Fluoranthene derivatives

Fluoranthene derivatives transform into cation radicals upon one-electron oxidation. These species are not stable and quickly undergo a further oxidation. For example, 7,14-dipheny-lacenaphtho[ 1,2-k]fluoranthene gives a ladder polymer according to Scheme 7-3 (Debad Bard 1998.) As a result, an insoluble transparent blue polymer film forms on the electrode. Electrochemical oxidation of the film in acetonitrile initiates a rapid color change from blue... 

Scheme 26. Oxidative /zoraocoupling of fluoranthene derivative 59 [7] 0 =CoF3/TFA, AlCl3/NaCl, Tl(OCOCF3)3 or bulk electrolysis...

It has subsequently been shown <86TL1105> that (146) and (147) are unique only in regard to their stability and not with respect to attack of nitrene at the sulfur atom. In a reinvestigation of the reaction of ethyl azidoformate with several thiophenes it has been shown that S,N-ylides are indeed formed as transient products in every case these could be trapped by cycloaddition with acenaphthylene (see Section 2.10.3.3) leading to fluoranthene derivatives. 

A soln. of l,8-bis(phenylethynyl)naphthalene in benzene allowed to react 60 hrs. at 20° under Ng with chlorotris(triphenylphosphine)rhodium, and the soln. of the intermediate complex treated with diethyl acetylenedicarboxylate fluoranthene deriv. Y 80%. - Similarly with carbon monoxide acecyclone. Y 50%. F. e., e. g. with sulfur, s. E. Muller et al., Tetrah. Let. 1971, 521. 

The synthesis of fluoranthene derivatives from l,8-his(arylethynyl)-naphthalenes 2.337 and alkynes 2.338 includes formal [(2- -2)- -2] cycloaddition [164, 165]. This method has been successfully applied... 

The radical-initiated reaction of substituted enediynes leads to the creation of fused rings such as fluoranthene and acephenanthrylene in a single step. For example, orr/70-substituted biphenyl (radical target) is prepared by coupling homoenediyne 3.647 with l-bromo-2-iodobenzene. Desilylation of the formed biphenyl derivative gives the enediyne 3.648. Next, its reaction with tin hydride/AIBN at 80°C generates free radicals which initiates cycloaromatization to form only one product, the fluoranthene derivative 3.649 (Scheme 3.60) [305]. 

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. 

Fluoranthene is one of the more prevalent PAH in the human environment. Although fluoranthene is not active as a carcinogen, its 2- and 3-methyl derivatives have been shown to be active as tumor initiators (105). The major mutagenic metabolite of fluoranthene in the Ames assay has been identified as the 2,3-dihydrodiol (31)... 

Synthesis of 31 by Method I (107,108) and its conversion to the related anti and syn diol epoxide derivatives (32,33) has been reported (108). The isomeric trans-1,lOb-dihydrodiot 37) and the corresponding anti and syn diol epoxide isomers (38,39) have also been prepared (108) (Figure 19). Synthesis of 37 from 2,3-dihydro-fluoranthene (109) could not be accomplished by Prevost oxidation. An alternative route involving conversion of 2,3-dihydrofluoranthene to the i8-tetrahydrodiol (3-J) with OsO followed by dehydration, silylation, and oxidation with peracid gave the Ot-hydroxyketone 35. The trimethylsilyl ether derivative of the latter underwent stereoselective phenylselenylation to yield 36. Reduction of 3 with LiAlH, followed by oxidative elimination of the selenide function afforded 3J. Epoxidation of 37 with t-BuOOH/VO(acac) and de-silylation gave 38, while epoxidation of the acetate of JJ and deacetylation furnished 39. 

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). 

Alle beschriebenen Derivate des 1,2-Benzazulens kristallisieren sehr gut und sind auBerordentlich bestandig. W. Treibs (160) gelangte durch Ringerweiterung des Tetrahydro-fluoranthens nach Buchner zu einem noch nicht kristallisiert erhaltenen, in seiner Struktur nicht eindeutigen tetracyclischen Azulen-carbonsaureester- dem 3-( 4- oder 12)-Trimethylen-... 

Seventeen priority pollutant compounds can be classified as polynuclear aromatics (PNA). These compounds consist of two or more benzene rings that share a pair of carbon atoms. They are all derived from coal tar, with naphthalene being the largest constituent. Naphthalene derivatives such as alpha-naphthylamine and alpha-naphthol are used in some pesticide processes therefore, naphthalene is by far the most prevalent PNA priority pollutant in the industry. Acenaphthene, anthracene, fluorene, fluoranthene, and phenathrene are found as raw material impurities. Acenaphthene is found in one pesticide process as a raw material. The remaining ten PNAs are not suspected to be present in pesticide processes. 

Figure 4.2 Top down mass spectromet using ETD. (a) Setup of ETD and PTR in a 3D HCTultra ion trap (BDaltonics). ETD and PTR reactants are ionized in an additional nCI source and injected into the transfer line from the same reservoir. Switching nCI parameters decides whether the radical anion for ETD (fluoranthene) or its derivative, a basic anion, for PTR (CieHn ) is extracted from...

Two years later, Craig and Robinson attempted an alternative synthesis of 8 with a more symmetrical pathway starting from derivatives of fluoranthene. Cycliza-tion of fluoranthene-7,10-diacetic acid 14 was attempted to produce diketone 15, expected to enolize to the dihydroxycorannulene 16. Unfortunately, several attempts at cyclization failed, including anhydrous hydrofluoric acid, concentrated sulfuric acid, and polyphosphoric acid. Friedel-Crafts cyclization of the corresponding acid chloride of 14 with aluminum or stannic chloride was similarly unsuccessful. However, although Craig and Robinson were not successful, they developed a convenient synthesis of 7,10-disubstituted fluoranthenes which turned out later to be of premium importance in a new, successful synthesis of corannulene. 

An alternative synthesis of corannulene, also involving a pyrolysis, was reported by Siegel and co-workers (Scheme 4), The tetrabromide may be directly pyro-lyzed to corannulene, or it may be converted to a bis-sulfone where extrusion of SO2 produces a mixture of 8 along with its di- and tetrahydro derivatives, and 5,6-dimethy 1-benzo [g/ir] fluoranthene. 

Tokiwa et al. (1981) reported that direct-acting mutagenic derivatives were formed when pyrene, phenan-threne, fluorene, fluoranthene, and chrysene (and car-bazole) were deposited on filter paper and exposed to... 

Tokiwa, H., T. Otofuji, R. Nakagawa, K. Horikawa, T. Maeda, N. Sano, I. Izumi, and H. Otsuka, Dinitro Derivatives of Pyrene and Fluoranthene in Diesel Emission Particulates and Their Tumorigenicity in Mice and Rats, in Carcinogenic and Mutagenic Effects of Diesel Engine Exhaust (N. Ishinishi, A. Koizumi, R. O. McClellan, and W. Stober, Eds.), pp. 253-270, Elsevier, Amsterdam/New York, 1986. 

Fluoranthene and derivs 6 FI20 dinitrofluoranthenes 6 FI20 mononitrofluoranthenes 6 FI 20 pentanitrofluoranthene 6 FI20 tetranitrofluoranthene 6 FI20 trinitrofluoranthene 6 FI20... 

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