Synthesis of bis-thiazolidin-4-ones from N,N,N″-(1,ω-alkanediyl)bis(N″-organylthiourea) derivatives

Article abstract of DOI:10.1515/znb-2014-0226

A new series of (2Z,2′E)-dimethyl 2,2′-[(2Z,2′Z)- 3,3′-(alkanediyl)bis(4-oxo-2-iminothiozolidin-3-yl- 5-ylidene)]acetates has been synthesized by the reaction of N,N″-(1,ω-alkanediyl)bis(N′-organylthiourea) derivatives with dimethyl acetylenedicarboxylate

Full text of DOI:10.1515/znb-2014-0226

Z. Naturforsch. 2015; 70(4)b: 243–248
Alaa A. Hassan*, Kamal M.A. El-Shaieb, Amal S. Abd El-Aal, Stefan Bräse and Martin Nieger
Synthesis of bis-thiazolidin-4-ones from
N,N,N″-(1,ω-alkanediyl)bis(N″-organylthiourea)
derivatives
Abstract: A new series of (2Z,2′E)-dimethyl 2,2′-[(2Z,2′Z)-
Conversely, N,N″-(1,ω-alkanediyl)bis(N′-organylthio-
3,3′-(alkanediyl)bis(4-oxo-2-iminothiozolidin-3-yl- urea) derivatives 1 constitute a core structure in various
5-ylidene)]acetates has been synthesized by the reaction synthetic heterocyclic compounds [30]. In recent years,
of N,N″-(1,ω-alkanediyl)bis(N′-organylthiourea) deriva- microwave assisted or conventional thermal intramo-
tives with dimethyl acetylenedicarboxylate. The structures lecular heterocyclization reactions of compound 1 have
were established by spectroscopic data, elemental analy- been reported [31]. Imidazolidine, diazepine, and thiadi-
ses, and single crystal X-ray crystallography. A rationale azepane derivatives were isolated upon treating ethene-
for the formation of the products is presented.
tetracarbonitrile with bithiourea derivatives 1 [32].
Recently, ithasbeenreportedthattheonepot, pseudo-
Keywords: bis-thiazolidin-4-ones; dimethyl acetylenedi- five-component reaction of an aliphatic diamine, iso-
carboxlate; N,N″-(1,ω-alkanediyl)bis(N′-organylthiourea) thiocyanatobenzene and dialkyl but-2-ynedioate at room
derivatives.
temperature in anhydrous CH2Cl2 gave bis[2(arylimino)-
1,3-thiazolidin-4-ones] [33].
The present investigation deals with the synthesis of
some new (2Z,2′E)-dimethyl 2,2′-[(2Z,2′Z)-3,3′-(alkanediyl-
bis(4-oxo-2-substituted imino)thiazolidin-3-yl-5-ylidene)]-
diacetates 3a–h in moderate yields from N,N″-(1-ω-
alkanediyl)-bis(N′-organylthiourea) derivatives 1a–h.
DOI 10.1515/znb-2014-0226
Received September 19, 2014; accepted November 28, 2014
1 Introduction
2 Results and discussion
Thiazolidinones are known to be privileged small ring
heterocycles because they exhibit different types of bio-
logical activities [1–6]. The 4-thiazolidinone ring system
comprises a large number of biologically active com-
pounds that have been evaluated for their anticonvul-
sant [7, 8], antidiarrheal [9], antiplatelet activating [10],
antimicrobial [3, 10, 11], anti-HIV [12–15], and anticancer
[16–18] activities. Several methods for the stereoselec-
tive synthesis of thiazolidin-4-ones are available in the
literature [19–29].
To obtain new bis(thiazolidin-4-ones) 3a–h, a mixture of
a doubled molar amount of dimethyl acetylenedicarbo-
xylate (DMAD, 2) with 1 mole of the respective bithiourea
derivatives 1a–h was heated for 4–12 h at reflux in abso-
lute ethanol. A yellow solid of 3a–h was obtained, which,
after spectroscopic characterization, was confirmed to be
the proposed compound (Scheme 1).
The synthesized compounds were characterized by
their IR, 1H NMR, 13C NMR, and mass spectral data, as well
as single crystal X-ray crystallography.
