Synthesis and characterization benzimidazole ring by using O-phenylinediamine with different compounds and using mannich reaction for preparation of some derivatives

Article abstract of DOI:10.13005/ojc/340152

The research includes synthesis and characterization Benzimidazole rings by using different compounds such as Urea, Thiourea and Carboxylic acid by reactant with O-phenylinediamine, then substitution hydrogen atom with present on nitrogen atom by reactant with primary and secondary amines according to Mannich reaction. Compounds was organized by using F.T.I.R and HNMR spectroscopy.

Full text of DOI:10.13005/ojc/340152

ISSN: 0970-020 X
CODEN: OJCHEG
2018, Vol. 34, No.(1):
Pg. 473-481
ORIENTAL JOURNAL OF CHEMISTRY
An International Open Free Access, Peer Reviewed Research Journal
www.orientjchem.org
Synthesis and Characterization Benzimidazole Ring by
Using O-phenylinediamine with Different Compounds and
Using Mannich reaction for Preparation of Some Derivatives
ABDULLAH JAWAD KADHIM
Chemistry Department, College of Education, University of Al-Qadisiyah, Iraq 2016-2017
Corresponding author E-mail: Abdullah.Kadhim@qu.edu.iq
http://dx.doi.org/10.13005/ojc/340152
(Received: July 24, 2017; Accepted: October 02, 2017)
ABSTRACT
The research includes synthesis and characterization Benzimidazole rings by using different
compounds such as Urea, Thiourea and Carboxylic acid by reactant with O-phenylinediamine,
then substitution hydrogen atom with present on nitrogen atom by reactant with primary and
secondary amines according to Mannich reaction. Compounds was organized by using F.T.I.R
and HNMR spectroscopy.
Keywords: Benzimidazole, O-phenylinediamine, Thiouoria, Amines, Mannich reaction.
INTRODUCTION
compounds are able to entering into N-alkylation
and N-acylation according to Mannich and Michael
reaction as in isatin compounds5, which are similar
with benzimidazoles. Mannich reaction very
important reaction by converting some of the
prepared compounds into other compounds are
more important than in the biological field6.
Benzimidazole is heterocyclic compound
found in many natural and non-natura1 products,
such as some vitamins1. Therefore, benzimidazole
substitutes tooks the attention of differents research
groups, especially as compensation or replacement
in the position 1,2 is very important sites in the impact
of drug effective2.InThis study reported some of the
ways to prepare benzimidazole 2-substitution, for
the importance of this compound in the field of
antibiotics,such as cancer,angiotensin-II receptor
antegonests and antimicrobial properties3
antifungal, antiparkinson,...etc4. The NH group
MATERIALS AND METHODS
1-
2-
Melting points were determined by using
Melting PointSMP3 apparatus.
F.T.I.R. spectra were recorded by using
Fourier Transform Infrared Spectrophotometer
This is an
Open Access article licensed under a Creative Commons Attribution-NonCommercial-ShareAlike
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474
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KADHIM., Orient. J. Chem., Vol. 34(1), 473-481 (2018)
(F.T.I.R) 8400 S Shimadzu apparatus.
NMR Spectrometer 400 MHz, Avance III 400
Bruker, Germany.
General procedure for synthesis of compounds
(A1) (B1) (C1)
A mixture of alcoholic solution with (A), with
(B), with (C) (0.01 mol) and formaldehyde (15 ml, 40 %)
was added slowly on alcoholic solution of
(4-chloro-aniline ) (0.01 mol) the reaction mixture
was stirred for three hours at room temperature and
kept full night in the fridge. The solid obtained was
filtered ,washed with cold ethanol, dried and
crystallized form aqueous ethanol to give
compounds (A1), (B1), (C1)8.
EXPERIMENTAL
Synthesis 1,3-dihydro-benzimidazol-2-subsititution
(A and B)
A mixture of o-phenylenediamine with
urea to yield (A) and with thiourea to yield (B) in
existence of HCl in equal concentrations was
0
heated at 130 C under reflux in alcohol solution
until the evolution of ammonia ceased7.
General procedure for the synthesis of compounds
(A2) (B2) (C2)
Synthesis 2-Phenol-1H-benzimidazol (C)
A mixture of equal concentration (0.01 mol)
of o-phenylenediamine and Salicylic acid in 4N HCl
(20 ml) was refluxed for 30 min. then cooled, filtered
and recrystallized from absolute alcohol3.
A mixture equimolar of (A), (B), (C) with
Diallylamine in presence formaldehyde were
carried out 0-5 oC by stirring with magnetic stirrer9.
Table. 1: show physical properties of compounds
Compound
Molecular formula
Solvent
Yield %
m.p. Co
Color
A
B
C
A1
B1
C1
A2
B2
C2
C7H6N2O
C7H6N2S
Ethanol
Ethanol
Ethanol
Ethanol
Ethanol
Ethanol
Ethanol
Ethanol
Ethanol
94
66
72
63
62
64
70
73
76
275-279
114-118
155-161
Oil
Yellow
Violet
Violet
Yellow
Nutty
Nutty
Yellow
Nutty
C13H10N2O
C21H18N4OCl
C14H12N3ClS
C20H16N3ClO
C21H28N4O
C14H17N3S
C20H21N3O
Oil
Oil
Oil
Oil
Oil
Nutty
H
N
N
NH2
NH3
H2N
H2N
HCl
O
C
C O
C
OH
130 co
N
H
N
H
(A)
H2N
Cl
2
2
N
N
C
N
OH
C
OH
N
H2C
N(CH2CH=CH2)2
Cl
H2C
NH
(A2)
(A1)
Scheme 1

