Solvent-free synthesis of new bis(benzimidazole-2-alkylthio) polyethylene oxides starting from dithiols

Article abstract of DOI:10.13005/ojc/330209

Polyethylene oxide (PEO) could be incorporated in molecular structure by several ways. A series of diacid S-alkylpolyethylene oxides 4a-i have been prepared from dithiols 1a-c through multistep reaction sequence. Novel symmetric bis-benzimidazoles (polyethylene oxide) 6a-i have been synthesized over green route. The condensation of the title compounds 4a-i on o-phenylenediamine 5, via the further deamination reaction and without catalyst, afforded the corresponding bis-benzimidazoles 6a-i in acceptable yields. The new compounds were established on the basis of their elemental analysis, IR, ¹H NMR, ¹³C NMR and mass spectral data.

Full text of DOI:10.13005/ojc/330209

ISSN: 0970-020 X
CODEN: OJCHEG
2017, Vol. 33, No. (2):
Pg. 622-627
ORIENTAL JOURNAL OF CHEMISTRY
An International Open Free Access, Peer Reviewed Research Journal
www.orientjchem.org
Solvent-Free Synthesis of New Bis(Benzimidazole-2-Alkylthio)
Polyethylene Oxides Starting from Dithiols
A. AkREMI1*and A. NOUBIgH2
1,2Department of Chemistry, Faculty of Sciences, Northern Border
University, Arar 91431, Kingdom of Saudi Arabia.
1Department of Chemistry, Faculty of science, El Manar University, Tunis, Tunisia.
2Laboratory of Physical Chemistry of Materials , Preparatory Institute for
Scientific and Technical Studies of La Marsa, 2070, Carthage University, Tunisia.
*Corresponding author E-mail: akrimimi@gmail.com
http://dx.doi.org/10.13005/ojc/330209
(Received: November 24, 2016; Accepted: January 22, 2017)
ABSTRACT
Polyethylene oxide (PEO) could be incorporated in molecular structure by several ways.
A series of diacid S-alkylpolyethylene oxides 4a-i have been prepared from dithiols 1a-c through
multistep reaction sequence.Novel symmetric bis-benzimidazoles (polyethylene oxide) 6a-i have been
synthesized over green route.The condensation of the title compounds 4a-i on o-phenylenediamine
5, via the further deamination reaction and without catalyst, afforded the corresponding bis-
benzimidazoles 6a-i in acceptable yields. The new compounds were established on the basis of
their elemental analysis, IR, 1H NMR, 13C NMR and mass spectral data.
keywords Green route, bis-benzimidazoles polyethylene oxides, condensation, NMR.
INTRODUCTION
oxide) surfaces have great potential as long
circulating systems after intravenous administration7-
.
11
Poly(ethyleneoxide) PEO is a biocompatible
eroding polymer available in a various molecules.
PEO have recently received wide attention as
sustained-release bioadhesive platform due to its
safety, ease of processing and possibility to control
drug release. In medicine, the polymer has been
incorporated in several drugs such as oral sustained-
release tablets1-5 and ocular inserts.6 in addition, it
has been shown that particles with poly(ethylene
Homobifunctional polyethylene oxides
derivatives are synthetic polyethers containing
two of the same type of functional group, available
in a range of molecular weights and various
functionalities, such as amines, maleimides, azides,
thiols, and NHS esters. Hence, they can be used for
many applications including surface functionalization

623
of a various nanoparticles12,13 and as cross-linkers we have developed an efficient one-pot solvent-free
AKREMI & NOUBIGH, Orient. J. Chem., Vol. 33(2), 622-627 (2017)
for proteins, peptides, and other biomolecules14,15
.
synthesis of a series of symmetric bis(benzimidazole-
2-alkylthio) polyethylene oxide derivatives 6a-i in
Furthermore, compounds containing acceptable yields.
benzimidazole core could exhibit a wide range of
various biological activities including anti-cancer,16
bactericidal,17 fungicidal,18,19 analgesic20 and anti-viral
properties.21 Thus, recognition of the great interest of
RESULTS AND DISCUSSIONS
The intermediates diesters 3a-i were
bis-benzimidazoles has led to a considerable effort prepared in basic medium from reaction of dithiols
being invested in designing and developing reliable 1a-c with various methyl esters bromide 2a-c.28 The
inexpensive and green synthetic routes for these saponification of compounds 3a-i was performed
compounds22-26
.
in boiling alkaline aqueous solution, giving after
acidification the corresponding diacids 4a-i (Scheme
In previous work,27, we reported the 1).Product 4a-c were isolated in good yields but 4g-i
synthesis of well-known biologically important could not be obtained probably because of the length
heterocycles starting from thiols.In the same context, of polyethylene chain which more soluble in water.
