Alcohols, tert., 2-functionalized ketones

Trimethylaluminum exhaustively methylates O-functions and thus converts tert. alcohols to alkanes, ketones to gem-dimethyl compounds, and carboxylic acids to terUhuiyX derivatives . AgC104-SnCl4 gives high yields of diarylmethanes by benzylation of arenes, e. g. with benzyl alcohol . 

The bulk of oxidations with tert-butyl hydroperoxide consists of epoxidations of alkenes in the presence of transition metals [147, 215, 216, 217, 218]. In this way, a,p-unsaturated aldehydes [219] and ketones [220] are selectively oxidized to epoxides without the involvement of the carbonyl function. Other applications of tert-butyl hydroperoxide such as the oxidation of lactams to imides [225], of tertiary amines to amine oxides [226, 227], of phosphites to phosphates [228], and of sulfides to sulfoxides [224] are rare. In the presence of a chiral compound, enantioselective epoxidations of alcohols are successfully accomplished with moderate to high enantiomeric excesses [221, 222, 223]. 

Substituted and Heat Reactive. The third class, substituted and heat-reactive resins, are made by using para-substituted phenols where the substituent is a four-carbon or higher group such as tert-butyl, tert-octyl, and phenyl. Small amounts of ortho-substituted phenols and unsubstituted phenols are sometimes coreacted but, in general, the functionality is 2, and only linear molecules are formed. They are brittle solids that do not form films. The substituent makes the resins less polar and hence they are soluble in ketones, esters, and aromatic hydrocarbons, with limited solubility in alcohols and aliphatic hydrocarbons. The phenolic resins based on longer chain aliphatic phenols are more compatible with drying oils, alkyds, and rubbers. 

The first step in this transform comprises formation of a radical dianion (1-2) from reaction of at the sites of lowest electron density (Scheme 4.1). In the case of steroids, this requirement rules out all but positions 1,4 of the aromatic ring A. The charges on the intermediate then strip protons from the alcohol in the reaction medium to yield the dihydrobenzene 1-3. The alcohol, frequently tert-butanol, thus acts as a quench. The enol ether function in the product is sufficiently robust to serve as a protecting group in many subsequent reactions. Mild acid hydrolysis of that enol ether affords the surprisingly stable unconjugated ketone 1-4. Treatment of this last intermediate with mineral acid causes the unsaturation to move over into conjugation at C4 (1-5). 

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