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KADHIM., Orient. J. Chem., Vol. 34(1), 473-481 (2018)
N
NH2
NH3
H2N
HCl
130 co
C
S
C
SH
H2N
N
H
(B)
H2N
Cl
2
2
N
N
N
C
SH
C
SH
NH
N
H2C
N(CH2CH=CH2)2
Cl
H2C
(B2)
(B1)
Scheme 2
HO
N
NH2
NH3
O
C
4N
HCl
C
N
H
HO
HO
H2N
(C)
C
O
H
Cl
H
O
C
HO
NH
N
N
C
C
N
N
HO
H2C
N(CH2CH=CH2)2
Cl
H2C
(C2)
(C1)
Scheme 3
1H-benzimidazole-2-ol (A)
RESULT AND DISCUSSION
Infrared spectroscopy of this compound
showed a broadband at 3348-3433 cm-1 refers to
O-H group, as well as the emergence of weak peak
at 1739 cm-1 indicate that O-H group turn to C=O
The aim of the research is to synthesis
mannich bases from different Benzimidazole rings
with primary and secondary amines by using
formaldehyde as catalyst.

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KADHIM., Orient. J. Chem., Vol. 34(1), 473-481 (2018)
group by resonance between O-H and N atom , the
spectroscopy showed too other peaks at
3132-3178cm-1 refers to N-H group and at 3024
cm-1 to C-H aromatic. Table (2) shows other peaks
to this compound. 1HNMR (400 MHz , DMSO) δ(ppm)
Ar(6.97 Hz 1H),OH(5.45 Hz 1H),NH(5.45 Hz 1H)
1-[(diprop-2-en-1-ylamino)methyl]-1Hbenzimidazole-
2-thiol (B2)
Infrared spectrum showed disappearance
absorption peak of (N-H) after substitution of (H)
atom by compound (Diallylamine) and appearance
absorption peak at 2950 cm-1 indicated to (C-H)
aliphatic. Table. (2) shows other absorption peaks
1-{[(4-chlorophenyl)amino]methyl}-1H-benzimida
zol-2-ol (A1)
1
for this compound. HNMR (400 MHz, DMSO)
δ(ppm) Ar(7.27,7.31 and 7.72 Hz ), SH(2.54 Hz 1H),
CH2(4.70 2H), CH2-CH= (3.51-3.52 Hz 4H), CH=
(5.07 Hz 2H) , =CH2(4.85-4.95Hz 4H).
Infrared spectroscopy showed overlap of
(O-H) peak with (N-H) peaks at 3261-3481 cm-1
after substitution (H) atom by compound
(4-chloro aniline), also emergence absorption peak
at 2921-2979 cm-1 refers to (C-H) aliphatic. Table
2-(2-hydroxyphenyl)-1H-Benzimidazol (Compound)
Infrared spectrum showed broadband at
(2) shows the other peaks for this compound.
1HNMR (400 MHz , DMSO) δ(ppm) Ar (7.09,7.10 Hz
and 7.25), OH(5.24Hz), CH2(5.77-5.81Hz),
NH(3.84-3.88Hz).
3402-3421cm-1 indicated to (OH) group and
absorption peak at 3236 cm-1 indicated to (NH)
group. Table. (2) shows other absorption peaks for
this compound. 1HNMR (400 MHz , DMSO) δ(ppm)
