Dithiocarbamates reaction with halogens

Several papers report on the nucleophilic reactivity of dithiocarbamate ions towards alkyl halides, 1,2-dibromoalkyl compounds, alkyl and aryl chloroformates, chloroacetic acid, chloroacetates, 3-halo-genophthalides, sulphenyl chlorides, sultones, and trialkylam-monium compounds. Examples of a similar reactivity of dithiocarbazate anions have also appeared. " A series of papers deal with addition or addition-elimination reactions of dithiocarbamate - or dithiocarbazate anions with w-nitrostyrene, 2-thioxo-, 2-oxo-, and 2-imino-5-methoxycarbonylmethylidene-4-thiazolidones, dimethyl acetylenedicar-boxylate, and NN -dialkyl phenylpropiolamidines. S-Monoalkylated N-cyanodithioimidocarbonates (492) underwent oxidative ring-closure to give 3-halogeno-l,2,4-thiadiazole sulphides (493) on treatment with halogenating agents. ... 

A number of compounds of the types RSbY2 and R2SbY, where Y is an anionic group other than halogen, have been prepared by the reaction of dihalo- or halostibines with lithium, sodium, or ammonium alkoxides (118,119), amides (120), azides (121), carboxylates (122), dithiocarbamates (123), mercaptides (124,125), or phenoxides (118). Dihalo- and halostibines can also be converted to compounds in which an antimony is linked to a main group (126) or transition metal (127). 

Iron(III) tris(dithiocarbamate) complexes display practically no photochemical activity in solutions free of halogenated hydrocarbons, however, the addition of even small quantities of chlorocarbons results in an increase for the quantum yield of initial product disappearance. Pignolet and co-workers (1237) showed that photolysis of tris(dithiocarbamate) complexes in chlorinated solvents yields [FeCl(S2CNR2)2]. The reaction is thought to occur via electron transfer from an excited iron complex to the chlorocarbon with subsequent steps as shown below (Fig. 146) (24). 

The reaction of dithiocarbamates and diselenocarbamates with a-halogenated carbonyl compounds has proved to be a useful first step in the synthesis of l,3-dithiole-2-thiones and their analogues. Thus 2-dimethylamino-l,3-dithiolium salts (38) > and diselenolium salts (39) " are readily obtainable by this route, and these salts are converted into thiones (40 X = Y = S or Se, Z = S) or selones (40 X = Y = S or Se, Z = Se) with hydrogen sulphide or hydrogen selenide. The dihydroxybenzo-l,3-dithiole-2-thione (41) has been prepared from p-benzoquinone and dithiocarbamic acids. ... 

Polymers with a dithiocarbamate photoiniferter group in a side-chain end were also synthesized by a chemical reaction. For example, halogenated linear polymers, such as poly(vinyl chloride) partially chloromethyl-... 

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