Superacid systems

My work on long-lived (persistent) carbocations dates back to the late 1950s at Dow and resulted in the first direct observation of alkyl cations. Subsequently, a wide spectrum of carbocations as long-lived species was studied using antimony pentafluoride as an extremely strong Lewis acid and later using other highly acidic (superacidic) systems. 

My research during the Cleveland years continued and extended the study of carbocations in varied superacidic systems as well as exploration of the broader chemistry of superacids, involving varied ionic systems and reagents. I had made the discovery of how to prepare and study long-lived cations of hydrocarbons while working for Dow in 1959-1960. After my return to academic life in Cleveland, a main... 

The vastly increased acidity of superacidic systems resulted in the significant new field of superacid chemistry. I began to ask myself whether a similar but more general approach could be used to produce electrophiles of greatly enhanced electron deficiency and thus reactivity. Over the years, there were a number of unexpected results in my own research work, as well as some previously unexplained observations buried in the literature, that seemed worth pursuing. 

The significance of the possible diprotonation of water under extremely acidic conditions directly affects the question of acid strength achievable in superacidic systems. The leveling effect mentioned above limits the acidity of any system to that of its conjugate acid. Thus, in... 

In superacidic systems, water is completely protonated and no equilibrium containing free water is indicated. However, the nonbonded electron pair of H30 is still a potential electron donor and at very high acidities can be further protonated (however limited the equilibrium with H30 may be). Thus the acidity of such superacidic systems can exceed that of H30 and the leveling ont is by that of H40 . We found that similar situations exist with other electrophiles, raising their electrophilic nature (electrophilicity) substantially. 

Lower alkanes such as methane and ethane have been polycondensed ia superacid solutions at 50°C, yielding higher Hquid alkanes (73). The proposed mechanism for the oligocondensation of methane requires the involvement of protonated alkanes (pentacoordinated carbonium ions) and oxidative removal of hydrogen by the superacid system. 

The extent to which rearrangement occurs depends on the structure of the cation and foe nature of the reaction medium. Capture of carbocations by nucleophiles is a process with a very low activation energy, so that only very fast rearrangements can occur in the presence of nucleophiles. Neopentyl systems, for example, often react to give r-pentyl products. This is very likely to occur under solvolytic conditions but can be avoided by adjusting reaction conditions to favor direct substitution, for example, by use of an aptotic dipolar solvent to enhance the reactivity of the nucleophile. In contrast, in nonnucleophilic media, in which fhe carbocations have a longer lifetime, several successive rearrangement steps may occur. This accounts for the fact that the most stable possible ion is usually the one observed in superacid systems. 

Strong acids or superacid systems generate stable fluorinated carbocations [40, 42] Treatment of tetrafluorobenzbarrelene with arenesulfonyl chlorides in nitro-methane-lithium perchlorate yields a crystalline salt with a rearranged benzo barrelene skeleton [43] Ionization of polycyclic adducts of difluorocarbene and derivatives of bornadiene with antimony pentafluonde in fluorosulfonyl chloride yields stable cations [44, 45]... 

The superacid system HS03F/SbF5/S03 is employed when generating the Br3+ ion by the reaction... 

Variations in the absolute concentration of the carbocation solutions and temperature had minor effects on chemical shifts. The counter ion effect and the equilibrium could be minimized by going to higher superacidity systems with lower nucleophilicity counter ions. Resonances due to the PAH itself were considerably shielded. Solvation by FSO3H and the formation of ion pair-molecule clusters were suggested as possible reasons. 

Any condensation of methane to ethane and subsequently to higher hydrocarbons must overcome the unfavorable thermodynamics. This can be achieved in condensation processes of oxidative nature, where hydrogen is removed by the oxidant. SbF5- or FS03H-eontaining superacid systems also act as oxidants. The oxidative condensation of methane was subsequently found to take place with more economical cooxidants such as halogens, oxygen, sulfur, or selenium 91... 

Improved yields of adamantane up to 65% were achieved by using superacidic systems [HF-SbF5, CF3S020H-B(0S02CF3)3, various solid superacids]40"42 and chlorinated Pt on alumina.43 More recently near-quantitative isomerization with conjugate superacids promoted by 1-haloadamantanes as the source of 1-ada-mantyl cation and sonication was reported.44... 

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... 

A four-center molecular syn addition ([2 + 2]-cycloaddition) is also consistent with experimental observations.202 Molecular-orbital calculations and experimental observations by NMR spectroscopy in superacidic systems rule out the existence of the bridged fluoronium ion.204-206... 

Superacid systems, such as HF—BF3 and CF3S03H, allow further improvement of the Koch reaction.109 Triflic acid proved to be far superior to 95% H2S04 at atmospheric pressure.110 This was attributed to the higher acidity of triflic acid and the higher solubility of CO in this acid. FS03H—SbF5 combined with Cu(I) is also effective.111... 

More recent studies with superacidic systems (TfOH, TfOH—SbF5), used also in the Gattermann reaction, indicated that strong acids significantly increase reactivities of benzene with benzonitrile.33 104 It is concluded that the superelectrophilic 14 dication formed as a results of protonation of 13 is the reactive species in the Houben-Hoesch reaction. 

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