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Der Chemica Sinica, 2011, 2(5):136-146
ISSN: 0976-8505
CODEN (USA) CSHIA5
Synthesis and spectroscopic characterization of some new
azo-thiazolidinone derivatives
Awaz J. Hussein* and Hashim J. Aziz*
Department of Chemistry , College of Education/ Scientific Depts., University of Salahaddin, Hawler,
Kurdistan Region, Iraq
_____________________________________________________________________________
ABSTRACT
A series of new compounds, 2-(4-(benzyloxy)-3-((4-bromophenyl)diazenyl)phenyl)-3(substitutedphenyl)thiazolidin-4-one ( 4a-j) have been synthesized according to the following
reaction types, the first step has been started by diazotization of 4-bromoaniline and its coupling
reaction with 4-hydroxy benzaldehyde, followed by benzyloxation of the hydroxyl group to give
an intermediate [4-benzyloxy-3-(4-bromophenylazo)- benzaldehyde (2)].The prepared compound
(2) reacted with different substituted anilines to give imine derivatives N-(4-(benzyloxy)-3-(4bromophenyl)diazenyl)benzylidene)substituted anilines (3a-j) , and the later compounds were
treated with mercapto acetic acid to afford a new compounds (4a-j) .finally the structures of the
synthesized compounds were characterized on the basis of FT-IR, 1H-NMR ,13C-NMR, &13CDEPT spectral data.
Keywords : Azo ;Benzyloxy; Imine; Thiazolidinone.
_____________________________________________________________________________
INTRODUCTION
Azo-compounds and imines constitute important classes of the synthesized organic compounds,
They are useful as a precursors of the synthesis of different organic compounds[1-5] ,both
groups show variety of interesting biological activities, such as antifungal[6], pesticidal[7] and
antibacterial activity[8,9] .Thiazolidinones are important classes of heterocyclic compounds
containing sulfur and nitrogen in five membered rings which can be prepared by the most
important method from imines and mercapto acetic acid. These well known compounds possess
impressive biological activities. Such as: antibacterial[10-15], antihyperglycemia[16],
antifungal[17-19] , Antagonist[20], insecticidal[21] , Anticonvulsant[22], ,
Antitubercular
agents[23]. The presence of azo- linkage in the compound generate colors which makes the
compound interesting synthetic dyes[24,25] and leads to increasing the biological functions[26]
. Herein , we have described the synthesis of some new azo-thiazolidinone compounds derived
from p-bromoaniline and p-hydroxybenzaldehyde and their spectroscopic studies.
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MATERIALS AND METHODS
Melting points were determined using an Electrothermal melting point apparatus .IR spectra
were recorded on a Bio-rad Merlin FT-IR spectroscopy Mod FTS 3000, using KBr disc and
nujol. 1H-NMR and C13-NMR and 13C-DEPT-135 spectra were recorded on a Bruker(300MHz)
with TMS as internal reference in( Jordon) :
1-Preparation of 3-(4-bromophenyl azo)-4-hydroxybenzaldehyde (1)[27]
Step1: Formation of diazonium salt
p- Bromoaniline (6.88gm, 0.04mol) was dissolved by heating gently in a (32ml) of 3M
hydrochloric acid. After most of the solid has dissolved the solution was cooled in an ice bath to
0Co.While stirring, added slowly (40ml) of freshly prepared 1M of sodium nitrite solution, in
which the temperature remains below 10 Co. The solution kept in the ice bath and immediately
proceeded to the next step.
