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Aerobic Oxidation of Cyclopentane by Using Fluorinated N-Hydroxyphthalimide Derivatives

Received: Mar. 03, 2020    Accepted: Apr. 07, 2020    Published: Apr. 28, 2020
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Abstract

N-Hydroxyphthalimide derivatives, F15- and F17-NHPI, bearing fluorinated carboxylate and alkyl chains, respectively, were prepared and their catalytic performances were compared with those of N-hydroxyphthalimide (NHPI). Thus, the oxidation of cyclopentane under 10 atm of air in the presence of catalytic amount of fluorinated NHPI or NHPI, Co(OAc)2, and Mn(OAc)2 in TFT as solvent at 100°C afforded cyclopentanol, cyclopentanone, succinic acid and glutaric acid. It was assumed that F-NHPI derivatives bearing electron withdrawing fluorocarbon groups showed higher catalytic activity than the NHPI by enhancement of the electrophilicity of N-oxy radicals generated from the F-NHPI derivatives. In the oxidation of cyclopentane, F-NHPI showed better catalytic activity than NHPI. Cyclopentanol and glutaric acid were obtained as the major products in case of NHPI, whereas, cyclopentanone and glutaric acid were obtained as the major products in case of fluorinated NHPIs. However, only glutaric acid was obtained as the major product when a increased amount of Co(OAc)2 was used in the present ocidation by using NHPI or F-NHPIs. The effect of temperature and air was also investigated in the oxidation of cyclopentane. When the oxidation was performed at 90°C, cyclopentanol was obtained as the major product, whereas, no significant changes were observed when the reaction was performed at 20 atm instead of 10 atm. The great advantage of the fluorinated NHPI derivatives is that it could be recovered after the oxidation.

DOI 10.11648/j.sjc.20200802.13
Published in Science Journal of Chemistry ( Volume 8, Issue 2, April 2020 )
Page(s) 36-41
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This is an Open Access article, distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution and reproduction in any medium or format, provided the original work is properly cited.

