The synthesis of new thiosubstituted compounds with butadienyl and butenynyl groups

Article abstract of DOI:10.1080/10426501003781624

Mono(thio)substituted butadiene 3a, tetrakis(thio)substituted butadiene 4b, and bis(thio)substituted butadiene 10j were synthesized from 1,1,3,3,4,4-hexachloro butene and aromatic thiols in dimethylformamide at room temperature in the presence of triethyl

Full text of DOI:10.1080/10426501003781624

Phosphorus, Sulfur, and Silicon, 186:58–66, 2011
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426501003781624
THE SYNTHESIS OF NEW THIOSUBSTITUTED
COMPOUNDS WITH BUTADIENYL AND BUTENYNYL
GROUPS
˙
Cemil Ibis and Sibel S¸ahinler Ayla
Faculty of Engineering, Department of Chemistry, Istanbul University,
Avcilar-Istanbul, Turkey
GRAPHICAL ABSTRACT
RS
RS
RS
RS
H
H
H
SR
SR
SR
Cl
H
Cl
Cl
Cl Cl
RS
Cl
Cl
+ 3 RSH
C
CH
RS
RS
SR
RS
RS
NaOH, EtOH
Cl Cl
Cl
Cl
SR
Abstract Mono(thio)substituted butadiene 3a, tetrakis(thio)substituted butadiene 4b, and
bis(thio)substituted butadiene 10j were synthesized from 1,1,3,3,4,4-hexachloro butene and
aromatic thiols in dimethylformamide at room temperature in the presence of triethylamine.
Thiosubstituted butenyne compounds 5c, 6a, 7a,h, and 11i and butadiene compounds 3f,g, 4d,
8g, 9d, and 10i were synthesized from 1,1,3,3,4,4-hexachloro butene and different thiols in
EtOH with NaOH solution. The thiosubstituted butadienes 13e and 14f were obtained from
the reactions of 2H-1,1,3,4,-tetrachloro-4-bromo-butadiene and thiols in EtOH/H2O solution
of NaOH. The structures of the new compounds were determined by microanalysis, FT-IR,
UV/Vis, 1H NMR, 13C NMR, 19F NMR, MS, and fluorescence spectrophotometry.
Keywords Coumarin; fluorescence property; spectroscopy; thioethers; thiosubstituted butadi-
ene and butenyne compounds
INTRODUCTION
Reactions of butadiene compounds are important from both practical and theorical
points of view. The ethylenic bond activates the functional group, with the result that the
compounds undergo replacement reactions much more readily than analogous saturated
compounds.1 Dihalo-1,3-butadienes are useful for organic synthesis because of the vinyl-
halide moiety and the butadienyl skeleton.2–4 The other importance of butadiene structures
refers to their biological proporties.5 Bis-, tris-, tetrakis(thio)subsituted diene, triene, and
Received 24 November 2009; accepted 15 March 2010.
We thank the Research Fund of the University of Istanbul for financial support of this work.
˙
Address correspondence to Cemil Ibis, Faculty of Engineering, Department of Chemistry, Istanbul Univer-
sity, 34320 Avcilar-Istanbul, Turkey. E-mail: ibiscml@istanbul.edu.tr
58

NEW THIOSUBSTITUTED COMPOUNDS
59
butenyne compounds were synthesized by nucleophlilic substitution of butadiene com-
pounds.6–10
Because of their widespread occurence in nature, coumarins have received increased
attention in chemistry, acting as antioxidants, enzyme inhibitors, and precursors of toxic
substances.11 The chemical and biological proporties of coumarin derivatives depend upon
the type of substituents.12,13 Their fluorescence properties have also been used as an ad-
vantage for the biochemical assay of enzymes.14 The biological activities of coumarins and
mercaptobenzoazoles are well known and include antiviral, anticonvulsant, antimicrobial,
antibacterial, anticancer, and anti-HIV properties.15,16
The aim of this study is the synthesis and characterization of novel thiosubstituted bu-
tadiene and butenyne compounds with different types of substituents including the coumarin
and benzoazole moieties.
