Phenanthrene, hydrogenation products

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. 

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).

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

The partially hydrogenated phenanthrene derivative 18 (entry 4) is a very moderate diene due to the steric crowding caused by the substituents and the anulated rings, and it reacts even with highly reactive dienophiles such as maleic anhydride (MA) or N-phenylmaleic imide only at high pressure. The minor product 20 in the reaction with MA obviously stems from diene 21. This can be explained by a double-bond isomerization 18 - 21 prior to the cycloaddition, certainly catalyzed by traces of acid present in the MA. In the absence of acid only the Diels-Alder adduct 22 derived from diene 18 was observed. In the reaction of diene 23 with MA (entry 5) a similar sequence of steps was observed. A [1,5] shift of the C—O bond in 23, again certainly acid-catalyzed, produces the diene 26 followed by the Diels-Alder reaction with MA to give 24 and 25. 

Addition of carbenes to Jt-electron excessive aromatic compounds, or those which possess a high degree of bond fixation, is well established. Dihalocarbenes react with naphthalenes with ring expansion to produce benztropylium systems (Scheme 7.8). Loss of hydrogen halide from the initially formed product leads to an alkene which reacts with a second equivalent of the carbene to yield the spirocyclopropyl derivatives in high yield (>95%) [14, 50]. Insertion into the alkyl side chain (see Section 7.2) also occurs, but to a lesser extent [14]. Not unexpectedly, dichlorocarbene adds to phenanthrenes across the 9,10-bond [9, 10, 14], but it is remarkable that the three possible isomeric spiro compounds could be isolated (in an overall yield of 0.05% ) from the corresponding reaction with toluene [14]. 

When phenanthrene (0.65 mg/L) in hydrogen-saturated deionized water was exposed to a slurry of palladium catalyst (1%) at room temperature for approximately 2 h, 1,2,3,4,5,6,7,8-octahydro-phenanthrene and l,2,3,4,4a,9,10,10a-octahydrophenanthrene formed as products via the intermediates 1,2,3,4-tetrahydrophenanthrene and 9,10-dihydrophenanthrene, respectively (Schiith and Reinhard, 1997). 

Phenanthrene purified by the sodium treatment was found superior to that from the azeotropic distillation, but both products gave satisfactory results. A good grade of commercially available phenanthrene ( white label grade supplied by the Eastman Kodak Company), although recrystallized and treated with Raney nickel, resisted hydrogenation under the described conditions. 

Gulf Research and Development Co. Two of the coals were processed in the Gulf continuous flow reactor, fed at the rate of about 1.5 kg coal/hr for 15-18 hrs. The third coal was processed in a conventional batch autoclave run. In all three runs, the coal was processed at about 400 °C and 3000 psi pressure of hydrogen using a proprietary catalyst. In the continuous runs, distillate from previous experiments was used as vehicle while in the autoclave experiment, partly hydrogenated phenanthrene was used. The vehicle-to-coal ratio was 2 1. In each case the reaction products were filtered on a steam-heated Buchner funnel. 

If reactions of the above type occur during extraction, one would expect that gradually less hydrogen exchange takes place as the extraction proceeds because the number of reactive groups decreases. This assumption was tested in the last experiment shown in Table V. The coal was heated for 6 hours at 340°C. with nontritiated phenanthrene prior to extraction with tritiated phenanthrene. When this pretreated coal was extracted, the tritium content of the product was only 15.6% as compared with 21.4%, in the nonpretreated product. This decreased tritium content supports the above assumption and agrees with the proposed reaction mechanism. 

In the vapor phase phenanthrene and hydrogen were products of the photolysis of c/.v-stilbene in addition to the expected mww-stilbene.65 The photolysis of 1,4-diphenyl-1,3-butadiene to give a-phenylnaphtha-lene is an analogous process.65 It was proposed that the intermediate dihydrophenanthrene was a cis form.66... 

We know that C6-cyclization of 1-(naphthyl-2)-butene is possible without metal catalysts. The products are dihydrophenanthrene over quartz and 1,2,3,4-tetrahydrophenanthrene plus phenanthrene over alumina (50). The latter apparently catalyzes the redistribution of hydrogen in dihydrophenanthrene. Neither anthracene nor dihydro- or tetrahydroanthracene are formed over quartz or alumina from 1-(naphthyl-2)-butene. Plate and Erivanskaya concluded from this that the 2-alkylnaphthalene - anthracene reaction does not involve naphthylbutene intermediate (27). 

THF at room temperature to produce substituted phenylallenes (231). Various arynes and terminal and internal alkynes can be used. The reaction of alkyne without propar-gylic hydrogen gave an acetylenic C-H addition product (a phenylalkyne) and a dehydro-Diels-Alder product (a phenanthrene).266... 

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