Perfluorocycloalkene Explained

A perfluorocycloalkene (PFCA) fluorocarbon structure with a cycloalkene core. PFCAs have shown reactivity with a wide variety of nucleophiles including phenoxides, alkoxides, organometallic, amines, thiols, and azoles.[1] They or their derivatives are reported to have nonlinear optical activity,[2] and be useful as lubricants,[3] etching agents,[4] components of fuel cells,[5] low-dielectric materials, and superhydrophobic and oleophobic coatings.[6]

Reactivity

Derivatization of these PFCA rings via displacement of fluorine atoms with nucleophiles occurs through an addition-elimination reaction in the presence of a base. Attack of the nucleophile on the PFCA ring generates a carbanion which can eliminate a fluoride ion, resulting in vinyl substituted and allyl substituted products (Scheme 1). The ratio of vinylic to allylic products depends on the ring size, reaction conditions, and nucleophile.[1] [7]

Under favorable conditions, a good nucleophile can replace all the fluorine atoms on PFCA ring (Scheme 2).[8]

PFCAs have a huge potential to be used as a monomer to produce a variety of polymers. The first time, Smith et al. showed the polycondensation of bisphenols with PFCAs. A unique class of aromatic ether polymers containing perfluorocyclopentenyl (PFCP) enchainment was prepared from the simple step-growth polycondensation of commercial available bisphenols and octafluorocyclopentene (OFCP) in the presence of triethylamine (Scheme 3 and 4).[6] [9]

Smith et al. further extended his recently published work on perfluorocyclopentenyl (PFCP) aryl ether polymers and perfuorocycloalkenyl (PFCA) aryl ether monomers, and reported the synthesis of a new class of fluoropolymers, namely, perfluorocyclohexenyl (PFCH) aryl ether polymers, via step-growth polycondensation of commercial bisphenols and decafluorocycloalkene (DFCH) in the presence of triethylamine (Scheme 5).[7] [10]

Notes and References

  1. Chiral Discrimination in Photochromic Helicenes . Journal of the American Chemical Society . 127 . 20 . 7272–3 . 2005 . Wigglesworth . Tony J. . Sud . David . Norsten . Tyler B. . Lekhi . Vikram S. . Branda . Neil R. . 15898750 . 10.1021/ja050190j.
  2. Synthesis of azo chromophores containing a perfluorocyclo-alkenyl moiety and their second-order optical nonlinearity . Journal of Fluorine Chemistry . 97 . 207–12 . 1999 . Matsui . Masaki . Tsuge . Michinori . Funabiki . Kazumasa . Shibata . Katsuyoshi . Muramatsu . Hiroshige . Hirota . Kazuo . Hosoda . Masahiro . Tai . Kazuo . Shiozaki . Hisayoshi . Kim . Misa . Nakatsu . Kazumi . 1–2 . 10.1016/S0022-1139(99)00050-0.
  3. Web site: Organometallic Derivatives Of Perfluorocycloalkenes - Minnesota Mining Mfg Co,Us . Freepatentsonline.com . 1971-08-25 . 2017-01-05.
  4. Radical kinetics for polymer film deposition in fluorocarbon (C4F8, C3F6 and C5F8) plasmas . Thin Solid Films . 374 . 2 . 303–10 . 2000 . Takahashi . Kazuo . Itoh . Atsushi . Nakamura . Toshihiro . Tachibana . Kunihide . 2000TSF...374..303T . 10.1016/S0040-6090(00)01160-3.
  5. Web site: Patent US20140162173 - Sulfonated perfluorocyclopentenyl polymers and uses thereof - Google Patents . Google.com . 2013-10-09 . 2017-01-05.
  6. Ultra low dielectric, self-cleansing and highly oleophobic POSS-PFCP aryl ether polymer composites . Journal of Materials Chemistry C . 1 . 43 . 7222–7 . 2013 . Sharma . Babloo . Verma . Rajneesh . Baur . Cary . Bykova . Julia . Mabry . Joseph M. . Smith . Dennis W. . 10.1039/C3TC31161A .
  7. Triarylamine-enchained semifluorinated perfluorocycloalkenyl (PFCA) aryl ether polymers . Applied Petrochemical Research . 5 . 35 . 2014 . Sharma . Babloo . Faisal . Mohammad . Liff . Shawna M. . Smith . Dennis W. . 10.1007/s13203-014-0063-0 . free.
  8. Azoles as Reactive Nucleophiles with Cyclic Perfluoroalkenes . Chemistry: A European Journal . 15 . 40 . 10554–62 . 2009 . Garg . Sonali . Twamley . Brendan . Zeng . Zhuo . Shreeve . Jean'ne M. . 19746368 . 10.1002/chem.200901508.
  9. Perfluorocyclopentenyl (PFCP) Aryl Ether Polymers via Polycondensation of Octafluorocyclopentene with Bisphenols . Macromolecules . 45 . 2 . 766–71 . 2012 . Cracowski . Jean-Marc . Sharma . Babloo . Brown . Dakarai K. . Christensen . Kenneth . Lund . Benjamin R. . Smith . Dennis W. . 2012MaMol..45..766C . 10.1021/ma2024599.
  10. Perfluorocyclohexenyl aryl ether polymers via polycondensation of decafluorocyclohexene with bisphenols . Journal of Polymer Science Part A: Polymer Chemistry . 52 . 2 . 232–8 . 2014 . Sharma . Babloo . Hill . Sarah C. . Liff . Shawna M. . Pennington . William T. . Smith . Dennis W. . 2014JPoSA..52..232S . 10.1002/pola.26995 .

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