A novel multicomponent approach to the synthesis of 1,3-thiazolidine-2- thiones

Article abstract of DOI:10.1016/j.tet.2010.12.055

An easy, efficient, and simple one-pot approach for the synthesis of 1,3-thiazolidine-2-thiones via multicomponent reaction is reported. The reaction of a primary amine with carbon disulfide in the presence of dibenzoylacetylene or bis(4-methyl-1-benzoyl)

Full text of DOI:10.1016/j.tet.2010.12.055

Tetrahedron 67 (2011) 1709e1715
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A novel multicomponent approach to the synthesis of 1,3-thiazolidine-2-thiones
*
Abdolali Alizadeh , Nasrin Zohreh, Hamideh Sabahnoo, Zohreh Noaparast
Department of Chemistry, Tarbiat Modares University, P.O. Box 14115-175, Tehran, Iran
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 27 May 2010
Received in revised form 6 December 2010
Accepted 20 December 2010
Available online 25 December 2010
An easy, efficient, and simple one-pot approach for the synthesis of 1,3-thiazolidine-2-thiones via
multicomponent reaction is reported. The reaction of a primary amine with carbon disulfide in the
presence of dibenzoylacetylene or bis(4-methyl-1-benzoyl)acetylene in a mixture of CH2Cl2 and H2O
after 5 h, afforded the title compound as alkene diastereomers.
Ó 2010 Elsevier Ltd. All rights reserved.
Keywords:
1,3-Thiazolidine-2-thiones
Primary amine
Carbon disulfide
Multicomponent reaction
1. Introduction
Ph
S
During the past decade, combinatorial chemistry has provided
access to chemical libraries based on privileged structures,1 with
heterocyclic structures receiving special attention as they belong to
a class of compounds with proven utility in medicinal chemistry.2
There are numerous biologically active molecules with five-mem-
bered rings, containing two heteroatoms. Thiazolidine 1 and its
derivatives are important scaffolds for drug candidates. Anticon-
vulsant, sedative, antidepressant, anti-inflammatory, antihyper-
tensive, antihistaminic, and antiarthritic activities are a few among
many other biological responses shown by this scaffold (Fig. 1).3
N
S
N
3: Fezatione
Fig. 2.
S
As part of our work devoted to the synthesis of important het-
erocycles especially heterocycles with two heteroatoms,7 herein we
report a novel, one-pot, three-component reaction for the synthesis
of 1,3-thiazolidine-2-thiones.
HN
HN
S
S
2
1
(Thiazolidine-2-thione)
(Thiazolidine)
2. Results and discussion
Fig. 1.
Compounds containing the 1,3-thiazolidine-2-thioneone 2 ring
have showed a wide range of pharmacological activities. For ex-
ample, Fezatione 3 is an antifungal and antitrichophytic (Fig. 2).4 In
addition, these compounds display a central role in modern syn-
thetic organic chemistry.5 Metal enolates of N-acyl-1,3-oxazoli-
dine-2-tiones have been used as chiral auxiliaries for aldol type
reactions with high diastereoselectivity.6
Our research group reported the synthesis of a novel series of
heterocycles using the reaction of dibenzoylacetylene with various
zwitterions and electrophiles8 and recently the synthesis of bi-
ologically active rhodanines from the reaction of primary amines,
carbon disulfide, and dialkyl acetylenedicarboxylates or fumaryl
chloride were reported by our research group (Scheme 1).9 Trap-
ping of the amineeCS2 zwitterion by dialkyl acetylenedicarboxy-
late, afforded only one of the two possible stereoisomers for all
derivatives, however we were unable to identify the configuration
of the alkenes.
* Corresponding author. Tel.: þ98 21 8800663; fax: þ98 21 88006544; e-mail
address: aalizadeh@modares.ac.ir (A. Alizadeh).
0040-4020/$ e see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2010.12.055

1710
A. Alizadeh et al. / Tetrahedron 67 (2011) 1709e1715
S
S
S
•
R'O
O
O
R
R
H2O/CH2Cl2
1 h, rt
S
S
N
N
Or
R
R
NH2 +
NH2 +
+
+
OR'
S
CO2R
O
O
for all derivatives
RO2C
S
O
S
•
H2O
R
Cl
N
S
Cl
rt 5 h
S
O
CO2H
O
Scheme 1.
Along the same lines, we have become interested in application
of dibenzoylacetylene or bis(4-methyl-1-benzoyl)acetylene instead
of dialkyl acetylenedicarboxylates in this reaction for the synthesis
of title compound. Our new synthetic route is given in Scheme 2. The
reaction of primary amine 4, CS2 and dibenzoylacetylene or bis
(4-methyl-1-benzoyl)acetylene proceeds in a mixture of CH2Cl2 and
H2O at room temperature to produce 2-(3-alkyl-4-hydroxy-4-aryl-
2-thioxo-1,3-thiazolan-5-yliden)-1-aryl-1-ethanone derivatives 5,
6 in total 76e97% yields (Scheme 2). As stated below, both of the E
for 6a appears as a doublet at 4.35 ppm with 2JHH¼6.0 Hz. The most
important difference between 1H NMR spectrum of 5a and 6a is due
to the chemical shift of their OH group. Compound 5a can not orient
for an intramolecular hydrogen bonding and thus the OH signal
appears as a broad band at 4.77 ppm while for 6a, the intra-
molecular hydrogen bond result in the proton resonating down
field at 11.08 ppm. The three phenyl moieties of both of 5a and 6a
gave rise to characteristic signals in the corresponding aromatic
region of the spectrum. The 1H decoupled 13C NMR spectrum of 5a
Scheme 2.
and Z setereoisomers were obtained from the reaction in all
instances.
and 6a showed 19 distinct signals in agreement with proposed
structure. The carbon of C]CH of 5a and 6a resonances at 113.5 and
127.2 ppm are appeared, respectively.
The data obtained from elemental analysis, IR, and high-field 1H
and 13C NMR spectra confirmed all products and stereoisomers. The
mass spectrum of 5a and 6a showed no molecular ion peak at m/z
431; however, for other derivatives this peak was detected. The
most important absorption band in IR spectrum of 5a is due to the
OH stretching frequency, that is, appeared as a broad band at
3275 cmꢀ1. Absorption bands at 1641 and 1595 cmꢀ1 are due to the
C]O and C]C groups. In the 1H NMR spectrum of 5a, two sharp
singlet peaks at dH¼2.26 and 7.02 ppm readily recognized as arising
from methyl of amine and C]CH moiety. In 1H NMR spectrum of
6a, these two moieties are appearing at 2.30 and 5.81 ppm. Two
hydrogens of CH2N of 5a are appeared as two separated diaster-
eotopic doublets at dH¼4.58 and 5.17 ppm (2JHH¼14.9 Hz), whereas
Although we have not established the mechanism of our reaction
in an experimental manner, a possible explanation is proposed in
Scheme 3. The reaction mechanism leading to product 5 and 6 pre-
sumably proceeds through an initial addition of the amine 4 to the
carbon disulfide to afford zwitterion 7.10 Subsequently; intermediate
7 is trapped by bisaroylacetylene to produce intermediate 8. Proba-
bly, the thiocarbamate 8 undergoes intramolecular cyclization to
convert to the products 5 and 6 in 76e97% total yield. (It is important
to note that the five-membered ring formation is kinetically more
favorable than the six membered ring).11
When we used allyamine or ethylamine in the reaction, only the
intermediate 8 (9a, 9b) was obtained and product 5 or 6 wasn’t

A. Alizadeh et al. / Tetrahedron 67 (2011) 1709e1715
1711
4. Experimental
S
4.1. General
RH2N
RHN
S
S
•
ArOC
COAr
FT-IR spectra were recorded as KBr pellets on a Shimadzu IR-460
spectrometer. 1H NMR (500.13 MHz) and 13C NMR (125.75 MHz)
spectra were obtained using a Bruker DRX-500 AVANCE spec-
trometer. All NMR spectra were determined in CDCl3 at ambient
temperature. Melting points measured on an Electrothermal 9100
apparatus. Elemental analyses for C, H, and N performed using
a Heraeus CHNeOeRapid analyzer. Mass spectra were recorded on
a FINNIGAN-MATT 8430 mass spectrometer operating at an ioni-
zation potential of 70 eV. All chemicals were purchased from Merck
or Aldrich and were used without further purification. Dibenzoy-
lacetylene, and bis(4-methyl-1-benzoyl)acetylene was prepared
according to the literature procedure.17,18
+
R
R
NH2
S
S
SH
4
7
S
N
S
H
O
5 + 6
Ar
COAr
4.2. General synthesis procedure: (for example, 5a)
8
To a magnetically stirred 5 mL flat bottom flask containing
p-methylbenzylamine (0.12 g, 1 mmol) and H2O (2 mL as solvent),
was added CS2 (0.15 g, 2 mmol). Then, a solution of dibenzoylace-
tylene (0.23 g,1 mmol) in dichloromethane (3 mL) was added to the
reaction mixture and was allowed to stir vigorously at room tem-
perature for 5 h. After completion of the reaction (monitoring by
Scheme 3.
