16411-18-0Relevant articles and documents
Extended Pummerer fragmentation mediated by carbon dioxide and cyanide
Liu, Jian,Kragh, Rasmus R.,Kamounah, Fadhil S.,Lee, Ji-Woong
supporting information, (2020/10/30)
Pummerer rearrangement reactions generate sulfur (II) oxidation state from sulfur (IV) starting materials in the presence of activating reagents. We found unprecedented transformation of vinyl sulfoxide; disulfide formation reactions mediated by atmospheric pressure of carbon dioxide in extended Pummerer rearrangement reactions. Only under CO2 atmosphere, we observed moderate to high yields of disulfide starting from sulfur (IV) starting materials. Investigations on the reaction mechanism revealed that the degradation of the starting materials and the products was significant in the absence of CO2. Further evidence for the suggested reaction mechanism was obtained by a cross-over experiment and a radical trapping reagent.
RAFT polymerization of s -vinyl sulfide derivatives and synthesis of block copolymers having two distinct optoelectronic functionalities
Nakabayashi, Kazuhiro,Abiko, Yohei,Mori, Hideharu
, p. 5998 - 6012 (2013/09/02)
Well-defined sulfur-containing polymers and block copolymers were synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization of S-vinyl sulfide derivatives, in which the thioether moiety is directly connected to the vinyl group. We initially investigated RAFT polymerization of four different S-vinyl sulfide derivatives, phenyl vinyl sulfide (PVS), 4-chlorophenyl vinyl sulfide (CPVS), 2,4-dichlorophenyl vinyl sulfide (DCPVS), and 4-bromophenyl vinyl sulfide (BPVS). Three xanthate-type chain transfer agents (CTAs), a dithiocarbamate-type CTA, and a dithioester-type CTA were compared for these RAFT polymerizations. Reasonable control of the polymerization of PVS was confirmed by an observed linear increase in the molecular weight with the conversion, feasibility to control molecular weight based on the ratio of monomer consumed to the amount of CTA used, chain end structure determined by 1H NMR, and chain extension experiment. The RAFT polymerization of the bromo-substituted monomer (BPVS) also proceeded in the controlled fashion under the same conditions. Incorporation of optoelectronic groups, including anthracene, fluorene, diphenylamine, and phenothiazine on the bromophenyl pendant group of poly(BPVS) were accomplished by palladium-catalyzed postmodifications. We also investigated characteristic optoelectronic properties of modified polymers and block copolymers with two distinct electronic functionalities.
Ring-opening metathesis polymerization using alkenyl sulfides as chain-transfer agents: Efficient route to unsymmetrical poly(norbornene)-based macroinitiators bearing a terminal hydroxy group
Katayama, Hiroyuki,Fukuse, Yosuke,Nobuto, Yuko,Akamatsu, Kensuke,Ozawa, Fumiyuki
, p. 7020 - 7026 (2007/10/03)
Convenient routes to hydroxy-terminated poly(norbornene)s (PNBEs) have been developed. Hydroboration of PNBEs bearing a terminal vinyl group with 9-BBN followed by oxidation with H2O2/ NaOH forms of hydroxy-terminated PNBEs in high yields. The parent PNBEs are prepared by ring-opening metathesis polymerization (ROMP) of norbornene using vinylic sulfides as chain-transfer agents (CTAs). On the other hand, ROMP of norbornene using (Z)-1-phenylthio-1-propen-3-ol as a CTA causes one-step synthesis of ω-hydroxy-terminated PNBE, where the molecular weight of polymer depends linearly on the initial feed ratio of CTA to monomer. Similarly, ROMP reactions using (Z)-1-phenylthio-1-propen-3-ols having bromo, amino, and 4-(chloromethyl)benzamido substituents at the para position of the phenyl group as CTAs afford the corresponding α,ω-heterodifunctionalized (heterotelechelic) PNBEs. The resulting PNBEs serve as macroinitiators for anionic ring-opening polymerization (AROP) of εcaprolactone and atom-transfer radical polymerization (ATRP) of styrene, giving AB- and ABC-type block copolymers.
