENYL-SUBSTITUTED PIPERAZINES, Phosphorus, Sulfur, and Silicon and the Related Elements, 179:10,
1975-1982, DOI: 10.1080/10426500490467101
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Phosphorus, Sulfur, and Silicon, 179:1975–1982, 2004
Copyright ꢀC Taylor & Francis Inc.
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500490467101
SOME NEW S-, S,S- AND N,S-SUBSTITUTED
2
-NITRODIENES AND BUTADIENYL-SUBSTITUTED
PIPERAZINES
˙
Cemil Ibi s¸ , F. G u¨ lay Kırba s¸ lar, and G o¨ k s¸ in Aydınlı
Istanbul University, Department of Chemistry, Avcılar,
Istanbul, Turkey
(
Received January 22, 2004; accepted February 20, 2004)
Nitrodiene 1 reacted with 2a,b and gave the novel compounds 3a,b,
4
a,b, and 5a. Monosubstituted diene compound 3a gave the compounds
a with morpholine, 11a with piperidine, and 13a with homopiper-
9
azine. Compound 3a gives the thioether compound 15 by the reaction
with the dithiol (HS (CH ) O (CH ) SH) in ethanol containing
2
2
2 2
sodium hydroxide.
Keywords: 2-Nitrodiene; dibutadienyl piperazine; dibutadienyl piperi-
dine; homopiperazine; monothiosubstituted dienes; morpholine; thiols
It has been reported before in a U.S. patent that some thio-
1
substituted dienes exhibit high biological activity. The reactions
of thiols with hexachlorobutadiene (Cl2C CCl CCl CCl2), per-
chlorobutadiene (Cl2C CH CCl CCl2), and 1H-pentachlorobutadiene
2
−5
(
Cl2C CCl CCl CH Cl) have been observed previously.
Thiosub-
stituted butadienes, butatrienes, and butenins have been obtained
from these reactions,6 and N,N-, N,S-, N,O-, and O,S-substituted 1,3-
–13
1
4−17
nitrobutadiene compounds have been published before.
It is known that some crown ethers and thio crown ethers give
some complex compounds with alkali metals. Moreover some hetero-
cyclic compounds from the reactions of 2-nitrodiene and mono(thio) sub-
stituted nitrodienes (Cl2C CCl C(NO2) CCl(SR)) with dithiols were
obtained. In these reactions, compounds carrying a diene with a
S S group in the ring and some open-chain compounds were also
1
8−23
obtained.
We thank the Research Fund of this University of Istanbul for financial support of
this work.
˙
Address correspondence to Cemil Ibi s¸ , Istanbul Universitesi, Muhendislik Fakultesi,
Kimya Bolumu, Avcilar, Istanbul, Turkey.
1
975

˙
C. Ibi s¸ et al.
1
976
Our aim in this study was to synthesize and characterize new
S,S- and S,N-substituted nitrodiene compounds from the reactions of
some new mono(thio)substituted 2-nitrobutadienes with various thiols,
piperazin, and piperidine.
The reaction of 1 mole 2-nitrodiene 1 with 1 mole thiol gives only
one reaction product after mixing them for a long time without sol-
vent. However 2-nitrodiene gave two thiosubstituted diene compounds
(
mono- and di-) with p-methoxy thiophenol. This is probably due to the
inductive and resonance effect of the methoxy group on the ring.
-Nitrodiene 1 reacted with thiols 2a,b and gave 3a,b, and 4b after
2
mixing them for a long time. 2-Nitrodiene 1 gave 4a, 5a, and 4b in the
reaction with 2a,b in EtOH containing sodium hydroxide.
Compounds 3a,b are unknown new mono(thio)substituted diene
compounds. Compounds 4a,b are also unknown new bis(thio)substi-
tuted diene compounds, and 5a is a new tris(thio)substituted diene
compound. These new compounds are stable, and some of them are
yellow in color. The structure of the reaction products were verified by
1
microanalysis and spectroscopic data such as IR, MS, and H NMR.
We have obtained mono- and disubstituted amine compounds from the
reactions of monothiosubstituted dienes with some amines (piperazine,
piperidine, etc.) before. The piperazine compounds are important for
therapeutical use and also some piperazine compounds were used in
2
4–26
gen transfer.
Compounds 7a–e were obtained from the reactions of
3
a,b with piperazine derivates 6a–e.
The IR spectrum of 7d showed a characteristic >C O band in the
−1
1720 cm region.
