Anthracene, sulfonation derivatives

Derivation (1) From crude anthracene cake by selective solution of the phenanthrene with crude solvent naphtha, removal of the anthracene by conversion into a sulfonic derivative, and extraction by means of water. (2) Synthetically from o-aminobi-phenyl. 

These differences in ease of sulfonation (and correspondingly of desul-fonation, as discussed in a subsequent section) have formed the basis of a chemical method for the separation of mixtures of compounds otherwise hard to separate. The sulfonation of polycyclic hydrocarbons, such as anthracene or phenanthrene, occurs so easily that polysulfonates are formed even under such mild conditions that some of the hydrocarbon remains unsulfonated. For this reason, such sulfonations have been investigated relatively little and what data exist tend to be contradictory. Sulfonates derived from anthracene are usually prepared from anthraquinone, which yields fewer by-products than the hydrocarbon, although some disul-fonation does occur even with the usual industrial practice of partial sulfonation of the quinone. 

Contaminants in the soil can adversely impact the health of animals and humans when they ingest, inhale, or touch contaminated soil, or when they eat plants or animals that have been affected by soil contamination. The exposure of an organism to a carcinogen or other ecotoxic compound in soil is not related to the total concentration of that substance in soil but rather to the amount that is actually available (bioavailability) [34]. Most chemical extraction methods reported in literature were studied in terms of their ability to recover all the contaminants (PAH, pesticides, etc.) from a soil matrix [30,35]. In this chapter we propose the use of a fast and simple analytical extraction method to mimic the bioaccessibility determined by pollution of benzene, naphthalene and anthracene chloride, amino and sulfonate derivatives. The method, based on an ultrasonic extraction [36,37], was performed within a short time (2 minutes) and with a little amount of solvent (10 mL) [31]. 

The raw materials used to synthesize organic dyes are commonly referred to as dye intermediates. Largely, they are derivatives of aromatic compounds obtained from coal tar mixtures. The majority of these derivatives are benzene, naphthalene, and anthracene based compounds. This section provides an overview of the chemical reactions used to prepare the key intermediates employed in dye synthesis. In this regard, emphasis is placed on halogenated, aminated, hydroxy-lated, sulfonated, and alkylated derivatives of benzene, naphthalene, and anthraquinone. 

The resulting aromatic polyether sulfone contains two types of tet-ramethyl-substituted anthracene units. One isomer was derived from a diphenyl methane unit in which the methylene linkage was formed as the result of meta-substitution of a DMPPS molecule and the para-substitution of the other DMPPS. The other isomer was formed as result of para-substitution of both DMPPS molecules [40]. The polymer was crystalline (Tm = 280° C) [41]. 

The first thiete fused to an aromatic system 219 (and an anthracene derivative) was reported in 1965 and was prepared by reduction of a naphthothiete sulfone. An attempt to prepare benzothiete by desulfurization of benzo-l,2-dithiolane was unsuccessful. Photolysis of benzo-l,2-dithiolane 1,1-dioxide in an attempt to extrude sulfur dioxide to give benzothiete also was unsuccessful. The naphthothiete 205, however, was prepared by extrusion of sulfur dioxide from 220 and nitrogen from 221. Thiete 205 also is obtained in 6-8% yield by treatment of 1,8-dehydronaphthalene with carbon disulfide. The unstable thiolactone 211 was formed by a photochemical extrusion of benzaldehyde from 222 and from 222a at 350°C. The benzothietes 209, 223, " and 224 have been... 

Hyoscyamine can be determined by fluorimetric technique as follows (100). A solution of hyoscyamine or an eluate of it from a LiChrosorb DIOL HPLC column is treated with 9,10-dimethoxy anthracene-2-sulfonate solution. The resulting derivative is determined fluorimetrically at 446 nm with excitation at 383 nm. 

Derivation Anthracene is oxidized to anthraqui-none, the sulfonic acid of which is then fused with caustic soda and potassium chlorate the melt is run into hot water and the alizarin precipitated with hydrochloric acid. Occurs naturally in madder root. 

FIGURE 9.3 Structures of benzene, naphthalene, and anthracene derivatives analyzed sodium benzenesulfonate (1), 4-chloroaniline (2), 3,4-dichloroaniline (3), 2-naphthylamine (4), sodium 2-naphthalenesulfonate (5), sodium anthraquinone 2-sulfonate monohydrate (6), 1,2-diamineanthraquinone (7), 2-anthraceencarboxilic acid (8), and 2-anthramine (9). 

When anthracene-2-sulfonate is irradiated with light in the absence of -CyD, four [2+2] photo-adducts are formed (Fig. 4.3 (a)). Upon the irradiation in its presence, however, only one isomer (1) is dominantly formed (see Fig. 4.3(a)) [19]. Anthracene-2-sulfonate forms a 2 2 complex with fi-CyD, in which the mutual orientation of two anthracene derivative molecules are regulated by two / -CyD molecules (Fig. 4.3(b)). Accordingly, isomer 1 is selectively formed by the photoreaction. Consistently, little product-selectivity is observed when y-CyD is used in place of yS-CyD. The cavity of y-CyD is large enough to accommodate two anthracene-2-sulfonate molecules and in this complex, they move rather freely relative to each other (Fig. 4.3(c)). 

The effects of cyclodextrins on [4+4]-photodimerizations of anthracene derivatives have been studied quite extensively. For example, it has been found that such reactions of anthracene-2-sulfonate and -2-carboxylate in water are accelerated by both j8- and 7-cyclodextrin. y-Cyclodextrin has very little effect on the ratio of the four possible cycloadducts but, with each of the anthracene derivatives, j8-cyclodextrin inaeases the proportion of the anft-head-to-tail cycloadduct from less than 45% to more than 85% (Figure 3.9). - The effects observed with the natural cyclodextrins generally arise from the fortuitous way the reagents self-assemble in the cyclodextrin annulus. By comparison, modifled cyclodextrins offer the additional benefit of providing a means to control the... 

Practically any aromatic hydrocarbon or aryl halide can be sulfonated if the proper conditions are chosen. As the compound becomes more complex, however, the tendency toward the production of by-products and mixtures of isomers is increased. It is usually difficult to prevent polysubstitution of a reactive hydrocarbon. For example, even when phenanthrene is sulfonated incompletely at room temperature, some disulfonic acids are formed. The sulfonation of anthracene follows such a complex course that the 1- and 2-sulfonic acid derivatives are made from the readily available derivatives of anthraquinone. The foUowii sections include comments.on the accessibility of the reaction products of the commonly available hydrocarbons and aryl halides. The examples cited and still others are listed in Tables I-XIII. 

Another striking observation is that the formation of the 2-acid can be depressed to as little as 1% by the use of pyridine-sulfur trioxide as the sulfonating agent, even when the reaction is carried out at temperatures (150-175°) that, with oleum, favor substitution in the 2-posi-tion. Although the two sulfonic acids can be separated from each other and from polysulfonic acids fairly adily by fractional crystallization of the sodium or barium salts, the sulfbnation reaction of anthracene is not employed commonly, since the monosulfonic acids are prepared more conveniently from the corresponding derivatives of anthraquinone. 

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