Ionic liquid reactions

Lee found that the reaction gave good yields (70-99 %) in the ionic liquids [BMIM][PF6], [BMIM][OTf, and [BMIM][SbF6] with Lewis acids such as Yb(OTf)3, Sc(OTf)3, Dy(OTf)3, Sm(OTf)3, and InCl3. The reaction was also performed in [BMIM][PF(3] or dichloromethane with Sm(OTf)3 as the catalyst. The ionic liquid reaction gave a yield of 99 %, compared with 70 % for the reaction in dichloromethane [73]. 

The product distribution in the reaction of benzene with dodecene was determined for a number of catalysts (Table 5.1-4). As can be seen, the reaction with the zeolite H-Beta gave predominantly the 2-phenyldodecane, whereas the reaction in the pure ionic liquid gave a mixture of isomers, with selectivity similar to that of aluminium chloride. The two supported ionic liquid reactions (H-Beta / IL and T 350 / IL) again gave product distributions similar to aluminium(III) chloride (T350 is a silica support made by Degussa). 

Ionic liquid Reaction Molar ratio IL Ar-H % Conversion % Selectivity... 

The distribution of the products obtained from this reaction depends upon the reaction temperature (Figure 5.1-4) and differs from those of other poly(ethene) recycling reactions in that aromatics and alkenes are not formed in significant concentrations. Another significant difference is that this ionic liquid reaction occurs at temperatures as low as 90 °C, whereas conventional catalytic reactions require much higher temperatures, typically 300-1000 °C [100]. A patent filed for the Secretary of State for Defence (UK) has reported a similar cracking reaction for lower molecular weight hydrocarbons in chloroaluminate(III) ionic liquids [101]. An... 

Figure 5.3-4 Turnover frequency of Rh-catalyzed hydroformylation as a function of 1-hexene solubility in ionic liquids. Reactions conditions Rh(CO)2(acac) 0.075 mmol, 1 -hexene/Rh = 800, TPPTS/Rh = 4, heptane as internal standard, CO/Hj = 1 (molar ratio), P = 2 MPa, T = 80 °C, TOP determined at 25 % conversion of 1 -hexene ([BMP]= N,N-butylmethylpyrolidinium [BMMIM] = 1-butyl-2,3-dimethylimidazolium)...

Entry Biocatalyst Ionic liquid Reaction system Ref. 

The resolution of chiral alcohols through lipase-mediated enantioselective acylation (transesterification) is one of the major industrial applications of lipases [50]. Hence, the effects of ionic liquid reaction media on the resolution of various... 

The resolution of chiral amines via lipase-catalyzed enantioselective acylation is now a major industrial process, but interest in adopting ionic liquid reaction media has been surprisingly scant. Interestingly, acids could be used as the acyl donor (Figure 10.15) rather than the usual activated ester in a range ofionic liquids. CaLB was employed as the biocatalyst, and water was removed to shift the equilibrium toward the product [130, 131]. The highest rates were found in [BMMIm][TfO], [EMIm][TfO], and [EMIm][BF4]. 

Togo, H., Hirai, T. Environmentally-friendly Wohl-Ziegler bromination Ionic-liquid reaction and solvent-free reaction. Synlett 200Z, 702-704. Greenwood, J. R., Vaccarella, G., Capper, H. R., Mewett, K. N., Allan, R. D., Johnston, G. A. R. Theoretical studies on the free-radical bromination of methylpyridazines in the synthesis of novel heterocyclic analogs of neutro-transmitters. THEOCHEM1996, 368, 235-243. Gainsforth, J. L., Klobukowski, M., Tanner, D. D. Structure and Reactions of the Succinimidyl Radical A Density Functional Study. J. Am. Chem. Soc. 1997,119, 3339-3346. 

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