Nafion reaction

Many superacid-catalyzed reactions were found to be carried out advantageously not only using liquid superacids but also over solid superacids, including Nafion-H or certain zeolites. We extensively studied the catalytic activity of Nafion-H and related solid acid catalysts (including supported perfluorooctanesulfonic acid and its higher ho-... 

Whereas superaeid (HF/BF3, HF/SbF, HF/TaF FS03FI/SbF3, etc.)-eatalyzed hydroearbon transformations were first explored in the liquid phase, subsequently, solid aeid eatalyst systems, sueh as those based on Nafion-H, longer-chain perfluorinated alkanesulfonic acids, fluorinated graphite intercalates, etc. were also developed and utilized for heterogeneous reactions. The strong acidic nature of zeolite catalysts was also successfully explored in cases such as FI-ZSM-5 at high temperatures. 

Another type of soHd supetacid is based on perfluorinated resin sulfonic acid such as the acid form of Du Font s Nafion resin, a copolymer of a perfluorinated epoxide and vinylsulfonic acid or soHd, high molecular weight petfluotoalkanesulfonic acids such as petfluotodecanesulfonic acid, CF2(CF2)qS02H. Such sohd catalysts have been found efficient in many alkylations of aromatic hydrocarbons (225) and other Friedel-Crafts reactions (226). 

Me3SiCH2CH=CH2i TsOH, CH3CN, 70-80°, 1-2 h, 90-95% yield. This silylating reagent is stable to moisture. Allylsilanes can be used to protect alcohols, phenols, and carboxylic acids there is no reaction with thiophenol except when CF3S03H is used as a catalyst. The method is also applicable to the formation of r-butyldimethylsilyl derivatives the silyl ether of cyclohexanol was prepared in 95% yield from allyl-/-butyldi-methylsilane. Iodine, bromine, trimethylsilyl bromide, and trimethylsilyl iodide have also been used as catalysts. Nafion-H has been shown to be an effective catalyst. 

An interesting development of this research is the preparation of polymer-supported FITS reagent from bis(trifluoroacetoxy)iodoperfluoroalkanes and Nafion-H [145]. FITS-Nafion reacts with organic substrates that react to usual FITS reagents, but the products of the perfluoroalkylation reaction can be separated easily from the insoluble resin by filtration [145]... 

As catalysts Lewis acids such as AICI3, TiCU, SbFs, BF3, ZnCh or FeCl3 are used. Protic acids such as FI2SO4 or FIF are also used, especially for reaction with alkenes or alcohols. Recent developments include the use of acidic polymer resins, e.g. Nafion-Fl, as catalysts for Friedel-Crafts alkylations and the use of asymmetric catalysts. ... 

Deng and Peng have found that certain ionic liquids catalyze the Biginelli reaction [62]. Usually, this reaction is catalyzed by Lewis acids such as InCl3, [Fe(H20)6]Cl3, or BF3.0(C2H5)2, or by acid catalysts such as Nafion-H. The reaction was found to give yields in the 77-99 % range in the ionic liquids [BMIM][PF6] or [BMIM][BF4] for the examples in Scheme 5.1-34. The reaction fails if there is no ionic liquid present or in the presence of tetrabutylammonium chloride. 

This equation is always valid at steady state and has been originally derived for the case of NEMCA in alkaline solutions.37 In the present case of the acidic environment in the Nafion electrolyte the following two electrocatalytic (net charge transfer) reactions take place at the Pt working electrode, presumably at the three-phase-boundaries (tpb) Pt-Nafion-gas ... 

The isomerization of 1-butene to cis- and trans- 2-butene onPd/C/Nafion and Pd-Ru/Nafion electrodes is one of the most remarkable and astonishing electrochemical promotion studies which has appeared in the literature.39,40 Smotkin and coworkers39,40 were investigating the electrocatalytic reduction of 1-butene to butane on high surface area Pd/C and Pd-Ru cathodes deposited on Nafion 117 when, to their great surprise, they observed at slightly negative overpotentials (Fig. 9.31) the massive production of 1-butene isomerization, rather than reduction, products, i.e. cis- and trans-2-butenes. This is extremely important as it shows that electrochemical promotion can be used also to enhance nonredox catalytic reactions such as isomerization processes. 

