3838
C. Vel ꢀa zquez, E. E. Knaus / Bioorg. Med. Chem. 12 (2004) 3831–3840
À1
2
(
CO), 1649 (C@C), 1508 (NO
2
), 1313, 829 (N–O) cm ;
5.8.6. O -Acetoxymethyl-1-(4-ethylpiperazin-1-yl)diazen-
1
H NMR (CDCl
H-2), 8.42 (dd, J5;6 ¼ 4:8, J ¼ 1:5 Hz, 1H, pyridyl H-
4;6
3
) d 8.50 (d, J2;4 ¼ 1:8 Hz, 1H, pyridyl
1-ium-1,2-diolate 4-(2-pyridyl)-1,4-dihydro-2,6-dimethyl-
3-nitropyridine-5-carboxylate (23). Yellow powder
(29%); mp 170–171 ꢁC; IR (KBr): 3328 (NH), 1602
6
J
), 8.31 (s, 1H, NH), 7.77 (ddd, J4;5 ¼ 7:8, J2;4 ¼ 1:8,
À1
1
4;6 ¼ 1:5 Hz, 1H, pyridyl H-4), 7.25 (dd, J4;5 ¼ 7:8,
(C@C), 1427 (NO ), 1266, 897 (N–O) cm ; H NMR
2
J5;6 ¼ 4:8 Hz, 1H, pyridyl H-5), 5.76 (s, 2H, OCH O),
(CDCl ) d 8.74 (s, 1H, NH), 8.26 (d, J ¼ 6:3 Hz, 1H,
2
3
5;6
5
3
2
.35 (s, 1H, H-4), 4.22–4.26 (m, 2H, CO
2
CH
2
), 3.55–
pyridyl H-6), 7.37 (dd, J3;4 ¼ 7:5, J4;5 ¼ 6:3 Hz, 1H,
pyridyl H-4), 7.25 (d, J3;4 ¼ 7:5 Hz, 1H, pyridyl H-3),
.63 (m, 2H, CH
CH ), 2.35 (s, 3H, C-6 CH ), 2.11 (s, 3H, COCH ).
2 3
N), 3.01 (s, 3H, NCH ), 2.51 (s, 3H, C-
6.90 (dd, J5;6 ¼ J ¼ 6:3 Hz, 1H, pyridyl H-5), 5.61 (s,
4;5
3
3
3
Anal. Calcd for C19
1
H
24
N
6
O
8.10. Found: C, 49.00; H, 5.07; N, 17.87.
8
: C, 49.14; H, 5.21; N,
2
2H, OCH O), 5.34 (s, 1H, H-4), 3.95–4.00 (m, 2H,
CO
2
2
CH ), 3.18–3.30 (m, 4H, piperazin-1-yl H-2, H-6),
.59 (m, 2H, CH CH N), 2.44 (m, 4H, piperazin-1-yl H-
, H-5), 2.38 (s, 3H, C-2 CH ), 2.19 (s, 3H, C-6 CH ),
3
.96 (s, 3H, COCH
50.86; H, 5.63; N, 18.87. Found: C, 50.46; H, 5.39; N,
18.69.
