ISSN 1070-4272, Russian Journal of Applied Chemistry, 2014, Vol. 87, No. 3, pp. 289−293. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © A.V. Grekova, P.A. Ivanchenko, I.I. Seifullina, 2014, published in Zhurnal Prikladnoi Khimii, 2014, Vol. 87, No. 3, pp. 323−327.
It is a common knowledge that tertiary hydroperoxides
ﬁ nd use as initiators of liquid-phase chain processes of
hydrogenation, oxidation, and polymerization of hydro-
carbons [1–6]. The mechanism of their action is due to
the formation of active radicals at elevated temperatures.
Therefore, it is necessary to ﬁ nd compounds with which
these processes are possible in a milder temperature mode.
Among these compounds, the researchers’ attention is
attracted by complexes of metals capable of exhibiting
variable oxidation states with sulfur-containing ligands
and, in particular, with diethyldithiocarbamates of 3d
The goal of our study was to examine the decomposi-
tion kinetics of cumene hydroperoxides and tert-butyl in
the presence of N,N-diethyldithiocarbamates of Mn(III),
Co(III), Cr(III), Fe(III), Ni(II), and Cu(II) in ethylbenzene
as a model solvent in the temperature range 333–393 K.
As objects of study served tertiary hydroperoxides of
cumene (CHP) and tert-butyl (TBHP), puriﬁ ed by the
method described in . The purity of the initiators used
in the study was 95–97%.
N,N-Diethyldithiocarbamates of 3d metals (ML
where n = 2 and 3) Mn(III), Co(III), Cr(III), Fe(III), Ni(II),
and Cu(II) were synthesized by the procedures described
in [1, 9]. The dithiocarbamate precipitates formed as
a result of the syntheses: blue-violet of chromium(III),
green of cobalt(III) and nickel(II), black of iron(III) and
copper(II), and brown of manganese(III), were ﬁ ltered
off with a membrane ﬁ lter (0.6 μm) and dried in air at
room temperature to constant mass. The dried products
were twice puriﬁ ed by reprecipitation with ethanol from
solutions in chloroform at a volume ratio of 5 : 1.
According to the results of an elemental analysis
(metal, nitrogen, sulfur) , the purity of diethyldithio-
carbamates of the above metals was 97–98%. Ethylben-
zene was used as a solvent simulating styrene.
The kinetics of the CHP and TBHP decomposition in
the presence of N,N-diethyldithiocarbamates of the met-
als was studied in ethylbenzene in a thermostated glass
reactor with argon bubbling and a sampling device. The
content of ROOH in ethylbenzene was 5 × 10
that of ML
, 5 × 10
RESULTS AND DISCUSSION
It is known that hydroperoxides of cumene and tert-
butyl can generate free radicals at elevated temperatures,
at 393–423 K. In the ﬁ rst stage of the study, we performed
a set of experiments aimed to analyze the kinetics
of ROOH decomposition in the presence of ML
N,N-Diethyldithiocarbamates of 3d Metals as Catalysts
for Decomposition of Tertiary Hydroperoxides
A. V. Grekova, P. A. Ivanchenko, and I. I. Seifullina
Odessa I.I. Mechnikov National University, ul. Dvoryanskaya 2, Odessa, 65082 Ukraine
Received March 28, 2014
Abstract—Decomposition kinetics of tertiary cumene hydroperoxides and tert-butyl in ethylbenzene in the
presence N,N-diethyldithiocarbamates of 3d metals was studied at moderately low temperatures, 323–383 K.
The kinetic parameters of the catalytic decomposition of the hydroperoxides were calculated and a decrease in
the activation energy as compared with the thermal decomposition was noted.