Compounds 7a–e are stable monobutadienyl-substituted piper-
azines. Compound 3a gave the N,S-substituted diene compound 9a
with morpholine, 11a with piperidine, and 13a with homopiperazine
(
Scheme 1).
ꢁ
Compound 3a reacted with 2,2 -oxydiethanthiol (HS (CH2)2 O
(
CH2)2 SH) 14 and gave the compound 15. Compound 15 is an un-
saturated interesting compound that has a cyclic structure (Scheme 2).
EXPERIMENTAL SECTION
1H NMR: Bruker AC 200 L. IR: Shimadzu Fourier transform infrared
(
FTIR) 8101. Microanalyses: Carlo-Erba 1110 elemental analyzer. Melt-
ing Points: B u¨ chi SMP 20. Products were isolated by column chromatog-
raphy on SiO2 (Fluka Kieselgel 60, particle size 63–200 µm). TLC plates
silica: 60 F254 (Merck, Darmstadt), detection with ultraviolet light
(
254 nm).

Some New S-, S,S- and N,S-Substituted 2-Nitrodienes
1977
SCHEME 1
Preparation of S-Substituted Polyhalonitrodienes:
General Procedure I
Equimolar amounts of 2-nitro-1,3,4,4-pentachloro-1,3-butadiene 1 and
thiols were stirred for 36 h at room temperature until completion of the
reaction. Chloroform was added to the reaction mixture. The organic
layer was separated and washed with water (4 × 30 ml) and dried

˙
1
978
C. Ibi s¸ et al.
SCHEME 2
with CaCl2 or MgSO4. The solvent was evaporated and the residue was
purified by column chromatography on silica gel.
2
-Nitro-1,3,4,4-tetrachloro-1-(4-methoxyphenylthio)-1,3-
butadiene (3a)
Yellow oil. Yield, 0.585 g (42%). Rf = 0.571 (CCl4). −IR (film):
−1
1
ν = 2950, 3050 cm (C H), 1650 (C C), 1250, 1550 (C NO2). − H
NMR(CDCl3, TMS int.): δ = 3.7–4.0 ppm (m, 3H, OCH3), 6.9–7.6 (m,
4H, Harom.). C11H7SNCl4O3 (375.06) Calcd.: C, 35.23; H, 1.88; N, 3.73.
Found: C, 35.46; H, 2.34; N, 4.18. MS m/z 374.9.
2
-Nitro-1,3,4,4-tetrachloro-1-(2-furanylmethanethio)-1,3-
butadiene (3b)
◦
Yield, 0.995 g (77%). m.p. 64–65 C. Rf = 0.888 (CCl4). IR (KBr): ν =
−1
1
2
900, 3000, 3100 cm (C H), 1610 (C C), 1240, 1540 (C NO2). − H
NMR(CDCl3, TMS int.): δ = 4.4–4.6 ppm (m, 2H, S CH2), 6.3–7.5 (m,
H, Harom). C9H5SNCl4O3 (349.021). MS m/z 348.9.
3
2
-Nitro-3,4,4-trichloro-1,1-bis(4-methoxyphenylthio)-1,3-
butadiene (4a)
◦
Yield, 0.835 g (47%). m.p. 105–106 C. Rf = 0.285 (CCl4). IR (KBr):
−1
1
ν = 2950, 3000 cm (C H), 1595 (C C), 1280, 1520 (C NO2). − H
NMR(CDCl3, TMS int.): δ = 3.7–4.0 ppm (m, 6H, 2 OCH3), 6.6–7.2 (m,
8H, Harom). C18H14S2NCl3O4 (478.805) Calcd.: C, 45.15; H, 2.94; N, 2.92.
Found: C, 45.78; H, 2.85; N, 2.75. MS m/z 478.9.
Preparation of S,S-Substituted Polyhalonitrodienes:
General Procedure II
To a mixture of thiols and 1 or monosubstituted dienes in 30 ml of
ethanol, 2 g of NaOH (in 10 ml of water) was added at room tempera-
ture. The mixture was stirred for 1 h until completion of the reaction.
Chloroform was added to the reaction mixture. The organic layer was
separated and washed with water (4 × 30 ml) and dried with CaCl2 or

Some New S-, S,S- and N,S-Substituted 2-Nitrodienes
1979
MgSO4. The solvent was evaporated and the residue was purified by
column chromatography on silica gel.
