Formazan metal complexes

Yano etal, US Patent 6,645,595 (November 11, 2003) Assignee Kabushiki Kaisha Hayashibara Seibutsu Kagaku Kenkyujo Utility Organic Dyes 

2-Pyridylhydrazine (5 g) and 3-pyridylaldehyde (5 g) were dissolved in 100 ml methanol, heated to 60 °C 2 hours, cooled to 10 °C, mixed with 50 ml of water, and stirred 30 minutes. Thereafter, the crystals were collected by filteration, washed with water then methanol, dried by heating to 65 °C, and 7.4 g product isolated. 

A reaction vessel was charged with 100 ml 1,4-dioxane/methanol, 3 2, aniline (0.93 g), the product from Step (2.0 g), 2.5 ml concentrated HCl and 5 ml of water and cooled to 0° to — 3°C. While at this temperature, 5 ml of an aqueous solution of sodium nitrite (0.72 mg) was added over 20 minutes followed by 10 ml solution of NaOH (1.38 g) and the mixture stirred 2 hours. Thereafter, the product was purified as in Step 1 and 1.6 g product isolated. 

A reaction vessel was charged with 40 ml methyl alcohol and the product from Step 2 (2.0 g), heated to 50°C, and 40 ml methyl alcohol containing nickel acetate tetrahydrate (1.0 g) added over 30 minutes. Thereafter, 80 ml of water was added, the mixture cooled to 10°C, filtered, and 0.9 g purple solid isolated. 

The preparation of other formazans and metallized derivatives is provided (1,2). 

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Triphenylformazan behaves as a bidentate ligand forming 2 1 complexes (217) with divalent copper, nickel, and cobalt.377 Formazan metal complexes can be compared to complexes of azo dyes or beta diketones due to structural similarity.301,302 In general, formazan metal complexes have low stability toward acids. However, when electron-donating substituents are added to the aromatic ring, a considerable enhancement in stability is observed. Cationic complexes of type 218 are also known. The complexation of formazan with metal cation can be accompanied by oxidation to the tetrazolium salt and the formation of a complex... 

Another class of metal complex dyes is derived from the formazan stmcture. These dyes are appHed to wool and nylon from a neutral or weakly acidic dyebath analogous to the 2 1 premetallized OjO -dihydroxyazo complexes. The bluish-gray dye Cl Acid Black 180 [11103-91-6] (61) (Cl 13710) is a 2 1 cobalt complex of the formazan type. 

Formazan, l-(2-hydroxy-5-suIfophenyl)-3-phenyl-5-(2-carboxyphenyl)-zinc detection, 6, 83 Formazans cobalt complexes dyes, 6, 81 metal complexes bidentate, 6, 78 color photography, 6,111 dyes, 6, 77 tetradentate, 6, 81 tridentate, 6, 79... 

The physical and chemical properties of formazans have been reviewed in detail.1,2 In this discussion only those properties that directly or indirectly affect the choice of a tetrazolium salt as a leuco dye will be discussed. Spectral, acid—baseyedox, and metal complexing properties will be stressed. 

A variety of complexes, e.g., 224 and 225, can be formed from the tetradentate formazans.384,385,388 396 Tetradentate formazans containing heterocycles, e.g., 226 and 227, also form metal complexes.385... 

Tables 15 and 16 show the absorption maxima of some metal complexes of benzothiazolyl-substituted formazans 230 and 231.283 The wavelengths are metal ion dependent, making formazans useful reagents for the identification of specific metal ions or the simultaneous determination of two ions. The wavelengths are much longer than those of the formazan anion (Table 14). The general trend for electron-rich substituents is toward a larger shift this is to be expected as it tends to enhance the aromatic character of the ring and increase the covalent character of the metal — nitrogen bond. The sharpness of the absorption band has been attributed to coordination to the heterocyclic nitrogen as in 232.57S...

Formazans and their metal complexes are used as textile dyes by direct application. The in situ reduction of tetrazolium salts has not been used to introduce the dyes to their substrates. Treatment with triaryl mono and bis tetrazolium salts followed by a reducing agent such as ascorbic acid or thioglycolic acid has been claimed as a method of introducing formazans as permanent hair dyes.641 There are some references to their use as therapeutic agents.642 544... 

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... 

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. 

In general, metal complexes of bidentate formazans have low stability towards acids and, following the comparable work on metal complexes of azo compounds, Wizinger116 was prompted to investigate tri- and tetra-dentate formazans in an endeavour to obtain metal complexes having enhanced stability. 

The intensity of the colours of metal complex formazans has, however, found applications in the analytical field for example, it has been reported131 that l-(2-hydroxy-5-sulfophenyl)-3-phenyl-5-(2-carboxyphenyl)formazan (186) can be used for the detection of zinc at a concentration of 1 50000000. 

As far as dyes are concerned, chelates of type Cb are termed 1 2 or symmetrical 1 2 metal complexes if the two tridentate ligands are equal, and mixed or unsymmetrical 1 2 metal complexes in the other case. Chelates of type Bb represent 1 1 metal complexes. The types Cb and Bb include, in general, azo and azo-methine metal complex dyes, whereas chelates of the quadridentate types Ac and Be are derived predominantly from formazan and phthalocyanine chromophores. 

Metallization. Bident ate formazans that are insoluble in water can be warmed with cobalt, nickel, and copper salts (preferably acetates) to form metal chelates in solvents such as methanol, ethanol, acetone, and dimethylformamide. Metal complexes of tri- and tetradentate formazans are much more stable. Metallization with divalent salts occurs rapidly at room temperature. On reaction with diazo-tized 2-aminophenols or 2-aminonaphthols, coupling and metallization with divalent metal salts can take place concurrently under the same conditions. When coupling is complete, the dye is usually fully metallized. 

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. 

Metal-Complex (Formazan) Dyes. The hydrazone from 2-carboxyphenylhydra-zine-4-sulfonic acid and benzaldehyde is suspended in water and then dissolved by adding aqueous sodium hydroxide to obtain pH 6.5 -7.0. This solution is added to the aqueous diazonium salt solution obtained from a typical aqueous diazotiza-tion of 4-(2-sulfooxyethylsulfonyl)-2-aminophenyl-6-sulfonic acid. The mixture is then dripped into an aqueous solution of copper sulfate, while the pH is maintained with soda at 5.5 - 6.5. After complete coupling the pH is adjusted to 1 with concentrated hydrochloric acid. The strongly acidic solution is then neutralized with alkali to pH 5.5. The copper - formazan complex is salted out along with sodium chloride, filtered, washed with dilute aqueous sodium chloride solution, and dried. A dark powder results which gives a dark blue solution in water. It consists of an electrolyte-containing powdered sodium salt of the acid 25 ... 

Finally, as detailed in reference 1, p.739 various ortAo-metallated complexes have been generated from the ligand o-CH2=CHC6H4PPh2 (SP) e.g. reaction of [RuCl2(CO)2(SP)2] with boiling 2-methoxyethanol gives, as the major product [Ru(o-CHMeC6H4PPh2)Cl(CO)(SP)] (200). Other more complex products from this reaction are discussed in reference 1489. See Section 45.5.4.6.v for an example of a cyclometallated formazan derivative. 

Particularly fine colors are displayed by the metal complexes of formazans derived from viscose rayon. The copper, cobalt, and uranium cellulose complexes represent a new type of the so-called chemically colored threads. 

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