Phenanthrene from naphthalene

Preparation of phenanthrenes from naphthalenes via a series of steps including a Friedel-Crafts acylation and two Clemmensen or Wolff-Kishner reductions, q.q.v. ... 

The red solution of polystyryl carbanions can be kept for days without change in color or viscosity. No changes are observed on addition of further amounts of naphthalene to the red solution. These observations raise some questions. An electron transfer, say for example, between naphthalene" and phenathrene, is a reversible process and it leads eventually to an equilibrium between naphthalene , naphthalene, phenathrene-, and phenanthrene. Is the reaction involving styrene irreversible Now, the initial process of electron transfer from naphthalene to styrene that produces... 

A cytochrome P450 has been purified from Saccharomyces cerevisiae that has benzo[a]pyrene hydroxylase activity (King et al. 1984), and metabolizes benzo[fl]pyrene to 3- and 9-hydroxybenzo[fl]pyrene and benzo[fl]pyrene-7,8-dihydrodiol (Wiseman and Woods 1979). The transformation of PAHs by Candida Upolytica produced predominantly monohydroxyl-ated products naphth-l-ol from naphthalene, 4-hydroxybiphenyl from biphenyl and 3- and 9-hydroxybenzo[fl]pyrene from benzo[fl]pyrene (Cerniglia and Crow 1981). The transformation of phenanthrene was demonstrated in a number of yeasts isolated from littoral sediments and of these, Trichosporumpenicillatum was the most active. In contrast, biotransformation of benz[fl]anthracene by Candida krusei and Rhodotorula minuta was much slower (MacGillivray and Shiaris 1993). 

Extension of -conjugation from naphthalene to anthracene and phenanthrene has a small effect on the tmax of the photomerocyanine form. Replacement of the indoline ring with piperidine, benzoxazole, or benzo-thiazole83 has resulted in hypsochromic shift by ca. 10 nm.72... 

Some evidence for the process (AQ) - (AQ) when QsA, or for photoassociation of the triplet A + A - (AA)(, has been provided by Hoytink and co-workers,<1B8) who reported excimer phosphorescence from cooled ethanolic solutions of phenanthrene and naphthalene. 

Aromatic hydrocarbons were found in more recent analyses pyrene, fluoran-threne, phenanthrene and naphthalene in the ratio of 10 10 5 1 (Cronin, 1998). The majority (around 70%) of the hydrocarbons extracted from the Murchison meteorite are polar compounds such as ... 

Figure 2. Log kQ versus AEdeioc/3 plots for the spontaneous hydrolysis of tetrahydroepoxides. Rates were measured at 25 °C in 1 9 dioxane.-t O, ionic strength 0.1 (NaC104) except in the case of the phenanthrene and naphthalene tetrahydroepoxides, whose rates were measured at 30 °C in 1 0, ionic strength 1.0 (KC1). (Adapted from Refs. 25, 26, and 27.)...

Human activities have resulted in exposure of Antarctic fishes to petroleum-derived PAHs (McDonald et al. 1992). Fish captured near Palmer station on the Antarctic peninsula had induced EROD activities and elevated concentrations of biliary PAH metabolites of phenanthrene and naphthalene when compared to conspecifics from reference sites (McDonald et al. 1995). Artificial reefs consisting of oil and coal flyash stabilized with cement and lime in Florida waters near Vero Beach contained elevated PAH levels ranging from as high as 1.2 mg fluoranthene/kg and 0.25 mg naphthalene/kg. But there is negligible leaching because seawater is not an effective medium for removing PAHs from reef bricks or the ash (Frease and Windsor 1991). 

The arene (5 mmol) in CHCl3 (100 ml) is added to aqueous NaOCl (0.6 M, 250 ml) and the pH is adjusted to 8-9 by the addition of cone. HCl. TBA-HS04 (0.34 g, l mmol) is added and the mixture is stirred until TLC analysis shows complete conversion of the arene. The organic phase is separated, washed well with H20, dried (K2CO ), and evaporated to yield the epoxide (e.g. 90% from phenanthrene, 76% from 1,2-benz-anthracene, 70% from acenaphthene, 19% 2,3 4,5-bis-epoxide from naphthalene). 

The adduct formed by two lithium atoms with polycondensed aromatic hydrocarbons crystallizes with two solvating molecules of TMEDA. The structure of the crystals derived from naphthalene (73) and anthracene (74) was elucidated by XRD. This arrangement of the unsolvated lithium atoms, in 7 -coordination fashion on the opposite sides of two contiguous rings, was found by MNDO calculations to be the most favorable one for naphthalene, anthracene and phenanthrene (75) . 

