A simple, sensitive method for the determination of primary and secondary aliphatic amines is based upon their conversion to N-substituted cinnamides by reaction with trans-cinnamic anhydride. After acylation of the amine in acetonitrile solution, the excess anhydride is hydrolyzed, the cinnamide is extracted into chloroform, and the amide is measured spectrophotometrically. The method is applicable to amine samples in the 1-5 pmole range; the standard deviation is 0.5-1.0%. Water and methanol do not interfere. The kinetics of the acylation and hydrolysis reactions have been studied, and a correlation can be demonstrated between acylation rate and basicity for many primary amines; sterically hindered amines react more slowly than would be anticipated from their basicity.
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