One-pot synthesis of substituted 3-amino-2-nitrothiophenes and selenophenes

Article abstract of DOI:10.1016/j.tet.2008.01.078

In this work, we described an easy preparation of substituted 3-amino-2-nitrothiophenes and selenophenes. Substituted β-chloroacrylonitriles were reacted with sodium sulfide or sodium selenide and bromonitromethane to yield the expected compounds in a one-pot three-step procedure in good yields.

Full text of DOI:10.1016/j.tet.2008.01.078

Available online at www.sciencedirect.com
Tetrahedron 64 (2008) 3232e3235
www.elsevier.com/locate/tet
One-pot synthesis of substituted 3-amino-2-
nitrothiophenes and selenophenes
b
David Thomae a, Juan Carlos Rodriguez Dominguez a, Gilbert Kirsch a, , Pierre Seck
*
a Laboratoire d’Inge´nierie Mole´culaire et Biochimie Pharmacologique, Institut Jean Barriol, FR CNRS 2843, 1 Boulevard Arago, 57070 METZ, France
b Laboratoire de Chimie, Faculte´ des Sciences, de la Technologie et de la Communication, Universite´ du Luxembourg, 162a,
avenue de la Fa€ıencerie, L-1511 Luxembourg, Luxembourg
Received 11 December 2007; received in revised form 15 January 2008; accepted 17 January 2008
Available online 25 January 2008
Abstract
In this work, we described an easy preparation of substituted 3-amino-2-nitrothiophenes and selenophenes. Substituted b-chloroacrylonitriles
were reacted with sodium sulfide or sodium selenide and bromonitromethane to yield the expected compounds in a one-pot three-step procedure
in good yields.
Ó 2008 Elsevier Ltd. All rights reserved.
Keywords: 3-Amino-2-nitrothiophenes; 3-Amino-2-nitroselenophenes; Bromonitromethane; Substituted b-chloroacrylonitriles
1. Introduction
NH2
NO2
CN
SH
BrCH2NO2
BrCH2NO2
Nitrothiophene derivatives have some versatile biological
uses.1,2 It has been showed that they inhibit the growth of Es-
cherichia Coli, Micrococcus Luteus and Aspergillus Niger.1
They were also used as the precursors of N-(5-substituted)-thio-
phene-2-alkylsulfonamides, which are potent inhibitors of 5-lip-
oxygenase.2 Moreover, 3-amino-2-nitrobenzo[b]thiophene was
used as starting material for the preparation of dyes.3
S
I
R2
NH2
NO2
R2
R1
CN
R1
S
Na
S
II
The synthesis of substituted 3-amino-2-nitrothiophenes has
notbeenverymuchdescribedespeciallybyusingbromonitrome-
thaneas oneof the reagents. Only a few teams worked inthis field
of investigation. Fishwick et al. described the preparation of
3-amino-2-nitrobenzo[b]thiophene (I) starting from 2-sulfanyl-
benzonitrile and bromonitromethane (Scheme 1).4 In the same
paper, theysynthesized some3-amino-2-nitrothiophenesstarting
from the sodium salt of disubstituted 3-sulfanyl-2-propeneni-
triles and bromonitromethane (Scheme 1).4 They obtained
compounds (II) in yields ranging from 30% to 70%. Only one
thiophene (III) was synthesized by Gewald and Hain starting
NC
Ph
NH2
NO2
NC
Ph
CN
Cl
1) Na2S.9H2O
2) BrCH2NO2
S
III
NC
NH2
NO2
NC
Ph
CN
Cl
1) Se, NaBH4
2) BrCH2NO2
Ph
Se
IV
Scheme 1. 3-Amino-2-nitrophenes and 3-amino-2-nitroselenophene in the
literature. R1¼eSeMe, R2¼eCN, eCO2Et, eCONH2; R1¼eNHePh,
R2¼eCN, eCO2Et, eSO2PH.
* Corresponding author. Tel.: þ33 3 87 31 52 95; fax: þ33 3 87 31 58 01.
E-mail address: kirsch@univ-metz.fr (G. Kirsch).
0040-4020/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2008.01.078

D. Thomae et al. / Tetrahedron 64 (2008) 3232e3235
3233
Table 1.
Prepared substituted 3-amino-2-nitrothiophenes
from a disubstituted b-chloroacrylonitrile using sodium sulfide
andbromonitromethane.5 In thesame publication, they described
the formation of 5-phenyl-3-amino-2-nitroselenophene IV
(Scheme 1).