Step2: Coupling process: (addition of p-hydroxybenzaldehyde)
p-hydroxybenzaldehyde (4.88gm, 0.04mol) was dissolved in (60ml) of 1M sodium hydroxide
then cooled with stirring in the ice bath and added slowly to the diazonium salt solution. The
mixture allowed to stir for 15min. until crystallization is completed. The solid azo dye was
collected by vacuum filteration, washed several times with water, dried and recrystallized from
the mixture of (1:3) DMSO: H2O to obtain yellow crystals, of 3-(4-bromophenyl azo)-4hydroxybenzaldehyde (1). (C13H9BrO2N2), m.p. (180-181Co), yield of (11.2gm, 92%). IR (cm1
)str. 3420 (OH), 2736 and 2825 (CHO); 1693 (C=O), 1604 (C=C), 1481 (-N=N-), 1276 (C-O).
1
H-NMR (ppm):)13.35, (s,1H, OH), 10.2(s, 1H, CHO) , 8.5(s , 1H , H7) ; 7.95(d , 1H , H3) ;7.8(d
, 2H , H9,9`) ; 7.7(d , 2H , H10,10`) ; 7.19 (d , 1H , H4) ;13C-NMR: 189.9(C1), 158.18(C5),
148.8(C8), 136.4(C3), 132.8(C10,10`), 129.6(C2), 126.6(C6), 124.2(C11), 123.8(C9,9`), 119.5(C7),
115(C4). 13C-Dept-135: 189.9(C1), 136.4(C3), 132.8(C10,10`), 126.6(C6), 123.8(C9,9`), 119.5(C7),
115(C4).
2-Preparation of 3-(4-bromophenylazo)-4-benzyloxybenzaldehyde (2) [28]
A mixture of 3-(4-bromophenylazo)-4-hydroxy benzaldehyde (2.05gm, 0.01 mol), benzyl
bromide (2.64 gm, 0.015 mol) and anhydrous K2CO3 (4.4gm, 0.03mol) in ethanol (30 ml - 96%)
was refluxed with stirring for 6hrs. The cooled solution poured into water, solid materials
immediately was obtained. The solid product was filtered off, washed several times with cold
water, dried and recrystallized with a mixture (1:3) (DMSO: H2O) to obtain orange crystals of 3(4-bromophenylazo)-4-benzyloxybenzaldehyde (2).C20H15BrO2N2), m.p. (103-105 Co), yield (2
gm, 74%). IR (cm-1) str., 1683 (C=O), 1595 (C=C), 1498 (-N=N-), 1262 (C-O); 1H-NMR (ppm)
:9.62(s , 1H ,CHO);; 8.2(s , 1H , H7), 7.97(d , 1H , H3) ; 7.8(d , 2H , H9,9`) ; 7.6(d , 2H , H10,10`) ;
7.5(d , 1H , H4), 7.38(m , 5H , H14,14`,15,15`,16), 5.41 (s , 2H , H12) ; 13C-NMR: 190.71(C1),
160.6(C5), 151.8(C8), 142.4(C13),135.9(C6), 132.0(C3), 132.4(C10,10`), 129.8(C2),128.7(C15,15`),
128.2(C14,14`) ,127(C16), 125.9(C11), 124.6(C9,9`), 119.35(C7), 115(C4).71.4(C12) 13C-Dept-135:
190.71(C1), 133.0(C3), 132.4(C10,10`), 128.7(C15,15`), 128.2(C14,14`) ,127(C16), 124.6(C9,9`),
119.35(C7), 115(C4).71.4(C12).
3-Synthesis of imines: (4-(benzyloxy)-3-(4-bromophenyl)diazenyl)benzylidene)substituted
anilines(3a-j)[29]:- According to the modified procedure, Imines (3a-j) were synthesized by
dissolving (0.01 mol) of 3-(4-bromophenyl azo)-4-benzyloxybenzaldehyde (2) in 96% ethanol
(20ml ), and mixed with the solution of an appropriate substituted anilines (0.01 mol) in 96%
ethanol (10 ml) with a few drops of acetic acid . The mixture was refluxed for (1-3 hr.) until the
formation of imines which was monitored by TLC., the cooled mixture was filtered , dried and
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recryystallized from hexane to give pure crystals of compounds (3a-j) , the physical parameters
are summarized in table (1) .