RESULTS AND DISCUSSION
The mono(thio)substituted compound 3a, tetrakis(thio) substituted compound 4b, and
bis(thio)substituted butadiene 10j were synthesized by the reaction between the halobutene
1 and 2a, 2b, and 2j in the presence of DMF and triethylamine, respectively. The new
butenynes 5c, 6a, 7a,h, and 11i and the thiosubstituted butadienes 3f,g, 4d, 8g, 9d, and 10i
were obtained from the reaction of halobutenes 1 and the corresponding thiols (Scheme 1)
in the presence of an EtOH/H2O solution of NaOH. The thiosubstituted butadienes 13e
and 14f were prepared by the reaction of 2H-1,1,3,4,-tetrachloro-4-bromo-butadiene and
respective thiols in an EtOH/H2O solution of NaOH.
1
The H NMR spectrum of compound 3a exhibited the presence of a vinyl proton
at 6.27 ppm. The IR spectrum of compounds 3g and 8g showed sharp peaks at 1720 and
1731 cm−1, indicative for the C = O stretching. The fluorescence properties of the two
thiosubstituted butadienes 3g and 8g containing a coumarin group are presented in Table 1.
The excitation and emission spectra for these compounds are shown in Figure 1.
Regarding the reaction mechanism, it is possible that 2H-pentachlorobutadiene
(Cl2C CH CCl CCl2), formed by elimination of HCl from halobutene 1, undergoes
a second elimination of HCl leading to perchlorobutenyne (Cl2C CCl C≡C Cl). The
new butenynes 5c, 6a, 7a, and 7h are obtained by substitution at this perchlorobutenyne
compound.6 In the IR spectra of 6a and 7a, characteristic bands at 2144 and 2153 cm−1
for the (C≡C) streching were observed, respectively. The IR spectra of compound 5c also
showed a characteristic band for the carbonyl group at 1671 cm−1 as a result of conjugated
group effect. The mass spectrum of 3f in the positive ion mode for ESI confirms the pro-
posed structure; the protonated molecular peak was identified at m/z (%) 341 (100) [M+H]+
(Figure 2). The fragmantation of the molecular peak gave a fragment ion corresponding to
the cleavage of a chlorine atom at m/z (%) 304 (100).
The 19F NMR spectrum of compound 4b shows the presence of fluorine atoms in
meta, para, and ortho positions on the phenyl rings (−137.36, −158.23, −158.60 ppm),
Table 1 Excitation and emission maximum wavelengths
Compound
Solvent
λex.(max.)
λem.(max.)
3g
8g
CHCl3
CHCl3
326.00
327.07
396.00
393.07

˙
C. IBIS AND S. S¸AHINLER AYLA
60
RS
Cl
H
Cl
Cl
Cl
Cl
Cl
+ RSH
2
H
+ RSH
2
Cl
Cl
Cl Cl
Cl
SR
5
3
C
CH
NaOH, EtOH
Cl
Cl
RS
DMF, Et3N
RS
H
Cl
RS
RS
Cl Cl
1
SR
SR
RS
6
SR
7
NaOH, EtOH
SR
+ 3 RSH
Cl
4
RS
RS
H
RS
RS
H
RS
RS
H
Cl
Cl
SR
RS
RS
SR
SR
SR
Cl
10
Cl
Cl
RS
SR
9
11
8
Cl
Br
Cl
SR
SR
+ RSH
Cl
Br
Cl
2
Cl
Cl
H
13
NaOH, EtOH
H
Cl
Br
Cl
12
Cl
SR
H
14
R
Product
R
Product
N
OCH3
OCH3
3a, 6a, 7a
3f, 14f
a
f
N
H
CH3
F
F
F
F
3g, 8g
7h
4b
5c
b
c
g
O
O
F
HO-(CH2)3-
h
COOH
CF3-CH2-
4d, 9d
13e
10i, 11i
10j
d
e
i
HO-(CH2)6-
j
NO2
Scheme 1 Synthesis of novel butadiene and butenyne compounds.
respectively.17,18 The IR spectra of compounds 7h and 13e show broad bands at 3344 and
1
3341 cm−1 for the OH streching. In the H NMR spectrum of compounds 4d and 14f,
the vinyl protons are detected at 6.90 and 6.23 ppm, respectively.
