Platinum(II) cationic complexes with derivatives of 2-acyl-1,3- cyclopentanedions

Article abstract of DOI:10.1134/S107036320605001X

Cis-Diammineplatinum(II) complexes containing 2-acyl-1,3-cyclopentadion fragments as a bidentate acido ligand were prepared by the transformation of cis-diamminediiodoplatinum(II) to cis-diamminesulfatoplatinum(II) under the action of silver sulfate with

Full text of DOI:10.1134/S107036320605001X

ISSN 1070-3632, Russian Journal of General Chemistry, 2006, Vol. 76, No. 5, pp. 669 676.
Pleiades Publishing, Inc., 2006.
Original Russian Text
pp. 705 712.
T.S. Khlebnikova, I.V. Merkushin, F.A. Lakhvich, 2006, published in Zhurnal Obshchei Khimii, 2006, Vol. 76, No. 5,
Platinum(II) Cationic Complexes with Derivatives
of 2-Acyl-1,3-Cyclopentanedions
T. S. Khlebnikova, I. V. Merkushin, and F. A. Lakhvich
Institute of Bioorganic Chemistry, National Academy of Sciences of Belorussia,
ul. Akad. Kuprevicha 5/2 Minsk, 220141 Belorussia
e-mail: prostan@iboch.bas-net.by
Received May 4, 2005
Abstract cis-Diammineplatinum(II) complexes containing 2-acyl-1,3-cyclopentadion fragments as a
bidentate acido ligand were prepared by the transformation of cis-diamminediiodoplatinum(II) to cis-di-
amminesulfatoplatinum(II) under the action of silver sulfate with the subsequent treatment of the resulting
complex by barium hydroxide and by the reaction of the synthesized base with a twofold amount of 2-acyl-
1,3-cyclopentanedion. The products are the cationic complexes of cis-diammineplatinum(II) and contain
2-acyl-1,3-cyclopentanedionate as a bidentate acido ligand, which chelates platinum atom by the carbonyl
groups of side acyl chain and one group connected with five-membered cycle, whereas a 2-acyl-1,3-cyclo-
pentadion enolate anion forms counter ion.
DOI: 10.1134/S107036320605001X
Discovery of strong antineoplastic properties of cis-
dichlorodiammineplatinum(II) (cislatine), the inor-
ganic compound known even in XIX century, again
caused an interest to complexes of metals, in parti-
cular of platinum [1]. Intensive search for new anti-
neoplastic substances among the platinum complex
compounds begun and the study of the mechanism of
their action was launched. At present a number of
antineoplastic drugs [cis-diammine(1,1-cyclobutane-
dicarboxylato)platinum(II) (carboplatine), (trans-L-
1,2-diaminocyclohexane)oxalatoplatinum(II) (oxali-
platine), etc.] have been elaborated on the basis of
platinum(II) coordination compounds, which are ef-
fectively used in treatment of oncology diseases.
Among these compounds, cisplatine still belongs to
antineoplastic drugs most widely used for antineo-
plastic chemotherapy of cancer (in particular, for
especially heavy metastasis forms) [2 4].
O
O
H3N
H3N
Cl
Cl
H3N
H3N
H2N
O
O
OCO
OCO
Pt
Pt
Pt
H2N
Cisplatine
Carboplatine
Oxaliplatine
Alongside with effective oncological action, cis-
platine is rather toxic, in particular with respect to
nephrosis, which is badly transmitted. It is poorly
soluble in water and can be administered only intra-
venously for a long period; for certain tumors de-
velopment of resistency is observed. It has been found
that the high toxicity is caused basically by the forma-
tion of toxic oligomers at hydrolysis of cis-dichloro-
diammineplatinum(II), and the replacement of chlo-
rine atoms by ligands strongly bound to platinum(II)
reduces toxicity and increases solubility in water.
Compared to normal cells, tumoral cells are cha-
racterized by a higher level of DNA synthesis, whereas
DNAs are macromolecules at which the action of
some antineoplastic drugs is directed, in particular of
alkylating substances. It has been shown that pla-
tinum(II) complexes possessing an antineoplastic ac-
tion are alkylating compounds which selectively sup-
press the synthesis of DNA, but affect the synthesis of
RNA and proteins only slightly. Thus, one of principal
causes of the antineoplastic action of platinum com-
plexes is the inhibition of DNA copying [5].
669

670
KHLEBNIKOVA et al.
that allows considering them as bidentate acido
Platinum(II) can also be bound to endocellular
thiols, among which there are cytoplasmic non-protein
thiol glutathione and the main fraction of cytoplasmic
protein thiols, metalthioneines. As a result of this
concurrent reaction, inactive particles are formed and
resistance to this chemical develops [6].
ligands.
OH
O H
O
O
O
O
O
O
R
R
R
O
Thus, the inclusion of platinum(II) compounds
preventing deactivations on the reaction with endo-
cellular thiols in complexes and the replacement of
chlorine atoms in the inner sphere of cis-dichlorodi-
ammineplatinum(II) by acido ligands capable of form-
ing compounds with strong chelated platinum(II) shall
result in the reduction of toxicity and also can pro-
mote overcoming resistance development.
I
It seems promising for the expanding therapeutic
action and for increasing the efficiency of platinum(II)
coordination compounds to introduce in their com-
position fragments of , -triketones of natural and
allied structure, which in some cases possess antineo-
plastic properties alongside with antibiotic, hypoten-
sive, and other kinds of useful activity.
Last years cyclic , -triketones and their deri-
vatives find significant application in organic syn-
thesis, including the preparation of biologically active
materials, that is connected with rich synthetic op-
portunities of the multifunctional , -tricarbonyl
systems in these compounds, which can be considered
as rather universal block-synthons in full syntheses of
steroids, certain antibiotics, pheromones, prostaglan-
dins, medicines, etc., depending on the structure of a
cyclic part of a molecule and a side acyl chain [7 10].
