Acenaphthylene and Fluoranthene

Heilbronner, E., Weber, J.P., Michl, J., and Zahradnik, R., The electronic spectra of acenaphthylene and fluoranthene. A comment on the classification of electronic spectra, Theoret. Chim. Acta, 6, 141, 1966. 

Similarly, perfluorinated naphthalenes,139,142,143 acenaphthylenes.144 anthracenes,145 phenan-threnes,140 and fluoranthene l147 have been substituted with N-nucleophiles. 

In case study 1, only certain compounds absorb above 330 nm, the main ones being pyrene, fluoranthene, acenaphthylene and benzanthracene (note that the small absorbance due to a fifth component may be regarded as an interferent, although including this in the model will, of course, result in better predictions). It is possible to choose four wavelengths, preferably ones in which the absorbance ratios of these four compounds differ. In Fig. 4, the wavelengths 331, 335, 341 and 349 nm are indicated, and chosen for calibration. 

Hence, the chemical evidence presented for anthracene was confirmed spectroscopically. Furthermore, Mullen et al. (12) categorized a number of hydrocarbons in Li-NH3 solutions into two classes group 1 hydrocarbons that exist as monoanions in ammonia and group 2 hydrocarbons that exist as dianions in ammonia. Group 1 includes anthracene and its 9-methyl, 9-phenyl, and 9,10-diphenyl derivatives acenaphthylene azulene fluoranthene phenanthrene and pyrene. Group 2 includes aceheptylene, cyclooc-tatetraene, and perylene. 

In this study, a spectrographic analysis of the by-products of the decomposition of methane revealed the presence of large amounts of acetylene, ethylene, and benzene, plus a variety of compounds consisting mostly of the polyaromatic hydrocarbons (PAH) such as naphthalene, anthracene, phenantrene, acenaphthylene, pyrene, and fluoranthene, in addition to the deposited pyrolytic graphite. Some of these compounds form the soot and tar-like deposits which are often observed on the wall of CVD reactors during carbon deposition. 

Fluoranthene (65) is formally a benzoannelated acenaphthylene and has an enthalpy of formation of 289.0 1.0 kj/mol. The enthalpy of benzoannelation is ca. 30 kJ/mol, which is typical for benzoannelation of unstrained olefins (see the related discussion earlier in this text). By contrast, the related benzoannelation of indene to form fluorene (66) corresponds to an increase of enthalpy of formation of only 10 kj/mol. It is not apparent why the two values for benzoannelation are so different. 

In fish, the half-lives of PAHs are generally very short. Half-lives of 6-9 days for fluorene, phenanthrene, anthracene, and fluoranthene were reported in rainbow trout [Oncorhynchus mykiss (Salmo gairdneri)] fed oil spiked with PAHs (Niimi and Palazzo 1986). Niimi and Dookhran (1989) also reported half-lives of 1-4 d for acenaphthylene, methylanthracene, triphenylene, and perylene in rainbow trout. They reported a much longer half-life (25 d) for phenylnaphthalene compared to other PAHs and speculated that it may be more recalcitrant to metabolism because its aromatic rings are not all fused. 

Figure 3 depicts profiles of Total PAH fluxes vs. time (36). The following polycyclic hydrocarbons have been determined by high performance liquid chromatography, variable wavelength absorption detection Naphthalene, acenaphthylene, 7,12-dimethylbenzanthracene, 2-methylnaphtalene, fluorene, acenaphtene, phenanthrene, 2,3-dimethylnaphtalene, anthracene, fluoranthene, 1-methylphenanthrene, pyrene, 2,3-benzofluorene, triphenylene, benz(a)anthracene, chrysene, benzo(b)fluoranthene, benzo(k)fluoranthene, perylene, benzo(e)pyrene, 1,2,3,4-dibenzanthracene, benzo(a)pyrene, and 1,2,5,6-dibenzanthracene. 

