Phenanthrene-1,4-diones

Reduction of phenanthrene-9,10-dione with HI in acetic acid afforded 9-hydroxyphenanthrene as sole product, while an analogous reaction without acetic acid furnished phenanthrene essentially quantitatively. 

Phenanthrene-9,10-dione 7 gives 1,4-diazocine 8 on reaction with biphenyl-2,2 -diamine.30... 

Solutions of biphenyl-2,2 -diamine (7.4 g, 40.2 mmol) in hot HOAc (40 mL) and phenanthrene-9,10-dione (8.3 g, 40 mmol) in HOAc (160 mL) were mixed and kept at 100°C for 2 h. After 12 h cooling, a canary yellow, crystalline powder was filtered off yield 11 g (77%). Recrystallization from excess boiling HOAc gave small, compact crystals mp 268-269 C. 

Phenanthrene-l,4-diones have been prepared [52] by cycloaddition of a-substituted styrenes with an excess of 1,4-benzoquinone (Equation 2.18). Initial cycloadducts are oxidized by 1,4-benzoquinone. 

Scheme 6/1.86. Synthesis of substituted 5,6-dihydro-8/-/-[5,7-a]diazacyclohepta[/7c] phenanthrene-4,7-diones.

The phenanthrene 1,2- and 3,4-diones are synthetically accessible from the related 8 phenols. Oxidation of 2-phenanthrol with either Fremy s salt ((KS0 )2N0) or phenylseleninic anhydride gave phenanthrene 1,2-dione directly (55). Unexpectedly, oxidation of 3-phenanthrol with (KSOg NO yielded 2,2-dihydroxybenz(e)indan-l,3-d-ione (Figure 10). However, phenanthrene 3,4-dione was readily obtained from 3-phenanthrol by Fieser s method entailing diazonium coupling, reduction, and oxidation of the resulting 4-amino-3-phen-anthrol with chromic acid (56). 

Peroxyacyl nitrates, see Acetaldehyde, Butane, 2-Bntanone, 2,3-Dimethylbntane Peroxybenzoic acid, see Toluene Peroxynitric acid, see Formaldehyde Peroxypropionyl nitrate, see 2-Methylpentane, Pentane Phenanthrene, see Anthracene, Bis(2-ethylhexyl) phthalate, Naphthalene Phenanthrene-9,10-dione, see Phenanthrene 9,10-Phenanthrenequinone, see Phenanthrene 4-Phenanthroic acid, see Pyrene... 

Methyl 3a,6a-dihydroxycholanate, 240 1-Methylestrone 3-methyl ether, 10, 27 4b/3-Methyl-7-ethylenedioxy-1,2,3,4, 4a ,4b/3,5,6,7,8,10,1 Oaa-dodecahydro-phenanthrene-1 /3,4/3-diol, 236 14C-Methyl iodide, 211 ds-Methyl iodide, 210, 214 Methyl lithocholate tosylate, 329 1-Methyl-19-nortestosterone, 27 6a-Methylprednisolone, 410 6a-Methylprednisolone BMD, 410 16/3-Methylprednisone, 87 18-Methylpregn-4-ene-3/3,17a,20f-triol, 243 20-Methylpregn-5-en-3/3-ol, 415 17a-Methylpregnenolone acetate, 48 17a-Methyltestosterone, 438 16/3-Methyl- 11a,17a,21 -trihydroxy- 5 /3-pregnane-3,20-dione 21-acetate, 299, 300 20-Methyl-3/3-trityloxypregn-5-ene, 415 3/3-Methoxycholestane, 136 1-Methoxycyclohexene, 18 3-Methoxyestra-3,5(10)-diene, 18, 27... 

The thermal intramolecular 2 + 2-cycloaddition of 4,4,-disubstituted-2,2/-bis(phenyl-ethynyl)biphenyls (1) yielded the intermediate l,2-diphenylcyclobuta[l]phenanthrenes (2), which could be trapped with 2,3,4,5-tetraphenylcyclopenta-2,4-dione (3) to produce the Diels-Alder adduct (4). Thermal decarbonylative ring opening of (4) gave 9,10,11,12,13,14-hexaphenylcycloocta[l]phenanthrenes (5) as the final product in 12-23% yield (Scheme l).1... 

