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Journal of Chemical Crystallography

, Volume 40, Issue 4, pp 296–301 | Cite as

Synthesis and Crystal Structure Determination of Methyl 2-acetyl-5′-phenyl-2H-spiro[benzo[d]isothiazole-3,3′-pyrazole]-1,1-dioxide-2′(4′H)-carboxylate and Methyl 2-acetyl-5′-(2-thienyl)-2H-spiro[benzo[d]isothiazole-3,3′-pyrazole]-1,1-dioxide-2′(4′H)-carboxylate

  • Clyde R. Metz
  • John D. Knight
  • Anna C. Dawsey
  • William T. Pennington
  • Donald G. VanDerveer
  • Jordan B. Brown
  • Kevin J. Bigham
  • Charles F. Beam
Original Paper

Abstract

Dilithiated C(α), N-carbomethoxyhydrazones were condensed with lithiated methyl 2-(aminosulfonyl)benzoate to afford intermediates that were isolated and not characterized but cyclized with acetic anhydride, which also resulted in N-acetylation. The X-ray crystal structure determinations of methyl 2-acetyl-5′-phenyl-2H-spiro[benzo[d]isothiazole-3,3′-pyrazole]-1,1-dioxide-2′(4′H)-carboxylate and methyl 2-acetyl-5′-(2-thienyl)-2H-spiro[benzo[d]isothiazole-3,3′-pyrazole]-1,1-dioxide-2′(4′H)-carboxylate products were a follow up for absorption spectra, and they confirmed their structures. Mechanistic intermediates to describe the reaction may include C-acylated intermediates that cyclize to spiro(N-benzoisothiazole dioxide-pyrazole) instead of N-carbomethoxypyrazole-ortho-benzenesulfonamides. Crystals of C19H17N3O5S 7 are monoclinic, P21/c, a = 11.899(2) Å, b = 17.562(4) Å, c = 9.484(2) Å, β = 111.03(3)°, Z = 4, V = 1849.9(6) Å3, R 1 = 0.0857 and wR 2 = 0.2216 for reflections with I > 2σ(I); crystals of C17H15N3O5S2 8 are orthorhombic, Pbca, a = 16.045(3) Å, b = 10.746(2) Å, c = 20.389(4) Å, Z = 8, V = 3516(1) Å3, R 1 = 0.0841 and wR 2 = 0.2179 for all reflections with I > 2σ(I).

Graphical Abstract

X-ray crystal analysis was important for determining the conformation of the structure of N-acetyl-N′-carbomethoxy-spiro(benzoisothiazole–pyrazole)dioxides prepared by the condensation and twofold cyclization of dilithiated C(α), N-carbomethoxyhydrazones and methyl 2-(aminosulfonyl)benzoate.

Keywords

Spiro(benzoisothiazole-pyrazoles) Multiple anions Anion–anion condensations 

Notes

Acknowledgements

We wish to thank the following sponsors: the Research Corporation, the National Science Foundation Grants CHE # 9708014 and # 0212699 for Research at Undergraduate Institutions, the United States Department of Agriculture, NRICGP # 2003-35504-12853, and the Petroleum Research Fund, Administered by the American Chemical Society. The College of Charleston awarded summer grants through its Summer Undergraduate Research Forum (SURF-2006 and 2007) to J. D. Knight and (SURF-2007) A. C. Dawsey.

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Copyright information

© Springer Science+Business Media, LLC 2009

Authors and Affiliations

  • Clyde R. Metz
    • 1
  • John D. Knight
    • 1
  • Anna C. Dawsey
    • 1
  • William T. Pennington
    • 2
  • Donald G. VanDerveer
    • 2
  • Jordan B. Brown
    • 1
  • Kevin J. Bigham
    • 1
  • Charles F. Beam
    • 1
  1. 1.Department of Chemistry and BiochemistryCollege of CharlestonCharlestonUSA
  2. 2.Department of ChemistryClemson UniversityClemsonUSA

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