Cyclization of N-alkyldithiocarbamates in alkaline media, a counter example of well-known chemistry – an experimental and theoretical study

Abstract

In strong alkaline media, the reaction of 2-(tert-butylamino)ethanol (3: R ¼ Bu t ) with CS 2 at 0 C produced a cyclic dithiocarbamate, 3-tert-butylthiazolidine-2-thione (1: R ¼ Bu t ), rather than alkaline metal or ammonium salts of [S 2 CN(Bu t )CH 2 CH 2 OH] À . This is in contrast to isolation of stable alkaline metal or ammonium salts of [S 2 CN(R)CH 2 CH 2 OH] À (R ¼ Me, Et, Pr, or CH 2 CH 2 OH) obtained in analogous reactions. The use of Ni(OAc) 2 , both as a source of Ni(II) and a weaker base, in a one-pot reaction with (3: R¼ Bu t ) and CS 2 , successfully gave the first reported metal complex of [S 2 CN(Bu t )CH 2 CH 2 OH] À , namely [Ni{S 2 CN(Bu t )CH 2 CH 2 OH} 2 ] (2: R ¼ Bu t ). Compounds 1 and 2 have been fully characterized by infrared and NMR spectroscopies, and by X-ray crystallography. DFT calculations on the cyclization and stabilities of [S 2 CN(R)CH 2 CH 2 OH] À (R ¼ Pr and Bu t ) have been carried out.

Synthesis, characterization and antifungal activity of new dithiocarbamate-based complexes of Ni(II), Pd(II) and Pt(II)

“…As previously observed all complexes display monomeric structure in the unit cell with no significant intermolecular interaction involving the metal center [36][37][38][39][40]. The X-ray diffraction showed (3) suggest a partial double bond character, as a consequence of higher electronic density expected upon coordination, confirming the delocalization of electron density in the dithiocarbamate fragment, as revealed by IR and 13 C NMR experiments.…”

1-(2-Hydroxyethyl)imidazolidine-2-thione

“…Several closely related cyclic compounds have been observed in the literature as a result of the decomposition reaction between sodium N-isopropyl-N-hydroxyethyldithiocarbamate with a cadmium salt [18], benzimidazole based thiones [19,20], and as a side product from the cyclization of (2-t-butyl)ethanol dithiocarbamate [21]. It is likely the presence of a strong alkaline medium that promotes the formation of these cyclic compounds [22].…”