Synthesis of thiazolo[2,3-c]-s-triazoles using poly[(4-diacetoxyiodo) styrene]

Article abstract of DOI:10.1081/SCC-200063923

Arenecarbaldehyde-4-arylthiazol-2-ylhydrazones underwent ring closure with poly[(4-diacetoxyiodo)styrene] (PSDIB) to 3,5-diarylthiazolo[2,3-c]-s-triazoles in dichloromethane. Copyright Taylor & Francis, Inc.

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Synthesis of
Thiazolo[2,3‐c]‐s‐triazoles
Using
Poly[(4‐diacetoxyiodo)styrene]
Shi‐juan Liu a , Ji‐zhen Zhang b , Guan‐rong Tian c
&
Ping Liu c
a College of Chemistry, Jilin Normal University,
Siping, China
b Provincial Key Constructive Laboratory of Precious
Metals Processing Technology and Application,
Jiangsu Teachers University of Technology,
Changzhou, China
c Department of Chemistry, Yanbian University,
Yanji, China
Version of record first published: 15 Aug 2006.
To cite this article: Shi‐juan Liu , Ji‐zhen Zhang , Guan‐rong Tian & Ping Liu (2005):
Synthesis of Thiazolo[2,3‐c]‐s‐triazoles Using Poly[(4‐diacetoxyiodo)styrene],
Synthetic Communications: An International Journal for Rapid Communication of
Synthetic Organic Chemistry, 35:13, 1753-1758
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Synthetic Communicationsw, 35: 1753–1758, 2005
Copyright # Taylor & Francis, Inc.
ISSN 0039-7911 print/1532-2432 online
DOI: 10.1081/SCC-200063923
Synthesis of Thiazolo[2,3-c]-s-triazoles
Using Poly[(4-diacetoxyiodo)styrene]
Shi-juan Liu
College of Chemistry, Jilin Normal University, Siping, China
Ji-zhen Zhang
Provincial Key Constructive Laboratory of Precious Metals Processing
Technology and Application, Jiangsu Teachers University of
Technology, Changzhou, China
Guan-rong Tian and Ping Liu
Department of Chemistry, Yanbian University, Yanji, China
Abstract: Arenecarbaldehyde-4-arylthiazol-2-ylhydrazones underwent ring closure
with poly[(4-diacetoxyiodo)styrene] (PSDIB) to 3,5-diarylthiazolo[2,3-c]-s-triazoles
in dichloromethane.
Keywords: Arenecarbaldehyde-4-arylthiazol-2-ylhydrazone, 3,5-diarylthiazolo[2,3-
c]-s-triazole, poly[(4-diacetoxyiodo)styrene]
Because
thiazolo[2,3-c]-s-triazoles
possess
particular
biological
activities, their synthesis and physiological activities have received
attention.[1] Hypervalent iodine reagents have an important role in the
synthesis of heterocyclic compounds.[2] Om Prakash and coworkers
have synthesized a series of thiazolo[2,3-c]-s-triazoles with phenyliodine
diacetate(IBD).[3]
Received in Japan March 4, 2005
Address correspondence to Guan-rong Tian, Department of Chemistry, Yanbian
University, Yanji, Ji Lin 133002, China. Tel.: 0086-433-2732289; Fax: 0086-433-
2758088; E-mail: grtn@ybu.edu.cn
1753

