Synthesis of some new selenonitrone compounds

Article abstract of DOI:10.13005/ojc/330615

The carbonyl selenonitrile and dicarbonyl diselane compounds were prepared by using the inorganic reagent such as potassium selenocyanate. New nitrone compounds were synthesized from the condensation of carbonyl group in the selenocarbonyl compounds with substituted N-phenylhydroxylamine and N-benzyl hydroxylamine. The resulting products were identified by physical properties such as melting point (M.p.), retardation factor (Rf) and color. Also compounds showed the expected data in identification techniques such as FTIR, 1H NMR, 13 C NMR, mass spectroscopy and Elemental analysis (CHN). The results proved the validity of the expected chemical structures of synthesized compounds.

Full text of DOI:10.13005/ojc/330615

ISSN: 0970-020 X
CODEN: OJCHEG
2017, Vol. 33, No.(6):
Pg. 2821-2826
ORIENTAL JOURNAL OF CHEMISTRY
An International Open Free Access, Peer Reviewed Research Journal
www.orientjchem.org
Synthesis of Some New Selenonitrone Compounds
BATOOL SALEH HADDAD
Department of Chemistry, College of Science, University of Basrah, Basrah, Iraq.
Corresponding author E-mail: batoolsalih16@yahoo.com
http://dx.doi.org/10.13005/ojc/330615
(Received: July 11, 2017; Accepted: August 02, 2017)
ABSTRACT
The carbonyl selenonitrile and dicarbonyl diselane compounds were prepared by using
the inorganic reagent such as potassium selenocyanate. New nitrone compounds were
synthesized from the condensation of carbonyl group in the selenocarbonyl compounds with
substituted N-phenylhydroxylamine and N-benzyl hydroxylamine. The resulting products were
identified by physical properties such as melting point (M.p.), retardation factor (Rf) and color.
Also compounds showed the expected data in identification techniques such as FTIR, 1H NMR,
13 C NMR, mass spectroscopy and Elemental analysis (CHN). The results proved the validity of
the expected chemical structures of synthesized compounds.
Keywords: Nitrones, Potassium selenonitryl, Carbonyl selenonitrile,
INTRODUCTION
compounds containing selenonitrile group and
diselenide7 group were prepared. Diphenyl
diselenide [(PhSe)2] is being carried out by the
alkaline hydrolysis of substiuted phenylselenonitrile
(the synthesis of phenylselenonitrile) is being
carried out by the reaction between potassium
cyanide and selenium metal8. For the preparation
of nitrones, the most popular method is the
condensation of aldehydes or ketones with N-
monosubstituted hydroxylamines9, 10, 11. Recently,
organ-oselenium compound has gradually
investigated because of their interesting reactivates
and their pharmaceutical applications12, 13. The
nitrone compounds are of marked interest because
of their anti-tumor14, 15, antibacterial16 and of anti-
cancer agents by intercalating DNA17, 18, 19 with
higher affinity and found it was easily metabolized
with low toxicity20. The aim of the study : according
Interest in nitrone is due to their successful
application, can be used as building blocks in the
synthesis of various natural and biologically active
compounds. Nitrone has been extensively
investigated, because of their utility as versatile
synthetic intermediates. Interest in nitrone also due
to their successful application, can be used as
building blocks in the synthesis of various natural
and biologically active compounds. The synthesis
of nitrone containing sulfur and nitrogen have been
extensively studied1, 2, while the synthesis of nitrone
containing selenonitrile and diselenide analogues
have not been appreciably investigated3, 4. This is
mainly due to the easily decomposed of nitrone
and organoselenium compounds in light and
moisture. In this research5, 6, several new carbonyl

