Phenanthrenes, hydrogenation selective

In summary, the A1- and A2-dialin isomers have been shown to be appreciably more active than etralin (and decalin) in transferring hydrogen to anthracene and phenanthrene. The observed selectivity of this hydrogen transfer is in accord with the Woodward-Hoffman rules for group transfer reactions, anthracene conversions being in the ratio ( 3 / 0 ) = 12/1 >> 1 while phenanthrene conversions are in the ratio ( 0/(33 ) = 0.6/1 < 1. The quantitative differences in the selectivities observed with anthracene and phenanthrene are being further explored. 

Lithium aluminum hydride reduced p-benzoquinone to hydroquinone (yield 70%) [576] and anthraquinone to anthrahydroquinone in 95% yield [576]. Tin reduced p-benzoquinone to hydroquinone in 88% yield [174] Procedure 35, p. 214). Stannous chloride converted tetrahydroxy-p-benzoquinone to hexa-hydroxybenzene in 70-77% yield [929], and 1,4-naphthoquinone to 1,4-di-hydroxynaphthalene in 96% yield [180]. Other reagents suitable for reduction of quinones are titanium trichloride [930], chromous chloride [187], hydrogen sulfide [248], sulfur dioxide [250] and others. Yields are usually good to excellent. Some of the reagents reduce the quinones selectively in the presence of other reducible functions. Thus hydrogen sulfide converted 2,7-dinitro-phenanthrene quinone to 9,10-dihydroxy-2,7-dinitrophenanthrene in 90% yield [248]. 

Anthracene and phenanthrene are converted to their 9,10-dihydro derivatives in high yield. Other partially hydrogenated intermediates formed by further stepwise hydrogen addition can also be isolated under suitable experimental conditions.10 18 Platinum and palladium exhibit different selectivities in the partial hydrogenation of polycyclic aromatics under mild conditions 108... 

Pletcher et al. (204) and Lassard and co-workers (205) have investigated the influence of the nature of the electrode material on rate, current yields, and selectivities of the electrocatalytic hydrogenation of acetophenone, phenanthrene, and other unsaturated compounds. They showed that substances that are inherently difficult to hydrogenate (for instance, styrene and benzonitrile) cannot be electrocatalytically hydrogenated at Pt electrodes at which hydrogen evolution is strongly catalyzed therefore, the activity of the... 

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 direct synthesis of anthraquinone from phthalic anhydride and benzene has been reported to proceed over zeolite Beta [50] in a shape selective manner. In a conventional anthraquinone synthesis, anthracene is used as a feedstock for oxidation. Once there is a shortage of it in the market, additional anthracene could be produced by isomerization of its isomer, viz. phenanthrene. This, however, is not possible by direct isomerization of the trinuclear aromatic system but involves the partially (symmetrically) hydrogenated species. Consequently, isomerization of symmetrical octahydrophenanthrene to symmetrical octahydro-anthracene was studied by Song and Moffatt [51]. As sketched in Figure 3, a high yield of symmetrical octahydroanthracene can be obtained over zeolite H-mordenite (ngj/nyy = 8) at 250 °C (liquid phase, decalin as solvent). These examples show that (shape selective) catalysis on zeolites is more and more expanding into the conversion of polycyclic aromatics, and we foresee continued interest and success in this field of zeolite catalysis. 

Naphthalene and its derivatives are one of the more dominant aromatics present in various diesel and jet fuel feedstocks. Therefore, several investigators have reported the influence of naphthalene on HDS of model compounds. One of the first reports was by Lo who found naphthalene to weakly inhibit the conversion and selectivity of the HDS of DBT. Similarly, LaVopa and Satterfield found little effect of naphthalene and phenanthrene on the HDS of thiophene. Other researchers have, however, found naphthalene to be a stronger inhibitor of HDS activ-ity. Nagai and Kabe, in fact, found naphthalene to significantly reduce catalyst selectivity for the hydrogenation pathway.Isoda et al., on the basis of similar selectivity inhibition, concluded that naphthalene severely inhibits the hydrogenation active sites in a... 

Catalytic hydrogenations over CojfCOjg (using Hj and CO) or with stoichiometric quantities of preformed hydridocarbonyl complex CoH(CO)4 are useful for the partial selective reductions of polycyclic aromatic compounds. Isolated benzene rings are not affected. Naphthalene is reduced to tetralin, at 200°C under a pressure of 20 X 10 kPa and anthracene to 9,10-dihydroanthracene (99%). The substituted phenanthrene nucleus is stable under these conditions as illustrated by hydrogenation of perylene 1 and pyrene 2. ... 

Schmitt (1984) verified the entrainer behavior reported by Kurnik and Reid. Schmitt and Reid (1984) show that very small amounts of an entrainer in the SCF-rich phase have very little effect on the solubility of a second component in that phase. This observation is consistent with the work of Kohn and Luks for ternary mixtures at cryogenic temperatures. The data of Kurnik and Reid have been corroborated for the naphthalene-phenanthrene-carbon dioxide system (Gopal et al., 1983). Lemert and Johnston (1989, 1990) also studied the solubility behavior of solids in pure and mixed solvents at conditions close to the upper critical end points. Johnston finds that adding a cosolvent can reduce the temperature and pressure of the UCEP while simultaneously increasing the selectivity of the solid in the SCF-rich phase. In these studies Johnston found the largest effects with a cosolvent capable of hydrogen bonding to the solute. 

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. 

Only one ring is saturated at a time and with phenanthrenes and anthracenes initial saturation occurs at the 9,10-position34. This takes place under the same conditions used for the selective hydrogenation of naphthalenes to tetralins (vide supra). Further hydrogenation proceeds under the conditions used for the hydrogenation of alkylbenzenes (Section 2.5.1.1.1.1.6.1.). The major product is the all-m-fused isomer35. 

Catalytic properties of complexes of multi-valenced metals with poly(ethylene glycol) (PEG) and polyurethane (PU) have been studied during liquid-phase oxidation processes such as the liquid-phase oxidation of hydrocarbons (phenanthrene, tetralin, cyclohexene), decomposition of hydroperoxides, hydrocarbons and decomposition of hydrogen peroxide [101 -106]. The kinetics of these reactions have been studied. The rate and selectivity of a particular reaction process depend not only on the properties... 

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