SULFONATION OF 10-CARBOXYMETHYLENE-9-ACRIDANONE
693
Under the microwave irradiation, the sulfonation
with concentrated sulfuric acid was carried out under
the same temperature conditions. The reaction time
was reduced to 240 min at 140°C, 130 min at 150°C,
The IR spectra were recorded on a Nicolet IR-200
FTIR spectrometer from KBr pellets. The H NMR
spectra were taken on a Bruker AV600SF spectrometer
1
from DMSO-d solutions.
6
1
and 55 min at 160°C. The IR and H NMR spectra of
the isolated product were identical with the spectra of
the product obtained in oleum and sulfuric acid in the
thermal conditions.
Sulfonation of 10-carboxymethylene-9-acridanone
under the thermal conditions. A mixture of 10 g
0.039 mol) of 10-carboxymethylene-9-acridanone and
0 ml (0.38 mol) of concentrated sulfuric acid was
(
2
To evaluate the effect of microwave irradiation on
the rate of sulfonation of 10-carboxymethylene-9-
acridanone we estimated the kinetic parameters of the
reaction. The kinetic studies were carried out by thin
layer chromatography with densitometry. Chromato-
grams obtained were treated on a Sorbfil video-
densitometer at a wavelength of 254 nm using the
Sorbfil 1.8 software [4].
heated at the desired temperature with stirring for a
specified period of time. The mixture was poured into
5
1
4
0 ml of glacial acetic acid and allowed to stand for 8–
0 h, then the precipitate was filtered off, washed with
0–50 ml of glacial acetic acid and then with acetone.
Yield 60–65%, mp 282–284°C (decomp., acetic acid).
–1
IR spectrum, ν, cm : 3400.00–2362.67 (OH, CH),
1
738 (C=Ocarboxy), 1620 (>C=O ), 1586–1500 (С=С),
acr
1
A consumption degree of the starting 10-carboxy-
methylene-9-aridanone (CMA) and an accumulation
degree of the sulfonation product were calculated from
1217.52–1031 (S=O). Н NMR spectrum, δ, ppm:
13.12 s (2Н, ОН), 8.59 s (1Н, С Н), 8.36 d (1Н, С Н,
J 7.0 Hz), 7.66 d (1Н, С Н, J 8,8 Hz), 7.67 d (1Н,
С Н, J 8,8 Hz), 7.37 t (1Н, С Н, J 7.2 Hz), 7.82 t (1Н,
1
3
4
0
5
6
the experimental data obtained (αCMA = cCMA/cCMA).
7
8
С Н, J 7.0 Hz), 7.97 d (1Н, С Н, J 7.92 Hz), 5.34 s
It was found that under the studied conditions the
reaction progress corresponds to the kinetics of the
first order reaction. The consumption curves of 10-
carboxymethylene-9-aridanone and the straight lines in
the log (1/α)−τ coordinates are presented in Figs. 1, 2.
9
(
2Н, С Н).
Sulfonation of 10-carboxymethylene-9-acridanone
under the microwave irradiation. A mixture of 10 g
0.039 mol) of 10-carboxymethylene-9-acridanone and
0 ml (0.38 mol) of concentrated sulfuric acid was
(
2
The rate constants at different temperatures were
determined by the quantitative thin-layer chromato-
graphy with densitometry according to [4] (Fig. 1, 2).
heated to the desired temperature with stirring for a
specified period of time in a MARS microwave system
at 400 W. The mixture was poured into 50 ml of
glacial acetic acid and allowed to stand for 8–10 h,
then the precipitate was filtered off, washed with 40–
50 ml of glacial acetic acid and then with 25 ml of
acetone. Yield 60–80%.
Based on the data obtained, we calculated the
–
1
activation energies, which reached 121 kJ mol in the
–
1
thermal conditions and 118 kJ mol in the microwave
radiation conditions (see table).
As can be seen from the above data, in the studied
reactions there is a microwave effect, which results in
a faster sulfonation of 10-carboxymethylene-9-acridanone.
REFERENCES
The microbiological studies of 0.5–2.0% solutions
of the sulfonated product showed a moderate anti-
bacterial activity against the test strains of some micro-
organisms.
1
2
.
.
Ershov, F.I., Kovalenko, A.L., Romantsov, M.G., and
Golubev, S.Yu., Tsikloferon 12.5% dlya injektsii: itogi i
perspectivy klinicheskogo primeneniya (Cycloferon for
Injection: Results and Future Clinical Applications), St.
Petersburg: Apollo, 1999.
EXPERIMENTAL
Markovich, Yu. D., Pelevin, N.A., Akimova, N.S.,
Klimova, L.G., Kudryavtseva, T.N., Mukhacheva, E.S.,
and Gubina, T.I., Izv. KurskGTU, no. 1, 2007, p. 35.
The purity of the starting materials and the reaction
products was tested by thin layer chromatography
(
TLC). Chromatogram processing and kinetic studies
3. Markovich, Yu. D., Kudryavtseva, T.N., Chevyche-
lov, S.V., Markovich, D.Yu., and Pelevin, N.A., Izv.
KurskGTU, no. 2, 2005, p. 38.
were carried out on a highly efficient Sorbfil and
PTLC-AF-B-UV plates using a Sorbfil densitometer
[
4]. A benzene–acetone–ethanol–acetic acid (5:8:10:0.2)
4
.
Markovich, Yu. D., Kudryavtseva, T.N., Pelevin, N.A.,
mixture was used as an eluent.
and Lotorev, D.S., Zav. Lab., no. 4, 2008, p. 7.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 4 2013