6
82
P. Toto et al.
4-Hydroxy-3-iodo-1-methyl-1H-thieno[2,3-c]-pyrazole-5-carboxylic
Acid Ethyl Ester (14)
Thieno[2,3-c]pyrazole 14 was obtained from 12 using the same procedure as
2
1 l
in the case of compound 13. Yield: 92%; Mp: 1408C; IR (KBr): 1651 cm ; H
NMR (DMSO-d ): d 1.28 (t, 3H, J ¼ 7.5 Hz, CH -CH -O), 3.90 (s, 3H,
6
3
2
1
3
N-CH ), 4.28 (q, 2H, J ¼ 7.5 Hz, CH -O), 10.45 (s, 1H, O-H); C NMR
3
2
(
DMSO-d ): d 15.1 (CH CH -O), 38.7 (N-CH ), 61.5 (O-CH ), 87.9 (Cq),
6 3 2 3 2
þ
1
01.9 (Cq), 145.0 (Cq), 153.2 (Cq), 165.2 (C 55 O); MS 353 [M þ H] .
Anal. calcd. for C H IN O S: C, 30.70; H, 2.58; N, 7.95. Found: C,
11 15 2 4
3
0.76; H, 2.60; N, 7.89.
Imine of the 3-Amino-4-hydroxy-1-methyl-1H-thieno[2,3-c]-pyrazole-
-carboxylic Acid Ethyl Ester (15)
5
Compound 15 was obtained from aminopyrazole 11 using the same procedure
2
1
as in the case of compound 13. Yield: 90%; mp: 2058C; IR (KBr): 1698 cm
,
2
l
21 1
1
732 cm , 1741 cm ; H NMR (DMSO-d ): d 1.25 (t, 3H, J ¼ 6.9 Hz, CH -
6
3
CH -O), 1.26 (t, 3H, J ¼ 6.9 Hz, CH -CH -O), 3.66 (s, 3H, N-CH ), 3.80
2 3 2 3
(
s, 3H, N-CH ), 3.86 (s, 2H, N-H þ O-H), 4.18 (q, 2H, J ¼ 6.9 Hz, CH -
2 2
3
2
1
3
O), 4.20 (q, 2H, J ¼ 6.9 Hz, CH -O), 5.50 (s, 2H, NH ). C NMR
(
DMSO-d ): d 12.9 (CH -CH -O), 13.2 (CH -CH -O), 35.1 (N-CH ), 36.1
6 3 2 3 2 3
(
N-CH ), 58.2 (O-CH ), 58.7 (O-CH ), 98.6 (Cq), 109.5 (Cq), 124.2 (Cq),
3 2 2
1
35.0 (Cq), 142.9 (Cq), 149.2 (Cq), 155.5 (Cq), 161.1 (C 55 O), 161.9
þ
(C 55 O), 167.0 (C 55 N); MS 465 [M þ H] . Anal. calcd. for C H N O S :
1
8 20 6 5 2
C, 46.54; H, 4.34; N, 18.09. Found: C, 46.62; H, 4.38; N, 17.98.
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