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T. Fukuyama Department of Chemistry, Graduate School of Science, Osaka Prefecture University, Gakuen-cho1-1, Naka-ku, Sakai, Osaka, 599-8531, Japan

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Md. T. Rahman Department of Chemistry, Graduate School of Science, Osaka Prefecture University, Gakuen-cho1-1, Naka-ku, Sakai, Osaka, 599-8531, Japan

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N. Kamata Department of Chemistry, Graduate School of Science, Osaka Prefecture University, Gakuen-cho1-1, Naka-ku, Sakai, Osaka, 599-8531, Japan

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M. Tokizane Department of Chemistry, Graduate School of Science, Osaka Prefecture University, Gakuen-cho1-1, Naka-ku, Sakai, Osaka, 599-8531, Japan

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Y. Fukuda Department of Chemistry, Graduate School of Science, Osaka Prefecture University, Gakuen-cho1-1, Naka-ku, Sakai, Osaka, 599-8531, Japan

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I. Ryu Department of Chemistry, Graduate School of Science, Osaka Prefecture University, Gakuen-cho1-1, Naka-ku, Sakai, Osaka, 599-8531, Japan

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Abstract

Fluorous multi-phase bromination reaction of alkenes could be successfully transformed to a continuous microflow system in which a fluorous polyether, Galden® HT135, is employed as a recyclable molecular bromine support. This microflow bromination of alkenes could be carried out without any temperature control or an inert gas atmosphere. The circulatory continuous microflow reaction system for bromination of cyclohexene was created which gave 8.3 g (85%) of dibromocyclohexane after continuous operation for 6 h.

  • 1. Reviews on fluorous solvents: (a) Maul, J. J.; Ostrowski, P. J.; Ublacker, G. A.; Linclau, B.; Curran, D. P. Top. Curr. Chem. 1999, 206, 79;

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    (b) Matsubara, H.; Ryu, I. Top. Curr. Chem. 2012, 308, 135.

  • 2. (a) Ryu, I.; Matsubara, H.; Yasuda, S.; Nakamura, H.; Curran, D. P. J. Am. Chem. Soc. 2001, 124, 12946;

    (b) Matsubara, H.; Yasuda, S.; Ryu, I. Synlett 2003, 247;

    (c) Rahman, M. T.; Kamata, N.; Matsubara, H.; Ryu, I. Synlett 2005, 2664;

    (d) Matsubara, H.; Tsukida, M.; Ishihara, D.; Kuniyoshi, K.; Ryu, I. Synlett 2010, 13, 2014.

  • 3. Review on phase vanishing methods, see: Ryu, I.; Matsubara, H.; Nakamura, H.; Curran, D. P. Chem. Rec. 2008, 8, 351.

  • 4. For selected reviews, see: (a) Wirth, T. Microreactors in Organic Synthesis and Catalysis, Wiley-VCH, Weinheim, 2008;

    (b) Hessel, V.; Renken, A.; Schouten, J. C.; Yoshida, J. Micro Process Engineering, Wiley-VCH, Verlag, 2009;

    (c) Mason, B. P.; Price, K. E.; Steinbacher, J. L.; Bogdan, A. R.; McQuade, D. T. Chem. Rev. 2007, 107, 2300;

    (d) Yoshida, J.; Nagaki, A.; Yamada, T. Chem. Eur. J. 2008, 14, 7450;

    (e) Lin, W.-Y.; Wang, Y.; Wang, S.; Tseng, H.-R. Nano Today 2009, 4, 470;

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    (g) Webb, D.; Jamison, T. F. Chem. Sci. 2010, 675;

    (h) Yoshida, J. Chem. Rec. 2010, 10, 332;

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    (l) Ley, S. V. Chem. Rec. 2012, 12, 378;

    (m) Wiles, C.; Watts, P. Green Chem. 2012, 14, 38.

  • 5. For our reviews, see: (a) Fukuyama, T.; Rahman, M. T.; Sato, M.; Ryu, I. Synlett 2008, 151;

    (b) Fukuyama, T.; Ryu, I. Green Process Synth. 2012, 1, 412.

  • 6. For bromination using a microreactor, see: (a) Löb, P.; Löve, H.; Hessel, V. J. Fluorine Chem. 2004, 125, 1677;

    (b)Cygan, Z. T.; Cabral, J. T.; Beers, K. L.; Amis, E. J. Langmuir 2005, 21, 3629;

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  • 7. Physical properties were taken from http://www.solvayplastics.com/sites/solvayplastics/EN/specialty_polymers/Pages/solvay-specialty-polymers.aspx.

  • 8. http://www.michs.jp/.

  • 9. (a) Liu, S.; Fukuyama, T.; Sato, M.; Ryu, I. Org. Process Res. Dev. 2004, 8, 477;

    (b) Fukuyama, T.; Rahman, M. T.; Sumino, Y.; Ryu, I. Synlett 2012, 23, 2279.

  • 10. Continuous microflow bromination of cyclohexene with a circulatory recycling of Galden: a hexane solution of cyclohexene (75 mmol, 6.16 g) was loaded into a container (0.75 M, 100 mL). Galden HT135 (50 mL), bromine (excess), and water were loaded into another container. Saturated Br2 solution in Galden HT135 was prepared with gentle stirring. Flow rates were adjusted to 0.15 mL/min for cyclohexene solution and 1.2 mL/min for saturated bromine solution, and the two solutions were mixed in a T-shaped micromixer (MiChS®α-400, 400 μm i.d.). The mixture was then fed into the residence time unit (500 μm i.d. × 3.4 m, residence time: 2 min). The reaction mixture was then mixed with 0.3 M basic Na2S2O3 aqueous solution in another T-shaped mixer (MiChS®α-400, 400 μm i.d.), and the entire mixture was collected in a Y-shaped flask, where a small amount of CHCl3 was placed. The bottomed fluorous solvent was pumped back to the container containing bromine. This system was operated for 6 hours, and consumed 40.5 mmol of cyclohexene. The top organic phase was separated from the aqueous phase, and the aqueous phase was extracted with hexane. Combined organic phase was dried over MgSO4. The solvent was removed under reduced pressure to give colorless oil (8.91 g), which was purified by short silica gel column chromatography to give pure dibromocyclohexane (8.3 g, 85%).

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Journal of Flow Chemistry
Language English
Size A4
Year of
Foundation
2011
Volumes
per Year
1
Issues
per Year
4
Founder Áramlásos Kémiai Tudományos Társaság
Founder's
Address
H-1031 Budapest, Hungary Záhony utca 7.
Publisher Akadémiai Kiadó
Springer Nature Switzerland AG
Publisher's
Address
H-1117 Budapest, Hungary 1516 Budapest, PO Box 245.
CH-6330 Cham, Switzerland Gewerbestrasse 11
Responsible
Publisher
Chief Executive Officer, Akadémiai Kiadó
ISSN 2062-249X (Print)
ISSN 2063-0212 (Online)