Benzene-free synthesis of hydroquinone.
All current routes for the synthesis of hydroquinone utilize benzene as the starting material. An alternate route to hydroquinone has now been elaborated from glucose. While benzene is a volatile carcinogen derived from nonrenewable fossil fuel feedstocks, glucose is nonvolatile, nontoxic, and derived from renewable plant polysacharrides. Glucose is first converted into quinic acid using microbial catalysis. Quinic acid is then chemically converted into hydroquinone. Under fermentor-controlled conditions, Escherichia coli QP1.1/pKD12.138 synthesizes 49 g/L of quinic acid from glucose in 20% (mol/mol) yield. Oxidative decarboxylation of quinic acid in clarified, decolorized, ammonium ion-free fermentation broth with NaOCl and subsequent dehydration of the intermediate 3(R),5(R)-trihydroxycyclohexanone afforded purified hydroquinone in 87% yield. Halide-free, oxidative decarboxylation of quinic acid in fermentation broth with stoichiometric quantities of (NH(4))(2)Ce(SO(4))(3) and V(2)O(5) afforded hydroquinone in 91% and 85% yield, respectively. Conditions suitable for oxidative decarboxylation of quinic acid with catalytic amounts of metal oxidant were also identified. Ag(3)PO(4) at 2 mol % relative to quinic acid in fermentation broth catalyzed the formation of hydroquinone in 74% yield with K(2)S(2)O(8) serving as the cooxidant. Beyond establishing a fundamentally new route to an important chemical building block, oxidation of microbe-synthesized quinic acid provides an example of how the toxicity of aromatics toward microbes can be circumvented by interfacing chemical catalysis with biocatalysis.
Ran
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N
Department of Chemistry, Michigan State University, East Lansing, MI 48824-1322, USA.
Knop
D R
DR
Draths
K M
KM
Frost
J W
JW
D001554:Benzene / Q000737:chemistry*; D002712:Chlorides / Q000737:chemistry; D004926:Escherichia coli / Q000187:drug effects; D005285:Fermentation; D005947:Glucose / Q000737:chemistry*; D006873:Hydroquinones / Q000138:chemical synthesis* / Q000633:toxicity; D006997:Hypochlorous Acid / Q000737:chemistry; D010084:Oxidation-Reduction; D011801:Quinic Acid / Q000737:chemistry
D002712:Chlorides; D006873:Hydroquinones; D011801:Quinic Acid; D006997:Hypochlorous Acid; D005947:Glucose; D001554:Benzene; C031927:hydroquinone