2
3
1
2
2
3
3
). Anal. Calcd for C22
H
29
N
7
O
8
: C,
2
5.8.3. O -Acetoxymethyl-1-(N-methyl-N-ethylamino)dia-
zen-1-ium-1,2-diolate 4-(4-pyridyl)-1,4-dihydro-2,6-dime-
thyl-3-nitropyridine-5-carboxylate (20). Yellow powder
(
19%); mp 150–152 ꢁC; IR (KBr): 3180 (NH), 1763
À1
2
(
CO), 1649 (C@C), 1494 (NO
2
), 1313, 829 (N–O) cm ;
) d 8.48 (d, Jortho ¼ 5:4 Hz, 2H, pyridyl
5.8.7. O -Acetoxymethyl-1-(4-ethylpiperazin-1-yl)diazen-
1
H NMR (CDCl
3
1-ium-1,2-diolate 4-(3-pyridyl)-1,4-dihydro-2,6-dimethyl-
3-nitropyridine-5-carboxylate (24). Yellow powder
(19%); mp 75–77 ꢁC; IR (KBr): 3308 (NH), 1763 (CO),
1649 (C@C), 1474 (NO
NMR (CDCl
1H, pyridyl H-2), 8.42 (dd, J5;6 ¼ 4:8, J4;6 ¼ 1:2 Hz, 1H,
pyridyl H-6), 7.74 (ddd, J4;5 ¼ 7:5, J2;4 ¼ 2:1, J4;6
1:2 Hz, 1H, pyridyl H-4), 7.24 (dd,
H-2, H-6), 7.62 (s, 1H, NH), 7.28 (d, Jortho ¼ 5.4 Hz, 2H,
pyridyl H-3, H-5), 5.76 (s, 2H, OCH O), 5.39 (s, 1H, H-
), 4.23–4.29 (m, 2H, CO CH ), 3.57–3.67 (m, 2H,
CH N), 3.00 (s, 3H, NCH ), 2.53 (s, 3H, C-2 CH ), 2.38
2
À1
1
4
2
2
2
), 1273, 742 (N–O) cm ; H
3
) d 8.55 (s, 1H, NH), 8.52 (d, J2;4 ¼ 2:1 Hz,
2
3
3
(
s, 3H, C-6 CH ), 2.11 (s, 3H, COCH ). Anal. Calcd for
3 3
C
4
19
H
24
N
9.05; H, 5.08; N, 17.88.
6
O
8
: C, 49.14; H, 5.21; N, 18.10. Found: C,
¼
J
4;5 ¼ 7:5,
2
J
5
3
5;6 ¼ 4:8 Hz, 1H, pyridyl H-5), 5.79 (s, 2H, OCH O),
.39 (s, 1H, H-4), 4.13–4.19 (m, 2H, CO CH ), 3.40–
2
2
.49 (m, 4H, piperazin-1-yl H-2, H-6), 2.56–2.64 (m, 6H,
CH N), 2.53 (s, 3H, C-2
CH ), 2.38 (s, 3H, C-6 CH ), 2.05 (s, 3H, COCH ).
2
piperazin-1-yl H-3, H-5, CH
2
2
5
.8.4. O -Acetoxymethyl-1-(N-methyl-N-ethylamino)dia-
zen-1-ium-1,2-diolate 4-(2-trifluoromethylphenyl)-1,4-di-
hydro-2,6-dimethyl-3-nitropyridine-5-carboxylate (21).
Yellow powder (36%); mp 91–93 ꢁC; IR (KBr): 3328
3
3
3
Anal. Calcd for C22 O
8.87. Found: C, 50.79; H, 5.79; N, 18.65.
H
29
N
7
8
: C, 50.86; H, 5.63; N,
1
(
(
1
7
2
NH), 1763 (CO), 1656 (C@C), 1494 (NO ), 1313, 776
À1
1
N–O) cm ; H NMR (CDCl ) d 7.51 (d, J ¼ 7:8 Hz,
3
3;4
2
5
1
3
.8.8. O -Acetoxymethyl-1-(4-ethylpiperazin-1-yl)diazen-
-ium-1,2-diolate 4-(4-pyridyl)-1,4-dihydro-2,6-dimethyl-
-nitropyridine-5-carboxylate (25). Yellow powder
H, phenyl H-3), 7.40–7.44 (m, 2H, phenyl H-5, H-6),
.27 (dd, J4:5 ¼ 6:9, J3;4 ¼ 7.8 Hz, 1H, phenyl H-4), 7.03
(
2
s, 1H, NH), 5.90 (s, 1H, H-4), 5.75 (s, 2H, OCH O),
0
.27–4.37 (m, 1H, CO CHH ), 4.07–4.15 (m, 1H,
2
(
(
29%); mp 180–182 ꢁC; IR (KBr): 3053 (NH), 1716
4
CO
À1
2 3
CO), 1602 (C@C), 1427 (NO ) cm ; H NMR (CDCl )
1
0
0
2
CHH ), 3.65–3.75 (m, 1H, CHH N), 3.49–3.57 (m,
0
d 8.46 (d, Jortho ¼ 5:4 Hz, 2H, pyridyl H-2, H-6), 7.60 (s,
1
CH ), 2.29 (s, 3H, C-6 CH ), 2.11 (s, 3H, COCH ).
