The synthesis of new cyclic thioquinone derivatives

Article abstract of DOI:10.1002/hc.20634

New bis(thio)substituted, S-,O-substituted, and S-,S-substituted benzoquinone compounds were synthesized from the reaction of p-chloranil (1) with S-,O-substituted thiols, dithiols, and monothiols. The ¹³C NMR spectra and the IR spectra of hete

Full text of DOI:10.1002/hc.20634

Heteroatom Chemistry
Volume 21, Number 6, 2010
The Synthesis of New Cyclic Thioquinone
Derivatives
Cemil Ibis1 and Zeliha Ozsoy-Gunes2
1Department of Chemistry, Engineering Faculty, Istanbul University, Avcilar 34320,
Istanbul, Turkey
2Hasan Ali Yucel Education Faculty, Department of Elementary Education, Division of Science
Education, Istanbul University, Vefa 34070, Istanbul, Turkey
Received 21 June 2010
that are related to biology [2]. From the perspectives
ABSTRACT: New bis(thio)substituted, S-,O-
of designing magnetic materials [3] and understand-
substituted, and S-,S-substituted benzoquinone
ing photophysical properties [4], the coordination
compounds were synthesized from the reaction of
chemistry of quinones is also very significant.
p-chloranil (1) with S-,O-substituted thiols, dithiols,
Much functionality of organic materials is in-
and monothiols. The 13C NMR spectra and the
duced by π-electron-oriented intermolecular in-
IR spectra of heterocyclic compounds 3, 4 and 7,
teractions [5]. Quinonoid compounds have large
8 showed different behavior; that of 3, 7 showed
π-conjugated systems and strong intramolecular
a carbon signal and a >C O group band for the
charge-transfer chromophoric systems in which sul-
carbonyl group and that of 4, 8 showed two carbon
fur and hydroxyl groups act as donor moieties and
signals and split bands for the carbonyl group. The
para-quinone groups act as an acceptor moiety [6].
structures of the novel compounds were character-
A great number of heterocyclic quinones have
ized by microanalysis, FT-IR, 1H NMR, 13C NMR,
been extensively investigated for their biologi-
MS, and UV–vis spectroscopy. The crystal structure
cal activity. In recent years, some S-,S- and
of 2,3,5,6-tetrakis(4-fluorobenzylthio)cyclohexa-2,5-
S-,O-substituted cyclic benzoquinone and thio-
diene-1,4-dione (15) was determined by the X-ray
substituted quinone compounds have been synthe-
ꢀ
C
diffraction method.
2010 Wiley Periodicals, Inc.
sized from the reactions of p-chloranil with difunc-
tional thiols [5–13]. Their solid-state spectrum and
crystal structure have been investigated [5,7].
S-substituted p-benzoquinone compounds have
been prepared by the reactions of p-chloranil with
linear chain alkyl mercaptan, cycloalkyl mercaptan,
aryl mercaptan, etc. [14–16]. The present paper de-
scribes the reactions between some dithiols, difunc-
tional and monothiols, and p-chloranil in different
solvents and also the synthesis of acyclic and cyclic
p-benzoquinone compounds.
Heteroatom Chem 21:446–452, 2010; View this article
online at wileyonlinelibrary.com. DOI 10.1002/hc.20634
INTRODUCTION
A
substantial number of naturally occurring
quinines have been shown to be essential to life. The
ability to carry electrons makes them an important
component of photosynthetic and respiratory elec-
tron transfer chain [1]. Quinonic compounds are of
great importance to understand different processes
RESULTS AND DISCUSSION
It has been reported earlier that from the reactions
of p-chloranil with difunctional thiols the cyclic
thioquinones were obtained. In a previous study,
a 2,5-O; 3,6-S-substituted benzoquinone compound
Correspondence to: Cemil Ibis; e-mail: ibiscml@istanbul.edu.tr.
Contract grant sponsor: Research Fund of the Istanbul Univer-
sity.
c
ꢀ
2010 Wiley Periodicals, Inc.
446

Synthesis of New Cyclic Thioquinone Derivatives 447
SCHEME 1 Synthesis of compounds 3–5, 7–9, 11, 12.
was synthesized by the reaction of p-chloranil (1)
with 2-mercaptoethanol (HO CH CH SH) [5]. In
ethanol at room temperature, compounds 3, 4, 5,
7, 8, 9, 11a and 12b were, respectively, synthesized
(Scheme 1). The reaction of 1 with 13 gave com-
pounds 14–16 in the presence of sodium carbonate
in ethanol and compounds 14, 15, 17, and 18 in
chloroform in the presence of triethylamine at room
temperature (Scheme 2).
