3
84
W. Zhang et al. / Journal of Alloys and Compounds 620 (2015) 383–389
2.3. General procedure for synthesis of the target compound (L1–4
)
/CDCl on Brucker spectrophotome-
1H NMR spectra was recorded in DMSO-d
6
3
ter (400 MHz) with TMS as an internal standard. Mass spectra were measured with
ꢁ
1
As the synthesis methods of compounds L1–4 were similar, the synthesis of the
target compound L1 was described as an example., the 2,2 -(1,3,4-oxadiazole-2,5-
diyl)diphenol (2 mmol, 0.51 g) and anhydrous potassium carbonate (10 mmol,
1.38 g) were dissolved in a 100 mL single-necked flask with 50 mL DMF solution.
The resulting mixture was refluxed at 80 °C for 1 h, the 2-chloro-N-phenylacet-
amide compound B1 (7 mmol, 1.18 g) and a little of KI were added and continued
to reflux for 24 h. After completion of the reaction, the reaction mixture was cooled
to room temperature, and then gradually poured into distilled water (500 mL) and
stirred for 2 h. The resulting mixture was concentrated under reduced pressure and
washed several times with distilled water until the pH value reached 7. The result-
ing product was further purified by recrystallization from the mixture of ethanol
and chloroform (1:1), and dried in vacuum for 24 h. Thus the target compound L1
was obtained.
the MAT95XP Mass Spectrometer. IR spectra (400–4000 cm ) were obtained in KBr
discs by a PERKIN–ELMER Spectrum One. UV spectra (190–450 nm) were recorded
by LabTech UV-2100 spectrophotometer, with DMSO as solvent and reference. Ele-
mental analysis of the complexes was carried out on a VarioEL 111 CHNS analyzer.
Melting points of all compounds were determined on an X-4 binocular microscope.
Thermal gravimetric analysis were carried out on a NETZSCH STA 409PC thermal
gravimetric analyzer. Cyclic voltammetry curve testing using three electrodes were
glassy electrode, a platinum electrode and a saturated calomel electrode, ferrocene
as external standard, nitrite solution was used as the supporting electrolyte and
0
ꢁ
1
dimethyl sulfoxide as the solvent, the test scanning speed was 100 mV s and
the sensitivity was 1 mA. The fluorescence spectra were measured by using powder
samples on a Hitachi F-2700 Fluorescence Spectrophotometer at room temperature.
0 0
,2 -(2,2 -(1,3,4-oxadiazole-2,5-diyl)bis(2,1-phenylene))bis(oxy)bis(N-phen-
2
2
2
.2. General procedure for synthesis of the intermediates
1
1
ylacetamide) (L ). White powder, yield (84%). m.p. 265–266 °C; H NMR (400 MHz,
CDCl ) d/ppm: 10.55 (s, 2H, NH), 8.10 (dd, J = 7.8, J = 1.6 Hz, 2H, ArH), 7.73–7.68 (m,
H, ArH), 7.65–7.59 (m, 2H, ArH), 7.26–7.22 (m, 2H, ArH), 7.13 (d, J = 8.2 Hz, 2H,
ArH), 7.06 (dd, J = 10.8 Hz, J = 5.1 Hz, 4H, ArH), 6.86 (t, J = 7.4 Hz, 2H, ArH), 4.85 (s,
3
.2.1. Synthesis of the compound A
4
The polyphosphate (15 mmol, 5.07 g) was added into a 150 mL three-neck flask
and maintained the temperature at 50 °C for some time, and then a solution of
hydrazine hydrate (80%, 6.5 mL) and salicylic acid (10 mmol, 1.38 g) was added
with stirring. The reaction mixture was heated to 130 °C and refluxed for 7 h with
stirring in the oil bath. After completion of the reaction, the resulting mixture was
poured into the 500 mL cold water and standed over night with stirring. Then fil-
tered and washed with water, evaporated to obtained the crude product, the com-
pound A was obtained by recrystallization from the absolute ethanol. Yield, 76%
ꢁ
1
4
(
1
H, CH
EI) m/z (%): 522 (M + 2, 2), 520 (M, 4), 311 (100), 254 (78), 226 (18), 121 (47),
06 (24), 93 (51); Anal. Calcd. for C30 : C, 69.22; H, 4.65; N, 10.76. Found:
C, 69.21; H, 4.55; N, 10.56.
