Anthracene and derivatives

Anthracene and derivs 1 A457-A458 anthracene peroxide 1 A458 dinitroanthracenes 1 A458 mononitroanthracenes 1 A458... 

Some information is available about the nitration of polycyclic hydrocarbons and their derivatives, but it is of no quantitative significance. The formation of a cr-complex from anthracene and nitronium ions has been mentioned ( 6.2.3, 6-3)-... 

The reaction of methoxy-substituted 1,4-dihydroatomatic systems is a general one. Other condensed systems react ia a similar manner, for example, 3,6-dimethoxy-1,4,S,8-tetrahydronaphtha1ene and derivatives of anthracene (35) and xanthene (36) (74). The proposed method enables synthesis of the tri-and tetracarbocyanines where the whole chromophore is iategrated iato a rigidizing skeleton. Asymmetrical polymethines can also be obtained similarly. 

The synthetic procedure described is based on that reported earlier for the synthesis on a smaller scale of anthracene, benz[a]anthracene, chrysene, dibenz[a,c]anthracene, and phenanthrene in excellent yields from the corresponding quinones. Although reduction of quinones with HI and phosphorus was described in the older literature, relatively drastic conditions were employed and mixtures of polyhydrogenated derivatives were the principal products. The relatively milder experimental procedure employed herein appears generally applicable to the reduction of both ortho- and para-quinones directly to the fully aromatic polycyclic arenes. The method is apparently inapplicable to quinones having an olefinic bond, such as o-naphthoquinone, since an analogous reaction of the latter provides a product of undetermined structure (unpublished result). As shown previously, phenols and hydro-quinones, implicated as intermediates in the reduction of quinones by HI, can also be smoothly deoxygenated to fully aromatic polycyclic arenes under conditions similar to those described herein. 

The results are consistent with the rate-determining step being addition of the aryl radical to the aromatic ring, Eq. (9). Support for this mechanism is derived from the results of three other studies (a) When A -nitrosoacetanilide is decomposed in pyridine, the benzene formed by abstraction of hydrogen from pyridine by phenyl radical accounts for only 1 part in 120 of the reaction leading to phenyl-pyridines. (b) 9,9, 10,lCK-Tetrahydro-10,10 -diphenyl-9,9 -bianthryl is formed in the reaction between phenyl radicals and anthracene, probably by the addition mechanism in Eq. (11). Adducts are also formed in the reactions of benzyl radicals with anthracene- and acridine. ... 

Coman et al. [82] used a new modeling of the chromatographic separation process of some polar (hydroxy benzo[a]pyrene derivatives) and nonpolar (benzo[a]pyrene, dibenz[a,/ ]anthracene, and chrysene) polycyclic aromatic compounds in the form of third-degree functions. For the selection of the optimum composition of the benzene-acetone-water mobile phase used in the separation of eight polycyclic aromatic compounds on RP-TLC layers, some computer programs in the GW-BASIC language were written. 

Midinger and Wilkinson<54> have used flash photolysis and fluorescence quenching by heavy atoms to determine the intersystem crossing efficiencies of anthracene and a number of its derivatives. As discussed in Section 5.2b, heavy atoms present as molecular substituents or in the solvent serve to promote multiplicity forbidden transitions. When anthracene is excited the following processes can occur ... 

Microautoclave data was also obtained with Wilsonville Batch I solvent utilizing Indiana V coal. Batch I solvent was obtained from Wilsonville in mid-1977. Other batches of recycle solvent were received later. Batch I solvent had inspections most like the Allied 24CA Creosote Oil used for start-up at the Wilsonville Pilot Plant. Succeeding batches of solvent received by CCDC showed substantial differences, presumably due to equilibration at various operating conditions. As the Wilsonville solvent aged and became more coal derived, the solvent aromaticity decreased with an increase in such compounds as indan and related homologs. The decrease in aromaticity has also been verified by NMR. A later solvent (Batch III) also showed an increase in phenolic and a decrease in phenanthrene (anthracene) and hydrogenated phenanthrene (anthracene) type compounds. 

At typical coal liquefaction conditions, namely temperatures from 300 to 400 C and reaction times on the order of 1 hr, hydrogen transfer from model CIO donors, the A1- and A2-dialins, to model C14 acceptors, anthracene and phenanthrene, occurs in the sense allowed by the Woodward-Hoffman rules for supra-supra group transfer reactions. Thus, in the conversion of the C14 substrates to their 9, 10 dihydro derivatives the dialins exhibited a striking reversal of donor activity, the A dialin causing about twice as much conversion of phenanthrene but only one-tenth as much conversion of anthracene as did A2-dialin. 

This chapter focuses on recent developments in the design and applications of fluorescent organic markers, such as coumarins, benzoxadiazoles, acridones, acridines, polyaromatics (naphthalene, anthracene, and pyrene), fluorescein, and rho-damine derivatives, which display maximum fluorescence emission in the UV/ visible region and have been applied in the labeling of relevant biomolecules, namely DNA, RNA, proteins, peptides, and amino acids, among others. 

Polycyclic aromatic compounds, namely naphthalene, anthracene and pyrene derivatives are widely used as fluorescent probes in relevant biomolecules. 

GC of aqueous simulant or water extract of olive oil using cold on-column injector. 1,4 butane diol internal standard Solvent extraction with dichloromethane and concurrent derivatisation with 9-(methylaminomethyl)anthracene. Fluorescent derivatives analysed by HPLC with fluorescence detection... 

Dimethyl anthracene and diphenyl isobenzofuran form remarkably stable233 cyclopropanone derivatives (353/354), whilst with other diene components (butadiene, tetracyclone, and fulvene) the primarily formed Diels-Alder adducts either suffer ketalizing attack of the solvent (356 - 357, 359 - 358/360) or undergo irreversible changes such as decarbonylation to 362 or rearrangement to 355. 

Although benz(a)anthracene (BA) is generally considered noncarcino-genic (27), it is a weak tumor initiator when administered with a phorbol ester promoter (28). More importantly, BA is a convenient model for the highly potent carcinogenic PAH 7,12-dimethylbenz(a)-anthracene and 3-methylcholanthrene (27), both of which are BA derivatives but which offer more serious synthetic problems. 

The DMBA metabolite model compounds which have been examined include the benz[a]anthracene (BA) derivatives, 1,2,3,4-tetrahydro-BA 02, U), 5,6-dihydro-BA U2), and 8,9,10,11-tetrahydro-BA (12,... 

The literature of mechanistic aromatic photochemistry has produced a number of examples of [4 + 4]-photocycloadditions. The photodimerization of anthracene and its derivatives is one of the earliest known photochemical reactions of any type97. More recently, naphthalenes98, 2-pyridones" and 2-aminopyridinium salts100 have all been shown to undergo analogous head-to-tail [4 + 4]-photodimerization. Moreover, crossed [4+4]-photocycloaddition products can be obtained in some cases101. Acyclic 1,3-dienes, cyclohexadienes and furan can form [4 + 4]-cycloadducts 211-214 with a variety of aromatic partners (Scheme 48). 

Generally, benzene and naphthalene derivatives show only little reactivity as dienes in Diels-Alder synthesis, contrary to anthracene and the higher acene derivatives which are frequently used as dienes. Exceptions are the reactions of benzene and naphthalene derivatives with highly reactive dienophiles such as dicyanoacetylene (DCA), which... 

---