Quinones preparation

Anodic oxidation of catechols enables the unstable quinones to be prepared and reacted in situ. Reaction of the 1,2-quinone with a 1,3-dicarbonyi compound gives a high yield of a benzofuran [123, 124]. Both 1,2- and 1,4-quinones, prepared electrochemically in nitromethane, are efficiently topped in Diels-Alder reactions with butadienes [125]. 

A mixture of 1,4-anthraquinone and pyridine containing a little 1,4-anthrahydro-quinone (prepared by shaking 1,4-anthraquinone with aq. 6% sodium dithionite soln. in ether) stored 40 hrs. at room temp, under Ng cyclotri-l,4-anthra-quinone. Y 81%. H. Brockmann and H. Laatsch, B. 106, 2058 (1973). 

Parker, K.A. and Casteel, D.A. (1988) Isoquinoline quinones. Preparation of saframydn intermediates and a total synthesis of mimosamycin. J. Org. Chem., 53, 2847-2850. 

CgHgNa. While crystals m.p. 147 C, b.p. 267"C, darken rapidly in air. Prepared by reducing p-nitroaniline or aminoazobenzene. Oxidizing agents convert it to quinone derivatives, hence it cannot be diazotized with nitric acid. 

For an example of sublimation, see the preparation of anthra-quinone, p. 259 for semi-micro sublimation, see p. 69. 

Oxidation, (a) Ammoniacal silver nitrate. To a few ml. of ammoniacal AgNOj (preparation, p. 525), add a few drops of cold aqueous benzo quinone solution a silver mirror or (more generally) a dark precipitate of metallic silver is formed in the cold. 

Benzoquinone ( quinone ) is obtained as the end product of the oxidation of aniline by acid dichromate solution. Industrially, the crude product is reduced with sulphur dioxide to hydroquinone, and the latter is oxidised either with dichromate mixture or in very dilute sulphuric acid solution with sodium chlorate in the presence of a little vanadium pentoxide as catalyst. For the preparation in the laboratory, it is best to oxidise the inexpensive hydroquinone with chromic acid or with sodium chlorate in the presence of vanadium pent-oxide. Naphthalene may be converted into 1 4-naphthoquinone by oxidation with chromic acid. 

When a solution of, say, 1 g. of hydroquinone in 4 ml. of rectified spirit is poured into a solution of 1 g. of quinone in 30 ml. of water, qulnhydrone C,HA.C,H (0H)3, a complex of equimolecular amounts of the two components, is formed as dark green crystals having a gfistening metallic lustre, m.p. 172°. In solution, it is largely dissociated into quinone and hydroquinone. Quinhydrone is more conveniently prepared by the partial oxidation of hydroquinone with a solution of iron alum. 

Naphthalenediol. This diol can be prepared by the chemical or catalytic reduction of 1,4-naphthoquinone. Both the diol and quinone are of interest because of their relation to the vitamin K family. Carboxylation of 1,4-naphthalenediol with CO2—K2CO2 followed by neutralization gives... 

Uses. About 35% of the isophthahc acid is used to prepare unsaturated polyester resins. These are condensation products of isophthahc acid, an unsaturated dibasic acid, most likely maleic anhydride, and a glycol such as propylene glycol. The polymer is dissolved in an inhibited vinyl monomer, usually styrene with a quinone inhibitor. When this viscous hquid is treated with a catalyst, heat or free-radical initiation causes cross-linking and sohdification. A range of properties is possible depending on the reactants used and their ratios (97). 

Synthesis by oxidation remains the first choice for commercial and laboratory preparation of quinones the starting material (1) provided the generic name quinone. This simple, descriptive nomenclature has been abandoned by Chemicaly hstracts, but remains widely used (2). The systematic name for (2) is 2,5-cyclohexadiene-l,4-dione. Several examples of quinone synonyms are given in Table 1. Common names are used in this article. 1,2-Benzoquinone (3,5-cydohexadiene-l,2-dione) (3) is also prepared by oxidation, often with freshly prepared silver oxide (3). Compounds related to (3) must be prepared using mild conditions because of their great sensitivity to both electrophiles and nucleophiles (4,5). 

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). 

