New many fold 1,2,3-selenadiazole aromatic derivatives

Article abstract of DOI:10.1002/jhet.5570410607

The many fold aromatic ketones 2a-d are versatile compounds for the synthesis of the many fold 1,2,3-selenadiazole aromatic derivatives 5a-d. The preparation starts with the reaction between the many fold bromomethylene benzene derivatives 1a-d and 4-hydroxyacetophenone, which are transformed through the reaction with semicarbazide hydrochloride or ethylhydrazine carboxylate into the corresponding semicarbazones derivatives 3a-d or hydrazones 4a-d. The reaction with selenium dioxide leads to regiospecific ring closure of semicarbazones or hydrazones to give the many fold 1,2,3-selenadiazole aromatic derivatives in high yield.

Full text of DOI:10.1002/jhet.5570410607

Nov-Dec 2004
887
New Many Fold 1,2,3-Selenadiazole Aromatic Derivatives
Mousa Al-Smadi* and Samer Ratrout
Department of Applied Chemical Sciences, Jordan University of Science and Technology
P.O.Box 3030, Irbid 22110, Jordan
Received March 30, 2004
The many fold aromatic ketones 2a-d are versatile compounds for the synthesis of the many fold 1,2,3-
selenadiazole aromatic derivatives 5a-d. The preparation starts with the reaction between the many fold bro-
momethylene benzene derivatives 1a-d and 4-hydroxyacetophenone, which are transformed through the
reaction with semicarbazide hydrochloride or ethylhydrazine carboxylate into the corresponding semicar-
bazones derivatives 3a-d or hydrazones 4a-d. The reaction with selenium dioxide leads to regiospecific
ring closure of semicarbazones or hydrazones to give the many fold 1,2,3-selenadiazole aromatic deriva-
tives in high yield.
J. Heterocyclic Chem., 41, 887 (2004).
Scheme 1
Heterocyclic systems with multi-arm 1,2,3-thiadia-
zoles were recently prepared from the corresponding
multi-arm ketones using the Hurd and Mori method by
Meier et. al [1-2], however heterocyclic systems con-
taining two 1,2,3-selenadiazole rings were also recently
prepared through reacting the corresponding multiple
diazoketones with Lawesson reagent by Reddy et. al [3-
4]. But multi-arm 1,2,3-selenadiazoles are still
unknown. Therefore depending on a previous knowledge
of the principal investigator in synthesizing multi-arm
1,2,3-thiadiazoles, the analogous multi-arm selenadia-
zoles are prepared.
On the other hand, selenium containing heterocycles are
of increasing interest because of their chemical properties
specially their wide application in synthesizing other hete-
rocyclic compounds [5-10] and biological activities as
antibacterial and antifangi [11-13].
Remarkable differences are known between Se- and S-
containing compounds. Due to the large size of the Se-
atom. Selenium compounds show an increased polarizabil-
ity and therefore they are in general, less stable than the S-
analogues [14-17].
We reported herein on our efforts to generate the many-
fold branched benzene derivative compounds 5a, 5b, 5c
and 5d in which the 1,2,3-selenadiazole rings are linked to
the core via phenoxymethylene spacers.
Synthesis of the Compounds 5a-d.
Our synthetic procedure started from the manyfold bro-
momethylbenzene derivatives 1a-d. The multiple ketones
2a-d were prepared by reacting derivatives 1a-d with 4-
hydroxyacetophenone in acetone in the presence of
The preparation was carried out following the method
that is first reported by Lalezari et. al [18-20], through
reacting the corresponding semicarbazones or hydrazones
of α -ketomethylene functionality, which contain
aminocarbonyl or ethoxycarbonyl groups as good leaving
groups with selenium dioxide in the presence of acetic
acid. The (E)-configuration around the CN double bond
K CO . Condensation of 2a-d with semicarbazide in
2
3
absolute ethanol or with ethoxyhydrazine in chloroform
forms the corresponding semicarbazones 3a-d or the
ethoxycarbonyl hydrazones 4a-d, respectively. Treatment
of 3a-d or 4a-d with selenium dioxide in acetic acid using
Lalezari procedure provided compounds 5a-d in high
chemical yield.
