Methylbenzo phenanthrene

Staggered configurations have also been observed for the tricarbonyl chromium complexes of phenanthrene 294, 295), 9,10-dihydro-phenanthrene 293, 295), anthracene 202), naphthalene 262), and 1-aminonaphthalene 58). The eclipsed configuration has been observed for the tricarbonyl complexes of anisole (57, 229), toluidine 60, 61), methylbenzoate (59), o-methoxyacetylbenzene, o-hydroxyacetylbenzene 101), 2-methoxy-[l-hydroxy-ethyl]benzene (99), and 2-methyl-[l-hydroxy-l-phenylpropyl]benzene (97). It is apparent that the orientation of the chromium tricarbonyl moiety is in many cases controlled by the substituents on the ring to which it is coordinated, and this has been attributed to mesomeric electron repulsion or withdrawal by the substituents 374). 

Thermolysis of the isolated aminonitrile (89), mp. 169° (85%) obtained by condensing (88) with (7b) in pyridine, gives rise to the formation of a mixture (83%) of two different isomeric nitriles in nearly equal amounts, the expected 2-methyl-benzo(c)phenanthrene-4-carbonitrile (90) and the 9-methylbenzo(a)anthracene-l 1-carbonitrile (91). 

By calculation the angular benzannelation of the yellow benz(c)phenanthrene derivative (98), from condensation of ll-methylbenzo(c)phenanthrene-2-acetonitrile with (7b) obtained, should favored by 0.292 0 above the linear annelation. 

To a 10" M solution of 2-(4-methylstyryl)naphthalene (one isomer or a mixture of both) in methanol was added about 25 mg of iodine. The solution was irradiated by a high-pressure mercury lamp (Philips, HPK 125) which was surrounded by a pyrex tube and immersed into the solution. After 16 h the solvent was evaporated. A small volume of CCI4 was added to the residue and again evaporated. This procedure was repeated until the violet color of iodine was not present anymore in the distillate. The residue was purified by chromatography on silica gel and toluene. 2-methylbenzo[c]phenanthrene was isolated in 70% yield and melted at 82 - 83 °C. 

Methylbenzo[c]phenanthrene rocked and heated 65 hrs. at 250° with aq. Na-dichromate 2-carboxybenzo[c]phenanthrene. Y 64% recovery of startg. m. 19%.—This method is remarkably clean and does not attack a ring sensitive to other oxidizing agents. Also isomeric carboxybenzo[c]phenanthrenes s. M. S. Newman and H. Boden, J. Org. Ghem. 26, 1759 (1961) also selective oxidation... 

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