Rhodanine in fused-heterocycles syntheses

Article abstract of DOI:10.1080/10426500600919181

The reaction of 3-aminothiazolidine-2-thione-4-one (3-aminorhodanine, 1) with some π-deficient compounds afforded three types of products: bicyclic noncondensed derivatives such as bis(3-aminothiazole-2-thione-4-one), the condensation product 2-(3-amino-2-thioxothiazolo)-1,3-indanedione, as well as the fused heterocyclic compounds thioxothiazolo[3,4-c]oxadiazine, furo[2,3-b]thiazole, thiazolo[3,4-c]benzoxadiazine, and naphthoquinothiazolo[3, 4-c]oxadiazine. Copyright Taylor & Francis Group, LLC.

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Rhodanine in Fused-
Heterocycles Syntheses
Aboul-Fetouh E. Mourad a , Alaa A. Hassan a , Ashraf
A. Aly a , Nasr K. Mohamed a & Bahaa A. Ali a
a Chemistry Department , El-Minia University , El-
Minia, A. R., Egypt
Published online: 18 Feb 2007.
To cite this article: Aboul-Fetouh E. Mourad , Alaa A. Hassan , Ashraf A. Aly , Nasr
K. Mohamed & Bahaa A. Ali (2007) Rhodanine in Fused-Heterocycles Syntheses,
Phosphorus, Sulfur, and Silicon and the Related Elements, 182:2, 321-331, DOI:
10.1080/10426500600919181
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Phosphorus, Sulfur, and Silicon, 182:321–331, 2007
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500600919181
Rhodanine in Fused-Heterocycles Syntheses
Aboul-Fetouh E. Mourad
Alaa A. Hassan
Ashraf A. Aly
Nasr K. Mohamed
Bahaa A. Ali
Chemistry Department, El-Minia University, El-Minia, A. R. Egypt
The reaction of 3-aminothiazolidine-2-thione-4-one (3-aminorhodanine, 1) with
some π-deficient compounds afforded three types of products: bicyclic noncon-
densed derivatives such as bis(3-aminothiazole-2-thione-4-one), the condensation
product 2-(3-amino-2-thioxothiazolo)-1,3-indanedione, as well as the fused hetero-
cyclic compounds thioxothiazolo[3,4-c]oxadiazine, furo[2,3-b]thiazole, thiazolo[3,4-
c]benzoxadiazine, and naphthoquinothiazolo[3,4-c]oxadiazine.
Keywords 3-Aminorhodanine; π-deficients; oxadiazine and thiazole derivatives
INTRODUCTION
Considerable attention has been drawn to the condensation reaction be-
tween 3-aminothiazolidine-2-thione-4-one (3-aminorhodanine, 1) and
both aldehydes and ketones to give 3-alkylidene and/or arylidene
rhodanines.1−4 The reaction could be regioselectively controlled to in-
volve either the 3-amino or 5-methylene groups in condensation.1,3 The
main target of this synthesis is the investigation of biological activity of
the condensation products formed.5 On the other hand, bicyclic noncon-
densed derivatives of rhodanine containing amino acid groups6 or two
thiazole moieties7 have been reported. Recently it has been reported
that compounds containing two thiazole moieties linked to each other
either directly or through different bridges display biological activities,
especially antifungal, antimicrobial, antiviral, sedative, and analgesic
activity.4,5,7−10 In light of the aforementioned findings and pursuing
our research in the field of the synthesis of heterocyclic as well as
Received March 18, 2006; accepted July 8, 2006.
Dedicated to Professor Henning Hopf on occasion of his 65th birthday.
Address correspondence to Ashraf A. Aly, El-Minia University, Chemistry Depart-
ment, Faculty of Science, El-Minia, 61519 A. R. Egypt. E-mail: ashraf160@yahoo.com
321

322
A.-F. E. Mourad et al.
O
O
NH2
S
NC
NC
CN
CN
CN
CN
N
S
(TCNE, 2)
O
1
(CNIND, 3)
O
O
Cl
Cl
NC
X
X
PhOC
NC
O
COPh
(DBE, 4)
O
(DDQ, 5)
X = Cl, (DCHNQ, 6)
X = CN, (DCNQ, 7)
SCHEME 1
fused heterocyclic compounds via reaction of π-defficient compounds
with electron-donor compounds,11−23 we investigated the reactions of
3-aminorhodanine with some π-deficient compounds (Scheme 1).
