The reactions of some alkyl(thio)-substituted 2-nitrodienes with piperazines and a structural study

Article abstract of DOI:10.1515/znb-2006-0921

Thiosubstituted nitrodiene compound 1a was obtained from 2-nitropentachlorobutadiene and dodecanethiol. Compound 1b was prepared from 2-nitropentachlorobutadiene and hexadecanethiol. Monosubstituted diene compounds 1a and 1b reacted with piperazines such as derivatives of 2 and 4 in CH ₂Cl₂ and gave the novel compounds. 2-Nitro-3,4,4- trichloro-1-dodecylthio-1-(2-fluorophenyl-piperazinyl]-1,3-butadiene (3d) was synthesized and its crystal structure was determined.

Full text of DOI:10.1515/znb-2006-0921

The Reactions of Some Alkyl(thio)-Substituted 2-Nitrodienes with
Piperazines and a Structural Study
Cemil Ibis, Cigdem Sayil, and Funda Ozkok
Istanbul University, Faculty of Engineering, Department of Chemistry,
34320 Avcılar-Istanbul, Turkey
Reprint requests to Prof. Dr. C. Ibis. E-mail: ibiscml@istanbul.edu.tr
Z. Naturforsch. 61b, 1174 – 1179 (2006); received January 18, 2006
Thiosubstituted nitrodiene compound 1a was obtained from 2-nitropentachlorobutadiene and do-
decanethiol. Compound 1b was prepared from 2-nitropentachlorobutadiene and hexadecanethiol.
Monosubstituted diene compounds 1a and 1b reacted with piperazines such as derivatives of 2 and 4
in CH2Cl2 and gave the novel compounds. 2-Nitro-3,4,4-trichloro-1-dodecylthio-1-(2-fluorophenyl-
piperazinyl]-1,3-butadiene (3d) was synthesized and its crystal structure was determined.
Key words: Thiosubstituted Nitrodiene, N,S-Substituted Nitrodienes, Piperazine Derivatives
Introduction
reacted with the piperazine derivatives 2a – f to give
the new compounds 3a – l. Novel compounds 5a and
6b were obtained from the reaction of 1a, b with
perhydro-1,4-diazepane.
In the IR spectrum of compound 5a no band is ob-
served in the region 3200– 3450 cm−1 attributable to
the streching vibration of a NH group, indicating the
formation of 1,4-disubstituted homopiperazine. In con-
trast, the IR spectrum of 6b showed a characteristic
>NH band at 3450 cm−1. Microanalysis and further
spectroscopic data verify these structures. The IR spec-
tra showed a characteristic >C=O band at 1720 cm−1
for 3e, 3f and at 1700 cm−1 for 3l.
The aromatic protons are observed as multiplet
at δ = 6.9 – 7.4 ppm for compounds of 3b – d, and
3g – k. In the 1H NMR spectra of the novel com-
pounds containing the piperazine ring (3a – l), the
piperazine protons are observed as broad singlets at
δ = 3.16– 3.84 ppm for 3a– d and 3f – l, and as mul-
tiplets at 3.55– 3.86 ppm for 3e. In the APT spectra
of 3c, d, f, h, k the CH2 signals of the piperazine ring
are identified in the range 49.46– 62.34 ppm, the aro-
matic ring carbon atoms at 114.83– 127.11 ppm, and
the C=O peak is observed at 169.92 ppm for 3f. In
the APCI mass spectrum 5a the molecular ion peak
is observed at m/z = 901.8. The major fragment of
compound 5a was observed at m/z = (M-46), corre-
sponding most likely to [NO2]+. The obtained prod-
ucts were stable and some of them are yellow in
color.
In recent years, some mono-, di-, tris(thio)-
substituted compounds were obtained from the reac-
tions of nitrodienes with thiols and dithiols [1 – 9].
N,S-substituted diene compounds were prepared by the
reactions of some mono(thio)-substituted compounds
with some amines (primary amine, piperazine, mor-
pholine, piperidine, etc. [10– 15]). The piperazine and
piperidine compounds have been submitted to medic-
inal applications and gen transfer studies due to their
interesting biological activity and chemical effects
[16– 20]. According to an US patent, some thiosubsti-
tuted dienes also exhibit high biological activity [21].
