Skip to main content
SpringerLink
Log in

Nucleus Exchange Reaction

  • Chapter
Methods in Lignin Chemistry

Part of the book series: Springer Series in Wood Science ((SSWOO))

Abstract

A chemical method to degrade lignin in a medium consisting of boron trifluoride and excess phenol was originally developed by Funaoka and Abe (1978a,b, 1980a,b, 1982a,b,c,d,e,f,g). In this method, Cα-aryl carbon-carbon linkages in phenylpropane units are selectively and quantitatively cleaved, following phenolation at the Cα position, releasing phenyl nuclei typified by guaiacol (1) (see Fig. 6.6.1 for structures of compounds) from guaiacyl (softwood) lignins. The guaiacol subsequently is partially demethylated to catechol (2). These transformations are illustrated in Fig. 6.6.2. The key step in this sequence, the release of a phenyl nucleus on reaction with phenol, was termed nucleus exchange (NE) by the original authors.

This is a preview of subscription content, log in via an institution to check access.

Access this chapter

Log in via an institution
Chapter
USD 29.95
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
eBook
USD 149.00
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
Softcover Book
USD 199.99
Price excludes VAT (USA)
  • Compact, lightweight edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info

Tax calculation will be finalised at checkout

Purchases are for personal use only

Institutional subscriptions

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  • Abe I, Funaoka M, Kodama M (1987) Phenolic nuclei of condensed tannins. Approaches by the phenyl nucleus-exchange method. Mokuzai Gakkaishi 33: 582–588

    CAS  Google Scholar 

  • Adler E, Lundquist K (1961) Estimation of uncondensed phenolic units in spruce lignin. Acta Chem Scand 15: 223–228

    Article  CAS  Google Scholar 

  • Chiang VL, Funaoka M (1988) The formation and quantity of diphenylmethane-type structures in residual lignin during kraft delignification of Douglas-fir. Holzforschung 42: 385–391

    Article  CAS  Google Scholar 

  • Chiang VL, Funaoka M (1990a) The dissolution and condensation reactions of guaiacyl and syringyl units in residual lignin during kraft delignification of sweetgum. Holzforschung 44: 147–155

    Article  CAS  Google Scholar 

  • Chiang VL, Funaoka M (1990b) The difference between guaiacyl and guaiacyl-syringyl lignins in their responses to kraft delignification. Holzforschung 44: 309–313

    Article  CAS  Google Scholar 

  • Chiang VL, Funaoka M, Wang X (1988) Structural changes of lignin is soda and soda-AQ delignification of wheat straw. Nonwood plant fiber pulping series No. 18, Tappi Press, Atlanta, GA, 51–55

    Google Scholar 

  • Chiang VL, Kolppo K, Stokke DD, Funaoka M (1989a) Structure changes of lignin in kraft and acid sulphite delignification of western hemlock. Proc Int Symp Wood Pulp Chem, Raleigh, NC. Tappi Press, Atlanta, GA, pp. 593–597

    Google Scholar 

  • Chiang VL, Stokke DD, Funaoka M (1989b) Lignin fragmentation and condensation reactions in middle lamella and secondary wall regions during kraft pulping of Douglas-fir. J Wood Chem Technol 9: 61–83

    Article  CAS  Google Scholar 

  • Funaoka M (1984) Studies on the reaction of lignin in the presence of phenol and boron trifluoride. Bull Mie Univ For Tsu, Japan 13: 1–154

    Google Scholar 

  • Funaoka M, Abe I (1978a) The reaction of lignin under the presence of phenol and boron trifluoride. I. On the formation of catechol from MWL, dioxane lignin and kraft lignin Mokuzai Gakkaishi 24:256–261

    CAS  Google Scholar 

  • Funaoka M, Abe I (1978b) The reaction of lignin under the presence of phenol and boron trifluoride. II. The effect of methoxyl group and ethylene double bond on the formation of catechol. Mokuzai Gakkaishi 24: 892–897

    CAS  Google Scholar 

  • Funaoka M, Abe I (1980a) The reaction of lignin under the presence of phenol and boron trifluoride. III. The chemical structure of lignin required for the liberation of phenyl nucleus. Mokuzai Gakkaishi 26: 334–341

    CAS  Google Scholar 

  • Funaoka M, Abe I (1980b) The reaction of lignin under the presence of phenol and boron trifluoride. IV. The structure formed by the nuclear exchange for phenol. Mokuzai Gakkaishi 26: 342–346

    CAS  Google Scholar 

  • Funaoka M, Abe I (1982a) The reaction of lignin under the presence of phenol and boron trifluoride. V. The role of boron trifluoride and phenol on the formation of catechol. Mokuzai Gakkaishi 28: 522–528

    CAS  Google Scholar 

  • Funaoka M, Abe I (1982b) The reaction of lignin under the presence of phenol and boron trifluoride. VI. The behavior of lignin units unable to form the diphenylmethane structure. Mokuzai Gakkaishi 28: 529–534

