Aniline → HCID 67267939, compound

Participants

Reaction Conditions

Reaction Steps

To 10 g (83 mmol) of 2,4-dimethylaniline in 200 mL of methanol was added 80 mL (50% solution in toluene, 410 mmol) of ethyl gyloxalate. The mixture was heated to 70° C. for 7 h and then allowed to stand at room temperature overnight. The reaction was concentrated in vacuo, dissolved in dichloromethane and concentrated onto silica gel. The product was eluted with a 93-100% ethyl acetate/hexanes gradient mixture to give 8.0 g (47%) of ethyl 2-(2,4-dimethylphenylimino)acetate as an oil containing approximately 20% starting aniline by LCMS analysis. This material was used without further purification. MS Calcd.: 205. Found: 206 (M+H). To 7.2 g (35 mmol) of ethyl 2-(2,4-dimethylphenylimino)acetate, 11 g (56 mmol) of tosylmethylisocyanide and 9.7 g (70 mmol) of potassium carbonate was added 200 mL of a 2:1 ethanol:1,2-dimethoxyethane mixture. The resulting slurry was heated to 90° C. for 1 h. The cooled mixture was diluted with 300 mL of ethyl acetate and filtered through GFF paper. The resulting filter cake was washed with an additional 500 mL of ethyl acetate and the resulting filtrate was added to the previous filtrate. The combined filtrates were then concentrated in vacuo to give a brown semisolid. The crude material thus obtained was then purified by flash chromatography eluting with a 45% ethyl acetate/hexanes mixture to give 4.3 g (62%) of the title compound as a tan solid.

Provenance & Evidence