The IR spectrum of 3g as an example was char-
acterized by the presence of a new Cꢀ=ꢀO band at 1730
cm–1, which agrees with those found for other thiazolidin-
4-ones [34–36]. The ester carbonyl (Cꢀ=ꢀO) and conjugated
double bond (Cꢀ=ꢀC) absorption bands were observed at
1695 and 1620 cm–1, respectively. The N–H bands of bithi-
ourea derivatives 1a–h were not evident in the IR spectra
of 3a–h, whereas an absorption band at 1640 cm–1, attrib-
uted to the Cꢀ=ꢀN stretching vibration, was observed for 3g
as an example.
*Corresponding author: Alaa A. Hassan, Faculty of Science,
Chemistry Department, Minia University, 61519 El-Minia, A. R.
Egypt, Fax: +2-086-2363011, E-mail: alaahassan2001@mu.edu.eg,
alaahassan2001@yahoo.com
Kamal M.A. El-Shaieb and Amal S. Abd El-Aal: Faculty of Science,
Chemistry Department, Minia University, 61519 El-Minia, A. R. Egypt
Stefan Bräse: Institute of Organic Chemistry, Karlsruhe Institute of
Technology, Fritz-Haber-Weg 6, 76131 Karlsruhe, Germany
Martin Nieger: Laboratory of Inorganic Chemistry, Department of
Chemistry, University of Helsinki, PO Box 55 (A. I. Virtasen aukio 1),
00014 Helsinki, Finland
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ꢀA.A. Hassan et al.: Synthesis of bis-thiazolidin-4-ones
HS
N
N
n
NHPh
SH
R
CO2Me
MeO2C
NHPh
N
O
S
CO2Me
ethanol,
+
S
N
N
( )n
O
N
CO2Me
R
H
H
S
N
N
NHPh
n
3a−h
2
NHPh
S
1a−h
R
n
Yield of 3 (%)
66 3e
62 3f
R
n
Yield of 3 (%)
3a
3b
3c
3d
Et
2
Et
3
3
3
3
63
Allyl
Ph
2
2
Allyl
Ph
66
61
64
67
62
3g
3h
Benzyl 2
Benzyl
Scheme 1:ꢁSynthesis of bis(4-oxo-2-iminothiazolidine-5-ylidene)acetates.
1
The H NMR chemical shifts of compounds 3a–h sup-
In conclusion, an efficient cyclization protocol for
ported the proposed structure. In 3g, signals assigned to N,N″-(1,ω-alkanediyl)bis(N′-organylthiourea) derivatives
N-(CH2)3-N, were detected at δ ꢀ=ꢀ 2.35 and 4.00 ppm, whereas with dimethyl acetylenedicarboxylate to a new series of
singlet signals were observed at 3.75 and 6.88 ppm due bis(thiazolidin-4-ones) has been developed. In a different
to OCH3 and vinyl-CH, respectively, in addition to phenyl manner to the reported heterocyclization of the bithiou-
protons. The absence of resonances assigned to NH, N″H, reas [30, 31], the present reaction course has been found
HN′-phenyl protons of 1a–h supported the exact structure. to be independent on the length of the alkanediyl chain.
In the 13C NMR spectra of 3a–h, the prominent signals
corresponding to the carbons of the thiazolidin-4-one ring
in all compounds were observed. The 13C NMR spectrum of
3 Experimental section
3g showed five signals at δ ꢀ=ꢀ 166.28, 164.89, 150.82, 141.52,
and 116.16 ppm, due to Cꢀ=ꢀO (ester), Cꢀ=ꢀO (ring), thiazoli-
All melting points were determined using open capil-
dinone C-2, thiazolidinone C-5, and vinyl-CH respectively.
laries on a Gallenkamp melting point apparatus (Weiss-
According to elemental analyses and mass spectrom-
Gallenkamp, Loughborough, UK). The IR spectra were
etry, a net release of methanol (M.W. 32) had occurred.
recorded with a Shimadzu 408 (Shimadzu Corporation,
There are possibilities for formation of various isomers
Kyoto, Japan) instrument using potassium bromide. The
that would behave very similarly spectroscopically
1
400 MHz H NMR and 100 MHz 13C NMR were recorded
(Fig. 1). Similarly, all products observed are formed from
on a Bruker AM 400 spectrometer (Bruker BioSpin,
one of the four labile 1:1 adducts A–D (Fig. 1).
