Skip to main content
SpringerLink
Log in

Fluoroponytailed Crown Ethers and Quaternary Ammonium Salts as Solid-Liquid Phase Transfer Catalysts in Organic Synthesis

  • Chapter
  • First Online:
Fluorous Chemistry

Part of the book series: Topics in Current Chemistry ((TOPCURRCHEM,volume 308))

Abstract

Fluorous derivatives of dibenzo-18-crown-6 ether were prepared, and then successfully applied in representative solid–liquid phase transfer catalysis reactions, which were performed in standard organic solvents, such as chlorobenzene and toluene, as well as in fluorous solvents, such as perfluoro-1,3-dimethylcyclohexane. It was clearly shown that properly designed fluoroponytailed crown ethers could promote the disintegration of the crystal lattice of alkali salts, and transfer anions from the solid surface into an apolar, non-coordinating perfluorocarbon phase, for phase transfer catalysis reactions in organic synthesis. Furthermore, 3,5-bis(perfluorooctyl)benzyl bromide and triethylamine were reacted under mild conditions to provide an analogue of the versatile phase transfer catalyst, benzyltriethylammonium chloride, containing two fluoroponytails. This fluoroponytailed quaternary ammonium salt was also successfully employed as a catalyst in a variety of organic reactions conducted under solid–liquid phase transfer catalysis conditions, without a perfluorocarbon phase. Thus, being both hydrophobic and lipophobic, fluorous crown ethers and ammonium salts, could be rapidly recovered in quantitative yields, and reused without loss of activity, over several reaction cycles.

This is a preview of subscription content, log in via an institution to check access.

Access this chapter

Log in via an institution
Chapter
USD 29.95
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
eBook
USD 259.00
Price excludes VAT (USA)
  • Available as EPUB and PDF
  • Read on any device
  • Instant download
  • Own it forever
Softcover Book
USD 329.99
Price excludes VAT (USA)
  • Compact, lightweight edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info
Hardcover Book
USD 329.99
Price excludes VAT (USA)
  • Durable hardcover edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info

Tax calculation will be finalised at checkout

Purchases are for personal use only

Institutional subscriptions

References

  1. Gokel G (1991) Crown ethers and cryptands. The Royal Society of Chemistry, Cambridge

    Google Scholar 

  2. Montanari F, Quici S, Banfi S (1996) Phase-transfer catalysis. In: Reinhoudt DN (ed) Comprehensive supramolecular chemistry, vol 10. Pergamon, Oxford

    Google Scholar 

  3. Yadav GD (2004) Insight into green phase transfer catalysis. Top Catal 29:145–161

    Article  CAS  Google Scholar 

  4. Quici S, Manfredi A, Pozzi G (2004) Phase-transfer catalysis in environmentally benign reaction media. In: Atwood JL, Steed JW (eds) Encyclopedia of supramolecular chemistry. Dekker, New York

    Google Scholar 

  5. Starks CM, Liotta CL, Halpern M (1994) Phase-transfer catalysis: fundamentals, applications, and industrial perspectives. Chapman & Hall, New York

    Google Scholar 

  6. Sasson Y, Neumann R (eds) (1997) Handbook of phase transfer catalysis. Blackie, London

    Google Scholar 

  7. Desikan S, Doraiswamy LK (1995) The diffusion-reaction problem in triphase catalysis. Ind Eng Chem Res 34:3524–3537, and references cited therein

    Article  CAS  Google Scholar 

  8. Albanese D, Benaglia M, Landini D et al (2002) Use of a quaternary ammonium salt supported on a liposoluble poly(ethylene glycol) matrix for laboratory and industrial synthetic applications of phase-transfer catalysis. Ind Eng Chem Res 41:4928–4935, and references cited therein

    Article  CAS  Google Scholar 

  9. Horváth IT, Rábai J (1994) Facile catalyst separation without water: fluorous biphase hydroformylation of olefins. Science 266:72–75

