Benzanthracenes derivatives

Fig. 15 Structures of representative benzanthracene derivatives and their derived carbocations/carboxonium ions (and comparison with model anthracene cations).

Fig. 3. Directed rooted trees of the Kekule patterns of benzanthracene derived by (R) performing the sextet and counter-sextet rotations. The double (JR) circle represents the root Kekule pattern...

An apparent influence of the solvent was noted in the action of aluminum chloride on the chloride of XCVI, which gave mixtures of the two ketones in which the benzanthracene derivative (XCVII) predominated. This isomer constituted about two-thirds of the total using benzene as a solvent, and a still higher proportion (about nine-tenths) in nitrobenzene solution. A difference in reaction temperatures also may have influenced these ratios. That the temperature may affect the proportion of isomers is indicated by the fact that, when cyclization with stannic chloride was conducted at room temperature instead of in the cold, a mixture of ketones resulted instead of a single ketone.107... 

It is noteworthy that l,3-dimethylnaphtho[l,2-c]thiophene (1,3-dimethyl-4,5-benzisothianaphthene in the literature) (67) has been prepared its properties have been compared with those of the benzanthracene derivative (68).65... 

At this pH, the phosphotriesters formed mainly lose alcohol to re-form the phosphodiester, but at higher pH, hydrolysis with chain scission takes place. Alkylation also proceeds at nucleophilic centres on the base and sugar moieties, and the modification likely to cause most damage in vivo has not been defined. Studies involving aflatoxin Bi and benzanthracene derivatives have tended to concentrate on the modification of the bases, to the exclusion of possible effects at the phosphate group, but there is good evidence that the latter should not be ignored. ... 

Lilly also disclosed two series of conformationally restricted benzanthracene derivatives [185]. These tetracyclic compounds showed high ERa affinity, but subtype selectivity was modest. Thus, benzothiophene analog 149 expressed 5-fold preference for ERa and similar ERa selectivity was noted for benzanthracene analog 150. The latter compound showed high MCF-7 antagonistic activity, whereas analog 149 was 20-fold less active. 

Besides aromatic hydrocarbons such as pyrene (above), benzanthracene (Becker et al., 1977a), benzoin derivatives (Baumann et al., 1982), aromatic and heteroaromatic ketones (Fomin et al., 1980 Baumann et al., 1985), azo dyes (Timpe et al., 1982), methylene blue (Becker et al., 1986 a Becker and Kohrs, 1990), acridine yellow... 

These findings indicate that PGH synthase in the presence of arachidonate can catalyze the terminal activation step in BP carcinogenesis and that the reaction may be general for dihydrodiol metabolites of polycyclic hydrocarbons. Guthrie et. al. have shown that PGH synthase catalyzes the activation of chrysene and benzanthracene dihydrodiols to potent mutagens (33). As in the case with BP, only the dihydrodiol that is a precursor to bay region diol epoxides is activated. We have recently shown that 3,4-dihydroxy-3,4-dihydro-benzo(a)anthracene is oxidized by PGH synthase to tetrahydrotetraols derived from the anti-diol epoxide (Equation 4) (34). 

Basicity constants of methyl derivatives of 1,2-benzanthracene according to Mackor e< al. (1956). For explanation, see text... 

Fig. 27. Semilogarithmic plot of the nonradiative triplet rate constant against (E— o)/> for the normal and deuterated hydrocarbons listed in Ref. t)). The broken line, derived from phosphorescence spectra, is taken from Ref. t). The slopes of the two solid lines differ by a factor 1.35. (O.Ci-jjH, E = 4000 cm l 0 Ci fl Z>u, =5500 cm t). The following totally deuterated hydrocarbons are included benzene, triphenylene, acenaphtene, naphthalene, phenanthrene, chrysene, biphenyl, p-terphenyl, pyrene, 1,2-benzanthracene, anthracene (in the order of increasing /S). (From Siebrand and Williams, Ref. l)...

These alternatives may be distinguished by examining the concentration dependence of the molecular fluorescence yield given by Eq. (1) the observation of self-quenching invalidates condition (b) and provides strong evidence for photoassociation in systems where qD 0. These criteria are applied to the behavior of anthracene and certain of its derivatives in Table V, from which it is concluded that photoassociation of 9,10-diphenyl-anthracene (as in 9,10-dimethyl-1,2-benzanthracene and rubrene) is prohibited by steric hindrance of the bulky substituents (Table III). 

