Xanthene acidity

REE ions with 1,10-phenanthroline form cationic complexes such as [La(phen)3 which give ion-associates with xanthene acid dyes, eosin or Erythrosin [117,118]. Molar absorptivities are of the order of 1-10. Europium(II) has been determined by an indirect method, after reduction of Fe(III) and reaction of the resulting Fe(II) with 1,10-phenanthroline [119]. 

It has been reported that y3-CD could improve the selectivity of the color reactions of various metal ions with triphenylmethane, xanthene acid dyes and some other coloring reagents. The effect of fi-CD on the association compound system of metal (Mo, Zn, Co)-thiocyanate basic dyes such as malachite green, crystal violet, rhodamine B, rhodamine 6G and butyhhodamine B, has been investigated and the result shows that /3-CD could contribute to a more sensitive and stable system which improve the solubility of the basic dyes and produce a favorable microenviromnent for the color reactions [63]. /3-CD could be employed to solubilize the 1,2-amino anthraquinone in water due to the formation of inclusion complex which acts as a ligand for metal ions could be used for the determination of palladium at trace levels by spectrophotometry. In the spectrophotometric determination of microamounts of Zn based on the Zn-dithizone color reaction, -CD could increase the apparent molar absorptivity at 538 nm by 8.37 times. In the presence of cr-CD, the determination sensitivity of copper in leaves based on the color reaction of Cu(II) and mesotetrakis (4-methoxy-3-sulfophenyl) porphyrin was enhanced by 50% in the spectrophotometric analysis [64,65]. 

Xanthenes date from 1871 when von Bayer synthesized fluorescein (5) by the condensation of two moles of resorcinol with one mole of phthaUc anhydride in the presence of concentrated sulfuric acid (1). 

Most xanthene dyes are classified as basic dyes by their method of appHcation acid dyes can be produced by introduction of sulfonic acid groups. The fluoresceins, which contain carboxy and hydroxy substituents, are also acid dyes for coloration of silk. Some of the fluoresceins in which the carboxy group has been esterified, are soluble in alcohol or other organic solvents and can be classified as solvent dyes. Mordant dyes can be produced by introducing o-dihydroxy or sahcyhc acid groups (2), which when metallised can have very good lightfastness. 

In general, the xanthenes are synthesized by the reaction of two moles of a nucleophilic / -substituted phenol (10) with an electrophilic carbonyl compound (11), the reaction occurring most readily with an acid catalyst at temperatures of 100—200°C. 

These acid rhodamines are usually used for sHk and wool because they have level dyeing properties and show good fastness to alkaU however, they have poor lightfastness. An improved process for manufacturing 3,6-diaminosubstituted xanthenes is reaction of the inner salts of... 

Unsyimnetiical rhodainines can be piepaied by the condensations of one mole of a yW-aminophenol with phthahc anhydride to give an o-benzoyl benzoic acid (27) which is then further condensed with a different yW-aminophenol to give the requited product, Rhodamine 3GO (28) (2). A general route to asymmetrical acid xanthenes has been patented (39). 

Aminohydroxy-substituted xanthenes ate of Httle commercial importance. They are synthesized by condensing one mole of y -diaLkylaminophenol with phthahc anhydride, and then condensing that product with an appropriately substituted phenol. For example. Mordant Red 77 [6528-43 ] (Cl45300) (45) is prepared by condensing m- dim ethyl am in opb en o1 with phthaUc anhydride, and then condensing the product with 2,4-dihydroxybenzenesulfonic acid. 

A series of water-soluble fiber-reactive xanthene dyes has been prepared from the reaction of ben2oxanthenedicatboxylic acid anhydride disulfonic acid with, for example, 3-aminophenyl-P-hydtoxyethyl sulfone to yield dyes, with high brilliance and good fastness properties for dyeing of or printing on leather, wool, sHk, or ceUulosic fibers (53). 

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. 

