Carbonium ions protonation

Undoubtedly, it seems plausible that the large difference observed in the CH3T yield from the protonation of butane (15%) and isobutane (23%) reflects the higher probability that a carbonium ion protonated on a primary carbon is formed from the attack of HeT+ on isobutane. The decomposition of the intermediate according to equation 52 represents a direct route to tritiated methane ... 

Three major types of cationic species that can be derived from saturated hydrocarbons are alkyl carbenium ions (R+), alkane radical cations (RH +) and alkyl carbo-nium ions (RH2+). The term carbocations is usually reserved to denote alkyl carbenium and carbonium ions only. Pentacoordinated alkyl carbonium ions (proton-ated alkanes) are the species that result from protonation of alkane molecules they are of paramount importance as reactive intermediates/transition states in the initiation of (Br0nsted) acid-catalyzed conversions of saturated hydrocarbons. Upon dissociation of alkyl carbonium ions, trivalent alkyl carbenium ions are formed and these are responsible for the further progression of acid-catalyzed conversions of alkanes. Alkyl carbenium ions may also be formed by ionization of neutral alkyl radicals and by proton addition to olefins. In both carbenium and carbonium ions, the positive charge is very much located on a particular part of the cation. 

Unlike the isomerization of l-chloro[l- C]butane with aluminium trichloride, which proceeds without major participation of protonated cyclo-propanes, the isotopic scrambling from the reaction of [l- C]-l-propyl-mercuric perchlorate in trifluoroacetic acid does require intermediate protonated cyclopropanes. The isolated 1-propyl trifluoroacetate (565) was shown by degradation to have the label distributed as shown in Scheme 76. The greater scrambling from C-1 to C-3 than from C-1 to C-2 requires an edge-rather than a comer-protonated ion. Full details have appeared of the liquid-phase thermolyses of cycloalkyl and cycloalkylmethyl chloroformates which take place via carbonium ions. Protonated cyclopropanes are believed to be intermediates for 5-10% of the products. The alkylation of benzene and toluene by cyclopropane with acidic catalysts also involves initial formation of a protonated cyclopropane. ... 

Saunders M, Hagen EL, Rosenfeld J. Rearrangement reactions of secondary carbonium ions. Protonated cyclopropane intermediates formed from sec-butyl cation. J Am Chem Soc 1968 90 6882-4. 

Saunders, M., E. L. Hagen, and J. Rosenfeld Rearrangement Reactions of Secondary Carbonium Ions. Protonated Cyclopropane Intermediates Formed from sec-Butyl Cation. J. Amer. Chem. Soc. 90, 6882 (1968). 

The base [FeBr4] facilitates the elimination of a proton from the carbonium ion (I). 

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 mechanism of the alkylation reaction is similar to curing. The methylo1 group becomes protonated and dissociates to form a carbonium ion intermediate which may react with alcohol to produce an alkoxymethyl group or with water to revert to the starting material. The amount of water in the reaction mixture should be kept to a minimum since the relative amounts of alcohol and water determine the final equiHbrium. 

According to this mechanism, the reaction rate is proportional to the concentration of hydronium ion and is independent of the associated anion, ie, rate = / [CH3Hg][H3 0 ]. However, the acid anion may play a marked role in hydration rate, eg, phosphomolybdate and phosphotungstate anions exhibit hydration rates two or three times that of sulfate or phosphate (78). Association of the polyacid anion with the propyl carbonium ion is suggested. Protonation of propylene occurs more readily than that of ethylene as a result of the formation of a more stable secondary carbonium ion. Thus higher conversions are achieved in propylene hydration. 

The initiating step in these reactions is the attachment of a group to the sulfoxide oxygen to produce an activated intermediate (5). Suitable groups are proton, acyl, alkyl, or almost any of the groups that also initiate the oxidations of alcohols with DMSO (40,48). In a reaction, eg, the one between DMSO and acetic anhydride, the second step is removal of a proton from an a-carbon to give an yUde (6). Release of an acetate ion generates the sulfur-stabilized carbonium ion (7), and the addition of acetate ion to the carbonium ion (7) results in the product (eq. 15) ... 

This donates a proton to the monomer to produce a carbonium ion Figure... 

