Subject alkoxide equilibrium

A much more extensive investigation of the effect of alkalies has been made in the case of polysaccharides, especially cellulose this is understandable in view of the industrial importance of mercerization, of the viscose process, and of cellulose ethers. Various complexes have been reported for cellulose and alkalies depending upon the nature of the alkali, upon its concentration, upon the washing treatment used, and upon the pretreatment of the cellulose. A discussion of this subject has been published by Nicoll and Conaway.84 There is general agreement on the formation of several compounds, which are susceptible to hydrolysis. The question as to whether these compounds are molecular complexes (XLVII), true alkoxides (XLVIII), or an equilibrium mixture of the two has not been answered. In recent studies Lauer65 has reached... 

Completion of the reaction by transfer of a proton from the solvent to the carbanion will then give a product (3a -f- 3b) of composition corresponding to thermodynamic equilibrium of the anionic species. That this approximates closely to an equilibrated mixture of the alcohols has been confirmed by subjecting some steroid alcohols to equilibration with alkoxide ions, under conditions sufficiently Mastic to allow thermodynamic equilibrium to be attained through a reversible oxidation/reduction process. Reduction of steroidal 20 ketones is of considerable interest in providing a mixture of epimers, each present in considerable proportion. The reduced mixture contains a modest preponderance of the 20a-epimer [34], although recent experiments [34M] confirm indications from molecular models that the 20/ -alcohol is the more stable. Further work is needed to clarifythis situation (see alsop. 139). 

The acid-base reaction of a ketone or aldehyde with an acid will give an oxocarbenium ion (44), which is resonance stabilized and subject to attack by a nucleophile at the acyl carbon. If ethanol reacts with 44, the product is 45, an unstable species that is in equilibrium with 44. Intermediate 45 is more stable than 42 because a C-OH unit replaces the alkoxide unit (C-0 ) found in 42. 

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