New functionalized 8-hydroxyquinoline-5-sulfonic acid mesoporous silica (HQS-SBA-15) as an efficient catalyst for the synthesis of 2-thiohydantoin derivatives

Article abstract of DOI:10.1016/j.tet.2016.07.034

Mesoporous silica SBA-15 functionalized with 8-hydroxyquinoline-5-sulfonic acid (HQS-SBA-15) was used as a new recyclable nanocatalyst for the one-pot synthesis of 2-thiohydantoin derivatives under solvent-free conditions. The catalyst exhibited excellent recyclability at least for 3 times with a high catalytic activity.

Full text of DOI:10.1016/j.tet.2016.07.034

Accepted Manuscript
New functionalized 8-hydroxyquinoline-5-sulfonic acid mesoporous silica (HQS-
SBA-15) as an efficient catalyst for the synthesis of 2-thiohydantoin derivatives
Vaezeh Fathi Vavsari, Ghodsi Mohammadi Ziarani, Saeed Balalaie, Arezoo Latifi,
Mehdi Karimi, Alireza Badiei
PII:
S0040-4020(16)30657-3
10.1016/j.tet.2016.07.034
TET 27930
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 12 April 2016
Revised Date: 3 July 2016
Accepted Date: 7 July 2016
Please cite this article as: Vavsari VF, Ziarani GM, Balalaie S, Latifi A, Karimi M, Badiei A, New
functionalized 8-hydroxyquinoline-5-sulfonic acid mesoporous silica (HQS-SBA-15) as an efficient
catalyst for the synthesis of 2-thiohydantoin derivatives, Tetrahedron (2016), doi: 10.1016/
j.tet.2016.07.034.
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ACCEPTED MANUSCRIPT
Graphical abstract
New functionalized 8-hydroxyquinoline-5-sulfonic acid mesoporous silica
(HQS-SBA-15) as an efficient catalyst for the synthesis of 2-thiohydantoin
derivatives
Vaezeh Fathi Vavsari, Ghodsi Mohammadi Ziarani, Saeed Balalaie*, Arezoo Latifi, Mehdi
Karimi, Alireza Badiei

ACCEPTED MANUSCRIPT
New functionalized 8-hydroxyquinoline-5-sulfonic acid mesoporous
silica (HQS-SBA-15) as an efficient catalyst for the synthesis of 2-
thiohydantoin derivatives
Vaezeh Fathi Vavsari1, Ghodsi Mohammadi Ziarani1, Saeed Balalaie*2, 3, Arezoo Latifi2,
Mehdi Karimi4, Alireza Badiei4
1Department of Chemistry, Alzahra University, Tehran, 1993891176, Iran
2Peptide Chemistry Research Center, K. N. Toosi University of Technology, 15875-4416, Tehran,
Iran, E-mail: balalaie@kntu.ac.ir , Tel:+98-21-23064226, Fax: +98-21-22889403
3Medical Biology Research Center, Kermanshah University of Medical Sciences, Kermanshah,
Iran
4School of Chemistry, College of Science, University of Tehran, Tehran, 14155-6455, Iran
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Abstract
Mesoporous silica SBA-15 functionalized with 8-hydroxyquinoline-5-sulfonic acid
(HQS-SBA-15) was used as a new recyclable nanocatalyst for the one-pot synthesis of 2-
thiohydantoin derivatives under solvent-free conditions. The catalyst exhibited excellent
recyclability at least for 3 times with a high catalytic activity.
Keywords: SBA-15, Mesoporous Silica, 8-hydroxyquinoline-5-sulfonic acid, 2-
thiohydantoin
Dedicated to Prof. Majid Jafarian on the occasion of his birthday
2

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Introduction
Acidic reaction conditions are essential to perform some of the named organic reactions
such as condensations and esterifications, Aldol Reactions, alcohol dehydrodimerizations
and some of multicomponent reactions.1 Considering the drawbacks of homogeneous
acid catalysts including difficult separations, need for neutralizing the chemical wastes,
reactor corrosion, and so on; preparation and application of solid acid catalysts have long
been a subject of immense interest.2
Santa Barbara Amorphous (SBA-15)3, a new nonporous silica with a hexagonal structure,
large pore size, high surface area, and high thermal stability, opens a new window
towards promising solid acids. Up to now, SBA-15 was used in different fields of study
for example as a support for the delivery of natural and synthetic drugs.4 However,
integration of the acidic functional groups (e.g., -SO3H) into the SBA-15’s pores has only
been recently explored.5 Some studies have been reported for applying several types of
sulfonic acid functionalized SBA-15 (SBA-Pr-SO3H) in chemical transformations. For
example, it has been used in the synthesis of isoindigo derivatives,6 the Pechmann
reaction7 and one-pot synthesis of spiroquinazolinones.8
Immobilization of acidic compounds onto the pores of SBA-15 is an interesting demand
in the field of solid phase organic synthesis due to its higher acidic character.