produced. The reaction with 1-phenyl-1-ethanamine produces 9c
in addition of two stereoisomers (5e, and 6e) (Scheme 4).
Me
S
S
S
Ph
Me
N
S
N
N
S
S
COPh
COPh
COPh
H
H
H
O
O
O
H
H
H
Ph
Ph
Ph
9b
9c
9a
Scheme 4.
3. Conclusion
TLC), the organic layer was extracted with CH2Cl2 (16 mL). The
solvent was removed on a rotary evaporator and both of products
were separated by silica gel (Merck 230e240 mesh) column chro-
matography using n-hexaneeEtOAc (7:1).
In summery, in this paper we developed a novel method for the
synthesis of 1,3-Thiazolidine-2-thiones of potential synthetic and
pharmacological interest using the simple and inexpensive starting
materials. For example, 2-amino-5-arylidene-1,3-thiazol-4(5H)-one
can be obtained from the reaction between 5-arylidene-rhodanine
and amine by sulfur/nitrogen displacement under solvent-free mi-
crowave irradiation (Scheme 5).12 Compounds containing 2-amino-
5-arylidene-1,3-thiazol-4(5H)-one moiety are reported to have
antiviral,13 antimicrobial,14 cardiotonic,15 and anti-inflammatory16
effects.
4.2.1. 2-[4-Hydroxy-3-(4-methylbenzyl)-4-phenyl-2-thioxo-1,3-thia-
zolan-5-yliden]-1-phenyl-1-ethanone (5a). Yellow powder, mp
188e190 ꢁC, 0.11 g, yield: 26%. Rf (12% EtOAc/n-hexane): 0.23; IR
(KBr) (nmax, cmꢀ1): 3275 (OH), 1641 (C]O), 1595 (C]C), 1558 and
1463 (Ar), 1052 (C]S). Anal. Calcd for C25H21NO2S2 (431.56): C,
69.58; H, 4.90; N, 3.25%. Found: C, 69.63; H, 4.92; N, 3.27%. MS (EI,
70 eV): m/z (%)¼429 (Mþꢀ2, 5), 307 (23), 264 (29), 236 (17), 202
(31),168 (51),146 (44),105 (78), 91 (69), 77 (83), 58 (56), 43 (100). 1H
NMR (500.13 MHz, CDCl3): dH¼2.26 (3H, s, Me), 4.58 (1H, d,
2
2JHH¼14.9 Hz, CH2N), 4.77 (1H, br, OH), 5.17 (1H, d, JHH¼14.9 Hz,
X
CH2N), 6.95 (2H, d, 3JHH¼7.8 Hz, 2CH of Ar), 7.02 (1H, s, C]CH), 7.14
(2H, d, 3JHH¼7.9 Hz, 2CH of Ar), 7.27 (2H, d, 3JHH¼7.1 Hz, 2CH of Ar),
7.31e7.32 (3H, m, 3CH of Ar), 7.35 (1H, t, 3JHH¼7.2 Hz, CH of Ar), 7.47
(2H, t, 3JHH¼7.3 Hz, 2CH of Ar), 7.72 (2H, d, 3JHH¼7.4 Hz, 2CH of Ar).
13C NMR (125.75 MHz, CDCl3): dC¼21.1 (CH3), 48.7 (CH2N), 102.2
(COH), 113.5 (C]CH), 125.5 (2CH of Ar),128.4 (2CH of Ar),128.6 (2CH
of Ar), 128.8 (2CH of Ar), 128.8 (2CH of Ar), 128.9 (2CH of Ar), 129.4
(CH of Ar), 133.3 (CH of Ar), 133.4 (CipsoeMe),136.6 (CipsoeCOH), 137.0
(CipsoeCH2N), 138.9 (CipsoeCO), 161.7 (C]CH), 188.6 (CO), 193.7 (CS).
S
N
S
X
NH
Ar
S
Ar
N
N
R
O
O
Scheme 5.
The reaction is one pot and performed under neutral condition.
The simplicity of the present procedure makes it an interesting
alternative to the complex multistep approaches.
4.2.2. 2-[3-(4-Chlorobenzyl)-4-hydroxy-4-phenyl-2-thioxo-1,3-thia-
zolan-5-yliden]-1-phenyl-1-ethanone (5b). Pale yellow powder, mp
184e186 ꢁC, 0.13 g, yield: 29%. Rf (12% EtOAc/n-hexane): 0.30; IR

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A. Alizadeh et al. / Tetrahedron 67 (2011) 1709e1715
(KBr) (nmax, cmꢀ1): 3205 (OH), 1641 (C]O), 1620 (C]C), 1554 and
1442 (Ar), 1048 (C]S). Anal. Calcd for C24H18ClNO2S2 (451.98): C,
63.78; H, 4.01; N, 3.10%. Found: C, 63.81; H, 4.03; N, 3.13%. MS (EI,
70 eV): m/z (%)¼451 (Mþ, 5), 430 (9), 416 (17), 400 (37), 310 (18),
268 (7),163 (18),125 (44),105 (100), 89 (6), 77 (91), 51 (19). 1H NMR
(500.13 MHz, CDCl3): dH¼3.61e4.42 (1H, br, OH), 4.84 (1H, d,
2JHH¼16.2 Hz, CH2N), 5.31 (1H, d, 2JHH¼16.2 Hz, CH2N), 7.06 (1H, s,
7.13e7.23 (4H, m, 4CH of Ar), 7.32e7.39 (4H, m, 4CH of Ar),
3
7.43e7.49 (3H, m, 3CH of Ar), 7.52 (2H, t, JHH¼7.4 Hz, 2CH of Ar),
7.77 (2H, d, 3JHH¼8.1 Hz, 2CH of Ar). 13C NMR (125.75 MHz, CDCl3):
dC¼17.0 (CHCH3), 57.0 (CHCH3), 103.2 (COH), 113.0 (C]CH), 125.6
(2CH of Ar), 127.9 (2CH of Ar), 128.2 (2CH of Ar), 128.3 (2CH of Ar),
128.7 (2CH of Ar), 128.7 (2CH of Ar), 128.8 (CH of Ar), 133.2 (CH of
Ar), 136.9 (CipsoeCOH), 138.7 (CipsoeCHN), 138.9 (CipsoeCO), 162.4
(C]CH), 188.5 (CO), 192.0 (CS).
