A convenient synthesis of 3,5-diaryl-1,2,4-selenadiazoles

Article abstract of DOI:10.1081/SCC-120022171

3,5-Diaryl-1,2,4-selenadiazoles were prepared in high yields from primary selenoamides using poly[styrene(iodosodiacetate)] as oxidant. The polymer reagent could be regenerated and reused.

Full text of DOI:10.1081/SCC-120022171

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Õ
SYNTHETIC COMMUNICATIONS
Vol. 33, No. 16, pp. 2823–2827, 2003
A Convenient Synthesis of
,5-Diaryl-1,2,4-selenadiazoles
3
1
,2,
1
Xian Huang * and Jiangmin Chen
1
Department of Chemistry, Zhejiang University,
Xixi Campus, Hangzhou, P.R. China
2
State Key Laboratory of Organometallic Chemistry,
Shanghai Institute of Organic Chemistry, Chinese
Academy of Sciences, Shanghai, P.R. China
ABSTRACT
3
,5-Diaryl-1,2,4-selenadiazoles were prepared in high yields from
primary selenoamides using poly[styrene(iodosodiacetate)] as oxidant.
The polymer reagentcould be regenera te d and reused.
Key Words: Primary selenoamide; 3,5-Diaryl-1,2,4-selenadiazole;
Poly[styrene(iodosodiacetate)].
*
Correspondence: Xian Huang, Department of Chemistry, Zhejiang University,
Xixi Campus, No. 148, Tianmushan Road, Hangzhou, 310028, P.R. China; State
Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic
Chemistry, Chinese Academy of Sciences, Shanghai, 200032, P.R. China;
Fax: þ86-571-88807077; E-mail: huangx@mail.hz.zj.cn.
2
823
DOI: 10.1081/SCC-120022171
Copyright & 2003 by Marcel Dekker, Inc.
0039-7911 (Print); 1532-2432 (Online)
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2
824
Huang and Chen
1
,2,4-Selenadiazole derivatives have potential biological activities and
[
1]
are important intermediates in medicinal chemistry. 1,2,4-Selenadiazoles
were firstly synthesized by treatment of selenocarboxamides with iodine in
[
2]
1904. Up to now, several methods have been developed for the prepara-
tion of 1,2,4-selenadiazole derivatives.
[
3–6]
[3]
Geordeler described a method
for the synthesis of 5-amino-3-alkyl- and 5-amino-3-aryl-1,2,4-selenadia-
[
zoles from N-haloamidies and potassium selenocyanate. Shafiee
4]
reported the reaction of a-bromoketones with selenobenzamide to form
the title compounds. The title compounds can also be obtained from the
[
reaction of primary selenoamides with I2, NBS or other oxidants.
5]
[6]
[6]
However, most of these methods seem to have some limitations such
as laborious manipulation or low yields. In this article, we report a
convenient method for the synthesis of 3,5-diaryl-1,2,4-selenadiazoles.
We firstly prepared the 3,5-diaryl-1,2,4-selenadiazoles from primary
selenoamides with (diacetoxyiodo)benzene which was extensively used in
[
7–9]
organic synthesis as an efficient oxidant.
treated with (diacetoxyiodo)benzene in CH Cl at room temperature for
Primary selenoamide 1a was
2
2
10 min to afford 2a in high yield (Table 1, Entry 1). This result encour-
aged us to examine oxidation of other primary selenoamides with (dia-
cetoxyiodo)benzene. As we can see from Table 1 (Entries 1–3), this
method is applicable to oxidizing primary selenoamides to 3,5-diaryl-
1,2,4-selenadiazoles in high yields. But the desired oxidation products
Table 1. Synthesis of 3,5-diaryl-1,2,4-selenadiazoles.
a
Yield (%)
b
Entry
Substrate, Ar
1a, C H
Product
Purity
c
1
2
3
4
5
6
7
8
9
2a
2b
2e
2a
2b
2c
2d
2e
2f
95
—
—
6
5
c
1b, p-ClC
1e, p-CH
1a, C
1b, p-ClC H
6
H
4
92
c
93
3
C
6
H
4
—
d
H
6 5
93
>90
>90
>90
>90
>90
>90
>90
>90
d
90
6
4
4
d
1c, p-BrC
1d, p-FC
1e, p-CH C H
6
H
88
d
6
H
4
83
d
87
3
6
4
d
1f, p-CH
1g, p-(CH
1a, C H
3
OC
)
6
H
4
85
d
1
1
0
1
3
2
NC
6
H
4
2g
2a
80
92
e
6
5
a
Yields based on 1.
1
b
Determined by H NMR (400 MHz) of crude product.
Reaction with (diacetoxyiodo)benzene.
c
d
Reaction with poly[styrene(iodosodiacetate)].
Use regenerated poly[styrene(iodosodiacetate)].
e