    CAS  Google Scholar 

  • Funaoka M, Abe I (1982c) The reaction of lignin under the presence of phenol and boron trifluoride. VII. The cleavage of C-C linkage by disproportionation. Mokuzai Gakkaishi 28: 563–569

    CAS  Google Scholar 

  • Funaoka M, Abe I (1982d) The reaction of lignin under the presence of phenol and boron trifluoride. VIII. The decomposition of softwood lignin. Mokuzai Gakkaishi 28: 627–634

    CAS  Google Scholar 

  • Funaoka M, Abe I (1982e) The reaction of lignin under the presence of phenol and boron trifluoride. IX. The decomposition of hardwood lignin. Mokuzai Gakkaishi 28: 635–643

    CAS  Google Scholar 

  • Funaoka M, Abe I (1982f) The reaction of lignin under the presence of phenol and boron trifluoride. X. The properties of residual lignin and the degradation mechanism of lignin. Mokuzai Gakkaishi 28: 705–717

    CAS  Google Scholar 

  • Funaoka M, Abe I (1982g) The reaction of lignin under the presence of phenol and boron trifluoride. XI. The decomposition of industrial lignin. Mokuzai Gakkaishi 28: 718–726

    CAS  Google Scholar 

  • Funaoka M, Abe I (1983a) The nuclear exchange method for estimation of lignin structure. Proc Int Symp Wood Pulp Chem, Tsukuba City, Japan, Vol. 4. Tappi Press, Tokyo, pp. 79–84

    Google Scholar 

  • Funaoka M, Abe I (1983b) Structures of softwood lignins dissolved by successive acidolysis. Mokuzai Gakkaishi 29: 781–788

    CAS  Google Scholar 

  • Funaoka M, Abe I (1983c) On the distribution of condensed structure in kraft lignin. Bull Mie Univ For, Tsu, Japan 12: 27–39

    Google Scholar 

  • Funaoka M, Abe I (1984) Analysis of chemical structures of hardwood lignins by nuclear-exchange method. Mokuzai Gakkaishi 30: 68–73

    CAS  Google Scholar 

  • Funaoka M, Abe I (1985) Degradation of protolignin by the nuclear exchange method. Mokuzai Gakkaishi 31: 671–676

    CAS  Google Scholar 

  • Funaoka M, Abe I (1986) Condensation degree of softwood protolignin. Bull Fac Agric, Mie Univ, Tsu, Japan 73: 67–74

    Google Scholar 

  • Funaoka M, Abe I (1987a) Phenyl nucleus-exchange method for the degradation of lignin. Wood Sci Technol 21: 261–279

    CAS  Google Scholar 

  • Funaoka M, Abe I (1987b) Selective cleavage of Ca-aryl bonds in lignin. Bull Mie Univ, For, Tsu, Japan 15: 97–109

    Google Scholar 

  • Funaoka M, Abe I, Yoshimura M (1977) On the reaction of hydrotropic lignin with phenol and formaldehyde. Mokuzai Gakkaishi 23: 571–578

    CAS  Google Scholar 

  • Funaoka M, Kako T, Abe I (1990a) Condensation of lignin during heating of wood. Wood Sci Technol 24: 277–288

    Article  CAS  Google Scholar 

  • Funaoka M, Shibata M, Abe I (1990b) Structure and depolymerization of acid-condensed lignin. Holzforschung 44: 357–366

    Article  CAS  Google Scholar 

  • Funaoka M, Shibata M, Kako T, Abe I (1988) Structure of highly condensed lignins and their depolymerization by phenolation. Proc Cellucon 88 Japan, Nov.28–Dec.1. Kyoto, Japan, The Society of Fiber Science and Technology, Kyoto, Japan, p 160

    Google Scholar 

  • Gierer J (1982) The chemistry of delignification. A general concept. Holzforschung 36: 43–51

    Article  CAS  Google Scholar 

  • Ishikawa H (1958) Phenolation of lignin. Memoirs of Ehime Univ, Sect 6 (Agric) 4: 1–94

    Google Scholar 

  • Kratzl K, Buchtela K, Gratzl J, Zauner J, Ettingshausen O, (1962) Lignin and plastics: the reactions of lignin with phenol and isocyanates. Tappi 45: 113–119

    CAS  Google Scholar 

  • Kratzl K, Oburger M (1980a) Kondensationsreaktionen von Lignin-Modellsubstanzen mit Phenol unter saurer Katalyse. Holzforschung 34: 11–16

    Article  CAS  Google Scholar 

  • Kratzl K, Oburger M. (1980b) Kondensationsreaktionen von Lignin-Modellsubstanzen mit Phenol unter saurer Katalyse. 2. Mitt. Holzforschung 34: 191–196

    Article  CAS  Google Scholar 

  • Lai YZ, Sarkanen KV (1971) Isolation and structural studies. In: Sarkanen KV, Ludwig CH (eds) Lignin. Occurrence, formation, structure and reaction. Wiley-Interscience, New York, 165–240

