Alcohols, aromatic tertiary

Reaction kinetics with the various reagents becomes faster as their nucleophilicity is increased. The following order of reactivity can be given primary aliphatic amine > primary aromatic amine > secondary aliphatic amine primary alcohol > secondary alcohol > water > tertiary alcohol phenol > mercaptan. 

Alcohols, including tertiary alcohols, react readily with the reagent. The reagent adds stereospecifically (Irons) to unhindered olefins, for example, to the 2-butenes tetrasubstituted olefins do not react. The reagent can be used for Friedel-Crafts substitution of aromatic compounds, including azulene. The 2,4-dinitrobenzene-sulfenyl derivatives formed are colored solids readily purified by crystallization or chromatography and hence are useful for purposes of identification. 

If the para- substituent group R- (above) is an alkyl group of about four or more carbon atoms (e.g. tertiary butyl, (CH3)3 C-), the product is soluble in oils otherwise in alcohols, ether-alcohols or alcohol/aromatic hydrocarbon mixtures. If the resin is made from a phenol blocked in the para-position, with a high formaldehyde level and using an alkaline catalyst, it will react when heated with un-saturatcd materials, such as drying oils or rosin to produce a modified phenolic resin. The mechanism is thought to be of the type ... 

Acid-catalyzed alkylation of aromatics with alcohols themselves is widely used. Whereas tertiary (and secondary) alcohols react with rel-... 

Alkyl groups attached to aromatic rings are oxidized more readily than the ring in alkaline media. Complete oxidation to benzoic acids usually occurs with nonspecific oxidants such as KMnO, but activated tertiary carbon atoms can be oxidized to the corresponding alcohols (R. Stewart, 1965 D. Arndt, 1975). With mercury(ll) acetate, allyiic and benzylic oxidations are aJso possible. It is most widely used in the mild dehydrogenation of tertiary amines to give, enamines or heteroarenes (M. Shamma, 1970 H. Arzoumanian. 1971 A. Friedrich, 1975). 

This group decreases the electron density on the aromatic ring and thus inhibits solvolysis of the tertiary alcohol i and the derived acetate ii. ... 

Many aromatic steroids submitted to the Birch reduction contain hydroxyl groups which are deprotonated to the corresponding alkoxides during the reduction, particularly if a tertiary alcohol is used as the proton donoi. The steroidal alkoxides and the one derived from the proton donor often precipitate and cause foaming of the reaction mixture, as was noted by Wilds and Nelson. These alkoxides can be kept in solution by adding an excess of the proton donor alcohol to the mixture the alcohol also assists in dissolving the starting hydroxylic steroid. A particularly useful reaction medium for hydroxylic steroids contains ammonia, tetrahydrofuran and -butyl alcohol in the volume ratio of 2 1 (Procedure 2, section V). This mixture... 

Caglioti et al.201 suggested a mechanism for the action of hexachlorocydotriphos-photriazene in the polyesterification of carboxylic acids with phenols. Higashi291 catalyzed the reaction of various aromatic acids and alcohols by poly(ethyl phosphate). Both Caglioti201 and Higashi291 studied the influence of tertiary amines on the reactivity. 

---