The 19F NMR spectrum of compound 9d displays the presence of five different
CF3CH2-groups resonating at −68.41, −68.48, −68.54, −68.52, and −68.68 ppm.19 The
pentakis(thio)substituted compound 9d is formed by the addition of one thiol molecule to
the butatriene or butenyne compound 11.20 The mass spectrum of 10j in the positive ion
mode for ESI confirms the proposed structure; the molecular peak was identified at m/z

NEW THIOSUBSTITUTED COMPOUNDS
61
200
150
100
50
326,00
396,00
0
300
400
500
Wavelength (nm)
(a)
600
400
200
0
327,07
393,07
250
300
350
400
450
500
Wavelength (nm)
(b)
Figure 1 Excitation and emission spectra measured for 10−4 M solutions for (a) compound 3g and (b) compound
8g in CHCl3. Excitation and emission slit widths were set at 5 nm.
(%) 486 (38) [M+Na]+. The fragmentation of the molecular peak gives a fragment ion at
m/z (%) 452 (100) corresponding to the cleavage of one chlorine atom from the molecule.
The new butadiene 10i and new butenyne 11i are obtained from the reaction of
the halobutene 1 and cyclopentyl mercaptan (2i). These two compounds show different
patterns in the IR spectrum. For compound 11i, a characteristic sharp peak at 2150 cm−1 is
observed, indicating the presence of a triple bond in the molecule, while compound 10i does
not show any peak in this area of IR. Regarding the reaction mechanism, it is possible that
the tetrakisbutatriene is formed first and subsequently isomerizes to the butenyne 11i.20,21
Results from the spectroscopic characterization of all compounds are reported in the
Experimental section.
EXPERIMENTAL
Melting points were measured using a Bu¨chi B-540 melting point apparatus and are
uncorrected. Microanalyses were performed on a Thermo Finnigan Flash EA 1112 series
elemental analyser. Infrared (IR) spectra were recorded in KBr pellets or in Nujol mulls on
a Perkin Elmer Precise Spectrum One FTIR spectrometer. UV spectra were recorded on
a Perkin Elmer Precise Lambda 35 UV-Vıs spectrometer. Fluorescence spectra were run

˙
62
C. IBIS AND S. S¸AHINLER AYLA
Figure 2 Full-MS spectrum of compound 3f in the positive mode of ESI.
on a Varian Cary Eclipse Fluorescence spectrophotometer. 1H, 13C, and 19F NMR spectra
were recorded in CDCl3 or DMSO-d6 with a Varian Unıty INOVA spectrometer. In the case
1
of the H NMR spectra, the FIDs were obtained at a sweep width of 8 KHz for a digital
resolution of 0.49 Hz/point. Chemical shifts δ are given in ppm, coupling constants in Hz.
Internal standards used: TMS for 1H and 13C and CFCl3 for 19F.
Mass spectra were obtained on a Thermo Finnigan LCQ Advantage MAX LC/MS/MS
spectrometer using ion-trap mass analyzer for ESI source. Products were isolated by column
chromatography on silica gel (Fluka silica gel 60, particle size 63–200 µm). Thin-layer
chromatography was performed on Merck silica gel plates (60F254), and detection was
carried out with ultraviolet light (254 nm). All reagents and solvents were of reagent grade,
obtained from commercial suppliers, and used without further purification.
General Procedure 1
1,1,3,3,4,4-Hexachloro butene (1.0 g, 3.8 mmol) and the aromatic thiol (15.2 mmol)
were stirred in a mixture of DMF (30 mL) and triethylamine (3 mL) for 2 h at room
temperature. Chloroform was added to the reaction mixture to separate the organic layer. The
organic layer was washed with water (4 × 30 mL) and dried with Na2SO4. After filtering,
the solvent was evaporated, and the residue was purified by column choromatography on
silica gel.
General Procedure 2
1,1,3,3,4,4-Hexachloro butene (1.0 g, 3.8 mmol) and different amounts of the re-
spective thiol were stirred in a mixture of EtOH (30 mL) and aqueous solution of NaOH
(1.2 g NaOH and 8 mL of water) for 2 h at room temperature. Chloroform was added to the
reaction mixture to separate the organic layer. The organic layer was washed with water

NEW THIOSUBSTITUTED COMPOUNDS
63
(4 × 30 mL) and dried with Na2SO4. The solvent was evaporated, and the residue was
purified by column choromatography on silica gel.