Nitrodienes, and especially their halogen deriva-
tives, were used to develop preparative methods for
the synthesis of complex polyfunctional derivatives of
different classes. 2-Nitropentachloro-1,3-butadieneis a
very reactive compound. In a substitution reaction pro-
ceeding by the addition-elimination reactions [22], a
1-chloro substituent is easily replaced with N- and S-
nucleophiles.
The aim in this study was to synthesize and char-
acterize new N,S-subtituted nitrodiene compounds and
to determine the crystal structure of one representative
product.
Results and Discussion
2-Nitro-1,3,4,4-tetrachloro-1-(dodecylthio)-1,3-bu-
tadiene (1a) and the hexadecylthio analogue 1b [12]
c
0932–0776 / 06 / 0900–1174 $ 06.00 ꢀ 2006 Verlag der Zeitschrift fu¨r Naturforschung, Tu¨bingen · http://znaturforsch.com
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C. Ibis et al. · The Reactions of Some Alkyl(thio)-Substituted 2-Nitrodienes
1175
Scheme 1.
Table 1. Crystallographic data and structure refinement for
3d.
Sum formula
C26H37N3O2Cl3FS
581.01
triclinic
P-1
7.0933
Mw [g·mol−1
]
Crystal system
Space group
˚
a [A]
˚
b [A]
8.3802
˚
c [A]
27.40930(10)
76.418(4)
77.526(4)
71.231(4)
1481.955(5)
2
1.302
4.13
612.00
α [◦]
β [◦]
γ [◦]
3
˚
V [A ]
Z
Dcalcd. [g·cm−3
]
Fig. 1. The molecular structure of compound 3d. (ORTEP-III
[26]) Displacement ellipsoids are plotted at the 50% proba-
bility level.
µ [cm−1
F(000)
]
Index ranges, h, k, l
Reflections collected
Independent reflections
Data / restraints / parameters
Goodness-of-fit on F2
Final R indices [I > 2σ(I)]
−8/8, −9/9, −32/32
84762
X-ray crystal structure of 3d
5239 [R(int) = 0.140]
1447 / 0 /362
1.105
R = 0.039, wR = 0.044
0.29 and −0.22
The structure of the compound 3d is shown in
Fig. 1. It contains the expected N,S-substituted butadi-
enyl skeleton. Selected bond geometry values are given
in Table 2. The X-ray analysis of 3d reveals that chlo-
rine substitution at C4 has occured in the C4 atom.
The butadiene moiety assumes a configuration close to
cisoid.
−3
˚
Largest diff. peak and hole [e·A
]
In the structure of 3d the equivalent isotropic dis-
placement coefficients (thermal parameters) of the car-
bon atoms of the dodecyl chain generally increase
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1176
C. Ibis et al. · The Reactions of Some Alkyl(thio)-Substituted 2-Nitrodienes
◦
˚
Table 2. Selected bond lengths [A] and angles [ ] with e.s.d.
in parentheses for 3da,b
umn chromatography on SiO2 (Fluka Kieselgel 60, particle
size 63 – 200 µm). TLC plates: silica 60F254 (Merck, Darm-
.
S1-C4
S1-C5
C20-C17
Cl1-C1
C4-C3
C2-C1
1.756(5)
1.801(6)
1.514(7)
1.724(6)
1.398(6)
1.320(9)
C18-C19
N1-C4
N1-C17
N2-C19
C2-C3
1.494(7) stadt), detection with ultraviolet light (254 nm).
