Efficient synthesis of new stable 1,4-diionic organosulfurs and corresponding mesoionic compounds from N -heterocyclic ylides

Article abstract of DOI:10.1080/10426507.2013.819866

N-Phenacyl heterocyclic salts such as isoquinolinium, quinolinium, and pyridinium bromide react quickly with benzoyl isothiocyanate in the present of triethylamine to produce 1,4-diionic organosulfur derivatives. Cyclization and dehydrogenation of 1,4-dii

Full text of DOI:10.1080/10426507.2013.819866

This article was downloaded by: [Erciyes University]
On: 31 December 2014, At: 01:36
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered
office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK
Phosphorus, Sulfur, and Silicon and the
Related Elements
Publication details, including instructions for authors and
subscription information:
http://www.tandfonline.com/loi/gpss20
Efficient Synthesis of New Stable 1,4-
diionic Organosulfurs and Corresponding
Mesoionic Compounds from N-
Heterocyclic Ylides
Fahimeh Shahrekipour a , Reza Heydari a , Batool Tahamipour b
Hamideh Saravani a & Claudia Graiff c
,
a Department of Chemistry, Faculty of Science , University of Sistan
and Balouchestan , Zahedan , Iran
Click for updates
b Farhangian University of Kerman , Kerman , Iran
c Dipartimento di Chimica , Universitá di Parma , Parma , Italy
Accepted author version posted online: 12 Aug 2013.Published
online: 03 Dec 2013.
To cite this article: Fahimeh Shahrekipour , Reza Heydari , Batool Tahamipour , Hamideh Saravani &
Claudia Graiff (2014) Efficient Synthesis of New Stable 1,4-diionic Organosulfurs and Corresponding
Mesoionic Compounds from N-Heterocyclic Ylides, Phosphorus, Sulfur, and Silicon and the Related
Elements, 189:2, 263-273, DOI: 10.1080/10426507.2013.819866
To link to this article: http://dx.doi.org/10.1080/10426507.2013.819866
PLEASE SCROLL DOWN FOR ARTICLE
Taylor & Francis makes every effort to ensure the accuracy of all the information (the
“Content”) contained in the publications on our platform. However, Taylor & Francis,
our agents, and our licensors make no representations or warranties whatsoever as to
the accuracy, completeness, or suitability for any purpose of the Content. Any opinions
and views expressed in this publication are the opinions and views of the authors,
and are not the views of or endorsed by Taylor & Francis. The accuracy of the Content
should not be relied upon and should be independently verified with primary sources
of information. Taylor and Francis shall not be liable for any losses, actions, claims,
proceedings, demands, costs, expenses, damages, and other liabilities whatsoever or
howsoever caused arising directly or indirectly in connection with, in relation to or arising
out of the use of the Content.
This article may be used for research, teaching, and private study purposes. Any
substantial or systematic reproduction, redistribution, reselling, loan, sub-licensing,

systematic supply, or distribution in any form to anyone is expressly forbidden. Terms &
Conditions of access and use can be found at http://www.tandfonline.com/page/terms-
and-conditions

Phosphorus, Sulfur, and Silicon, 189:263–273, 2014
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426507.2013.819866
EFFICIENT SYNTHESIS OF NEW STABLE 1,4-DIIONIC
ORGANOSULFURS AND CORRESPONDING MESOIONIC
COMPOUNDS FROM N-HETEROCYCLIC YLIDES
Fahimeh Shahrekipour,1 Reza Heydari,1 Batool Tahamipour,2
Hamideh Saravani,1 and Claudia Graiff3
1Department of Chemistry, Faculty of Science, University of Sistan and
Balouchestan, Zahedan, Iran
2Farhangian University of Kerman, Kerman, Iran
3Dipartimento di Chimica, Universita´ di Parma, Parma, Italy
GRAPHICAL ABSTRACT
Abstract N-Phenacyl heterocyclic salts such as isoquinolinium, quinolinium, and pyridinium
bromide react quickly with benzoyl isothiocyanate in the present of triethylamine to produce 1,4-
diionic organosulfur derivatives. Cyclization and dehydrogenation of 1,4-diionic organosulfurs
gave thiazoloisoquinolinium, quinolinium, or pyridinium benzimidates.
[Supplementary materials are available for this article. Go to the publisher’s online edition of
Phosphorus, Sulfur, and Silicon and the Related Elements for the following free supplemental
files: Figures.].
Keywords 2-Bromoacetophenone; mesoionic compounds; benzoyl isothiocyanate; 1,3-dipolar
cycloaddition; nitrogen ylides
Received 13 March 2013; accepted 24 June 2013.
The authors would like to thank the financial support from the Research Council of the University of Sistan
and Balouchestan, Zahedan, Iran.
Address correspondence to Dr. Reza Heydari, Department of Chemistry, Faculty of Science, University of
Sistan and Balouchestan, 98135-674 Zahedan, Iran. E-mail: heydari@chem.usb.ac.ir
263

