REACTION OF CARBOXYLIC ACID ESTERS WITH PHENOLATES
595
amines used as bases; in other cases, the base hydrol-
ysis takes place.
EXPERIMENTAL
REFERENCES
1. Holmberg, K., Curr. Opin. Colloid Interface Sci.,
2003, vol. 8, no. 1, p. 187.
We used commercial cetyltrimethylammonium
bromide (Sigma) containing about 99.9% main sub-
stance. The solvents, phenols, amines, and p-nitro-
phenyl esters of carboxylic acids were purified by
distillation or recrystallization, following standard
procedures. The emulsion was prepared from 9.42 g
of cetyltrimethylammonium bromide, 9.42 g of butan-
ol, and 2.0 g of hexane; the volume fraction of water
was 0.74.
2. Schwuger, M.J., Stichdom, K., and Schomacker, R.,
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The acid base properties of the reagents used were
studied by potentiometric titration or spectrophoto-
metrically, by measuring the absorption of the ionized
and nonionized species at different pH values (in
borate and methylmorpholine buffers and in 0.01 M
NaOH).
6. Mirgorodskaya, A.B. and Kudryavtseva, L.A., Russ.
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The reaction kinetics was studied spectrophotomet-
rically (Specord UV Vis) at 25 C in freshly prepared
microemulsions. The reaction progress was monitored
by variation of the optical density of solutions at
400 nm (formation of p-nitrophenolate anion). The
9. Elbert, A. and Serjeant, E., Ionization Constants of
Acids and Bases. A Laboratory Manual, New York:
Wiley, 1962.
5
initial concentration of the substrate was 5 10 M,
and the conversion, >90%.
10. Bel’skii, V.E., Valeeva, F.G., Kudryavtseva, L.A.,
and Ivanov, B.E., Dokl. Akad. Nauk SSSR, 1983,
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The apparent pseudo-first-order rate constants kapp
were determined from the dependence log(D
Dt) =
0.434kappt + const, where Dt and D are the optical
densities of the solutions at time t and after the reac-
tion completion, respectively. The kapp values were
calculated by the least-squares method.
11. Bel’skii, V.E., Valeeva, F.G., Kudryavtseva, L.A.,
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Katal., 2006, vol. 47, no. 1, p. 9.
Formation of the ester interchange product in the
microemulsion was confirmed in an experiment with
equimolar amounts (0.01 M) of the p-nitrophenyl ester
and sodium phenolate. The amount of the released
acid was determined by potentiometric titration.
13. Selig, I., Spin Labeling: Theory and Applications,
Berliner, L.J., Ed., New York: Academic, 1976.
Translated under the title Metod spinovykh metok.
Teoriya i primenenie, Moscow: Mir, 1976, p. 404.
The ESR spectra were recorded on an RE-1306
radiospectrometer equipped with a temperature unit
and interfaced with a computer. The ESR spectra were
taken under conditions of slow passing through the
resonance and in the absence of saturation. As spin
probe we used 4-(2-n-undecyl-3-oxyl-4,4-dimethylox-
azolidinyl)butyric acid. The procedure for introduction
of spin probes into microemulsions is described in
[18]. The ESR spectra were recorded in the range 20
70 C starting from higher temperatures at 4-isononyl-
phenol concentrations of 0 and 0.04 M. The tempera-
ture was measured with an accuracy of 0.5 C.
14. Vasserman, A.M. and Kovarskii, A.L., Spinovye metki
i zondy v fizikokhimii polimerov (Spin Markers and
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va, L.Ya., and Bel’skii, V.E., Izv. Ross. Akad. Nauk,
Ser. Khim., 1998, no. 7, p. 1333.
ACKNOWLEDGMENTS
The study was financially supported by the Russian
Foundation for Basic Research (project no. 03-03-
32952).
18. Zuev, Yu.F., Vylegzhanina, N.N., Idiyatullin, B.Z.,
and Mirgorodskaya, A.B., Appl. Magn. Reson., 2003,
vol. 25, p. 65.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 76 No. 4 2006