1
was found by NOE measurements in the H-nmr to pre-
dominate largely. Irradiation at the N-H protons frequency
of semicarbazones 3a-d or hydrazones 4a-d leads to an
interaction with the CH -protones of the keto groups. The
3
Conclusion.
E/Z-isomerization of the (C=N) bond has no influence on
the following ring closure process with selenium diox-
ide/acetic acid.
New multi-arm benzene derivatives 5a-d containing
two, three, four and six 1,2,3-selenadiazole rings were

888
M. Al-Smadi and S. Ratrout
Vol. 41
Table 1
Chemical Percentage Yield of Compounds 2-, 3-, 4- and 5a-d
spectra were acquired by using the instrument MAT95 of the
Finnigan Company (FD: 5 kV Ionizing energy, field desorption).
The signals were given as m/z with the relative intensity between
brackets. The Elemental analyses were performed in the analyti-
cal laboratory of the institute of organic chemistry of university
of Mainz, Germany. Bromo compounds (Di-, Tri-, Tetra- and
hexa-bromomethylbenzene), ethylhydrazine carboxylate, semi-
carbazide hydrochloride and sodium acetate were obtained from
Aldrich.
synthesized and characterized. The synthesis of the com-
pounds 5a-d was carried out in a multi-step procedure
starting from the corresponding multi-arm ketones and
applying the Lalezari method. All the compounds 5a-d
were obtained in a high chemical yield. Since the com-
pounds 5a-d are solids it was found that the mp of the
compound decreases by increasing the number of the
1,2,3-selenadiazole rings.
General Procedure for the Preparation of Multiple Ketones (3a-
d)[1].
EXPERIMENTAL
A mixture of 4-hydroxyacetophenone (4.10 g, 30.10 mmol)
and (3.56 g, 13.55 mmol) of 1,4-di(bromomethyl)benzene 1a or
(3.23 g, 9.03 mmol) of 1,3,5-tris(bromomethyl)benzene 1b or
(2.85 g, 6.32 mmol) of 1,2,4,5-tetrakis(bromomethyl)benzene 1c
or (2.64 g, 4.20 mmol) of 1,2,3,4,5,6-hexakis(bromomethyl)ben-
zene 1d, respectively, potassium carbonate (4.17 g, 30.10 mmol)
and the same equivalent amount of potassium iodide as the
bromo compound with few drops of Aliquat 336 in dry acetone
(100 mL) were refluxed for 48 hours. Reaction progress was fol-
lowed by TLC with chloroform as the mobile phase until
The solvents were purified by standard procedures. The melt-
ing points (mp) were determined on electrothermal digital melt-
ing point apparatus and are uncorrected. Infrared (ir) spectra
were recorded using a NICOLET 410 FT-IR spectrometer (ν in
-1
cm ). The ir spectra of pure substances were measured as KBr-
1
13
pellets. The H and C nmr spectra were recorded on Bruker
AM400 and AC200 spectrometers in deuteriochloroform or
DMSO-d with TMS as internal standard. The spectral data were
6
reported in delta (δ) units relative to TMS reference line. Mass

Nov-Dec 2004
New Many Fold 1,2,3-Selenadiazole Aromatic Derivatives
889
completion. After cooling, the reaction mixture was diluted with
water (50 mL) and extracted with dichloromethane (3 × 40 mL).
The combined organic layers were dried over magnesium sul-
phate. The solvent was evaporated under vacuum and the residual
solid was washed with diethyl ether. When necessary, a recrystal-
ization from acetone or chloroform was performed.
A mixture of semicarbazide hydrochloride (3.33 g, 30.00
mmol) and sodium acetate (2.5 g, 30.00 mmol) was dissolved in
absolute ethanol (40 mL). The mixture was heated for 15 min
under reflux. The mixture was filtered while hot to remove pre-
cipitated sodium chloride. The filtrate was mixed with ketone 2a
(5.05 g, 13.50 mmol) or ketone 2b (4.67 g, 9.00 mmol) or ketone
2c (4.20 g, 6.30 mmol) or ketone 2d (4.10 g, 4.20 mmol), respec-
tively. The reaction mixture was heated till refluxing then two
drops of concentrated hydrochloric acid were added. The mixture
was heated under reflux overnight with continuously removal of
generated water; after which the solvent was removed under vac-
uum and the residue was washed with diethyl ether.