Entry
Substituted
b-chloroacrylonitrile 1
Substituted 3-amino-2-
nitrothiophene 2
Yield (%)
a
b
c
d
e
f
R1¼p-CH3ePhe
R1¼p-CH3OePhe
R1¼p-ClePhe
R1¼t-Bue
R1¼p-CH3ePhe
R1¼p-CH3OePhe
R1¼p-ClePhe
R1¼t-Bue
60
62
64
70
80
70
78
Recently, we have described some examples of preparation
of substituted 2-nitrothiophenes V starting from b-substituted-
b-chloroacroleins (Scheme 2).10 In this work, in continuation
of previous research on the synthesis of 3-aminothiophenes
and selenophenes and their use for condensed systems,6e9
we describe the preparation of new substituted 3-amino-2-
nitrothiophenes and selenophenes (Scheme 2).
R1¼p-FePhe
R1¼p-NO2ePhe
R1¼p-PhePhe
R1¼p-FePhe
R1¼p-NO2ePhe
R1¼p-PhePhe
g
NH2
CN
Cl
h
80
CHO
i, ii, iii
NO2
S
R
NO2
S
R
Cl
Table 2.
Prepared substituted 3-amino-2-nitroselenophenes
V
Scheme 2. Substituted 2-nitrothiophenes synthesized by our team. (i)
Na2S$9H2O, DMF; (ii) BrCH2NO2; (iii) NaOH.
Entry
Substituted
b-chloroacrylonitrile 1
Substituted 3-amino-2-
nitroselenophene 3
Yield (%)
a
b
c
R1¼p-CH3ePhe
R1¼p-CH3OePhe
R1¼p-ClePhe
R1¼t-Bue
R1¼p-CH3ePhe
R1¼p-CH3OePhe
R1¼p-ClePhe
R1¼t-Bue
58
66
57
62
2. Results and discussion
d
From b-chloroacroleins, the access to the b-chloroacrylo-
nitriles gave us the opportunity to prepare the substituted
3-amino-2-nitrothiophenes 2(aeh) and 3-amino-2-nitroseleno-
phenes 3(aed) in a one-pot procedure (Scheme 3).
of a solution of sodium hydroxide. Pouring the reaction mixture
in water gave the compounds 2(aeh) in good yields (Table 1).
As for 2(aeh), the preparation of substituted 3-amino-2-
nitroselenophenes 3(aed) was very straightforward. Sodium
selenide was prepared by a known method.9a Freshly prepared
sodium selenide reacts with b-chloroacrylonitriles 1(aed) in
DMF at 60 ꢀC to form the selenolate. After 2 h, bromonitro-
methane was added dropwise at 0 ꢀC and then heated to
60 ꢀC for 2 h. Cyclization was performed by the addition of
a solution of sodium hydroxide. Pouring the reaction mixture
in water gave compounds 3(aed) in good yields (Table 2).
NH2
NO2
CN
Cl
i, ii, iii
R1
R1
S
2 (a-h)
60-80%
1 (a-h)
NH2
NO2
CN
Cl
iv, v, vi
3. Conclusion
R1
R1
Se
3 (a-d)
57-68%
1 (a-d)
In conclusion, an easy way of synthesizing 3-amino-2-
nitrothiophenes and selenophenes was developed. These new
compounds open many possibilities for further synthesis.
Scheme 3. 3-Amino-2-nitrothiophenes and 3-amino-2-nitroselenophenes. (i)
Na2S$9H2O, DMF; (ii) BrCH2NO2; (iii) NaOH; (iv) Na2Se, DMF; (v)
BrCH2NO2; (vi) NaOH.
4. Experimental section
4.1. General
Starting material 1 was prepared by VilsmeiereHaacke
Arnold reaction, oximation and dehydration. This method
has already been described by different groups.6e8,11 Bromo-
nitromethane was obtained with a slight modification to the
method established by Fishwick et al.4 Freshly distilled nitro-
methane was used and bromine was added at 0 ꢀC in only 5 s in-
stead of 35 s as reported. With this change, bromonitromethane
was obtained in 61% yield avoiding the formation of dibromo-
nitromethane and tribromonitromethane as we described recen-
tly.10a Bromonitromethane was used without further purification.