Karlsruhe, Germany) with tetramethylsilane as the
The molecular structure of 3g was established by a
single crystal X-ray analysis (Fig. 2). The thiazolidinone
R
R
R
CO2Me
ring and the adjacent benzene rings adopt a twisted geom-
etry and the angle between the least-squares planes of the
thiazolidine ring and the benzene ring are 97° (C1, C2, S3
C4, N5 and C42, C43, C44, C45, C46, C47) and 55° (N9, C10,
C11, S12, C13 and C132, C133, C134, C135, C136, C137), while
the thiazolidine ring and the acetate are coplanar. The X-ray
structure analysis confirms a cisoid geometry between the
vinylic CH bond and the thiazolidine carbonyl group.
The formation of the products 3a–h may be rational-
ized as an initial attack by SH group of 1a–h at the C≡C triple
bond of 2 to give the adduct C. Elimination of two molecules
of MeOH affords bis(thiazolidinones) 3a–h (Scheme 2).
HN
SS
NH
MeO2C
HN
N
N
S
R
( )n
N
N
CO2Me
( )n
O
MeO2C
S
HN
CO2Me
MeO2C
CO2Me
OMe
B
A
H
MeO2C
CO2Me
R
N
CO2Me
H
H
R
MeO2C
N
N
N
CO2Me
S
H
H
( )n
N
N
S
MeO2C
S
S
CO2Me
( )n
MeO2C
NR
NR
D
C
Fig. 1:ꢁStructures of putative intermediates A–D.
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A.A. Hassan et al.: Synthesis of bis-thiazolidin-4-onesꢀ
ꢀ245
to published procedures in literature: 1a [37], 1b [38], 1c
[39], 1d [30], 1e [40], 1f [31], 1g [41], and 1h [42]. DMAD (2)
was bought from Fluka.
3.2 Reaction of N,N″-(1,ω-alkanediyl)bis(N′-
organylthiourea) derivatives 1a–h with
DMAD(2)
Into a 100 mL round bottom flask containing (284 mg,
2 mmol) of 2 in 15 mL of absolute ethanol, a solution of
1 mmol of 1a–h in absolute ethanol (20 mL) was added
dropwise with stirring. The mixture was gently refluxed
with stirring for 4–12 h (4 h for 1b and 1d; 9 h for 1c; 10 h
for 1a and 1e; 12 h for 1f). The reactions were monitored
by TLC analyses. The solvent was concentrated and the
residue was subjected to preparative layer chromatogra-
phy (plc) using toluene-ethyl acetate (5:1) as the develop-
ing solvent to give one main zone and numerous other
ones.
Fig. 2:ꢁMolecular structure of 3g in the crystal with displacement
parameters drawn at the 50 % probability level. The crystallographic
numbering does not reflect the systematic IUPAC numbering.
internal standard; s ꢀ=ꢀ singlet, t ꢀ=ꢀ triplet, q ꢀ=ꢀ quartet,
m ꢀ=ꢀ multiplet. The 13C NMR signals were assigned on
the basis of DEPT 135/90 spectra. The mass spectra (70
eV, electron impact mode) were recorded on a Finnigan
MAT (Germany) instrument. Elemental analyses were
carried out at the Microanalytical Center, Cairo Univer-
sity, Egypt. Reactions were monitored by thin-layer chro-
matography (TLC) on pre-coated silica gel HF 254 plates
from Merck, and compounds visualized by exposure to
3.3 (2Z,2′E)-dimethyl-2,2′-[(2Z,2′Z)-3,3′-
(ethane-1,2-diyl)bis-(2-ethylimino)-
4-oxothiazolidin-3-yl-5-ylidene)]
diacetate (3a)
UV light. Preparative layer chromatography (plc) used Yellow crystals (300 mg, 66 %), m. p. 176–177 °C (acetoni-
air-dried 1.0 mm thick layers of slurry of silica gel (Merck trile). – IR (KBr): υ ꢀ=ꢀ 2990 (aliph. CH), 1720, 1700 (Cꢀ=ꢀO),
1
PF254) on 48 cm wide and 20 cm high glass plates using 1640 (Cꢀ=ꢀN), 1615 (Cꢀ=ꢀC) cm–1. – H NMR (400 MHz, CDCl3,
the solvents listed. Zones were detected by quenching 20 °C, TMS): δ ꢀ=ꢀ 6.8 (s, 2H, 2 vinyl CH), 3.86 (s, 6H, 2 OCH3),
of indicator fluorescence upon exposure to 254 nm light 3.55 (s, 4H, 2 CH2N), 3.35 (q, 4H, J ꢀ=ꢀ 7.64 Hz, 2 CH2), 1.15–
and eluted with acetone.