3
C]CH), 7.10 (2H, d, JHH¼7.9 Hz, 2CH of Ar), 7.18 (1H, t,
3
3JHH¼6.30 Hz, CH of Ar), 7.28 (2H, t, JHH¼6.7 Hz, 2CH of Ar), 7.30
(2H, d, 3JHH¼6.5 Hz, 2CH of Ar), 7.32 (2H, d, 3JHH¼7.8 Hz, 2CH of Ar),
4.2.6. 2-(4-Hydroxy-3-methyl-4-phenyl-2-thioxo-1,3-thiazolan-5-
yliden)-1-phenyl-1-ethanone (5f). Yellow oil, 0.22 g, yield: 66%. Rf
(12% EtOAc/n-hexane): 0.22; IR (KBr) (nmax, cmꢀ1): 3240 (OH),
1677 (C]O), 1596 (C]C), 1555 and 1447 (Ar), 1055 (C]S). Anal.
Calcd for C18H15NO2S2 (341.44): C, 63.32; H, 4.43; N, 4.10%.
Found: C, 63.36; H, 4.42; N, 4.13%. MS (EI, 70 eV): m/z (%)¼341
(Mþ, 43), 325 (7), 268 (26), 220 (6), 163 (100), 135 (10), 105 (93),
85 (28), 77 (81), 72 (66), 51 (26). 1H NMR (500.13 MHz, CDCl3):
dH¼3.09 (3H, s, NMe), 5.31e5.80 (1H, br, OH), 7.08 (1H, s, C]CH),
7.28 (2H, t, 3JHH¼7.5 Hz, 2CH of Ar), 7.34 (1H, t, 3JHH¼7.2 Hz, CH of
3
3
7.41 (1H, t, JHH¼7.3 Hz, CH of Ar), 7.50 (2H, t, JHH¼6.9 Hz, 2CH of
Ar), 7.76 (2H, d, JHH¼7.4 Hz, 2CH of Ar). 13C NMR (125.7 MHz,
3
CDCl3): dC¼45.8 (CH2N), 101.9 (COH), 113.9 (C]CH), 125.5 (2CH of
Ar), 126.5 (2CH of Ar), 128.3 (2CH of Ar), 128.4 (2CH of Ar), 128.7
(2CH of Ar), 128.8 (2CH of Ar), 128.8 (CH of Ar), 129.2 (CH of Ar),
132.5 (CipsoeCl), 136.5 (CipsoeCOH), 136.5 (CipsoeCH2N), 138.3
(CipsoeCO), 161.3 (C]CH), 188.7 (CO), 194.1 (CS).
4.2.3. 2-[4-Hydroxy-3-(4-methoxybenzyl)-4-phenyl-2-thioxo-1,3-
thiazolan-5-yliden]-1-phenyl-1-ethanone (5c). Pale yellow powder,
mp 179e181 ꢁC, 0.10 g, yield: 22%. Rf (12% EtOAc/n-hexane): 0.28; IR
(KBr) (nmax, cmꢀ1): 3265 (OH), 1638 (C]O), 1610 (C]C), 1551 and
1459 (Ar), 1043 (C]S). Anal. Calcd for C25H21NO3S2 (447.56): C,
67.09; H, 4.73; N, 3.13%. Found: C, 67.14; H, 4.75; N, 3.14%. MS (EI,
70 eV): m/z (%)¼355 (15), 307 (9), 264 (27), 250 (34), 183 (43), 167
(18), 146 (39), 105 (100), 91 (56), 77 (77), 57 (60), 43 (57). 1H NMR
(500.13 MHz, CDCl3): dH¼2.48e2.60 (1H, br, OH), 3.76 (3H, s, OMe),
4.38 (1H, d, 2JHH¼14.7 Hz, CH2N), 5.28 (1H, d, 2JHH¼14.7 Hz, CH2N),
6.73 (2H, d, 3JHH¼8.7 Hz, 2CH of Ar), 7.08 (1H, s, C]CH), 7.29 (1H, t,
3JHH¼7.1 Hz, 1CH of Ar), 7.36e7.39 (5H, m, 5CH of Ar), 7.40e7.42
(1H, m, CH of Ar), 7.46 (1H, t, 3JHH¼7.4 Hz, CH of Ar), 7.50e7.52 (2H,
3
3
Ar), 7.38 (1H, t, JHH¼7.4 Hz, CH of Ar), 7.41 (2H, t, JHH¼7.6 Hz,
3
2CH of Ar), 7.49 (2H, d, JHH¼7.6 Hz, 2CH of Ar), 7.74 (2H, d,
3JHH¼7.8 Hz, 2CH of Ar). 13C NMR (125.7 MHz, CDCl3): dC¼31.9
(NCH3), 101.5 (COH), 113.9 (C]CH), 128.3 (2CH of Ar), 128.5 (2CH
of Ar), 129.0 (2CH of Ar), 129.7 (2CH of Ar), 130.9 (CH of Ar), 133.4
(CH of Ar), 136.5 (CipsoeOH), 138.7 (CipsoeCO), 161.4 (C]CH), 188.7
(CO), 192.5 (CS).
4.2.7. 2-((4-Hydroxy)-4-phenyl-3-propyl-2-thioxo-1,3-thiazolan-5-
yliden)-1-phenyl-1-ethanone (5g). Yellow powder, mp 198e200 ꢁC,
0.05 g, yield: 13%. Rf (12% EtOAc/n-hexane): 0.35; IR (KBr) (nmax
,
cmꢀ1): 3250 (OH), 1640 (C]O), 1595 (C]C), 1552 and 1447 (Ar),
1048 (C]S). Anal. Calcd for C20H19NO2S2 (369.49): C, 65.01; H, 5.18;
N, 3.79%. Found: C, 65.04; H, 5.20; N, 3.82%. MS (EI, 70 eV): m/z (%)¼
369 (Mþ, 14), 355 (10), 269 (19), 264 (16), 211 (11), 163 (37), 105
(100), 91 (10), 85 (18), 77 (79), 58 (24), 43 (65), 41 (16). 1H NMR
3
m, 2CH of Ar), 7.82 (2H, t, JHH¼7.3 Hz, 2CH of Ar). 13C NMR
(125.75 MHz, CDCl3): dC¼48.2 (CH2N), 55.3 (OMe), 102.0 (COH),
113.4 (C]CH), 125.3 (2CH of Ar), 128.3 (2CH of Ar), 128.7 (2CH of
Ar), 128.9 (2CH of Ar), 129.0 (2CH of Ar),129.6 (2CH of Ar), 130.3 (CH
of Ar), 133.3 (CH of Ar), 134.1 (CipsoeCH2N), 136.5 (CipsoeCOH), 138.9
(CipsoeCO), 154.9 (CipsoeOMe), 161.1 (C]CH), 181.3 (CO), 188.2 (CS).
