Benzo phenanthrenes synthesis

Methods for the synthesis of the biologically active dihydrodiol and diol epoxide metabolites of both carcinogenic and noncarcinogenic polycyclic aromatic hydrocarbons are reviewed. Four general synthetic routes to the trans-dihydrodiol precursors of the bay region anti and syn diol epoxide derivatives have been developed. Syntheses of the oxidized metabolites of the following hydrocarbons via these methods are described benzo(a)pyrene, benz(a)anthracene, benzo-(e)pyrene, dibenz(a,h)anthracene, triphenylene, phen-anthrene, anthracene, chrysene, benzo(c)phenanthrene, dibenzo(a,i)pyrene, dibenzo(a,h)pyrene, 7-methyl-benz(a)anthracene, 7,12-dimethylbenz(a)anthracene, 3-methylcholanthrene, 5-methylchrysene, fluoranthene, benzo(b)fluoranthene, benzo(j)fluoranthene, benzo(k)-fluoranthene, and dibenzo(a,e)fluoranthene. 

Arai, S., Ishikura, M., and Yamagishi, T. (1988) Synthesis of polycyclic azonia-aromatic compounds by photo-induced intramolecular quaternization azonia derivatives of benzo[c]phenanthrene, [5] helicene and [6]helicene. Journal of the Chemical Society, Perkin Transactions 1, 1561-1567. 

One pathway to benzo(c)phenanthrene by the cyclization-elimination method has been outlined already (Section III., B. 2.) and another we will see later. A synthesis by benzannelation should start with phenanthrene-4-acetonitrile or with phenanthrene 3-acetonitrile (88) as the one component. For steric reasons the preparation of the first has only poor chances, but (88) is readily available 3-methylphenanthrene, mp. 62—63°56), obtained by hydrolysis and decarboxylation from the nitrile (72 b) (Section III., C. 3.) in an overall yield of 92% was side-chain brominated by N-bromo-succinimide in CC14, and the 3 bromomethylphenanthrene, mp. 116—117° (67%), converted to (88), mp. 82-83° (91%). 

AI3-00867 1,2-Benzphenanthrene Benz(a)phen-anthrene Benzo(a)phenanthrene 1,2-Benzophen-anthrene CCRIS 161 Chrysene Coal tar pitch volatiles chrysene 1,2,6,6-Dibenzonaphthalene EINECS 205-923-4 HSDB 2810 NSC 6175 RCRA waste number U050. Found in coal tar. Used in chemical synthesis, mp = 258.2° bp = 448° 1.274 X.m = 257, 267, 294,... 

Analogues of Anthracene and Phenanthrene.—The tandem-directed metalla-tion reaction between thiophen-3-aldehyde and thiophen-3-carboxylic acid diethylamide has been found to be a very useful method for the synthesis of thiophen analogues of anthraquinones. A detailed procedure for the synthesis of benzo[l,2-6 4,5-f)]dithiophen has been published. The reaction of l-(2-naphthyl)-5,5-dimethyl-3-oxocyclohexene with sulphur gave (168). ... 

The synthetic strategy outlined in Scheme 5 for 4,5-bis(2-pyridyl)phenanthrenes 28 also found success in the synthesis of l,12-bis(2-pyridyl)benzo[c]phenanthrene 81 (Scheme 16) [75]. Condensation between 4a, 10a-diazoniaanthra[l,2-a]anthracene diperchlorate (80) and 1,1-diethoxypropene led to 81 in 53% overall yield. 

Scheme 16 Synthesis of l,12-bis(2-pyridyl)benzo[c]phenanthrene-2,ll-diol 81 [75]...

Scheme 18 Synthesis of benzo[c]phenanthrene 89 bearing a crown ether [81]...

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