Sodium diethyldithiocarbamate

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Sodium diethyldithiocarbamate
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Sodium diethyldithiocarbamate, 2015-10-22 (2).jpg
Names
Preferred IUPAC name
Sodium diethylcarbamodithioate
Identifiers
3D model (JSmol)
ChEMBL
ChemSpider
ECHA InfoCard 100.005.192 OOjs UI icon edit-ltr-progressive.svg
PubChem CID
UNII
  • InChI=1S/C5H11NS2.Na/c1-3-6(4-2)5(7)8;/h3-4H2,1-2H3,(H,7,8);/q;+1/p-1 Yes check.svgY
    Key: IOEJYZSZYUROLN-UHFFFAOYSA-M Yes check.svgY
  • InChI=1/C5H11NS2.Na/c1-3-6(4-2)5(7)8;/h3-4H2,1-2H3,(H,7,8);/q;+1/p-1
    Key: IOEJYZSZYUROLN-REWHXWOFAF
  • [Na+].[S-]C(=S)N(CC)CC
Properties
C5H10NS2Na
Molar mass 171.259 g/mol (anhydrous)
AppearanceWhite, slightly brown, or slightly pink crystalline solid
Density 1.1 g/cm3
Melting point 95 °C (203 °F; 368 K)
Soluble
Solubility soluble in alcohol, acetone
insoluble in ether, benzene
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
Harmful
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Sodium diethyldithiocarbamate is the organosulfur compound with the formula NaS2CN(C2H5)2. It is a pale yellow, water soluble salt.

Contents

Preparation

This salt is obtained by treating carbon disulfide with diethylamine in the presence of sodium hydroxide:

CS2 + HN(C2H5)2 + NaOH → NaS2CN(C2H5)2 + H2O

Other dithiocarbamates can be prepared similarly from secondary amines and carbon disulfide. They are used as chelating agents for transition metal ions and as precursors to herbicides and vulcanization reagents.

Reactions

Iron tris(diethyldithiocarbamate), a black solid that is soluble in organic solvents, is a representative complex of diethyldithiocarbamate. Fe(Et2NCS2)3.svg
Iron tris(diethyldithiocarbamate), a black solid that is soluble in organic solvents, is a representative complex of diethyldithiocarbamate.

Oxidation of sodium diethyldithiocarbamate gives the disulfide, also called a thiuram disulfide (Et = ethyl):

2 NaS2CNEt2 + I2 → (S2CNEt2)2 + 2 NaI

Dithiocarbamates are nucleophiles and thus can be alkylated. Even dichloromethane suffices: [1]

2 NaS2CNEt2 + CH2Cl2 → CH2(S2CNEt2)2 + 2 NaCl

Diethyldithiocarbamate reacts with many metal salts to give transition metal dithiocarbamate complexes. The ligands coordinate via the two sulfur atoms. Other more complicated bonding modes are known including binding as unidentate ligand and a bridging ligand using one or both sulfur atoms. [2]

Laboratory and practical use

By the technique of spin trapping, complexes of dithiocarbamates with iron provide one of the very few methods to study the formation of nitric oxide (NO) radicals in biological materials. Although the lifetime of NO in tissues is too short to allow detection of this radical itself, NO readily binds to iron-dithiocarbamate complexes. The resulting mono-nitrosyl-iron complex (MNIC) is stable, and may be detected with Electron Paramagnetic Resonance (EPR) spectroscopy. [3] [4] [5]

The zinc chelation of diethyldithiocarbamate inhibits metalloproteinases, which in turn prevents the degradation of extracellular matrix, an initial step in cancer metastasis and angiogenesis. [6]

Diethyldithiocarbamate inhibits superoxide dismutase, which can both have antioxidant and oxidant effects on cells, depending on the time of administration. [6]

Related Research Articles

<span class="mw-page-title-main">Hydroxide</span> Chemical compound

Hydroxide is a diatomic anion with chemical formula OH. It consists of an oxygen and hydrogen atom held together by a single covalent bond, and carries a negative electric charge. It is an important but usually minor constituent of water. It functions as a base, a ligand, a nucleophile, and a catalyst. The hydroxide ion forms salts, some of which dissociate in aqueous solution, liberating solvated hydroxide ions. Sodium hydroxide is a multi-million-ton per annum commodity chemical. The corresponding electrically neutral compound HO is the hydroxyl radical. The corresponding covalently bound group –OH of atoms is the hydroxy group. Both the hydroxide ion and hydroxy group are nucleophiles and can act as catalysts in organic chemistry.

