Phenanthrene quinone

Sphenomeris chusana (L.) Copel. Wu Ju (whole plant) Sphenone A, phenanthrene-1, 4-quinone. 60-229 Treat feverish conditions and bladder difficulties. 

Weak to moderate chemiluminescence has been reported from a large number of other Hquid-phase oxidation reactions (1,128,136). The Hst includes reactions of carbenes with oxygen (137), phenanthrene quinone with oxygen in alkaline ethanol (138), coumarin derivatives with hydrogen peroxide in acetic acid (139), nitriles with alkaline hydrogen peroxide (140), and reactions that produce electron-accepting radicals such as HO in the presence of carbonate ions (141). In the latter, exemplified by the reaction of h on(II) with H2O2 and KHCO, the carbonate radical anion is probably a key intermediate and may account for many observations of weak chemiluminescence in oxidation reactions. 

Photoredox systems involving carbonyl compounds and amines are used in many applications. Carbonyl compounds employed include benzophenone and derivatives, a-diketones [e.g. benzil, cainphoroquinone (85),2W 291 9,10-phenanthrene quinone], and xanthone and coumarin derivatives. The amines are tertiary and must have a-hydrogens [e.g. N,A7-dimethylani 1 ine, Michler s ketone (86)]. The radicals formed are an a-aminoalkyl radical and a ketyl radical. 

The redox system consists of pyrene or 9,10-phenanthrene quinone as oxidant and an alkyl ester of 3,3, 3"-nitrilopropionic acid as reductant.121 This system deactivates oxidation by bisimidazole when irradiated at 380-550nm, since the quinone is reduced to hydroquinone and thus stabilizing the previously generated dye image.122,123... 

The chemical sensitization effect was 0.006 (calculated from the quantum yield of the photochemical transformation of 130 to 131, the yield of 131 obtained with the oxalate/hydrogen peroxide reaction, and the moles of oxalate employed). Higher chemical sensitization efficiencies (about 0.04) were observed when the oxalate/hydrogen-peroxide system was used in the addition of ethyl vinyl ether onto phenanthrene quinone... 

Fig. 15.8 Redox-active polymers for heterogeneous dehydrogenation catalysis, (a) trimerized phenanthrene quinone [42], (b) benzoquinone biphenyl copolymer [41], (c) polynaphthoquinone [40], (d) polyaniline [43], (e) pyrolyzed polyacrylonitrile [44].

Lithium aluminum hydride reduced p-benzoquinone to hydroquinone (yield 70%) [576] and anthraquinone to anthrahydroquinone in 95% yield [576]. Tin reduced p-benzoquinone to hydroquinone in 88% yield [174] Procedure 35, p. 214). Stannous chloride converted tetrahydroxy-p-benzoquinone to hexa-hydroxybenzene in 70-77% yield [929], and 1,4-naphthoquinone to 1,4-di-hydroxynaphthalene in 96% yield [180]. Other reagents suitable for reduction of quinones are titanium trichloride [930], chromous chloride [187], hydrogen sulfide [248], sulfur dioxide [250] and others. Yields are usually good to excellent. Some of the reagents reduce the quinones selectively in the presence of other reducible functions. Thus hydrogen sulfide converted 2,7-dinitro-phenanthrene quinone to 9,10-dihydroxy-2,7-dinitrophenanthrene in 90% yield [248]. 

The photocycloaddition of 3-acetyl-2(3//)-oxazolone 84 with 9,10-phenanthrene-quinone 244 gives the spirooxetane 245 regioselectively as a major cycloadduct. Irradiation of 3,4,5-trisubstituted-2(37/)-oxazolones 247 in the presence of 244 results in the predominant formation of dioxane derivatives 248. When duroquinone 249 is irradiated in the presence of the 3,4,5-trisubstituted-2(37/)-oxazolone 247a,... 

Diphenic acid was first prepared by oxidizing phenanthrene-quinone with chromic acid.1 Many later workers2 have modified this process in minor details. Vorlander and Meyer 3 were the first to prepare diphenic acid from diazotized anthranilic add and cuprous oxide, but their process is not well adapted to large scale preparation. Inasmuch as pure phenanthrene is now very difficult to obtain in quantity, the present process was devised for relatively large scale operation. 

Figure 3. Four parameter, simplex-optimized SFC separation of a 12-component mixture. Chromatographic conditions as in Vertex 13 of Table II. Sample components isoquinoline, n-octadecane (n-CigH3g), naphthalene, quinoline, acetophenone, undecylbenzene, benzophenone, 2 -acetonaphthone, diphenylamine, o-dioctylphthalate, unidentified impurity, N-phenyl-1-naphthylamine, phenanthrene quinone. Other conditions as described in the experimental section.

Information to support the transfer of these selectable markers is shown in Figure 17. Figure 17A shows the results of a paper electrophoresis separation of petunia calli which were selected on the basis of nopaline production. Comparison of the spots observed, after staining with phenanthrene quinone reagent, demonstrates that opines are being produced by these plant cells. 

Eq. (29)], and phenanthrene quinone [Eq. (28b)], leads to the [4 + 2] Diels-Alder adducts the two benzoquinone adducts add a second molecule of the quinone 1 resp. 2, forming the trioxyphosphoranes. The mechanism of this [4 + 2] cycloaddition, either symmetry allowed or stepwise, is not yet clear (73). 

