Friedel ketone synthesis

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). 

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),... 

Ketone synthesis by Friedel-Crafts reaction, 12, 16, 62 Knoevenagel reaction, 10, 58... 

The fact that hydrogen in combination with carbon can be replaced by an add radical by the use of an add-chloride is of spedal importance. In this connection, the Friedel-Crafts ketone synthesis is particularly mentioned- This will be taken up later, in practice. The reaction is indicated by the following equation ... 

The use of an acyl chloride in the presence of aluminum chloride constitutes the most frequently used type of Friedel-Crafts ketone synthesis. Many examples from the earlier literature are reported in the reviews mentioned at the beginning of this chapter.The reactivity of acyl halides in reactions of acyl halides with aluminum halides decreases in the order I > Br > Cl > F, but a different order was report for reactions catalyzed by boron halides. In the latter case the order was acyl fluoride > acyl bromide > acyl chloride. We shall concentrate our attention on recently reported examples. 

Perrier procedure with the Friedel-Crafts ketone synthesis... 

Benzophen-oae, Diphenylmethanone diphenyl ketone benzoylbenzene. CwHwO mol wt 182.21. C 85.69%, H 5.53%, O 8.78%. CtHsCOCsHj. Prepd by the Friedel-Crafts ketone synthesis from benzene and benzoyl chloride in the presence of ASCI, Marvel, Sperry, Org Syn. call. vol. I (Wiley, New York, 2nd ed., 1941) p 95. By decarboxylation of o-benzoytbenzoic acid in the presence of copper catalyst L. F. Fieser, Organic Experiments (D. C. Heath Co., Boston, 1964) pp 201-203. 

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-... 

With the above discussion about the Friedel-Crafts acylation, and the general equations for the ketone synthesis, problems (a) and (b) can be derived. 

Synthesis (s. a. C-Chain extension. Condensation, Friedel-Crafts ketone synthesis, Oxalic ester -)... 

Aliphatic Friedel-Crafts ketone synthesis Allylic acylation... 

C-acylation s. Friedel-Crafls ketone synthesis —, C-alkylation 21, 815 special s. diaryl. . . stilbenes styr. . . ... 

Free radical... s. Radical... Friedel-Crafts ketone synthesis 31, 773... 

Baeyer-Villiger oxidation—Phenols from arenes—Friedel-Grafts ketone synthesis s. 19, 190 Baeyer-Villiger oxidation s. a. R. Granger, H. Orzalesi, and P. Joyeux, G.r. 260, 923 (1965)... 

Aluminum chloride-nitromethane Friedel-Crafts ketone synthesis s. 18,900... 

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