The synthesis of cross-linked poly[styrene(iodoso diacetate)] and application in preparation of pyrazoline

Article abstract of DOI:10.1081/SCC-100000186

The 2% cross-linked poly[styrene(iodoso diacetate)] was synthesized, which was applied effectively to the synthesis of pyrazoline derivative, and can be regenerated and reused for the same reaction.

Full text of DOI:10.1081/SCC-100000186

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THE SYNTHESIS OF CROSS-LINKED
POLY[STYRENE(IODOSO DIACETATE)] AND
APPLICATION IN PREPARATION OF PYRAZOLINE
Xian Huang a & Qing Zhu a
a Chemistry Department, Xixi Campus, Zhejiang University, Hangzhou, 310028, P.R. China
Published online: 09 Nov 2006.
To cite this article: Xian Huang & Qing Zhu (2001): THE SYNTHESIS OF CROSS-LINKED POLY[STYRENE(IODOSO DIACETATE)]
AND APPLICATION IN PREPARATION OF PYRAZOLINE, Synthetic Communications: An International Journal for Rapid
Communication of Synthetic Organic Chemistry, 31:1, 111-115
To link to this article: http://dx.doi.org/10.1081/SCC-100000186
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SYNTHETIC COMMUNICATIONS, 31(1), 111–115 (2001)
THE SYNTHESIS OF CROSS-LINKED
POLY[STYRENE(IODOSO DIACETATE)]
AND APPLICATION IN PREPARATION
OF PYRAZOLINE
Xian Huang∗ and Qing Zhu
Chemistry Department, Xixi Campus, Zhejiang University,
Hangzhou, 310028 P.R. China
ABSTRACT
The2%cross-linkedpoly[styrene(iodosodiacetate)]wassyn-
thesized, which was applied effectively to the synthesis of pyrazo-
line derivative, and can be regenerated and reused for the same
reaction.
Recently, hypervalent iodine compounds were widely used in organic syn-
thesis in view of their potential utility for oxidation and radical reactions (1–3).
The phenyliodine diacetate (PID) is the most frequently used and easily available
reagent in the family of hypervalent iodine compounds. It has some advantages,
such as mild reaction conditions, easily handling, and high selectivity (1,4). But
PID has three major shortcomings: (1) the byproduct iodobenzene is difficult to
remove from the product; (2) the iodobenzene cannot be reused; and (3) it pol-
lutes the environment. The poly[styrene(iodoso diacetate)] is the ideal reagent to
solve the problem. It can be recovered just by filtration and reused. This is also
environmentally safe.
∗ To whom correspondence should be addressed.
111
Copyright ꢀ 2001 by Marcel Dekker, Inc.
www.dekker.com
C

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HUANG AND ZHU
First, weprepared the2% cross-linkedpoly[styrene(iodosodiacetate)] (5). In
presenceof50%sulfuricacid, commerciallyavailable2%cross-linkedpolystyrene
[CPS](200–400 mesh) reacted with iodine and iodine pentoxide in nitrobenzene
at 90◦C for 50 hours to give iodinated polystyrene [CPIS].
Elemental analysis revealed that CPIS contains 33.5% iodine. It shows the resin’s
functional group is 2.64 mmol/g, indicating that 41.2% of the aromatic rings had
been successfully iodinated. This intermediate was then nearly quantitatively con-
verted into the poly[styrene(iodoso diacetate)] [CPSID] by treatment with freshly
prepared peracetic acid at 40◦C overnight.
The loading capacity of the polymer was obtained by iodometry and deter-
mined to be 1.99 mmol/g, indicating that 98.5% of the iodinated benzene ring had
been converted to phenyliodine diacetate. The resin product was best stored away
from direct sunlight and in a refrigerator.
It is known that pyrazoline derivatives were useful compounds not only as
intermediates in the synthesis of pyrazoles, but also as effective chemical bleach-
ing agents and as luminescent and fluorescent substances (6). It has been reported
(7) that aldehyde hydrazones and acrylonitrile could be used to synthesize 1,3-
disubstituted-2-pyrazoline-5-carbonitriles in the presence of phenyliodine diac-
etate. Based on these results, under an N2 atmosphere, we carried out this reaction
with2%cross-linkedpoly[styrene(iodosodiacetate)]at−10◦Cfor4hours. Thisre-
action took place smoothly and got 1,3-disubstituted-2-pyrazoline-5-carbonitriles
in good yields.
Furthermore, the regeneration and reuse of cross-linked poly[styrene(iodoso
diacetate)] from recovered poly iodostyrene were also studied. The result is shown
in Table 1.
In conclusion, 2% cross-linked poly[styrene (iodoso diacetate)] has good
reactivity in this reaction. After the reaction with CPSID, poly (iodostyrene), which
was a by-product in the reaction, can be recovered by simple filtration in good yield
and the poly[styrene(iodoso diacetate)] can be regenerated and reused.