Ar(7.23,7.24 and 7.77 Hz ) and (6.77, 6.89 and
7.05), OH(6.74Hz ), NH(6.77Hz ).
1-[(diallyl-amino)methyl]- 1H-benzimidazol-2-ol (A2)
Infrared measurements of this compound
showed disappearance (N-H) peak duo to
substitution H atom by compound (diallyl amine)
and emergence new peak at 2908-2958 cm-1 refers
to (C-H) and (CH=CH) respectively in addition to
(O-H) group in 3355-3394 cm-1. Table. (2) shows
2-(2-hydroxyphenyl)-1-{[(4-chlorophenyl)
amino]methyl}-1H-Benzimidazol (Compound 1)
Infrared spectrum showed appearance
broadband at 3317-3417 cm-1 indicated to (OH)
group and absorption peak at 3186 cm-1 indicated
to (NH) group and new absorption peak at 2981cm-1
indicated to (C-H) aliphatic. Table. (2) shows other
absorption peaks for this compound. 1HNMR
(400 MHz , DMSO) δ(ppm) Ar(7.03),(7.19-7.21),
(7.76, 7.39) and (6.76, 6.86Hz), OH(4.97Hz 1H),
CH2 (5.49 Hz), NH(4.14 - 4.17Hz 1H).
1
other peaks to this compound. HNMR (400 MHz ,
DMSO) δ(ppm) Ar (7.18,7.19 Hz and 7.32 Hz),
OH(4.89 Hz), CH2 (4.76 Hz), CH=(5.87 Hz), CH2
(3.41 Hz), =CH2(5.30 and 5.43 Hz).
1H-Benzimidazole-2-thiol (B)
Infrared spectrum for this compound
showed absorption peaks sharp at 3379 cm-1
indicate to (N-H) group, also appearance absorption
peak at 2360 cm-1 indicate to (S-H) group. Table. (2)
shows other absorption peaks for this compound.
1HNMR (400 MHz , DMSO) δ(ppm) Ar (broad 7.19-
7.28Hz 2H) and (broad 7.64-7.73 Hz 2H),
2-(2-hydroxyphenyl)-1-[(diprop-2-enamino)
methyl]-1H-Benzimidazol (Compound 2)
Infrared spectrum showed survival of
broadband for (OH) group at 3398 cm-1 and
disappearance absorption peak of (N-H) for
Benzimidazole ring duo to substitution hydrogen
atom by formaldehyde and secondary amine and
new absorption peaks at 2800-2977 cm-1 indicated
to C-H aliphatic in propene. Table. (2) shows other
absorption peaks for this compound. 1HNMR
(400 MHz , DMSO) δ(ppm) Ar(7.25-7.29Hz) and
(7.32,7.44 , 7.70 , 7.79Hz ), OH(4.79Hz) ,
CH2(4.68Hz) , =CH(5.49-5.55Hz) , CH2-CH= (3.67-
369Hz), =CH2(5.16-5.18 Hz).
1-{[(4-chlorophenyl)amino]methyl}-Benzimidazole-2-
thiol (B1)
Infrared spectrum showed stay of
absorption peaks of (N-H) group at 3224 cm-1
after substitution of (H) atom by compound
(4-chloroaniline) and emergence absorption peak
at 2923 cm-1 indicate to (C-H) aliphatic. Table. (2)
shows other absorption peaks for this compound.