1-{4-[4-Mono(4-acetylphenoxymethyl)benzyloxy]phenyl}-1-
ethanone (2a).
This compound was obtained as colorless crystals (acetone),
mp 181-182°; ir (potassium bromide): 1668 (C=O), 1591, 1239,
-1
1
996, 823 cm ; H nmr (deuteriochloroform): δ 2.53 (s, 6H,
CH ), 5.12 (s, 4H, CH O), 7.00 and 7.90 (d, d, 4H, 4H, AA'BB'),
3
2
1-{4-[4-Mono(4-acetylphenoxymethyl)benzyloxy]phenyl}-1-
ethanone-N-aminocarbonylsemicarbazone) (3a).
13
7.44 (s, 4H, Central benzene ring protons); C nmr (deuteri-
ochloroform): δ 26.40 (CH ), 69.70 (C3), 127.80 (C1), 136.20
3
(C2), 114.50 and 130.60 (C5 and C6), 130.60 and 162.40 (C4 and
C7), 196.70 (C=O); ms: (5 kV, fd) m/z (%) 374 (100).
This compound was obtained as white powder, mp 300° (dec);
ir (potassium bromide): 3417 (NH ), 3212 (NH), 1681(C=O),
2
-1
1
Anal. Calcd. for C
H
O : C, 76.99; H, 5.92. Found: C,
1604, 1502, 1418, 1239, 1014, 829 cm ; H nmr (dimethyl sul-
foxide-d ): δ 2.12 (s, 6H, CH ), 5.20 (s, 4H, CH O), 5.90 (s, 4H,
24 22
4
76.78; H, 5.81.
6
3
2
NH ), 7.08 and 7.89 (d, d, 4H, 4H, AA'BB'), 7.45 (s, 4H, Central
benzene ring protons), 9.21 (s, 2H, NH); C nmr (dimethyl sul-
2
1-{4-[3,5-Di(4-acetylphenoxymethyl)benzyloxy]phenyl}-1-
ethanone (2b).
13
foxide-d ): δ 13.30 (CH ), 69.30 (C3), 127.80 (C1), 136.41 (C2),
6
3
This compound was obtained as pale yellow powder, mp 82-
83°; ir (potassium bromide): 2910, 1670 (C=O), 1591, 1500,
114.50 and 128.00 (C5 and C6), 131.17 and 159.70 (C4 and C7),
143.00 (C=N), 158.70 (C=O); ms: (5 kV, fd) m/z (%) 488.5
(100).
-1 1
1250, 1172, 836 cm ; H nmr (dimethyl sulfoxide-d ): δ 2.49 (s,
6
9H, CH ), 5.22 (s, 6H, CH O), 7.09 and 7.90 (d, d, 6H, 6H,
Anal. Calcd. for C H N O : C, 63.92; H, 5.78; N, 17.20.
Found: C, 63.71; H, 5.72; N, 17.15.
3
2
26 28
6 4
13
AA'BB'), 7.53 (s, 3H, Central benzene ring protons); C nmr
(dimethyl sulfoxide-d ): δ 26.30 (CH ), 69.20 (C3), 126.60
6
3
1-{4-[3,5-Di(4-acetylphenoxymethyl)benzyloxy]phenyl}-1-
ethanone-N-aminocarbonylsemi-carbazone (3b).
(C1), 137.20 (C2), 114.61 and 130.50 (C5 and C6), 130.10 and
162.00 (C4 and C7), 196.30 (C=O); ms: (5 kV, fd) m/z (%) 523
(100).
This compound was obtained as pale yellow powder, mp 240°
Anal. Calcd. for C
75.81; H, 5.68.
H
O : C, 75.84; H, 5.79. Found: C,
(dec); ir (potassium bromide): 3417 (NH ), 3250 (NH), 1681
(C=O), 1579, 1508, 1470, 1226, 829 cm ; H nmr (dimethyl sul-
33 30
6
2
-1 1
foxide-d ): δ 2.13 (s, 9H, CH ), 5.15 (s, 6H, CH O), 6.55 (s, 6H,
6
3
2
1-{4-[2,4,5-Tri(4-acetylphenoxymethyl)benzyloxy]phenyl}-1-
ethanone (2c).
