Dithiocarbamate


A dithiocarbamate is a functional group in organic chemistry. It is the analog of a carbamate in which both oxygen atoms are replaced by sulfur atoms.
A common example is sodium diethyldithiocarbamate. Dithiocarbamates and their derivatives are widely used in the vulcanization of rubber.

Formation

Many primary and secondary amines react with carbon disulfide and sodium hydroxide to form dithiocarbamate salts:
Ammonia reacts with CS2 similarly:
Dithiocarbamate salts are pale colored solids that are soluble in water and polar organic solvents.

Reactions

Dithiocarbamates are readily S-alkylated. Thus, methyl dimethyldithiocarbamate can be prepared by methylation of the dithiocarbamate:
Oxidation of dithiocarbamates gives the thiuram disulfide:
Thiuram disulfides react with Grignard reagents to give esters of dithiocarbamic acid:

Structure and bonding

Dithiocarbamates is described by invoking resonance structures that emphasize the pi-donor properties of the amine group. This bonding arrangement is indicated by a short C–N distance and the coplanarity of the NCS2 core as well as the atoms attached to N.
Because of the pi-donation from nitrogen, dithiocarbamates are more basic than structurally related anions such as dithiocarboxylates and xanthates. Consequently, they tend to bind as bidentate ligands. Another consequence of the C–N multiple bonding is that rotation about that bond is subject to a high barrier.

Applications

Zinc dithiocarbamates are used to modify the crosslinking of certain polyolefins with sulfur, a process called vulcanization. They are used as ligands for chelating metals.
Dithiocarbamates specifically ethylene bisdithiocarbamates, in the form of complexes with manganese, zinc or a combination of manganese and zinc, have been used extensively as fungicides in agriculture from the 1940s.
is an additive in some extreme pressure gear oils, serving as an antioxidant and protecting metal surfaces.