2
); IR (KBr) v/cm : 3306, 3020, 1759, 1692, 1601, 1255, 1165, 866; MS
24 4 5
H N O
0 0
,2 -(2,2 -(1,3,4-oxadiazole-2,5-diyl)bis(2,1-phenylene))bis(oxy)bis(N-p-tol-
2
2
1
ylacetamide) (L ). Yellow crystals, yield (71%). m.p. 259–260 °C; H NMR (400 MHz,
CDCl ) d/ppm: 10.45 (s, 2H, NH), 8.10 (dd, J = 7.8 Hz, J = 1.6 Hz, 2H, ArH), 7.64–7.59
m, 2H, ArH), 7.53 (d, J = 8.4 Hz, 4H, ArH), 7.23 (d, J = 7.8 Hz, 2H, ArH), 7.12 (d,
3
[
11].
(
J = 8.3 Hz, 2H, ArH), 6.81 (d, J = 8.2 Hz, 4H, ArH), 4.82 (s, 4H, CH
2
), 2.12 (s, 6H,
2
.2.2. Synthesis of the compound B1–4
As the synthesis methods of the compounds B
ꢁ1
3
CH ); IR (KBr) v/cm : 3325, 3132, 2151, 1680, 1600, 1268, 1166, 866; MS (EI) m/
1
–4
were similar, only synthesis of
z (%): 550 (M + 2, 8), 549 (M + 1, 37), 548 (M, 100), 442 (97), 443 (26), 415 (61),
68 (72), 121 (44); Anal. Calcd. for C32 : C, 70.06; H, 5.14; N, 10.21. Found:
C, 70.04; H, 5.12; N, 10.11.
1
the 2-chloro-N-phenylacetamide compound B was described. A solution of aniline
2
28 4 5
H N O
(
66 mmol, 6.14 g) in glacial acetic acid (50 mL) was added into a 100 mL single-neck
flask and then the acetyl chloride (74 mmol, 8.36 g) was gradually dropwise added
under stirring in the ice water bath. The resulting reaction mixture was stirred for
1
0 0
,2 -(2,2 -(1,3,4-oxadiazole-2,5-diyl)bis(2,1-phenylene))bis(oxy)bis(N-(4-
methoxyphenyl)acetamide) (L ). White powder, yield (70%). m.p. 225–226 °C;
2
3
h at room temperature and then poured into 300 mL saturated sodium acetate
1
H NMR (400 MHz, CDCl
3
) d/ppm: d 10.45 (s, 2H, NH), 8.13–8.08 (m, 2H, ArH),
solution. Filtered off and washed several times with cold water. The compound
7
.64–7.56 (m, 6H, ArH), 7.24 (d, J = 7.6 Hz, 2H, ArH), 7.13 (d, J = 8.3 Hz, 2H,
1
B
was obtained by recrystallization from the mixture of ethanol and water (1:1)
and dried in vacuum for 12 h.
-chloro-N-phenylacetamide (B1). White crystals, yield (81%). 1H NMR
400 MHz, DMSO) d/ppm: 10.29 (s, 1H, NH), 7.77–7.47 (m, 2H, ArH), 7.40–7.22
m, 2H, ArH), 7.18–6.95 (m, 1H, ArH), 4.25 (s, 2H, CH ); MS (EI) m/z (%): 172
ArH), 6.57 (d, J = 8.9 Hz, 4H, ArH), 4.83 (s, 4H, CH2), 3.66 (s, 6H, CH3O); IR
ꢁ1
(
(
KBr) v/cm : 3229, 3132, 1964, 1735, 1671, 1250, 1162, 964; MS (EI) m/z
2
%): 582 (M + 2, 3), 581 (M + 1, 12), 580 (M, 31), 458 (27), 300 (29), 283 (46),
(
(
(
(
1
36 (47), 123 (100), 121 (72), 108 (59); Anal. Calcd. for C32
28 4 7
H N O : C, 66.20;
2
H, 4.86; N, 9.65; O 19.29. Found: C, 66.12; H, 4.62; N, 9.55.
M + 3, 3), 171 (M + 2, 25), 169 (M, 80), 121 (3), 120 (40), 106 (7), 94 (10), 93
100), 77 (22), 65 (28).