3
(500.13 MHz, CDCl3): dH¼0.79 (3H, t, JHH¼7.4 Hz, NCH2CH2CH3),
1.37e1.41 (1H, m, NCH2CH2CH3), 1.64e1.68 (1H, m, NCH2CH2CH3),
3.28e3.33 (1H, m, NCH2CH2CH3), 3.70e3.76 (1H, m, NCH2CH2CH3),
4.19 (1H, br, OH), 7.04 (1H, s, C]CH), 7.35 (2H, t, 3JHH¼7.4 Hz, 2CH of
4.2.4. 2-(3-Benzyl-4-hydroxy-4-phenyl-2-thioxo-1,3-thiazolan-5-yli-
den)-1-phenyl-1-ethanone(5d). Pale yellow powder, mp 195e197 ꢁC,
3
Ar), 7.39e7.44 (4H, m, 4CH of Ar), 7.52 (2H, d, JHH¼8.1 Hz, 2CH of
3
0.11 g, yield: 25%. Rf (12% EtOAc/n-hexane): 0.27; IR (KBr) (nmax
,
Ar), 7.78 (2H, d, JHH¼7.5 Hz, 2CH of Ar). 13C NMR (125.75 MHz,
cmꢀ1): 3225 (OH), 1640 (C]O), 1596 (C]C), 1555 and 1447 (Ar),
1050 (C]S). Anal. Calcd for C24H19NO2S2 (417.54): C, 69.04; H, 4.59;
N, 3.35%. Found: C, 69.03; H, 4.60; N, 3.33%. MS (EI, 70 eV): m/z (%)¼
417 (Mþ, 8), 401 (5), 312 (10), 269 (31), 223 (12), 163 (84), 149 (37),
105 (91), 91 (100), 77 (68), 65 (19), 51 (22). 1H NMR (500.13 MHz,
CDCl3): dC¼10.98 (NCH2CH2CH3), 20.4 (NCH2CH2CH3), 47.5
(NCH2CH2CH3), 101.4 (COH), 113.1 (C]CH), 125.4 (2CH of Ar), 128.4
(2CH of Ar), 128.6 (CH of Ar), 128.9 (2CH of Ar), 129.6 (CH of Ar),
133.3 (2CH of Ar), 133.7 (CipsoeOH), 134.8 (CH of Ar), 138.3
(CipsoeCO), 162.1 (C]CH), 189.2 (CO), 191.9 (CS).
2
CDCl3): dH¼4.21e4.33 (1H, br, OH), 4.67 (1H, d, JHH¼15 Hz, CH2N),
5.20 (1H, d, 2JHH¼15 Hz, CH2N), 7.01 (1H, s, C]CH), 7.12e7.17 (3H, m,
3CH of Ar), 7.23e7.32 (7H, m, 7CH of Ar), 7.37 (1H, t, 3JHH¼7.0 Hz, CH
of Ar), 7.45e7.49 (2H, m, 2CH of Ar), 7.72 (2H, d, 3JHH¼7.4 Hz, 2CH of
Ar). 13C NMR (125.7 MHz, CDCl3): dC¼48.8 (CH2N), 102.1 (COH), 113.5
(C]CH), 125.5 (2CH of Ar), 127.0 (2CH of Ar), 128.1 (2CH of Ar), 128.3
(2CH of Ar), 128.5 (2CH of Ar), 128.7 (2CH of Ar), 129.0 (CH of Ar),
129.5 (CH of Ar), 133.3 (CH of Ar), 136. 5 (CipsoeCOH), 136.5 (Cipsoe
CH2N), 138.7 (CipsoeCO), 161.5 (C]CH), 188.6 (CO), 193.9 (CS).
4.2.8. 2-(4-Hydroxy-3-isobutyl-4-phenyl-2-thioxo-1,3-thiazolan-5-
yliden)-1-phenyl-1-ethanone (5h). Orange powder, mp 141e143 ꢁC,
0.14 g, yield: 38%. Rf (12% EtOAc/n-hexane): 0.37; IR (KBr) (nmax
,
cmꢀ1): 3285 (OH), 1623 (C]O), 1595 (C]C), 1540 and 1446 (Ar),
1051 (C]S).Anal. Calcd for C21H21NO2S2 (383.52): C, 65.77; H,
5.52; N, 3.65%. Found: C, 65.83; H, 5.55; N, 3.66%. MS (EI, 70 eV):
m/z (%)¼327 (4), 300 (12), 290 (16), 268 (35), 262 (9), 163 (41), 146
(17), 115 (20), 105 (100), 91 (38), 77 (95), 57 (28), 43 (37), 41 (39).
1H NMR (500.1 MHz, CDCl3): dH¼0.81 (3H, d, 3JHH¼6.7 Hz, NCH2CH
3
4.2.5. 2-[4-Hydroxy-4-phenyl-3-(1-phenylethyl)-2-thioxo-1,3-thia-
zolan-5-yliden]-1-phenyl-1-ethanone (5e). Pale yellow powder, mp
163e165 ꢁC, 0.03 g, yield: 7%. Rf (12% EtOAc/n-hexane): 0.30; IR
(KBr) (nmax, cmꢀ1): 3220 (OH), 1636 (C]O), 1594 (C]C), 1529 and
1443 (Ar), 1056 (C]S). Anal. Calcd for C25H21NO2S2 (431.56): C,
69.58; H, 4.90; N, 3.25%. Found: C, 69.60; H, 4.95; N, 3.27%. MS (EI,
70 eV): m/z (%)¼422 (6), 322 (10), 268 (43), 236 (29), 167 (17), 149
(51), 105 (100), 91 (38), 77 (71), 57 (44), 43 (41). 1H NMR
(500.13 MHz, CDCl3): dH¼1.74 (3H, d, 3JHH¼7.2 Hz, CHCH3), 4.61 (1H,
(CH3)2), 0.88 (3H, d, JHH¼6.9 Hz, NCH2CH(CH3)2), 2.09e2.16 (1H,
2
3
m, NCH2CH(CH3)2), 3.13 (1H, dd, JHH¼13.7 Hz, JHH¼8.0 Hz,
2
3
NCH2CH2CH3), 3.79 (1H, dd, JHH¼13.7 Hz, JHH¼6.8 Hz,
NCH2CH2CH3), 3.80e3.98 (1H, br, OH), 7.04 (1H, s, C]CH), 7.31
(2H, t, 3JHH¼7.4 Hz, 2CH of Ar), 7.37e7.41 (4H, m, 4CH of Ar), 7.52
(2H, d, 3JHH¼7.5 Hz, 2CH of Ar), 7.76 (2H, d, 3JHH¼7.2 Hz, 2CH of Ar).
13C NMR (125.75 MHz, CDCl3): dC¼20.6 (NCH2CH(CH3)2), 20.8
(NCH2CH(CH3)2), 27.5 (NCH2CH(CH3)2), 53.5 (NCH2CH(CH3)2),
102.2 (COH), 113.3 (C]CH), 125.3 (2CH of Ar), 128.3 (2CH of Ar),
128.6 (2CH of Ar), 129.0 (2CH of Ar), 129.5 (CH of Ar), 133.2 (CH of
3
br, OH), 5.39 (1H, q, JHH¼7.2 Hz, CHCH3), 6.96 (1H, s, C]CH),

A. Alizadeh et al. / Tetrahedron 67 (2011) 1709e1715
1713
Ar), 136.7 (CipsoeOH), 139.3 (CipsoeCO), 162.0 (C]CH), 188.6 (CO),
193.7 (CS).
(KBr) (nmax, cmꢀ1): 3460 (OH), 1669 (C]O), 1595 (C]C), 1551 and
1449 (Ar), 1031 (C]S). Anal. Calcd for C25H21NO3S2 (447.56): C,
67.09; H, 4.73; N, 3.13%. Found: C, 67.12; H, 4.74; N, 3.12%. MS (EI,
70 eV): m/z (%)¼445 (Mþꢀ2, 7), 385 (9), 371 (15), 280 (21), 266 (26),
147 (12), 121 (100), 105 (51), 91 (9), 77 (41), 51 (8). 1H NMR
(500.13 MHz, CDCl3): dH¼3.76 (3H, s, OMe), 4.32 (2H, d,
4.2.9. 2-[4-Hydroxy-3-(4-methylbenzyl)-4-(4-methylphenyl)-2-thi-
oxo-1,3-thiazolan-5-yliden]-1-(4-methylphenyl)-1-ethanone
(5i). Yellow powder, mp 23e205 ꢁC, 0.12 g, yield: 27%. Rf (12% EtOAc/
n-hexane): 0.26; IR (KBr) (nmax, cmꢀ1): 3247 (OH), 1631 (C]O), 1562
(C]C), 1520 and 1452 (Ar), 1046 (C]S). Anal. calcd for C27H25NO2S2
(459.62): C, 70.56; H, 5.48; N, 3.05%. Found: C, 70.60; H, 5.42; N, 3.07%.
