2905-52-4Relevant articles and documents
1-Alkyl-4-ethoxythiocarbonyl-5-hydroxy-3-methylpyrazole: Synthesis, copper complexes and solvent extraction studies
Oliva, Alfonso,Molinari, Aurora,Toro, Carolina
experimental part, p. 329 - 335 (2009/05/31)
1-Alkyl-4-ethoxythiocarbonyl-5-hydroxy-3-methylpyrazole, HETCP, (alkyl = n-octyl ; n-dodecyl) were prepared in high yield by the reaction of 1-alkyl-3-methyl-2-pyrazolin-5-one with bis (ethoxythiocarbonyl)sulfide and sodium acetate in dimethylformamide. These reagents act as O, S bidentate ligands in solvent extraction/reextraction studies of Cu (II) from acid aqueous solutions and the extracted specie resulted to be Cu(ETCP)2.
Kinetics and Mechanism of the Reactions of S-Ethoxycarbonyl O-Ethyl Dithiocarbonate with O-Ethyl Xanthate and O-Ethyl Thiocarbonate Ions
Castro, Enrique A.,Meneses, Beatriz,Santos, Jose G.,Vega, Juan C.
, p. 1863 - 1866 (2007/10/02)
The forward and back reactions of S-ethoxycarbonyl O-ethyl dithiocarbonate (1) with O-ethyl thiocarbonate (4) and O-ethyl xanthate (5) in 95percent ethanol are studied kinetically.The back reaction products are bis(ethoxycarbonyl) sulfide (3) with 5 and bis(ethoxythiocarbonyl) sulfide (2) with 4, respectively.Compound 1 reacts faster than 2 with 4, which means that the carbonyl group is more reactive than the thiocarbonyl toward 4.On the other hand, the reaction of 5 with 1 is faster than that with 3, which indicates that 5 reacts more readily with the thiocarbonyl than the carbonyl group.Two mechanisms are proposed to account for the kinetics results: one through tetrahedral intermediates (two-step reactions) and the other concerted.The reactions of 4 exibit ΔS >0, whereas those of 5 show ΔS 0.These ΔS values are explained by a larger solvation of 4 relative to 5 and similar degrees of solvation of transition states and substrates.The observed activation parameters do not allow discrimination between the two mechanisms.
PYROTHIOCARBONATES I. AMINOLYSIS OF S-(ETHOXYCARBONYL) O-ETHYL DITHIOCARBONATE
Palominos, Mario A.,Santos, Jose G.,Valderrama, Jaime A.,Vega, Juan C.
, p. 245 - 252 (2007/10/02)
The reaction of S-(ethoxycarbonyl) O-ethyl dithiocarbonate (1) with equimolar amounts of butylamine, benzylamine, diethylamine and piperidine in ethanol solution at 0 deg C is reported.The mole ratio of O-ethyl thiocarbamate (2) and O-ethyl carbamate (3) formed as main products is larger than unity during all the reaction.Bis(ethoxythiocarbonyl) sulfide (4) and bis(ethoxycarbonyl) sulfide (5) are also produced and their formation is explained in terms of the reaction of 1 with EtOCS2- and EtOCOS-, respectively, which are the leaving groups in the aminolysis of 1.Reactions 4 -> 2 and 5 -> 3 also take place.When 50percent of 1 has been consumed compound 4 is not detected and compound 5 is found at very low concentration, indicating that generation of 4 and 5 occurs mainly after aminolysis of 1.The fact that the ratio of 2 : 3 is larger than unity in this aminolysis step, and that S-methyl O-ethyldithiocarbonate is aminolyzed more readily than S-methyl O-ethylmonothiocarbonate under the same conditions as the aminolysis of 1, suggests that the thiocarbonyl group of 1 is more reactive than the carbonyl group.
