Phenols, Properties Salts

Pyrazoles, isoxazoles and isothiazoles with a hydroxyl group in the 3-position (491 Z = NR, O, S) could isomerize to 3-azolinones (492). However, these compounds behave as true hydroxy derivatives and show phenolic properties. They give an intense violet color with iron(III) chloride and form a salt (493) with sodium hydroxide which can be O-alkylated by alkyl halides (to give 494 R = alkyl) and acylated by acid chlorides (to give 494 R = acyl). 

Later, Farnham and Johnson reported the synthesis of higher molecular weight, tiiermoplastic polyfarylcnc etiier)s with good thermal, oxidative, chemical stability, and physical properties by reacting (at 120-260°C) a phenolate metal salt... 

Nitrosophenols are formed very easily by the action of nitrous acid on phenols. Some salts of heavy metals have weak initiating properties. These are lead dini-trosophenate and lead trinitrosophloroglucinate. 

Dihvdroxyselenazole crystallises in centimetre-long prisms, M.pt. 1475 C., readily soluble in alcohol, moderately soluble in water forming supersaturated solutions. It sublimes at 100° C., and is feebly acid towards litmus, showing some phenolic properties. It does not form salts with acids. 

As hydroxyl substitution products possessing both acid and alcohol properties the phenols yield salts, esters and ethers. The salts and esters have been sufficiently considered. The ethers of phenols, especially of those which contain an unsaturated side chain, include several important compounds. 

Glaziovine (6), which has interesting psychopharmacological properties, has been prepared in satisfactory yield via photolysis of the phenolic diazonium salt (9). 

Coloured salts loith alkalis. Dissolve a few crystals of o-nitro-phenol in a few ml. of 10% NaOH solution. An orange-coloured solution is produced, and becomes almost colourless on the addition of acids. Alkali restores the orange coloration, and so the solution exhibits the properties of an indicator. 

The above simple experiments illustrate the more important properties of aliphatic acid chlorides. For characterisation, the general procedure is to hydrolyse the acid chloride by warming with dilute alkali solution, neutralise the resulting solution with dilute hydrochloric acid (phenol-phthalein), and evaporate to dryness on a water bath. The mixture of the sodium salt of the acid and sodium chloride thus obtained may be employed for the preparation of solid esters as detailed under Aliphatic Acids, Section 111,85. The anilide or p-toluidide may be prepared directly from the acid chloride (see (iii) above and Section III,85,i). 

Separations based upon differences in the chemical properties of the components. Thus a mixture of toluene and anihne may be separated by extraction with dilute hydrochloric acid the aniline passes into the aqueous layer in the form of the salt, anihne hydrochloride, and may be recovered by neutralisation. Similarly, a mixture of phenol and toluene may be separated by treatment with dilute sodium hydroxide. The above examples are, of comse, simple apphcations of the fact that the various components fah into different solubihty groups (compare Section XI,5). Another example is the separation of a mixture of di-n-butyl ether and chlorobenzene concentrated sulphuric acid dissolves only the w-butyl other and it may be recovered from solution by dilution with water. With some classes of compounds, e.g., unsaturated compounds, concentrated sulphuric acid leads to polymerisation, sulphona-tion, etc., so that the original component cannot be recovered unchanged this solvent, therefore, possesses hmited apphcation. Phenols may be separated from acids (for example, o-cresol from benzoic acid) by a dilute solution of sodium bicarbonate the weakly acidic phenols (and also enols) are not converted into salts by this reagent and may be removed by ether extraction or by other means the acids pass into solution as the sodium salts and may be recovered after acidification. Aldehydes, e.g., benzaldehyde, may be separated from liquid hydrocarbons and other neutral, water-insoluble hquid compounds by shaking with a solution of sodium bisulphite the aldehyde forms a sohd bisulphite compound, which may be filtered off and decomposed with dilute acid or with sodium bicarbonate solution in order to recover the aldehyde. 

Phenol s chemical properties are characterized by the influences of the hydroxyl group and the aromatic ring upon each other. Although the stmcture of phenol is similar to cyclohexanol, phenol is a much stronger acid. Its piC in aqueous solution at 25°C is 9.89 x 10 ° (8). This characteristic allows aqueous hydroxides to convert phenol into their salts. The salts, especially those of sodium and potassium, are converted back into phenol by aqueous mineral acids or carboxyhc acids. 

Resoles are usually those phenolics made under alkaline conditions with an excess of aldehyde. The name denotes a phenol alcohol, which is the dominant species in most resoles. The most common catalyst is sodium hydroxide, though lithium, potassium, magnesium, calcium, strontium, and barium hydroxides or oxides are also frequently used. Amine catalysis is also common. Occasionally, a Lewis acid salt, such as zinc acetate or tin chloride will be used to achieve some special property. Due to inclusion of excess aldehyde, resoles are capable of curing without addition of methylene donors. Although cure accelerators are available, it is common to cure resoles by application of heat alone. 

