Phenanthren-9 -one

Nicolaides and co-workers " conducted extensive studies on preparing 2-aryl- and 2-heteroarylphenanthro[9,10-(i]oxazoles. For instance, refluxing a solution of 10-(methoxyimino)phenanthrene-9-one 304 in an aromatic or heterocyclic methylated hydrocarbon affords a 2-aryl- or a 2-heteroarylphenanthro[9,10-d] oxazole 305 directly (Scheme 1.81). The yields are variable and poor to modest. However, using a substituted methyl analog, i.e., ArCH2Y in this reaction markedly improved the yield of 305 for several cases. Examples of 305 prepared from aromatic and heterocyclic alkanes are shown in Table 1.25. 

TABLE 1.25. 2-ARYL- AND 2-HETEROARYLPHENANTHRO [9,10- i]OXAZOLES FROM 10-(METHOXYIMINO)PHENANTHRENE-9-ONE ... 

To a flask were added 60 mL CH2CI2, 2.7 g 2-(2-chloro-4,6-dimethoxy-pyrimidin-5-yl)-cyclohex-l-enecarboxylic acid ethyl ester (8.3 mmol), and 41 mL 1.0 M BBrs solution in CH2CI2. The mixture was refluxed for 16 h and then cooled to 0°C 20 mL MeOH was added. The reaction mixture was mixed with water and finally extracted with CH2CI2. Upon evaporation of solvent, the residue was suspended in hexane then filtrated and washed withhexane to give, after drying, 1.57 g2-chloro-4-methoxy-5,6,7,8-tetrahydro-10-oxa-1,3-diaza-phenanthren-9-one, in a yield of 71%, m.p., 184-186°C. 

Common Name 13-methyl-17-ethynyl-l7-hydroxy-1,2,3,4,6,7,8,9,11,12,13,14,16,17-tetra-decahydro-15H-cyclopenta(a)phenanthren-3-one... 

Convenient starting materials are the ethers of 3-hydroxy-13-methyl-1,4,6,7,8,9,11,12,13,-14,16,17-dodecahydro-15H-cyclopenta(a)phenanthren-17-one described in U.S. Patent 2,655,518, according to U.S. Patent 2,691,028 mhere the folloming preparation is also de-scribad. The methyl ether is also designated as 3-methoxy-17-oxo-2,5-estradlene. 

Intramolecular arylations can also be carried out photochemically. Huisgen and Zahler (1963 a) prepared fluoren-9-one by irradiation of benzophenone-diazonium salts in dilute sulfuric acid. The classical Pschorr synthesis of phenanthrene-9-carb-... 

Attempts were reported119,129 to synthesize the ortho-linked diphenyl cyclo-propenone phenanthreno cyclopropenone 173 by dehydrohalogenation of the dibromo derivative 174 of dibenzo cyclohepta-l,3-diene-6-one. The only product isolated was the anhydride 175 of phenanthrene-9-carboxilic acid, which was shown not to arise from 173l29 ... 

Pschorr s synthesis of phenanthrene (1893) in five steps with the essential dediazoniation and ring closure of 2-diazonio-a-phenylcinnamic acid giving, on addition of copper powder, phenanthrene-9-carboxylic acid, is today still the highest yielding one of all the reactions discussed in this section, Pschorr was able to get 93% yield, and today electrochemically induced Pschorr and related reactions141 give almost quantitative yields in several cases. 

Pschorr Synthesis. In this synthesis of phenanthrene derivatives, one of the steps involves the union of two aryl nuclei through a diazotiza-tion reaction. By treatment of diazotized a-phenyl-o-aminocinnamic add with copper, 9-phenanthroic add is obtained.24... 

Studies of the photodecomposition of phenanthrene 9,10-imine, 1-benzyloxypyrid-2-one, and methyl phenobarbital have also been reported, and the effect of an external field on photoinduced substitution in 4-methylquinoline-2-carbonitrile has been described. ... 

The dihydro-cyclopentano-phenanthrene (120) has been synthesized (Scheme 9) from 2-acetyl-3-methylnaphthalene (115), which was converted into the fur-furylidene derivative (116). Treatment with acid afforded the expected dioxo-heptanoic acid (117), which on treatment with base provided the cyclopentenone (118). This keto-acid (118) readily underwent cyclization when boiled with acetic anhydride, furnishing ll-acetoxy-15,16-dihydro-7-methylcyclopenta[a]-phenanthren-17-one (119a). Deoxygenation at C(ll) was performed through... 

Prior to our work, fluorenones had been synthesized by methods characterized by the limited accessibility of the starting substrate [28,30,32,33] (substrate being fluorene, biphenyl-1-carboxylic acid, benzophenone, fluoranthene, cyclohexene, phenanthrene or phenylpropionic acid derivatives), a lack of stereoselectivity [28,29,31,33] and poor yields. We therefore developed a simple methodology for synthesizing fluoren-9-ones via domino acylation-cycloalkylation/alkylation-cycloacylation (Chart-19). 

Table 1 IRa Spectroscopic data and melting points,6 and references for the synthesis and crystallography of substituted phenyl (pcydH), biphenyl (bpcydH), naphthalene (nacydH), phenanthrene (phcydH), pyrene (pycydH) and fluoren-9-one (flcydH) cyanamides, substituted 1,4-dicyanamidebenzene (dicydH2) derivatives, 4,4 -biphenyldicyanamide (bpdcydH2) and azo(diphenyl) mono- (apcH) and di-cyanamides (adpcH2).

The photoisomerisation kinetics and other properties of the 1 1 inclusion complexes formed between aromatic derivatives of norbomadiene and P-cyclo-dextrin have been measured." (S)- or (R)-2-Chloropropiophenone affords partially racemised (S)- or (R)-2-phenylpropionic acid respectively by a photo-induced rearrangement via what is probably an ion or radieal intermediate," and (Z)-N-substituted benzoyl-a-dehydrophenylalanines such as (7) are photo-isomerised to 1-azetidine derivatives (8) by a 1,3-acyl migration. Irradiation of 9,9 -bifluorene-9,9 -diol (9) gives a mixture of fluoren-9-one and spiro[9H-fluorene-9,9 (10 -H)-phenanthren]-10 -one (10) whose composition is solvent dependent with the more polar solvents favouring (10). Laser flash photolysis shows the presence of two transients, one of which can be identified with the 9-fluorenyl cation (11), and which originates from photoheterolysis of the diol (9). There is also evidence to support the view that unimolecular rearrange-... 

Cycloaddition reaction of 2,3-diphenylcyclopropenone with l,3-diphenyl-2//-cyclopenta[/]-phenanthren-2-one in chlorobenzene at 150°C for 80 hours under argon in a sealed tube produced 9,10,12,13-tetraphenyl-ll//-cyclohepta[/]phenanthren-ll-one in 29% yield. 

Perhydrohistrionicotoxin, 75, 611 Perhydrophenanthrene-9-one, 535 Periodates, 454 Periodic acid, 124 Peropyrene, 499 Peroxy adds, 260 Peroxybenzimidio acid, 455-456 Peroxycyclohexanecarboylic acid, 260 Persulfoxides, 241 Peterson reaction, 631, 636 Pfitzner-Moffatt oxidation, 227-228, 467 Phase-transfer catalysts, 10, 136, 159, 174-175, 191, 219, 249, 271, 404-406, 452, 565, 566, 586, 640-641 Phenacyldimethylsuifonium bromide, 456 Phenacyiidinedimethylsulfurane, 456 Phenanthrene, 35, 533, 669-670 9,10-Phenanthrenequinones, 47 6-477 Phenazines, 513... 

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