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.
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Literatur
J. H. Ross undS. C. Hill, Pulp Paper Mag. Can.27, 541 (1929).
J. Marton, T. Marton, S. I. Falkehag undE. Adler, in: Lignin, Structure and Reactions, S. 129. Advances in Chemistry Series59, ACS Washington. 1966.
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).
H. Mikawa, K. Sato, C. Takasaki undK. Ebisawa, Bull. Chem. Soc. Japan29, 259 (1956).
F. Gaslini, Tappi41, 162 A (1958).
G. G. Allan, US-Pat. 3 470 148 (1969).
H. Musso, in: Oxidative Coupling of Phenols, S. 4–51 (W. I. Taylor undA. R. Battersby, ed.), New York: Marcel Dekker Inc. 1967.
E. Müller, R. Mayer, U. Heilmann undK. Scheffler, Ann. Chem.645, 66 (1966).
E. McNelis, J. Amer. Chem. Soc.88, 1074 (1966); J. Org. Chem.31, 1255 (1966).
J. J. Lindberg undA. Savolainen, Kem. Teollisuus26 (1), 25 (1969); Chem. Abstr.71, 39 400 w (1969).
W. A. Waters, J. Chem. Soc. [London]B 1971, 2026.
C. D. Cook, E. S. English undB. J. Wilson, J. Org. Chem.23, 755 (1958).
A. S. Hay, H. S. Blanchard, G. F. Endres undJ. W. Eustance, J. Amer. Chem. Soc.81, 6335 (1959).
K. Kratzl, J. S. Gratzl undP. Claus, in: Lignin, Structure and Reactions, Advances in Chemistry Series59, S. 157, ACS, Washington 1966.
W. Brackman undE. Havinga, Rec. trav. chim.74, 937, 1070, 1108 (1955).
J. J. Lindberg, A. Savolainen undP. Starck, Suomen KemistilehtiB 42 (3), 120 (1969).
G. Goethals, Naturw. Tijdskr.18, 249 (1936);H. v. euler, E. Adler undD. Friedmann, Arkiv Kemi Mineral. Geol.13 B, Nr. 12, 7 (1939).
H. Jensch, Chem. Zentralbl.1928, I, 2307.
J. Knabe, H. Methews undA. Schepers, Arch. Pharm.296, 650 (1963).
G. M. Coppinger undT. W. Campbell, J. Amer. Chem. Soc.75, 734 (1953).
E. Ziegler undK. Mayer, Mh. Chem.92, 246 (1961).
O. Manasse, Ber. dtsch. chem. Ges.35, 3844 (1902).
K. Hultzsch, Ber. dtsch. chem. Ges.74, 1533 (1941).
M. Brink, Acta Chem. Scand.19, 255 (1965).
L. Andersen, Soc. Sci. Fennica Commentationes Phys. Math.19, Nr. 11, 51 (1956); Chem. Abstr.54, 22442e (1956).
T. Yamasaki, J. Chem. Soc. Japan, Ind. Chem. Sect.58, 972 (1955).
S. R. Finn undJ. W. G. Musty, J. Appl. Chem.2, 88 (1952).
E. Adler undS. Hernestam, Acta Chem. Scand.9, 314 (1955).
H. Kämmerer undA. Casacuberta, Makromol. Chem.67, 167 (1963).
H. Finger undW. Schott, J. prakt. Chem.115, 288 (1927).
H. H. Hodgson undJ. Nixon, J. Chem. Soc. [London]1929, 1461.
H. Lindemann, Ann. Chem.431, 283 (1923).
T. A. Henry undT. M. Sharp, J. Chem. Soc. [London]121, 1055 (1922).
K. Freudenberg, V. Jovanovic undF. Topfmeier, Chem. Ber.94, 3227 (1961).
C. F. H. Allen undG. W. Leubner, Org. Synth., Coll. Vol. IV, 865 (1963).
K. Auwers, Ber. dtsch. chem. Ges.40, 2528 (1907).
L. Gattermann, Ann. Chem.357, 327 (1907).
R. Raymond, M. Hann undG. C. Spencer, J. Amer. Chem. Soc.49, 535 (1927).
R. L. Shriner undP. McCutchan, J. Amer. Chem. Soc.52, 2194 (1929).
G. D. Thorn undC. B. Purves, Can. J. Chem.32, 373 (1954).
B. Leopold, Acta Chem. Scand.4, 1523 (1950).
T. J. Barnes undW. J. Hickinbottom, J. Chem. Soc. 1961, 153.
E. Müller, A. Schick, R. Mayer undK. Scheffler, Chem. Ber.93, 2649 (1960).
R. L. Alimchandani, J. Chem. Soc. [London]125, 542 (1924).
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Herrn Prof. Dr.E. Ziegler zum 60. Geburtstag gewidmet.
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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
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DOI: https://doi.org/10.1007/BF00905194