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Crystal and Molecular Structure, and Spectral Characteristics of Sodium 3,5-Bis(Hydroxyimino)-1-Methyl-2,4,6-Trioxocyclohexanide

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DOI: 10.4236/csta.2012.13009    2,958 Downloads   6,046 Views   Citations

ABSTRACT

Sodium 3,5-bis(hydroxyimino)-1-methyl-2,4,6-trioxocyclohexanide C7H5N2NaO5 (I) has been isolated as the only product of the reaction of nitrosation of methylphloroglucinol. The structure of the titled compound has been determined from single crystal X-ray diffraction data. The hydrated C7H5N2NaO52.5H2O crystallizes in the monoclinic space group C2/c, with a(?) 16.408(3); b(?) 12.446(3); c(?) 13.716(3); (o) 126.34(3). The planar organic anion exists in a triketo-dihydroxyimino form with the C–O and C–N distances from 1.220(2) to 1.271(2) ? and from 1.292(2) to 1.293 ? respectively. In the IR spectrum of I, the sharp absorption band occurred at 1681 cm-1 due to C=O stretching indicating the strong H-interactions. The correlations of theoretical (DFT-B3LYP/aug-cc-pVDZ) and experimental UV-vis absorption spectra in neutral and alkaline ethanolic solutions showed the existence of hydroxyimino-nitroso tautomerism while ionization of I.

Conflicts of Interest

The authors declare no conflicts of interest.

Cite this paper

O. Kovalchukova, N. Do, A. Stash, V. Bel’sky, P. Strashnov, A. Alafinov, O. Volyansky, S. Strashnova and K. Kobrakov, "Crystal and Molecular Structure, and Spectral Characteristics of Sodium 3,5-Bis(Hydroxyimino)-1-Methyl-2,4,6-Trioxocyclohexanide," Crystal Structure Theory and Applications, Vol. 1 No. 3, 2012, pp. 46-51. doi: 10.4236/csta.2012.13009.

References

[1] W. S. Atkins and J. Wilson, “Synthesis of Polynitrodiazo-phenols,” The Journal of Organic Chemistry, Vol. 51, No. 13, 1986, pp. 2572-2578. doi:10.1021/jo00363a033
[2] S. A. Shevelev, A. Kh. Shakhnes, B. J. Ugrak and S. S. Vorob’ev, “Highly Selective One-Step Synthesis of 2-Amino-4,6-Dinitrotoluene and 2,6-Diamino-4-Nitrotoluene from 2,4,6-Trinitrotoluene,” Synthetic Communications, Vol. 37, No. 17, 2001, pp. 2557-2561. doi:10.1081/SCC-100105379
[3] J. Herzing, J. Pollak and K. Rohm, “Studien über Die Halogenderivate der Phloroglucine,” Monatshefte für Chemie—Chemical Monthly, Vol. 21, No. 6, 1900, pp. 498-511. doi:10.1007/BF01525541
[4] F. H. Curd and A. Robertson, “Usnic Acid. Part I. Derivatives of Methylphloroglucinol,” Journal of Chemical Society, 1933, pp. 437-444. doi:10.1039/jr9330000437
[5] H. Brockmann and K. Mayer, “über das Rottlerin,” Justus Liebigs Annalen der Chemie, Vol. 535, No. 1, 1938, pp. 149-175. doi:10.1002/jlac.19385350109
[6] F. H. Curd and A. Robertson, “Usnic Acid. Part II. Usneol,” Journal of Chemical Society, 1933, pp. 714-720. doi:10.1039/jr9330000714
[7] F. M. Dean and A. Robertson, “Usnic Acid. Part VIII. C-Diacetyl Derivatives of Phloroglucinol and C-Methyl-phloroglucinol,” Journal of Chemical Society, 1953, pp. 1241-1249. doi:10.1039/jr9530001241
[8] P. Karrer, “über Oxycarbonylverbindungen II. Synthe-tische Versuche in der Filixgruppe,” Helvetica Chimica Acta, Vol. 2, No. 1, 1919, pp. 466-481. doi:10.1002/hlca.19190020149
[9] R. Boehm, “Ueber Methylenverbindungen in der Phloroglucinreihe,” Justus Liebigs Annalen der Chemie, Vol. 329, 1903, pp. 269-301. doi:10.1002/jlac.19033290302
[10] V. Ushkarov, K. Kobrakov, A. Alafinov, G. Stankevich, S. Shevelev and A. Shakhnes, “Methyl Phlorogluci-nol-Based Dyes for Chemical Fibres,” Fibre Chemistry, Vol. 38, No. 2, 2006, pp. 188-190. doi:10.1007/s10692-006-0067-3
[11] V. I. Ushkarov, “Synthesis and Studies of Properties of Azo-Compound Based on Methylfloroglucinol,” Ph.D. Thesis, Moscow State Textile University, Moscow, 2006.
[12] G. S. Stankevich, K. I. Kobrakov, O. V. Volyansky, O. V. Kovalchukova, V. I. Ushkarov, A. I. Alafinov, A. Kh. Shakhness, M. D. Dutov, S. A. Shevelev, P. V. Strashnov and E. P. Romashkina, “Trinitrotoluene as a Precursor in Synthesis of Effective Azodyes and Azopygments,” Proceedings of the 13th Seminar on New Trends in Research of Energetic Materials. Part I, Pardubice, 21-23 April 2010, pp. 255-258.
[13] O. V. Kovalchukova, S. A. Shevelev, A. H. Shakhnes, K. K. Kobrakov, A. I. Alafinov, O. V. Volyansky and P. V. Strashnov, “Some Physico-Chemical Properties of Products of Chemical Transformation of 2,4,6-Trinitro-toluene,” Proceedings of the 14th Seminar on New Trends in Research of Energetic Materials. Part I, Pardubice, 13-15 April 2011, pp. 264-268.
[14] J. Nagypal and M. T. Beck, “Rules Governing Concentration Distribution in Complex Equilibrium Systems,” Journal of Chemical Society, Vol. 80, No. 7, 1980, pp. 722-726. doi:10.1021/j100444a008
[15] G. M. Sheldrick, “SHELXL 93. Program for the Refine- ment of Crystal Structures,” University of Gottingen, 1993.
[16] O. Kovalchukova, S. Strashnova and B. Zaitsev, “Polyo- xo-Compounds of Carbocyclic and Heterocyclic Series,” LAP Lambert Academic Publishing GmbH & Co., Saar- brücken, 2011.
[17] G. C. Bassler, T. C. Morrill and R. M. Silverstein, “Spec- trometric Identification of Organic Compounds,” Wiley, New York, 1991.
[18] A. I. Mikhaleva, A. B. Zaitsev and B. A. Trofimov, “Oxi- mes as Reagents,” Russian Chemical Reviews, Vol. 75, No. 9, 2006, pp. 797-823. doi:10.1070/RC2006v075n09ABEH003594

  
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