阅读说明：本技术 基于量化计算对设计的丙烯氢氰化反应路线的验证方法 (Verification method for designed propylene hydrocyanation reaction route based on quantitative calculation ) 是由 李晓君 赵莉莉 于 2020-06-08 设计创作，主要内容包括：本发明涉及一种基于量子化学计算对设计的丙烯氢氰化反应路线的验证方法。设计的丙烯氢氰化反应路线包括三个阶段：1,钯金属发生氧化加成反应,随后进行钯的迁移,最后通过β-H消除反应得到中间体IM3；2,加入一分子丙烯发生反马氏加成反应生成稳定的中间体IM5；3,金属钯发生还原消除反应得到丙烯氢氰化后的最终产物。再完成反应路线设计后,我们搭建反应物的初始结构,然后利用量子化学程序结合密度泛函理论在溶剂模型下对反应路线进行完整的计算,随后进行能量校正对整个催化循环的位垒进行分析。(The invention relates to a verification method for a designed propylene hydrocyanation reaction route based on quantum chemical calculation. The designed reaction route for the hydrocyanation of propylene comprises three stages: 1, carrying out oxidation addition reaction on palladium metal, then carrying out palladium migration, and finally obtaining an intermediate IM3 through a beta-H elimination reaction; 2, adding one molecule of propylene to perform an anti-Markov addition reaction to generate a stable intermediate IM 5; and 3, carrying out reduction elimination reaction on the metal palladium to obtain a final product after hydrocyanation of propylene. And after the reaction route design is completed, building an initial structure of a reactant, then, completely calculating the reaction route under a solvent model by using a quantum chemical program in combination with a density functional theory, and then, analyzing the potential barrier of the whole catalytic cycle by performing energy correction.)

1. A verification method for a designed propylene hydrocyanation reaction route based on quantum chemical calculation is characterized by comprising the following steps:

a, designing a complete olefin hydrocyanation reaction route;

and B, carrying out quantum chemical calculation on the whole reaction route under a solvent model by using a quantum chemical program combined with a density functional theory, and then carrying out energy correction to analyze the potential barrier of the whole catalytic cycle.

2. The reaction scheme of claim 1 wherein the designed hydrocyanation catalyst is palladium metal and triphenylboron.

3. The catalytic metallic palladium of claim 2 wherein the metallic palladium catalyst is bis (2-diphenylphosphinophenyl) ether.

4. The scheme of claim 1, characterized by that the designed solvent for hydrocyanation is 1, 4-dioxane.

5. A quantum chemistry procedure as claimed in claim 1 wherein the quantification procedure used is gaussian 09.

6. Quantum chemistry calculations incorporating density functional theory according to claim 1, characterized in that the method used is BP86, the basis set used being either the def2svp or the def2tzvpp basis set.

7. Quantum chemistry calculations incorporating density functional theory according to claim 1 or 5, characterized in that the solvent model is a SMD model.

Technical Field

The invention relates to the field of computational chemistry analysis, in particular to a verification method for a designed propylene hydrocyanation reaction route based on quantum chemical computation.

Background

Hydrocyanation is one of the important reactions of organic hydrogenation functionalization. The hydrocyanation of olefins proceeds mainly in the course of: in 1998, Cardellii teaches the topic group and their collaborators to use aromatic compounds containing cyclohexadiene core structure as cyanogen source donor, and under the condition of free radical initiator, the hydrogenation alkylation reaction of olefin is realized. In 2002, Studer teaches that hydrosilylation and amination of olefins are achieved with silylated aromatic compounds containing cyclohexadiene core structures as cyanide donors under the presence of free radical initiators. In 2017, a subject group taught by Oestreich improves experimental conditions, and hydrogermanization and silanization reaction of olefin are realized under the catalysis of Lewis acid. Based on the three reactions, the hydrocyanation reaction of propylene under the co-catalysis of palladium and triphenylboron is designed. Most of the existing methods for verifying chemical reaction routes are characterized by specific experimental operations, and the verification method has a complex operation flow and has certain dangers in the operation process.

In recent years, with the rapid development of the field of computational chemistry and the great increase in computational computing power, it has become possible to verify the reaction route using a computational chemistry method. Due to the fact that important intermediate structures in the reaction route are given, the possibility is provided for obtaining the whole catalytic cycle by directly calculating based on the important structures in the reaction route by combining the proposition and development of a density functional theory method.

Thus, a method for validating a designed reaction route for hydrocyanation of propylene based on quantum chemical calculations is invented herein.

Disclosure of Invention

The invention relates to a verification method for a designed propylene hydrocyanation reaction route based on quantum chemical calculation.

The method comprises the following specific steps:

a, designing a complete olefin hydrocyanation reaction route;

and B, carrying out quantum chemical calculation on the whole reaction route under a solvent model by using a quantum chemical program combined with a density functional theory, and then carrying out energy correction to analyze the potential barrier of the whole catalytic cycle.

The designed reaction route for the hydrocyanation of propylene comprises three stages: 1, carrying out oxidation addition reaction on palladium metal, then carrying out palladium migration, and finally obtaining an intermediate IM3 through a beta-H elimination reaction; 2, adding one molecule of propylene to perform an anti-Markov addition reaction to generate a stable intermediate IM 5; and 3, carrying out reduction elimination reaction on the metal palladium to obtain a final product after hydrocyanation of propylene. And after the reaction route design is completed, building an initial structure of a reactant, then, completely calculating the reaction route under a solvent model by using a quantum chemical program in combination with a density functional theory, and then, analyzing the potential barrier of the whole catalytic cycle by performing energy correction. The method has the advantages of simple operation and no danger in the operation process.

Drawings

FIG. 1 is a complete route to the olefin hydrocyanation designed in this invention;

FIG. 2 is the optimized molecular configuration of IM3 and IM5 in the reaction scheme designed by the present invention;

FIG. 3 is a catalytic cycle diagram for olefin hydrocyanation in example 1.

Detailed Description

We have designed a process for the hydrocyanation of propylene in a solvent of 1, 4-dioxane under the co-catalysis of palladium and triphenylboron, the ligand of the metal palladium catalyst being bis (2-diphenylphosphinophenyl) ether, L₁. The designed reaction route for the hydrocyanation of propylene comprises three stages: 1, carrying out oxidation addition reaction on palladium metal, then carrying out palladium migration, and finally obtaining an intermediate IM3 through a beta-H elimination reaction; 2, adding one molecule of propylene to perform an anti-Markov addition reaction to generate a stable intermediate IM 5; and 3, carrying out reduction elimination reaction on the metal palladium to obtain a final product after hydrocyanation of propylene. And after the reaction route design is completed, building an initial structure of a reactant, completely calculating the reaction route by using a Gaussian 09 program under a BP86/def2tzvpp// BP86/def2svp computer by using an SMD solvent model to obtain a correct intermediate and transition state molecular structure, calculating the vibration frequency of the intermediate and the transition state molecular structure under the same calculation level, and obtaining the electronic energy of the intermediate and the transition state molecular structure, and corrected zero energy, enthalpy change energy, entropy energy and Gibbs free energy. From FIG. 3, we can know that the designed reaction route is thermodynamically and kinetically feasible, and the highest barrier of the reaction is 10.2kcal/mol, which indicates that the designed reaction route can occur under mild conditions, and verifies the correctness of the designed propylene hydrocyanation reaction route.