<span class="mw-page-title-main">Inorganic chemistry</span> Field of chemistry

Inorganic chemistry deals with synthesis and behavior of inorganic and organometallic compounds. This field covers chemical compounds that are not carbon-based, which are the subjects of organic chemistry. The distinction between the two disciplines is far from absolute, as there is much overlap in the subdiscipline of organometallic chemistry. It has applications in every aspect of the chemical industry, including catalysis, materials science, pigments, surfactants, coatings, medications, fuels, and agriculture.

Carbon compounds are defined as chemical substances containing carbon. More compounds of carbon exist than any other chemical element except for hydrogen. Organic carbon compounds are far more numerous than inorganic carbon compounds. In general bonds of carbon with other elements are covalent bonds. Carbon is tetravalent but carbon free radicals and carbenes occur as short-lived intermediates. Ions of carbon are carbocations and carbanions are also short-lived. An important carbon property is catenation as the ability to form long carbon chains and rings.

<span class="mw-page-title-main">Nitrogen</span> Chemical element, symbol N and atomic number 7

Nitrogen is a chemical element; it has symbol N and atomic number 7. Nitrogen is a nonmetal and the lightest member of group 15 of the periodic table, often called the pnictogens. It is a common element in the universe, estimated at seventh in total abundance in the Milky Way and the Solar System. At standard temperature and pressure, two atoms of the element bond to form N2, a colorless and odorless diatomic gas. N2 forms about 78% of Earth's atmosphere, making it the most abundant uncombined element in air. Because of the volatility of nitrogen compounds, nitrogen is relatively rare in the solid parts of the Earth.

<span class="mw-page-title-main">Organometallic chemistry</span> Study of organic compounds containing metal(s)

Organometallic chemistry is the study of organometallic compounds, chemical compounds containing at least one chemical bond between a carbon atom of an organic molecule and a metal, including alkali, alkaline earth, and transition metals, and sometimes broadened to include metalloids like boron, silicon, and selenium, as well. Aside from bonds to organyl fragments or molecules, bonds to 'inorganic' carbon, like carbon monoxide, cyanide, or carbide, are generally considered to be organometallic as well. Some related compounds such as transition metal hydrides and metal phosphine complexes are often included in discussions of organometallic compounds, though strictly speaking, they are not necessarily organometallic. The related but distinct term "metalorganic compound" refers to metal-containing compounds lacking direct metal-carbon bonds but which contain organic ligands. Metal β-diketonates, alkoxides, dialkylamides, and metal phosphine complexes are representative members of this class. The field of organometallic chemistry combines aspects of traditional inorganic and organic chemistry.

<span class="mw-page-title-main">Thiol</span> Any organic compound having a sulfanyl group (–SH)

In organic chemistry, a thiol, or thiol derivative, is any organosulfur compound of the form R−SH, where R represents an alkyl or other organic substituent. The −SH functional group itself is referred to as either a thiol group or a sulfhydryl group, or a sulfanyl group. Thiols are the sulfur analogue of alcohols, and the word is a blend of "thio-" with "alcohol".

<span class="mw-page-title-main">Nitric oxide</span> Colorless gas with the formula NO

Nitric oxide is a colorless gas with the formula NO. It is one of the principal oxides of nitrogen. Nitric oxide is a free radical: it has an unpaired electron, which is sometimes denoted by a dot in its chemical formula. Nitric oxide is also a heteronuclear diatomic molecule, a class of molecules whose study spawned early modern theories of chemical bonding.

