Dibenzo phenanthrene

Figure 1 Plot of weathering ratio (C3-dibenzo thiophenes C3-ehrysenes) versus souree ratio (C3-dibenzothio-phenes C3-phenanthrenes) for fresh and degraded oil samples from three different erude oil spills (Reprinted with permission from Environ. Sci. Technol, 30, 2332. 1996 Ameriean Chemieal Soeiety)...

Elimination of sulfur from methyl dibenzo[/),/]thiepin-10-carboxylatcs 15 (R2 = Me) can be achieved in moderate yields (39-55%) upon refluxing in diethyl phthalate in the presence of copper bronze.60 For the dibenzo[A,/]thiepin-10-carboxylic acids 15 (R2 = H), the loss of sulfur is accompanied by decarboxylation. Thus, treatment of these acids with copper bronze in refluxing quinoline for four hours gives the corresponding phenanthrenes 16 (R3 = H) in moderate yield (50%). However, the exposure time to high temperatures influences the product formation. Thus, the decarboxyiated dibenzothiepins are obtained after refluxing for only five minutes.60... 

Hydrazine reacts with biphenyl-2,2 -dicarbaldehyde (3, R = H). under elimination of nitrogen, to give phenanthrene,17 most probably not via the intermediate formation of a diazocine system. With other 2,2 -diacylbiphenyl compounds the expected dibenzo[[Pg.520]

Carbazole, A-methylcarbazole, IV-ethylcarbazole, dibenzofuran, dibenzothiophene, fluorene, dibenzo-p-dioxin, phenoxathiin, phenoxazine, phenothiazine, xanthene, biphenyl, naphthalene, phenanthrene, anthracene, and fluoranthene could be transformed by E. coli, [314] which was transformed using a plasmid bearing the carAa, Ac, and Ad genes, and expressing only the carA-encoded proteins. Further work is needed to develop a final biocatalyst and to prove the advantages that this degradative pathway would incorporate in a refining bioprocess. 

Attempts were reported119,129 to synthesize the ortho-linked diphenyl cyclo-propenone phenanthreno cyclopropenone 173 by dehydrohalogenation of the dibromo derivative 174 of dibenzo cyclohepta-l,3-diene-6-one. The only product isolated was the anhydride 175 of phenanthrene-9-carboxilic acid, which was shown not to arise from 173l29 ... 

Methods for the synthesis of the biologically active dihydrodiol and diol epoxide metabolites of both carcinogenic and noncarcinogenic polycyclic aromatic hydrocarbons are reviewed. Four general synthetic routes to the trans-dihydrodiol precursors of the bay region anti and syn diol epoxide derivatives have been developed. Syntheses of the oxidized metabolites of the following hydrocarbons via these methods are described benzo(a)pyrene, benz(a)anthracene, benzo-(e)pyrene, dibenz(a,h)anthracene, triphenylene, phen-anthrene, anthracene, chrysene, benzo(c)phenanthrene, dibenzo(a,i)pyrene, dibenzo(a,h)pyrene, 7-methyl-benz(a)anthracene, 7,12-dimethylbenz(a)anthracene, 3-methylcholanthrene, 5-methylchrysene, fluoranthene, benzo(b)fluoranthene, benzo(j)fluoranthene, benzo(k)-fluoranthene, and dibenzo(a,e)fluoranthene. 

Figure 5.12 Polyaromatic hydrocarbon species (1) phenanthrene, (2) anthracene, (3) pyrene, (4) benz[o]anthracene, (5) chrysene, (6) naphthacene, (7) benzo[c]phenanthrene, (8) benzo[ghi] fluoranthene, (9) dibenzo[c,g]phenanthrene, (10) benzo[g/ ]perylene, (11) triphenylene, (12) o-terphenyl, (13) m-terphenyl, (14) p-terphenyl, (15) benzo[o]pyrene, (16) tetrabenzonaphthalene, (17) phenanthro[3,4-c]phenanthrene, (18) coronene...

Finally, three additional individual data matrices were obtained for soil (so1 so2, and so3), in this case with the same number of samples (rows) for each of them. A new soil data matrix (SO) was obtained after individual matrix concatenation containing 36 samples in total (12 samples analyzed in 3 sampling campaigns) (see Fig. 7). Fifteen variables (all of them detected in SE as well) were measured in every sample PAHs (acenaphtylene, phenanthrene, anthracene, fluoranthene, pyrene, benzo(a)anthracene, chrysene, benzo(b)fluoranthene, benzo(a)pyrene, indeno (l,2,3-cd)pyrene, dibenzo(a,h)anthracene, and benzo(g,h,i)perylene), an organophosphate compound (tributylphosphate), and an OC (4,4 -DDE). 

Fig. 10 Composition and spatial distribution of the main patterns of contamination identified in sediment of the Ebro River basin from year 2004 to 2006. Different temporal distribution of the PAHs pattern of contamination over the territory and constant distribution in time of the APs and heavier PAHs as well as the OCs pattern. Big circles representing higher levels of pattern contribution than small circles. Variables identification 1, naphthalene 2, acenaphtylene 3, acenapthene 4, fluorene 5, phenanthrene 6, anthracene 7, fluoranthene 8, pyrene 9, benzo(a) anthracene 10, chrysene 11, benzo(b)fluoranthene 12, benzo(k)fluoranthene 13, benzo(a)pyr-ene 14, indeno(l,2,3-cd)pyrene 15, dibenzo(a,h)anthracene 16, benzo(g,h,i)perylene 17, octyl-phenol 18, nonylphenol 19, tributylphosphate 20, a-HCH 21, HCB 22,2,4-DDE 23,4,4-DDE 24, 2,4-DDD 25, 4,4-DDD 26, 2,4-DDT 27, 4,4-DDT...

