Abstract
Effects of side chain hydroxyl groups on pyrolytic β-ether cleavage of phenolic model dimers were studied with various deoxygenated dimers under pyrolysis conditions of N2/400°C/1 min. Although phenolic dimer with hydroxyl groups at the C α − and C γ −positions was much more reactive than the corresponding nonphenolic type, deoxygenation at the C γ -position substantially reduced the reactivity up to the level of the nonphenolic type. These results are discussed with the cleavage mechanism via quinone methide intermediate formation, which is activated through intramolecular hydrogen bonds between C α − and C γ − hydroxyl groups.
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Haw JF, Schultz TP (1985) Carbon-13 CP/MAS NMR and FT-IR study of low-temperature lignin pyrolysis. Holzforschung 39:289–296
Brežný R, Mihálov V, Kováčik V (1983) Low temperature thermolysis of lignins. I. Reactions of β-O-4 model compounds. Holzforschung 37:199–204
Kawamoto H, Horigoshi S, Saka S (2006) Pyrolysis reactions of various lignin model dimers. J Wood Sci. DOI:10.1007/s10086-006-0834-z
Whiting P, Goring DAI (1982) Phenolic hydroxy analysis of lignin by pyrolytic gas chromatography. Paperi ja Puu 10:592–595
Klein MT, Virk PS (1983) Model pathways in lignin thermolysis. 1. Phenethyl phenyl ether. Ind Eng Chem Fundam 22:35–45
Kislitsyn AN, Rodionova ZM, Savinykh VI (1971) Thermal decomposition of monophenylglycol ether. Khim Drev 9:131–136
Autrey ST, Alnajjar MS, Nelson DA, Franz JA (1991) Absolute rate constants for β-scission reaction of the 1-phenyl-2-phenoxypropyl radical: a model for radical reactions of lignin. J Org Chem 56:2197–2202
Britt PF, Buchanan AC, Thomas KB, Lee S-K (1995) Pyrolysis mechanisms of lignin: surface-immobilized model compound investigation of acid-catalyzed and free-radical reaction pathways. J Anal Appl Pyrolysis 33:1–19
Evans RJ, Milne TA, Soltys MN (1986) Direct mass-spectrometric studies of the pyrolysis of carbonaceous fuels III. Primary pyrolysis of lignin. J Anal Appl Pyrolysis 9:207–236
Sano Y (1975) Hydrolysis of lignin with dioxane and water XV. Hydrolysis of 1-guaiacyl-2-guaiacoxy-1-propene-3-ol and guaiacylglycerol-β-guaiacyl ether. Mokuzai Gakkaishi 21:508–519
Sano Y (1989) Reactivity of β-O-4 linkages in lignin during solvolysis pulping. Degradation of β-O-4 lignin model compounds. Mokuzai Gakkaishi 35:813–819
Kishimoto T, Sano Y (2002) Delignification mechanism during high-boiling solvent pulping. Part 2. Homolysis of guaiacylglycerol β-guaiacyl ether. Holzforschung 56:623–631
Tanahashi M, Karina M, Tamabuchi K, Higuchi M (1989) Degradation mechanism of lignin accompanying steam explosions I. Degradation products of lignin and β-O-4 lignin substructure model dimmers. Mokuzai Gakkaishi 35:135–143
Kawamoto H, Nakamura T, Saka S (2004) Mechanism of the pyrolytic cleavage of ether structures in lignin. Proceedings of the 49th Lignin Symposium, Tsukuba, November 18, 19, pp 85-88
Freudenberg K, Müller HG (1953) Synthetische Versuche im Zusammenhang mit dem Lignin. Liebigs Ann Chem 584:40–53
Johanson B, Miksche GE (1972) über die Benzyl-arylätherbindung im Lignin II. Versuche an Modellen. Acta Chem Scand 26:289–308
Dimmel DR, Shepard D (1982) Synthesis of lignin model dimers by novel techniques. J Wood Chem Technol 2:297–315
McKague AB, Kang GJ, Reeve DW (1993) Reaction of a lignin model dimer with chlorine and chlorine dioxide. Horzforschung 47:497–500
Sundholm F (1968) On the synthesis of guaiacyl ethers of 1-veratryl-2-propanol and 1-guaiacyl-2-propanol. Acta Chem Scand 22:854–858
Ponomarev DA (1997) Formation of quinone methides: an alternative pathway to thermal degradation of some β-O-4-ether as compounds modeling lignin. Russ J Appl Chem 70:824–826
Smith GG, Yates BL (1965) Pyrolysis studies. XV. Thermal retrograde aldol condensation of b-hydroxy ketones. J Chem Soc 2067–2078
Mole T (1960) Thermal retro-aldol reaction. Chem Ind 1164–1165
Smith GG, Taylor R (1961) Kinetic evidence for the mechanism of pyrolysis of β-hydroxyolefines. Chem Ind (London) 949–950
Arnord RT, Elmer OC, Dodson RM (1950) Thermal decarboxylation of unsaturated acids. J Am Chem Soc 72:4359–4361
Smith GG, Blau SE (1964) Decarboxylation. I. Kinetic study of the vapor phase thermal decarboxylation of 3-butenoic acid. J Phys Chem 68:1231–1234
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Kawamoto, H., Horigoshi, S. & Saka, S. Effects of side-chain hydroxyl groups on pyrolytic β-ether cleavage of phenolic lignin model dimer. J Wood Sci 53, 268–271 (2007). https://doi.org/10.1007/s10086-006-0839-7
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DOI: https://doi.org/10.1007/s10086-006-0839-7