caa a22 4500 475762037 CHVBK 20180406123554.0 cr unu---uuuuu 170329e20000201xx s 000 0 eng 10.1007/BF02494685 doi (NATIONALLICENCE)springer-10.1007/BF02494685 Van Boi Luu N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., 117913, Moscow, Russian Federation aut Thiocarbamoylation of amine-containing compounds [Elektronische Daten] 5. The mechanism of reactions of tetramethylthiuram disulfide with aliphatic amines [Luu Van Boi] Thiocarbamoylation of aliphatic amines with tetramethylthiuram disulfide (TMTD) was studied. The reactions were established to proceed according to a two-stage mechanism. In the first stage,S-(thiocarbamoyl)thiohydroxylamines and dimethyl dithiocarbamates are formed. The latter exist in equilibrium with dimethyldithiocarbamic acid, which can undergo decomposition to give dimethylamine and carbon disulfide. In the second stage, several competitive transformations of these intermediates into the final products occur,viz., (1) the reactions of CS2 with primary amines on heating (70-110 °C) yield mixed and symmetrical thioureas and the reactions of CS2 with secondary amines give symmetrical dithiocarbamates, and (2) insertion of CS2 intoS-(thiocarbamoyl)thiohydroxylamines affords thiuram disulfides. Thiuram disulfides formed from primary amines decompose to give isothiocyanates, which are converted into thioureas by condensation with amines, whereas thiuram disulfides which are obtained in the reactions with secondary amines and which cannot form thioureas react with amines analogously to TMTD. Kluwer Academic/Plenum Publishers, 2000 tetramethylthiuram disulfide nationallicence aliphatic amines nationallicence dialkyl(cycloalkyl)ammonium dialkyl(cycloalkyl)dithiocarbamates nationallicence S -( N,N -dimethylthiocarbamoyl)- N -alkyl(dialkyl)-(cycloalkyl)thiohydroxylamines nationallicence mixed N ′-alkyl(dialkyl)(cycloalkyl)- N,N -dimethylthiuram disulfides nationallicence dialkyl(dicycloalkyl)thioureas nationallicence benzyl and cyclohexyl isothiocyanates nationallicence Russian Chemical Bulletin Kluwer Academic Publishers-Plenum Publishers 49/2(2000-02-01), 335-343 1066-5285 49:2<335 2000 49 11172 https://doi.org/10.1007/BF02494685 text/html Onlinezugriff via DOI 1 research-article jats NATIONALLICENCE 856 40 https://doi.org/10.1007/BF02494685 text/html Onlinezugriff via DOI NATIONALLICENCE 100 1- Van Boi Luu N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., 117913, Moscow, Russian Federation aut NATIONALLICENCE 773 0- Russian Chemical Bulletin Kluwer Academic Publishers-Plenum Publishers 49/2(2000-02-01), 335-343 1066-5285 49:2<335 2000 49 11172 Metadata rights reserved Springer special CC-BY-NC licence nationallicence SWISSBIB 474883051 BK010053 XK010053 XK010000 NATIONALLICENCE NATIONALLICENCE NL-springer