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KADHIM., Orient. J. Chem., Vol. 34(1), 473-481 (2018)
50
%T
40
30
20
10
-0
4000
3500
3000
2500
2000
1750
1500
1250
1000
750
500
FTIR Measurement
1/cm
Fig. 1. F.T.I.R Spectroscopy of Compound (A)
50
%T
40
30
20
10
0
-10
4000
3500
3000
2500
2000
1750
1500
1250
1000
750
500
1/cm
FTIR Measurement
Fig. 2. F.T.I.R Spectroscopy of Compound (A1)

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KADHIM., Orient. J. Chem., Vol. 34(1), 473-481 (2018)
75
%T
60
45
30
15
-0
4000
3500
3000
2500
2000
1750
1500
1250
1000
750
500
FTIR Measurement
1/cm
Fig. 3. F.T.I.R Spectroscopy of compound (A1)
100
%T
90
80
70
60
50
40
30
20
4000
3500
3000
2500
2000
1750
1500
1250
1000
750
500
FTIR Measurement
1/cm
Fig. 4. F.T.I.R Spectroscopy of compound (B)

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KADHIM., Orient. J. Chem., Vol. 34(1), 473-481 (2018)
150
%T
125
100
75
50
25
-0
4000
3500
3000
2500
2000
1750
1500
1250
1000
750
500
FTIR Measurement
1/cm
Fig. 5. F.T.I.R Spectroscopy of compound (B1)
N
SH
N
H2C
N(CH2-CH=CH2)2
Fig. 6. H-NMR Spectroscopy of compound (B2)

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KADHIM., Orient. J. Chem., Vol. 34(1), 473-481 (2018)
N
N
H
HO
Fig. 7. H-NMR Spectroscopy of compound (C)
HO
N
N
H
H2C
N
Cl
Fig. 8. H-NMR Spectroscopy of compound (C1)

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KADHIM., Orient. J. Chem., Vol. 34(1), 473-481 (2018)
75
%T
70
65
60
55
50
45
40
4000 3500
FTIR Measurement
3000
2500
2000
1750
1500
1250
1000
750
500
1/cm
Fig. 9. F.T.I.R Spectroscopy of compound (C2)
Table. 2: Show F.T.I.R absorption packs of compounds
Compounds C-H aryl C=CC=N
C-N
C-O
C-S
C-Cl
A
3024 1670-1627 1361
3093 1620-1496 1280
3055 1654-1612 1249
3066 1697-1683 1238
3039 1630-1596 1377
3066 1666-1573 1584
3058 1685-1670 1375
3055 1616-1542 1272
3024 1662-1577 1218
1195
⎯
⎯
1890
⎯
⎯
⎯
⎯
⎯
705-736
B
729
759
759
748
763
759
756
759
C
1157
1093
⎯
⎯
⎯
A1
B1
C1
A2
B2
C2
⎯
632
605
632
⎯
827
825
848
⎯
1890
⎯
1091
1045
⎯
⎯
1747
⎯
⎯
⎯
1095
⎯
⎯
CONCLUSION
were prepared. These derivatives confirmed from
spectral data analysis; F.T.I.R and H-NMR.
In this study
I
am reported
synthesis of many Benzimidazol rings from
o-phenylinediamineas starting material with
different compounds by using HCl as catalyst in all
synthesis works and note the higher of percentage
ratio for the results, then using Mannich reaction to
prepared derivatives of the Benzimidazol rings
ACKNOWLEDGEMENT
The author gratefully acknowledges
Chemistry department, University of Al-Qadissiah,
Iraq for providing lab facilities to carry out this work.
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