4- Synthesis of Thiazolidinones:
2-(4-(benzyloxy)-3-((4-bromophenyl)diazenyl)phenyl)-3(substitutedphenyl)-thiazolidin-4-one ( 4a-j) [17] :
According to the modified procedure ,a mixture of imine (0.005mol) and mercapto acetic acid
(0.006mole) in benzene (20ml ) was refluxed with stirring for (12 hr.) .The solvent was
evaporated by using rotary evaporator . The remained solid compound was neutralized by
adding cold saturated sodium bicarbonate and allowed to stand overnight. The solid products
were isolated by suction filteration, washed with water, dried and purified by recrystallization
from hexane . The physical properties of the synthesized thiazolidinones (4 a-j) are
summarized in the, table-2 .
Br
NH2
HCl
NaNO2
0 oC
Br
N
O
O
HO
H
H
N Cl
Br
N N
NaOH
HO
1
CH2Br
K2CO3, EtOH
reflux 6 hrs.
O
NH2
H
N
Br
Br
N N
N N
R
O
R
AcOH
EtOH
O
3a-j
2
HSCH2COOH
Benzene
reflux
Br
N
N
N
R
S
O
O
4a-j
R=H, , 4-Cl, 2-Cl, 4-F, 4-Br, 4-CH3, 4-OCH3, 4-NO2, 4-OC2H5, 4-N(CH3)2
Scheme (1)
RESULTS AND DISCSSION
The present study involves the synthesis of a new series of thiazolidin-4-one, with an azolinkage side-chain(4a-j) . The work started by the preparation of the key intermediate azo
compound (1) from the coupling reaction of 4-bromo diazonium salt with 4-hydroxy
benzaldehyde. For further synthesis, the preparation followed by benzyloxation of the hydroxyl
group of compound (1) to give an intermediate [4-benzyloxy-3-(4-bromophenylazo)138
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benzaldehyde (2)]. Compound (2) was allowed to react with different substituted anilines (
bearing electron donating and electron with-drawing groups ) to give imine derivatives: N-(4(benzyloxy)-3-(4-bromophenyl)diazenyl)benzylidene)substituted anilines (3a-j) , and the later
were treated with mercapto acetic acid to afford a new desired compounds (4a-j) scheme (1).
In the study of the influence of the substituents of the substituted anilines on the rate and the
yield of the formation of imine products , typically any factor that increase the nucleophilicity of
nitrogen atom of amine group , should increase reactivity ; while any factor that makes the amine
less nucleophilic should decrease reactivity . Hence, electron-releasing substituents , release
electrons to the ring and makes the lone pare of electron on nitrogen more available for sharing
with carbonyl group to afford the desiared imines , thus, increase the rate and the yield of the
imine products. While , electron-withdrawing substituents acts oppositely. These effects are
shown in table (1).
The structures of the prepared compounds were confirmed by spectroscopic methods such as :
FT-IR, 1H-NMR, 13C-NMR and 13C-DEPT-135. The IR spectrum of compound (1) shows a
broad band at (3420) cm-1 attributed to (OH) str. group , a characteristic N=N band at (1481) cm-1
, two characteristic bands at 2825 and 2736 for the Fermi resonance of aldehydic C-H group, and
two strong bands at 1680cm-1 and 1601cm-1 for carbonyl and carbon-carbon double bonds
respectively. The 1H-NMR spectrum of compound (1) shows two singlets at 13.3 and 10.01ppm
attributed to hydroxyl and CHO protons respectively, four doublets at (7.95, 7.8, 7.7 and 7.19)
and a singlet at (8.54) ppm for seven protons of the two phenyl rings. 13C-NMR shows eleven
singlet signals for eleven carbons different in chemical shifts. 13C-Dept-135 appeared six
singlets for six mono-protonated carbons.
