DFT studies of solvent effect in hydrogen abstraction reactions from different allyl-type monomers with benzoyl radical

BMC Chemistry

Research

Shibo Lin¹  Xi Chen¹  Xuanhao Li¹  Lihui He¹  Xiaotian Zhao¹  Chun Liu¹  Xirui Guo¹  YaMing Li²  Guodong Ye³ 

[1]Department of Pharmacy, Chengdu Second Peoples Hospital, 610017, Chengdu, People’s Republic of China

[2]Department of Stomatology, Chengdu Second Peoples Hospital, 610017, Chengdu, People’s Republic of China

[3]Guangzhou Municipal and Guangdong Provincial Key Laboratory of Molecular Target and Clinical Pharmacology, the NMPA and State Key Laboratory of Respiratory Disease, School of Pharmaceutical Sciences and the Fifth Affiliated Hospital, Guangzhou Medical University, 511436, Guangzhou, China

关键词: Allyl;    Solvent effect;    DFT calculations;    Hydrogen abstraction reaction;    Transition state;   

DOI  :  10.1186/s13065-023-01027-9

 received in 2023-04-04, accepted in 2023-08-29,  发布年份 2023

来源: Springer

【 摘 要 】

Inert allyl-type monomers have been widely documented due to reduce degradation chain transfer. Recently, we and others discovered that the [3 + 2] cyclization reaction process by a photo-driven radical reaction, which can accelerate the polymerization. It was discovered that allyl ether monomers had much higher reactivity than other allyl monomers in the suspension photopolymerization initiated by Type I photoinitiator. Since the hydrogen abstraction reaction (HAR) is the initial step of cyclization, and in order to clarify the influence of solvents effect, three allyl-type monomers were employed, containing “O”, “N” and “S” atom as hydrogen donors. The benzoyl radical obtained from cleavage of photoinitiator was chosen as hydrogen acceptors. We explored the hydrogen abstraction reaction in different solvents (methanol, water and DMSO) by quantum chemistry for geometry and energy. An investigation was undertaken regarding the structural orbital by electrostatic potential (ESP) and topological analysis (ELF and LOL). The findings were also combined with the distortion model and transition state theory. We obtained the molecular interactions used independent gradient method in the Hirshfeld molecular density partition (IGMH). The Eckart’s correction allowed to examine the driving factors of the hydrogen abstraction reaction tunnels and these reactions constant rates are determined in the range of 500–2500 K depending on the modified Arrhenius form in different solvents effect. Our results can provide an answer for the different reactivities.

【 授权许可】

CC BY   
© Springer Nature Switzerland AG 2023

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