Eq. (4.4 a) is satisfied in the position 1 of azulene. Eq. (4.4b) is valid in position 6 of fulvene, position 6 of azulene, position 3 of fluoranthene, and position 5 of acenaphthylene. Even in a few exceptional cases where the previous relations do not hold, a consideration of the coulombic effect of attacking reagents leads to a conclusion favorable to the hypothesis of frontier density growth. An example of such cases is position 3 of... 

In fact, it may even be difficult to ascertain its existence as was shown by several authors (cf. Scheme 2). The C(ll) and C(12) signals in benzo-[g/u ]fluoranthene (1) are 6.6 ppm apart. Since this value is much larger than the 0.3-ppm difference of the corresponding signals in acenaphthylene (2), it was ascribed to ring-current effects (67). The 7-ppm difference of the two carbonyl chemical shifts in 3 (8 = 206.1) and 4 (8 = 213.0) has been attributed the same origin (68). 

FIGURE 19.24 HPLC separation of a standard mixture of 16 EU-priority PAHs plus EPA-priority PAHs, benzo[e]pyrene and benzo[fc]chrysene. Na=naphthalene, Ac = acenaphthylene, E=fluorene, Pa=phenan-threne, A = anthracene, El = fluoranthene, P = pyrene, BcE = benzo[c]fluoranthene, CPP = cyclopenta[c,4] pyrene, BaA = benz[a]anthracene, Ch = chrysene, 5-MeCh = 5 methylchrysene, BeP = benzo[e]pyrene, BjE = benzo[/ ]fluoranthene, BbF = benzo[h]fluoranthene, BkE = benzo[l ]fluoranthene, BaP = benzo[a]pyrene, DBahA = dibenz[a,/j]anthracene, DBalP = dibenzo[a,l]pyrene, BghiP = benzo[g,/j,i]perylene, IP = indeno [l,2,3-c4]pyrene, DBaeP = dibenzo[a,e]pyrene, BbCh = benzo[h]chrisene, DBaiP = dibenzo[a,i]pyrene,... 

Fig. 2.20. Composition (mean%) of 16 individual polycyclic aromatic hydrocarbons (PAHs) to total PAHs detected in various environmental media in (a) air (n = 24), (b) soil (n = 226), (c) freshwater (n = 46), and (d) marine sediment (n = 159), from the South Korea. Naphthalene NAP, Acenaphthylene ACY, Acenaphthene ACE, Fluorine FLU, Phenanthrene PHE, Anthracene ANT, Fluoranthene FLT, Pyrene PYR, Benz[a]ant-hracene BaA, Chrysene CHR, Benzo[6]fluoranthene BbF, Benzo[ ]fluoranthene BkF, Benzo[a]pyrene BaP, Indeno[l,2,3,c,d]pyrene I123cdP, Dibenz[a,/z]anthracene DahA, Ben-zo[g,/y ]perylene BghiP.

Pyka separated 16 PAHs (naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo [a] anthracene, chrysene, benzo[/>]fluoranthene, benzo[fe]fluoranthene, benzo[a]py-rene, dibenzo[a,/z]anthracene, benzo[g,/i,i]perylene, and indeno[l,2,3-C(i]pyrene) according to the Environmental Protection Agency (EPA) by gradient HPLC on a LiChrospher PAH column using acetonitrile and water as mobile phases. Retention times fr (sec) of investigated PAHs were correlated with topological indices based on the adjacency matrix (M, 012) and the... 

The - C NMR spectrum for C ) (18 h integration) consists of a single line (Fig. 3n), as required, at 142.68 ppm, and unaltered by proton decoupling. This is significantly down-field from the peaks for the corresponding positions in naphthalene (133.7 ppm), acenaphthylene (128.65 ppm), and benzo(g./i,i,]fluoranthene (126.85,128.05 and 137.75 ppm). This is not unexpected since strain produces downfield shifts which may be attributed to strain-induced hybridisation changes, as shown for example by the C peaks for the bridgehead carbons in tetralin (136.8 ppm), indane (143.9 ppm) and benzcyclobutene (146.3 ppm). ... 

