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.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
References
Gokel G (1991) Crown ethers and cryptands. The Royal Society of Chemistry, Cambridge
Montanari F, Quici S, Banfi S (1996) Phase-transfer catalysis. In: Reinhoudt DN (ed) Comprehensive supramolecular chemistry, vol 10. Pergamon, Oxford
Yadav GD (2004) Insight into green phase transfer catalysis. Top Catal 29:145–161
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
Starks CM, Liotta CL, Halpern M (1994) Phase-transfer catalysis: fundamentals, applications, and industrial perspectives. Chapman & Hall, New York
Sasson Y, Neumann R (eds) (1997) Handbook of phase transfer catalysis. Blackie, London
Desikan S, Doraiswamy LK (1995) The diffusion-reaction problem in triphase catalysis. Ind Eng Chem Res 34:3524–3537, and references cited therein
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
Horváth IT, Rábai J (1994) Facile catalyst separation without water: fluorous biphase hydroformylation of olefins. Science 266:72–75
Gladysz JA, Curran DP, Horváth IT (eds) (2004) Handbook of fluorous chemistry. Wiley-VCH, Weinheim
Pozzi G, Quici S, Fish RH (2008) Fluorous phase transfer catalysts: from onium salts to crown ethers. J Fluor Chem 129:920–929
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
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
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
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
Pozzi G, Quici S, Fish RH (2008) Perfluorocarbon soluble crown ethers as phase transfer catalysts. Adv Synth Catal 350:2425–2436
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
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
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
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
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
Klyatskaya SV, Tetyakov EV, Vasilevsky SF (2003) Synthesis and chemical properties of polyacetylenic derivatives of benzo- and dibenzo-crown ethers. ARKIVOC 13:21–34
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
Jeffery T (1996) On the efficiency of tetraalkylammonium salts in Heck type reactions. Tetrahedron 52:10113–10130
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
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
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
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
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
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
Starks CM, Owens RM (1973) Phase-transfer catalysis. II. Kinetic details of cyanide displacement on 1-halooctanes. J Am Chem Soc 95:3613–3617
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
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
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
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
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
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
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
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
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
Mercs L, Pozzi G, Quici S (2007) Efficient condensation of carboxylic acids with alcohols catalyzed by fluorous ammonium triflates. Tetrahedron Lett 48:3053–3056
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
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
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
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
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
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
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
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
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
Corresponding author
Editor information
Editors and Affiliations
Rights 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
DOI: https://doi.org/10.1007/128_2011_240
Published:
Publisher Name: Springer, Berlin, Heidelberg
Print ISBN: 978-3-642-25233-4
Online ISBN: 978-3-642-25234-1
eBook Packages: Chemistry and Materials ScienceChemistry and Material Science (R0)