NDLI: Transition state leading to β-O′ quinonemethide intermediate of p-coumaryl alcohol analyzed by semi-empirical molecular orbital calculation

Content Provider	Springer Nature Link
Author	Shigematsu, Mikiji Kobayashi, Takayuki Taguchi, Hiroyasu Tanahashi, Mitsuhiko
Copyright Year	2006
Abstract	The radical coupling reaction leading to the β-0′ quinonemethide intermediate of p-coumaryl alcohol was analyzed by semi-empirical molecular orbital calculation with MOPAC2002. By analyzing the radical monomer in a one-electron oxidation, the spin density of the unpaired electron at the 4-oxygen was less than half of the values at the C1, C3, C5, and Cβ positions. By analyzing the transition state during the radical coupling reaction, the activation enthalpy was evaluated as 9.76 kcal/mol, which corresponds to the activation energies for the propagation of common vinyl polymers. From the analysis of atomic interactions in the transition state, it was found that the activation enthalpy was largely composed of a high coulombic repulsion between Cβ of the first monomer and the phenolic oxygen of the second monomer. After passing the transition state, the two radical monomers formed a metastable quinone-methide intermediate. The optimum conformation of the quinonemethide intermediate was formed from the meta-stable conformation through a second transition state with a small energy barrier.
Starting Page	128
Ending Page	133
Page Count	6
File Format	PDF
ISSN	14350211
Journal	Journal of Wood Science
Volume Number	52
Issue Number	2
e-ISSN	16114663
Language	English
Publisher	Springer-Verlag
Publisher Date	2006-04-07
Publisher Place	Tokyo
Access Restriction	Subscribed
Subject Keyword	Lignin Radical coupling reaction Transition state Molecular orbital calculation Activation enthalpy Characterization and Evaluation Materials Ceramics, Glass, Composites, Natural Methods Wood Science & Technology
Content Type	Text
Resource Type	Article
Subject	Biomaterials Forestry

Sl.	Authority	Responsibilities	Communication Details
1	Ministry of Education (GoI), Department of Higher Education	Sanctioning Authority	https://www.education.gov.in/ict-initiatives
2	Indian Institute of Technology Kharagpur	Host Institute of the Project: The host institute of the project is responsible for providing infrastructure support and hosting the project	https://www.iitkgp.ac.in
3	National Digital Library of India Office, Indian Institute of Technology Kharagpur	The administrative and infrastructural headquarters of the project	Dr. B. Sutradhar bsutra@ndl.gov.in
4	Project PI / Joint PI	Principal Investigator and Joint Principal Investigators of the project	Dr. B. Sutradhar bsutra@ndl.gov.in Prof. Saswat Chakrabarti will be added soon
5	Website/Portal (Helpdesk)	Queries regarding NDLI and its services	support@ndl.gov.in
6	Contents and Copyright Issues	Queries related to content curation and copyright issues	content@ndl.gov.in
7	National Digital Library of India Club (NDLI Club)	Queries related to NDLI Club formation, support, user awareness program, seminar/symposium, collaboration, social media, promotion, and outreach	clubsupport@ndl.gov.in
8	Digital Preservation Centre (DPC)	Assistance with digitizing and archiving copyright-free printed books	dpc@ndl.gov.in
9	IDR Setup or Support	Queries related to establishment and support of Institutional Digital Repository (IDR) and IDR workshops	idr@ndl.gov.in

Substituent effects of 3,5-disubstituted p-coumaryl alcohols on their oxidation using horseradish peroxidase–H2O2 as the oxidant

Analysis on residue formation during wood liquefaction with polyhydric alcohol

Solvent effects on the electronic state of monolignol radicals as predicted by molecular orbital calculations

Semi-quantitative method to evaluate the α-carbonyl content in lignin

Quantitative evaluation of milling effects on lignin structure during the isolation process of milled wood lignin

Stereochemistry and biosynthesis of 8-O-4′ neolignans in Eucommia ulmoides: diastereoselective formation of guaiacylglycerol-8-O-4′-(sinapyl alcohol) ether

Effect of ozone treatment of wood on its liquefaction

Lignin fragments rich in detached side-chain structures found in water-soluble LCC

Biosynthesis of a syringyl 8-O-4′ neolignan in Eucommia ulmoides: formation of syringylglycerol-8-O-4′-(sinapyl alcohol) ether from sinapyl alcohol

Transition state leading to β-O′ quinonemethide intermediate of p-coumaryl alcohol analyzed by semi-empirical molecular orbital calculation

Similar Documents

Substituent effects of 3,5-disubstituted p-coumaryl alcohols on their oxidation using horseradish peroxidase–H2O2 as the oxidant

Analysis on residue formation during wood liquefaction with polyhydric alcohol

Solvent effects on the electronic state of monolignol radicals as predicted by molecular orbital calculations

Semi-quantitative method to evaluate the α-carbonyl content in lignin

Quantitative evaluation of milling effects on lignin structure during the isolation process of milled wood lignin

Stereochemistry and biosynthesis of 8-O-4′ neolignans in Eucommia ulmoides: diastereoselective formation of guaiacylglycerol-8-O-4′-(sinapyl alcohol) ether

Effect of ozone treatment of wood on its liquefaction

Lignin fragments rich in detached side-chain structures found in water-soluble LCC

Biosynthesis of a syringyl 8-O-4′ neolignan in Eucommia ulmoides: formation of syringylglycerol-8-O-4′-(sinapyl alcohol) ether from sinapyl alcohol

Transition state leading to β-O′ quinonemethide intermediate of p-coumaryl alcohol analyzed by semi-empirical molecular orbital calculation