From what is currently known about benzo[a]pyrene. the federal government has developed regulatory standards and guidelines to protect people from the potential health effects of PAHs in drinking water. EPA has provided estimates of levels of total cancer-causing PAHs in lakes and streams associated with a risk of human cancer development. If the following amounts of individual PAHs are released to the environment within a 24-hour period, EPA must be notified 1 pound of benzo[b]fluoranthene, benzo[a]pyrene, or dibenz[a.h]anthracene 10 pounds of benz[a]anthracene 100 pounds of acenaphthene, chrysene, fluoranthene, or indeno[1,2,3-c,d]pyrene or 5,000 pounds of acenaphthylene, anthracene, benzo[k]fluoranthene, benzo[g,h,i]perylene, fluorene, phenanthrene, or pyrene. 

The composition of PAH emissions varies with the combustion source. For example, emissions from residential wood combustion contain more acenaphthylene than other PAHs (Perwak et al. 1982), whereas auto emissions contain more benzo[g,h,i]perylene and pyrene (Rogge et al. 1993a Santodonato et al. 1981). PAHs in diesel exhaust particulates are dominated by three- and four-ring compounds, primarily fluoranthene, phenanthrene, and pyrene (Kelly et al. 1993 Rogge et al. 

PAHs may also volatilize from soil. Volatilization of acenaphthene, acenaphthylene, anthracene, fluorene, and phenanthrene (low molecular weight PAHs) from soil may be substantial (Coover and Sims 1987 Southworth 1979 Wild and Jones 1993). However, of 14 PAHs studied in two soils, volatilization was found to account for about 20% of the loss of 1 -methyinaphthalene and 30% of the loss of naphthalene volatilization was not an important loss mechanism for anthracene, phenanthrene, fluoranthene, pyrene, chrysene, benz[a]anthracene, benzo[b]fluoranthene, dibenz[a,h]anthracene, benzo[a]pyrene, and indeno[1,2,3-c,d]pyrene (Park et al. 1990). 

PAHs have been detected in surface waters of the United States. In an assessment of STORET data covering the period 1980-82, Staples et al. (1985) reported median concentrations in ambient water of >10 ug/L for 15 PAHs (acenaphthene, acenaphthylene, anthracene, benz[a]anthracene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[g,h,i]perylene, benzo[a]pyrene, chrysene, fluoranthene, fluorene, indeno[1,2,3-c,d]pyrene, naphthalene, phenanthrene, and pyrene). The number of samples ranged from 630 (naphthalene) to 926 (fluoranthene) the percentage of samples in which these PAHs were detected ranged from 1.0 (benzo[g,h,i]perylene) to 5.0 (phenanthrene) and 7.0 (naphthalene). 

PAHs have generally not been detected in surveys of human tissue, presumably because the compounds are fairly rapidly metabolized. Phenanthrene was the only PAH detected in the 1982 National Human Adipose Tissue Survey it was found in trace concentrations in 13% of the samples (EPA 1986). Acenaphthylene, acenaphthene, fluorene, and chrysene were not found at levels below the detection limit (0.010 pg/g 10 ppt). However, autopsies performed on cancer-free corpses found PAH levels of 11-2,700 ppt (ng/g) in fat samples (Obana et al. 1981). Several PAHs were detected, including anthracene, pyrene, benzo[e]pyrene, benzo[k]fluoranthene, benzo[a]pyrene, and benzo[g,h,i]perylene, with pyrene being detected in the highest concentrations. A similar study done on livers from autopsied cancer-free corpses found levels of 6-500 ppt (ng/g) of all of the same PAHs except benzo[e]pyrene, which was not detected (Obana et al. 1981). As in the fat sample studies, pyrene appeared in the highest concentrations in the liver, but the overall levels were less than in fat. 

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