Preparation of substituted 3-amino-2-nitrothiophenes 2(aeh)
wasverystraightforward. Sodiumsulfidenonahydratewasadded
to b-chloroacrylonitriles 1(aeh) in DMF and heated at 55 ꢀC to
form the thiolate. Bromonitromethane was added dropwise at
room temperature. Cyclization was performed by the addition
Reagents were purchased from ACROS Organics. Thin Layer
Chromatography (TLC) was carried out by using Silica Gel 60
F-254 plates and n-hexane/ethyl acetate (3:1) as an eluent. Melt-
ingpointswere determined onaStuartScientificSMP3 capillary
meltingpointapparatusandare uncorrected. IRspectrawereper-
formedin a Perkin Elmer Spectrum BxFT-IR spectrophotometer.
Elemental analyses were done in a LECO CHNS 932 equipment.
4.2. Synthesis of substituted b-chloroacrylonitriles 1(aeh):
general procedure
Compounds 1(aeh) were prepared as described earlier.6e8,11
Derivatives 1(aeh) recrystallized in cyclohexane gave better

3234
D. Thomae et al. / Tetrahedron 64 (2008) 3232e3235
yields in the following reaction as when using the crude
product.
4.3.5. 3-Amino-5-(4-fluorophenyl)-2-nitrothiophene (2e)
Yield: 80%. Filtration while hot in ethanol gave a green
solid; mp 230e232 ꢀC. IR (KBr): 3442 (s), 3304 (s), 1525
1
(s) cmꢁ1. H NMR (250 MHz, DMSO): d 6.97 (s, 1H, CH),
4.3. Synthesis of substituted 3-amino-2-nitrothiophenes
2(aeh): general procedure
7.32 (m, 2H, 2ꢂCH), 7.75 (m, 2H, 2ꢂCH), 8.18 (s, 2H,
NH2). 13C NMR (62.9 MHz, DMSO): d 115.13, 116.25,
120.17, 128.41, 148.39, 151.92, 161.30, 165.26. Anal. Calcd
for C10H7FN2O2S: C, 50.41; H, 2.96; N, 11.76. Found: C,
50.16; H, 2.77; N, 11.96.
Na2S$9H2O (0.05 mol) was suspended in DMF (98 mL)
and stirred at 40 ꢀC for 30 min. After that time, the corre-
sponding b-chloroacrylonitriles 1(aeh) (0.05 mol) were
added. The mixture is heated at 55 ꢀC for 90 min and left to
reach room temperature. Bromonitromethane (0.05 mol) was
slowly dropped at room temperature and left to stir at 55 ꢀC
for another 90 min. The reaction was followed by TLC [n-hex-
ane/ethyl acetate (3:1)] and once finished NaOH (0.05 mol) in
water (10 mL) was added and left to stir 30 min at the same
temperature. The mixture was poured onto water (500 mL)
with good stirring. The precipitate was filtered, washed with
water, dried at room temperature until constant weight and
purified by recrystallization or column chromatography.
4.3.6. 3-Amino-2-nitro-5-(4-nitrophenyl) thiophene (2f)
Yield: 70%. Recrystallization in EtOH gave a brown solꢁid1;
mp 244e246 ꢀC. IR (KBr): 3458 (s), 3308 (s), 1511 (s) cm
.
1H NMR (250 MHz, DMSO): d 7.19 (s, 1H, CH), 7.96 (d,
J¼7.5 Hz, 2H, 2ꢂCH), 8.26 (s, 2H, NH2), 8.28 (d,
J¼7.5 Hz, 2H, 2ꢂCH). 13C NMR (62.9 MHz, DMSO):
d 117.80, 121.39, 124.44, 127.24, 137.33, 146.05, 148.01,
151.84. Anal. Calcd for C10H7N3O4S: C, 45.28; H, 2.66; N,
15.84. Found: C, 45.13; H, 2.79; N, 15.72.
4.3.1. 3-Amino-5-(4-methylphenyl)-2-nitrothiophene (2a)
4.3.7. 3-Amino-5-[1,10-biphenyl]-4-yl-2-nitrothiophene (2g)
Yield: 78%. Column chromatography with eluent cyclohex-
ane/ethyl acetate (8/2) gave a brown solid; mp 126e128 ꢀC
Yield: 60%. Recrystallization in EtOH gave a brown solꢁid1;
mp 224e227 ꢀC. IR (KBr): 3437 (s), 3307 (s), 1554 (s) cm
.