Development of heterocycles synthesis is one of the most important areas in organic
chemistry since these compounds exhibit different biological activities. Among them,
anomeric spironucleosides9 have been identified to display a wide range of biological
activities (Fig. 1). For example, phenytoin is an antiarrhythmic, anticonvulsant,
antineuralgic, and trigeminal neuralgia agent and skeletal muscle relaxant.10 It was
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reported that glucopyranosylidene-spiro thiohydantoin is as an efficient inhibitor of
muscle and liver glycoen phosphorylases.11
Fig. 1. Examples of medicinally interesting hydantoin analogs.
Fused thiohydantoin derivatives also exhibit weak antioxidant activity.12 Though,
hydantoin and thiohydantoin derivatives have diverse therapeutic applications, the
biological mechanisms of these compounds have not been fully elucidated. So far,
different types of thiohydantoin derivatives were obtained by intermolecular reaction of
N-alkyl amines and thiocyanato sugars,13 or intramolecular reaction of amino acids (thio)
urea14. Additionally, microwave irradiation15 and/or the use of polyethyleneglycol as
solvent in the presence of K2CO316 were successful methods for this aim. However, these
methods are time-consuming and require a large amount of toxic solvents, and reagents.
Thus, developing a more green and efficient method for the synthesis of these
compounds, from readily available reagents, remains one of the major challenges in
organic synthesis. Hence, for the first time the present work illustrates the immobilization
of 8-hydroxyquinoline-5-sulphonic acid groups onto the pores of SBA-15 (HQS-SBA-15)
(Scheme 1) for its use as recyclable solid acid catalyst for the synthesis of 2-
thiohydantoin derivatives 6a-i through the reaction of amino acid methylesters and
isothiocyanates in solvent-free reaction conditions (Scheme 2).
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OH
OH
OH
I
I
OH
O
O
S
Si
O
O
O
Toluene
Si
OEt
OEt
EtO
N
Reflux, 24 h
OH
I-SBA-15
2
SBA-15
1
O
S
OH
O
O
O
Methanol/Water
Et3N
Si
O
N
O
Reflux, 24 h
HQS-SBA-15
Scheme 1. Schematic process for preparation of the HQS-SBA-15
Scheme 2. HQS-SBA-15 as a heterogeneous catalyst for the synthesis of 2-thiohydantoin
derivatives
Results and Discussion
At first the SBA-15 was prepared according to the reported method in the literature.17
Then, the iodo-functionalized SBA-15 was reacted with 8-hydroxyquinoline-5-sulphonic
acid 2 to prepare the (HQS-SBA-15) as a new silica-based catalyst. TEM, FT-IR, TGA,
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XRD and N2 adsorption-desorption isotherms were used to characterize the prepared
HQS-SBA-15.
In FT-IR spectra of SBA-15, I-SBA-15 and HQS-SBA-15 (Fig. 2), a series of
characteristic bands located around 800, 960, 1100, 1640 and 3434 cm-1 are related to the
symmetric stretching vibrations of Si-O, symmetric stretching vibration of Si-OH,
asymmetric stretching vibrations of Si-O-Si, physically absorbed water molecules, and
stretching vibrations of -OH, respectively. The new appeared band around 2890 cm-1 in I-
SBA-15 spectrum is due to the stretching vibrations of the -CH2- units of the propyl
chains while in HQS-SBA-15, two new bands around 1405 and 1475 cm-1 are related to
the C=N and C=C aromatic stretching vibrations, respectively.