RESULTS AND DISCUSSION
Synthesis and Spectroscopic Characterization
3-Aminorhodanine (1) reacted with 1,1,2,2-ethenetetracarbonitrile
(TCNE, 2) in acetonitrile at r.t. Chromatographic separation of the
reaction mixture gave numerous colored zones, from which products 8
and 10 could be isolated (Scheme 2). Two possible structures were con-
sidered for the dimeric product (structures 8 and 9 in Scheme 2). Struc-
tural assignment of 8 was based on spectroscopic data and combustion
analysis. The IR spectrum showed absorption bands at υ = 3300–3200
1
(NH2), 1700, and 1690 cm−1 (CO). The H NMR spectrum displayed
only one singlet at δ5.75 ppm indicating the presence of NH2 and ab-
sence of the thiazole-CH2 group. Furthermore, the 13C NMR spectrum
of 8 showed two signals at δ = 167.0 and 199.8 charactersitic of the C O
and C S carbon atoms, respectively, in addition to the signal for C-5 of
the thiazole ring at δ = 138.1 ppm. According to semi-empirical calcula-
tions at the MM2 level of theory24 for compound 8, its trans form (ꢀE =
235.74 kcal/mol) was energetically more favorable compared with its
cis form (ꢀE = 479.39 kcal/mol).
Compound 10 was another product isolated from the reaction of 1
1
with 2 in a low yield. The simplicity of the H NMR spectrum by the
appearance of only one singlet at δ = 7.3 ppm, corresponding to an
oxadiazine-NH proton, left no doubt about the symmetrical structure
of 10. This structure was also supported by correct elemental analysis

Rhodanine in Fused-Heterocycles Syntheses
323
O
H2N
N
S
S
S
S
N
O
NH2
O
8 (61%)
S
S
N
O
N
1 + TCNE
N
N
S
S
9
S
NC
S
H
O
N
N
NC
CN
N
N
O
H
S
CN
S
10 (28%)
SCHEME 2
and by the mass spectrum, which exhibited a molecular ion peak at
m/z 442 (100%). The IR spectrum showed a characteristic absorption
band at υ = 3388 cm−1 (oxadiazine-NH) and another at 2210 cm−1
,
confirming the presence of cyano groups. Moreover, the 13C NMR signals
of compound 10 were assigned, and the appearance of only seven carbon
signals indicated the symmetrical feature of the proposed structure.
These signals appeared at δ = 117.2, 117.4 (CN), 194.8 (C S), 148.9
(thiazole-C-4), 115.0, 118.1 (oxadiazine-C-5 and -C-6), and δ = 91.2 due
to C-5 of the thiazole ring. Semi-empirical calculations for compound
10 using the MM2 level of theory indicated a larger stability of its trans
form (ꢀE = 237.41 kcal/mol) compared with its cis form (ꢀE = 807.58
kcal/mol).
On the other hand, 2-dicyanomethyleneindane-1,3-dione (CNIND,
3) interacted with 1 to give the condensation product 11 via a nu-
cleophilic attack of the rhodanine methylene function on the di-
cyanomethylene carbon atom of 3, followed by elimination of a molecule
of malononitrile (Scheme 3). The IR spectrum of 11 indicated the pres-
ence of carbonyl and amino groups and excluded any cyano groups. The
1H NMR spectrum showed a broad singlet for NH2 at δ = 5.7 ppm in ad-
dition to signals of aromatic protons. The 13C NMR spectrum revealed
resonances at δ = 186.4 (C O of indanedione), 167.4 (C O of thiazole),
and 199.8 (C S), as well as signals for aromatic carbon atoms. The

324
A.-F. E. Mourad et al.
O
O
H2N
S
NH2
S
O
DBE, 4
CNIND, 3
N
N
1
- H2C(CN)2
(i) - PhCHO
(ii) - H2
S
S
COPh
12 (67%)
O
11
SCHEME 3
structure of compound 11 was also assigned on the basis of elemental
analysis, supporting the sum formula C12H6N2S2O3, and was confirmed
also by the mass spectrum, which gave a correct molecular ion at m/z =
290 (92%).
