Hydrogen ions phenols

Rate studies show that base-cataly2ed reactions are second order and depend on the phenolate and methylene glycol concentrations. The most likely path involves a nucleophilic displacement by the phenoxide on the methylene glycol (1), with the hydroxyl as the leaving group. In alkaline media, the methylolated quinone intermediate is readily converted to the phenoxide by hydrogen-ion abstraction (21). 

Phthaleins. Dyes of this class are usually considered to be triaryhnethane derivatives. Phenolphthalein [77-09-8] (23, R = CO) and phenol red [143-74-8] (23, R = SO2) are used extensively as indicators in colorimetric and titrimetric determinations (see Hydrogen-ION activity). These compounds are prepared by the condensation of phenol with phthaUc anhydride or i9-sulfoben2oic anhydride, respectively, in the presence of a dehydrating agent. 

The kinetics of desulphonation of sulphonic acid derivatives of m-cresol, mesitylene, phenol, p-cresol, and p-nitrodiphenylamine by hydrochloric or sulphuric acids in 90 % acetic acid were investigated by Baddeley et a/.701, who reported (without giving any details) that rates were independent of the concentration of sulphuric acid and nature of the catalysing anion, and only proportional to the hydrogen ion concentration. The former observation can only be accounted for if the increased concentration of sulphonic acid anion is compensated by removal of protons from the medium to form the undissociated acid this result implies, therefore, that reaction takes place on the anion and the mechanism was envisaged as rapid protonation of the anion (at ring carbon) followed by a rate-determining reaction with a base. 

Rate constants for the protonation of radical-anions in dimethylformamide by added phenol can be determined by electrochemical techniques [8], Pulse radiolysis methods have been used to measure the rate constants in an alcohol solvent. This technique generates the radical-anion on a very short time scale and uv-spectroscopy is then be used to follow the protonation of this species to give the neutral radical with different uv-absorption characteristics [9]. In the case of anthracene, the protonation rate is 5 x 10 M" s with phenol in dimethylformamide and 5 x 10 s in neat isopropanol. Protonation by hydrogen ions approaches the diflusion-controlled limit with a rate constant of 10 M s in ethanol [9]. 

Phthaleins. Dyes of Uiis class are usually considered to be tnaryl-methane derivatives. Phenolphthalein and phenol red are used extensively as indicators in colorimetric and titrimetric determinations. See also Hydrogen-Ion Activity. 

Because of their high acidity, phenols are often called carbolic acids. The phenol molecule is highly acidic because it has a partial positive charge on the oxygen atom due to resonance, and the anion that is formed by loss of a hydrogen ion is also resonance stabilized. 

In conclusion, the major role in these examples is played by the basic oxygen ions, which can display nucleophilic reactivity and abstract hydrogen ions from methanol, phenol, and even ammonia to form reactive negatively charged intermediates (264). 

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