<span class="mw-page-title-main">Xanthate</span> Salt that is a metal-thioate/O-esters of dithiocarbonate

A xanthate is a salt or ester of a xanthic acid. The formula of the salt of xanthic acid is [R−O−CS2]M+. Xanthate also refers to the anion [R−O−CS2]. The formula of a xanthic acid is R−O−C(=S)−S−H, such as ethyl xanthic acid, while the formula of an ester of a xanthic acid is R−O−C(=S)−S−R', where R and R' are organyl groups. The salts of xanthates are also called O-organyl dithioates. The esters of xanthic acid are also called O,S-diorganyl esters of dithiocarbonic acid. The name xanthate is derived from Ancient Greek ξανθός (xanthos) meaning 'yellowish' or 'golden', and indeed most xanthate salts are yellow. They were discovered and named in 1823 by Danish chemist William Christopher Zeise. These organosulfur compounds are important in two areas: the production of cellophane and related polymers from cellulose and for extraction of certain sulphide bearing ores. They are also versatile intermediates in organic synthesis.

<span class="mw-page-title-main">Metal carbonyl</span> Coordination complexes of transition metals with carbon monoxide ligands

Metal carbonyls are coordination complexes of transition metals with carbon monoxide ligands. Metal carbonyls are useful in organic synthesis and as catalysts or catalyst precursors in homogeneous catalysis, such as hydroformylation and Reppe chemistry. In the Mond process, nickel tetracarbonyl is used to produce pure nickel. In organometallic chemistry, metal carbonyls serve as precursors for the preparation of other organometallic complexes.

The chemical element nitrogen is one of the most abundant elements in the universe and can form many compounds. It can take several oxidation states; but the most common oxidation states are -3 and +3. Nitrogen can form nitride and nitrate ions. It also forms a part of nitric acid and nitrate salts. Nitrogen compounds also have an important role in organic chemistry, as nitrogen is part of proteins, amino acids and adenosine triphosphate.

<span class="mw-page-title-main">Triiron dodecacarbonyl</span> Chemical compound

Triiron dodecarbonyl is the organoiron compound with the formula Fe3(CO)12. It is a dark green solid that sublimes under vacuum. It is soluble in nonpolar organic solvents to give intensely green solutions. Most low-nuclearity clusters are pale yellow or orange. Hot solutions of Fe3(CO)12 decompose to an iron mirror, which can be pyrophoric in air.The solid decomposes slowly in air, and thus samples are typically stored cold under an inert atmosphere. It is a more reactive source of iron(0) than iron pentacarbonyl.

<span class="mw-page-title-main">Metal nitrosyl complex</span> Complex of a transition metal bonded to nitric oxide: Me–NO

Metal nitrosyl complexes are complexes that contain nitric oxide, NO, bonded to a transition metal. Many kinds of nitrosyl complexes are known, which vary both in structure and coligand.

<span class="mw-page-title-main">Dithiocarbamate</span> Chemical group (>N–C(=S)–S–)

In organic chemistry, a dithiocarbamate is a functional group with the general formula R2N−C(=S)−S−R and structure >N−C(=S)−S−. It is the analog of a carbamate in which both oxygen atoms are replaced by sulfur atoms.

Sulfur mononitride is an inorganic compound with the molecular formula SN. It is the sulfur analogue of and isoelectronic to the radical nitric oxide, NO. It was initially detected in 1975, in outer space in giant molecular clouds and later the coma of comets. This spurred further laboratory studies of the compound. Synthetically, it is produced by electric discharge in mixtures of nitrogen and sulfur compounds, or combustion in the gas phase and by photolysis in solution.

<span class="mw-page-title-main">Disulfur dioxide</span> Chemical compound

Disulfur dioxide, dimeric sulfur monoxide or SO dimer is an oxide of sulfur with the formula S2O2. The solid is unstable with a lifetime of a few seconds at room temperature.

