Nitrophenols, reduction

Ditrophenol, -nitropbenol, C H NOj. Colourless needles m.p. 114 C. Prepared as 2-nitrophenol. Reduction with iron and hydrochloric acid gives 4-aminophenol. 

The kinetics of 4-nitrophenol reduction in presence of microgel-metal nanocomposite particles was studied by UV/Vis spectroscopy. Figure 9 shows the UV spectra for the reduction of 4-nitrophenol measured at different times. For a typical measurement, successive decrease of peak intensity at 400 nm with time can be utilized to obtain the rate constant [59, 72, 73]. This peak is attributed due to the presence of 4-nitrophenate ions in the system. The formation of 4-nitrophenate ions... 

S. Harish, J. Mathiyarasu, K.L.N. Phani, and V. Yegnaraman, Synthesis of conducting polymer supported Pd nanoparticles in aqueous medium and catalytic activity towards 4-nitrophenol reduction, Catal. Lett., 128, 197-202 (2009). 

Selvaraju etal [11] reported the use of Au-NPs as catalytic labels to achieve ultrasensitive DNA detection via fast catalytic reactions involved in p-nitrophenol reduction in presence of NaBH4. In order... 

It has been observed for silver nanoparticles that and a values are altered at nanoelectrodes from their values for the bulk material, as is the case for 4-nitrophenol reduction in water, as compared to the reaction at bulk silver (F.W. Campbell et al, ChemPhysChem. 11 (2010) 2820]. 

Fig. 5.9 Plot of ln(Ct/Co) versus time for Au Si02 yolk-shell nanocatalysts with different core sizes in / -nitrophenol reduction reaction. Adapted from ref. [49]...

Prepared by reduction of 4-nitrophenol or 4-nitrosophenoi. Can be diazotized and used as a first component in azo-dyes. Chief outlet is for sulphur dyes in which it is fused with sodium polysulphides. L/sed as a photographic developer. 

Reduction to aminophenol. Reduce about 0 5 g. of o-nitrophenol with cone. HCl and tin as described on p. 385. After a few minutes the yellow molten o-nitrophenol disappears completely, the solution becoming homogeneous and colourless due to the formation of 0-aminophenol (which is soluble in HCl). Cool and add 30% aqueous NaOH solution note that a white precipitate is first formed and then redissolvcs in an excess of NaOH, and that the solution does not develop an orange coloration, indicating that the nitro-group has been reduced. 

A) Benzoyl Derivative. Since acetylation and benzoylation do not always proceed smoothly with nitrophenols, it is best to reduce them to the aminophenol as in (3) above. Add an excess of 20% aqueous sodium hydroxide to the reaction mixture after reduction, cool and then add a small excess of benzoyl chloride, and shake in the usual way. The dibenzoyl derivative wiU separate. Filter, wash with water and recrystalUse. (M.ps., p. 551.)... 

Although this reduction is more expensive than the Bnchamp reduction, it is used to manufacture aromatic amines which are too sensitive to be made by other methods. Such processes are used extensively where selectivity is required such as in the preparation of nitro amines from dinitro compounds, the reduction of nitrophenol and nitroanthraquinones, and the preparation of aminoazo compounds from the corresponding nitro derivatives. Amines are also formed under the conditions of the Zinin reduction from aromatic nitroso and azo compounds. 

Aminophenols are either made by reduction of nitrophenols or by substitution. Reduction is accompHshed with iron or hydrogen in the presence of a catalyst. Catalytic reduction is the method of choice for the production of 2- and 4-aminophenol (see Amines BY reduction). Electrolytic reduction is also under industrial consideration and substitution reactions provide the major source of 3-aminophenol. 

Iron Reduction. The reduction of nitrophenols with iron filings or turnings takes place in weakly acidic solution or suspension (30). The aminophenol formed is converted to the water soluble sodium aminopheno1 ate by adding sodium hydroxide before the iron-iron oxide sludge is separated from the reaction mixture (31). Adjustment of the solution pH leads to the precipitation of aminophenols, a procedure performed in the absence of air because the salts are very susceptible to oxidation in aqueous solution. 

Insoluble red lakes are formed as by-products which decrease yields when 2-nitrophenol [88-75-5] is reduced with iron. Consequendy, the iron reduction of this nitro compound to 2-aminophenol is of minor industrial importance today. 

Industrial production is by reduction of the corresponding nitrophenol with iron or hydrazine (167,168). 2-Amino-4,6-dichlorophenol finds important use as an azo-dye intermediate (see Azo dyes). 

Production is by the acetylation of 4-aminophenol. This can be achieved with acetic acid and acetic anhydride at 80°C (191), with acetic acid anhydride in pyridine at 100°C (192), with acetyl chloride and pyridine in toluene at 60°C (193), or by the action of ketene in alcohoHc suspension. 4-Hydroxyacetanihde also may be synthesized directiy from 4-nitrophenol The available reduction—acetylation systems include tin with acetic acid, hydrogenation over Pd—C in acetic anhydride, and hydrogenation over platinum in acetic acid (194,195). Other routes include rearrangement of 4-hydroxyacetophenone hydrazone with sodium nitrite in sulfuric acid and the electrolytic hydroxylation of acetanilide [103-84-4] (196). 

In freshwater systems, the only biodegradation product detected was 4-nitrophenol, which was rapidly utilized and transformed to undetectable metabolites by the microorganisms present. In seawater, the main initial product was methyl aminoparathion, formed by reduction of the nitro group (Badawy and El-Dib 1984). Studies in raw river water showed that 4-nitrophenol and dimethyl thiophosphoric acid are the main degradation products (Eichelberger and Lichtenberg 1971). 

This is the strategy of the manufacture of carbo-Jjran, though the mono alkylation of (28) is avoided by -sing available (29) and converting the NOg to OH by reduction and substitution. The acidic nitrophenol (30) rycllses on heating. 

It has been shown that some reductases can mediate the reduction of nitro groups and of the ring to Meisenheimer-type complexes that are analogous to those that have been observed in nitrophenols (which are described later) ... 

Endo et al. [96] prepared AuPt, AuPd, and PtPd bimetallic nanoparticles with 2 nm in particle size in order to investigate catalytic activity for reduction of p-nitrophenol in water. The binary features of the nanoparticles were characterized by UV-Vis spectroscopic measurements. 

Similar observation was recorded for the GME and FGME catalyzed reduction of 4-nitrophenol (4NP) [46]. The GME and FGME nanoparticles are prepared in the... 

Synthetic routes that access appropriately substituted thienobenzazepines are also quite important for medicinal chemistry stracture activity relationship studies, and many involve similar bond connectivity strategies. One notable example employs the use of conunercially available 4-methyl-3-nitrophenol (Scheme 6.3). Methylation of the phenol followed by bromination, hydrolysis, and oxidation of the benzylic alcohol afforded aldehyde 9 in quantitative yield. Treatment of this aldehyde with 5-lithio-2-methylthiophene provided, after dehydroxylation, nitro intermediate A in good overall yield. Reduction of the nitro functionality and treatment with phosgene presented the corresponding isocyanide which upon cychzation using aluminum trichloride in a Friedel-Crafts fashion afforded the... 

Brezova, V., Blazkova, A., Surina, I., and Havlmova, B. (1997) Solvent effect on the photocatalytic reduction of 4-nitrophenol in titanium dioxide suspensions. Journal of Photochemistry and Photobiology A Chemistry, 107 (1-3), 233-237. 

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