Quinones sulfones

The excess negative charge located in the interior of metallic silver colloids could also be transferred to other electron acceptors, including methylviologen, nitrobenzene, nitropyridinium oxide, anthracene quinone sulfonic add, and potassium cyanohexaferrate(III)[506, 531], The efficiency and, indeed, the direction of electron transfer were found to depend on the position of the Fermi level of the surface-modified silver particles. For example, chemisorption of AgN to a silver particle is shown to result in a shift of the Fermi level to a more positive potential, as shown in the lower line in Fig. 84. 

Electron transfer was mediated by metallic silver colloids whose surfaces contained either a strong (SH ) or a weak (CN ) nucleophile [531]. The former case is illustrated by changes in the absorption spectrum of a 1.0 x 10 4 M, deaerated solution of metallic silver particles, subsequent to the consecutive addition of 2.0 x 10 4 M NaSH and 3.0 x 10-4 M anthracene quinone sulfonic acid, AQS (Fig. 85) [506]. The origin of the intensity decrease and the broadening of the silver plasmon absorption band upon the addition of nucleophilic SH is incompletely understood. However, that an absorption... 

Numerous modifications have been tried without improving the yield. The loss is probably due to a partial reduction of the quinone sulfonate by the sulfur dioxide liberated, but this was not prevented by adding manganese dioxide to the reaction mixture, and no pure product could be obtained from the mother liquor. 

Mw = 9300, Mw/Mn = 5.07). The poly (p-hydroxy styrene) was PHP-6817-24, obtained from Marusen Oil Co. (Mn = 3900, Mw = 10200, Mw/Mn = 2.62). Kodak micro positive developer 934 (934 developer) (predominantly tetramethyl ammonium hydroxide in water) was used at various dilutions with deionized water. M-cresyl naphthalene diazo-quinone sulfonate was prepsured by a pyridine catalyzed condensation of m-cresol with naphthalene diazoguinone sulfonyl chloride. 

An example of the Michael chemistry, typical of all quinones bearing a replaceable hydrogen, is the preparation of a sulfone (6) (in 55% yield), which was ultimately converted to a polystyrene redox polymer (11). 

The most extensive mechanistic studies of quinone Michael addition chemistry involve the arylsufinic acids, which yield reduced product (50,51). The sulfones produced in such reactions have been examined electrochemicaHy (48) and kineticaHy (52). The influence of substitutents in the quinone has... 

The kinetics of formation and hydrolysis of /-C H OCl have been investigated (262). The chemistry of alkyl hypochlorites, /-C H OCl in particular, has been extensively explored (247). /-Butyl hypochlorite reacts with a variety of olefins via a photoinduced radical chain process to give good yields of aUyflc chlorides (263). Steroid alcohols can be oxidized and chlorinated with /-C H OCl to give good yields of ketosteroids and chlorosteroids (264) (see Steroids). /-Butyl hypochlorite is a more satisfactory reagent than HOCl for /V-chlorination of amines (265). Sulfides are oxidized in excellent yields to sulfoxides without concomitant formation of sulfones (266). 2-Amino-1, 4-quinones are rapidly chlorinated at room temperature chlorination occurs specifically at the position adjacent to the amino group (267). Anhydropenicillin is converted almost quantitatively to its 6-methoxy derivative by /-C H OCl in methanol (268). Reaction of unsaturated hydroperoxides with /-C H OCl provides monocyclic and bicycHc chloroalkyl 1,2-dioxolanes. 

Naphtho-quinone-4-sulfonic acid sodium salt... 