1.328(6)
1.474(6)
1.465(6)
1.448(8)
Preparations
G e n e r a l p r o c e d u r e I f o r p r e p a r a t i o n o f S-s u b-
s t i t u t e d p o l y h a l o n i t r o d i e n e s 1a, b [12]
N2-C20
1.463(6)
Cl2-C1-C2
C4-N1-C18
C3-C4-S1
122.6(4)
125.3(4)
113.4(4)
121.6(3)
109.7(4)
123.0(4)
118.9(4)
111.2(4)
121.9(4)
C4-S1-C5
107.9(2)
Equimolar amounts of 1,1,3,4,4-pentachloro-2-nitro-1,3-
butadiene in 10 ml of ethanol and thiols in 10 ml ethanol were
mixed at r. t. The mixture was stirred for 24 h. Chloroform
was added to the reaction mixture. The organic layer was
separated and washed with water (4×30 ml) and dried with
Na2SO4. After the solvent was evaporated the residue was
purified by column chromatography on silica gel.
C17-N1-C18
C3-C4-N1
S1-C5-C6
N2-C19-C18
Cl1-C1-C2
C4-C3-C2
112.5(4)
125.0(5)
107.2(4)
109.0(4)
124.0(4)
123.0(5)
109.7(4)
113.4(4)
S1-C4-N1
C20-N2-C19
C3-C2-C1
C1-C2-Cl3
C17-C20-N2
N1-C17-C20
Cl2-C1-Cl1
C4-N1-C17
a
b
˚
Average C-C for C(5) to C(16)=1.498(5) A; average C-C-C for
C(5) to C(16)=116.2(4)◦.
G e n e r a l p r o c e d u r e I I f o r p r e p a r a t i o n o f N, S-
s u b s t i t u t e d p o l y h a l o n i t r o d i e n e s 3a – l, 5a, 6b
Table 3. Selected torsion angles of 3d.
Equimolar amounts of S-substituted polyhalonitrodienes
1a, b and piperazine derivatives 2a – f or perhydro-1,4-
diazepane (4) were mixed in dichloromethane at r. t. The
mixture was stirred for 2 – 3 h. Chloroform was added to
the reaction mixture. The organic layer was separated and
washed with water (4×30 ml) and dried with Na2SO4. After
the solvent was evaporated the residue was purified by col-
umn chromatography on silica gel. The yellow crystals of 3d
suitable for X-ray diffraction were obtained by recrystalliza-
tion by slow evaporation of ethanol at 20 ◦C.
C1-C2-C3-C4
−58.1(7)
179.8(4)
−179.0(3)
61.0(6)
N1-C4-C3-C2
C1-C2-C3- N3
C18-N1-C17-C20
139.1(6)
117.8(5)
51.7(6)
C3-C2-C1-Cl1
Cl3-C2-C1-Cl2
C19-N2-C20-C17
on going from C5 to C16, reflecting libration of the
chain. For C5-C16 of 3d, the average C-C bond length
˚
is 1.498(5) A and the average C-C-C bond angle is
116.2(4)◦. The torsion angles of 3d are given in Ta-
ble 3. All of the torsion angles within the dodecyl
chain deviate from 180◦ by less than 1.5◦. Thus the
C12 chain has a near trans-coplanar conformation. The
average deviation from the least-squares plane formed
3,4,4-Trichloro-1-(dodecylthio)-2-nitro-1-(4-phenylpiper-
azin-1-yl)-1,3-butadiene (3b)
Yield: 0.14 g (35%). – M.p. 62 – 63 ◦C. Rf = 0.67
(CH2Cl2). – IR (KBr): υ = 2800, 2900, 3050 (C-H),
1580, 1620 (C=C), 1300, 1540 cm−1 (NO2). – 1H NMR
(499.83 MHz, CDCl3): δ = 7.33 (m, 2 H, N-Harom), 6.96
(m, 3 H, Harom), 3.84 (s, br, 4 H, Hpiper), 3.36 (s, br, 4 H,
Hpiper), 3.0 (t, J = 7.08 Hz, 2 H, SCH2), 1.7 (m, J = 7.32 Hz,
˚
by C5-C16 is 0.040 A, with a maximum deviation of
˚
0.083 A for C5. Both the observed values in 3d are
consistent with the corresponding values in a similar
compound [28].
The piperazine ring is in the chair conformation.
The o-fluorophenyl ring is planar with a maximum de-
−
2 H, SCH2CH2), 1.26 – 1.44 (m, 18 H, -(CH2)9 ), 0.9 (t,
J = 6.84 Hz, 3 H, CH3). – C26H38SO2N3Cl3 (563.03): calcd.
