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Selective synthesis of aromatic dicarboxylic acid using cyclodextrin as catalyst
Author(s) -
Hirai Hidefumi
Publication year - 1997
Publication title -
polymers for advanced technologies
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.61
H-Index - 90
eISSN - 1099-1581
pISSN - 1042-7147
DOI - 10.1002/(sici)1099-1581(199711)8:11<666::aid-pat699>3.0.co;2-f
Subject(s) - carboxylation , terephthalic acid , aqueous solution , selectivity , nuclear overhauser effect , cyclodextrin , catalysis , dicarboxylic acid , organic chemistry , chemistry , benzoic acid , carboxylic acid , inorganic chemistry , materials science , nuclear magnetic resonance spectroscopy , polyester
The selective synthesis of terephthalic acid from benzoic acid with carbon tetrachloride, copper powder and aqueous alkali was achieved by the use of β‐cyclodextrin (β‐CyD) as a catalyst at 60°C under nitrogen of atmospheric pressure, producing terephthalic acid in 74 mol% yield with 100% selectivity. The carboxylation of 4‐biphenylcarboxylic acid with carbon tetrachloride, copper powder and aqueous alkali using β‐CyD under similar conditions produced 4,4′‐biphenyldicarboxylic acid in 71 mol% with 100% selectivity. 2,6‐Naphthalenedicarboxylic acid was synthesized by the carboxylation using β‐CyD under similar conditions in 67 mol% yield with 84% selectivity. When α‐CyD or γ‐CyD was used instead of β‐CyD, the reaction hardly proceeded. The conformations of CyD–aromatic monocarboxylate inclusion complexes in aqueous alkaline solution were determined by the nuclear magnetic resonance spectroscopy using 1 H homonuclear Overhauser enhancement on the rotating frame. The essential factor of the carboxylation was the inclusion complex formations of β‐CyD with aromatic monocarboxylate and β‐CyD with carbon tetrachloride in the reaction mixture. The high selectivity was ascribed to the conformation of the β‐CyD–aromatic monocarboxylate inclusion complex. © 1997 John Wiley & Sons, Ltd.