One-pot, three component synthesis of thiazol-2(3H)-imines using poly(4-vinylpyridine) as an efficient reusable heterogeneous basic catalyst

Article abstract of DOI:10.3987/COM-14-13122

Poly(4-vinylpyridine) is reported as a green, efficient and reusable basic catalyst for the synthesis of thiazol-2(3H)-imines under one-pot, three component reaction conditions. This simple method produces the products at room temperature in excellent yields (83-97%). Furthermore, this catalyst can be recovered by simple filtration and recycled up to four consecutive runs without any loss of its efficiency

Full text of DOI:10.3987/COM-14-13122

HETEROCYCLES, Vol. 91, No. 1, 2015, pp. -. © The 2015 Japan Institute of Heterocyclic Chemistry
Received, 10th November, 214, Accepted, 9th December, 2014, Published online,
DOI: 10.3987/COM-14-13122
.
ONE-POT,
THREE
COMPONENT
SYNTHESIS
OF
THIAZOL-2(3H)-IMINES USING POLY(4-VINYLPYRIDINE) AS AN
EFFICIENT REUSABLE HETEROGENEOUS BASIC CATALYST
Jafar Abbasi Shiran,a Asieh Yahyazadeh,a* Manouchehr Mamaghani,
Bohari M. Yamin,b and Farhad Shirini,a
a
Department of Chemistry, College of Science, University of Guilan, Rasht
Iran.
b
School of Chemical Sciences and Food Technology, Universiti Kebangsaan
Malaysia, UKM 43500 Bangi Selangor, Malaysia
Abstract –Poly(4-vinylpyridine) is reported as a green, efficient and reusable
basic catalyst for the synthesis of thiazol-2(3H)-imines under one-pot, three
component reaction conditions. This simple method produces the products at
room temperature in excellent yields (83-97%). Furthermore, this catalyst can be
recovered by simple filtration and recycled up to four consecutive runs without
any loss of its efficiency
One-pot, multi component reactions (MCR) are highly powerful and useful synthetic tools in synthetic
chemistry and drug discovery. MCRs improved economic and environmental aspects of synthetic
chemistry as a result of decreasing purification steps without isolating any intermediate.1-5
thiazol-2(3H)-imines display a central role in agriculture and medicinal chemistry,6, 7 which exhibit very
biological activities such as antimicrobial,8 bleaching herbicidal,9 anti-inflammatory,10 and antidepressant
activities.11 Moreover, these moieties have been found in insecticides and plant growth regulators.12, 13
Several alternative methods have been developed for synthesis of thiazolidines and thiazolines have been
developed, which include intramolecular cyclization of n-(2-hydroxyethyl)thiourea derivatives in the
presence of diethyl azodicarboxylate,14 condensation of α-haloketones with thiourea,15 base-catalyzed
cyclization of 1-(fluorobenzoyl)-3-(fluorophenyl)thiourea with 2-bromoacetone in aqueous media16 and
condensation of carbonyl compounds with thiourea and 1,3-disubstituted thiourea using
1,1'-(ethane-1,2-diyl)dipyridinium bistribromide (EDPBT) as brominating agent.17 For example, Balalaie
et al. reported the synthesis of 2-aminothiazole and 2-iminothiazolidine derivatives catalyzed by
diammonium hydrogen phosphate (DAP) and 1,4-diazabicyclo[2.2.2]octane (DABCO) in

aqueous-phase.18 Sravanthi et al. reported the synthesis of novel bis-thiazol-2-ylidenes derivatives in
ultrasonic condition.19 Also, with excellent regioselectivity, Mamaghani and co-workers have obtained
substituted iminothiazolines as the superior regioisomer through cyclization of unsymmetrical thioureas.20
In our previous studies, we have reported the synthesis of 3H-thiazoles from allylisothiocyanate, aryl
amines and fenacylbromide in the presence of triethylamine under reflux conditions.21 On the other hand,
heterogeneous basic catalysts are desirable in synthetic organic chemistry and green processes due to some
potential advantages such as facile recovery, eco-benign and easy product isolation.22, 23
Poly(4-vinylpyridine)-supported reagents are useful tools for organic reactions including reductions,
oxidations and halogenations.24 Bhanage et al. have reported the synthesis of dimethyl carbonate via
transesterification of ethylene carbonate with methanol using poly(4-vinylpyridine) (PVP) as a base
catalyst.25 recently, shirini et al. used poly(4-vinylpyridine) in chemoselective O-TMS protection of
alcohols and phenols and N-boc protection of amines.26
Herein, we report the application of PVP as an efficient recyclable basic catalyst in the regioselective
synthesis of thiazol-2(3H)-imines from arylamines, allylisothiocyanate and various phenacyl bromides
(Scheme 1).
