Hydroxides, alkali deprotonation with

Weakly basic resins have very few exchangeable hydroxide ions tertiary amines in the free base form exist predominantly as the amine, e.g. — N(CH3)2, and only to a very minor extent as the hydroxide of the protonated amine, e.g. — NH (CH3)2 OH. If a salt of a weakly basic resin is treated with an alkali, the hydroxide ions deprotonate the base, which becomes nonionic. For example, the equilibrium ... 

For the classical Williamson synthesis an alcohol is initially reacted with sodium or potassium to give an alkoxide, e.g. 1. Alternatively an alkali hydroxide or amide may be used to deprotonate the alcohol. Phenols are more acidic, and can be converted to phenoxides by treatment with an alkali hydroxide or with potassium carbonate in acetone. ... 

The 1,2,3-tri-f-butylphosphirane 1-oxide (129) is surprisingly stable. Brief treatment with concentrated alkali metal hydroxide solutions, trifluoroacetic acid or trifluoromethanesulfonic acid has no effect. LiNMe2 gives rise to ring opening, probably by deprotonation of the 2-position (equation (80)). 

The alkali metal oxides will deprotonate ammonia to give a mixture of hydroxide and amide (equation 31),57 while P4O10 reacts with amines as shown in equation (32).58... 

In the series of the alkali metal carbonates and -hydroxides the cesimn compounds are the strongest bases [14]. For reasons of simpler handling the less hygroscopic carbonate is often preferred to the hydroxide. In dipolar aprotic solvents, carboxylic acids [15], phenols [16], thiols [17, 18] and sulfonamides [19] are easily deprotonated by cesium carbonate, whereas with carbamates such as e.g. benzyloxycarbonyl- ( Z -)protected amino acids no reaction occurs [20]. 

With cold aqueous alkaline hydroxides, 2,6-diarylpyrylium salts form reversibly 1,5-enediones (pseudobases), but pseudobases of 2-methyl(ene) pyrylium salts react intramolecularly with hot alkali hydroxides affording phenolates. Another reversible reaction of methyl/methylene/methine groups in neutral or slightly acidic media is deprotonation to... 

Amidinium salts (obtainable by various methods, compare Section 2.1.2.5) which are not peralkylated at nitrogen are converted to amidines by treatment with strong bases, e.g. aqueous alkali metal hydroxides, alcoholic alkoxides, tertiary amines etc. As already mentioned it is not difficult to alkylate amidines (see Section 2.7.2.5.4), thus by subsequent alkylation and deprotonation reactions amidines can be synthesized carrying the desired substituents at nitrogen, e.g. (308 Scheme 47). A series of trisubstituted formamidines have been prepared by reaction of anilines with the azavinylogous form-amidinium salt (309). ... 

In principle, deprotonation of any of the sulfanes gives polysulfide anions In practice, this route is not employed and rather fewer anions are known compared with the sulfanes. It was established last century that sulfur dissolves in basic media to give intensely colored (often blue) solutions. The well-known polysulfide solution [NH4]2Sjt, which contains mostly X = 4 and 5, is obtained by bubbling H2S through a suspension of sulfur in ammonium hydroxide. It is accepted nowadays that the blue coloration of many of these solutions is a consequence of the 83 radical. This species has characteristic EPR, visible, and Raman spectra that have enabled its detection in a variety of solutions including liquid ammonia,DMF, and HMPA. 82 can be introduced as an impurity into alkali metal halides. In lapis lazuli (lazurite that is made synthetically as ultramarine blue Na8[Al68i6024]8 , n = 2-4), the blue color is due to the presence of 83 radicals, which has also been identified by Resonance Raman Spectroscopy ... 

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