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HADDAD., Orient. J. Chem., Vol. 33(6), 2821-2826 (2017)
to the literature, study has been done on nitrone and refluxed for 2 h. The reaction was followed by
compounds and organoselenium compounds TLC. The result was filtered, washed, dried and
separately. These two classes of compounds have recrystallized from absolute ethanol.
been combined in this study.
The general procedure of preparation
MATERIALS AND METHODS
diorgano diselenide23: To a stirred solution of (0.28
gm; 1.02 mole) in 25ml absolute ethanol of carbonyl
selenonytrile, a solution of (0.16 g, 2.47 mole ) in
15 ml absolute ethanol sodium hydroxide was
added. The mixture was stirred for 50 min. at 40oC.
After one h of reflux, the reaction was followed by
TLC, the mixture reaction cooled to R .T. and filtered.
The filtrate was acidified with 10% HCL. A red solid
compound was obtained, washed with a small
amount of benzene and dried. Recrystalization from
a mixture of methanol and dichloro methane (1:4),
gave a red solid compounds.
FT.IR spectra were measured by an
instrument called BRUKER and the range was
1
between 375-4500 cm-1. H NMR spectra were
measured by an instrument called BRUKER 300
MHz. The samples were recorded in DMSO
solutions containing TMS as internal standard.
Chemical shifts for all 1H and 13C NMR spectra were
reported in ä units downfield from internal reference
Me4Si. Elemental analyses (C, H and N) were
obtained and Mass spectra were measured by
instruments called MP- H- Vario Elemental analyzer
and Agilent- O.T-LABRO, respectively.
The General Procedure of synthesis
nitrone24-26: In a 250 ml one-necked round bottomed
flask (0.02 mole) of selenocarbonyl compounds
were placed and a solution of 15gm of anhydrous
CaCl2 with added 30 ml of absolute ethanol was
added. The solution was stirred and warmed to
All the carbonyl selenonitrile compounds
being carried out by the reaction of the
corresponding benzoyl chloride with potassium
selenocyanate. Nitrone compounds were prepared
from the condensation of carbonyl selenonitrile with
N-phenyl hydroxylamine and N-benzyl hydroxyl
amine compounds.
0
50 C and a solution of (0.02mol) of [(N-phenyl
hydroxylamine) in 30 ml of absolute ethanol was
added, to synthesis the compounds ( N1, N2, N3 and
N4) while the compound N5 was synthesized by
added N-benzyl hydroxylamine]25. 3 drops of
benzene sulfunic acid was added to the mixture.
After the addition was completed the reaction
mixture was kept with stirring in dark, overnight at
room temperature. The reaction was followed by
TLC, the mixture was cooled and then the
The general procedure of preparation
carbonyl selenonitrile21,22: To a stirred Solution
of (0.8) KCN in absolute ethanol (50 ml), (1 g.; 125
mole) of selenium metal was added. The reaction
was in red color. After 3 h. of reflux, (206 ml 0.025
mole) of substituted benzoyl chloride was added
Fig.1. IR spectrum of compound (N4)

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HADDAD., Orient. J. Chem., Vol. 33(6), 2821-2826 (2017)
benzoylchloride as explain in equation (a).
O
O
R
Cl
abs. EtOH
3 hrs
KCN + Se
KSeCN
SeCN
R
abs.EtOH
2 hrs
H3C
H3C
,
N
MeO
R =
Equation (a)
Dicarbonyl dislenide can be prepared by
the alkaline hydrolysis of carbonyl selenonitrile
compounds, as explain in equation (b).
Fig.2. Mass spectrum of compound (N4)
O
precipitated was filtered by suction filtration and
the product was recrystallized by abs. ethanol. All
the synthesized compounds were characterized by
FTIR, 1H NMR, 13C NMR, mass spectroscopy and
Elemental analysis (CHN) and all the results were
in agreement with the theoretical calculation. For
example the spectra are represented in the figures
(1 – 4) for compound (N4). Chemical structure and
some physical properties of nitrones are
represented in Table (1).
O
Cl
CH3O
SeCN
EtOH
abs. EtOH
3 hrs
KCN + Se
KSeCN
abs.EtOH
CH3O
2 hrs
O
NaOH
reflux, 1hr
Se
OCH3
CH3O
Se
O
Equation (b)
N-phenylhydroxylamine were synthesized
by the reduced of nitro aromatic compounds with
zinc dust and using water as a solvent while N-
benzylhydroxylamine was prepared by the reaction
between hydroxyl amine hydrochloride and benzyl
chloride, in the presence of sodium carbonate.
The carbonyl selenonitril compounds was
prepared by the reaction of potassium cyanide with
Table. 1: Chemical structure and some physical properties of nitrones
Symbols
N1
Time of
reflux
Color
Yield% Solution of TLC
Rf
Structures
9
Orange
55
57
70
61
69
Ethylacetate
hexane 2.5:7.5
0.54
N2
N3
N4
N5
9
Yellow
Orange
Yellow
Orange
Ethylacetate
hexane 6.5:3.5
0.66
0.61
0.59
0.66
11
10
9
Ethylacetate
hexane 5.0:5.5
Ethylacetate
hexane 7.5:2.5
Ethylacetate
hexane 5.0:5.0

