Skip to main content
SpringerLink
Log in

Darstellung und Oxydation von Hydroxybenzylalkoholen

Preparation and oxidation of hydroxybenzyl alcohols

  • Organische Chemie und Biochemie
  • Published:
Monatshefte für Chemie / Chemical Monthly Aims and scope Submit manuscript

Abstract

Several hydroxy benzyl alcohols were prepared by reaction of phenols with formaldehyde, or by reduction of the corresponding hydroxy benzaldehydes with NaBH4. Oxidation with K3Fe(CN)6 yielded mainly polymeric products by radicalic coupling and loss of hydroxymethyl groups as formaldehyde (in case of 2,6-disubstituted p-hydroxy benzyl alcohols linear poly-phenyleneoxides were obtained). p-Hydroxybenzyl alcohols with electran withdrawing substituents gave the corresponding benzaldehydes. Oxidation with O2 inDMSO in the presence of Cu(I)Cl afforded in the case of o-hydroxy derivatives mainly oligomeric products, whilst in the case of p-derivatives the corresponding benzaldehydes were obtained as main products besides some oligomeres and p-quinones.

Zusammenfassung

Eine Reihe von Hydroxybenzylalkoholen wurde durch Reaktion von Phenolen mit Formaldehyd bzw. durch NaBH4-Reduktion der entsprechenden Hydroxybenzaldehyde dargestellt. Die Oxydation mit K3Fe(CN)6 führte in den meisten Fällen unter Abspaltung von Hydroxymethylgruppen als Formaldehyd zu polymeren Kupplungsprodukten, im Falle von 2,6-disubstituierten p-Hydroxybenzylalkoholen zu linearen Polyphenylenäthern. p-Hydroxybenzylalkohole mit elektronenanziehenden Substituenten ergaben die entsprechenden p-Hydroxybenzaldehyde. Die Oxydation mit O2 inDMSO in Gegenwart von Cu(I)Cl führte im Falle der o-Derivate meist zu oligomeren Produkten, die p-Derivate hingegen ergaben neben Oligomeren und p-Chinonen zumeist die entsprechenden Benzaldehyde als Hauptprodukte.

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

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

Literatur

  1. J. H. Ross undS. C. Hill, Pulp Paper Mag. Can.27, 541 (1929).

    Google Scholar 

  2. J. Marton, T. Marton, S. I. Falkehag undE. Adler, in: Lignin, Structure and Reactions, S. 129. Advances in Chemistry Series59, ACS Washington. 1966.

  3. Y. Hachihama undS. Yjodai, J. Chem. Soc. Japan52, 306 (1949);J. H. Carroll undH. C. Wallin, Can. Pat. 707 382 (1965);F. J. Ball, J. B. Doughty undW. G. Vardell, US-Pat. 3 185 654 (1965).

    Google Scholar 

  4. H. Mikawa, K. Sato, C. Takasaki undK. Ebisawa, Bull. Chem. Soc. Japan29, 259 (1956).

    Google Scholar 

  5. F. Gaslini, Tappi41, 162 A (1958).

    Google Scholar 

  6. G. G. Allan, US-Pat. 3 470 148 (1969).

  7. H. Musso, in: Oxidative Coupling of Phenols, S. 4–51 (W. I. Taylor undA. R. Battersby, ed.), New York: Marcel Dekker Inc. 1967.

    Google Scholar 

  8. E. Müller, R. Mayer, U. Heilmann undK. Scheffler, Ann. Chem.645, 66 (1966).

    Google Scholar 

  9. E. McNelis, J. Amer. Chem. Soc.88, 1074 (1966); J. Org. Chem.31, 1255 (1966).

    Google Scholar 

  10. J. J. Lindberg undA. Savolainen, Kem. Teollisuus26 (1), 25 (1969); Chem. Abstr.71, 39 400 w (1969).

    Google Scholar 

  11. W. A. Waters, J. Chem. Soc. [London]B 1971, 2026.

  12. C. D. Cook, E. S. English undB. J. Wilson, J. Org. Chem.23, 755 (1958).

    Google Scholar 

  13. A. S. Hay, H. S. Blanchard, G. F. Endres undJ. W. Eustance, J. Amer. Chem. Soc.81, 6335 (1959).

    Google Scholar 

  14. K. Kratzl, J. S. Gratzl undP. Claus, in: Lignin, Structure and Reactions, Advances in Chemistry Series59, S. 157, ACS, Washington 1966.

    Google Scholar 

  15. W. Brackman undE. Havinga, Rec. trav. chim.74, 937, 1070, 1108 (1955).

    Google Scholar 

  16. J. J. Lindberg, A. Savolainen undP. Starck, Suomen KemistilehtiB 42 (3), 120 (1969).

    Google Scholar 

  17. G. Goethals, Naturw. Tijdskr.18, 249 (1936);H. v. euler, E. Adler undD. Friedmann, Arkiv Kemi Mineral. Geol.13 B, Nr. 12, 7 (1939).

