Quinol

The great affinity of quinone for hydrogen leads to the formation of anilinoquinone which can now, in the same way, add a further equivalent of aniline to the half of the molecule not yet involved. The dianilino-quinol is converted into dianilinoquinone in the same way as the first reaction product was changed. (Write the equation.) 

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.—Anilinoquinone.1 Dissolve 4 g. of quinone in 400 c.c. of water. Cool the solution and add 1 -72 g. of aniline dissolved in 10 c.c. of 20 per cent acetic acid. Leave the mixture in the cold for three hours with frequent shaking, then collect the reddish-brown crystalline precipitate at the pump, dry it in vacuo, and free it from the monoanilino-compound by repeated careful boiling with petrol ether (boiling point 80°-90°). From the petrol ether this compound separates on cooling in the form of small golden-brown needles. Melting point 119°. The insoluble portion consists of dianilinoquinone. 

In an alkaline or neutral medium this polymerises to azobenzene 2 C6H5N —C6H5.N=N.C6H5. in an acid medium to a quinonoid substance phenylquinonediimine. 

Phenylquinonediimine is at once further polymerised to the so-called emeraldine (in conformity with stage II on p. 322). 

---

A special case of adsorption in cavities is that of clatherate compounds. Here, cages are present, but without access windows, so for adsorption to occur the solid usually must be crystallized in the presence of the adsorbate. Thus quinol crystallizes in such a manner that holes several angstroms in diameter occur and, if crystallization takes place in the presence of solvent or gas... 

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. 

Electron Transport Between Photosystem I and Photosystem II Inhibitors. The interaction between PSI and PSII reaction centers (Fig. 1) depends on the thermodynamically favored transfer of electrons from low redox potential carriers to carriers of higher redox potential. This process serves to communicate reducing equivalents between the two photosystem complexes. Photosynthetic and respiratory membranes of both eukaryotes and prokaryotes contain stmctures that serve to oxidize low potential quinols while reducing high potential metaHoproteins (40). In plant thylakoid membranes, this complex is usually referred to as the cytochrome b /f complex, or plastoquinolplastocyanin oxidoreductase, which oxidizes plastoquinol reduced in PSII and reduces plastocyanin oxidized in PSI (25,41). Some diphenyl ethers, eg, 2,4-dinitrophenyl 2 -iodo-3 -methyl-4 -nitro-6 -isopropylphenyl ether [69311-70-2] (DNP-INT), and the quinone analogues,... 

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. 

In equation 7, ttimer radical (4) is produced when (3) dissociates. Whenever (4) couples with the other product of equation 7, ie, the 2,6-dimethylphenoxy radical, the tetramer is produced as described. These redistribution reactions of oligomers that proceed by ketal formation and subsequent dissociation ultimately generate terminal quinol ethers which enolize to the more stable terminal phenol (eq. 8). 

Hydrogen Abstra.ction. These important reactions have been carried out using a variety of substrates. In general, the reactions involve the removal of hydrogen either direcdy as a hydrogen atom or indirectly by electron transfer followed by proton transfer. The products are derived from ground-state reactions. For example, chlorarul probably reacts with cycloheptatrienyl radicals to produce ether (50) (39). This chemistry contrasts with the ground-state reaction in which DDQ produces tropyhum quinolate in 91% yield (40). 

Dissolve in Et20, add quinol (500mg for 300mL), dry over Na2S04, filter, evaporate and distil under dry N2. It is a clear liquid if dry and decompose very slowly. In the presence of H2O traces of tributyl tin hydroxide are formed in a few days. Store in sealed glass ampoules in small aliquots. It is estimated by reaction with aq NaOH when H2 is liberated. CARE stored samples may be under pressure due to liberated H2. [J Appl Chem 7 366 1957.]... 

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

Quinol. The other half nt the iiiodiul is Ireattd with. 1... 

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 ... 

Plicnoh.— If it is a free phenol, ether will extiact it from its ac ueous solution. If it is present in alkaline solution, the solution should first be saturated with cat bon dioxide. (n.B.—The alkaline solutions of catecliol, quinol and pyrogallol daiken rapidly m the air.) The following tests should then be applied. 

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). 

Probably the most familiar of all clathrates are those formed by Ar, Kr and Xe with quinol, l,4-C6H4(OH)2, and with water. The former are obtained by crystallizing quinol from aqueous or other convenient solution in the presence of the noble gas at a pressure of 10-40 atm. The quinol crystallizes in the less-common -form, the lattice of which is held together by hydrogen bonds in such a way as to produce cavities in the ratio 1 cavity 3 molecules of quinol. Molecules of gas (G) are physically trapped in these cavities, there being only weak van der Waals interactions between... 

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. ... 

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. ... 

In 1951, Witkop et al. interpreted the infrared spectra of quinol-2-and -4-ones to favor the oxo formulation. Since then, many investigators, especially Mason, have reported that potential a- and y-hydroxy compounds show infrared absorption bands in the vN—H (3500-3360 cm ) and vC—O (1780-1550 cm ) regions of the spectrum and, hence, exist predominantly in the oxo form references to this work appear in Table I. A study of the bands which occur in the NH-stretching region of the infrared spectra of a series of substituted pyrid-2-ones and quinol-2-ones also supported an oxo formulation for these compounds. Detailed band assignments have been published for pyrid-2- and -4-one. Mason has reported that solutions of j8-hydroxy compounds in chloroform or carbon tetrachloride show... 

The pKa method was first used by Tucker and Irvin to determine the proportion of the tautomers of quinol-4-one present at equilibrium and was subsequently applied to many other potentially tautomeric hydroxy compounds " these results are summarized in Table I. 

In 1939, the ultraviolet spectrum of 4-methylquinol-2-thione was reported to differ from that of the 2-alkylthio analog, and the former compound was concluded to exist in the thione form. However, other investigators were unable to reach any conclusions from ultraviolet and infrared spectral data concerning the tautomerism of quinol-2- and -4-thione. A definitive pK and ultraviolet spectral investigation by Albert and Barlin has recently established that the thione forms of quinol-2- and -4-thione and of isoquinol-1- and -3-thione (cf. 202) greatly predominate (Table V). The infrared... 

A different type of tautomeric relationship exists between compounds of types 323 and 324. Both types of structure can be isolated, pyridones (324, Z = N—Me) and pyrones (324, Z = 0) being formed when 323 (Z = N—Me or 0) is heated with palladium on charcoal in ethylene glycol. Similar isomerizations in the quinol-4-one series have been reported."... 

The benzoquinone adduct is a 2 1 molecular complex of 2,3-dimethylquinoxaline and quinol, and is readily prepared by crystallizing quinol from toluene in the presence of excess of 2,3-dimethyl-quinoxaline. 2,3-Dimethylquinoxaline and A -phenylmaleimide undergo Michael addition to form the quinoxalinylmethyl-A -phenylsuccinimide... 

---