Acidic phenols

Particularly suitable for amines. Obviously cannot be used for any liquids affected by alkalis, e.., acids, phenols, esters. 

Physical properties. All solid except m -cresol, CH3CJH4OH, which is a liquid. All colourless when pure, but frequently slightly coloured due to atmospheric oxidation. All have in varying degrees a characteristic odour of carbolic acid. Phenol, the cresols and resorcinol have a caustic action on the skin. 

If the third substance dissolves in both liquids (and the solubility in each of the liquids is of the same order), the mutual solubility of the liquids will be increased and an upper C.S.T. will be lowered, as is the case when succinic acid or sodium oleate is added to the phenol - water system. A 0 083 molar solution of sodium oleate lowers the C.S.T. by 56 -7° this large effect has been applied industrially in the preparation of the disinfectant sold under the name of Lysol. Mixtures of tar acids (phenol cresols) do not mix completely with water at the ordinary temperature, but the addition of a small amount of soap ( = sodium oleate) lowers the miscibility temperature so that Lysol exists as a clear liquid at the ordinary temperature. 

Sodium and potassium hydroxides. The use of these efficient reagents is generally confined to the drying of amines (soda lime, barium oxide and quicklime may also be employed) potassium hydroxide is somewhat superior to the sodium compound. Much of the water may be first removed by shaking with a concentrated solution of the alkali hydroxide. They react with many organic compounds (e.g., acids, phenols, esters and amides) in the presence of water, and are also soluble in certain organic liquids so that their use as desiccants is very limited... 

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). 

Aryloxyacetic acids. Phenols, in the presence of alkah, react with chloroacetic acid to give aryloxyacetic acids ... 

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. 

Supplement (combined with Volume XII) XI, 2nd 1933 1605-1739 2. Sulphonic acids Benzenesulphonic acid, 26. p-Toluenesulphonic acid, 97. Naphthalene - sulphonic acid, 155. Hydroxy-Sulphonic acids Phenol-sulphonic acid, 234. Naphthol-sulphonic... 

Because of its acidity phenol was known as carbolic acid when Joseph Lister intro duced It as an antiseptic in 1865 to prevent postopera tive bacterial infections that were then a life threatening hazard in even minor surgi cal procedures... 

The most characteristic property of phenols is their acidity Phenols are more acidic than alcohols but less acidic than carboxylic acids Recall that carboxylic acids have s of approximately 5 whereas the pK s of alcohols are m the 16-20 range The pK for most phenols is about 10... 

In the reaction of phenol with hydroxide ion the stronger acid (phenol) is on the left side of the equation and the weaker acid (water) is on the nght... 

Fig. 28. Traditional duv-resist design using derivatives of polyhydroxystyrene. Monomer (a) contributes hydrophilic character to the polymer, and its acidic phenol group enhances aqueous base solubiUty monomer (b) provides acid-labile pendent groups.

Mild acid converts it to the product and ethanol. With the higher temperatures required of the cyano compound [1003-52-7] (15), the intermediate cycloadduct is converted direcdy to the product by elimination of waste hydrogen cyanide. Often the reactions are mn with neat Hquid reagents having an excess of alkene as solvent. Polar solvents such as sulfolane and /V-m ethyl -pyrrol i don e are claimed to be superior for reactions of the ethoxy compound with butenediol (53). Organic acids, phenols, maleic acid derivatives, and inorganic bases are suggested as catalysts (51,52,54,59,61,62) (Fig. 6). 

Some primaries have articles devoted to them and their derivatives, ie, Benzoic ACID, Phenol, Salicylic acid, and Phthalic anhydride as a derivative of phthahc acid. The primary p-naphthol is discussed in Naphthalene derivatives. 

Potassium carbonate (anhydrous). Has a moderate efficiency and capacity, forming the dihydrate. Suitable for an initial drying of alcohols, bases, esters, ketones and nitriles by shaking with them, then filtering off. Also suitable for salting out water-soluble alcohols, amines and ketones. Unsuitable for acids, phenols, thiols and other acidic substances. 

For example, nylon 66 will dissolve in formic acid, glacial acetic acid, phenol and cresol, four solvents which not only have similar solubility parameters but also are capable of acting as proton donors whilst the carbonyl groups on the nylon act as proton acceptors (Figure 5.6). 

