Quinolic acid

In 1886 Pfltzinger reported a formal extension of the known Friedlander protocol for the synthesis of quinolic acids. This new protocol relied on the use of isatin which is much more stable than the ort/io-aminoaryl intermediates that are required in the Friedlander quinoline synthesis. In this early paper, Pfitzinger reports that upon heating of isatin 3 in the presence of aqueous sodium hydroxide, the former is. hydrolyzed to the isatic acid 4 which then in the presence of acetone reacts to give aniluvitonic acid 6. ... 

Functional end products of the essential amino acid tryptophan arise mainly through two distinctive pathways. The major pathway is degradation of tryptophan by oxidation, which fuels the kynurenine pathway (See 02011). The second and quantitatively minor pathway is hydroxylation of tryptophan and its subsequent decarboxylation to the indoleamine 5-hydroxytryptamine (serotonin) and subsequently melatonin. The metabolites of the kynurenine pathway, indicated as kynurenines, include quinolic acid and kynurenic acid. Quinolinic acid is an agonist of the NMDA receptor (see also section on glutamic acid), while kynurenic acid is a nonselective NMDA-receptor antagonist with a high affinity for the glycine site of the NMDA receptor (see also section on... 

Reduction, (a) By sulphurous acid. Benzoquinone, /> toluquinone, 1,2-naphthoquinone are readily reduced by SOj ultimately to the dihydroxy-compound. Thus benzoquinone gives colourless hydro-quinone or quinol, />-C2H4fOH)2. 

Conversion of Aromatic Rings to Nonaromatic Cyclic Structures. On treatment with oxidants such as chlorine, hypochlorite anion, chlorine dioxide, oxygen, hydrogen peroxide, and peroxy acids, the aromatic nuclei in lignin typically ate converted to o- and -quinoid stmctures and oxinane derivatives of quinols. Because of thein relatively high reactivity, these stmctures often appear as transient intermediates rather than as end products. Further reactions of the intermediates lead to the formation of catechol, hydroquinone, and mono- and dicarboxyhc acids. 

Chemical Designations - Synonyms 1,4-Benzenediol p-Dihydroxybenzene Hydroquinol Pyrogentisic acid Quinol Chemical Formula 1,4-CjH4(OH)2. 

Quinone and Quinol. (ininonc, which weis oiiginally obtai ied h the oxiilation of quinlt acid (the add associated... 

In addition to the above, Grignaid s leagent has been utilised m preparing olefines, etheis, ketonic esters, hydroxy-acids, quinols, amides, hydroxylammes, c., for details of wliicti books of reference must be consulted ... 

Fe7-ric chloride reaclion.—Dissolve a drop of the free phenol in water and add a drop of ueutral ferric chloride. A green (catechol), blue (orcinol, pyiogallol) or purple (phenol, resorcinol) colouration is produced, which is often destroyed by acid or alkali. Quinol is o.xidised to quinone, and turns biown (p. 193). The naphthols give precipitates of dinaphthol (p. 220). 

Attempts have been made to deduce the structure of the predominant form of a potentially tautomeric compound from the shifts which occur in the ultraviolet spectrum of the compound in question on passing from neutral to basic or acidic solutions. The fact that no bathochromic shifts were observed for 2- and 4-hydroxy quinoline and 1-hydroxyisoquinoline under these conditions was taken as evidence that they existed in the oxo form [similar work on substituted quinol-4-ones led to no definite conclusions ]. A knowledge of the dissociation constants is essential to studies of this type, and the conclusions can, in any case, be only very tentative. A further dif-... 

Recently, many investigators have extended the early observations that the ultraviolet spectra of - and y-hydroxypyridines resemble those of their A -methyl (not the 0-methyl) derivatives. This spectral resemblance is found both in aqueous solutions and in solutions of solvents with low dielectric constants, e.g., quinol-4-one in benzene, indicating that these compounds exist predominantly in the oxo form under all conditions. These data are summarized in Table I. In contrast, 4-hydroxyquinoline-3-carboxylic acid has been tentatively concluded to exist in the hydroxy form %- pjTid-2-one-4-carboxylic acid has also been formulated as a hydroxy compound, but this has been disputed. ... 

Hydroxylammonium chloride. 10 per cent aqueous solution, or benzene-1,4-diol (quinol), 1 per cent solution in an acetic acid buffer of pH ca 4.5 (mix 65 mL of 0.1M acetic acid and 35 mL of 0.1M sodium acetate solution). Prepare when required. 

Procedure. Take an aliquot portion of the unknown slightly acid solution containing 0.1-0.5 mg iron and transfer it to a 50 mL graduated flask. Determine, by the use of a similar aliquot portion containing a few drops of bromophenol blue, the volume of sodium acetate solution required to bring the pH to 3.5 1.0. Add the same volume of acetate solution to the original aliquot part and then 4 mL each of the quinol and 1,10-phenanthroline solutions. Make up to the mark with distilled water, mix well, and allow to stand for 1 hour to complete the reduction of the iron. Compare the intensity of the colour produced with standards, similarly prepared, in any convenient way. If a colorimeter is... 