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113
Table 1. 1,3-Disubstituted-2-pyrazoline-5-carbonitriles Prepared
m.p./◦C
Found Lit. (5)
Yield (%)a
Pyrazoline (2)
R
CPSID DIB
2a
2ab
2b
2c
2d
2e
2f
C6H5
C6H5
p-CH3OC6H4
P-NO2C6H5
C6H5CH CH 154–156 154–156
145–147 145–147
145–147 145–147
147–148 145–147
209–211 209–211
60
58
60
68
69
69
68
60
60
58
70
69
==
p-ClC6H4
m-ClC6H4
140–142
133–134
aYield of isolated product based on 1.
bReaction with regenerated CPSID.
EXPERIMENTAL
Aldehyde hydrazones 1 were prepared according to reported method (8)
by refluxing aldehyde with hydrazine in ethanol in the presence of some acetic
and water. 2% cross-linked polystyrene was purchased from Aldrich. All melting
1
points are uncorrected. H-NMR spectra were recorded at 60 MHz or a Varian
EM-300 spectrometer from a solution in CDCl3 or d6-DMSO of the product.
Infrared spectra were recorded on a Perkin Elmer 683 spectrophotometer in KBr
with absorption in cm−1
.
Iodination of 2% Cross-Linked Polystyrene
A 250-ml three-necked round-bottomed flask was charged with 10 g
polystyrene, 10 g iodine, 4 g I2O5 in mixture of 40 mL CCl4, 40 mL 50%H2SO4,
and 120 mL of nitrobenzene. The reaction was carried out under reflux at 90◦C for
50 h total. The polymer was washed by 15 mL ether, acetone, and CH2Cl2 three
times. Iodinated polystyrene (14.3 g) was obtained. I%: 33.5%. About 41.2%
benzene ring was iodinated. IR ν cm−1 1000, 817, 760, 700.
Preparation of Cross-Linked Poly[Styrene (Iodoso Diacetate)]
Hydrogen peroxide (30%, 40 mL) was added dropwise to acetic anhydride
solution (145 mL) at 40◦C and was stirred for another 4 h. The temperature was not
allowed to rise over 45◦C. To this solution, 2% cross-linked poly (iodostyrene)(6 g)
was added, then the solution was kept at 40◦C overnight. The product was collected