As an example for another π-deficient compound, we investigated
of the reaction of 1 with E-1,2-dibenzoylethene (DBE, 4). Equimolar
amounts of 1 and 4 were refluxed in acetic acid and afforded the prod-
uct 12 in 67% yield (Scheme 3). The formation of 12 may be explained in
terms of the nucleophilic attack of the rhodanine methylene group to the
-C=C- double bond in 4 followed by the elimination of a molecule of ben-
zaldehyde and dehydrogenation. The structural proof of 12 was based
1
on spectroscopic and analytical data. The H NMR spectrum clearly
indicated the absence of rhodanine-CH2 protons. It showed a broad sin-
glet at δ = 5.75 ppm due to the exocyclic NH2 group as well as signals for
the furane ring proton and aromatic protons. The IR spectrum indicated
the presence of an amino group (υ = 3338 cm−1) and a carbonyl group
(υ = 1680 cm−1). Furthermore, the 13C NMR spectrum gave strong ev-
idence for the formation of compound 12, and showed signals for C O
at δ = 181.6; for C S at δ = 194.5, and for carbon atoms of the furane
ring at δ = 153.4, 143.6, 132.3, and 117.9.
Particularly interesting is the chemical behavior of 1 toward benzo-
and naphthoquinones (Scheme 4). An addition of 2,3-dichloro-5,6-
dicyano-1,4-benzoquinone (5) to 1 results in the formation of the dimeric
product 8 in addition to products 13 and 14. The molecular formulas
of the products are evidenced by their elemental analyses as well as
by mass spectra. The structure of 13 was confirmed on the basis of its
spectroscopic properties. The IR spectrum of 13 indicated the presence
of bands characteristic for the OH, NH, and CN groups.
The 1H-NMR spectrum clearly revealed the absence of any sig-
nals due to rhodanine-CH2 or exocyclic NH2 groups. It confirmed the
presence of a CH moiety in the thiazole ring (δ = 7.66) as well as of
oxadiazine-NH at δ = 7.24 and exocyclic NH and OH protons. More-
over, a singlet appeared at δ = 4.50, related to thiophene-H-3. The
13C NMR spectrum of compound 13 showed signals at δ = 79.3, 85.6
(thiazole-CH-5), 112.5 (Ar-C-Cl), 114.8 (CN), 116.8 (Ar-C-CN), 138.0,

Rhodanine in Fused-Heterocycles Syntheses
325
8 (21%)
S
S
OH
O
H
Cl
(i) - HCl
(ii) - HCN
N N
DDQ
5
1
(iii - H O
)
OH
2
NC
NH
N
S
13 (36%)
CN
S
CN
HO
Cl
CN
OH
O
(i) - 2HCl
(ii) - H2O
CN
OH
S
N
N
H
S
Cl
14 (28%)
SCHEME 4
139.8 (Ar-C-NH), 152.8, 154.5, 156.6, and 160.9 (Ar-C-O, thiazole-C-O
and oxadiazine-C-O) next signals for the C=S groups at δ = 192.8 and
194.6. On the other hand, the assignment of signals in the 13C NMR
spectrum of 14 supported the structure shown in Scheme 4, with reso-
nances at δ = 79.8 (thiazol-CH-5), 111.8, 112.4 (Ar-C-Cl), 113.2, 113.8,
114.0, 114.8 (CN), 115.0, 115.2, 115.6, 115.8 (Ar-C-CN), 124.4 (thiazole-
C-5), 137.7 (Ar-C-NH), 150.0, 154.2, 156.9, 158.0, and 161.6 (C-O) and
at δ = 194.7 for the C S group. Several alternative structures for 13 and
14 were excluded based on elemental compositions and spectroscopic
properties.
The addition of
a
pyridine solution of 2,3-dichloro-1,4-
naphthoquinone (6) to a solution of 1 in pyridine afforded the naph-
thoquinothiazolooxadiazine derivative 15, rather than naphthoquino-
furothiazole 16 (Scheme 5). The 1H NMR spectrum of 15 indicated
the presence of oxadiazine-NH and thiazole-CH protons in addition to
1
aromatic protons. No H NMR resonance for an exocyclic NH2 group
was observed. The 13C NMR spectrum displayed further evidence for
the proposed structure and revealed resonances for C O (δ = 186.7),
C S (δ =194.6), thiazole-CH (δ = 73.9), and oxadiazine-C-3 (δ = 154.9),
as well as signals for aromatic carbon atoms.