Copyright

Copyright © The Author(s), 2024. Published by Science Publishing Group

Keywords

Aerobic Oxidation, Cyclopentane, F-NHPI Catalyst, Recovery

References
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[2] K. Weissermel and H.-J. Arpe, Industrial Organic Chemistry (4th edn., Wiley-VCH, Weinheim, 2003) pp 239–246.
[3] N. M. Emanuel, E. T. Denisov and Z. K. Marizus, Liquid-Phase Oxidation of Hydrocarbons (Plenum Press, New York, 1967) pp. 309-346.
[4] T. F. Garetto and C. R. Apesteguía, Oxidative catalytic removal of hydrocarbons over Pt/Al2O3 catalysts, Catal. Today, 2000, 62, pp 189-199.
[5] J. G. D. Schulz and A. Onopchenko, Process for converting cyclopentane to glutaric acid, US 4158739 A (June 19, 1979).
[6] G. S. Mishra, J. J. R. F. Silva and A. J. L. Pombeiro, Supported bis(maltolato)oxovanadium complexes as catalysts for cyclopentane and cyclooctane oxidations with dioxygen, J. of molecular catalysis A: Chemical, 2007, 265, pp 59-69.
[7] D. Lisicki and B. Orlinska, Oxidation of cycloalkanes catalysed by N-hydroxyimides in supercritical carbon dioxide, Chem. Papers, 2020, 74, pp 711-716.
[8] R. Singh, M. S. Guzmand and A. Bose, Anaerobic oxidation of ethane, propane and butane by marine microbes: A mini review, Front. Microbiol, 2017, 8, pp 1-8.
[9] A. Staykov and K. Yoshizawa, Aerobic oxidation of alkanes on icosahedron gold nanoparticle Au55, J. of Catal., 2018, 364, pp 141-153.
[10] A. E. Shilov and G. B. Shul’pin, Activation and Catalytic Reactions of Saturated Hydrocarbons in the Presence of Metal Complexes (Kluwer Academic Publishers, Dordrecht, The Netherlands, 2000) pp 55 and 388.
[11] F. Recupero and C. Punta, Free Radical Functionalization of Organic Compounds Catalyzed by N-Hydroxyphthalimide, Chem. Rev., 2007, 107, pp 3800-3842.
[12] Y. Ishii and S. Sakaguchi, Recent progress in aerobic oxidation of hydrocarbons by N-hydroxyimides, Catal. Today, 2006, 117, pp 105-113.
[13] Y. Ishii, K. Nakayama, M. Takeno, S. Sakaguchi, T. Iwahama and Y. Nishiyama, Novel catalysis by N-hydroxyphthalimide in the oxidation of organic substrates by molecular oxygen, J. Org. Chem., 1995, 60, pp 3934-3935.
[14] Y. Ishii, T. Iwahama, S. Sakaguchi, K. Nakayama and Y. Nishiyama, Alkane oxidation with molecular oxygen using a new efficient catalytic system: N-hydroxyphthalimide (NHPI) combined with Co(acac)n (n = 2 or 3), J. Org. Chem., 1996, 61, pp 4520-4526.
[15] Y. Ishii, S. Sakaguchi and T. Iwahama, Innovation of hydrocarbon oxidation with molecular oxygen and related reactions, Adv. Synth. Catal., 2001, 343, pp 393-427.
[16] N. Sawatari, T. Yokota, S. Sakaguchi and Y. Ishii, Alkane oxidation with air catalyzed by lipophilic N-hydroxyphthalimides without any solvent, J. Org. Chem., 2001, 66, pp 7889-7891.
[17] S. K. Guha, Y. Obora, D. Ishihara, H. Matsubara, I. Ryu and Y. Ishii, Aerobic oxidation of cyclohexane using N-hydroxyphthalimide bearing fluoroalkyl chains, Adv. Synth. Catal., 2008, 350, pp 1323-1330.
[18] B. B. Wentzel, M. P. J. Donners, P. L. Alsters, M. C. Feiters and R. J. M. Nolte, N-hydroxyphthalimide/Cobalt (II) catalyzed low temperature benzylic oxidation using molecular oxygen, Tetrahedron, 2000, 56, pp 7797-7803.
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    Samar Kumar Guha, Yasutaka Ishii. (2020). Aerobic Oxidation of Cyclopentane by Using Fluorinated N-Hydroxyphthalimide Derivatives. Science Journal of Chemistry, 8(2), 36-41. https://doi.org/10.11648/j.sjc.20200802.13

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    ACS Style

    Samar Kumar Guha; Yasutaka Ishii. Aerobic Oxidation of Cyclopentane by Using Fluorinated N-Hydroxyphthalimide Derivatives. Sci. J. Chem. 2020, 8(2), 36-41. doi: 10.11648/j.sjc.20200802.13

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    AMA Style

    Samar Kumar Guha, Yasutaka Ishii. Aerobic Oxidation of Cyclopentane by Using Fluorinated N-Hydroxyphthalimide Derivatives. Sci J Chem. 2020;8(2):36-41. doi: 10.11648/j.sjc.20200802.13