MS (EI, 70 eV): m/z(%)¼460(Mþþ1,12), 443(6), 297(47), 279(10), 264
(15), 177 (51), 119 (100), 105 (59), 91 (55), 77 (10), 65 (21). 1H NMR
(500.13 MHz, CDCl3): dH¼2.22 (3H, s, Me), 2.27 (3H, s, Me), 2.32 (3H, s,
Me), 4.60 (1H, d, 2JHH¼14.8Hz, CH2N), 4.79 (1H, br, OH), 5.15 (1H, d,
2JHH¼14.8 Hz, CH2N), 6.95 (2H, d, 3JHH¼7.8 Hz, 2CH of Ar), 7.96 (1H, s,
C]CH), 7.06 (2H, d, 3JHH¼7.7 Hz, 2CH of Ar), 7.10 (2H, d, 3JHH¼7.9 Hz,
2CH of Ar), 7.13 (2H, d, 3JHH¼7.6 Hz,2CH ofAr), 7.33(2H, d, 3JHH¼7.7 Hz,
2CH of Ar), 7.61 (2H, d, 3JHH¼7.7 Hz, 2CH of Ar).13C NMR (125.75 MHz,
CDCl3): dC¼21.1 (CH3), 21.1 (CH3), 21.6 (CH3), 48.6 (CH2N),102.2 (COH),
113.5 (C]CH), 125.4 (2CH of Ar), 128.5 (2CH of Ar), 128.7 (2CH of Ar),
128.8(2CHofAr),129.3(2CHofAr),129.4(2CHofAr),133.5(CipsoeMe),
134.1 (CipsoeMe), 136.0 (CipsoeCOH), 136.9 (CipsoeCH2N), 139.5
(CipsoeMe), 144.3 (CipsoeCO), 161.1 (C]CH), 188.2 (CO), 193.8 (CS).
3
2JHH¼6.2 Hz, CH2N), 5.80 (1H, s, C]CH), 6.80 (2H, d, JHH¼8.6 Hz,
3
2CH of Ar), 7.16 (2H, d, JHH¼8.6 Hz, 2CH of Ar), 7.38 (2H, t,
3JHH¼7.1 Hz, 2CH of Ar), 7.45 (1H, t, 3JHH¼7.2 Hz, CH of Ar), 7.50 (2H,
3
3
t, JHH¼7.6 Hz, 2CH of Ar), 7.65 (1H, t, JHH¼7.4 Hz, CH of Ar), 7.84
(2H, d, 3JHH¼7.2 Hz, 2CH of Ar), 8.02 (2H, d, 3JHH¼7.2 Hz, 2CH of Ar),
11.04 (1H, s, OH). 13C NMR (125.75 MHz, CDCl3): dC¼48.4 (OCH3),
55.3 (CH2N), 91.2 (COH), 114.2 (2CH of Ar), 125.4 (C]CH), 127.2
(2CH of Ar), 128.3 (2CH of Ar), 128. 9 (2CH of Ar), 129.1 (2CH of Ar),
129.4 (CipsoeCH2N), 130.2 (2CH of Ar), 131.4 (CH of Ar), 134.6 (CH of
Ar), 134.7 (CipsoeOH), 139.4 (CipsoeCO), 159.3 (CipsoeOMe), 160.5
(C]CH), 190.1 (CO), 191.7 (CS).
4.2.13. 2-(3-Benzyl-4-hydroxy-4-phenyl-2-thioxo-1,3-thiazolan-5-
yliden)-1-phenyl-1-ethanone (6d). Pale yellow powder, mp
180e182 ꢁC, 0.22 g, yield: 54%. Rf (12% EtOAc/n-hexane): 0.32; IR
(KBr) (nmax, cmꢀ1): 3431 (OH), 1651 (C]O), 1577 (C]C), 1560 and
1447 (Ar), 1046 (C]S). Anal. Calcd for C24H19NO2S2 (417.54): C,
69.04; H, 4.59; N, 3.35%. Found: C, 69.06; H, 4.62; N, 3.34%. MS (EI,
70 eV): m/z (%)¼315 (41), 296 (17), 250 (10), 155 (63), 140 (12), 91
(100), 65 (29), 51 (5). 1H NMR (500.13 MHz, CDCl3): dH¼4.39 (2H, d,
2JHH¼6.3 Hz, CH2N), 5.82 (1H, s, C]CH), 7.23e7.30 (5H, m, 5CH of
Ar), 7.39 (2H, t, 3JHH¼7.2 Hz, 2CH of Ar), 7.46 (1H, t, 3JHH¼7.1 Hz, CH
of Ar), 7.50 (2H, t, 3JHH¼7.5 Hz, 2CH of Ar), 7.65 (1H, t, 3JHH¼7.4 Hz,
4.2.10. 2-[4-Hydroxy-3-(4-methylbenzyl)-4-phenyl-2-thioxo-1,3-thia-
zolan-5-yliden]-1-phenyl-1-ethanone (6a). Yellow powder, mp
98e100 ꢁC, 0.26 g, yield: 60%. Rf (12% EtOAc/n-hexane): 0.34; IR (KBr)
(
nmax, cmꢀ1): 3325 (OH), 1668 (C]O), 1595 (C]C), 1552 and 1448
(Ar), 1070 (C]S). Anal. Calcd for C25H21NO2S2 (431.56): C, 69.58; H,
4.90; N, 3.25%. Found: C, 69.61; H, 4.93; N, 3.26%. MS (EI, 70 eV): m/z
(%)¼357 (8), 356 (17), 355 (50), 250 (31), 235 (14),146 (21),105 (100),
91 (42), 77 (38), 51 (31). 1H NMR (500.13 MHz, CDCl3): dH¼2.30 (3H,
s, Me), 4.35 (2H, d, 2JHH¼6.0 Hz, CH2N), 5.81 (1H, s, C]CH), 7.08 (2H,
d, 3JHH¼7.9 Hz, 2CH of Ar), 7.13 (2H, d, 3JHH¼7.9 Hz, 2CH of Ar), 7.39
(2H, t, 3JHH¼7.2 Hz, 2CH of Ar), 7.45 (1H, t, 3JHH¼7.2 Hz, CH of Ar), 7.50
(2H, t, 3JHH¼7.7 Hz, 2CH of Ar), 7.65 (1H, t, 3JHH¼7.4 Hz, CH of Ar), 7.85
(2H, d, 3JHH¼7.1 Hz, 2CH of Ar), 8.02 (2H, d, 3JHH¼7.1 Hz, 2CH of Ar),
11.08 (1H, s, OH). 13C NMR (125.75 MHz, CDCl3): dC¼21.0 (CH3), 48.7
(CH2N), 91.2 (COH), 127.2 (C]CH), 127.2 (2CH of Ar), 127.7 (2CH of
Ar),128.3 (2CH of Ar),128.9 (2CH of Ar),129.4 (2CH of Ar),130.2 (2CH
of Ar), 131.4 (CH of Ar), 134.2 (CipsoeMe), 134.6 (CH of Ph), 134.7
(CipsoeCOH), 137.5 (CipsoeCO), 139.5 (CipsoeCH2N), 1160.5 (C]CH),
190.1 (CO), 191.7 (CS).