S
Br
EtOH/ PVP
rt, 12-48 h
Ar
NCS
2
Ar NH2
1
+
X
+
N
N
X
O
3
4a-n
83-97%
Ar = 3-MeOC6H4, 4- MeOC6H4, 3,4-di-MeOC6H3, 4-EtOC6H4, 4-EtC6H4,1-naphthyl, 2-MeOC6H4, 3-OHC6H4, 4-
MeC6H4, 3-ClC6H4, 4-ClC6H4, 4-IC6H4
X= H, OMe, Br
Scheme1. Synthesis of 3-allyl-2-(arylimino)-4-aryl-3H-thiazole derivatives
In order to achieve the optimal reaction conditions for the synthesis of thiazol-2(3H)-imines, synthesis of
4b was chosen as a model, and studied under several conditions (Table 1).
Table 1. Effect of various catalysts in the synthesis of 4b
Catalysta
triethylamine
UBDc
Conditions
TmiT (h)
Yield (%)b
reflux
reflux
2
8
76
60
93
PVP
room temp.
20
aAmount of the catalyst: 0.02 g/1 mmol substrate. bIsolated yields.
c1,8-Diazabicyclo[5.4.0]undec-7-ene

Among the tested basic catalysts, the best result was achieved by carrying out the reaction in the presence
of 0.02 g of PVP at room temperature in ethanol. As shown in Table 2, under the optimized condition,
thiazol-2(3H)-imines 4a-n were obtained in high yields (83-97%).
Table 2. Synthesis of thiazol-2(3H)-imine derivatives catalyzed by
PVP
Product
X
Ar
Time (h)
Yielda (%)
H
H
3-MeOC6H4
4-MeOC6H4
3,4-diMeOC6H3
4-EtOC6H4
4-EtC6H4
24
20
20
18
20
30
36
48
40
18
12
15
18
18
91
93
94
96
90
87
85
83
85
89
97
94
92
91
4a
4b
H
4c
H
4d
H
4e
H
1-naphthyl
3-HOC6H4
1-naphthyl
4-MeC6H4
4-MeC6H4
4-EtOC6H4
4-MeOC6H4
4-IC6H4
4f
H
4g
OMe
OMe
Br
Br
Br
Br
Br
4h
4i
4j
4k
4l
4m
4-ClC6H4
4n
a Isolated yield
The results revealed that an electronic effect by the p-substituent (X) of phenacyl bromide was observed.
An electron-withdrawing group (Br) enhanced the reaction rate, while the substrate with an electron-
donating substituent (OMe) needed longer reaction time.
All products were cleanly isolated by filtration and recrystallization from a mixture of ethanol/water (1: 1
v/v). The structures of compounds (4a-n) were fully confirmed by spectral (1H-NMR, 13C-NMR, IR) and
1
elemental analyses. The appearance of a singlet in the region of 5-6 ppm in the H-NMR spectra which
correspond to the H at the 5-position of the thiazole ring confirms skeleton of thiazol-2(3H)-imines. The
structure of 4d was also confirmed by single-crystal X-ray crystallography.27,28 Thecompound crystallized
in monoclinic system with space group P21/n, a = 5.7886(4), b = 24.3201(19), c = 12/6329(11)Å,
β = 94.450(2)°, Z = 4 and V = 1173.1(2)Å3. The molecular structure with the numbering scheme of the
compound is shown in Figure 1.