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HADDAD., Orient. J. Chem., Vol. 33(6), 2821-2826 (2017)
Fig.3. 1H NMR spectrum of compound (N4)
Fig.4. 13C NMR spectrum of compound (N4)
Nitrones were synthesized by the
O
O_
N+
condensation of substituted caronyl selenonitrile
with N-phenylhydroxylamine and N benzylhy-
droxylamine as explain in equation (c) and scheme (1).
_H2O
NHOH
R1
R2
+
R2
R1
SeCN
H2O
+
CaCl2
abs.EtOH
SeCN
+
O_ OH
O
HO
H+
H O H
N
+
MeO
R2
R2=
,
NCSe
C
N
H3C
H3C
R2
R1
SeCN
R1
SeCN
,
,
N
MeO
=
R1
H
R1
Equation (c)
RESULTS
+
_
H
OH
C
O_
O_
R2
R1
_H2O
+
+
C
N
NCSe
N
R2
NCSe
H
The resulting data were obtained for the
R1
synthesized compounds from analysis data as
following:
Scheme (1)
The mechanism of synthesis nitrone compounds

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HADDAD., Orient. J. Chem., Vol. 33(6), 2821-2826 (2017)
N-(1,1-(4-methoxyphenyl) selenonitrilemethylene)
aniline oxide (N1)
N, N’-(diselanediyl bis ((4-methoxyphenyl)
methan-1-yl-1-ylidene)) bis(1-(3-methoxy
phenyl) methanamine oxide) (N5)
Yield: 55 %. M.p. 100-99oC. FTIR υ /cm-1: 1600
(C=N), 1394 (C=C), 1377 (C-N), 588 (C-Se), 2101
(C N), 1199 (N-O), 2988 (C-H aliph), 3099 (C-H
Yield: 69%. M.p. 90-92oC. FTIR υ /cm-1: 1589
(C=N), 1378 (C=C), 1378 (C-N), 581 (C-Se), 2976
1187 (N-O), (C-H aliph), 3108 (C-H arom.).1H NMR
[300MHz, (DMSO), δ (ppm)]; 1.7 (CH3), 7.6 (ph-N)
7.3 (ph-O). 13C NMR [300MHz, (DMSO), δ (ppm)];
161.0, 161.5 (C=N), 34.9, 35.1, 35.4, 35.9 (CH3),
60.4, 60.7 (CH2)121.5, 122.4, 122.9, 123.9, 124.3,
124.9, 125.6,125.5, 127.6, 128.7, 162.5, 163.9 (ph-
O), 1298, 130.6, 130.9, 131.4, 1329, 133.3, 133.9,
1
arom.). H NMR [300MHz, (DMSO), δ (ppm)]; 6.6
(4H-ph), m 7.9 (5H-ph), 3.6 (CH3). 13 C NMR
[300MHz, (DMSO), δ (ppm)]; 50.6(CH3), 123.4,
123.6, 129.0, 129.7, 129.9, 149.0 (ph-N), 130.5,
130.6, 130.8,131, 13I.7, 160.4 (ph-O), 165 (C=N),
110 (CN). For C15H12N2OSe. (Found) 54.11 % C,
3.50 % H and 8. 55 % N. MS: m/z: 330.9 (M+).
134.0, 134.6, 134.8, 135.0, 146.5 (ph-N),For
C32H28N2O6Se2. (Found) 55.38 % C, 4.20 % H and
4.12 % N. MS: m/z: 693.8 (M+).
N-(1, 1-(N, N-dimethylamino phenyl) selenonitrile
methylene) aniline oxide (N2)
Yield: 57 %. M.p. 80-82oC. FTIR υ /cm-1: 1605
(C=N), 1390 (C=C), 1380 (C-N), 589 (C-Se), 2110
(CN), 1188 (N-O), 2998 (C-H aliph), 3100 (C-H
DISCUSSION
1
arom.). H NMR [300MHz, (DMSO), δ (ppm)]; 6.4
(4H-ph), m 7.7 (5H-ph), 2.9 (CH3). 13 C NMR
[300MHz, (DMSO), δ (ppm)]; 50.6, 50.9 (CH3-N),
121.4, 121.6, 122.9, 123.3, 126.9, 147.0 (ph-N),
129.5, 129.9, 130.4, 130.5, 13I.8, 161.0 (ph-O), 162
(C=N), 115 (CN). For C16H15N3OSe. (Found) 55.30
Five new nitrone compounds were
synthesized by using the condensation method
between carbonyl group (carbonyl selenonitryl and
dicarbonyl diselenide) and N-(phenyl and
benzyl)hydroxylamine group. Various substituted
carbonyl selenonitrile compounds were
synthesized by the reaction of potassium
selenocyanate as inorganic reagent with benzoyl
chloride. This method was easier than other
methods to synthesis organoselenium compounds.
