Dithiocarbamates as hazardous remediation agent: A critical review on progress in environmental chemistry for inorganic species studies of 20th century

This article provides a critical review and a wide range of applications of dithiocarbamates (DTCs) in environmental samples. The characteristics of DTCs are reviewed with particular emphasis on inorganic speciation studies using state-of-the-art analytical instrumentation coupled with computational methods of analysis.     

Dithiocarbamates as Precursors in Organic Chemistry; Synthesis and Uses

Abstract

Organic dithiocarbamates have received great attention due to their interesting chemistry and wide utility as radical precursors and intermediates in organic synthesis. They also have found many of applications, that is, in agriculture and medicine. They are in use as pesticides, as well as in the rubber industries as vulcanization accelerators; and as antioxidants. Because they exhibit strong metal-binding capacity, they can act as in inhibitors of enzymes and have a profound effect on biological systems. Moreover, they have found application in the treatment of cancer and HIV.     

STRUCTURE OF OXIDIZED DISULFIDE BONDS AS CALCULATED BY THE CNDO/2 METHOD

Abstract

ONDO/2 calculations indicate that disulfide cation radicals, e.g. HSSH⁺ and CH₃SSCH₃ ⁺, have a trans-planar structure in contrast to the twisted structure of the parent molecule. The main reason for this difference is the removal of an electron from the sulfur lone-pair orbitals. The bond energy in the disulfide cation radical is much lower than in the parent molecule, which makes the reaction CH₃SSCH₃ ⁺ → CH₃S→ + CH₃S⁺ allowed, as observed previously in radiolysis of CH₃SSCH₃ single crystals.     

Interpretation of the cytostatic properties of sodium morpholyldithiocarbamate,a chelating agent

Summary The antioxidant properties of sodium morpholyldithiocarbamate (MorDTC) were studied in order to contribute to the interpretation of its antitumor activity and synergetic effect overcis-platinum.MorDTC inhibits pyrogallol autooxidation better than vitamin C but does not dismutate the superoxide radical generated by the xanthine — xanthine oxidase system. Nevertheless, the complexes formedin situ betweenMorDTC and Mn(II), Co(II), Ni(II), and Cu(II) do dismutate the superoxide radical with a SOD-like activity (SOD=superoxide dismutase), expressed in terms of IC₅₀ values within the range of 3.2 to 62 µM. The highest activity corresponds to Mn(II) and Cu(II) complexes. The possible inhibitory action ofMorDTC on erythrocyte SOD was also studiedin vitro; however, the results were negative. Therefore,MorDTC should dismulate the superoxide radical after chelating metals without inhibiting SOD, the enzyme playing this rolein vivo.

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Interpretation der cytostatischen Eigenschaften von Natriummorpholyldithiocarbamat, einem komplexbildenden Reagens

Zusammenfassung Die antioxidativen Eigenschaften von Natriummorpholyldithiocarbamat (MorDTC) wurden im Hinblick auf seine Wirkung gegen Tumore und seinem synergistischen Effekt im Zusammenhang mitcis-Platin untersucht.MorDTC hemmt die Autoxidation von Pyrogallol besser als Vitamin C, greift aber das vom System Xanthin-Xanthinoxidase gebildete Superoxidradikal nicht an. Dieses wird jedoch von demin situ ausMorDTC und Mn(II), Co(II), Ni(II) und Cu(II) gebildeten Komplexen mit einer SOD-vergleichbaren Aktivität umgesetzt (SOD=Superoxiddismutase; IC₅₀ im Bereich von 3.2 bis 62 µM). Die höchste Aktivität wurde für Mn(II)- und Cu(II)-Komplexe gefunden. Die hemmende Wirkung vonMorDTC auf erythrocytische SOD wurdein vitro untersucht. Die Ergebnisse waren negativ.MorDTC ist daher nach der Komplexierung mit Metallen in der Lage, das Superoxidradikal anzugreifen, ohne SOD, das Enzym, das Enzym, das diese Aufgabein vivo übernimmt, zu hemmen.

     

Synthesis,characterization, interactions with DNA and bovine serum albumin (BSA), and antibacterial activity of cyclometalated iridium(III) complexes containing dithiocarbamate derivatives

Three mononuclear cyclometalated iridium(III) complexes having dithiocarbamate ligands, [Ir^III(2-C₆H₄py)₂(L)] (where 2-C₆H₄py?=?2-phenylpyridine; and L¹H?=?4-MePipzcdtH, L²H?=?MorphcdtH, and L³H?=?4-BzPipercdtH for 1, 2, and 3, respectively), were synthesized from [Ir(2-C₆H₄py)₂Cl]₂·1/4CH₂Cl₂ by displacing the two bridging chlorides with one dithiocarbamate ligand. The complexes were characterized using physicochemical and spectroscopic tools along with structural analysis of [Ir(2-C₆H₄py)₂(L²)] (2) by single crystal X-ray diffraction. Structural analysis of 2 showed a distorted octahedron in which the nitrogen donor of one 2-phenylpyridine and the carbon donor of another 2-phenylpyridine are in axial positions, trans to one another. Electrochemical analysis by cyclic voltammetry showed the irreversible two-electron equivalent reduction voltammograms of 1, 2, and 3 attributable to Ir(III) to Ir(I). Electronic characterizations of these complexes are consistent with significant delocalization of the sulfur electron density onto the empty metal d-orbital. The intercalative interaction of the complexes with calf thymus DNA was evaluated using absorption, fluorescence quenching, and viscosity measurements. The binding affinities of these complexes with bovine serum albumin were estimated in terms of quenching constants using the Stern–Volmer equation. Study of antibacterial activities of the complexes by agar disk diffusion against some species of pathogenic bacteria was also performed.     

