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Anhydrous Aluminum Chloride Catalyzed Methylene Group Inclusion: Mechanistic, Spectral and Single Crystal X-Ray Structural Study on Methanediyl Bis(Cyclohexylmethylcarbamodithioate)

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In this study anhydrous AlCl3 is used as a catalyst for the inclusion of a methylene group in to cyclohexylmethyldithiocarbamic acid to form methanediyl bis(cyclohexylmethylcarbamodithioate). Dichloromethane is used as a methylene group bearer in the reaction. A suitable mechanistic pathway involving +CH2Cl is discussed. FTIR, NMR and Mass spectral techniques have been used in the analysis. Single crystal X-ray structure of the compound was determined. FTIR spectrum of the compound showed υc-s band at 1073 cm-1 and υC-H vibrations appeared at 2853 and 2928 cm-1. Thioureide stretching band was observed at 1473 cm-1. The molecular ion peak in the Mass spectroscopy confirmed the proposed formula. H1 NMR spectrum of the compound showed a signal at 4.33(s) ppm for α-CH of the cyclohexyl ring and -CH3 protons attached to nitrogen appeared at 3.40 ppm. Methylene proton (S-CH2-S) signal appeared at 3.16 ppm which is largely deshielded by the presence of two electronegative sulphur atoms on either side. The characteristic methylene carbon (S-CH2-S) signal appeared at 45.46 ppm in the 13C NMR spectrum. Single crystal X-ray structural analysis of the compound showed it to be monomeric. Methylene carbon in S-CH2-S, C(9) is tetrahedrally bonded to two hydrogen atoms and two sulphur atoms S(2), S(3). The molecule stacks its cyclohexyl rings along ‘c’ axis of the unit cell. Short contacts in the form of supramolecular interactions such as C---S and S---S exist in the solid state at 3.49 and 3.50 Å respectively.


International Letters of Chemistry, Physics and Astronomy (Volume 68)
K. Ramalingam et al., "Anhydrous Aluminum Chloride Catalyzed Methylene Group Inclusion: Mechanistic, Spectral and Single Crystal X-Ray Structural Study on Methanediyl Bis(Cyclohexylmethylcarbamodithioate)", International Letters of Chemistry, Physics and Astronomy, Vol. 68, pp. 61-70, 2016
Online since:
July 2016

[1] T. Cohen, M. Bhupathy, Organoalkali compounds by radical anion induced reductive metalation of phenyl thioethers, Acc. Chem. Res. 22 (1989) 152-161.

[2] C.G. Screttas, Stoichiometry and Synthetic Utility of the Reaction of Alkyl Halides with Lithium Dihydronaphthylides, J. Chem. Soc., Chem. Commun. (1972) 752-753.

[3] T. Cohen, J.R. Matz, Reductive Lithiation of Some Thioketals Using Lithium 1-(Dimethylamino)naphthalenide, Synth. Commun. 10 (1980) 311-317.

[4] N. Kennedy, P. Liu, T. Cohen, Fundamental Difference in Reductive Lithiations with Preformed Radical Anions versus Catalytic Aromatic Electron-Transfer Agents: N, N-Dimethylaniline as an Advantageous Catalyst, Angew. Chem. Int. Ed. Engl. 4(55) (2016).

[5] M.A. Perry, S.D. Rychnovsky, Generation, structure and reactivity of tertiaryorganolithium reagents, Natural Product Reports. 32 (2015) 517-533.

[6] J.H. Lee, H.J. Jeong, C.K. Jin, S.H. Jang, M.K. Kim, Y.J. Yoon and S.G. Lee. Development of a Novel Method for the Preparation of Dithioacetal in the Presence of Titanium(IV) Chloride/Zinc in Dimethoxymethane, Bull. Korean Chem. Soc. 26 (2005).

[7] E.J. Corey, D. Seebach, Angew. Chem., Int. Ed. Engl. 4 (1965).

[8] C. G. Screttas, M. Micha-Screttas, Hydrolithiation of . alpha. -olefins by a regiospecific two-step process. Transformation of alkyl phenyl sulfides to alkyllithium reagents, J. Org. Chem. 43 (1978) 1064-1071.

[9] C. G. Screttas, M. Micha-Screttas, Markownikoff two-step hydrolithiation of . alpha. -olefins. Transformation of secondary and tertiary alkyl phenyl sulfides to the relevant alkyllithium reagents, J. Org. Chem. 44 (1979) 713-719.

[10] T. Fujiwara, Y. Kato,T. Takada, Ring-Closing Metathesis of Titanium–Carbene Complexes Prepared from Thioacetals Having a Carbon–Carbon Double Bond, Tetrahedron. 56 (2000) 4859- 4869.

[11] D. Seebach, R. Bürstinghaus, S-Methyl thiocarboxylates from aldehydes and ketones through ketene thioacetals. Reductive nucleophile thiocarbonylation, Synthesis. 31 (1975) 461-462.