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HUANG AND ZHU
by filtration. IR ν cm−1 1654, 1500, 1410, 1360, 1280, 1000, 817, 760, 700. The
loading of capacity of the polymer was obtained by iodometry. The functional
group is 1.99 mmol/g.
Typical Procedure for Preparation of
1,3-Disubstituted-2-pyrazoline-5-carbonitriles 2
CPSID (1.2 mmol) was added at –10◦C to a stirred suspension of 1 mmol of
aldehyde hydoazone 1 in 5 mL acrylonitrile under an N2 atmosphere. The starting
material disappearance (monitored by TLC) was about 4 h. The reaction mixture
was filtrated and the liquid was concentrated under vacuum. To the residue was
added 20 mL CH2Cl2 and the organic layer was washed with 10 mL 5% aq.
Na2CO3 solution, 10 ml H2O, and dried over MgSO4. After evaporation of the
solvent, the crude material was purified by column chromatograph on silica gel
using CH2Cl2-petroleum ether (1:1) as eluent.
1
2a: White solid; mp 145◦–147◦C (lit (7) 145◦–147◦C); H-NMR (CDCl3)
δ: 8.0–7.3 (m, 10H, ArH), 5.0 (t, J 8 Hz, 5-H), 3.7 (d, J 8 Hz, 2H, 4-H); IR (KBr)
+
ν (cm−1); 2234 (C N), 1600 (C N); MS: m/z (relative intensity) 247 (M 100),
==
≡
220 (39), 194 (17), 91 (82), 77 (61).
2b: White solid: mp 147◦–148◦C (lit (7) 145◦–147◦C); H-NMR (CDCl3)
1
δ: 7.8–6.9 (m, 9H, ArH), 4.9 (t, J 8 Hz, 1H, 5-H), 3.8 (s, 3H, OCH3), 3.6 (d, J
8 Hz, 2H, 4H); IR (KBr) ν (cm−1), 2240 (C N), 1605 (C N). MS: m/z (relative
==
≡
intensity) 277 (M+ 100), 250 (61), 224 (7), 91 (48), 77 (28).
2c:Yellowsolid;mp209◦–211◦C(lit(7)209◦–211◦C);1H-NMR(d6-DMSO)
δ: 8.4–8.10 (m, 4H, ArH) δ: 7.4–7.1 (m, 5H, ArH), 5.80 (q, J 9 Hz, 1H, 5-H) 3.9
(t, J 9 Hz, 2H, 4H); IR (KBr) ν (cm−1): 1605 (C N); MS m/z (relative intensity)
==
292 (M+100), 265 (31), 91 (70), 77 (47).
2d: Greenish solid; mp 154◦–156◦C (lit (7) 154◦–156◦C); 1H-NMR (CDCl3)
==
δ: 7.8–6.6 (m., 12H, ArH, -CH CH-), 4.9 (t, J 8 Hz, 1H, 5-H), 3.4 (d, J 8 Hz, 2H,
+
4-H) IR (KBr) ν (cm−1): 1610 (C N); MS m/z (relative intensity) 273 (M 100),
==
245 (44), 220 (23), 91 (31), 77 (32).
2e: White solid; mp 140◦–142◦C; 1H-NMR (CDCl3) δ: 7.9–7.4 (m, 9H, ArH)
5.1 (t, J 8 Hz, 1H, 5-H), 3.7 (d, J 8 Hz, 2H, 4-+H); IR (KBr) ν (cm−1): 2240 (C N);
≡
==
1610 (C N); MS m/z (relative intensity) M 281 (83.85), 254 (83.62), 91 (100),
77 (83.01). Anal. Calcd for C16H12N3Cl: C, 68.21; H, 4.29; N, 14.91. Found: C,
68.43; H, 4.32; N, 14.68.
1
2f: White solid; mp 133◦–134◦C; H-NMR (CDCl3) δ: 7.9–7.5 (m, 9H,
ArH), 5.0 (t, J 8 Hz, 1H, 5-H), 3.8 (d, J 8 Hz, 2H, 4-H) IR (KBr) ν (cm−1): 1610
+
==
(C N): MS m/z (relative intensity) 281 (M 84), 254 (30), 91 (100), 77 (65) Anal.
Calcd for C16H12N3Cl: C, 68.21; H, 4.29; N, 14.91. Found: C, 67.81; N, 14.38; H:
4.15.

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115
Regeneration and Reuse of CPSID from Recovered
Poly (Iodostyrene)
After the reaction, poly (iodostyrene), to which CPSID was converted, was
recovered by simple filtration. Then, the recovered PIS was oxidized to CPSID
with peracetic acid, and was assayed again by iodometry. IR ν cm−1 1654, 1500,
1410, 1360, 1280, 1000, 817, 760, 700. The functional group is 1.97 mmol/g. It
was applied to the reaction and has the same activity as the first prepared CPSID.
ACKNOWLEDGMENTS
The project 29932020 was supported by the National Natural Foundation
of China and this work was also supported by the Laboratory of Organometallic
Chemistry, Shanghai Instituted of Chemistry, Academic Sinica.
REFERENCES
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3. Varroglis, A. Chem. Soc. Rev. 1981, 10, 377.
4. Yang. R.Y.; Dai, L.X. J. Org. Chem. 1993, 58, 3381.
5. Yamada, Y.; Okawara, M. Markromol Chem. 1972, 152, 153.
6. Kost, A.N.; Grandberg, I.I. Advances in Heterocyclic Chemistry; Academic
Press: New York, 1966; Vol. 6, 347.
7. Chen, D.W.; Chen, Z.C. Syn. Comm. 1995, 25, 1617.
8. Vecea, M.; Gasparic, J. Detection and Identification of Organic Compounds;
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Received April 4, 2000

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