Carbonium ions , applications

This method is suitable only for the preparation of 4-substituted and/or 3,4-disubstituted derivatives, the substituents being only alkyl, aryl or heteroaryl groups. The presence of electron-withdrawing groups in the unsaturated side chain prevents the cyclization step. This is understandable if the influence of such groups on the stability of the intermediate carbonium ion is considered. Of more limited application is the analogous cyclization of diazotized o-aminophenylpropiolic acids, the reaction being referred to as the Richter synthesis (Scheme 70). A related synthesis (also referred to as the Neber-Bossel synthesis)... 

Carbonium ions are well-defined transition states in many reactions. Indeed, one of the earliest applications of MM method to the reactivity problem was concerned with carbonium ions. At present, only the Schleyer force field (26b) and its predecessor (253) are capable of handhng carbonium ions, although the parameterization principle used earlier can be readily improved upon to the present standards. Schleyer s measure of steric strain in carbonium ions, Ajtrain (the difference in steric energies of free carbonium ion and its... 

Whitmore (16), when developing the idea of carbonium ions, included reactions over dehydrating catalysts. The application of carbonium ion mechanism to the dehydration of alcohols over alumina has found several supporters (17, 18). 

Pillai and Pines (84) found that neopentyl alcohol, mixed with 10% by weight of piperidine and passed over alumina prepared from aluminum isopropoxide, yielded 2-methyl-l-butene and 2-methyl-2-butene, in a maximum ratio of 3, and small amounts of 1,1-dimethylcyclo-propane. However, lert-pentyl alcohol yielded these two olefins in a maximum ratio of only 1.4, and none of the cyclopropane was produced (Table VI). Because of these facts a carbonium ion mechanism which is applicable to ferf-pentyl alcohol is not adequate to explain the rearrangement taking place during the dehydration of neopentyl alcohol,... 

Five years ago a brief review focused on the applications of nuclear magnetic resonance (nmr) as a method for determining charge density in carbonium ions and pointed out some of the precautions required (Fraenkel and Famum, 1968). Since then, proton nmr (pnmr), which was emphasized in that review, has continued to attract primary attention as a probe into the structure and charge density of organic cations and anions (Olah and Schleyer, 1968,1970, 1972, 1973 Oth ef al., 1972 Takahashi et a/., 1973 van... 

The acid-catalyzed reactions of olefin polymerization and aromatic alkylation by olefins have been very well explained by the carbonium ion mechanism developed by Whitmore (21). This mechanism provides the basis of the ensuing discussion, which is devoted to the application of such concepts (7,17) to catalytic cracking systems and to the provision of much added support in terms of recently developed structural energy relationships among hydrocarbons and new experimental evidence. 

From the general principles of carbonium ion systems, a host of applications may be made to important reactions of the catalytic cracking system. Some of these follow ... 

The mechanism proposed in Reaction 3—i.e., the generation of a polymeric carbonium ion by the reaction of Et2AlCl with PVC and the addition of the carbonium ion to a double bond in cts-1,4-polybutadiene —would appear to be applicable to the polymer-polymer grafting reaction. The monomer-polymer grafting reaction may involve polymerization of butadiene on the polymeric carbonium ion site or the reaction between polybutadiene generated in situ and the polymeric carbonium ion. 

The reaction of 13-hydroxysparteine with acetic anhydride in DMSO was shown earlier to give the inverted acetate (axial equatorial) instead of the expected ketone, and this has been confirmed. Application of the reaction to 3-hydroxylupanine (18) (axial OH) and to 13-ep/-hydroxylupanine (19) (equatorial OH) gave the corresponding ketone (10% yield) and an approximately equimolecular mixture of epimeric acetate (20) in each case. The mechanism proposed (Scheme 2) indicates facile formation of a carbonium ion through transannular interactions.23... 

Dacarbazine is a synthetic compound that functions as an alkylating agent following metabolic activation by liver microsomal enzymes by oxidative N-demethylation to the monomethyl derivative. This metabolite spontaneously decomposes to 5-aminoimidazole-4-carboxamide, which is excreted in the urine, and diazomethane. The diazomethane generates a methyl carbonium ion that is believed to be the likely cytotoxic species. Dacarbazine is administered parenterally and is not schedule-dependent. It produces marked nausea, vomiting, and myelosuppression. Its major applications are in melanoma, Hodgkin s disease, and soft tissue sarcomas. 

The catalytic activity of amorphous silica-alumina ([Si—Al]) in reactions via carbonium ions is due to the existence of Bronsted acid sites on their surface. Consequently, amorphous [Si-Al] acid catalysts provide acid sites and transport to the active sites easily. As a result, amorphous [Si-Al] acid catalysts have been widely operated as cracking catalysts. Acid zeolites have been successfully applied as cracking catalysts. However, in some industrial applications of acid catalysts, for example, in the cracking of hydrocarbons of high molecular weight, zeolites are not useful, since... 

Paushkin and Topchiev also used H3P()4-BF3 at room temperature to alkylate benzene with olefins (287,402). For alkylation of benzene with alcohols, temperatures of 90-97° and a feed mole ratio of 0.5 alcohol 1.0 benzene 0.5 catalyst were recommended (394). In a recent study (400a) these authors supplemented their previously published views (396) concerning the properties of boron fluoride complexes with phosphoric acid, alcohols, and sulfuric acid as catalysts. Data on the electroconductivity of these catalysts was correlated with their activity in alkylation of isobutane and it was concluded (400a) that the acid ion concentration did not affect the alkylation or polymerization reactions over these catalysts, and therefore the carbonium ion mechanism was not applicable. 

A very early application of a superacid solvent was the use of 100% H2S04 for the preparation of stable solutions of carbonium ions, such as the triphenylcarbonium ion (Hantzsch, 1908c) (C6H5)8C+, e.g.,... 

The experimental procedures were adapted to allow the application of a number of physical and chemical techniques, including the use of radical scavengers, ionic interceptors, deuteriated reagents, pressure-dependence studies, competition kinetics, etc. A serious problem, already encountered in the study of the carbonium ions directly formed from the decay of tritiated hydrocarbons (vide supra), arises from the possibility that radiolytic processes, promoted by the j8-radiation of... 

To date, crystalline zeolite catalysts have been most effective in catalyzing carbonium ion reactions such as catalytic cracking and hydrocracking. Other carbonium ion reactions such as alkylation and isomerization also are catalyzed by certain forms of zeolites. I expect to see these applications expand— provided suitable catalyst compositions are developed to allow economically viable processes. Although X- and Y-type faujasite can be used in catalytic cracking and hydrocracking, the Y-type is preferred for paraffin-olefin alkylation. Y-type faujasite is suitable for use in hydroisomerization catalysts, but synthetic mordenite is also a promising material. 

The application of the ideas of Lewis on acids, which correlate a wide range of phenomena in qualitative fashion, has as yet led to very few quantitative studies of reaction velocity but has led to detailed speculations as to mechanisms (Luder and Zuffanti, 118). Friedel-Crafts reactions are considered to be acid-catalyzed, the formation of a car-bonium ion being the first step. The carbonium ion then acts as an acid relative to the base benzene which, upon loss of a proton, yields the alkylated product. Isomerizations of isoparaffins can be explained in similar fashion (Schneider and Kennedy, 119). An alkyl halide yields a carbonium ion on reaction with acids such as boron trifluoride, aluminum chloride, and other metal halides. 

An interesting application of this reaction is in the formation of 1-azido-l-ferrocenylethane (12) in 57% yield from the alcohol (13). The exceptionally stable carbonium ion (14) has been suggested as an intermediate in this reaction... 

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