ZINC COMPLEXES
CH3
469
C3H7
N
CH3
CH3
N
NH2
N
Zn
A
O S O
A
O S O
N
O S O
HN
O S O
Zn
HN
N
O2N
H2N
H2N
N
N
N
[H]
Zn(A)
2
N
N
CH3
C3H7
(HL1)
C3H7
(HL2)
C3H7
(I)
Ia: A = CH3COO–
Ib: A = (CH3)(CH3)3CCOO–
Scheme 1.
IR,
(vibrations of benzimidazole ring), 1522 s
1334 v.s νas(SO2), 1166 v.s νs(SO2). 1H NMR (DMSOꢀ
d6), , ppm: 0.70 (3H, t, = 7.3 Hz, CH2CH2CH3), 10.15 (1H, br.s, NH).
1.56 (2H, q, = 7.4 Hz, CH2CH2CH3), 2.25 (3Н, s,
CAr–CH3), 3.97 (2H, t, = 7.5 Hz, CH2CH2CH3),
7.17 (2H, d, = 8.1 Hz, CAr–H), 7.32–7.55 (6H, m,
CAr–H), 7.91 (1H, d, = 9.0 Hz, CAr–H), 8.23 (1H,
dd, = 8.9 Hz, = 2.2 Hz, CAr–H), 8.59 (1H, d,
2.2 Hz, CAr–H), 10.07 (1H, s, NH).
ν
, cm–1: 3147
w
ν
(NH), 1618 w, 1 5 9 5 w, 1 5 7 7 w
6
.91–6.93 (3H, m, CAr–H), 7.15–7.25 (4H, m,
CAr⎯H), 7.39 (1H, d, = 8.1 Hz, CAr–H), 7.42 (1H, d,
= 7.8 Hz, CAr–H), 7.61 (1H, d, = 7.8 Hz, CAr–H),
ν
(NO2)
,
J
J
J
δ
J
J
Synthesis of bis(μ2ꢀ(1ꢀpropylꢀ2ꢀ(2ꢀtosylaminopheꢀ
nylꢀ N)ꢀ5ꢀaminobenzimidazolatoꢀ
2N,N')bis(acetato)ꢀ
)dizincII) (Iа, A = CH3COO–). A hot solution of
Zn(CH3COO)2 2H2O (92 mg, 0.5 mmol) in methaꢀ
J
κ
κ
J
κ
O
J
⋅
nol (6 mL) was poured to a hot solution of HL2
(210 mg, 0.5 mmol) in methanol (4 mL), and the mixꢀ
ture was refluxed for 2 h. The solution was evaporated
to a volume of 4 mL, and the formed precipitate was
filtered off, washed with methanol, and dried. Colorꢀ
less crystals (mp > 250°C) were obtained by recrystalꢀ
lization from acetonitrile. The yield was 158 mg
(58%).
J
J
J =
Synthesis of 1ꢀpropylꢀ2ꢀ(2ꢀtosylaminophenyl)ꢀ5ꢀ
aminobenzimidazole (HL2). A solution of polysulfides,
prepared of sodium sulfide nonahydrate (6.48 g,
27 mmol) and sulfur (0.87 g, 27 mmol) in water
(15 mL), was added to a solution of 1ꢀpropylꢀ2ꢀ(2ꢀ
tosylaminophenyl)ꢀ5ꢀnitrobenzimidazole (6.08 g,
13.5 mmol) in ethanol (50 mL). The mixture was
refluxed for 4 h. The alcohol layer was separated, and
the solvent was filtered off. The residue was dissolved
in 15% hydrochloric acid (90 mL) and filtered. The filꢀ
trate was treated with a 22% solution of ammonia to
pH 7. The formed precipitate was filtered off, washed
with water, and dried. Creamꢀcolored crystals (mp =
For C50H52N8O8S2Zn2
anal. calcd., %: C, 55.20;
Found, %: C, 55.09;
H, 4.82;
H, 4.92;
N, 10.30.
N, 10.39.
IR,
1629
1135 vs νs(SO2)
Synthesis of bis(μ2ꢀ(1ꢀpropylꢀ2ꢀ(2ꢀtosylaminopheꢀ
nylꢀ N)ꢀ5aminobenzimidatazolatoꢀ
2N,N')bis(pivalatoꢀ
)dizonc(II) (Ib, A = (CH3)3CCOO–). A hot soluꢀ
ν
, cm–1: 3373 w νas(NH2), 3247
(NH2), 1565 s (C=O), 1239 vs νas(SO2),
w νs(NH2),
w
δ
140–141°С) were obtained by recrystallization from
ethanol. The yield was 4.54 g (80%).
.
κ
κ
For C23H24N4O2S
κ
O
anal. calcd., %: C, 65.69;
Found, %: C, 65.59;
H, 5.75;
H, 5.82;
N, 13.32.
N, 13.39.
tion of [Zn((CH3)3CСOO)2]n (0.11 g, 0.4 mmol) [13]
in acetonitrile (8 mL) was poured to a hot solution of
HL2 (0.17 g, 0.4 mmol) in acetonitrile (7 mL), and the
IR,
3374
1164 vs νs(SO2). H NMR (DMSOꢀd6),
(3H, t, = 7.4 Hz, CН2CН2СH3), 1.64 (2H, q,
7.6 Hz, CН2CН2СH3), 2.27 (3Н, s, CAr–СН3), 3.67 orless crystals (mp > 250°C) were obtained by recrysꢀ
(2H, t, = 7.8 Hz, CН2CН2СH3), 4.84 (2H, br.s, tallization from acetonitrile. The yield was 310 mg
NН2), 6.71 (1H, dd, = 8.6 Hz, = 1.6 Hz, CAr–H), (66%).
ν
, cm–1: 3462
νs(NH2), 1629
w
νas(NH2), 3440
w
ν
(NH), mixture was stirred for 3 h at 60
concentrated under reduced pressure to a volume of
, ppm: 0.82 5 mL and cooled. The precipitate formed was filtered
off, washed with benzene and hexane, and dried. Colꢀ
°С. The solution was
w
w (NH2), 1335 vs νas(SO2),
δ
1
δ
J
J =
J
J
J
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 40
No. 7
2014