Figure 1. Molecular structure of compound 4d with numbering scheme drawn at 50% probability ellipsoid
The central five-membered N1/C7/C8/S1/C9 thiazole ring, (C1-C6) and (C10-C15) benzene rings are
planar with maximum deviation of 0.016(4)Å for C10 atom from the least square plane of the benzene
ring. The central thiazole ring makes dihedral angle with the (C10-C15) ring of 61.6(2)° and 46.5(2)°
with (C1-C6) ring. The two benzene rings are perpendicular to each other at an angle of 73.2(2)°. The
propenyl group attached at the thiazole N1 atom is also vertical to the thiazole ring with C8-C7-N1-C18
and S1-C9-N1-C18 torsonal angles of 165.4(4) and 167.2(3)°, respectively. The C7-C8 and C19-C20 are
double bonds with bond length of 1.333(6) and 1.29(7)°, respectively. Other bond lengths and angles are
in normal ranges. In the crystal structure the molecule is stabilized by C8-H8A…N2 intermolecular
hydrogen bond (D-H=0.93Å, H…A = 2.43Å, D…A = 3.359(5)Å D-H…A = 175°) forming a one
dimensional chain along a-axis and C20-H20A…π bond with H20A…(C1-C6),(-1+x, y,z) centroid
distance of 2.82Å and D-H…centroid angle 146°.
In addition, recyclability of the catalyst is significant. To investigate these properties for PVP as a basic
catalyst, the synthesis of 4k was selected as the model (Table 2). After completion of the reaction, the
catalyst was filtered, washed with aqueous Na2CO3 (10%), distillated water and hot acetone. Then
catalyst was dried and used for another consecutive run. The results showed that during four consecutive
runs the activity of PVP was the same as the freshly used catalyst (Table 3).
Table 3. Recyclability of PVP in the synthesis of
thiazol-2(3H)-imine derivatives
1
2
3
4
Run
Time (h)
24
97
24
92
28
87
36
87
Yield (%)a
a Isolated yield

The plausible mechanism for the formation of 3-allyl-2-(aryl imino)-4-aryl-3H-thiazoles (4a-n) were
outlined in Scheme 2.
O
Br
S
S:
X
NCS
Ar
NH2
+
Ar
Ar
N
H
N
N
N
H
H
n
1
2
5
N
Ar
S
Ar
S
N
N
HN
N
N
-H2O
N
O
Ar
S
OH
X
X
X
4
6
7
Scheme 2. Plausible mechanism for the formation of 4a-n
EXPERIMENTAL
Materials and methods: All chemicals were purchased from Merck, Fluka and Aldrich chemical
companies and used without further purification. All yields refer to isolated products. Melting points were
measured on an Electrothermal 9100 apparatus and are uncorrected. FT-IR spectra were recorded on a
Shimadzu 8400S spectrophotometer. The NMR spectra were recorded on a Bruker AVANCE DMX400
spectrometer, operating at 400 MHz (1H NMR) and 100 MHz (13C NMR). The chemical shift values are
expressed in ppm relative to TMS as an internal standard. Elemental analyses were recorded with a CHN
model 2400 Perkin-Elmer and agreed with the calculated values. Poly(4-vinylpyridine) [∼60 mesh,
average MW: 60,000] purchased from Fluka Chemical company.
General procedure for synthesis of 3-allyl-2-(aryl imino)-4-aryl-3H-thiazoles. Arylamine (1 mmol),
allyl isothiocyanate (AITC) (1 mmol) and various phenacyl bromides (1 mmol) were added to a round-
bottom flask containing EtOH (10 mL). Polyvinylpyridine (0.02 g) was added at once to this mixture. The
mixture was stirred at room temperature for specified time according to Table 1. The progress of the
reaction was monitored by TLC. After completion, PVP was filtered, washed with aqueous Na2CO3
(10%), distilled water and hot acetone and recovered to use subsequently. The remained solution was
poured into ice bath. Then solid residue was filtered washed with aqueous Na2CO3 (10%), distilled water
and recrystallized from EtOH/H2O (1: 1 v/v) to give a pure product.
