Hydroxyl group, in phenol

I. DETERMINATION OF NUMBER OF HYDROXYL GROUPS IN PHENOL. CjHjOH. Molecular Weight, 94. 

Vrocttd precisely as in the Determination of the Number of Hydroxyl Groups in Phenol, except that after weighing the flask A, run in about i ml. of pure aniline, and weigh again. Then continue exactly as before. The acetanilide which is formed usually remains in solution when the contents of the flask A are diluted with water for hydrolysis. 

Ozone reacts slowly with many types of water contaminants such as alicyclic taste or odor compounds, e. g. geosmin or THMs and unactivated aromatics such as chlorinated benzenes. Ozone will react faster with certain types of aromatic compounds, e. g. those carrying electron supplying substituents such as the hydroxyl group in phenol. If there is no... 

The presence of the hydroxyl group in phenols facilitates the substitution of the nuclear hydrogen atoms by halogen the number and position of the substituent atoms varies with the nature of the phenol. This method is an indirect means of identification, as the formation of a substitution derivative is not a characteristic reaction of the phenol group but of the benzene nucleus. Phenol reacts with bromine to give 2,4,6-tribromophenol ... 

Typically, substitution reactions occur by attack of a nucleophilic reagent on a benzyl carbon present in the form of a carbonium ion or a methine group in a quinonemethide structure. Several representative substitution reactions are illustrated in Fig. 1.5. At moderate temperatures ( 100°C) and under mildly alkaline conditions, benzylic hydroxyl groups in phenolic units are converted to thiols by reaction with bisulfide (Q, Fig. 1.5). At higher temperatures and alkalinities, e.g., under kraft pulping conditions, the mercaptide group undergoes a series of transformations in which the sulfur is ultimately eliminated. 

Reaction with Aldehydes and Ketones. The pyrryl carbinols can also be synthesized by another approach the reaction of the electrophilic carbonyl group of aldehydes and ketones with pyrroles. This reaction (Scheme 7.10) is found also in benzene chemistry where the ring is activated, e.g., by the electron-releasing hydroxyl group in phenols. 

To ascertain the configuration of the 6-hydroxyl group in phenolic steroids produced by incubation with rat liver, it was necessary to establish the configuration of the synthetic epimeric 6-hydroxy compounds. This was achieved by aromatizing 6a-hydroxy-4-androstene-3,17-dione and... 

We can understand this effect by noting that the carbon atom which bears the hydroxyl group in phenol is hybridized, whereas in cyclohexane it is hybridized. Because of their greater r character, i/) -hybridized carbon atoms are more electronegative than i -hybridized carbon atoms (Section 3.8A). 

Hindered Phenols. The aromatic hydroxyl group in phenols... 

The hydroxyl group in phenol activates the benzene ring towards substitution in the 2-, 4- and 6-positions. Upon reaction of phenol with formaldehyde, methylol substituent groups are formed, e.g. 

Breuer, H., Knuppen, R., and Pangels, G. (1961). Configuration of the 6-hydroxyl groups in phenolic steroids formed during enzymic reactions. 

Estimation of the Number of Hydroxyl Groups in a given Polyhydric Alcohol or Phenol. 

Ion-exchange resins. The constituent phenolic hydroxyl groups in the insoluble phenol-formaldehyde resins react with cations of salts ... 

The phenolic hydroxyl group of tyrosine, the imidazole moiety of histidine, and the amide groups of asparagine and glutamine are often not protected in peptide synthesis, since it is usually unnecessary. The protection of the hydroxyl group in serine and threonine (O-acetylation or O-benzylation) is not needed in the azide condensation procedure but may become important when other activation methods are used. 

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). 

Since a few protective groups cannot satisfy all these criteria for elaborate substrates, a large number of mutually complementary protective groups are needed and, indeed, are becoming available. In early syntheses the chemist chose a standard derivative known to be stable to the subsequent reactions. In a synthesis of callistephin chloride the phenolic —OH group in 1 was selectively protected as an acetate. In the presence of silver ion the aliphatic hydroxyl group in 2 displaced... 

Catechols can be protected as diethers or diesters by methods that have been described to protect phenols. However, formation of cyclic acetals and ketals (e.g., methylenedioxy, acetonide, cyclohexylidenedioxy, diphenylmethylenedioxy derivatives) or cyclic esters (e.g., borates or carbonates) selectively protects the two adjacent hydroxyl groups in the presence of isolated phenol groups. 

The esterification of the phenolic hydroxyl group in salicylic acid with acetic acid results not only in an... 

The reaction was also found to be inhibited by addition of dioxan and tetra-hydropyran, the rate decrease being proportional to the ether concentration. The results were rationalised by the assumption that 2 1 and 1 1 phenol ether complexes were formed, respectively. The inhibition was attributed to participation of the hydroxyl group in solvation of the halogen atom of the alkyl halide, though this seems much less likely than a straightforward modification of the electron-supplying effect of the substituent3 54. 

All these steps proceed to afford free or N -substituted crystalline cytidines 6 in high yields [11] (cf. the preparation of N (tetramethylene)cytidine 6b in 95.4% yield in Section 1.1.). This simple one-pot reaction is also very easy to perform on a technical scale, as are the subsequently discussed analogous silylation-aminations of purine nucleosides and other hydroxy-N-heterocycles (cf. Sections 4.2.4 and 4.2.5). The concept of silylation-activation while simultaneously protecting hydroxyl groups in alcohols, phenols, or phosphoric acids by silylation was subsequently rediscovered and appropriately termed transient protection [16-18]. 

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