Friedel-Crafts ketone synthesis

B. The Phthaleins.—If two molecules of a phenol and one molecule of phthalic anhydride are caused to interact under the conditions which prevail during the Friedel-Crafts synthesis (Chap. IX. p. 342), the tendency of the ketone first formed to combine with a second molecule of the phenol outweighs condensation to the anthraquinone derivative in this way are formed the phthaleins, discovered by Baeyer in 1871. This process may be discussed by taking phenolphthalein as an example. 

At the time the chemistry of (OC)9Co3CCO+PF6 was being developed (27, SO), another route to this novel acylium ion was found in these laboratories (31, 32). This discovery was a result of our intention to adapt the Friedel-Crafts synthesis of benzylidynetricobalt nonacarbonyl complexes of Dolby and Robinson (15) to the preparation of alkyl derivatives of methylidynetricobalt nonacarbonyl, whose general preparation was not well in hand. The reaction chosen for investigation was the aluminum chloride-induced interaction of tetraalkyltin compounds with ClCCo3(CO)9 In analogy to a known ketone synthesis (33),... 

Since the polycyclic ketones required for the Scholl reaction are generally prepared by the Friedel-Crafts synthesis, the two reactions can be combined thus, passing a stream of oxygen into an aluminum chloride-sodium chloride melt containing 1-benzoylpyrene and /7-toluoyl chloride yields 3-methyl-8,16-... 

Synthesis of Aromatic Ketones (Friedel-Crafts Acylation)... 

The polymerization of a,P-unsaturated carbonyl compounds is very similar to the Friedel-Crafts synthesis of aromatic ketones, where tiie catalyst forms a complex with the reaction products and therefore is necessarily to be used in equimolecular amount. In order to avoid the WCle consumption via doping of polyacetylenes we tried to perform COER with highly substituted olefins (tetraphenylethylene, stylbene, 1,1-diphenylethylene) and simple carbonyl compounds (benzophenone, terephthalaldehyde) using WClfunctional groups are in different molecules and the results should be new olefins and new carbonyl compounds, not a conjugated... 

Intramolecular photo-Friedel-Crafts synthesis Cyclic ketones from thiolic acid esters... 

The Friedel-Crafts ketone synthesis is of commercial importance in upgrading duoroben2ene for dmg, polymer, and electronic appHcations (Table... 

Table 2. Friedel-Crafts Ketone Synthesis with Fluorobenzene ...

Ketone Synthesis. In the Friedel-Crafts ketone synthesis, an acyl group is iatroduced iato the aromatic nucleus by an acylating agent such as an acyl haUde, acid anhydride, ester, or the acid itself. Ketenes, amides, and nittiles also may be used aluminum chloride and boron ttitiuotide are the most common catalysts (see Ketones). 

The most important method for the synthesis of aromatic ketones 3 is the Friedel-Crafts acylation. An aromatic substrate 1 is treated with an acyl chloride 2 in the presence of a Lewis-acid catalyst, to yield an acylated aromatic compound. Closely related reactions are methods for the formylation, as well as an alkylation procedure for aromatic compounds, which is also named after Friedel and Crafts. 

Synthesis of the prototype begins with Friedel Crafts acetylation of salicylamide ( ). Bromination of the ketone (25) followed by displacement with amine gives the corresponding ami noketone ( ). Catalytic hydrogenation to the ami noalcohol completes the synthesis of labetolol (24). The presence of two chiral centers at remote positions leads to the two diastereomers being obtained in essentially equal amounts. 

Figure 7-11 shows a Friedel-Crafts acylation reaction. The reaction produces an aryl ketone, which is useful in synthesis because it makes it relatively easy to convert the ketone (RCOR) group to an alkyl (R) group. The procedure involves the catalytic hydrogenation of the aryl ketone, and it s particularly useful when the electrophile in a Friedel-Crafts alkylation is susceptible to rearrangement. 

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