1.30 (t, 6H, J ꢀ=ꢀ 7.64 Hz, 2 CH3). – 13C NMR (100 MHz, CDCl3):
δ ꢀ=ꢀ 166.5 (ester Cꢀ=ꢀO), 164.72 (cyclic Cꢀ=ꢀO), 150.10 (thiazoli-
dine C-2), 141.33 (thiazolidine C-5), 115.42 (vinyl CH), 52.93
(OCH3), 49.14 (CH2N), 40.18 (CH2), 15.79 (CH3). – MS (EI, 70
3.1 Starting materials
+
+
eV): m/z (%) ꢀ=ꢀ 452 (75) [M] , 240 (100) [M–C8H9N2O3S] ,
+
+
N,N″-(1,ω-alkanediyl)bis(N′-organylthiourea)
deriva- 226 (20) [C9H11N2O3S] , 212 (12) [M–C10H13N2O3S] , 87 (5)
+ +
tives 1a–h were prepared by the reaction of the diamine [M–C15H9N3O6S] , 43 (5) [C2H5N] . – C18H22N4O6S2 (452.52):
(1,2-diaminoethane, 1,3-diaminopropane) with ethyl-, calcd. C 47.56, H 4.88, N 12.33, S 14.11; found: C 47.69, H
phenyl-, benzyl-, or allylisothiocyanate in DMF according 4.97, N 12.19, S 13.95.
H
R
MeO2C
N
O
CO2Me
S
CO2Me
MeO2C
Ethanol
H
N
H
S
N
( )n
N
S
N
NR
−2 MeOH
H
( )n
CO2Me
1a−h + 2
O
N
∆
NR
S
R
C
CO2Me
3a−h
Scheme 2:ꢁRational for formation of 3a–h.
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ꢀA.A. Hassan et al.: Synthesis of bis-thiazolidin-4-ones
246ꢀ
1720, 1700 (Cꢀ=ꢀO), 1645 (Cꢀ=ꢀN), 1610 (arom. Cꢀ=ꢀC) cm–1. – 1H
NMR (400 MHz, CDCl3, 20 °C, TMS): δ ꢀ=ꢀ 7.34 (m, 10H, arom.
H), 6.85 (s, 2H, 2 vinyl CH), 4.86 (s, 4H, 2 benzyl CH2), 3.86
(s, 6H, 2 OCH3), 3.65 (s, 4H, 2 CH2N). – 13C NMR (100 MHz,
3.4 (2Z,2′E)-dimethyl-2,2′-[(2Z,2′Z)-3,3′-
(ethane-1,2-diyl)bis-(2-allylimino)-4-oxo-
thiazolidin-3-yl-5-ylidene)]diacetate (3b)
Yellow crystals (296 mg, 62 %), m. p. 154–155 °C (acetoni- CDCl3): δ ꢀ=ꢀ 166.44 (ester Cꢀ=ꢀO), 164.75 (cyclic Cꢀ=ꢀO), 150.24
trile). – IR (KBr): υ ꢀ=ꢀ 2950 (aliph. CH), 1720, 1695 (Cꢀ=ꢀO), (thiazolidine C-2), 141.26 (thiazolidine C-5), 135.63 (arom.
1
1645 (Cꢀ=ꢀN), 1610 (Cꢀ=ꢀC) cm–1. – H NMR (400 MHz, CDCl3, C), 135.61, 128.86, 128.59, 128.47, 128.38, 127.24 (arom. CH),
20 °C, TMS): δ ꢀ=ꢀ 6.85 (s, 2H, 2 vinyl CH), 5.92–5.93 (m, 2H, 115.81 (vinyl CH), 56.16 (benzyl CH2), 52.93 (OCH3), 41.82
+
allyl CHꢀ=ꢀ), 5.25–5.27 (m, 4H, allyl CH2ꢀ=ꢀ), 4.50 (s, 4H, allyl (ethane CH2N). – MS (EI, 70 eV): m/z (%) ꢀ=ꢀ 578 (91) [M] ,
+
+
CH2N), 3.85 (s, 6H, 2 OCH3), 3.52 (s, 4H, 2 CH2N). – 13C NMR 461 (23) [M–C8H7N] , 289 (42) [M–C14H13N2O3S] , 91 (100)
+
(100 MHz, CDCl3): δ ꢀ=ꢀ 166.36 (ester Cꢀ=ꢀO), 164.42 (cyclic [PhCH2] . – C28H26N4O6S2 (578.66): calcd. C 58.12, H 4.53, N
Cꢀ=ꢀO), 149.54 (thiazolidine C-2), 141.28 (thiazolidine C-5), 9.68, S 11.08; found: C 57.97, H 4.62, N 9.78, S 10.94.
