2
034
Synthesis, Inhibition of Mycobacterium tuberculosis Enoyl-acyl Carrier Protein Reductase
J. Braz. Chem. Soc.
DMSO-d ) d 6.67 (Br, 1H, Fur-H*), 7.00 (d, 1H, J 3.3 Hz,
Fur-H), 7.78-7.88 (m, 3H, Fur-H, Py-H*), 8.38 (s, 1H,
Pentacyano[(E)-(4-methylbenzylidene)isonicotinohydrazide]
ferrate(II) (4b)
6
-1
vinylic-H), 8.80 (d, 2H, J 5.8 Hz, Py-H), 12.02 (s, 1H,
Yield: 95%; λ (H O) / nm 451; IR (UATR) ν / cm
2
1
3
NH); C NMR (100.6 MHz, DMSO-d ) d 112.2, 114.2,
2,032 (CN), 1,626 (C=O), 1,528 (C=N), 1,265, 711, 670;
6
1
1
20.9, 121.4, 138.6, 145.5, 150.1, 150.3, 163.8; HRMS
H NMR (400.1 MHz, D O) d 2.17 (s, 3H, Me), 7.15
2
+
(
FTMS + pESI) m/z, calcd. for C H N O [M + H] :
(d, 2H, J 8 Hz, Ar-H), 7.32 (d, 2H, J 8 Hz, Py-H*), 7.56
(d, 2H, J 8 Hz, Ar-H), 8.15 (s, 1H, vinylic-H), 9.02 (d,
1
1
9
3
2
2
*
16.0768, found: 216.0773; *Fur-H: fur-2-yl hydrogens;
Py-H: pyridine hydrogens.
1
3
2H, J 8 Hz, Py-H); C NMR (100.6 MHz, D O) d 20.7,
2
1
20.4, 127.9, 129.7, 130.0, 142.5, 152.7, 156.8, 163.1,
General procedure for synthesis of compounds 4a-e
175.0, 179.5; E : 337 mV (vs. Ag|AgCl); anal. calcd. for
1/2
C H FeN Na O + 3H O: C, 41.63; H, 3.49; N, 20.44,
1
9
13
8
3
2
The coordination complexes 4 were prepared by a
two-step synthetic procedure with minor modifications
from an earlier reported method described for the
found: C, 41.26; H, 3.27; N, 20.19%; *Py-H: pyridine
hydrogens.
1
7,23
isoniazid ligand (IQG607).
All synthetic processes
Pentacyano[(E)-(4-methoxybenzylidene)isonicotino-
hydrazide]ferrate(II) (4c)
were carried out at controlled temperature and protected
from light. In a 250 mL flask, 0.298 g (1 mmol) of sodium
nitroprusside was dissolved in 10 mL of ammonium
-1
Yield: 76%; λ (H O) / nm 450; IR (UATR) ν / cm
2
2,031 (CN), 1,606 (C=O), 1,513 (C=N), 1,262, 833, 702;
1
solution (25%) with stirring. NH gas was bubbled into
H NMR (400.1 MHz, D O) d 3.55 (s, 3H, OMe), 6.81 (d,
3
2
the reaction mixture for 4 h on an ice bath at temperatures
ranging from –1 to –2 °C. After the reaction was
complete, a yellow solid was formed, characteristic of
2H, J 8 Hz, Ar-H), 7.32 (d, 2H, J 4 Hz, Py-H*), 7.58 (d,
2H, J 8 Hz, Ar-H), 7.99 (s, 1H, vinylic-H), 9.06 (d, 2H,
13
J 4 Hz, Py-H); C NMR (100.6 MHz, D O) d 55.7, 114.4,
2
23
aminpentacyanoferrate(II) as an intermediate compound.
120.3, 125.7, 129.8, 138.1, 146.1, 157.4, 161.3, 164.6,
Lastly, the solid formed was filtered off, washed with
absolute ethanol, and dried under reduced pressure.
