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B. Shivarama Holla et al. / European Journal of Medicinal Chemistry 38 (2003) 759Á767
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Table 1
Characterization data of 3-substituted-4-[5-(4-methoxy-2-nitrophenyl)-2-furfurylidene] amino-1,2,4-triazole-5-thiones 3aÁh
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Compound
R
Melting point (8C)
Yield (%) Molecular formula
Analysis (%) found (calculated)
C
H
N
3a
3b
3c
3d
3e
3f
H
188Á
223Á
183Á
189Á
176Á
200Á
178Á
160Á
/
190
225
185
191
178
202
180
162
82
84
76
88
92
90
83
80
C14H11N5O4S
C15H13N5O4S
C16H15N5O4S
C17H17N5O4S
C21H16ClN5O5S
C21H16ClN5O5S
C21H15Cl2N5O5S
C22H18ClN5O5S
48.52 (48.69) 3.12 (3.19) 20.25 (20.28)
50.34 (50.14) 3.57 (3.62) 19.30 (19.49)
51.61 (51.47) 3.96 (4.02) 18.70 (18.76)
52.83 (52.71) 4.31 (4.39) 17.95 (18.08)
51.80 (51.95) 3.22 (3.29) 14.35 (14.43)
51.82 (51.95) 3.17 (3.29) 14.33 (14.43)
48.38 (48.55) 2.77 (2.89) 13.39 (13.48)
52.71 (52.90) 3.49 (3.60) 13.94 (14.02)
CH3
C2H5
C3H7
/
/
/
2-ClC6H4Ã
4-ClC6H4Ã
2,4-Cl2C6H3Ã
4Cl,3-CH3C6H3Ã
/
OCH2Ã
OCH2Ã
OCH2Ã
OCH2Ã
/
/
/
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3g
3h
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IR: (KBr, cmꢀ1): 3c, 3117 and 3050 (NH/SH str.), 2935 (CÃ
str.). 1H-NMR (CDCl3, 300 MHz): 3b, d 13.35 (bs, 1H, SH), 10.48 (s, 1H, Ã
8.6 Hz), 7.21Á7.29 (dd, 1H, ArÃH, Jꢁ8.6, 2.4 Hz), 7.17Á7.18 (d, 1H, furan-H, Jꢁ
1.2 (s, 3H, CH3); 3e, d 10.61 (bs, 1H, SH), 10.3 (s, 1H, ÃNÄCHÃ), 5.3 (s, 2H, ÃOCH2), 3.91 (s, 3H, OMe), 6.68Á
7.06Á7.07 (d, 1H, furan-H, Jꢁ3.6 Hz), 6.95Á7.34 (complex multiplet, 5H, ArÃH), 7.66Á7.69 (d, 1H, ArÃH, Jꢁ
Jꢁ
8 Hz). Mass: 3a, m/z 345 (Mꢂ, 45%), 244 (4-methoxy-2-nitrophenylfuronitrile, 56%), 101 (3-mercapto-4(H)-1,2,4-triazole, 100%); 3d, m/z 387
(Mꢂ, 2%), 341 (MꢂꢀNO2, 3%), 244 (o-nitro-4-methoxyphenylfuronitrile, 5%), 154 (4-methoxy-2-nitro phenyl cation, 100%), 77 (Phꢂ, 43.9%); 3f,
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H str.), 1603 (CÄ
NÄCHÃ
3 Hz), 6.7Á
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N str.), 1543 (NO2 asym), 1380 (NO2 sym), 1233 (CÄ
), 7.72Á7.75 (d, 1H, ArÃH, Jꢁ8.6 Hz), 7.46 (d, 1H, ArÃ
6.71 (d, 1H, furan-H, Jꢁ3 Hz), 3.92 (s, 3H, OCH3),
6.69 (d, 1H, furan-H, Jꢁ3.6 Hz),
8 Hz), 7.73Á7.76 (d, 1H, ArÃH,
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S), 1032 (CÃ
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S
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H, Jꢁ
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m/z 167 (p-chlorophenoxy methylacetonitrile, 45%).
respectively. The IR spectral data are given under the
to one of the aromatic protons, while the remaining
Tables 1Á
In the 1H-NMR spectrum of compound 4d, the ÈNÃ
CH2ÃNÇ protons resonated as a singlet at d 5.1
integrating for two protons. The signal due to the Ã
NÄCHÃ was seen as a singlet at d 10.42. The two b-
protons of the furan ring appeared as two closely spaced
doublets at d 6.67Á6.68 (Jꢁ3.0 Hz) and d 7.05Á7.07
(Jꢁ3.0 Hz), respectively integrating for two protons. A
doublet appeared at d 7.69Á7.73 (Jꢁ7 Hz) corresponds
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3.