C 55.46, H 6.80, N 7.46; found C 55.02, H 6.29, N 7.14.
˚
viation of 0.007 A.
Experimental Section
3,4,4-Trichloro-1-(dodecylthio)-1-[4-(4-fluorophenyl)piper-
azin-1-yl]-2-nitro-1,3-butadiene (3c)
Melting points were measured on a Bu¨chi B-540 melt-
ing point apparatus and are uncorrected. Elemental analyses
were perform with a Carlo Erba 1106 Elemental analyser.
Yield: 0.16 g (40%). Oil. Rf = 0.21 (CHCl3). – IR (KBr):
Infrared (IR) spectra were recorded in KBr pellets in Nujol υ = 2800, 2900, 3100 (C-H), 1580, 1620 (C=C), 1300,
1
1505 cm−1 (NO2). – H NMR (499.83 MHz, CDCl3): δ =
mulls on a Shimadzu FTIR-8101 spectrometry. NMR spec-
˙
tra were recorded on a VarianUNITY INOVA instrument op-
6.96 (m, 2 H, F-Harom), 6.84 (m, 2 H, N-Harom), 3.72 (s, br,
erating at 500 MHz for 1H and 125 MHz for 13C. The mass 4H, Hpiper), 3.16 (s, br, 4H, Hpiper), 2.90 (t, J = 7.08 Hz,
spectra were obtained on a Finnigan MAX spectrometer in
2 H, SCH2), 1.60 (m, J = 7.32 Hz, 2 H, SCH2CH2), 1.16 –
the APCI made.
−
1.34 (m, 18 H, -(CH2)9 ), 0.80 (t, J = 6.84 Hz, 3 H,
All chemicals and solvents were obtained commercially CH3). – 13C NMR (125.68 MHz, CDCl3): δ = 14.33 (CH3),
and used without purification. Products were isolated by col- 22.91, 28.93, 29.26, 29.55, 29.60, 29.74, 29.83, 30.02, 32.13,
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C. Ibis et al. · The Reactions of Some Alkyl(thio)-Substituted 2-Nitrodienes
1177
1
35.83 (CH2), 50.73, 53.29 (NCH2), 116.09, 116.26, 119.01, (C=C), 1290, 1540 cm−1 (NO2). – H NMR (499.83 MHz,
119.07 (CHarom), 125.00, 127.01 (Carom), 118.75, 146.74, CDCl3): δ = 3.74 (s, br, 4 H, Hpiper), 2.90 (t, J = 7.32 Hz,
157.33, 159.25 (Cbutad). – C26H37N3SFO2Cl3 (581.02): 2 H, SCH2), 2.62 (s, br, 4 H, Hpiper), 2.44 (s, 3 H, N-
calcd. C 53.74, H 6.41, N 7.23; found C 53.55, H 5.80, CH3) 1.65 (m, J = 7.32 Hz, 2 H, SCH2CH2), 1.20 – 1.40
N 7.14.
(m, 26 H, -(CH2)13-), 0.88 (t, J = 6.84 Hz, 3 H, CH3). –
C25H44N3O2Cl3S (557.07): calcd. C 56.55, H 7.11, N 6.59;
found C 56.59, H 6.73, N 6.81.
3,4,4-Trichloro-1-(dodecylthio)-1-[4-(2-fluorophenyl)piper-
azin-1-yl]-2-nitro-1,3-butadiene (3d)
Yield: 0.17 g (43%). – M. p. 79 – 80 ◦C. Rf = 0.52
(CHCl3). – IR (KBr): υ = 2800, 2900, 3050 (C-H),
1580, 1620 (C=C), 1290, 1505 cm−1 (NO2). – 1H NMR
(499.83 MHz, CDCl3): δ = 6.94 – 7.12 (m, 4 H, Harom), 3.84
(s, br, 4 H, Hpiper), 3.26 (s, br, 4 H, Hpiper), 3.10 (t, J =
7.32 Hz, 2 H, SCH2), 1.70 (m, J = 7.32 Hz, 2 H, SCH2CH2),
1.24 – 1.44 (m, 18 H, -(CH2)9− ), 0.90 (t, J = 6.84 Hz, 3 H,
CH3). – 13C NMR (125.68 MHz, CDCl3): δ = 14.34 (CH3),
22.91, 28.93, 29.26, 29.56, 29.61, 29.74, 29.84, 30.02, 32.13,
35.81 (CH2), 50.60, 53.63 (N-CH2), 116.63, 116.79, 118.65,
119.61 (CHarom), 124.91, 127.11(Carom), 138.74, 138.82,
155.03, 156.99 (Cbutad). – C26H37N3SO2FCl3 (581.02):
calcd. C 53.74, H 6.41, N 7.23; found C 53.06, H 5.92,
N 6.96.
