KINETICS AND MECHANISM OF OXIDATION OF DIMETHYL SULFOXIDE
889
in a mortar under Ar. Solvents were dried over CaO,
vacuum-distilled, and stored over 4 molecular
sieves [19]. Compound I was prepared according to
20] and recrystallized three times from ethanol. The
4. Madesclaire, M., Tetrahedron, 1986, vol. 42, no. 20,
p. 5459.
5. Nikitin, Yu.E., Murinov, Yu.I., Rozen, A.M., and
Abramova, A.A., Zh. Neorg. Khim., 1973, vol. 18,
no. 3, p. 765.
[
purity of I was 99.5 99.8%. To avoid induced decom-
position of I and radical-chain oxidation of the solvent
with atmospheric oxygen [21], experiments without
superbasic media were performed under Ar in the
presence of -naphthol as radical reaction inhibitor.
Special experiments [6, 22] showed that -naphthol is
consumed in the system under consideration only in
reactions with free radicals. No additional consump-
tion of I was detected. The -naphthol concentration
6
. Emanuel’, N.M., Denisov, E.T., and Maizus, Z.K.,
Tsepnye reaktsii okisleniya uglevodorodov v zhidkoi
faze (Chain Reactions of Liquid-Phase Oxidation of
Hydrocarbons), Moscow: Nauka, 1965.
7
. Kovtun, G.O., Kuz’menko, O.I., Lisenko, D.L., and
Pustarnakova, G.F., Dopov. Akad. Nauk Ukr. RSR,
1
991, no. 2, p. 120.
8
9
. Kuz’menko, A.I., Cand. Sci. (Chem.) Dissertation,
Kiev, 1993.
. Dutka, V.S., Kinet. Katal., 1991, vol. 32, no. 4,
3
was 2 10 M, which is sufficient to suppress in-
duced decomposition of I under our conditions.
The experimental procedure was as follows. The
cell was charged with a weighed portion of the inhib-
itor or base (in experiments with superbasic media)
and the required volume of the solvent; the mixture
was brought to the required temperature over a period
of 30 min, and compound I was added. The reaction
progress was monitored by iodometric titration [23].
Liquid products were analyzed by gas chromatography
p. 960.
10. Dutka, V.S., Pankevich, R.V., and Derkach, Yu.V.,
Ukr. Khim. Zh., 1997, vol. 63, no. 1, p. 51.
1
1
1
1
1
1
1. Lyavinets, A.S. and Choban, A.F., Ukr. Khim. Zh.,
997, vol. 63, no. 2, p. 117.
1
2. Dutka, V.S., Tsvetkov, N.S., and Markovskaya, R.F.,
Kinet. Katal., 1982, vol. 23, no. 5, p. 1071.
3. Dutka, V.S., Ukr. Khim. Zh., 1987, vol. 53, no. 9,
p. 973.
4. Lyavinets, A.S., Zh. Fiz. Khim., 1999, vol. 73, no. 4,
p. 661.
5. Zolotova, N.V., Gervits, L.L., and Denisov, E.T.,
Neftekhimiya, 1975, vol. 15, no. 1, p. 146.
6. Ivanov, V.G., Chirkunov, E.V., Latypov, R.Sh., and
Kharlampidi, Kh.E., Zh. Obshch. Khim., 1997, vol. 67,
no. 3, p. 434.
(
Chrom-5 chromatograph, flame ionization detector,
stationary phase SE-30, carrier gas Ar, 3000 3-mm
glass column, programmed heating from 323 to 523 K
at a rate of 8 deg min ). Quantitative chromatograph-
1
ic analysis was performed with an internal reference.
Benzoic anhydride and tert-butyl benzoate (chro-
matographic references) were prepared by independent
synthesis from sodium benzoate and benzoyl chloride
in DMSO and from sodium tert-butylate and benzoyl
chloride in HMPA, respectively [24].
1
7. Gutmann, V., Coordination Chemistry in Non-
Aqueous Solutions, Wien: Springer, 1968.
To determine sodium benzoate, the reaction mix-
ture was acidified with sulfuric acid and extracted
with diethyl ether; the ether extract was analyzed by
gas chromatography. The presence of benzoic acid in
the ether extract was indicative of formation of sodi-
um benzoate.
18. Reichardt, Ch., Solvents and Solvent Effects in Or-
ganic Chemistry, Weinheim: VCH, 1988.
19. Gordon, A.J. and Ford, R.A., The Chemist’s Com-
panion. A Handbook of Practical Data, Techniques,
and References, New York: Wiley, 1972.
20. Karnojitzki, V., Les peroxides organiques, Paris:
Hermann, 1958. Translated under the title Organi-
cheskie perekisi, Moscow: Inostrannaya Literatura,
The reaction rate constants were determined by
plotting the kinetic curves of consumption of available
oxygen in semilog coordinates [22].
1
961, pp. 61 62.
2
2
1. Lyavinets, A.S., Choban, A.F., and Chervinskii, K.A.,
Neftekhimiya, 1997, vol 37, no. 3, p. 254.
2. Emanuel’, N.M. and Knorre, D.G., Kurs khimicheskoi
kinetiki (Course of Chemical Kinetics), Moscow:
Vysshaya Shkola, 1974.
REFERENCES
1
. Prilezhaeva, E.I., Reaktsiya Prilezhaeva. Elektrofil’-
noe okislenie (Prilezhaev Reaction. Electrophilic
Oxidation), Moscow: Nauka, 1974.
2
3. Antonovskii, V.L. and Buzlanova, M.M., Analitiches-
kaya khimiya organicheskikh peroksidnykh soedinenii
(Analytical Chemistry of Organic Peroxy Com-
pounds), Moscow: Khimiya, 1978.
2
3
. Curci, R., Di Preste, R.A., Edvards, J.O., and Mo-
dena, G., J. Org. Chem., 1970, vol. 35, no. 3, p. 740.
. Tolstikov, G.A., Reaktsii gidroperekisnogo okisleniya
(
Hydroperoxide Oxidation Reactions), Moscow:
24. Lyavinets, A.S., Ukr. Khim. Zh., 1998, vol. 64, no. 2,
Nauka, 1976.
p. 74.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 6 2004