Xanthene Dyes. This class is best represented by Rhodamine B. It has high fluorescent brilliance but poor light and heat stabihty it may be used in phenohcs. Sulfo Rhodamine is stable and is useflil in nylon-6,6. Other xanthenes used in acryhcs, polystyrene, and rigid poly(vinyl chloride) are Solvent Green 4, Acid Red 52, Basic Red 1, and Solvent Orange 63 (see Xanthene dyes). 

Acid Dyes. These water-soluble anionic dyes ate appHed to nylon, wool, sUk, and modified acryHcs. They ate also used to some extent for paper, leather, food, and cosmetics. The original members of this class aU had one or mote sulfonic or catboxyHc acid groups in thein molecules. This characteristic probably gave the class its name. Chemically, the acid dyes consist of azo (including preformed metal complexes), anthraquiaone, and ttiaryHnethane compounds with a few azHie, xanthene, ketone imine, nitro, nitroso, and quHiophthalone compounds. 

Xanthene-2-carboxylic acid, 7-hydroxy-9-oxo-synthesis, 3, 837 Xanthenes... 

Xanthene-9-carboxylic acid 3-Diisopropylaminoethyl chloride Methyl bromide... 

Direct acid-catalyzed dehydration of 2,3,6-trimethoxy-6,l l-dihydrodibenz[6,/]oxepin-1()-ol leads to a mixture of the corresponding dibenz[b,/]oxepin and the rearranged alcohol with a 9/7-xanthene structure.262... 

In a similar fashion, 9-(a-hydroxybenzyl)xanthene is converted to 10-phenyldibenz[b,/]oxepin (6) by treatment with p-toluenesulfonic acid in formic acid.196 Substituents in one of the benzene rings can give rise to the formation of two different products. In this study,196 the location... 

In a similar reaction, 2,3,6-trimethoxydibenz[6,/]oxepin gives 10,11-dihydro-2,3,6-trimeth-oxydibenz[/>,/]oxepin-cw-10,l 1-diol upon treatment with osmium(VIII) oxide in the presence of A-methylmorpholine A -oxide.262 When treated with acid the diol undergoes a pinacol rearrangement to the corresponding xanthene-9-carbaldehyde. 

C14H9CIO2 26454-53-5) see Propantheline bromide xanthene-9-carboxylic acid (C HioO, 82-07-5) see Propantheline bromide 9ff-xanthene-9-carboxylic acid 2-[bis(l-methylethyl)-amino]ethyl ester... 

Polymer supported xanthene derivatives have been used in the solid phase synthesis of 1-aminophosphinic acids, RCH(NH2)PH(0)0H, <%TL1647> and of C-terminal peptide amides <96JOC6326>. Xanthene units also feature in crown ethers <96JCS(P2)2091>, calixarenes <96JOC5670> and in a flexible template for a P-sheet nucleator <96JOC7408>. 

Fluorenone derived linker 17 prepared in two steps was coupled to aminomethyl-PS via DIPCDI [21]. Due to the presence of an electron-withdrawing carboxamide group, the release of carboxylic acids from this support requires strong acids, such as trifluoromethanesulfonic acid (TFMSA) (Scheme 1). Insertion of an oxygen adjacent to the biphenyl rings to the fluorenone scaffold provides xanthene 18 handle [22]. The oxygen is strategically located to decrease the acid concentration required... 

The yellow ink jet dyes (and pigments) are metal-free azo dyes, such as Cl Direct Yellow 132 and Cl Acid Yellow 23 (Tartrazine).48,49 Most of the magentas are azo dyes derived from H-acid (l-amino-8-naphthol-3,6-disulfonic acid), such as (62), and xanthenes, such as Cl Acid Red 52 and Cl Acid Red 289.48,49 Where high lightfastness is a requirement, a copper complex azo dye, Cl Reactive Red 23 (63), is used. However, such dyes are dull (see Section 9.12.3.2). Nickel complex PAQ dyes, such as (22), are claimed to be brighter and to have similar high lightfastness... 

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