4
WU ET AL.
e
p‐Bromo phenoxy acetyl hydrazide (3´ ). White crystals, 87%
CH
2
); MS (EI) m/z (%): 358 (M + 3, 7), 357 (M + 2, 28), 355 (M, 80),
1
yield. H NMR (CDCl
3
) δ/ppm: 7.69 (s, 1H, NH), 7.42 (d, J = 9.0 Hz,
), 3.94 (s,
); MS (EI) m/z (%): 246 (M + 1, 18), 244 (M‐1, 18), 187 (14),
214 (38), 187 (13), 186 (100), 158 (65), 130 (27), 111 (10).
2
2
1
1
H, ArH), 6.80 (d, J = 9.0 Hz, 2H, ArH), 4.56 (s, 2H, CH
2
2‐Formyl‐8‐hydroxyquinoline p‐bromo phenoxy acetyl hydrazide
5
1
H, NH
2
(Y ). Red solid, 88% yield. m.p. 214–216°C; H NMR (400 MHz,
DMSO) δ 12.05 (s, 1H, N‐NH), 9.90 (s, 1H, CH=N), 8.49 (d,
J = 11.3 Hz, 1H, ArH, 8.34 (d, J = 8.7 Hz, 1H, ArH), 8.23 (s, 1H, OH),
8.12 (d, J = 8.9 Hz, 1H, ArH), 7.53–7.37 (m, 4H, ArH), 7.13 (t,
85 (20), 174 (94), 172 (100), 157 (50), 155 (48), 145 (10), 143 (6),
06 (9), 93 (10), 77 (20), 65 (22).
f
p‐Nitro phenoxy acetyl hydrazide (3´ ). Yellowish crystals, 82%
1
yield. H NMR (CDCl
3
) δ/ppm: 8.25 (d, J = 8.0 Hz, 2H, ArH), 7.63 (s,
), 3.96 (s, 2H,
); MS (EI) m/z (%): 212 (M + 1, 8), 211 (M, 24), 153 (8), 152 (26),
2
J = 6.3 Hz, 1H, ArH), 6.97 (t, J = 7.6 Hz, 2H, ArH), 5.28 (s, 2H, CH );
1
H, NH), 7.00 (d, J = 8.0 Hz, 2H, ArH), 4.66 (s, 2H, CH
2
MS (EI) m/z (%): 403 (M + 3, 12), 401 (M + 1, 13), 214 (24), 187
(13), 186 (100), 158 (79), 130 (45), 103 (13), 77 (11).
NH
2
1
23 (14), 122 (22), 106 (10), 92 (14), 76 (16), 73 (100), 65 (8).
2‐Formyl‐8‐hydroxyquinoline p‐nitro phenoxy acetyl hydrazide
6
1
(
Y ). Red solid, 76% yield. m.p. 220–222°C; H NMR (400 MHz,
DMSO) δ 12.11 (s, 1H, N–NH), 9.93 (s, 1H, CH=N), 8.49 (t,
J = 8.4 Hz, 1H, ArH), 8.35 (d, J = 8.7 Hz, 1H, ArH), 8.26–8.20 (m,
2H, ArH, 1H, OH), 8.15 (d, J = 8.1 Hz, 1H, ArH), 7.51–7.38 (m, 2H,
ArH), 7.21 (d, J = 9.2 Hz, 2H, ArH), 7.13 (d, J = 7.3 Hz, 1H, ArH),
2
.2
|
Synthesis of the target compounds
As the synthesis methods for the 2‐formyl‐8‐hydroxyquinoline
1–6
phenoxy acetyl hydrazine derivatives (Y ) were similar, only synthesis
1
of the 2‐formyl‐8‐hydroxyquinoline phenoxy acetyl hydrazide (Y ) is
2
5.48 (s, 2H, CH ); MS (EI) m/z (%): 367 (M + 1, 3), 366 (M, 18), 308
described. 2‐Formyl‐8‐hydroxyquinoline (5 mmol, 0.865 g) and 30 ml
of absolute ethanol were added into a 100 ml three‐necked flask and
heated to 80°C until fully dissolved. Phenoxy acetyl hydrazide (4 mmol,
(10), 214 (17), 186 (92), 158 (100), 145 (16), 131 (30), 130 (65), 103
(22), 102 (17), 77 (14).
0
.664 g) was dissolved in 20 ml of absolute ethanol, and then slowly
2
.3
|
Synthesis of the target Eu(III) complexes
added dropwise into a 100 ml three‐necked flask, and an appropriate
amount of acetic acid was added as a catalyst. The reaction mixture
was stirred at reflux for 5 h, filtered and washed several times. The 2‐
As the synthesis and purification of the target europium complexes
were similar, only the synthesis of the europium complexes of com-
1
1
1
pound Y is described. A mixture of compound Y (0.50 mmol) and
formyl‐8‐hydroxyquinoline phenoxy acetyl hydrazide (Y ) was obtained
absolute ethanol (40 ml) was added into a 100 ml three‐neck flask
by recrystallization from absolute ethanol and dried in a vacuum.