The IR spectrum of compound (2) shows the
disappearance of a broad band of hydroxyl group and shifting the absorption band of carbonyl
group from 1693 cm-1 to 1683 cm-1, due to the disappearance of the hydrogen bond between azogroup(N=N) and hydroxyl groups which considered as a good evidence for benzyloxation of OH
group and produce 3-(4-chlorophenylazo)-4-benzyloxybenzaldehyde (2). The1H-NMR spectrum
of compound (2) shows two distinct singlet signals at (5.4 and 9.9) ppm due to benzyl -OCH2ph
and CHO aldehyde respectively ,which confirm benzyloxation of OH and remaining CHO group
as an active group for further reactions , with other bands at aromatic region for protons of
aromatic rings. The 13C-NMR spectrum,Fig.(1) showed sixteen singlet signals, belongs to sixteen
type of carbons different in chemical shifts. The 13C-DEPT spectrum [30] (Distortionless
Enhancement by Polarization Transfers)Fig.(2) is the most commonly used method to determine
the multiplicity of 13C-signals showed downward signal at (71. 4) corresponding to the diprotonated carbon atom (-O-CH2-) group, and nine up ward signals for nine monoprotonated
carbons. The FT-IR spectra of the synthsized imines (3a-j) showed the disappearance of
carbonyl bands and appearance of C=N group band around 1620 cm-1 considered as a good
evidence for the formation of imine groups. Table(6).
The 1H-NMR spectra of imines (3 g, h and i) table (3),Fig.(3) beside the normal peaks , show a
singlet signals at 8.4 ppm [1], belongs to imine or azomethene( CH=N- )group , with a
characteristic bands for each compound such as : compound 3g showed a singlet at(2.4ppm) due
to three protons of CH3 group, compound (3h) appears a singlet at 3.86ppm belongs to three
protons of OCH3 group and compound (3i) shows a distinct two peaks a triplet at 1.42 and
quartet at 4.04ppm for CH3 and CH2 in side chain (OCH2CH3) respectively. The 13C-NMR and
Dept spectra Fig.(4,5)for each compound were matching perfectly with the expectations. Table
(4&5). In the IR spectra of thiazolidinones (4 a-j) table(6), showed a characteristic band at
(1670-1690) cm-1 due to carbonyl group stretching , of cyclic amides[26] and the appearance of
imine bands at 1620 cm-1 indicates the formation of thiazolidinone ring. The 1H-NMR spectra
of thiazolidinones(4g, h &i) Table(7),Fig.(6)showed characteristic signals dd at 3.8 ,4 and a
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singlet at 6ppm corresponding to proton of C21 and C5 of thiazolidinones ring; confirming the
nonequivalence of protons at C21 of the five membered ring of thiazolidinones ,which
appearance as two doublet to doublet (dd) and a singlet of mono proton of (C5). Table(7), also
as imines the 13C-NMR and Dept spectra Fig. (7,8)for each compound were matching perfectly
with the expectations. Table (8&9).
H
O
`10
9`
1
7
`10
Br
9`
11
N
8
11
Br
O
2
6
10
N
5
9
7
N
9
`15
14`
16
HO
13
15
`3
N
H
3
5
4
1
2
6
3
(1)
10
N
8
4
O
12
14
(2)
2`
4
1
R
5
3
2
6
11
`
13
`14
N
12
7
10
8
N
9
13
15
O
14
Br
16
18
17
(3a-j)
19
`18
20
19
`
O
21
22
S
`3
N
2`
4
1
R
5
3
2
6
11
4`
`
`14
12
N
10
N
15
Br
7
8
9
13
O
14
16
18
17
19
(4a-j)
`18
20
19
`
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Table-1:- Some physical properties for the synthesized imines (3a-j).
Prod.