134.29 (allyl CHꢀ=ꢀ), 118.31 (allyl CH2), 115.25 (vinyl CH),
54.60 (OCH3), 49.68 (CH2-N), 44.22 (allyl CH2N). – MS (EI,
+
+
70 eV): m/z (%) ꢀ=ꢀ 478 (44) [M] , 447 (10) [M–CH3O] , 267 3.7 (2Z,2′E)-dimethyl-2,2′-[(2Z,2′Z)-3,3′-
+
+
(38) [M–C8H7N2O3S] , 239 (27) [M–C10H11N2O3S] , 152 (100)
(propane-1,3-diyl)bis-(2-ethylimino)-
4-oxo-thiazolidin-3-yl-5-ylidene)]
diacetate (3e)
+
+
[M–C13H16N3O5S] , 137 (41) [M–C14H17N2O4S2] . – C20H22N4O6S2
(478.54): calcd. C 50.20, H 4.63, N 11.71, S 13.40; found: C
50.06, H 4.71, N 11.84, S 13.28.
Yellow crystals (294 mg, 63 %), m. p. 105–106 °C (acetoni-
trile). – IR (KBr): υ ꢀ=ꢀ 2970 (aliph. CH), 1725, 1700 (Cꢀ=ꢀO),
3.5 (2Z,2′E)-dimethyl-2,2′-[(2Z,2′Z)-3,3′-
(ethane-1,2-diyl)bis-(4-oxo-2-
phenylimino)thiazolidin-3-yl-
5-ylidene)]diacetate (3c)
1
1645 (Cꢀ=ꢀN), 1605 (Cꢀ=ꢀC) cm–1. – H NMR (400 MHz, CDCl3,
20 °C, TMS): δ ꢀ=ꢀ 6.88 (s, 2H, vinyl CH), 3.86 (s, 6H, 2 OCH3),
3.81 (t, 4H, J ꢀ=ꢀ 7.62 Hz, 2 CH2N), 2.5 (m, 2H, propane CH2),
3.55 (q, 4H, J ꢀ=ꢀ 7.66 Hz, CH2), 1.30 (t, 6H, J ꢀ=ꢀ 7.66 Hz, 2CH3).
– 13C NMR (100 MHz, CDCl3): δ ꢀ=ꢀ 166.51 (ester Cꢀ=ꢀO), 164.78
Yellow crystals (368 mg, 67 %), m. p. ꢀ=ꢀ 166–167 °C (ace- (cyclic Cꢀ=ꢀO), 148.80 (thiazolidine C-2), 141.47 (thiazolidine
tonitrile). – IR (KBr): υ ꢀ=ꢀ 3080 (arom. CH), 2970 (aliph. C-5), 115.15 (vinyl CH), 52.48 (OCH3), 49.78 (CH2), 40.95
CH), 1725, 1695 (Cꢀ=ꢀO), 1640 (Cꢀ=ꢀN), 1620 (arom. Cꢀ=ꢀC) cm–1. (propane CH2N), 28.52 (propane CH2), 15.89 (CH3). – MS
+
+
– 1H NMR (400 MHz, CDCl3, 20 °C, TMS): δ ꢀ=ꢀ 7.40–7.32 (m, (EI, 70 eV): m/z (%) ꢀ=ꢀ 468 (100) [M] , 437 (10) [M–CH3O] ,
+
+
2H, arom. H), 7.30–7.21 (m, 6H, arom. H), 7.18–7.10 (m, 2H, 255 (75) [M–C8H9N2O3S] , 227 (35) [M–C10H13N2O3S] , 213 (12)
+
+
arom. H), 6.80 (s, 2H, 2 vinyl CH), 3.80 (s, 6H, 2 OCH3), 3.58 [M–C11H15N2O3S] , 59 (7) [COOMe] . – C19H24N4O6S2 (468.55):
(s, 4H, 2 CH2N). – 13C NMR (100 MHz, CDCl3): δ ꢀ=ꢀ 166.49 calcd. C 48.70, H 5.16, N 11.96, S 13.69; found: C 48.59, H
(ester Cꢀ=ꢀO), 164.88 (cyclic Cꢀ=ꢀO), 150.96 (thiazolidine C-2), 5.24, N 12.08, S 13.82.