The reaction of 2,3-dicyano-1,4-naphthoquinone (DCNQ, 7) as an
electron acceptor with 1 as an electron donor yielded naphthoquinone
derivative 17 as the only product, rather than compound 18 (Scheme
1
5). H and 13C NMR spectra of 17 confirmed the presence of the CH

326
A.-F. E. Mourad et al.
S
S
O
O
N
OH
NC
S
H
N
HN
N
S
O
O
O
15 (76%)
DCNQ, 7
DCHNQ, 6
O
1
17 (66%)
- 2 HCl
- HCN
O
O
NH2
S
CN
OH
N
S
NH2
O
16
N
O
S
18
S
SCHEME 5
function of the thiazole ring. At the same time, the 13C NMR spectrum
excluded the presence of a thiazolone carbonyl carbon atom, the signal
of which usually appears at δ = 167.00.3
In conclusion, the results described in this article demonstrate that
the reaction of 1 with π-deficient compounds used afforded three types
of products. These are bicyclic noncondensed derivatives, condensation
products, as well as interesting fused-heterocyclic compounds, which
were easily synthesized in one step and that cannot be easily prepared
by conventional synthetic methods. Furthermore, to the best of our
knowledge, there are no literature reports about rhodanine fused with
heterocycles.
EXPERIMENTAL
Apparatus and Chemical Methods
Melting points are uncorrected. Combustion analyses were carried out
at the microanalytical unit at Cairo University (Cairo, Egypt). IR spec-
tra were recorded on a Nicolet 320 FTIR and Shimadzu 408 spectropho-
tometers using potassium bromide pellets. 1H-NMR (400.13 MHz) and
13C-NMR (100.6 MHz): Bruker AM 400 spectrometer; chemical shifts
are given as δ (ppm) with TMS as an internal standard. Mass spectra
(70 eV, electron impact mode) were obtained on a Finnigan MAT 8430
instrument. Preparative Layer Chromatography (PLC) was used with
air-dried 1.0-mm thick layers of slurry-applied silica gel Merck PF254
(Merck, Darmsta¨dt, Germany) on 48-cm wide and 20-cm high glass
plates. Zones were detected by quenching indicator fluorescence upon
exposure to 254-nm UV light and eluting with acetone.

Rhodanine in Fused-Heterocycles Syntheses
327
Starting Materials
3-Aminothiazolidine-2-thione-4-one (3-aminorhodanine, 1) and
E-1,2-dibenzoylethene (DBE, 4) were purchased from Aldrich
(Mu¨nchen, Germany). 1,1,2,2-Ethenetetracarbonitrile (TCNE, 2,
Merck, Darmsta¨dt, Germany) was recrystallized from chlorobenzene
and sublimed. 2-dicyanomethyleneindane-1,3-dione (CNIND, 3) was
prepared according to the procedure described by Chatterjee.25 2,3-
dichloro-5,6-dicyano-1,4-benzoquinone (DDQ, 5, Aldrich, Mu¨nchen,
Germany) was recrystallized from benzene/chloroform (2:3). 2,3-
Dicyano-1,4-naphthoquinone (DCNQ, 7) was prepared from 2,3-
dichloro-1,4-naphthoquinone (DCHNQ, 6, Merck, Darmsta¨dt,
Germany) according to Budni and Jayadevappa.26
Reaction of 1,1,2,2-Ethenetetracarbonitrile (TCNE, 2) with 1
A solution of 1 (148 mg, 1 mmol) in dry acetonitrile (20 mL) was added
to a solution of 2 (256 mg, 2 mmol) in dry acetonitrile (15 mL), and
the reaction mixture was stirred for 48 h at r.t. The solvent was evapo-
rated in vacuo, and the obtained reddish-brown residue was dissolved
in acetone, chromatographed (PLC), and eluted with toluene/ethyl ac-
etate (2:1) to give only a reddish-brown zone containing compound 8.
The material confined to the start was rechromatographed using chlo-
roform/methanol (5:1) to give compound 10.
