Carbocations, and

The formal carbanions and carbocations used as units in synthesis are called donor synthons and acceptor synthons. They are derived from reagents with functional groups. 

A theory is our best present interpretation of why things happen the way they do The modern ver Sion of Markovnikov s rule which is based on mecha nistic reasoning and carbocation stability recasts the rule in terms of theoretical ideas Mechanisms and explanations grounded in them belong to the theory part of the scientific method... 

Alkyl substituents stabilize a carbonyl group m much the same way that they sta bilize carbon-carbon double bonds and carbocations—by releasing electrons to sp hybridized carbon Thus as then heats of combustion reveal the ketone 2 butanone is more stable than its aldehyde isomer butanal... 

The reactions of copper salts with diacyl peroxides have been investigated quite thoroughly, and the mechanistic studies indicate that both radicals and carbocations are involved as intermediates. The radicals are oxidized to carbocations by Cu(II), and the final products can be recognized as having arisen from carbocations because characteristic patterns of substitution, elimination, and rearrangement can be discerned " ... 

Table 23. Chemical Shifts of Fluorinated Carbanions and Carbocations...

Figure 5.4 An energy diagram for the first step in the reaction of ethylene with HBr. The energy difference between reactants and transition state, AG, defines the reaction rate. The energy difference between reactants and carbocation product, AG°, defines the position of the equilibrium.

Many variations of the reaction can be carried out, including halogenation, nitration, and sulfonation. Friedel-Crafts alkylation and acylation reactions, which involve reaction of an aromatic ling with carbocation electrophiles, are particularly useful. They are limited, however, by the fact that the aromatic ring must be at least as reactive as a halobenzene. In addition, polyalkylation and carbocation rearrangements often occur in Friedel-Crafts alkylation. 

The complete dissociation of the hydrocarbons [l 2 ], [28" 2 ] and [40" 2 ] in DMSO has been demonstrated by quantitative generation of both Kuhn s carbanion [2 ] and carbocations [1" ], [28" ] and [40" ] as determined by UV-vis spectra (Table 6 and Eig. 4). However, since carbocation [24 ] has no absorptions at a wavelength region longer than 220 nm in the UV spectrum, there remained an ambiguity that this cation might have decomposed in the DMSO solution. A clue to this problem could be obtained by determination of the electric conductivity of DMSO solutions of hydrocarbon salts (Table 7) (Okamoto et al., 1990). 

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