Synthesis, characterization and antimicrobial activity of imidazole derivatives based on 2-chloro-7-methyl-3-formylquinoline

Article abstract of DOI:10.1155/2012/164235

A series of oxazole and thereof imidazole derivatives were prepared from 2-chloro-7-methyl-3-formyl quinoline. The structures of all synthesized compounds were elucidated by elemental, IR, ¹HNMR, ¹³CNMR spectra. Supplementary to these, they were assayed in vitro for their antimicrobial activity; it was revealed that some synthesized derivatives were exhibiting competent biological activity against both gram negative & gram positive bacterial species and fungal microorganisms.

Full text of DOI:10.1155/2012/164235

ISSN: 0973-4945; CODEN ECJHAO
E-Journal of Chemistry
http://www.ejchem.net
2012, 9(3), 1188-1195
Synthesis, Characterization and Antimicrobial
Activity of Imidazole Derivatives Based on 2-chloro-7-
methyl-3-formylquinoline
R. H. PARAB* and B. C. DIXIT
Chemistry Department, V.P. & R.P.T.P Science College, Vallabh Vidyanagar-388120, India
parabr@rocketmail.com
Received 19 October 2011; Accepted 30 December 2011
Abstract: A series of oxazole and thereof imidazole derivatives were prepared
from 2-chloro-7-methyl-3-formyl quinoline. The structures of all synthesized
compounds were elucidated by elemental, IR, 1HNMR, 13CNMR spectra.
Supplementary to these, they were assayed in vitro for their antimicrobial
activity; it was revealed that some synthesized derivatives were exhibiting
competent biological activity against both gram negative & gram positive
bacterial species and fungal microorganisms.
Keywords: Quinoline, Imidazole, Antibacterial activity.
Introduction
Heterocyclic compounds of nitrogen containing five membered ring systems have been
described for their biological activity against various micro organisms.1,2 Besides this, the
chemistry of quinoline and imidazoles have also been reviewed in literature. A number of
derivatives of quinoline serve as valuable therapeutic agents.1-5 Considerable interest has
been created in the chemistry of quinoline derivatives due to their versatile therapeutic
activities like bactericidal, antihistaminic, antimalarial, antidepressant, analgesic, anti-ulcer,
antiviral, herbicidal, antitumor, anti-allergic, anticonvulsant, anti-inflammatory etc.6-9
Almost every class of imidazole derivatives has been used for different reactions to produce
enormous number of heterocycles. Later, in the last three decades many scientists have
synthesized various imidazole heterocyclic precursors containing active hydrogen atom on
nitrogen and evaluated in terms of their pharmacological activity.10-15 The emergence of
powerful and elegant imidazole has stimulated major advances in chemotherapeutic agents
of remarkable significance in medicine, biology and pharmacy. Besides this, it is also
reported15-16 that imidazole compounds are one of the effective antifungal agents.
Considering the importance of both moieties Quinoline and Imidazole, extending our
previous work17, 18 we planned to synthesize imidazole derivatives from 2-chloro-7-methyl-
3-formylquinoline. The whole synthesis route is shown in scheme 1.

