Sulfonic Acid Resin Research Articles

Solid superacid catalyzed organic synthesis. 6. Perfluorinated resinsufonic acid (Nafion-H) catalyzed ring closure reaction of 2,2'-dihydroxybiphenyls. A preparative route to dibenzofurans

We report an efficient and mild procedure for the ring closure of 2,2'-dihydroxybiphenyls in the presence of the solid superacid, Nafion-H (a solid perfluorinated resinsulfonic acid) to afford dibenzofuran derivatives in good to moderate yields

Solid superacid-catalyzed organic synthesis. 4. Perfluorinated resinsulfonic acid (Nafion-H) catalyzed Friedel-Crafts benzylation of benzene and substituted benzenes

Nafion-H, a perfluorinated resinsulfonic acid, catalyzes Friedel-Crafts benzylation of benzene and substituted benzenes with benzyl alcohols under relatively mild experimental conditions. Reactions are clean, and water formed as a byproduct does not deactivate the catalyst. It was also found that this method is applicable to the intramolecular cycloalkylation and oligomerization of methoxybenzyl alcohols

A new route to perfluorinated sulphonic acid resin intermediates

A short route to trifluoroethenyloxy-2-polyperfluoropropyloxy tetrafluoroethyl sulphide or sulphonyl chloride is described. This method involves the reaction of an alcoholate with tetrafluoroethylene in the presence of an alkyl thiocyanate. Alkyl ether was formed in the first step to generate the necessary COF function. The precursor to sulphonyl chloride was a sulphide. This function can be chloro-oxidized in the second step or retained until the last steps of the synthesis. Hexafluoropropene oxide was still used to generate the CF 2CFO group by defluorocarbonylation over a Na 2CO 3 bed.

Phosphoric acid cation exchange resins from chemically modified polyvinyl chloride

AbstractPVC modified by Cl displacement reaction with meta‐aminophenol (MAP), bisphenol A (BISA), and phenolphthalein (PHEN) has been converted into phosphoric acid cation exchange resins. These resins have been characterized in regard to their structure, ion exchange properties, and thermal stability. The ion exchange capacities fall into the range 5.5–8.0 (meq/g) for the resins. The overall thermal stability is considerably higher than that for the corresponding sulfonic acid resins, as well as for the PVC–MAP, PVC–BIS A, and PVC–PHEN condensates. The resins exhibit ca. 4–6% capacity losses under isothermal hydrolytic cleavage at 100°C for 24 h.

ChemInform Abstract: Amberlyst‐15 Promoted Synthesis of Fused and Spiro γ‐Butyrolactones from β‐Hydroxy Esters.

AbstractThe β‐hydroxy esters (I), (III), and (V) undergo dehydration and subsequent cyclization upon refluxing in the presence of a sulfonic acid resin, forming the γ‐lactones (II), (IV), and (VI) respectively.

Nafion-H catalyzed tert-butylation of aromatic compounds with 2,6-DI(tert-butyl)-p-cresol [1

Convenient and high yield tert-butylation of aromatic compounds can be achieved by the Nafion-H, a superacidic perfluorinated resinsulfonic acid, catalyzed irreversible trans-tert-butylation from 2,6-ditert-butyl-p-cresol.

Nafion-H catalyzed condensation of acetophenone derivatives. A preparative route of 1,3,5-Triarylbenzenes [1

Nafion-H, a perfluorinated resinsulfonic acid, catalyzes condensation of acetophenones to provide 1,3,5-triarylbenzenes under relatively mild conditions. Reaction are clean, and water formed as by-product does not deactivate the catalyst. However, ortho-substituted

New pellicular ion exchangers by grafting onto polypropylene beads: Part II. Catalysis of the sucrose inversion

Highly accessible polymer-supported catalysts have been prepared by grafting linear polystyrene onto polypropylene beads and appropriate functionalization. The catalytic activity of the grafted, and subsequently sulphonated, polystyrenes was investigated in the hydrolysis of sucrose at 60 °C. Compared to conventional crosslinked polystyrene sulphonic acid resins, the grafted catalysts showed higher accessibility and an activity similar to that of homogeneous acid catalysts.

