Phenols nitrophenols

It has been shown that in some compounds the active species is the non-ionized molecule while the ion is inactive (benzoic acid, phenols, nitrophenols, salicylic acid, acetic acid). Thus, conditions of pH which favour the formation of the ions of these compounds will also reduce their activity. The effect of pH on the ability of acetic acid and phenol to inhibit the growth of a mould is shown in Fig. 11.4. 

Hammett s equation was also established for substituted phenols from the elementary hydroxyl radical rate constants. The Hammett resonance constant was used to derive a QSAR model for substituted phenols. The simple Hammett equation has been shown to fail in the presence of electron-withdrawing or electron-donating substituents, such as an -OH group (Hansch and Leo, 1995). For this reason, the derived resonance constants such as o°, cr, and o+ were tested in different cases. In the case of multiple substituents, the resonance constants were summed. Figure 5.24 demonstrates a Hammett correlation for substituted phenols. The least-substituted compound, phenol, was used as a reference compound. Figure 5.24 shows the effects of different substituents on the degradation rates of phenols. Nitrophenol reacted the fastest, while methoxyphenol and hydroxyphenol reacted at a slower rate. This Hammett correlation can be used to predict degradation rate constants for compounds similar in structure. 

Gas chromatography has also been applied to the determination of the following types of organic compounds in potable waters (see Table 15.11) aliphatic hydrocarbons, phenols, nitrophenols, chlorinated dioxins, anticholisterinase insecticides, chlorinated humic acid and chlorolignosulphonic acids. 

B-H in the above equation is a "blocking" agent, that is, a labile active hydrogen-containing compound, which includes phenol, nitrophenol, and epsilon-caprolactam. 

The retention characteristics of 29 aza-arenes (e.g., pyridine, acridine, quinoline, benz[a]acridine, and numerous substituted analogs) were studied on a diol column using a 97.5/2.5 iso-octane/ethanol mobile phase [611]. Dimethylbenz[a]acridine was least retained k < 3) and indole had the greatest retention (k > 9). The study also worked with 29 phenols (e.g., numerous alkyl-substituted phenols, nitrophenols, and halogenated phenols). They were studied in detail on the diol column using a 50/50 iso-octane/dichloromethane mobile phase. Appropriate selection of solvent composition provided baseline resolution of isomeric groups (e.g., dimethylphenols using hexane/ethyl acetate). 

Si02 benzophenone, furfural, 9,10-anthraquinone a total of 37 aromatic amines, naphthols, phenols, nitrophenols, benzamide, benzaldehyde... 

Bright yellow needles m.p. 45 C, b.p. 2 4°C. Prepared together with 4-nitrophenol by careful nitration of phenol. Sodium sulphide reduces it to 2-aminophenol which is used in dyestuffs and photographic processes. 

If phenol is treated even with dilute nitric acid at room temperature, nitration readily occurs with the simultaneous formation of the yellow o-nitro-phenol and the white /> nitrophenol. These compounds can be readily... 

The o-nitrophenol is obtained as bright yellow crystals, m.p. 46°, possessing an odour which resembles both that of phenol and of nitrobenzene. 

Sodium carbonate solution [cf. Section 5, p. 330). Note that phenols (except those containing acidic groups, e.., nitrophenols) give no reaction with sodium carbonate solution. 

The Reaction has the following limitations (i) a compound that can liberate nitrous acid in acid solution is required (e.g., a metallic nitrite or a nitroso-amine, p. 204). (2) Nitrophenols and />-substituted phenols do not give the test. (3) Among the dihydroxyphenols. only resorcinol gives a satisfactory positive test. 

Note. Some substituted phenols, particularly nitrophenols, are sufficiently acidic to liberate CO, from Na,CO,. Nitrophenols, however, all give yellow or red solutions with NajCOj. 

Monohydric alcohols, aldehydes (including chloral hydrate), ketones, cinnamic acid, amines (2-naphthylaminc is odourless), nitrophenols (resemble both phenol and nitro-compound),... 