264
F. SHAHREKIPOUR ET AL.
INTRODUCTION
Mesoionic compounds are five-membered heterocyclic conjugated betains. They are
distinct types of heterocycles, which belong to the class of nonbenzenoid aromatics. These
compounds have attracted attention because of their structure, chemical and pharmacolog-
ical properties, and biological activities, such as antitumor, anti-inflammatory, antimalaric,
and analgesic.1–5 Since the introduction of the concept of mesoionic molecules by Baker
et al.,6 preparation and synthetic application of many mesoionic compounds have been re-
ported.7 The most reported routes are available for the synthesis of monocyclic mesoionic
compounds8,9 but reported methods for the preparation of ring fused analogues are more
limited.10,11
Among the various methods for mesoionic compounds formation, the 1,3-dipolar
cycloaddition method has been widely investigated by Huisgen et al.12 Recently, bicyclic
mesoionic thiazoles have been synthesized by 1,3-dipolar addition between isoquinolin-
ium, quinolinium, and pyridinium ylides with dipolarophiles, such as carbon disulfide,
isothiocyanates, and isocyanates.13–15
Herein, we prepared 1,4-diionic organosulfurs 3a–c and corresponding mesoionic
thiazoloisoquinolinium, quinolinium, and pyridinium benzimidates 4a–c by reaction of
N-phenacyl heterocyclic salts and benzoyl isothiocyanate in the presence of triethylamine
(Scheme 1).
Scheme 1 Reaction of N-phenacyl isoquinolinium, quinolinium, pyridinium bromide 1 with benzoyl isothio-
cyanate.

SYNTHESIS OF 1,4-DIIONIC ORGANOSULFURS, CORRESPONDING MESOIONIC COMPOUNDS 265
RESULTS AND DISCUSSION
The structures of all the synthesized compounds were established on the basis of
1
their spectroscopic data. The H-NMR spectrum of 3a exhibited a broad singlet at δ =
14.88 Sppm that readily recognized as enolic hydrogen; a singlet at δ = 8.53 and two
doublet signals at δ = 8.21 and δ = 7.85 ppm (3JHH = 7.6 Hz) are observed for protons
of nitrogen containing ring of isoquinoline moiety. Aromatic protons of isoquinoline and
benzoyl moiety gave rise to characteristic signals in the aromatic region of the spectrum (δ =
7.05–7.86 ppm). The proton-decoupled 13C-NMR spectrum of 3a showed enolic, carbonyl,
and C S− carbons appear at 179.0, 165.6, and 182.0 ppm, respectively. The mass spectrum
of 3a displayed the molecular ion (M+) peak at m/z = 410, which is consistent with the
1:1:1 adduct of isoquinoline, 2-bromoacetophenone, and benzoyl isothiocyanate. The IR
spectrum of the compound 3a showed absorptions at 1686, 1639, and 1373 cm−1 for enolic,
carbonyl, and thiocarbonyl groups.
1
The H-NMR spectrum of 4a exhibited two doublet signals at δ = 8.39 and
δ = 9.77 ppm (3JHH = 7.6 Hz) are observed for protons of nitrogen containing ring of
isoquinoline moiety. Aromatic protons of isoquinoline and benzoyl moiety gave rise to
characteristic signals in the aromatic region of the spectrum. The 13CNMR spectrum of
4a showed signals at 187.4 and 173.6 ppm for two carbonyl groups. The mass spectrum
of 4a displayed the molecular ion (M+) peak at m/z = 408, which is consistent with the
1:1:1 adduct of isoquinoline, 2-bromoacetophenone, and benzoyl isothiocyanate. In the IR
spectra of this compound, absorptions at 1603 and 1589 cm−1 are due to two carbonyl
groups and 1321 cm−1 for the C S band.
CRYSTALLOGRAPHY
The crystal structure of compound 4 was fully elucidated by X-ray diffrac-
tion analysis. An ORTEP view of the molecular structure of N-(3-benzoylthiazolo
[2,3-a]isoquinolinium-2-yl)benzimidate is reported in Figure 1, and a list of the most
important bond distances, angles, and torsion angles is reported in Table 1.
The thiazoloisoquinolinium moiety is essentially planar as well as the benzimidate
group, being the O1 atom at a distance of 0.152(1) Å from the mean plane of the benzimidate
system. The two above-mentioned mean planes form a dihedral angle of 6.02(1)◦. On the
other hand, the benzoyl group defined by atoms C13, C14, C15, C16, C17, C18, C19, O2
is not planar, being the O2 atom at a distance of 0.871(1) Å from the mean plane defined
by the carbon atoms. If we consider the dihedral angle between the mean plane of the
thiazoloisoquinolinium moiety and that of the above-mentioned benzoyl group, the value
is 70.40(1)◦.
The torsion angle S1-C11-N2-C12 = 1.7(2)◦ shows that the carbonyl group attached
to N2 is in cis with respect to the sulfur atom. There is a short intramolecular contact of
2.527(2) Å between O1 and S1.
The charges in compound 4a are divided between the thiazole ring and the imidate
fragment. In comparison with the C1–N1 (1.3525(15) Å) and C1–S1 (1.7184(12) Å) bonds,
the N1–C10 (1.4162(16) Å) and S1–C11 (1.7771(12) Å) bonds are significantly longer, the
shorted C1–N1 and C1–S1 bonds indicate that a positive charge is located at N1 and S1. On
the other hand, the elongated exo-C11–N2 bond (1. 3205(16) Å) and the shorted C10–C11
bond (1.3970(17) Å) show that a negative charge is located at imidate fragment.16 The
packing diagram of compound 4a is shown in Figure 2.