3
CH of Ar), 7.83 (2H, d, JHH¼8.2 Hz, 2CH of Ar), 8.02 (2H, d,
3JHH¼8.01 Hz, 2CH of Ar), 11.12 (1H, s, OH). 13C NMR (125.75 MHz,
CDCl3): dC¼48.8 (CH2N), 91.3 (COH), 127.1 (C]CH), 127.6 (2CH of
Ar), 127.7 (2CH of Ar), 128.3 (2CH of Ar), 128. 7 (2CH of Ar), 128.8
(2CH of Ar), 130.1 (2CH of Ar), 131.3 (CH of Ar), 134.5 (CipsoeCH2N),
134.6 (CH of Ar), 137.2 (CipsoeOH), 139.3 (CipsoeCO), 160.4 (C]CH),
190.1 (CO), 191.6 (CS).
4.2.14. 2-[4-Hydroxy-4-phenyl-3-(1-phenylethyl)-2-thioxo-1,3-
thiazolan-5-yliden]-1-phenyl-1-ethanone (6e). Pale yellow pow-
der, mp 124e126 ꢁC, 0.2 g, yield: 46%. Rf (12% EtOAc/n-hexane):
0.33; IR (KBr) (nmax, cmꢀ1): 3438 (OH), 1670 (C]O), 1570 (C]C),
1565 and 1440 (Ar), 1056 (C]S). Anal. Calcd for C25H21NO2S2
(431.56): C, 69.58; H, 4.90; N, 3.25%. Found: C, 69.61; H, 4.91; N,
3.28%. MS (EI, 70 eV): m/z (%)¼236 (24),130 (12),105 (47),102 (100),
77 (38), 51 (7). 1H NMR (500.13 MHz, CDCl3): dH¼1.60 (1H, d,
3JHH¼6.6 Hz, CHCH3), 4.61e4.67 (1H, m, CHCH3), 5.76 (1H, s, C]
CH), 7.14 (1H, t, 3JHH¼6.7 Hz, CH of Ar), 7.17e7.22 (4H, m, 4CH of Ar),
4.2.11. 2-[3-(4-Chlorobenzyl)4-hydroxy-4-phenyl-2-thioxo-1,3-thia-
zolan-5-yliden]-1-phenyl-1-ethanone (6b). Pale yellow powder, mp
70e72 ꢁC, 0.24 g, yield: 54%. Rf (12% EtOAc/n-hexane): 0.31; IR (KBr)
(
nmax, cmꢀ1): 3300 (OH), 1671 (C]O), 1596 (C]C), 1565 and 1436
3
(Ar),1044 (C]S). Anal. Calcd for C24H18ClNO2S2 (451.98): C, 63.78; H,
4.01; N, 3.10%. Found: C, 63.79; H, 4.04; N, 3.11%. MS (EI, 70 eV): m/z
(%)¼453 (Mþþ2, 5), 451 (Mþ, 16), 423 (10), 377(15), 368 (22), 313
(26), 299 (26), 264 (33), 236 (47),125 (90),105 (100), 77 (75), 67 (47),
57 (29), 43 (33). 1H NMR (500.13 MHz, CDCl3): dH¼4.50 (2H, d,
2JHH¼6.5 Hz, CH2N), 5.85 (1H, s, C]CH), 7.20 (2H, d, 3JHH¼7.3 Hz, 2CH
of Ar), 7.31 (2H, d, 3JHH¼7.3 Hz, 2CH of Ar), 7.39 (2H, t, 3JHH¼7.2 Hz,
2CH of Ar), 7.43 (1H, t, 3JHH¼7.5 Hz, CH of Ar), 7.49 (2H, t, 3JHH¼7.9 Hz,
2CH of Ar), 7.65 (1H, t, 3JHH¼7.4 Hz, CH of Ar), 7.85 (2H, d, 3JHH¼7.2 Hz,
7.38e7041 (4H, m, 4CH of Ar), 7.46 (1H, t, JHH¼7.0 Hz, CH of Ar),
7.57 (1H, t, 3JHH¼7.4Hz, CH of Ar), 7.86 (4H, d, 3JHH¼7.1 Hz, 4CH of
Ar), 11.26 (1H, s, OH). 13C NMR (125.75 MHz, CDCl3): dC¼24.2
(CHCH3), 54.3 (CHCH3), 91.4 (COH),126.2 (C]CH),127.1 (2CH of Ar),
127.2 (2CH of Ar), 128.3 (2CH of Ar), 128. 5 (2CH of Ar), 128.6 (2CH
of Ar), 130.0 (2CH of Ar), 131.3 (CH of Ar), 134.3 (CH of Ar), 134.5
(CipsoeCH2N), 139.3 (CipsoeOH), 143.1 (CipsoeCO), 159.9 (C]CH),
190.0 (CO), 191.6 (CS).
2CH of Ar), 8.03 (2H, d, 3JHH¼7.2 Hz, 2CH of Ar), 11.10 (1H, s, OH). 13
C
4.2.15. 2-(4-Hydroxy-3-methyl-4-phenyl-2-thioxo-1,3-thiazolan-5-
yliden)-1-phenyl-1-ethanone (6f). Orange oil, 0.09 g, yield: 27%. Rf
(12% EtOAc/n-hexane): 0.25; IR (KBr) (nmax, cmꢀ1): 3430 (OH), 1627
(C]O), 1593 (C]C), 1537 and 1443 (Ar), 1053 (C]S). Anal. Calcd for
C18H15NO2S2 (341.44): C, 63.32; H, 4.43; N, 4.10%. Found: C, 63.36;
H, 4.45; N, 4.11%. MS (EI, 70 eV): m/z (%)¼341 (5), 266 (73), 248 (19),
236 (7), 160 (95), 147 (17), 118 (12), 105 (100), 77 (63), 69 (8), 51
(27). 1H NMR (500.1 MHz, CDCl3): dH¼2.90 (3H, s, NMe), 5.74 (1H, s,
C]CH), 7.37 (2H, t, 3JHH¼7.8 Hz, 2CH of Ar), 7.41 (1H, t, 3JHH¼7.3 Hz,
NMR (125.75 MHz, CDCl3): dC¼46.7 (CH2N), 91.8 (COH), 127.1 (C]
CH),127.3 (2CH of Ar),127.9 (2CHof Ar),128.4 (2CH of Ar),128. 9 (2CH
of Ar), 129.6 (2CH of Ar), 130.2 (2CH of Ar), 131.5 (CH of Ar), 133.5
(CipsoeCl),134.7 (CH of Ph),134.7 (CipsoeCOH),135.0 (CipsoeCO),139.4
(CipsoeCH2N), 160.3 (C]CH), 190.3 (CO), 191.63 (CS).
4.2.12. 2-[4-Hydroxy-3-(4-methoxybenzyl)-4-phenyl-2-thioxo-1,3-
thiazolan-5-yliden]-1-phenyl-1-ethanone (6c). Pale yellow powder,
mp 133e135 ꢁC, 0.28 g, yield: 62%. Rf (12% EtOAc/n-hexane): 0.15; IR
3
CH of Ar), 7.54 (2H, t, JHH¼7.5 Hz, 2CH of Ar), 7.67 (1H, t,

1714
A. Alizadeh et al. / Tetrahedron 67 (2011) 1709e1715
3JHH¼7.3 Hz, CH of Ar), 7.81 (2H, d, 3JHH¼7.6 Hz, 2CH of Ar), 8.04 (2H,
137.4 (CipsoeCO), 141.8 (CipsoeCH2N), 145.9 (CipsoeMe), 160.6 (C]
CH), 189.9 (CO), 191.4 (CS).