3,3’-Diamino-2,2’-dithioxo-[5,5’]bithiazolidinylidene-4,4‘-
dione (8)
Yield 178 mg (61%), reddish-brown crystals (ethanol), m.p. 270–272◦C.
IR (KBr): υ = 3270, 3200 (NH2), 1710–1690 (CO) cm−1
.
1H NMR
(DMSO-d6): δ = 5.75 (br s, NH2). 13C NMR (DMSO-d6): δ = 138.1
(thiazole-C-5), 167.0 (C O), 199.8 (C S). MS (70 eV), m/z (%): 292 [M+]
(100), 218 (15), 190 (72), 162 (24), 116 (25), 88 (63), 79 (32). C6H4N4S4O2
(292.39): Calcd. C, 24.65; H, 1.38; N, 19.16; S, 43.87; Found: C, 24.81;
H, 1.32; N, 19.22; S, 43.72.
3,3’-Dithioxo-4H,4’H-[1,1’]bis[7-oxa-2-thia-3a,4-diazaindenyl]-
5,5’,6,6’-tetracarbonitrile (10)
Yield 125 mg (28%), brown crystals (methanol); m.p. 283–285◦C. IR
(KBr): υ = 3388 (NH), 2210 (CN), 1618 (C C) cm−1. 1H NMR (DMSO-
d6): δ = 7.30 (br s, 2H, 2 oxadiazine-NH). 13C NMR (DMSO-d6): δ =
115.0 (oxadiazine-C-5), 117.2 (CN), 117.4 (CN), 118.1 (oxadiazine-C-6),
91.2 (thiazole-C-5), 148.9 (oxadiazine-C-3), 194.8 (C S). MS (70 eV),

328
A.-F. E. Mourad et al.
m/z (%): 442 [M+] (100), 410 (35), 394 (22), 362 (18), 221 (62), 205 (81),
162 (21), 77 (15). C14H2N8O2S4 (442.49): Calcd.: C, 38.00; H, 0.46; N,
25.32; S, 28.99. Found: C, 37.89; H, 0.43; N, 25.49; S, 29.08.
Reaction of 2-Dicyanomethyleneindane-1,3-dione
(CNIND, 3) with 1
To a stirred solution of 208 mg (1 mmol) of 3 in dry acetonitrile (20 mL),
compound 1 (148 mg, 1 mmol) in dry acetonitrile (20 mL) was added
dropwise at r. t. and the stirring was continued for 96 h when compound
11 had precipitated.
2-(3-Amino-4-oxo-2-thioxothiazolidin-5-ylidene)-1,3-
indanedione (11)
Yield 206 mg (71%), red crystals (methanol), m.p. 263–265◦C. IR (KBr):
υ = 3379–3251 (NH2), 1729, 1708, 1680 (CO), 1597 (Ar-C C) cm−1
.
1H NMR (DMSO-d6): δ = 5.70 (br s, NH2), 7.22–7.58 (m, 4H, Ar-
H). 13C NMR (DMSO-d6): δ = 128.7, 132.6, 137.7 (Ar-C), 140.4, 159.1
(indanedione-C-2 and thiazole-C-5), 167.4 (thiazolone-C O), 186.4 (C
O of indanedione), 199.8 (C S). MS (70 eV), m/z (%): 290 [M+] (88),
217 (25), 189 (100), 161 (11), 104 (32), 76 (31). C12H6N2O3S2 (290.32):
Calcd.: C, 49.65; H, 2.08; N, 9.65; S, 22.09. Found: C, 49.53; H, 2.14; N,
9.59; S, 22.17.
Reaction of E-1,2-Dibenzoylethene (DBE, 4) with 1
A solution of E-1,2-dibenzoylethene (DBE, 4) (236 mg, 1 mmol) in
glacial acetic acid (15 mL) was added to a solution of 1 (148 mg, 1 mmol)
in glacial acetic acid (10 mL). The reaction mixture was refluxed for
6 h when a brown precipitate of 6-amino-3-benzoyl-5-thioxofuro[2,3-
b]thiazole (12) was formed.
3-Amino-6-benzoyl-2,3-dihydrofuro[2,3-d ]thiazole-2-thione (12)
Yield 188 mg (68%), brown crystals (DMF/ethanol), m.p. 128–130◦C.