NH ), 6.98 and 7.76 (d, d, 6H, 6H, AA'BB'), 7.49 (s, 3H, Central
2
13
benzene ring protons), 9.25 (s, 3H, N-H); C nmr (dimethyl sul-
This compound was obtained as colorless powder, mp 224-
226°; ir (potassium bromide): 1665 (C=O), 1590, 1502, 1250,
1170, 830 cm ; H nmr (deuteriochloroform): δ 2.53 (s, 12H,
foxide-d ): δ 13.38 (CH ), 69.15 (C3), 126.44 (C1), 137.76 (C2),
6
3
114.54 and 127.50 (C5 and C6), 131.20 and 158.73 (C4 and C7),
144.11 (C=N), 157.90 (C=O); ms: (5 kV, fd) m/z (%) 693.77
(100).
-1
1
CH ), 5.23 (s, 8H, CH O), 6.94 and 7.89 (d, d, 8H, 8H, AA'BB'),
3
2
13
7.65 (s, 2H, Central benzene ring protons); C nmr (deuteri-
Anal. Calcd. for C H N O : C, 62.33; H, 5.67; N, 18.17.
36 39
9 6
ochloroform): δ 26.30 (CH ), 67.70 (C3), 129.80 (C1), 135.10
Found: C, 62.29; H, 5.61; N, 18.03.
3
(C2), 114.41 and 130.60 (C5 and C6), 131.10 and 162.10 (C4 and
C7), 196.50 (C=O); ms: (5kV, fd) m/z (%) 670 (100).
1-{4-[2,4,5-Tri(4-acetylphenoxymethyl)benzyloxy]phenyl}-1-
Anal. Calcd. for C
H O : C, 75.21; H, 5.71. Found: C,
ethanone-N-aminocarbonylsemicarbazone (3c).
42 38 8
75.13; H, 5.59.
This compound was obtained as white powder, mp 250° (dec);
1-{4-[2,3,4,5,6-Penta(4-acetylphenoxymethyl)benzyloxy]-
phenyl}-1-ethanone (2d).
ir (potassium bromide): 3429 (NH ), 3180 (NH), 1670 (C=O),
1599, 1418, 1258, 836 cm ; H nmr (dimethyl sulfoxide-d ): δ
6
2
-1
1
2.12 (s, 12H, CH ), 5.34 (s, 8H, CH O), 5.99 (s, 8H, NH ), 7.06
3
2
2
This compound was obtained as colorless powder, mp 234-
235°; ir (potassium bromide): 1675 (C=O), 1604, 1508, 1239,
and 7.86 (d, d, 8H, 8H, AA'BB'), 7.71 (s, 2H, Central benzene
13
ring protons), 9.19 (s, 4H, NH); C nmr (dimethyl sulfoxide-d ):
-1
1
6
1002, 832 cm ; H nmr (deuteriochloroform): δ 2.50 (s, 18H,
CH ), 5.26 (s, 12H, CH O), 6.89 and 7.83 (d, d, 12H, 12H,
δ 13.38 (CH ), 67.08 (C3), 129.10 (C1), 134.80 (C2), 114.70 and
3
3
2
127.50 (C5 and C6), 130.50 and 159.70 (C4 and C7), 144.00
(C=N), 157.50 (C=O); ms: (5 kV, fd) m/z (%) 899 (100).
13
AA'BB'); C nmr (deuteriochloroform): δ 26.20 (CH ), 63.60
3
(C2), 137.70 (C1), 114.21 and 130.70 (C4 and C5), 131.30 and
161.80 (C3 and C6), 196.40 (C=O); ms: (5 kV, fd) m/z (%)
967(100).
Anal. Calcd. for C H N O : C, 61.46; H, 5.61; N, 18.70.
46 50 12
8
Found: C, 61.32; H, 5.51; N, 18.63.
Anal. Calcd. for C H O : C, 74.52; H, 5.63. Found: C,
1-{4-[2,3,4,5,6-Penta(4-acetylphenoxymethyl)benzyloxy]-
60 54 12
74.27; H, 5.54.
phenyl}-1-ethanone-N-aminocarbonylsemicarbazone (3d).
