Methyldithiocarbamate

V-Methyldithiocarbamic acid reacts with propiolic acid to give methylthiocarbamoylthio)acrylic acid (367), which when refluxed with phosphorus trichloride is cyclized to 3-methyl-3,4-dihydro-4-oxo-2-thiothiazine (368) [Eq. (54)]. It has recentiy been reported that... 

Methylthiourea has been prepared from methyl isothiocyanate and ammonia in alcoholic 1 or aqueous2 solution, from methylammonium thiocyanate,3 and by heating the methyl or ethyl ester of A-methyldithiocarbamic acid with alcoholic ammonia.4... 

The basic hydrolysis of a series of aryl AM4-X-benzenesull onyl)-/V-methyldithiocarbamates (65 X = MeO, Me, H, Cl, N02, CF3) in 30% aqueous dioxane at 25 °C proceeded via a BAc2 mechanism to give thiophenol, COS, and the corresponding (V-methyIsuI lonamidc, 4-X-CeH4S02NHMe.56... 

Sodium N- methyldithiocarbamate and methyl isothiocyanate fungicides Miscellar mobile phase UV [238]... 

Shih and Carr [277,278] showed that metal complexes of bis(/ -butyl-2-naphthyl-methyldithiocarbamate) are thermodynamically stable and chemically inert and that the nickel(II), iron(III), copper(II) and mercury (II) complexes of this dithiocarbamate can be separated by high performance liquid chromatography and detected with a variable wavelength detector. 

A typical chromatogram for the separation of the bis(/ -buty 1-2-naphthyl methyldithiocarbamate complexes of iron(III), nickel(II), copper(II),... 

Se03Sr Strontium selenite, 3 20 Se04H2 Selenic acid, 3 137 Se(S2CN(CH3)2)2 Selenium(II) di-methyldithiocarbamate, 4 93 Se(S2CN(C2H6)2)2 Selenium(II) di-ethyldithiocarbamate, 4 93 Se(S2COCH3)2 Selenium(II) meth-ylxanthate, 4 93... 

Tellurium bis N-2-hydroxyethyl-N-methyldithiocarbamate] (m.p. 140°) was similarly prepared in 60% yield2. 

Figure 4. Solutes 1. benzene 2. phenol 3. sodium N-methyldithiocarbamate 4. sodium N,N-dimethyldithiocarbamate 5. ammonium tetramethylenedithiocarbamate 6. sodium diethyldithiocarbamate. Conditions column, dimensions,...

Imidazole carboxylic esters of secondary or tertiary alcohols, such as 1053 and 1054,, form carbonates exclusively with primary alcohols (Scheme 253). Thus, 1054 is a useful reagent for the BOC-protection of primary hydroxyl groups < 19990L933>. In some cases, 1054 offers better selectivity than pivaloyl chloride in the protection of carbohydrates <1998S1787>. Similarly, l-(methyldithiocarbonyl)imidazole 1055 and its methyl triflate salt convert alcohols to ri -methyldithiocarbonates <1997SL1279> and amines to 6 -methyldithiocarbamates or thioureas <2000T629>. 

VPM [Du Pont]. TM for a solution containing 32.7% sodium methyldithiocarbamate used as a soil fumigant. 

Methyldithiocarbamic Acid Sodium Salt A145 Industrial —... 

Dazomet (7) is prepared by a somewhat similar route, via the formation of N-methyldithiocarbamate, as a result of the cyclisation of methylamine, carbon disulhde and formaldehyde (Delepine, 1897 Bodendorf, 1930). 

The simplest member of the first subgroup is methyldithiocarbamic acid or metham. The sodium (8) or the ammonium salt is form, depending on whether the reaction of carbon disulfide with methylamine is carried out in a sodium hydroxide or ammonium hydroxide medium. The free acid is not stable. 

Dazomet is hydrolysed by water formaldehyde and N-methyldithiocarbamate ester (12) are formed, and the latter is converted into methylisothiocyanate (Munnecke and Martin, 1964 Goksoeyr, 1964). 

The initial toxicity of a freshly prepared aqueous dazomet solution is low, but after 24 hours, when a substantial quantity of the N-methyldithiocarbamate ester has been converted into methylisothiocyanate, its fungicidal activity increases considerably. A similarly strong fungicidal action develops on the addition of copper ions to the freshly prepared solution, which indicates that the ester bond has been ruptered and the active copper complex of N-methyldithiocarbamate has formed. 

The sodium salt of N-methyldithiocarbamate is converted by oxidation into the compounds 4-methyl-5-methylimino-4-aza-l,2-dithiolane-3-thione (13) and... 

Two dithiocarbamates, sodium methyldithiocarbamate (metham, SMDC, 2) and 2-chloroallyl diethyldithiocarbamate (sulfallate, CDEC, 3) have been introduced as herbicides. These compounds were developed before the thiocar-bamate herbicides discussed in the preceding chapter. 

---