Phenol from aniline

Phenol should not be allowed to come into contact with the skin for it causes painful burns. The best antidote for phenol burns is a saturate l solution of bromine in glycerine if all undissolved bromine is allowed to settle out before the solution is used, tliere is no danger of bromine burns. Lime water may also be employed. 

Plienol shotild not be allowed to come into contact with the skin for it causes i 

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Preparation of Phenol from Aniline (SECTION 513).— Prepare some iodo-starch paper for use as an indicator for nitrous acid as follows Grind about 1 gram of starch with a few cubic centimeters of water and pour the mixture into 200 cc. of boiling water. Cool the solution and dissolve in it a crystal of potassium iodide. Insert pieces of filter-paper into the solution, and hang them up to dry in a place free from acid vapors. The moist paper can be used in the following preparation. 

The ammonolysis of phenol (61—65) is a commercial process in Japan. Aristech Chemical Corporation (formerly USS Chemical Division of USX Corporation) currently operates a plant at Ha verb ill, Ohio to convert phenol to aniline. The plant s design is based on Halcon s process (66). In this process, phenol is vapori2ed, mixed with fresh and recycled ammonia, and fed to a reactor that contains a proprietary Lewis acid catalyst. The gas leaving the reactor is fed to a distillation column to recover ammonia overhead for recycle. Aniline, water, phenol, and a small quantity of by-product dipbenylamines are recovered from the bottom of the column and sent to the drying column, where water is removed. 

A process for the production of DPA from phenol and ammonia has been reported (25). Typically, the reaction is carried out continuously ia a fixed-bed reactor usiag an acidic alumiaa catalyst at 300°C—420°C. The first product formed is aniline which is subsequently converted to DPA. Consequently, the reaction can be carried out to simultaneously produce DPA and aniline, ia any desired ratio, simply by varyiag the molar ratios of phenol (and aniline) ia the reactor feed stream. 

ULLMANN - FEOVAOJAN Acridine synthesis Synthesis ot polynuciear pyridines from anilines, phenols and formaldehyde... 

The major aromatics (organics having at least one ring structure with six carbon atoms) manufactured include benzene, toluene, xylene, and naphthalene. Other aromatics manufactured include phenol, chlorobenzene, styrene, phthalic and maleic anhydride, nitrobenzene, and aniline. Benzene is generally recovered from cracker streams at petrochemical plants and is used for the manufacture of phenol, styrene, aniline, nitrobenzene, sulfonated detergents, pesticides such as hexachlorobenzene, cyclohexane (an important intermediate in synthetic fiber manufacture), and caprolactam, used in the manufacture of nylon. Benzene is also used as a general purpose solvent. 

Figure 12.14 Chromatographic analysis of aniline (a) Precolumn chromatogram (the compound represented by the shaded peak is solvent flushed) (b) main column chromatogram without cryotrapping (c) main column chromatogram with ciyottapping. Conditions DCS, two columns and two ovens, with and without ciyottapping facilities columns OV-17 (25 m X 0.32 mm i.d., 1.0 p.m d.f.) and HP-1 (50 m X 0.32 mm, 1.05 p.m df). Peak identification is as follows 1, benzene 2, cyclohexane 3, cyclohexylamine 4, cyclohexanol 5, phenol 6, aniline 7, toluidine 8, nittobenzene 9, dicyclohexylamine. Reprinted with permission from Ref. (20).

It has become clear that benzoate occupies a central position in the anaerobic degradation of both phenols and alkylated arenes such as toluene and xylenes, and that carboxylation, hydroxylation, and reductive dehydroxylation are important reactions for phenols that are discussed in Part 4 of this chapter. The simplest examples include alkylated benzenes, products from the carboxylation of napthalene and phenanthrene (Zhang and Young 1997), the decarboxylation of o-, m-, and p-phthalate under denitrifying conditions (Nozawa and Maruyama 1988), and the metabolism of phenols and anilines by carboxylation. Further illustrative examples include the following ... 

This approach has been applied by Rovis and co-workers to the formation of saturated esters from a-haloaldehydes and alcohols. A range of aliphatic alcohols, phenol and aniline proved competent nucleophiles (Scheme 12.17) [30]. 

