2
026
ALIMARDANOV, GARIBOV
Reduction of the so obtained mixture with aqueous
The composition of catalysts was confirmed by IR,
EPR, and UV spectroscopy. Fourier IR absorption
spectra were registered with Perkin-Elmer FT-IR
Spectrum BX spectrometer in KBr pellets at 450–
4400 cm . EPR spectra were recorded with JEOL
YES-PE (9300 MHz) radiospectrometer at 77 and 300 K.
Diphenylpicrylhydrazyl (g = 2.0036) was used as
reference while evaluation of g-factor. Electron
absorption spectra were registered with UV/Vis
Specord M 40 spectrometer (Germany).
sodium hydroxide led to a complex mixture of un-
saturated alcohols. When the oxidation was catalyzed
by V or VI, the amount of 1,2-epoxy-4-vinylcyclo-
hexane obtained was practically equal to the total of
unsaturated alcohols.
–
1
In the case of 3-methylcyclohexene oxidation with
the catalysts V and VI, the amount of unsaturated
alcohol isomers was more than the corresponding
epoxide. However, the oxidation of 1-methylcyclo-
hexene revealed quite the opposite result. The presence
of methyl group at the double bond accelerated the
substrate epoxidation, and in presence of catalysts V
and VI the epoxide is the major product of 1-
methylcyclohexene oxidation.
REFERENCES
1
. Centi, G., Cavani, F., and Trifirro, F., Selective
Oxidation by Heterogeneous Catalysts, New York:
Kluwer Academic, 2001, p. 112.
2
3
4
. Rafel, Y.S. and Clark, Y.H., Catal. Today, 2000, vol. 57,
p. 33.
EXPERIMENTAL
. Van der Waal, Y.C., Rigutto, W.S., and Van Bekkum, H.,
Appl. Catal. (A), 1998, vol. 167, no. 2, p. 331.
. Kuznetsova, L.I., Kuznetsova, N.I., Lisitsyn, A.S.,
Beck, I.E., Likholobov, V.A., and Ansel, J.E., Kinet.
and Catal., 2007, vol. 48, no. 1, p. 38.
The parent cyclohexene and methylcyclohexenes
were obtained by dehydration of corresponding alcohols
on A-1 aluminum oxide containing 2.0 wt % of sodium
hydroxide. butadiene-1,3 according to [17].
5. Kholdeeva, O.A. and Trukhan, N.N., Russ. Chem. Rev.,
006, vol. 75, no. 5, p. 411.
2
The microstructured carbon material was obtained
by the reaction of metal aluminum with carbon tetra-
chloride according to [14]. To prepare the catalysts, the
carbon material was doped with ethanol solutions of
cobalt [Co(CH COO) , Co(NO ) , CoCl , and CoBr ]
6. Alimardanov, Kh.M., Sadygov, O.A., Suleimanova, E.T.,
Dzhafarova, N.A., Abdullaeva, M.Ya., and Babaev, N.R.,
Russ. J. Appl. Chem., 2009, vol. 82, no. 7, p. 1255.
7
. Alimardanov, Kh.M., Sadygov, O.A., Abdullaeva, M.Ya.,
and Dzhafarova, N.A., Azerb. Khim. Zh., 2010, no. 2, p. 130.
. Sheldon, R.A. and Kochi, Y.K., Metal Catalyzed
Oxidation of Organic Compounds, New York:
Academic Press, 1981.
3
2
3 2
2
2
8
and molybdenum [MoCl , MoOBr , (NH ) MoO , and
5
3
4 2
4
Na MoO ] salts during 24 h. Then, the catalyst was
2
4
dried at 120–140°C and treated with 85 wt %
phosphoric aci4-Vinylcyclohexene was prepared by di-
merization of d and 30 wt % hydrogen peroxide. The
fine dispersed AG-2 and AG-3 charcoals were used as
a support. Concentration of metals in the so prepared
individual cobalt, molybdenum, and mixed cobalt-
9
. Tolstikov, G.A., Reaktsiya gidroperekisnogo okisleniya
(Reaction of Hydroperoxide Oxidation), Moscow: Nauka,
1976.
1
0. Haines, A., Methods for Oxidation of Organic
Compounds. Alcohols, Alcohol Derivatives, Alky
Halides, Nitroalkanes, Alkyl Azides, Carbonyl Com-
pounds Hydroxyarenes and Aminoarenes, Elsevier, 1988.
1. Catalytic Oxidation with Hydrogen Peroxide as Oxidant,
Strukul, G., Ed., Dordrecht: Kluwer Akademic, 1992.
2. Puchkov, S.V., Buneeva, E.I., and Perkel’ A.L., Kinet.
and Catal., 2005, vol. 46, no. 3, p. 340.
–3
–1
molybdenum systems was of (0.5–3.0)×10 mol g .
1
1
1
The oxidation experiments were performed in glass
reactor of bubbling type equipped with the Schott
filter, the thermocouple, the system of condensers and
traps, without solvent. The purified oxygen flow rate
3. Krylov, A.I., Litvintsev, I.Yu., and Sapunov, V.I.,
Kinetika i Kataliz, 1983, vol. 24, no. 1, p. 47.
–
1
was of 30 L h per 100 g of the raw material. The
formed hydroperoxide was determined by iodometric
titration. The composition of oxidate was evaluated
after reduction with sodium hydroxide solution, by
GLC with Tsvet-500 chromatograph with flame
ionization detector, 2000×2 mm column filled with
14. Alimardanov, Kh.M., Sadygov, O.A., Garibov, N.I.,
Abbasov, M.F., Abdullaeva, M.Ya. and Dzhafarova, N.A.,
Russ. J. Appl. Chem., 2011, vol. 84, no. 2, p. 236.
1
1
1
5. Nikitin A.V., Pomogailo A.V., Maslov S.A., and Ru-
bailo V.L., Neftekhimiya, 1987, vol. 27, no. 2, p. 234.
6. Timofeeva M.N., Pai Z.N., Tolstikov A.G., Russ. Chem.
Bul., 2003, no. 2, p. 480.
7. Yur’ev, Yu.K., Prakticheskie raboty po organicheskoi
khimii (Laboratory Manual in Organic Chemistry),
Moscow: Mosk. Gos. Univ., 1964, p. 339.
5
wt % of polyethyleneglycol succinate on Chromosorb,
with helium as carrier gas, column temperature of 160°C,
and evaporator temperature of 280°C.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 11 2013