Synthesis, Characterization and Antimicrobial Activity 1189
Material and Methods
Acetanilide and their derivatives were purified by crystallization in R-spirit. DMF and
phosphorous oxychloride used were of analytical reagent grade. All of the organic solvents
and Hippuric acid, acetic anhydride, sodium acetate used were of analytical reagent grade.
Eight diamines were used after recrystallization. The 2-chloro-7-methyl-3-formyl quinoline
was synthesized by Vilsmeier-Haack reaction by the procedure reported in the literature.16,19
Melting points were measured in an open capillary tube and are uncorrected. Elemental
analysis was obtained using Perkin Elmer (USA) 2400, series II CHN-analyser. In addition
to this, the nitrogen content in all the imidazoles was estimated by Kjeldhal’s method.20 IR
1
spectra were recorded on a NICOLET-400 D spectrophotometer, H NMR spectra in
CDCl3/DMSO-d6 at 400 MHz on a FT-NMR, R-1500 spectrometer (chemical shift in δ
ppm) relative to TMS as an internal standard. Reactions were monitored by TLC, using
silica gel as an adsorbent and ethyl acetate-hexane in different ratios as eluent.
Experimental
Synthesis of 2-chloro-7-methyl-3-formylquinoline
The 2-chloro-7-methyl-3-formylquinoline was synthesized by Vilsmeier-Haack Reaction
by the procedure reported in the literature16,19-24
.
0
Dimethyl formamide (9.6 ml, 0.125 M) at 0 C was taken in a three necked flask
equipped with a drying tube and phosphoryl oxychloride (32.2 ml, 0.35 M) was added drop
wise under continuous stirring. To this solution, 3-methyl acetanilide (0.05 M) was slowly
added with continuous stirring. After five minutes, solution was heated under reflux for 1
0
hour at 80-90 C. The reaction mixture was poured into ice water (300 ml) and stirred for
0
further 30 mins at 0-10 C. The 2-chloro-7-methyl-3-formylquinoline so obtained, was
filtered and washed with water. It was crystallized using R-spirit. The yield was 82%.
(5Z)-3-(3-aminophenyl)-5-[(2-chloro-7-methyl-3-quinolinyl)methylene]-2-phenyl-
3,5-dihydro-4H-imidazol-4-one (IMMD)
(5Z)-3-(3-aminophenyl)-5-[(2-chloro-7-methyl-3-quinolinyl)methylene]-2-phenyl-3,5-
dihydro -4H-imidazol-4-one (IMMD) was prepared by refluxing benzoyl glycine (hippuric
acid) and (0.25 mol) 2-chloro-7-methyl-3-formyl quinoline (0.25 mol) in acetic anhydride
(0.75 mol) with freshly prepared sodium acetate (0.25 mol) for 2h (Erlenmeyer Oxazole
Condensation). After cooling, ethanol (10 ml) was added and was kept overnight at 50C. The
solid obtained was filtered, washed with alcohol, dried in vacuum and recrystallized by
using benzene. As a result ((4Z)-4-[(2-chloro-7-methyl-3-quinolinyl)methylene]-2-phenyl-
1,3-oxazol-5(4H)-one was separated out.
The synthesized ((4Z)-4-[(2-chloro-7-methyl-3-quinolinyl)methylene]-2-phenyl-1,3-
oxazol-5(4H)-one (0.01 M) was added to a solution of m-phenylene diamine (0.01 M) in 20
ml ethyl alcohol containing few drops of glacial acetic acid and the mixture was heated and
was later on cooled down. The solid mass, thus obtained was separated and was recrystallized
by using methanol which can be designated as (5Z)-3-(3-aminophenyl)-5-[(2-chloro-7-methyl-3-
quinolinyl) methylene]-2-phenyl-3,5-dihydro-4H-imidazol-4-one (IMMD). The other 2-chloro 7-
methyl-3-formylquinoline based imidazole derivatives were synthesized in a similar manner by
using remaining seven different diamines. 25,26

1190 R. H. Parab
COOH
CH2
NH
CO
CHO
Cl
+
N
H3C
2-chloro-7-methyl-3-formyl quinoline
Hippuric acid
CH3COONa
(CH3CO)2O
O
R2
R1
CH
Cl
N
O
R
H2N
+
N
H3C
Diamine
CH3OH
CH3COOH
O R2
R1
CH
N
N
R
Cl
N
H3C
Where,
-NH : IMDS
R1= R2 =H
R1, R2 =H
R1= R2 =H
R, R2 = H, R1 = NH2
R1, R2 = H, R = NH2
:
IMMD
IMPD
R = C6H4 SO2
R = C7H6-NH2 :
R = C6H5 SO2
2
:
IMDM
:
IMBD
R1, R2 = H, R = C6H4-NH2
R1= H, R2 =CH3
-NH : IMDA
2
:
R1= NH2, R2 = H, R = CH3
IMDT
: IMOTD
R = C7H6-NH2
Scheme 1 Reaction protocol of 2-chloro-7-methyl-3-formyl quinoline based imidazole
derivatives.

