ISSN:
1573-9171
Source:
Springer Online Journal Archives 1860-2000
Topics:
Chemistry and Pharmacology
Notes:
Summary 1. In the isomerization of carbonyl and hydroxy carbonyl compounds by reactions of intramolecular oxidation and reduction, the most electropositive hydrocarbon group becomes attached at the carbonyl and the most electro-negative group at the carbon atom adjacent to the carbonyl. 2. An explanation of the reaction mechanisms on the basis of the hypothesis of the role of unstable intermediate products meets with contradictions. The chief significance is to be given to the mobility of hydrogen atoms and hydrocarbon groups under the influence of neighboring groups and the reagent; the rearrangement occurs intramolecularly. 3. Specific effects were found for lead and copper hydroxides in the acid transformation of α-hydroxy and α-halo aldehydes and monoses, and for mercury salts in the aldehyde-ketone rearrangement. 4. The acid transformation of 2,3-dihydroxypropionaldehyde into lactic acid in presence of lead hydroxide can be represented as passing through a β-hydroxy epoxide, but the transformation of 2-chloro-3-hydroxypropionaldehyde into 3-hydroxypropionic acid-as passing through an a-hydroxy epoxide. The saccharinic rearrangement of monoses results from the mobility of hydroxy groups with passage through the stage ofα- and β-hydroxy epoxides.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1007/BF00912046
Permalink
