Expedient Synthesis of Glycidonitriles by Darzens Condensation of alpha-Halogenonitriles with Aldehydes and Ketones

摘要

Chloroacetonitrile(1),alpha-halogenopropionitriles 4,and alpha-chlorophenylacetonitrile(6)react with aldehydes 2a,b,h-o and ketones 2c-g,p-t in the presence of solid NaOH in THF or DME,without any added catalyst,affording substituted glycidonitriles 3a-t,5a,c-g,r,s and 7a,b,i,j,u,v,respectively(Darzens condensation).The glycidonitriles 3a-h,prepared from 1 and carbonyl compounds 2a-h,are obtained in high yields,exceeding those reported in the literature(Table 5).Expedient results of the reactions studied are due to increased reactivity of anions with Na~+as counterion in ethereal solvents.Investigation of the concentration of NaOH and the carbanion of diphenylacetonitrile in selected solvents reveals that ethereal solvents may increase the solubility of the anions participating in Darzens condensation.