Fig. 2. FT-IR (KBr, cm-1) pattern of (a) SBA-15, (b) I-SBA and (c) HQS-SBA-15
In order to analyze the structure of SBA-15 after functionalization steps, XRD patterns of
original SBA-15 and HQS-SBA-15 were obtained. Generally, mesoporous silica
materials exhibit three characteristic diffractions including a high intensity diffraction
around 2θ = 1º originated from the (100) plane and two weak diffractions originated from
the (110) and (200) planes indicating the long-range periodic order and two-dimensional
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hexagonal (p6mm) mesostructured, respectively. As can be seen in Fig. 3 (a,b), both
SBA-15 and HQS-SBA-15 samples showed these diffractions confirming the original
structure of SBA-15 was preserved after functionalization steps. However, the decrease in
the intensities of the 100, 110 and 200 planes in HQS-SBA-15 was due to the
incorporation of organic moieties onto the pore walls which leads to a partial lowering of
the crystallinity. TEM image (inset of Fig. 3) of SBA-15 particles showed the uniform
channels, which were open along the particles.
Fig. 3. XRD patterns of (a) SBA-15 and (b) HQS-SBA-15 (inset: TEM image of SBA-15)
For further insight into the functionalized SBA-15 structure, N2 adsorption-desorption
technique was used. The HQS-SBA-15 isotherm showed a type IV isotherm based on
standard IUPAC categories with a H1 type hysteresis loop indicating ordered structure of
the mesoporous materials (Fig. 4). The pore-size distribution has its maximum at 3.5 nm,
as shown in BJH pore size distribution curve of HQS-SBA-15 (the inset of Fig. 4).
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Fig. 4. N2 adsorption–desorption isotherms for HQS-SBA-15 (inset: BJH pore size distributions)
Thermogravimetric analysis was conducted to assess the amount of the attached organic
moieties. For both samples (Fig. 5), the weight loss up to 150 °C can be related to the
elimination of trapped water molecules within the pores of the SBA-15 channels.
°
Moreover, a major weight loss within the range of 150−600 C were due to the
degradation of organic moieties which were estimated to be about 8% and 18% for I-
SBA-15 and HQS-SBA-15 samples, respectively. Therefore, the amount of the attached
propyl chains and 8-hydroxyquinoline-5-sulphonic acid groups was estimated to be 0.48
and 0.45 mmol.g-1, respectively.
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Fig. 5. Thermogravimetric analysis of (a) I-SBA-15 and (b) HQS-SBA-15
To optimize the reaction conditions, methyl thiazolidine-4-carboxylate 4b (1.0 mmol),
and phenylisothiocyanate 5a (1.0 mmol) were used as the model reactants under solvent-
free conditions (Scheme 3).
Scheme 3. Model reaction to optimize solvent-free synthesis of 2-thiohydantoin 6a
To optimize the reaction conditions, the effect of solvent was studied as shown in Table
1. Accordingly, among the tested conditions, solvent-free condition was the best which
gave the product with the highest yield in the shortest reaction time. Additionally, the
effect of catalyst in this reaction was investigated (Table 1, Entry 6), it was found that the
efficiency of this catalyst is due to the strong acidic feature of HQS anchored onto the
pores of the modified SBA-15 as well as its high surface area (Fig. 6).
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Table 1 Study of model reaction in different conditions
Time
(h)
Entry
Solvent
Catalyst
Condition
Yield (%)
MeOH
H2O
HSQ-SBA-15
HSQ-SBA-15
HSQ-SBA-15
HSQ-SBA-15
HSQ-SBA-15
-
6
6
6
6
1
6
6
Reflux
Reflux
Reflux
Reflux
60 °C
60 °C
rt.
80
45
75
75
95
-
1
2
3
4
5
6
7
EtOH
CF3CH2OH
solvent-free
solvent-free
solvent-free
HSQ-SBA-15
65
Following the obtained results, we explored the scope of our methodology using a variety
of α-amino esters 4a-b and isothiocyanates 5a-e (Table 2). There was a general difference
in the yield of products between the cyclic and non-cyclic α‒amino esters. That is, cyclic
αamino esters were relatively more active than the others which can be definitely
attributed to the closer functional groups (amine and ester) and leads to increasing the
rate of intramolecular reaction and reducing the reaction times.
