Glycidic nitriles

Table 1. Cleavage of Glycidic Esters, Glycidic Amides, and Glycidic Nitriles by Hydrogen Fluoride-Pyridine Complex 110,11]...

Glycidk nitrUes. " Glycidic nitriles can be obtained in good yield by the reaction of ketones with chloroacelonitrile in aqueous sodium hydroxide with benzyltriethyl-ammonium chloride as catalyst. 

The preparation of glycidic nitriles has also been described under phase-transfer conditions (Eq. 77). ... 

Darzens condensation of chloroacetonitrile and carbonyl compounds to give glycidic nitriles can be carried out in the presence of aqueous sodium hydroxide and a quaternary ammonium catalyst, such as triethylbenzylammonium chloride (TEBA equation 32). In a subsequent study, interesting stereochemical control was obtained in an interfacial Darzens condensation. Condensation of a-chloro-phenylacetonitrile (93) with benzaldehyde, conducted in benzene in the presence of 50% aqueous sodium hydroxide and TEBA as a phase transfer catalyst, affords predominantly the traru-glycidonitrile (94) accompanied by the corresponding cis isomer (95 equation 33). Similar results are obtained when... 

Carbon acids such as chloroacetonitrile and chloromethyl p-tolyl sulfone are readily deprotonated by concentrated aqueous sodium hydroxide under phase transfer conditions. In the presence of aldehydes or ketones, the carbanion undergoes condensation to yield an intermediate a-alkoxy chloride. Intramolecular nucleophilic displacement of halide yields either a glycidic nitrile or a, j3-epoxysulfone. The overall process is, in fact, a phase transfer variant of the Darzens condensation [13] (see Eq. 5.9). Either benzyltriethylammonium chloride (BTEAC) or dibenzo-18-crown-6 (DB-18-C-6) catalyzes the phase transfer Darzens condensation of chloroacetonitrile [14, 15]. The results are presented in Table 5.8. 

Table 5.8. Phase transfer synthesis of glycidic nitriles...

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