Roger A. Mader

The application of toluene dioxygenase in the synthesis of acetylene-terminated resins

SummaryA biotransformation procedure has been developed to prepare intermediates for the synthesis of 3-hydroxyphenylacetylene (3-HPA), a high-value specialty chemical used in the manufacture of acetylene-terminated resins. Pseudomonas putida F39/D containing toluene dioxygenase was used to oxidize a series of substituted benzenes to their respective cis-2,3-dihydroxydihydrobenzene(cis-dihydrodiol) derivatives which in turn could be converted to 3-HPA via a meta-phenol intermediate obtained by acid-catalyzed dehydration. The cis-dihydrodiols derived from the oxidation of phenylacetylene, styrene, acetophenone, and bromobenzene dehydrated to yield predominantly ortho-phenols. Three different phenyl-1,3-dioxolanes were oxidized by P. putida F39/D to three previously undescribed cis-dihydrodiols. Unlike mono-substituted cis-dihydrodiols, phenyl-1,3-dioxolane cis-dihydrodiols were dehydrated to form meta-phenols exclusively. The dehydration products, 3-hydroxyacetophenone and 3-hydroxybenzaldehyde, are suitable precursors for the chemical synthesis of 3-HPA.