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Table 2. Synthesis of 2-thiohydantoin derivatives in the presence of HSQ-SBA-15
Yield
(%)
Entry
1
α-Amino ester
Isothiocyanate
Products*
m.p. (°C)
97
168-170
80
185-188
2
89
91
95
140-144
206-209
139-141
3
4
5
87
83
171-174
225-228
6
7
O
OMe
NH2
4a
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O
75
91
198-200
198-200
8
9
OMe
NH2
4a
O
OMe
NH2
4a
*Reaction condition:
α-amino ester 4a-b (1.0 mmol) and isothiocyanate 5a-e (1.0 mmol) were
reacted using 0.02 g of catalyst for 1 h under solvent-free system at 60 °C.
The plausible mechanism is shown in Scheme 4. Because of the high surface area of the
acidic nanocatalyst, accompanied by the inherent Br nsted acidity of -SO3H, which is
Ø
capable of bonding with the N atom of thiocyanate moiety the reactants are absorbed
easily. Afterwards, nucleophilic addition of the α-amino ester (4a-b) to the activated
thiocyanate (5a-e) results in the formation of the intermediate 7. Subsequently, through
intramolecular cyclization, the product (6a-i) is formed. In the other words, ionic
intermediate (7) is generated inside the nanocatalyst because of the strong polarity of the
–SO3H groups.
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H+
Ar N C S
(5a-e)
Ar N C SH
O
S
O
H
S
O
O
O
O
O
N Ar
O
H
N
(6a-i)
Ar N C S
OMe
(4a-b)
O
O
S
O
O
H
Si
O
S
O
NH
SO3H
O
N
- MeOH
H
HQS-SBA-15
OH
N
OMe
O
NH
S
Ar
N
S
OMe
H+
NH
(7)
Ar
Scheme 4. A plausible mechanism for the synthesis of 2-thiohydantoinin the presence of HQS-
SBA-15.
The reusability of the catalyst was determined under optimized conditions for the
preparation of compound 6a. The process of recycling was performed three times and no
significant decrease in activity was observed. The yields for the four runs were found to
be 90, 83, 81, and 80 %, respectively. The results showed the catalyst was efficient
without any significant reduce the yield was collected effectively and the recovered
catalyst was used in subsequent runs without observation of any significant reduction
yield (Table 3).
Table 3: Reuse of HQS-SBA-15 for the synthesis of 6a.
Entry
Time (h)
Yield (%)
1
2
3
4
1
1
1
1
90
83
81
80
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Conclusion
In summary, a new sulfonic acid-based nanocatalyst was used as a solid Br
Ønsted acid for
the one-pot synthesis of 2-thiohydantoin derivatives under solvent-free conditions. This
heterogeneous catalyst has various advantages, such as: easy handling and recovery, high
recyclability and low amount use of the catalyst (0.02 g). Thus, a mild and green
approach for this reaction through the catalysis of HQS-SBA-15 was developed in this
paper.
Acknowledgment
We gratefully acknowledge the support of the Iran National Science Foundation (INSF),
and University of Alzahra for financial supports of this project.
Experimental
Commercially available chemicals were bought and used. Melting points were recorded
on an Electrothermal 9100 apparatus. The Fourier transform infrared spectroscopy (FT-
IR) spectra were recorded using an ABB FT-IR (FTLA 2000) on KBr plates. High
resolution mass spectra were recorded on Jeol-JMS-700 mass spectrometer. Nuclear
magnetic resonance (NMR) spectra were obtained through a BRUKER AVANCE DRX-
1
13
500 (for H NMR) and DRX-125 MHz (for C NMR) in CDCl3 using tetramethylsilane
(TMS) as an internal standard. Transmission electron microscopy (TEM) was performed
using a Zeiss EM900 instrument at an accelerating voltage of 80 kV. Low-angle X-ray
scattering measurements were performed by an X'Pert Pro MPD diffractometer using Cu
Ka radiation (λ = 1.5418 Ǻ). N2 adsorption-desorption isotherms were obtained using a
BELSORP-mini II instrument at liquid nitrogen temperature (-196 °C).
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Thermogravimetric analysis (TGA) was carried out using a TGA Q50 V6.3 Build 189
instrument from ambient temperature to 800 °C with a ramp rate of 10 °C min-1 in air.
