The kinetics of the reactions of trimethylamine, dimethylamine, methylamine, and ammonia with methyl iodide in aqueous solutions have been investigated at temperatures ranging from 0 to 40°C. Kinetic analyses of the consecutive methylations of dimethylamine and methylamine have been conducted according to the method of French. In the case of ammonia a standard second-order kinetic treatment can be successfully used because of the relative sluggishness of the first stage as compared with the succeeding stages. The observed rates are in the sequence: Me3N>Me2NH>MeNH2>NH3. The factors which affect this rate sequence are discussed.

The rate of the reactions of methyl iodide with various aliphatic amines, e.g., methyl-, ethyl-, n-butyl-, ethanol- and benzyl-amines, have been measured in methanol solvent and compared with the previous results obtained in benzene solvent. Ethylamine, diethylamine, and triethylamine react slower in methanol than in benzene. In a similar fashion, butylamine, dibutylamine, tributylamine, methylamine and dimethylamine are less reactive in methanol than in benzene. These unusual results, e.g., the lower SN2 reactivity of amines in the more ionizing protic solvent, are attributed to the retardation by the higher activation energy in methanol solvent at the expense of the acceleration by higher values of the entropy of activation. The increase of the activation energy is ascribed to specific solvation, e.g., hydrogen bonding of methanol toward amines. Benzylamines and ethanolamines, which are comparatively less solvated by methanol exhibit the usual reactivity sequence toward methyl iodide, e.g., the higher SN2 reactivity in the more polar solvent.

The nucleophilicity of a series of primary, secondary and tertiary amines, i. e., methyl-amines, ethylamines, n-butylamines, ethanolamines and benzylamines, has been investigated by following the kinetics of the reaction of these amines with methyl iodide in benzene solvent. The effect of substituents attached to nitrogen atom on the nucleophilicity of these amines is interpreted in terms of the antagonism between steric retardation and inductive effect. The low nucleophilicity observed in the case of tertiary amines is ascribed to the steric retardation at the expense of the inductive acceleration by the substituents. No linear correlation of the nucleophilicity of amines with the pKa values has been observed.

Summary: A new application of the Catalytic Reforming Process is presented here for the production of aromatics.In this process, pure aromatics can be produced from "REFORMATE" by simple fractionation without solvent extraction. The process consists of three parts:(I) Prefractionation of naphtha into a narrow fraction which has specified boiling range, or a specified end point.(II) Aromatization of the fraction with a catalyst, like platinum on alumina, which has dehydrogenation-dehydrocyclization activity.(III) Separation of high purity aromatics from the reaction product (reformate) merely by simple fractionation without solvent extraction.