Fig. 11 Composition of the identified patterns of contamination (loadings) in sediment and soil of the Ebro River basin and patterns contribution to the analyzed samples (scores) in fall from year 2004 to 2006. Samples ordered for both compartments from first to third sampling campaigns and, for each campaign, from NW to SE. Variables identification 1, acenaphtylene 2, phenanthrene 3, anthracene 4, fluoranthene 5, pyrene 6, benzo(a)anthracene 7, chrysene 8, benzo(b)fluor-anthene 9, benzo(k)fluoranthene 10, benzo(a)pyrene 11, indeno(l,2,3-cd)pyrene 12, dibenzo (a.h)anthracene 13, benzo(g,h,i)perylene 14, tributylphosphate 15, 4,4-DDE...

Fig. 5a-c. A typical distribution of polycyclic aromatic hydrocarbons in a atmospheric fallout sample, Alexandria City - Egypt b bottom incineration ash leachate of municipal solid waste - USA c hydrothermal petroleum, Escanaba Trough, NE Pacific Ocean. PAH Compound identifications N = naphthalene, MN = methylnaphthalene, DMN = dimethylnaphthalenes, P = phenanthrene, MP = methylphenanthrene, Fl = fluoranthene, Py = pyrene, BaAN = benzol anthracene, DH-Py = dihydropyrene, 2,3-BF = 2,3-benzofluorene, BFL = benzo[fc,/c]fluoranthene, BeP = benzo[e]pyrene, BaP = benzo[a]pyrene, Per = perylene, Cx-228 = methyl-228 series, Indeno = indeno[ l,2,3-c,d]pyrene, DBAN = dibenz[a,/z]anthracene, BPer = benzo[g,/z,z] perylene, AAN = anthanthrene, DBTH = dibenzothiophene, Cor = coronene, DBP = dibenzo [a,e]pyrene, DBPer = dibenzo [g,h,i] perylene... 

A gas chromatography-flame ionization detector system can be nsed for the separation and detection of nonpolar organic componnds. Semivolatile constitnents are among the analytes that can readily be resolved and detected nsing the system. If a packed column is used, four pairs of compounds may not be resolved adequately and are reported as a quantitative sum anthracene and phenanthrene, chrysene and benzo[a]anthracene, benzo[/ ]fluoranthene and benzo[/ ]fluoranthene, and dibenzo[a,/i]anthracene and indeno[l,2,3-cd]pyrene. This issue can be resolved through the use of a capillary column in place of a packed column. 

One starts with the IUPAC preferred name (sometimes referred to as the trivial name ) used for certain of the simple PAHs, e.g., anthracene, phenanthrene, pyrene, and fluoranthene. More complicated structures are then built up by the addition of, for example, benzo, dibenzo, or naphtho groups to the skeleton of the simple PAH. 

For the kinetics and mechanisms of the gas-phase reactions of other 2- to 4-ring PAHs with OH radicals, N03 radicals, and 03, see, e.g., phenanthrene, Kwok et al. (1994a), and indan, indene, fluorene, and 9,10-dihy-droanthracene, Kwok et al. (1997) for dibenzo-thiophene, a volatile S-PAC that is ubiquitous in polluted ambient air environments and forms mutagenic photooxidation products, see Kwok et al. (1999) see also Kwok et al. (1994b) for a review of gas-phase NO-, radical reactions with aromatics. 

In general, only helicenes with six or more benzene or other rings will be treated. The lower homologs, dibenzo[c,g]phenanthrene (pentahelicene) and benzo[c]phen-anthrene will only be mentioned for comparison in some instances. 

A. 3,8-Dimethoxy-4,5,6,7-dibenzo-l,2-dioxacyclooctane. Theozo-nolysis of 10 g. (0.0562 mole) of phenanthrene in dry methanol is carried out as described in the diphenaldehyde preparation (p. 41). The reaction mixture is not reduced, however, but is acidified with 1-3 drops of concentrated hydrochloric acid (Note 1) and allowed to stand at room temperature for an hour and then in the refrigerator for several hours or overnight. Suction filtration yields 11.5-12.5 g. (75-82%) of crystals melting at 178-181°. Trituration with methyl ethyl ketone gives a 90-95% recovery of colorless crystals melting at 180-181° (Note 2). 

The benzo[a] (19), benzo[/t (15) and benzo[c] (16) fused heterocycles are heterocyclic analogues of naphthalene, with the dibenzo heterocycles (17) bearing a similar electronic relationship to phenanthrene. Some of these compounds are still known by their trivial names indole (15 Z = NH), isoindole (16 Z = NH), carbazole (18) and indolizine (19). The names thianaphthene and pyrrocoline for (15 Z = S) and (19) respectively are now little used. Particular confusion can arise in consulting... 

Naphtho fusion gives cyclopropa[6]anthracene. 2,3-Naphtho fusion gives cyclopropafajanthracene. Dibenzo fusion gives cyc)opropa[/]phenanthrene. 

Phenanthren-9-ylmethyl)phenyl trifluoromethanesulfonate 164 undergoes a palladium-catalyzed cyclization via S-0 bond cleavage to afford 14/f-dibenzo[ ,f]xanthene in moderate yield (Equation 76) <2002T5927>. 

A much more deep-seated photorearrangement than in the dibenzo[2.2.2] systems occurs in the dibenzo[3.2.1] compound 55 with chloride or bromine as nucleofugal group at C-8 (equation 49)229. 9-Functionalized phenanthrenes are formed, supposedly also by way of photoinduced intramolecular electron transfer in the (triplet) excited state. 

---