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采用从头算方法在3-21G基组上研究了1,3-环己二烯与丙烯生成exo和endo产物的反应机理.该反应生成exo和endo产物各存在三条反应途径,其中两条为分步途径,一条为协同途径.经计算研究表明:1,3-环己二烯与丙烯生成exo和endo产物的有利途径为经过一个双自由基中间体的分步过程,由丙烯端位碳原子先进攻的分步过程最为容易.对应于该过程,生成exo和endo产物的反应速控步骤的位垒值分别为80.69kJ/mol和75.58kJ/mol.表明生成endo产物的反应比生成exo产物的反应略为有利.
The ab initio method was used to study the reaction mechanism between 1,3-cyclohexadiene and propylene in exo and endo products on the 3-21G basis set. There are three reaction routes to produce exo and endo products, of which two are points Step by step and one as a synergistic route.The calculated results show that the favorable route of 1,3-cyclohexadiene with propylene to form exo and endo products is through the step-by-step process of a bidentate intermediate consisting of propylene at the terminal carbon atom The step-by-step process of the first attack is the easiest. Corresponding to this process, the barrier values for the reaction-rate control step for generating exo and endo products are 80.69 kJ / mol and 75.58 kJ / mol, respectively, indicating that the reaction to produce the endo product is more efficient than the exo product The response is slightly better.