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Metal-free direct oxidation of α-isophorone to ketoisophorone by I2 under photoirradiation

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Abstract

Molecular iodine was first utilized for direct oxidation of α-isophorone (α-IP) to ketoisophorone (KIP) with molecule oxygen at room temperature and the effects of amount of iodine, solvents and reaction time were investigated extensively. The optimized result shows that 70.2% conversion of α-isophorone and 82.6% selectivity of ketoisophorone are obtained with 15% iodine (molar fraction) in acetonitrile under photoirradiation for 5 h. Moreover, the possible mechanism is proposed.

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References

  1. MURPHY E F, MALLAT T, BAIKER A. Allylic oxofunctionalization of cyclic olefins with homogeneous and heterogeneous catalysts [J]. Catalysis Today, 2000, 57(1/2): 115–126.

    Article  Google Scholar 

  2. ERNST H. Recent advances in industrial carotenoid synthesis [J]. Pure and Applied Chemistry, 2002, 74(11): 2213–2226.

    Article  Google Scholar 

  3. KAZUHARU S, NOBORU K, TOMOHIRO K, YASUO M. Method for preparation of trimethylhydroquinone from isophorone: JP, 11255706 [P]. 1999-12-08.

  4. BONRATH W, SCHNEIDER M. Manufacture of trimethylhydroquinone diacylates: US, 7153994 [P]. 2006-12-26.

  5. FIBRICE A, BONRATH W. Process for the preparation of 2,3,5-trimethylhydroquinone diesters: US, 0123720 [P]. 2007-05-31.

  6. KILL S, HUTHMACHER K. Process for the production of 2,3,5-trimethylhydroquinone diesters: US, 6417409 [P]. 2002-07-09.

  7. BECK C, MALLAT T, BAIKER A. Oxidation-isomerization of an olefin to allylic alcohol using titania-silica and a base co-catalyst [J]. Journal of Catalysis, 2000, 195(1): 79–87.

    Article  Google Scholar 

  8. BECKER J J, HOCHSTRASSER U P, SKORIANETZ W. Process for the preparation of oxophorones: US, 3,944,620 [P]. 1976-03-16.

  9. WIDMER, MUNCHENSTEIN C H, EAST BRIGHTON A U. Ketoisophorone manufacture: US, 3,960,966 [P]. 1976-06-01.

  10. MURPHY E F, BAIKER A. Advances in homogeneous and heterogeneous catalytic aerobic oxidation of isophorone to ketoisophorone [J]. Journal of Molecular Catalysis A: Chemical, 2002, 179: 233–241.

    Article  Google Scholar 

  11. MURPHY E F, SCHNEIDER M, MALLAT T, BAIKER A. Enhanced catalytic activity and selectivity in oxidation of α-isophorone to ketoisophorone with phosphomolybdic acid [J]. Synthesis, 2001, 4: 547–549.

    Article  Google Scholar 

  12. JOSEPH T, HALLIGUDI S B, SATYANARAYAN C, SAWANT D P, GOPINATHAN S. Oxidation by molecular oxygen using zeolite encapsulated Co(II)saloph complexes [J]. Journal of Molecular Catalysis A: Chemical, 2001, 168(1/2): 87–97.

    Article  Google Scholar 

  13. MURPHY E F, MALLAT T, BAIKER A, SCHNEIDER M. Catalytic gas phase oxidation of isophorone to ketoisophorone [J]. Applied Catalysis A: General, 2000, 197: 295–301.

    Article  Google Scholar 

  14. HANYU A, SAKURAI Y, FUJIBAYASHI S, SAKAGUCHI S, ISHII Y. Selective aerobic oxidation of isophorone catalyzed by molybdovanadophosphate supported on carbon (NPMoV/C) Tetrahedron Letters, 1997, 38(32): 5659–5662.

    Article  Google Scholar 

  15. WANG Cong-min, WANG Guo-liang, MAO Jian-yong, ZHEN Yao, LI Hao-ran. Metal and solvent-free oxidation of α-isophorone to ketoisophorone by molecular oxygen [J]. Catalysis Communication, 2010, 11: 758–762.

    Article  Google Scholar 

  16. BASU M K, SAMAJDAR M K, BECKER F F, BANIK B K. A new molecular iodine-catalyzed acetalization of carbonyl compounds [J]. Synlett, 2002, 2: 319.

    Article  Google Scholar 

  17. YADAV J S, REDDY B V S, RAO C, SABITHA V, REDDY M J. Molecular iodine-catalyzed highly stereoselective synthesis of sugar acetylenes [J]. Synthesis, 2003(2): 247–250.

  18. ITOH A, KODAMA T, MASAKI Y. New synthetic method of benzaldehydes and α, β-unsaturated aldehydes with I2 under photoirradiation [J]. Chemistry Letters, 2001, 30(2): 686–687.

    Article  Google Scholar 

  19. CONSTANTINI M, DROMARD A, JOUFFRET M, BROSSARD B, VARAGNAT J. Selective oxidation of 3,5,5-trimethylcyclohexene-3 one ({β}-isophorone) to 3,5,5-trimethylcyclohexene-1,4, diones by oxygen catalyzed by MnII OR CoII chelates [J]. Journal Molecular Catalysis, 1980, 7(1): 89–97.

    Article  Google Scholar 

  20. TODRES Z V. Organic ion radicals: Chemistry and applications [M]. New York: Marcel Dekker Inc., 2003: 424.

    Google Scholar 

  21. YANG Guan-yu, MA Yin-fa, XU Jie. Biomimetic catalytic system driven by electron transfer for selective oxygenation of hydrocarbon [J]. Journal of the American Chemical Society, 2004, 126(34): 10542–10543.

    Article  Google Scholar 

  22. EVANS S, SMITH J R L. The oxidation of ethylbenzene by dioxygen catalyzed by supported iron porphyrins derived from iron(III) tetrakis(pentafluorophenyl)porphyrin [J]. Journal of the American Chemical Society, 2000, 121(2): 1511–1543.

    MathSciNet  Google Scholar 

  23. EVANS S, SMITH J R L. Justus Liebig’s Annalen der Chemie [J]. Journal of the American Chemical Society, 2001, 2(4): 174–188.

    Google Scholar 

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Authors and Affiliations

  1. School of Biology and Chemical Engineering, Jiaxing University, Jiaxing, 314000, China

    Ji-qing Bao  (保积庆)

  2. School of Chemistry and Chemical Engineering, Central South University, Changsha, 410083, China

    Li-hua Chen  (陈梨花), Rui-ren Tang  (唐瑞仁), Lin-ying Cao  (曹林英) & Shan Liang  (梁珊)

Authors
  1. Ji-qing Bao  (保积庆)
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  2. Li-hua Chen  (陈梨花)
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  3. Rui-ren Tang  (唐瑞仁)
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  4. Lin-ying Cao  (曹林英)
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  5. Shan Liang  (梁珊)
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Corresponding author

Correspondence to Rui-ren Tang  (唐瑞仁).

Additional information

Foundation item: Project(21071152) supported by the National Natural Science Foundation of China

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Bao, Jq., Chen, Lh., Tang, Rr. et al. Metal-free direct oxidation of α-isophorone to ketoisophorone by I2 under photoirradiation. J. Cent. South Univ. 19, 2755–2759 (2012). https://doi.org/10.1007/s11771-012-1338-1

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  • DOI: https://doi.org/10.1007/s11771-012-1338-1

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