3,4,4-Trichloro-1-(4-ethoxycarbonylepiperazin-1-yl)-1-
(hexadecylthio)-2-nitro-1,3-butadiene (3f)
Yield: 0.21 g (52%). Oil. Rf = 0.38 (CH2Cl2). – IR (KBr):
υ = 2990 (C-H), 1560, 1610 (C=C), 1250, 1520 cm−1
(NO2), 1700 (C=O). – 1H NMR (499.83 MHz, CDCl3):
δ = 4.12 (q, J = 7.08 Hz, 2 H, OCH2), 3.57 (s, br, 8 H,
Hpiper) 2.89 (t, J = 7.08 Hz, 2 H, SCH2), 1.60 (m, J =
7.32 Hz, 2 H, SCH2CH2), 1.20 – 1.40 (m, 26 H, -(CH2)13-),
0.80 (t, J = 6.84 Hz, 3 H, CH3). – 13C NMR (125.68 MHz,
CDCl3): δ = 14.32, 14.82 (CH3), 22.90, 28.93, 29.24,
29.57, 29.59, 29.73, 29.82, 29.87, 29.89, 29.90, 29.95, 32.14,
35.80, 43.47, (CH2), 53.07, 62.34 (N-CH2), 119.16, 125.12,
126.84, 155.30 (Cbutad), 169.92 (C=O). – C27H46N3SO4Cl3
(615.19): calcd. C 52.72, H 7.53, N 6.83; found C 52.32,
H 7.93, N 6.41.
3,4,4-Trichloro-1-(dodecylthio)-1-(4-formylpiperazin-1-yl)-
2-nitro-1,3-butadiene (3e)
3,4,4-Trichloro-1-(hexadecylthio)- 2-nitro-1-(4-phenylpiper-
azin-1-yl)-1,3-butadiene (3g)
Yield: 0.14
g (40%). Oil. Rf = 0.36 [CH2Cl2/
CCl4(1:1)]. – IR (KBr): υ = 2900, (C-H), 1560, 1610 (C=C),
1200, 1560 cm−1 (NO2), 1720 (C=O). – 1H NMR
(499.83 MHz, CDCl3): δ = 3.55 – 3.86 (m, 8 H, Hpiper),
2.93 (t, J = 7.32 Hz, 2 H, SCH2), 1.64 (m, J = 7.32 Hz,
2 H, SCH2CH2), 1.24 – 1.37 (m, 18 H, -(CH2)9− ), 0.86 (t,
J = 6.84 Hz, 3 H, CH3). – C21H34N3O3SCl3 (514.94): calcd.
C 55.46, H 6.80, N 7.46; found. C 55.02, H 6.29, N 7.14.
Yield: 0.09 g (26%). – M. p. 60 – 61 ◦C. Rf = 0.48
(CHCl3). – IR (KBr): υ = 2900, 3050 (C-H), 1580, 1610
1
(C=C), 1290, 1540 cm−1 (NO2). – H NMR (499.83 MHz,
CDCl3): δ = 7.28 (m, 2 H, N-Harom), 6.92 (m, 2 H, Harom),
3.80 (s, br, 4 H, Hpiper), 3.31 (s, br, 4 H, Hpiper), 2.96 (t, J =
7.08 Hz, 2 H, SCH2), 1.65 (m, J = 7.32 Hz, 2 H, SCH2CH2),
1.20 – 1.40 (m, 26 H, -(CH2)13-), 0.86 (t, J = 6.84 Hz, 3 H,
CH3). – C30H46N3O2SCl3 (619.14): calcd. C 58.19, H 7.48,
N 6.78; found C 57.94, H 7.43, N 6.76.