A brief account of aromatic substitution may be usefully given here as it will assist the student in predicting the orientation of disubstituted benzene derivatives produced in the different substitution reactions. For the nitration of nitrobenzene the substance must be heated with a mixture of fuming nitric acid and concentrated sulphuric acid the product is largely ni-dinitrobenzene (about 90 per cent.), accompanied by a little o-dinitrobenzene (about 5 per cent.) which is eliminated in the recrystallisation process. On the other hand phenol can be easily nitrated with dilute nitric acid to yield a mixture of ortho and para nitrophenols. It may be said, therefore, that orientation is meta with the... 

Phenol may be nitrated with dilute nitric acid to 3deld a mixture of o- and nitrophenols the 3deld of p-nitrophenol is increased if a mixture of sodium nitiute and dilute sulphuric acid is employed. Upon steam distilling the mixture, the ortho isomer passes over in a substantially pure form the para isomer remains in the distillation flask, and can be readily isolated by extraction with hot 2 per cent, hydrochloric acid. The preparation of m-nitrophenol from wt-nitroaniline by means of the diazo reaction is described in Section IV,70. 

Cautiously add 250 g. (136 ml.) of concentrated sulphuric acid in a thin stream and with stirring to 400 ml. of water contained in a 1 litre bolt-head or three-necked flask, and then dissolve 150 g. of sodium nitrate in the diluted acid. Cool in a bath of ice or iced water. Melt 94 g. of phenol with 20 ml. of water, and add this from a separatory funnel to the stirred mixture in the flask at such a rate that the temperature does not rise above 20°. Continue the stirring for a further 2 hours after all the phenol has been added. Pour oflF the mother liquid from the resinous mixture of nitro compounds. Melt the residue with 500 ml. of water, shake and allow the contents of the flask to settle. Pour oflF the wash liquor and repeat the washing at least two or three times to ensure the complete removal of any residual acid. Steam distil the mixture (Fig. II, 40, 1 or Fig. II, 41, 1) until no more o-nitrophenol passes over if the latter tends to solidify in the condenser, turn oflF the cooling water temporarily. Collect the distillate in cold water, filter at the pump, and drain thoroughly. Dry upon filter paper in the air. The yield of o-nitrophenol, m.p. 46° (1), is 50 g. 

The melting points of some 0-aryl saccharin derivatives are phenol, 182° o-cresol, 163° m-cresol, 146° p-cresol, 172° o-nitrophenol, 236° p-nitrophenol, 192°. 

Benzene and some of its derivatives react with solutions of mercuric nitrate in concentrated nitric acid to give nitrophenols. These reactions, known as oxynitrations may proceed by mercuration followed by nitroso-demercuration the resulting nitroso compound becomes a diazonium compound and then a phenol, which is nitrated. ... 

The catalysed nitration of phenol gives chiefly 0- and />-nitrophenol, (< 0-1% of w-nitrophenol is formed), with small quantities of dinitrated compound and condensed products. The ortho para ratio is very dependent on the conditions of reaction and the concentration of nitrous acid. Thus, in aqueous solution containing sulphuric acid (i 75 mol 1 ) and nitric acid (0-5 mol 1 ), the proportion of oriha-substitution decreases from 73 % to 9 % as the concentration of nitrous acid is varied from o-i mol l i. However, when acetic acid is the solvent the proportion of ortAo-substitution changes from 44 % to 74 % on the introduction of dinitrogen tetroxide (4-5 mol 1 ). 

Phenol. The change in the orientation of substitution into phenol as a result of the superimposition of nitrosation on nitration is a well-established phenomenon. In aqueous sulphuric acid it leads to a change from the production of 73 % of o-nitrophenol under nitrating... 

A meta nitro group is not directly conjugated to the phenoxide oxygen and thus stabi hzes a phenoxide ion to a smaller extent m Nitrophenol is more acidic than phenol but less acidic than either o or p nitrophenol... 

For phenols, the number of chlorines replaced depends in part on the acidity of the phenol. Under mild conditions, phenol or y -nitrophenol displaces only one chlorine from TiCl, whereas -chlorophenol, (9-nitrophenol, -nitrophenol, picric acid, or 2-naphthol gives (ArO)2TiCl2. If the mixtures are heated sufficiently, eg, in refluxing phenol, all four chlorines can be displaced (49—52). 

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