    Article  Google Scholar 

  10. Gladysz JA, Curran DP, Horváth IT (eds) (2004) Handbook of fluorous chemistry. Wiley-VCH, Weinheim

    Google Scholar 

  11. Pozzi G, Quici S, Fish RH (2008) Fluorous phase transfer catalysts: from onium salts to crown ethers. J Fluor Chem 129:920–929

    Article  CAS  Google Scholar 

  12. Shirakawa S, Tanaka Y, Maruoka K (2004) Development of a recyclable fluorous chiral phase-transfer catalyst: application to the catalytic asymmetric synthesis of α-amino acids. Org Lett 6:1429–1431

    Article  CAS  Google Scholar 

  13. Emnet C, Weber KM, Vidal JA et al (2006) Synthesis and properties of fluorous quaternary phosphonium salts that bear four ponytails: new candidates for phase transfer catalysts and ionic liquids. Adv Synth Catal 348:1625–1634

    Article  CAS  Google Scholar 

  14. Consorti CS, Jurisch M, Gladysz JA (2007) Ionic transformations in extremely nonpolar fluorous media: phase transfer catalysis of halide substitution reactions. Org Lett 9:2309–2312

    Article  CAS  Google Scholar 

  15. Stuart AM, Vidal JA (2007) Perfluoroalkylated 4,13-diaza-18-crown-6 ethers: synthesis, phase-transfer catalysis, and recycling studies. J Org Chem 72:3735–3740

    Article  CAS  Google Scholar 

  16. Pozzi G, Quici S, Fish RH (2008) Perfluorocarbon soluble crown ethers as phase transfer catalysts. Adv Synth Catal 350:2425–2436

    Article  CAS  Google Scholar 

  17. Pozzi G, Mihali V, Foschi F et al (2009) 3,5-Bis(n-perfluorooctyl)benzyltriethylammonium bromide (F-TEBA): an efficient, easily recoverable fluorous catalyst for solid-liquid PTC reactions Adv Synth Catal 351:3072–3076

    Google Scholar 

  18. Vincent J-M, Rabion A, Yachandra VK et al (1997) Fluorous biphasic catalysis: complexation of 1,4,7-[C8F17(CH2)3]3-1,4,7-triazacyclononane with [C8F17(CH2)2CO2)2] (M = Mn, Co) to provide perfluoroheptane-soluble catalysts for alkane and alkene functionalization in the presence of t-BuOOH and O2. Angew Chem Int Ed Engl 36:2346–2349

    Article  CAS  Google Scholar 

  19. Pozzi G, Cavazzini M, Quici S et al (1997) Metal complexes of a tetraazacyclotetradecane bearing highly fluorinated tails: new catalysts for the oxidation of hydrocarbons under fluorous biphasic conditions. Tetrahedron Lett 38:7605–7608

    Article  CAS  Google Scholar 

  20. Pozzi G, Mercs L, Holczknecht O et al (2006) Straightforward synthesis of a fluorous tetraarylporphyrin: efficient and recyclable sensitizer for singlet oxygen generation. Adv Synth Catal 348:1611–1620

    Article  CAS  Google Scholar 

  21. Dubois G, Reyé C, Corriu RJP et al (2000) Organic-inorganic hybrid materials. Preparation and properties of dibenzo-18-crown-6 ether-bridged polysilsesquioxanes. J Mater Chem 10:1091–1098

    Article  CAS  Google Scholar 

  22. Klyatskaya SV, Tetyakov EV, Vasilevsky SF (2003) Synthesis and chemical properties of polyacetylenic derivatives of benzo- and dibenzo-crown ethers. ARKIVOC 13:21–34

    Google Scholar 

  23. Gambaretto G, Conte L, Fornasieri G et al (2003) Synthesis and characterization of a new class of polyfluorinated alkanes: tetrakis(perfluoroalkyl)alkane. J Fluor Chem 121:57–63