General Procedure 3
Equimolar amounts of 2H-1,1,3,4-tetrachloro-4-bromo-butadiene (1.0 g, 3.7 mmol)
and the respective thiol (3.7 mmol) were stirred in a mixture of EtOH (30 mL) and an
aqueous solution of NaOH (1.2 g NaOH and 8 mL of water) for 2 h at room temperature.
Chloroform was added to the reaction mixture to separate the organic layer. The organic
layer was washed with water (4 × 30 mL) and dried with Na2SO4. The solvent was
evaporated, and the residue was purified by column choromatography on silica gel.
1,1,2,4-Tetrachloro-4-(3-4-dimethoxyphenylthio)-1,3-butadiene (3a). Yield
0.22 g (16%); oil, Rf = 0.3 with CHCl3 as an eluent; IR (KBr, cm−1): 2933, 1398 (C H),
1584 (C C); UV-VIS (CHCl3) λmax (nm) (log ε): 292 (3.60), 240 (3.84); 1H NMR (499.74
MHz, CDCl3): δ = 3.80 (s, 3H, OCH3), 3.81 (s, 3H, OCH3), 6.27 (s, 1H, >C CH),
6.6–7.1 (m, 3H, arom-H); 13C NMR (125.66 MHz, CDCl3): δ = 55.0 ( OCH3), 118.2,
118.4, 117.7 (CHarom), 148.7, 148.4, 132.8 (Carom), 114.1, 123.8, 128.5, 132.9 (Cbutad); MS
( ESI): m/z 359 (M H)−; C12H10SCl4 (M, 360.08). Calcd. C, 40.03; H, 2.80; S, 8.90.
Found. C, 40.10; H, 2.90; S, 8.54%.
1,1,2,4-Tetrachloro-4-(benzo-1,3-imidazolyl-(2)-thio)-1,3-butadiene (3f).
Yield 1.09 g (85%); white solid, mp: 175–177◦C; Rf = 0.35 with CHCl3 as eluent; IR (KBr,
cm−1): 3042 (Ar H), 2961, 2880 (C H), 3074 (N H), 1515 (C C); UV-VIS (CHCl3)
1
λmax (nm) (log ε): 286 (3.65), 264 (3.63), 239 (3.60); H NMR (499.74 MHz, CDCl3): δ
= 5.57 (s, 1H, NH), 6.6 (s, 1H, >C CH), 7.1–7.8 (m, 4H, arom-H); 13C NMR (125.66
MHz, CDCl3): δ = 147.1 (S C N), 116.6, 118.0, 122.4, 122.5 (CHarom), 131.8, 141.1,
142.2 (Carom), 120.7, 123.3, 126.5, 131.4 (Cbutad); MS (+ESI): m/z 341 (M+H)+, 304
(M Cl); C11H6Cl4N2S (M, 340.06). Calcd. C, 38.85; H, 1.78; S, 9.43. Found C, 38,70; H,
1.62; S, 9.35%.
1,1,2,4-Tetrachloro-4-(7-mercapto-4-methyl-coumarinyl)-1,3-butadiene
(3g). Yield 1.2 g (83%); yellow solid; mp: 125–127◦C; Rf = 0.45 with EtAc as an
eluent; IR (KBr, cm−1): 3059, 1385 (C H), 1733 (C O), 1599 (C C); UV-VIS (CHCl3)
λmax(logε) (nm): 330 (4.19), 283 (4.10), 240 (4.18); fluorescence: (CHCl3) λmax(ex): 326,
1
λmax(em): 396 nm; H NMR (499.74 MHz, CDCl3): δ = 2.36 (s, 3H, CH3), 6.26 (s, 1H,
>C CH), 6.70 (s, 1H, >C CH), 7.30–7.50 (m, 3H, arom-H); 13C NMR (125.66 MHz,
CDCl3): δ = 17.6 (CH3), 120.7, 122.4, 124.1, 125.6 (CHarom), 122.8, 135.3, 153.0, 158.9
(Carom), 113.3, 124.4, 128.1, 134.0 (Cbutad), 159.0 (C O); MS (+ESI): m/z 383 (M+H)+,
347 (M Cl); C14H8Cl4O2S (M, 382,09). Calcd. C, 44.21; H, 2.11; S, 8.39. Found C,
43.89; H, 2.20; S, 8.25%.