Synthesis and spectral studies on mixed ligand complexes of Cd(II) dithiocarbamates with nitrogen donors: single crystal X-ray structure of bis (4-methylpiperidinecarbodithioato-S,S′)(1,10-phenanthroline)cadmium(II)

The current article describes the synthesis and characterization of the following adducts: [Cd(2-mpipdtc)₂(1,10-phen)], [Cd(2-mpipdtc)₂(bipy)], [Cd(4-mpipdtc)₂(1,10-phen)], [Cd(4-mpipdtc)₂(bipy)] (where 2-mpipdtc^? = 2-methylpiperidinecarbodithioate anion, 4-mpipdtc^? = 4-methylpiperidinecarbodithioate anion, 1,10-phen = 1,10-phenanthroline and bipy = 2,2′-bipyridine). A single crystal X-ray structural analysis was carried out for [Cd(4-mpipdtc)₂(1,10-phen)]. IR spectra of the complexes show the contribution of the thioureide form to the structures. Reduction in ν_C–N(thioureide) for the mixed ligand complexes is attributed to the change in coordination number from four to six and the steric effect exerted by 1,10-phenanthroline or 2,2′-bipyridine. Deshielding of the protons adjacent to nitrogen in the ¹H NMR spectra is attributed to drift of electrons from the nitrogen of NR₂, forcing electron density towards sulfur via the thioureide π-system. Single crystal X-ray structural analysis of [Cd(4-mpipdtc)₂(1,10-phen)] showed that the cadmium is in a distorted octahedral environment with a CdS₄N₂ chromophore. The presence of 1,10-phenanthroline in the coordination sphere of Cd(dtc)₂ increases the Cd–S distances and decreases the S–Cd–S angles. VBS analysis supports the determined structure.     

One-Pot Convenient and High Yielding Synthesis of Dithiocarbamates

Summary. A convenient and high yielding method for the synthesis of diverse dithiocarbamates having various substituents including alkyl, aryl, heteroaryl, and alkylaryl at the thiol chain or at the amine chain or at both thiol and amine chains were developed by the one-pot reaction of mercaptans, amines, and bis(benzotriazolyl)methanethione in presence of amidine base under mild reaction conditions.     

On the reaction of dithiocarbamates with nitrogen-containing derivates of oxalic acid

Summary The action of bisimidochlorides of oxalic acid on dithiocarbamates produces 2-thioxo-3-aryl(alkyl)-4,5-diiminothiazolidines by cycloacylation. The molecular structure of 2-thioxo-3-(4-methoxyphenyl)-4,5-bis(phenylimino)-thiazolidine is confirmed by X-ray crystal structure analysis.

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Zur Reaktion von Dithiocarbaminaten mit stickstoffhaltigen Derivaten der Oxalsäure

Zusammenfassung Bei der Einwirkung von Bisimidchloriden der Oxalsäure auf Dithiocarbaminate entstehen durch Cycloacylierung 2-Thioxo-3-aryl(alkyl)-4,5-diiminothiazolidine. Die Molekülstruktur von 2-Thioxo-3-(4-methoxyphenyl)-4,5-bis(phenylimino)thiazolidin wird durch Röntgenkristallstrukturanalyse bestätigt.

     

Chloro-diorganotin(IV) complexes of 4-methyl-1-piperidine carbodithioic acid: Synthesis, X-ray crystal structures, spectral properties and antimicrobial studies

Chloro-diorganotin(IV) complexes of 4-methyl-1-piperidine carbodithioic acid (4-MePCDTA) have been synthesized by the reaction with diorganotin dichloride in 1:1 molar ratio in anhydrous toluene. These newly synthesized complexes have been characterized by elemental, IR, multinuclear NMR (¹H and ¹³C) and mass spectrometric studies. The crystal structures of complex 1 [Me₂SnCl(4-MePCDT)] and 3 [Ph₂SnCl(4-MePCDT)] have been determined by X-ray single crystal analysis, which show trigonal bipyramid geometry. These complexes were tested for their antimicrobial activity against six different plant and human pathogens. The screening results show that the complexes exhibit higher antibacterial and antifungal activity than the free ligand.     

Coordinating ability of the heterocycles 1,3-dithia-2-arsa and stiba-cyclopentanes toward sulfur containing ligands,part I. Dialkyl-dithiocarbamate complexes

Summary The heterocyclic compounds ClMS₂ (CH₂)₂ (M = As, Sb) are tested by first time as source of starting materials in the synthesis of complexes. The preparation and characterization of heterocyclic dithiocarbamatesR ₂NCS₂ MS₂ (CH₂)₂, (M = As, Sb;R =Me,Et,i-Pr) is reported. Spectroscopic and analytical data suggest a bidentate behavior of the dithiocarbamate entity and the presence of aMS₄ core.

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Die Koordinationsfähigkeit der Heterocyclen 1,3-Dithia-2-arsa- und-stiba-cyclopentan gegenüber Schwefel enthaltenden Liganden, I. Dialkyldithiocarbamat-Komplexe

Zusammenfassung Die heterocyclischen Verbindungen ClMS₂ (CH₂)₂ (M = As, Sb) werden erstmals als Quelle für Ausgangsmaterial zur Synthese von Komplexen herangezogen. Es wird über die Herstellung und Charakterisierung der heterocyclischen DithiocarbamateR ₂NCS₂ MS₂ (CH₂)₂ (M = As, Sb;R =Me,Et,i-Pr) berichtet. Spektroskopische und analytische Daten sprechen für ein bidentates Verhalten der Dithiocarbamat-Einheit und der Präsenz einerMS₄-Anordnung im Komplex.