Journal of Wood Science

, Volume 48, Issue 2, pp 153–158 | Cite as

Predicting the hydroxymethylation rate of phenols with formaldehyde by molecular orbital calculation

  • Tohru Mitsunaga
  • Anthony H. Conner
  • Charles G. HillJr.
Original Article


The rates (k) of hydroxymethylation of phenol, resorcinol, phloroglucinol, and several methylphenols in diluted 10% dimethylformamide aqueous alkaline solution were calculated based on the consumption of phenols and formaldehyde. Thek values of phloroglucinol and resorcinol relative to that of phenol were about 62000 and 1200 times, respectively. The phenols that have methyl or hydroxyl groups at the C-3 or C-5 position (or both) have larger rate constants than phenols with substituents at other positions. Several kinds of atomic charge of the carbons on the aromatic ring of phenols were calculated using the semiempirical orab initio method. The correlations between the averagek (Ave.k) and average electrostatic charges (Ave.q) at the carbons were fairly good. Highest occupied molecular orbitals (HOMO) were observed. The best correlation between Ave.k and Ave.q was obtained when diphenols and triphenols were assumed to exist in solution as their respective di-anion.

Key words

Chemical computation Ab initio Semiempirical Phenolic compounds Formaldehyde 


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. 1.
    Aldersley JW, Hope P (1972) A study of the methylolation of phenol using gel permeation chromatography. Die Ang Makromol Chem 24:137–153CrossRefGoogle Scholar
  2. 2.
    Astarloa-Aierbe G, Echeverria JM, Egiburu JL, Ormaetxea M, Mondragon L (1998) Kinetics of phenolic resol resin formation by HPLC. Polymer 39:3147–3153CrossRefGoogle Scholar
  3. 3.
    Dijkstra R, DeJonge J, Lammers MF (1962) The kinetics of the reaction of phenol and formaldehyde. Rec Trav Chim 81:285–296CrossRefGoogle Scholar
  4. 4.
    Grenier-Loustalot MF, Larroque S, Grenier P, Leca J-P, Bedel D (1994) Phenolic resins. 1. Mechanisms and kinetics of phenol and of the first polycondensates towards formaldehyde in solution. Polymer 35:3046–3054CrossRefGoogle Scholar
  5. 5.
    Grenier-Loustalot MF, Larroque S, Grande D, Grenier P (1996) Phenolic resins. 2. Influence of catalyst type on reaction mechanisms and kinetics. Polymer 37:1363–1369CrossRefGoogle Scholar
  6. 6.
    Walker JF (1972) Determination of formaldehyde. In: Formaldehyde. Krieger, Florida, pp 105–125Google Scholar
  7. 7.
    Dejong JI, Dejong J (1953) Kinetics of the hydroxymethylation of phenols in dilute aqueous solution. Rec Trav Chim 72:497–509CrossRefGoogle Scholar
  8. 8.
    Abe I, Ono H (1980) Effect of the acidity of some tropical wood extractives on the curing of the resol. Mokuzai Gakkaishi 26:686–692Google Scholar
  9. 9.
    Zavitsas AA, Beaulieu RD, Leblanc JR (1968) Base-catalyzed hydroxymethylation of phenol by aqueous formaldehyde: kinetics and mechanism. J Polym Sci 6:2533–2540CrossRefGoogle Scholar
  10. 10.
    Clark T (1985) A handbook of computational chemistry. Wiley. New York, pp 133–138Google Scholar
  11. 11.
    Fukui K (1971) Recognition of stereochemical paths by orbital interaction. Acc Chem Res 4:57–64CrossRefGoogle Scholar

Copyright information

© The Japan Wood Research Society 2002

Authors and Affiliations

  • Tohru Mitsunaga
    • 1
  • Anthony H. Conner
    • 2
  • Charles G. HillJr.
    • 3
  1. 1.Faculty of BioresourcesMie UniversityTsuJapan
  2. 2.USDA Forest ServiceForest Products LaboratoryMadisonUSA
  3. 3.Department of Chemical EngineeringUniversity of WisconsinMadisonUSA

Personalised recommendations