A structural fragment of 2-acyl-1,3-cycloalkanedions
(I) with a strong intramolecular bond existing as endo
and/or exo keto-enol tautomers enters in one or
another form into the composition of many bioactive
compounds produced by various plants, microor-
ganisms, insects, and also of synthesized compounds
[11]. The presence of an enolized carbonyl group and
a conjugated carbonyl group in the , -position
causes an opportunity of the participation of tricar-
bonyl compounds in chelation with transition metals
In view of the above-stated we have offered the
approach [12, 13] to the synthesis of new cationic cis-
diammineplatinum(II) complexes with the use of de-
rivatives of biologically active 2-acyl-1,3-cyclopenta-
nedions as bidentate acido ligands, which exist in the
form of enol tautomers with a strong chelating intra-
molecular bond and show properties of acid vinilog.
To obtain , -triketones of cyclopentane series
Ia Ig with the structure allowing these compounds to
be included in platinum(II) coordination compounds,
we used the method of O C isomerization of corres-
ponding enolacylates under the action of acetonecyano-
hydrine in the presence of triethylamine in absolute
acetonitrile [8]. Enolacylates IIa IIg were synthesized
by direct O-acylation of cyclopentane-1,3-dion by acid
chlorides of carboxylic acids in the presence of py-
ridine in absolute chloroform [14].
O
O
O
O
Me
Me
CN
OH
RCOCl, Py
R
OCOR
O
O
IIa IIg
Ia Ig
O
O
O
O
O
ArCHO, Pi
Ar
Me
O
Ia
Ih Ik, R = CH=CHAr
I, R = Me (a), Et (b), Oct (c), Ph (d), C6H4OMe-4 (e), C6H3(OMe)2-3,4 (f), C6H4Ph-4 (g); Ar = Ph (h), C6H4Me-4 (i),
C6H4OMe-3 (j), C6H4COOMe-4 (k); II, R = Me (a), Et (b), Oct (c), Ph (d), C6H4OMe-4 (e), C6H3(OMe)2-3,4 (f),
C6H4Ph-4 (g).
Reactivity of the methylene group in the side chain
of cyclic , -triketones is somewhat reduced because
of the participation of the carbonyl group in the
chelate formation. However, 2-acetyl-1,3-cycloalkane-
dions enter to the Claisen-Schmidt condensation with
aromatic aldehydes and form , -tricarbonyl com-
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PLATINUM(II) CATIONIC COMPLEXES WITH DERIVATIVES
671
pounds with unsaturated side acyl chain showing
hypotensive and other kinds of activity [15 17].
carboxylate complexes have been described in the li-
terature [19 21]. Two main procedures are given by
Eqs. (1), (2) and (3), (4), respectively.
Therefore we have carried out the synthesis of 2-(3-
aryl-acryloyl)-1,3-cyclopentadions Ih Ik,
R
=
cis-PtA2I2 + 2AgNO3
cis-[PtA2(H2O)2](NO3)2 + 2AgI,
CH=CHAr by condensation of 2-acetyl-1,3-cyclopen-
tanedion Ia with aromatic aldehydes in the presence
of piperidine in absolute benzene at reflux. The yield
of the obtained compounds reaches 61 68%.
(1)
(2)
(3)
(4)
cis-[PtA2(H2O)2](NO3)2 + 2NaX
cis-PtA2X2 + 2NaNO3,
To determine and prove the structure of synthe-
sized compounds Ia Ilk and IIa IIg, we used H
cis-PtA2I2 + Ag2SO4
cis-[PtA2(H2O)2](SO4) + 2AgI,
1
NMR and IR spectroscopy. A strong absorption band
cis-[PtA2(H2O)2](SO4) + BaX2
cis-PtA2X2 + 2BaSO4.
1
in the range 1680 1720 cm (absorption of the con-
jugated carbonyl group) and two rather narrow absorp-
1
tion bands in the region of 1565 1655 cm are ob-
Here A2 is a bidentate amine or two monodentate
amines, X is a bidentate ligand or two monodentate
carboxylaled ligands, and cis-PtA2I2 is obtained by
Dhara’s method [22].
served in the IR spectra of all obtained , -triketones
Ia Ik. The band separation can be caused by the dif-
ference in absorption of chelating carbonyl group and
the enol double bond, or two bands can correspond to
chelating carbonyl groups of various enol enol tauto-
mers [18]. In the last case the high-frequency band
corresponds to the carbonyl group connected to the
cyclopenane ring, i.e. it corresponds to the structure
of the enol with the enolyzed carbonyl group in the
side chain. The low-frequency band is caused by the
absorption of a chelating carbonyl group of a side
chain. In the 1H NMR spectra along with all necessary
resonance signals of protons of methyl and methylene
groups (for compounds Ih Ik the signals of vinyl
The drawbacks of the first method are a low yield,
a significant duration of the reaction, and a difficulty
to remove the water-soluble sodium nitrate. The ap-
plication of the second method for our purposes was
limited by a low solubility of barium salts of 2-acyl-
1,3-cyclopentanedions in water and organic solvents.
We synthesized the cis-diammineplatinum(II) com-
plexes IIIa IIIk containing fragments of 2-acyl-1,3-
cyclopentadions as acido ligands by the transforma-
tion of cis-diiodododiammineplatinum(II) to cis-sulfa-
todiammineplatinum(II) under the action of silver
sulfate with the subsequent treatment of this latter by
barium hydroxide and the treatment of the resulting
base with a twofold excess of 2-acyl-1,3-cyclopenta-
dion Ia Ik, yield was 65 85%.
protons at
7.9 8.0 ppm and aromatic protons at
7.50 8.10 ppm), in the low-field region ( 14 16 ppm)
a signal of the enol proton was found that points to
the presence of a strong intramolecular hydrogen bond.