Synthesis of HQS-SBA-15
SBA-15 was prepared according to our previous published procedure.17 3-(Iodopropyl)-
trimethoxysilane 1 (10 mmol) was slowly added to SBA-15 (2 g) dispersed in toluene
while vigorous stirring followed by refluxing for 24 h. Then, the resulted iodo-
functionalized SBA-15 (denoted as I-SBA-15) was filtered, washed with toluene and
dried overnight. Afterwards, a mixture of I-SBA-15 (1 g), 8-hydroxyquinoline-5-
sulphonic acid 2 (5 mmol in 100 mL of MeOH:H2O with a ratio of 3 : 1), and
triethylamine (10 mmol) was refluxed for 24 h. The final light yellow product (denoted as
HQS-SBA-15) was filtered, washed with an excess amount of ethanol and water and
dried overnight. The amount of the grafted propyl chains and HQS groups was estimated
to be ≈ 0.48 and 0.45 mmol.g.-1, respectively. Scheme 1 exhibits the overall synthetic
procedure of HQS-SBA-15.18
General Procedure for the synthesis of α-amino ester derivatives 4a-b
In a 50-mL round bottom flask, a solution of
L
-phenyl alanine 3a (826 mg, 5 mmol)
and/or -thiazolidine-4-carboxylic acid 3b (665 mg, 5 mmol) in MeOH (10 mL) was
L
stirred over a salty iced-water bath until the temperature reached to -10 °C, then followed
by slowly addition of thionyl chloride (SOCl2) (1.5 mL, 20 mmol). The reaction was
completed about 24 h, then, the solvent was evaporated under reduced pressure and the
obtained product was recrystallized in MeOH and Et2O.19
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General Procedure for the synthesis of 2-thiohydantoin derivatives 6a-i
To a mixture of α-amino ester 4a-b (1 mmol) and isothiocyanate 5a-e (1 mmol)
º
derivatives, HQS-SBA-15 (0.02 g) was added; it was then stirred for 1 h at 60 C. After
completion of the reaction (monitored by TLC), the solid precipitate was dissolved in hot
EtOH to remove the heterogeneous catalyst then, the pure product was obtained from the
filtrate.
Tetrahydro-6-phenyl-5-thioxoimidazo[1,5-c]thiazol-7(3H)-one (6a)
°
1
Colorless solid (0.245 g, 98%); mp: 168-170 C; FT-IR (KBr, cm-1): ν= 1110, 1755; H
NMR (500 MHz, CDCl3): δppm= 3.19 (dd, 1H, J= 11.1, 9.0 Hz, -CH2CH), 3.40 (dd, 1H,
J= 11.1, 7.7 Hz, -CH´2CH), 4.52 (d, 1H, J = 9.5 Hz, -SCH), 4.68 (t, 1H, J = 8.1 Hz, -
CHCH2), 5.43 (d, 1H, J = 9.5 Hz, -SCH´), 7.31 (d, 2H, J = 7.9 Hz, HAr), 7.45-7.53 (m,
3H, HAr); 13C NMR (125 MHz, CDCl3): δppm= 31.2, 50.0, 66.4, 95.2, 128.1, 129.4, 133.0,
170.6, 185.2; Mass: HR-MS (EI): calcd for C11H10N2OS2 [M]+ 250.0235,
250.0243.
found
Tetrahydro-6-(4-methoxyphenyl)-5-thioxoimidazo[1,5-c]thiazol-7(3H)-one (6b)
1
Colorless solid (0.224 g, 80%); mp: 185-188 °C; FT-IR (KBr, cm-1 ): ν = 1111, 1750; H
NMR (500 MHz, CDCl3): δppm= 3.17 (dd, 1H, J = 11.1, 8.9 Hz, -CH2CH), 3.39 (dd, 1H,
J = 11.1, 7.6 Hz, -CH´2CH), 3.84 (s, 3H, -OMe), 4.52 (d, 1H, J= 9.5 Hz, -SCH), 4.66 (t,
1H, J = 8.1 Hz, -CHCH2), 5.42 (d, 1H, J = 9.5 Hz, -SCH´), 7.02 (d, 2H, J = 8.8 Hz, HAr),
7.21 (d, 2H, J = 8.8 Hz, HAr); 13C NMR (125 MHz, CDCl3): δppm= 31.2, 50.0, 55.5, 66.3,
114.6, 125.5, 129.2, 160.1, 170.9, 185.7; Mass: HR-EI: calcd for C12H12N2O2S2 [M]+
280.3400, found 280.3570.