28
All results are given in Table 1.
Br
X
1a-c
+
HS
SH
Y
OMe
2a-c
Structures of compounds 4 were confirmed
by NMR and IR spectroscopy. Diacid 4b showed
a broad signal at 10.8 ppm which corresponds to
the acidic proton, its 13C NMR spectrum revealed a
peak at 179 ppm assigned to carbonyl group.The IR
spectra of product 4h displayed a stretching vibration
band at 1732 cm-1 due to C=O group.
O
NEt3/Acetone
MeO
Y
X
Y
S
OMe
S
S
O
O
3a-i
Bis-benzimidazole derivatives 6a-i were
prepared in acceptable yields without catalyst
by reaction of o-phenylenediamaine with various
diacids via melting method (Scheme 2). The
consumption of diacids was monitored by TLC (5:1,
v/v, dichloromethane: petroleum ether) as eluent.
This methodology was applied to synthetize various
bis(benzimidazole-2-alkylthio) polyethylene oxide
NaOH
HO
Y
X
Y
OH
S
O
O
4a-i
Scheme 1: Synthesis of diacid derivatives
Table 1: Yields of synthesized diacids 4a-i with various X andY groups
Entry
X
Y
Yield (%)
4a
4b
4c
4d
4e
4f
4g
4h
4i
-CH2-CH2-O-CH2-CH2-
-CH2-CH2-O-CH2-CH2-
-CH2-CH2-O-CH2-CH2-
-CH2-CH2-(O-CH2-CH2)2-
-CH2-CH2-(O-CH2-CH2)2-
-CH2-CH2-(O-CH2-CH2)2-
-CH2-CH2-(O-CH2-CH2)3-
-CH2-CH2-(O-CH2-CH2)3-
-CH2-CH2-(O-CH2-CH2)3-
-CH2-
82
79
72
58
62
57
44
51
49
-CH(CH3)-
-CH2-CH2-
-CH2-
-CH(CH3)-
-CH2-CH2-
-CH2-
-CH(CH3)-
-CH2-CH2-

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AKREMI & NOUBIGH, Orient. J. Chem., Vol. 33(2), 622-627 (2017)
derivatives and the results are summarized in Table
2.
slowly with lower yields. At the same time, diacids
containing short ethylene oxide chain, such as 6a-c,
afford acceptable yields with reduced reaction times.
The products were characterized by comparing with
authentic sample (IR, NMR and MS). NH signal
clearly appeared in the region between d 12.1 to
The effect of the length of polyethylene
oxide chain of different substituted diacids has
been investigated and the results show that diacids
bearing long polyethylene oxide chain reacted
1
13.1 in H NMR and quaternary carbon appeared
around d 150-154 in 13C NMR spectra, as expected.
In addition, the polyethylene oxide proton signal
appears as multiplet at ~3.8 ppm.The molecular ion
peak appeared at respective m/z values in GC-MS
spectrometry.
NH2
o
HO
Y
X
Y
OH
Y
X
Y
140
C
N
N
S
S
S
S
+
2
HN
O
O
NH
NH2
These new compounds may be useful
intermediates for the synthesis of organic-metal
complexes29-32 orforthepreparationoflipophiliccrown
or azathiacrown ethers bearing bis-benzimidazoles33,
34 (SCHEME 3).