2
-Nitro-3,4,4-trichloro-1,1-bis(2-furanylmethanethio)-1,3-
butadiene (4b)
Brown oil. Yield, 0.585 g (37%). Rf = 0.866 (CHCl3). IR (film): ν =
−1
1
2
950, 3050 cm
(C H), 1590 (C C), 1280, 1550 (C NO2). − H
NMR(CDCl3, TMS int.): δ = 3.6–4.5 ppm (m, 4H, 2S CH2), 6.9–706
(
m, 6H, Harom.). C14H10S2NCl3O4 (426.728). MS m/z 425.9.
2
-Nitro-1,1,4-tris(4-methoxyphenylthio)-3,4-dichloro-1,3-
butadiene (5a)
◦
Yield, 1.548 g (72%). m.p. 147–148 C. Rf = 0.925 (CHCl3). IR (KBr):
−1
ν = 2850, 2950, 3020 cm (C H), 1650 (C C), 1250, 1510 (C NO2).
1
−
H NMR(CDCl3, TMS int.): δ = 3.6–3.9 ppm (m, 9H, 3 OCH3), 6.5–7.5
(
m, 12H, Harom.) C25H21S3NCl2O5 (582.549) Calcd.: C, 51.55; H, 3.63; N,
.40. Found: C, 51.37; H, 3.40; N. 2.23.
2
5
1
-(4-Methoxyphenylthio)-6-nitro-7,8-dichloro-4,9-dithia-
-oxacycloun-decane-5,7-diene (15)
◦
Yield, 0.132 g (56%). m.p. 99–100 C. Rf = 0.667 (CHCl3). IR (KBr): ν =
−1
1
2
850, 2950 cm (C H), 1590 (C C), 1250, 1290, 1530 (C NO2). − H
NMR(CDCl3, TMS int.): δ = 2.5–3.6 ppm (m, 8H, (CH2)2 O (CH2)2),
.7–4.0 (m, 3H, OCH3), 6.6–7.4 (m, 4H, Harom.). C15H15S3NCl2O4
440.39) Calcd.: C, 40.91; H, 3.43; N, 3.18. Found: C, 40.67; H, 3.49;
3
(
N, 3.12.
Preparation of N,S-Substituted Polyhalonitrodienes:
General Procedure III
Equimolar amounts of S-substituted polyhalonitrodienes and amine
derivatives were stirred in dichloromethane until completion of the re-
action. Chloroform was added to the reaction mixture. The organic layer
was separated and washed with water (4 × 30 ml) and dried with CaCl2
or MgSO4. The solvent was evaporated and the residue was purified by
column chromatography on silica gel.
N-[1-(2-furanylmethanethio)-2-nitro-3,4,4-trichloro-1,3-
1
butadienyl)]-N -phenyl Piperazine (7a)
◦
Yield, 0.142 g (52%). m.p. 129–130 C. Rf = 0.227 (CHCl3). IR (KBr):
−1
1
v = 2850, 2930, 3100 cm (C H), 1600 (C C), 1285, 1540 (C NO2).− H
NMR(CDCl3, TMS int.): δ = 3.2–4.0 ppm (m, 8H, Hpiper.), 4.1–4.5 (m,
2
H, S CH2), 6.2–7.6 (m, 8H, Harom.). C19H18SN3Cl3O3 (474.797) Calcd.:
C, 48.06; H, 3.82; N, 8.85. Found: C, 47.34; H, 4.04; N, 7.94. MS m/z 475.

˙
C. Ibi s¸ et al.
1
980
N-[1-(4-methoxyphenylthio)-2-nitro-3,4,4-trichloro-1,3-
1
butadienyl)]-N -phenyl Piperazine (7b)
◦
Yield, 0.168 g (63%). m.p. 181–182 C. Rf = 0.280 (CHCl3). IR (KBr):
−1
1
ν = 2850, 2900, 3100 cm (C H), 1600(C C), 1275, 1530 (C NO2). − H
NMR(CDCl3, TMS int.): δ = 2.8–3.1 ppm (m, 3H, OCH3), 3.5–4.0 (m,
8
H, Hpiper.), 6.7–7.5 (m, 9H, Harom.). C21H20SN3Cl3O3 (500.836) Calcd.
C, 50.36; H, 4.025; N, 8.39. Found: C, 49.50; H, 3.68; N, 8.27. MS m/z 501.