General Procedure for the Preparation of Multiple
This compound was obtained as white powder, mp 300° (dec);
Semicarbazones (3a-d).
ir (potassium bromide): 3417 (NH ), 3212 (NH), 1687 (C=O),
2

890
M. Al-Smadi and S. Ratrout
Vol. 41
-1
1
15.19 (CH -C=N), 60.98 (CH CH O), 67.40 (C3), 129.37 (C1),
3 3 2
1597, 1431, 1239, 1014, 829 cm ; H nmr (dimethyl sulfoxide-
d ): δ 2.08 (s, 18H, CH ), 5.37 (s, 12H, CH O), 6.41 (s, 12H,
135.43 (C2), 115.08 and 128.00 (C5 and C6), 131.76 and 159.33
(C4 and C7), 148.70 (C=N), 154.80 (C=O); ms: (5 kV, fd) m/z
(%) 1015 (100).
6
3
2
NH ), 6.93 and 7.70 (d, d, 12H, 12H, AA'BB'), 9.18 (s, 6H, NH);
2
13
C nmr (dimethyl sulfoxide-d ): δ 13.29 (CH ), 63.90 (C2),
6
3
Anal. Calcd. for C H N O : C, 63.89; H, 6.16; N, 11.04.
137.60 (C1), 114.30 and 127.50 (C4 and C5), 130.40 and 159.60
(C3 and C6), 143.90 (C=N), 157.40 (C=O); ms: (5 kV, fd) m/z
(%) 1309.4 (100).
54 62 8 12
Found: C, 63.58; H, 6.09; N, 10.97.
1-{4-[2,3,4,5,6-Penta(4-acetylphenoxymethyl)benzyloxy]-
phenyl}-1-ethanone-N-ethoxycarbonylhydrazone (4d).
Anal. Calcd. for C H N O : C, 60.54; H, 5.54; N, 19.25.
66 72 18 12
Found: C, 60.35; H, 5.54; N, 19.30.
This compound was obtained as white solid powder, mp 293°
(dec); ir (potassium bromide): 3231(NH), 1719 (C=O), 1610,
General Procedure for the Preparation of Multiple Hydrazones
(4a-d)[1].
-1 1
1502, 1233, 1047, 829 cm ; H nmr (dimethyl sulfoxide-d ): δ
6
1.23 (t, 18H, CH CH O), 2.12 (s, 18H, CH -C=N)), 4.13 (q,
A solution of (3.74 g, 10.00 mmol) of di- or (5.22 g, 10.00
mmol) of tri- or (6.70 g, 10.00 mmol) of tetra- or (9.67 g, 10.00
mmol) of hexa-ketone 2a-d, a few drops of concentrated
hydrochloric acid and (6.23 g, 60.00 mmol) or (9.35 g, 90.00
mmol) or (12.50 g, 120.00 mmol) or (18.70 g, 180.00 mmol) of
ethylhydrazine carboxylate in dry chloroform (50 mL) was
heated under reflux for overnight with continuous removal of
generated water. The solution was concentrated and the residue
was washed with diethyl ether and chloroform.
3
2
3
12H, CH CH O), 5.29 (s, 12H, CH O), 6.95 and 7.58 (d, d, 12H,
3
2
2
13
12H, AA'BB'), 9.96 (s, 6H, NH); C nmr (dimethyl sulfoxide-
d ): δ 14.23 (CH CH O), 15.01 (CH -C=N), 60.95 (CH CH O),
6
3
2
3
3
2
64.36 (C2), 138.09 (C1), 114.86 and 127.94 (C4 and C5), 131.93
and 159.41 (C3 and C6), 149.25 (C=N), 154.76 (C=O); ms: (5
kV, fd) m/z (%) 1484 (100).
Anal. Calcd. for C H N O : C, 63.15; H, 6.11; N, 11.33.
78 90 12 18
Found: C, 62.79; H, 6.27; N, 11.44.
General Procedure for Preparation of Multiple 1,2,3-
Selenadiazoles 5a-d.
1-{4-[4-Mono(4-acetylphenoxymethyl)benzyloxy]phenyl}-1-
ethanone-N-ethoxycarbonylhydrazone (4a).
