Nitration Perylene

Fig. 5 Main contamination sources identified by PCA for sediments, fish, and suface water in the Ebro River basin, and explained variances for each principal component. Variable identification. Organic compounds in sediments 1, summatory of hexachlorocyclohexanes (HCHs) 2, summa-tory of DDTs (DDTs) 3, hexachlorobenzene (HCB) 4, hexachlorobutadiene (HCBu) 5, summatory of trichlorobenzenes (TCBs) 6, naphthalene 7, fluoranthene 8, benzo(a)pyrene 9, benzo(b) fluoranthene 10, benzo(g,h,i)perylene 11, benzo(k)fluoranthene 12, indene(l,2,3-cd)pyrene. Organic compounds in fish 1, hexachlorobenzene (HCB) 2, summatory of hexachlorocyclohexanes (HCHs) 3, o,p-DDD 4, o,p-DDE 5, o,p-DDT 6, p,p-DDD 7, />,/>DDE 8, />,/>DDT 9, summatory of DDTs (DDTs) 10, summatory of trichlorobenzenes (TCBs) 11, hexachlorobutadiene (HCBu) 12, fish length. Physico-chemical parameters in water 1, alkalinity 2, chlorides 3, cyanides 4, total coliforms 5, conductivity at 20°C 6, biological oxygen demand 7, chemical oxygen demand 8, fluorides 9, suspended matter 10, total ammonium 11, nitrates 12, dissolved oxygen 13, phosphates 14, sulfates 15, water temperature 16, air temperature...

Examples of mnltiplicity of nitration mechanisms that depend on IPs of substrates are the nitration of naphthalene (NaphFI + N02 system) and perylene (PerH -I- N02 system) (Scheme 4.40). 

Nentral perylene reacts with N02, giving the cation-radical. Flowever, its formation is, in principle, a result of a-complex splitting. Another possible route of a-complex splitting consists of proton elimination and nitro perylene formation. As experiments show, the nitration of perylene is accompanied with collateral reactions of PerH, such as recombination and interaction with solvent molecules (Eberson and Radner 1985). This testifies to the release of cation-radical. 

Cation-radicals of naphthalene and its homologues, pyrene, or perylene react with NOj" ion in AN, giving electron-transfer products, that is, ArH and NOj. The latter radical is not very active in these reactions and nitration takes place only with extremely reactive compounds such as perylene (Eberson and Radner 1985, 1986). This mechanism is seemingly distinctive of compounds with E° less or equal to 1 V in AN (or in other solvents solvating NOj ions sparingly). 

The generality of this reaction of N02 with particle-associated PAHs was demonstrated when, under similar laboratory conditions, perylene (a weak promutagen) was converted to 3-nitroperylene, and pyrene (a nonmutagen), at a slower rate, to 1-nitropyrene both nitro-PAHs are direct-acting frameshift mutagens. In a similar experiment, chrysene was not nitrated this is consistent with its low reactivity in the Nielsen reactivity scale (Table 10.30). 

Highly activated aromatics such as polycyclic aromatic hydrocarbons can be easily nitrated with NO alone. The investigation of the relative reactivity of the series of polycyclic aromatic hydrocarbons (naphthalene, triphenylene, phenantrene, chrysene, pyrene, anthracene, perylene) with NO - in solutions of dichloromethane at room temperature has been reported [40]. The nitration of naphthalene by NO led to 1-nitro- and 2-nitronaphthalene in a ratio l-nitro 2-nitro = 11. The... 

Relative rate constants of the nitration were obtained by direct competition between two aromatic hydrocarbons. The rate constants depend markedly on substrate structure, with >10 difference in values between the least reactive (benzene) and most reactive (perylene) compounds studied. The more reactive (and more easily ionised) polycyclic aromatic hydrocarbons interact with NO in solution by an electron transfer mechanism. 

Reductive Remediation of Nonhalogenated Molecules. Na/NHa treatments can also destroy nonhalogenated hazardous conqraunds. Three classes pollutants will be mentioned here polynuclear aromatic hydrocarbons (PNAs), nitro- and nitrate-type explosive wastes and chemical warfare agents. The treatment of neat sanq>les of PNAs leads to destmction efficiencies of 99.99% for many of these conq)ounds including such examples as acenaphthene, benzo[a]anthracene, benzo[b]fluoranthene, benzo[g,h,l]perylene, chrysene, fluorandiene, fluorine, naphdialene and phenanthrene. With the exception of naphthalene and anthracene, conq)lex product mixtures are formed. Radical anion formation followed by protonation occurs sequentially leading to dihydro, tetrahydro and further reduced products (see Scheme 3). Depending on the reaction conditions, dimerization of intermediate radicals can occur to give dimers in various states of reduction. 

Our experiences with nitrite-ion reactions show that both nitration and oxygen-atom transfer can occur. Thus, 6 " and 10 give 2-nitrodibenzodioxin (12) and 3-nitroperylene (10) respectively according to eq. 6. The cation radical of zinc tetra-phenylporphyrin is similarly nitrated at one of the pyrrolic carbon atoms (44). The perylene reaction is so facile that it... 

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