The relative reactivity of primary and secondary amine hydrogen atoms of aromatic amines with epichlorohydrin and N‐ and O‐glycidyl compounds

The relative value of the rate constants for the reactions between the secondary and primary amine hydrogen atoms of 3‐trifluoromethylaniline with epichlorohydrin, and of aniline with phenyl glycidyl ether and with some N‐alkyl‐N‐glycidylanilines were determined by HPLC analysis. Values ranged from 0.14 to 0.24 and are in agreement with the findings of earlier workers for the reactions of aromatic amines with O‐glycidyl compounds but in direct conflict with the claim of a recent publication. The value for the reaction between 3‐trifluoromethylaniline and epichlorohydrin was unaffected by the nature of the catalyst, which covered a wide range of strengths and steric requirements.