Amido acids phenols

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... 

The use of alkoxide or amide intermediates to form aryloxides is also quite common. Reaction of [NiMe(OMe)(PMe3)]2 with acidic phenols in the presence of PMes yields fra y-[NiMe(OAr)(PMe3)2]." " The bulky amido compound [PdCl N(SiMe3)2 (TMEDA)] reacts with phenols to yield [PdCl(OAr)(TMEDA)]." ... 

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). 

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-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. 

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. 

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)... 

The amido-sulphonic adds, since they are derivatives of a primary amine, may like them be diazotised by tile action of nitrous add upon tins fact depends their great technical importance. If the diazo-com-pounds thus obtained are combined with amines or phenols, azo dyes are formed which contain the sulphonic add group, and in the form of their alkali salts are soluble in water. Sulplianilic acid particularly, and its isomer, metanilic add, obtained by the reduction of m-nitro-benzenesulphonic add, as well as the numerous mono- and poly-sul-phonic acids derived from a and / naphthyl amines, find extensive technical application in the manufacture of azo dyes-... 

From this equation it is evident that by reduction, the amine which was diazotised—in the above case sulphanilic add—may be obtained again on the one hand, on the other an amido-group is introduced into the second component. If the constitution of this second product can be determined, then the constitution of the azo dyes is also determined. It may be stated as a general rule that, when a diazo-compound combines with an amine or phenol, the hydrogen atom in the para position to the amido- or hydroxyl-group is always substituted. In accordance with this, in the above case, p-amidodimethyl aniline ought to be obtained on reduction. If the para position is already occupied, then, the o-hydrogen atom Mites With the acid radical-... 

A chlorocyclopropane species is the preferential starting material if Af,0-acetals or )V,0-acylals possessing an AT-amido moiety are to be prepared. Thus heating 1-amido-l-chlorocyclopropanes with a mixture of triethylamine and alcohol, phenol or carboxylic acid in tetrahydrofuran... 

The fluid dimer polyamides and fatty amido amines also react with phenolic resins (23). These reactions are significantly different from those of epoxy resins. With the heat-reactive phenolic resins, the aminopolyamide portions react with methylol groups. A carbon-nitrogen bond or cross-link is formed and a volatile byproduct, water, is produced. This reaction requires external heat to remove water. At temperatures near 150 °C the reaction proceeds smoothly. Since curing at elevated temperatures is required, the pot life or shelf life at room temperature is relatively long. The liquid dimer polyamide and fatty amido amines also react with alpha, beta unsaturated acids and esters (29) and with polyesters (30). The unsaturated esters reduce viscosity, lengthen useful pot life, and reduce heat of reaction. Thus, they are useful diluents when low viscosity is desired. 

Amido Benzo Sulphonic Acids. Amido Phenols. 

The NO 2 group is at the moment of solution fixed upon the phenol with the production of mono-nitro-phenol, which is afterwards reduced by the action of the zinc-dust into the amido derivative. During the subsequent combustion, the nitrogen of the amido-phenol becomes fixed in the state of ammonia. M. Chenel is perfectly satisfied with the results obtained, but he points out that the success of the operation depends upon the complete conversion of the phenol into the mono-nitro derivatives. This takes place whenever the organic compoimd forms a clear solution in the cold sulphuric acid mixture. Substances like collodion or gun-cotton must be very finely divided for successful treatment. The following table shows some of the results obtained by M. Chenel —... 

In general, azo-, hydrazo-, and amido-compounds result from the electrolytic reduction of nitro-com-pounds. In this way Kendall obtained aniline from nitro-benzene, and Elbs and Haussermann prepared the normal reduction products of nitfo-phenol. The formation of azoxy-, azo-, amido-, or hydrazo-com-pounds was dependent upon whether acid or alkaline solutions were employed. If nitro-benzene is reduced in a concentrated acetic or formic acid solution, to which a few drops of concentrated sulphuric acid (to increase the conductivity) have been added, the corresponding salts of benzidene result a fact further confirmed by Lob. ... 

Noyes and Clement, on the reduction of nitrobenzene in a concentrated sulphuric acid solution, obtained p-amido-phenol-sulphonic acid. Gatter-mann, starting with a similar solution, by varying the conditions of the experiment obtained directly p-amido-phenol. He explains the reaction by assuming the intermediate formation of phenyl-hydroxyl-amine, which on further reduction changes by molecular rearrangement into the final product. By similar treatment were formed ... 

A further application of Gattermann s reaction has been found in the case of aromatic nitramines which if reduced in a concentrated solution of sulphuric acid give amido-phenol derivatives. The process can also be applied to the esters of nitro-carboxylic acids and results in the formation of amido-phenol-carboxylic esters. 

The influence of nitrates is eliminated by adding approx. 100 ml of amido-sulphonic acid or urea to the sample. If the sample contains phenols which may be transferred into the distillate, titration should not be carried out against phenolphthalein, but instead against a mixed indicator (methylene blue/neutral red). 

A series of patents issued to Asahi Chemical Industry Co., deal with the modification of hexamethylenediamine by reaction with (meth)acrylic-, glycidyl ether-, hydroxyl-, amino-, amido-, or carboxy-substituted vinyl compounds, isocyanate, and amino acid compounds (Table IV). These modified amine curing agents are active at low temperatures and, in some cases, on wet substrates. Amine-substituted resole phenolics have also been described as useful epoxy curing agents." " Preparation of these curing agents is via condensation of the phenol, formaldehyde, and polyamine (Eq. 8). 

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