Hydrazones 4a (0.15 g, 0.27 mmol) or hydrazone 4b (0.7 g, 0.9
mmol) or hydrazone 4c (0.60 g, 0.59 mmol) or hydrazone 4d
(0.70 g, 0.47 mmol) was dissolved in glacial acetic acid (30 mL)
with vigorouse stirring and gentle heating 40-45 °C. The solution
was treated with selenium dioxide powder (0.09 g, 0.81 mmol) or
(0.89 g, 8.1 mmol) or (0.79 g, 7.08 mmol) or (0.94 g, 8.46 mmol),
respectively and the mixture was kept under gentle heating with
vigorouse stirring. After 2 min, color of the mixture becomes red.
TLC analysis showed that the reaction was completed in two
days. The mixture was filtered and the filtrate was poured over
ice water and extracted with chloroform (3 × 50 mL). The com-
bined organic layers were washed with saturated sodium hydro-
gen carbonate solution, dried using magnesium sulphate. The sol-
vent was removed under vacuum. The crude product was chro-
matographed using methanol or ethyl acetate as eleuent. The
recrystalization was followed from chloroform/hexane.
This compound was obtained as white powder, mp 259-260°; ir
(potassium bromide): 3205 (NH), 3035, 1705 (C=O), 1600, 1500,
-1
1
1230, 822 cm ; H nmr (dimethyl sulfoxide-d ): δ 1.22 (t, 6H,
6
CH CH O), 2.15 (s, 6H, CH -C=N), 4.16 (q, 4H, CH CH O),
3
2
3
3
2
5.10 (s, 4H, CH O), 6.99 and 7.87 (d, d, 4H, 4H, AA'BB'), 7.43 (s,
2
13
4H, Central benzene ring protons), 9.99 (s, 2H, NH); C nmr
(dimethyl sulfoxide-d ): δ 13.60 (CH CH O), 14.70 (CH -C=N),
6
3
2
3
60.80 (CH CH O), 67.80 (C3), 127.60 (C1), 136.30 (C2), 114.50
3
2
and 127.60 (C5 and C6), 130.50, 160.10 (C4 and C7), 148.81
(C=N), 154.30 (C=O); ms: (5 kV, fd) m/z (%) 547 (100).
Anal. Calcd. for C H N O : C, 65.92; H, 6.27; N, 10.25.
30 34
4 6
Found: C, 65.99; H, 6.18; N, 10.15.
1-{4-[3,5-Di(4-acetylphenoxymethyl)benzyloxy]phenyl}-1-
ethanone-N-ethoxycarbonylhydrazone (4b).
This compound was obtained as pale yellow powder, mp 202-
204°; ir (potassium bromide): 3200 (NH), 3035, 1705 (C=O), 1600,
-1 1
1,4-Bis[4-(1,2,3-selenadiazole-4-yl)phenoxymethyl]benzene
(5a).
1503, 1238, 1040, 830 cm ; H nmr (dimethyl sulfoxide-d ): δ 1.24
6
(t, 9H, CH CH O), 2.17 (s, 9H, CH -C=N)), 4.15 (q, 6H,
3
2
3
CH CH O), 5.18 (s, 6H, CH O), 7.03 and 7.67 (d, d, 6H, 6H,
3
2
2
This compound was obtained as yellow-orange solid, mp 160-
162°; ir (potassium bromide): 3077, 2911, 1732, 1610, 1533,
AA'BB'), 7.52 (s, 3H, Central benzene ring protons), 9.99 (s, 3H,
13
NH); C nmr (dimethyl sulfoxide-d ): δ 14.30 (CH CH O), 15.20
-1
1
6
3
2
1456, 1239, 1008, 822 cm ; H nmr (dimethyl sulfoxide-d ): δ
6
(CH -C=N), 60.90 (CH CH O), 69.60 (C3), 126.90 (C1), 138.06
3
3
2
5.15 (s, 4H, CH O), 7.12 and 7.21 (d, d, 4H, 4H, AA'BB'), 7.47
2
(C2), 115.10 and 128.00 (C5 and C6), 131.60 and 159.50 (C4 and
C7), 148.70 (C=N), 154.20 (C=O); ms: (5 kV, fd) m/z (%) 781 (100).
