Secondary carbonium ion

A tertiary carbonium ion is more stable than a secondary carbonium ion, which is in turn more stable than a primary carbonium ion. Therefore, the alkylation of ben2ene with isobutylene is much easier than is alkylation with ethylene. The reactivity of substituted aromatics for electrophilic substitution is affected by the inductive and resonance effects of a substituent. An electron-donating group, such as the hydroxyl and methyl groups, activates the alkylation and an electron-withdrawing group, such as chloride, deactivates it. 

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. 

A convenient method leading to pyrans (38) consists in the nucleophilic addition of R anions to 2,6-disubstituted pyrjdium salts, in which the y-position (secondary carbonium ion) is more reactive than the a-positions (tertiary carbonium ions), in opposition to the reactivity of 2,4,6-trisubstituted pyrylium salts.Krohnke and Dickore as well as Dimroth and WolH showed that 2,6-diphenyl-pyrylium salts add the anions R of nitromethane, 1,3-diketones, malonodinitrile, ethyl cyanoacetate, and benzoylacetonitrile. Similar reactions are known in the flavylium series. -Nonactivated R ... 

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. 

This reaction exemplifies the important process of methyl removal, which becomes even more significant in the case of multiply branched paraffins. The rather large exothermicity of Reaction 11 results from the fact that a secondary carbonium ion is formed. The beta fission process can be illustrated using reactions in 8-ra-hexylpentadecane (compound 2) as an example. Table II shows that the ions formed by C-C fission at a branch point (Ci4+, m/e = 197 and Ci5+, m/e = 211) have intensities appreciably larger than the other alkyl ions in the same region... 

The formation of any vinyl products in electrophilic additions to RCH=C=CH2 and RCH=C=CHR is surprising, since central protonation should yield a secondary carbonium ion compared to terminal protonation and formation of a vinyl cation. Perhaps a secondary carbonium ion destabilized by... 

As a result of the inductive and hyperconjugative effects it is to be expected that tertiary carbonium ions will be more stable than secondary carbonium ions, which in turn will be more stable than primary ions. The stabilization of the corresponding transition states for ionization should be in the same order, since the transition state will somewhat resemble the ion. Thus the first order rate constant for the solvolysis of tert-buty bromide in alkaline 80% aqueous ethanol at 55° is about 4000 times that of isopropyl bromide, while for ethyl and methyl bromides the first order contribution to the hydrolysis rate is imperceptible against the contribution from the bimolecular hydrolysis.217 Formic acid is such a good ionizing solvent that even primary alkyl bromides hydrolyze at a rate nearly independent of water concentration. The relative rates at 100° are tertiary butyl, 108 isopropyl, 44.7 ethyl, 1.71 and methyl, 1.00.218>212 One a-phenyl substituent is about as effective in accelerating the ionization as two a-alkyl groups.212 Thus the reactions of benzyl compounds, like those of secondary alkyl compounds, are of borderline mechanism, while benzhydryl compounds react by the unimolecular ionization mechanism. 

Evidently, this reaction may take place wherever primary or secondary carbonium ions occur in the presence of secondary or tertiary methyl groups. The transfer of larger carbanions may, of course, also be found under appropriate circumstances but cannot be treated quantitatively at present. 

Isopropyl fluoride gives a substantially stable ionic complex with excess antimony pentafluoride (see Table 3). n-Propyl fluoride in antimony pentafluoride gave the identical secondary carbonium ion complex. 

Proton—Cl Spin-Spin Coupling Constants of Secondary Carbonium Ions and their Parent Hydrocarbons... 

The infra-red spectra of the trimethyl, dimethyl- and dimethylethyl-carbonium salts in excess antimony pentaduoride are shown in Figs. 4a, b, and c. The IRTRAN cells used are not transparent below 770 cm , thus obscuring the 650 cm SblY absorption which would, however, be overlapped by the solvent SbFs absorption. The broad, intense absorption band which appears in all the spectra near 1550 cm is present in the solvent spectrum. It was found to be dependent on the purity of the SbFs, but the nature of the impurity was not established. It should also be mentioned that Deno found an intense absorption at 1533 cm in cyclohexenyl cations thus, secondary carbonium ions formed from the reaction with olefins (which arise from deprotonation) could add to this broad absorption. 

The secondary carbonium ion could also collapse directly to the 2-olefin... 