Several procedures for the synthesis of platinum(II)
O
O
R
R
+
2+
(1) Ba(OH)2;
(2) Ia Ik
O
O
O
O
NH3
NH3
NH3
NH3
Pt(II)(H2O)2 SO42
Pt(II)
(NH3)2Pt(II)J2
IIIa IIIk
III, R = Me (a), Et (b), Oct (c), Ph (d), C6H4OMe-4 (e), C6H3(OMe)2-3,4 (f), C6H4Ph-4 (g), CH=CHPh (h), CH=CH
C6H4Me-4 (i), CH=CHC6H4OMe-3 (j), CH=CHC6H4COOMe-4 (k).
In view of the data recently published for the new
cationic platinum(II) complexes [23, 24], and also on
the basis of the data of elemental analysis, and H
starting triketone enter into composition of the syn-
thesized platinum(II) complexes. The complexes
contain 2-acyl-1,3-cyclopentanedionate chelated with
a platinum(II) atom by means of a carbonyl group in
a side acetyl chain and a carbonyl group connected to
a five-membered cycle, whereas enolate anion of
1
NMR and IR spectroscopy for the obtained com-
pounds we propose the structure of cis-diamminepla-
1
tinum(II) cationic complexes IIIa IIIk. The H NMR
1
spectra show that fragments of two molecules of the
2-acyl-1,3-cyclopentadion is a counter ion. In the H
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 76 No. 5 2006

672
KHLEBNIKOVA et al.
NMR spectra there are resonance signals of all pro-
tons of two above-mentioned fragments. Because of
significant descreening effect the signals of the side
chain protons and the methylene groups of the five-
membered ring of the chelating 2-acyl-1,3-cyclopen-
tadionate are observed downfield to the signals of
protons of similar groups of the 2-acyl-1,3-cyclopen-
tadion enolate anion. No signals of hydroxyl protons
of starting , -triketones are present in the spectra
either. In the region of 6.52 6.70 (Py-d5), 4.64
4.68 (CD3OD), and 4.82 5.00 ppm (Me2SO-d6) in
2-Propinyl-1,3-cyclopentanedion (Ib). Yield
1
62%, mp 75 77 C. IR spectrum, , cm : 1605, 1645,
1720. 1H NMR spectrum (CDCl3), , ppm: 1.16 t [3H,
3
C(O)CH2CH3, J 7.5 Hz], 2.54 m (2H, CH2 cycl.),
3
2.78 m (2H, CH2 cycl., 2.98 q [2H, C(O)CH2CH3, J
7.5 Hz], 14.08 br.s (1H, OH enol.).
2-Octanoyl-1,3-cyclopentanedion (Ic). Yield
1
67%, mp 23 24 C. IR spectrum, , cm : 1605,1645,
1
1720. H NMR spectrum (CDCl3), , ppm: 0.88 m
(3H, CH2CH3), 1.30 m (8H, 4CH2), 1.62 quintet [2H,
C(O)CH2CH2CH2, 3J 7.0 Hz], 2.50 m (2H, CH2 cycl.),
1
the H NMR spectra of complexes IIIa IIIk recorded
3
2.74 m (2H, CH2 cycl.), 2.92 t [2H, C(O)CH2CH2, J
in various solvents there are the signals of six protons
of the two ammonia molecules connected with the
platinum atom in the cis-position. The IR spectra of
the synthesized platinum(II) complexes are character-
ized by the presence of absorption bands of carbonyl
groups of an acido ligand and a counter ion in the
1
7.0 Hz], 14.88 br.s (1H, OH enol.). H NMR spec-
trum (CD3OD), , ppm: 0.90 m (3H, CH2CH3),
1.30 m (8H, 4CH2), 1.62 quintet [2H, C(O)CH2CH2
3
CH2, J 7.0 Hz], 2.63 s (4H, 2CH2 cycl.), 2.88 t [2H,
3
C(O)CH2CH2, J 7.0 Hz], 15.35 w. s (1H, OH enol.).
1
field of 1560 1710 cm , and also absorption bands
2-Benzoyl-1,3-cyclopentanedion (Id). Yield 65%,
1
of the ammine ligand in the region of 2900
mp 45 47 C. IR spectrum, , cm : 1580, 1635,
1
1
3230 cm . The absorption band characteristic of the
1680. H NMR spectrum (CDCl3), , ppm: 2.60 s
cyclopentane , -triketones corresponding to the
conjugated carbonyl not included to the chelated
system do not occur in the region of 1720 cm of the
(2H, CH2 cycl.), 2.84 s (2H, CH2 cycl.), 7.50 m (2H,
H arom.), 7.62 m (1H, H arom.), 8.08 m (2H, H
arom.), 15.40 br.s (1H, OH enol.).
1
IR spectra. The analytical data for the prepared
platinum(II) complexes IIIa IIIk agree with the
proposed general structure.
2-(3-Methoxybenzoyl)-1,3-cyclopentanedion (Ie).
1
Yield 60%, mp 78 80 C. IR spectrum, , cm : 1580,
1
1635, 1680. H NMR spectrum (CDCl3), , ppm:
2.62 m (2H, CH2 cycl.), 2.87 m (2H, CH2 cycl.),
3.88 s (3H, OCH3), 7.18 m (1H, H arom.), 7.40 m
(1H, H arom.), 7.70 m (2H, H arom.), 15.80 br.s (1H,
OH enol.).
