Ethyl dithiocarbonate

Potassium O-ethyl dithiocarbonate ( Potassium ethyl xanthate )... 

Dining interaction of the diazonium sulfide and the O-ethyl dithiocarbonate ( xanthate ) solutions, care must be taken to ensure that the intermediate diazonium dithiocarbonate decomposes to 2-thiocresol as fast as it is formed [1]. This can be assured by presence of a trace of nickel in the solution to effect immediate catalytic decomposition [2], When the 2 solutions were mixed cold and then heated to effect decomposition, a violent explosion occurred. 

The reaction of S-methyl O-ethyl dithiocarbonate with methyl ketones 289 (R1 = Me, i-Pr or Ph) in toluene in the presence of sodamide gives thioxo esters, which exist in the... 

See Potassium O-ethyl dithiocarbonate See also Carbon disulfide... 

C. N-Hydroxy-4-(p-chlorophenyl)thiazole-2(3H)-thione. O-Ethyl S-[2-oximino-2-(p-chlorophenyl)ethyl]dithiocarbonate (56.0 g, 0.19 mol) is placed in a 500-mL round-bottomed flask that is equipped with a magnetic stir bar. Diethyl ether (120 mL) is added and the slurry is treated at 0°C in small portions with solid anhydrous zinc chloride, ZnClj, 79.1 g, 0.58 mol) at such a rate that the solvent does not boil constantly (Note 8). After the addition is complete, the flask is stoppered with a drying tube (CaCl2) and stirring is continued for 48 hr at 20°C. The reaction mixture turns into a dear, dark brown solution that solidifies toward the end of the reaction. The flask is immersed in an ice bath and treated dropwise with 5.5 M hydrochloric add (140 mL, Note 9). The precipitate dissolves immediately. Stirring is continued for 30 min at 0°C whereupon a tan-colored solid separates. This material is collected by filtration. It is washed with small portions of diethyl ether (total of 110 mL) and dried to afford 39.8 g (86%) of N-hydroxy-4-(p-chlorophenyl)thiazole-2(3H)-thione (Note 10). The crude material is transferred to a 2-L, round-bottomed flask equipped with a reflux condenser. 2-Propanol (760 mL) is added and the reaction mixture is heated to reflux. Once a dear solution is obtained the heat source is immediately removed (Note 11). The solution is allowed to cool to room temperature. Precipitation of N-hydroxy-4-(p-chlorophenyl)thiazole-2(3H)-thione is completed by immersing the flask for 30 min in an acetone-dry ice bath (-78°C). The product is collected by filtration and dried to afford 21.9 g (53.5%) of N-hydroxy-4-(p-chlorophenyl)thiazole-2(3H)-thione as tan crystals (Notes 12,13). 

Ethyl S-[oximino-2-(p-chlorophenyl)ethyl]dithiocarbonate Carbonodithioic acid, S-[2-(4-chlorophenyl)-2-(hydroximino)ethyl], 0-ethyl ester (14) (195213-53-7)... 

Aminolysis of phenyl dithioacetates,8 pyridinolysis of O-ethyl dithiocarbonates,9 reaction of pyrrolidine with O-ethyl 5-aryl dithiocarbonates,10 aminolysis of chlorothionformates,11 pyridinolysis of alkyl aryl thioncarbonates,12 reaction of anionic nucleophiles with nitrophenyl benzoate and its sulfur analogues,36 hydrolysis of methyl benzoate and phenyl acetate containing SMe, SOMe and S02Me substituents,42 solvolysis of phenyl chlorothioformate,79 synthesis of new thiadiazoles,124 examination of a neighbouring sulfonium group in ester hydrolysis,136 hydrolysis of V-type nerve agents,250 and the reactions of peroxymonosulfate ion with phosphorus(V) esters have all been looked at previously in this review. 

S-dialkyldithiocarbonates (xanthate esters, e.g. O-ethyl S-ethyl dithiocarbon-ate (3)]. 

Potassium O-ethyl dithiocarbonate. Into a 500-ml round-bottomed flask, fitted with a reflux condenser, place 42 g (0.75 mol) of potassium hydroxide pellets and 120g (152 ml) of absolute ethanol. Heat under reflux for 1 hour. Allow to cool and decant the liquid from the residual solid into another dry 500-ml flask add 57 g (45 ml, 0.75 mol) of carbon disulphide (1) slowly and with constant shaking. Filter the resulting almost solid mass, after cooling in ice, on a sintered glass funnel at the pump, and wash it with three 25 ml portions of ether. Dry the potassium O-ethyl dithiocarbonate in a vacuum desiccator over silica gel. The yield is 74 g. If desired, it may be recrystallised from absolute ethanol but this is usually unnecessary. 

O-Ethyl A-ethyl dithiocarbonate. Place 32 g (0.2 mol) of potassium O-ethyl dithiocarbonate and 50 ml of absolute ethanol in a 500-ml round-bottomed flask provided with a double surface condenser. Add 32 g (16.5 ml, 0.205 mol) of ethyl iodide. No reaction appears to take place in the cold. Heat on a water bath for 3 hours a reaction sets in within 15 minutes and the yellow reaction mixture becomes white owing to the separation of potassium iodide. Add about 150 ml of water, separate the lower layer and wash it with water. Dry it with anhydrous calcium chloride or anhydrous calcium sulphate and distil collecting O-ethyl S-ethyl dithiocarbonate at 196-198 °C. The yield is 23 g (77%). 

Cognate preparation. O-Ethyl S-butyl dithiocarbonate. Use 32 g (0.2 mol) of potassium O-ethyl dithiocarbonate, 37 g (23 ml, 0.2 mol) of butyl iodide (Expt 5.58) and 50 ml of absolute ethanol. Reflux on a water bath for 3 hours. Pour... 

Potassium ethyl xanthate , see Potassium (9-ethyl dithiocarbonate, 1172... 

See Hydrogen trisulfide Benzenediazonium chloride 4-Chloro-2-methylbenzenediazonium salts, 2715 Hydrogen trisulfide Benzenediazonium chloride, 4479 3-Quinolinethiol preparation from the diazonium salt, 3116 3-Toluenediazonium salts, Ammonium sulfide, or Hydrogen sulfide, 2770 3-Toluenediazonium salts, Potassium O-ethyl dithiocarbonate, 2770... 

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