A 2-1. three-necked flask fitted with a stirrer (Notes 1 and 2), condenser, and dropping funnel (Note 3) is mounted in the hood, and in it are placed 20 g. (0.061 mole) of potassium anthra-quinone-a-sulfonate (p. 72), 500 cc. of water, and 85 cc. (1 mole) of concentrated hydrochloric acid. The solution is heated to boiling and stirred, while a solution of 20 g. (0.19 mole) of sodium chlorate (Note 4) in 100 cc. of water is added dropwise over a period of three hours (Note 5). The mixture is refluxed very slowly for an additional hour before the precipitated a-chloro-anthraquinone is collected by suction filtration and washed free from acid with hot water (about 350 cc.). After drying in vacuo at ioo°, the bright yellow product melts at 158-160° (corr.) and weighs 14.6-14.7 g. (97-98 per cent of the theoretical amount) (Notes 6 and 7). 

The only practical method for the preparation of anthra-quinone-a-sulfonates is that based upon the discovery 1 that in the presence of a small amount of mercuric salt anthraquinone is sulfonated chiefly in the a- rather than in the /3-position. Detailed procedures are described by Fierz-David,2 by Lauer,3 and by Groggins 4 the above directions are based largely upon the observations of Lauer.3... 

The major problem of these diazotizations is oxidation of the initial aminophenols by nitrous acid to the corresponding quinones. Easily oxidized amines, in particular aminonaphthols, are therefore commonly diazotized in a weakly acidic medium (pH 3, so-called neutral diazotization) or in the presence of zinc or copper salts. This process, which is due to Sandmeyer, is important in the manufacture of diazo components for metal complex dyes, in particular those derived from l-amino-2-naphthol-4-sulfonic acid. Kozlov and Volodarskii (1969) measured the rates of diazotization of l-amino-2-naphthol-4-sulfonic acid in the presence of one equivalent of 13 different sulfates, chlorides, and nitrates of di- and trivalent metal ions (Cu2+, Sn2+, Zn2+, Mg2+, Fe2 +, Fe3+, Al3+, etc.). The rates are first-order with respect to the added salts. The highest rate is that in the presence of Cu2+. The anions also have a catalytic effect (CuCl2 > Cu(N03)2 > CuS04). The mechanistic basis of this metal ion catalysis is not yet clear. 

The y-nitrogen atom of a sulfonic acid azide is electrophilic and reacts in an electrophilic aromatic substitution with an activated benzene or naphthalene derivative, e.g., a phenoxide ion, forming a l-tosyl-3-aryltriazene (2.47). The 1,4-quinone diazide is obtained by hydrolysis (Scheme 2-30, Tedder and Webster, 1960). The general applicability of this reaction seems to be doubtful. With 1-naphthol the 1,2-naphthoquinone diazide was obtained, not the 1,4-isomer. 

Quinoline-5-sulfonic acid, 8-hydroxy-7-iodo-metal complexes absorptiometry, 1,549 Quinolinium salts in gravimetry, 1, 535 Quinolinol metal complexes color photography, 6,107 8-Quinolinol biological activity, 6, 771 gallium and indium complexes radiopharmacology, 6, 971 radionuclide complexes radiopharmacology, 6,994 8-Quinolyl sulfate hydrolysis metal catalysis, 6,465 Quinones... 

TABLE 1. Sulfones from sulfinic acids RS02H and acceptor-substituted olefins, acetylenes or quinones ... 

CioHsNaOjS M, = 260.20 1,2-Naphtho-quinone-4-sulfonic acid sodium salt... 

Lillie RD, Pizzolato P, Dessauer HC, et al. Histochemical reactions at tissue arginine sites with alkaline solutions of /J-naphthoquinone-4-sodium sulfonate and other o-quinones and oxidized o-diphenols. J. Histochem. Cytochem. 1971 19 487 197. 

As hydroxyl or hydroxyl-like radicals are produced by the superoxide-driven Fenton reaction, superoxide overproduction must also occur in thalassemic cells. First, it has been shown by Grinberg et al. [382], who demonstrated that thalassemic erythrocytes produced the enhanced amount of superoxide in comparison with normal cells in the presence of prooxidant antimalarial drug primaquine. Later on, it has been found that the production of superoxide and free radical-mediated damage (measured through the MetHb/Hb ratio) was much higher in thalassemic erythrocytes even in the absence of prooxidants, although quinones (menadione, l,4-naphthoquinone-2-methyl-3-sulfonate) and primaquine further increased oxidative stress [383]. Overproduction of superoxide was also observed in thalassemic leukocytes [384]. 