[12] D.J. Ager, A new method for preparing 1-phenylthio-1-trimethylsilylalkanes: the preparation of Î ± - silylcarbanions and olefins, Tetrahedron Lett. 22 (1981) 2932 -2926.

[13] M.M. Khodaei, P. Salehi, M.A. Zolfigol, S. Sirouszadeh, Efficient synthesis of 3, 4-dihydropyrimidin-2(1H)-ones by aluminium hydrogensulfate in solution and under solvent free conditions, Polish J. Chem. 78 (2004) 385-388.

[14] E.J. Corey, D.J. Seebach, Phenylthiomethyllithium and Bis(phenylthio)methyllithium Org. Chem. 31(1966) 4097-4099.

[15] H.I. Mosberg, J.R. Omnaas, A. Goldstein, Structural requirements for δ opiod receptor binding, Mol. Pharmacol. 31 (1987) 599-602.

[16] A. Fürstner, A. Hupperts, A. Ptock, E. Janssen, Site Selective" Formation of Low-Valent Titanium Reagents: An "Instant, Procedure for the Reductive Coupling of Oxo Amides to Indoles J. Org. Chem. 59 (1994) 5215-5229.

[17] G. Delogu, O.D. Lucchi, P. Maglioli, Asymmetric reactions of thioacetals and their S-oxides derived from 1, 1'-binaphthalene-2, 2'-dithiol, J. Org. Chem. 60 (1991) 4467-4473.

[18] M. Ueki, T. Ikeo, K. Hokari, K. Nakamura, A. Saeki, H. Komatsu, A new efficient method for S-CH2-S bond formation and its application to a Djenkolic acid containing cyclic Enkephalin analogue, Bull. Chem. Soc. Jpn. 72 (1999) 829-838.

[19] R.S. Asquith, Chemistry of Natural Protein Fibers, Springer Science & Business Media, Berlin, (2012).

[20] N. Greenspoon, R. Hershkoviz, R. Alon, E. Gershonov, B. Lavie, O. Lider, Novel psi-S-CH2 peptide-bond replacement and its utilization in the synthesis of nonpeptidic surrogates of the Leu-Asp-Val sequence that exhibit specific inhibitory activities on CD4+ T cell binding to fibronectin, Int. J. Pept. Protein Res. 43 (1994).

[21] A.C.T. North, D.C. Phillips, F.S. Mathews, A semi-empirical method of absorption correction, Acta Crystallogr, Sect. A. 24 (1968) 351-359.

[22] Bruker, SADABS (Version 2007/4). Bruker AXS Inc., Madison, Wisconsin, USA, (2008).

[23] A. Altomare, M.C. Burla, M. Camalli, G.L. Cascarano, C. Giacovazzo, A. Guagliardi, A.G.G. Moliterni, G. Polidori, R. Spagna, A new tool for crystal structure determination and refinement, J. Appl. Crystallogr. 32 (1999) 115-119.

[24] G.M. Sheldrick, SHELXL 97, Program for Crystal Structure Refinement, Univ. of Gottingen, Germany, (1997).

[25] L.J. Faruggia, ORTEP-3 for Windows, University of Glasgow, Scotland, UK, (1999).

[26] N. Alexander, K. Ramalingam, C. Rizzoli, Supramolecularly Linked Linear Polymers of Thallium(I) Dithiocarbamates: Steric Influence on the Supramolecular Interaction of Methyl and Ethylcyclohexyl Dithiocarbamates of Thallium(I), Inorg. Chim. Acta. 365 (2011).

[27] S. Sivasekar, K. Ramalingam, C. Rizzoli, Metal dithiocarbamate precursors for the preparation of a binary sulfide and a pyrochlore: Synthesis, structure, continuous shape measure and bond valence sum analysis of antimony(III) dithiocarbamates, Polyhedron, 85(8) (2015).

[28] G. S. Sivagurunathan, K. Ramalingam, C. Rizzoli, Continuous Shape Measure of electronic effect free steric distortions in tris(dithiocarbamato)indium(III): Synthesis, spectral, electrochemical, single crystal X-ray structural investigations and BVS calculations on tris(dithiocarbamato)indium(III) complexes, Polyhedron, 72 ( 2014) 96-102.

[29] G. S. Sivagurunathan, K. Ramalingam, C. Rizzoli, Nanothallium(III) sulfide from dithiocarbamate precursors: Synthesis, single crystal X-ray structures and characterization, Polyhedron, 65 (2013) 316 – 321.

[30] S. Sivasekar, K. Ramalingam, C. Rizzoli, N. Alexander, Synthesis, structural, Continuous Shape Measure and bond valence sum characterization of bismuth(III) complexes of substituted dithiocarbamates and their solvothermal decomposition, Inorg. Chim Acta, 419 (2014).

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