Author/Authors :
Bulgarevich، نويسنده , , Dmitry S and Otake، نويسنده , , Katsuto and Sako، نويسنده , , Takeshi and Sugeta، نويسنده , , Tsutomu and Takebayashi، نويسنده , , Yoshihiro and Kamizawa، نويسنده , , Chiyoshi and Shintani، نويسنده , , Daisuke and Negishi، نويسنده , , Akira and Tsurumi، نويسنده , , Chikao، نويسنده ,
Abstract :
In situ ultraviolet absorption spectroscopy was applied to study the kinetics of N-alkylation of N-methyl-o-toluidine (NMOT) by supercritical (SC) methanol without any added catalysts. The pseudo-first-order rate constants of this reaction, estimated at temperatures between 250 and 300 °C and pressures between 5.4 and 30 MPa, were in the range of 1.8×10−5–1.5×10−4 per s. The reaction apparent activation energy and volume were determined to be 104 kJ/mol and −500 cm3/mol, respectively. The results were also discussed comparing the alkylation of NMOT and other related compounds. Two possible N-alkylation mechanisms were proposed, which involved the formation of methanol hydrogen-bonded dimer or methanol autoprotolysis at high temperatures.