2
2
the present study, we also synthesized 2,5-O; 3,6-S-
substituted (3, 7) and 2,6-O; 3,5-S-substituted (4, 8)
benzoquinone compounds. Compounds 3, 4 and 7,
8 were heterocyclic isomer thio-substituted quinone
compounds.
In this study, from the reaction of 1 with 2,
6, and 10 in the presence of sodium carbonate in
All of these products are new, stable, and colored
thioquinone compounds. Structures of the novel
SCHEME 2 Synthesis of compounds 14–18.
Heteroatom Chemistry DOI 10.1002/hc

448 Ibis and Ozsoy-Gunes
compounds were characterized by microanalysis
and spectroscopic data, containing FT-IR, 1H NMR,
13C NMR, MS, and UV–vis spectroscopy
In the mass spectrum, the positive ion mode
of ESI mass spectrum of compounds 7 and 8, the
respective molecular ion peaks were observed at
m/z(%) 381 (100) (M + H)+ and 381 (100) (M + H)+
(Table 2).
The reactions of 1 with 2 molar equiv of di-
functional thiols which are 3-mercapto-1-propanol
(2), 2-mercaptobenzyl alcohol (6) have been studied.
Our investigation was to synthesize S-,O-substituted
cyclic benzoquinone compounds. As intended, cyclic
thioquinone compounds 3, 4 and 7, 8 were obtained.
In addition, compound 5 and 9 were obtained as a
by-product.
1
The H NMR signal of the hydrogen protons of
the methylene groups (S CH ), (O CH ) adjacent to
2
2
the sulfur and oxygen atoms in compounds 3 and 4
was shifted to a higher field and displayed triplets
at 3.18 (J = 6.4 Hz) and 4.69 ppm (J = 5.9 Hz),
respectively.
Various tris(thio)-substituted products were ob-
tained as a by-product in reactions. Tris(thio)-
substituted products containing chlorine atom and
the alkoxy derivatives of tris(thio)-substituted com-
pounds have been observed due to the decreased
thiol amount in the medium of the reaction. This sit-
uation was discussed in our previous study [5]. The
tris(thio)-substituted compounds containing chlo-
rine atom and ethoxy group 5, 9, 14, and 16 were
synthesized in this way.
The reaction of 1 with 4 molar equiv 4-
fluorobenzyl mercaptan (13) has been studied in
the presence of sodium carbonate in ethanol.
Tetrakis(thio)-substituted product 15 and tris(thio)-
substituted products 14, 16 were synthesized from
this reaction. From the reaction of 1 with 2
molar equiv of 13, isomeric compounds were
obtained, namely 2,5-dichloro-3,6-S-disubstituted
benzoquinone (17), 2,6-dichloro-3,5-S-disubstituted
benzoquinone (18), and 14 and 15 in smaller
amounts in the presence of triethylamine in chlo-
roform (Scheme 2).
The 13C NMR spectra of compounds 3 and 7
gave carbonyl signals at 177.5 and 176.7 ppm (S-
C-CO-C-O) as one peak only while compounds 4 and
8 showed two carbonyl signals at 172.8, 181.5 and
171.8, 181.1 ppm (S-C-CO-C-S), (O-C-CO-C-O), re-
spectively. For compounds 4 and 8, this was due
to a carbonyl being beta to two oxygen atoms and
the other carbonyl being beta to two sulfur atoms.
Similarly, the spectrum of compound 17 gave a car-
bonyl signal at 171.0 (S-C-CO-C-Cl), whereas that of
compound 18 showed two carbonyl signals at 171.0
and 172.3 (S-C-CO-C-S), (Cl-C-CO-C-Cl), respectively
(Table 3).