2-Chloro-1,1,4,4-(pentafluorophenylthio)-1,3-butadiene (4b). Yield 0.30 g
(9%); oil, Rf = 0.4 with CHCl3:EtAc (2:1) as eluent; IR (KBr, cm−1): 2936, 1390 (C H),
1483 (C F), 1601 (C C); UV-VIS (CHCl3) λmax (nm) (log ε): 267 (3.44), 240 (3.45), 231
1
(3.25); H NMR (499.74 MHz, CDCl3): δ = 6.59 (s, 1H, >C CH); 13C NMR (125.66
MHz, CDCl3): δ = 147.3, 145.4, 141.3, 141.1, 139.4, 139.2, 135.6 (Carom), 101.8, 121.8,
123.3, 135.3 (Cbutad); 19F NMR (470.22 MHz, CDCl3, CCl3F) δ = −137.36 (m-F), −158.23
(p-F), −158.60 (o-F), MS ( ESI): m/z 880 (M H)−; C28HClF20S4 (M, 880.99). Calcd. C,
38.17; H, 0.11; S, 14.56. Found C, 38.29; H, 0.10; S, 14.30%.
2-Chloro-1,1,4,4-(2,2,2-trifluoroethylsulfanyl)-1,3-butadiene (4d). Yield
0.1 g (5%); oil, Rf = 0.25 with CHCl3 as eluent; IR (KBr, cm−1): 3000, 2950 (C H);

˙
C. IBIS AND S. S¸AHINLER AYLA
64
1083, 1309 (C F); UV-VIS (CHCl3) λmax (nm) (log ε): 315 (3.30), 267 (3.20), 238 (3.25);
1H NMR (499.74 MHz, CDCl3): δ = 3.35, 3.37, 3.38, 3.40 (s, 8H, S CH2), 6.9 (s,
1H, >C CH);13C NMR (125.66 MHz, CDCl3): δ = 34.0, 34.2, 34.6, 34.8 ( S CH2),
122.5, 124.8, 133.1, 141.6 (Cbutad), 132.7, 132.8, 135.6, 135.8 ( CF3); 19F NMR (470.22
MHz, CDCl3, CCl3F) δ = −68.53, −68.55, −68.85, −69.00 ( CF3); MS ( ESI): m/z
579 (M+Cl)−; C12H9ClF12S4 (M, 544.84). Calcd. C, 26.45; H, 1.66; S, 23.54. Found C,
26.20; H, 1.59; S, 23.50%.
1,1,2-Trichloro-4-(2-carboxy-phenyl-thio)-1-buten-3-in (5c). Yield 0.4 g
(34%); oil, Rf = 0.2 with EtAc as an eluent; IR (KBr, cm−1): 2159 (C≡C), 1671 (C O),
1
3444 ( OH); UV-VIS (DMF) λmax (nm) (log ε): 302 (3.70), 270 (3.47), 240 (3.65); H
NMR (499.74 MHz, CDCl3): δ = 7.81 (d, J = 7.8 Hz, 1H, arom-H), 8.20 (t, J = 7.8 Hz,
2H, arom-H), 7.25 (t, J = 6.8 Hz, 1H, arom-H); 13C NMR (125.66 MHz, DMSO): δ =
90.8, 92.3 (C≡C), 131.8, 134.8 (Carom), 124.6, 129.2, 131.8, 134.8 (CHarom), 112.5, 127.6
(C C), 167.9 (C O); C11H5Cl3O2S (M, 307.58). Calcd. C, 42.95; H, 1.64; S, 10.42.
Found C, 42.70; H, 1.60; S, 10.55%.