Recycling of the catalyst. After filtration, the catalyst was washed with aqueous Na2CO3 (10%),
distilled water and hot acetone and then was dried under vacuum at 50 ◦C before the next run.

Spectral data of compounds:
3-Allyl-2-(3′-methoxyphenylimino)-4-phenyl-3H-thiazole (4a): Yield 91%; white solid; mp 145-146
1
°C; H-NMR (CDCl3, 400 MHz): δH: 3.84 (s, 3H), 5.18 (d, 1H, J = 17.2 Hz), 5.32 (d, 1H, J = 10.4 Hz),
5.42 (d, 2H, J = 4.8 Hz), 5.85-5.95 (m, 1H), 6.66 (s, 1H), 6.91 (dd, 1H, J = 8.4, 2.4 Hz), 7.19 (dd, 1H, J =
13
7.8, 2.4 Hz), 7.31-7.40 (m, 4H), 7.52 (t, 2H, J = 7.2 Hz), 7.58 (dd, 1H, J = 8.4, 7.8 Hz) ppm ; C-NMR
(CDCl3, 100 MHz): δc : 51.0, 55.7, 104.2, 109.6, 114.8, 115.4, 118.9, 127.8, 129.3, 129.4, 129.6, 130.7,
131.1, 138.8, 143.5, 160.8, 168 ppm; FT-IR (KBr,cm-1): 3108, 2997, 2939, 2835, 1612, 1593, 1576,
1490, 1288, 1157, 1055, 1016, 996, 783, 698. Anal. Calcd for C19H18N2OS (322.41): C, 70.78; H, 5.62;
N, 8.68. Found: C, 70.76; H, 5.65; N, 8.70%.
3-Allyl-2-(4′-methoxyphenylimino)-4-phenyl-3H-thiazole (4b): Yield 93%; white solid; mp 145-146
1
°C; H-NMR (CDCl3, 400 MHz): δH: 3.83 (s, 3H), 4.45 (d, 2H, J = 3.6 Hz), 5.04 (d, 1H, J = 17.2 Hz),
5.17 (d, 1H, J = 10.4 Hz), 5.78 (s, 1H), 5.89-5.97 (m, 1H), 6.92 (d, 2H, J = 8.6 Hz), 7.03 (d, 2H, J = 8.6
13
Hz), 7.40-7.48 (m, 5H) ppm; C-NMR (CDCl3, 100 MHz): δc: 47.5, 55.4, 95.5, 114.6, 116.4, 122.4,
128.5, 128.9, 129.1, 131.7, 132.8, 140.4, 145.2, 155.0, 159.6 ppm; FT-IR (KBr,cm-1): 3110, 2995, 2939,
2836, 1610, 1592, 1571, 1490, 1361, 1281, 1057, 950, 781. Anal. Calcd for C19H18N2OS (322.41): C,
70.78; H, 5.62; N, 8.68. Found: 70.80; H, 5.59; N, 8.72%.
3-Allyl-2-(3′,4′-dimethoxyphenylimino)-4-phenyl-3H-thiazole (4c): Yield 94%; white solid; mp 145-
1
146 °C; H-NMR (CDCl3, 400 MHz): δH: 3.88 (s, 6H), 4.44 (d, 2H, J = 4.4 Hz), 5.04 (d, 1H, J = 17.2
Hz), 5.17 (d, 1H, J = 10.4 Hz), 5.78 (s, 1H), 5.89-5.98 (m, 1H), 6.66 (d, 1H, J = 8.8 Hz), 6.68 (s, 1H),
13
6.86 (d, 1H, J = 8.8 Hz), 7.38-7.46 (m, 5H) ppm; C-NMR (CDCl3, 100 MHz): δc: 50.1, 51.2, 57.2,
103.4, 116.5, 117.3, 122.4, 128.3, 128.7, 128.9, 130.3, 131.8, 136.7, 141.1, 145.6, 150.1, 155,6, 163.2
ppm; FT-IR (KBr,cm-1): 3096, 2976, 2926, 1614, 1560, 1458, 1238, 1058, 954, 900, 698, 605. Anal.