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  • @article{10.11648/j.sjc.20200802.13,
      author = {Samar Kumar Guha and Yasutaka Ishii},
      title = {Aerobic Oxidation of Cyclopentane by Using Fluorinated N-Hydroxyphthalimide Derivatives},
      journal = {Science Journal of Chemistry},
      volume = {8},
      number = {2},
      pages = {36-41},
      doi = {10.11648/j.sjc.20200802.13},
      url = {https://doi.org/10.11648/j.sjc.20200802.13},
      eprint = {https://download.sciencepg.com/pdf/10.11648.j.sjc.20200802.13},
      abstract = {N-Hydroxyphthalimide derivatives, F15- and F17-NHPI, bearing fluorinated carboxylate and alkyl chains, respectively, were prepared and their catalytic performances were compared with those of N-hydroxyphthalimide (NHPI). Thus, the oxidation of cyclopentane under 10 atm of air in the presence of catalytic amount of fluorinated NHPI or NHPI, Co(OAc)2, and Mn(OAc)2 in TFT as solvent at 100°C afforded cyclopentanol, cyclopentanone, succinic acid and glutaric acid. It was assumed that F-NHPI derivatives bearing electron withdrawing fluorocarbon groups showed higher catalytic activity than the NHPI by enhancement of the electrophilicity of N-oxy radicals generated from the F-NHPI derivatives. In the oxidation of cyclopentane, F-NHPI showed better catalytic activity than NHPI. Cyclopentanol and glutaric acid were obtained as the major products in case of NHPI, whereas, cyclopentanone and glutaric acid were obtained as the major products in case of fluorinated NHPIs. However, only glutaric acid was obtained as the major product when a increased amount of Co(OAc)2 was used in the present ocidation by using NHPI or F-NHPIs. The effect of temperature and air was also investigated in the oxidation of cyclopentane. When the oxidation was performed at 90°C, cyclopentanol was obtained as the major product, whereas, no significant changes were observed when the reaction was performed at 20 atm instead of 10 atm. The great advantage of the fluorinated NHPI derivatives is that it could be recovered after the oxidation.},
     year = {2020}
    }
    

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  • TY  - JOUR
    T1  - Aerobic Oxidation of Cyclopentane by Using Fluorinated N-Hydroxyphthalimide Derivatives
    AU  - Samar Kumar Guha
    AU  - Yasutaka Ishii
    Y1  - 2020/04/28
    PY  - 2020
    N1  - https://doi.org/10.11648/j.sjc.20200802.13
    DO  - 10.11648/j.sjc.20200802.13
    T2  - Science Journal of Chemistry
    JF  - Science Journal of Chemistry
    JO  - Science Journal of Chemistry
    SP  - 36
    EP  - 41
    PB  - Science Publishing Group
    SN  - 2330-099X
    UR  - https://doi.org/10.11648/j.sjc.20200802.13
    AB  - N-Hydroxyphthalimide derivatives, F15- and F17-NHPI, bearing fluorinated carboxylate and alkyl chains, respectively, were prepared and their catalytic performances were compared with those of N-hydroxyphthalimide (NHPI). Thus, the oxidation of cyclopentane under 10 atm of air in the presence of catalytic amount of fluorinated NHPI or NHPI, Co(OAc)2, and Mn(OAc)2 in TFT as solvent at 100°C afforded cyclopentanol, cyclopentanone, succinic acid and glutaric acid. It was assumed that F-NHPI derivatives bearing electron withdrawing fluorocarbon groups showed higher catalytic activity than the NHPI by enhancement of the electrophilicity of N-oxy radicals generated from the F-NHPI derivatives. In the oxidation of cyclopentane, F-NHPI showed better catalytic activity than NHPI. Cyclopentanol and glutaric acid were obtained as the major products in case of NHPI, whereas, cyclopentanone and glutaric acid were obtained as the major products in case of fluorinated NHPIs. However, only glutaric acid was obtained as the major product when a increased amount of Co(OAc)2 was used in the present ocidation by using NHPI or F-NHPIs. The effect of temperature and air was also investigated in the oxidation of cyclopentane. When the oxidation was performed at 90°C, cyclopentanol was obtained as the major product, whereas, no significant changes were observed when the reaction was performed at 20 atm instead of 10 atm. The great advantage of the fluorinated NHPI derivatives is that it could be recovered after the oxidation.
    VL  - 8
    IS  - 2
    ER  - 

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Author Information
  • Department of Arts and Sciences, Ahsanullah University of Science and Technology, Dhaka, Bangladesh

  • Department of Chemistry and Materials Engineering, Kansai University, Suita, Osaka, Japan

  • Section