Hydrogenation of phenanthrene

Figure 1 Products/intermediates of the hydrogenation of phenanthrene (1). ECH of Glucose...

The hydrogenation of phenanthrene proceeds stepwise leading predominantly to the sym-octahydro-stage rather than the asymmetrical form [J>]. Either form can function as an excellent donor solvent. 

Catalytic hydrogenation of phenanthrene to the octahydro-stage produces both sym- and asym-isomers, although the former predominate Additionally, interconversion of the two forms tends to occur at coal liquefaction conditions. Since the... 

Dihydrophenanthrene has been prepared from 2,2 -bis(bromomethyl)biphenyl and sodium 8 from the reduction of 2,2 -diiodobibenzy 1 in the presence of 1% palladium on barium carbonate catalyst 8 by the hydrogenation of phenanthrene in the presence of nickel8 or copper-chromium oxide catalyst 10 and by the coupling of 2,2 -bis(bromomethyl)biphenyl with lithium phenyl.11... 

Huang, C.S., K.C. Wang, and J. H.W. Haynes, Hydrogenation of Phenanthrene Over a Commercial Cobalt Molybdenum Sulfide Catalyst Under Severe Reaction Conditions, in Liquid Fuels from Coal, eds., Academic Press, 1977. 

Scheme 11.19 Hydrogenation of phenanthrene to hydrophenanthrenes over Raney Ni.

TABLE 11.23 Selectivity of Transition Metals in the Hydrogenation of Phenanthrene, 9,10-Dihydrophenanthrene, and 1,2,3,4-Tetrahydrophenanthrene a,b... 

The hydrogenation of phenanthrene proceeds through aromatic intermediates to the perhydrophenan-threne. Under mild conditions the product has the syn-cis-syn configuration, but more vigorous conditions yield products of lower selectivity, Similar results can be expected for the hydrogenation of more complex polycyclic aromatic hydrocarbons, ... 

The regioselectivity of the partial hydrogenation of polycyclic aromatics depends on both the substrate structure and the catalyst used. The hydrogenation of phenanthrene, (28) over Raney nickel or palladium takes place by way of the initial formation of the 9,10 dihydro species, 29 (Eqn. 17.27). 

The hydrogenation of monocyclic aromatics has been extensively studied and is thoroughly covered in reviews by Smith (8), Siegel and Dunkel (9), and Amano and Parravano (10). The hydrogenation of phenanthrene was intensively studied and is reported in the classic papers of Linstead and co-workers (11). By comparison the naphthalenes had been largely neglected. As early as 1901 Sabatier and Sen-derens (12) disclosed the vapor phase hydrogenation of naphthalene to... 

Hydrogenation of phenanthrene [equation (a)] and anthracene [equation (b)] over finely divided Ni results in reduction of the central aromatic nucleus. ... 

This new zeolite-catalyzed ring-shift isomerization could provide a new route to anthracene and its derivatives [Song, 1996], which are valuable chemicals in demand, from phenanthrene, which is rich in liquids from coal. Selective partial hydrogenation of phenanthrene would be needed as the first step. Possible applications of sym-OHAn include the manufacturing of anthracene (for dyestuffs and fine chemicals), anthraquinone (pulping agent), and pyromellitic dianhydride (the monomer for polyimides such as Du Pont s Kapton) [Song and Schol rt, 1993]. Fundamental research is needed to clarify the mechanisms and reaction pathways. 

FIGURE 8.9 Equilibrium constants and heats of reactions (kcal/mol) for the steps in the hydrogenation of phenanthrene. 

Qian, W., Yoda, Y., Hirai, Y., Ishihara, A., Kabe, T. (1999). Hydrodesulfurization of dibenzothiophene and hydrogenation of phenanthrene on alumina-supported Pt and Pd catalysts. Applied Catalysis A General, 184, 81—88. http //dx.doi.org/10.1016/S0926-860X(99)00083-6. 

Mahdavi B, Chapuzet JM, Lessard J (1993) The electrocatalytic hydrogenation of phenanthrene at Raney nickel electrodes the effect of periodic current control. Electrochim Acta 38 1377-1380 (and references therein)... 

A completely analogous explanation applies to the stereochemistry of the catalytic hydrogenation of phenanthrene derivatives with one aromatic ring. Thus, the hydrogenation of the trans-A/B derivative (230) leads to... 

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