13
(s, 4H, central benzene ring protons), 9.72 (s, 2H, CHSe);
C
nmr (dimethyl sulfoxide-d ): δ 70.00 (C3), 127.89 (C1), 129.18
6
Anal. Calcd. for C H N O : C, 64.60; H, 6.20; N, 10.76.
42 48
6 9
(C2), 116.10 and 130.00 (C5 and C6), 121.00 and 152.00 (C4 and
C7), 160.00 (C8), 138.00 (C9); ms: (5 kV, fd) m/z (%) 552 (100).
Found: C, 64.48; H, 6.13; N, 10.50.
Anal. Calcd. For C H N O Se : C, 52.18; H, 3.28; N, 10.14;
Se, 28.60. Found: C, 52.03; H, 3.25; N, 10.20.
24 18
4
2
2
1-{4-[2,4,5-Tri(4-acetylphenoxymethyl)benzyloxy]phenyl}-1-
ethanone-N-ethoxycarbonylhydrazone (4c).
4-(4-{3,5-Di[4-(1,2,3-selenadiazole-4-yl)phenoxymethyl]benzy-
loxy}phenyl)-1,2,3-selenadiazole (5b).
This compound was obtained as white powder, mp 211-213°;
ir (potassium bromide): 3200 (NH), 3045, 1700 (C=O), 1596,
-1
1
1492, 1235, 1040, 828 cm ; H nmr (dimethyl sulfoxide-d ): δ
This compound was obtained as yellow-orange solid, mp 100-
102°; ir (potassium bromide): 3096, 2917, 1738, 1610, 1534,
6
1.24 (t, 12H, CH CH O), 2.16 (s, 12H, CH -C=N)), 4.16 (q, 8H,
3
2
3
-1
1
CH CH O), 5.27 (s, 8H, CH O), 7.03, 7.65 (d, d, 8H, 8H,
1450, 1239, 1046, 835 cm ; H nmr (deuteriochloroform): δ
3
2
2
AA'BB'), 7.71 (s, 2H, Central benzene ring protons), 9.98 (s, 4H,
5.15 (s, 6H, CH O), 7.11 and 7.20 (d, d, 6H, 6H, AA'BB'), 7.49
2
13
13
NH); C nmr (dimethyl sulfoxide-d ): δ 14.28 (CH CH O),
(s, 3H, Central benzene ring protons), 9.72 (s, 3H, CHSe);
C
6
3
2

Nov-Dec 2004
New Many Fold 1,2,3-Selenadiazole Aromatic Derivatives
891
[2] M. Al-Smadi, N. Hanold and H. Meier, J. Heterocyclic
Chem., 34, 605 (1997).
[3] D. B. Reddy, N. C. Babu, V. Padmavathi and A. Padmaja,
Tetrahedron, Vol. 53, No.51, 17351
nmr (deuteriochloroform): δ 69.69 (C3), 126.00 (C1), 129.70
(C2), 115.99 and 130.03 (C5 and C6), 118.80 and 149.15 (C4 and
C7), 160.15 (C8), 137.60 (C9); ms: (5 kV, fd) m/z (%) 789 (100).
Anal. Calcd. For C H N O Se : C, 50.21; H, 3.06; N, 10.65;
33 24
6
3
3
(1997).
Se, 30.01. Found: C, 50.10; H, 3.00; N, 10.59.
[4] D. Bhaskar Reddy, A. Somasekhar Reddy and V.
Padmavathi, Synth. Commun., 31, 22, 3429
(2001).
4-(4-{2,4,5-Tri[4-(1,2,3-selenadiazole-4-yl)phenoxymethyl]ben-
zyloxy}phenyl)-1,2,3-selenadiazole (5c).
[5] Y. Zhou and H. Heimgartner, Helvetica Chemica Acta, 83,
539 (2000).
[6] M. L. Petrov, M. A. Abramov, W. Dehaen and S. Toppet,
Tetrahedron Lett., 40, 3903 (1999).
[7] H. Detert and H. Meier, Liebigs. Ann., 1557 (1997).
[8] Y. Zhou and H. Heimgartner, Helvetica Chemica Acta, 83,
539 (2000).
