Citation: JIANG Xiao-yan, LU Qiang, DONG Xiao-chen, HU Bin, DONG Chang-qing. Theoretical study on the effects of the substituent groups on the homolysis of the ether bond in lignin trimer model compounds[J]. Journal of Fuel Chemistry and Technology, ;2016, 44(3): 335-341. shu

Theoretical study on the effects of the substituent groups on the homolysis of the ether bond in lignin trimer model compounds

National Engineering Laboratory for Biomass Power Generation Equipment, North China Electric Power University, Beijing 102206, China

Corresponding author: LU Qiang, qianglu@mail.ustc.edu.cn
Received Date: 25 September 2015
Revised Date: 5 December 2015

Fund Project: National Natural Science Foundation of China 51576064and Fundamental Research Funds for the Central Universities 2014ZD17

Figures(2)

The homolytic bond dissociation energies (BDEs) of C_α-O and C_β-O bonds in 27 lignin trimer model compounds were calculated by employing density functional theory methods at M062X level with 6-31++G (d, p) basis set; the effects of various substituent groups (CH₃, CH₂OH and OCH₃) at different positions on the BDEs of C_α-O and C_β-O bonds were investigated. The results indicated that a single methoxyl group at R₂ or R₃ has a minor influence on the BDE of C_β-O bond, whereas two methoxyl groups at R₂ and R₃ lead to an obvious decrease in the BDE of C_β-O bond. The decrement in the BDE of C_β-O bond from the methoxyl groups at R₂ and R₃ can be enhanced by the methoxyl groups at R₄ and R₅, but is hardly influenced by the substituent groups at R₁. Meanwhile, the BDE of C_α-O bond is gradually reduced when the H atoms at R₄ and R₅ are successively substituted with methoxyl groups; the decrement in the BDE of C_α-O bond from the methoxyl groups at R₄ and R₅ can be strengthened by the methoxyl groups at R₂ and R₃. Furthermore, the methyl and hydroxymethyl groups at R₁ can gradually increase the BDE of C_α-O bond and this effect is weakened when the H atoms at R₂ and R₃ are successively substituted with methoxyl groups. The methyl group at R₁ has little influence on the BDE of C_β-O bond, which is however dramatically increased by the hydroxymethyl group at R₁.
- lignin trimer model compound,
- substituent group,
- homolysis,
- bond dissociation energy,
- density functional theory
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