Chemistry of Phenanthrene

FIGURE 8.24 Alternative pathways for transformation of phenanthrene by Phanerochaete chrysosporium. (From Neilson, A.H. and Allard, A.-S. The Handbook of Environmental Chemistry, Springer, 1998. With permission.)... 

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. 

Yoshikawa, T., L.P. Ruhr, W. Flory, D. Giamalva, D.F. Church, and W.A. Pryor. 1985. Toxicity of polycyclic aromatic hydrocarbons. I. Effect of phenanthrene, pyrene, and their ozonized products on blood chemistry in rats. Toxicol. Appl. Pharmacol. 79 218-226. 

L. F. Fieser, The Chemistry of Natural Products Related to Phenanthrene, Reinhold, New York, 1936. 

Kiyohara, H., Nagao, K. Nomi, R. (1976). Degradation of phenanthrene through o-phthalate by an Aeromonas sp. Agricultural and Biological Chemistry, 40, 1075-82. 

The yields of phenanthrene, dibenzothiophene, acenaph-thene, and biphenyl appear to be reconciliable with their known (44,18,22) or expected chemistry. 

Fieeer, "Chemistry of Natural Products Related to Phenanthrene," 2nd ed., Reinhold Publishing Corp., 1937. 

In practice, the valence bond picture has probably exerted more influence on how chemists actually think than the HMO picture. However most early applications were primarily qualitative in nature. This qualitative VB picture can be summarized under die name of resonance theory [10]. The basic concept is that in general the more ways one has of arranging the spin pairing in the VB wave function, the more stable the molecule is likely to be. Thus, VB theory predicts that phenanthrene with 14 carbon atoms and 5 Kekule structures should be more stable than anthracene with 14 carbon atoms but just 4 Kekule structures, in complete accord with the experimental evidence. It also predicts that benzenoid hydrocarbons with no Kekule structures should be unstable and highly reactive, and in fact no such compounds are knowa Extensions of this qualitative picture appear, for example, in Clar s ideas of resonant sextets [11], which seem to be very powerful in rationalizing much of the chemistry of benzenoid aromatic hydrocarbons. The early ascendancy of HMO theory was thus largely based on the ease with which it could be used for quantitative computations rather than on any inherent superiority of its fundamental assumptions. 

Two aromatic rings that share a pair of carbon atoms are said to be fused. In this chapter we shall study the chemistry of the simplest and most important of the fused-ring hydrocarbons, naphthalene, CioHg, and look briefly at two others of formula ChHio anthracene and phenanthrene. 

Further degradation of the methine and isomethine yields the same 3 4-dimethoxy-8-vinylphenanthrene [v], which can be oxidized, first to 3 4-dimethoxy-8-(a /3-dihydroxyethyl)-phenanthrene [vi] and finally to 3 4-dimethoxyphenanthrene-8-carboxylic acid [vn] [16, 66]. The latter has been converted via the 8-amino compound to 3 4 8-tri-methoxyphenanthrene [vm] [67], shown to be identical with an authentic specimen [68]. Two ethylphenanthrenes, not identical with 9-othylphenanthrene, are obtained by distilling [v] with zinc-dust [66]. Position 8 of the phenanthrene system was thus established as the point of attachment of thecarbon end of the side-chain in apomorphine. Position 9 as point attachment of the nitrogen was assumed on the basis of evidence derived from the chemistry of morphine and was finally proved by synthesis. 

The choice between isomers LII and LIII of the trans-syn-j rhydro-phenanthrene system was made by noting that the condition of relatively unhindered hydroxyl in compounds LV, LVII, and LVIII is satisfied only in isomer LIII but not LII. Thus the above arguments limit the stereochemistry of atisine to either L or LIII. Since anti-coupling of rings A and C is demanded by the known chemistry of ajaconine 26) the complete relative stereochemistry of atisine is expressed by structure L (3, 25). 

When aromatic pinacols are reacted with an acid, products often arise from dehydration and rearrangement.5 This general conversion is known as the pinacol rearrangement. The pinacol rearrangement may be promoted by both Brdnsted and Lewis acids.6 In the procedure described here, superacidic triflic acid is reacted with an aryl pinacol and a dehydrative cyclization occurs to give the substituted phenanthrene product. Related to this conversion, the chemistry of benzopinacol in sulfuric acid and triflic acid is contrasted in Scheme 1. We have proposed that the superacidic triflic acid causes the formation of diprotonated intermediates which promote the dehydrative cyclization.4... 

The past year has seen the publication of Comprehensive Organic Chemistry, one volume of which contains much information on the six-membered ring systems to be reviewed in this article a monograph on the chemistry of condensed pyrazines has also appeared. Reviews on 1,4-thiazines, l,3-benzothiazines," pyridazines, benzo[c]cinnolines, quinazolines, purines, pyrrolo[3,2-c]quino-lines, 1,10-phenanthroline and its complexes, polyaza-phenanthrenes, and 1,9- and 1,10-diaza-anthracenes have been published. Other specialist reviews are devoted to catalytic methods of obtaining pyridine bases pyridine N-oxides the stereochemistry of quinolizines, indolizines, and pyrrolizines benzothiazinone dioxides 2-quinazolones and their cyclic homologues (e.g. 

The types of reactions that can be carried out on the polycyclic aromatic hydrocarbons such as naphthalene, anthracene, phenanthrene, and larger analogs are the same as those discussed in detail for benzene derivatives. An acquaintance with the substitution chemistry of the polycyclic systems therefore requires only some general information concerning the reactivity of these ring systems and their position selectivity. Naphthalene is more reactive than benzene. There is a kinetic... 

Collaborative work by the Williams and Erase groups led to a short synthesis of phenanthrenes to serve as model systems towards the total synthesis of pamafungin (Scheme 13.23) (670). In addition, the Erase group also synthesized biaryls related to pamafungin 671), using tin chemistry (see Sect. 13.5.3). 

Ba turkmen, M., Rzaev, Z. M. O., Akovali, G., and Kisakirrek, D. 1995. Gomplex-radical terpolymerization of phenanthrene, maleic anhydride, and frans-stilbene. Journal of Polymer Science, Part A Polymer Chemistry 33 7-13. 

The history of the chemistry of l,12-dimethylbenzo[c]phenanthrene (2) resembles that of 4,5-dimethylphenanthrene (1). The first symthesis of 2 was reported by Newman and Wolf in 1952 [9]. The synthetic sequence included preparation of diacid 67 for the Friedel-Crafts acylation reactions to form diketone 68 (Scheme 15). Reduction followed by dehydration and dehydrogenation then produced 2. 

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