Calcd for C20H20N2O2S (352.43): C, 68.16; H, 5.71; N, 7.94. Found: C, 68.19; H, 5.73; N, 7.97%.
3-Allyl-2-(4′-ethoxyphenylimino)-4-phenyl-3H-thiazole (4d): Yield 96%; white solid; mp 145-146 °C;
1H-NMR (CDCl3, 400 MHz): δH: 1.44 (t, 3H, J = 6.8 Hz), 4.05 (q, 2H, J = 6.8 Hz), 4.45 (d, 2H, J = 4.4
Hz), 5.05 (d, 1H, J = 17.2 Hz), 5.17 (d, 1H, J = 10.4 Hz), 5.78 (s, 1H), 5.89-5.98 (m, 1H), 6.91 (d, 2H, J =
8.4 Hz), 7.02 (d, 2H, J = 8.4 Hz) 7.43-7.46 (m, 5H) ppm; FT-IR (KBr,cm-1): 2972, 2922, 1616, 1541,
1506, 1458, 1315, 1236, 1116, 1051, 954. Anal. Calcd for C20H20N2OS (336.44): C, 71.40; H, 5.99; N,
8.32. Found: C, 71.37; H, 6.04; N, 8.29%.
3-Allyl-2-(4'-ethylphenylimino)-4-phenyl-3H-thiazole (4e): Yield 90%; white solid; mp 145-146 °C;
1H-NMR (CDCl3, 400 MHz): δH: 1.17 (t, 3H, J = 7.6 Hz), 2.57 (q, 2H, J = 7.6 Hz) 4.46 (d, 2H, J = 3.6
Hz), 5.05 (d, 1H, J = 17.2 Hz), 5.17 (d, 1H, J = 10.4 Hz), 5.76 (s, 1H), 5.90-5.98 (m, 1H), 6.93 (d, 2H, J =
8 Hz), 7.04 (d, 2H, J = 8 Hz), 7.41-7.49 (m, 5H) ppm; FT-IR (KBr, cm-1): 3074, 2924, 2861, 1599, 1565,

1481, 1380, 1222, 1073, 918, 701, 533. Anal. Calcd for C20H20N2S (320.45): C, 74.96; H, 6.29; N, 8.74.
Found: C, 75.04; H, 6.21; N, 8.79%.
1
3-Allyl-2-(1′-naphthylimino)-4-phenyl-3H-thiazole (2f): Yield 87%; white solid; mp 150-152°C; H-
NMR (CDCl3, 400 MHz): δH: 4.62-4.63 (m, 2H), 5.19 (dd, 1H, J = 17.2, 1.2 Hz), 5.30 (dd, 1H, J = 10.4,
1.2 Hz), 5.83 (s, 1H), 6.03-6.11 (m, 1H), 7.44-7.55 (m, 9H), 7.60 (d, 1H, J = 8.4 Hz), 7.86 (d, 1H, J = 7.8
13
Hz), 8.27 (d, 1H, J = 7.8 Hz) ppm; C-NMR (CDCl3, 100 MHz): δc: 47.7, 96.0, 114.4, 116.6, 122.9,
123.8, 125.0, 126.0, 126.3, 127.8, 128.6, 128.7, 128.9, 129.2, 131.6, 133.0, 134.7, 140.3, 148.2, 159.4
ppm; FT-IR (KBr, cm-1): 3080, 2922, 1610, 1589, 1577, 1560, 1496, 1413, 1382, 1242, 1230, 1001, 966,
914, 844, 700. Anal. Calcd for C22H18N2S (342.45): C, 77.16; H, 5.29; N, 8.18. Found: C, 77.09; H, 5.36;
N, 8.10%.