Additions to Aromatic Hydrocarbons. A variety of photochemical additions to aromatic hydrocarbons have been reported. Benzene and its derivatives add to maleic anhydride74-76 as well as to simple olefins,77-80 isoprene,81 acetylene derivatives,79,82 and alcohols.83 The mechanism of the maleic anhydride-benzene reaction is discussed in Section IV. A.4. Naphthalene forms a photoadduct with dimethyl acetylenedicarboxylate62 and with acrylonitrile8211 while anthracene behaves similarly with maleic anhydride84 and with 1,2-benzanthracene.85 The photoaddition of several aromatic amines to anthracene has been reported to proceed via a charge transfer complex86,87 in fact, the majority of these addition reactions may proceed in this manner. 

Free dihydrodiol metabolites have been isolated from urine, following the administration of phenanthrene119 and chlorobenzene.120 The yields are low because, under mildly acidic conditions and gentle heating, the diols are easily dehydrated to phenols, or their D-glucuronic conjugates may be hydrolyzed and the aglycons reduced to the parent hydrocarbons. As a consequence, labile diols may be the true excretion products of many hydrocarbons whose phenolic derivatives have been isolated from urine, such as 1,2,5,6-dibenzanthracene, 1,2-benzanthracene, 3,4-benzopyrene, and 9,10-dimethyl-l,2-benzanthracene.121... 

Figure 8.12 Chromatography of anthracene derivatives with different detection modes (A) laser-induced fluorescence (B) UV absorbance. Conditions capillary, 115.1 cm X 10 /un I.D. with 1.27-/im coating stationary phase, silicone acrylate/ethylhexyl acrylate Vy Vm = 0.65 mobile phase, acetonitrile detection, (A) laser-induced fluorescence (AeX 325 nm, Aem 380 nm), pressure 13.8 bar, (B) UV (258 nm), pressure 13.0 bar. Peaks 1, salicylate 2, anthracene-methanol 3, anthracenecarbonitrile 4, anthracene 5, fluoranthracene 6,1,2-benzanthracene 7, 9-phenylanthracene. (Reprinted from Ref. 11 with permission.)...

J. W. Cook, Polycyclic Aromatic Hydrocarbons. Part XII. The Orientation of Derivatives of 1 2-Benzanthracene, with Notes on the Preparation of Some New Homologues and on the Isolation of 3 4 5 6-Dibenzphenanthrene, J. Chem. Soc. 1933, 1952-1957. 

Colpa et al. (1963) calculated p/if(S1 )-values for a series of aromatic hydrocarbons, but could not detect fluorescence changes in the regions of acidity indicated by the Forster cycle, although fluorescence spectra attributed to proton complexes of 3,4-benzopyrene and 1,2-benzanthracene were observed in some solutions containing only the neutral molecule in the ground state. Flurry and co-workers (1963, 1966, 1967) have carried out theoretical and Forster cycle calculation on the excited state basicities of poly-methylbenzenes and Kuz min et al. (1967) have also calculated p/ (Sj)- and p/ (Tj)-values for polycyclic aromatic hydrocarbons increases in base strength of from 7 to 30 powers of ten were derived for Sj. 

This synthesis is applicable to many aromatic compounds, including alkoxyl or N,N dimethylamino derivatives of benzene and naphthalene, naphthols, indole, and certain reactive hydrocarbons, namely, anthra-cene, 1,2-benzanthracene, 3,4-benzpyrene, ° and pyrene. The high-melting polynuclear hydrocarbons react best in the presence of a solvent, such as o-dichlorobenzene. For example, a solution of anthracene, methyl formanilide, and phosphorus oxychloride in o-dichlorobenzene is heated 1 hour at 90-95° then an aqueous solution of sodium acetate is added, and the solvent and N-methylaniline are removed by steam distillation. The solid residue is readily purified to yield 9-anthraldehyde (84%). With liquid or low-melting compounds a solvent is not required. 