4a-i
5
6a-i
Scheme 2: Synthesis of
bis-benzimidazole derivatives
H
N
N
N
Y
M
N
Y
X
Y
EXPERIMENTAL
S
S
X
N
S
S
N
N
M
Y
N
H
Apparatus and materials
O
O
Progress of the reaction was monitored by
O
O
thin layer chromatography (0.25 mm thick precoated
silica plates: Merck Fertigplatten Kieselgel 60F254),
although purification was effected by silica gel
column chromatography (Merck Kieselgel 60; 230-
400 mesh). Infrared spectra were recorded on a
Perkin-Elmer Fouriertransform (FT) Paragon 1000
Scheme 3: Useful Compounds that Could be
Derived from the Title Bis-Benzimidazoles
Table 2: Time RReaction andYields of
Synthesized Bis-Benzimidazoles 6a-i
Entry Product Molecular
Formula
Time Yield
(Hours) %
1
PC (PerkinElmer, France). H-NMR and 13C-NMR
spectra were obtained using a Bruker Avance 300
spectrometer (Bruker, France) at 300 and 75MHZ,
respectively. Chemical shifts were reported in ppm
from internal TMS for 1Hand 13C.The mass spectra
were performed on a Shimadzu GC MS-QP 1000EX
apparatus (Kyoto, Japan). Elemental analysis was
recorded on an Exeter Analytical CE-440 Elemental
instrument (Exeter Analytical, UK). Dithiols was
purchased from Sigma-Aldrich and used as received.
The synthesis of diesters has been described
elsewhere.
N
N
S
O
S
HN
NH
1
2
3
4
5
6
7
8
9
6a
6b
6c
6d
6e
6f
6g
6h
6i
5
5
5
8
8
8
8
8
8
61
57
55
44
46
51
39
43
41
N
N
S
O
S
HN
HN
NH
N
N
O
S
S
NH
N
N
S
O
O
S
NH
HN
N
N
N
N
N
S
O
O
O
O
S
NH
NH
HN
HN
general method for bis-(benzimidazole-alkylthio)
ethylene oxide formation
S
S
A mixture of diacid (1 mmol) and ortho-
phenylenediamine (1.25 mmol) were added to a
dry round-bottomed flask (50 mL). Then, the flask
fitted with a condenser was placed in an oil bath
N
S
S
O
O
O
S
S
NH
HN
N
N
N
N
O
O
O
O
O
NH
NH
HN
HN
o
S
O
S
and heated at 140 C for 5 h. The reaction was
monitored by TLC till the disappearance of the

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AKREMI & NOUBIGH, Orient. J. Chem., Vol. 33(2), 622-627 (2017)
starting diacid. Once the reaction was complete, CH2-O), 3JHH = 6.0 Hz), 3.65 (t, 4H, 2 S-CH2-CH2-O,
the mixture was dissolved in alcohol. The pH value 3JHH = 6.0 Hz), 7.1-7.2 (m, 4H, C5-H, C6-H, C5'-H
of the resulted solution was adjusted to 9-10 with and C6'-H), 7.5-7.6 (m, 4H, C4-H, C7-H, C4'-H and
KOH solution to give the crude product, which was C7'-H), 12.19 (br s, 2H, N1-H and N1'-H); 13C-NMR
purified by flash chromatography on silica gel (5:1, (DMSO-d6/TMS) d 27.1 (C2-CH2-CH2 and C2’-CH2-
v/v, dichloromethane: petroleum ether) as eluent to CH2), 30.8 (C2-CH2-CH2 and C2’-CH2-CH2), 35.3
afford the samples 6a-i for analysis.
(S-CH2-CH2-O)), 70.5 (S-CH2-CH2-O)), 115.2 (C4,
C7, C4' and C7'), 121.9 (C5 , C6 , C5' and C6'), 139.2 (C3a
2-((2-(2-((1H-benzo[d]imidazol-2-yl)methylthio) , C7a , C3a’ and C7a’ ) and 153.1 (C2 and C2'); IR (KBr):
ethoxy)ethylthio)methyl)-1H-benzo[d]imidazole 3378, 2862, 1588, 1454, 1303, and 1201 cm-1; MS
6a
[m/z, (%)]: 427.17 [M+H]+ (80); Elemental Analysis:
Light yellow solid; m.p.115°C; H-NMR Found, %: C 61.89; H 6.03; N 13.03; C20H26N4OS2,
1
(DMSO-d6/TMS) d 2.75 (t, 4H, 2 S-CH2-CH2-O, 3JHH Calculated, %: C 62.00; H 6.15; N 13.14.
