LIQUID-PHASE CATALYTIC OXIDATION OF C6–C7 CYCLOOLEFINS
241
To provide a high yield of a dicarboxylic acid, it is
speed of aqueous or aqueous-dioxane solutions.
REFERENCES
necessary to use an excess amount of hydrogen peroxide.
At a molar ratio [H2O2] : [Sub] = 6 : 1, the yields of
hexane-1,6-dioic, 2(3)-methylhexane-1,6-dioic, and
cyclopentane-1,3-dicarboxylic acids reach values of
78–85%.
1. Soldatenko, L.T., Kolyadina, I.M., and Shendrik, I.V.,
Osnovy organicheskoi khimii lekarstvennykh veshchestv
(Fundamentals of the Organic Chemistry of Medicinal
Substances), Moscow: Mir, 2003.
The dependence of the yield of hexane-1,6-dioic acid
on the ratio [H2O2]/[Sub] (Fig. 2) shows a maximum in
the range 3.0–5.0 mol/mol. To obtain a high yield of the
acid, it is necessary to introduce the hydrogen peroxide
solution into the reaction zone in several portions during
a run.
2. Syroezhko, A.M. and Begak, O.Yu., Zh. Prikl. Khim.,
2003, vol. 76, no. 6, pp. 990–994.
3. Comprehensive Organic Chemistry, Barton, D. and
Ollis, W.D., Eds., Oxford: Pergamon, 1979, vol. 3.
4. Neznamov, A.G. and Levanevskaya, O.E., Teoriya i
praktika zhidkofaznogo okisleniya (Theory and Practice
of Liquid-Phase Oxidation), Emanuel’, N.M., Ed.,
Moscow: Nauka, 1974.
CONCLUSIONS
(1) Liquid-phase oxidation of cyclohexene, isomers
of methylcyclohexene, and bicyclo[2.2.1]hept-2-ene
(norbornene) with hydrogen peroxide in the presence
of a pseudohomogeneous catalytic system prepared
from molybdenum, tungsten, and cobalt halides and
oxohalides and nanosize carbon particles was used to
obtain the corresponding dicarboxylic acids.
5. Freidlin, G.N., Alifaticheskie dikarbonovye kisloty
(Aliphatic DicarboxylicAcids), Moscow: Khimiya, 1978.
6. Liu Jing and Xu Zic, Chin. J. Appl. Chem., 2003, vol. 20,
no. 6, pp. 600–602.
7. Svetlakov, N.V., Nikitin, V.G., and Nikolaeva, E.A., Zh.
Org. Khim., 2007, vol. 43, no. 5, pp. 773, 775–776.
8. Godt, H.C. and Quinn, J.F., J. Am. Chem. Soc., 1956,
(2) The oxidation of cycloolefins into dicarboxylic
acids occurs selectively in the presence of two-
component highly dispersed Mo–Co and W–Co systems
on carbon nanoparticles at 75–85°C, H2O2 : hydrocarbon
molar ratio of no less than 4, and 300–600-rpm agitation
vol. 78, p. 1461.
9. Trubnikov, V.I., Preobrazhenskii, V.A., Gol’dman, A.M.,
et al., Khim. Prom–st’, 1970, no. 1, p. 12.
10. Suzuki, Y., Harad, E., Nakamaru, K., et al., J. Mol. Catal.
A, 2007, vol. 276, nos. 1–2, pp. 1–7.
11. Liang, X., Hu, B., Yuan, Y., et al., Huagang Xuebo, 2007,
Q, %
vol. 58, no. 3, p. 794.
12. Shi, X., Liu, S., Tong, F., and Wei, Z., J. Shanxi Norm.
Univ. Natur. Sci. Ed., 2005, vol. 33, no. 1, p. 7881.
13. Lee-Sang-Ok, Raja, R., Harris, K.D.M., et al., Angew.
Chem. Int. Ed., 2003, vol. 42, no. 13, pp. 1520–1523.
14. Pai, Z.P., Tolstikov, A.G., Berdnikova, P.V., and Kustova,
G.N., Izv. Ross. Akad. Nauk, Ser. Khim., 2005, no. 8,
pp. 1794–1801.
15. Li, H., Zhu, W., He, X., et al., React. Kinet. Catal. Lett.,
2007, vol. 92, no. 2, pp. 319–327.
16. Li, H., Zi, M., Lin, H., et al., Petrochem. Technol., 2003,
vol. 32, no. 5, p. 374.
17. Cai, L. and Liu, W.Y., Chin. J. Appl. Chem., 2006, vol. 23,
no. 1, p. 26.
18. Chen, H., Dai, W., Vang, X., et al., Petrochem. Technol.,
2006, vol. 35, no. 2, p. 118.
Fig. 2. Yield Q of hexane-1,6-dioic acid vs. the molar ratio
[H2O2]/[Sub] in the reaction of cyclohexene oxidation. Reaction
conditions: T = 80°C, τ = 10 h, catalyst WOnBrmCoBr2/C
(0.5 wt %). (1) Epoxide, (2) diol, (3) acid, and (4) keto-alcohol.
19. Cao, F. and Ziong, H., Chem. Synthetic Fiber. Ind., 2004,
vol. 27, no. 6, p. 34.
20. Zhang, M., Wei, J.F., Bai, Y.J., et al., Youji huaxue, 2006,
vol. 26, no. 2, p. 207.
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 84 No. 2 2011