1
3 3
and refluxed at 60°C for some time, and then 5 ml Eu(NO )
2
‐Formyl‐8‐hydroxyquinoline phenoxy acetyl hydrazide (Y ). Red
−
1
1
(0.1 mol L ) ethanol solution was added. When the precipitate was
formed, the mixture was continuously refluxed for 4.5 h, with hot suc-
tion filtration, the product was washed several times with absolute
ethanol, filtered and dried in a vacuum for 8 h.
solid, 72% yield. m.p. 158–160°C; H NMR (400 MHz, DMSO) δ
1
8
7
2.05 (s, 1H, N–NH), 9.91 (s, 1H, CH=N), 8.34 (d, J = 8.6 Hz, 1H, ArH),
.25 (s, 1H, OH), 8.13 (d, J = 8.7 Hz, 1H, ArH), 7.53–7.38 (m, 2H, ArH),
.32 (dd, J = 14.5, 6.7 Hz, 2H, ArH), 7.13 (d, J = 6.3 Hz, 1H, ArH), 6.99
(
(
(
2
dt, J = 19.6, 9.9 Hz, 3H, ArH), 5.26 (s, 2H, CH ); MS (EI) m/z (%): 322
2
.3.1
|
Solubility, elemental analysis and molar con-
M + 1, 12), 321 (M, 52), 214 (29), 187 (14), 186 (100), 158 (84), 131
17), 130 (46), 103 (14), 77 (34).
ductivity of the Eu(III) complexes
1
–6
The target ligands Y
were easily dissolved in strong polar solvents
2‐Formyl‐8‐hydroxyquinoline p‐methyl phenoxy acetyl hydrazide
2
1
such as dimethyl sulfoxide (DMSO) and dimethyl formamide (DMF).
They were soluble in hot chloroform and hot ethanol, and insoluble
in benzene and cyclohexane. While the Eu(III) complexes were soluble
in DMF and DMSO, slightly soluble in hot chloroform and hot ethanol
and other solvents, they were insoluble in benzene, ether and other
less polar solvents.
(
Y ). Red solid, 80% yield. m.p. 161–162°C; H NMR (400 MHz,
DMSO) δ 11.99 (s, 1H, N–NH), 9.90 (s, 1H, CH=N), 8.33 (d,
J = 8.6 Hz, 1H, ArH), 8.23 (s, 1H, OH), 8.11 (d, J = 8.7 Hz, 1H, ArH),
7
.52–7.26 (m, 2H, ArH), 7.12 (dd, J = 15.1, 6.9 Hz, 3H, ArH), 6.89
dd, J = 20.7, 8.4 Hz, 2H, ArH), 5.20 (s, 2H, CH ), 2.21 (s, 3H, CH );
MS (EI) m/z (%): 337 (M + 2, 2), 336 (M + 1, 12), 335 (M, 47), 214
30), 187 (14), 186 (100), 158 (85), 130 (43), 91 (22).
‐Formyl‐8‐hydroxyquinoline p‐methoxy phenoxy acetyl hydra-
(
2
3
The elemental analysis and molar conductivity data of Eu(III)
complexes at room temperature are given in Table 1.
(
2
3
1
It can be seen from Table 1 that the experimental data of the
target europium complexes were consistent with the theoretical
values, indicating that the composition of the target complexes were
zide (Y ). Red solid, 82% yield. m.p. 168–170°C; H NMR (400 MHz,
DMSO) δ 12.01 (s, 1H, N–NH), 9.90 (s, 1H, CH=N), 8.33 (d,
J = 8.6 Hz, 1H, ArH), 8.23 (s, 1H, OH), 8.11 (d, J = 8.7 Hz, 1H, ArH),
1
–6
EuY (NO
3 3 2
) .2H O, and three nitrate molecules were also coordi-
7
7
.43 (dd, J = 16.7, 7.7 Hz, 2H, ArH), 7.13 (t, J = 6.4 Hz, 1H, ArH),
.00–6.82 (m, 4H, ArH), 5.18 (s, 2H, CH ), 3.70 (s, 3H, CH ); MS (EI)
1–
nated to the europium ion. The molar conductivity of EuY
2
3
6
−3
−1
(
NO
3 3 2
) .2H O in DMF (10 mol.L ) solution at room temperature
m/z (%): 352 (M + 1, 15), 351 (M, 64), 187 (12), 186 (100), 158 (93),
45 (14), 130 (55), 124 (17), 109 (15), 103 (14).
2
−1
solution was less than 65 S.cm .mol , which indicated that the target
1
[
15]
europium complexes were non‐electrolytes.
2
‐Formyl‐8‐hydroxyquinoline p‐chloro phenoxy acetyl hydrazide
4
1
(
Y ). Red solid, 85% yield. m.p. 200–202°C; H NMR (400 MHz, DMSO)
2
.3.2
|
IR spectral analysis
δ 12.00 (s, 1H, N‐NH), 9.85 (s, 1H, CH=N), 8.33 (d, J = 8.7 Hz, 1H), 8.24
s, 1H, OH), 8.12 (d, J = 8.6 Hz, 1H, ArH), 7.56–7.25 (m, 4H, ArH), 7.12 (d,
J = 7.0 Hz, 1H, ArH), 7.03 (dd, J = 16.1, 8.8 Hz, 2H, ArH), 5.27 (s, 2H,
1
–6
(
The IR spectra data of the ligands Y
and their corresponding Eu(III)
complexes are presented in Table 2. As the IR spectra of the