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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

Abstract

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 

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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

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