1H NMR (250 MHz, DMSO): d 2.29 (s, 3H, CH3), 6.98 (s, 1H,
CH), 7.22 (d, J¼7.5 Hz, 2H, 2ꢂCH), 7.61 (d, J¼7.5 Hz, 2H,
2ꢂCH), 8.20 (s, 2H, NH2). 13C NMR (62.9 MHz, DMSO):
d 20.91, 114.29, 125.90, 128.68, 129.94, 140.76, 149.89,
152.10, 155.56. Anal. Calcd for C11H10N2O2S: C, 56.39; H,
4.30; N, 11.96. Found: C, 56.55; H, 4.51; N, 11.72.
1
(dec). IR (KBr): 3420 (s), 3305 (s), 1560 (s) cmꢁ1. H NMR
(250 MHz, DMSO): d 7.06 (s, 1H, CH), 7.50 (m, 4H,
4ꢂCH), 7.75 (m, 5H, 5ꢂCH), 8.22 (s, 2H, NH2). 13C NMR
(62.9 MHz, DMSO): d 114.95, 120.23, 126.59, 127.25,
127.49, 128.12, 129.04, 130.39, 138.80, 142.10, 149.13,
151.59. Anal. Calcd for C16H12N2O2S: C, 64.85; H, 4.08; N,
9.45. Found: C, 65.01; H, 4.27; N, 9.22.
4.3.2. 3-Amino-5-(4-methoxyphenyl)-2-nitrothiophene (2b)
Yield: 62%. Recrystallization in EtOH gave a yellow solꢁid1;
4.3.8. 3-Amino-2-nitro-4,5-dihydronaphtho[1,2-b]-
thiophene (2h)
mp 213e215 ꢀC. IR (KBr): 3430 (s), 3307 (s), 1552 (s) cm
.
1H NMR (250 MHz, DMSO): d 3.83 (s, 3H, CH3O), 6.92 (s,
1H, CH), 7.05 (d, J¼7.5 Hz, 2H, 2ꢂCH), 7.67 (d, J¼7.5 Hz,
2H, CH), 8.18 (s, 2H, NH2). 13C NMR (62.9 MHz, DMSO):
d 55.44, 113.37, 114.78, 119.58, 123.90, 127.68, 149.97,
152.33, 161.23. Anal. Calcd for C11H10N2O3S: C, 52.79; H,
4.03; N, 11.19. Found: C, 52.68; H, 4.17; N, 11.03.
Yield: 80%. Recrystallization in EtOH gave a yellow solꢁid1;
mp 217e218 ꢀC. IR (KBr): 3432 (s), 3307(s), 1545 (s) cm
.
1H NMR (250 MHz, DMSO): d 2.71 (t, J¼7.5 Hz, 2H, CH2),
2.97 (t, J¼7.5 Hz, 2H, CH2), 7.34 (m, 3H, 3ꢂCH), 7.43 (d,
J¼7.5 Hz, 2H, 2ꢂCH), 8.18 (s, 2H, NH2). 13C NMR
(62.9 MHz, DMSO): d 20.14, 26.85, 119.86, 124.06, 126.43,
127.31, 128.01, 128.44, 130.32, 136.59, 142.04, 150.10.
Anal. Calcd for C12H10N2O2S: C, 58.52; H, 4.09; N, 11.37.
Found: C, 58.23; H, 4.22; N, 11.41.
4.3.3. 3-Amino-5-(4-chlorophenyl)-2-nitrothiophene (2c)
Yield: 64%. Recrystallization in EtOH gave a yellow solꢁid1;
mp 269e270 ꢀC. IR (KBr): 3433 (s), 3284 (s), 1561 (s) cm
.
1H NMR (250 MHz, DMSO): d 7.04 (s, 1H, CH), 7.57 (d,
J¼7.5 Hz, 2H, 2ꢂCH), 7.73 (d, J¼7.5 Hz, 2H, 2ꢂCH), 8.22
(s, 2H, NH2). 13C NMR (62.9 MHz, DMSO): d 115.63,
120.34, 127.80, 129.41, 130.30, 135.21, 148.00, 151.82.
Anal. Calcd for C10H7ClN2O2S: C, 47.16; H, 2.77; N, 11.00.
Found: C, 47.23; H, 2.61; N, 10.82.
