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A. P. Rajput et al
A. P. Rajput et al
refluxed again for 2hrs, which resulted dark semi-solid. Solvent extraction, crystallization
gave creamy color powder. Mp.143-450C, yield-38%. FTIR (KBr/cm-1): 3265(NH),
1662(C=O), 1546, 1512, 1303, 815(para sub.). 1H-NMR (DMSO-d6 ): 2.30 ( s, 3H, CH3),
2.50 (s, 2H, CH2), 7.30 ( m, 7H, Ar-H), 10.3( s, br. NH), MS (m/e, %): 214 (M+-1, 2), 201(2),
183(100), 134.
2-(Benzimidazo-1-yl-)-4-methylacetanilide(6c):To a Benzmidazole-1-acetic acid ( 0.015 M,
2.6g ) in 5ml DMF, 2ml thionyl chloride was added drop wise with occasional stirring and
refluxed for 2 hrs. on a water bath. Reaction mixture was allowed to cool, p-Toluidine
(0.015M, 1.6g) in dry toluene was added drop wise and refluxed again for 3hrs, after which
whitish plates were separated. mp. 240-42, yield 42%, FTIR (KBr/cm-1) : 3321( NH), 2912,
2858, 1695(C=O), 815( para sub.). 1H-NMR (DMSO-d6 ): 2.50 ( s, 3H, CH3), 3.37 (s, 2H
CH2), 6.90-7.30 ( m, 8H, Ar-H), 7.48 (d,1H, Imi.H2), 8.68( s, br. NH), MS (m/e, %): 264
(M+-1, 2), 240.9(100), 148(10), 134(2), 106(11).
2-(Benzotriazo-1-yl-)acetanilide(8a): To a Benztriazole-1-acetic acid ( 0.015 M, 1.5g ) in 5ml
DMF, 1ml thionyl chloride was added drop wise with occasional stirring and refluxed for 1.5
hrs. on a water bath. Reaction mixture was allowed to cool, aniline (0.02 M, 1.8ml) in dry
benzene was added drop wise and refluxed again for 2hrs, white crystal crystallized. mp. 20204, yield 55%, FTIR (KBr/cm-1): 3281(NH), 3091, 1668(C=O), 746 and 700( mono sub.). 1HNMR (DMSO-d6 ): 3.40 ( s, 2H, CH2), 6.96 ( t,2H,B.Tz.H), 7.26 (t,2H, B.Tz.H), 7.46 ( d,
5H,Ar-H), 8.70( s, NH). MS (m/e, %): 263 (M+-1, 100), 160(2), 134(7), 132(2), 120(1).
2-(Benzotriazo-1-yl-)-2-methylacetanilide (8b): Synthesized by similar procedure as 8a , gave
brown crystal mp. 156-58 0C, hygroscopic, yield-46 %. FTIR (KBr/cm-1): 3352(NH), 2929,
2854, 1620 (C=O), 1288, 1132, 752 and 600(ortho sub.). 1H-NMR (DMSO- d6 ): 2.38 ( s,
3H, CH3), 2.54 (s, 2H, CH2), 7.4-7.9 ( m, 8H, Ar-H), 7.9 ( s, NH). MS (m/e, %): 266 (M+-1,
(5), 263 (37), 174(10), 120(100).
2-(Benzotriazo-1-yl-)-4-methylacetanilide (8c): Synthesized by similar procedure as 8a ,
white crystal mp. 230-32 0C, yield-52 %. FTIR (KBr/cm-1): 3437 (NH), 2928, 1645 (C=O),
1288, 1037,
(dia. sub.). 1H-NMR (DMSO- d6 ): 2.2 ( t, 3H, CH3), 3.4 (s, 2H, CH2),
7.0-7.33( m, 8H, Ar-H), 8.67 ( s, NH). MS (m/e, %): 266 (M+, 5), 263 (100), 235(8), 134(13).
2-(Benzotriazo-1-yl-)-4-chloroacetanilide (8e): Synthesized by similar procedure as 8a ,
brown crystal, mp. 244 0C, yield 46 %, FTIR (KBr/cm-1): 3192 (NH), 3047, 2841, 2607, 1650
(C=O), 1595, 821(para sub.). 1H-NMR (DMSO-d6 ): 2.5 ( s, 2H, CH2), 7.39-7.54( dd, 8H,
Ar-H), 8.9( s, br. NH). MS (m/e, %): (M+ absent), 263 (100), 168 (23), 154(3).
