1-Azaphenanthrene

Azonia substitution at a naphthalene bridgehead position gives the quinolizinium ion (16). Oxonia substitution, elsewhere, forms the 1- and 2-benzopyrylium ions (17) and (18). The two most well-known monoaza systems with three aromatie fused rings are aeridine (19), derived structurally from anthraeene, and phenanthridine (20), an azaphenanthrene. The better-known diaza systems inelude phenazine (21) and 1,10-phenanthroline (22), while systems with three linearly fused pyridine rings are ealled anthyridines, e.g. the 1,9,10-isomer (23). 

Azaphenanthrenes magnetic circular dichroism, 2, 129 Azaphenoxathiin synthesis, 3, 985... 

The position of quaternization in the isomeric ring system, 1,2,9-tri-azaphenanthrene, was not settled so clearly. The methiodide of 4-amino-10-phenyl-1,2,9-triazaphenanthrene (153) is converted by the action of alkali into a labile compound, which regenerates the quaternary salt on treatment with hydriodic acid. The labile compound gave 3-amino-2-phenylquinoline on heating with soda lime. 

Sytnik A, Del Valle JC (1995) Steady-state and time-resolved study of the proton-transfer fluorescence of 4-hydroxy-5-azaphenanthrene in model solvents and in complexes with human serum albumin. J Phys Chem 99 13028-13032... 

The 111 NMR spectmm (200MHz) of 10-benzyl-l,3-diphenyl-l,9,10,10a-tetrahydro-l,3,4a,10-tetra-azaphenanthrene-2,4-dione 46 <2000EJ02105> showed the presence of a singlet at 8 6.14 corresponding to C(4)-H. In the 111 NMR spectrum of 3,4-dihydro-27/,977-l-thia-4a,5,9,10-tetra-azaphenanthrene 50 <1999IJH75>, two triplets at 8 3.3 and 8 4.4 correspond to the SCH2 and NCH2, respectively, and a multiplet at 8 2.5 corresponds to the CH2 protons. 

The treatment of 1,4-di hydro-2 7/-pyrido[ 2,3-< [ 1,2,4]triazine-3-thione 82 with dimethyl acetylenedicarboxylate (DMAD) in methanol at room temperature leads to the formation of 5-oxo-8,8a,9,10-tetrahydro-5//-4,4b,9,10-tetra-azaphenanthrene-7-carboxylic acid methyl ester 83 <1998IJH303> (Equation 5). 

The pyridotriazine 84 on treatment with dibromopropane resulted in the formation of 3,4,10,10a-tetrahydro-277,9H-l-thia-4a,5,9,10-tetra-azaphenanthrene 85 <1999IJH75> (Equation 6). 

The treatment of (2-benzoylamino-5-iodobenzoyl-amino)acetic acid ethyl ester 88 with hydrazine hydrate for 4h yielded hydrazine derivative 2-benzoylamino-iV-hydrazinocarbonylmethyl benzamide 89, which on refluxing with sodium acetate and acetic acid for 8 h resulted in the formation of 6-iodo-10-phenyl-3//-3,4,9,10a-tetra-azaphenanthren-2-one 90 <2000IJH59> (Scheme 5). 

Aza-Payne rearrangements, 60, 1 Azaphenanthrenes, synthesis by photocyclization, 30, 1 Azides, synthesis and rearrangement of, 3, 9... 

The HMO method has been used to study models of all the aza analogues of pyridine, quinoline, isoquinoline, the monoazaanthra-cenes, and 1- and 9-azaphenanthrenes as well as of their derivatives such as aminopyridines and aminoquinolines.28 Again their energy characteristics are correlated with those of the parent systems. 

C-Styrylpyridines undergo photocyclization to give azaphenanthrenes, and Y-styrylpyridinium cation forms an azoniaophenanthrene (523 — 524). 

Replacement ttame a name describing compounds that have carbon replaced by a hetero atom also called a nomenclature e.g., 2-azaphenanthrene. 

Another synthetic method involves treating the parent aromatic hydrocarbon with sodium hypochlorite in water-chloroform, using phase transfer agents like tetrabutylammonium hydrogen sulfate or benzyltrimethylam-monium chloride.15 The epoxides are formed in high yields. The rate is pH dependent, and epoxide formation is most facile at pH 8-9. Many K-region arene oxides like 1,165, acenaphthylene 1,2-oxide (19), 1-azaphenanthrene 5,6-oxide (20), 4-azaphenanthrene 5,6-oxide (21), 1,10-phenanthroIine 5,6-oxide... 

Intramolecular nucleophilic ring opening of 4-methoxycarbonyl-l-azaphenanthrene 5,6-oxide (262) has been utilized in the total synthesis of eupolaramine (263).155... 

A number of examples are known where elimination gives six membered rings (Table 4). A carbocyclic ring is formed in the cyclization of stilbene to phenanthrene 13>. In a similar way stilbazol forms azaphenanthrene 19>. 

Six membered heterocyclics can be synthesized in various ways. Nitrogen analogues of stilbene, like the anilides of benzaldehyde or acetophenone sometimes form azaphenanthrenes 19). Similarly the plasma reaction of azobenzene yields a small amount of diazaphenanthrene 19>. Better results are observed in the cyclization of hydroxy, amino or nitro compounds. Suitable starting materials are molecules with two phenyl groups linked by a carbon or hetero atom. 

Table X. Moles of Azaanthracenes/Azaphenanthrenes and Their Hydrogenated Analogs at Molecular Weights 179-189 in Feed and Reactor-Sample 1.

The results in Table X reveal that hydrotreating under the reaction conditions and catalyst specified in Table I reduced the moles of azaanthracenes and azaphenanthrenes by ca. 83%. However, it is important to note that the decrease of 6.7 millimoles in reactants (mass 179) essentially equals, within the limits of data precision, the increase of 6.3 millimoles in products (masses 181 through 189). Consequently, for the given catalyst, the reaction conditions were insufficiently severe to convert intermediate products to hydrocarbons and NH. ... 

---