N-[1-(4-methoxyphenylthio)-2-nitro-3,4,4-trichloro-1,3-
1
butadienyl)]-N -methyl Piperazine (7c)
◦
Yield, 0.181 g (77%). m.p. 233–234 C. Rf = 0.280 (EtAc). IR (KBr): ν =
−1
2
750, 2850, 2900, 3020 cm (C H), 1590 (C C), 1290, 1540 (C NO2).
1
−
H NMR(CDCl3, TMS int.): δ = 2.1–2.4 ppm (m, 6H, 2CH3), 3.4–4.0 (m,
H, Hpiper.), 6.9–7.5 (m, 4H, Harom.). C16H18SN3Cl3O3 (438.762) Calcd.:
C, 43.80; H, 4.13; N, 9.57. Found: C, 43.61; H, 4.21; N, 9.25. MS m/z
38.9.
8
4
N-[1-(4-methoxyphenylthio)-2-nitro-3,4,4-trichloro-1,3-
1
butadienyl)]-N -ethoxycarbonyl Piperazine (7d)
◦
Yield, 0.208 g (78%). m.p. 165–166 C. Rf = 0.814 (EtAc). IR (KBr):
−
1
ν = 2850, 2900, 3050, 3100 cm (C H), 1580 (C C), 1250, 1280, 1530
1
(
3
C NO2). − H NMR(CDCl3, TMS int.): δ = 2.9–3.6 ppm (m, 8H, Hpiper.),
.7–3.9 (m, 3H, −OCH3), 4.0–4.4 (m, 5H, OCH2 CH3), 6.8–7.6 (m, 4H,
Harom.). C18H20SN3Cl3O5 (496.801) Calcd.: C, 43.52; H, 4.05; N, 8.46.
Found: C, 43.53; H, 3.96; N, 9.04. MS m/z 496.9.
N-[1-(4-methoxyphenylthio)-2-nitro-3,4,4-trichloro-1,3-
1
butadienyl)]-N -[4-fluorophenyl]-piperazine (7e)
◦
Yield, 0.145 g (52%). m.p. 156–157 C. Rf = 0.777 (CHCl3). IR (KBr):
−1
ν = 2830, 2950, 3010 cm
(C H), 1595 (C C), 1215, 1240, 1510
1
(
C NO2). − H NMR(CDCl3, TMS int.): δ = 2.6–3.0 ppm (m, 3H, OCH3),
3
(
.4–4.0 (m, 8H, Hpiper.), 6.6–7.5 (m, 8H, Harom.). C21H19SN3Cl3O3F
518.824) Calcd.: C, 48.61; H, 3.69; N, 8.09. Found: C, 48.86; H, 3.48;
N, 7.72. MS m/z 519.
1
-(4-Methoxyphenylthio)-2-nitro-3,4,4-trichloro-1-
(
4-morpholino)-1,3-butadiene (9a)
◦
Yield, 0.145 g (63%). m.p. 133–134 C. Rf = 0.294 (CHCl3). IR
−
1
(
1
KBr): ν = 2820, 2980, 3030 cm
(C H, 1595 (C C), 1230, 1280,
545 (C NO2). –1H NMR(CDCl3, TMS int.): δ = 1.0–1.5 ppm (m, 4H,
N(CH2)2), 3.0–3.6 (m, 4H, O(CH2)2), 3.7–3.9 (m, 3H, OCH3), 6.8–7.4
m, 4H, Harom.). C15H15SN2Cl3O4 (425.722) Calcd.: C, 42.32; H, 3.55; N,
.58. Found: C, 43.09; H, 3.68; N, 6.36.
(
6

Some New S-, S,S- and N,S-Substituted 2-Nitrodienes
1981
1
-(4-Methoxyphenylthio)-2-nitro-3,4,4-trichloro-1-
(
piperidino)-1,3-butadiene (11a)
◦
Yield, 0.122 g) 54%). m.p. 125–126 C. RF = 0.353 (CHCl3). IR (KBr):
−1
ν = 2835, 2950 cm (C H), 1595 (C C), 1220, 1260, 1540 (C NO2).
1
−
H NMR(CDCl3, TMS int.): δ = 0.8–2.2 ppm (m, 6H, (CH2)3), 2.9–
3
.8 (m, 4h, N(CH2)2), 3.8–4.0 (m, 3H OCH3), 6.8–7.6 (m, 4H, Harom.).
C16H17SN2Cl3O3 (423.747) Calcd.: C, 45.35; H, 4.04; N, 6.61. Found: C,
45.42; H, 3.68; N, 6.73.