The chemical resistance of PCTFE is good but not as good as that of PTFE. Under certain circumstances substances such as chlorosulphonic acid, molten caustic alkalis and molten alkali metal will adversely affect the material. Alcohols, acids, phenols and aliphatic hydrocarbons have little effect but certain aromatic hydrocarbons, esters, halogenated hydrocarbons and ethers may cause swelling at elevated temperatures. 

Nylons 46, 6, 66, 610, 11 and 12 are polar crystalline materials with exceptionally good resistance to hydrocarbons. Esters, alkyl halides, and glycols have little effect. Alcohols generally have some swelling action and may in fact dissolve some copolymers (e.g. nylon 66/610/6). There are few solvents for the nylons, of which the most common are formic acid, glacial acetic acid, phenols and cresols. 

Carbon, hydrogen and possibly oxygen Resin and derivatives Natural drying oils Cellulose derivatives Alkyd resins Epoxy resins (uncured) Phenol-formaldehyde resins Polystyrene Acrylic resins Natural and synthetic rubbers Carbon monoxide Aldehydes (particularly formaldehyde, acrolein and unsaturated aldehydes) Carboxylic acids Phenols Unsaturated hydrocarbons Monomers, e.g. from polystyrene and acrylic resins... 

Special procedures apply to certain chemicals, e.g. anhydrous hydrogen fluoride, aqueous hydrofluoric acid, phenol and related compounds)... 

Orthophosphoric acid, phenol, 53% yield. Methods 7 and 8 were used to remove the benzyl group from a biotin precursor. 

Obtain energies for each ion and for their correspondin precursors benzoic acid,phenol and cyclohexanol). Us this information to calculate the energy for each of the abov deprotonation reactions. (The energy of proton is given left.) Is the trend consistent with the experimental pKa dat (see table at left) Does deprotonation energy parade charge delocalization in these systems Explain ho electron delocalization affects the reactivity of these acidf... 

A variety of nucleophiles can be employed—e.g. carboxylic acids, phenols, imides, thiols, thioamides, and even /3-ketoesters as carbon nucleophiles. Of major importance however is the esterification as outlined above, and its use for the clean inversion of configuration of a chiral alcohol. 

Benzo persaure,/. peroxybenzoic acid, perben-zoic acid. phenol, n, phenol (CaHeOH), schwarzblau, n, benzo black-blue, benzoylieren, v.t. benzoylate, introduce benzoyl into. 

Carbol. carbolic, carbolized, carbolated. kalk, n. carbolated lime. >dl( n. carbolated oil. salbe,/. Pharm.) ointment of phenol. carbolic acid, phenol. ldsung, /. carbolic acid solution. seife, /. carbolic acid soap. 

Phensaure,/. phenic acid (phenol, CeHiOH). Phenyl-arsenchlorur, n. dichlorophenylarsine, GiHi. Ch. -ather, m. phenyl ether, -bor-chlorid, n. dichlorophenylborine, CeHiBCb. -braim, n. phenyl brown. 

Phenyl-jodidchlorid, n. phenyl iodochloride, -milchsaure, /. phenyllactic acid, -saure, /. phenylic acid (phenol, CeHaOH). -schwefel-saure, /. phenylsulfuric acid, -senfol, n. phenyl mustard oil. -siliciumchlorid, n. trichlorophenylsilane, CaHiSiCla. -verbindung, /. phenyl compound, -wasserstoff, m. phenyl hydride, benzene. 

Oxygen compounds in crude oils are more complex than the sulfur types. However, their presence in petroleum streams is not poisonous to processing catalysts. Many of the oxygen compounds found in crude oils are weakly acidic. They are carboxylic acids, cresylic acid, phenol, and naphthenic acid. Naphthenic acids are mainly cyclopentane and cyclohexane derivatives having a carboxyalkyl side chain. 

The reaction is generally believed to proceed via the formation of ionic acylam-monium intermediate compounds (Reaction 1, Scheme 2.27). The equilibrium constant of the acylammonium formation depends mostly on steric and resonance factors, while the basicity of the tertiary amine seems to play a secondary role.297 In die case of the less basic compounds, such as acidic phenols, and of strong tertiary amines, such as Uialkylamines, the reaction has been reported to proceed through a general base mechanism via the formation of hydroxy-amine H-bonded complexes (Reaction 2, Scheme 2.27).297... 

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