[9] Y. Nishiyama, Y. Hada, M. Anjiki, S. Hanita and N.
Sonoda, Tetrahedron Lett., 40, 6293
This compound was obtained as yellow-orange solid, mp 87-
88°; ir (potassium bromide): 3096, 2930, 1725, 1611, 1527,
1469, 1245, 1040, 822 cm ; H nmr (deuteriochloroform): δ 5.25
-1 1
(s, 8H, CH O), 7.12 and 7.22 (d, d, 8H, 8H, AA'BB'), 7.70 (s, 2H,
2
13
Central benzene ring protons), 9.71 (s, 4H, CHSe); C nmr (deu-
teriochloroform): δ 67.70 (C3), 124.00 (C1), 129.80 (C2), 115.89
and 130.12 (C5 and C6), 118.80 and 152.60 (C4 and C7), 159.92
(C8), 136.40 (C9); ms: (5kV, fd) m/z (%) 1026 (100).
Anal. Calcd. For C H N O Se : C, 49.13; H, 2.95; N, 10.92;
42 30
8
4
4
(1999).
Se, 30.77. Found: C, 49.10; H, 2.75; N, 10.71.
[10] P. Arsenyan, K. Oberte, O. Pudova and E. Lukevies,
Chemistry of Heterocyclic Compounds,
38 1437 (2002).
4-(4-{2,3,4,5,6-Penta[4-(1,2,3-selenadiazole-4-yl)phe-
noxymethyl]benzyloxy}phenyl)-1,2,3-selenadiazole (5d).
[11] F. T. Burling and B. M. Goldenstein, J. Am. Chem. Soc,
114, 2313 (1992).
[12] A. R. Jalilian, S. Sattari, M. Bineshmarvasti, M.
Daneshtalab and A. Shafiee, Farmaco, 58, 63
(2003).
[13] I. Lalezari, A. Shafiee, J. Khorrami and A. Soltani, J. of.
Pharm. Sci., 67, 1336 (1987).
[14] M. A. Abramov, W. Dehaen, B. D' Hooge, M. L. Petrov, S.
Smeets, S. Toppet and M. Voets,
This compound was obtained as yellow-orange solid, mp 77-
78°; ir (potassium bromide): 3096, 2975, 1739, 1611, 1527,
1469, 1220, 989, 841 cm ; H nmr (deuteriochloroform): δ 5.27
-1
1
(s, 12H, CH O), 7.06 and 7.17 (d, d, 12H, 12H, AA'BB'), 9.68 (s,
2
13
6H, CHSe); C nmr (deuteriochloroform): δ 63.62 (C2), 128.50
(C1), 115.36 and 130.20 (C4 and C5), 119.20 and 152.40 (C3 and
C6), 159.61 (C8), 137.70 (C9); ms: (5kV, fd) m/z (%) 1500 (100).
Anal. Calcd. For C
H N O Se : C, 48.02; H, 2.82; N,
60 42 12 6 6
11.20; Se, 31.57. Found: C, 47.91; H, 2.74; N, 11.11.
Tetrahedron, 56, 3933 (2000).
[15] D' Hooge, B. Smeets, S. Toppet and S. Dehaeam, J. Chem.
Soc, Chem. Commun., 1753
Acknowledgements.
(1997).
We are grateful to the Deanship of Scientific Research of the
Jordan University for Science and Technology for financial sup-
port. Also, we thank Prof. H. Meier from Mainz University-
Germany for help and worthful discussion.
[16] G. L'abbe, B. Haelterman and W. Dehaen, J. Chem. Soc.
Perkin Trans, 2203 (1994).
[17] F. Malek-Yazdi and M. Yalpani, Synthesis, 328 (1977).
[18] I. Lalezari and A. Shafiee, Tetrahedron Lett., 58, 5105
(1969).
REFERENCES AND NOTES
[19] I. Lalezari and A. Shafiee, J. Org. Chem., 36, 19, 2836
(1971).
[20] I. Lalezari, A. Shafiee and M. Yalpani, J. Org. Chem., 38,
2, 338 (1973)
[1] M. Al-Smadi and H. Meier, Liebigs Ann. Chem., 2357
(1997).