aromatic protons appeared as a singlet at d 7.26 and a
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doublet of doublet at d 7.13Á
integrating for three protons. A singlet observed at d 3.9
was ascribed to methoxy protons. The ÃNCH3 protons
were observed as a singlet at d 3.7, while a triplet was
observed at d 2.76Á2.85 due to ÃCH2ÃNÃCH2Ã pro-
tons. The propyl protons of the triazole ring appeared as
a triplet at d 2.43 (Jꢁ6 Hz), a multiplet at d 2.27 and a
triplet at d 1.27Á1.34 (Jꢁ6 Hz) integrating for seven
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7.16 (Jꢁ/1.5, 1.5 Hz)
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Table 2
Characterization data of 3-substituted-1-(N-methyl piperazino)methyl-4-[5-(4-methoxy-2-nitrophenyl)-2-furfurylidene]amino1-2,4-triazole-5-thiones
4aÁ
/g
Compound
R
Melting point (8C)
Yield (%) Molecular formula
Analalysis (%) found (calculated)
C
H
N
4a
4b
4c
4d
4e
4f
H
107
83
68
70
60
72
65
68
74
C
20H23N7O4S
51.34 (52.51) 4.92 (5.03) 21.24 (21.44)
53.63 (53.50) 5.24 (5.30) 20.68 (20.80)
54.60 (54.43) 5.45 (5.56) 20.11 (20.20)
55.14 (55.31) 5.72 (5.81) 19.50 (19.63)
54.55 (54.27) 4.65 (4.69) 16.47 (16.58)
51.16 (51.34) 4.20 (4.27) 15.42 (15.53)
54.78 (54.99) 4.81 (4.90) 15.88 (16.03)
CH3
C2H5
C3H7
C21H25N7O4S
C22H27N7O4S
C23H29N7O4S
C27H22ClN7O5S
C27H27Cl2N7O5S
C28H30ClN7O5S
74
78
2-ClC6H4Ã
2,4-Cl2 C6H3Ã
4Cl,3-CH3C6H3Ã
/
OCH2Ã
OCH2Ã
OCH2Ã
/
155
162
159
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4g
/
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IR (KBr, cmꢀ1): 4d, 2917 (CÃ
NMR (300 MHz): 4b, d 10.5 (s, 1H, Ã
H, Jꢁ6, 2.7 Hz), 7.07Á7.09 (d, 1H, furan-H, Jꢁ
2.87Á2.88 (s, 4H, ÃCH2ÃNÃCH2Ã), 2.47Á2.57 (s, 4H, Ã
7.69Á7.73 (d, 1H, ArÃH, Jꢁ7 Hz), 7.26 (s, 1H, ArÃH), 7.13Á
(d, 1H, furan-H, Jꢁ3 Hz), 5.1 (s, 1H, ÈNÃCH2ÃNÇ), 3.9 (s, 3H, OCH3), 2.76Á
(t, 2H, ÃCH2Ã, Jꢁ6 Hz), 2.27 (m, 6H, CH2 and ÃCH2ÃN(Me)ÃCH2Ã), 1.27Á1.34 (t, 3H, CH3, Jꢁ
2H, ÃOCH2), 5.15 (s, 2H, ÈNÃCH2ÃNÇ), 3.91 (s, 3H, ÃOMe), 3.7 (s, 3H, ÃNMe), 2.92 (s, 4H, Ã
CH2Ã), 6.67Á6.68 (d, 1H, furan-H, Jꢁ3.6 Hz), 7.1Á7.11 (d, 1H, furan-H, Jꢁ3.6 Hz), 7.6Á7.63 (d, 1H, ArÃ
H, Jꢁ8.2, 2.2 Hz), 7.15Á7.27 (m, 4H, ArÃH); 4g, d 10.48 (s, 1H, ÃNÄCHÃ), 7.6Á7.63 (d, 1H, ArÃH, Jꢁ8.6 Hz), 7.4Á
Hz), 7.2Á7.4 (dd, 1H, ArÃH, Jꢁ7.8, 2.1 Hz), 7.4Á7.5 (d, 1H, ArÃH, Jꢁ7.8 Hz), 6.9Á6.91 (d, 1H, furan-H, Jꢁ3 Hz), 6.83Á
Jꢁ6, 3 Hz), 7.1Á7.12 (d, 1H, ArÃH, Jꢁ3.6 Hz), 6.64Á6.66 (d, 1H, furan-H, Jꢁ3 Hz), 5.63 (s, 2H, ÃOCH2), 5.21 (s, 2H, ÈNÃ
3H, OMe), 2.47 (s, 4H, ÃCH2ÃN(Me)ÃCH2), 2.89 (s, 4H, ÃCH2ÃNÃCH2Ã), 1.25 (s, 3H, CH3). Mass: 4a, m/z 113 (N-methylpiperazinomethyl
cation, 8%), 218 (4-methoxy-2-nitrophenyl cation, 100%).
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H str.), 1600 (CÄ
NÄCHÃ), 7.71Á
3.6 Hz), 6.68Á
CH2ÃN(Me)Ã
7.16 (dd, 1H, ArÃ
/
N), 1530 (NO2 asym.), 1350 (NO2 sym.), 1283 (CÄ
7.74 (d, 1H, ArÃH, Jꢁ8.7 Hz), 7.27Á7.28 (d, 1H, ArÃ
6.69 (d, 1H, furan-H, Jꢁ3.6 Hz), 5.1 (s, 2H, ÈNÃ
CH2Ã), 3.7 (s, 3H, ÃNCH3), 1.25 (s, 3H, CH3); 4d d 10.42 (s, 1H, Ã
H, Jꢁ9.8, 1.5 Hz), 7.05Á7.07 (d, 1H, furan-H, Jꢁ3 Hz), 6.67Á
2.85 (t, 4H, ÃCH2ÃNÃCH2Ã, Jꢁ2.4 Hz), 3.7 (s, 3H, NCH3), 2.43
6 Hz); 4f, d 10.37 (s, 1H, ÃNÄCHÃ), 5.25 (s,
CH2ÃNÃCH2), 2.55 (s, 4H, ÃCH2ÃN(Me)Ã
H, Jꢁ8.7 Hz), 7.29Á7.3 (dd, 1H, ArÃ
7.5 (d, 1H, ArÃH, Jꢁ8.6
6.84 (dd, 1H, ArÃH,
CH2ÃNÇ), 3.91 (s,
/
S str.), 1033 (CÃ
H, Jꢁ8.7 Hz), 7.15Á
CH2ÃNÇ), 3.91 (s, 3H, OCH3),
NÄCHÃ),
6.68
/
S str.), 800 (ArÃ
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H str.). H-
1
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7.18 (dd, 1H, ArÃ
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