0 0
,2 -(2,2 -(1,3,4-oxadiazole-2,5-diyl)bis(2,1-phenylene))bis(oxy)bis(N-(4-
2
4
1
chlorophenyl)acetamide) (L ). Yellow crystals, yield (74%). m.p. 288–289 °C;
NMR (400 MHz, CDCl ) d/ppm: 10.68 (s, 2H, NH), 8.14 (dd, J = 7.8 Hz, J = 1.5 Hz,
H, ArH), 7.67–7.63 (m, 2H, ArH), 7.56 (d, J = 8.8 Hz, 4H, ArH), 7.28 (d, J = 7.5 Hz,
H
2
-chloro-N-p-tolylacetamide (B2). White crystals, yield (75%). 1H NMR
3
(
(
1
400 MHz, DMSO-d
m, 2H, ArH), 4.22 (s, 2H, CH
85 (M + 2, 25), 183 (M, 75), 148 (4), 134 (27), 107 (100), 106 (76), 91 (16), 77
6
) d/ppm: 10.21 (s, 1H, NH), 7.42–7.46 (m, 2H, ArH), 7.16–7.18
2
2
2
), 2.21 (s, 3H, CH ); MS (EI) m/z (%): 186 (M + 3, 3),
3
H, ArH), 7.13 (d, J = 8.3 Hz, 2H, ArH), 6.99–6.95 (m, 4H, ArH), 4.85 (s, 4H, CH
);
2
ꢁ1
IR (KBr) v/cm : 3223, 3040, 1879, 1691, 1604, 1267, 1164, 868; MS (EI) m/z (%):
(
26), 51 (10).
592 (M + 4, 7), 591 (M + 3, 12), 590 (M + 2, 38), 589 (M + 1, 17), 588 (M, 56), 462
-chloro-N-(4-methoxyphenyl)acetamide (B ). White crystals, yield (87%). 1H
3
2
(
97), 435 (86), 288 (60), 148 (57), 121 (100); Anal. Calcd. for C30 Cl : C,
H
22
4
N O
5
2
1
NMR (400 MHz, DMSO-d
6
) d/ppm: H NMR (400 MHz, DMSO) d/ppm: 10.43 (s, 1H,
61.13; H, 3.76; N, 9.51. Found: C, 61.10; H, 3.56; N, 9.42.
NH), 7.67–7.57 (m, 2H, ArH), 7.46–7.34 (m, 2H, ArH), 4.26 (s, 2H, CH
2
); MS (EI) m/z
%): 207 (M + 3, 5), 205 (M + 1, 33), 203 (M-1, 52), 156 (4), 154 (13), 129 (32), 127
100), 126 (15), 111 (5), 99 (14), 77 (5), 63 (7).
(
(
2.4. Synthesis of the target rare earth complexes
-chloro-N-(4-chlorophenyl)acetamide (B ). Yellow crystals, yield (85%). 1H
4
2
NMR (400 MHz, DMSO) d/ppm: 10.18 (s, 1H, NH), 7.54–7.48 (m, 2H, ArH), 6.95–
.87 (m, 2H, ArH), 4.22 (s, 2H, CH ), 3.73 (s, 3H, CH ); MS (EI) m/z (%): 202
M + 3, 3), 201 (M + 2, 32), 199 (M, 100), 124 (29), 123 (72), 108 (72), 95 (13), 80 (6).
The synthesis methods of the target rare earth complexes were similar, the syn-
1
6
(
2
3
thesis of the europium complexes of compound L was described as an example. A
mixture of compound L1 (0.40 mmol), chloroform (40 mL) was added into a 100 mL
N
N
OH
COOH
a
N
2
H
4
·H
2
O
O
N N
OH HO
O
A
c
O
O
NH
2
NH
O
O
Cl
HN
R
NH
R
b
O
R
R
L1~4
B1~4
1
2
3
4
B , R=4-H; B , R=4-CH ; B , R=4-CH O; B , R=4-Cl
3
3
1
2
3
4
L , R=4-H; L , R=4-CH ; L , R=4-CH O; L , R=4-Cl
3
3
(
a) H P O , reflux, 7 h; (b) ClCH COCl, CH COOH, r.t., 1.5 h; (c) DMF, K CO , KI, reflux, 24 h
6 4 13 2 3 2 3
Scheme 1. The synthesis route for the ligands L1–4
.