    Google Scholar 

  18. H. Jensch, Chem. Zentralbl.1928, I, 2307.

  19. J. Knabe, H. Methews undA. Schepers, Arch. Pharm.296, 650 (1963).

    Google Scholar 

  20. G. M. Coppinger undT. W. Campbell, J. Amer. Chem. Soc.75, 734 (1953).

    Google Scholar 

  21. E. Ziegler undK. Mayer, Mh. Chem.92, 246 (1961).

    Google Scholar 

  22. O. Manasse, Ber. dtsch. chem. Ges.35, 3844 (1902).

    Google Scholar 

  23. K. Hultzsch, Ber. dtsch. chem. Ges.74, 1533 (1941).

    Google Scholar 

  24. M. Brink, Acta Chem. Scand.19, 255 (1965).

    Google Scholar 

  25. L. Andersen, Soc. Sci. Fennica Commentationes Phys. Math.19, Nr. 11, 51 (1956); Chem. Abstr.54, 22442e (1956).

    Google Scholar 

  26. T. Yamasaki, J. Chem. Soc. Japan, Ind. Chem. Sect.58, 972 (1955).

    Google Scholar 

  27. S. R. Finn undJ. W. G. Musty, J. Appl. Chem.2, 88 (1952).

    Google Scholar 

  28. E. Adler undS. Hernestam, Acta Chem. Scand.9, 314 (1955).

    Google Scholar 

  29. H. Kämmerer undA. Casacuberta, Makromol. Chem.67, 167 (1963).

    Google Scholar 

  30. H. Finger undW. Schott, J. prakt. Chem.115, 288 (1927).

    Google Scholar 

  31. H. H. Hodgson undJ. Nixon, J. Chem. Soc. [London]1929, 1461.

  32. H. Lindemann, Ann. Chem.431, 283 (1923).

    Google Scholar 

  33. T. A. Henry undT. M. Sharp, J. Chem. Soc. [London]121, 1055 (1922).

    Google Scholar 

  34. K. Freudenberg, V. Jovanovic undF. Topfmeier, Chem. Ber.94, 3227 (1961).

    Google Scholar 

  35. C. F. H. Allen undG. W. Leubner, Org. Synth., Coll. Vol. IV, 865 (1963).

    Google Scholar 

  36. K. Auwers, Ber. dtsch. chem. Ges.40, 2528 (1907).

    Google Scholar 

  37. L. Gattermann, Ann. Chem.357, 327 (1907).

    Google Scholar 

  38. R. Raymond, M. Hann undG. C. Spencer, J. Amer. Chem. Soc.49, 535 (1927).

    Google Scholar 

  39. R. L. Shriner undP. McCutchan, J. Amer. Chem. Soc.52, 2194 (1929).

    Google Scholar 

  40. G. D. Thorn undC. B. Purves, Can. J. Chem.32, 373 (1954).

    Google Scholar 

  41. B. Leopold, Acta Chem. Scand.4, 1523 (1950).

    Google Scholar 

  42. T. J. Barnes undW. J. Hickinbottom, J. Chem. Soc. 1961, 153.

  43. E. Müller, A. Schick, R. Mayer undK. Scheffler, Chem. Ber.93, 2649 (1960).

    Google Scholar 

  44. R. L. Alimchandani, J. Chem. Soc. [London]125, 542 (1924).

    Google Scholar 

Download references

Author information

Author notes

  1. P. Schilling

    Present address: Dept. of Chemistry, Case Western Reserve University, 44106, Cleveland, OH, USA

  2. J. S. Gratzl

    Present address: School of Forest Resources, North Carolina State University, Box 5488, 27607, Raleigh, NC, USA

Authors and Affiliations

  1. Lehrkanzel für Allgemeine und Organische Chemie, Organisch-Chemischen Institut der Universität Wien, Wien, Österreich

    P. Claus, P. Schilling, J. S. Gratzl & K. Kratzl

Authors
  1. P. Claus
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. P. Schilling
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. J. S. Gratzl
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. K. Kratzl
    View author publications

    You can also search for this author in PubMed Google Scholar

Additional information

Herrn Prof. Dr.E. Ziegler zum 60. Geburtstag gewidmet.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Claus, P., Schilling, P., Gratzl, J.S. et al. Darstellung und Oxydation von Hydroxybenzylalkoholen. Monatshefte für Chemie 103, 1178–1193 (1972). https://doi.org/10.1007/BF00905194

Download citation

  • Received:

  • Issue Date:

  • DOI: https://doi.org/10.1007/BF00905194

Search

Navigation