The first kinetic study appears to have been that of Martinsen148, who found that the sulphonation of 4-nitrotoluene in 99.4-100.54 wt. % sulphuric acid was first-order in aromatic and apparently zeroth-order in sulphur trioxide, the rate being very susceptible to the water concentration. By contrast, Ioffe149 considered the reaction to be first-order in both aromatic and sulphur trioxide, but the experimental data of both workers was inconclusive. The first-order dependence upon aromatic concentration was confirmed by Pinnow150, who determined the equilibrium concentrations of quinol and quinolsulphonic acid after reacting mixtures of these with 40-70 wt. % sulphuric acid at temperatures between 50 and 100 °C the first-order rate coefficients for sulphonation and desulphonation are given in Tables 34 and 35. The logarithms of the rate coefficients for sulphonation... 

RATE COEFFICIENTS FOR SULPHONATION(s) AND DESULPHONATION (d) OF QUINOL AND QUINOLSULPHONIC ACID, RESPECTIVELY, AT 100 °C150... 

Supplement XXII, 2nd Supplement 1935 3032-3457 Quinol e carboxylic acid, 74. Cin-chomeromc acid, 155. 

Figure 18.4 Structures of heme/Cu oxidases at different levels of detail, (a) Position of the redox-active cofactors relative to the membrane of CcO (left, only two obligatory subunits are shown) and quinol oxidase (right), (b) Electron transfer paths in mammalian CcO. Note that the imidazoles that ligate six-coordinate heme a and the five-coordinate heme are linked by a single amino acid, which can serve as a wire for electron transfer from ferroheme a to ferriheme as. (c) The O2 reduction site of mammalian CcO the numbering of the residues corresponds to that in the crystal structure of bovine heart CcO. The subscript 3 in heme as and heme 03 signifies the heme that binds O2. The structures were generated using coordinates deposited in the Protein Data Bank, lari [Ostermeier et al., 1997] Ifft [Abramson et al., 2000] (a) and locc [Tsukihara et al., 1996] (b, c).

Mejorado, L. H. Hoarau, C. Pettus, T. R. R. Diastereoselective dearomatization of resorcinols directed by a lactic acid tether unprecedented enantioselective access to p-quinols. Org. Lett. 2004, 6, 1535-1538. 

Hydroxylation at C-5 or C-l3 has also been successfully achieved by lead tetraacetate oxidation, which was extensively studied in connection with isoquinoline alkaloids by Umezawa s group. (+)-Govanine (96) and (+)-discretine (97) were oxidized with lead tetraacetate in acetic acid to afford 5-acetoxy products 100,101, and 102 via p-quinol acetates (e.g., 99) (Scheme 23)... 

Hydroxyprotoberberine 59a and ( )-corytencine (98) led to 13-acetoxy compounds 104,105, and 107 moreover, the 2,3,9,10,12-pentaoxy-genated protoberberine 108 was also obtained from 98 via the p-quinol acetate 106 through a retro-Mannich reaction followed by recyclization (74,75). Oxidation in dichloromethane instead of acetic acid proceeded differently, namely, 97 and 98 led to pentaoxygenated protoberberines 103 and 109 by introduction of an acetoxyl group at C-4 and C-12, respectively, via o-quinol acetates (76). 

Dimethyl sulfoxide has found application as a solvent for electrochemical studies of Mo(VI) and Mo(V) complexes of quinol derivatives (287). Sulfoxides have also been examined as extractants for the separation of molybdenum and tungsten from acid solutions (218). 

Of the compounds prepared by the student triphenylcarbinol, /9-naphthol, quinol, and benzoic acid may be used. 

Quinone is produced in small yield by direct oxidation of benzene itself with silver peroxide, but better by the action of oxidising agents on a large number of its p-disubstitution products. Thus, in addition to quinol, p-aminophenol (experiment, p. 176), p-anisidine, p-toluidine, and sulphanilic acid as well as p-phenylenediamine and many of its derivatives yield quinone in this way. 

Experiment.—Qninol from Quinone. Suspend about 2 g. of quinone in 50 c.c. of water and while shaking frequently saturate the suspension with sulphur dioxide. Keep for some time and then extract the now colourless liquid twice with ether, dry the ethereal extract with calcium chloride, and evaporate the ether. The residue of quinol crystallises. Recrystallise it from a little water. Melting point 169°. Warm a sample with dilute sulphuric acid and a few drops of dichromate solution the odour of quinone is emitted. 

Experiment.1—Heat as much finely powdered indigo as amply covers the tip of a knife with about twice as much lead peroxide, a few granules of calcium chloride, and 5 c.c. of benzene in a test tube held in a boiling water bath for five minutes. Filter the reddish-brown solution obtained and divide the filtrate into two portions in test tubes. To one portion add quinol dissolved in very little alcohol, to the other dilute solution of stannous chloride in hydrochloric acid. The dehydroindigo is converted into the dye which separates in blue flocks. 

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