Thiuram disulfide
![](http://upload.wikimedia.org/wikipedia/commons/thumb/2/27/Thiuram-disulfide-2D.png/200px-Thiuram-disulfide-2D.png)
Thiuram disulfides are a class of
Preparation, structure, reactions
Thiuram disulfides are prepared by oxidizing the salts of the corresponding dithiocarbamates (e.g. sodium diethyldithiocarbamate). Typical oxidants employed include chlorine and hydrogen peroxide:
- 2 R2NCSSNa + Cl2 → (R2NCSS)2 + 2 NaCl
Thiuram disulfides react with Grignard reagents to give esters of dithiocarbamic acid, as in the preparation of methyl dimethyldithiocarbamate:[2]
- [Me2NC(S)S]2 + MeMgX → Me2NC(S)SMe + Me2NCS2MgX
The compounds feature planar dithiocarbamate subunits and are linked by an S−S bond of 2.00
![](http://upload.wikimedia.org/wikipedia/commons/thumb/2/2f/METHUS03skew2.png/220px-METHUS03skew2.png)
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:
- (R2NCSS)2 + PPh3 → (R2NCS)2S + SPPh3
Chlorination of thiuram disulfide affords the
Applications
The tetramethyl derivative, known as thiram, is a widely used fungicide. The tetraethyl derivative, known as disulfiram, is commonly used to treat chronic alcoholism. 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.
Safety
In 2005–06, thiuram mix was the 13th most prevalent allergen in patch tests (3.9%).[5]
References
- ISBN 978-3527306732.
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- doi:10.15227/orgsyn.035.0055).
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