Hydrazone tautomerization

Azocrown ethers pyrazoles, 5, 228 Azo dyes, 1, 328-331 colour and constitution, 1, 342 heterocyclic, 1, 325-326 Azo-hydrazone tautomerism, 1, 331, 334 Azoles acetic acids decarboxylation, 5, 92 acetoxymercurio reactions, 5, 107 acetyl... 

Thiadiazoiyi hydrazones tautomerism, 6, 552 Thiafuivenes, synthesis, 6, 457 Thiaidine, 3, 1084 acidity, 3, 1057 Thiambutene, ethylmethyl-as analgesic, 1, 168 Thiamine... 

There are two main factors to consider in order to understand the bonding and structures of metal complex azo colorants, namely (i) azo/hydrazone tautomerism and (ii) the nature of the azo-to-metal bonding. 

Dyes based on 4-phenylazo-l-naphthol (6) have been used extensively to study azo/hydrazone tautomerism since they exist as an equilibrium mixture of both the azo and hydrazone tautomers.8 However, they are of little use commercially and of no use whatsoever for metal complex azo dyes since the hydroxy group is not ortho to the azo group so these cannot act as chelating ligands. 

The l-phenylazo-2-naphthol (7) and particularly the 2-phenylazo-l-naphthol (8) systems are used extensively, providing many of the commercial metal complex azo colorants. Azo pigments are derived from (7) whilst azo dyes are obtained from (8). Both these types of colorant exist predominantly, if not exclusively, in the hydrazone tautomeric form.8,9... 

However, the ligand itself is the anionic dye formed by deprotonation of the hydroxy group(s). Anionic dyes, even from dyes shown to exist totally in the hydrazone tautomeric form, such as Orange II (9, R = S03H) and Para Red (9 R = N02), have been shown by resonance Raman spectroscopy to exist in the azo form (10).10 This isn t surprising oxygen is... 

Hydrazone reduction, 73 572 Hydrazones, 73 576, 580 hydrazone tautomeric form, 9 365-367 Hydride ions, 73 767 Hydride reagents, functional group behavior toward, 73 615-616t... 

The phenomenon of azo—hydrazone tautomerism is firmly established75 in the benzeneazo-phenol, -naphthol, and -anthranol series, the azo form predominating in the first of these (65), the hydrazone form in the second (66), whilst the third exists exclusively in the hydrazone form (67). The situation is less clear in the analogous o-aminodiarylazo series. Thus, whilst it is known that o-aminoazobenzene (68) exists exclusively in the azo form, it has not been established whether... 

Azo-hydrazone tautomerism Azo-hydrazone tautomerism (83) (Section 58.2.3.2) is a well-established phenomenon in o,o -dihydroxydiarylazo compounds, the various species existing in solution as an equilibrium mixture the composition of which is determined by a number of factors including substituents in the azo compound, the nature of the solvent, etc. It has been invoked to account for the formation of isomeric 2 1 cobalt(III) complexes by symmetrical o,o -dihydroxydi-... 

Copper and nickel Chromium and cobalt N -Np Na-Np Meridional/facial coordination Azo/hydrazone tautomerism Non-planarity due to azo/hydrazone tautomerism Formation of two copper and two nickel complexes by unsymmetrical o.o -dihydroxyazobenzenes78 Detection of isomeric 2 1 chromium complexes 79 proton magnetic resonance80 Isolation of isomeric 2 1 chromium and cobalt complexes 86 87 limited X-ray crystallographic89 90 Proton magnetic resonance80 Detection of five isomeric 2 1 chromium complexes of symmetrical o.o -dihydroxydiarylazo compounds... 

Azo/hydrazone tautomerism was discovered in 1884 [3], The same orange dye was obtained by coupling benzenediazonium chloride with 1-naphthol and by condensing phenylhydrazine with 1,4-naphthoquinone. The expected products were the azo dye (62) (R=H) and the hydrazone (63) (R=H). It was correctly assumed that there was an equilibrium between the two forms, i.e., tautomerism. 