Cr(III) or Ce(IV) Impregnated Perfluorinated Resin–Sulfonic Acid Catalyst for the Oxidation of Alcohols

Abstract Several polymer supported catalysts are prepared by treatment of Nafion®551 (abbreviated NAFK below) with metal salts. Cr/NAFK and Ce/NAFK are found to be effective catalysts for the dehydrogenative oxidation of alcohols to the corresponding ketones by means of t-butyl hydroperoxide. Selective oxidation of secondary alcohols in the presence of primary ones was performed using a Ce/NAFK–NaBrO3 system.

Alkylation of Phenol by C9 and C12 Olefins

Abstract Alkylation of phenol by 1-dodecene, propylene tetramer and trimer is investigated using a variety of acid catalysts. The catalytic activity of perfluorinated sulfonic acid resin Nafion-H, the recently described ‘sulfate treated’ zirconia and trifluoromethanesulfonic acid is compared with that of cation exchange resin (CER) catalyst which is commonly employed in industrial practice. The activity of zirconia is observed to be comparable to CER and Nafion-H. In view of its low cost and higher thermal and structural stability, this catalyst shows considerable promise for practical application.

ChemInform Abstract: Hydration of Isopentenes in an Acetone Environment over Ion‐Exchange Resin: Thermodynamic and Kinetic Analysis.

Abstract2‐Methyl‐2‐butanol is synthesized in the 60‐103 °C temp. range over sulfonic acid resin as the catalyst and in the presence of a sufficient quantity of acetone to obtain a single liquid phase.

Nafion-H R catalyzed baeyer-villiger oxidation and ritter reaction[1

Nafion-H, a perfluorinated resinsulfonic acid, is shown to be an effective catalyst for the Baeyer-Villiger oxidation of ketones to lactones in the presence of either 30% H 2O 2 or meta-chloroperbenzoic acid, as well as for the Ritter reaction of alcohols in the presence of nitriles to give the corresponding amido compounds.

Calcium Isotope Effect in Calcium Ion Exchange with a Fluid Phase Containing a Macrocyclic Compound

Abstract The separation coefficient for calcium isotope exchange with a macrocyclic polyether was measured by ion exchange chromatography. The isotopic enrichment proceeds according to the chemical exchange reaction: where L represents the macrocyclic polyether 18-crown-6. The observed -separation coefficient for the calcium 40/44 isotope pair, e(40/44), was 4.9×10−4 (±1.3×10, 95% C.L.) with calcium-40 enriched in the fluid phase. A sulfonic acid resin was used with a fluid phase consisting of a 70/30 volume percent mixture of ethanol and water. The isotope effect was smaller than metal-crown isotope effects reported in the literature, and possible reasons for this are discussed.

Dual mechanism bifunctional polymers: Phosphinic acid ion-exchange/redox resins and the kinetics of metal-ion complexation

The detailed study of bifunctional phosphinic acid resins has recently been introduced. It has been shown that they operate through the dual mechanism of ion exchange and metal-ion reduction. A key component in the synthesis is the Friedel-Crafts catalyst used for the reaction between PCl 3 and polystyrene. We now find that the order of catalyst activity is AlCl 3 > FeCl 3 > ZnCl 2 > SnCl 4 . Ferric chloride catalysis also operates by an additional redox mechanism which yields a phosphonic acid resin. The extent of loading onto phosphinic and sulfonic acid resins by zinc ions at equilibrium was studied as a function of the anion present both with and without the presence of an excess of sodium ions. Both sets of resins exchange at a comparable rate upon the introduction of macroporosity into the polystyrene support. The influence of the redox process as an additional variable in the phosphinic resin kinetics was studied with silver and mercury(II) nitrate solutions. All of the primary acid sites are oxidized after a 9-hour contact time with Ag(I) ions and a 2-hour contact time with Hg(II) ions. The mercury loading curves and the different behavior of silver, which shows more ion exchange than redox at short times while leaving a residual ion concentration on the resin irrespective of whether all of the primary acid sites have been oxidized or not, can be explained by the termolecular nature of the Ag(I) redox reaction in contrast to the bimolecular nature of the Hg(II) reaction. Studies with other ions show that the minimum metal-ion reduction potential below which no redox occurs with the phosphinic resins is probably between 0.0 and 0.3 V.

Hydration of isopentenes in an acetone environment over ion-exchange resin: Thermodynamic and kinetic analysis

2-Methyl-2-butanol was synthesized in the 60–103 °C temperature range over sulfonic acid resin as the catalyst and in the presence of a sufficient quantity of acetone to obtain a single liquid phase. Equilibrium constants and rate constants are given as a function of temperature, and the reaction enthalpy and activation energy were determined. The activity of Amberlyst 15 is compared to that of other catalysts. Reactivities of isopentenes are compared to that of isobutene. The UNIFAC predictive method was used to determine activity coefficients so as to describe the non-ideality of the liquid phase and to compare experimental and thermodynamic constants. Since the isomerization of the double bond occurs during hydration, the mechanism of hydration can be discussed.