3a
3b
3c
3d
3e
3f
3g
3h
3i
3j
R
H
4-F
2-Cl
4-Cl
4-NO2
4-Br
4-CH3
4-OCH3
4-O-C2H5
4-N(CH3)2
Molecular formula
C26H20BrN3O
C26H19BrFN3O
C26H19BrClN3O
C26H19BrClN3O
C26H19BrN4O3
C26H19Br2N3O
C27H22BrN3O
C29H23Cl N2O3O
C28H24BrN3O2
C28H25BrN4O
color
Orange-yell.
Red
Yellow-red
Yellow
Red
Red
Yellow-red
Yellow
Yellow
Yellow-red
M.P. / 0C
150-152
163-165
135-137
160-162
139-140
180-182
160-162
155-157
143-145
140-142
Time(hr)
3
3
3
3
3
3
2.5
2
2
2.5
% Yield
75
63
60
70
65
67
82
84
85
81
Table-2: Some physical properties for the synthesized thiazolidinones (4a-j).
Prod.
4a
4b
4c
4d
4e
4f
4g
4h
4i
4j
R
H
4-F
2-Cl
4-Cl
4-NO2
4-Br
4-CH3
4-OCH3
4-O-C2H5
4-N(CH3)2
Molecular formula
C28H22BrN3O2S
C28H21BrFN3O2S
C28H21BrClN3O2S
C28H21BrClN3O2S
C28H21BrN4O4S
C28H21Br2N3O2S
C29H24BrN3O2S
C29H24BrN3O3S
C30H26BrN3O3S
C30H27BrN4O2S
color
Yellow
Red
Yellow
Yellow
Red
Red
Yellow
Yellow
Yellow
Yellow-red
M.P./0C
90-92
77-79
76-77
84-86
65-67
70-72
80-82
92-93
140-142
100-102
%Yield
65
60
60
62
50
55
66
68
75
70
Table-3: The 1H-NMR data for the synthesized imines (3 g,h& i): Solvent CDCl3
Product
3g
3h
3i
δ / ppm
Multiplicity
Intensity
Assignment
2.4(s, 3H, CH3); 5.41 (s, 2H -O-CH2-C22); 7.15- 8.27 (m, 12H , four aromatic rings), 8.47(s,1H, imine proton CH=N-).
3.86( s, 3H, OCH3) ; 5.42 (s , 2H -O-CH2ph), 6.94-8.12 (m, 12H , four aromatic rings); 8,45(s, 1H, imine proton CH=N-).
1.42( t, 3H, OCH2CH3) ; 4.04( q, 2H, OCH2CH3) ; 5.38 (s , 2H -O-CH2ph), 6.90-8.13 (m, 12H , four aromatic rings);
8,45(s, 1H, imine proton -CH=N-).
Table-4: The 13C-NMR data for the synthesized imines (3 g,h& i): Solvent CDCl3.
3g
3h
3i
21(CH3); 71.4:O-CH2C16;
115.2:C8 ;
117.8:C11, 120.8:C3,3` ; 124.6:C13,13` ; 125.5: C10 ; 127.28: C18,18`;
127.6: C6,15` ; 128.1: C20 ; 128.6: C19,19` ; 129.8: C2,2` ; 132.27: C7 ; 132.37: C14,14` ; 135.7 : C1; 136.4: C17;
142.50: C4 ; 149.3: C12; 151.7 :C9 ; 158.2 : C5 .
55.5(OCH3); 71.5:O-CH2C16; 114.4: C2,2` ; 115.32:C8 ; 117.71:C11, 122.15:C3,3` ; 124.6:C13,13`; 125.4: C10 ;
127.0: C18,18 ; 128.1: C20` ; 128.6: C19,19` ; 129.9: C15,6` ; 132.09: C7 ; 132.36 : C14,14` ; 136.48: C17; 142.50: C4 ;
144.8: C12; 151.74 :C9 ; 157.12: C5; 158.3 : C1 .