Synthesis, Characterization and Antimicrobial Activity 1191
Antimicrobial assay: The antimicrobial activities were determined using agar–cup method
by measuring the zone of inhibition in mm. All newly synthesized compounds were
screened in vitro for their antibacterial activity against Gram positive species (Bacillus
subtilis, Bacillus megaterium) and Gram negative species (Escherichia coli, Pseudomonas
aeruginosa), while antifungal activity was tested against Aspergillus niger and C. albicans at
concentration of 75 μg/ml. Streptomycin was used as a standard drug for antibacterial
screening, while Imidil was used as a standard drug for antifungal screening and solvent
DMSO was used as a control. Each experiment was made in triplicate and the average
reading was taken. The results are summarized in Table-3.
Synthesis, characterization and antimicrobial activity of imidazole derivatives
based on 2-chloro-7-methyl-3-formylquinoline
The test was performed by using the agar cup borer method, with some modifications using
Streptomycin and Imidil as reference for bacterial and fungal culture respectively.27 A test
tube containing sterile melted top agar (1.5 %) previously cooled at room temperature with
0.2 ml suspension of the test culture, mixed methodically and poured in the petri dish
containing sterile base agar medium (autoclaved at 121°C for 15 min.) then allowed it to
solidify. The cup borer was sterilized by dipping into absolute ethanol and flaming it then
allowed to cool it. With the help of sterile cup-borer, three cups in the agar-plate were
marked and were injected with 0.1 ml of test solution, 0.1 ml of standard solution and 0.1 ml
of DMSO solvent respectively. Then the plates were allowed to diffuse for 20 min. in
refrigerator at 4-5°C. The plates were then incubated in upright position at 37°C for 24 hrs.
After incubation, the relative susceptibility of the micro-organisms to the potential
antimicrobial agent is demonstrated by a clear zone of growth inhibition around the cup. The
inhibition zone caused by the various compounds on the micro-organisms was measured and
the activity was rated on the basis of the size of the inhibition zone.
Results and Discussion
The elemental analysis of the prepared compounds is given in Table-1. Where,
Code
Heterocyclic
substrate
Diamines
MPD
IUPAC name
(5Z)-3-(3-aminophenyl)-5-[(2-chloro-7-methyl- IMMD
3-quinolinyl)methylene]-2-phenyl-3,5-dihydro-
4H-imidazol-4-one
(5Z)-3-(4-aminophenyl)-5-[(2-chloro-7-methyl- IMPD
3-quinolinyl)methylene]-2-phenyl-3,5-dihydro-
4H-imidazol-4-one
PPD
(5Z)-3-(4'-amino[1,1'-biphenyl]-4-yl)-5-[(2-
chloro-7-methyl-3-quinolinyl)methylene]-2-
phenyl-3,5-dihydro-4H-imidazol-4-one
(5Z)-3-(4'-amino-3,3'-dimethyl[1,1'-biphenyl]-
4-yl)-5-[(2-chloro-7-methyl-3-
IMBD
2-chloro-7-
methyl-3-
formylquinoline
BD
OTD
IMOTD
quinolinyl)methylene]-2-phenyl-3,5-dihydro-
4H-imidazol-4-one
DDS
(5Z)-3-{4-[(4-aminophenyl)sulfonyl]phenyl}-5- IMDS
[(2-chloro-7-methyl-3-quinolinyl)methylene]-2-