In small-scale syntheses, a wide variety of oxidants have been employed in the preparation of quinones from phenols. Of these reagents, chromic acid, ferric ion, and silver oxide show outstanding usefulness in the oxidation of hydroquinones. Thallium (ITT) triduoroacetate converts 4-halo- or 4-/ f2 -butylphenols to l,4-ben2oquinones in high yield (110). For example, 2-bromo-3-methyl-5-/-butyl-l,4-ben2oquinone [25441-20-3] (107) has been made by this route. 

Reactions of acetylene and iron carbonyls can yield benzene derivatives, quinones, cyclopentadienes, and a variety of heterocycHc compounds. The cyclization reaction is useful for preparing substituted benzenes. The reaction of / fZ-butylacetylene in the presence of Co2(CO)g as the catalyst yields l,2,4-tri-/ f2 butylbenzene (142). The reaction of Fe(CO) and diphenylacetylene yields no less than seven different species. A cyclobutadiene derivative [31811 -56-0] is the most important (143—145). 

Most vat dyes are based on the quinone stmcture and are solubilized by reduction with alkaline reducing agents such as sodium dithionite. Conversion back to the insoluble pigment is achieved by oxidation. The dyes are appHed by either exhaust or continuous dyeing techniques. In both cases the process is comprised of five stages preparation of the dispersion, reduction, dye exhaustion, oxidation, and soaping. 

Various alkylating agents are used for the preparation of pyridazinyl alkyl sulfides. Methyl and ethyl iodides, dimethyl and diethyl sulfate, a-halo acids and esters, /3-halo acids and their derivatives, a-halo ketones, benzyl halides and substituted benzyl halides and other alkyl and heteroarylmethyl halides are most commonly used for this purpose. Another method is the addition of pyridazinethiones and pyridazinethiols to unsaturated compounds, such as 2,3(4//)-dihydropyran or 2,3(4//)-dihydrothiopyran, and to compounds with activated double bonds, such as acrylonitrile, acrylates and quinones. 

This derivative is prepared from an A-protected amino acid and the anthrylmethyl alcohol in the presence of DCC/hydroxybenzotriazole. It can also be prepared from 2-(bromomethyl)-9,10-anthraquinone (Cs2C03). It is stable to moderately acidic conditions (e.g., CF3COOH, 20°, 1 h HBr/HOAc, / 2 = 65 h HCl/ CH2CI2, 20°, 1 h). Cleavage is effected by reduction of the quinone to the hy-droquinone i in the latter, electron release from the —OH group of the hydroqui-none results in facile cleavage of the methylene-carboxylate bond. The related 2-phenyl-2-(9,10-dioxo)anthrylmethyl ester has also been prepared, but is cleaved by electrolysis (—0.9 V, DMF, 0.1 M LiC104, 80% yield). ... 

A series of carbamates have been prepared that are cleaved by liberation of a phenol, which, when treated with base, cleaves the carbamate by quinone methide formation through a 1,6-elimination. ... 

Silylated cyanohydrins have also been prepared via silylation of cyanohydrins themselves and by the addition of hydrogen cyanide to silyl enol ethers. Silylated cyanohydrins have proved to be quite useful in a variety of synthetic transformations, including the regiospecific protection of p-quinones, as intermediates in an efficient synthesis of a-aminomethyl alcohols, and for the preparation of ketone cyanohydrins themselves.The silylated cyanohydrins of heteroaromatic aldehydes have found extensive use as... 

The only satisfactory method of preparing /3-naphthoquinone is by the oxidation of 1,2-aminonaphthol in acid solution, and the chief problem involved is that of the preparation of this intermediate in suitable yield and purity. This problem and the literature pertaining to it are discussed elsewhere. Most reports of the preparation of the aminonaphthol include some description of its oxidation, but the only particularly helpful comment on the reaction is that ferric chloride is a better oxidizing agent than chromic acid because at a low temperature it docs not attack the quinone, even when present in excess. ... 

One other method is from 1,2-bromonaphthol through the keto-nitrobromide. Though the parent quinone itself is such a sensitive compound that the material so obtained decomposed within a few hours, the method is of considerable value for the preparation of certain substituted -naphthoquinones. ... 

Quinones are colored p-benzoquinone, for exanple, is yellow. Many occur naturally and have been used as dyes. Alizarin is a red pigment extracted from the roots of the madder plant. Its preparation from anthracene, a coal tar derivative, in 1868 was a significant step in the development of the synthetic dyestuff industry. 

---