The discovery prompted extensive research into azo/hydrazone tautomerism, a phenomenon which is not only interesting but also extremely important as far as commercial azo dyes are concerned because the tautomers have different colors, different properties (e.g., lightfastness), different toxicological profiles, and, most importantly, different tinctorial strengths. Since the tinctorial strength of a dye primarily determines its cost-effectiveness, it is desirable that commercial azo dyes should exist in the strongest tautomeric form. This is the hydrazone form. 

Many yellow dyes were of the azopyrazolone type, but these have now been largely superseded by azopyridone dyes. Azopyridone yellow dyes are brighter, stronger and generally have better fastness properties than azopyrazolone dyes. Both azopyrazolone and azopyridone dyes exist in the hydrazone tautomeric form. Typical dyes are the azopyrazolone C.I. Acid Yellow 23 (88) and the azopyridone (89). 

From the viewpoint of stereochemistry the most interesting metal complexes are the octahedrally coordinated 1 2 chromium and cobalt complex dyes, which are medially metallized azo and azomethine compounds with functional groups in the o- and o -positions. Three types of isomerism can be discriminated geometrical, N-a, 3, and that arising from azo-hydrazone tautomerism. 

Azo-hydrazone tautomerism is a property that is indivisibly linked to azo dyes. NMR techniques used for its characterization were described in the previous review.1 Since its publication, data on several model compounds have been measured. 

Although 2-hydroxy-5-tcrt-butylazobenzene (29) exists as a true azo compound, annelation of the benzene ring results in 1,2-naphthoquinone 1-phenylhydrazone (35, R = H) and 1,2-naphthoquinone 2-phenylhydrazone (34, R = H) being in a prevailing tautomeric form in compounds derived from 1-naphthol and 2-naphthol. 4-Hydroxyazobenzene (32) and l-hydroxy-4-phenylazonaphthalene (36, R = H) exist in DMSO as true azo compounds. Next step in annelation of the benzene ring in the passive component led to anthracene derivatives. These compounds exist almost completely in hydrazone tautomeric forms (>95%) irrespective of the fact they were formally derived from 1-hydroxyanthraquinone or 2-hydroxyanthraquinone.50 15N chemical shifts show nicely the dramatic changes for compounds 32, 36, (R = H) and 1,4-anthraquinone phenylhydrazone (44). 

Mazzola et a/.114 studied azo-hydrazone tautomerism and acid-base equilibria of FD C Yellow 6 (52). The compound exists as a hydrazone below pH 9 and as an azo anion species at pH 14. A dynamic NMR effect was observed at pH 12 (corresponding to pKa according to potentiometric titration), where the midpoint of the azo-hydrazone equilibrium occurs. The observed NMR line broadening is due to slow proton transfer between... 

C chemical shifts of C — OH/C=0 groups were used with the aim of determining azo-hydrazone tautomeric equilibrium in derivatives of squaric acid and in hydrazones of ortho-hydroxy aldehydes.116... 

Because azo dyes are of commercial importance as colouring materials, the azo/ hydrazone tautomerism of hydroxy-substituted azo compounds has been intensively studied [71, 228]. In the case of 4-phenylazo-l-naphthol (16a), an increase in the solvent polarity displaces the tautomeric equilibrium towards the more dipolar quinone hydra-zone form (16b) [72-74, 74a, 74b, 150-154]. In addition, the NH and OH groups of both tautomers are capable of forming hydrogen bonds with suitable solvents. Due to... 

The azo/hydrazone tautomeric equilibrium 4-phenylazo-l-naphthol 1,4-naphthoquinone-1-phenylhydrazone [cf. (16a) (16b) in Section 4.3.2] has been studied in various liquids and in liquid and supercritical carbon dioxide [910]. The less dipolar azo tautomer 10 ° Cm) is dominant in the dilute gas phase, in com-... 

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