Aprotic superacids

Volpin called the CH3COCI lAlCk complex an aprotic superacid. The results indicate that the acetyl cation is activated by further 0-complexation with a second molecule of AIX3 (the equivalent of protonation or protosolvation). 

The pH-neutral ionic liquids are highly polar and noncoordinating. These liquids have potential applications as solvents for metallic and organometallic reagents in two-phase reactions, and as replacements for polar, aprotic solvents like dimethyl-foimamide. The Lewis-acidic and superacidic ionic liquids are being investigated for use as catalytic solvents. 

Novel highly active aprotic superacid systems have been more recently found by Vol pin and coworkers to initiate rapid transformation of alkanes as well as C5—C6 cycloalkanes.43 The reaction, for example, of excess cycloalkanes without solvent... 

The formation of l-acetyl-2-methylcyclopentene was also observed when either cyclohexane or cyclopentene was reacted by Vol pin and coworkers with an excess of the aprotic organic superacid MeCOCl—2AlBr3 130131... 

Substitution reactions, aromatic, hydrogen isotope effects in, 2, 163 Substitution reactions, bimolecular, in protic and dipolar aprotic solvents, 5, 173 Sulphur, organic oxyacids of, and their anhydrides, mechanisms and reactivity in reactions of, 17, 65 Superacid systems, 9, 1... 

Lewis superacids, such as SbF5, AsF5, PF5, TaF5, NbF5, BF3, tris(pentafluoro-phenyl) borane, boron tris(trifluoromethanesulfonate), and aprotic organic superacids developed by Vol pin and co-workers. 

The superelectrophilic AcBr- AlBr3 complexes, called aprotic organic superacids developed by Vol pin and co-workers,119,120 were used in the isomerization of C12H2o tricyclanes with the main component being perhydroacenaphthene to dimethyl- and ethyladamantanes121 [Eq. (5.51)]. 

The one-step double functionalization of aromatics—that is, alkylation and acylation—can be accomplished with alkanes or cycloalkanes (in large excess) using the aprotic organic superacids RCO+Al2X7 (R = alkyl, aryl, X = Cl, Br)391 [Eq. (5.152)]. However, the method can be used only for benzene and bromobenzene. 

Akhrem and co-workers417 have successfully applied aprotic organic superacids in the carbonylation of a series of alkanes. Butane was transformed into isomeric carboxylic acids depending on the superelectrophilic reagent and isolated as the... 

Carbon-Halogen Vicinal-Dieations Trihalomethyl cations are shown to have enhanced reactivities in superacid solution, while poly-halomethanes in the presence of excess AlBr3 or AICI3 exhibit the properties of aprotic superacids.79 The trihalomethyl cations CX3+ (178, X=C1, Br, I) have been characterized by NMR and IR spectroscopy. The stability of these species is attributed to substantial resonance-stabilization by back-donation from the nonbonded electron pairs of the halogen atoms.22 Trihalomethyl cations are capable of hydride abstraction from alkanes and alkyl groups when the reactions are carried out in the presence of Bronsted or Lewis superacids (eq 46-48).80... 

There are numerous ways to determine experimentally pK values of chemical compounds (205). Classical methods are potentiometric titration and ultraviolet (UV) spectroscopy, among others. These techniques have been widely applied for nucleobases and also for metal-nucleobase complexes. For the extremes such as negative pK values (pK < —2) of singly or multiply protonated nucleobases, or very high pK values (pK >15) for deprotonation of exocyclic amino groups of nucleobases (C, G, A), modifications have to be employed. These include the consideration of the Hammett acidity function in superacidic solvents or solvent mixtures (206), as well as extrapolative techniques according to Bunnett-Olsen and Marziano-Cimino-Passerini to be applied in polar, aprotic solvents (45, 207). 

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