Quinoids

Sennosides, primarily sennosides A and B, derived from Cassia angustifolia and C. acutifolia, are employed as a mixture for the alleviation of constipation. 

Podophyllotoxin is used externally to treat condylomata acuminata (soft warts). Etoposide is a semi-synthetic derivative of epipodophyllotoxin glycoside, currently being used for the treatment of cancer. 

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However, benzylidene derivatives show a strong bathochromic shift in comparison with alkylidene derivatives. Thus absorption is a result of the whole conjugated system that is comparable to that of the quinoid dyes. The color of this type of compound is sensitive to acids and bases. 

The primary dihydro product (3) can be obtained by reduction of the quinoid (4). Compound 3, in which Ri = CeH= -CH= and Rj CgH can also be obtained by direct condensation of benzylidene selenosemicar-bazone with 2.3-dibromo-l,4-diphenyl-l,4-butanedione (Scheme 49). 

This reaction is proof of the structure of the dye, easily obtained from the dihydro compound (3). Yields are low as a result of numerous side reactions. The stereochemical configuration of these quinoid dyes is trans. 

Hydrazono-5-(p-dialkylaminophenylimino)seienazoles, pyrazolone azomethin selenazoles, quinoid dyes, and formazans are other important dyes used in photography and the color industry (cf. previous sections). 

Despite the inconveniences, a certain number of studies have been carried out, particularly concerning dyes containing azomethine groups. Such as hydrazones, pyrazolones, formazans, and selenazoles quinoids. Saturated heterocycles, that is, selenazolines and selenazolidines. have also been tackled. Selenium derivatives for pharmacological or physiological applications are little developed by comparison with their thiazole homologs. 

Not all of the hydrogens in phenol are equally reactive. Under acid conditions the quinoid structure... 

PX forms j xylylene when heated above 1200°C. The stmctuie of J-xylylene is represented by a i)-quinoid stmcture or as a i)-ben2enoid brtadical. Condensation yields poly(p-xylylene) (19—22) (see Xylene polymers). 

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. 

Conversion of Cyclic to Acyclic Structures. Upon oxidation, the aromatic rings of lignin may be converted direcdy to acycHc stmctures, eg, muconic acid derivatives, or indirectly by oxidative splitting of o-quinoid rings. Further oxidation creates carboxyUc acid fragments attached to the lignin network. 

Formation and Elimination of Multiple Bond Functionalities. Reactions that involve the formation and elimination of multiple bond functional groups may significantly effect the color of residual lignin in bleached and unbleached pulps. The ethylenic and carbonyl groups conjugated with phenoHc or quinoid stmctures are possible components of chromophore or leucochromophore systems that contribute to the color of lignin. 

Ultraviolet radiation causes cleavage of the aryl ether linkage (23). DMPPO undergoes oxidation when exposed to ultraviolet light and oxygen by direct attack on the aromatic ring to produce a variety of ring-cleaved and quinoidal stmctures (24). 

The aminophenols are chemically reactive, undergoing reactions involving both the aromatic amino group and the phenoHc hydroxyl moiety, as weU as substitution on the benzene ring. Oxidation leads to the formation of highly colored polymeric quinoid stmctures. 2-Aminophenol undergoes a variety of cyclization reactions. 

Diels-Alder Reaction. In 1928, Diels and Alder discovered that 1,3-unsaturated organic compounds reacted with quinoid systems to give partially hydrogenated, cycHc compounds. In the course of their work, they found that 1 mol of 1,4-naphthoquinone [130-15-4] reacted readily with 1 mol of 1,3-butadiene [106-99-0] to give a partially hydrogenated anthraquinone (11) l,4,4a,9a-tetrahydro-9,10-anthracenedione [56136-14-2] which, on oxidation with chromic oxide, produced anthraquinone (43) ... 

Xanthene dyes (qv) can be either acidic or basic. Acid xanthenes are known to exist in two tautomeric forms. The phenoHc type, or fluorans, are free-acid stmctures such as D C Orange No. 10 (17b) and D C Red No. 21 (17c). Most have poor water solubHity. In contrast to these, the quinoids or xanthenes are usuaHy the highly water-soluble sodium salt counterparts of the fluorans such as D C Orange No. 11 (18) and D C Red No. 22 (21a). Presendy, there are no certifiable basic xanthene colorants. 

Because of tfiek pH sensitivity, antiiocyanins have found littie use as industtial dyes. However, a few having the quinoidal form of anthocyanidin (28) were formedy used as dyes. Two of these were carajurin [491 -93-OJ (29) and dracorhodin [643-56-1] (30) ... 

Another important factor affecting the electronic properties is the steric barrier to planarity along the polymer chain. Since polyheterocycles and polyarylenes must adopt a planar geometry in the ionized state to form quinoid-like segments, steric factors that limit the ability of the polymer to adopt geometries which are planar with respect to adjacent rings have a detrimental effect on the electronic properties (181). 

Aromatic nitro compounds are often strongly colored. They frequently produce characteristic, colored, quinoid derivatives on reaction with alkali or compounds with reactive methylene groups. Reduction to primary aryl amines followed by diazotization and coupling with phenols yields azo dyestuffs. Aryl amines can also react with aldehydes with formation of Schiff s bases to yield azomethines. 

Greater reactivity gamma to an azine-nitrogen would be expected on the basis of the greater ara-quinoid than orf/io-quinoid interactions between various substituents and azine-nitrogens in ground states and excited states. Such a difference in interaction is supported by several kinds of data spectral,basicity, dipole moment, and chlorine quadrupole resonance of halo, methoxy,... 

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