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1H), 6.85 ppm (t, J=7.3 Hz, 1H); 13C NMR (400 MHz, MeOD): d=
155.48, 148.78, 145.92, 138.26, 130.23, 129.26, 125.18, 123.32, 121.60,
113.90 ppm.
Zn[PyCHNNHPy]2ACHTUGNRTNEUN(G ClO4)2 2H2O (7): During the exchange reaction of 2-
.
E with 2-pyridinecarboxaldehyde, an equivalent of ZnACHTUNGTRNEG(UN ClO4)2 6H2O was
added. After 6 h the solvent was removed in vacuum and the solid redis-
solved in ethanol. The product was recrystallized three times in ethanol.
1H NMR (400 MHz, MeOD): d=8.59 (s, 1H), 8.24 (d, J=4.8 Hz, 1H),
8.11 (td, J=7.7, 1.5 Hz, 1H), 7.96–7.76 (m, 3H), 7.48 (dd, J=6.7, 5.1 Hz,
1H), 7.12 (d, J=8.5 Hz, 1H), 7.01–6.91 ppm (m, 1H); 13C NMR
(101 MHz, MeOD): d=153.59, 149.36, 148.97, 146.13, 143.05, 142.51,
137.41, 128.22, 127.28, 119.97, 111.95 ppm. MS (ESI): m/z: 459.118 ([Zn-
(E)-2-((2-(Pyridin-2-yl)hydrazono)methyl)quinoline (3-E): The product
was synthesized by using the method described above and obtained in
90% yield after recrystallization in ethanol. M.p.: 217–2168C; 1H NMR
(400 MHz, DMSO): d=11.39 (s, 1H), 8.33 (d, J=8.7 Hz, 1H), 8.24–8.11
(m, 3H), 7.97 (t, J=6.8 Hz, 2H), 7.79–7.66 (m, 2H), 7.62–7.53 (m, 1H),
7.40 (d, J=8.4 Hz, 1H), 6.89–6.81 ppm (m, 1H); 13C NMR (101 MHz,
DMSO): d=156.57, 154.69, 147.90, 147.44, 139.28, 138.12, 136.18, 129.81,
128.57, 127.89, 127.39, 126.50, 117.19, 115.88, 106.73 ppm; MS (ESI): m/z:
249.154; elemental analysis calcd (%) for C15H12N4: C 72.56, H 4.87, N
22.57; found: C 72.78, H 4.83, N 22.91.
(ligand)2ꢀ1H]+), 230.059 ([Zn
(ligand)2]2+), 199.101 ([ligand]+); elemen-
ACHTUNGTRENNUNG
tal analysis calcd (%) for C22H24N8O10Cl2Zn: C 37.89, H 3.44, N 16.07;
found: C 38.15, H 3.54, N 16.07.
(E)-4-(Dimethylamino)-N’-(pyridin-2-ylmethylene)benzohydrazide (8-E):
The product was synthesized by using the method described above and
obtained in a 90% yield. M.p.: 225–2268C; H NMR (400 MHz, MeOD):
d=8.59–8.52 (m, 1H), 8.40–8.25 (m, 2H), 7.93–7.83 (m, 3H), 7.42 (ddd,
J=7.5, 5.0, 1.2 Hz, 1H), 6.83–6.74 (m, 2H), 3.05 ppm (s, 6H); 13C NMR
(101 MHz, MeOD): d=154.90, 154.88, 150.03, 147.71, 147.69, 138.57,
130.62, 125.73, 122.15, 119.50, 112.12, 40.16 ppm; MS (ESI): m/z: 269.139;
elemental analysis calcd (%) for C15H18N4O2 (8-E, H2O): C 62.92, H 6.34,
N 19.57; found: C 62.87, H 6.29, N 19.46.
(Z)-2-((2-(Pyridin-2-yl)hydrazono)methyl)quinoline (3-Z): A solution of
3-E in methanol was irradiated with UV light for 40 min. The isomeric
mixture was then purified by aluminum oxide chromatography using
CHCl3 as eluent. Compound 3-Z was obtained in 81% yield. 1H NMR
(400 MHz, DMSO): d=14.66 (s, 1H), 8.53 (d, J=8.6 Hz, 1H), 8.27 (d,
J=4.6 Hz, 1H), 8.05 (dd, J=15.5, 8.3 Hz, 2H), 7.88 (t, J=7.7 Hz, 1H),
7.82–7.63 (m, 3H), 7.54 (s, 1H), 7.44 (d, J=8.4 Hz, 1H), 6.94 ppm (t, J=
6.0 Hz, 1H); 13C NMR (400 MHz, DMSO): d=156.45, 153.05, 148.11,
145.65, 138.34, 137.54, 130.73, 130.21, 128.17, 127.95, 127.45, 126.58,
122.49, 116.91, 106.56 ppm.
