2-Amino- hydroxy-, mercapto

Tautomerism of the ligating amino- (hydroxy-, mercapto-) hetarylazomethines... 

Immobilization Method. For the immobUization of proteins, a selection of amino, hydroxy, mercapto, and carboxy group spedfic methods should be used. For example, cyanogen bromide, tresyl, N-hydroxysucdriiriiide, epoxy, divinyl-sulfone, cyanuric chloride, and carbodiimide. The most promising method can then be further optimized. 

This method has mainly been used to prepare thiazoles nonsubstituted in the 2-position and involves the replacement of a functional substituent (amino, halo, mercapto, hydroxy, or carboxy) by a hydrogen. In this way the often delicate cyclization of thioformamide can be avoided. 

Multifunctional Hydroxy, Mercapto, and Amino Compounds. These are used to cross-link halogenated polymers. Depending on the labihty of the halogen, the cross-linking agents can be capped to reduce reactivity or used in combination with accelerators to increase the rate of reaction. Benzoyl capping is common with hydroxy and mercapto compounds forming the carbamate by reaction with one equivalent of carbon dioxide is used with diamines. 

Table 11 summarizes the main results on the tautomerism of mono-hydroxy-, -mercapto-, -amino- and -methyl-azines and their benzo derivatives, in water. At first sight the equilibrium between 2-hydroxypyridine (71) and pyridin-2-one (72) is one between a benzenoid and a non-benzenoid molecule respectively (71a 72a). However, the pyridinone evidently... 

The effect of amino, hydroxy or mercapto substituents is to increase hydrogen bonding properties. However, if stable hydrogen bonds are found in the crystal, then this can decrease... 

Other solvents can be divided into several classes. In hydrogen bond-breaking solvents (dipolar aprotics), the simple amino, hydroxy and mercapto heterocycles all dissolve. In the hydrophobic solvents, hydrogen bonding substituents greatly decrease the solubility. Ethanol and other alcohols take up a position intermediate between water and the hydro-phobic solvents (63PMH 1)177). 

Thiazole, 5-amino-4-ethoxycarbonyl-2-methyl-synthesis, 6, 306 Thiazole, 2-amino-4-(2 -furyl)-bromination, 6, 256 Thiazole, 2-amino-4-hydroxy-synthesis, 6, 296 Thiazole, 5-amino-2-hydroxy-synthesis, 6, 301 Thiazole, 5-amino-2-mercapto-synthesis, 6, 301 Thiazole, 2-amino-4-methyl-alkylation, 6, 256 synthesis, 6, 300 Thiazole, 2-amino-5-nitro-antiparasitic activity, 1, 180... 

Hoffman and Gronowitz - have applied this technique with marked success to the study of hydroxy-, amino-, and mercapto-thiophenes. Similarly, it has been shown that pyrid-4-one exists predominantly as such and that 4-hydroxypyridine 1-oxide is in equilibrium with comparable amounts of l-hydroxypyrid-4-one. - The method has also been used to investigate the structure of ions (see Section II,C, of article II by Katritzky and Lagowski). 

A strictly dehned region of chemical shifts of C2, C4, and C5 atoms in A-oxides of 4A-imidazoles allows to dehne clearly the position of the A-oxide oxygen atom (102). Chemical shifts of the a-C nitrone group in a-N-, O-, and S-substituted nitrones are located in the region of 137 to 150 ppm (388, 413). On the basis of 13C NMR analysis of 3-imidazoline-3-oxide derivatives, the position of tautomeric equilibria in amino-, hydroxy-, and mercapto- nitrones has been estimated. It is shown that tautomeric equilibria in OH- and SH-derivatives are shifted toward the oxo and thioxo forms (approximately 95%), while amino derivatives remain as amino nitrones (413). In the compounds with an intracyclic amino group, an aminonitrone (A) - A-hydroxyaminoimino (B) tautomeric equilibrium was observed (Scheme 2.76), depending on both, the nature of the solvent and the character of the substituent in position 2 of the heterocycle (414). 

Often, the exact position of tautomeric equilibria (Section III,A,4,a) is uncertain for fused troponoids substituted by hydroxy, mercapto, or amino groups. In such cases the structures preferred by the authors or the most probable tautomeric forms will be used here. 

Table 11 summarizes the main results on the tautomerism of mono-hydroxy-, -mercapto-, -amino- and -methyl-azines and their benzo derivatives, in water. At first sight the equilibrium between 2-hydroxypyridine (71) and pyridin-2-one (72) is one between a benzenoid and a non-benzenoid molecule respectively (71a 72a). However, the pyridinone evidently has a continuous cyclic p- orbital system, containing six it- electrons, the usual aromatic count, if the carbonyl group contributes none. This assumption implies the formula (72b), from which by redistribution of electrons we arrive at (72c), which has the same benzenoid system as (71a). Further canonical forms (71b, 71c) can be drawn of (71) which correspond to the non-benzenoid forms of (72). The elusive property of aromaticity is therefore possessed by both tautomers, although not necessarily by both equally. When the carbonyl oxygen of (72) is replaced by less electronegative atoms, as in the imine tautomers of amino heterocycles, or the methylene tautomers of methyl derivatives, the tendency towards polarization in forms corresponding to (72b) and (72c) is considerably less, and the amino and methyl tautomers are therefore favoured in most instances. 

Simple considerations such as these account adequately for many of the familiar reactions of substituted 7r-deficient heterocycles, such as nucleophilic displacement, tautomerism in hydroxy, mercapto and amino heterocycles, facile deprotonation of alkyl substituents, decarboxylation of carboxymethyl groups and electrophilic substitution of benzo-fused and aryl-substituted heterocycles. These individual effects are discussed separately in the following subsections. 

Bei Imidazolen, die an einem oder zwei Ring-C-Atomen Hydroxy-, Mercapto- oder Amino-Gruppen tragen, sind durch Keto-Enol-Tautomerie mehrere tautomere Formen moglich. Als Beispiel mogen die vier moglichen Tautomeren von 2-Hydroxy-imidazol dienen ... 

Hydroxy-, Mercapto- oder Amino-benzimidazole besitzen weitere acide Protonen, die am Gleichgewicht tcilnchmcn z. B.33 ... 

The Tautomerism of Heterocycles J. Elguero etal., Adv. Heterocycl. Chetn., Suppl. 1,1976. Ring-Chain Isomeric Transformations of Hydroxy-, Amino-, and Mercapto-Derivatives of Carbonyl Compounds and Their Heteroanalogues R. Valters, Russ. Chem. Rev. Engl. Transl.), 1974, 43, 665-678. 

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