4.4. Preparation of sodium selenide: general procedure
Selenium (0.01 mol) was added to a solution of NaOH
(0.056 mol) and
sodium
formaldehyde
sulfoxylate
(0.024 mol) in water (10 mL). After stirring for 1 h at 50 ꢀC,
the white precipitate was filtered under an inert atmosphere
and rapidly used in the next step.
4.3.4. 3-Amino-5-tert-butyl-2-nitrothiophene (2d)
Yield: 70%. Recrystallization in cyclohexane/ethanol gave
a yellow solid; mp 132e134 ꢀC. IR (KBr): 3431 (s), 3312
4.5. Synthesis of substituted 3-amino-2-nitroselenophenes
3(aed): general procedure
1
(s), 1557 (s) cmꢁ1. H NMR (250 MHz, DMSO): d 1.25 (s,
9H, 3ꢂCH3), 6.46 (s, 1H, CH), 8.02 (s, 2H, NH2). 13C
NMR (62.9 MHz, DMSO): d 30.60, 35.00, 114.66, 115.95,
151.63, 165.40. Anal. Calcd for C8H12N2O2S: C, 47.98; H,
6.04; N, 13.99. Found: C, 47.84; H, 6.14; N, 14.18.
Na2Se (0.01 mol) was suspended in DMF (10 mL) and
stirred at 60 ꢀC for 30 min. After that time, the corresponding
b-chloroacrylonitriles 1(aed) (0.01 mol) dissolved in 5 mL of

D. Thomae et al. / Tetrahedron 64 (2008) 3232e3235
3235
DMF was added. The mixture was heated at 60 ꢀC for 2 h and
cooled to 0 ꢀC. Bromonitromethane (0.01 mol) was slowly
dropped at 0 ꢀC. After addition, the mixture was heated for
2 h at 60 ꢀC. The reaction is followed by TLC (CH2Cl2) and
once finished NaOH (0.01 mol) in water (7 mL) was added
and left to stir for 1 h at the same temperature. The mixture
was poured onto water (150 mL) with good stirring. The pre-
cipitated was filtered, washed with water, dried at room tem-
perature until constant weight and recrystallized in EtOH.
4.5.4. 3-Amino-5-tert-butyl-2-nitro-3-selenophene (3d)
Yield: 62%. Recrystallization in EtOH gave an orange
solid; mp 136e138 ꢀC. IR (KBr): 3415 (s), 3302 (s), 2965
1
(s), 1617 (s) cmꢁ1. H NMR (250 MHz, DMSO): d 1.23 (s,
9H, 3ꢂCH3), 6.74 (s, 1H, CH), 8.28 (s, 2H, NH2). 13C
NMR (62.9 MHz, DMSO): d 31.40, 36.78, 117.60, 118.23,
153.90, 172.07. Anal. Calcd for C8H12N2O2Se: C, 38.88; H,
4.89; N, 11.33. Found: C, 38.95; H, 4.71; N, 11.47.
Acknowledgements
4.5.1. 3-Amino-5-(4-methylphenyl)-2-nitro-3-selenophene
(3a)
Yield: 76%. Recrystallization in EtOH gave a green solid; mp
`
We are grateful to the ‘Ministere de l’Education Nationale,
de l’Enseignement Superieur et de la Recherche’ for a Ph.D.
´
1
246e248 ꢀC. IR (KBr): 3427 (s), 3305 (s), 1606 (s) cmꢁ1. H
`
grant to D.T. We thank the ‘Ministere de la Culture, de l’En-
seignement Superieur et de la Recherche de Luxembourg’ for
NMR (250 MHz, DMSO): d 2.33 (s, 3H, CH3), 7.23 (s, 1H,
CH), 7.22 (d, J¼7.5 Hz, 2H, 2ꢂCH), 7.44 (d, J¼7.5 Hz, 2H,
2ꢂCH), 8.44 (s, 2H, NH2). 13C NMR (62.9 MHz, DMSO):
d 20.89, 117.88, 118.28, 126.19, 129.27, 129.52, 140.87,
154.36, 154.79. Anal. Calcd for C11H10N2O2Se: C, 46.99; H,
3.58; N, 9.96. Found: C, 46.89; H, 3.39; N, 10.01.
´
the financial support to J.C.R.D. and P.S. We also thank Mrs.
Veronique Poddig for recording NMR spectra.
