J. Org. Chem. 1989,54, 4993-4998 Commercial Ion Exchange Resins as Catalysts in Solid-Solid-Liquid Reactions 4993 Onn Arrad and Yoel Sasson* The Casali Institute of Applied Chemistry, The Hebrew University of Jerusalem, School of Applied Science and Technology, 91904 Jerusalem, Israel Received March 13, 1989 Nucleophilic substitutions, base-catalyzed alkylations, and oxidation of a secondary alcohol have been carried out in a nonpolar solvent with inorganic solid reagents using polymer-bound quarternary ammonium or phcephonim catalysts. The products could be isolated simply by filtration and evaporation of the solvent. Some commercial ion exchange resins, which are known to be inactive in liquid-liquid systems, were found to have a similar or even superior activity in comparison with the usual “triphase catalysts”. The resins were chemicallystable under the reaction conditions, but their mechanical breakdown could be reduced only by application of unconventional means of agitation. Introduction The use of phase-transfer catalysis (PTC) for reactions between organic soluble substrates and inorganc reagents has become extremely popular over the past years and continues to grow in importance in synthetic organic chemistry.’s2 Soluble phase-transfer catalysts are usually difficult to separate from the reaction mixture and are seldom r e ~ s e d . ~ Much effect has therfore been put in the research of polymer supported catalysts (triphase catalysis, TC).44 Besides a reduced catalytic a ~ t i v i t y ~ ? ~ they still suffer from a very limited commercial supply at extremely high prices? which make them rather inconvenient to the synthetic chemist. The catalytic activity of typical com- mercial benzyltrimethylammoniumion exchange resins has been reported to be negligible in most TC reactions,4-6J0J1 most likely because of their strong preference for the aqueous phase, which prevents any contact between the active site and the organic substrate. Besides a few ex- ception~>’~-~~ they are of value only when applied stoi- chiometrically as reagents after they have been converted into the required anionic form and dried.’”17 So-called solid-liquid PTC has been used often with reagents unreactive or unstable in the presence of water or in order to improve reaction kinetics.’?l8 Recently it (1) Dehmlow, E. V.; Dehmlow, S. S. Phase Transfer Catalysis, 2nd ed.; (2) Starks, C. M. Isr. J. Chem. 1985,2, 211. (3) Chiles, M. S.; Jackson, D. D.; Reeves, P. C. J. Org. Chem. 1980,45, (4) Regen, S. L. J. Org. Chem. 1977, 42, 875. (5) Molinari, H.; Montanari, F.;Quici, S.; Tundo, P. J. Am. Chem. SOC. (6) Ford, W. T.; Tomoi, M. Adu. Polm. Sci. 1984, 55, 49. (7) Montanari, F. Now. J. Chim. 1982,6,635. (8) Balakrishnan, T.; Ford, W. T. J. Org. Chem. 1983, 48, 1029. (9) Fluka Chemie AG-Suisse, offers polymer-bound benzyltributyl- ammonium or phosphonium chloride a t a price of 110 SFr/25 gr, which is about 50 times the price charged for Ambertlyst A27 ion exchange resin (85 SFr/kg). (10) Regen, S. L.; Heh, J. C. K.; McLick, J. J. Org. Chem. 1979, 44, 1961. (11) Ford, W. T.; Lee, J.; Tomoi, M. Macromolecules 1982,15, 1246. (12) Zadeh, H. K.; Dou, H. J. M.; Metzger, J. J. Org. Chem. 1978,43, (13) Schneider, M.; Weber, J. V.; Faller, P. J. Org. Chem. 1982,47,364. (14) Hodge, P.; Khoshdel, E.; Waterhouse, J. Macromol. Chem. 1984, (15) Akelah, A.; Sherrington, D. C. Chem. Reu. 1981, 81, 557 and (16) Cainelli, G.; Manescalchi, F. Synthesis 1979, 141. (17) Miller, J. M.; Cater, S. R.; So, K. H. Can. J. Chem. 1979,57,2629. Verlag Chemie: Weinheim/Bergstr., Germany, 1983. 2915. 1979,101, 3920. 156. 185, 489. references 114-5, 128-9, 217-34 therein. has been shown that the maximum conversion obtainable in exchange reactions of alkyl halides with formate, fluoride, or bromide ions can be dramatically increased by application of solid inorganic reagents.lS2’ The combination of both techniques, namely the per- formance of reactions with a solid reagent together with a solid catalyst, has been used only rarely, either with large amounts of neutral a l ~ m i n a ~ ~ - ~ ~ or with specially syn- thesized catalysts such as silica gel and cellulose-based phosphonium and ammonium ions,25*26 as well as poly- ethylene glycols and crown ethers on various s u p p ~ r t s . ~ - ~ Concerning polystyrene bound phosphonium or ammo- nium ions, only the oxidation of alcohols with periodate ion (and a preconverted catalyst) has been carried out suc~essfully.~~J~ In other reactions the yields of the re- sulting products were either small or not much larger than the yields obtained in the absence of any p01ymer.l~ In a recent mechanistic investigation on triphase cata- lysis, it was found that the reaction rates can be drastically improved through proper adjustment of the volume ratio of the two liquid phases.31 Thus the use of the very hydrophilic commercial ion exchange resins as triphase catalysts should be generally feasible if the presence of excess water is prevented. Indeed, Ford et have found these resins to be very active triphase catalysts in the presence of strongly desiccant 50% aqueous sodium hy- droxide. Concerning the mechanism of solid-liquid PTC reactions, it has been suggested quite often that a certain amount of water is necessary to carry out the reaction effecti~ely.~~-~~ We have shown in a recent paper that in (18) Landini, D.; Maia, A. D.; Montanari, F. J. Chem. Soc., Chem. (19) Yonovich-Weiss, M.; Sasson, Y. Zsr. J. Chem. 1985, 26, 243. (20) Dermeik, S.; Sasson, Y. J. Org. Chem. 1985, 50, 879. (21) Zahalka, H. A,; Sasson, Y. J. Chem. Soc., Chem. Commun. 1983, (22) Quici, S.; Regen, S. L. J. Org. Chem. 1979, 44, 3436. (23) Regen, S. L.; Czech, B.; Quici, S. Pol. J. Chem. 1981, 55, 843. (24) Ando, T.; Kawate, T.; Yamawaki, J.; Hanafusa, T. Chem. Lett. (25) Akelah, A.; Sherrington, D. C. Eur. Polym. J. 1982, 18, 301. (26) Tundo, P. J. Chem. Soc., Chem. Commun. 1977, 641. (27) Yanagida, S.; Takahashi, K.; Okahara, M. J. Org. Chem. 1979,44, (28) Kelly, J.; MacKenzie, W. M.; Sherrington, D. C. Polymer 1979, (29) MacKenzie, W. M.; Sherrington, D. C. Polymer 1980, 21, 791. (30) Manecke, G.; Kraemer, A.; Winter, H. J.; Reuter, P. Now. J. (31) Telford, S.; Schlunt, P.; Chau, P. C. Macromolecules 1986, 19, (32) Starks, C. M.; Owens, R. M. J. Am. Chem. SOC. 1973,95,3613. (33) Zahalka, H. A.; Sasson, Y. J. Chem. SOC., Chem. Commun. 1984, Commun. 1975, 950. 1347. 1982,935. 1099. 20, 1048. Chim. 1982, 6,623. 2435. 1652. 0022-3263/89/1954-4993$01.50/0 0 1989 American Chemical Society