1
(E)-4-Methoxy-N’-(pyridin-2-ylmethylene)benzohydrazide (9-E): The
product was synthesized by using the method described above and ob-
tained in a 87% yield. M.p.: 130–1318C. 1H NMR (400 MHz, MeOD):
d=8.56 (ddd, J=4.9, 1.5, 0.9 Hz, 1H), 8.38 (s, 1H), 8.30 (d, J=7.8 Hz,
1H), 8.03–7.83 (m, 3H), 7.42 (ddd, J=7.5, 5.0, 1.0 Hz, 1H), 7.11–6.99 (m,
2H), 4.86 ppm (s, 3H); 13C NMR (101 MHz, MeOD): d=166.81, 164.68,
154.68, 150.11, 148.75, 138.57, 130.93, 125.89, 125.74, 122.22, 115.00,
56.02 ppm. MS (ESI): m/z: 256.275; elemental analysis calcd (%) for
C14H13N3O2: C 65.87, H 5.13, N 16.46; found: C 65.59, H 5.02, N 16.32.
ZnACHTUNGTRENNUNG(C15H12N4)Cl2 ACHTUNGTRENNUNG ACHTUNGTRENNUNG(3-E)]: Two hot ethanolic solutions of the previous-
[ZnII
ly prepared 3-Z compound and ZnCl2 in stoichiometric proportions were
mixed and then allowed to cool. The complex salt crystallized out. Then
the product was collected and recrystallized from ethanol. Crystals suita-
ble for X-ray diffraction were obtained by slow diffusion of a DMSO so-
lution of the zinc complex and methanol. After two weeks yellow crystals
were obtained.
(E)-N’-(Pyridin-2-ylmethylene)benzohydrazide (10-E): The product was
synthesized by using the method described above and obtained in a 87%
yield. M.p.: 108–1098C. 1H NMR (400 MHz, MeOD): d= 8.62–8.53 (m,
1H), 8.45–8.36 (m, 1H), 8.36–8.26 (m, 1H), 7.93 (ddd, J=15.4, 7.5,
3.8 Hz, 3H), 7.62 (t, J=7.4 Hz, 1H), 7.53 (t, J=7.5 Hz, 2H), 7.43 ppm
(dd, J=6.6, 5.2 Hz, 1H); 13C NMR (400 MHz, MeOD): d=167.32,
154.59, 150.19, 149.43, 138.61, 133.91, 133.56, 129.79, 128.91, 126.03,
122.31 ppm. MS (ESI): m/z: 248.078 (10-EꢀNa+); elemental analysis
calcd (%) for C13H11N3O: C 69.32, H 4.92, N 18.66, O 7.10; found: C
68.89, H 5.01, N 18.58, O 6.94.
Crystal structure data for C15H12Cl2N4Zn (see also Supporting Informa-
¯
tion): Space group P1, a=7.5293(4), b=7.9985(5), c=12.7274(7) ꢄ, a=
84.7510(10), b=87.7510(10), g=86.3420(10)8, V=760.94 ꢄ3, Z=2, Z’=0,
1calcd =1.678 Mgmꢀ3, T=173 K, R1=0.0269. CCDC-788538 contains the
supplementary crystallographic data for this paper. These data can be ob-
tained free of charge from The Cambridge Crystallographic Data Centre
(E)-3-((2-(Pyridin-2-yl)hydrazono)methyl)quinoline (4-E): The product
was synthesized by using the method described above and obtained in
85% yield after recrystallization in ethanol. M.p.: 241–2428C. 1H NMR
(400 MHz, DMSO): d=11.14 (s, 1H), 9.32 (d, J=2.1 Hz, 2H), 8.45 (d,
J=1.8 Hz, 2H), 8.21 (s, 2H), 8.14 (dd, J=4.8, 0.9 Hz, 2H), 8.01 (dd, J=
7.7, 4.4 Hz, 4H), 7.68 (dddd, J=25.6, 14.9, 7.4, 1.0 Hz, 6H), 7.37 (d, J=
8.4 Hz, 2H), 6.81 ppm (dd, J=6.7, 5.2 Hz, 2H); 13C NMR (400 MHz,
DMSO): d=156.87, 156.76, 148.21, 147.84, 147.22, 138.05, 136.16, 132.49,
129.55, 128.85, 128.65, 128.29, 127.66, 127.18, 118.02, 115.43, 106.61 ppm.
