Simultaneous kinetic determination of secondary amines and their isomers by a spectrophotometric stopped-flow method based on the formation of dialkyldithiocarbamates

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Secondary amines react with carbon disulphide to form stable dialkyldithiocarbamates at high pH in aqueous Triton X-100 solution. The formation rates of dimethyl-, diethyl-, di- n-propyl-, diisopropyl-, di- n-butyl- and diisobutyldithiocarbamates and pyrrolidinedithiocarbamate were measured by a stopped-flow spectrophotometric method. The reaction rates were a function of the pH of the solution and depended on the size and structure of the amines. The rate of isoalkylamines was far slower than that of the n-alkyl analogues. Individual concentrations of amines were determined in a mixture of di- n- and diisopropylamine and in a mixture of diiso- and di- n-butylamine.