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6-(4-Chlorophenyl)-tetrahydro-5-thioxoimidazo[1,5-c]thiazol-7(3H)-one (6c)
1
Colorless solid (0.252 g, 89%); mp: 140-144 °C; FT-IR (KBr, cm-1 ): ν = 1091, 1762; H
NMR (500 MHz, CDCl3): δppm= 3.18 (dd, 1H, J = 11.1, 8.9 Hz, -CH2CH), 3.39 (dd, 1H,
J = 11.1, 7.6 Hz, -CH´2CH), 4.52 (d, 1H, J = 9.5 Hz, -SCH), 4.68 (t, 1H, J = 8.1 Hz, -
CHCH2), 5.41 (d, 1H, J= 9.5 Hz, -SCH´), 7.27 (d, 2H, J = 8.4 Hz, HAr), 7.47 (d, 2H, J =
13
8.4 Hz, HAr); C NMR (125 MHz, CDCl3): δppm= 31.2, 50.0, 66.3, 129.4, 129.5, 131.3,
35
135.4, 170.4, 184.7; Mass: HR-EI: calcd for C11H9 ClN2OS2 [M]+ 283.9845, found
37
283.9828; calcd for C11H9 ClN2OS2 [M+2]+ 285.9815, found 285.9790.
Tetrahydro-6-(4-nitrophenyl)-5-thioxoimidazo[1,5-c]thiazol-7(3H)-one (6d)
°
Colorless solid (0.266 g, 91%); mp: 206-209 C; FT-IR (KBr, cm-1 ): ν = 1107, 1771,
3121,; 1H NMR (500 MHz, CDCl3): δppm= 3.22 (dd, 1H, J = 11.2, 8.8 Hz, -CH2CH), 3.42
(dd, 1H, J = 11.2, 7.6 Hz, -CH´2CH), 4.54 (d, 1H, J = 9.6 Hz, -SCH), 4.73 (t, 1H, J = 8.1
Hz, -CHCH2), 5.42 (d, 1H, J = 9.6 Hz, -SCH´), 7.58 (d, 2H, J = 9.0 Hz, HAr), 8.35 (d, 2H,
J =9 Hz, HAr);13C NMR (125 MHz, CDCl3): δppm= 31.2, 50.0, 66.4, 124.4, 129.0, 138.2,
147.7, 169.9, 183.5; Mass: HR-MS (EI): calcd for C11H9N3O3S2 [M]+ 295.0086, found
295.0097.
Tetrahydro-5-thioxo-6-m-tolylimidazo[1,5-c]thiazol-7(3H)-one (6e)
°
Colorless solid (0.252 g, 95%); mp: 139-141 C; FT-IR (KBr, cm-1 ): ν = 1096, 1767,
3049; 1H NMR (500 MHz, CDCl3): δppm= 2.41 (s, 3H, -CH3), 3.18 (dd, 1H, J = 11.1, 8.9
Hz, -CH2CH), 3.39 (dd, 1H, J = 11.1, 7.6 Hz, -CH´2CH), 4.52 (d, 1H, J = 9.5 Hz, -SCH),
4.67 (t, 1H, J= 8.1 Hz, -CHCH2), 5.43 (d, 1H, J= 9.5 Hz, -SCH´), 7.10 (s, d, 2H, HAr),
7.27 (d, 1H, J = 8.2 Hz, HAr), 7.39 (t, 1H, J = 8.0 Hz, HAr);13C NMR (125 MHz, CDCl3):
17

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δ
ppm= 21.4, 31.2, 50.0, 66.4, 125.1, 128.6, 129.1, 130.4, 132.9, 139.4, 170.8, 185.4; Mass:
HR-MS (EI): calcd for C12H12N2OS2 [M]+ 264.0392, found 264.0403.
