CAJ | 학술논문

对对甲酚在SO3H-功能化离子液体催化下于甲基叔丁基醚的烷基化反应机理迚行研究。计算结果表明反应的选择性是由叔丁基和对甲酚的反应活性位的原子电荷、分子轨道性质及位阻效应决定的。对甲酚的2位碳原子由于由对叔丁基具有较高的库伦引力、较低的空间位阻、在前沿占有轨道中具有较高轨道系数并且形成具有较低能量的中间体A，并因此在对甲酚叔丁化反应中具有最大的活性，而2位碳原子上的叔丁基化产物2-叔丁基对甲酚和2,6-二叔丁基对甲酚是对甲酚反应最易生成的产物。并对所选离子液体的催化机理迚行了分析。
대대갑분재SO3H-공능화리자액체최화하우갑기숙정기미적완기화반응궤리중행연구。계산결과표명반응적선택성시유숙정기화대갑분적반응활성위적원자전하、분자궤도성질급위조효응결정적。대갑분적2위탄원자유우유대숙정기구유교고적고륜인력、교저적공간위조、재전연점유궤도중구유교고궤도계수병차형성구유교저능량적중간체A，병인차재대갑분숙정화반응중구유최대적활성，이2위탄원자상적숙정기화산물2-숙정기대갑분화2,6-이숙정기대갑분시대갑분반응최역생성적산물。병대소선리자액체적최화궤리중행료분석。
The reaction mechanism oftert-butylation of p-cresol catalyzed by SO3H-functionalized ionic liquid was investigated. The calculation resultsindicate that selectivity of the product dependson the fundamental natures of the reactive sites, including the molecular orbital distribution, the atomic charge distribution and the steric effect in the interaction between thetert-butyl and the p-cresol. The C2 of p-cresol has a higher superiority in Coulomb attraction, lower steric hindrance, a large orbital coefficient in the frontal occupied molecular orbitals of p-cresol. And the C2 can form intermediate A, which has the lowest total energy. Consequently, the C2 has the greatest reactivity in the tert-butylation of p-cresoland the2-tert-butyl-p-cresol and 2,6-di-tert-butyl-p-cresolare the main products of the tert-butylation of p-cresol. And the catalytic mechanism of the selected ionic liquid was discussed.