141.92 (thiazolidine C-5), 130.11, 129.37 (arom. C), 129.05,
129.29, 128.88, 127.88, 125.79, 125.99 (arom. CH), 115.76
(vinyl CH), 53.48 (OCH3), 41.45 (ethane CH2N). – MS (EI, 70
3.8 (2Z,2′E)-dimethyl-2,2′-[(2Z,2′Z)-3,3′-
+
+
eV): m/z (%) ꢀ=ꢀ 550 (45) [M] , 289 (100) [M–C14H13N2O3S] ,
(propane-1,3-diyl)-bis(2-allylimino)-4-oxo-
thiazolidin-3-yl-5-ylidene)]diacetate (3f)
+
+
135 (35) [M–C19H17N3O6S] , 91 (10) [C6H5N] . – C26H22N4O6S2
(550.61): calcd. C 56.72, H 4.03, N 10.18, S 11.65; found: C
56.84, H 3.91, N 10.05, S 11.80.
Yellow crystals (323 mg, 66 %), m. p. 153–154 °C (acetoni-
trile). – IR (KBr): υ ꢀ=ꢀ 2980 (aliph. CH), 1735, 1715 (Cꢀ=ꢀO),
1640 (Cꢀ=ꢀN), 1610 (Cꢀ=ꢀC) cm–1. – H NMR (400 MHz, CDCl3,
1
3.6 (2Z,2′E)-dimethyl-2,2′-[(2Z,2′Z)-3,3′-
(ethane-1,2-diyl)bis-(2-benzylimino)-
4-oxo-thiazolidin-3-yl-5-ylidene)]
diacetate (3d)
20 °C, TMS): δ ꢀ=ꢀ 6.84 (s, 2H, 2 vinyl CH), 5.92 (m, 2H, allyl
CHꢀ=ꢀ), 5.20 (m, 4H, allyl CH2ꢀ=ꢀ), 4.38 (m, 4H, allyl CH2N),
3.78 (s, 6H, 2 OCH3), 3.48 (t, 4H, J ꢀ=ꢀ 7.61 Hz, CH2N), 2.45 (m,
2H, propane CH2). – 13C NMR (100 MHz, CDCl3): δ ꢀ=ꢀ 166.45
(ester Cꢀ=ꢀO), 164.72 (cyclic Cꢀ=ꢀO), 149.55 (thiazolidine C-2),
Yellow crystals (360 mg, 62 %), m. p. 160–161 °C (acetoni- 141.27 (thiazolidine C-5), 134.38 (allyl CHꢀ=ꢀ), 118.54 (allyl
trile). – IR (KBr): υ ꢀ=ꢀ 3110 (arom. CH), 2960 (aliph. CH), CH2ꢀ=ꢀ), 115.46 (vinyl CH), 54.60 (OCH3), 49.53 (allyl CH2N),
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ꢀ247
41.03 (propane CH2N), 28.50 (propane CH2). – MS (EI, (592.69): calcd. C 58.77, H 4.76, N 9.45, S 10.82; found: C
+
+
70 eV): m/z (%) ꢀ=ꢀ 492 (100) [M] , 461 (10) [M–CH3O] , 58.64, H 4.83, N 9.56, S 10.94.
+
+
267 (35) [M–C9H9N2O3S] , 225 (15) [M–C12H15N2O3S] , 99
+
+
(54) [M–C17H19N3O6S] , 59 (38) [COOMe] . – C21H24N4O6S2
(492.57): calcd. C 51.21, H 4.91, N 11.37, S 13.03; found: C
51.36, H 5.04, N 11.21, S 12.94.
