Formazan Dyes

For example, by chromatographic techniques it can be shown that the 1 2 chromium complex 15 exhibits only one isomer (a,a form), the mixed 1 2 chromium complex 16 two (a,a and a,(3 forms), and the symmetric 1 2 chromium complex 17 three isomers (a,a, a,(3 and (3,(3 forms), assuming that these dyes exist only in the mer configuration. 

Chromium, cobalt and copper chelates are applied mainly in textile dyeing. The use of the less stable iron chelates is restricted to leather dyeing, and the nickel chelates are employed mostly as pigments. 

Formazan dyes are closely related to azo dyes and are derived from the following basic structure  

The position of the substituents is given according to IUPAC nomenclature using the prefixes 1-, 3-, and 5-. Formazans unsubstituted in the 1- and 5-positions and 1,5-dialkyl-substituted formazans are unknown. Aryl or heteroaryl groups are the most common 1,5-substituents. The 3- or meso position can be occupied by a variety of substituents (e.g., aryl, heteroaryl, H, OH, SR, halogen, N02, CN, and alkyl). 

5-diphenyl and 1,3,5-triphenyl derivatives were discovered almost simultaneously by H. von Pechmann [38] and E. Bamberger [39] in 1892. Interest in those compounds was renewed in 1939 when G. Lakon [40] and R. Kuhn and D. Jerchel [41] found that colorless tetrazolium salts were very sensitive to biological reduction processes and were converted to deeply colored formazans  

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Theoretically, the dye or chromogen can be any colored species. Of course, requirements for fastness, solubiUty, tinctorial value, ecology, and economy must be met. Most commonly used chromophores parallel those of other dye classes. Azo dyes (qv) represent the largest number with anthraquiaone and phthalocyanine making up most of the difference. Metallized azo and formazan dyes are important and have gained ia importance as a chromophore for blue dyes duriag receat years (6) (see Dyes and dye intermediates). 

Tetrazolium salts Formazan dyes are produced on reaction of [33]... 

Selenazole formazans, dyes, photography and color industry, 274 from selenazole benzylidenehydrazones. 254... 

The well-known triphenyltetrazolium chloride (TTC) reaction for the detection of a-ketolsteroids, pyridinium carbinols and pyridinium glycols can also be included here [20-23]. The chromophore system of the red-colored formazan dye produced by reduction of the TTC is composed of highly conjugated double bonds resulting from the combination of a phenylhydrazone group with an azo group ... 

Tetrazolium salts to a large extent are prepared from the corresponding formazans and to a lesser extent from tetrazoles. Therefore, synthetic methods for both formazans and tetrazoles will be discussed. Also discussed will be some properties of formazan dyes that influence the choice of the tetrazolium salt for any particular application. 

The coordination chemistry of formazan dyes has been extensively reviewed in Venkataraman s classic treatise on synthetic dyes,374,375 and more recently in Wilkinson s treatise on coordination compounds.376... 

With few exceptions, by far most applications of tetrazolium salts (e.g., analytical, photographic, and biochemical) utilize their reducibility to the corresponding formazan dyes. Tetrazolium salts, due to their resistance to acid and oxidation and the presence of a positive charge, find use in other applications such as antistatic agents and phase transfer catalysts. Over the past two decades, there have been thousands of citations regarding the applications of tetrazolium salts. Most of these citations are patents with similar or overlapping and even identical claims. Any attempt at completeness would be futile. The applications are sorted where discernible, and the earliest or the broadest claims are cited. 

Lactate dehydrogenase (LDH) LDH released by cells with damaged membrane results in the conversion of a tetrazolium compound into a water-soluble fluorescent formazan dye Cell membrane Yes [32]... 

There are bi-, tri-, and tetradentate formazan dyes7 but only the tetradentate copper complex formazan dyes have found use as commercial products. The dye Cl Reactive Blue 160, of generic structure (41), is a representative example. Because of the intensity of their colors, the metal complex formazan dyes have also found application in analysis. Thus, the dye (42) detects zinc at a concentration of 1 part in 50 million.31... 

An appropriate ion-specific electrode was found to provide a convenient, precise and relatively inexpensive method for potentiometry of copper(II) ion in copper-complex azo or formazan dyes. Copper(II) ion in copper phthalocyanine dyes can be quantified after anion exchange. Twelve commercial premetallised dyes evaluated using this technique contained copper(II) ion concentrations in the range 0.007 to 0.2%. Thus many copper-complex direct or reactive dyes are likely to contribute low but possibly significant amounts of ionic copper to textile dyeing effluents [52]. 

Rate constants and the products formed in the hydrolysis of Cl Reactive Red 194 (7.76) at 50 °C and pH values in the 10-12 region were determined by high-pressure liquid chromatography. In addition to the normal hydrolysis of the two reactive systems, the imino link between the triazine and benzene nuclei was also hydrolysed [67]. The heterobifunctional copper formazan dye Cl Reactive Blue 221 and two blue anthraquinone monofunctional reactive dyes of the bromamine acid type, namely the aminochlorotriazine Blue 5 and the sulphatoethylsulphone Blue 19, were compared in terms of their sensitivity to... 

Miscellaneous Dyes. Other classes of dyes that still have some importance are the stilbenc dyes and the formazan dyes. Slilbene dyes are in most cases mixtures of dyes of indeterminate constitution that are formed from the condensation of sulfonated nilroaromutic compounds in aqueous caustic alkali cither alone or with other aromatic compounds, typically arylamincs. The sulfonated nitrostilbene is the most important nitroaromatic. and the aminoazohenzenes are Ihe most important arylamines. 

Formazan dyes bear a formal resemblance to azo dyes, since they contain an azo group. The most important formazan dyes are the metal complexes, particularly copper complexes, of letradentate formazans. They are used as reactive dyes far cotton. 

Formazan dyes have become important reactive dyes for cotton. Formazan dyes are also used in analytical chemistry because of the high color intensity of many of their metal complexes. The chemistry of formazans was first exploited in 1962 by MacDonald to produce color photographs [81],... 

Virtually every conceivable chromophore has been used in the synthesis of reactive dyes, including monoazo and disazo species, metal complexes of azo dyes, formazan dyes, anthraquinones, triphenodioxazines, and phthalocyanines. The product lines offered by the major dye producers in most cases feature comparable chromophores, differing primarily in the nature of the reactive systems and the particular substitution patterns adopted. 

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