Phenanthrenes Friedel-Crafts reaction

There are no reported alternatives to the current procedure for the acylation of a phenanthrene using the Friedel-Crafts reaction. Indeed, alternative methods to cleanly prepare 3,6-disubstituted derivatives of phenanthrene by means of electrophilic substitution are not known,5> >" nor is there a... 

This test is given by any aromatic compound that can undergo the Friedel-Crafts reaction, with the particular color produced being characteristic of the aromatic system involved orange to red from halobenzenes, blue from naphthalene purple from phenanthrene, green from anthracene (Chap. 30). 

Naphthalene, anthracene and phenanthrene can be prepared by an intramolecular Friedel-Crafts reaction in which initially a cyclic anhydride reacts with benzene or naphthalene. 

Thiophen Analogues of Polycyclic Aromatic Hydrocarbons Analogues of Anthracene and Phenanthrene. - Keto-enol tautomerism in a naphtho- and several anthra-thiophen systems [such as (241) (242)] has been studied. The system (241) (242) was obtained via the Friedel-Crafts reaction of thiophen with naphthalene-2,3-dicarboxylic anhydride followed by ring-closure. A [c] -fused system was similarly obtained by starting from... 

The latter reagent also methylates certain heterocyclic compounds (e.g., quinoline) and certain fused aromatic compounds (e.g., anthracene, phenanthrene). The reactions with the sulfur carbanions are especially useful, since none of these substrates can be methylated by the Friedel-Crafts procedure (11-12). It has been reported that aromatic nitro compounds can also be alkylated, not only with methyl but with other alkyl and substituted alkyl groups as well, in ortho and para positions, by treatment with an alkyllithium compound (or, with lower yields, a Grignard reagent), followed by an oxidizing agent such as Bra or DDQ (P- 1511). 

Another Friedel-Crafts route to phenanthrenes is the Bardhan-Sengupta phenanthrene synthesis. When phenethylcyclohexanol 222 was cyclized with phosphorus pentoxide at 140°C, the product was 223. Aromatization was accomplished by heating with selenium to give the phenanthrene derivative 224 (1-methyl-7-isopropylphenanthrene, otherwise known as retene). An improvement in the reaction used hydrogen fluoride (HF) to induce cyclization.l ... 

This reaction is related to the Friedel-Crafts Alkylation, Darzens Olefin Acylation, Fries Rearrangement, Haworth Phenanthrene Synthesis, and Nencki Reaction. 

The history of the chemistry of l,12-dimethylbenzo[c]phenanthrene (2) resembles that of 4,5-dimethylphenanthrene (1). The first symthesis of 2 was reported by Newman and Wolf in 1952 [9]. The synthetic sequence included preparation of diacid 67 for the Friedel-Crafts acylation reactions to form diketone 68 (Scheme 15). Reduction followed by dehydration and dehydrogenation then produced 2. 

The Haworth reaction is a classical method for the synthesis of tetralone, beginning with benzene and succinic anhydride. The three-step protocol involves a Friedel-Crafts acylation, followed by reduction of the arylketone, and an intramolecular Friedel-Crafts acylation. The tetralone analog may be further reduced and dehydrogenated to form new aromatic species, in what is known as the Haworth phenanthrene synthesis. 

Several name reactions are promoted by AICI3. For example, the Darzens-Nenitzescu reaction is simply the acylation of alkenes. The Ferrario reaction generates phenoxathiins from diphenyl ethers (eq 19) The rearrangement of acyloxy aromatic systems is known as the Fries rearrangement (eq 20). Aryl aldehydes are produced by the Gatterman aldehyde synthesis (eq 21). The initial step of the Haworth phenanthrene synthesis makes use of a Friedel-Crafts acylation. The acylation of phenolic cort tounds is called the Houben-Hoesch reaction (eq 22). The Leuckart amide s)oithesis generates aryl amides from isocyanates (eq 23). ... 

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