IR (KBr): υ = 3338 (NH2), 2924 (Aliph-CH), 1680 (CO), 1596 (Ar-C C)
cm−1. 1H NMR (DMSO-d6): δ = 5.75 (br s, 2H, NH2), 7.25–7.80 (m, 6H,
furane-CH and Ar-H). 13C NMR (DMSO-d6): δ = 117.9 (furane-CH),
126.9 (C-m), 128.2 (C-p), 128.8 (C-o), 132.3 (furane-C-3), 133.0 (C-i),
143.6 (furane-C-3a), 153.4 (furane-C-3b), 181.6 (C O), 194.5 (C S). MS
(70 eV), m/z (%): 276 [M+] (12), 248 (31), 232 (34), 171 (41), 105 (100), 84
(62), 56 (60). C12H8N2S2O2 (276.34): Calcd.: C, 52.16; H, 2.92; N, 10.14;
S, 23.21. Found: C, 52.24; H, 3.05; N, 10.21; S, 23.14.

Rhodanine in Fused-Heterocycles Syntheses
329
Reaction of 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone
(DDQ, 5) with 1
To a solution of 5 (227 mg, 1 mmol) in dry acetonitrile (10 mL) was
added a solution of 1 (148 mg, 1 mmol) in dry acetonitrile (20 mL), and
the reaction mixture was stirred for 48 h at r. t. The color of the reaction
mixture changed from dark green to reddish brown. The solvent was
removed in vacuo, and the residue was subjected to preparative plates
chromatography using toluene/ethyl acetate (2:1) to give only one zone
containing compound 8 (21%). The material confined to the start was
rechromatographed using toluene/ethyl acetate (1:1) as an eluent. The
fastest migrating zone contained compound 13, and the slowest migrat-
ing contained compound 14. Extraction of the zones with acetone and
recrystallization from the respective solvents (see the following section)
to afford the pure compounds.
5-Chloro-6-hydroxy-7-(4’-hydroxy-2’-thioxo-2’,3’-
dihydrothiophen-3’-ylamino)-3-thioxo-4H-9-oxa-2-thia-3a,
4-diaza-cyclopenta[b]naphthalene-8-carbonitrile (13)
Yield 160 mg (36%), reddish-brown crystals (DMF/ethanol), m.p. 210–
212◦C. IR (KBr): υ = 3456–3228 (OH, NH), 2924 (aliphatic-CH), 2210
(CN), 1636 (Ar-C C) cm−1
.
1H NMR (DMSO-d6): δ = 4.50 (s, 1H,
thiophene-H-3), 6.20 (br s, 1H, NH), 7.24 (br s, 1H, oxadiazine-NH),
7.34 (s, 1H, OH), 7.66 (s, 2H, thiazole-CH), 8.30 (s, 1H, OH). 13C NMR
(DMSO-d6): δ = 79.3, 85.6 (thiazoles-CH-5), 112.5 (Ar-C-Cl), 114.8 (CN),
116.8 (Ar-C-CN), 138.0, 139.8 (Ar-C-NH), 152.8, 154.5, 156.6, 160.9 (Ar-
C-O, thiazole-C-O and oxadiazine-C-O), 192.8, 194.6 (C S). MS (70 eV),
m/z (%): 446 [M+2] (52), 445 [M+1] (20), 444 [M+] (100), 338 (62), 182
(100), 149 (39), 77 (21). C13H7ClN5O3S4 (444.94): Calcd.: C, 35.09; H,
1.59; N, 15.74; S, 28.83. Found: C, 34.89; H, 1.59; N, 15.72; S, 28.87.
5-Chloro-1-(2’-chloro-4’,5’-dicyano-3’,6’-dihydroxyphenyl)-
6-hydroxy-3-thioxo-4H-9-oxa-2-thia-3a,4-
diazacyclopenta[b]naphthalene-7,8-dicarbonitrile (14)
Yield 145 mg (28%), brown crystals (DMF/ethanol), m.p. 283–284◦C. IR
1
(KBr): υ = 3355–3175 (OH, NH), 2208 (CN), 1630 (Ar-C C) cm−1. H
NMR (DMSO-d6): δ = 7.22 (br s, 1H, oxadiazine-NH). 13C NMR (DMSO-
d6): δ = 79.8 (thiazole-CH-5), 111.8, 112.4 (Ar-C-Cl), 113.2, 113.8, 114.0,
114.8 (CN), 115.0, 115.2, 115.6, 115.8 (Ar-C-CN), 124.4 (thiazole-C-5),
137.7 (Ar-C-NH), 150.0, 154.2, 156.9, 158.0, 161.6 (C-O), 194.7 (C S).
