Reaction of Grignard reagents with tetramethylthiuram disulfide [yielding dithiocarbamates]

New Functional Polyolefins: Towards a Bridge Between Catalytic and RAFT Polymerizations?

“…More than 30 years ago, Grunwell et al [18] reported an alternative route to the synthesis of dithiocarbamate esters (Me 2 NC(S)SR 0 ) based on reactions of Grignard reagents (R 0 MgX, X ¼ halogen) with tetramethylthiuram disulfide ((Me 2 NC(S)S-S(S)CNMe 2 ).…”

Dyn[n]arenes: Versatile Platforms To Study the Interplay between Covalent and Noncovalent Bonds

“…Thiophenols can also be formed from strong nucleophiles such as aromatic Grignard reagents, by coupling them with tetramethylthiuram disulfide. The intermediate N,N‐dimethyl‐dithiocarbamate obtained can then be reduced to thiophenol by hydrides [8,9] . Since these early examples, many strategies involving catalytic amounts of transition metals have been developped to enable the conversion of aryl halides or triflates to thiophenols in greener and milder conditions [10–13] .…”

“…Whereas both cis and trans diastereoisomers of D underwent thiol to disulfide chain elongation during the first 24 h, linear oligomers made from the latter overoxidized, while those made from the former quantitatively converted into a cyclotetramer D 4 . Thorough examination of mass spectra and especially of isotopic patterns indicated that the dyn [8]arene was coeluting with D 4 . MS-/MS, multinuclear NMR and computational modelling revealed that maximization of internal dispersion (London) forces and minimization of steric repulsion were the intramolecular driving forces during the formation of D 4 which was obtained with 80 % conversion (Figure 4b).…”

Synthese und Eigenschaften von Diethyldithiocarbaminsäureperfluororganylestern, (C2H5)2NC(S)SRf (Rf = CF3, C2F5, i-C3F7, n-C4F9, C6F5)

“…In Anlehnung an eine Arbeit von Grunwell [6] u È ber die Synthese verschiedener Ester der Dimethyldithiocarbaminsa È ure aus [(CH 3 ) 2 NC(S)S] 2 und Grignard-Reagenzien kann ein zyklischer Ûbergangszustand (Schema 1) formuliert werden, wobei das Metallatom an das Schwefelatom der Thiocarbonylgruppen koordiniert und der organische Rest unter Spaltung der S±S-Bindung an ein Schwefelatom der zweiten Dithiocarboxylgruppe gebunden wird. 2 ] u È ber einen 6-gliedrigen zyklischen Ûbergangszustand (R f = CF 3 , C 2 F 5 , i-C 3 F 7 , n-C 4 F 9 , C 6 F 5 ; M = Ag, CdR f ; R = C 2 H 5 ) in Anlehnung an [6].…”

“…2 J( 19 F, 13 C) = 21 3 J( 19 F, 13 C) = 5 (C 2 H 5 ) 2 NC(S)SC 6 F 5 (C 2 H 5 ) 2 NC(S)SC 6 F 5 (C-2,6) (C 2 H 5 ) 2 NC(S)SC 6 F 5 (C-4) (C 2 H 5 ) 2 NC(S)SC 6 F 5 (C-3,5) (C 2 H 5 ) 2 NC(S)SC 6 F 5 (C-1) 48,3/45, 6 11,3/10,3 s s CH 2 CH 3 c) CH 2 CH 3 a) Diese Zuordnung ist austauschbar. b) Das Signal des C(S)S-Atoms wurde nicht detektiert.…”