1
N,N -[1-(4-methoxyphenylthio)-2-nitro-3,4,4-trichloro-1,3-
butadienyl)]-homopiperazine (13a)
◦
Yield, 0.141 g (34%). m.p. 158–159 C. Rf = 0.812 (EtAc/CHCl3
−
1
1
1
1
:1). −IR (KBr): ν = 2850, 3010 cm
(C H), 1580 (C C), 1240,
1
535 (C NO2). − H NMR(CDCl3, TMS int.): δ = 0.7–1.9 ppm (m,
0H, Hhomopip.), 3.4–3.9 (m, 6H, 2 OCH3), 6.8–7.4 (m, 8H, harom.).
C27H24S2N4Cl6O6 (777.362) Calcd.: C, 39.71; H, 3.11; N, 7.20. Found:
C, 39.46; H, 3.18; N, 6.50.
REFERENCES
[
1] Diamond Alkali Company (Ert. H. Bluestone), U.S. Patent 3021370 (13 Feb. 1962),
Chem. Abstr., 57, 3293c (1962).
[
[
[
[
[
2] A. Roedig and G. Zaby, Liebigs Ann. Chem., 1979, 1614.
3] A. Roedig, G. Zaby, and W. Scharf, Chem. Ber., 110, 1484 (1977).
˙
4] A. Roedig, C. Ibi s¸ , and G. Zaby, Chem. Ber., 114, 684 (1981).
˙
5] C. Ibi s¸ , Liebigs Ann. Chem., 1984, 1873.
6] Yu. A. Ol’dekop, R. V. Kaberdin, and V. I. Potkin, Zh. Org. Khim., 14, 1594
(
1978).
˙
[
[
[
7] C. Ibi s¸ and G. Aydınlı, Phosphorus Sulfur Silicon, 188, 77 (2002).
8] C. Ibi s¸ and N. Yılmaz, Phosphorus Sulfur Silicon, 159, 87 (2000).
˙
9] Yu. A. Ol’dekop, R. V. Kaberdin, V. I. Potkin, and I. A. Shingel, Zh. Org. Khim., 15,
4
6 (1979).
˙
[
[
[
[
[
[
[
10] C. Ibi s¸ and Z. G o¨ kmen, Phosphorus Sulfur Silicon, 143, 67 (1998).
11] C. Ibi s¸ and C¸ . Sayıl, Rev. Roum. Chim., 46, 211 (2001).
˙
12] Yu. A. Ol’dekop, R. V. Kaberdin, and V. I. Potkin, Zh. Org. Khim, 16, 543 (1980).
˙
13] C. Ibi s¸ and C¸ . Sayıl, Phosphorus Sulfur Silicon, 106, 29 (1995).
˙
˙
14] C. Ibi s¸ and C¸ . Sayıl, Synth. Commun., 24, 2797 (1994).
15] C. Ibi s¸ , Bull. Soc. Chim. Belg., 105, 317 (1996).
16] Yu. A. Ol’dekop, R. V. Kaberdin, V. I. Potkin, and I. A. Shingel, Zh. Org. Khim., 15,
2
76 (1979).
˙
[
17] C. Ibi s¸ , F. S. G o¨ ksel, and G. Aydınlı, Phosphorus Sulfur Silicon, 178, 777
2003).
(
[
[
[
18] C. J. Pedersen, J. Org. Chem., 36, 254 (1971).
19] W. Rosen and D. H. Bush, J. Am. Chem. Soc., 91, 4694 (1969).
20] R. D. Bach and H. B. Vardhan, J. Org. Chem., 51, 1609 (1986).

˙
C. Ibi s¸ et al.
1
982
[
[
[
[
[
[
21] J. M. Desper, D. R. Powell, and J. H. Gellman, J. Am. Chem. Soc., 112, 4321 (1990).
22] S. Shimkai, T. Minami, Y. Araragi, and D. Monabe, J. Chem. Soc., 1985, 503.
˙
23] C. Ibi s¸ and M. Onul, Phosphorus Sulfur Silicon, 178, 1881 (2003).
24] I. Solodin and T. D. Heath, Synlett, 7, 619 (1996).
25] F. Kerrigon, C. Martin, and G. H. Thomas, Tetrahedron Lett., 39, 2219 (1998).
26] M. Nishiyoma, T. Yamamoto, and Y. Koie, Tetrahedron Lett., 39, 617 (1998).