MS (70 eV), m/z (%): 517 [M+3] (20), 516 [M+2] (74), 515 [M+] (100),

330
A.-F. E. Mourad et al.
513 (39), 511 (24), 475 (12), 346 (17), 292 (11), 256 (8), 105 (27), 79 (90),
60 (100). C19H4Cl2N6O4S2 (515.32): Calcd.: C, 44.29; H, 0.78; Cl, 13.76;
N, 16.31; S, 12.45. Found: C, 44.17; H, 0.75; Cl, 13.83; N, 16.24; S, 12.56.
Reaction of 2,3-Dichloro-1,4-naphthoquinone (DCHNQ, 6)
with 1
To a stirred solution of 227 mg (1 mmol) of 6 in dry pyridine (10 mL),
compound 1 (148 mg, 1 mmol) in dry pyridine (10 mL) was added at r. t.
The reaction mixture was stirred at r. t. for 72 h until the reaction was
completed and blue crystals of 15 had precipitated.
3-Thioxo-4H-11-oxa-2-thia-3a,4-
diazacyclopenta[b]anthracene-5,10-dione (15)
Yield 229 mg (76%), blue crystals (DMF), m.p. 186–188◦C. IR (KBr): υ =
1
3310 (NH), 1680 (CO), 1620 (Ar-C C) cm−1. H NMR (DMSO-d6): δ =
7.28 (br s, 1H, oxadiazine-NH), 7.54–8.28 (m, 5H, Ar-H and thiazole-
CH). 13C NMR (DMSO-d6): δ = 73.9 (thiazole-C-5), 128.5, 132.8, 133.1,
137.5, 139.8 (Ar-C), 154.9 (thiazole-C-4), 186.7 (C O), 194.6 (C S).
MS (70 eV), m/z (%): 302 [M+] (16), 274 (100), 246 (90), 190 (52), 76
(55). C13H6N2O3S2 (302.33): Calcd.: C, 51.65; H, 2.00; N, 9.27; S, 21.21.
Found: C, 51.72; H, 1.93; N, 9.33; S, 21.33.
Reaction of 2,3-Dicyano-1,4-naphthoquinone (7) with 1
To a stirred solution of 208 mg (1 mmol) of 7 in dry acetonitirile (15 mL),
compound 1 (148 mg, 1 mmol) in dry acetonitrile (20 mL) was added
dropwise at r. t. and stirring was continued for 48 h. The color of the
reaction mixture changed from dark green to bluish-violet. The solvent
was removed in vacuo, and the residue was subjected to PLC using
toluene/ethyl acetate (3:1) to give only 1 zone containing compound 17.
1,4-Dioxo-3-(2-thioxothiazol-3-ylamino)-1,4-
dihydronaphthalene-2-carbonitrile (17)
Yield 217 mg (66%), violet-blue crystals (methanol), m.p. 295–297◦C
IR (KBr): υ = 3422–3216 (OH, NH), 2220 (CN), 1685–1671 (CO), 1617
1
(Ar-C C) cm−1. H NMR (DMSO-d6): δ = 6.60 (br s, 1H, NH), 7.50–
8.30 (m, 5H, Ar-H and thiazole-CH). 13C NMR (DMSO-d6): δ = 73.9
(thiazole-C-2), 97.2 (C-CN), 117.2 (CN), 128.5, 132.8 and 137.5 (Ar-C),
156.6, 177.5 (C-OH, C-NH), 187.0 (C O), 199.8 (C S) MS (70 eV), m/z
(%): 329 [M+] (36), 257 (17), 240 (16), 209 (12), 166 (10), 127 (21), 66 (28),

Rhodanine in Fused-Heterocycles Syntheses
331
28 (100). C14H7N3O3S2 (329.35): Calcd. C, 51.05; H, 2.14; N, 12.76; S,
19.47. Found: C, 51.14; H, 2.18; N, 12.72; S, 19.39.
REFERENCES
[1] W. Hanefeld and M. A. Jalili, Arch. Pharm. (Weinheim), 320, 329 (1987).
