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Anhydrides of Arylfuran and Arylpyran Pseudoacids: Formation and Structures; C–O Bond Lengths Trends in Pseudo o-Formylbenzoic Acid Derivatives

  • Emily O’Loughlin
  • Edward J. ValenteEmail author
Original Paper

Abstract

Three methods for producing anhydrides of arylfuran and arylpyran pseudoacids were explored. These included thermal dehydration, phosgene or thionly chloride activation and decomposition, and dicyclohexylcarbodiimide activation and coupling. Derivatives of the cyclic forms of o-formylbenzoic acid, o-acetylbenzoic acid, 2-carboxyphenylacetaldehyde and of 4,4-dimethyl-3,4-dihydro-3-hydroxy-[1H]-isobenzopyran-1-one were formed including dipseudoanhydides and normal-pseudo anhydrides. Crystal and molecular structures for meso and (R,R/S,S)-bis(1[3H]-isobenzofuranone-3-yl)ether, (R,R/S,S)-bis(3-methyl-1[3H]-isobenzofuranone-3yl)ether, meso (3,4-dihydro-[1H]-isobenzopyran-1-one-3-yl)ether, 3-benzoyloxy-1[3H]-isobenzofuranone, 3-benzoyloxy-3-methyl-1[3H]isobenzofuranone, 3-(4′-nitrobenzoyloxy)-4,4-dimethyl-3,4-dihydro-[1H]-isobenzopyran-1-one, and (1[3H]-isobenzofuranone-3-yl)(4,4,dimethyl-3,4-dihydro-[1H]-isobenzopyran-1-one-3-yl)ether are reported. Endocyclic pseudoacyl C–O bonds are always longer than the exocyclic pseudoacyl C–O bonds. It is possible to refine the previously established C–O bond length dependencies on the pKa (of the conjugate acids) of the leaving groups for 3-substituted 1-[3H]-isobenzofuranones. Of six dipseudoanhydrides studied, conformations are found with exocyclic C–O(ether) linkages synclinal to the endocyclic C–O and away from the ring (exo conformation) in two meso structures, two of three RR/SS forms and in a chiral unsymmetrical form. An endo conformation is observed in one of the RR/SS forms. In three normal-pseudo anhydrides, both endo and exo conformations are observed.

Graphic Abstract

Synthetic methods for formation of anhydrides of several arylfuran and arylpyran pseudoacids are described, and the pseudoacyl C–O bond length trends are determined for leaving groups spanning over 30 pKa units.

Keywords

Pseudoacids Anhydrides Coupling reactions C–O bonds Bürgi-Dunitz angle 

Notes

Acknowledgements

We thank Marilyn Brooks, Brian MacFarland, Derek Thomas Letort for early synthetic explorations. EJV thanks the National Science Foundation for support of crystallographic equipment (MRI-0604188).

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Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Department of ChemistryUniversity of PortlandPortlandUSA

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