Phenanthrenes, hydrogenation

Figure 1. Gas chromatogram of product from phenanthrene hydrogenation run 3 (30QOC for 24h).

Figure 2. GC/MS of product from phenanthrene hydrogenation run 2 (350OC for 18h).

In the USA, this plan was directed from 1929-1939 by the Committee on Drug Addiction of the National Research Council (NRC) with financial support from the Rockefeller Foundation. The program consisted of modification of the morphine molecule at all accessible points and also targeted (modified) partial structures of the morphine molecule, such as phenanthrene, hydrogenated phenanthrene, isoquinoline, dibenzofuran, and carbazole. More than 150 derivatives of morphine and more than 300... 

Diphenic acid. Phenanthrene upon oxidation in acetic acid solution at 85° with 30 per cent, hydrogen peroxide gives diphenic acid (diphenyl-2 2 -di-carboxyHc acid) no phenanthraquinone is formed under these experimental conditions. The reaction is essentially an oxidation of phenanthrene with peracetic acid. (For another method of preparation, see Section I V,74.)... 

Weak to moderate chemiluminescence has been reported from a large number of other Hquid-phase oxidation reactions (1,128,136). The Hst includes reactions of carbenes with oxygen (137), phenanthrene quinone with oxygen in alkaline ethanol (138), coumarin derivatives with hydrogen peroxide in acetic acid (139), nitriles with alkaline hydrogen peroxide (140), and reactions that produce electron-accepting radicals such as HO in the presence of carbonate ions (141). In the latter, exemplified by the reaction of h on(II) with H2O2 and KHCO, the carbonate radical anion is probably a key intermediate and may account for many observations of weak chemiluminescence in oxidation reactions. 

Hydrogen and sodium do not react at room temperature, but at 200—350°C sodium hydride is formed (24,25). The reaction with bulk sodium is slow because of the limited surface available for reaction, but dispersions in hydrocarbons and high surface sodium react more rapidly (7). For the latter, reaction is further accelerated by surface-active agents such as sodium anthracene-9-carboxylate and sodium phenanthrene-9-carboxylate (26—28). 

A more complex reaction model was proposed from the results of a kinetic study of thermal liquefaction of subbituminous coal. Data were obtained over a temperature range of 673 to 743 K (752 to 878°F) at 13.8 MPa (2000 psia) by using two solvents, hydrogenated anthracene oil (HAO), and hydrogenated phenanthrene oil (HPO), at a coal-solvent ratio of 1 15. Results were correlated with the following model ... 

Photoredox systems involving carbonyl compounds and amines are used in many applications. Carbonyl compounds employed include benzophenone and derivatives, a-diketones [e.g. benzil, cainphoroquinone (85),2W 291 9,10-phenanthrene quinone], and xanthone and coumarin derivatives. The amines are tertiary and must have a-hydrogens [e.g. N,A7-dimethylani 1 ine, Michler s ketone (86)]. The radicals formed are an a-aminoalkyl radical and a ketyl radical. 

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

Microautoclave data was also obtained with Wilsonville Batch I solvent utilizing Indiana V coal. Batch I solvent was obtained from Wilsonville in mid-1977. Other batches of recycle solvent were received later. Batch I solvent had inspections most like the Allied 24CA Creosote Oil used for start-up at the Wilsonville Pilot Plant. Succeeding batches of solvent received by CCDC showed substantial differences, presumably due to equilibration at various operating conditions. As the Wilsonville solvent aged and became more coal derived, the solvent aromaticity decreased with an increase in such compounds as indan and related homologs. The decrease in aromaticity has also been verified by NMR. A later solvent (Batch III) also showed an increase in phenolic and a decrease in phenanthrene (anthracene) and hydrogenated phenanthrene (anthracene) type compounds. 

The table also shows the results of experiments with the donors and coal in phenanthrene as solvent. Consistent with the transfer of hydrogen in a radical process, those donors less reactive toward C130 than Tetralin are also less effective than Tetralin in conversion of coal to a phenanthrene-soluble product. However, in contrast to the chemistry of Step 2 we see that those donors that are more reactive toward C130 than Tetralin are also less effective in their action with coal. Thus this simple conversion scheme is suspect. 

To illustrate how this applies in the present circumstances we consider a passible group transfer reaction between A2 dihydro-naphthalene, (gQ) > a hydrogen donor, and phenanthrene,(g gr > a substrate (hydrogen acceptor) which models a polynuclear aromatic moiety commonly found in coal. In the overall group transfer reaction ... 

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