EXPERIMENTAL
The IR spectra were obtained on a UR-20 spec-
trometer in KBr for crystalline substances or films for
1
oily substances. The H NMR spectra were recorded
2-(3,4-Dimethoxyphenylacetyl)-1,3-cyclopenta-
on a Bruker AC-200 spectrometer in CDCl3, Me2SO-
d6, CD3OD, and Py-d5 with TMS as an internal re-
ference and in D2O with 2,2-dimethyl-2-silapentane-5-
sulfoacid as an the internal reference.
nedion (If). Yield 87%, oily substance. IR spectrum,
1
, cm : 1545, 1610, 1710. 1H NMR spectrum
(CDCl3), , ppm: 2.56 m (2H, CH2 cycl.), 2.76 m
(2H, CH2 cycl.), 3.89 s (6H, 2OCH3), 4.18 s [2H,
C(O)CH2Ar], 6.86 m (3H, H arom.), 15.80 br.s (1H,
OH enol.).
The melting and decomposition points were
measured on a Boetius heating table.
2-(4-Phenylbenzoyl)-1,3-cyclopentanedion (Ig).
1
The reaction courses and the purity of the syn-
thesized products were monitored by ™LC on Silufol
UV-254 plates.
Yield 86%, mp 154 156 C. IR spectrum, , cm :
1
1580, 1610, 1700. H NMR spectrum (CDCl3),
,
ppm: 2.62 m (2H, CH2 cycl.), 2.87 m (2H, CH2 cycl.),
7.45 m (3H, H arom.), 7.68 m (4H, H arom.), 8.20 m
(2H, H arom.), 15.24 br.s (1H, OH enol.).
2-Acyl-1,3-cyclopentanedions Ia Ig were ob-
tained by the technique [8]. Recrystallization from an
ether hexane mixture, 3:1, colorless crystalline
substances.
Condensation of 2-acetyl-1,3-cyclopentanedion
with aromatic aldehydes. To a solution 0.01 mol of
2-acetyl-1,3-cyclopentanedion Ia in 40 ml of absolute
benzene 0.15 mol of piperidine and 0.09 mol of a cor-
responding aromatic aldehyde were added. The reac-
tion mixture was boiled with a Dyne-Stark trap for 5 h
and kept at room temperature. Benzene was removed
on a rotary evaporator, a remainder was acidified with
hydrochloric acid up to pH 2. The resulting crystalline
2-Acyl-1,3-cyclopentanedion (Ia). Yield 72%, mp
1
72 75 C. IR spectrum, , cm : 1595, 1655, 1715.
1H NMR spectrum (CD3OD), , ppm: 2.44 s [3H,
1
C(O)CH3], 2.64 s (4H, 2CH2 cycl.). H NMR spec-
trum (Me2SO-d6), , ppm: 2.40 s [3H, C(O)CH3],
2.56 s (4H, 2CH2 of cycle).
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PLATINUM(II) CATIONIC COMPLEXES WITH DERIVATIVES
673
condensation product was filtered off, washed with
1 N hydrochloric acid (25 ml), then with water (3
25 ml), dried in air, and recrystallized from acetone
as a yellow crystalline substance. Yield 61 68%.
3-Octanoyloxy-2-cyclopentene-1-on (IIc). Yield
1
70%, mp 28 29 C. IR spectrum, , cm : 1165, 1615,
1
1690, 1725, 1800. H NMR spectrum (CDCl3),
,
ppm: 0.9 m (3H, CH2CH3), 1.34 m (8H, 4CH2), 1.71
3
quintet (2H, CO2CH2CH2CH2, J 7.0 Hz), 2.46 t (2H,
2-(3-Phenylacriloyl)phenylacriloyl)-1,3-cyclo-
3
CO2CH2CH2, J 7.0 Hz), 2.56 m (2H, CH2 cycl.),
pentanedion (Ih). Yield 67%, mp 108 109 C. IR
2.76 m (2H, CH2 cycl.), 6.24 m (1H, H vinyl).
1
1
spectrum, , cm : 1590, 1635, 1705. H NMR spec-
trum (Me2SO-d6), , ppm: 2.62 s (4H, 2CH2 cycl.),
7.50 m (3H, H arom.), 7.74 m (2H, H arom.), 7.9 q
(2H, H vinyl).
3-Benzoyloxy-2-cyclopentene-1-on (IId). Yield
1
67%, mp 102 104 C. IR spectrum, , cm : 1170,
1
1605, 1690, 1720, 1760. H NMR spectrum (CDCl3),
, ppm: 2.52 m (2H, CH2 cycl.), 2.92 m (2H, CH2
cycl.), 6.39 m (1H, H vinyl), 7.52 m (2H, H arom.),
7.68 m (1H, H arom.), 8.12 m (2H, H arom.).
2-[3-(4-Methylphenyl)acriloyl]-1,3-cyclopenta-
nedion (Ii). Yield 61%, mp 86 91 C. IR spectrum,
1
, cm : 1590, 1640, 1700. 1H NMR spectrum
3-(3-Methoxybenzoyloxy)-2-cyclopentene-1-on
(Me2SO-d6), , ppm: 2.14 s (3H, C6H4Me), 2.62 s
1
3
(IIe). Yield 59%, mp 86 89 C. IR spectrum, , cm :
(4H, 2CH2 cycl.), 7.58 d (2H, H arom., J 8.5 Hz),
1
7.72 d (2H, H arom., 3J 8.5 Hz), 7.94 m (2H, H vinyl).
1H NMR spectrum (CDCl3), , ppm: 2.41 s (3H,
C6H4Me), 2.60 m (2H, CH2 cycl.), 2.75 m (2H, CH2
1170, 1605, 1690, 1720, 1775. H NMR spectrum
(CDCl3), , ppm: 2.54 m (2H, CH2 cycl.), 2.92 m
(2H, CH2 cycl.), 3.88 s (3H, OCH3), 6.40 m (1H, H
vinyl), 7.20 m (1H, H arom.), 7.43 m (1H, H arom.),
7.62 m (1H, H arom.), 7.74 m (1H, H arom.).
