Heteroatom Chemistry
5
1
621, 1581, 1486, 1373, 1277, 1140, 1094, 1038, 951, 896, 867, 848,
J = 6.9). 13C NMR (75 MHz, DMSO) ꢆ/ppm: 21.5, 31.8, 44.3,
834, 766, 735, 697, 643.
55.7, 117.9, 118.2, 118.7, 122.6, 126.9, 127.1, 129.8, 129.9, 137.1, 141.1,
1
45.5, 150.7, 163.8, 166.0. MALDI ꢌOF MS calcd: m/z = 347.17
+
3
.2.4. 2-Hydroxy-5-(p-tolyldiazenyl)benzaldehyde (1c). Yield
Da. Found m/z = 348.4 [M+1] . HR-MS(M): for C H N O:
20
21
5
∘
1
−1
8
9%, mp: 154 C. H NMR (300MHz, DMSO) ꢆ/ppm: 11.53
347.1746found: 347.1745.Selected IR bands (cm ) 3105, 2943,
1634, 1580, 1485, 1445, 1377, 1283, 1229, 1107, 999, 959, 905, 851,
756, 689, 662. Anal. Calc. for C H N O: C, 69.14 %; H, 6.09
(
s, 1H), 10.39 (s,1H), 8.19 (d, 1H, J = 3), 8.10 (dd, 1H, J = 6, J =
3
), 7.80 (d, 2H, J = 6), 7.42 (dd, 2H, J = 6, J = 3), 7.22 (d, 1H, J
2
0
21
5
13
=
9), 2.42 (s, 3H). C NMR (75 MHz, DMSO) ꢆ/ppm: 190.6,
%; N, 20.16 %. Found: C, 69.23 %; H, 6.01 %; N, 20.07 %.
1
63.1, 149.9, 144.8, 141.3, 129.9, 129.6, 123.5, 122.6, 122.4, 118.3,
2
1.0. MALDI ꢌOF MS calcd: m/z = 240.09 Da. Found m/z
3.2.9. Schiꢀ Base Ligand L4. Propylamine (4 mmol) was
added to a methanol solution (30 mL) of 2-Hydroxy-5-
(o-tolyldiazenyl)benzaldehyde (4 mmol). Te mixture was
reꢂuxed for 2h and cooled to room temperature. Te solvent
was removed on a rotatory evaporator and the orange product
solid was recrystallized with mixture of methanol and ether.
+
−1
=
241.10 [M+1] . Selected IR bands (cm ) 3170, 2866, 1650,
1
602, 1572, 1477, 1375, 1275, 1166, 1105, 1013, 951, 908, 850, 825,
7
77, 763, 739, 725, 688, 614.
3
.2.5. General Procedure for the Synthesis of the Schiꢀ Bases
1
Based on Imidazole: L1-L3. N-(3-Aminopropyl)imidazole
Product was obtained as orange crystals. Yield 90 %. H
1
(
2
4mmol) was added to a methanol solution (30 mL) of
-Hydroxy-5-((aryl)diazenyl)benzaldehyde (4 mmol). Te
NMR(300MHz, DMSO) ꢆ/ppm: H NMR(300MHz, DMSO)
ꢆ/ppm: 14.42 (s,1H), 8.45 (s, 1H), 8.02 (dd, 1H, J = 2.4, J
mixture was reꢂuxed for 2 h and cooled to room temperature.
Te solvent was removed on a rotatory evaporator and the
orange products were rinsed and recrystallized with mixture
of methanol and ether. Te products were obtained as orange
crystals.
=
9), 7.92 (d, 1H, J = 2.4), 7.65-7.63 (m, 1H), 7.37-7.33 (m,
2
H), 7.32-7.27 (m, 1H), 7.09 (d, 1H, J = 9), 3.65 (t, 2H, J =
13
6
), 2.74 (s, 3H), 1.8 (m, 2H), 1.06 (t, 3H, J = 9). CNMR
(
1
1
75 MHz, DMSO) ꢆ/ppm: 11.2, 17.1, 23.2, 56.5, 115.04, 116.4,
20.6, 126.0, 126.5, 130.0, 131.1, 131.2, 136.6, 142.9, 150.0, 165.8,
70.7. MALDI ꢌOF MS calcd: m/z = 281.15 Da. Found m/z =
∘
1
+
3
.2.6. Schiꢀ Base Ligand L1. Yield 84 %, m.p 110 C. H NMR
2
2
82.4 [M+1] . HR-MS(M): for C H N O: 281.1528 found:
1
7
19
3
−
1
(
300MHz, DMSO) ꢆ/ppm: 8.65 (s, 1H), 8.03 (d, 1H, J = 2.4),
81.1522. Selected IR bands (cm ): 3115, 2956, 1640, 1612,
7
.91(dd, 1H, J = 6.6, J = 2.4), 7.78 (dd, 2H, J = 7. 2, J = 1.5),
1
510, 1478, 1461, 1434, 1396.66, 1366, 1301, 1258, 1237, 1201, 1169,
151, 1115, 1027, 944, 914, 887, 836, 761, 750, 715, 678, 628. Anal.
7
. 65 (s, 1H), 7. 55-7. 5 (m, 2H), 7. 46-7. 48 (m, 1H), 7. 2 (s, 1H), 6. 92-
1
6
.89 (m, 2H), 4.04 (t, 2H, J = 6.9), 3.56 (t, 2H, J = 6.9),
Calc. for C17H19N3O C, 72.57 %; H, 6.81 %; N, 14.94 %. Found
C, 72.46 %; H, 6.81 %; N, 14.74 %.
