Fungicides complexes with dithiocarbamates

Chemical Name manganese ethylenebis(dithiocarbamate) (polymeric) complex with zinc salt CAS Registry No 8018-01-7 Uses fungicide... 

They can react with metal-containing enzymes (e.g., polyphenoloxidase and ascorbic acid oxidase) to form a copper-dithiocarbamate complex with high fungicidal activity (thiram and ziram probably owe their fungicidal activity to this type of reaction). 

Dithiocarbamate and dithiophosphinate complexes have important uses. The former are used as fungicides and for solvent extraction and the latter as high pressure lubricants. Dithiocarbamates stabilize high oxidation states as in [FeIV(dtc)3]+ or [NiIV(dtc)3]+. Although dithiocarbamates are usually made from sodium salts such as NaS2CNMe2 or by oxidations using thiuram disulfides, they can also be made by insertion reactions of CS2 with dialkylamides, for example,... 

Due to the threat to discolor with heavy metal traces the dithiocarbamates, a very effective class of bactericides, fungicides, and algiddes, namely Ziram [II, 11.11.3.] and Thiuram [II, 11.13.1.], respectively, are not often considered to be used in coatings. Their application is almost limited to interior coatings in industrial environments. It has to be noticed, that the complexing activity of the dithiocarbamates is deactivating the heavy metal driers used in chemically drying alkyds. 

From these early studies, dithiocarbamates and their transition metal complexes soon found a host of applications. For example, as a result of their insoluble nature they are widely used in inorganic analysis (3,4). They can also be used to separate different metal ions by high-performance liquid chromatography (HPLC) (5-10) and capillary gas chromatography (GC) (11, 12), and find use as rubber vulcanization accelerators (13), fungicides (14), and pesticides (15). Concomitant with the development of these applications came a burgeoning interest in their general transition metal chemistry and the characteristics and properties of the complexes formed. 

Dithiocarbamates can also be prepared from diamines. For example, as early as 1872, Hofmann (97) reported the reaction of carbon disulfide with 1,2-diaminoethane. Later in the 1960s, addition of 2 equiv of sodium hydroxide and carbon disulfide to 1,2-diaminoethane was shown to afford the bis(dithiocarba-mate) compound in an exothermic reaction (98-102) 1,6-diaminohexane behaving in a similar manner (98). A wide range of polymeric transition metal complexes have been prepared using these salts (98). All are insoluble in water and common organic solvents, and some examples have been developed as fungicides (14, 31). 

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