3
cycl.), 7.25 d (2H, H arom., J 8.5 Hz), 7.60 d (2H,
3
H arom., J 8.5 Hz), 7.94 m (2H, H vinyl).
3-(3,4-Dimethoxyphenylacetyloxy)-2-cyclo-
2-[3-(3-Methoxyphenyl)acriloyl]-1,3-cyclo-
pentene-1-on (IIf). Yield 82%, oily substance. IR
pentanedion (Ij). Yield 68%, mp 112 114 C. IR
1
1
1
1
spectrum, , cm : 1170, 1610, 1690, 1720, 1790. H
NMR spectrum (CDCl3), , ppm: 2.44 m (2H, CH2
cycl.), 2.76 m (2H, CH2 cycl.), 3.78 s (2H, CO2
CH2Ar), 3.88 s (6H, 2OCH3), 6.24 m (1H, H vinyl),
6.82 s (1H, H arom.), 6.85 m (2H, H arom.).
spectrum, , cm : 1585, 1640, 1710. H NMR spec-
trum (CDCl3), , ppm: 2.62 m (2H, CH2 cycl.),
2.76 m (2H, CH2 cycl.), 3.86 s (3H, OCH3), 7.01 m
(1H, H arom.), 7.19 m (1H, H arom.), 7.35 m (2H,
H arom.), 7.94 m (2H, H vinyl).
3-(4-phenylbenzoyloxy)-2-cyclopentene-1-on
2-[3-(4-Methoxycarbonylphenyl)acriloyl]-1,3-c
(IIg). Yield 71%, mp 184 186 C. IR spectrum,
,
yclopentanedion (Il). Yield 65%, mp 186 188 C. IR
1
1
1
1
cm : 1165, 1665, 1695, 1710, 1750. H NMR spec-
trum (CDCl3), , ppm: 2.54 m (2H, CH2 cycl.), 2.94
m (2H, CH2 cycl.), 6.42 m (1H, H vinyl), 7.36
7.58 m (3H, H arom.), 7.62 7.80 m (4H, H arom.),
8.15 8.26 m (2H, H arom.).
spectrum, , cm : 1575, 1640, 1725. H NMR spec-
trum (Me2SO-d6), , ppm: 2.65 s (4H, 2CH2 cycl.),
3
3.90 s (3H, C6H4CO2Me), 7.85 d (2H, H arom., J
3
8 Hz), 7.90 d (2H, H arom., J 8 Hz), 8.05 m (2H,
1
H vinyl). H NMR spectrum (CDCl3), , ppm: 2.64 m
(2H, CH2 cycl.), 2.78 m (2H, CH2 cycl.), 3.96 s (3H,
Synthesis of platinum(II) coordination com-
pounds IIIa IIIk. In a solution of 0.0125 mol with a
3% deficit of silver sulfate in 100 ml of distilled water
0.0125 mol of cis-diodidodiammineplatinum(II) was
added with stirring. The reaction mixture was stirred
for 24 h at room temperature in the dark. A precipitate
was filtered off and a suspension of 0.0125 mol of
barium hydroxide octahydrate in 60 ml of distilled
water was added to a filtrate and stirred for 12 h. The
precipitate was filtered off, and the aqueous solution
was evaporated by 2/3 of volume on a rotary eva-
porator [50 C (15 mm Hg)]. To a transparent filtrate a
solution 0.025 mol of 2-acyl-1,3-cyclo-pentanedion
Ia Ik in 40 ml of EtOH was added dropwise and the
mixture was stirred for 24 h in the dark. The solvent
was removed on a rotary evaporator [45 C (15 mm
Hg)]. The resulting precipitate was washed out with
acetone (2 30 ml), diethyl ether (2 30 ml), and
3
PhCO2CH3), 7.75 d (2H, H arom., J 8 Hz), 7.99 s
3
(2H, H vinyl), 8.10 d (2H, H arom., J 8 Hz).
3-Acyloxy-2-cyclopentene-1-ons (IIa IIg) pre-
pared by the procedure [14]. Recrystallization from a
diethyl ether-hexane mixture, 2:1, colorless crystal-
line substances.
3-Acetoxy-2-cyclopentene-1-on (IIa). Yield 75%,
oily substance. Identical to an independently syn-
thesized sample [14].
3-Propionyloxy-2-cyclopentene-1-on (IIb). Yield
1
69%, oily substance. IR spectrum, , cm : 1165,
1
1605, 1690, 1720, 1795. H NMR spectrum (CDCl3),
3
, ppm: 1.11 t (3H, CO2CH2CH3, J 7.5 Hz), 2.38 m
(2H, CH2 cycl.), 2.64 q (2H, CO2CH2CH3, 3J 7.5 Hz),
2.74 m (2H, CH2 cycl.), 6.05 m (1H, H vinyl)
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674
KHLEBNIKOVA et al.
3
dried in vacuum ( 50oC). Synthesized complexes
IIIa IIIk represent crystal substances of light yellow
color.
quintet [4H, 2C(O)CH2CH2CH2, J 7.0 Hz], 2.42 s
(8H, 4CH2 cycl.), 3.38 t [4H, 2C(O)CH2CH2, 3J
1
7.0 Hz], 6.70 br.s (6H, 2NH3). H NMR spectrum
(CD3OD), , ppm: 0.90 m (6H, 2CH2CH3), 1.30 m
(16H, 8CH2), 1.57 m [4H, 2C(O)CH2CH2CH2], 2.26
2.50 m (6H, 3CH2 cycl.), 2.57 m (2H, CH2 cycl.),
cis-Diammine-(2-acetyl-1,3-cyclopentadionato)-
platinum(II) 2-acetyl-1,3-cyclopentadionate (IIIa).
