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Volumn 65, Issue 5, 2000, Pages 1376-1389

Flash vacuum pyrolysis of methoxy-substituted lignin model compounds

Author keywords

[No Author keywords available]

Indexed keywords

BENZALDEHYDE; BIBENZYL DERIVATIVE; LIGNIN; PROTON; TOLUENE;

EID: 0034629342     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo991479k     Document Type: Article
Times cited : (253)

References (121)
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    • (a) Antal, M. J., Jr. Biomass Pyrolysis: A Review of the Literature. In Advances in Solar Energy; Boer, K. W., Duffie, J. A., Eds.; ASES Publication: New York, 1985; Vol. 2, pp 175-255 and references therein.
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    • Importance of Surface Reactions in Pyrolysis Units. In Albright, L. F., Crynes, B. L., Corcoan, W. H., Eds.; Academic: New York
    • (a) Albright, L. F.; Tsai, T. C.-H. Importance of Surface Reactions in Pyrolysis Units. In Pyrolysis: Theory and Industrial Pratice; Albright, L. F., Crynes, B. L., Corcoan, W. H., Eds.; Academic: New York, 1983; pp 233-254.
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    • Albright, L.F.1    Tsai, T.C.-H.2
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    • Laboratory Reactors for Pyrolysis Reactions. In Albright, L. F., Crynes, B. L., Corcoan, W. H., Eds.; Academic: New York
    • (b) Come, G.-M. Laboratory Reactors for Pyrolysis Reactions. In Pyrolysis: Theory and Industrial Pratice; Albright, L. F., Crynes, B. L., Corcoan, W. H., Eds.; Academic: New York, 1983; pp 255-275.
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  • 41
    • 33847555839 scopus 로고    scopus 로고
    • At 600 C, thé conversion of PPE was 46.8%, and the mass balance was 99.6%. The pyrolysis products included phenol (56.2 mol %), styrène (40.1 mol %), benzène (1.5 mol %), benzaldehyde (0.7 mol %), toluène (0.6 mol %), ethylbenzene (0.35 mol %), bibenzyl (0.2 mol %), and o-(2-phenylethyl)phenol (0.1 mol %) and p-(2-phenylethyl)phenol (0.1 mol %).
    • At 600 C, thé conversion of PPE was 46.8%, and the mass balance was 99.6%. The pyrolysis products included phenol (56.2 mol %), styrène (40.1 mol %), benzène (1.5 mol %), benzaldehyde (0.7 mol %), toluène (0.6 mol %), ethylbenzene (0.35 mol %), bibenzyl (0.2 mol %), and o-(2-phenylethyl)phenol (0.1 mol %) and p-(2-phenylethyl)phenol (0.1 mol %).
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    • and references therein.
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    • -1.34
    • -1.34
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    • note
    • + and the slope, p, was -1.36 (at 335 °C) indicating that moderate carbocationic character developed on the carbon containing the leaving group in the transition state,
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    • 2 and PPE is 0.55 ±0.08% and 0.71 ±0.2%, respectively.
    • 2 and PPE is 0.55 ±0.08% and 0.71 ±0.2%, respectively.
  • 64
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    • This ratio can also be calculated by the yield of benzyl fragments (i.e., toluene plus 2 × bibenzyl), but toluene and o-cresol (0.45 ±0.05 mol %) are also formed by C-C homolysis of o-(2-phenylethyl)phenol.
    • This ratio can also be calculated by the yield of benzyl fragments (i.e., toluene plus 2 × bibenzyl), but toluene and o-cresol (0.45 ±0.05 mol %) are also formed by C-C homolysis of o-(2-phenylethyl)phenol.
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    • note
    • -1 11
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    • note
    • 5 - 62.7/θ. At 500 °C, the ratio of the rate constants is 3.98:1.
  • 73
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    • note
    • + and σ, respectively, indicating that in the anisoles, direct conjugation with the aromatic ring is not important,
  • 77
    • 33847565167 scopus 로고    scopus 로고
    • Phenoxy radicals abstract hydrogen atoms slightly faster (16-fold at 375 °C) than benzyl radicals
    • Phenoxy radicals abstract hydrogen atoms slightly faster (16-fold at 375 °C) than benzyl radicals,
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    • note
    • -1) = 8.6-21.8/0. Assuming no polar effects in the hydrogen transfer reaction, the Evans-Polanyi correlation (E = αAWnn) + C) can be used with a = 0.5, i.e., a symmetrical transition state, and C is determined from the base reaction. To construct the hypothetical thermoneutral reaction for reaction between aliphatic and benzylic centers, C = EtîK - 0.5(Aff°base).
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    • note
    • 34-57 Another method to estimate this number uses the O-H BDE of guaiacol, (ABDE 3.9 kcal mol"1, relative to phenol in solution)64 estimated as 83.1 kcal mol"1 in the gas phase,26 and the ΔH°t (guaiacol) = -58 kcal mol'1.27 The A/T298 of o-CH3OC6H4O' is estimated as -27.0 kcal mol"1. The A//°29a of o-'CH2OC6H40H is estimated as -17.1 kcal mol-J from ΔH°298 of C6H5OCH2- (25 kcal mol-1)11 and group additivity (~CB-H + CB-O + O-CaH). Another method to estimate this number uses the BDE of the OCHz-H bond as 93.3 kcal mol"1, which is assumed to be similar to that of dimethyl ether.11 The tf°29s of o-'CHzOCeHtOH is estimated as -16.8 kcal mol"1 by this procedure. An average value for the 1,5hydogen shift (8.9 kcal mol'1) will be used.
  • 89
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    • and references therein. The rate constant for the 1,5hydrogen shift from 1-hexyl to 2-hexyl radical has been measured as log (s-1) = 9.5-11.6/0.
    • Dôbé, S.; Berces, T.; Réti, F.; Màrta, F. Int. J. Chem. Kinet. 1987, 19, 895 and references therein. The rate constant for the 1,5hydrogen shift from 1-hexyl to 2-hexyl radical has been measured as log (s-1) = 9.5-11.6/0.
    • (1987) Int. J. Chem. Kinet. , vol.19 , pp. 895
    • Dôbé, S.1    Berces, T.2    Réti, F.3    Màrta, F.4
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    • Dorigo, A. E.; McCarrick, M. A.; Loncharich, R. J.; Houk, K. N. J. Am. Chem. Soc. 1990,112, 7508. Theoretical calculations (UMP2/ 6-31G) on a series of 1,5-hydrogen atom transfer reactions'to oxygen from the Barton reaction, Norrish Type II reaction, alcohol radical cation rearrangement, and retro-ene reaction have also found lower (-3.6, -4.8, -7.1, and -4.9 cal mol'1 K'1, respectively) than that found experimentally.
    • (1990) J. Am. Chem. Soc. , vol.112 , pp. 7508
    • Dorigo, A.E.1    McCarrick, M.A.2    Loncharich, R.J.3    Houk, K.N.4
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    • note
    • -1).
  • 100
    • 33847543675 scopus 로고    scopus 로고
    • note
    • -1) was calculated from ΔH°29S (o-benzoquinone) and other known group contributions.57
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    • Fisher, H., Ed.; Landolt-Börnstein; Springer: Germany, VolII/18Dl, pp
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    • Assuming the rate constant for decarbonylation is similar to the benzoyl radical (log k (s'1) = 14.6-29.4/0). Solly, R. K.; Benson, S. W. J. Am. Chem. Soc. 1971, 93, 2127.
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  • 114


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