1192 R. H. Parab
phenyl-3,5-dihydro-4H-imidazol-4-one
DDM
(5Z)-3-[4-(4-aminobenzyl)phenyl]-5-[(2-chloro- IMDM
7-methyl-3-quinolinyl)methylene]-2-phenyl-
3,5-dihydro-4H-imidazol-4-one
DASA
N-(4-aminophenyl)-4-{(4Z)-4-[(2-chloro-7-
methyl-3-quinolinyl)methylene]-5-oxo-2-
phenyl-4,5-dihydro-1H-imidazol-1-
yl}benzenesulfonamide
IMDA
DT
(5Z)-3-(5-amino-2-methylphenyl)-5-[(2-chloro- IMDT
7-methyl-3-quinolinyl)methylene]-2-phenyl-
3,5-dihydro-4H-imidazol-4-one
Table 1. Elemental analysis of imidazoles based on 2-chloro-7-methyl-3-formylquinoline.
Elemental Analysis
Imidazole
code
Molecular
Formula
MW
%C
%H
%N
g/mol
Calc. Found Calc. Found Calc. Found Found*
IMMD
IMPD
IMBD
IMOTD
IMDS
IMDM
IMDA
IMDT
C26H19ClN4O
C26H19ClN4O
C23H23ClN4O
C34H27ClN4O
C32H23ClN4O3S
C33H25ClN4O
C32H24ClN5O3S
C27H21ClN4O
438
438
514
542
578
528
593
452
71.15 71.12
71.15 71.14
74.63 74.60
75.20 75.19
66.37 66.30
74.92 74.90
64.70 64.68
71.60 71.58
4.36
4.36
4.50
5.01
4.00
4.76
4.07
4.67
4.30
4.31
4.45
5.00
4.02
4.70
4.05
4.65
12.76 12.70
12.76 12.70
10.88 10.81
10.32 10.30
12.71
12.72
10.88
10.31
9.65
9.68
9.60
10.59 10.55
11.79 11.75
12.37 12.35
10.59
11.79
12.31
* Found by the Kjeldhal’s Method
MW = Molecular Weight
In all the imidazole derivatives vinylic proton is seen around 6 ppm (δ). The aromatic
protons are assigned to resonances in the range of (δ) 7.00 to 8.2 ppm. The resonance due to
–NH2 moiety is attributed to the peak in the range of 6.5 to 6.8 ppm. The resonance due to –
CH3 is observed at 2-2.2 ppm. The compounds containing 4,4’-diamino diphenyl methane
has a >CH2 moiety attached to benzene ring and this >CH2 is highly deshielded. This is
reflected in the proton NMR signal of >CH2 group seen at 3.69 ppm. The 13C NMR peaks
are quite interesting in all these imidazoles derivatives where the peak around 165 ppm is
attributed to C of >C=O (Table-2). In all the compounds the peak at 158 ppm is assigned to
Cl-C=N moiety. The peak at 148 ppm is likely due to >C=N moiety. The peaks in the region
110-130 ppm are attributed to aromatic ring. The compounds containing 4,4’-diamino
diphenyl methane shows a peak at 40 ppm which is due to =CH2 group attached to both the
rings.