Yield 65%, decomp. point 240 C (from an ethanol
3
2.83 t [4H, 2C(O)CH2CH2, J 7.0 Hz], 4.65 br.s (6H,
1
diethyl ether mixture). IR spectrum, , cm : 1365,
2NH3). 1H NMR spectrum (Me2SO-d6), , ppm:
0.96 m (6H, 2CH2CH3), 1.23 m (16H, 8CH2), 1.53 m
[4H, 2C(O)CH2CH2CH2], 2.42-2.67 m (8H, 4CH2
1435, 1480, 1560, 1590, 1620, 1695, 2830, 2930,
1
3120. H NMR spectrum (D2O), , ppm: 2.20 s (3H,
CH3CO), 2.22 s (3H, CH3CO), 2.32 s (4H, 2CH2
cycl.), 2.38 m (2H, CH2 cycl.), 2.52 m (2H, CH2
3
cycl.), 2.74 t [4H, 2C(O)CH2CH2, J 7.0 Hz], 4.82
br.s (3H, NH3), 4.92 br.s (3H, NH3). Found, %: C
44.54; H 6.20; N 4.20; Pt 28.97. C26H44N2O6Pt.
Calculated, %: C 46.22; H 6.51; N 4.14; Pt 28.89.
1
cycl.). H NMR spectrum (CD3OD), , ppm: 2.30 m
(10H, 2CH2 + 2CH3CO), 2.44 m (2H, CH2 cycl.),
2.55 (2H, CH2 cycl.), 4.68 br.s (6H, 2NH3). 1H
NMR spectrum (Me2SO-d6), , ppm: 2.00 s (5H, CH2
cycl. + CH3CO), 2.12 s (3H, CH3CO), 2.28 s (2H,
CH2 cycl.), 2.40 m (2H, CH2 cycl.), 4.90 br.s (6H,
cis-diammine(2-benzoyl-1,3-cyclopentanedio=
nato)platinum(II) 2-benzoyl-1,3-cyclopentanedi-
onate (IIId). Yield 85%, decomp. point 176 C (from
1
an ethanol diethyl ether mixture). IR spectrum,
,
2NH3). H NMR spectrum (Py-d5), , ppm: 2.44 s
1
cm : 1430, 1460, 1525, 1560, 1590, 1605, 1665,
(8H, 4CH2 cycl.), 2.84 s (6H, 2CH3CO), 6.62 br.s
(6H, 2NH3). Found, %: C 33.89; H 3.91; N 5.62 Pt
38.30. C14H20N2O6Pt. Calculated, %: C 33.14; H
3.95; N 5.52; Pt 38.46.
1
1710, 2830, 2930, 3065, 3230. H NMR spectrum
(D2O), , ppm: 2.46 s (4H, 2CH2 cycl.), 2.49 m (2H,
CH2 cycl.), 2.62 m (2H, CH2 cycl.), 7.37 7.74 m
(10H, H arom.). 1H NMR spectrum (CD3OD), , ppm:
2.46 s (4H, 2CH2 cycl.), 2.54 m (4H, 2CH2 cycl.),
4.64 br.s (6H, 2NH3), 7.28-7.50 m (5H, H arom.),
7.52 7.70 m (5H, H arom.). 1H NMR spectrum
(Me2SO-d6), , ppm: 2.11 s (4H, 2CH2 cycl.), 2.48 s
(4H, 2CH2 cycl.), 4.90 br.s (3H, NH3), 5.00 br.s (3H,
cis-Diammine(2-propanoyl-1,3-cyclopentane-
dionato)platinum(II) 2-propanoyl-1,3-cyclopen-
tanedionate (IIIb). Yield 73%, decomp. point 205 C
(from an ethanol diethyl ether mixture). IR spectrum,
1
, cm : 1430, 1480, 1560, 1600, 1680, 1705, 2840,
1
2945, 2930, 2985, 3150. H NMR spectrum (Me2SO-
1
3
NH3), 7.23 7.62 m (10H, H arom.). H NMR spec-
d6), , ppm: 0.92 t [3H, C(O)CH2CH3, J 7.5 Hz],
trum (Py-d5), , ppm: 2.54 s (8H, 4CH2 cycl.), 6.52
br.s (6H, 2NH3), 7.40 m (6H, H arom.), 8.14 m (6H,
H arom.). Found, %: C 46.01; H 4.18; N 3.9; Pt 30.88.
C24H24N2O6Pt. Calculated, %: C 45.64; H 3.80; N
4.44; Pt 30.90.
