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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

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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.

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Notes

  1. CCDC for compound 7 (689212) and for compound 8 (689211) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.

References

  1. Martins MAP, Cunico W, Pereira CMP, Sinhorin AP, Flores AFC, Bonacorso HG, Zanatta N (2004) Current Org Synth 1:391

    Article  CAS  Google Scholar 

  2. Muniz-Miranda M, Cardini G, Schettino V (2004) Theor Chem Acc 111:264

    CAS  Google Scholar 

  3. Lipton AS, Wright TA, Bowman MK, Reger DL, Ellis PD (2002) J Am Chem Soc 124:5850

    Article  CAS  Google Scholar 

  4. Boyer G, Galy JP, Faure R, Barbe J (1994) Magn Res Chem 32:537

    Article  CAS  Google Scholar 

  5. Okafor EC, Uzoukwu BA (1991) Syn React Inorg Metal Org Chem 21:825

    Article  CAS  Google Scholar 

  6. Sanz D, Claramunt RM, Alkorta I, Elguero J (2007) Struct Chem 18:703

    Article  CAS  Google Scholar 

  7. Shi F-Q, Song B-A (2008) Int J Quantum Chem 108:1107

    Article  CAS  Google Scholar 

  8. Wang H, Wang X, Wang H, Wang L, Liu A (2007) J Mol Model 13:147

    Article  CAS  Google Scholar 

  9. Menegatti R, Silva GMS, Zapata-Sudo G, Raimundo JM, Sudo RT, Barreiro EJ, Fraga CAM (2006) Bioorgan Med Chem 14:632

    Article  CAS  Google Scholar 

  10. Elguero J, Goya P, Jagerovic N, Silva AMS (2002) Targets Heterocycl Syst 6:52

    CAS  Google Scholar 

  11. Akbas E, Berber I (2006) Eur J Med Chem 41:904

    Article  CAS  Google Scholar 

  12. Bajpai VK, Lee TJ, Kang SC (2009) J Sci Food Agriculture 89:109

    Article  CAS  Google Scholar 

  13. Stanovnik B, Svete J (2002) Sci Synth 12:15

    CAS  Google Scholar 

  14. Elguero J (1996) Comp Heterocycl Chem II 3:1, 817

  15. Shcherbakova I, Elguero J, Katritzky AR (2000) Adv Heterocycl Chem 77:51

    Article  CAS  Google Scholar 

  16. Redkin RG, Shemchuk LA, Chernykh VP, Shishkin OV, Shishkina SV (2007) Tetrahedron 63:11444

    Article  CAS  Google Scholar 

  17. Khodairy A, El-Sayed AM, Salah H, Abdel-Ghany H (2007) Synth Commun 37:3245

    Article  CAS  Google Scholar 

  18. Holzer W, Claramunt RM, Perez-Torralba M, Guggi D, Brehmer TH (2003) J Org Chem 68:7943

    Article  CAS  Google Scholar 

  19. Raghunathan R, Shanmugasundaram M, Bhanumathi S, Malar EJP (1998) Heteroatom Chem 9:327

    Article  CAS  Google Scholar 

  20. Mishriky N, Girgis AS, Hosni HM, Farag H (2006) J Heterocycl Chem 43:1549

    Article  CAS  Google Scholar 

  21. Dawood KM (2005) Tetrahedron 61:5229

    Article  CAS  Google Scholar 

  22. Sammelson RE, Gurusinghe CD, Kurth JM, Olmstead MM, Kurth MJ (2002) J Org Chem 67:876

    Article  CAS  Google Scholar 

  23. Khalil S, Hossain MB, van der Helm D, Alam M, Sanduja R (1996) Acta Crystallographica C 52:1272

    Google Scholar 

  24. Grant BJ, Kramp CR, Knight JD, Meierhoefer MA, Vella JH, Sober CL, Jones SS, Metz CR, Beam CF, Pennington WT, VanDerveer DG, Camper ND (2007) J Heterocycl Chem 44:627

    Article  CAS  Google Scholar 

  25. Wrobel J, Dietrich A (1994) Heterocycles 38:1823

    Article  CAS  Google Scholar 

  26. Grant SP, Embree MC, Downs JR, Townsend JD, Beam CF (2003) Ind Eng Chem Res 42:5721

    Article  CAS  Google Scholar 

  27. Meierhoefer MA, Dunn SP, Hajiaghamohseni LM, Walters MJ, Embree MC, Grant SP, Downs JR, Townsend JD, Metz CR, Beam CF, Pennington WT, VanDerveer DG, Camper ND (2005) J Heterocycl Chem 42:1095

    Article  CAS  Google Scholar 

  28. Dunn SP, Walters MJ, Metz CR, Beam CF, Pennington WT, Krawiec M (2004) J Heterocycl Chem 41:1005

    Article  CAS  Google Scholar 

  29. Knight JD, Brown JB, Overby JS, Beam CF, Camper ND (2008) J Heterocycl Chem 45:189

    Article  CAS  Google Scholar 

  30. Mirone P, Vampiri M (1952) Atti Accad Nazl Lincei Rend Classe Sci Fis Mat e Nat 583 (Chem Abstr 46:9423)

    Google Scholar 

  31. Johnson AL, Sweetser PB (1976) J Org Chem 41:110

    Article  CAS  Google Scholar 

  32. Rigaku Corporation (1999) Crystal clear. Rigaku Corporation, Danvers.

  33. Jacobson RA (1998) Absorption correction used REQABS v 1.1. Molecular Structure Corp, College Station

  34. Sheldrick, GM (1997) SHELX-97, Crystallographic Computing System–Windows Version; University of Gottingen, Germany

  35. Cromer DT, Waber JT (1974) International tables for X-ray crystallography, Vol IV, Tables 2.2 B and 2.3.1. Kluwer Academic Publisher, Dordrecht

    Google Scholar 

  36. Farrugia LJ (1997) ORTEP-3 for windows. J Appl Cryst 30:565

    Article  CAS  Google Scholar 

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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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Authors and Affiliations

  1. Department of Chemistry and Biochemistry, College of Charleston, Charleston, SC, 29424, USA

    Clyde R. Metz, John D. Knight, Anna C. Dawsey, Jordan B. Brown, Kevin J. Bigham & Charles F. Beam

  2. Department of Chemistry, Clemson University, Clemson, SC, 29634, USA

    William T. Pennington & Donald G. VanDerveer

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  1. Clyde R. Metz
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Correspondence to Charles F. Beam.

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Metz, C.R., Knight, J.D., Dawsey, A.C. et al. 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. J Chem Crystallogr 40, 296–301 (2010). https://doi.org/10.1007/s10870-009-9649-2

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