Aromatic compounds have very high molar absorptivities that usually lie in the vacuum ultraviolet region and are not useful for routine analysis. Modest absorption peaks are found between 200 and 300 nm. Substituted benxene compounds show dramatic effects from electron-withdrawing substituents. These substituents are known as auxo-chromes since they do not absorb electromagnetic radiation but they have a significant effect on the main chromophore. For example, phenol and aniline have molar absorptivities that are six times the molar absorptivity of benzene or toluene at similar wavelengths. 

Retention volumes of monosubstituted benzenes, benzoic acid, phenols, and anilines have been measured in RPLC [76]. Buffered acetonitrile/water and tetrahydrofuran/water eluents were used with an octadecylsilica adsorbent. From the net retention volumes, a substituent interaction effect was calculated and described with the linear free energy relationship developed by Taft. The data was interpreted in terms of hydrogen bonding between the solutes and the eluent. 

A. Proton Loss from and Potential Tautomerism of Phenol and Aniline... 

Note The above mechanism of CO loss from phenols is perfectly analogous to HCN loss from aniline and other aminoarenes (Chap. 6.14.2). 

Picryl chloride (87) reacts with pyridine to form picrylpyridinium chloride (93), a useful intermediate which reacts with a range of nucleophiles 2,4,6-trinitrodiphenylamine and 2,4,6-trinitrodiphenylether can be formed from aniline and phenol respectively. 2,4,6-Trinitrodiphenylamine is readily nitrated with mixed acid to the high explosive 2,2, 4,4, 6,6 -hexanitrodiphenylamine (hexyl). 

There ate many environmental applications of adsorption in practice and many others are being developed (Noble and Terry, 2004). Activated carbons and clays are frequently used for the removal of organic contaminants, such as phenol and aniline, both of which are prevalent in industry wastewaters and are known to have a significant negative impact on marine life and human health (IRIS, 1998 Dabrowski et al., 2005). Moreover, the adsorption on inexpensive and efficient solid supports has been considered a simple and economical viable method for the removal of dyes from water and wastewater (Forgacsa et al., 2004). Activated carbon, clays, coal, vermiculite, and other adsorbents have been used for this purpose. Specifically, adsorption can be employed in (Noble and Terry, 2004 Dabrowski, 2001) ... 

The impurities present in aromatic nitro compounds depend on the aromatic portion of the molecule. Thus, benzene, phenols or anilines are probable impurities in nitrobenzene, nitrophenols and nitroanilines, respectively. Purification should be carried out accordingly. Isomeric compounds are likely to remain as impurities after the preliminary purifications to remove basic and acidic contaminants. For example, o-nitrophenol may be found in samples of p-nitrophenol. Usually, the o-nitro compounds are more steam volatile than the p-nitro isomers, and can be separated in this way. Polynitro impurities in mononitro compounds can be readily removed because of their relatively lower solubilities in solvents. With acidic or basic nitro compounds which cannot be separated in the above manner, advantage may be taken of their differences in pKg values. The compounds can thus be purified by preliminary extractions with several sets of aqueous buffers of known pH (see for example Table 19, p. 43) from a solution of the substance in a suitable solvent such as ethyl ether. This method is more satisfactory and less laborious the larger the difference between the pK value of the impurity and the desired compound. Heterocyclic nitro compounds require similar treatment to the nitroanilines. Neutral nitro compounds can be steam distilled. 

The photoisomerization of normal and isodiazoates from aniline, halosubstituted anilines and sulfanilic acid, has been studied by Le t evre and Sousa.170 Irradiated solutions of diazoates in quartz cells show a rapid decrease of the maxima due to the isodiazoates. The latter form the normal diazoates which undergo irreversible decomposition to phenolic products. 

We have stated earlier that because of proximity effects, no generally applicable aj values may be derived for ortho substitution. Nevertheless, one can determine a set of apparent 0)ortho values for a specific type of reaction, as for example, for the dissociation of substituted phenols. Table 8.7 gives such apparent O)ortho constants for estimating pKa values of substituted phenols and anilines. Of course, in cases of multiple substitution, substituents may interact with one another, thereby resulting in larger deviations of experimental from predicted pKa values. Some example calculations using the Hammett equation are given in Illustrative Example 8.2. 

We conclude our short discussion of relationships between chemical structure and light absorbance by considering some cases in which an acid or base function forms part of a chromophore. Important examples of compounds exhibiting such chro-mophores are phenols and anilines. As is evident from the spectra shown in Fig. 15.5, deprotonation of a phenolic group results in a substantial bathochromic shift... 

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