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3
,5-Diaryl-1,2,4-selenadiazoles
2825
Ar
I(AcO)2
Se
Se
2
N
,
CH Cl rt
N
Ar
NH2
2
2
Ar
1
2
Scheme 1.
are contaminated by the by-product iodobenzene after reaction.
Sometimes, chromatographic techniques should be used to purify the
[
10]
products. Therefore, we chose poly[styrene(iodosodiacetate)]
was prepared from linear polystyrene and had the similar reactivity to
diacetoxyiodo)benzene to replace (diacetoxyiodo)benzene to carry out
which
(
the corresponding reaction (Sch. 1).
Compared with (diacetoxyiodo)benzene, the use of poly[styrene(io-
dosodiacetate)] offers a simple and convenient work-up and the by-
product poly(iodostyrene) can be regenerated and reused with no loss
of activity. The results of this reaction are summarized in Table 1
(
Entries 4–11).
In conclusion, we have developed a convenient method to prepare
3,5-diaryl-1,2,4-selenadiazoles from primary selenoamides using poly[-
styrene(iodosodiacetate)] as oxidant with the advantages of ease of
manipulation, short reaction times, high yields and regeneration, and
recycling of the polymer reagent with no loss of reactivity.
EXPERIMENTAL
[
10]
Poly[styrene(iodosodiacetate)] was prepared as Lit. described and
its functional group is 2.80 mmol/g by iodometry. Melting points were
1
uncorrected. H NMR spectra were recorded at 400 MHz on a Brucker
AC-400 spectrometer in CDCl with TMS as internal standard.
3
1
3
C NMR spectra were recorded on a Bruker AC-400 (100 MHz)
spectrometer in CDCl . Infrared spectra were determined on a Bruker
3
Vector 22 instrument using KBr pellets. Mass spectra were recorded on a
HP 5989B MS spectrometer. Elemental analyses were performed on an
EA-1110 instrument.
General Procedure for the Synthesis of
3,5-Diaryl-1,2,4-selenadiazoles
Poly[styrene(iodosodiacetate)] (0.36 g, 1.0 mmol) was added at room
temperature to a stirred solution of primary selenoamide (1.0 mmol)