3
1.08 t [3H, C(O)CH2CH3, J 7.5 Hz], 2.08 s (4H,
2CH2 cycl.), 2.42 m (2H, CH2 cycl.), 2.52 m (2H,
3
CH2 cycl.), 2.64 q [2H, C(O)CH2CH3, J 7.5 Hz],
3
2.77 q [2H, C(O)CH2CH3, J 7.5 Hz], 4.96 br.s (6H,
1
2NH3). H NMR spectrum (CD3OD), , ppm: 1.02 t
3
cis-Diammine[2-(3-methoxybenzoyl)-1,3-cyclo-
pentanedionato]platinum(II) 2-(3-methoxybenzo-
yl)-1,3-cyclopentanedionate (IIIe). Yield 66%,
decomp. point 165 C (from an ethanol-diethyl ether
[3H, C(O)CH2CH3, J 7.5 Hz], 1.10 t [3H, C(O)CH2
3
CH3, J 7.5 Hz], 2.31 s (4H, 2CH2 cycl.), 2.43 m (2H,
CH2 cycl.), 2.54 m (2H, CH2 cycl.), 2.76 q [2H,
3
C(O)CH2CH3, J 7.5 Hz], 2.82 q [2H, C(O)CH2CH3,
1
1
mixture). IR spectrum, , cm : 1445, 1525, 1565,
3J 7.5 Hz], 4.64 br.s (6H, 2NH3). H NMR spectrum
1
3
1665, 1710, 2840, 3080. H NMR spectrum (D2O), ,
(D2O), , ppm: 1.03 t [3H, C(O)CH2CH3, J 7.5 Hz],
3
ppm: 2.48 s (4H, 2CH2 cycl.), 2.52 m (2H, CH2 cycl.),
2.64 m (2H, CH2 cycl.), 3.85 s (6H, 2OCH3), 7.08
1.06 t [3H, C(O)CH2CH3, J 7.5 Hz], 2.41 s (4H,
2CH2 cycl.), 2.48 m (2H, CH2 cycl.), 2.62 m (2H,
1
3
7.30 m (6H, H arom.), 7.41 m (2H, H arom.). H
CH2 cycl.), 2.73 q [2H, C(O)CH2CH3, J 7.5 Hz],
3
NMR spectrum (CD3OD), , ppm: 2.41 s (4H, 2CH2
cycl.), 2.54 m (4H, 2CH2 cycl.), 3.79 s (3H, OCH3),
3.82 s (3H, OCH3), 4.67 br.s (6H, 2NH3), 7.00 m
(1H, H arom.), 7.14 m (3H, H arom.), 7.27 m (4H, H
arom.). 1H NMR spectrum (Me2SO-d6), , ppm:
2.12 s (4H, 2CH2 cycl.), 2.16 s (4H, 2CH2 cycl.),
3.76 s (3H, OCH3), 3.80 s (3H, OCH3), 4.91 br.s (3H,
NH3), 5.02 br.s (3H, NH3), 6.92 7.40 m (8H, H
2.75 q [2H, C(O)CH2CH3, J 7.5 Hz]. Found, %: C
35.45; H 4.24; N 5.82 Pt 36.30. C16H24N2O6Pt.
Calculated, %: C 35.88; H 4.48; N 5.23; Pt 36.45.
cis-Diammine(2-octanoyl-1,3-cyclopentanedio-
nato)platinum(II) 2-octanoyl-1,3-cyclopentanedi-
onate (IIIc). Yield 70%, decomp. point 180 C (from
an ethanol diethyl ether mixture). IR spectrum,
,
1
1
cm : 1430, 1470, 1585, 1605, 1680, 1710, 2860,
2930, 3065. 1H NMR spectrum (Py-d5), , ppm:
0.80 m (6H, 2CH2CH3), 1.16 m (16H, 8CH2), 1.86
arom.). H NMR spectrum (Py-d5), , ppm: 2.52 s
(8H, 4CH2 cycl.), 3.64 s (6H, 2OCH3), 6.64 br.s (6H,
2NH3), 7.00 7.40 m (5H, H arom.), 7.76 m (3H, H
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 76 No. 5 2006

PLATINUM(II) CATIONIC COMPLEXES WITH DERIVATIVES
675
arom.). Found, %: C 44.71; H 3.89; N 4.16; Pt 29.50.
C26H28N2O8Pt. Calculated, %: C 45.15; H 4.05; N
4.05; Pt 28.22.
cis-diammine-{2-(3-(4-methylphenyl)acriloyl)-
1,3-cyclopentanedionato]}platinum(II) 2-[3-(4-
methylphenyl)acriloyl]-1,3-cyclopentanedionate
(IIIi). Yield 74%, decomp. point 195 C (from THF).
cis-Diammine[2-(3,4-dimethoxyphenylacetyl)-
1,3-cyclopentanedionato]platinum(II) 2-(3,4-di-
methoxyphenylacetyl)-1,3-cyclopentanedionate
(IIIf). Yield 70%, decomp. point 250 C (from an
1
IR spectrum, , cm : 1290, 1465, 1560, 1590, 1635,
1
1670, 1700, 2845, 2930, 3090. H NMR spectrum
(Me2SO-d6), , ppm: 2.10 s (3H, C6H4Me), 2.13 s
(3H, C6H4Me), 2.32 m (8H, 4CH2 3cycl.), 4.95 br.s
(6H, 2NH3), 7.22 d (2H, H arom., J 8 Hz), 7.34 d
(2H, H arom., 3J 8 Hz), 7.46 d (2H, H arom., 3J 8 Hz),
1
acetone diethyl ether mixture). IR spectrum, , cm :
1
1455, 1525, 1615, 1685, 2845, 2935. H NMR spec-
trum (D2O), , ppm: 2.40 s (8H, 4CH2 cycl.), 3.82 s
(12H, 4OCH3), 3.84 s [2H, C(O)CH2Ar], 3.87 s [2H,
3
7.60 d (2H, H arom., J 8 Hz), 8.14 m (4H, H vinyl).
1
1H NMR spectrum (CD3OD), , ppm: 2.36 s (12H,
3CH2 cycl. + 2C6H4Me), 2.57 m (2H, CH2 cycl.),
4.66 br.s (6H, 2NH3), 7.20 m (4H, H arom.), 7.54 m
C(O)CH2Ar], 6.86 7.08 m (6H, H arom.). H NMR
spectrum (Me2SOd6), , ppm: 2.40 br.s (8H, 4CH2
cycl.), 3.78 s (12H, 4OCH3), 3.82 s [4H, 2C(O)
CH2Ar], 5.00 br.s (6H, 2NH3), 6.74 7.10 m (6H, H
arom.). Found, %: C 45.91; H 4.53; N 3.55; Pt 24.86.
C30H36N2O10Pt. Calculated, %: C 46.21; H 4.62;
N 3.59; Pt 25.03.
