Innovating Organocatalysis as Promising Trend in Oxidation Reactions with Molecular Oxygen

1Opeida, IO
1Department of Physics and Chemistry of Combustible Minerals, Litvinenko Institute of Physic, Organic and Coal Chemistry, the NAS of Ukraine, Lviv
Sci. innov. 2015, 11(6):55-59
https://doi.org/10.15407/scine11.06.055
Section: The World of Innovations
Language: English
Abstract: 

The prospects for innovative organocatalytic aerobic oxidation developed by IPOCC of the NAS of Ukraine have been outlined. The practice of oxidizing the hydrocarbons and 5-hydroxymethylfurfural with molecular oxygen under mild conditions has been improved by using the organic compound, N-hydroxyphthalimide, as key catalyst. For the oxidation of coal and substrates whole molecules are capable of keto-enol tautomerism, the use of dimethyl sulfoxide as a solvent is an innovative method that ensures the action of basic catalysts.

Keywords: 5 hydroxymethylfurfural, aerobic oxidation, coal, dimethyl sulfoxide, hydrocarbons, N hydroxyphthalimide, organocatalysis
References: 
1. Shi Zh., Zhang Ch., Tanga C., Jiao N. Recent advances in transition-metal catalyzed reactions using molecular oxygen as the oxidant. Chem. Soc. Rev. 2012. V. 41: 3381-3430.
http://dx.doi.org/10.1039/c2cs15224j
2. Bregeault J-M. Transition-metal complexes for liquidphase catalytic oxidation: some aspects of industrial reactions and of emerging technologies. Dalton Trans. 2003: 3289-3302.
http://dx.doi.org/10.1039/b303073n
3. Sheldon R., Dakka J. Heterogeneous catalytic oxidations in the manufacture of fine chemicals. Catal Today. 1994. V. 19: 215-246.
http://dx.doi.org/10.1016/0920-5861(94)80186-X
4. Ishii Ya., Sakaguchi S., Iwahamab T. Innovation of Hydrocarbon Oxidation with Molecular Oxygen and Related Reactions. Adv. Synth. Catal. 2001. 343(5): 393-427.
http://dx.doi.org/10.1002/1615-4169(200107)343:5<393::AID-ADSC393>3.0.CO;2-K
5. Litvinenko L.M., Olejnik N.M. Organicheskie katalizatory i gomogennyj kataliz. Kyiv: Nauk. Dumka, 1981 [in Russian].
6. Savelova V.A., Olejnik N.M. Mehanizmy dejstvija organicheskih katalizatorov. Bifunkcional’nyj i vnutrimolekuljarnyj kataliz. Kyiv: Nauk. Dumka, 1990 [in Russian].
7. Ishii Y., Nakayama K., Takeno M. et al. Sakaguchi S., Iwahama T., Nishiyama Y. Novel Catalysis by N-Hydroxyphthalimide in the Oxidation of Organic Substrates by Molecular Oxygen. J. Org. Chem. 1995. 60(13): 3934-3935.
http://dx.doi.org/10.1021/jo00118a002
8. Iwahama T., Sakaguchi S., Nishiyama Yu, Ishii Ya. Aerobic oxidation of alcohols to carbonyl compounds catalyzed by n-hydroxyphthalimide (NHPI) combined with Co(acac)3.Tetrahedron Letters. 1995. 36(38): 6923-6926.
http://dx.doi.org/10.1016/00404-0399(50)1431G-
9. Hermans I., Jacobs P., Peeters J. Autoxidation catalysis with N-hydroxyimides: more-reactive radicals or just more radicals? Phys. Chem. Chem. Phys. 2007. V. 9: 686-690.
http://dx.doi.org/10.1039/b616392k
10. Opejda I.A., Kompanec M.A., Kushh O.V., Matvienko A.G. Iniciirovanie N-gidroksiftalimidom radikal’noj polimerizacii vinil’nyh monomerov. Zhurnal prikladnoj himii. 2007. 80(10): 1688-1691 [in Russian].
11. Opeida I.O., Kompanets M.O., Kusch O.V., Litvinov Ju.E. The oxidation of methylmethacrylate by molecular oxygen under mild conditions in the presence of N-hydroxyphthalimide. Oxidation Communications. 2010. 34 (1): 43-54.
12. Opejda I.A., Kompanec M.A., Kushh O.V., Jastrebova E.G. O roli N-gidroksiftalimida v reakcijah okislenija alkilarenov molekuljarnym kislorodom. Neftehimija. 2009. 49(5): 409-412.
13. Opejda I.A., Kompanec M.A., Kushh O.V., Papajanina E.S. Dejstvie N-gidroksiftalimida na stereoreguljarnost’ cepi v radikal’noj polimerizacii metilmetakrilata. TJeH. 2011. 47(1): 26-31.
14. Kompanets M.O., Kushch O.V., Litvinov Yu.E. et al. Oxidation of 5-hydroxymethylfurfural to 2,5-diformylfuran with molecular oxygen in the presence of the N-hydroxyphthalimide. Cat. Commun. 2014. V. 57: 60-63.
http://dx.doi.org/10.1016/j.catcom.2014.08.005
15. Pat. Ukrai'ny 107400. MPK S 07 D 307/46. Sposib oderzhannja 2,5 dyformilfuranu. Opejda J.O., Kushh O.V., Kompanec M.O., Novikova K.V., Litvinov Ju.Je. [in Ukrainian].
16. Serdjuk A. A., Kasjanchuk M. G., Opejda I. A. Kataliticheskaja aktivnost’ aminov v reakcii okislenija antrona. Zhurn. org. himii. 2014. 50(10): 1460-1464 [in Russian].
17. A.s. # 1129875 SSSR. Sposob poluchenija d,l-kamfornoj kisloty. Jemanujel’ N.M., Skibida I.P., Saharov A.M., Vasil’ev Ju.A., Opejda I.A., Simonov M.A., Timohin V.I., Mironenko N.I., Baranova N.V. [in Russian].
18. Opejda L.I., Simonov M.A., Matvienko A.G. Kinetika okislenija sapropelitovyh uglej v shhelochnyh seredah. Naukovi praci DonNTU. 2009. Serija «Himija i himichna tehnologija», vip. 144: 104-109 [in Russian].
19. Opejda L.I. Kinetika okislenija gumusovyh uglej v dimetilsul’fokside. Himija tverdogo topliva. 2010, N 2: 41-46 [in Russian].
20. Kucher R.V., Kompanec V.A., Butuzova L.F. Struktura iskopaemyh uglej i ih sposobnost’ k okisleniju. Kyiv: Nauk. Dumka, 1980 [in Russian].
21. Suresh A.K., Sharma M.M., Sridhar T. Engineering aspects of industrial liquid phase air oxidation of hydrocarbons. Industrial & Engineering Chemistry Research. 2000. V. 39: 3958-3997.
http://dx.doi.org/10.1021/ie0002733
22. Opejda I. A., Kasjanchuk M. G. Okislenie antrona kislorodom v DMSO. Zhurnal organicheskoj himii. 2002. T. 38. Vyp. 6: 946-947 [in Russian].
23. Serdjuk A. A., Kasjanchuk M. G., Kapitanov I. V., Opejda I. A. Mehanizm kataliza alifaticheskimi aminami reakcii okislenija antrona molekuljarnym kislorodom. Teor. i jeksperim. himija. 2011. 47(2): 122-125 [in Russian].