Reduction of aromatic hydrocarbons. Anthracene is reduced quantitatively to 9,10-dihydroanthraccncby sodium in HMPT with THF as cosolvent. The reaction has been extended to benzanthracene, tetracene, and 9-alkyl- and 9,10-dialkylanthraocnes to give the corresponding mejo-dihydro derivatives. Water or methanol diluted in THF is used as the proton source. ... 

Much of the interest in complex polynuclear hydrocarbons has arisen because a considerable number of them have cancer-producing properties. Some of the most powerful carcinogens are derivatives of 1,2-benzanthracene ... 

Petroleum. The presence of PCAH in petroleum is well known. Naphthalene, phenanthrene, fiuorene, pyrene, chrysene, triphenylene, perylene, several benzanthracenes, and various alkyl substituted derivatives of these compounds have been foimd in crude petroleum (7). In addition, the PCAH content of those petroleum products which have been produced by thermal cracking is much greater than in the crude oil. 

Sandin and Fieser developed an efficient synthesis of the potently carcinogenic 9,10-dimethyl-l,2-benzanthracene from 1,2-benzanthraquinone (1) involving addition of methyl Grignard reagent, reaction of the adduct (2) with hydriodic acid to give the 9-methyl-10-iodomethyl derivative (3) and reduction with stannous chloride in dioxane-hydrochloric acid. 

Coal tar creosote-derived phenanthrene, 1,2-benzanthracene, and benzo[a]pyrene have been detected in river sediments at concentrations of up to 231, 62, and 16 mg/kg (wet basis), respectively, directly downstream from the site of a former wood treatment facility. At 4,000 meters from the source, these levels decreased to 0.35, 1.02, and 0.40 mg/kg (wet basis), respectively (Black 1982). Creosote-derived PAHs were also detected in the sediments of Pensacola Bay and a drainage stream in the vicinity of a former wood treatment facility near Pensacola, Florida. PAH concentrations ranged from 200 pg/g for naphthalene to 140 mg/kg for anthracene in stream sediments concentrations in Pensacola Bay ranged from 75 (ig/kg for benzanthracene to 190 pg/kg for fluoranthene (Elder and Dresler 1988). 

St -> Sn Spectra.—A description has been given of a method for recording ultrafast absorption spectra using a passively mode-locked ruby laser with a ruby amplifier, a pulsed flashlamp probe source, and streak-camera detection for ps time resolution. Results for the dye 3,3 -diethylthiatricarbocyanine in methanol were reported.2870 These results can be compared with those obtained by an alternative method 29711 which permits nm spectral resolution and ps time resolution over the entire visible region, and which was first used on the Sx -> Sn absorption of 3,3 -diethyloxadicarbocyanine iodide, and which has recently been used to record the Si - Sn absorption spectra of bis-(4-dimethylaminodithio-benzil) nickel(n), and of SnIV, Pd11, and Cu" porphyrins.298 The use of time-resolved Si - Sn, Ti - Tn absorption and emission spectroscopy to assist in the selection of laser dyes has been illustrated with respect to anthracene and its derivatives.299 Si - Sn Spectra of coronene, 1 2-benzanthracene, l 12-benz-perylene, 1,2,3,4-dibenzanthracene, and benzo[6]chrysene in poly(methyl methacrylate) and toluene have been reported, the method of detection being modulation spectrophotometry, for which it is claimed that species of lifetime down to... 

The modulation technique mentioned above has been used to identify triplet excimers in 1,2-benzanthracene and 1,2 3,4-dibenzanthracene at high solute concentrations167 and the differences between luminescence from naphthalene in fluid solution in the temperature range 353—173 and naphthalene in a rigid solution at 77 have been ascribed to phosphorescence from a triplet excimer.168 Excimer formation in solid poly-(2-vinylnaphthalene) and polystyrene is found to be dependent on the temperature at which the film is cast, and a statistical model based on the rotational isomeric state approximation has been used to formulate an expression for the fraction of excimer sites in the solid systems.168 Kinetic equations for dimer formation and decay, based on the statistical mechanics of ideal gases, have been obtained. These equations, derived from the N-atom von Neumann equation, take into account both bimolecular and termolecular equations.157 158 160... 

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