The crystal structure of compound 15 was fur-
ther determined by X-ray single-crystal diffraction
analyses. As shown in Fig. 1, the bond lengths of
C1–C2, C3–C4, C4–C5, and C6–C1 in the benzo-
quinone ring were 1.493(2), 1.489(3), 1.494(2), and
From the reaction of 1 with 1 molar equiv
of dithiol 1,6-hexanedithiol (10a) and the reac-
tion of 1 with 2 molar equiv of dithiols 1,8-
octanedithiol (10b), bis(thio)-substituted compound
11a and tetrakis(thio)-substituted compound 12b
were, respectively, synthesized.
In the IR spectra of the synthesized compounds,
typical strong quinonic carbonyl absorptions were
observed between 1633 and 1676 cm−1. The IR spec-
tra of cyclic compounds 3, 4 and 7, 8 showed dif-
ferent behavior; that of 3 and 7 showed a carbonyl
(>C O) group band at 1643, 1646 cm−1 and that of
4 and 8 displayed split bands for carbonyl group at
1633, 1659 cm−1 and 1630, 1676 cm−1 for the car-
bonyl (>C O) group, respectively. For compounds
3, 4 and 7, 8, no bands were observed in the region
3400–3600 cm−1 attributable to the stretching vibra-
tion of the bonded OH group, indicating that the
cyclization reaction had taken place yielding these
compounds. The IR spectra of compounds 5 and 9
showed broad bands at 3340 and 3403 cm−1 for the
–OH stretching, respectively (Table 1).
FIGURE 1 Molecular structure of compound 15 (50% prob-
ability ellipsoids).
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Synthesis of New Cyclic Thioquinone Derivatives 449
TABLE 1 Synthesis of Thio-Substituted Quinone Compounds
Found Calculated
No.
Yield (%)
Mp (◦C)
IR (KBr, cm−1
)
C (%)
H (%)
S (%)
3
34
26
5
285–287
276–277
–
2969, 2951, 2887 (C H), 1643 (C O), 1559
(C C)
2951, 2924, 2853 (C H), 1659, 1633 (C O),
1556 (C C)
3340 (OH), 2934, 2880 (C H), 1644 (C O),
1583 (C C)
3057 (Ar-H), 1646 (C O), 1568 (C C)
50.42
50.69
50.47
50.69
43.26
43.63
63.10
63.14
63.21
63.14
61.32
61.46
44.39
44.59
57.32
57.85
57.21
57.59
57.43
57.59
61.21
61.06
61.34
61.06
60.50
60.82
52.87
52.53
52.72
52.53
4.34
4.25
4.34
4.25
5.17
5.13
3.21
3.18
3.32
3.18
4.85
4.62
3.54
3.74
7.11
7.06
3.18
3.22
3.24
3.22
3.35
3.62
3.45
3.62
4.10
4.05
2.81
2.64
2.50
2.64
23.01
22.55
22.98
22.55
23.65
23.29
16.21
16.86
16.98
16.86
17.01
16.97
19.13
19.84
27.69
28.08
17.56
17.08
17.82
17.08
19.43
19.18
19.02
19.18
17.11
16.80
14.85
14.02
14.81
14.02
4
5
7
23
18
8
270–272
281–283
137–138
88–90
8
3070 (Ar-H), 1676, 1630 (C O), 1565 (C C)
9
3403 (OH), 3076 (Ar H), 2963 (C H), 1665
(C O), 1566 (C C)
2932, 2851 (C H), 1666 (C O), 1515 (C C)
11a
12b
14a
14b
15a
15b
16
17
18
18
11
17
9
117–118
106–107
106–107
169–171
169–171
–
2920, 2848 (C H), 1660 (C O), 1578 (C C).
3041 (Ar H), 2940 (C H), 1660, 1651 (C O),
1506 (C C), 1217 (Ar F)
3041 (Ar H), 2940 (C H), 1660, 1651 (C O),
1506 (C C), 1217 (Ar F)
3039 (Ar H), 2996 (C H), 1654 (C O), 1508
(C C), 1236, 1226 (Ar F)
3039 (Ar H), 2996 (C H), 1654 (C O), 1508
(C C), 1236, 1226 (Ar F)
3042 (Ar H), 2981, 2928 (C H), 1652 (C O),
1508 (C C), 1225 (Ar F)
3058 (Ar H), 2917, 2849 (C H), 1658 (C O),
1507 (C C), 1226 (Ar F)
3076 (Ar H), 2995, 2890 (C H), 1675, 1663
(C O), 1506 (C C), 1223 (Ar F)
52
7
30
12
28
158–160
87–90
aGeneral procedure 1.
bGeneral procedure 2.
