Anthracene-phenanthrene derivatives

This cyclization also gives good results in the case of derivatives of naphthalene, anthracene, phenanthrene, and other aromatic substrates [76]... 

The chloromethylation can be generally employed in aromatic chemistry benzene, naphthaline, anthracene, phenanthrene, biphenyls and many derivatives thereof are appropriate substrates. The benzylic chlorides thus obtained can be further transformed, for example to aromatic aldehydes. Ketones like benzophe-none are not reactive enough. In contrast phenols are so reactive that polymeric products are obtained. ... 

An interesting reaction of dimsyl anion 88 is the methylation of polyaromatic compounds. Thus naphthalene, anthracene, phenanthrene, acridine, quinoline, isoquinoline and phenanthridine were regiospecifically methylated upon treatment with potassium t-butoxide and DMSO in digyme or with sodium hydride in DMSO123-125. Since ca. 50% of D was found to remain in the monomethyl derivative 93 derived from 9-deuteriophenanthrene 92, the mechanistic route shown in Scheme 2 was suggested125. 

A quantitative correlation has been derived based on experimental data for 11 aromatic compounds (biphenyl, naphthalene, anthracene, phenanthrene, pyrene, phenol, p-toluidine, p-nitrotoluene, and o-, m-, and p-nitrophenol) at 20°C [74] ... 

The most abundant aromatics in the mid-distillate fractions are di- and trimethyl naphthalenes. Other one and two ring aromatics are undoubtedly present in small quantities as either naphtheno- or alkyl-homologues in the Cn-C2orange. In addition to these homologues of alkylbenzenes, tetralin, and naphthalene, the mid-distillate contains some fluorene derivatives and phenanthrene derivatives. The phenanthrene structure appears to be favored over that of anthracene structure (Tissot and Welte, 1978 Speight, 1999). 

The only cases of cyclization of 7-2-naphthylbutyric acids in which the ring does not close into the reactive 1-position to form a phenanthrene derivative are those in which either this position is blocked or the 8-position is substituted. The latter clearly seems to be an example of hindrance. An illustration is afforded by the cyclization of 7-8-methyl-2-naphthylbutyric acid (XXXIX) to the linear anthracene derivative XLI instead of the expected ketotetrahydrophenanthrene.26 The orientation influence of the methyl substituent would not be expected to affect the course of the reaction in such a manner. In like manner the tetramethyl derivative XL gave the product of linear ring closure XLII in good yield.27 A similar abnormal course of cyclization 28 has been observed in the benzylbenzoic acid derivative, o-(8-methyl-2-naphthyl- ... 

Figure 10 shows the orthogonal even mass maps of the C H2 -eO C H2 -i8 components that correspond to phenol-alkyl phenols and the anthracene-phenanthrenes and alkyl derivatives, respectively. There is a clear increase in relative concentration of these polyaromatics with the... 

Theories of Formation of Benzene, etc.—Theories of the formation of these benzene products in the distillation of coal have been investigated principally by Berthelot, and his conclusions are, in general In the first place, coal decomposes by heat yielding simple paraffin compounds such as methane, ethylene, acetylene, alcohol, acetic acid, etc. These compounds when subjected to higher temperatures polymerize into benzene, and the higher hydrocarbons naphthalene, anthracene, phenanthrene, etc., and into derivatives of these such as phenol, aniline, pyridine, etc. 

Similar studies of the relationship between bond structures and the Claisen rearrangement have been made with allyloxy derivatives of other aromatic compounds, among them anthracene, phenanthrene, hy-drindene, fluorene, chromone, flavone, fluorenone, and 2-methylbenzothiazole. ... 

As pointed out in Vol. 1, irinitrobenzene and its derivatives possess the ability to form addition compounds, especially with aromatic hydrocarbons composed of condensed rings, such as naphthalene, anthracene, phenanthrene, acenaphthene etc. Addition compounds of picric acid have been known since 18S8 [82] and those of sym-trinitrobenzene since 1882 [83]. Complexes of sym-trinitro-benzene with aromatic amines were also described in 1882 [84]. 