= 6.0 Hz), 3.44 (s, 4H, 2 C2-CH2 and C2’-CH2), 3.59
3
(t, 4H, 2 S-CH2-CH2-O, JHH = 6.0 Hz), 12.34 (br, 1,2-bis(2-((1H-benzo[d]imidazol-2-yl)methylthio)
2H, N1-H and N1'-H); 13C-NMR (d (ppm), DMSO-d6/ ethoxy)ethane 6d
TMS): 26.33 (s, C2-CH2 and C2’-CH2), 34.8 (s, 2
White solid;m.p.91°C;1H-NMR (DMSO-d6/
O-CH2-CH2-S), 70.9 (s, 2 O-CH2-CH2-S), 115.1 (C4, TMS) d 2.69 (t, 4H, 2 S-CH2-CH2-O,3JHH = 6.0 Hz),
C7, C4' and C7'), 121.8 (C5 , C6 , C5' and C6'), 140.2 (C3a 3.50 (s, 4H, C2-CH2, and C2’-CH2), 3.62 (t, 4H, 2
3
, C7a , C3a’ and C7a’ ) and 153.7; IR (KBr): 3380, 2870, S-CH2-CH2-O, JHH = 6.0 Hz), 3.79 (s, 4H, S-CH2-
1590, 1461, 1303, and 1205cm-1; MS [m/z, (%)]: CH2-O), 13.15 (br, 2H, 2 NH); 13C-NMR (d (ppm),
399.13 [M+H]+ (90); Elemental Analysis: Found, %: DMSO-d6/TMS): 26.2 (s, C2-CH2, and C2’-CH2), 35.1
C 60.18; H 5.51; N 13.97; C20H22N4OS2, Calculated, (s, 2 O-CH2-CH2-S), 71.2 (s, 2 O-CH2-CH2-S), 71.5
%: C 60.34; H 5.57; N 14.07.
(s, O-CH2-CH2-O), 115.1 (C4, C7, C4' and C7'), 122.3
(C5 , C6 , C5' and C6'), 139.6 (C3a , C7a , C3a’and C7a’) and
2-(1-(2-(2-(1-(1H-benzo[d]imidazol-2-yl)ethylthio) 151.3 (C2 and C2');IR (KBr):3380, 2872, 1580, 1451,
ethoxy)ethylthio)ethyl)-1H-benzo[d]imidazole 1299, and 1199 cm-1; MS [m/z, (%)]: 443.15 [M+H]+
6b
(60);Elemental Analysis:Found, %:C 59.62;H 5.88;
Light yellow solid; m.p.107°C; H-NMR N 12.59; C22H26N4O2S2, Calculated, %: C 59.76; H
1
(DMSO-d6/TMS) d 1.42 (d, 6H, 2CH(CH3),3JHH = 6.0 5.92; N 12.67.
Hz), 2.73 (t, 4H, 2 S-CH2-CH2-O, 3JHH = 6.0 Hz), 3.48
(m, 2H, 2CH(CH3)), 3.48 (t, 4H, 2 S-CH2-CH2-O, 3JHH 1,2-bis(2-(1-(1H-benzo[d]imidazol-2-yl)ethylthio)
= 6.0 Hz), 12.99 (br, 2H, N1-H and N1'-H); 13C-NMR ethoxy)ethane 6e
1
(d (ppm), DMSO-d6/TMS):d 18.5 (s, CH(CH3)), 34.84
White solid; m.p. 88°C; H-NMR (DMSO-
(s, 2 O-CH2-CH2-S), 37.29 (s, CH(CH3)), 70.8 (s, 2 d6/TMS) d 1.49 (d, 6H, 2CH(CH3), 3JHH = 6.0 Hz),
O-CH2-CH2-S), 71.2 (s, O-CH2-CH2-O), 115.7 (C4, C7, 2.69 (t, 4H, 2 O-CH2-CH2-S,3JHH = 6.0 Hz), 3.44 (m,
3
C4' and C7'), 122.3 (C5 , C6 , C5' and C6'), 140.6 (C3a , 2H, 2CH(CH3)), 3.62 (t, 4H, O-CH2-CH2-S, JHH
=
C7a , C3a’ and C7a’ ) and 153.2; IR (KBr): 3385, 2871, 6.0 Hz), 3.81 (s, 4H, O-CH2-CH2-O), 12.31 (br s,
1592, 1464, 1301, and 1197 cm-1; MS [m/z, (%)]: 2H, N1-H and N1'-H); 13C-NMR (d (ppm), DMSO-d6/
427.16 [M+H]+ (100);Elemental Analysis:Found, %: TMS): 18.1 (CH(CH3)) 37.2 (s, CH(CH3)), 35.0 (s,
C 61.91; H 6.01; N 13.04; C22H26N4OS2, Calculated, 2 O-CH2-CH2-S), 71.4 (s, 2 O-CH2-CH2-S), 71.2 (s,
%: C 62.00; H 6.15; N 13.14.
