Electrophiles alcohols

The reaction of trivalent carbocations with carbon monoxide giving acyl cations is the key step in the well-known and industrially used Koch-Haaf reaction of preparing branched carboxylic acids from al-kenes or alcohols. For example, in this way, isobutylene or tert-hutyi alcohol is converted into pivalic acid. In contrast, based on the superacidic activation of electrophiles leading the superelectrophiles (see Chapter 12), we found it possible to formylate isoalkanes to aldehydes, which subsequently rearrange to their corresponding branched ketones. 

Because the protonation of ozone removes its dipolar nature, the electrophilic chemistry of HOs, a very efficient oxygenating electrophile, has no relevance to conventional ozone chemistry. The superacid-catalyzed reaction of isobutane with ozone giving acetone and methyl alcohol, the aliphatic equivalent of the industrially significant Hock-reaction of cumene, is illustrative. 

Aryl and vinylic bromides and iodides react with the least substituted and most electrophilic carbon atoms of activated olefins, e.g., styrenes, allylic alcohols, a,p-unsaturated esters and nitriles. 

We can extend the general principles of electrophilic addition to acid catalyzed hydration In the first step of the mechanism shown m Figure 6 9 proton transfer to 2 methylpropene forms tert butyl cation This is followed m step 2 by reaction of the car bocation with a molecule of water acting as a nucleophile The aUcyloxomum ion formed m this step is simply the conjugate acid of tert butyl alcohol Deprotonation of the alkyl oxonium ion m step 3 yields the alcohol and regenerates the acid catalyst... 

Many of the properties of phenols reflect the polarization implied by the resonance description The hydroxyl oxygen is less basic and the hydroxyl proton more acidic in phenols than m alcohols Electrophiles attack the aromatic ring of phenols much faster than they attack benzene indicating that the ring especially at the positions ortho and para to the hydroxyl group is relatively electron rich... 

Various electrophiles other than iodine have been used to induce alkenyl coupling (9). Alkyl haUdes and protic acids react with alkynylborates to yield mixtures of stereoisomeric alkenylboranes. Nevertheless, oxidation of these products is synthetically useful, providing single ketones (296—298). Alcohols are obtained from the corresponding alkenylborates. 

Aldehydes react with alkenylborates to give 1,3-diols upon oxidation of the intermediate (300). Alkynylborates ate transformed by epoxides into homoallyhc alcohols and alkenylborates into 1,4-diols (300,301). Carbon dioxide reacts with alkenylborates to yield catboxyhc acids (302). The scope of these transformations is further extended by the use of functionalized electrophiles and borates, often reacting with high stereoselectivity. For example, in the... 

If the initiation reaction is much faster than the propagation reaction, then all chains start to grow at the same time. Because there is no inherent termination step, the statistical distribution of chain lengths is very narrow. The average molecular weight is calculated from the mole ratio of monomer-to-initiator sites. Chain termination is usually accompHshed by adding proton donors, eg, water or alcohols, or electrophiles such as carbon dioxide. 

Many other reactions of ethylene oxide are only of laboratory significance. These iaclude nucleophilic additions of amides, alkaU metal organic compounds, and pyridinyl alcohols (93), and electrophilic reactions with orthoformates, acetals, titanium tetrachloride, sulfenyl chlorides, halo-silanes, and dinitrogen tetroxide (94). 

Other carbon electrophiles which are frequently employed include aldehydes, ketones, esters, nitriles and amides of the type RCONMei. An indirect method of acylation involves the initial reaction of a lithio compound with an aldehyde followed by oxidation of the resulting secondary alcohol to the corresponding acyl derivative. 

In aqueous or alcoholic solution, certain alkylazoles react with bases to give traces of anions of type (367). With suitable electrophilic reagents, these anions undergo reasonably rapid and essentially non-reversible reaction. 

A poor leaving group can be made more reactive by coordination to an electrophilic species. Hydroxide is a very poor leaving group. Normally, alcohols therefore do not undergo direct nucleophilic substitution. It has been estimated that the reaction... 

The Friedel-Crafts reaction is a very important method for introducing alkyl substituents on an aromatic ring. It involves generation of a carbocation or related electrophilic species. The most common method of generating these electrophiles involves reaction between an alkyl halide and a Lewis acid. The usual Friedel-Crafts catalyst for preparative work is AICI3, but other Lewis acids such as SbFj, TiC, SnCl4, and BF3 can also promote reaction. Alternative routes to alkylating ecies include protonation of alcohols and alkenes. 

Alcohols and alkenes can also serve as sources of electrophiles in Friedel-Crafts reactions in the presence of strong acids ... 

Because of Us high polarity and low nucleophilicity, a trifluoroacetic acid medium is usually used for the investigation of such carbocationic processes as solvolysis, protonation of alkenes, skeletal rearrangements, and hydride shifts [22-24] It also has been used for several synthetically useful reachons, such as electrophilic aromatic substitution [25], reductions [26, 27], and oxidations [28] Trifluoroacetic acid is a good medium for the nitration of aromatic compounds Nitration of benzene or toluene with sodium nitrate in trifluoroacetic acid is almost quantitative after 4 h at room temperature [25] Under these conditions, toluene gives the usual mixture of mononitrotoluenes in an o m p ratio of 61 6 2 6 35 8 A trifluoroacetic acid medium can be used for the reduction of acids, ketones, and alcohols with sodium borohydnde [26] or triethylsilane [27] Diary Iketones are smoothly reduced by sodium borohydnde in trifluoroacetic acid to diarylmethanes (equation 13)... 

Mercury(II) trifluoroacetate is a good electrophile that is highly reactive toward carbon-carbon double bonds [52, 53, 54] When reacting with olefins in nucleophilic solvents, it usually gives exclusively mercurated solvoadducts, but never products of skeletal rearrangement Solvomercuration-demercuratton of alkenes with mercury(II) trifluoroacetate is a remarkably effective procedure for the preparation of esters and alcohols with Markovnikov s regiochemistry [52, 5J] (equation 24)... 

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