266
F. SHAHREKIPOUR ET AL.
Table 1 Selected bond lengths (Å), bond angles (◦), and torsion angles (◦) for compound 4a
Bond lengths (Å)
S1–C1
C11–S1
C1–N1
1.7184(12)
1.7771(12)
1.3525(15)
1.4162(16)
1.3970(17)
1.4599(18)
1.2291(16)
1.3205(16)
1.3568(17)
1.2410(17)
1.4187(17)
1.3954(16)
1.4902(17)
1.4932(18)
1.3419(19)
1.4180(19)
N1–C10
C10–C11
C10–C13
C13–O2
C11–N2
N2–C12
C12–O1
C1–C2
N1–C9
C12–C20
C13–C14
C9–C8
C8–C7
Bond angles (◦)
N1–C1–S1
112.92(8)
90.85(6)
C1–S1–C11
S1–C11–C10
C11–C10–N1
C10–N1–C1
C10–C13–O2
N1–C10–C13
S1–C11–N2
C11–N2–C12
O1–C12–N2
C10–C13–C14
C9–N1–C10
N1–C1–C2
C1–N1–C9
O1–C13–C14
110.23(9)
112.04(10)
113.95(10)
121.87(12)
121.54(10)
124.26(9)
118.12(11)
124.28(12)
119.13(11)
125.69(10)
121.26(11)
120.23(10)
118.99(12)
120.93(12)
O1–C12–C20
Bond torsion angles (◦)
N1–C1–S1–C11
N1–C10–C13–O2
N1–C10–C11–N2
N1–C10–C13–C14
S1–C1–N1–C10
S1–C1–N1–C9
S1–C11–N2–C12
S1–C11–C10–C13
C1–S1–C11–N2
C1–S1–C11–C10
C1–N1–C10–C13
C11–C10–N1–C1
C11–S1–C1–C2
C11–N2–C12–O1
C9–N1–C10–C13
C13–C10–C11–N2
−1.26(9)
19.6(2)
−179.03(11)
−159.78(11)
1.11(13)
177.12(9)
1.66(16)
169.11(10)
179.45(11)
1.09(9)
−170.52(11)
−0.24(14)
177.64(11)
−3.53(19)
13.73(18)
−9.2(2)

SYNTHESIS OF 1,4-DIIONIC ORGANOSULFURS, CORRESPONDING MESOIONIC COMPOUNDS 267
Figure 1 ORTEP view of compound 4a together with the atom-numbering scheme. The ellipsoids are drawn at
50% probability level. (Color figure available online).
Illustrative mechanism for the generation of compounds 3a and 4a are shown in
Scheme 2. In the first step, N-phenacyl isoquinolinium bromide 1 obtained from the reaction
of isoquinoline and 2-bromoacetophenone. In the next step, nitrogen ylide 2 was produced
by deprotonation of N-phenacylisoquinolinium bromide 1 in the presence of triethylamine.
This ylide intermediate undergoes reaction with benzoyl isotiocyanat to produce 3a, which
leads to 4a by dehydration12,17 (Scheme 2).
CONLUSION
In summary, we have developed a protocol for the synthesis of three new 1,4-diionic
organosulfurs (3a–c) and their corresponding mesoionic compounds (4a–c) with good
yields and short reaction time, using easily available starting material.
EXPERIMENTAL
General
The structure of compounds was determined based on its elemental analyses, IR,
1H, 13C NMR spectroscopy, mass spectra, and single-crystal X-ray analysis. Melting
points were measured on an Electrothermal 9100 apparatus (Model 9100, England), IR
spectra were measured on a Shimadzu IR-460 spectrometer (Model 460, Kyoto). The
1H and 13C NMR spectra were recorded at 400.2 and 100.6 MHz, respectively, on a
BRUCKER DRX-400 AVANCE instrument with CDCl3 as solvent and tetramethylsi-
lane (TMS) as internal standard. Mass spectra were recorded on an Agilent Technology
5975C mass spectrometer (Model DRX-400, Agilent Technology 5975C) operating at
an ionization potential of 70 eV. Elemental analysis for C, H, and N were performed
using a Heraeus CHN-O-Rapid analyzer (Germany). All reagents were purchased from