3.11 Single-crystal X-ray structure
determination of 3g
Single crystals were obtained by recrystallization from
acetonitrile. The single crystal X-ray diffraction study was
carried out on a Bruker–Nonius Kappa CCD diffractometer
at T ꢀ=ꢀ 123 K using MoKα radiation (λ ꢀ=ꢀ 0.71073 Å). Direct
Methods (shelxs-98) [43] were used for structure solution
and refinement was carried out using Shelxl-2013 [43]
(full-matrix least-squares on F2). Hydrogen atoms were
localized by different Fourier synthesis map and refined
using a riding model. A semi-empirical absorption cor-
rection was applied. Crystal structure data: C27H24N4O6S2,
Mr ꢀ=ꢀ 564.62, yellow rods, crystal size 0.50 ꢀ×ꢀ 0.08 ꢀ×ꢀ 0.04
mm3, monoclinic space group P21/n (no. 14), a ꢀ=ꢀ 8.992(1),
b ꢀ=ꢀ 10.093(1), c ꢀ=ꢀ 30.033(3) Å, β ꢀ=ꢀ 96.28(1)°, V ꢀ=ꢀ 2709.3(5)
Å3, Z ꢀ=ꢀ 4, dcalcd. ꢀ=ꢀ 1.384 mg m–3, F(000) ꢀ=ꢀ 1176 e, μ(MoKα) ꢀ=ꢀ
0.25 mm–1, 20 956 measured reflections, 2 θmax ꢀ=ꢀ 55°, 6139
independent, Rint ꢀ=ꢀ 0.046, 222 ref. parameters, R1 (for 4839
data with I ꢀ>ꢀ 2 σ(I)] ꢀ=ꢀ 0.056, wR2 (all data) ꢀ=ꢀ 0.121, S ꢀ=ꢀ 1.16,
largest diff. peak/hole ꢀ=ꢀ 0.33/–0.30 e A–3.
3.9 (2Z,2′E)-dimethyl-2,2′-[(2Z,2′Z)-3,3′-
(propane-1,3-diyl)bis-(4-oxo-2-
phenylimino)thiazolidin-3-yl-5-ylidene)]
diacetate (3g)
Yellow crystals (346 mg, 61 %), m. p. 176–177 °C (acetoni-
trile). – IR (KBr): υ ꢀ=ꢀ 2960 (aliph. CH), 1730, 1695 (Cꢀ=ꢀO),
1
1640 (Cꢀ=ꢀN), 1620 (arom. Cꢀ=ꢀC) cm–1. – H NMR (400 MHz,
CDCl3, 20 °C, TMS): δ ꢀ=ꢀ 7.18–7.22 (m, 6H, arom. H), 7.12–7.14
(m, 4H, arom. H) 6.88 (s, 2H, vinyl CH), 4.00 (t, 4H, J ꢀ=ꢀ 7.65
Hz, 2 CH2N), 3.75 (s, 6H, 2 OCH3), 2.35 (m, 2H, propane CH2).
– 13C NMR (100 MHz, CDCl3): δ ꢀ=ꢀ 166.28 (ester Cꢀ=ꢀO), 164.89
(cyclic Cꢀ=ꢀO), 150.82 (thiazolidine C-2), 141.52 (thiazolidine
C-5), 129.64, 129.36, 129.07, 125.26, 121.06, 120.73 (arom.
CH), 116.16 (vinyl CH), 52.52 (OCH3), 40.57 (CH2N), 25.75
+
(propane CH2). – MS (EI, 70 eV): m/z (%) ꢀ=ꢀ 564 (91) [M] ,
+
+
303 (100) [M–C12H9N2O3S] , 289 (26) [M–C13H11N2O3S] ,
CCDC 958575 contains the supplementary crystallo-
graphic 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.
+
+
135 (76) [M–C20H19N3O6S] , 91 (21) [C6H5N] . –C27H24N4O6S2
(564.63): calcd. C 57.43, H 4.28, N 9.92, S 11.36; found: C
57.55, H 4.36, N 10.12, S 11.22.
3.10 (2Z,2′E)-dimethyl-2,2′-[(2Z,2′Z)-3,3′-
(propane-1,3-diyl)-bis(2-benzylimino)-
4-oxo-thiazolidin-3-yl-5-ylidene)]
diacetate (3h)
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Yellow crystals (377 mg, 64 %), m. p. 181–182 °C (acetoni-
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ꢁꢁꢁꢂ
ꢀA.A. Hassan et al.: Synthesis of bis-thiazolidin-4-ones
248ꢀ
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