<span class="mw-page-title-main">Cyclopentadienyliron dicarbonyl dimer</span> Chemical compound

Cyclopentadienyliron dicarbonyl dimer is an organometallic compound with the formula [(η5-C5H5)Fe(CO)2]2, often abbreviated to Cp2Fe2(CO)4, [CpFe(CO)2]2 or even Fp2, with the colloquial name "fip dimer". It is a dark reddish-purple crystalline solid, which is readily soluble in moderately polar organic solvents such as chloroform and pyridine, but less soluble in carbon tetrachloride and carbon disulfide. Cp2Fe2(CO)4 is insoluble in but stable toward water. Cp2Fe2(CO)4 is reasonably stable to storage under air and serves as a convenient starting material for accessing other Fp (CpFe(CO)2) derivatives (described below).

<span class="mw-page-title-main">Sodium nitroprusside</span> Medication for lowering blood pressure

Sodium nitroprusside (SNP), sold under the brand name Nitropress among others, is a medication used to lower blood pressure. This may be done if the blood pressure is very high and resulting in symptoms, in certain types of heart failure, and during surgery to decrease bleeding. It is used by continuous injection into a vein. Onset is nearly immediate and effects last for up to ten minutes.

<span class="mw-page-title-main">Iron tris(diethyldithiocarbamate)</span> Chemical compound

Iron tris(diethyldithiocarbamate) is the coordination complex of iron with diethyldithiocarbamate with the formula Fe(S2CNEt2)3 (Et = ethyl). It is a black solid that is soluble in organic solvents.

<span class="mw-page-title-main">Transition metal dithiocarbamate complexes</span>

Transition metal dithiocarbamate complexes are coordination complexes containing one or more dithiocarbamate ligand, which are typically abbreviated R2dtc. Many complexes are known. Several homoleptic derivatives have the formula M(R2dtc)n where n = 2 and 3.

<span class="mw-page-title-main">Iron bis(diethyldithiocarbamate)</span> Chemical compound

Iron bis(diethyldithiocarbamate) is a coordination complex with the formula [Fe(S2CNEt2)2]2 where Et = C2H5. A red solid, it is representative of several ferrous dithiocarbamates with diverse substituents in place of ethyl. In terms of structure, the species is dimeric, consisting of two pentacoordinate iron(II) centers. It is isostructural with [Zn(S2CNEt2)2]2, which in turn is similar to zinc bis(dimethyldithiocarbamate).

References

  1. Heckley PR, Holah DG, Hughes AN, Leh F (1970). "Reactions of Sodium N,N-Diethyldithiocarbamate with Some Organic Solvents". Canadian Journal of Chemistry. 48 (24): 3827–3830. doi:10.1139/v70-645.
  2. Cotton, F. Albert, Wilkinson, Geoffrey, Murillo, Carlos A., Bochmann, Manfred (1999), Advanced Inorganic Chemistry (6th ed.), New York: Wiley-Interscience, ISBN   0-471-19957-5
  3. Henry Y.; Guissani A.; Ducastel B. (eds); "Nitric oxide research from chemistry to biology: EPR spectroscopy of nitrosylated compounds." Landes, Austin 1997.
  4. Vanin A, Huisman A, van Faassen E (2002). "Iron dithiocarbamate as spin trap for nitric oxide detection: Pitfalls and successes". Nitric Oxide, Part D: Oxide Detection, Mitochondria and Cell Functions, and Peroxynitrite Reactions. Methods in Enzymology. Vol. 359. pp. 27–42. doi:10.1016/s0076-6879(02)59169-2. ISBN   978-0-12-182262-0. PMID   12481557.
  5. van Faassen E.E.; Vanin A.F. (eds); "Radicals for life: The various forms of nitric oxide." Elsevier, Amsterdam 2007.
  6. 1 2 diethyldithiocarbamate National Cancer Institute - Drug Dictionary

Further reading