˚
Finnigan Flash EA 1112 elemental analyzer. In-
frared (IR) spectra were recorded in KBr pellets
in Nujol mulls on a Perkin Elmer Precisely Spec-
trum One FTIR spectrometer. UV spectra in CHCl3
and dioxane were recorded using a TU-1901 UV–
vis spectrometer. 1H NMR (500 MHz) and 13C NMR
(125 MHz) spectra were recorded in CDCl3 on a
Varian Unity INOVA spectrometer. Mass spectra
were obtained on a Thermo Finnigan LCQ Advan-
tage MAX LC/MS/MS spectrometer using the ESI
technique. Products were isolated by column chro-
matography on silica gel (Fluka silica gel 60, particle
size 63–200 μm). Thin-layer chromatography (TLC)
was performed on Merck silica gel plates (60F254),
and detection was carried out with ultraviolet light
(254 nm). All chemicals were reagent grade and used
without further purification. Moisture was excluded
from the glass apparatus using CaCl2 drying tubes.
1.500(3) A, respectively. The double bond lengths of
˚
C2–C3 and C5–C6 were 1.354(2) and 1.356(2) A in
15, respectively, which were smaller than expected
due to substituents such as C O. The double bond
length of the quinone unit agreed well with the corre-
sponding distance in a similar compound [17]. The
bond lengths of C1–O1 and C4–O2 were 1.214(2)
˚
and 1.212(2) A, respectively, typical of C O bonds.
In compound 15, C C C and C C O angles were
close to 120◦, as expected for sp2 hybridized atoms.
The crystallographic data and details on structure
refinement are summarized in Table 4.
EXPERIMENTAL
Melting points were measured using a Buchi
B-540 melting point apparatus and are uncorrected.
Elemental analyses were performed on a Thermo
Heteroatom Chemistry DOI 10.1002/hc

450 Ibis and Ozsoy-Gunes
TABLE 2 Some Physical and Spectroscopic Data of the Synthesized Compounds
Absorption maximum
(nm) (logε)a (nm) (logε)b
Molecular Formula,
No.
Weight
MS
Color
λ
max
λ
max
3
4
C12H12O4S2, 284.35
285 (M + H)+
Red
Blue
389(3.69), 261(3.86)
391(2.80), 281(2.70),
248(2.92)
381(3.90), 258(4.08)
383(3.87), 290(3.61),
248(4.02)
C12H12O4S2, 284.35
–
5
C15H21ClO5S3, 412.98
413 (M)−
Brown
396(3.49), 334(3.91),
394(3.37), 283(3.73),
283(3.86),
246(4.04)
246(4.17)
410(3.32), 282(3.88),
244(3.85)
414(3.60), 281(4.11),
246(4.20)
401(3.78), 278(4.34),
245(4.53)
522(3.57), 326(4.06),
251(4.39)
407(3.58), 281(3.58),
7
C
20H12O4S2, 380.44
381 (M + H)+
381 (M + H)+
–
Yellow
Green
394(3.77), 278(4.07),
241(4.04)
398(3.63), 279(4.16),
242(4.26)
393(3.54), 242(4.34)
8
C20H12O4S2, 380.44
9
C29H26O6S3, 566.72
C12H12Cl2O2S2, 323.26
C22H32O2S4, 456.76
Dark Brown
Brown
11a
12b
322 (M − H)−
455 (M − H)−
289(3.80), 245(3.84)
Brown
401(3.60), 292(3.70),
246(3.94)
400(3.72), 242(4.10)
407(3.86), 242(4.17)
252(3.88)
14
15
C27H18ClF3O2S3, 563.08
C34H24F4O2S4, 668.82
562 (M − H)−
Brown
Black
405(3.88), 250(4.21)
410(3.68), 272(3.80).
248(3.94)
402(3.53), 338(3.54),
248(4.04)
335(3.22), 273(3.24),
246(3.48)
522(2.95), 323(3.53),
668 (M)−
16
17
18
C
29H23F3O3S3, 572.69
C20H12Cl2F2O2S2, 457.35
20H12Cl2F2O2S2, 457.35
573 (M)+
Brown
Yellow
Pink
399(3.71), 336(3.63),
242(4.23)
395(3.51), 335(3.84),
242(4.23)
511(3.29), 319(3.81),
242(4.09)
456 (M − H)−
456 (M − H)−
C
250(3.72)
aCHCl3.
bDioxane.