MS (ESI): m/z: 249.112; elemental analysis calcd (%) for C15H12N4: C
72.56, H 4.87, N 22.57; found: C 72.38, H 4.90, N 22.51.
(E)-4-Nitro-N’-(pyridin-2-ylmethylene)benzohydrazide (11-E): The prod-
uct was synthesized by using the method described above and obtained
in 85% yield. M.p.: 240–2418C; 1H NMR (400 MHz, DMSO): d= 12.31
(s, 1H), 8.64 (d, J=4.5 Hz, 1H), 8.50 (s, 1H), 8.39 (d, J=8.7 Hz, 2H),
8.17 (d, J=8.7 Hz, 2H), 8.00 (d, J=7.9 Hz, 1H), 7.91 (t, J=7.1 Hz, 1H),
7.45 ppm (dd, J=6.5, 5.2 Hz, 1H); 13C NMR (400 MHz, DMSO): d=
161.73, 152.98, 149.58, 149.37, 149.12, 138.82, 136.92, 129.24, 124.61,
123.66, 120.05 ppm; MS (ESI): m/z: 271.084; elemental analysis calcd
(%) for C13H10N4O3: C 57.78, H 3.73, N 20.73; found: C 57.54, H 3.49, N
20.38.
(E)-4-((2-(Pyridin-2-yl)hydrazono)methyl)quinoline (5-E): The product
was synthesized by using the method described above and obtained in
88% yield after recrystallization in ethanol. M.p.: 170–1718C. 1H NMR
(400 MHz, DMSO): d=11.35 (s, 1H), 8.91 (d, J=4.6 Hz, 1H), 8.72 (s,
1H), 8.59 (d, J=7.9 Hz, 1H), 8.19 (dd, J=4.9, 1.0 Hz, 1H), 8.07 (d, J=
7.7 Hz, 1H), 7.87–7.68 (m, 4H), 7.37 (d, J=8.4 Hz, 1H), 6.91–6.83 ppm
(m, 1H); 13C NMR (400 MHz, DMSO): d=156.45, 150.20, 148.49, 147.96,
138.32, 138.26, 134.98, 129.80, 129.38, 127.12, 124.55, 123.80, 117.80,
116.01, 106.71 ppm. MS (ESI): m/z: 249.068; elemental analysis calcd
(%) for C15H12N4: C 72.56, H 4.87, N 22.57; C 72.35, H 4.85, N 22.66.
Acknowledgement
We thank Lydia Brelot and the Service de Cristallographie of the
Chemistry Department for the determination of the crystal structure of
complex [ZnII
ACTHNUTRGNEUNG(3-E)], (see the Supporting Information). We thank Jean-
Louis Schmitt for his help with NMR spectroscopy measurements. We
also thank the Collꢅge de France and the Spanish Government for post-
doctoral fellowships to M. N. C. and D. C., respectively. Financial support
was provided by the Collꢅge de France, the Universitꢀ de Strasbourg,
and the CNRS (UMR 7006) .
(E)-2-(2-Benzylidenehydrazinyl)pyridine (6-E): The product was synthe-
sized by using the method described above and obtained in 94% yield.
1
Melting point: 153–1548C. H NMR (400 MHz, MeOD): d=8.05 (dd, J=
5.1, 0.9 Hz, 1H), 7.94 (s, 1H), 7.74–7.61 (m, 3H), 7.43–7.25 (m, 4H),
6.83–6.74 ppm (m, 1H); 13C NMR (400 MHz, MeOD): d=158.33, 148.26,
141.31, 139.54, 136.94, 129.81, 129.64, 127.43, 116.29, 108.73 ppm; MS
(ESI): m/z: 198.123; elemental analysis calcd (%) for C12H11N3: C 73.07,
H 5.62, N 21.30; found: C 73.06, H 5.71, N 21.54.
Chem. Eur. J. 2011, 17, 248 – 258
ꢂ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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