A biopolymer produced by a particular strain of bacteria is becoming widely used as a substitute for clay in low-solids muds. Since the polymer is attacked readily by bacteria, a bactericide such as paraformaldehyde or a chlorinated phenol also must be used with the biopolymer. The system has more stable properties than the extended bentonite system, because biopolymer exhibits good rheological properties in its own right, and has a better tolerance to salt and calcium. The system can be formulated to include salt, such as potassium chloride. Such a system, however, would then be classed as a nondispersed inhibitive fluid. 

Phenol was the first commercial antiseptic its introduction into hospitals in the 1870s led to a dramatic decrease in deaths from postoperative infections. Its use for this purpose has long since been abandoned because phenol burns exposed tissue, but many modern antiseptics are phenol derivatives. Toluene has largely replaced benzene as a solvent because it is much less toxic. Oxidation of toluene in the body gives benzoic acid, which is readily eliminated and has none of the toxic properties of the oxidation products of benzene. Indeed, benzoic acid or its sodium salt (Na+, C6H5COO ions) is widely used as a preservative in foods and beverages, including fruit juices and soft drinks. 

Commercial Mononitrophenol. Yel cryst mass mp about 45° mostly ortho- with some para-nitrophenol. Can be prepd by the nitration of phenol with dil nitric acid (1 3) at a temp below 35° (see Ref, p 283). Although it does not possess expl properties and does not gelatinize NC, it has been used as the fuel component of some commercial expls. It forms salts, some of which are weak expls which were used in expl compns, for example, Voight Explosives (qv)... 

Sowinski M. Warman, Lead Salts of Trinitro Phenols. I. Preparation and Properties of Methoxy Picric Acid and Lead Methoxy Picrate , PATR 3344(1966)... 

A mixture of monolauryl phosphate sodium salt and triethylamine in H20 was treated with glycidol at 80°C for 8 h to give 98% lauryl 2,3-dihydro-xypropyl phosphate sodium salt [304]. Dyeing aids for polyester fibers exist of triethanolamine salts of ethoxylated phenol-styrene adduct phosphate esters [294], Fatty ethanolamide phosphate surfactant are obtained from the reaction of fatty alcohols and fatty ethanolamides with phosphorus pentoxide and neutralization of the product [295]. A double bond in the alkyl group of phosphoric acid esters alter the properties of the molecule. Diethylethanolamine salt of oleyl phosphate is effectively used as a dispersant for antimony oxide in a mixture of xylene-type solvent and water. The composition is useful as an additive for preventing functional deterioration of fluid catalytic cracking catalysts for heavy petroleum fractions. When it was allowed to stand at room temperature for 1 month it shows almost no precipitation [241]. 

Complexes. The structure of an n a charge-transfer complex between quinoxaline and two iodine atoms has been obtained by X-ray analysis and its thermal stability compared with those of related complexes. The hydrogen bond complex between quinoxaline and phenol has been studied by infrared spectroscopy and compared with many similar complexes. Adducts of quinoxaline with uranium salts and with a variety of copper(II) alkano-ates have been prepared, characterized, and studied with respect to IR spectra or magnetic properties, respectively. 

Thermal properties of several chlorinated phenols and derivatives were studied by differential thermal analysis and mass spectrometry and in bulk reactions. Conditions which might facilitate the formation of stable dioxins were emphasized. No two chlorinated phenols behaved alike. For a given compound the decomposition temperature and rate as well as the product distribution varied considerably with reaction conditions. The phenols themselves seem to pyro-lyze under equilibrium conditions slowly above 250°C. For their alkali salts the onset of decomposition is sharp and around 350°C. The reaction itself is exothermic. Preliminary results indicate that heavy ions such as cupric ion may decrease the decomposition temperature. 

PCP presents a different picture from that of the lower chlorophenols and their derivatives. The corresponding dioxin shows much more stability to light than does TCDD, enough to permit its prolonged existence at low concentrations in a photoreactor. As a phenol it can directly yield dioxins, a process favored by its normal mode of application as the sodium salt. Although octachlorodibenzo-p-dioxin has much lower mammalian toxicity than TCDD (6), its formation, properties, and effects demand additional investigation. Technical preparations of PCP are frequently mixtures of tetra- and pentachlorophenols consequently, hepta-and possibly hexachlorodibenzo-p-dioxins might be expected as photolysis products in addition to the octachloro derivative. 

Although phenols would appear to be alcohols, because they have an -OH group like alcohols, they do not react like alcohols but instead have the chemical properties of acids. For example, they form salts when reacted with a base. This is the reason that the common name for phenol for many years was carbolic acid. 

For thermographic recording materials, thermochromic properties of the spiroindolino- and spirobenzothiazolino-benzopyrans have been utilized. As an example, thermal paper patented by National Cash Register38 can be cited. In this paper, the colored merocyanine form is fixed by reacting with phenols or metallic salts.2... 

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