    Google Scholar 

  • Lenz BL (1968) Application of nuclear magnetic resonance spectroscopy to characterization of lignin. Tappi 51: 511–519

    CAS  Google Scholar 

  • Ludwig CH, Nist BJ, McCarthy JL (1964) Lignin XIII. The high resolution nuclear magnetic resonance spectroscopy of protons in acetylated lignins. J Am Chem Soc 86: 1196–1201

    Article  CAS  Google Scholar 

  • Manders WF (1987) Solid-state C-13 NMR determination of the syringyl/guaiacyl ratio in hardwoods. Holzforschung 41: 83–88

    Article  Google Scholar 

  • Marton J (1964) On the structure of kraft lignin. TAPPI 47: 713–719

    CAS  Google Scholar 

  • Meshitsuka G, Nakano J (1985) Structural characteristics of compound middle lamella lignin. J Wood Chem Technol 5: 391–404

    Article  CAS  Google Scholar 

  • Morohoshi N, Sakakibara A (1971) The chemical composition of reaction wood. Mokuzai Gakkaishi 17: 393–399

    CAS  Google Scholar 

  • Nimz H (1969) Kondensationsreaktionen des Lignins, Umsetzung von Lignin-Modellsubstanzen mit Resorcin und Salzaure. Holzforschung 23: 84–88

    Article  CAS  Google Scholar 

  • Oda R, Ogata Y (1941) Reaction of diphenylmethane and its derivatives with aluminium chloride. Kogyo Kagaku Zasshi 44: 961–963

    Google Scholar 

  • Radziewanowski C (1894) Beiträge zur Kenntnis der Wirkungsweise des Aluminiumchlorids. Berichte 27: 3235–3238

    CAS  Google Scholar 

  • Tai S, Nakano J, Migita N (1968) Studies on utilization of lignin VI. Activation of thiolignin with phenol. Mokuzai Gakkaishi 14: 40–45

    CAS  Google Scholar 

  • Terashima N, Seguchi Y (1987) Factors affecting the formation of condensed structures in lignin. Proc Int Symp Wood Pulp Chem, Paris, France, Vol. 2. Imprimerie Jacques Poncet, Bresson, France, pp. 1–4

    Google Scholar 

  • Terashima N, Tomimura Y, Araki H (1979) Heterogeneity in formation of lignin III. Formation of condensed type structure with bond at position 5 of guaiacyl nucleus. Mokuzai Gakkaishi 25: 595–599

    CAS  Google Scholar 

  • Tomimura Y, Yokoi T, Terashima (1979) Heterogeneity in formation of lignin. IV. Various factors which influence the degree of condensation at position 5 of guaiacyl ring. Mokuzai Gakkaishi 25: 743–748

    CAS  Google Scholar 

  • Tsuge O, Tashiro M (1962) Studies on diarylalkanes (II). Reaction of diaryl-methanes and ethanes with aluminium chloride (1). The Coal Tar 14: 513–519

    CAS  Google Scholar 

  • Tsuge O, Tashiro M (1965) Studies of diarylalkanes (III). The cleavage of diarylmethanes under the influence of aluminium chloride. Bull Chem Soc Jpn 38: 184–188

    Article  CAS  Google Scholar 

  • Wang X (1987) Structure changes of lignin in soda and soda-anthraquinone delignification of wheat straw. M.S. Thesis, Michigan Technological University, Houghton, Michigan

    Google Scholar 

  • Yasuda S, Terashima N (1982) Chemical structures of sulfuric acid lignin V. Reaction of three arylglycerol-ß-aryl ether [α-, ß-, γ-13C] with seventy two percent sulfuric acid. Mokuzai Gakkaishi 28: 383–387

    CAS  Google Scholar 

Download references

Authors
  1. M. Funaoka
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. I. Abe
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. V. L. Chiang
    View author publications

    You can also search for this author in PubMed Google Scholar

Editor information

Editors and Affiliations

  1. LignoTech USA Inc., 100 Highway 51 South, 54474, Rothschild, WI, USA

    Stephen Y. Lin

  2. 600 Black Walnut Court, 28792, Hendersonville, NC, USA

    Carlton W. Dence

Rights and permissions

Reprints and permissions

Copyright information

© 1992 Springer-Verlag Berlin Heidelberg

About this chapter

Cite this chapter

Funaoka, M., Abe, I., Chiang, V.L. (1992). Nucleus Exchange Reaction. In: Lin, S.Y., Dence, C.W. (eds) Methods in Lignin Chemistry. Springer Series in Wood Science. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-74065-7_25

Download citation

  • DOI: https://doi.org/10.1007/978-3-642-74065-7_25

  • Publisher Name: Springer, Berlin, Heidelberg

  • Print ISBN: 978-3-642-74067-1

  • Online ISBN: 978-3-642-74065-7

  • eBook Packages: Springer Book Archive

Publish with us

Policies and ethics

Search

Navigation