2-(4-methylpiperazine-1-yl-)-acetanilide (10a): Synthesized by similar procedure as 8a ,
colorless needle , mp. 234-36 0C, yield- 42 %, FTIR (KBr/cm-1): 3234 (NH), 2976, 2941,
2739 (ali. H), 1660 (C=O), 1475, 1398, 1172, 1035, 806, 750 and 700(mono sub.). 1H-NMR
(CDCl3 ): 1.25 ( s, N-CH3), 1.64 (s, 8H, 4CH2), 2.5 (s, 2H, CH2) [22], 7.3 ( s, 5H, Ar-H),
9.3( s, br. NH).
General procedure for the synthesis of (5a, 5b, 5e, 7a, 7d)
Azole-1-acetic acids were chlorinated by using same method. To a cool reaction mixture
limiting amount, half moles of aromatic primary amines (3a-e) were added slowly and
refluxed at slightly higher temperature for 3-4 hrs.
54
A. P. Rajput et al
A. P. Rajput et al
Molecular Formula
C5H6N2O2
C9H8N2O2
C8H7N3O2
C7H14N2O2
Molar mass
126.10
176.17
177.16
158.20
M.P.(oC)
230-32
120-24
50-52
106-08
Yield (%)
53
40
45
69
56
A. P. Rajput et al
DMF
N
CH2 COOH
SOC l2
reflux
CH2 COC l
CH2 CO
2a
4c
R
Scheme 2
4c: R= 4 CH3,
NH2
DMF
+ SOC l2
reflux
CH2 COOH
CH2CO C l
CH2CO
2b
6c
R
Scheme 3
6c: R= 4 CH3
NH2
N
N
DMF
reflux
+ SOC l2
N
N
N
CH2 COC l
CH2 COOH
CH2 CO
H
N
2c
8a: R= H,
8b: R= 2 CH3,
8 a,b,c,e
8e: R=4 Cl
Scheme 4
NH2
DMF
reflux
CH2COC l
CH2 CO
SOC l2
CH2 COOH
H
N
2d
10 a
10a: R= H
No.
4c
6c
8a
8b
8c
8e
10a
Scheme 5
Yield
(%)
38
42
55
46
52
46
42
Motivated by this fact we have carried out acylation taking limiting amount of amines
particularly aniline, o-Toluidine o- chlororaniline and p-chloroaniline. We succeeds in
obtaining diacetylderivative a few (5 a,b,e , 7a,7d ) but in poor yields. (Scheme-6,7). The
1
H-NMR of the compounds (5a,b,e, 7a, 7d) showed absence of N-H signal relevant to
57
A. P. Rajput et al
diacetylderivative. The satisfactory mass spectrum results confirmed the diacetyl nature of
synthesized compound 5a,b,e and 7a,d.
Synthesis of compounds 5 a,b,e, and 7a,7d.
DMF
NH2
reflux
CH2 CO C l
N
CH2 CO
CO CH2
half mole
R
5e: R= 4C l
Scheme 6.
NH2
DMF
reflux
CH2COC l
N
N
CH2CO
N
N
N
CO CH2
half mole
R
7a : R= H,
Table 3
No.
5a
5b
5e
7a
7d
7d : R=2C l
Scheme 7
Molecular
Formula
C16H15N5O2
C17H17N5O2
C16H14N5O2Cl
C24H19N5O2
C24H18N5O2Cl
Molar mass
Calc.
Exp.(MS)
309
309
323
322(M+-1)
343.8
343.5
409
409
443.9
443
M.P.(oC)
170-72
92-94
138-40
196-200
208-10
Yield
(%)
11
09
10
08
12
This study reports the synthesis of some new mono and diacetanilides incorporating azoles
moiety, one of the active component present in many drugs. N-methylpiperazine is also
possessing wide spectrum of biological activity. In some reaction we does not have desired
product in workup. The structure of the new compounds was assigned by FTIR, 1H-NMR,
and Mass spectroscopy. Biological activity of synthesized compounds will be carried out
later on.
Acknowledgement:
We are grateful to the Head UDCT, North Maharashtra University, Jalgaon, Principal, Z. B.
Patil College, Deopur, Dhule for providing necessary facilities for research work. Our thanks
are also to SAIF, IIT, Bombay for spectral analysis.
58
A. P. Rajput et al
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