Anthraquinone attachment

Reactive dyes generally contain colored anthraquinones with various reactive groups attached to the nonchromophotic portions of the molecule. 

A recent addition to Table 3, Reactive Blue 246 differs from the other dyes and is not added to a finished lens. The dye molecule has methacrylate groups attached to an anthraquinone and is incorporated directiy into the polymer matrix during polymer cure (175). This in-monomer concept has the potential to reduce dramatically the cost of visibiUty tinting of a contact lens. 

The 40 percent, fuming sulpluim acid is removed from tlu-bottle by cautiously melting il in a sand-bath,, iiul it is then weighed out in a flask ( litre). The anthraquinone is aikled. and the flask attached by a coik to an an-condenser. TIh-... 

Fig. 2 Structures of the anthraquinone-linked sensitizers. AQ is covalently attached to the 5 -end of one strand. UAQ can be placed at any position, and the attached anthraquinone intercalates in duplex DNA at the 3 -side of its linked nucleotide...

Two different chemical classes contribute to this sector. Initially it was entirely dominated by anthraquinone dyes typified by structure 7.102. The dye bases for attachment of haloheterocyclic (Z) systems are prepared by condensing bromamine acid (7.103) with various phenylenediamines. The outstandingly successful Cl Reactive Blue 19 (7.3 7) is the... 

Reaction LXX. Oxidation of certain Hydrocarbons. (B., 14, 1944 A. Spl., 1869, 300 E.P., 1948 (1869).)—This reaction is confined in the aliphatic series almost exclusively to the replacement by hydroxyl of the hydrogen attached to tertiary carbon atoms. A powerful oxidising agent, e.g., chromic acid in glacial acetic acid, is necessary. In the aromatic series the reaction is somewhat more easy to accomplish when the sodium salt of anthraquinone-jS-monosulphonic acid, for example, is fused under pressure with caustic soda and a little potassium chlorate, replacement of both a hydrogen atom and the sulphonic acid group by hydroxyl occurs, and alizarin ( /f-dihydroxyanthraquinone) is obtained. 

In a DTA study of 14 anthraquinone dyes, most had high flash points (225—335°C) and ignition points (320—375°C). Purpurin dianilide [107528-40-5] was exceptional with the much lower values of 110 and 155°C, respectively [1]. A similar study of indigo type dyes and vat solubilised modifications is reported. The basic dyes decompose over 350°C, destabilised to around 200°C for solubilised dyes. The relation between functional groups, structure and flammability is discussed [2]. Sulfonyl azides have been employed for attachment of reactive dyes, it is claimed they are safer used in supercritical carbon dioxide than in water [3]. 

Fiber reactive, sulfur, vat, and mordant dyes all undergo reactions which enhance their attachment to the substrate. Fiber reactive dyes contain a reactive group that forms a covalent bond with a group on the substrate, usually hydroxyl or amine. Fiber reactive dyes are often of the azo or anthraquinone type. 

When covalently attached to electron transfer active subunits, the DHA-VHF couple can facilitate chemical and physical switching of electronic properties, as a result of photochemically induced rearrangement accompanied by a change in the redox potential. An interesting example of such a switching system is the compound containing a dihydroazulene component and a covalently attached anthraquinone moiety.1311 This system is able to act as a multimode switch, assisted by various processes such as photochromism, reversible electron transfer, and protonation-deprotonation reactions (Scheme 8). 

Electron acceptors, such as 11,11,12,12-tetracyanoanthraquinodimethane (TCAQ) and its 9,10-anthraquinone (AQ) precursor have been also attached to fulleropyrrolidine materials, since they are good candidates for obtaining fullerene-based electroactive hybrid systems [245,258,259]. 

In late 1996, a new family of DNA-mediated ET experiments began to be reported. In these the ET donor is comprised of one or more DNA nucleotides (either G, GG, GGG, or a covalent thymine dimer) while the other is a covalently attached, photoactivated electron acceptor (either anthraquinone, pyrene, or an tris-polypyridyl M(III) complex, where M = Ru or Rh) [74-80]. These experiments have much in common with the kind of experiments outlined immediately above and with the new hairpin studies recently reported. They will be discussed toward the end of this chapter. They differ from the pre-1997 ET kinetics experiments that will be discussed immediately below in that none of them has reported ET rate measurements. Rather, yields of net photochemistry (either DNA strand cleavage or thymine dimer scission) are presented as evidence that photoinduced ET events occurred. For comparison of experimental results with ET theory it is clear that at a minimum ET rates must be measured and at a maximum several rates should be measured for a given D/A pair at a variety of separation distances. 

The central ring systems found to yield antiviral compounds have included fluorene (fluorenone), dibenzofuran, dibenzothiophene, fluoranthene, anthraquinone, acenaphthene, xanthene, thioxanthene, phenothiazine, carbazole, phenanthrene and others. The side chains were represented by basic ethers, basic ketones, basic esters plus carboxamides, sulphonamides, alkanols, methylene and others attached to the various ring systems. The amine function was usually substituted to the tertiary amine with various alkyl substituents although a few ring types (e.g., pyrrole or piperidino) were synthesized. 

The second product identified by Meyer, oxanthrone acetate (5, better 10-acetoxy-9-anthrone), was obtained in moderate amount by oxidation of 9-acetoxy-anthracene (3) with lead tetraacetate in acetic acid. Oxidation of (3) in refluxing benzene resulted in 1,4-addition to give the triacetoxy compound (4). This substance when heated in acetic acid is converted largely into lO-acetoxy-9-anthrone (5) by loss of acetic anhydride and to a lesser extent into 9,10-diacetoxyanthracene (7) by loss of acetic acid. If (4) is an intermediate in the oxidation of (3) in acetic acid lo (5), the acetoxy group in the product (5) must be attached to a different meso carbon atom (5) than in (3), and this inference was shown to be correct by oxidation of 2-methyl-9-acetoxyanthracene and identification of the product as 2-methyl-I O-acetoxy-9-anthrone by synthesis. Both (5) and (7) on further oxidation with lead tetraacetate in acetic acid yield anthraquinone, probably via the products of acetoxylation of (5) and 1,4-addition to (7). 

When a catalyst is essential, copper, its oxides, and salts are preferred, and these are almost always used in the ammonolysis of compounds wherein the halogen is attached to an aromatic nucleus not containing negative substituents (e.g., chlorobenzene, chlorobiphenyl (chloroxenene), and chloronaphthalene). In the treatment of alkylene, nitrophenyl, and anthraquinone halides, copper catalysts are not essential but may be used to accelerate the reaction. In the typical reactions of Class 1, presented... 

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