These mechanistic interpretations can also be applied to the hydrogenation of cyclohexanones. In acid, the carbonium ion (19) is formed and adsorbed on the catalyst from the least hindered side. Hydride ion transfer from the catalyst gives the axial alcohol (20). " In base, the enolate anion (21) is also adsorbed from the least hindered side. Hydride ion transfer from the catalyst followed by protonation from the solution gives the equatorial alcohol (22). 

The Bamford-Stevens decomposition of tosylhydrazones by base has been applied to steroids, although not extensively. It has been demonstrated that the reaction proceeds via a diazo compound which undergoes rapid decomposition. The course of this decomposition depends upon the conditions in proton-donating solvents the reaction has the characteristics of a process involving carbonium ions, and olefins are formed, often accompanied by Wagner-Meerwein-type rearrangement. In aprotic solvents the diazo compound appears to give carbene intermediates which form olefins and insertion products ... 

The formation of 88 is postulated to be occurring by the nucleophilic attack of a hydride ion (47), abstracted from the secondary amine, on the a-carbon atom of the iminium salt (89). The resulting carbonium ion (90) then loses a proton to give the imine (91), which could not be separated because of its instability (4H). In the case of 2-methyIhexamethylenimine, however, the corresponding dehydro compound /l -2-methylazacyclo-heptene (92) was isolated. The hydride addition to the iminium ion occurs from the less hindered exo side. 

A carbonium ion, CHj, is formed by adding a hydrogen ion (H ) to a paraffin molecule (Equation 4-6). This is accomplished via direct attack of a proton from the catalyst Bronsted site. The resulting molecule will have a positive charge with 5 bonds to it. 

The addition of a spillover proton to an adsorbed alkene to yield a secondary carbonium ion followed by abstraction of a proton from the C3 carbon would yield both isomers of 2-butene. The estimated faradaic efficiencies show that each electromigrated proton causes up to 28 molecules of butene to undergo isomerization. This catalytic step is for intermediate potentials much faster than the consumption of the proton by the electrochemical reduction of butene to butane. However, the reduction of butene to butane becomes significant at lower potentials, i.e., less than 0.1V, with a concomitant inhibition of the isomerization process, as manifest in Fig. 9.31 by the appearance of the maxima of the cis- and tram-butene formation rates. 

Several types of proton transfer reactions can be studied conveniently by a neutral product analysis. Until now, the most extensive investigations have been concerned with (1) proton transfer from H3+ and CH5 + to various hydrocarbon molecules, and (2) the transfer of a proton from carbonium ions to larger olefins or other organic compounds. 

Aquilante and Volpi indicate (2) that propanium ions formed by proton transfer from H3 + are not collisionally stabilized at propane pressures as great as 0.3 mm. and that they decompose by elimination of hydrogen or a smaller saturated hydrocarbon to form an alkyl carbonium ion. Others (16, 19) have proposed one or the other of these fates for unstabilized propanium ions. Our observations can be rationalized within this framework by the following mechanisms ... 

Perhaps the most important single function of the solution environment is to control the mode of decomposition of reaction intermediates and hence the final products. This is particiflarly true in the case of electrode reactions producing carbonium ion intermediates since the major products normally arise from their reaction with the solvent. It is, however, possible to modify the product by carrying out the electrolysis in the presence of a species which is a stronger nucleophile than the solvent and, in certain non-nucleophilic solvents, products may be formed by loss of a proton or attack by the intermediate on further starting material if it is unsaturated. The major reactions of carbonium ions are summarized in Fig. 6. 

In the case of carbanion and radical intermediates the solvent is less important but the products are partially determined by the resistance of the medium to proton or hydrogen atom abstraction respectively. The increased stability of these intermediates compared with carbonium ions allows the reaction mechanism to be more readily modified by the addition of trapping agents. For example, carbanions are trapped in high yields by the presence of carbon dioxide in the electrolysis medium (Wawzonek and Wearring, 1959 Wawzonek et al., 1955). 

An early process in the cure reaction is protonation of a methylolphenol, followed by loss of a molecule of water to produce a benzylic carbonium ion (see reaction 4.3). This may be followed by reaction with a second phenol to generate a bridged structure, as illustrated in Reaction 4.4. Alternatively the... 

---