1,4-Bis[3,4,4-trichloro-1-(dodecylthio)-2-nitro-1,3-butadi-
enyl]perhydro-1,4-diazepane (5a)
Yield: 0.20 g (33%). Oil. Rf = 0.45 (CH2Cl2). – IR (KBr):
υ = 2990, (C-H), 1560, 1605 (C=C), 1280, 1505 cm−1
(NO2). – 1H NMR (499.83 MHz, CDCl3): δ = 3.60 (m,
6 H, Hhomopiper), 2.96 (s, br, 4 H, Hhomopiper), 2.65 (t,
J = 7.56 Hz, 4 H, 2 SCH2), 1.65 (m, J = 7.32 Hz, 4 H,
3,4,4-Trichloro-1-[4-(4-fluorophenyl)piperazin-1-yl]-1-
(hexadecylthio)-2-nitro-1,3-butadiene (3h)
Yield: 0.22 g (26%). – M. p. 64 – 65 ◦C. Rf = 0.22
(CHCl3). – IR (KBr): υ = 2800, 3050 (C-H), 1560, 1620
−
2 SCH2CH2), 1.20 – 1.33 (m, 36 H, 2-(CH2)9 ), 0.97 (t,
1
(C=C), 1290, 1505 cm−1 (NO2). – H NMR (499.83 MHz,
J = 6.84 Hz, 6 H, 2 CH3). – MS (APCI): m/z (%) = 901.8
(40) [M+], 854.95 (14) [M+-NO2]. – C37H60N4O4S2Cl6
(901.74): calcd. C 49.28, H 6.70, N 6.21; found C 49.52,
H 7.35, N 6.90.
CDCl3): δ = 6.96 (m, 2 H, F-Harom), 6.87 (m, 2 H, N-
Harom), 3.77 (s, br, 4 H, Hpiper), 3.21 (s, br, 4 H, Hpiper), 2.95
(t, J = 7.08 Hz, 2 H, SCH2), 1.64 (m, J = 7.32 Hz, 2 H,
SCH2CH2), 1.17 – 1.40 (m, 26 H, -(CH2)13-), 0.86 (t, J =
6.84 Hz, 3 H, CH3). – 13C NMR (125.68 MHz, CDCl3): δ =
13.09 (CH3), 21,67, 27.69, 28.02, 28.34, 28.36, 28.50, 28.59,
28.64, 28.67, 28.68, 28.79, 30.91, 34.58, (CH2), 49.46, 52.09
3,4,4-Trichloro-1-(hexadecylthio)-1-(4-methylpiperazin-1-
yl)-2-nitro-1,3-butadiene (3a)
Yield: 0.15
g (47%). Oil. Rf = 0.41 [CH2Cl2/ (N-CH2), 114.83, 115.00, 117.71, 117.77 (CHarom), 123.75,
EtOAc(1:1)]. – IR (KBr): υ = 2900, (C-H), 1560, 1600 125.77 (Carom), 117.70, 145.60, 56.03, 157.94 (Cbutad). –
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1178
C. Ibis et al. · The Reactions of Some Alkyl(thio)-Substituted 2-Nitrodienes
C30H45N3O2SCl3F (637.13): calcd. C 56.55, H 7.11, N 6.59; 3,4,4-Trichloro-1-(hexadecylthio)-2-nitro-1-(perhydro-1,4-
found C 56.13, H 6.60, N 6.77.
diazepanyl)-1,3-butadiene (6b)
◦
Yield: 0.20 g (33%). – M. p. 124 – 125 C. Rf = 0.43
(CCl4/CH2Cl21:1). – IR (KBr): υ = 2900, (C-H), 1560,
1650 (C=C), 1200, 1530 cm−1 (NO2), 3450 (N-H). –
1H NMR (499.83 MHz, CDCl3): δ = 3.69 (m, 6 H,
Hhomopiper), 2.89 (s, br, 4 H, Hhomopiper), 2.61 (t, J = 7.32 Hz,
2 H, SCH2), 1.60 (m, J = 7.32 Hz, 2 H, SCH2CH2), 1.19 –
1.38 (m, 26 H, -(CH2)13-), 0.81 (t, J = 6.84 Hz, 3 H, CH3). –
C25H44N3O2SCl3 (557.07): calcd. C 53.90, H 7.96, N 7.54;
found C 54.62 H 8.70, N 7.08.