14.9: (OCH2CH3) ; 63.69(OCH2CH3); 71.46:O-CH2C16; 114.97: C2,2` ; 115.28:C8 ; 117.67:C11, 122.17:C3,3` ;
124.61:C13,13`; 125.49: C10 ; 127.0: C18,18 ; 128.08: C20` ; 128.66: C19,19` ; 129.98: C15,6 ; 132.11: C7 ; 132.36 :
C14,14` ; 136.49: C17; 142.51: C4 ; 144.67: C12; 151.73 :C9 ; 157.63: C5; 158.28 : C1 .
Table-5: The 13C- DEPT data for the synthesized imines (3 g,h& i): Solvent CDCl3
3g
3h
3i
21(CH3); 71.4:O-CH2C16;
115.2:C8 ;
117.8:C11, 120.8:C3,3` ; 124.6:C13,13` ; 127.28: C18,18` ; 128.1: C20 ;
128.6: C 19,19` ; 129.8: C2,2` ; 132.27: C7 ; 132.37: C14,14` ; 158.2 : C5 .
55.5(OCH3); 71.5:O-CH2C16; 114.4: C2,2` ; 115.32:C8 ; 117.71:C11, 122.15:C3,3` ; 124.6:C13,13`; 127.0: C18,18
; 128.1: C20` ; 128.6: C19,19` ; 132.09: C7 ; 132.36 : C14,14` ; 157.12: C5.
14.9: (OCH2CH3) ; 63.69(OCH3); 71.46:O-CH2C16; 114.97: C2,2` ; 115.28:C8 ;
117.67:C11, 122.17:C3,3` ;
124.61:C13,13`; 127.0: C18,18 ; 128.08: C20` ; 128.66: C19,19` ; 132.11: C7 ; 132.36 : C14,14` ; 157.63: C5.
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Table-6: Assignment of characteristic frequencies (cm-1) of IR spectra for the synthesized imines(3a-j) and
thiazolidinones (4 a-j)
Product
R
A
B
C
D
E
F
G
H
I
J
H
4-F
2-Cl
4-Cl
4-NO2
4-Br
4-CH3
4-OCH3
4-O-C2H5
4-N(CH3)2
Imines (3 a-j)
C=N C=CAr.
1622
1601
1628
1609
1623
1600
1627
1607
1626
1607
1624
1609
1622
1600
1619
1601
1620
1602
1618
1603
Thiazolidinones (4 a-j)
C=O
C=C Ar.
1677
1606
1693
1622
1674
1603
1689
1625
1675
1608
1683
1593
1685
1595
1580
1602
1686
1604
1682
1595
Table-7: The 1H-NMR data for the synthesized thiazolidinones (4 g,,h & i ) : Solvent CDCl3.
Product
4g
4h
4i
δ / ppm
Multiplicity
Intensity
Assignment
2.31(s, 3H, CH3) ; 3.9, 4(dd, 2H,CH2-H21) ; 5.27(s, 2H, OCH2-H16) ; 6.05(s, 1H,H5) ; 6.92-7.77( m, 16H, four
aromatic rings).
3.74(s, 3H, OCH3) ; 3.91, 4.02(dd, 2H,CH2-H21) ; 5.28(s, 2H, OCH2-H16) ; 5.99(s, 1H,H5) ; 6.5-7.38( m, 16H, four
aromatic rings).
1.36(t, 3H, OCH2CH3) ; 3.66(q, 2H, OCH2CH3); 3.94, 4.02(dd, 2H,CH2-H21) ; 5.27(s, 2H, OCH2-H16) ; 5.99(s,
1H,H5) ; 6.45-7.21( m, 16H, four aromatic rings).
Table-8: The 13C-NMR data for the synthesized thiazolidinones (4 h & i ): Solvent CDCl3.