X-Ray Structure Determination
Data Centre as supplementary publication no. CCDC
751691 for 15.
General Procedure 1 of the Synthesis of Thio-
Substituted-1,4-benzoquinone 3–5, 7–9, 11a, 12b,
and 14–16 from Thiols 2, 6, 10, and 13
Sodium carbonate (1.52 g) was dissolved
in ethanol as reaction media (65 mL). 2,3,5,6-
Tetrachloro-1,4-benzoquinone (p-chloranil) (1) and
thiol were added to this solution sequentially. With-
out heating, the mixture was stirred for 6–8 h. The
color of the solution changed quickly, and the ex-
tent of the reaction was monitored by TLC. The
reaction mixture was extracted in a Soxhlet ex-
tractor with dichloromethane. After recovery of the
solvent, the crude product was purified by column
chromatography.
Black chunk crystals of compound 15 suitable
for X-ray diffraction analysis were obtained by
slow evaporation of an ethanol solution at room
temperature. Data collection for 15 was carried
out on a Rigaku R-Axis Rapid-S imaging plate area
detector with graphite monochromated Mo Kα
˚
radiation (λ = 0.71070 A). The data were collected
at room temperature to a maximum 2θ value of
60.3◦.
The structure was solved by SIR 92 [18] and
refined with CRYSTALS [19]. The non-hydrogen
atoms were refined anisotropically. The positions of
the H atoms bonded to C atoms were calculated
˚
(C–H distance 0.95 A) and refined using a riding
model. The H atom displacement parameters were
restricted to e 1.2 Ueq of the parent atom. An ORTEP
III with 50% probability displacement ellipsoid view
of the molecular structure of 15 is given in Fig. 1
[20]. Crystallographic data (excluding structure fac-
tors) for the structure reported in this paper have
been deposited with the Cambridge Crystallographic
General Procedure 2 of the Synthesis of Thio-
Substituted-1,4-benzoquinone 14, 15, 17, and 18
from Thiol 13
p-Chloranil and thiol were stirred in chloroform
as solvent (50 mL). Triethylamine (1 mL) was added
Heteroatom Chemistry DOI 10.1002/hc

Synthesis of New Cyclic Thioquinone Derivatives 451
TABLE 3 1H NMR, 13C NMR Data of the Synthesized Compounds
No.
3
1H NMR (CDCl3, δ, ppm)
13C NMR (CDCl3, δ, ppm)
2.12–2.17 (m, 4H, CH2), 3.18 (t, J = 6.4 Hz, 4H,
S CH2), 4.69 (t, J = 5.9 Hz, 4H, O CH2)
26.6, 29.1, 70.9 (CH2), 123.5, 153.2 (C C O), 177.5
(C O)
26.5, 29.1, 70.9 (CH2), 125.6, 152.1 (C C O), 172.8,
181.5 (C O)
29.4, 30.6, 30.9, 30.9, 32.4, 34.2, 60.0, 60.4, 71.2 (CH2),
126.9, 143.0, 147.3, 148.3 (C C O), 173.3, 178.2
(C O)
4
2.14–2.17 (m, 4H, CH2), 3.18 (t, J = 6.4 Hz, 4H,
S CH2), 4.69 (t, J = 5.9 Hz, 4H, O CH2)
5
1.68–2.00 (m, 6H, CH2), 2.75, 2.83, 2.94 (t, 6H, S CH2),
3.67–3.70 (m, 6H, O CH2), 6.35, 7.10 (s, 3H, OH)
7
8
9
5.50 (s, 4H, O CH2), 7.24–7.30 (m, 6H, Harom), 7.39 (d,
72.0 (CH2), 116.9, 127.8, 129.1, 129.2, 130.0, 134.0