1754
S.-j. Liu et al.
Recently we successfully prepared thiazole[2,3-c]-s-triazoles with
poly[(4-diacetoxyiodo)-styrene] (PSDIB), and the results of the study are
described in this article.
PSDIB was prepared from the commercial linear polystyrene (average
molecular weight (MW) ¼ 250,000) and 1% cross-linked polystyrene by the
reported method.[4] The exact loading capacity of PSDIB was measured by
iodometry and determined to be 2.62 mmol/g (linear) and 2.03 mmol/g (1%
cross-linked).
The a-tosyloxy-acetophenones (1) (Table 1, Scheme 1), which were
prepared from corresponding acetophenones by [hydroxy(tosyloxy)iodo]ben-
zene (HTIB) in acetonitrile,[5] reacted with arenecarbaldehyde of thiosemicar-
bazone to give arenecarbaldehyde-4-arylthiazol-2-ylhydrazones (2) (Table 2,
Scheme 1).[3]
The reaction of arenecarbaldehyde-4-arylthiazol-2-ylhydrazone and
PSDIB (linear) in refluxing dichloromethane resulted in the formation
of 3,5-diarylthiazolo[2,3-c]-s-triazoles (3) (Table 2, Scheme 1). The
PSDIB (linear) could be reused and the yield was still excellent. The
experimental results showed PSDIB (recycled) had almost the same
functional group as the originally prepared PSDIB. We also applied 1%
cross-linked PSDIB and got the same results; furthermore, its treatment
is much simpler than linear reagent after reaction. The yields of
thiazole[2,3-c]-s-triazoles are approximately 70%. Probably the short
time resulted in the low yield. If the reaction time is lengthened, the
yield may be improved.
Polystyrene-supported hypervalent iodine reagent has these distinguish-
ing features: the polyiodobenzen that is formed from PSDIB easily
separated from products after reaction by simple filtration; the inconvenient
operation of separating and refining iodobenzene that is formed
from phenyliodine diacetate(IBD) is avoided; the polystyrene-supported
Table 1. Results of the formation of 1 and 2
Mp (8C)
Entry
Ar0
Ar
Found
Lit.
Yield (%)
1a
1b
1c
2a
2b
2c
2d
2e
2f
Ph
91–92
122–123
81–82
192–193[3]
193–194
200–203
195–196[3]
200–202
166–168
91–92[5]
122[5]
82[5]
95
90
92
90
92
87
90
94
89
p-ClPh
p-MePh
Ph
Ph
p-MeOPh
Ph
Ph
194[6]
194[7]
p-ClPh
p-ClPh
p-MePh
p-MePh
p-MeOPh
Ph
p-MeOPh
197[8]
165–6[9]

Synthesis of Thiazolo[2,3-c]-s-triazoles
1755
Scheme 1.
hypervalent iodine reagent can be recycled and this recycling is environ-
mentally safe.[4,10]
EXPERIMENTAL
Linear polystyrene was purchased from J&K Chemical Ltd. and 1% cross-
linked polystyrene (200–400 mesh) was purchased from Nankai Share
Group. The melting points were determined by the capillary method and are
1
uncorrected. H NMR and 13C NMR spectra were recorded at 300 MHz and
75 MHz respectively on a Bruker AV-300 instrument. Elemental analyses
were performed on a CYB 08.35-91. IR spectra were recorded at FT-IR
1730. MS spectra were recorded at HP 1100 LC/MSD 1946A.
Table 2. Results of the formation of 3
Mp (8C)
Entry
Ar0
Ph
Ar
Time (h)
Found
Lit.[3]
Yield (%)
3a
3b
3b
3c
3d
3d
3e
3f
Ph
2
l
165–166
140–141
140–141
190–192
187–188
187–188
155–156
165
164–165
139–141
139–141
68a
63
62b
65
Ph
Ph
p-MeOPh
p-MeOPh
Ph
l
p-ClPh
p-ClPh
p-ClPh
p-MePh
p-MePh
2
1
1
2
l.5
p-MeOPh
p-MeOPh
Ph
187–188
187–188
72
70b
68
p-MeOPh
72a
(decomp.)
aBy applying 1% cross-linked PSDIB.
bBy applying recycled PSDIB (linear).