O-CH2-CH2-O), 115.3 (C4, C7, C4' and C7'), 122.1 (C5
, C6 , C5' and C6'), 139.5 (C3a , C7a , C3a’ and C7a’ ) and
2-(2-(2-(2-(2-(1H-benzo[d]imidazol-2-yl)ethylthio) 151.9 (C2 and C2');IR (KBr):3379, 2871, 1579, 1452,
ethoxy)ethylthio)ethyl)-1H-benzo[d]imidazole 1300, and 1200 cm-1; MS [m/z, (%)]: 471.19 [M+H]+
6c
(70);Elemental Analysis:Found, %:C 61.22;H 6.40;
Light yellow solid; m.p. 111°C; H-NMR N 11.81; C24H30N4O2S2, Calculated, %: C 61.31; H
1
(DMSO-d6/TMS) d 2.76 (t, 4H, 2 CH2, 3JHH = 6.0 Hz), 6.43; N 11.91.
3.26 (m, 4H, CH2-CH2-C2), 2.69 (t, 4H, 2 S-CH2-

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AKREMI & NOUBIGH, Orient. J. Chem., Vol. 33(2), 622-627 (2017)
1,2-bis(2-(2-(1H-benzo[d]imidazol-2-yl)ethylthio)
2 O-CH2-CH2-S), 71.5 (s, O-CH2-CH2-O), 115.5 (C4,
C7, C4' and C7'), 122.2 (C5 , C6 , C5' and C6'), 140.1 (C3a
, C7a , C3a’ and C7a’ ) and 150.5 (C2 and C2'); IR (KBr):
3375, 2872, 1580, 1451, 1301, and 1202 cm-1; MS
[m/z, (%)]: 515.21 [M+H]+ (40); Elemental Analysis:
Found, %: C 60.61; H 6.59; N 10.81; C26H34N4O3S2,
Calculated, %: C 60.73; H 6.22; N 11.52.
ethoxy)ethane 6f
White solid; m.p. 94°C; H-NMR (DMSO-
d6/TMS) d 2.75 (t, 4H, 2 O–CH2–CH2–S, JHH
1
3
=
6.0 Hz), 3.24 (m, 4H, CH2-CH2-C2), 3.66 (t, 4H,
O–CH2–CH2–S, 3JHH = 6.0 Hz), 3.83 (s, 4H, O-CH2-
CH2-O) 7.1-7.2 (m, 4H, C5-H, C6-H, C5'-H and C6'-H),
7.5-7.6 (m, 4H, C4-H, C7-H, C4'-H and C7'-H), 12.19
(br s, 2H, N1-H and N1'-H);13C-NMR (DMSO-d6/TMS)
d 27.3 (C2-CH2-CH2 and C2’-CH2-CH2), 30.5 (C2-CH2-
CH2 and C2’-CH2-CH2), 35.4 (S-CH2-CH2-O)), 70.5
(S-CH2-CH2-O)), 71.6 (s, O-CH2-CH2-O), 115.2 (C4,
C7, C4' and C7'), 121.9 (C5 , C6 , C5' and C6'), 139.2 (C3a
, C7a , C3a’ and C7a’ ) and 151.1 (C2 and C2'); IR (KBr):
3378, 2862, 1588, 1454, 1303, and 1201 cm-1; MS
[m/z, (%)]: 471.18 [M+H]+ (60); Elemental Analysis:
Found, %: C 61.18; H 6.38; N 11.84; C24H30N4O2S2,
Calculated, %: C 61.31; H 6.43; N 11.91.