Synthesis, Characterization and Antimicrobial Activity 1193
Table 2. Assignment of NMR (1H and 13C) peaks in imidazole derivatives of 2-chloro-7-
methyl-3-formyl quinoline.
Imidazole
code
Peaks
observed (δ)
ppm
Assignment 1H
NMR
Peaks
observed (δ)
ppm
Assignment 13C
NMR
IMMD
2.47
CH3
165
C = O
6.03
6.80
7.10– 8.42
= CH Vinylic
- NH2
Aromatic Protons 109 – 132
147
157
C = N
Cl-C = N
C in aromatic ring
CH3
18
IMPD
2.47
6.0
6.78
7.2– 8.42
CH3
= CH Vinylic
- NH2
165
148
158
C = O
C = N
Cl- C = N
C in aromatic ring
CH3
Aromatic Protons 115 – 135
17
IMBD
IMOTD
2.47
5.7
6.64
7.2– 8.42
CH3
= CH Vinylic
- NH2
165
148
157
C = O
C = N
Cl- C = N
C in aromatic ring
CH3
Aromatic Protons 112 – 135
18
165
2.14
CH3
C = O
2.24
CH3
147
C = N
2.47
6.2
6.38
CH3
= CH Vinylic
- NH2
158
110 – 135
17
Cl- C = N
C in aromatic ring
CH3
7.3– 8.42
Aromatic Protons 18
CH3
IMDS
2.47
CH3
165
C = O
6.0
6.43
7.2– 8.38
= CH Vinylic
- NH2
Aromatic Protons 110 – 130
148
158
C = N
Cl- C = N
C in aromatic ring
CH3
18
IMDM
2.47
CH3
165
C = O
3.69
CH2
148
C = N
6.2
6.42
7.2 – 8.42
= CH Vinylic
- NH2
Aromatic Protons 17
40
158
115 – 135
Cl- C = N
C in aromatic ring
CH3
CH2
IMDA
IMDT
2.47
6.25
6.55
6.64
7.2– 8.42
2.47
CH3
= CH Vinylic
NH
165
148
158
112 – 132
C = O
C = N
Cl- C = N
C in aromatic ring
CH3
- NH2
Aromatic Protons 18
CH3
165
C = O
2.18
CH3
147
C = N
6.03
6.52
7.2 – 8.42
= CH Vinylic
- NH2
Aromatic Protons 17
156
112 – 130
Cl- C = N
C in aromatic ring
CH3
Practically in all the compounds –NH2 asymmetric stretching vibration is assigned to a
peak around 3400 cm-1, while a peak around 3250 cm-1 is attributed to –NH2 symmetric

1194 R. H. Parab
stretching vibration. The =CH stretching vibration in the vinyl moiety is attributed to the
absorption at ~3040 cm-1. The aromatic C-H stretching frequency, as expected is observed at
around ~3010 cm-1. The strong absorption at ~1700 cm-1 is found to be present in majority
of the compounds. The absorption will have contributions from stretching of >C=O and
>C=N. The strong absorption at 1650 cm-1 have contributions from υ C=N, υ C=C and
bending of -NH2. In most of the compounds the C-C stretching of the aromatic ring is
around 1540 cm-1.
A fairly strong absorption at ~1300 cm-1 is assigned to C-N stretching. The strong
absorption in the region 810-840 cm-1 is due to C-H out of plane bending in aromatic ring.
The C-Cl stretching is attributed to the strong absorption in the region 740-720 cm-1.
Compounds containing O=S=O moiety show strong absorption in the region of 1050-1200
cm-1 is due to O=S=O stretching. The C-H bending in the vinyl moiety is seen as a strong
band around 800 cm-1 in all the compounds. The compounds containing –CH3 group shows
peaks due to asymmetric and symmetric bending of –CH3 group at 1475 and 1375 cm-1
respectively and absorption at ~550 cm-1 in the bromo compounds is assigned to C-Br
stretching.
The synthesized compounds were screened 'in vitro' for antimicrobial activity. From the
data presented in Table-3, it is clear that out of 8 imidazole compounds IMMD, IMBD,
IMDM exhibited moderate inhibition against gram negative bacterial species and especially
against Escherichia coli while IMBD, IMDM and IMOTD showed maximum activity
against most gram negative organisms. Against gram positive organisms almost all
compound of the series exhibited maximum inhibition, especially IMPD and IMBD showed
highest inhibition against B. megaterium, while IMMD and IMDT showed good inhibition
against fungal organism especially C. albicans. The other compounds exhibited moderate to
less inhibition against fungal species, but IMMD showed good inhibition.
Table 3. Antimicrobial activity of imidazoles.
Inhibition zone against (in mm)
Compound
E.
P.
B.
B.
A.
niger
C.
albicans
code
coli
aeruginosa
subtilis
megaterium
IMMD
IMPD
IMBD
IMOTD
IMDS
16
14
20
19
14
20
17
15
35
-
13
12
17
16
12
14
15
12
34
-
25
27
28
20
20
21
23
19
35
-
27
28
30
23
20
25
26
20
36
-
15
12
16
14
11
14
13
17
-
19
16
17
15
14
13
15
20
-
IMDM
IMDA
IMDT
Streptomycin
Imidil
33
35