268
F. SHAHREKIPOUR ET AL.
Figure 2 The Packing diagram of compound 4a hydrogen bonds are shown as dashed lines. (Color figure available
online).
Merck companies (Merck, Hohenbrunn, Germany) and used without further purifica-
tion. All yields refer to isolated products after purification. Benzoyl isothiocyanate was
prepared according to the reported procedure.18 N-phenacyl derivatives of isoquinolin-
ium, quinolinium, and pyridinium bromides were synthesized according to the literature
methods.19
Preparation of N-Benzoyl-3-hydroxy-2-(isoquinolinium-2-yl)-3-phenyl-
prop-2-enimidothiolate (3a) as a Typical Procedure
To a stirred solution of phenacylisoquinolinium bromide 1 (0.33 g, 1 mmol) and
benzoyl isothiocyanate (0.16 g, 1 mmol) in 5 mL of acetonitrile was added dropwise
triethylamine (0.10 g, 1 mmol) in acetonitrile (2 mL) at room temperature for more than
5 min. The reaction was followed by TLC. After approximately half an hour stirring at
room temperature, the product was filtered off and recrystallized from methanol and was
finally obtained as a yellow crystal in 85% yield, 0.35 g, mp 166–168◦C, IR (KBr)(νmax
,

SYNTHESIS OF 1,4-DIIONIC ORGANOSULFURS, CORRESPONDING MESOIONIC COMPOUNDS 269
Scheme 2 Mechanism of the preparation of 3a and 4a.
cm−1): 3460 (OH), 3056 (CAr-H), 1686 ( C–OH), 1636 (C O), 1373 (C–S−), 1263(C–O).
1H NMR (400.2 MHz, CDCl3): δH 7.06 (1H, d, 3JHH = 7.2 Hz, CH, Ph), 7.15 (1H, d, 3JHH
= 7.2 Hz, CH, Ph), 7.27 (2H, m, 2CH, Ph), 7.57 (5H, m, 5CH, Ph), 7.63 (3H, m, CH, Ph
and 2CH, isoquinoline), 7.80 (1H, t, 3JHH = 7.6 Hz, CH, isoquinoline), 7.85 (1H, d, 3JHH
= 8.0 Hz, CH, isoquinoline), 8.21 (2H, d, 3JHH = 7.6 Hz, 2CH, isoquinoline), 8.53 (1H, s,
CH, isoquinoline), 14.88 (1H, s, C C–OH). 13C NMR (100.6 MHz, CDCl3): δC 116.6 (C),
126.1 (C), 126.3(CH), 126.9 (C), 127.4 (2CH), 128.1 (2CH), 128.4 (2CH), 128.8 (3CH),
128.9 (CH), 129.1 (CH), 130.4 (CH), 132.6 (CH), 133.7 (C), 134.0 (CH), 134.6 (C), 137.9
(CH), 139.4 (CH), 165.6 (C O), 179.0 ( C–OH), 182.0 (C-S−). MS (m/z,%): 410.4 (M.+,
5), 376.1 (22), 354.1 (26), 285.1 (40), 256.2 (32), 129 (58), 81.1 (100), 77 (68). Anal.
Calcd. for C25H18N2O2S (410.49): C, 73.15; H, 4.42; N, 6.82. Found: C, 73.02; H, 4.49;
N, 6.70%.
N-Benzoyl-3-hydroxy-3-phenyl-2-(quinolinium-1-yl)prop-2-enimidothiolate
(3b)
Orange crystal, 0.33 g, yield 80%, mp 183–185◦C, IR (KBr) (νmax, cm−1): 3444
(OH), 3061 (CAr-H), 1684 ( C–OH), 1620 (C O), 1364 (C–S−), 1240 (C–O). 1H NMR
(400.2 MHz, CDCl3): δH 6.99 (2H, t, 3JHH = 7.2 Hz, 2CH, Ph), 7.07 (3H, m, 3CH, Ph), 7.57
(3H, m, 3CH, Ph), 7.70 (1H, d, 3JHH = 7.6 Hz, CH, Ph), 7.76 (1H, t, 3JHH 7.6 = Hz, CH,
Ph), 7.98 (2H, t, 3JHH 8.2 = Hz, 2CH, quinoline), 8.26 (2H, m, 2CH, quinoline), 8.39 (1H,
d, 3JHH = 8 Hz, CH, quinoline), 8.64 (1H, d, 3JHH = 8.4 Hz, CH, quinoline), 8.90 (1H, d,
3JHH = 5.6 Hz, CH, quinoline), 15.59(1H, bs, C C–OH). 13C NMR (100.6 MHz, CDCl3):
δC 120.8 (C), 120.9 (CH), 125.6 (C), 128.0(3CH), 128.1(2CH), 128.7(3CH), 129.2 (CH),
129.3 (CH), 129.4 (CH), 129.5 (CH), 132.2 (CH), 135.0 (C), 135.4 (CH), 140.2 (C), 142.2
(C), 145.8 (CH), 151.0 (CH), 165.9 (C O), 176.0 ( C–OH), 184.0 (C-S−). MS (m/z,%):
410.3 (M.+, 1), 129.0 (100), 105 (87), 77 (20). Anal. Calcd. for C25H18N2O2S (410.49): C,
73.15; H, 4.42; N, 6.82. Found: C, 73.09; H, 4.45; N, 6.74%.

