Phenanthrene numbering system

The chemical structure of vitamin D3 is closely related to its precursor, 7-dehydrocholesterol, from which it is produced by a photochemical reaction. Therefore, vitamin Do is closely related structurally to the four-ring nucleus of steroids derived from the cyclopentanoperhydro-phenanthrene ring system. No vitamin D activity is noticed until the B ring of 7-dehydrocholesterol is opened between C-9 and C-10. Thus, vitamin D3 is a 9,10-seco steroid and its carbon skeleton is numbered accordingly (Scheme I). The important aspects of its chemistry center about the 5,6,7-cis-triene structure. The formula for vitamin D3 is C27H44O and its formula weight is 384.64. 

Phenanthrene is best represented as a hybrid of the five canonical forms 20-24. It has a resonance energy of 380 kJ mol and is more stable than anthracene. In four of the five resonance structures, the 9,10-bond is double and its length is about the same as an alkenic C=C bond. The numbering system for phenanthrene is shown in 20. Five different mono-substituted products are possible. 

Naphthalene, anthracene, and phenanthrene are the three simplest members of this class. They are all present in coal tar, a mixture of organic substances formed by heating coal at about 1000°C in the absence of air. Naphthalene is bicyclic and its two benzene rings share a common side. Anthracene and phenanthrene are both tricyclic aromatic hydrocarbons. Anthracene has three rings fused in a linear fashion an angular fusion characterizes phenanthrene. The structural formulas of naphthalene, anthracene, and phenanthrene are shown along with the numbering system used to name their substituted derivatives ... 

This treatment could be applied to anthracene and phenanthrene, with 429 linearly independent structures, and to still larger condensed systems, though not without considerable labor. It is probable that the empirical rule6 of approximate proportionality between the resonance energy and the number of benzene rings in the molecule would be substantiated. 

Nucleophilic Trapping of Radical Cations. To investigate some of the properties of Mh radical cations these intermediates have been generated in two one-electron oxidant systems. The first contains iodine as oxidant and pyridine as nucleophile and solvent (8-10), while the second contains Mn(0Ac) in acetic acid (10,11). Studies with a number of PAH indicate that the formation of pyridinium-PAH or acetoxy-PAH by one-electron oxidation with Mn(0Ac)3 or iodine, respectively, is related to the ionization potential (IP) of the PAH. For PAH with relatively high IP, such as phenanthrene, chrysene, 5-methyl chrysene and dibenz[a,h]anthracene, no reaction occurs with these two oxidant systems. Another important factor influencing the specific reactivity of PAH radical cations with nucleophiles is localization of the positive charge at one or a few carbon atoms in the radical cation. 

The numbering and lettering system for several PAHs is also given. Compounds are (1) naphthalene, (2) fluorene, (3) anthracene, (4) phenanthrene, (5) aceanthrylene, (6) benzo[a]-fluorene, (7) benzo[a]fluorene, (8) benzo[a]-fluorene, (9) fluoranthene, (10) naphthacene, (11) pyrene, (12) benzofluoranthene, (13) benzo[g,/r,fluoranthene, (14) perylene, (15) benzo[e]pyrene, (16) benzo[g,/),/]perylene, (17) anthanthrene, and (18) coronene. 

At first sight, electrodeposition of metals from nonaqueous solutions seems to offer a complete solution, there being no source of H present (in a system consisting of e.g., palladium chloride in a phenanthrene-anisole mixture). The potential limits inside which electrodeposition can take place can be far wider than those in aqueous solutions (some 2.0 V). A number of redox potentials in nonaqueous systems are given in Table 7.22. 

The resonance energies of fused systems increase as the number of principal canonical forms increases, as predicted by rule 6 (p. 35).75 Thus, for benzene, naphthalene, anthracene, and phenanthrene, for which we can draw, respectively, two, three, four, and five principal canonical forms, the resonance energies are, respectively, 36, 61, 84, and 92 kcal/mol (152, 255, 351, and 385 kJ/mol), calculated from heat-of-combustion data.76 Note that when phenanthrene, which has a total resonance energy of 92 kcal/mol (385 kJ/mol), loses the 9,10 bond by attack of a reagent such as ozone or bromine, two complete benzene rings remain, each with 36 kcal/mol (152 kJ/mol) that would be lost if benzene was similarly attacked. The fact that anthracene undergoes many reactions across the 9,10 positions can... 

First, recall that the nondimensional Damkohler number, Da (Eq. 22-11 b), allows us to decide whether advection is relevant relative to the influence of diffusion and reaction. As summarized in Fig. 22.3, if Da 1, advection can be neglected (in vertical models this is often the case). Second, if advection is not relevant, we can decide whether mixing by diffusion is fast enough to eliminate all spatial concentration differences that may result from various reaction processes in the system (see the case of photolysis of phenanthrene in a lake sketched in Fig. 21.2). To this end, the relevant expression is L (kr / Ez)1 2, where L is the vertical extension of the system, Ez the vertical turbulent diffusivity, and A, the first-order reaction rate constant (Eq. 22-13). If this number is much smaller than 1, that is, if... 

---