838
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 5, May, 2002
Lermontov et al.
The alkoxy group (in this case, the phenoxy group) can
Isomeric butylenecarbonates were isolated by distillation,
and their b.p. and NMR spectra corresponded to those deꢀ
play a role of a base activating the СО molecule.
2
2
1—23
scribed in the literature.
The IR spectra of the reaction mixtures contained only an
A comparison with the previously described catalysts
shows that we succeeded in finding the group of active
catalytic systems based on 8ꢀhydroxyquinolates of trivaꢀ
–1
absorption band of monocarbonates (ν(СО) = 1798—1803 cm ).
lent metals for the reaction of СО with epoxides. These
2
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 00ꢀ03ꢀ
catalytic systems catalyze the synthesis of cyclocarbonates
at temperatures <180 °С, contain no halogens, and proꢀ
vide, to a great extent, retention of the configuration of
substituents in the initial epoxides.
3
2846).
References
1
. Xu Xiaoding and J. A. Moulijn, Energy and Fuels, 1996,
0, 305.
Experimental
1
2
3
. A.ꢀA. G. Shaikh and S. Sivaram, Chem. Rev., 1996, 96, 951.
. US Pat 4,314,945; RZhKhim. [Abstract Chemical J.], 1982,
Reactions were carried out in a stainless steel 40ꢀmL autoꢀ
clave designed for a maximum working pressure of 600 atm and
equipped with a pocket for a thermocouple and a Dꢀ60
tensometric sensor for precision pressure monitoring.
2
4N85 (in Russian).
. A. L. Shapiro and I. S. Lyubovskii, in Alkilenkarbonaty
Alkylenecarbonates], Nauka, Leningrad, 1975, 6 (in Russian).
4
[
Aluminum hydroxyquinolate was synthesized by a previꢀ
5
6
7
. W. J. Kruper and D. V. Dellar, J. Org. Chem., 1995, 60, 725.
. T. Aida and S. Inoue, J. Am. Chem. Soc., 1983, 105, 1304.
. K. Kasuga, S. Nagao, T. Fukumoto, and M. Handa, Polyꢀ
hedron, 1996, 15, 69.
1
2
III
III
ously described procedure. The Fe and Cr hydroxyꢀ
1
8
quinolates were prepared using a known method. Propylene
oxide (Merck) and Ph PO (Chemapol) were used as received.
3
Butꢀ2ꢀene and isobutylene oxides prepared as described preꢀ
viously19 were distilled above CaH2 before the reaction.
Butꢀ2ꢀene oxide was enriched in transꢀ or cisꢀisomers by the
rectification of a mixture with a transꢀisomer : cisꢀisomer ratio
of 60 : 40.
8
9
. V. Shibata, V. Baba, V. Iwasaki, and H. Matsuda, J. Org.
Chem., 1986, 51, 2177.
. A. Baba, T. Nozaki, and H. Matsuda, Bull. Chem. Soc.
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1
0. R. L. Paddock and S. T. Nguyen, J. Am. Chem. Soc., 2001,
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11. C. A. Eckert, D. Bush, J. S. Brown, and C. L. Liotta, Ind.
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12. A. V. Vinogradov and S. V. Elinson, Oksikhinolin [Hydroxyꢀ
quinoline], Nauka, Moscow, 1979, 22 pp. (in Russian).
3. I. Fujii, N. Hirayama, J. Ohtani, and K. Kodama, Anal.
Sci., 1996, 12, 153.
1Н NMR spectra were recorded on a Bruker DPXꢀ200
1
spectrometer (200 MHz) relatively to the Me Si external stanꢀ
4
dard, and 27Al NMR spectra were recorded on a Bruker
CXPꢀ200 spectrometer using Al(NO3) as external standard.
3
IR spectra were obtained on a Bruker IFSꢀ113 spectrometer.
In a typical experiment, propylene oxide (0.42 g, 7.2 mmol),
1
aluminum hydroxyquinolate (0.017 g, 0.038 mmol), and Ph PO
3
(
0.11 g, 0.38 mmol) were placed in an autoclave, which then
1
4. M. UlꢀHaque, W. Horne, and S. J. Lyle, J. Crystallogr.
Spectrosc. Res., 1991, 21, 411.
15. H. Schmidbaur, J. Lettenbauer, D. L. Wilkinson, G. Muller,
was filled to a specified pressure with carbon dioxide prelimiꢀ
narily passed (as a liquid) through columns packed with SiO2
and active carbon. The charged autoclave was heated in a furꢀ
and O. Kumberger, Z. Naturforsch., 1991, 46B, 901.
nace equipped with a device for automated temperature mainꢀ
tenance (Miniterm 300), and the temperature and pressure
inside the autoclave were monitored during heating. After the
end of the reaction, the autoclave was cooled, excess СО2 was
let out to the atmosphere, and the reaction mixture was diluted
with the specified amount of acetone and analyzed by GLC on
a column with SEꢀ30. In experiments with supercritical СО2,
the autoclave preliminarily charged with the epoxide and cataꢀ
lyst samples was heated to a temperature higher than the СО2
critical temperature (usually 40—50 °С), after which it was
charged with carbon dioxide using a highꢀpressure pump until
the necessary density was achieved,20 closed, and heated as
described above.
1
1
6. J. W. Akitt, Progress in NMR Spectroscopy, 1989, 21, 1.
7. S. A. Lermontov, S. V. Shkavrov, A. S. Lermontov, and
S. I. Zavorin, Izv. Akad. Nauk, Ser. Khim., 1998, 1649 [Russ.
Chem. Bull., 1998, 47, 1607 (Engl. Transl.)].
8. A. K. Lavrukhina and L. V. Yukina, Analiticheskaya khimiya
khroma [Analytical Chemistry of Chromium], Nauka, Mosꢀ
cow, 1979, 30 pp. (in Russian).
9. L. I. Kirkovsky, S. A. Lermontov, S. I. Zavorin, I. I.
Sukhozhenko, V. O. Zavelsky, R. Their, and H. M. Bolt,
Environmental Toxicology and Chemistry, 1998, 17, 2141.
0. V. V. Altunin, Teplofizicheskie svoistva dvuokisi ugleroda
1
1
2
[
Thermophysical Properties of Carbon Dioxide], Izdꢀvo
Standartov, Moscow, 1975, 303 pp. (in Russian).
In a preparation experiment, propylene carbonate was obꢀ
tained after distillation in 80% yield (2.45 g) from propylene
oxide (1.74 g, 30 mmol), aluminum hydroxyquinolate (71.8 mg,
2
2
1. A. Baba, K. Seki, and H. Matsuda, J. Heterocycl. Chem.,
1
990, 27, 1928.
2. T. Aida and S. Inoue, J. Am. Chem. Soc., 1983, 105, 1304.
0
.156 mmol), and Ph PO (433.7 mg, 1.56 mmol) at an initial
3
23. A. Baba, T. Nozaki, and H. Matsuda, Bull. Chem. Soc.
Jpn., 1987, 60, 1553.
1
СО pressure of 50 atm and 20 °С. The Н NMR spectrum and
2
retention time of the product (GLC, SEꢀ30) coincided with
the corresponding characteristics of the propylene carbonate
sample (Merck).
Received November 30, 2001;
in revised form February 28, 2002