Allylcarbinyl cation

A recent study of photoelectron spectra of isomeric C4H7 radicals has provided heats of formation of the allylcarbinyl cation (231 3 kcal mol" ) and the cyclobutyl cation (225.1 1.1 kcalmol" ) but the failure of attempts to generate the cyclopropylcarbinyl radical meant that no heat of formation of the corresponding cation could be obtained Similarly, the heats of formation of geometrically reorganized structures such as puckered cyclobutyl cations and bicyclobutonium ions could not be assigned. Further experiments along these lines are clearly indicated, as well as further calculations to resolve the current dichotomy in the theoretical studies. 

The investigations carried out in this area were done primarily to determine the magnitudes of steric and electronic effects on the solvolytic rates and products of reaction in the cyclopropylcarbinyl cation system. The goal of most of these studies was to learn more about the nature of the charge delocalization in the cyclopropylcarbinyl system and of the stereochemistry of the cyclopropylcarbinyl-cyclobutyl and cyclopropyl-carbinyl-allylcarbinyl cation rearrangements. Key papers in these studies were those in 1966 by Schleyer and Van Dine, in 1971 by Majerski and Schleyer and in 1974 by Poulter and Spillner which demonstrated that in the simple cyclopropylcarbinyl system... 

The data is consistent with the initial formation of a cyclopropylcarbinyl cation which then undergoes rapid ring-opening to the allylcarbinyl cation from which the products are derived. 

When a gaseous flow of cyclopropylcarbinyl chloride is passed over NaY zeolite at room temperature, formation of cyclobutyl chloride and allylcarbinyl chloride was observed (scheme 4), as well as cyclopropylcarbinyl chloride (product and unreacted starting material). These data are consistent with formation of the C4H7+ cation with internal return of the chloride ion. 

To check this possibility we performed experiments with different concentrations of NaBr in the NaY zeolite. Table 2 presents the results. It can be seen that upon increasing the amount of NaBr impregnated on NaY, there is preference to formation of the cyclobutyl bromide over allylcarbinyl bromide, indicating that the relative position between the bromide ions and bicyclobutonium governs the product distribution. Hence, zeolites may act as solid solvent, favoring ionization of alkyl halides and nucleophilic substitution reactions. In contrast to liquid solvents, where solvation is mostly uniform, the zeolite surface seems to provide unsymmetrical solvation of the cations, leading to product distribution that is different from solution. 

The results of cyclopropylcarbinyl chloride rearrangement over NaY impregnated with NaBr suggest that there is an equilibrium between the bicyclobutonium cation and the alkyl-aluminumsilyl oxonium ion, explaining the preferred formation of the allylcarbinyl bromide in the rearranged products. It also suggests that zeolites may act as solid solvents, providing unsymmetrical solvation for the ions inside the cavities. 

Solvolytic studies provided the first structural indication for almost every carbocation-ic intermediate and the C4H,+ ion is no exception. Roberts observed that the solvolysis of cyclopropylcarbinyl or cyclobutyl systems and the diazotative deamination reactions of cyclopropylcarbinyl amine or cyclobutyl amine gave similar product mixtures consisting of cyclopropylcarbinyl, cyclobutyl and allylcarbinyl derivatives in essentially the same ratio1,2. A common cationic intermediate of C3v structure, the tricyclobutonium ion 1, was... 

In 1951 Roberts observed that most cationic reactions of cyclopropylcarbinyl and of cyclobutyl derivatives give the same products in nearly the same ratio.73 For example, cyclopropylcarbinyl and cyclobutyl amines on deamination form the products shown in Equation 6.31.74 Moreover, when allylcarbinyl tosylate (63)... 

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