3-Allyl-2-(m-hydroxyphenylimino)-4-phenyl-3H-thiazole (4g): Yield 85%, white solid; mp 145-147
°C; 1H-NMR (DMSO, 400 MHz): δH: 4.70 (s, 2H), 4.94 (d, 1H, J = 17.2 Hz), 5.24 (d, 1H, J = 10.8 Hz),
5.82-5.91 (m, 1H), 6.83 (d, 1H, J = 8.0 Hz), 6.85 (s, 1H), 6.90 (d, 1H, J = 8.0 Hz), 7.10 (s, 1H), 7.35 (t,
1H, J = 8.0 Hz), 7.49-7.59 (m, 5H), 10.02 (br, 1H) ppm; FTIR (KBr, cm-1) νmax 3157, 3047, 2937, 2881,
1608, 1566, 1500, 1450, 1371, 1213, 1161, 970, 869, 700. Anal. Calcd for C18H16N2OS (308.41): C,
70.10; H, 5.23; N, 9.08. Found: C, 70.06; H, 5.26; N, 9.10%.
3-Allyl-2-(1′-naphthylimino)-4-(4′-methoxyphenyl)-3H-thiazole (4h): Yield 83%, cream solid; mp 96-
97 °C; 1H-NMR (CDCl3, 400 MHz): δH: 4.11 (s, 3H), 4.33 (m, 2H), 5.21 (dd, 1H, J = 9.6, 1.4 Hz), 5.28
(dd, 1H, J = 10.0, 1.2 Hz), 5.88 (m, 1H), 6.13 (s, 1H), 6.93 (d, 2H, J = 8.4 Hz), 7.07 (d, 2H, J = 8.4 Hz)
7.43-7.46 (m, 4H), 7.55 (d, 1H, J = 8.2 Hz), 7.76 (d, 1H, J = 7.6 Hz), 8.01 (d, 1H, J = 7.6 Hz) ppm; FTIR
(KBr, cm-1) νmax 3055, 2976, 2933, 2837, 1683, 1597, 1508, 1394, 1255, 1176, 1016, 775, 551. Anal.
Calcd for C23H20N2OS (372.48): C, 74.16; H, 5.41; N, 7.52. Found: C, 74.20; H, 5.37; N, 7.49%.
3-Allyl-2-(p-tolylimino)-4-(4′-methoxyphenyl)-3H-thiazole (4i): Yield 85%, white solid; mp 107-108
1
°C; H-NMR (CDCl3, 400 MHz): δH: 2.37 (s, 3H), 4.73 (s, 3H), 4.29 (m, 2H), 5.14 (dd, 1H, J = 9.6, 1.2
Hz), 5.18 (dd, 1H, J = 10.0, 1.2 Hz), 5.85 (m, 1H), 6.01 (s, 1H), 6.93 (d, 2H, J = 8.6 Hz), 7.04 (d, 2H, J
= 8.6 Hz), 7.12 (d, 2H, J = 8.6 Hz), 7.24 (d, 2H, J = 8 Hz) ppm; 13C-NMR (CDCl3, 100 MHz): δc: 21.0,
47.8, 51.4, 97.3, 113.1, 117.0, 120.6, 121.2, 125.6, 128.9, 129.2, 130.0, 133.1, 133.3, 137.7, 148.8 ppm;
FTIR (KBr, cm-1) νmax 3080, 3010, 2912, 1550, 1529, 1315, 1236, 1134, 958, 819, 659, 563, 493. Anal.
Calcd for C20H20N2OS (336.45): C, 71.39; H, 5.99; N, 8.32. Found: C, 71.41; H, 5.43; N, 8.36%.
