Thiuram Disulfide on:
[Wikipedia]
[Google]
[Amazon]
Thiuram disulfides are a class of
Thiuram disulfides are weak oxidants. They can be reduced to dithiocarbamates. Treatment of a thiuram disulfide with triphenylphosphine, or with cyanide salts, yields the corresponding thiuram sulfide:
:
Chlorination of thiuram disulfide affords the thiocarbamoyl chloride.
organosulfur compound
Organosulfur chemistry is the study of the properties and synthesis of organosulfur compounds, which are organic compounds that contain sulfur. They are often associated with foul odors, but many of the sweetest compounds known are organosulfur der ...
s with the formula (R2NCSS)2. Many examples are known, but popular ones include R = Me and R = Et. They are disulfide
In chemistry, a disulfide (or disulphide in British English) is a compound containing a functional group or the anion. The linkage is also called an SS-bond or sometimes a disulfide bridge and usually derived from two thiol groups.
In inorg ...
s obtained by oxidation of the dithiocarbamate
In organic chemistry, a dithiocarbamate is a chemical compound with the general formula . It contains the functional group with the Chemical structure, structure . It is the analog of a carbamate in which both oxygen atoms are replaced by sulfur ...
s. These compounds are used in sulfur vulcanization
Sulfur vulcanization is a chemical process for converting natural rubber or related polymers into materials of varying hardness, elasticity, and mechanical durability by heating them with sulfur or sulfur-containing compounds. Sulfur forms cros ...
of rubber as well as in the manufacture of pesticides and drugs. They are typically white or pale yellow solids that are soluble in organic solvents.
Preparation, structure, reactions
Thiuram disulfides are prepared by oxidizing the salts of the corresponding dithiocarbamates (e.g. sodium diethyldithiocarbamate). Typical oxidants employed includechlorine
Chlorine is a chemical element; it has Symbol (chemistry), symbol Cl and atomic number 17. The second-lightest of the halogens, it appears between fluorine and bromine in the periodic table and its properties are mostly intermediate between ...
and hydrogen peroxide
Hydrogen peroxide is a chemical compound with the formula . In its pure form, it is a very pale blue liquid that is slightly more viscosity, viscous than Properties of water, water. It is used as an oxidizer, bleaching agent, and antiseptic, usua ...
:
:
Thiuram disulfides react with Grignard reagents to give esters
In chemistry, an ester is a chemical compound, compound derived from an acid (either organic or inorganic) in which the hydrogen atom (H) of at least one acidic hydroxyl group () of that acid is replaced by an organyl group (R). These compounds c ...
of dithiocarbamic acid, as in the preparation of methyl dimethyldithiocarbamate:
:
The compounds feature planar dithiocarbamate subunits and are linked by an S−S bond of 2.00 Å. The C(S)−N bond is short (1.33 Å), indicative of multiple bonding. The dihedral angle between the two dithiocarbamate subunits approaches 90°.
Thiuram disulfides are weak oxidants. They can be reduced to dithiocarbamates. Treatment of a thiuram disulfide with triphenylphosphine, or with cyanide salts, yields the corresponding thiuram sulfide:
:
Chlorination of thiuram disulfide affords the thiocarbamoyl chloride.
Applications
The tetramethyl derivative, known as thiram, is a widely used fungicide. The tetraethyl derivative, known as disulfiram, is commonly used to treat chronicalcoholism
Alcoholism is the continued drinking of alcohol despite it causing problems. Some definitions require evidence of dependence and withdrawal. Problematic use of alcohol has been mentioned in the earliest historical records. The World He ...
. It produces an acute sensitivity to alcohol ingestion by blocking metabolism of acetaldehyde by acetaldehyde dehydrogenase, leading to a higher concentration of the aldehyde in the blood, which in turn produces symptoms of a severe hangover
A hangover is the experience of various unpleasant physiological and psychological effects usually following the consumption of alcohol (beverage), alcohol, such as wine, beer, and liquor. Hangovers can last for several hours or for more than ...
.
Safety
In 2005–06, thiuram mix was the 13th most prevalentallergen
An allergen is an otherwise harmless substance that triggers an allergic reaction in sensitive individuals by stimulating an immune response.
In technical terms, an allergen is an antigen that is capable of stimulating a type-I hypersensitivi ...
in patch tests (3.9%).
References
{{Reflist, 30em