3
d, JHH¼7.8 Hz, 2CH of Ar), 10.71 (1H, s, OH). 13C NMR (125.7 MHz,
CDCl3): dC¼31.5 (NCH3), 90.6 (COH), 125.1 (C]CH), 127.2 (2CH of
Ar), 128.3 (2CH of Ar), 129.1 (2CH of Ar), 130.1 (2CH of Ar), 131.3 (CH
of Ar),134.5 (CipsoeOH),134.9 (CH of Ar),139.5 (CipsoeCO),161.8 (C]
CH), 188.3 (CO), 190.2 (CS).
4.2.19. 1-(2-{[(Isopropylamino)carbotioyl]sulfanyl}-4-oxo-4-phenyl-
2-butenoyl)benzene (9a). Yellow powder, mp 168e170 ꢁC, 0.22 g,
yield: 61%. Rf (12% EtOAc/n-hexane): 0.17; IR (KBr) (nmax, cmꢀ1):
3410 (NH), 1627 and 1604 (C]O), 1578 (C]C), 1532 and 1445 (Ar),
1069 (C]S). Anal. Calcd for C20H19NO2S2 (369.49): C, 65.01; H, 5.18;
N, 3.79%. Found: C, 65.06; H, 5.22; N, 3.80%. MS (EI, 70 eV): m/z (%)¼
361 (5), 300 (12), 268 (15), 230 (21), 149 (37), 113 (46), 105 (56), 86
(27), 77 (71), 58 (44), 43 (100). 1H NMR (500.13 MHz, CDCl3):
4.2.16. 2-((4-Hydroxy)-4-phenyl-3-propyl-2-thioxo-1,3-thiazolan-5-
yliden)-1-phenyl-1-ethanone (6g). Yellow powder, mp 100e102 ꢁC,
0.25 g, yield: 69%. Rf (12% EtOAc/n-hexane): 0.42; IR (KBr) (nmax
,
cmꢀ1): 3195 (OH), 1677 (C]O), 1595 (C]C), 1553 and 1447 (Ar),
1056 (C]S). Anal. Calcd for C20H19NO2S2 (369.49): C, 65.01; H, 5.18;
N, 3.79%. Found: C, 65.06; H, 5.22; N, 3.81%. MS (EI, 70 eV): m/z (%)¼
369 (Mþ, 19), 341 (7), 269 (33), 236 (11), 163 (76), 105 (100), 85 (13),
77 (64), 51 (13), 43 (8). 1H NMR (500.13 MHz, CDCl3): dH¼0.93 (3H,
3
dH¼0.98 (3H, t, JHH¼7.2 Hz, NCH2CH2), 3.45 (1H, heptet,
3
3JHH¼6.8 Hz, NCH2CH3), 3.65 (1H, heptet, JHH¼6.8 Hz, NCH2CH3),
6.26 (1H, s, C]CH), 7.06 (2H, d, 3JHH¼7.9 Hz, 2CH of Ar), 7.13 (2H, t,
3JHH¼7.4 Hz, 2CH of Ar), 7.30 (1H, t, 3JHH¼7.3 Hz, CH of Ar), 7.36 (1H,
3
3
3
3
t, JHH¼7.4 Hz, NCH2CH2CH3), 1.61 (2H, t, JHH¼7.2 Hz,
NCH2CH2CH3), 3.13 (2H, q, 3JHH¼6.7 Hz, NCH2CH2CH3), 5.73 (1H, s,
C]CH), 7.37 (2H, t, 3JHH¼7.7 Hz, 2CH of Ar), 7.42 (1H, t, 3JHH¼7.2 Hz,
t, JHH¼7.2 Hz, CH of Ar), 7.41 (2H, t, JHH¼7.5 Hz, 2CH of Ar), 7.70
(2H, d, JHH¼7.5 Hz, 2CH of Ar), 10.95 (1H, s, NH). 13C NMR
3
(125.75 MHz, CDCl3): dC¼15.2 (NCH2CH3), 40.1 (NCH2CH3), 124.6
(C]CH), 127.6 (2CH of Ar), 128.1 (2CH of Ar), 128.2 (2CH of Ar),
128.9 (2CH of Ar),131.7 (CH of Ar),133.2 (CH of Ar),136.8 (CipsoeCO),
138.8 (CipsoeCO), 153.9 (C]CH), 177.5 (CO), 192.4 (CO), 194.6 (CS).
3
CH of Ar), 7.53 (2H, t, JHH¼7.7 Hz, 2CH of Ar), 7.66 (1H, t,
3JHH¼7.4 Hz, CH of Ar), 7.83 (2H, d, 3JHH¼7.2 Hz, 2CH of Ar), 8.06 (2H,
d, 3JHH¼7.4 Hz, 2CH of Ar), 10.89 (1H, s, OH). 13C NMR (125.75 MHz,
CDCl3): dC¼11.1 (NCH2CH2CH3), 23.9 (NCH2CH2CH3), 47.0
(NCH2CH2CH3), 90.3 (COH), 125.4 (C]CH), 127.1 (2CH of Ar), 128.3
(2CH of Ar), 129.0 (2CH of Ar), 130.1 (2CH of Ar), 131.3 (CH of Ar),
134.6 (CipsoeOH), 134.8 (CH of Ar), 139.5 (CipsoeCO), 161.4 (C]CH),
190.0 (CO), 191.7 (CS).
4.2.20. 1-(2-{[(Allylamino)carbotioyl]sulfanyl}-4-oxo-4-phenyl-2-
butenoyl)benzene (9b). Yellow powder, mp 164e166 ꢁC, 0.27 g,
yield: 75%. Rf (12% EtOAc/n-hexane): 0.20; IR (KBr) (nmax, cmꢀ1):
3320 (NH), 1633 and 1599 (C]O), 1577 (C]C), 1534 and 1445 (Ar),
1068 (C]S). Anal. Calcd for C20H17NO2S2 (367.48): C, 65.37; H, 4.66;
N, 3.81%. Found: C, 65.39; H, 4.68; N, 3.83%. MS (EI, 70 eV): m/z (%)¼
279 (15), 255 (12), 186 (48), 167 (57),149 (81), 135 (61),113 (22),105
(43), 84 (35), 77 (51), 71 (30), 57 (78), 43 (100). 1H NMR
(500.13 MHz, CDCl3): dH¼4.02e4.05 (1H, m, NCH2CH]CH2),
4.19e4.22 (1H, m, NCH2CH]CH2), 5.06e5.11 (2H, m, NCH2CH]
CH2), 5.50e5.55 (1H, m, NCH2CH]CH2), 6.28 (1H, s, C]CH), 7.00
(2H, d, 3JHH¼7.3 Hz, 2CH of Ar), 7.15 (2H, t, 3JHH¼7.5 Hz, 2CH of Ar),
7.29 (1H, t, 3JHH¼7.3 Hz, CH of Ar), 7.36 (1H, t, 3JHH¼7.2 Hz, CH of Ar),
7.41 (2H, t, 3JHH¼7.5 Hz, 2CH of Ar), 7.69 (2H, d, 3JHH¼7.2 Hz, 2CH of
Ar), 10.92 (1H, s, NH). 13C NMR (125.75 MHz, CDCl3): dC¼47.4
(NCH2CH]CH2), 118.1 (NCH2CH]CH2), 126.9 (C]CH), 127.5 (2CH
of Ar), 127.6 (2CH of Ar), 128.1 (2CH of Ar), 129.0 (2CH of Ar), 129.9
(NCH2CH]CH2), 131.8 (CH of Ar), 133.2 (CH of Ar), 136.8 (CipsoeCO),
138.9 (CipsoeCO), 153.6 (C]CH), 177.2 (CO), 192.6 (CO), 194.7 (CS).
