Phenols, Quinones, and Related Compounds

MELTING point 51-52°C SPECTRAL data UV, PMR, Mass Spec organism Balanoglossus biminiensis (Chordata/ Hemichordata) and Phoronopsis viridis Hilton (Phoronidea) reference 24, 380 

282 MELTING point 115-1 16°C organism Thelepus setosus (Annelida) reference 179, 180 

MELTING point 193-195°C (dec.) Acetate, 185°C SPECTRAL data UV, IR, PMR, Mass Spec organism Verongia fistularis a.nd Verongia cauliformis (Porifera) 

206 MELTING point 200-210°C SPECTRAL data UV organism Echinothrix diadema Linn, and Echinothrix calamaris Pallis (Echinodermata) reference 308, 390 

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Typical examples of enzymes involved in food applications are cholinesterase for organophosphorous and carbamate pesticide analysis tyrosinase or laccase for analysis of phenols, quinones, and related compounds glucose oxidase for sugar content analysis, carboxyl esterase, alcohol oxidase, carboxypeptidase, L-aspartase, peptidase, aspartate... 

These zwitterions come mainly from acidic phenols or some acidic heterocycles their precursors include 2-hydroxy or 2-amino-1,4-quinones and related compounds... 

There are several ways in which phenols have been categorized. Harbome and Simmonds categorized polyphenols based on the number of carbon atoms, which includes simple phenols (Ce) phenolic acids and related compounds (Ce—Ci) acetophenones and phenyl acetic acids (Cg—C2) cinnamic acids, cinamyl aldehydes, and alcohols (Cg—C3) coumarins, isocoumarins, and chromones (Cg—C3) flavonoids (C15) biflavonyls (C30) stilbenes (Cg—C2—Cg) benzophenones and xanthones (Cg—C2—Cg) quinones (Cg, Cio, Cm) betacyanins (Cjg) and lignans, lignins, tannins, and phlobaphenes (which are dimmers, oligomers, or polymers) [19]. Polyphenols have also been categorized by some researchers based on their... 

A considerable amount of v ork on the stimulatory effects on plant growth of phenolic acids and related compounds, including quinones, was carried out by Flaig and co-workers, and... 

C. A. Buehler and D. E. Pearson, Survey of Organic Syntheses, Wiley-lnterscience, 1970, Chapter 5 (phenols), Chapter 12 (quinones and related substances), Chapter 20 (nitro compounds). 

Thallium trifluoroacetate has not enjoyed widespread use as a reagent for quinone synthesis, possibly because it is still a relatively new reagent but more probably because of its toxicity. One example of its use lies in the synthesis of metacyclophanes and related compounds as reported by Tashiro et al Thus the r-butylphenol (59) gave the bisquinone (61), while the phenol (60) afforded the monoquinone (62). An alternative and more practical synthesis of the bisquinone (61) for large scale work involved dealkylation to afford the bisphenol (63) which was then treated with sodium nitrite to give the bisoxime (64). Hydrolysis of the bisoxime did not give the quinone (61), but it could be obtained by zinc/acetic acid reduction of the bisoxime followed by oxidation with nitric acid (Scheme 13). 

From the viewpoint of organic synthesis, nature provides us with a number of target molecules, which have novel structures and a variety of biological activities. As already shown in Section II.A, electrochemical oxidation of phenols has been applied successfully to natural products synthesis. Hypervalent (diacyloxyiodo)benzenes have also been proved to be effective for natural products synthesis. Generally, oxidation of o- and p-methoxyphenols in MeOH provides the corresponding o- and p-quinone monoketals, respectively. They are utilized as promising synthons for natural products and related bioactive compounds, as demonstrated by Swenton . Recently, these quinone monoketals have been utilized for syntheses of terpenoids, neolignans, anthraquinones, alkaloids and related compounds. 

In attempting to predict the direction that future research in carbon black technology will follow, a review of the literature suggests that carbon black-elastomer interactions will provide the most potential to enhance compound performance. Le Bras demonstrated that carboxyl, phenolic, quinone, and other functional groups on the carbon black surface react with the polymer and provided evidence that chemical crosslinks exist between these materials in vul-canizates (LeBras and Papirer, 1979). Ayala et al. (1990, 1990) determined a rubber-filler interaction parameter directly from vulcanizatemeasurements. The authors identified the ratio a jn, where a = slope of the stress-strain curve that relates to the black-polymer interaction, and n = the ratio of dynamic modulus E at 1 and 25% strain amplitude and is a measure of filler-filler interaction. This interaction parameter emphasizes the contribution of carbon black-polymer interactions and reduces the influence of physical phenomena associated with networking. Use of this defined parameter enabled a number of conclusions to be made ... 