1,2-Dichloro-1,4-(3,4-dimethoxyphenylthio)-1-buten-3-in (6a). Yield 0.3 g
(17%); oil, Rf = 0.3 with CHCl3 as eluent; IR (KBr, cm−1): 2957, 1339 (C H), 2153
(C≡C), 1585 (C C); UV-VIS (CHCl3) λmax (nm) (log ε): 289 (3.52), 239 (3.72); 1H NMR
(499.74 MHz, CDCl3): δ = 3.79 (s, 3H, OCH3), 3.82 (s, 3H, OCH3), 6.7–7.1 (m, 6H,
arom-H); 13C NMR (125.66 MHz, CDCl3): δ = 86.1, 88.4 (C≡C), 55.1 ( OCH3), 116.8,
125.9, 127.4 (CHarom), 134.8, 148.3, 149.4 (Carom), MS (+ESI): m/z 458 (M+H)+, 422
(M Cl); C20H18Cl2O4S2 (M, 457.39). Calcd. C, 52.52; H, 3.97; S, 14.02. Found C, 52.48;
H, 3.90; S, 14.10%.
2-Chloro-1,1,4-(3,4-dimethoxyphenylthio)-1-buten-3-in (7a). Yield 0.2 g
(10%); oil, Rf = 0.3 with CHCl3 as eluent; IR (KBr, cm−1): 2932, 1398 (C H), 2144
(C≡C), 1584 (C C); UV-VIS (CHCl3) λmax (nm) (log ε): 256 (4.30), 242 (4.29), 209
(4.69); 1H NMR (499.74 MHz, CDCl3): δ = 3.80 (s, 3H, OCH3), 3.81 (s, 3H, OCH3),
6.7–7.1 (m, 6H, arom-H); 13C NMR (125.66 MHz, CDCl3): δ = 88.3, 89.1 (C≡C), 55.1
( OCH3), 116.0, 116.2, 118.1, 123.3, 123.4, 123.5, 124.0 (CHarom), 126.1, 126.5, 127.0,
138.4, 148.2, 148.7, 149.4, 149.8 (Carom); MS (+ESI): m/z 591 (M)+; C28H27ClO6S3 (M,
591.16). Calcd. C, 56.89; H, 4.60; S, 16.27. Found C, 56.48; H, 4.48; S, 15.90%.
2-Chloro-1,1,4,4-(1-propanol-3-sulfanyl)-1-buten-3-yne (7h). Yield 0.45 g
(34%); oil, Rf = 0.45 with EtAc: CHCl3 (1:1) as eluent; IR (KBr, cm−1): 3344 ( OH),
2934 (C H), 2151 (C≡C); UV-VIS (CHCl3) λmax (log ε) (nm): 288 (3.78), 277 (3.83),
240 (4.01); 1H NMR (499.74 MHz, CDCl3): δ = 1.2–1.8 (m, 6H, S CH2 CH2), 2.81
(t, J = 6.8 Hz, 6H, S CH2); 3.83 (t, J = 7.3 Hz, 6H, O CH2); 4.1 (s, 3H, OH),13C
NMR (125.66 MHz, CDCl3): δ = 85.1, 91.9 (C≡C); 24.3, 26.9, 28.3 ( CH2), 31.5, 31.6,
34.9 ( S CH2), 59.3, 61.8, 61.9 ( O CH2), 166.2 (C S); C13H21ClO3S3 (M, 356,03).
Calcd. C, 43.74; H, 5.93; S, 26.95. Found C, 43.45; H, 5.82; S, 26.45%.