[2] W. Hanefeld, M. Schlitzer, S. Wocadlo, and W. Massa, Liebigs Ann. Chem., 337,
(1992).
[3] W. Hanefeld, V. Helfrich, M. A. Jalili, and M. Schlitzer, Arch. Pharm. (Weinheim),
326, 359 (1993).
[4] W. Hanefeld, M. Schlitzer, N. Debski, and H. Euler, J. Heterocycl. Chem., 33, 1143
(1996).
[5] V. Y. Gorishnii, O. V. Vladzimirska, P. N. Steblijuk, I. L. Demchuk, K. M. Ali,
N. V. Silenko, and A. Bondarenko, Zh. Farm. (Kiev), 2, 66 (1995); C.A., 124, 260906a
(1996).
[6] H. T. Y. Fahmy, 7th Ibn Sina International Conference on Pure and Applied Hetero-
cyclic Chemistry, Cairo, Egypt, vol. 112, p. 25 (2000).
[7] W. Hanefeld and M. Schlitzer, J. Heterocyclic Chem., 31, 391 (1994).
[8] A. M. A. Makhlouf and A. S. Mohamed, Pharmazie, 51, 430 (1996).
[9] V. Ya. Gorishnii, Zh. Farm. (Kiev), 5, 40 (1990); C.A., 114, 101812u (1991).
[10] K. Tanaka, K. Matsuo, A. Nakanishi, M. Jo, H. Shiota, M. Yamaguchi, S. Yoshino,
and K. Kawaguchi, Chem. Pharm. Bull., 38, 3291 (1984).
[11] A. A. Hassan, N. K. Mohamed, Y. R. Ibrahim, K. U. Sadek, and A. E. Mourad, Bull.
Chem. Soc. Jpn., 66, 2612 (1993).
[12] A. A. Hassan, N. K. Mohamed, E. H. El-Tamany, A. A. Ali, and A. E. Mourad,
Monatsh. Chem., 126, 623 (1995).
[13] A. A. Aly, A. A. Hassan, N. K. Mohamed, and A. E. Mourad, Phosphorus, Sulfur, and
Silicon, 116, 261 (1996).
[14] A. A. Hassan, N. K. Mohamed, B. A. Ali, and A. E. Mourad, Tetrahedron, 50, 9997
(1994).
[15] N. K. Mohamed, A. A. Aly, A. A. Hassan, A. E. Mourad, and H. Hopf, J. Prakt. Chem.,
338, 745 (1996).
[16] A. A. Hassan, N. K. Mohamed, A. A. Aly, and A. E. Mourad, J. Chem. Res. (S), 208
(1996); Bull. Soc. Chim. Belg., 105, 159 (1996).
[17] A. A. Hassan, N. K. Mohamed, A. A. Aly, and A. E. Mourad, Monatsh. Chem., 128,
61 (1997).
[18] A. A. Aly, A. A. Hassan, N. K. Mohamed, and A. E. Mourad, Pharmazie, 52, 2821
(1997).
[19] A. A. Hassan, D. Do¨pp, and G. Henkel, J. Heterocycl.Chem., 35, 121 (1998).
[20] A. A. Aly, N. K. Mohamed, A. A. Hassan, and A. E. Mourad, Tetrahedron, 55, 1111
(1999).
[21] A. A. Aly, S. H. El-Tamany, and A. E. Mourad, Heterocycl. Commun., 3, 175 (1997).
[22] A. A. Aly and M. A.-M. Gomaa, Can. J. Chem., 83, 57 (2005).
[23] A. A. Hassan, N. K. Mohamed, A. A. Aly, and A. E. Mourad, Pharmazie, 52, 23
(1997).
[24] (a) N. L . Allinger, MM2 (91) Force Field Program, Indiana University; (b) Molec-
ular Mechanics PM3 Program 5 (ACD/3D), Advanced Chemical Development Inc.,
Toronto, Canada (1988).
[25] S. Chatterjee, J. Chem. Soc. B., 725 (1969).
[26] M. L. Budni and E. S. Jayadevappa, Spectrochim. Acta., 44A, 607 (1988).