Kinetic Study of Synthesizing Ether and Inimide Compounds under Phase Transfer Catalysis

• Main Authors: Chen, Chau-je, 陳朝杰
• Other Authors: Wang, Maw-ling
• Format: Others
• Language: zh-TW
• Published: 2011
• Online Access: http://ndltd.ncl.edu.tw/handle/62080487573934951579

博士 === 國立中正大學 === 化學工程研究所 === 99 === In this dissertation, (I) the O-alkylation of phenol and hydrocinnamyl cinnamyl bromide to synthesize ether compounds in a two-phase alkaline solution of KOH/organic solvent medium under phase transfer catalysis (PTC) was studied. Those products from PTC reaction can be used as the plasticizers, anesthetics, perfume, and liquid crystal materials and others in industries. (II) The N-alkylation of succinimide and hydrocinnamyl bromide to synthesize inimide compounds in a two-phase alkaline free-solution of KOH/organic solvent medium under phase transfer catalysis (PTC) was also studied in this thesis. Those products from PTC reaction can be used in biochemical activities, cosmetics, and medical drugs etc in industries. Besides, the technologies of phase transfer catalysis are more and more diversity, and the ways of the power are also update. Including traditional heat and mechanical agitations, we can use the ways of ultrasonic chemistries or microwave chemistries in phase transfer catalysis. The primary purposes of this dissertation are to study the phase-transfer catalytic reaction for ether and inimide compounds, reaction mechanism, kinetics, distribution of active catalyst, and other related theories. Several rigid conclusions were obtained from the experimental results.(a)In the present study, systems are confined within the alkylationreactions. (i)The reaction of phenol and hydrocinnamyl bromide to synthesize ether compounds divided by phase transfer catalysis and to combination ultrasonic chemistries in the reaction of O-alkylation. (ii)The reaction of phenol and hydrocinnamyl bromide to synthesize nine kinds of ether compounds divided by phase transfer catalysis and to combination ultrasonic chemistries in the reaction of O-alkylation. (iii)The reaction of succinimide and hydrocinnamyl bromide to synthesize inimide compounds divided by phase transfer catalysis, and to combination ultrasonic chemistries and microwave chemistries in the reaction of N-alkylation. High reactivity of organophilic catalysts were obtained by reacting the aqueous reactants and the phase transfer catalysts. For this, the O-alkylation and N-alkylation reaction are effectively enhanced by the phase transfer catalyst. The reaction type was confirmed as an SN2 reaction by using various bromoalkanes.(b)In the reaction of O-alkylation, the pseudo steady-state hypothesis, and two-film theory are successfully applied to describe the reaction behaviors. In the reaction of N-alkylation, the chemical reaction rate, dynamical equilibrium, and induction period are successfully applied to describe the reaction behaviors. In the opinion, the reaction rates of O- (N-) alkylation follow the pseudo first-order rate law.(c) The two-phase mass transfer rate of the active catalyst is rapid, because of its high organophilicity in the two-phase transfer. Thus, the concentration of the active catalyst in the organic phase keeps at a constant value at a high agitation speed. The organic reaction is the rate-determining step and the active energy is larger than 10 kcal/mol. (d) The O-alkylation and N-alkylation reactions are effectively enhanced in the mild conditions via the phase transfer catalyst. Besides, the ultrasonic and microwave technologies can contact reactants fully and effectively raise the rate of the reaction. (e) As the results of experiments, the reaction rate is increased with the increase in agitation speed, amounts of KOH, temperature, amounts of catalyst, the dielectric constant of solvent, symmetry and organophilicity of the catalyst cation. The reason for these factors can be explained by mass transfer rate, Arrhenius equation, concentration and reactivity of the active catalyst. The amounts of water were effected the concentration of alkali salt, solvation, contact area of the reaction, and the concentration of anion in aqueous-phase. However, the concentration of anion in aqueous-phase was decreased by using larger amount of water as described in the reaction of O-alkylation. Thus, an optimal value of amounts of water is obtained.