1,2-Dichloro-1,4,4-(7-mercapto-4-methyl-coumarinyl)-1,3-butadiene
(8g). Yield 0.3 g (10%); yellow solid, mp: 130–132◦C; Rf = 0.35 with CHCl3 as eluent;
IR (KBr, cm−1): 2924, 1385 (C H), 1731 (C O), 1600 (C C); UV-VIS (CHCl3) λmax
(log ε) (nm): 332 (3.56), 284 (3.34), 239 (3.59); Fluorescence: (CHCl3) λmax(ex): 327.07,
1
λmax(em): 393.07 nm; H NMR (499.74 MHz, CDCl3): δ = 2.34 (s, 9H, CH3), 6.21 (s,
1H, >C CH), 6.23 (s, 1H, >C CH), 6.24 (s, 1H, >C = CH), 6.68 (s, 1H, >C CH),
7.33 (d, J = 8.3 Hz, 6H, arom-H); 7.46 (d, J = 8.2 Hz, 3H, arom-H); 13C NMR (125.66
MHz, CDCl3): δ = 17.6 ( CH3), 121.1, 123.5, 124.3, 124.4 (CHarom), 129.3, 136.4,
139.9, 152.3, 152.8 (Carom), 113.4, 126.1, 142.4 (Cbutad), 159.1, 153.1, 150.8 (C O); MS

NEW THIOSUBSTITUTED COMPOUNDS
65
(+ESI): m/z 716 (M+Na)+; C34H22Cl2O6S3 (M, 693,64). Calcd. C, 58.87; H, 3.20; S,
13.87. Found C, 58.60; H, 3.07; S, 13.40%.
2-Chloro-1,1,3,4,4-(2,2,2-trifluoro-ethyl-sulfanyl)-1,3-butadiene (9d). Yield
0.4 g (17%); oil, Rf = 0.25 with CHCl3 as eluent; IR (KBr, cm−1): 3002, 2950 (C H);
1083, 1308 (C F); UV-VIS (CHCl3) λmax (nm) (log ε): 312 (3.96), 239 (3.84); 1H NMR
(499.74 MHz, CDCl3): δ = 3.35, 3.37, 3.38, 3.40, 3.41 (s, 10H, S CH2), 6.75 (s, 1H,
>C CH); 13C NMR (125.66 MHz, CDCl3): δ = 33.9, 34.3, 34.6, 34.7, 34.9 ( S CH2),
127.6, 124.7, 122.7, 141.8 (Cbutad), 132.7, 132.8, 135.4, 135.8 (CF3); 19F NMR (470.22
MHz, CDCl3, CCl3F): δ = −68.41, −68.48, −68.54, −68.52, −68.68 (CF3); MS ( ESI):
m/z 660 (M+Cl)−; C14H11F15S5 (M, 624.54). Calcd. C, 26.92; H, 1.78; S, 25.67. Found C,
26.72; H, 1.72; S, 25.32%.
1,1,2-Trichloro-4,4-(cyclopentil-sulfanyl)-1,3-butadiene (10i). Yield 0.3 g
(22%); oil, Rf = 0.35 with CHCl3 as eluent; IR (KBr, cm−1): 2957 (C H), 1546 (C C);
UV-VIS (CHCl3) λmax (log ε) (nm): 306 (4.05), 239 (4.07), 280 (3.99); 1H NMR (499.74
MHz, CDCl3): δ = 1.8–2.1 (m, 8H, CH2), 3.45–3.55 (m, 8H, CH2), 3.6–3.7 (m, 2H,
>CH S), 6.87 (d, J = 6.3, 1H, >C CH); 13C NMR (125.66 MHz, CDCl3): δ = 49.4,
49.3 (>C S), 32.3, 32.2, 32.1, 31.8, 23.8, 23.8, 23.7, 23.60 ( CH2), 143.9, 132.0, 120.9,
126.1 (Cbutad); MS (+ESI): m/z 358 (M+H)+, 288 (M 2Cl); C14H19S2Cl3 (M, 359.79).
Calcd. C, 47.0; H, 5.35; S, 17.92. Found C, 46.87; H, 5.15; S, 17.23%.
1,1,3-Trichloro-4,4-(4-nitrophenyltiyo)-1,3-butadiene (10j). Yield 0.3 g
(17%); oil, Rf = 0.3 with CHCl3 as eluent; IR (KBr, cm−1): 3039 (C H), 1341 (Ar NO2),
1
1519 (C C); UV-VIS (CHCl3) λmax (log ε) (nm): 334 (3.65), 241 (3.64), 230 (3.61); H
NMR (499.74 MHz, CDCl3): δ = 6.89 (s, 1H, >C CH), 7.1–7.9 (m, 4H, arom-H); 13C
NMR (125.66 MHz, CDCl3): δ = 119.7, 122.7, 123.3, 130.0 (Cbutad), 125.5, 128.0, 128.6,
129.8, 131.5 (CHarom), 140.9, 144.5, 146.1 (Carom); MS (+ESI): m/z 486 (M+Na)+, 452
(M Cl); C16H9Cl3N2O4S2 (M, 463.74). Calcd. C, 41.44; H, 1.96; S, 13.83. Found C,
41.33; H, 1.85; S, 13.75%.