The electrochemical cell consists of high surface area Pd/C or unsupported Pd-Ru cathodes interfaced to Nafion with a Pt-black/H2 counter electrode. The cell configuration, as well as the reactions taking place on the anode and the cathode are the following ... 

E. Smotkin The group of Professor Smotkin at Illinois (IIT) was first to demonstrate NEMCA for an isomerization reaction (1-butene to cis-and trans-2-butene) over a Pd/Nafion catalyst at room temperature. This important and spectacular discovery underlines the great potential ofNafion for inducing NEMCA at low temperatures for numerous important organic synthesis reactions. 

Nafion-H (144), a perfluorinated resin-sulfonic acid, is an efficient Bronsted-acid catalyst which has two advantages it requires only catalytic amounts since it forms reversible complexes, and it avoids the destruction and separation of the catalyst upon completion of the reaction [94], Thus in the presence of Nafion-H, 1,4-benzoquinone and isoprene give the Diels-Alder adduct in 80% yield at 25 °C, and 1,3-cyclohexadiene reacts with acrolein at 25 °C affording 88 % of cycloadduct after 40 h, while the uncatalyzed reactions give very low yields after boiling for 1 h or at 100 °C for 3.5 h respectively [95], Other examples are given in Table 4.24. In the acid-catalyzed reactions that use highly reactive dienes such as isoprene and 2,3-dimethylbutadiene, polymerization of alkenes usually occurs with Nafion-H, no polymerization was observed. 

Recently Nafion-H was successfully used in the Diels-Alder reaction of olefin acetals with isoprene and cyclopentadiene (Scheme 4.27). The reactions work well in DCM at room temperature and Nafion-H did not cleave the acetal group [96]. The recovered Nafion-H was used four or five times without affecting the yield of the cycloadducts. 

Table 4.24 Nafion-H catalyzed Diels-Alder reactions in refluxing benzene...

Studies in Lewis acid and LiCi04 (or nafion-H) catalyzed ionic Diels-Alder reactions of chiral and achiral olefinic acetals respectively [96]... 

Other reactions of small inorganic molecules are the oxidation of chloride ion at a Nafion electrode impregnated with a ruthenium 0x0 complex and the reduction of nitrogen monoxide to ammonia at a Co phthalocyanine modified electrode... 

Fewer examples are reported for organic electrode reactions some alkyl halides were catalytically reduced at electrodes coated with tetrakis-p-aminophenylporphy-rin carboxylate ions are oxidized at a triarylamine polymer and Os(bipy)3 in a Nafion film catalytically oxidizes ascorbic acid Frequently, modified electrodes fail to give catalytic currents for catalyst substrate combinations that do work in the homogeneous case even when good permeability of the film is proven... 

The hydration of triple bonds is generally carried out with mercuric ion salts (often the sulfate or acetate) as catalysts. Mercuric oxide in the presence of an acid is also a common reagent. Since the addition follows Markovnikov s rule, only acetylene gives an aldehyde. All other triple-bond compounds give ketones (for a method of reversing the orientation for terminal alkynes, see 15-16). With allqmes of the form RC=CH methyl ketones are formed almost exclusively, but with RC=CR both possible products are usually obtained. The reaction can be conveniently carried out with a catalyst prepared by impregnating mercuric oxide onto Nafion-H (a superacidic perfluorinated resinsulfonic acid). ... 

Table 7. As can be seen, both Dowex and Deloxan led to poor enantioselec-tivities, which further decreased after catalyst recovery. Better results, which are comparable with those obtained in homogeneous phase, were obtained with Nation (Table 7) [53], although it was necessary to carry out the reaction at 60 °C due to the low copper content in the soHd. This low copper level is a consequence of the low surface area of this polymer (< 0.02 m g ) and, for this reason, a nafion-silica nanocomposite was used as the support [53]. With this catalyst, the reaction took place at room temperature and with similar enantioselectivity (Table 7).