The major problem of these diazotizations is oxidation of the initial aminophenols by nitrous acid to the corresponding quinones. Easily oxidized amines, in particular aminonaphthols, are therefore commonly diazotized in a weakly acidic medium (pH 3) so-called neutral diazotization or in the presence of zinc or copper salts. This process, which is due to Sandmeyer, is important in the manufacture of diazo components for metal complex dyes, in particular those derived from l-amino-2-naphthol-4-sulfonic acid. 

It should be noted that one of these diols, the hydroquinone, did not provide any oligomer in the first step. This was due to the formation of the quinone structure which made it impossible to use hydroquinone directly in the substitution reaction. An alternate method was used to overcome this problem which involved the use of 4-methoxyphenol to obtain the sulfone product, followed by cleavage of the methyl ether to the diol (VIII) with boron tribromide. This set of reactions is outlined in Figure 5. 

In a simulated atmosphere, direct epoxidation by ozone led to the formation of benzo[a]pyrene-4,5-oxide. Benzo [a] pyrene reacted with benzoyl peroxide to form the 6-benzoyloxy derivative (quoted, Nikolaou et al, 1984). It was reported that benzo [a] pyrene adsorbed on fly ash and alumina reacted with sulfur dioxide (10%) in air to form benzo[a]pyrene sulfonic acid (Nielsen et al., 1983). Benzo [a] pyrene coated on a quartz surface was subjected to ozone and natural sunlight for 4 and 2 h, respectively. The compounds 1,6-quinone, 3,6-quinone, and the 6,12-quinone of benzo[a]pyrene were formed in both instances (Rajagopalan et al., 1983). 

As described, other nucleophilic reactions in the anthraquinone series also involve the production of anion-radicals. These reactions are as follows Hydroxylation of 9,10-anthraquinone-2-sulfonic acid (Fomin and Gurdzhiyan 1978) hydroxylation, alkoxylation, and cyanation in the homoaromatic ring of 9,10-anthraquinone condensed with 2,1,5-oxadiazole ring at positions 1 and 2 (Gorelik and Puchkova 1969). These studies suggest that one-electron reduction of quinone proceeds in parallel to the main nucleophilic reaction. The concentration of anthraquinone-2-sulfonate anion-radicals, for example, becomes independent of the duration time of the reaction with an alkali hydroxide, and the total yield of the anion-radicals does not exceed 10%. Inhibitors (oxygen, potassium ferricyanide) prevent formation of anion-radicals, and the yield of 2-hydroxyanthraquinone even increases somewhat. In this case, the anion-radical pathway is not the main one. The same conclusion is made in the case of oxadiazoloanthraquinone. 

Reductions with aluminum are carried out almost exclusively with aluminum amalgam. This is prepared by immersing strips of a thin aluminum foil in a 2% aqueous solution of mercuric chloride for 15-60 seconds, decanting the solution, rinsing the strips with absolute ethanol, then with ether, and cutting them with scissors into pieces of approximately 1 cm [141,142]. In aqueous and non-polar solvents aluminum amalgam reduces cumulative double bonds [143], ketones to pinacols [144], halogen compounds [145], nitro compounds [146, 147], azo compounds [148], azides [149], oximes [150] and quinones [151], and cleaves sulfones [141, 152, 153] and phenylhydrazones [154] (Procedure 30, p. 212). 

Air (NB) Collection in ethanol reaction with concentrated HCl and zinc dust react with sodium salt of 1,2-naphtho-quinone-4 sulfonic acid at pH 8.0 extraction with CCl concentration separation by paper chromatography extraction of fractions with CCl ... 

---