1,1,2,4-(Cyclopentil-sulfanyl)-1-buten-3-yne (11i). Yield 0.15 g (9%); oil, Rf
= 0.4 with CHCl3 as eluent; IR (KBr, cm−1): 2951 (C H), 2150 (C≡C); UV-VIS (CHCl3)
λmax (log ε) (nm): 240 (3.33), 235 (3.08), 231 (3.05); 1H NMR (499.74 MHz, CDCl3): δ =
1.71–2.00 (m, 16H, CH2), 3.42–3.55 (m, 16H, CH2), 3.65–3.68 (m, 4H, >CH S); 13
C
NMR (125.66 MHz, CDCl3): δ = 49.1, 48.9, 46.9, 42.2 (>C S), 33.6, 33.5, 33.4, 33.0,
32.1, 29.9, 29.8, 29.6, 25.1, 25.0, 24.9, 24.8, 24.91, 24.89 ( CH2), 86.7, 93.3 (C≡C); MS
(+ESI): m/z 478 (M+Na)+; C24H36S4 (M, 452.80). Calcd. C, 63.66; H, 8.01; S, 28.33.
Found C, 63.41; H, 7.98; S, 28.24%.
1-Bromo-1,2-dichloro-4,4-(1-propanol-3-sulfanyl)-1,3-butadiene (13e).
Yield 0.2 g (11%); oil, Rf = 0.2 with CHCl3 as eluent; IR (KBr, cm−1): 3341 ( OH),
2930, 2857 (C H), 1542 (C C); UV-VIS (CHCl3) λmax (log ε) (nm): 290 (4.27), 278
(3.54), 240 (3.81); 1H NMR (500 MHz): δ = 1.2–1.4 (m, 12H, (CH2)3), 1.8–2.2 (m, 4H,
S CH2 CH2), 2.90 (t, J = 6.8 Hz, 4H, S CH2); 3.82 (t, J = 7.3 Hz, 6H, O CH2),
5.2 (s, 2H, OH), 6.44 (s, 1H, >C CH); 13C NMR (125.66 MHz, CDCl3): δ = 18.1, 20.9,
21.2, 28.7 ( CH2), 36.6, 39.5 ( S CH2), 59.3, 60.5, 65.7 ( O CH2), 167.5 (C S),
137.0, 125.9, 123.1, 121.4 (Cbutad); MS (+ESI): m/z 467 (M+H)+; C16H27Cl2O2S2Br (M,
466.32). Calcd. C, 41.21; H, 5.84; S, 13.75. Found C, 41.18; H, 5.45; S, 13.63%.
1-Bromo-1,2,4-Trichloro-4-(benzo-1,3-imidazolyl-(2)-thio)-1,3-butadiene
(14f). Yield 0.3 g (21%); oil; Rf = 0.3 with CHCl3 as eluent; IR (KBr, cm−1): 2980
(Ar H), 2961, 2855 (C H), 3071 (N H), 1563 (C C); UV-VIS (CHCl3) λmax (nm) (log
1
ε): 290 (3.45), 270 (2.98), 240 (3.54); H NMR (499.74 MHz, CDCl3): δ = 5.5 (s, 1H,

˙
66
C. IBIS AND S. S¸AHINLER AYLA
NH), 6.23 (s, 1H, >C CH), 7.1–7.8 (m, 4H, arom-H); 13C NMR (125.66 MHz, CDCl3):
δ = 144.5 (S C N), 115.5, 123.6, 123.5 (CHarom), 138.5, 140.5 (Carom), 119.4, 124.6,
138.5, 138.7 (Cbutad); MS (+ESI): m/z 407 (M+Na)+; C11H6BrCl3N2S (M, 384.51).
Calcd. C, 34.37; H, 1.57; S, 8.34. Found C, 34,32; H, 1.30; S, 8.56%.
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