The preliminary results showed a correlation between physicochemical characteristics of inhibitor (activator) molecules and changes in kinetic parameters of bioluminescent reaction. For example the comparison of the effects of the quinones and phenols on three bacterial bioluminescence systems of different complexity indicates that the influence of the compounds on the bioluminescence intensity depends on the structure and redox characteristics. The inhibitory activity of quinones depends on their hydrophobic substituents and the size of the aromatic part. Such correlations are closely related to the physical mechanism of bioluminescence they are the biophysical basis for bioluminescent ecological monitoring. 

The diazotization products of 2- and 4-aminophenols, -naphthols (etc.), possess a mesomeric (zwitterionic) phenolate-diazonium and quinone-diazide structure. We discussed these structures in the context of aromatic diazotization (Zollinger, 1994 Sect. 2.4) because the synthetic methods used are closely related to those used for aromatic diazonium salts. This is also the case for the diazotization of amino-di-, tri- and tetrazoles, which, in their neutral form, contain a heterocyclic NH group in the )8-position to the amino group. After diazotization, the NH group is very acidic. Following deprotonation the product corresponds to a heterocyclic diazoalkane. Similarly, the diazotization product of 4-(dicyano)methylaniline ((4-amino-phenyl)malonitrile) may lose the CH proton. This compound is, therefore, sometimes called a vinylene homolog of diazomalonitrile (Regitz and Maas, 1986, p. 205). 

The parent compound, coumarin, has been found to cause chromosome breakage in animal tissues [207, 336]. The mechanism of this action and the effect on chromosomes by chemical mutagens has not yet been elucidated [337], There is hardly any structural relationship of action between these compounds. Good chromosome breakers of mammalian cells or plants include bromouracil, caffein and derivatives, alkylating agents, phenols, quinones, colchicine, methyl-phenyl-nitrosamine [337-343]. However, there is another plant product, podophyl-lotoxin, related to coumarin, which also causes chemical mutagenesis [338, 344]. 

Abstract All plants produce compounds that are phytotoxic to another plant species at some concentration. In some cases, these compounds function, at least in part, in plant/plant interactions, where a phytotoxin donor plant adversely affects a target plant, resulting in an advantage for the donor plant. This review discusses how such an allelochemical role of a phytotoxin can be proven and provides examples of some of the more studied phytochemicals that have been implicated in allelopathy. These include artemisinin, cineoles, P-triketones, catechin, sorgoleone, juglone and related quinones, rice allelochemicals, benzoxazinoids, common phenolic acids, l-DOPA, and m-tyrosine. Mechanisms of avoiding autotoxicity in the donor species are also discussed. 

In addition to antitumor activity, diospyrin exhibits antileishmanial properties , perhaps by ET . Based on common functionalities (quinone and phenol), diospyrin is structurally related to several other compounds that are physiologically active. The antiviral agent, sakyomicin A, which contains a hexose residue and the juglone skeleton, generates H2O2 after... 

Quinone oximes and nitrosoarenols are related as tautomers, i.e. by the transfer of a proton from an oxygen at one end of the molecule to that at the other (equation 37). While both members of a given pair of so-related isomers can be discussed separately (see, e.g., our earlier reviews on nitroso compounds and phenols ) there are no calorimetric measurements on the two forms separately and so discussions have admittedly been inclusive—or very often sometimes, evasive—as to the proper description of these compounds. Indeed, while quantitative discussions of tautomer stabilities have been conducted for condensed phase and gaseous acetylacetone and ethyl acetoacetate, there are no definitive studies for any pair of quinone oximes and nitrosoarenols. In any case. Table 4 summarizes the enthalpy of formation data for these pairs of species. 

Almost every class of natural phenolic compounds contains examples of substances with a 2,2-dialkylchromene ring, and the number of those that are discovered increases every year. It would be difficult to give an exhaustive list of these compounds. Their chemistry will be discussed here only when it is related to some particular behavior of the benzo-pyran ring. Examples include simple chromenes substituted in the aromatic ring,3,4,35-44 benzodipyrans,3,39 dimers of chromenes,45 naphthopyrans,46,47 quinones,48 flavones,49 flavonols,49 chalcones,49 flavanones,49 isoflavonoids,50 rotenoids,50 pterocarpans,50 couma-rins,17,51-53 3-arvl-4-hydroxycouniarins,50 4-phenylcoumarins,54 chroma-... 

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