Evidence for photoassociation in the triplet manifold is at present inconclusive. Although Hoytink et al.20 have reported excimer phosphorescence from cooled ethanolic solutions of phenanthrene and naphthalene, concentration and temperature-dependent studies of the emission characteristics must be extended in order to distinguish photoassociation of the triplet state from intersystem crossing of the singlet excimer and possible triple-triplet annihilation. Certainly the decay constant of the molecular triplet state in fluid media is relatively insensitive to solute concentration21 although this... 

Fig. 25. Sensitized anti-Stokes delayed fluorescence from naphthalene.60 (1, 2) Delayed fluorescence from 10 "s3/ phenanthrene, and from mixture of phenanthrene (10"W) and naphthalene (3 X 10-3M), in ethanol. (3) Normal fluorescence from solutions 1 and 2 at 260 times less sensitivity. (4) Spectral distribution of exciting light for curves 1, 2, and 3, 0.7 X IQ-8 einstein liter"1 sec.-1 absorbed. (5, 6) Normal and delayed fluorescence from 3 X 10 lM naphthalene in ethanol excited by 313 m/i, 2 X 10-4 einstein liter-1 sec.-1 absorbed. Curve (5) at a sensitivity 100 times less than curve (6). Temperature for all curves was — 72° 3°C.

Unfortunately, diaromatic hydrocarbons are not the only potential hydrocarbon inhibitors present in gas oils and diesel fuels. Triaromatic hydrocarbons are also present in significant amounts (see Fig. 2) (12). It is known that triaromatics, such as phenanthrene, are even stronger inhibitors than diaromatics for the HDS of thiophene compounds. Equilibrium adsorption constants for phenanthrene and naphthalene have been reported to be 65 and 11 atm-1, respectively (131). In Iranian gas oil, triaromatics have been reported to be present at about one-tenth the concentration of diaromatics (109). Thus, the contribution to inhibition of HDS reactions by triaromatics (XTri[Tri]) could be about the same as that from diaromatics, even though triaromatics are present in smaller amounts. 

Quinones of the more reactive, polycyclic, aromatic systems can usually be obtained by direct oxidation, which is best carried out with chromium(vi) compounds under acidic conditions. In this way 1,4-naphthoquinone, 9,10-anthraquinone and 9,10-phenanthraquinone are prepared from naphthalene, anthracene and phenanthrene respectively (Expt 6.128). Also included in this section is the reduction of anthraquinone with tin and acid to give anthrone, probably by the sequence of steps formulated below. 

Detailed experimental procedures have been previously reported (Ko, 1998 Ko et al., 1998a,b) therefore, they are only briefly described here. Phenanthrene (Aldrich, 99.5+%), naphthalene (Aldrich, 99+%), SDS (Sigma, 99.5+%), and Tween 80 (Aldrich, no purity reported) were used as received selected physicochemical properties for these compounds are shown in Table 1. Kaolinite, a nonswelling 1 1 layer phyllosilicate clay and common constituent of many subsurface environments, was used as received from Sigma. Solution pH and ionic strength were adjusted as necessary with 0.5 M HC1 and/or 0.5 M NaOH and NaCl, respectively. Aqueous phenanthrene and naphthalene concentrations were quantified by fluorescence (PTI, Inc.) at the excitation/emission wavelengths of 250/364 and 278/322 nm, respectively. A total organic carbon (TOC) analyzer (Shimadzu Model 5050) was used to determine aqueous SDS concentrations and Tween 80 concentrations were determined by UV absorbance at 234 nm. 

Micellar partition coefficient (Kmic) values for phenanthrene and naphthalene below their aqueous solubility limits were determined from experimental fluorescence measurements using nonlinear regression analysis of the following equation ... 

Figure 4 shows phenanthrene and naphthalene sorption isotherms to kaolinite covered with varying levels of sorbed surfactant these levels of surfactant coverage correspond to the different regions existing in the surfactant sorption isotherms discussed earlier (Fig. 1). The linearity of each isotherm was evaluated using Freundlich and linear sorption models. It is apparent from Fig. 4 and Table 4 that HOC partitioning to kaolinite with and without adsorbed surfactants results in linear or near-linear isotherms. As the amount of surfactant adsorbed on the kaolinite surface increased, the sorption of phenanthrene and naphthalene to the solid phase also increased. However, upon normalizing by the amount of sorbed surfactant present, the sorbed surfactant partition coefficient (Kss) decreased with increasing sorbed surfactant amounts (Table 4).