(Carom), 136.6, 153.6 (C C O), 176.7 (C O)
72.0 (CH2), 119.5, 127.8, 129.1, 130.0, 134.0 (Carom),
136.7, 152.3 (C C O), 171.8, 181.1 (C O)
14.5 (CH3), 63.0, 69.5, 71.9, 72.0 (CH2), 119.5, 120.2,
127.5, 127.6, 127.7, 127.8, 127.82, 127.9, 128.0,
128.2, 128.3, 129.0, 129.1, 130.0, 131.0, 132.4, 134.0
(Carom), 136.7, 141.4, 152.7, 154.8 (C C O), 173.3,
181.6 (C O)
J = 6.8 Hz, 2H, Harom
)
5.46 (s, 4H, O CH2), 7.19–7.29 (m, 6H, Harom), 7.41 (d,
J = 7.3 Hz, 2H, Harom
)
1.08 (t, 3H, CH3), 4.15 (m, 2H, O CH2), 4.80 (s, 6H,
HO CH2), 5.46 (s, 3H, HO), 7.22–7.31 (m, 10H,
Harom), 7.37–7.39 (m, 2H, Harom
)
11a
1.22–1.29 (m, 4H, CH2), 1.68–1.70 (m, 4H, CH2), 3.23 (t,
J = 6.3 Hz, 4H, S CH2)
23.7, 24.0, 33.4 (CH2), 140.8, 148.7 (C C O), 172.3
(C O)
21.7, 24.5, 27.1, 34.6 (CH2), 149.0 (C C O), 173.8
(C O)
12b 1.18–1.30 (m, 4H, CH2), 1.53–1.63 (m, 8H, CH2), 2.95 (t,
4H, S CH2)
14
4.10, 4.23, 4.27 (s, 6H, S CH2), 6.86–6.93 (m, 6H,
Harom), 7.07 (dd, J = 8.8, 8.8 Hz, 2H, Harom), 7.13 (dd,
J = 8.3, 8.3 Hz, 2H, Harom), 7.17 (dd, J = 8.8, 8.8 Hz,
36.3, 37.1, 37.4 (CH2), 114.6, 114.7, 114.8 (d,
J = 21.6 Hz, CHarom), 129.6, 129.7, 129.9 (d,
J = 8.2 Hz, CHarom), 130.9, 131.3, 131.6 (d,
J = 3.4 Hz, Carom), 136.9, 143.5, 144.5, 145.4
(C C O), 161.1, 161.2, 161.3 (d, J = 247.3 Hz,
F–Carom), 170.3, 174.2 (C O)
2H, Harom
)
15
16
4.10 (s, 8H, S CH2), 6.88 (t, J = 8.8 Hz, 8H, Harom),
7.09 (dd, J = 8.8, 8.8 Hz, 8H, Harom
36.9 (CH2), 114.5 (d, J = 21.6 Hz, CHarom), 129.6 (d,
J = 8.2 Hz, CHarom), 131.5 (d, J = 2.9 Hz, Carom),
144.6 (C C O), 161.6 (d, J = 246.8 Hz, F–Carom),
173.5 (C O)
14.7 (CH3), 35.6, 36.9, 37.4, 69.0 (CH2), 114.4, 114.5,
114.6 (d, J = 21.6 Hz, CHarom), 129.5, 129.6, 129.8
(d, J = 8.2 Hz, CHarom), 131.8, 131.9, 132.0, (d,
J = 2.9 Hz, Carom), 140.9, 145.8, 161.1, 161.2 (d,
J = 246.8 Hz, F–Carom), 156.6, 166.7 (C C O),
174.0, 177.6 (C O)
)
1.22 (t, J = 7.3 Hz, 3H, CH3), 4.08 (q, J = 7.3 Hz, 2H,
O CH2), 4.04, 4.20, 4.22 (s, 6H, S CH2), 6.85–6.91
(m, 6H, Harom), 7.08–7.12 (m, 6H, Harom
)
17
18
4.43 (s, 4H, S CH2), 6.84–6.92 (m, 4H, Harom),
7.02–7.08 (m, 2H, Harom), 7.18–7.22 (m, 2H, Harom
36.8 (CH2), 114.5 (d, J = 21.6 Hz, CHarom), 129.9 (d,
J = 8.6 Hz, CHarom), 130.8 (d, J = 3.4 Hz, Carom),
136.6, 144.4 (C C O), 161.4 (d, J = 247.8 Hz,
F–Carom), 171.0 (C O)
37.6 (CH2), 114.7 (d, J = 21.6 Hz, CHarom), 129.8 (d,
J = 8.2 Hz, CHarom), 131.3 (d, J = 3.4 Hz, Carom),
139.9, 143.4 (C C O), 161.2 (d, J = 247.3 Hz,
F–Carom), 171.0, 172.3 (C O)
)
4.43 (s, 4H, S CH2), 6.89 (t, J = 8.3 Hz, 4H, Harom),
7.13 (dd, J = 8.3, 8.3 Hz, 4H, Harom
)
to the reaction mixture slowly. Without heating,
the mixture was stirred for 4 h. The color of the
solution changed quickly, and the extent of the reac-
tion was monitored by TLC. Chloroform was added
to the reaction mixture to separate the organic layer.