2-(2-(2-(2-(2-(2-(2-(1H-benzo[d]imidazol-2-yl)
ethylthio)ethoxy)ethoxy)ethoxy)ethylthio) ethyl)-
1H-benzo[d]imidazole 6i
Semisolid;1H-NMR (DMSO-d6/TMS) d 2.74
(t, 4H, 2 O-CH2-CH2-S, 3JHH = 6.0 Hz), 3.26 (m, 4H,
CH2-CH2-C2), 3.64 (t, 4H, 2 O-CH2-CH2-S, 3JHH = 6.0
Hz), 3.80 (s, 4H, 2 O-CH2-CH2-O), 7.1-7.2 (m, 4H,
C5-H, C6-H, C5'-H and C6'-H), 7.5-7.6 (m, 4H, C4-H,
C7-H, C4'-H and C7'-H), 12.94 (br s, 2H, N1-H and
N1'-H);13C-NMR (DMSO-d6/TMS) d 27.0 (C2-CH2-CH2
and C2’-CH2-CH2), 30.1 (C2-CH2-CH2 and C2’-CH2-
CH2), 35.9 (S-CH2-CH2-O), 70.8 (S-CH2-CH2-O),
71.9 (s, O-CH2-CH2-O),, 115.5 (C4, C7, C4' and C7'),
122.1 (C5 , C6 , C5' and C6'), 139.4 (C3a , C7a , C3a’ and
C7a’ ) and 151.0 (C2 and C2'); IR (KBr): 3376, 2868,
1589, 1451, 1301, and 1200 cm-1; MS [m/z, (%)]:
515.20 [M+H]+ (50); Elemental Analysis: Found, %:
C 60.65;H 6.59;N 10.83;C26H34N4O3S2, Calculated,
%: C 60.37; H 6.66; N 10.89.
2-((2-(2-(2-(2-((1H-benzo[d]imidazole–2-yl)
methylthio)ethoxy)ethoxy)ethoxy)ethylthio)
methyl) -1H-benzo[d]imidazole 6g
Semisolid;1H-NMR (DMSO-d6/TMS) d 2.70
(t, 4H, 2 O-CH2-CH2-S,3JHH = 6.0 Hz), 3.48 (s, 4H, 2
C2-CH2, and C2’-CH2), 3.60 (t, 4H, O-CH2-CH2-S, 3JHH
= 6.0 Hz), 3.80 (s, 4H, 2 O-CH2-CH2-O), 13.02 (br,
2H, 2 NH);13C-NMR (d (ppm), DMSO-d6/TMS):26.9
(s, C2-CH2 and C2’-CH2), 35.3 (s, 2 O-CH2-CH2-S),
71.4 (s, 2 O-CH2-CH2-S), 72.1 (s, O-CH2-CH2-O),
115.1 (C4, C7, C4' and C7'), 122.3 (C5 , C6 , C5' and
C6'), 139.6 (C3a , C7a , C3a’ and C7a’ ) and 150.3 (C2
and C2'); IR (KBr): 3370, 2871, 1582, 1450, 1299,
and 1202 cm-1;MS [m/z, (%)]: 487.18 [M+H]+ (40);
Elemental Analysis: Found, %: C 59.22; H 6.17; N
11.47;C24H30N4O3S2, Calculated, %:C 59.29;H 6.22;
N 11.52.
CONCLUSION
New bis-(benzimidazole-2-alkylthio)
ethylene and polyethylene oxides were prepared
from various dithiols. The synthesized products
may be useful intermediates for the preparation of
several interesting well-known compounds such as
bis-benzimidazole metal complexes or azathiacrown
ethers bearing bis-benzimidazole.The study related
to the application of these new bisbenzimidazoles in
biological and industrial fields is in progress.
2-(1-(2-(2-(2-(2-(1-(1H-benzo[d]imidazol-2-yl)
ethylthio)ethoxy)ethoxy)ethoxy)ethylthio) ethyl)-
1H-benzo[d]imidazole 6h
Semisolid;1H-NMR (DMSO-d6/TMS) d 1.50
ACkNOwLEDgEMENT
(d, 6H, 2CH(CH3),3JHH = 6.0 Hz), 2.70 (t, 4H, 2 O-CH2-
CH2-S,3JHH = 6.0 Hz), 3.41 (m, 2H, 2CH(CH3)), 3.60
(t, 4H, 2 O-CH2-CH2-S, 3JHH = 6.0 Hz), 3.81 (s, 4H,
2 O-CH2-CH2-O), 12.55 (br s, 2H, N1-H and N1'-H);
13C-NMR (d (ppm), DMSO-d6/TMS):18.7 (CH(CH3))
37.0 (s, CH(CH3)), 35.1 (s, 2 O-CH2-CH2-S), 71.2 (s,
The authors wish to acknowledge the
approval and the support of this research study
by the grant N°. 5-15-1436-5 from the Deanship of
Scientific Research in Northern Border University,
Arar, KSA.

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