270
F. SHAHREKIPOUR ET AL.
N-Benzoyl-3-hydroxy-3-phenyl-2-(pyridinium-1-yl)prop-2-enimidothiolate
(3c)
Pale yellow crystal, 0.31 g, yield 87%, mp 145–147◦C, IR (KBr) (νmax, cm−1): 3443
(OH), 3080 (CAr H), 1686 ( C–OH), 1624 (C O), 1374 (C–S−), 1239 (C–O). 1H NMR
(400.2 MHz, CDCl3): δH 7.19 (5H, m, 5CH, Ph), 7.56 (3H, m, 3CH, Ph), 7.74 (2H, t, 3JHH
=
7.2 Hz, 2CH, Ph), 8. 21 (3H, m, 3CH, pyridine), 8.58 (2H, d, 3JHH = 5.2 Hz, 2CH, pyridine),
15.34 (1H, bs, C C OH). 13C NMR (100.6 MHz, CDCl3): δC 116.7(C), 126.2 (2CH),
126.4 (2CH), 128.1 (2CH), 128.4 (2CH), 128.7 (2CH), 129.3 (CH), 132.2 (CH), 135.0
(C), 140.0 (C), 144.3 (CH), 150.6 (2CH), 166.0 (C O), 179.8 ( C–OH), 184.9 (C S−).
MS (m/z,%): 360.1 (M.+, 5), 281.0 (6), 239.1 (9), 122.0 (94), 105 (100), 79 (78). Anal.
Calcd. for C21H16N2O2S (360.43): C, 69.98; H, 4.47; N, 7.77. Found: C, 69.85; H, 4.17; N,
7.51%.
Preparation of N-(3-Benzoylthiazolo[2,3-a]isoquinolinium-2-yl)benzimi-
date (4a) as a Typical Procedure
A suspension of 3a (0.4 g, 1 mmol) in 5 mL of dimethylformamide was refluxed for
2 h. After completion of the reaction, precipitated product was filtered off and recrystallized
from dimethyl sulfoxide and was finally obtained as an orange cubic crystal in 76% yield,
0.31 g, mp 281–283◦C, IR (KBr) (νmax, cm−1): 3053 (CAr-H), 1603 and 1589 (C O), 1321
(C–S), 1250 (C–O). 1H NMR (400.2 MHz, CDCl3): δH 7.27 (2H, t, 3JHH = 7.6 Hz, 2CH,
Ph), 7.40 (1H, t, 3JHH = 7.2 Hz, CH, Ph), 7.55 (2H, t, 3JHH = 7.6 Hz, 2CH, Ph), 7.65 (3H,
d, 3JHH = 6.8 Hz, 3CH, Ph), 7.80 (1H, d, 3JHH = 7.6 Hz, CH, isoquinoline), 7.88 (2H, m,
2CH, Ph), 7.97 (3H, t, 3CH, isoquinoline), 8.39 (1H, d, 3JHH = 7.6 Hz, CH, isoquinoline),
9.75 (1H, d, 3JHH = 7.2 Hz, CH, isoquinoline).13C NMR (100.6 MHz, CDCl3): δC 120.2
(CH), 120.5(C), 124.9 (C), 125.5 (CH), 127.1 (CH), 127.7 (2CH), 127.8 (CH), 128.1 (2CH),
129.1 (2CH), 129.7 (2CH), 130.4 (CH), 131.2 (CH), 131.7 (CH), 132.2 (CH), 136.6 (C),
140.3 (2C), 147.5 (C), 158.2 (C), 173.6 and 187.4 (C O). MS (m/z,%): 408.1 (M.+, 5),
376.0 (60), 317.0 (37), 285.0 (92), 283.0 (100), 223.0 (81). Anal. Calcd. for C25H16N2O2S
(408.47): C, 73.51; H, 3.95; N, 6.86. Found: C, 73.48; H, 3.99; N, 6.89%.
N-(1-Benzoylthiazolo[3,2-a]quinolinium-2-yl)benzimidate (4b)
Yellow crystal, 0.29 g, yield 71%, mp 305–307◦C, IR (KBr) (νmax, cm−1): 3060
(CAr-H), 1627 and 1613 (C O), 1373 (C–S), 1250 (C–O). 1H NMR (400.2 MHz, CDCl3):
δH 7.27 (2H, t, 3JHH = 7.6 Hz, 2CH, Ph), 7.40 (1H, t, 3JHH = 7.2 Hz, CH, Ph), 7.56 (2H, t,
3JHH = 7.6 Hz, 2CH, Ph), 7.67 (3H, dd, 3JHH = 8.0 Hz, 4JHH = 1.4 Hz, 3CH, Ph), 7.82 (1H,
d, 3JHH = 7.6 Hz, CH, quinoline), 7.90 (2H, m, 2CH, quinoline), 7.96(2H, d, 3JHH = 7.6 Hz,
3
3
2CH, Ph), 8.0 (1H, d, JHH = 7.2 Hz, CH, quinoline), 8.41 (1H, d, JHH = 7.6 Hz, CH,
quinoline), 9.79 (1H, d, 3JHH = 7.6 Hz, CH, quinoline). 13C NMR (100.6 MHz, CDCl3): δC
120.2 (CH), 125.0 (C), 125.6 (CH), 127.1 (CH), 127.7 (2CH), 127.8 (CH), 128.1 (2CH),
128.4 (C), 128.5 (C), 129.1 (2CH), 129.7 (2CH), 129.8 (C), 130.4 (CH), 131.2 (CH),
131.7 (CH), 132.2 (CH), 134.3 (C), 136.6 (C), 140.3 (C), 173.6 and 187.4 (C O). MS
(m/z,%): 408.1 (M.+, 35), 379.1 (15), 287.0 (40), 129.0 (25), 105 (100), 77 (12). Anal.
Calcd. for C25H16N2O2S (408.47): C, 73.51; H, 3.95; N, 6.86. Found: C, 73.34; H, 3.61; N,
6.72%.