Synthesis, Characterization and Antimicrobial Activity 1195
Conclusion
The present study showed that the antimicrobial activity of newly synthesized compounds
may change by introduction or elimination of a specific group. Thus, the imidazole
derivatives could be powerful and elegant factor to stimulate major advances in
chemotherapeutic agents of remarkable significance in medicine, biology and pharmacy.
References
1. Jain R , Jain S, Gupta R C, Anand N, Dutta G P, Puri S K, Indian J. Chem.,1994,
338, 251.
2. Mohammed A, Abdel-Hamid N, Maher F, Farghaly A, Czech. Chem. Commun.,1992,
57(7), 1547.
3. Cairns H, Cox D, Gould K J, Ingall A H, Suschitzky J L, J. Med. Chem.,1985,
28(12), 1832 .
4. Croisy-Delcey M, Coroisy A, Carrez D, C Huel, A Chiaroni, P Ducrot, E Bisagni,
Jin, G Leclercq, Bioorg. Med. Chem.,2000, 8(ii), 2629.
5. Dlugosz A, Dus D, Farmaco.,1996, 51, 367.
6. Abadi A H, Brun R,Arzneimforsch Drug Res.,2003, 53, 655 .
7. Grachenva T N, Loffinna D I,Khim-Farm. Zh, 1991,25, 18.
8. Tripathi R C, Saxena M, Chaudhari I M, Ind. J. Chem, 1995,34 B, 164.
9. Geiss K H, Traunt M, Ind. J. Chem.,1995, 34 B, 179.
10. Feldman J R, Oschmann L, Chem. Ber.,1954 87, 1684.
11. Mannich C, Hof W, Arch. Pharm.,1927, 265, 589.
12. Feldman J R, Wagner W C, J. Org. Chem.,1942, 7, 31.
13. Moore M B, Rapela R T, J. Am. Chem. Soc.,1946 68, 1657.
14. Atkinson R O, J. Chem.,1954, 1329 .
15. David A W, Thomas L L, “Foyes principle of medicinal chemistry”, 5th Ed.,
International Student Edition,2002, 819.
16. Pawar R A, Kohak A L, GogteVG, Indian. J. Chem.,1976, 14B, 375.
17. Parab R H, Chudasama C J, Patel H N, Dixit B C, Desa D J, Asian. J. Chem.,2010,
22(10), 7641.
18. Parab R H, Dixit B C,Desai D J, Asian. J. Chem.,2011, 23(6), 2725.
19. Pawar R A, Borase P B, J. Indian. Chem.,1989, 28B, 866.
20. vogel A I, “Elementary Practical Organic Chemistry”, Vol.III Quantitative Organic
Analysis.1958.
21. Rajput A P, Asian. J. Chem., 2004,16, 1374.
22. Arulprakash G, Sampathkumar N, Rajendran S P, Asian. J. Chem.,2002, 14, 1303.
23. Kalluary B, Gupta P, Banji B, Isloor A, Boll. Chim. Farm., 2001,140,
24. Verma M, Chaturvedi A K, Choudhari A, J. Pharm. Sci.,1974, 63, 1740.
428.
25. Upadhyay P S, Joshi S N, Baxi A J, Parikh A, J. Indian. Chem. Soc.,1991 68, 364.
26. Saravanan V S, VinothkumarS P,Gupta J, Asian. J. Chem., 2005,17 (1), 576.
27. Colle G J, Fraser G , Marmion P B , Simmons A, “Practical Medical Microbiology”,
14th Edn.,1996, Vol. 11, Churchill Livingstone: Edinburgh, 163.

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