Phenols amido

During the hardening of PMF-resins no co-condensation occurs in the hardened state two independent interpenetrating networks exist [58]. Indications for a co-condensation via methylene bridges between the phenolic nucleus and the amido group of the melamine had been found by H-NMR only in model reactions between phenolmethylols and melamine. 

With pyridine/S03 complex at higher temperatures (70-80 °C), in addition to sulfation of phenolic, hydroxy, and thiol groups, sulfation of amino, guanidino, and primary amido... 

The nitro groups in 3,5-dinitrodiaryl ethers may be readily replaced with the residues of mono-and bis-phenols. The simplest 3,5-dinitrodiaryl ether - 3,5-dinitrodiphenyl ether - was reacted with 4-aminophenol or 4-acetamidophenol with the formation of 3-nitro-5-[4-amino(amido)]-phenoxydiphenyl ether subsequent transformation of this product led to 3-amino-5-(4-aminophenoxy)-diphenyl ether [24] (Scheme 4.9). 

The dinuclear alkoxides and phenoxides of Mom and WnI can only be obtained in any reasonable yield via the amido intermediates.78,79 With bulky phenols the reaction can be slow and in some cases lead only to partial substitution.80... 

Acid black, agalma black, alphanol black, amido acid black, amido naphthol black, amido black, anthracite black, azo acid black, azo merino black, Biebnch patent black, bnlhant black, Coomassie wool black, ethyl black, fast sulphon black, M Gumea black, kresol black, naphthalene acid black, naphthol black, naphthylamme black, nerol, ortho black, palatme ° black, phenol black, phenylamme black, sulphon acid black, sulphocyamne black, supramme black, tolyl black, Victoria black, wool black... 

Under II tribromaniline adds hydrogen chloride but is a weak base. Nitro groups are more effective than the halogens in decreasing basicity, and dinitroaniline does not add on hydrogen chloride at all. Amido-phenol is a weak base and so is phenylhydroxylamine. 

The arylation of N-H and 0-H containing compounds, such as amines, amidos, imines, and phenols, with arylboronic acids is promoted by copper(ll) acetate (1 equivalent) and tertiary amine (2-5 equivalents) at room temperature [244-248]. The mild reaction conditions at room temperature permit the synthesis of phenolic amino acids without racemization, methodology that has been applied to an efficient synthesis of (S,S)-isodityrosine from two natural amino acids [248] (Scheme 45). 

In addition to attack by a basic nitrogen, there exists also the possibility of an intramolecular attack by an anionic nitrogen, i.e., a deprotonated amido nitrogen. This is exemplified by A-(2-carbamoylphenyl)carba-mates of model phenols (Fig. 5 X = H, Cl,... 

Intramolecular cyclizations are not restricted to attack by a nucleophilic nitrogen (basic amino or acidic amido group). They can also be catalyzed by a nucleophilic oxygen as found in a carboxylate, phenolic, or alcoholic group. Illustration of the catalytic role of a carboxylate group can be found in hemiester prodrugs of phenol (taken as model compound) or paracetamol (Fig. 6 R = H or NHCOCH3, respectively). In addition to enzymatic hydrolysis, three mechanisms of chemical hydrolysis were seen, namely, acid-catalyzed, base-catalyzed, and an intramolecular nucleophilic attack. 

The nitro-compounds, which are almost the only class in which a monatomic group acts as chromophor, would also be difficult to bring under the above ring classification. There is no doubt, however, that in amido- and hydroxyl derivatives of nitro-bodies there is a certain relationship between the nitro-group and the liydroxyl or amido-group. It is not improbable that the nitro-phenols possess a similar constitution to the nitrosophenols, which are now generally regarded as quinoneoximes. VThe azo-dye-stuffs are a class of bodies the properties of which are not in accordance with their constitution, and this is especially marked in the first member of the series, azobenzene. 

The nitro-derivatives of amines and phenols are dyestuffs, of a more or less pronounced character. The phenol derivatives have the greater tinctorial power, as the nitro-group is a chromophor which confers acid properties, and therefore possesses the power of decreasing the basic properties of the amido-group. Indeed, in the case of certain bodies of only feebly basic properties, the introduction of several nitro-groups may produce an acid dyestuff, for example, diphenylamine is a.body of this class. 

Substituted azo-compounds are generally prepared by the action of diazo-compounds on phenols and amines. With the latter bodies the intermediate formation of diazo-amido compounds is often observed. 

After diazotisation is completed the liquid is allowed to run into an alkaline solution of the phenol or its sulphonic acid, care being taken that the mixture remains alkaline. After some time the dyestuff is salted out, and is generally filtered through a filter-press. The combination of diazo-compounds with amines is somewhat more complicated. Some of these, for instance metaphenylenediamine, combine with diazo-compounds in neutral aqueous solutions while others, like diphenylamine, are dissolved in alcohol, and a concentrated solution of the diazo-compound gradually added. In the manufacture of amidoazobenzene and all compounds in which an intermediate formation of a diazo-amido-compound takes place, a large excess of the amine has to be employed, to hold the diazoamido-compound formed in solution. 

A second class contains only the azo-groups in one ring, while the auxochrome is in another. They may be prepared by acting upon amines or phenols with diazoazo-compounds (from amido-azo-bodies), or by diazotisation of diamines and subsequent combination with amines or phenols [43,46]. 

The nitroazo-compounds obtained by combination of nitrodiazo-compounds with primary amines may be diazotised and combined with phenols resulting nitrodisazo-compounds on reduction yield amido-compounds, which, when again diazotised and combined with a phenol, yield tertiary azo-compounds, containing three azo-groups. 

That a close relationship exists between azo-compounds and hydrazides is seen from the fact that certain oxyazo-compounds obtained from diazo-compounds and phenols are identical with the hydrazides of certain quinones. Indeed all coloured hydrazides show a great similarity to the azo-compounds, and probably belong to this class. Both classes of compounds, for example, behave similarly on reduction. The hydrazine group, like the azo-group, is split, yielding two amido-groups, one of which remains in combination with the phenyl group, the other with the carbon atom. 

This series of dyestuffs, which were first prepared by Witt and Koechlin, by simultaneous oxidation of paradiamines or para-amido phenols with phenols, exhibit, both as regards constitution and general behaviour, a close relationship to the indamines. Like the latter, they are decomposed by acids with formation of a quinone. In general they possess a weak basic nature, but, unlike the indamines, form colourless salts, and have mostly a blue or violet colour in the free state. 

H2N-C,H,(N02)-(N20)-C,H,(N0a)-N l, mw 3I8.25, N 26.41% orn-red tabular ndls (from phenol + ale), mp 328-30(decompn). This compd was prepd by refluxing with acetic acid and coned llCl 4,4 -bis (acet-amido)-3,3 -dinitroazoxybenzene, previously obtd by oxidn of 4-amino-2-nitroacetanilide in dioxane with Caro s acid soln. No other props of the dinitroazoxyaniline were given Ref l)Beil — not found 2)C.M.Atkinson et al, JCS 1954, 2026-7 CA 49, 5486-7 (1955)... 

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