3
(4H, H arom.), 8.10 d (2H, H vinyl, J 16 Hz), 8.23 d
3
(2H, H vinyl, J 16 Hz). Found, %: C 50.45; H 4.40;
N 4.13; Pt 27.62. C30H32N2O6Pt. Calculated, %: C
50.63; H 4.50; N 3.94; Pt 27.43.
cis-Diammine{2-[(3-(3-methoxyphenyl)acrilo-
yl)-1,3-cyclopentanedionato]}platinum(II) 2-[3-(3-
methoxyphenyl)acriloyl]-1,3-cyclo-pentanedionate
(IIIj). Yield 68%, decomp. point 215 C (from THF).
cis-Diammine[2-(4-phenylbenzoyl)-1,3-cyclo-
pentanedionato]platinum(II) 2-(4-phenylbenzoyl)-
1,3-cyclopentanedionate (IIIg). Yield 84%, decomp.
point 192 C (from an ethanol-diethyl ether mixture).
1
1
IR spectrum, , cm : 1290, 1445, 1560, 1590, 1635,
IR spectrum, , cm : 1430, 1560, 1580, 1605, 1670,
1
1
1670, 1715, 2840, 2950, 3090. H NMR spectrum
1715, 2840, 2925, 3070. H NMR spectrum (CDCl3),
(Me2SO-d6), , ppm: 2.12 s (4H, 2CH2 cycl.), 2.42 m
(2H, CH2 cycl.), 2.54 m (2H, CH2 cycl.), 3.74 s (3H,
OCH3), 3.78 s (3H, OCH3), 4.95 br.s (6H, 2NH3),
7.16 m (2H, H arom.), 7.34 7.62 m (6H, H arom.),
8.26 m (4H, H vinyl). Found, %: C 48.30; H 4.20;
N 3.90; Pt 26.40. C30H32N2O8Pt. Calculated, %: C
48.45; H 4.31; N 3.77; Pt 26.24.
, ppm: 2.34 br.s (8H, 4CH2 cycl.), 4.23 br.s (6H,
1
2NH3), 7.43 m (18H, H arom.). H NMR spectrum
(Me2SO-d6), , ppm: 2.16 s (8H, 4CH2 cycl.), 4.94
br.s (3H, NH3), 5.02 br.s (3H, NH3), 7.34 7.54 m
(8H, H arom.), 7.60 s (4H, H arom.), 7.64 7.81 m
1
(6H, H arom.). H NMR spectrum (Py-d5), , ppm:
2.78 s (8H, 4CH2 cycl.), 6.62 br.s (6H, 2NH3), 7.39 m
(6H, H arom.), 7.69 m (8H, H arom.), 8.26 m (6H,
H arom.). 1H NMR spectrum (CD3OD), , ppm:
2.44 s (4H, 2CH2 cycl.), 2.57 m (4H, 2CH2 cycl.),
4.66 br.s (6H, NH3), 7.32 7.52 m (6H, H arom.),
7.58 7.78 m (6H, H arom.). Found, %: C 55.00; H
3.99; N 3.70; Pt 25.08. C36H32N2O6Pt. Calculated,
%: C 55.17; H 4.09; N 3.58; Pt 24.90.
cis-Diammine{2-[(3-(4-methoxyphenyl)acriloyl)-
1,3-cyclopentanedionato]}platinum(II) 2-[3-(4-
methoxycarbonylphenyl)acriloyl]-1,3-cyclopentane-
dionate (IIIl). Yield 67%, decomp. point 205 C
1
(from THF). IR spectrum, , cm : 1290, 1435, 1555,
1
1590, 1635, 1680, 1720, 2830, 2960. H NMR spec-
trum (Me2SO-d6), , ppm: 2.14 s (4H, 2CH2 cycl.),
2.40 m (2H, CH2 cycl.), 2.58 m (2H, CH2 cycl.),
3.88 s (3H, C6H4CO2Me), 3.90 s (3H, C6H4CO2Me),
5.00 br.s (6H, 2NH3), 7.69 d (2H arom., J 8.5 Hz),
cis-diammine[2-(3-phenylacriloyl)-1,3-cyclo-
pentanedionato]platinum(II) 2-(3-phenylacriloyl)-
1,3-cyclopentanedionate (IIIh). Yield 78%, decomp.
3
3
3
1
7.80 d (2H arom., J 8.5 Hz), 7.98 d (2H arom., J
point 215 C (from THF). IR spectrum, , cm : 1440,
3
1
8.5 Hz), 8.08 d (2H arom., J 8.5 Hz), 8.20 d (2H
1570, 1595, 1650, 1685, 1705, 2840, 2930, 3075. H
3
3
NMR spectrum (Me2SO-d6), , ppm: 2.16 s (8H,
4CH2 cycl.), 5.02 br.s (6H, 2NH3), 7.38 m (4H
arom.), 7.52 m (4H, H arom.), 7.68 m (2H, H arom.),
vinyl, J 16 Hz), 8.30 d (2H, H vinyl, J 16 Hz).
Found, %: C 47.92; H 3.90; N 3.67; Pt 24.57. C32
H32N2O10Pt. Calculated, %: C 48.06; H 4.01; N 3.50;
Pt 24.21.
1
8.16 8.34 m (4H, H vinyl). H NMR spectrum (Py-
d5), , ppm: 2.44 s (8H, 4CH2 cycl.), 6.64 br.s (6H,
2NH3), 7.22 m (6H, H arom.), 7.68 m (4H, H arom.),
ACKNOWLEDGMENTS
3
8.06 d (2H, H vinyl, J 16 Hz), 9.18 d (2H, H vinyl,
3J 16 Hz). Found, %: C 49.04; H 4.00; N 4.25; Pt
28.71. C28H28N2O6Pt. Calculated, %: C 49.19; H
4.10; N 4.10; Pt 28.55.
This work was financially supported by the Belo-
russian Foundation for Basic Research (grant
no. ŒO3-048).
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676
KHLEBNIKOVA et al.
s’ezd po obshchei i prikladnoi khimii (XVII Mendele-
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