Phenanthrene-3,4-dicarboxylic acid

Under the Schmidt reaction conditions, the lactol (152) of 4-formyl-5-phenanthroic acid gives 1 -aza-pyren-2(lW)-one (153) and phenathrene-4,5-dicarboximide (154)." The compound (153) may be formed by attack of hydrazoic acid at the latent aldehyde site in preference to the carboxy site (see Section 4.4.4.2). Phenanthrene-4,5-dicarboxylic acid (155), obtained by oxidation of (152), similarly affords... 

Phthaloyl peroxide, in contrast to diphenoyl peroxide cannot decarboxylate readily to give a stable lactone. The corresponding lactone (25) is unreasonably strained. The as yet unknown phenanthrene dicarboxylic acid and naphthalic peroxides (26) and (27) could form stable lactone radical anions by loss of CO2 on acceptance of an electron from the activator. 

The photochemical transformation of phenanthrene sorbed on silica gel (Barbas et al. 1996) resulted in a variety of products including c -9,10-dihydrodihydroxyphenanthrene, phenanthrene-9,10-quinone, and a number of ring fission products including biphenyl-2,2 -dicarboxaldehyde, naphthalene-l,2-dicarboxylic acid, and benzo[c]coumarin. 

Note that Ramakrishnan and Bickarr have isolated an anomalous product (2) in the reductive silylation of phenanthrene-3,4-dicarboxylic acid (1). 

Phenanthrene is oxidized with 40% peroxyacetic acid in glyme at 100-110 °C to a,a -diphenic acid in 65-70% yield [256]. Quinoxaline affords a 75-77% yield of pyridazine-2,3-dicarboxylic acid on refluxing for 1.5 h with potassium permanganate [876]. 

Therefore, the method described allows a novel economic as well as ecologically sound synthesis of quinone derivatives. Higher condensed arenes, e.g., anthracene, are converted to the quinones or cleaved to dicarboxylic acids, as in the case of phenanthrene (yield ca. 50 %). Besides MTO, in principle all alkyl- and to some extent also aryl-substituted trioxorhenium compounds, e.g., cyclopropylrhenium trioxide or cyclopentadienylrhenium trioxide, can be used as active catalysts. However, until now MTO apparently constitutes the most active and easy-to-handle catalyst (see Figure 1, p. 439). The solvent of choice for the reaction and the workup procedure, is concentrated acetic acid, also used to dilute the H2O2 (85 wt.%), yielding a water-poor reaction medium which is advantageous for the catalyst lifetime. 

Pure benz(c)phenanthrene, mp. 67—68° and 2,1 l-dimethylbenz(c)phenanthrene, mp. 129—130°, can be simply obtained hydrolyzing 148a) or 148 b) by potassium hydroxide in triglycol at 180° and decarboxylation of the dicarboxylic acids in boiling quinoline in the presence of copper powder, giving a 91% or 70% yield, respectively32 The sterically screened carbonitrile groups in 148 d) and 148 e) cannot be saponified. 

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

Epoxidation. Hoft and Ganschow report that this reagent converts olefins into epoxides, Schiff bases into oxaziridines, and tertiary amines into N-oxides. Epoxidation can be performed more simply by addition of benzoyl isocyanate to a solution of the alkene in THF containing excess anhydrous H2O2 and a trace of a radical inhibitor. Under these conditions phenanthrene is converted at 25° into biphenyl-2,2 -dicarboxylic acid. 

Diazaphenanthrenes are obtained by irradiation of benzylidenaminopyridines in concentrated sulphuric acid 27 the failure of this cyclization to occur in organic solvents is attributed to a rapid photochemical cis -> trans isomerization. Cyclization of 3-phenylazopyridine to give 2,9,10-triaza- and 4,9,10-triaza-phenanthrene has also been observed in sulphuric acid,28 whereas irradiation of azobenzene-2,2,-dicarboxylic acid (32) under the same conditions yields equal quantities of the expected benzo[c]cinnoline (33) and the indazolo[2,l-a]indazole... 

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. 

These results show that reduction of the multiple bonds takes place through trans-addition. By reduction of diphenylacetylene in dimethylformamide in the presence of carbon dioxide Wawzonek and Wearring [103] obtained diphenylfumaric acid, diphenylmaleic anhydride and meso-diphenylsuccinic acid in the proportions 2,5 1 7. If it is assumed that the meso acid is formed from fumaric acid, these results demonstrate the stereospecificity of the process, contrary to the assertions made by Wawzonek and Wearring [103], From phenanthrene in the presence of carbon dioxide they obtained trans- 9,10-dihydrophenanthrene-9,10-dicarboxylic acid. 

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