Dimethyl aminophenol

NOTE No higher nitrated derivs of Dimethyl-aminophenol were found in the literature thru... 

V,/V-dimethy1amino)pheno1 (177). In addition, 3-aminophenol may be methylated with dimethyl sulfate under neutral conditions, or its hydrochloride salt heated with methanol at 170°C under pressure for 8 h to give the desired product (178). The compound is used primarily as an intermediate in the production of basic (Red 3 and Red 11) and mordant (Red 77) dyes. 

Bindschedler s Green (6.204) can be made by condensing p-nitroso-N,N-dimethylaniline with N,N- dimethyl aniline. A similar condensation with 2-naphthol gives Meldola s Blue (6.209 Cl Basic Blue 6), the first oxazine dye, discovered in 1879. The symmetrical Cl Basic Blue 3 (6.210) is of more commercial significance. It is synthesised by nitrosation of N,N-diethybrn-anisidine followed by condensation with N,N-diethybm-aminophenol, and is used for dyeing acrylic fibres. This dye is now classified by ETAD as toxic [73]. 

The polymer resulting from oxidation of 3,5-dimethyl aniline with palladium was also studied by transmission electron microscopy (Mallick et al. 2005). As it turned out, the polymer was formed in nanofibers. During oxidative polymerization, palladium ions were reduced and formed palladium metal. The generated metal was uniformly dispersed between the polymer nanofibers as nanoparticles of 2 mm size. So, Mallick et al. (2005) achieved a polymer- metal intimate composite material. This work should be juxtaposed to an observation by Newman and Blanchard (2006) that reaction between 4-aminophenol and hydrogen tetrachloroaurate leads to polyaniline (bearing hydroxyl groups) and metallic gold as nanoparticles. Such metal nanoparticles can well be of importance in the field of sensors, catalysis, and electronics with improved performance. 

The reaction of triphenylphosphine and dimethyl acetylenedicarboxylate (DMAD) in the presence of either 2-, 3-, or 4-aminophenol and 2-amino-3-hydroxypyridine gives a vinylphosphonium salt which undergoes Michael addition to give a range of highly functionalized heterocyclic systems <2002T6895>. 

Fused oxygen and nitrogen-containing rings may also be prepared in reactions with thioureas thus, dihydrobenzoxazine products are obtained on treatment of salicyloyl chloride with thioureas371 or on fusion of salicylate esters with thiopseudoureas.320 When the thio-pseudoureas are treated with o-aminophenol, the products are benzoxa-zoles.320 A naphthyl analog of a benzoxazole is produced on treatment of l-(2-hydroxy-l-naphthyl)-2-thiourea with dimethyl sulfate.372... 

Nitro-4-methoxyaniline has been prepared by heating nitro-hydroquinone dimethyl ether with aqueous ammonia 2 by heating the tetramethylammonium salt of 3-nitro-4-aminophenol 3 by the hydrolysis of 2-nitro-4-methoxyacetanilide la with alcoholic potassium hydroxide 11 lc or hydrochloric acid ld and by the hydrolysis of the />-toluenesul fonamide,4 the 3-nitrobenzenesul-fonamide,5 the 3-nitro-/>-toIuenesulfonamide,3 and the acetyl derivative of the />-toluenesulfonamide6 of 2-nitro-4-methoxyani-line with concentrated sulfuric acid. 

Aromatic and heterocyclic nitro compounds are readily reduced in good yield to the corresponding amines (e.g. o-aminophenol, Expt 6.50) by sodium borohydride in aqueous methanol solution in the presence of a palladium-on-carbon catalyst. In this reduction there is no evidence for the formation of intermediates of the azoxybenzene or azobenzene type, although if the reaction is carried out in a polar aprotic solvent, such as dimethyl sulphoxide, azoxy compounds may sometimes be isolated as the initial products. 

Pumera et al. [34] used gold nanoparticle enhanced open channel NCEC for the separation of p-aminophenol, o-aminophenol, and m-aminophenol in a bare glass channel and polydiallyl dimethyl ammonium chloride (PDADMAC) gold coated channel. The mobile phase used was acetate buffer (20 mM, pH 5.0) with electrokinetic sample injection at 1.5kV/cm for 3 seconds and 2.0kV/cm as separation voltage (Fig. 7.15). Broyles... 

Condensation of chloromethyldimethylchlorosilane with o-phenylene diamine and o-aminophenol leads almost quantitatively to 4-aza- and 4-oxo-3,3-dimethyl-3-silaquino-line. With aminophenol, it should be noted that the O-Si bond is formed first. This same observation may be made starting from o-aminobenzyl alcohol. 

Currently, adiponitrile is the only organic chemical produced in large quantity (108 kg/yr) by an electrochemical route. Other smaller-scale products include gluconic acid, piperidine, and p-aminophenol. Electroorganic syntheses in supercritical organic electrolytes have been demonstrated in bench-scale reactors. Production of dimethyl carbonate from the mixture-critical region was performed. There are at least a dozen electroorganic processes that are... 

An extension of this synthetic route to alkyl-substituted o-amino-phenols gave symmetrically substituted dialkyl phenoxazines, but chloro- and methoxy-substituted o-aminophenols failed to react under similar conditions. 4-Methyl- (or 4-ethyl-)2-aminophenol, by reaction with the corresponding hydrochloride, yielded 2,8-dimethyl-and 2,8-diethylphenoxazine, respectively.8... 

The above method of sulfonation with sulfurous acid finds further application in the preparation of p-aminophenoldisulfonic acad from nitrosodimethylaniline and sodium bisulfite. In the rearrangement to the disulfom c acad, the dimethylamino group is split off with the formation of the p-aminophenol derivative. Pure dimethyl-amine is formed in the reaction. 

Dichlorophenol has been prepared by the chlorination of phenol with chlorine gas in the presence of nitrobenzene and fuming sulfuric acid, by the decomposition of the diazotate of 2,6 dichloro-4-aminophenol, eind by the decarboxylation of 3,5-dichloro-4-hydroxybenzoic acid in quinoline or dimethyl-aniline. ... 

Apart from its use in the synthesis of dyes, m-aminophenol (19) is used in the manufacture of agrochemicals, pharmaceuticals and specialty polymers. A,iV-dimethyl-w -aminophenol (20) is used in the manufacture of fluorescent dyes and pharmaceuticals. 

This ring is formed in high yield from a mercapto-amine and either phosgene or disuccinimido carbonate (see Section 1.3). Ethyl potassium xanthate is also effective [3038]. An aminophenol in which the hydroxy group is masked as its dimethyl aminothiocarbamate cyclizes under conditions which generate the amine from the nitro group. The product is the result of a Newman-Kwart rearrangement [B-40, Vol. 3, p. II). 

However, in contrast to strychnidine, vomicidine is phenolic (0-acetate (21) and 0-benzoate (14) ), it being soluble in alkali. While this sensitive aminophenol has been methylated with dimethyl sulfate, only an intractable black resin results from the action of diazomethane. 

The almost quantitative monoalkylation of p-aminophenol is claimed by Zimmerli by first forming an aldehyde amine before treating with the methylating agent. With the use of furfural and dimethyl sulfate, the reaction in dry chlorobenzene as a solvent can be represented by the following equations ... 

---