Then, the organic layer was washed with water (5 ×
30 mL) and dried with Na2SO4. After filtering, the
solvent was evaporated, and the residue was puri-
fied by column chromatography on silica gel.
See Table 1 for yields, melting points, IR, and ele-
mental analysis; Table 2 for MS and UV–vis data; and
Table 3 for 1H NMR and 13C NMR data of synthesized
compounds 3–5, 7–9, 11a, 12b, and 14–18 obtained
from 2, 6, 10, and 13.
Heteroatom Chemistry DOI 10.1002/hc

452 Ibis and Ozsoy-Gunes
TABLE 4 Crystal Data and Structure Refinement for 15
been deposited with the Cambridge Crystallo-
graphic Data Centre as supplementary publication
no. CCDC 751691. Copies of the data can be ob-
tained, free of charge, on application to CCDC, 12
Union Road, Cambridge CB2 1EZ, UK fax: +44(0)-
1223-336033; e-mail: deposit@ccdc.cam.ac.uk; web:
http://www.ccdc.cam.ac.uk/products/csd/request/.
Empirical formula
CCDC deposit number
Formula weight
Crystal system
C34H24F4O2S4
751691
668.80
Triclinic
P-1
9.7018(10)
10.2541
Space group
˚
a (A)
˚
b (A)
˚
c (A)
16.0095(10)
77.576(3)
80.403(4)
78.090(3)
α (◦)
β (◦)
γ (◦)
REFERENCES
3
˚
V (A )
1509.38(2)
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[11] Gompper, R.; Binder, R.; Wagner, H-U. Tetrahedron
Lett 1986, 27, 691.
Z
2
Density (calculated)
1.471
(g cm−3
)
Absorption coefficient
(mm−1
F(000)
Crystal size (mm)
Theta range for data
collection (◦)
0.0371
)
688.00
0.60 × 0.40 × 0.10
0.95–30.17
Index ranges
−13 ≤ h ≤ 12; −14 ≤ k ≤ 14;
−22 ≤ l ≤ 22
Reflections collected
Independent reflections
Absorption correction
Maximum and minimum
transmission
107434
8329 [Rint = 0.034]
Multiscan
0.737 and 0.964
Refinement method
Full-matrix least-square on F
Data /restraints/parameters 8027/0/421
Goodness of fit on F2
1.106
Final R indices [I > 2σ(I )]
Larges−t 3diff. peak and hole
R = 0.081, wR = 0.051
0.26 and −0.29
˚
(e.A
)
[12] Becker, J. Y.; Bernstein, J.; Bittner, S.; Harlev, E.;
Sarma, J. A. R. P., Shaik, S. S. New J Chem 1988, 12,
875.
CONCLUSION
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J-Y.; Junk, O-J.; Lee, J. Y.; Jeong, S. H. Eur J Med
Chem 2005, 40, 438.
The synthesis of heterocyclic and acyclic (thio)
substituted-1,4-benzoquinone compounds has been
described in this paper. These compounds were
obtained from the reactions between some dithi-
ols, monothiols, and p-chloranil according to two
different procedures. The synthesized heterocyclic
quinones compounds were isomer compounds for
3, 4 and 7, 8, and these compounds were identi-
fied by the 13C NMR spectra and the IR spectra. The
compound 15 was confirmed by the X-ray crystallo-
graphic study.
[18] Altomare, A.; Cascarano, G.; Giacovazzo, C.;
Guagliardi, A.; Burla, M.; Polidori, G.; Camalli, M.
SIR 92, J Appl Cryst. 1994, 27, 435.
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565.
SUPPLEMENTARY MATERIAL
Crystallographic data (excluding structure factors)
for the structure 15 reported in this paper have
Heteroatom Chemistry DOI 10.1002/hc