A DFT study of the chemical reactivity of thiobencarb and its oxidized derivatives in the aqueous phase

Luis Humberto Mendoza-Huizar


In the present work, the global and local reactivity of S-(4-chloro­ben­zyl)-N,N-diethylthiocarbamate (TB) and its oxidized derivatives (sulfone (TBSu) and sulfoxide (TBS) were analyzed. In addition, the chemical reacti­vities of the dechlorinated forms of TB (DTB), TBSu (DTBSu) and TBS (DTBS) were studied. The calculations were performed at the wB97XD/6-
-311++G(2d,2p) level of theory in the aqueous phase. The condensed Fukui functions indicated that for TB and DTB, the most preferred sites for donating electron in a reaction are located on the S and N atoms, while the most reactive sites for accepting electrons are associated with the aromatic ring (AR). For TBS and DTBS, the more reactive sites are located on AR, S and AR for nuc­leophilic, electrophilic and free radical attacks, respectively. In the case of TBSu and DTBSu, the results showed AR to be the more reactive zone for the three kinds of attacks. These last results suggest that cleavage of the C–S bond in TB, TBS and their dechlorinated forms is favored by electrophilic attacks. Additionally, the obtained results suggest that in TB, it is plausible that the cleavage of the C–N is favored on attack of this molecule by electrophiles.


thiobencarb; Fukui function; dual descriptor; DFT


J. L. Maclean, D. C. Dawe, B. Hardy, G. P. Hettel, Rice Almanac: Source Book for the Most Important Economic Activity of Earth, CABI Publishing, Wallingford, UK, 2002

V. Singh, M. L. Jat, Z. A. Ganie, B. S. Chauhan, R. K. Gupta, Crop Prot. 81 (2016) 168

Y. H. Moon, S. Kuwatsuka, J. Pesticide Sci. 9 (1984) 745

Y. Tanetani, K. Kaku, M. Ikeda, T. Shimizu, J. Pestic. Sci. 38 (2013) 39

S. A. Mabury, J. S. Cox, D. G. Crosby. Rev. Environ. Contam. Toxicol. 147 (1996) 71

E. Sancho, M. Sánchez, M.D. Ferrando, E. Andreu-Moliner, J. Environ. Sci. Heal. B 36 (2001) 55

K. Ishikawa, J. Pest. Sci. 5 (1980) 287.

M. Saka, Ecotox. Environ. Saf. 73 (2010) 1165

X. Huang, J. He, X. Yan, Q. Hong, K. Chen, Q. He, L. Zhang, X. Liu, S. Chuang, S Li, J Jiang, Pestic. Biochem. Physiol. doi: 10.1016/j.pestbp.2016.11.010

S. Kodama, A. Yamamoto, A. Matsunaga, J. Agric. Food Chem. 45 (1997) 990

H.D. Burrows, M. Canle, J.A. Santaballa, S. Steenken, J. Photochem. Photobiol., B 67 (2002) 71

D. Vialaton, C. Richard, J. Photoch. Photobio. A 136 (2000) 169

W.M. Draper, D.G. Crosby, J. Agr. Food Chem. 32 (1984) 231

Y. Magara, T. Aizawa, N. Matumoto, F. Souna, Water Sci. Technol. 30(7) (1994) 119

P. Sapari, B.S. Ismail, Environ Monit Assess. 184(10) (2012) 6347

I. A. Mahzabin, M. R. Rahman, Fundam. Appl. Agric. 2(2) (2017) 277

W. C. Quayle, D. P. Oliver, S. Zrna, J. Agr. Food Chem. 54(19) (2006) 7213

C. Fernández-Vega, E. Sancho, M. D. Ferrando, Chemosphere 135 (2015) 94

R. Shoji, M. Kawakami, Mol. Diver. 10 (2006) 101

M. Cassotti, QSAR study of aquatic toxicity by chemometrics methods in the framework of REACH regulation. University of Milano, Italy, Bicocca, 2015

J. L. Gázquez, J. Mex. Chem. Soc. 52 (2008) 3

P. Geerlings, F. De Proft, W. Langenaeker, Chem. Rev. 103 (2003) 1793

H. Chermette, J. Comput. Chem. 20 (1999) 129

P. W. Ayers, J. S. M. Anderson, L. J. Bartolotti, Int. J. Quantum Chem. 101 (2005) 520

P. K. Chattaraj, U. Sarkar, D.R. Roy, Chem. Rev. 106 (2006) 2065

P. A. Johnson, L. J. P. Bartolotti, W. Ayers, T. Fievez, P. Geerlings, Modern Charge Density Analysis, ed(s) Gatti C and Macchi P Springer New York: 2012

S. B. Liu, Acta Phys. Chim. Sin. 25 (2009) 590

R. G. Parr, R. A. Donnelly, M. Levy, W. E. Palke, J. Chem. Phys. 68 (1978) 3801

R. G. Parr, R. G. Pearson, J. Am. Chem. Soc. 105 (1983) 7512

R. G. Pearson, J. Chem. Educ. 64 (1987) 561

R.G. Parr, L. Szentpaly, S. Liu, J. Am. Chem. Soc. 121 (1999) 1922

J. L. Gázquez, A. Cedillo, A. Vela, J. Phys. Chem. A 111 (2007) 1966

R. G. Parr, W. Yang, J. Am. Chem. Soc. 106 (1984) 4048

R. G. Parr, W. Yang, Functional Theory of Atoms and Molecules, 1st ed., Oxford University Press: New York, 1989

S. B. Liu, in: Chemical reactivity theory: A density functional view; Chattaraj, P. K., ed.; Taylor and Francis: Boca Raton, 2009.

C. Morell, A. Grand, A. Toro-Labbe, J. Phys. Chem., A 109 (2005) 205

R. Krishnan, J. S. Binkley, R. Seeger, J. A. Pople, J. Chem. Phys 72 (1980) 650

A. D. McLean, G. S. Chandler, J. Chem. Phys. 72 (1980) 5639

S. Miertus, J. Tomasi, J. Chem. Phys. 65 (1982) 239

S. Miertus, E. Scrocco, J. Tomasi, J. Chem. Phys. 55 (1981) 117.

Gaussian 09, Revision A.01, Gaussian, Inc., Wallingford CT, 2009

Gaussview Rev. 3.09, Windows version. Gaussian Inc., Pittsburgh

A. Poland, D. Palen, E. Glover, Nature 300 (1982) 271

D. Wondrousch, A. Böhme, D. Thaens, N. Ost, G. Schüürmann, J. Phys. Chem. Lett. 1 (2010) 1605

A. U. Orozco-Valencia, A. Vela, J. Mex. Chem. Soc. 56(3) (2012) 294

L. O. Ruzo, J.E. Casida, J. Agric. Food Chem. 33 (1985) 272

L. Senthilkumar, P. Umadevi, K.N. Nithya, P. Kolandaivel, J. Mol. Model. 19(8) (2013) 3411.

DOI: https://doi.org/10.2298/JSC170927034M

Copyright (c) 2018 J. Serb. Chem. Soc.

Creative Commons License
This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.

IMPACT FACTOR 0.828 (140 of 172 journals)
5 Year Impact Factor 0.917 (140 of 172 journals)