13
2
3
.12 (qd, 2H, J = 6.9). C NMR (75 MHz, DMSO) ꢆ/ppm:
1.8, 44.3, 55.7, 118.0, 118.2, 118.7, 122.6, 127.1, 127.2, 131.0, 130.0,
1
37.1, 145.4, 152.6, 164.1, 165.91. MALDI ꢌOF MS calcd: m/z
3
.2.10. Microorganisms. Antifungal activity was assayed on
+
=
333.16 Da. Found m/z = 334.4 [M+1] . HR-MS(M): for
human pathogenic fungi, including Candida albicans (AꢌCC
1066), Aspergillus fumigatus (CBS 11326), and Scedosporium
apiospermum (IHEM 15115). Te yeast was obtained from
the American ꢌype Culture Collection (AꢌCC, Manassas,
VA, USA) and the opportunistic molds were furnished for
A. fumigatus by the Centraalbureau voor Schimmelcultures
C H N O: 333.1589 found: 347.1589. Selected IR bands (cm-
19
19
5
1
1
) 3104, 2946, 1630, 1584, 1497, 1480, 1437, 1383, 1350, 1275,
250, 1195, 977, 926, 906, 852, 837, 769, 745, 665, 641. Anal.
Calc. for C H N O: C, 68.45 %; H, 5.74 %; N, 21.01 %. Found
19
19
5
C, 68.25 %; H, 5.79 %; N, 20.82 %.
(
CBS, Delꢋ, Netherlands) and for S. apiospermum by the
∘
3
.2.7. Schiꢀ Base Ligand L2. Yield 79 %, m.p. 82 C. 1H MR
Institute of Hygiene and Epidemiology-Mycology section,
Institute of Public Health (IHEM, Brussels, Belgium). All the
strains were maintained on yeast extract-peptone-dextrose
agar (YPDA) plates which contained 0.05 % chloramphenicol
(
(
300MHz, DMSO) ꢆ/ppm: 8.65 (s,1H), 8.01 (d,1H, J = 2.4), 7.91
dd,1H, J = 6.6, J = 2.4), 7.65 (s, 1H), 7.52 (dd, 1H, J = 7. 8, J = 1.5),
7
. 35-7. 3 4 (m, 1H), 7. 33 (dd, 1H, J = 7. 6, J = 1.5), 7.28-7.25 (m,1H),
∘
7.20 (s,1H), 6.93-6.90 (m, 2H), 4.01 (t, 2H, J = 7.2), 3.55 (t,2H, J
at 37 C during an incubation time of 48 h for yeast, 72 h for
13
=
6.9), 2.61 (s, 3H), 2.10 (qd, 2H, J = 6.9). C NMR (75 MHz,
A. fumigatus, and 7 days for S. apiospermum.
DMSO) ꢆ/ppm: 17.6, 31.7, 44.2, 53.7, 115.4, 117.6, 119.8, 120.1,
1
1
26.5, 127.0, 130.4, 130.8, 131.7, 137.2, 137.8, 144.1, 150.4, 166.8,
3.2.11. Determination of Antifungal Activity. Disk Diꢀusion
68.6. MALDI ꢌOF MS calcd: m/z = 347.17 Da. Found m/z =
Method on Solid Medium. Antifungal activities of the diꢀerent
ligands were evaluated using a disk diꢀusion method adapted
from routinely antifungal tests [55]. Casitone agar plates of
+
3
3
48.4 [M+1] . HR-MS(M): for C H N O: 347.1746 found:
20
21
5
47.1745. Selected IR bands (cm-1): 3136, 2941, 1621, 1567, 1486,
1
381, 1308, 1274, 1146, 1095, 1031, 961, 906, 830, 748, 703, 670.
9
0 mm diameter were used for the experiences. Antifungal
Anal. Calc. for C H N O: C, 69.14 %; H, 6.09 %; N, 20.16 %.
Found C, 68.84 %; H, 6.13 %; N, 19.95 %.
20
21
5
inocula were prepared for yeast by suspending one colony in
0 mL of sterile distilled water. For the ꢁlamentous fungi, the
1
mycelium was recovered by scrapping the YPDA plates with
10 mL of sterile distilled water. Conidia were then harvested
from the suspension aꢋer a centrifugation at 1500 g for 5 min.
Te supernatant was then adjusted by spectrophotometry at
630 nm to an absorbance of 0.1. Casitone Petri dishes were
ꢂooded with 10 mL of the spore suspensions. Excess of the
∘
1
3
.2.8. Schiꢀ Base Ligand L3. Yield 82%, m.p 95 C. H MR
(
(
300MHz, DMSO) ꢆ/ppm: 8.63 (s,1H), 7.99 (d,1H,J= 2.7), 7.88
dd, 1H, J = 6.6, J = 2.4), 7.71 (d, 2H, J = 8.1), 7.65 (s, 1H),
7
.32 (d, 2H, J = 8.1), 7.19 (s, 1H), 6.90-7.00 (m, 2H), 4.04 (t,
2
H, J = 7.2), 3.55 (t, 2H, J = 6.6), 2.34 (s,3H), 2.13 (qd, 2H,