3-Allyl-2-(p-methylphenylimino)-4-(4′-bromophenyl)-3H-thiazole (4j): Yield 89%, yellowish solid;
mp 117-118 °C; 1H-NMR (CDCl3, 400 MHz): δH: 2.35 (s, 3H), 4.42 (d, 2H, J = 4.8 Hz), 5.04 (dd, 1H, J
= 17.2, 1.2 Hz), 5.18 (dd, 1H, J = 10.4, 1.2 Hz), 5.79 (s, 1H), 5.88-5.97 (m, 1H), 6.97 (d, 2H, J = 7.4
Hz), 7.16 (d, 2H, J = 8.0 Hz), 7.30 (d, 2H, J = 8.0 Hz), 7.57 (d, 2H, J = 7.4 Hz) ppm; 13C-NMR (CDCl3,
100 MHz): δc: 20.9, 47.5, 96.2, 116.5, 120.6, 121.2, 123.4, 125.7, 130.0, 131.8, 132.4, 132.7, 139.2

149.0, 159.1 ppm; FTIR (KBr, cm-1) νmax 3043, 2973, 2902, 1606, 1589, 1506, 1375, 1230, 1126, 1010,
825, 669, 474. Anal. Calcd for C19H17N2SBr (385.32): C, 59.22; H, 4.44; N, 7.26. Found: C, 59.19; H,
4.47; N, 7.29%.
3-Allyl-2-(p-ethoxylphenylimino)-4-(4′-bromophenyl)-3H-thiazole (4k): Yield 97%, yellow solid; mp
119-121 °C; 1H-NMR (CDCl3, 400 MHz): δH: 1.43 (t, 3H, J = 6.8 Hz), 4.04 (q, 2H, J = 6.8 Hz), 4.41 (d,
2H, J = 4.8 Hz), 5.05 (dd, 1H, J = 1.2, 16.0 Hz), 5.18 (dd, 1H, J = 1.2, 10.4 Hz), 5.78 (s, 1H), 5.88-5.97
(m, 1H), 6.90 (d, 2H, J = 6.8 Hz), 6.99 (d, 2H, J = 6.8 Hz), 7.29 (d, 2H, J = 9.2 Hz), 7.57 (d, 2H, J = 9.2
Hz) ppm; FTIR (KBr, cm-1) νmax 3053, 2983, 2920, 1612, 1593, 1506, 1467, 1321, 1238, 1114, 1010, 916,
840, 555, 480. Anal. Calcd for C20H19N2SOBr (415.35): C, 58.83; H, 4.61; N, 6.74. Found: C, 58.85; H,
4.59; N, 6.72%.
3-Allyl-2-(p-methoxyphenylimino)-4-(4′-bromophenyl)-3H-thiazole (4l): Yield 94%, yellow solid; mp
1
114-116 °C; H-NMR (CDCl3, 400 MHz): δH: 3.82 (s, 3H), 4.42 (d, 2H, J = 4.8 Hz), 5.04 (dd, 1H, J =
1.2, 17.2 Hz), 5.18 (dd, 1H, J = 1.2, 9.4 Hz), 5.79 (s, 1H), 5.88-5.97 (m, 1H), 6.90 (d, 2H, J = 6.8 Hz),
13
7.00 (d, 2H, J = 7.4 Hz), 7.29 (d, 2H, J = 7.4 Hz), 7.57 (d, 2H, J = 6.8 Hz) ppm; C-NMR (CDCl3, 100
MHz): δc: 47.5, 55.45, 96.2, 114.6, 116.5, 123.4, 127.4, 130.3, 130.5, 131.8, 132.7, 139.2, 144.9, 155.6,
159.3 ppm; FTIR (KBr, cm-1) νmax 3064, 2897, 2831, 1610, 1589, 1506, 1396, 1242, 1033, 840, 756, 669,
491. Anal. Calcd for C19H17N2SOBr (401.32): C, 56.86; H, 6.98; N, 4.26. Found: C, 56.88; H, 7.01; N,
4.24%.
