4396-19-4Relevant articles and documents
Some features of the reduction of poly(methylene sulfides) and poly(methylene polysulfides)
Trofimov, Boris,Sukhomazova, Emma,Russavskaya, Natal'ya,Alekminskaya, Ol'ga,Deryagina, Eleonora,Myachina, Galina,Korzhova, Svetlana,Skotheim, Terje
, p. 51 - 63 (2000)
The reductive destruction of poly(methylene sulfides) and poly(methylene polysulfides) in the system hydrazine hydrate - NaOH at 70-115°C involves cleavage of the C-S bond and the formation of sulfide, disulfide and trisulfide unions. Nitrogen and methane
NHC-CDI Betaine Adducts and Their Cationic Derivatives as Catalyst Precursors for Dichloromethane Valorization
Sánchez-Roa, David,Mosquera, Marta E. G.,Cámpora, Juan
, p. 16725 - 16735 (2021/11/18)
Zwitterionic adducts of N-heterocyclic carbene and carbodiimide (NHC-CDI) are an emerging class of organic compounds with promising properties for applications in various fields. Herein, we report the use of the ICyCDI(p-Tol) betaine adduct (1a) and its cationic derivatives2aand3aas catalyst precursors for the dichloromethane valorization via transformation into high added value products CH2Z2(Z = OR, SR or NR2). This process implies selective chloride substitution of dichloromethane by a range of nucleophiles Na+Z-(preformed or generatedin situfrom HZ and an inorganic base) to yield formaldehyde-derived acetals, dithioacetals, or aminals with full selectivity. The reactions are conducted in a multigram-scale under very mild conditions, using dichloromethane both as a reagent and solvent, and very low catalyst loading (0.01 mol %). The CH2Z2derivatives were isolated in quantitative yields after filtration and evaporation, which facilitates recycling the dichloromethane excess. Mechanistic studies for the synthesis of methylal CH2(OMe)2rule out organocatalysis as being responsible for the CH2transfer, and a phase-transfer catalysis mechanism is proposed instead. Furthermore, we observed that1aand2areact with NaOMe to form unusual isoureate ethers, which are the actual phase-transfer catalysts, with a strong preference for sodium over other alkali metal nucleophiles.
Novel dithioether-silver(I) coordination architectures: Structural diversities by varying the spacers and terminal groups of ligands
Li, Jian-Rong,Ba, Xian-He,Jiao, Jiao,Du, Wen-Ping,Xu, Xiu-Hua,Zhang, Ruo-Hua
, p. 464 - 474 (2007/10/03)
An investigation into the dependence of the framework formation of coordination architectures on ligand spacers and terminal groups was reported based on the self-assembly of AgClO4 and eight structurally related flexible dithioether ligands, RS(CH2)nSR (L an, R = ethyl group, Lbn, R = benzyl group, n = 1-4). Eight novel metal-organic architectures, [Ag(L a1)3/2ClO4]n (1a), [Ag2(La2)2(ClO4) 2]2 (2a), [AgLa3ClO 4]n (3a), {[Ag(La4) 2]ClO4}n (4a), [AgLb 1ClO4]2 (1b), [Ag(Lb 2)2]ClO4 (2b), {[Ag(Lb 3)3/2(ClO4)1/2](ClO 4)1/2}n(3b) and [Ag(Lb 4)3/2ClO4]n (4b), were synthesized and structurally characterized by X-ray crystallography. Structure diversities were observed for these complexes: 1a forms a 2-D (6,3) net, while 2a is a discrete tetranuclear complex, in which the Ag1 ion adopts linear and tetrahedral coordination modes, and the S donors in each ligand show monodentate terminal and μ2-S bridging coordination fashions; 3a has a chiral helical chain structure in which two homo-chiral right-handed single helical chains (Ag-La3-)n are bound together through μ2-S donors, and simultaneously gives rise to left-handed helical entity (Ag-S-)n. In 4a, left- and right-handed helical chains formed by the ligands bridging Ag1 centers are further linked alternately by single-bridging ligands to form a non-chiral 2-D framework. 1b has a dinuclear structure showing obvious ligand-sustained Ag Ag interaction, while 2b is a mononuclear complex; 3b is a 3-D framework formed by ClO4- linking the 2-D (6,3) framework, which is similar to that of 1a, and 4b has a single, double-bridging chain structure in which 14-membered dinuclear ring units formed through two ligands bridging two Ag 1 ions are further linked by single-bridging ligands. In addition, a systematic structural comparison of these complexes and other reported AgClO4, complexes of analogous dithioether ligands indicates that the ligand spacers and terminal groups take essential roles on the framework formation of the Ag1 complexes, and this present feasible ways for adjusting the structures of such complexes by modifying the ligand spacers and terminal groups.
Reactions of diorganyl disulfides with dihaloalkanes in basic reductive media. Synthesis of bis(organylthio)alkanes
Alekminskaya,Russavskaya,Korchevin,Deryagina
, p. 75 - 78 (2007/10/03)
A convenient preparative synthesis of bis(organylthio)alkanes was developed. It is based on alkylation with dihaloalkanes of solutions of diorganyl disulfides in the basic reductive system hydrazine hydrate-alkali. The generation of organylthiolate anions
