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Mucochloric Pseudoanhydrides

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Abstract

Thermal or chemical dehydration of mucochloric acid produces diastereomeric mucochloric pseudoanhydrides. The meso form crystallizes in the monoclinic system, space group P2(1)/n, with a = 6.77742(15) Å, b = 18.8757(5) Å, c = 9.0724(2) Å, β = 93.959(2)°, V = 1157.85(5) Å3. The racemate crystallizes in the tetragonal space group I4(1)/a with a = b = 26.4089(8) Å, c = 6.5757(3) Å, V = 4586.1(3) Å3. The central exocyclic C–O bonds are shortened [average 1.398(4) Å] compared to the endocyclic C–O bonds [average 1.430(5) Å]. This is attributed to the weaker basicity of the open carboxylate compared to the conjugate base of the pseudoacid. Modest ab initio calculations support the distinction.

Graphical Abstract

Both diastereomeric pseudoanhydrides of mucochloric acid have dissimilar endocyclic and exocyclic C–O bond lengths, supported by the weaker basicity of the carboxylate compared to the pseudo acyloxy late group.

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Acknowledgments

The authors thank Mr. Corey Parrish for experimental assistance, EJV acknowledges the National Science Foundation (MRI Grant 0604188) for support of crystallographic equipment.

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  1. Department of Chemistry, University of Portland, 5000 N. Willamette Blvd., Portland, OR, 97203, USA

    Megan Supinski & Edward J. Valente

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  1. Megan Supinski
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  2. Edward J. Valente
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Correspondence to Edward J. Valente.

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Supinski, M., Valente, E.J. Mucochloric Pseudoanhydrides. J Chem Crystallogr 46, 263–268 (2016). https://doi.org/10.1007/s10870-016-0655-x

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