4h
4i
33.4:(C21) ; 55.33 :(OCH3); 65.53 : (C5) ; 71.68:O-CH2C16;
114.58: C2,2` ; 115.76: C8 ;
116.18: C3,3` ;
124.56:C13,13`; 125.50(C10) ; 127.06: C18,18,11 ; 127.6 : C20` ; 128.66: C19,19` ; 129. 8: C15, ; 131.16: C7 ; 132.34 :
C14,14` ; 132.46: C6 ; 136.5: C4; 142.22: C17 ; 151.65 :C9 ; 157.67: C12; 158.28 : C1 .171.0:(C=O).
14.7: (OCH2CH3) ; 33.4:(C21) ; 63.56 :(OCH2CH3); 65.56 : (C5) ; 71.65:O-CH2C16; 115.06: C2,2` ; 115.72: C8 ;
116.18: C3,3` ; 124.57:C13,13`; 125.52(C10) ; 127.06: C18,18,11 ; 127.6 : C20` ; 128.66: C19,19` ; 129.98: C15 ; 131.19: C7
; 132.34 : C14,14` ; 132.46: C6 ; 136.57: C4; 142.12: C17 ; 151.65 :C9 ; 157.67: C12; 158.28 : C1 .171.07:(C=O).
Table-9: The 13C- DEPT data for the synthesized thiazolidinones (4 h & i ): Solvent CDCl3.
4h
4i
-33.4:(C21) ; 55.33 :(OCH3); 65.53 : (C5) ; -71.68:O-CH2C16;
114.58: C2,2` ; 115.76: C8 ; 116.18: C3,3` ;
124.56:C13,13`;; 127.06: C18,18,11 ; 127.6 : C20` ; 128.66: C19,19` ;; 131.16: C7 ; 132.34 : C14,14`.
14.7: (OCH2CH3) ; -33.4:(C21) ;- 63.56 :(OCH2CH3); 65.56 : (C5) ; -71.65:O-CH2C16; 115.06: C2,2` ; 115.72: C8 ;
116.18: C3,3` ; 124.57:C13,13`; 127.06: C18,18,11 ; 127.6 : C20` ; 128.66: C19,19` ; 131.19: C7 ; 132.34 : C14,14`.
Figure-1-: 13C-NMR spectrum of compound (2).
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Figur-2: 13C-DEPT-NMR spectrum of compound (2).
Figure-3: 1H-NMR spectrum of compound (3 i)
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Figure-4-: 13C-NMR spectrum of compound (3i).
Figur-5: 13C-DEPT-NMR spectrum of compound (3i).
Figure-6: 1H-NMR spectrum of compound (4 i)
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Figure-7-: 13C-NMR spectrum of compound (4i).
Figur-8: 13C-DEPT-NMR spectrum of compound (4i).
CONCLUSION
The presence of the free aldehyde or acetyl group besides the activating hydroxyl group on the coupling
agent, will serve to use the product as very useful intermediate for the synthesis of a wide variety of
organic compounds , as in the presence study the free aldehyde group in the coupling reagent changed to
imine followed by cyclization giving the new biological active azo-thiazolidinone compounds.
REFERENCES
[1] H. Karaer &_I. E. Gumerukcuoglu , Turk J Chem , (1999).23 , 67 -71.
[2] A. A. Jarrahpour and M. Zarei , Molbank (2004), M376, 1-3.
[3] J. P. LI , P. LIU, and Y. L .Wang , Chinese Chemical Letters(2003) Vol. 14, No. 7, pp 677
– 680 .
[4] M. C. Sharma, D. V. Kohli , Smita Sharma and A. D. Sharma, Der Pharmacia Sinica, 2010,
1 (1): 124-135.
[5] S. Gopalakrishnan , N. T. Nevadith and C. V. Mythili, Der Chemica Sinica, 2011, 2 (3):138146
145
Pelagia Research Library
Awaz J. Hussein et al
Der Chemica Sinica, 2011, 2(5):136-146
______________________________________________________________________________
[6] A. A. Jarrahpour , M. Motamedifar , K. Pakshir, N. Hadi and M. Zarei , Molecules, (2004),
9, 815-824 .