4.2.17. 2-(4-Hydroxy-3-isobutyl-4-phenyl-2-thioxo-1,3-thiazolan-
5-yliden)-1-phenyl-1-ethanone (6h). Yellow oil, 0.18 g, yield: 47%.
Rf (12% EtOAc/n-hexane): 0.50; IR (KBr) (nmax, cmꢀ1): 3440 (OH),
1676 (C]O), 1595 (C]C), 1553 and 1462 (Ar), 1051 (C]S). Anal.
Calcd for C21H21NO2S2 (383.52): C, 65.77; H, 5.52; N, 3.65%. Found:
C, 65.85; H, 5.54; N, 3.67%. MS (EI, 70 eV): m/z (%)¼338 (5), 308
(25), 307 (54), 264 (47), 202 (34), 146 (100), 128 (11), 105 (39), 91
(15), 77 (29), 57 (18). 1H NMR (500.13 MHz, CDCl3): dH¼0.89 (3H, d,
3
3JHH¼6.5 Hz, NCH2CH(CH3)2), 0.92 (3H, d, JHH¼6.6 Hz, NCH2CH
(CH3)2), 1.81e1.85 (1H, m, NCH2CH(CH3)2), 3.01 (2H, t,
3JHH¼6.5 Hz, NCH2CH(CH3)2), 5.65 (1H, s, C]CH), 7.26 (2H, t,
3
3JHH¼7.6 Hz, 2CH of Ar), 7.37 (1H, t, JHH¼7.4 Hz, CH of Ar), 7.55
(2H, t, 3JHH¼7.5 Hz, 2CH of Ar), 7.68 (1H, t, 3JHH¼7.3 Hz, CH of Ar),
7.76 (2H, d, 3JHH¼8.1 Hz, 2CH of Ar), 8.06 (2H, d, 3JHH¼8.1 Hz, 2CH
of Ar), 10.91 (1H, s, OH). 13C NMR (125.7 MHz, CDCl3): dC¼19.9
(NCH2CH(CH3)2), 29.4 (NCH2CH(CH3)2), 53.0 (NCH2CH(CH3)2),
90.3 (COH), 125.3 (C]CH), 127.2 (2CH of Ar), 128.3 (2CH of Ar),
129.1 (2CH of Ar), 130.1 (2CH of Ar), 131.3 (CH of Ar), 134.5
(CipsoeOH), 134.9 (CH of Ar), 139.4 (CipsoeCO), 162.2 (C]CH), 190.1
(CO), 191.6 (CS).
4.2.21. 1-[4-Oxo-4-phenyl-2-({[(1-phenylethyl)amino]carbothioyl}
sulfanyl)-2-butenoyl]benzene (9c). Yellow powder, mp 156e158 ꢁC,
0.19 g, yield: 44%. Rf (12% EtOAc/n-hexane): 0.29; IR (KBr) (nmax
,
cmꢀ1): 3360 (NH), 1664 and 1612 (C]O), 1578 (C]C), 1530 and
1444 (Ar), 1066 (C]S). Anal. Calcd for C25H21NO2S2 (431.56): C,
69.58; H, 4.90; N, 3.25%. Found: C, 69.63; H, 4.94; N, 3.27%. MS (EI,
70 eV): m/z (%)¼255 (9), 225 (10), 202 (7), 167 (16), 149 (19), 135
(37),122 (28),105 (82), 91 (39), 84 (31), 77 (100), 69 (27), 57 (38), 51
(58), 43 (95), 41 (87). 1H NMR (500.13 MHz, CDCl3): dH¼1.74 (3H, d,
3JHH¼6.7 Hz, CHCH3), 5.30e5.33 (1H, CHCH3), 6.66 (1H, s, C]CH),
6.88e6.91 (2H, m, 2CH of Ar), 7.06e7.16 (5H, m, 2CH of Ar),
7.22e7.28 (2H, m, 2CH of Ar), 7.31e7.40 (4H, m, 4CH of Ar), 7.46 (2H,
d, 3JHH¼7.4 Hz, 2CH of Ar), 11.33 (1H, d, 3JHH¼10.3 Hz, NH). 13C NMR
(125.75 MHz, CDCl3): dC¼21.7 (CHCH3), 54.5 (CHCH3), 125.7 (C]
CH),126.3 (CH of Ar),127.5 (2CH of Ar),127.6 (2CH of Ar),128.0 (2CH
of Ar), 128.4 (2CH of Ar), 131.7 (CH of Ar), 133.1 (CH of Ar), 136.8
(CipsoeCO), 139.0 (CipsoeCO), 141.5 (CipsoeNCH), 153.6 (C]CH), 175.7
(CO), 192.4 (CO), 194.2 (CS).
4.2.18. 2-[4-Hydroxy-3-(4-methylbenzyl)-4-(4-methylphenyl)-2-thi-
oxo-1,3-thiazolan-5-yliden]-1-(4-methylphenyl)-1-ethanone
(6i). Yellow oil, 0.25 g, yield: 54%. Rf (12% EtOAc/n-hexane): 0.30; IR
(KBr) (nmax, cmꢀ1): 3426 (OH), 1669 (C]O), 1572 (C]C), 1550 and
1451 (Ar), 1177 (C]S). Anal. Calcd for C27H25NO2S2 (459.62): C,
70.56; H, 5.48; N, 3.05%. Found: C, 70.58; H, 5.45; N, 3.09%. MS (EI,
70 eV): m/z (%)¼457 (Mþꢀ2, 7), 443 (18), 383 (32), 366 (7), 264
(28), 195 (4), 177 (9), 119 (100), 105 (95), 91 (26), 77 (5), 65 (10). 1H
NMR (500.13 MHz, CDCl3): dH¼2.30 (3H, s, Me), 2.37 (3H, s, Me),
2
2.45 (3H, s, Me), 4.32 (2H, d, JHH¼6.2 Hz, CH2N), 5.78 (1H, s, C]
3
3
CH), 7.08 (2H, d, JHH¼7.9 Hz, 2CH of Ar), 7.13 (2H, d, JHH¼8.0 Hz,
3
2CH of Ar), 7.19 (2H, d, JHH¼8.0 Hz, 2CH of Ar), 7.30 (2H, d,
3JHH¼8.0 Hz, 2CH of Ar), 7.75 (2H, d, JHH¼8.2 Hz, 2CH of Ar), 7.93
3
(2H, d, JHH¼8.2 Hz, 2CH of Ar), 11.02 (1H, br, OH). 13C NMR
3
(125.75 MHz, CDCl3): dC¼21.0 (CH3), 21.4 (CH3), 21.9 (CH3), 48.8
(CH2N), 90.9 (COH), 113.2 (C]CH), 127.2 (2CH of Ar), 127.6 (2CH of
Ar), 129.0 (2CH of Ar), 129.4 (2CH of Ar), 129.6 (2CH of Ar), 130.3
(2CH of Ar), 132.3 (CipsoeMe), 134.3 (CipsoeCOH), 136.8 (CipsoeMe),
Supplementary data
Supplementary data related to this article can be found online at
doi:10.1016/j.tet.2010.12.055.

A. Alizadeh et al. / Tetrahedron 67 (2011) 1709e1715
1715
2414; (c) Alizadeh, A.; Zohreh, N. Synthesis 2008, 429; (d) Alizadeh, A.; Zoh-
reh, N.; Rostamnia, S. Tetrahedron 2007, 63, 8083.
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