The product from Step 2 (1.0 mmol), diphenylphosphoryl azide (1.2 mmol), triethylamine (5 mmol), phenanthrene-9,10-dione (0.7 mmol) and triphenyl arsen oxide (0.05 mmol) were dissolved in 12 ml toluene and heated 3 hours at 60 °C. The product was purified by chromatography on silica gel using CH2Cl2/hexane, 2 1, re-crystallized in CH2Cl2/hexane, and the product isolated in 100% yield. H- and C-NMR data supplied. 

Heterocyclic Synthesis. - The reactions of phosphorus ylides with phenan-threne-9,10-quinone (113) have been used to prepare phenanthrene [9,10-x]-fused compounds with four, five, and six membered heterocyclic rings. (E)-4-carbethoxymethylene-l,2,3,4-tetrahydro-2-quinolones 114 have been obtained from the stereoselective reaction of 3-hydroxy-1,2,3,4-tetrahydroquinoline-2,4-diones and ethyl(triphenylphosphoranylidene)acetate. A -trifluoroacetylanilines 115 react with Ph3P=C02Et producing enamine derivatives 116 as a mixture of (E)- and (Z)-isomers. Enamines 116 are useful precursors for the synthesis of indoles and quinolones. 

Dipotassium platinum tetrachloride, 182 Dipotassium rhodizonate, 262 N,N -Disalicyle(hylenediamine, 360 Disodium acetylide, 182 Disodium phenanthrene, 182 Dispiro[2.0.2.2]octene-7, 388 Dispiro[5.1.5. l]tetradecane-7,14-dione, 428, 429... 

Alkylbenzenes. Abstraction of benzylic hydrogen proceeds readily and was observed in the early years of dione photochemistry. Reactions of phenanthrenequinone have been reported iB,ioi,ii8,i8a,i48,i78> with toluene, o-, m- and -xylene, ethylbenzene, isopropylbenzene, cumene, pseudocumene, -cymene, f-butyltoluene, -methoxytoluene, >-nitro-toluene, diphenylmethane, thioxanthene, tetralin, collidine, and quinal-dine. Only dimers of the hydrocarbon radicals were described 148> in the reactions of diphenylmethane and thioxanthene and only phenanthrene-... 

Diphenylcyclobutene- dione benzene acetonitrile sun phenanthrene-9,10-dicarboxylic acid anhydride 24)... 

Ozonation of benzo[r,s,t]pentaphene (7) followed by oxidative workup led to benzo[r,s,t]pentaphene-5,8-dione (12) (14%), phthalic acid (13) (4%), p-terphenyl-2,2, 3, 2"-tetra-carboxylic acid-2, 3 -anhydride (14) (10%), and 2-(o-car-boxyphenyl)- ,10-phenanthrenedicarboxylic acid anhydride (15) (3%), with a 56% recovery of unreacted 7, Ozonation of pentaphene (11) led to a peroxidic mixture which on oxidative workup led to 2,2 -binaphthyl-3,3 -dicarboxalde-hyde (16) (16%), 2,2 -binaphthyl-3,3 -dicarboxylic acid (17) (16%), and 13 (2%), with a 28% recovery of unreacted 11. A comparison of the reactivity to ozone of carcinogenic polycyclic aromatics benzo c]phenanthrene (1), 7,12-di-methylbenz [a] anthracene (2), 3-methylcholanthrene (3), dibenz[si,]] - (4), and dibenzlsi, ]anthracene (5), benzo Si -pyrene (6) and 7, and the noncarcinogen 11, all determined in our laboratory, leads us to conclude that there is no simple, consistent correlation between carcinogenicity, K-and L-region additivity towards ozone and the Pullmans electronic theory of carcinogenesis. 

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