[7] H. Kumar and R. Pal Chaudhary , Arch. Appl. Sci. Res (2010) , 2 (5): 407-413.
[8] S. Ampati, R. Jukanti, V. Sagar, R. Ganta, S. Manda, Der Chemica Sinica, 2010, 1 (3): 157168
[9] I. A Mohammed , E. V S Subrahmanyam , A. R. Hareesh and R. Kowti1 , Int J Pharm Sci
Bio (2010) 1(2):80-85.
[10] K. M. Mistry and K. R. Desal , E-Journal of Chemistry,(2004) Vol. 1, No. 4, pp 189-193.
[11] K.H.Patel and A.G., E-Journal of Chemistry, (2006) ,Vol. 3, No.11, pp 103-109.
[12] N.B. Patel and F.M. Shaikh , J. Sci. I. R. Iran, (2010) ,Vol. 21 No. 2,121-129..
[13] D. Patel , P.Kumari1& Navin Patel , Arch. Appl. Sci. Res(2010) , 2 (6):68-75.
[14] D. Pareek, M. Chaudhary, P. K. Pareek, R. Kant, K. G. Ojha , R.Pareek, and A. Pareek ,
Der Pharmacia Sinica, (2011) 2 (1): 170-181.
[15] D. Pareek, M. Chaudhary, P. K. Pareek, R. Kant, K. G. Ojha R.Pareek, S M. U Iraqi and A.
Pareek, Der Chemica Sinica, 2010, 1 (3): 22-35.
[16] P. Sharma , B. Shrivastava, H .S . Lamba, J. Sharma and L. Sharma , Pharmacie Globale
(IJCP)(2010) , 3 (9) .
[17] D. Patel , P. Kumari1, N. Patel , J. Chem. Pharm. Res,(2010) 2(5): 84-91 .
[18] J. B. Patel, V. A. Desai , Int. J. Ind. Chem, (2011)Vol. 2, No. 1, , pp. xx-xx.
[19] M. K. Ahirwar and S.P. , E-Journal of Chemistry, (2011) ,8(2), 931-937.
[20] M.T. Shreenivas , B.P Chetan1 and A.R.Bhat , Journal of Pharmaceutical Science and
Technology (2009) Vol. 1 (2), 88-94.
[21] V. K. Tirlapur and T. Tadmalle, Der Pharmacia Sinica, 2011, 2 (1): 135-141
[22] A. Gursoy , N. Terzioglu ,Turk J Chem, (2005),29 , 247 - 254.
[23] H.H. Parekh, K.A. Parikh, and A.R. Parikh , J. Sci. I. R. Iran, (2004) ,Vol. 15 No. 2 ,143148.
[24] L. Yang , G. Wang, J. Wang, G. Wang, and Z. Xu, Optik ,(2002),113, No. 4 , 189–19.
[25] K. K. Karukstis, L. A. Perelman, and W. K. Wong , Langmuir ,(2002), 18, 10363-10371.
[26] H. N. Chopde , J. S. Meshram , R. Pagadala1& A. J. Mungole, International Journal of
ChemTech Research(2010), Vol.2, No.3, pp 1823-1830.
[27] M. C. Hamzaçebi, S. Rollas,S. G.Kucukguzel, and B. K.Kaymakcioglu, ARKIVOC,(2008)
(xii), 188-190.
[28] Z. Ngaini, S. M. Haris-Fadzillah, H. Hussain and K. Kamaruddin, World J. Chemistry,
(2009) ,4, 1-9.
[29] S. Ramachandran , P. Shanmugapandiyan and C. N. Nalini , IJPSR,(2011) , Vol. 2(6):
1564-1568.
[30] L. D. Field, S. Stern hell and J. R. Kalman, Organic Structures from Spectra, 3rdeddition,
John Wiley and Sons,(2005).
146
Pelagia Research Library