5-Benzyl-3-phenyl-2-thioxoimidazolidin-4-one (6f)
°
Colorless solid (0.244 g, 87%); mp: 171-174 C; FT-IR (KBr, cm-1 ): ν = 1099, 1753,
3159; 1H NMR (500 MHz, CDCl3): δppm= 3.1 (d, 2H, J = 4.1 Hz, -CHCH2), 4.8 (t, 1H, J=
4.1 Hz, -CHCH2), 6.76 (d, 2H, J = 6.65 Hz, HAr), 7.2 (d, 2H, J = 6.4 Hz, HAr), 7.29-7.37
13
(m, 6H, HAr), 10.61 (s, 1H, -NH); C NMR (125 MHz, CDCl3): δppm= 36.1, 60.2, 127.1,
128.2, 128.4, 128.7, 129.8, 133.2, 134.5, 136.1, 173.4, 182.2; Mass: HR-EI: calcd for
C16H14N2OS [M]+ 280.0827, found 280.0843.
5-Benzyl-3-(4-chlorophenyl)-2-thioxoimidazolidin-4-one (6g)
°
Colorless solid (%83, 0.262 gr); mp: 225-228 C; FT-IR (KBr, cm-1 ): ν = 1091, 1754,
3171; 1H NMR (500 MHz, CDCl3): δppm= 3.12 (dd, 1H, J = 14.0, 7.1 Hz, CH2CH), 3.33
(dd, 1H, J= 14.0, 3.9 Hz, CH´2CH), 4.54 (dd, 1H, J = 7.1, 3.9 Hz, -CHCH2), 6.99 (d, 2H,
J = 8.5 Hz, HAr), 7.2 (d, 2H, J = 7.8 Hz, HAr), 7.35 (t, 3H, J = 7.0 Hz, HAr), 7.42 (d, 2H, J
= 8.6 Hz, HAr), 7.85 (s, 1H, -NH);13C NMR (125 MHz, CDCl3): δppm= 37.6, 60.8, 127.9,
129.0, 129.4, 129.5, 130.8, 133.9, 135.3, 172.4, 183.2; Mass: HR-EI: calcd for C16H1335Cl
N2OS [M]+ 316.0437, found 316.0441.
5-Benzyl-3-(4-nitrophenyl)-2-thioxoimidazolidin-4-one (6h)
°
Colorless solid (0.245 g, 75%); mp: 198-200 C; FT-IR (KBr, cm-1 ): ν = 1105, 1755,
3185; 1H NMR (500 MHz, CDCl3): δppm= 3.15 (dd, 1H, J = 14.0, 6.8 Hz , CH2CH), 3.36
(dd, 1H, J =14.0 Hz, CH´2CH), 4.61 (s, 1H, -CHCH2), 7.25-7.38 (m, 7H, HAr), 7.71 (s,
13
1H, -NH), 8.3 (d, 2H, J = 8.5 Hz, HAr); C NMR (125 MHz, CDCl3): δppm= 37.7, 61.0,
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ACCEPTED MANUSCRIPT
124.3, 128.1, 129.1, 129.2, 129.4, 133.7, 137.8, 147.7, 171.8, 182.2; Mass: HR-EI: calcd
for C16H13N3O3S [M]+ 327.0678, found 327.0684.
5-Benzyl-2-thioxo-3-m-tolylimidazolidin-4-one (6i)
Yellow solid (0.268 g, 91%); mp: 183-185 °C; FT-IR (KBr, cm-1 ): ν = 1091, 1758, 3165;
1H NMR (500 MHz, CDCl3): δppm= 2.37 (s, 3H, -CH3), 3.13 (dd, 1H, J = 14.0, 7.0 Hz,
CH2CH), 3.33 (dd, 1H, J = 14.0, 3.4 Hz, CH´2CH), 4.52 (t, 1H, J = 4.5 Hz, -CHCH2),
6.82 (d, 2H, J = 7.7 Hz, HAr), 7.23 (d, 2H, J = 7.4 Hz, HAr), 7.28 (d, 2H, J = 6.8 Hz, HAr),
7.32-7.36 (m, 4H, HAr), 8.03 (s, 1H, -NH);13C NMR (125 MHz, CDCl3): δppm= 21.3,
37.5, 60.9, 125.2, 127.8, 128.7, 128.9, 129.6, 130.2, 132.3, 134.1, 139.2, 172.8, 183.8;
Mass: HR-EI: calcd for C17H16N2OS [M]+ 296.0983, found 296.1000.
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