19576-38-6Relevant articles and documents
Beyond PEG2000: Synthesis and functionalisation of monodisperse pegylated homostars and clickable bivalent polyethyleneglycols
Szekely, Gyoergy,Schaepertoens, Marc,Gaffney, Piers R.J.,Livingston, Andrew G.
supporting information, p. 10038 - 10051 (2014/08/18)
A new strategy to access highly monodisperse, heterobifunctional linear polyethylenglycols (PEGs) has been designed. This was built around unidirectional, iterative chain extension of a 3-arm PEG homostar. A mono-(4,4′-dimethoxytriphenylmethyl) octagol building block, DmtrO-EG 8-OH, was constructed from tetragol. After six rounds of chain extension, the monodisperse homostar reached the unprecedented length of 56 monomers per arm (PEG2500). The unique architecture of the synthetic platform greatly assisted in facilitating and monitoring reaction completion, overcoming kinetic limitations, chromatographic purification of intermediates, and analytical assays. After chain terminal derivatisation, mild hydrogenolytic cleavage of the homostar hub provided heterobifunctional linear EG56 chains with a hydroxyl at one end, and either a toluene sulfonate, or a tert-butyl carboxylate ester at the other. A range of heterobifunctional, monodisperse PEGs was then prepared having useful cross-linking functionalities (-OH, -COOH, -NH2, -N3) at both ends. A rapid preparation of polydisperse PEG homostars, free of multiply cross-linked chains, is also described. The above approach should be extendable to other high value oligomers and polymers.
The effect of the oxidation state of molybdenum complexes on the catalytic transformation of terminal alkynes: Cyclotrimerization vs. polymerization
Czelu?niak, Izabela,Kociecka, Paulina,Szymańska-Buzar, Teresa
, p. 70 - 78 (2012/11/13)
Reactions of monosubstituted alkynes (PhC≡CH, tBuC≡ CH, nBuC≡CH, HOCH2C≡CH, HO(CH 3)2CC≡CH) in the presence of molybdenum(0) and molybdenum(II) carbonyl complexes (Mo(CO)6/hv, [Mo(CO) 4(pip)2] (pip = piperidine), [Mo(CO)4(pip) 2]/SnCl4, [Rpip]2[{(μ-Cl)Mo(μ-Cl) (SnCl3)(CO)3}2] (R = C3H 5, H)) lead to the formation of cyclotrimerization and polymerization products, which were characterized by chromatography (GC-MS, GPC) and by 1H and 13C NMR spectroscopy. The effect of the oxidation state of the molybdenum catalyst on the transformation of the terminal alkynes was observed: cyclotrimerization vs. polymerization. Only molybdenum(II) complexes lead to the formation of polyenic polymers. Moreover, reaction of prop-2-yn-1-ol initiated by [Mo(CO)4(pip)2] in dichloromethane leads to the formation of oligomers containing the vinylidene unit. Mechanistic NMR studies show that η2-alkyne complex formation is the principal feature of all transformations of alkynes catalyzed by molybdenum complexes.
Cobalt-catalyzed cyclotrimerization of alkynes in aqueous solution [10]
Sigman,Fatland,Eaton
, p. 5130 - 5131 (2007/10/03)
-