SYNTHESIS OF 1,4-DIIONIC ORGANOSULFURS, CORRESPONDING MESOIONIC COMPOUNDS 271
N-(3-Benzoylthiazolo[3,2-a]pyridinium-2-yl)benzimidate (4c)
Yellow crystal, 0.28 g, yield 78%, mp 258–260◦C, IR (KBr) (νmax, cm−1): 3035
(CAr-H), 1589 (C O), 1321 (C–S), 1286 (C–O). 1H NMR (400.2 MHz, CDCl3): δH 7.26
(2H, m, 2CH, Ph), 7.40 (1H, t, 3JHH = 7.2 Hz, 1CH, Ph), 7.53 (2H, t, 3JHH = 7.6 Hz, 2CH,
3
3
Ph), 7.61 (4H, m, 4CH, Ph), 7.80 (1H, t, JHH = 7.6 Hz, CH, Ph), 7.87 (2H, d, JHH
7.8 Hz, 2CH, pyridine), 8.05 (1H, d, 3JHH = 8.0 Hz,, CH, pyridine), 10.26 (1H, d, 3JHH
=
=
6.8 Hz, CH, pyridine). 13C NMR (100.6 MHz, CDCl3): δC 120.1 (C), 121.1 (CH), 121.9
(CH), 127.7 (2CH), 128.1 (2CH), 129.2 (3CH), 129.3 (3CH), 131.3(C), 131.4 (2C), 132.6
(C), 147.6 (CH), 155.0 (CH), 177.0 and 186.0 (C O). MS (m/z,%): 358.08 (53), 357.1
(100), 329.1 (23), 253.0 (15), 237.0 (42), 105 (62), 77 (5). Anal. Calcd. for C21H14N2O2S
(358.41): C, 70.37; H, 3.94; N, 7.82. Found: C, 70.07; H, 3.71; N, 7.53%.
CRYSTAL STRUCTURE ANALYSIS
The X-ray diffraction measurement was made on a Bruker APEX II,20 single crystal
diffractometer equipped with an area detector using a graphite monochromated Mo- Kα
radiation (λ = 0.71073 Å). An orange cubic crystal was mounted on a glass fiber and used for
Table 2 Crystal data and structure refinement for compound 4a
Formula
C25 H16 N2 O2 S
408.46
293(2)
0.71073
Monoclinic
P21/n
0.1 × 0.1 × 0.1
a = 9.7901(10)Å
b = 18.6652(19)Å
c = 10.8800(11)Å
β = 101.603(2)◦
1947.5(3)Å3
4
1.393
2.18◦–30.56◦
848
Formula weight
Temperature (K)
Wavelength (Å)
Crystal system
Space group
Crystal size/mm3
Unit cell dimensions
Volume
Z
Density(calculated) g cm−3
Theta ranges for data collection
F (000)
Absorption coefficient
Index ranges
0.192 mm−1
−13 ≤ h ≤ 14
−26 ≤ k ≤ 26
−15 ≤ l ≤ 15
31202
Data collected
Unique data (Rint)
5959 (0.0274)
4469
Observed reflections
Parameters/restraints
Final R1, wR2a (Obs. data)
Final R1, wR2a (all data)
Goodness of fit on F2 (S)
Largest diff peak and hole/e.Å−3
Completeness to θ
271/0
0.0402, 0.1109
0.0563, 0.1216
1.046
0.323, −0.181
99.9
CCDC
914063
aR1 = ꢀꢁFo|-|Fcꢁ/ꢀ|Fo|, wR2 = [ꢀ[w(Fo2-Fc2)2]/ꢀ[w(Fo2)2]].