Coal tars are by-products of the carbonization of coal to produce coke and/or natural gas. Physically, they are usually viscous liquids or semi-solids that are black or dark brown with a naphthalene-like odor. The coal tars are complex combinations of polycyclic aromatic hydrocarbons, phenols, heterocyclic oxygen, sulfur, and nitrogen compounds. By comparison, coal tar creosotes are distillation products of coal tar. They have an oily liquid consistency and range in color from yellowish-dark green to brown. The coal tar creosotes consist of aromatic hydrocarbons, anthracene, naphthalene, and phenanthrene derivatives. At least 75% of the coal tar creosote mixture is polycyclic aromatic hydrocarbons (PAHs). Unlike the coal tars and coal tar creosotes, coal tar pitch is a residue produced during the distillation of coal tar. The pitch is a shiny, dark brown to black residue which contains polycyclic aromatic hydrocarbons and their methyl and polymethyl derivatives, as well as heteronuclear compounds... 

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... 

According to different mechanisms of coke formation, we have observed different products of polycondensation using chromatographic, luminiscent, and UV-spectroscopic methods. For example, in the case of decomposition of benzene on different catalysts only products of the dehydrocondensation of benzene with preservation of nuclei were observed (biphenyl, biphenylbenzenes, triphenylene, products of condensation of more than four benzene nuclei, etc.) and such products as naphthalene, anthracene, and phenanthrene were not observed. In tar and coke formation from ethylene on silica gel and aluminosilicates the formation of naphthalene, chrysene, 1,2-dibenzanthracene, fluorene, its derivatives, and others, takes place and if the process is carried out on alumina at a temperature lower than 500°, mainly anthracene, phenanthrene, pyrene, and coronene are formed, but aliphatic hydrocarbons, etc., do not appear. 

There are seemingly no thermochemical data for any methylated anthracenes. For solid methylated phenanthrenes, there are enthalpies of formation of the unhindered 2,7- and 9,10-dimethylated species for which the methylation has incurred an ca. 40 and 35 kJ mol per methyl decrease in enthalpies of formation, while for the hindered 4,5-species the decrease was only ca. 14 kJ mol per methyl. Consider now the isomeric 3,4,5,6- and 2,4,5,7-tetramethylphenanthrenes. In that it is methylation in both the 4- and 5-positions that results in the smaller decrease of enthalpies of formation, we would expect a decrease of ca. (2 35)+(2-14) kJ mol or ca. 100 kJ mol for both of these species from the parent hydrocarbons. Using measured values, the decreases are 93 and 104 kJ mol , respectively, in encouraging agreement. For benz[a]phenanthrene derivatives, the strained 1,12-dimethyl derivative exhibits a 30 kJ mol total decrease from the parent hydrocarbon while the unstrained 1,12-isomer shows the much more normal decrease for two methyl groups of ca. 76 kJ mol . All of this is quite sensible, and so we are not prepared for the nearly identical 41 and 37 kJ mol decreases on going from the 1,12- and 7,12-dimethylbenz[a]anthracene to the parent hydrocarbon. We are even more surprised by the only ca. 13 kJ mol decrease of the enthalpies of formation upon... 

Coal tar derivatives, such as anthracene, phenanthrene pyridine anthraquinone dyes sulfanilamide aminobenzoic acid derivatives tetracyclines chloropromazine many nonsteroidal anti-inflammatory drugs (NSAIDs) sulfonamides Aminobenzoic acid derivatives chloropromazine sulfonamides ... 

The types of reactions that can be carried out on the polycyclic aromatic hydrocarbons such as naphthalene, anthracene, phenanthrene, and larger analogs are the same as those discussed in detail for benzene derivatives. An acquaintance with the substitution chemistry of the polycyclic systems therefore requires only some general information concerning the reactivity of these ring systems and their position selectivity. Naphthalene is more reactive than benzene. There is a kinetic... 

Of the six purely-aromatic tetracyclic hydrocarbons, only chrysene, benz[a] anthracene and benzo[ft]phenanthrene possess even marginal activity but, as shown (Tables 4.1,4.2, and 4.3), many benz[a] anthracene derivatives are active, as are some benzo[c]phenanthrene derivatives. Substitution of one, two, or three methyl groups at 6, 7, 8, or 12 in benz[a] anthracene markedly increases activity [41]. Studies of N-mustard derivatives of anthracenes and benz[a] anthracenes [42] emphasise the parallelism between carcinogenic and carcino-static properties of poly-nuclear derivatives [43]. The marked influence of a small change in chemical structure is illustrated by the sequence of anti-tumour activities lO-ethyl-9-anthryl > 9-anthryl lO-methyl-9-anthryl for the change of meso substituent from Et to H to Me [42]. 

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