Product selectivities ( 2 mol%) (taking into account 2- and 3-etho entane only) from the reaction of 0-ethanol and S-2-pentanol ( 0) over Nafion-H and HZSM-5 catalysts at 100°C and 1 MPa and in concentrated H2SO4 solution at 100°C and 0.1 MPa, where the true inversion (I) was calculated by using the equation given above. 

Schneider, M., Zimmermann, K., Aquino, F., Bonrath, W. (2001) Industrial Application of Nafion-Systems in Rearrangement - Aromatisation, Transesterification, Alkylation, and Ring-Closure Reactions. Applied Catalysis A-General, 220, 51-58. 

Fischer and Holderich (1999) have shown that Bayer-Villiger reaction of cyclopentanone with aqueous 30 % H2O2, to give delta-valerolactone, is amenable to catalysis with cationic ion-exchange resin (CIER), Amberlyst-I5 without cataly.sts the conversion and the yield of the product are poor. Nafion on silica also works but was found to be poor compared to Amberlyst-15. Beta zeolite also works but was found to be inferior to Amberlyst-I5. 

Yamato (1995) has given an extensive coverage of a variety of reactions such as alkylation of benzene, condensation of benzene/toluene with benzyl alcohol, and condensation of benzoyl chloride with benzene/toluene using Nafion resin. 

Olah et al. (1999) have been able to realize selective cyclisation of o-benzoyl benzoic acid to anthraquinone using dichlorobenzene as a solvent and Nafion-H as a catalyst. This may lead to avoidance of the Friedel-Crafts reaction using a stoichiometric amount of aluminium chloride and resulting in a lot of wa,ste. Many other examples of similar reactions have been reported. 

The availability of Nafion on silica has not only lowered the cost of the resin but also has made it versatile (Sun et al., 1997 Harmer et al., 1998). A number of industrially important reactions have been attempted, with considerable success, with these catalysts. Consider the Fries rearrangement of phenyl acetate to p-acetyl phenol (/t-hydroxy acetophenone). This has been accomplished by Hoelderich and co-workers (Heidekum, 1998). In the ca.se of alkylation of benzene with benzyl alcohol, Amberlyst-15 and p-toluene sulphonic acid are ineffective and Nafion on silica works well at 80 °C. 

There are several claims in literature for the reaction of acetone and ammonia, at temperatures like 50°C, to give triacetoneamine (2,2,6,6-tetramethyl 4-piperidone), using Nafion and other CIERs (Eqn. (10)). This product is the starting material for the renowned hindered amine light stabilizers. 

Parthasarathy A, Srinivasan S, Appleby AJ, et al. 1992b. Pressure dependence of the oxygen reduction reaction at the platinum microelectrode/Nafion interface Electrode kinetics and mass transport. J Electrochem Soc 139 2856-2862. 

In PEMFCs, the membrane electrode assembly (MEA, Eig. 15.2a) is a multilayer sandwich composed of catalytic layers (CLs) where electrochemical reactions take place, gas-diffusion media providing access of gases to the CLs, and a proton exchange membrane (PEM) such as Nafion . The CL is a multiphase multicomponent medium comprising ... 

Antoine O, Bultel Y, Durand R. 2001. Oxygen reduction reaction kinetics and mechanism on platinum nanoparticles inside Nafion . J Electroanal Chem 499 85-94. 

Jiang J, Kucernak A. 2004. Investigations of fuel cell reactions at the composite microelectrode solid polymer electrol3de interface. I. Hydrogen oxidation at the nanostructured Pt Nafion membrane interface. J Electroanal Chem 567 123-137. 

Photocatalytic oxidation of ethanol on Pt/ri02 and Nafion coated Ti02 catalysts were studied using in situ infrared IR techniques. Infrared studies show that the reaction produced acetaldehyde, acetic acid, acetate, formic acid, formate, and CO2/H2O. Modification of the Ti02 catalyst by Pt and Nafion slowed down the oxidation reaction through site blocking. Incorporation of Pt was found to favor formation of formate (HCOO ), indicating Pt decreases the rate of oxidation of formate more than that of its formation. 

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