The mass spectral fragmentation of thiosemicarbazones synthesized from acetophenones has been studied by CG/MS. These carbonyl compounds exhibit chromatographic peaks which are not observed in aliphatic analogues or those synthesized from aldehydes. The analysis of the corresponding spectra has allowed structural assignment to the dimerization of gas phase neutral fragments. Theoretical calculations (DFT level) also provide evidence to support the experimental observations.
References
[1]
Tenorio, R.P., et al. (2005) Tiossemicarbazonas: Metodos de obtencao, aplicacoes sinteticas e importancia biologica. Quimica Nova, 28, 1030. http://dx.doi.org/10.1590/S0100-40422005000600018
[2]
Du, X., et al. (2002) Synthesis and Structure-Activity Relationship Study of Potent Trypanocidalthiosemicarbazone Inhibitors of the Trypanosomal Cysteine Protease Cruzain. Journal of Medicinal Chemistry, 45, 2695-2707.
http://dx.doi.org/10.1021/jm010459j
[3]
Ershov, A.Yu., Koshmina, A.N.V., Mokeev, M.V. and Gribanov, A.V. (2003) The Isoxazolidine-1,2,4-Triazolidine-3-Thione Tautomeric System. Chemistry of Heterocyclic Compounds, 39, 1257-1258.
http://dx.doi.org/10.1023/B:COHC.0000008277.45834.c5
[4]
Zelenin, K., Kuznetsova, O. and Alekseyev, V. (1993) Ring-Chain Tautomerism of N-Substituted Thiosemicarbazones. Tetrahedron, 49, 1257-1270. http://dx.doi.org/10.1016/S0040-4020(01)85816-6
[5]
Singh, N.K., et al. (2001) Spectral, Magnetic and Biological Studies of 1,4-Dibenzoyl-3-Thiosemicarbazide Complexes with Some First Row Transition Metal Ions. Proceedings of the Indian Academy of Sciences: Chemical Sciences, 113, 257-273. http://dx.doi.org/10.1007/BF02708645
[6]
Offiong, O.E. and Martelli, S. (1997) Stereochemistry and Antitumor Activity of Platinum Metal Complexes of 2-Ace-tylpyridine Thiosemicarbazones. Transition Metal Chemistry, 22, 263-269.
http://dx.doi.org/10.1023/A:1018416624951
[7]
Samanta, B., Chakraborty, J., Shit, S., Batten, S.R., Jensen, P., Masuda, J.D. and Mitra, S. (2007) Synthesis, Characterization and Crystal Structures of a Few Coordination Complexes of Nickel(II), Cobalt(III) and Zinc(II) with N'-[(2- Pyridyl)Methylene]Salicyloylhydrazone Schiff Base. Inorganica Chimica Acta, 360, 2471-2484.
http://dx.doi.org/10.1016/j.ica.2006.12.019
[8]
Yildiz, M., ünver, H., Erdener, D., Kiraz, A. and OcakIskeleli, N. (2009) Synthesis, Spectroscopic Studies and Crystal Structure of (E)-2-(2,4 Dihydroxybenzylidene) Thiosemicarbazone and (E)-2-[(1H-indol-3-yl)Methylene]Thiosemicar-bazone. Journal of Molecular Structure, 919, 227-234. http://dx.doi.org/10.1016/j.molstruc.2008.09.008
[9]
Wheeler, A.S. and Bost, R. (1924) 4-Para-Tolylsemicarbazide and Certain Derivatives. Journal of the American Chemical Society, 46, 2813-2816. http://dx.doi.org/10.1021/ja01677a032
[10]
Cheronis, N.D.I., Hodnett, E.M.A. and Entrikin, J.B.E. (1968) Semimicro Qualitative Organic Analysis: The Systematic Identification of Organic Compounds.
[11]
Hohenberg, P. and Kohn, W. (1964) Inhomogeneous Electron Gas. Physical Review, 136, B864-B871.
http://dx.doi.org/10.1103/PhysRev.136.B864
[12]
Kohn, W. and Sham, J. (1965) Self-Consistent Equations including Exchange and Correlation Effects. Physical Review, 140, A1133-A1138. http://dx.doi.org/10.1103/PhysRev.140.A1133
[13]
Parr, R.G. and Yang, W. (1989) Density-Functional Theory of Atoms and Molecules. Oxford University Press, Oxford.
[14]
Becke, A.D. (1993) Density-Functional Thermochemistry. III. The Role of Exact Exchange. The Journal of Chemical Physics, 98, 5648-5652. http://dx.doi.org/10.1063/1.464913
[15]
Lee, C., Yang, W. and Parr, R.G. (1988) Development of the Colle-Salvetti Correlation-Energy Formula into a Functional of the Electron Density. Physical Review, B37, 785-789. http://dx.doi.org/10.1103/PhysRevB.37.785
[16]
Stephens, P.J., Devlin, F.J., Chabalowski, C.F. and Frisch, M.J. (1994) Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields. The Journal of Physical Chemistry, 98, 11623-11627. http://dx.doi.org/10.1021/j100096a001
[17]
Goerigk, L. and Grimme, S. (2011) Efficient and Accurate Double-Hybrid-Meta-GGA Density Functionals—Evaluation with the Extended GMTKN30 Database for General Main Group Thermochemistry, Kinetics, and Noncovalent Interactions. Journal of Chemical Theory and Computation, 7, 291-309. http://dx.doi.org/10.1021/ct100466k
[18]
Grimme, S., Antony, J., Ehrlich, S. and Krieg, J. (2010) A Consistent and Accurate ab Initio Parametrization of Density Functional Dispersion Correction (DFT-D) for the 94 Elements H-Pu. The Journal of Chemical Physics, 132, Article ID: 154104. http://dx.doi.org/10.1063/1.3382344
[19]
Grimme, S., Ehrlich, S. and Goerigk, L. (2011) Effect of the Damping Function in Dispersion Corrected Density Functional Theory. Journal of Computational Chemistry, 32, 1456-1465. http://dx.doi.org/10.1002/jcc.21759
[20]
Weigend, F. and Ahlrichs, R. (2005) Balanced Basis Sets of Split Valence, Triple Zeta Valence and Quadruple Zeta Valence Quality for H to Rn: Design and Assessment of Accuracy. The Journal of Physical Chemistry, 7, 3297-3305.
[21]
Neese, F. (2012) The ORCA Program System. WIREs Computational Molecular Science, 2, 73-78.
http://dx.doi.org/10.1002/wcms.81
