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ZHUKOVSKAYA et al.
present of the bonds C–H(cyclopentadienyl) 3100±10;
S–H(aliph.) 2955±5, 2925±10, 2855±5; C=O 1755±20;
C=C(cyclopentadienyl) 1600±5, 1460±10, 1330±10,
1303±5; CO 1170±25, 1065±25 cm–1. In the IR
spectrum of nitrile XXVIII an absorption band of C≡N
is observed at 2223 cm–1. In the IR spectra of
nitrobenzoates (XXIX–XXXI) there are two
characteristic absorption bands of NO2 group at
1535±10 and 1345±3 cm–1. In the IR spectra of
carboranes XXXIII and XXXIV there are absorption
bands C–H(carb) 3071 (XXXIII) and 3032 (XXXIV);
B–H 2680±25 cm–1.
1,1'-Diacetylferrocene dioxime esters III–
XXXIV (general procedure). 0.01 mol of oxime II was
dissolved in 50 ml of anhydrous ether, and 0.02 mole
of anhydrous pyridine was added to the solution. To
the obtained solution at cooling to 15°С and stirring
with a magnetic stirrer was added 0.02 mole of the
respective carboxylic acid chloride. The mixture was
stirred for 8 h and then left at the temperature 20–23°С
for 24– 36 h. The liquid 1,1'-diacetylferrocene dioxime
esters V, VII, VIII, X–XV, XXIII were separated as
follows: the reaction mixture was diluted with water
and the product was extracted with ether. Organic
layer was separated, washed with water and 5%
solution of NaHCO3 and dried over CaCl2 The solvent
was then removed at a reduced pressure (10–15 mm
Hg) avoiding heating above 25–30°С. The final
purification was carried out by column chromato-
graphy on the silica gel L 5/40 μm, the products were
eluted with ether–hexane 1:1 mixture. Crystalline
esters III, IV, VI, IX, XVI–XXII, XXIV–XXXIV
were isolated by filtration of the reaction mixture
through the porous glass filter, the precipitate was
washed on the filter with a small amount of ether and
then washed with water for removing pyridine
hydrochloride. The products were dried in air, final
purification was carried out by recrystallization from
methanol.
In the UV spectra of the 1,1'-diacetylferrocene
dioxime esters III–XXXIV there are absorption bands
with the following maxima [λmax, nm (ε)]: 223 (18000),
282 (9000), 334 (3000), 453 (300), caused by the
presence in the molecules of 1,1'-diacetylferrocene di-
O-acyloxime fragments. In the 1H NMR spectra of the
1,1'-diacetylferrocene dioxime esters III–XXXIV the
signals of the protons of methyl group are singlets in
the region of 2.19–2.32 ppm, the signals of С5Н4
protons of cyclopentadienyl groups are two broad
singlets in the region of 4.40–4.95 ppm.
1
In the IR, UV and H NMR spectra of the 1,1'-
diacetylferrocene dioxime esters III–XXXIV there are
also the absorption bands and the proton signals which
confirm the presence of the corresponding structural
fragments of ester groups.
ACKNOWLEDGMENTS
This work was carried out with the financial
support of the Belorussian Republic Fund for Basic
Research (grant no. X 07-050).
EXPERIMENTAL
The IR spectra of compounds were registered on a
Protege-460 Nicolet IR Fourier spectrophotometer
from KBr pellets, the UV spectra, on the Specord UV-
Vis instrument from 1×10–4 M solutions of compounds
REFERNECES
1. Perevalova, E.G., Reshetova, M.D., and Grandberg, K.I.,
Metody elementoorganicheskoi khimii. Zhelezoor-
ganicheskie soedineniya. Ferrotsen (Methods of Hetero-
Organic Chemistry. Ironorganic Compounds. Ferro-
cene), Moscow: Chemistry, 1983.
1
in methanol, the H NMR spectra, on the spectrometer
Tesla BS-587A (100 MHz) from 5% solutions in
chloroform-d or DMSO-d6, chemical shifts were
determined relative to internal reference TMS. The
elemental analysis was carried out on a Vario EL-III
Elementar C,H,N,O,S-analyzer, an error in the
determination was 0.1%. The molecular weight (M) of
the compounds soluble in benzene was determined by
cryoscopy. 1,1'-Diacetylferrocene (I) was used of
“analytically pure” grade, of 99% purity, with mp 126–
127°С, 1,1'-diacetylferrocene dioxime II was
synthesized by the reaction of 1,1'-diacetylferrocene I
with hydroxylamine in ethanol, mp 141–142°С [1].
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 8 2009
Zhukovskaya
