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Aerobic oxidation behavior of α-ionone catalyzed by N-hydroxyphthalimide combined with acetylacetone cobalt(II)

  • Rui-ren Tang (唐瑞仁)Email author
  • Ya-ping Zhou (周亚平)
  • Nian-hua Gong (龚年华)
  • Yu Zhao (赵瑜)
Article
  • 103 Downloads

Abstract

A practical catalytic method to oxidize α-ionone with molecular oxygen using N-hydroxyphthalimide(NHPI) combined with acetylacetone cobatt(II) (Co(acac)2) was developed, and the probable catalytic mechanism was proposed. The influences of the reaction conditions on conversion of α-ionone and the selectivity of the major product (5-keto-α-ionone) were investigated, and the technical parameters for 5-keto-α-ionone were optimized. The results show that the primary product is 5-keto-α-ionone, and by-products include epoxy-α-ionone, as well as rearrangement products 4-keto-β-ionone and epoxy-β-ionone, which are characterized by infrared spectra, proton nuclear magnetic resonance spectra, mass spectra and elemental analysis. The selectivity of 5-keto-α-ionone and the conversion of α-ionone are 55.0% and 97.0%, respectively, when 30%(molar fraction) NHPI, 1.0%(molar fraction) Co(acac)2 and no solvent are employed under O2 pressure of 1.0 MPa and the reaction temperature of 65 °C for 11 h. The procedure shows good reproducibility in the parallel experiments.

Key words

catalytic oxidation α-ionone 5-keto-α-ionone N-hydroxyphthalimide 

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References

  1. [1]
    PUNNIYAMURTHY T, VELUSAMY S, IQBAL J. Recent advances in transition metal catalyzed oxidation of organic substrates with molecular oxygen [J]. Chemical Reviews, 2005, 105(6): 2329–2363.CrossRefGoogle Scholar
  2. [2]
    RAJABI F, KARIMI B. Efficient aerobic oxidation of alcohols using a novel combination N-hydroxyphthalimide(NHPI) and a recyclable heterogeneous cobalt complex [J]. Journal of Molecular Catalysis A: Chemical, 2005, 232(1/2): 95–99.CrossRefGoogle Scholar
  3. [3]
    KOGUCHI S, KITAZUME T. Synthetic utilities of ionic liquid-supported NHPI complex [J]. Tetrahedron Lett, 2006, 47(16): 2797–2801.CrossRefGoogle Scholar
  4. [4]
    COSERI S, MENDENHALL G D, INGOLD K U. Mechanisms of reaction of aminoxyl (nitroxide), iminoxyl, and imdoxyl radicals with alkenes and evidence that in the presence of lead tetraacetate, N-Hydroxyphthalimide reacts with alkenes by both radical and nonradical mechanisms [J]. Journal of Organic Chemistry, 2005, 70(12): 4629–4636.CrossRefGoogle Scholar
  5. [5]
    ISHII Y, SAKAGUCHI S. A new strategy for alkane oxidation with O2 using N-hydroxyphthalimide(NHPI) as a radical catalyst [J]. Catalysis Surveys from Japan, 1999, 3(1): 27–35.CrossRefGoogle Scholar
  6. [6]
    IWAHAMA T, HATTA G, SAKAGUCHI S, ISHII Y. Epoxidation of alkenes using alkyl hydroperoxides generated in situ by catalytic autoxidation of hydrocarbons with dioxygen [J]. Chemical Communications, 2000(2): 163–164.Google Scholar
  7. [7]
    JIANG Si-cui, WU Yang, LI Jun, LIÜ Zhi-ping, LIU Hui. Synthesis of rare fragrance precursor used in tobacco [J]. Fragrance Flavor Cosmetic, 2003, 5(5): 5–6. (in Chinese)Google Scholar
  8. [8]
    ALEU J, BRENNA E, FUGANTI C, SERRA S. Lipase-mediated synthesis of the enantiomeric forms of 4,5-epoxy-4,5-dihydro-α-ionone and 5, 6-epoxy-5, 6-dihydro-β-ionone: A new direct access to enantiopure (R)-and (S)-α-ionone[J]. Journal of the Chemical Society, Perkin Transactions. 1: Organic and Bio-Organic Chemistry, 1999, 999(3): 271–278.CrossRefGoogle Scholar
  9. [9]
    LIU J, COLMENARES L U, LIU R S M. Fluorinated astaxanthins [J]. Tetrahedron Lett, 1997, 38(49): 8495–8498.CrossRefGoogle Scholar
  10. [10]
    LUO Yi-ming, LIU Chang-hui, TANG Rui-ren, YANG Hua-wu. Synthesis of 4-oxo-β-ionone by oxidation of sodium chlorate [J]. Journal of Central South University: Science and Technology, 2006, 37(3): 521–526. (in Chinese)Google Scholar
  11. [11]
    PENG Qian-rong, YANG Min, XIE Ru-gang, SONG Guang-fu, LIU Zhong-xiang, WANG Dong-shan, CAI Yuan-qing. A synthesis method of oxo-α-ionone, oxo-β-ionone and their ether and ester derivatives by one step. China: 1817842A [P]. 2006-08-16. (in Chinese)Google Scholar
  12. [12]
    ZHUO Guang-lan, ZHAO Wei-juan, JIANG Xuan-zhen. A novel catalyst system for the oxidation of toluene to benzoic acid [J]. Chinese Journal of Organic Chemistry, 2004, 24(8): 962–965. (in Chinese)Google Scholar
  13. [13]
    HIRAI N, SAWATARI N, NAKAMURA N, SAKAGUCHI S, ISHII Y. Oxidation of substituted toluenes with molecular oxygen in the presence of N, N′, N″-trihydroxyisocyanuric acid as a key catalyst [J]. Journal of Organic Chemistry, 2003, 68(17): 6587–6590.CrossRefGoogle Scholar
  14. [14]
    TANG Rui-ren, LIU Chang-hui, LUO Yi-ming, GUO Can-cheng. Studies on the catalytic oxidation of β-ionone to 4-oxo-β-ionone [J]. Journal of Applied Chemistry, 2006, 23(7): 718–723. (in Chinese)Google Scholar
  15. [15]
    SHELDON R A, ARENDS I W C E. Organocatalytic oxidations mediated by nitroxyl radicals [J]. Advanced Synthesis and Catalysis, 2004, 346(9/10): 1051–1071.CrossRefGoogle Scholar
  16. [16]
    FAN Qian, LI Yao-zhong, CHENG Pu-ming, HU Jia-yuan, LI Xian-jun. Studies on allylic oxidation in cyclohexene [J]. Chemical Research and Application, 2001, 13(5): 557–559. (in Chinese)Google Scholar
  17. [17]
    ISHII Y, SAKAGUCHI S. Recent progress in aerobic oxidation of hydrocarbons by N-hydroxyimides [J]. Catalysis Today, 2006, 117(1/3): 105–113.CrossRefGoogle Scholar

Copyright information

© Central South University Press and Springer-Verlag GmbH 2008

Authors and Affiliations

  • Rui-ren Tang (唐瑞仁)
    • 1
    Email author
  • Ya-ping Zhou (周亚平)
    • 1
  • Nian-hua Gong (龚年华)
    • 1
  • Yu Zhao (赵瑜)
    • 2
  1. 1.School of Chemistry and Chemical EngineeringCentral South UniversityChangshaChina
  2. 2.Technology CenterChina Tobacco Hunan Industrial CorporationChangshaChina

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