References and notes
4.5.2. 3-Amino-5-(4-methoxyphenyl)-2-nitro-3-selenophene
(3b)
1. Morley, J. O.; Matthews, T. P. Org. Biomol. Chem. 2006, 4, 359.
2. Beers, S. A.; Malloy, E. A.; Wu, W.; Wachter, M.; Ansell, J.; Singer, M.;
Steber, M.; Barbone, A.; Kirchner, T.; Ritchie, D.; Argentieri, D. Bioorg.
Med. Chem. 1997, 5, 779.
Yield: 66%. Recrystallization in EtOH gave a yellow solꢁid1;
mp 228e230 ꢀC. IR (KBr): 3441 (s), 3325 (s), 1597 (s) cm
.
3. Hallas, G.; Towns, A. D. Dyes Pigments 1997, 3, 219.
4. Fishwick, B. R.; Rowles, D. K.; Stirling, C. J. M. J. Chem. Soc., Perkin
Trans. 1 1986, 1171.
1H NMR (250 MHz, DMSO): d 3.78 (s, 3H, CH3), 7.04 (d,
J¼7.5 Hz, 2H, 2ꢂCH), 7.17 (s, 1H, CH), 7.58 (d, J¼7.5 Hz,
2H, 2ꢂCH), 8.38 (s, 2H, NH2). 13C NMR (62.9 MHz,
DMSO): d 55.44, 103.55, 114.34, 114.59, 117.21, 127.97,
129.76, 154.62, 161.31. Anal. Calcd for C11H10N2O3Se: C,
44.46; H, 3.39; N, 9.43. Found: C, 44.32; H, 3.27; N, 9.55.
5. Gewald, K.; Hain, U. Monatsh. Chem. 1992, 123, 455.
6. Migianu, E.; Kirsch, G. Synthesis 2002, 1096.
7. Thomae, D.; Kirsch, G.; Seck, P. Synthesis 2007, 1027.
8. Thomae, D.; Kirsch, G.; Seck, P. Synthesis 2007, 2153.
9. (a) Sommen, G.; Comel, A.; Kirsch, G. Synlett 2003, 855; (b) Sommen,
G.; Comel, A.; Kirsch, G. Synthesis 2004, 451; (c) Cagniant, P.; Perin,
P.; Kirsch, G.; Cagniant, D. C.R. Hebd. Seances Acad. Sci. Ser. C 1973,
277, 37; (d) Cagniant, P.; Perin, P.; Kirsch, G.; Cagniant, D. C.R. Hebd.
Seances Acad. Sci. Ser. C 1974, 279, 851.
4.5.3. 3-Amino-5-(4-chlorophenyl)-2-nitro-3-selenophene
(3c)
Yield: 57%. Recrystallization in EtOH gave a green solid;
mp 274e276 ꢀC. IR (KBr): 3420 (s), 3280 (s), 3160 (s),
10. (a) Rodriguez Dominguez, J. C.; Thomae, D.; Kirsch, G.; Seck, P. Synlett
2008, 286; (b) Cagniant, P.; Kirsch, G. C.R. Hebd. Seances Acad. Sci. Ser. C
1975, 281, 35.
1
1624 (s) cmꢁ1. H NMR (250 MHz, DMSO): d 7.29 (s, 1H,
11. (a) Ren, W.-Y.; Rao, K.; Kein, R. J. Heterocycl. Chem. 1986, 23, 1757; (b)
Vega, S.; Gil, M. S. J. Heterocycl. Chem. 1991, 28, 1757; (c) Hartmann,
H.; Liebscher, J. Synthesis 1984, 275; (d) Hartmann, H.; Liebscher, J.
Synthesis 1984, 276; (e) Liebscher, J.; Neumann, B.; Hartmann, H.
J. Prakt. Chem. 1983, 325, 915; (f) Hartmann, H.; Liebscher, J. Synthesis
1979, 241.
CH), 7.52 (d, J¼7.5 Hz, 2H, 2ꢂCH), 7.65 (d, J¼7.5 Hz, 2H,
2ꢂCH), 8.41 (s, 2H, NH2). 13C NMR (62.9 MHz, DMSO):
d 97.63, 119.37, 128.05, 129.56, 130.32, 135.22, 152.81,
154.00. Anal. Calcd for C10H7ClN2O2Se: C, 39.82; H, 2.34;
N, 9.29. Found: C, 39.73; H, 2.22; N, 9.41.