3-Allyl-2-(p-iodophenylimino)-4-(4′-bromophenyl)-3H-thiazole (4m): Yield 92%, yellow solid; mp
1
116-118 °C; H-NMR (CDCl3, 400 MHz): δH: 4.41 (d, 2H, J = 4.8 Hz), 5.03 (dd, 1H, J = 1.2, 17.2 Hz),
5.19 (dd, 1H, J = 1.2, 10.4 Hz), 5.83 (s, 1H), 5.86-5.95(m, 1H), 6.86 (d, 2H, J = 8.8 Hz), 7.29 (d, 2H, J =
8.8 Hz), 7.58 (d, 2H, J = 8.8 Hz), 7.63 (d, 2H, J = 8.8 Hz) ppm; 13C-NMR (CDCl3, 100 MHz): δc: 47.6,
86.1, 96.4, 116.7, 123.6, 123.8, 130.2, 130.4, 131.8, 132.5, 138.3, 139.3, 151.1, 159.4 ppm; FTIR (KBr,
cm-1) νmax 3043, 2920, 2850, 1610, 1568, 1375, 1002, 840, 813, 756, 624, 480. Anal. Calcd for
C18H14N2SBrI (497.19): C, 43.48; H, 2.83; N, 5.63. Found: C, 43.45; H, 2.85; N, 5.61%.
3-Allyl-2-(p-chlorophenylimino)-4-(4′-bromophenyl)-3H-thiazole (4n): Yield 91%, yellow solid; mp
1
109-111 °C; H-NMR (CDCl3, 400 MHz): δH: 4.27-4.30 (m, 2H), 5.01 (dd, 1H, J = 1.6, 17.2 Hz), 5.08
(dd, 1H, J = 1.6, 10.0 Hz), 5.82-5.92 (m, 1H), 6.00 (s, 1H), 6.95 (d, 2H, J = 6.8 Hz), 7.27 (d, 2H, J = 6.8
Hz), 7.50 (d, 2H, J = 7.6 Hz), 7.57 (d, 2H, J = 7.6 Hz) ppm; FTIR (KBr, cm-1) νmax 3043, 1616, 1577,
1483, 1315, 1232, 1087, 1010, 835, 719, 632, 482. Anal. Calcd for C18H14N2SBrCl (405.74): C, 53.28; H,
3.47; N, 6.90. Found: C, 53.26; H, 3.45; N, 6.93%.

ACKNOWLEDGEMENTS
We are very grateful to research council of university of guilan for financial support of this work and the
instrumentation center (crim) of universiti kebangsaan malaysia (ukm-dip-011-2012) for the x-ray analysis.
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27. X-Ray data for 4d: (C20H20N2OS), M = 336.44 g/mol, monoclinic system, space group P 21/n, a =
5.7886(4) Å, b = 24.3201(19) Å, c = 12.6329(11) Å, β= 94.450(2)°, V = 1773.1(2) Å3, Z = 4, Dc=
1.320 Mg/m3, μ = 0.205 mm-1, crystal size = 0.500 × 0.220 × 0.140 mm3. The structure was solved by
using SHELXS. The structural refinement was carried out with SHELXL. The non-hydrogen atoms
were refined anisotropically by full-matrix least-squares on F2 values to final R1 = 0.0791, wR2 =
0.1983 and S = 1.095 with 241 parameters using 3106 independent reflection (θ range = 2.988 to
24.993°). The hydrogen atoms were placed in calculated positions. All hydrogen atoms were refined
isotropically in riding model with Uiso(H) = 1.2 Ueq(C) and 1.5Ueq(Cmethyl) However the olefenic
proton H20A and H20B were located from Fourier map and refined isotropically. Crystallographic
data for the structural determination has been deposited with the Cambridge Crystallographic Data
Centre, CCDC No 1008333. This information may be obtained free of charge at
http://www.ccdccam.ac.uk/const/retrieving.html or from the Cambridge Crystallographic Centre
(CCDC), 12 Union Road, Cambridge CB2, 1EZ, UK. Fax: +44 1223 336033 or e-mail:
deposite@ccdc.cam.ac.uk.
28. G. M. Shldrick, ; SHELXTL. Structure Determination Software Suite. Version 6.14. Bruker AXS,
Madison, Wisconsin, USA 2000.