ISSN:
0021-8383
Keywords:
Chemistry
;
Organic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Determination of Configurations by the Aid of Sterically Corresponding Epoxides. XI. Glycidic Nitriles. IV. Synthesis of 1α-Methyl-2α-aryl-cyclohexane-1ß-carboxylic Acids from 4α-Aryl-2-methyl-1α-oxaspiro[2, 5]octane-2-nitrilesThe opening of an epoxide ring of the C-2-isomeric glycidic nitriles 1a-b with anhydrous HCl in dry Et2O yields the corresponding chlorocyanohydrines 2a-b. Treatment of these chlorocyanohydrines with diluted NaOH does not give the expected α-chloroketones 3a-b, but only the original glycidic nitriles. Dehydrocyanation of the chlorocyanohydrines 2a-b is carried out by column chromatography on silica or neutral Al2O3. Favorskii rearrangement of the resulting α-chloroketones 3a-b gives the angular methylated carboxylic acid methyl esters 4a-b, which are converted to the acids 5a-b by saponification with NaOH in quantitative yield.Better reaction conditions for the Favorskii rearrangement of 1-acetyl-1-chloro-cyclohexanes are described.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/prac.19843260413