Without any further purification, 0.326 g (1 mmol) of
aminpentacyanoferrate(II) (Na [Fe(CN) (NH )]·3H O)
175.1, 179.4; E : 381 mV (vs. Ag|AgCl); anal. calcd. for
1/2
C H FeN Na O + 3H O: C, 40.45; H, 3.39; N, 19.86,
19
13
8
3
2
2
found: C, 40.19; H, 3.16; N, 19.49%; *Py-H: pyridine
hydrogens.
3
5
3
2
was dissolved in 8 mL of ultrapure water under
argon flow. To the resulting solution, the respective
isonicotinoylhydrazone (3 mmol) was added and the
mixture was stirred for 10 h at 25 °C. Subsequently, the
reaction mixture was filtered and the resulting solution
was added dropwise to another vessel containing 100 mL
of cold NaI solution in ethanol (1:10, m/v). Because of
the efficiency of the precipitation process, the flask was
stored at 4 °C for at least 16 h. Finally, the solid product
was separated by centrifugation, washed with cold ethanol
Pentacyano[(E)-(4-fluorobenzylidene)isonicotinohydrazide]
ferrate(II) (4d)
-1
Yield: 98%; λ (H O) / nm 457; IR (UATR) ν / cm
2
2,027 (CN), 1,626 (C=O), 1,527 (C=N), 1,263, 711;
1
H NMR (400.1 MHz, D O) d 7.11-7.15 (m, 2H, Ar-H),
2
7.40 (d, 2H, J 4 Hz, Py-H*), 7.72-7.75 (m, 2H,Ar-H), 8.25
1
3
(s, 1H, vinylic-H), 9.02 (d, 2H, J 8 Hz, Py-H); C NMR
(100.6 MHz, D O) d 116.2, 120.5, 129.5, 130.4, 138.4,
2
151.8, 157.7, 162.9, 164.0, 175.1, 179.7; E : 377 mV
1
/2
(
2 × 25 mL) and dried under reduced pressure.
(vs. Ag|AgCl); anal. calcd. for C H FFeN Na O + 3H O:
18 10 8 3 2
C, 39.15; H, 2.92; N, 20.29, found: C, 38.91; H, 2.74; N,
20.01%; *Py-H: pyridine hydrogens.
Pentacyano[(E)-benzylideneisonicotinohydrazide]ferrate(II)
(
4a)
-1
Yield: 94%; λ (H O) / nm 456; IR (UATR) ν / cm
Pentacyano[(E)-(thiophen-2-ylmethylene)isonicotino-
2
2
,038 (CN), 1,653 (C=O), 1,546 (C=N), 1,295, 758, 690;
hydrazide]ferrate(II) (4e)
1
-1
H NMR (400.1 MHz, D O) d 7.24-7.36 (m, 5H, Ar-H),
7
8
Yield: 78%;λ (H O) / nm 452; IR (UATR) ν / cm 2,034
2
2
1
.59 (d, 2H, J 8 Hz, Py-H*), 8.15 (s, 1H, vinylic-H),
(CN), 1,622 (C=O), 1,542 (C=N), 1,296, 757, 686; H NMR
13
.99 (d, 2H, J 4 Hz, Py-H); C NMR (100.6 MHz, D O)
(400.1 MHz, D O) d 6.44 (s, 1H, Fur-H*), 6.77 (s, 1H,
2
2
d 120.3, 127.7, 129.0, 131.7, 132.5, 152.4, 157.3, 164.3,
74.9, 179.3; E : 390 mV (vs. Ag|AgCl); anal. calcd. for
Fur-H), 7.31 (d, 2H, J 4 Hz, Py-H*), 7.50 (s, 1H, Fur-H),
8.04 (s, 1H, vinylic-H), 8.99 (d, 2H, J Hz, Py-H); C NMR
13
1
1
/2
C H FeN Na O + 3H O: C, 40.47; H, 3.21; N, 20.98,
(100.6 MHz, D O) d 112.5, 117.3, 120.3, 138.2, 140.9,
1
8
11
8
3
2
2
found: C, 40.33; H, 3.09; N, 20.56%; *Py-H: pyridine
hydrogens.
146.3, 147.8, 157.3, 164.4, 175.0, 179.5; E : 426 mV
1
/2
(vs. Ag|AgCl); anal. calcd. for C H FeN Na O + 3H O:
16
9
8
3
2
2