    Article  CAS  Google Scholar 

  24. Jeffery T (1996) On the efficiency of tetraalkylammonium salts in Heck type reactions. Tetrahedron 52:10113–10130

    Article  CAS  Google Scholar 

  25. Gourdet B, Singh K, Stuart AM et al (2010) Di(1 H,1 H,2 H,2 H-perfluorooctyl)-dibenzo-18-crown-6: a “light fluorous” recyclable phase transfer catalyst. J Fluor Chem 131:1133–1143

    Article  CAS  Google Scholar 

  26. Pannell KH, Yee W, Lewandos GS et al (1977) Electronic substituent effects upon the selectivity of synthetic ionophores. J Am Chem Soc 99:1457–1461

    Article  CAS  Google Scholar 

  27. Landini D, Maia A (2003) Phase transfer catalysis (PTC): search for alternative organic solvents, even environmentally benign. J Mol Catal A Chem 204–205:235–243, and references therein

    Article  Google Scholar 

  28. Yadav GD, Lande SV (2005) Liquid-liquid-liquid phase transfer catalysis: a novel and green concept for selective reduction of substituted nitroaromatics. Adv Synth Catal 347:1235–1241, and references therein

    Article  CAS  Google Scholar 

  29. Wilson MJ, Pethrick RA, Pugh D et al (1997) Nuclear magnetic resonance and ab initio theoretical studies of 18-crown-6, benzo- and dibenzo-18-crown-6 and their alkali-metal complexes. J Chem Soc Faraday Trans 93:2097–2104

    Article  CAS  Google Scholar 

  30. Gladysz JA, Tesevic V (2008) Temperature-controlled catalyst recycling: new protocols based upon temperature-dependent solubilities of fluorous compounds and solid/liquid phase separations. In: Leitner W, Hölscher M (eds) Regulated systems for multiphase catalysis. Topics in Organometallic Chemistry, vol 23. Springer, Heidelberg, pp 67–89

    Google Scholar 

  31. Starks CM, Owens RM (1973) Phase-transfer catalysis. II. Kinetic details of cyanide displacement on 1-halooctanes. J Am Chem Soc 95:3613–3617

    Article  CAS  Google Scholar 

  32. Arrad O, Sasson Y (1988) Thin-layer phase-transfer catalysis in the reaction of alkyl chlorides and solid formate salt. J Am Chem Soc 110:185–189

    Article  CAS  Google Scholar 

  33. Liotta CL, Berkner J, Wright J et al (1997) Mechanisms and applications of solid-liquid phase-transfer catalysis. In: Halpern ME (ed) Phase transfer catalysis–mechanisms and synthesis. American Chemical Society, Washington DC

    Google Scholar 

  34. Chaouchi M, Loupy A, Marque S et al (2002) Solvent-free microwave-assisted aromatic nucleophilic substitution – synthesis of aromatic ethers. Eur J Org Chem:1278–1283 and references therein

    Google Scholar 

  35. Paradisi C, Quintily U, Scorrano G (1983) Anion activation in the synthesis of ethers from oxygen anions and p-chloronitrobenzene. J Org Chem 48:3022–3026

    Article  CAS  Google Scholar 

  36. Starks CM, Liotta CL, Halpern M (1994) Phase-transfer-catalyzed oxidations. In: Starks CM, Liotta CL, Halpern M (eds) Phase-transfer catalysis: fundamentals, applications, and industrial perspectives. Chapman & Hall, New York

    Google Scholar 

  37. Mandal D, Jurisch M, Consorti CS et al (2008) Ionic transformations in extremely nonpolar fluorous media: easily recoverable phase-transfer catalysts for halide-substitution reactions. Chem Asian J 3:1772–1782

    Article  CAS  Google Scholar 

  38. Mandal D, Gladysz JA (2010) Syntheses of fluorous quaternary ammonium salts and their application as phase transfer catalysts for halide substitution reactions in extremely nonpolar fluorous solvents. Tetrahedron 66:1070–1077

    Article  CAS  Google Scholar 

  39. Shirakawa S, Ueda M, Tanaka Y et al (2007) Design of binaphthyl modified symmetrical chiral phase-transfer catalysts: substituent effect of 4,4’,6,6’-positions of binaphthyl rings in the asymmetric alkylation of a glycine derivative. Chem Asian J 2:1276–1281