ChemInform Abstract: Perfluorinated Resinsulfonic Acid (Nafion‐H) Catalysis in Synthesis

Chemischer InformationsdienstVolume 17, Issue 51 Reviews ChemInform Abstract: Perfluorinated Resinsulfonic Acid (Nafion-H) Catalysis in Synthesis G. A. OLAH, G. A. OLAHSearch for more papers by this authorP. S. IYER, P. S. IYERSearch for more papers by this authorG. K. S. PRAKASH, G. K. S. PRAKASHSearch for more papers by this author G. A. OLAH, G. A. OLAHSearch for more papers by this authorP. S. IYER, P. S. IYERSearch for more papers by this authorG. K. S. PRAKASH, G. K. S. PRAKASHSearch for more papers by this author First published: December 23, 1986 https://doi.org/10.1002/chin.198651349Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume17, Issue51December 23, 1986 RelatedInformation

Thermally stable sulfonic acid resins

AbstractPolystyrene‐divinylbenzene resins 2 and 3 containing carboxysulfoalkyl groups were prepared by Michael addition of phenyl ethylenesulfonate to the reaction products of the chloromethylated resins with cyanide and diethyl malonate, respectively. They display an unusually high thermal stability in water: less than 5–10% loss of SO3H after 100 hat 200°C. Their catalytic activities (hydrolysis of sucrose), expressed per equivalent of SO3H, are twice as high as those of corresponding ring‐sulfonated resins.

Thermochemical comparisons of homogeneous and heterogeneous acids and bases. 1. Sulfonic acid solutions and resins as prototype Broensted acids

Heats of ionization by thermometric titration for a series of bases (or acids) can be used to compare solid acids (or bases) with liquid analogues bearing the same functionalities in homogeneous solutions. The method is demonstrated for Broensted acids by reacting a series of substituted nitrogen bases with solutions of p-toluenesulfonic acid (PTSA) in acetonitrile and with suspensions of the microporous polymeric arylsulfonic acid resin-Dowex 50W-X8 in the same solvent. Under well-controlled anhydrous conditions there is a good correlation (r = 0.992) between the heats of reaction of the bases with the homogeneous and heterogeneous acid systems, but the homogeneous system gives a more exothermic interaction by 3-4 kcal mol/sup -1/ for a series of 29 substituted pyrimidines, anilines, and some other amines. This difference may be attributed to homohydrogen bonding interactions between excess acid and sulfonate anion sites which are more restricted geometrically in the resin than in solution. Other factors which affect the enthalpy change for the acid-base interaction are the acid/base ratio, the water content of the sulfonic acid, the solvent, and the resin structure (e.g., microporous vs. macroporous). Steric hindrance in the base does not differentiate solid from homogeneous acid. In addition to the use ofmore » titration calorimetry, heats of immersion are reported for the Dowex-arylsulfonic acid resins and the Nafion-perfluorinated sulfonic acid resin in a series of basic liquids. The results are compared with each other and with those from a previous study of several varieties of coal.« less

Kinetic Study of Liquid-Phase Esterification with Sulfonic Acid Cation-Exchange Resin of the Macroreticular Type. I. Heterogeneous–Pseudohomogeneous Resin Catalysis

Abstract The rates of the esterification of octanoic acid with 1-butanol catalyzed by macroreticular sulfonated ion-exchange resin were measured by the use of a batch reactor. The effects on the rate were investigated for variations in the amount of the catalyst, the temperature, and the reactant alcohol concentrations as well as those of water and butyl octanoate. From these data, it is considered that alcohol and water solvate the matrix-bound sulfo groups, and so this esterification system consists of a heterogeneous reaction catalyzed by un-ionized sulfo groups and a pseudo-homogeneous reaction catalyzed by solvated protons; in other words, catalysis by sulfonic acid resin is both heterogeneous and pseudo-homogeneous in liquid-phase esterification.

Perfluorinated Resinsulfonic Acid (Nafion-H®) Catalysis in Synthesis

Revue des applications catalytiques du Nafion H et de ses derives modifies en synthese organique