3,4,4-Trichloro-1-[4-(2-fluorophenylpiperazin-1-yl)]-1-
(hexadecylthio)-2-nitro-1,3-butadiene (3k)
Yield: 0.14 g (38%). – M. p. 89 – 90 ◦C. Rf = 0.27
(CHCl3). – IR (KBr): υ = 2900, 3050 (C-H), 1560,
1620 (C=C), 1290, 1540 cm−1 (NO2). – 1H NMR
(499.83 MHz, CDCl3): δ = 6.90 – 7.24 (m, 4 H, Harom), 3.79
(s, br, 4 H, Hpiper), 3.21 (s, br, 4 H, Hpiper), 2.96 (t, J =
7.32 Hz, 2 H, SCH2), 1.65 (m, J = 7.32 Hz, 2 H, SCH2CH2),
1.17 – 1.40 (m, 26 H, -(CH2)13-), 0.86 (t, J = 6.84 Hz, 3 H,
CH3). – 13C NMR (125.68 MHz, CDCl3): δ = 14.33 (CH3),
22.92, 28.94, 29.27, 29.59, 29.61, 28.50, 29.75, 29.84, 29.89,
29.91, 29.92, 30.02, 32.16, 35.80 (CH2), 50.60, 53.63 (N-
CH2), 116.64, 119.59, 123.98, 124.87 (CHarom), 118.66,
124.91, (Carom), 127.08, 138.74, 155.04, 157.00 (Cbutad). –
C30H45N3O2SCl3F (637.13): calcd. C 56.55, H 7.11, N 6.59;
found C 56.59, H 6.73, N 6.81.
X-ray structure determination of 3d
Data collection was carried out on a Rigaku R-Axis
Rapid-S diffractometer with graphite monochromatized Mo-
˚
Kα radiation (λ = 0.71093 A). Experimental conditions are
summarized in Table 1. The structure was solved by SIR 92
[23] and refined with CRYSTALS [24]. The positions of the
H atoms bonded to C atoms were calculated (C-H distance
˚
0.96 A), and refined using a riding model. The H atom dis-
placement parameters were restricted to be 1.2Ueq of the par-
ent atom. All calculations were performed using a crystallo-
graphic software package [25]. Selected bond distances and
bond angles for 3d are listed in Table 2. Crystallographic
data (excluding structure factors) for the structure reported
in this paper have been deposited with the Cambridge Crys-
tallographic Data Centre as supplementary publication no.
CCDC-267314 for 3d [27].
3,4,4-Trichloro-1-(4-formylpiperazin-1-yl)-1-(hexadecyl-
thio)-2-nitro-1,3-butadiene (3l)
◦
Yield: 0.16 g (47%). – M. p. 128 – 129 C. Rf = 0.63
(CH2Cl2/CCl4). – IR (KBr): υ = 2900 (C-H), 1560, 1610
1
(C=C), 1200, 1560 cm−1 (NO2). – H NMR (499.83 MHz,
CDCl3): δ = 3.60 – 3.86 (m, 8 H, Hpiper), 2.90 (t, J =
7.32 Hz, 2 H, SCH2), 1.65 (m, J = 7.32 Hz, 2 H, SCH2CH2),
1.13 – 1.41 (m, 26 H, -(CH2)13-), 0.86 (t, J = 6.84 Hz, 3 H,
CH3). – C25H42N3O3SCl3 (571.05): calcd. C 52.58, H 7.41,
N 7.35; found C 51.93, H 6.62, N 7.73.
Acknowledgement
We thank the Research Fund of the University of Istanbul
for financial support of this work.
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