H, CHH N), 2.97 (s, 3H, NCH
3
), 2.46 (s, 3H, C-2
1
5
2
6
H, NH), 7.24 (d, Jortho ¼ 5:4 Hz, 2H, pyridyl H-3, H-5),
.79 (s, 2H, OCH O), 5.36 (s, 1H, H-4), 4.21–4.27 (m,
H, CO CH ), 3.39–3.47 (m, 4H, piperazin-1-yl H-2, H-
3
3
3
Anal. Calcd for C21
1
H
24
F
3
N
3.18. Found: C, 47.21; H, 4.58; N, 13.06.
5
O
8
: C, 47.46; H, 4.55; N,
2
2
2
), 2.52–2.61 (m, 6H, piperazin-1-yl H-3, H-5,
CH N), 2.51 (s, 3H, C-2 CH ), 2.36 (s, 3H, C-6
CH ), 2.05 (s, 3H, COCH ). Anal. Calcd for
CH
2
2
3
3
3
2
5
.8.5. O -Acetoxymethyl-1-(N-methyl-N-ethylamino)dia-
C
50.79; H, 5.61; N, 18.63.
22
H
29
N
7
O
8
: C, 50.86; H, 5.63; N, 18.87. Found: C,
zen-1-ium-1,2-diolate 4-(benzofurazan-4-yl)-1,4-dihydro-
,6-dimethyl-3-nitropyridine-5-carboxylate (22). Yellow
powder (28%); mp 120–122 ꢁC; IR (KBr): 3348 (NH),
756 (CO), 1649 (C@C), 1474 (NO ), 1273, 803 (N–O)
) d 7.60 (d, J6;7 ¼ 8:7 Hz, 1H,
benzofurazan-4-yl H-7), 7.39 (d, J5;6 ¼ 6:3 Hz, 1H,
benzofurazan-4-yl H-5), 7.30 (dd, J6;7 ¼ 8:7, J5;6
:3 Hz, 1H, benzofurazan-4-yl H-6), 6.46 (s, 1H,
NH), 5.72 (s, 1H, H-4), 5.70 (s, 2H, OCH O), 4.12–4.17
2
2
1
2
5.8.9. O -Acetoxymethyl-1-(4-ethylpiperazin-1-yl)diazen-
1-ium-1,2-diolate
À1
1
cm ; H NMR (CDCl
3
4-(2-trifluoromethylphenyl)-1,4-dihy-
dro-2,6-dimethyl-3-nitropyridine-5-carboxylate (26). Yel-
low powder (26%); mp 70–72 ꢁC; IR (KBr): 3321 (NH),
¼
6
2
1763 (CO), 1649 (C@C), 1501 (NO ), 1320, 769 (N–O)
À1
1
cm ; H NMR (CDCl ) d 7.53 (d, J ¼ 7:5 Hz, 1H,
2
3
3;4
(
m, 2H, CO
2
CH
H, NCH ), 2.48 (s, 3H, C-2 CH
2
), 3.50–3.55 (m, 2H, CH
2
N), 2.95 (s,
), 2.29 (s, 3H, C-6
phenyl H-3), 7.40–7.44 (m, 2H, phenyl H-3, H-5), 7.26–
7.28 (m, 1H, phenyl H-4), 6.45 (s, 1H, NH), 5.93 (s, 1H,
H-4), 5.78 (s, 2H, OCH O), 4.21–4.25 (m, 1H,
3
CH ), 2.05 (s, 3H, COCH ). Anal. Calcd for
3
3
3
3
2
0
0
C
4
20
H
7.13; H, 4.68; N, 19.05.
23
N
7
O
9
: C, 47.53; H, 4.59; N, 19.40. Found: C,
CO CHH ), 4.06–4.19 (m, 1H, CO
piperazin-1-yl H-2, H-6), 2.54–2.56 (m, 6H, piperazin-1-
2
2
CHH ), 3.37 (m, 4H,