    Article  CAS  Google Scholar 

  40. Maayan G, Fish RH, Neumann R (2003) Polyfluorinated quaternary ammonium salts of polyoxometalate anions: fluorous biphasic oxidation catalysis with and without fluorous solvents. Org Lett 5:3547–3550

    Article  CAS  Google Scholar 

  41. Mercs L, Pozzi G, Quici S (2007) Efficient condensation of carboxylic acids with alcohols catalyzed by fluorous ammonium triflates. Tetrahedron Lett 48:3053–3056

    Article  CAS  Google Scholar 

  42. Shen W, Wang L-M, Tian H (2008) Quaternary ammonium salt gemini surfactants containing perfluoroalkyl tails catalyzed one-pot Mannich reactions in aqueous media. J Fluor Chem 129:267–273

    Article  CAS  Google Scholar 

  43. Slávik Z, Tárkányi G, Gömöry Á et al (2001) Convenient syntheses and characterization of fluorophilic perfluorooctyl-propyl amines and ab initio calculations of proton affinities of related model compounds. J Fluor Chem 108:7–14

    Article  Google Scholar 

  44. Albanese D, Landini D, Penso M et al (1999) Synthesis of N-sulfonyl aziridines through regioselective opening of epoxides under solid-liquid PTC conditions. Tetrahedron 55:6387–6394

    Article  Google Scholar 

  45. Penso M, Lupi V, Albanese D et al (2008) A straightforward synthesis of enantiopure 2,6-disubstituted morpholines by a regioselective O-protection/activation protocol. Synlett:2451–2454

    Google Scholar 

  46. Landini D, Penso M (1991) N-Alkylation of trifluoroacetamide with 2-bromo carboxylic esters under PTC conditions: a new procedure for the synthesis of α-amino acids. J Org Chem 56:420–423

    Article  CAS  Google Scholar 

  47. Albanese D, Landini D, Lupi V et al (2000) N-Monoalkylation of α-amino acid esters under solid-liquid PTC conditions. Eur J Org Chem:1443–1449

    Google Scholar 

  48. Lupi V, Penso M, Foschi F et al (2009) Highly stereoselective intramolecular α-arylation of self-stabilized non-racemic enolates: synthesis of α-quaternary α-amino acid derivatives. Chem Commun:5012–5014

    Google Scholar 

  49. Montanari F, Landini D, Rolla F (1982) Phase-transfer catalyzed reactions. In: Vögtle F (ed) Host guest complex chemistry II. Topics in Current Chemistry, vol 101. Springer, Heidelberg

    Google Scholar 

Download references

Acknowledgments

Support by CNR (G.P.) and by the US Department of Energy under Contract No DE AC02-012315CH1 (R.H.F.) is gratefully acknowledged.

Author information

Authors and Affiliations

  1. CNR-Istituto di Scienze e Tecnologie Molecolari, via Golgi 19, 20133, Milano, Italy

    Gianluca Pozzi

  2. Lawrence Berkeley National Laboratory, University of California, Berkeley, CA, 94720, USA

    Richard H. Fish

Authors
  1. Gianluca Pozzi
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Richard H. Fish
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Richard H. Fish .

Editor information

Editors and Affiliations

  1. , Department of Biology and Chemistry, City University of Hong Kong, Tat Chee Avenue, Kowloon, China, People's Republic

    István T. Horváth

Rights and permissions

Reprints and permissions

Copyright information

© 2011 Springer-Verlag Berlin Heidelberg

About this chapter

Cite this chapter

Pozzi, G., Fish, R.H. (2011). Fluoroponytailed Crown Ethers and Quaternary Ammonium Salts as Solid-Liquid Phase Transfer Catalysts in Organic Synthesis. In: Horváth, I. (eds) Fluorous Chemistry. Topics in Current Chemistry, vol 308. Springer, Berlin, Heidelberg. https://doi.org/10.1007/128_2011_240

Download citation

Publish with us

Policies and ethics

Search

Navigation