1756
S.-j. Liu et al.
General Procedure for Synthesis of Arenecarbaldehyde-4-
arylthiazol-2-ylhydrazones
A suspension of arenecarbaldehyde of thiosemicarbazone (534 mg, 3 mmol)
and a-tosyloxy-acetophenone (870 mg, 3 mmol) in ethanol (30 ml) were
refluxed for 1–3 h. During the reaction, the starting material disappears
when the temperature of the mixture reached 558C or so, and a new solid
appears at once. It dissolved in dichloromethane, which was washed with
2% Na2CO3 and water; the organic layer was dried over Na2SO4 and evapor-
ated in vacuo to give a solid.
Preparation of 3,5-Diaryl 1,2,4-thiazolo [2,3-c]-s-triazoles
To a solution of arenecarbaldehyde-4-arylthiazol-2-ylhydrazone (1 mmol) in
20 ml of dichloromethane was added linear PSDIB (0.7 g). The contents
were refluxed for 1–2 h. The resulting dark brown solution was evaporated,
the remainder was poured into 80 ml of anhydrous ethanol in stirring
conditions, and the linear iodinated polystyrene was filtrated. The ethanol
was evaporated. The residue was dissolved in dichloromethane, washed with
2% NaHCO3 and water, and dried over Na2SO4. The crude product was
purified by column chromatography using a petroleum ether–ethyl acetate
mixture followed by crystallization to afford 3,5-diaryl-l,2,4-thiazolo[2,3-c]-
s-triazoles.
3c, 3-Phenyl-5-p-chlorophenyl-1,2,4-thiazolo[2,3-c]-s-triazole
1
IR (KBr): n max 1650 (C55C, C55N), 1610, 1575 (C-N) cm21. H NMR
(d, CDCl3): 7.54 (m, 5H), 7.93 (d, J ¼ 8.20 Hz, 2H), 8.49 (d, J ¼ 8.80 Hz,
2H), 8.76 (s,1H). 13C NMR (d, CDCl3): 127.0, 129.0 (2), 129.5 (2), 129.6
(2), 132.2 (2), 133.2, 137.1, 140.2, 165.2, 167.9, 168.0, 190.1. MS: M/Z
310.0 (M-1)þ. Anal. calcd. for C16H10ClN3S: C, 61.63; H, 3.20; N, 13.47.
Found: C, 62.04; H, 3.15; N, 13.74.
3e, 3-Phenyl-5-p-methylphenyl-1,2,4-thiazolo[2,3-c]-s-triazole
1
IR (KBr): n max 1650 (C55C, C55N), 1610, 1575 (C-N) cm21. H NMR (d,
CDCl3): 2.47 (s, 3H), 7.29–7.37 (m, 2H), 7.50–7.56 (m, 3H), 7.91–7.94
(m, 2H), 8.43 (d, J ¼ 8.30 Hz, 2H), 8.75 (s, 1H).13C NMR (d, CDCl3): 21.9,
126.4, 128.9 (2), 129.5 (2), 129.9 (2), 131.1 (2), 132.6, 133.3, 145.3, 164.7,
167.7, 168.8, 190.1. MS: M/Z 290.1 (M-1)þ. Anal. calcd. for C17H13N3S:
C, 70.07; H, 4.50; N, 14.42. Found: C, 69.55; H, 4.37; N, 15.22.

Synthesis of Thiazolo[2,3-c]-s-triazoles
1757
3f, 3-p-Methoxyphenyl-5-p-methylphenyl-l,2,4-thiazolo[2,3-c]-
s-triazole
IR (KBr): n max 1650 (C55C, C55N), 1610, 1575 (C-N) cm21. 1H NMR (d,
CDCl3): 2.47 (s, 3H), 3.91 (s, 3H), 7.01 (d, J ¼ 8.80 Hz, 2H), 7.34
(d, J ¼ 8.20 Hz, 2H), 7.88 (d, J ¼ 8.80 Hz, 2H), 8.43 (d, J ¼ 8.20 Hz, 2H),
8.72 (s, 1H). 13C NMR (d, CDCl3): 21.9, 55.5, 114.5 (2), 125.0, 126.2,
126.5, 129.8 (2), 130.6 (2), 131.5 (2), 145.0, 164.3, 167.2, 168.0, 190.1.
MS: M/Z 320.1(M-1)þ. Anal. calcd. for C18H15N3OS: C, 67.27; H, 4.70;
N, 13.07. Found: C, 67.30; H, 4.00; N, 13.12.
Regeneration of Linear Poly[(4-diacetoxyiodo)styrene]
Recovered iodinated polystyrene (2.5 g) was added to 40 ml of CH2Cl2 and
heated to make it dissolve. The solution then was put in 200 ml of methanol
and 2.1 g of puried iodinated polystyrene, from which 2.9 g of poly[(4-diace-
toxyiodo)styrene] was prepared by the reported method,[4] too. Its exact
loading capacity was 2.51 mmol/g.
ACKNOWLEDGMENTS
This work was supported by the grants from the Science and Technology
Committee of Ji Lin Province, China.
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