Depending on the desired treatment methodology and goals, addition of surfactants to a subsurface system should either increase HOC distribution coefficients (i.e., immobilization approach) or decrease them (i.e., mobilization objective as in many SEAR applications). For example, distribution coefficients for phenanthrene and naphthalene to kaoiinite are 0.002 and 0.0003 L/g, respectively (Table 4). Therefore, if enhanced mobilization of these HOCs in a similar type of aquifer system was desired, addition of a surfactant would have to bring the distribution coefficients below these values. However, as can be seen in Fig. 5, all distribution coefficients for the surfactant doses investigated here are larger than these values, even when the doses and subsequent aqueous surfactant concentrations are well above the CMC. This observation results from a combination of surfactant sorption followed by HOC partitioning to the sorbed surfactant. 

Ortiz, et. al (1999) measured overall mass transfer coefficients for the aqueous dissolution of naphthalene, pyrene, and phenanthrene from oils ranging in viscosities from a light lubricating oil (86 cp) to a high viscosity oil ( 1000cp). These measurements were performed in continuous-flow systems for time periods ranging from several months up to one year. The authors hypothesize that naphthalene, pyrene, and phenanthrene dissolution from a high viscosity oil (1000 cp) results in a depleted zone within the NAPL that increases with dissolution time. 

PAHs in soil may partition into soil organic matter (SOM) or adsorb on soil minerals. The sorptive properties of SOM fractions for organic contaminants in soil play an important role on the transportation of PAHs in soil. Xiao et al. (2004) has reported that soil/sediment organic matter can be fractionated into four fractions with a combined wet chemical procedure and that kerogen and black carbon (BC) are major SOM components in soil/sediment samples collected from the industrialized suburban areas of Guangzhou, China. Phenanthrene and naphthalene were used as the sorbates to study PAH s sorption isotherms on four original and four Soxhlet-extracted soil/sediment samples, 15 isolated SOM fractions, and a char as the sorbents. The sorption isotherms of phenanthrene and naphthalene on all the sorbents were variously nonlinear. The particulate kerogen and black carbon (KB) fractions... 

This test is given by any aromatic compound that can undergo the Friedel-Crafts reaction, with the particular color produced being characteristic of the aromatic system involved orange to red from halobenzenes, blue from naphthalene purple from phenanthrene, green from anthracene (Chap. 30). 

When taken together with the previous data on the aromatic hydrocarbons present in the water (1), it is now apparent that PCAH ranging from naphthalene to dibenzopyrene are present in the Charles River Basin system. The more water-soluble of these PCAH, the naphthalenes, are found in the water only those of intermediate solubility, anthracenes or phenanthrenes, are found in both water and sediment and those of... 

Chemical Synthesis. If cholesterol is heated with elemental sulfur at 150°C for several days, a mixture of PCAH results (J2), the detailed composition of which is not known. Other dehydrogenation reagents, such as selenium, catalyze the production of alkyl naphthalenes and phenanthrenes from naturally occurring terpenes (J3). Thus, in principle, it is possible that the PCAH in an anoxic sediment could result from the chemical dehydrogenation of various naturally occurring compounds. These reactions may take place slowly over the years and may be catalyzed by trace elements, elemental sulfur, and clay minerals. 

A set of fluorophores derived from naphthalene, phenanthrene, pyrene, phenazine and fluorene have been conjugated to the 5 -ends of DNA and RNA to compare their physico-chemical properties. Decreasing the Ji-electron density led to an enhancement in thermal stability, attributable to more favourable Jt-Ji interactions. Stability is further enhanced by using nitrated fluorophores. Fluorescent labelling of ODNs using oxyamino modified fluorescein has been reported by the incorporation into DNA of aldehyde functions. The aldehyde function was attached either at the 5 -end via a phosphate linker or internally via 8-mercaptobutanal. Reduction of the resulting oxime was not necessary. 

The structure of the substrates is not necessarily restricted to monocyclic aromatic compounds such as those shown in Scheme 16.1-2. The dioxygenase activity of Pseudomonas putida and Beijerinckia species has been used exclusively for the synthesis of cis dihydrodiols from polycyclic 202 and heterocyclic 203 derivatives. Such products have been obtained from naphthalene, anthracene, phenanthrene, benz[a]pyrene, benz[a]anthracene, and methylsubstituted benz[a]anthracenes, and... 

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