272
F. SHAHREKIPOUR ET AL.
data collection. Cell constants and an orientation matrix for data collection were obtained by
least-squares refinement of diffraction data from 999 reflections. The structure was solved
by direct methods and refined by full-matrix least-squares procedures (based on Fo ),21 first
2
with isotropic thermal parameters and then with anisotropic thermal parameters in the last
cycles of refinement for all the nonhydrogen atoms. The hydrogen atoms were introduced
into the geometrically calculated positions and refined riding on the corresponding carbon
atoms. The CIF file is deposited at The Cambridge Crystallographic Data Centre. CCDC
914063 contains the supplementary crystallographic data for this paper. These data can
be obtained free of charge from The Cambridge Crystallographic Data Centre via www.
ccdc.cam.ac.uk/data request/cif. A summary of the crystal data, experimental details, and
refinement results is given in Table 2.
REFERENCES
1. Kawase, M.; Sakagami, H.; Motohashi, N. Top. Heterocycl. Chem. 2009, 16, 135-152.
2. Panwar, H.; Singh, S.; Chaudhary, N. Indo. J. Chem. 2011, 11, 201-206.
3. Oliveira, C. S.; Lira, B. F.; Falcao-Silva, V. S.; Siqueira-Junior, J. P.; Barbosa-Filho, J. M.;
Athayde-Filho, P. F. Molecules 2012, 17, 5095-5107.
4. Oliveira, C. S.; Falcao-Silva, V. S.; Siqueira-Junior, J. P.; Harding, D. P.; Lira, B. F.; Lorenzo, J.
G. F.; Barbosa-Filho, J. M.; Athayde-Filho, P. F. Molecules 2011, 16, 2023-2031.
5. Satyanarayana, K.; Rao, M. N. A. J. Pharm. Sci. 1995, 84, 263-266.
6. Baker, W.; Ollis, W. D.; Poole, V. D. J. Chem. Soc. 1949, 307–314; ibid 1950, 1542-1551.
7. (a) Bhosale, S. K.; Deshpande, S. R.; Wagh, R. D. J. Chem. Pharm. Res. 2012, 4, 1185-1199.
(b) Chandrasekhar, R.; Gopalan, B.; Nanjan, M. J. Int. J. Chem. Tech. Res. 2011, 3, 1125-1128.
(c) Jogul, J. J.; Badami, B. V. J. Serb. Chem. Soc. 2006, 71, 851-860. (d) Sulojeva, E.; Yure,
M.; Gudrinicce, E. Chem. Heterocycl. Compd. 2000, 36, 885-898. (e) Osterhout, M. H.; Nadler,
W. R.; Padwa, A. Synthesis 1994, 123-140.
8. (a) Avalos, M.; Babiano, R.; Cintas, P.; Diaz, J.; Jimenez, J. L.; Lopez, I.; Palacios, J. C. Eur. J.
Org. Chem. 2004, 2805-2809. (b) Reis, C. M.; Echevarria-Lima, J.; Miranda, A. F.; Echevarria,
A. J. Braz. Chem. Soc. 2011, 22, 1505-1510. (c) Asundaria, S. T.; Patel, K. C.; Mehta, K. M.
Phosphorus, Sulfur Silicon Relat. Elem. 2011, 186, 1554-1562.
9. (a) Lyra, B. F.; Morais, S. A.; Rocha, G. B.; Miller, J.; Moura, G. L. C.; Simas, A. M.; Peppe,
C.; Athayde-Filho, P. F. J. Braz. Chem. Soc. 2010, 21, 934-940. (b) Rakov, N.; Arau´jo, C. B.;
Rocha, G. B.; Simas, A. M.; Athayde-Filho, P. A. F.; Miller, J. Chem. Phys. Lett. 2000, 332,
13-18. (c) De Oliveira, M. B.; Miller, J.; Pereira, A. B.; Galembeck, S. E.; De Moura, G. L. C.;
Simas, A. M. Phosphorus, Sulfur Silicon Relat. Elem. 1996, 108, 75-84.
10. (a) Araki, S.; Hattori, H.; Yamamura, H.; Kawai, M. J. Heterocycl. Chem. 2000, 37, 1129-1144.
(b) Jazwinski, J.; Kamienski, B.; Staszewska-Krajewska, O.; Webb, G. A. J. Mol. Struct. 2003,
646, 1-9. (c) Wasfy, A. A. F. Phosphorus, Sulfur Silicon Relat. Elem. 2003, 178, 1901-1910.
11. (a) Fedotov, K. V.; Shumeiko, T. P.; Romanov, N. N.; Tolmachev, A. I.; Ilchenko, A. Ya. Chem.
Heterocycl. Compd. 2011, 47, 622-630. (b) Kolos, N. N.; Orlov, V. D.; Paponov, B. V.; Shishkin,
O. V. Chem. Heterocycl. Compd. 2001, 37, 338-345. (c) Lo, Chok W.; Chan, W. L.; Szeto, Y.
S.; Yip, C. W. Heterocycles 1999, 51, 1433-1436.
12. (a) Huisgen, R.; Funke, E.; Schaefer, F. C.; Gotthardt, H.; Brunn, E. Tetrahedron Lett. 1967, 8,
2401809–240814. (b) Huisgen, R.; Grashey, R.; Krishke, R. ibid 1962, 387-391. (c) Huisgen,
R.; Gotthardt, H.; Grashey, R.; Chem. Ber. 1968, 101, 536-551.
13. Mironov, M. A.; Maltsev, S. S.; Mokrushin, V. S.; Bakulev, V. A. Mol. Divers. 2005, 9, 221-227.
14. (a) Rybakov, V. B.; Bush, A. A.; Troyanov, S. I.; Babaev, E. V.; Kemnitz, E. Acta. Cryst. 2006,
E62, 1673-1675. (b) Babaev, E. V.; Rybakov, V. B.; Orlova, I. A.; Bush, A. A.; Maerle, K. V.;