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826
Huang and Chen
in CH Cl (20 mL) and the reaction mixture was stirred at room tem-
2
2
perature for 30 min. The reaction mixture was filtrated and the filtrate
was washed with saturated NaHCO (20 mL), extracted with CH Cl
2
3
2
(
2 ꢀ 10 mL) and dried over MgSO . After evaporating the solvent,
4
ether (20 mL) was added to cause precipitation, the precipitate was col-
lected by filtration for reusing, and the filtrate was evaporated the solvent
to give the product.
ꢁ
[5]
ꢁ
1
Compound 2a. M.p.: 84–85 C (Lit : 85 C). H NMR: ꢀ (ppm):
.40–8.42 (m, 2H), 8.00–8.02 (m, 2H), 7.46–7.67 (m, 6H). IR (KBr):
8
3
7
050, 2923, 1517, 1485, 1453, 1444, 1322, 1300, 1234, 1104, 967, 756,
ꢂ1
03, 680 cm
.
Compound 2b. M.p.: 166–167 C (Lit : 168 C). H NMR: ꢀ (ppm):
ꢁ
[5]
ꢁ
1
7
1
.62 (d, J ¼ 8.4 Hz, 4H), 7.47 (d, J ¼ 8.7 Hz, 4H); IR (KBr): 2924, 1590,
ꢂ1
507, 1477, 1399, 1090, 1014, 832, 735 cm .
Compound 2c. M.p.: 161–162 C (Lit : 162 C). H NMR: ꢀ (ppm):
ꢁ
[5]
ꢁ
1
8
2
7
.24–8.26 (m, 1H), 7.84–7.86 (m, 1H), 7.60–7.65 (m, 4H), 7.51–7.53 (m,
H); IR (KBr): 2924, 1584, 1507, 1474, 1394, 1311, 1069, 1012, 965, 830,
ꢂ1
32 cm
.
Compound 2d. Colorless needle, m.p.: 171–172 C. H NMR: ꢀ (ppm):
ꢁ
1
8
1
.37–8.40 (m, 2H), 7.99–8.02 (m, 2H), 7.14–7.22 (m, 4H). IR (KBr): 2924,
ꢂ1
604, 1511, 1487, 1409, 1232, 1156, 1114, 1104, 969, 842, 832, 739 cm
.
MS (m/z): 50 (12.9), 75 (14.5), 94 (35.1), 95 (10.9), 121 (100), 122 (8.8),
1
3
2
1
8
01 (56.3); 322 (4.9, M þ 1). C NMR: 130.9, 130.8, 130.4, 130.3, 116.7,
16.5, 115.8, 115.6. Anal. calcd. for C H F N Se: C, 52.34; H, 2.49 ; N,
2
.72; Found: C, 52.28 ; H, 2.56; N, 8.83.
Compound 2e. M.p.: 121–122 C (Lit : 122 C). H NMR: ꢀ (ppm):
.27–8.29 (d, J ¼ 8.0 Hz, 2H), 7.87–7.89 (d, J ¼ 8.0 Hz, 2H), 7.27–7.30 (m,
H), 2.41 (s, 6H). IR (KBr): 3013, 2917, 1607, 1522, 1485, 1401, 1314,
1
4
8
2
ꢁ
[5]
ꢁ
1
8
4
1
6
292, 1275, 1231, 1201, 1173, 1094, 1036, 1019, 964, 829, 816, 735,
ꢂ1
93 cm .
Compound 2f. M.p.: 136–137 C (Lit : 137 C). H NMR: ꢀ (ppm):
.32–8.34 (m, 1H), 7.92–7.94 (m, 1H), 7.57–7.59 (m, 4H), 6.93–7.00
ꢁ
[5]
ꢁ
1
8
(
m, 2H), 3.85–3.88 (m, 6H). IR (KBr): 3000, 2938, 2840, 1606, 1509,
1
6
490, 1413, 1303, 1279, 1250, 1176, 1167, 1090, 1025, 963, 831, 742,
ꢂ1
82 cm
.
ꢁ
1
Compound 2g. Colorless needle, m.p.: 143–144 C. H NMR: ꢀ (ppm):
.45–7.47 (d, J ¼ 8.0 Hz, 4H), 6.62–6.64 (d, J ¼ 8.0 Hz, 4H), 3.03 (s, 12H);
7
IR (KBr): 2909, 1608, 1527, 1447, 1372, 1226, 1173, 1123, 1066, 942, 818,
ꢂ1
6
56 cm . MS (m/z): 42 (10.7), 51 (3.5), 77 (4.0), 91 (2.5), 102 (11.9), 129
1
3
(
11.8), 145 (67.2), 147 (10.7), 226 (8.10), 372 (12.7, M þ 1). C NMR:
152.5, 133.4, 120.8, 111.4, 97.4, 39.9. Anal. calcd. for C H N Se: C,
18 20 4
58.22; H, 5.39; N, 15.09. Found: C, 58.31; H, 5.32; N, 15.11.

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3
,5-Diaryl-1,2,4-selenadiazoles
ACKNOWLEDGMENT
The project 29932020 was supported by the National Natural
2827
Foundation of China and this work was also supported by the
Laboratory of Organometallic Chemistry, Shanghai Institute of
Chemistry, Academia Sinica.
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Received in Japan November 12, 2002

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