1228
KOÇAK et al.
then filtered, washed with distilled water, ethanol and
diethyl ether, and dried in vacuum at 60 . The prodꢀ
uct was obtained as a light green solid in 74% yield
NH2
N
°C
H+
O
+
NH2NH3OH
(0.092 g). m.p. 237
°
C
(with degradation); IR (KBr)
ν
:
.
3520, 2940, 1615, 1645, 1663, 1410, 960, 515, 430 cm–1
H
NOH
H
NOH
Anal. calcd. for C30H22Cl2N6O2Ni: C 57.36, H 3.52, N
13.37 Ni 9.34; found C 57.17, H 3.25, N 13.67 Ni 9.18.
Fig. 1. Synthesis of isonitrosophenylhydrazine.
Preparation of Cu(II) complex of L1. This comꢀ
pound was prepared by the procedure mentioned for
the preparation of (L1)2Ni. The product was obtained
Anal, calcd. for C8H9N3O: C 58.85, H 5.58, N 25.76;
found C 58.67, H 5.39, N 25.54.
as a green solid in 83% yield (0.105 g). m.p. 227 C
°
(with degradation); IR (KBr) : 3500, 2950, 1617,
ν
Synthesis of 4ꢀchlorobenzalꢀhydrazine (Fig. 2). To a
1645, 1665, 1465, 1000, 520, 440 cm–1. Anal. calcd.
for C30H22Cl2N6O2Cu: C 56.92, H 3.50, N 13.27 Cu
10.04; found C 56.62, H 3.39, N 13.06 Cu9.95.
stirred solution of hydrazinehydrate (1 g, 80 mmol) in
20 mL ethanol at –5 C was added dropwise to a soluꢀ
°
tion of pꢀchlorobenzaldehyde (2.8 g, 20 mmol) in
20 mL ethanol. Then the mixture was diluted with disꢀ
tilled water (20 mL) and allowed to stand two days in
the refrigerator. The precipitate was filtered, dried in a
Preparation of Co(II) complex of L1. Complexes of
L1 with Co(II) ion was prepared by the procedure
above mentioned for the preparation of (L1)2Ni. The
product was obtained as a grey solid in 78% yield
vacuum at 65
yield, m.p. 145oC; 1H NMR (DMSOꢀ
4.84 (s, 2H), 7.54–7.81 (m, = 8.4 Hz, 4H), 8.42 (s,
1H); IR (KBr)
: 3380, 3290, 1650, 1610, 760 cm–1
°C
and afforded 2.51 g of product in 81%
d6, 300 MHz) :
δ
(0.098 g). m.p. 214
°
C
(with degradation); IR (KBr) :
ν
J
3620, 2940, 1619, 1650, 1664, 1420, 975, 528, 435 cm–1
.
ν
.
Anal. calcd. for C30H22Cl2N6O4Co: C 57.34, H 3.53,
N 13.37 Co 9.38; found C 57.30, H 3.45, N 13.30,
Co 9.31.
Anal. calcd. for C7H7ClN2: C 54.36, H 4.57, N 18.13;
found C 54.22, H 4.46, N 17.95.
Synthesis of 4ꢀchlorobenzalꢀazinoꢀisonitrosoaceꢀ
tophenone (L1) (Fig. 3). 4–chlorobenzalhydrazine
(0.77 g, 5 mmol) was dissolved in 20 mL ethanol, then
a solution of isonitrosoacetophenone (0.69 g, 5 mmol)
in 20 mL ethanol was added dropwise to above soluꢀ
tion. After K2CO3 (0.69 g, 5 mmol) was added to reacꢀ
tion mixture, it was refluxed for 1 h. Then mixture was
left to cool to r.t. Distilled water was added to mixture
with stirring until precipitate was formed. After 2 h,
precipitated solid was filtered off, washed with water,
Preparation of Zr(IV) complex of L1. Complexes of
L1 with Zr(IV) ion was prepared by the procedure
above mentioned for the preparation of
product was obtained as a yellow solid in 89% yield
(0.118 g). m.p. 269 (with degradation); IR (KBr)
3500, 2960, 1618, 1640, 1670, 1460, 950, 535, 420 cm–1
(L1)2Ni. The
°C
ν:
.
Anal. calcd. for C30H22Cl2N6O2ZrCl2: C 49.25,
H 3.03, N 11.49, Zr 12.47; found C 49.00, H 2.97,
N 11.50 Zr 12.35.
dried in vacuum at 65 C and afforded 0.90 g of prodꢀ
°
Synthesis of 4ꢀmethylbenzalꢀazinoꢀisonitrosoaceꢀ
tophenone (L2) (Fig. 4). A solution of isonitrosopheꢀ
nylhydrazine (0.815g, 5 mmol) in 20 mL of ethanol
was added slowly to a solution of 4ꢀmethylbenzaldeꢀ
hyde (0.6 g, 5 mmol) in 20 mL of ethanol. The mixture
was refluxed for 1 h and then diluted with distilled
water. The mixture was stirred for 2 h and precipitate
was filtered, washed with water, dried in vacuum at
uct as a light yellow solid in 63% yield. The final prodꢀ
uct was soluble in dioxane, chloroform, diethylether
and DMF. m.p. 209
300 MHz) : 7.08–8.29 (m,
°
C; 1H NMR (DMSOꢀd6
,
δ
J
= 8.2 Hz, 9H), 8.58 (s,
: 3560,
1H), 8.77 (s, 1H), 11.65 (s, 1H); IR (KBr)
ν
3020, 1612, 1642, 1656, 1470, 920 cm–1. Anal. calcd.
for C15H12ClN3O: C 63.05, H 4.23, N 14.70; found
C 62.86, H 3.99, N 14.59.
60–70 C. The final product was weighed 1.06 g as a
°
Preparation of Ni(II) complex of L1: 4ꢀchlorobenzalꢀ yellow solid in 80% yield. The final product was soluꢀ
azinoꢀisonitrosoacetophenone (0.057 g, 0.2 mmol) was ble in ethanol, chloroform, acetone, DMSO, and
1
dissolved in 20 mL of dioxane. Then, 10 mL of aqueꢀ DMF. m.p. 133
ous solution of NiCl2 6H2O (0.12 g, 0.5 mmol) was
°
C; H NMR (DMSOꢀ
d
6, 300 MHz)
= 7.7 Hz, 9H), 9.34
: 3440
⋅
δ
: 2.50 (s, 3H), 7.06–8.80 (m,
J
added dropwise to above solution by stirring. The pH (s, 1H), 9.57 (s, 1H), 12.16 (s, 1H); IR (KBr)
ν
,
of the reaction mixture was adjusted to 5.0–5.5 by 3000, 1610, 1635, 1660, 1460, 975 cm–1. Anal. calcd.
adding an aqueous solution of NaOH (1%, wt). Precipiꢀ for C16H15N3O: C 72.43, H 5.69, N 15.83; found
tated solid was kept on a water bath at 60°C for 30 min, C 72.29, H 5.48, N 15.45.
+
NH2NH3OH
Cl
CHO
Cl
N NH2
Fig. 2. Synthesis of 4ꢀchlorobenzalꢀhydrazine.
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 57 No. 9 2012