SYNTHESIS OF 1,4-DIIONIC ORGANOSULFURS, CORRESPONDING MESOIONIC COMPOUNDS 273
Nasonov, A. F. Russ. Chem. Bull. Int. Ed. 2004, 53, 176-180. (c) Babaev, E. V.; J. Heterocyclic.
Chem. 2000, 37, 519-526.
15. Hopkin, M. D.; Baxendale, I. R.; Ley, S. V. Synthesis 2008, 11, 1688-1702.
16. (a) Dyadyusha, G. G.; Romanov, N. N.; Kachkovskii, A. D.; Tolmachev, A. I. Chem. Heterocycl.
Comp. 1980, 16, 1221-1226. (b) Ottersen, T.; Cheristophersen, C.; Treppendahl, S. Acta. Chem.
Scand. 1975, 29, 45-50. (c) Babaev, E. V.; Bush, A. A.; Orlova, I. A.; Rybakov, V. B.; Iwataki,
I. Russ. Chem. Bull. Int. Ed. 2005, 54, 231-237.
17. (a) Baldwin, J. E.; McDaniel, M. C.; Newton, M.; Paul, I. C. Tetrahedron Lett. 1966, 7, 4239-
4241. (b) Kianmehr, E.; Faramarzi, R.; Estiri, H. Heterocycles 2009, 78, 415-423.
18. (a) Mukerjee, A. K.; Ashare, R. Chem. Rev. 1991, 91, 1. (b) Plut´ın, A. M.; Sua´rez, M.; Ochoa,
E.; Machado, T.; Mocelo, R.; Concello´n, J. M.; Rodr´ıguez-Solla, H. Tetrahedron 2005, 61,
5812-5817.
19. (a) Bunting, J. W.; Meathrel, W. G. Can. J. Chem. 1974, 52, 962-974. (b) Tasdelen, M. A.;
Karagoz, B.; Bicak, N.; Yagci, Y. Polym. Bull. 2008, 59, 759.
20. MART Software Users Guide, Version 5.1; Bruker Analytical X-ray Systems: Madison, WI, 1999.
21. SAINT Software Users Guide, Version 6.0; Bruker Analytical X-ray Systems: Madison, WI,
1999; G. M. Sheldrick. SADABS; Bruker Analytical X-ray Systems, Madison, WI, 1999; G.
M. Sheldrick, SHELXL-97, Program for crystal structure refinement; University of Go¨ttingen:
Germany, 1997.