The intermediate has a finite lifetime, but it is not free the less stable secondary carbonium ion is stabilized by specific interaction with two molecules of water. The same kinetic study on primary alcohols made by Dostrovsky and Klein (79) shows that oxygen exchange in dilute acid solution does not proceed by way of an ion, but by a concerted mechanism. For the same reason the elimination reaction has to be of a concerted nature and cannot proceed via an unsolvated carbonium ion. 

Formation of XXVII by loss of a proton from the tertiary carbon atom in the neopentyl group of XXVI rather than from the tertiary carbon atom in the secondary isopentyl group is, however, hardly to be expected. Furthermore, the addition of a tertiary olefin to a secondary carbonium ion is also unexpected (compare the results on the copolymerization of n-butylene with isobutylene, page 46). A somewhat more likely combination consists of the addition of the tertiary carbonium ion. XXVIII to fert-butylethylene (XXIX) followed by a 1,3-shift of a... 

Radioactive tracer experiments reported by Lombardo and Hall (4) showed that each butene isomer can be directly interconverted into the other two. These results are consistent with a common intermediate being in operation in this reaction. In Figure 3 the linear relationship between catalytic activity and percentage of Na+ replaced by H+ strongly favors a Bronsted acid catalyzed mechanism in which the common intermediate could be a secondary carbonium ion. This conclusion is also supported by the tracer experiments. 

Two secondary carbonium ions can be formed in this case one allowing the interconversion of the three isomers while the other only permits... 

On the other hand, the n-pentylbenzene - methylnaphthalene reaction proceeds through C6H5-CH2-CH2-CH2-C+H-CH3, a secondary carbonium ion. As a consequence, acid-catalyzed cyclization produces both five- and six-membered rings. The possible carbonium ion intermediates leading to five- or six-membered ring closure may have similar structures (e.g., both are secondary carbonium ions, as in the case of n-pentylbenzene). If so, acid-catalyzed cyclization favors six-membered ring products, as shown by the k5/k6 ratios (Table IV). 

For internally branched methylalkanes, a-cleavage at the branch point causes formation of two secondary carbonium ions, one an odd-numbered mass ion [CnH2n+i]+ and the... 

The ratio of the even- to odd-mass ion can aid in interpretation of spectra, and a series of idealized mass spectra of mono-, di- and trimethylalkanes is presented in Figure 2.2 (from Blomquist et al., 1987). Depending upon the size of the molecule and the size of the secondary carbonium ion, the even-mass ion of the pair is frequently larger than the odd-mass ion (Blomquist et al., 1987 Nelson and Sukkestad, 1970 Pomonis et al., 1978). The formation of the primary (straight-chain) carbonium ion is much less favored than the secondary carbonium ion (which contains the methyl branch of the original molecule). 

Both 2- and 4-methylalkanes have an ion of low intensity at M-15, owing to loss of a methyl group. The major ion of signihcant intensity in the high-mass region of the mass spectra for both isomers is due to the M-43 ion a primary carbonium ion formed by loss of isopropyl from the 2-methylalkane and a secondary carbonium ion formed by the loss of n-propyl from the 4-methylalkane. In addition, the 4-methylalkane has a primary carbonium ion of low intensity at the M-71 M-72 due to cleavage internal to the methyl branch point. The presence of this primary ion pair establishes the structure of a 4-methylalkane. However, in mass spectra of low intensity or in which other isomers are present, the ions at M-71 M-72 may not be readily apparent. 

Protonation of glycerol 6.4 catalyses dehydration via secondary carbonium ion 6.5 to give enol 6.6. Acid catalysed elimination of a second water molecule affords acrolein 6.7. Thus glycerol acts essentially as a protected form of acrolein, slowly releasing this unstable a,p unsaturated aldehyde into the reaction medium. Better yields are realised with this approach than if acrolein itself is present from the start. The reaction proceeds with a Michael addition of aniline 6.3 to acrolein, producing saturated aldehyde 6.8 which cyclises via an aromatic substitution reaction to alcohol 6.9. Acid-catalysed dehydration to 6.10 then oxidation yields quinoline 6.1. Nitrobenzene can be used as a mild oxidant, as can iodine and ferric salts. 

Allyltrimethylsilane reacts rapidly with PTAD to generate a 1,4-dipolar species (230) leading to three products, including (232), different from those expected from the usual ene reaction (81JOC614). In the formation of the pyrazolo[ 1,2-a]-s-triazole (232), a three-membered ring intermediate (231), a co-contributor to the resonance hybrid along with (230), may be involved. A direct transformation of (230) to (232) appears to be rather difficult, since it includes transformation of a secondary carbonium ion to a primary one. 

R+ attacks the allylbenzene which yields the secondary carbonium ion, +... 

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