Further evaporation of the reduction mixture precipitates a second fraction whose properties are not very characteristic. This fraction is not a single compound. It gives no characteristic reaction with ferric chloride, showing the absence of a phenolic hydroxyl group, and it must be, therefore, a naphthylaminesulfonic acid or some other amino compound which gives no condensation product with phenanthrene-quinone. 

A different mode of the reaction of dimethylzinc and diethylzinc was observed in reactions with various o-quinones and benzils 122). The treatment of phenanthrene quinone with dimethylzinc gives (XLV), while diethylzinc affords (XLVI). 1,2-Naphthoquinone derivatives also give carbinol ketones with dimethylzinc, while they afford monoethyl... 

Witt obtained such a compound by action of phenanthrene-quinone on orthoamidophenyl- 8-naphthylamine,... 

Reactions of another type involve cleavage of a carbon-carbon bond. Phenanthrene-quinone is oxidized smoothly to diphenic acid by hydrogen peroxide in warm acetic acid. Use of the reaction in structure elucidation is illustrated as follows. One of five disulfonic acids formed on sulfonation of phenanthrene was converted into the dimethoxyphenanthrene, which on oxidation afforded a dimethoxy-9,10-phenan-threnequinone. Oxidation of this quinone with HjOa-AcOH gave an acidic product... 

Use Dyestuffs, explosives, synthesis of drugs, biochemical research, manufacturing phenanthrene-quinone. 

By using 10mol% of benzoylquinidine (BQD, la), a variety of acid chlorides reacted efficiently with o-chloranil at — 78 °C in the presence of nonnucleophilic Hiinig base (iPr2EtN, DIPEA) (Scheme 10.2). The desired lactones 2 were produced in up to 91% yield with excellent enantiopurity. On the other hand, o-bromanil and 9,10-phenanthrene quinone were also successfully applied in this cycloaddition reaction. 

Treatment of o-benzoquinone dioxime with sulphur dichloride gives a mixture of 2,1,3-benzothiadiazole (38%) and its l-W-oxide (34%). The presence of three chlorine atoms in the benzene ring reduces the yield [2177]. 9,10-Phenanthrene-quinone dioxime gives a low yield of mainly the thiadiazole the 5-oxide of this may be prepared from the quinone di(trimethylsilylimine) and thionyl chloride. 

Rabek [498, 505] examined the rapid degradation of cis-1,4-polyisoprene on exposure to light in the presence of p-quinones p-quinone, chloranil, 1,4-naphthoquinone, anthraquinone, phenanthrene-quinone and 1,2-benzanthraquinone (Fig. 20). Later, Rabek [504] also found that p-quinone sensitizes the photo-oxidation of polystyrene in benzene in the presence of UV radiation. 

Vanadium pentoxide Fused asbestos 425 Phenanthrene Phenanthrene quinone (41)... 

Vanadium pentoxide Pumice 400 Phenanthrene Phenanthrene- quinone (46, 47)... 

In conjunction with hydrogen donors such as dimethylaniline and triethyla-mine, benzils and various quinones, such as anthraquinone, 9,10-phenanthrene quinone, and camphor quinone (see Chart 10.4), can be used as visible-light-sensitive photoinitiators [8]. Some of these compounds are used to cure dental restorative systems (see Section 11.3). Another application concerns the curing of waterborne pigmented latex paints, which do not contain volatile organic compounds (VOCs) [48]. 

Pyle AM, Long EC, Barton JK. Shape-selective targeting of DNA by phenanthrene-quinone diiminerhodium(III) photocleaving agents. J Am Chem Soc. 1989 111 4520-4522. 

Quinone oximes are prepared, for example, by heating quinone with a double excess of hydroxylamine hydrochloride in a mixture of ethanol and chloroform (6 1). Under these circumstances phenanthrene quinone yields a monoxime, while anthraquinone does not react even after prolonged heating. Quinones also react with phenylhydrazine in various ways a- and jS-naphthoquinone as well as phenanthrenequinone yield condensation products with phenylhydrazine which can be formulated as azo compounds (19). 

Benzil and quinones, such as 9,10-phenanthrene quinone and camphor qui-none in combination with hydrogen donors can be used as photoinitiators both in the UV and visible region [120,152,153]. Photopolymerization of methyl methacrylate using benzil was elaborately studied by Hutchinson et al. [120]. They have observed a threefold increase in the polymerization rate when a hydrogen-donating solvent such as THF was used in the system, indicating the importance of hydrogen abstraction. 

Benzo[l,2-c 3,4-c 5,6-c ]tris[l,2,5]thiadiazole.—Four related condensed tetracyclic ring systems incorporating 1,2,5-thiadiazole (202 X = S, Se, CH, or CH=CH) are accessible from a common starting material, benzo[l,2-c 3,4-c ]-bis[l,2,5]thiadiazole (200), which is converted into the diamine (201) and variously cyclized to (202). The condensation of (201) and 9,10-phenanthrene-quinone in boiling acetic acid similarly yields the heptacyclic ring system dibenzo-[a,c]bis[l,2,5]thiadiazolo[3,4-/r.3, 4V]phenazine. 2... 

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. 

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