The chemical structures of new selenonitrone
compounds were characterized by identification
methods.
% C, 4.30 % H and 12.30 % N. MS: m/z: 344(M+).
N-(1, 1-(N, N-dimethylamino phenyl) selenonitrile
methylene)-4-methoxy aniline oxide (N3).
Yield: 70 %. M.p. 83-82oC. FTIR υ /cm-1: 1590
(C=N), 1375 (C=C), 1385 (C-N), 590 (C-Se), 2111
(CN), 1180 (N-O), 2988(C-H aliph), 3110 (C-H
1
arom.). H NMR [300MHz, (DMSO), δ (ppm)]; 6.7
(4H-ph-O), 7.9 (4H-ph-N), 3.9 (CH3-N), 2.7 (CH3-
O). 13 C NMR [300MHz, (DMSO), δ (ppm)]; 49.8, 50.1
(CH3-N), 50.4 (CH3-O), 122.6, 122.8, 122.9, 124.3,
124.6, 166.9 (ph-O), 127.1, 127.9, 131.4, 131.1,
133.7, 147.7 (ph-N), 162.5 (C=N), 113 (CN). For
C17H17N3O2Se. (Found) 54.57 % C, 4.90 % H and
11.22 % N. MS: m/z: 373.9(M+).
All IR spectra of nitrone compounds
showed the disappearance of (C=O) of carbonyl
selenonitrile band in the region (1700) cm-1 and
the appearance of (C=N), (N-O) and (C-N) bands
in the regions (1589-1607) cm-1, (1180-1199) cm-1
and (1377-1388) cm-1 respectively. The IR spectra
of compounds (N4, N5) showed the disappearance
of (Ca≡N) band due to the alkali hydrolysis of
(Ca≡N) group to synthesis diselenide group, while
the other synthesized nitrone compounds
containing (Ca≡N) band in the region (2101-2111)
cm-1. Mass spectroscopy gives the molecular ion
and other fragments which indicated the structure
of synthesized nitrone compounds. The nitrone
compounds have been diagnosed by elemental
analysis, and all the results were in agreement with
the theoretical. The yield of products depends on
the type of substituted groups. The presence of the
both electron donating and drawing groups in the
nitrone compound (N3) increases the yield of
products more than the donating group as in
compound (N1) or drawing group as in compound
N, N’-(diselanediyl bis (4-methoxyphenyl
methan-1-yl-1-ylidene)) bis (aniline oxide). (N4)
Yield: 61%. M.p. 90-92oC. FTIR υ /cm-1: 1620
(C=N), 13710 (C=C), 1328 (C-N), 587 (C-Se), 1186
(N-O), 2872 (C-H aliph), 31285 (C-H arom.) .1H
NMR [300MHz, (DMSO), δ (ppm)]; 3.0 (CH3), 7.3
(ph-N) 6.6 (ph-O). 13C NMR [300MHz, (DMSO), δ
(ppm)]; 161.0, 160.5 (C=N), 30.3, 31.2 (CH3), 121.8,
121.9, 122.3, 122.9, 123.3, 123.9, 123.6, 124.5,
124.6, 124.7.166.3, 166.9 (ph-O), 124.8, 124.6,
124.9, 125.4, 125.9, 127.3, 127.9, 128.6, 129.0,
129.2, 147.0, 146.5 (ph-N),For C28H24N2O4Se2.
(Found) 55.30 % C, 3.86 % H and 4.44 % N. MS: m/
z: 610 (M+).

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HADDAD., Orient. J. Chem., Vol. 33(6), 2821-2826 (2017)
(N2). The diselane nitrone containing four donating
groups as in compounds (N5) is more yield than the
diselenide nitrone containing two donating groups
as in compound (N4). Anhydrous CaCl2 was using
as a drying agent to removed the water from the
product and shifted the reaction to the right director.
ACKNOWLEDGMENT
I’m gratefully and thankful to Prof. Dr.
Graham. J. Bodwell, college of science, University
of Memorial NL-Canada for his help to complete
this research in his lab.
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