16411-16-8Relevant academic research and scientific papers
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.
Synthesis of vinyl thioethers and bis-thioethenes from calcium carbide and disulfides
Rodygin, Konstantin S.,Gyrdymova, Yuliya V.,Zarubaev, Vladimir V.
, p. 476 - 478 (2017/10/05)
Bis-thioethenes and vinyl thioethers were obtained from the reaction of disulfides and calcium carbide in good to high yields using a simple synthetic procedure and common laboratory setup. The tolerance of the reaction was investigated by the examples of aliphatic, aromatic, heteroaromatic and sesquiterpenic substrates.
Difluoro- and trifluoro diazoalkanes-complementary approaches in batch and flow and their application in cycloaddition reactions
Hock, Katharina J.,Mertens, Lucas,Metze, Friederike K.,Schmittmann, Clemens,Koenigs, Rene M.
, p. 905 - 909 (2017/08/14)
Herein we report on applications of fluorinated diazoalkanes in cycloaddition reactions, with the emphasis on studying subtle differences between diverse fluorinated diazo compounds. These differences led to two major synthetic protocols in batch and flow that allow the safe and scalable synthesis of fluoroalkyl-, sulfone-substituted pyrazolines.
Palladium-Catalyzed Synthesis of Aryl Vinyl Sulfides via 1,3-Oxathiolanes As Vinyl Sulfide Surrogates
Schmink, Jason R.,Dockrey, Summer A. Baker,Zhang, Tianyi,Chebet, Naomi,Van Venrooy, Alexis,Sexton, Mary,Lew, Sarah I.,Chou, Steffany,Okazaki, Ami
supporting information, p. 6360 - 6363 (2016/12/23)
A nontraditional approach to synthesizing aryl vinyl sulfides is described. 2,2-Diphenyl-1,3-oxathiolane slowly liberates a vinyl sulfide anion under basic conditions. Using a Pd/Xantphos catalyst system to activate a wide range of aryl bromides, this transient sulfide species can be effectively trapped and fed into a traditional Pd0/PdII catalytic cycle. Scope and limitations of the methodology are presented along with significant discussion of a competitive C-S bond activation by this catalyst system.
An efficient metal-free pathway to vinyl thioesters with calcium carbide as the acetylene source
Rodygin, Konstantin S.,Ananikov, Valentine P.
supporting information, p. 482 - 486 (2016/01/30)
Chemical reactions involving high-pressure acetylene are not easily performed in a standard laboratory setup. The risk of explosion and technical difficulties drastically complicate the equipment and greatly increase the cost. In this study, we propose th
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.
Pyrolysis of α- and β-heteroatoms substituted ethyl phenyl sulfoxides
Yoshimura, Toshiaki,Sakae, Hironori,Yoshizawa, Masaki,Hasegawa, Kiyoshi,Tsukurimichi, Eiichi
experimental part, p. 1162 - 1173 (2010/08/06)
A study on the mechanism of the thermal decomposition of α- and β-heteroatoms substituted ethyl phenyl sulfoxides was carried out using 1-chloroethyl phenyl sulfoxide (1); two diastereomeric 1-acetoxyethyl (substituted phenyl) sulfoxides (2a) and (2b); and 2-chloroethyl phenyl, 2-bromoethyl phenyl, and 2-methoxyethyl phenyl sulfoxides (3, 4, 5). The rate of pyrolysis of 1 was 4.8 times faster at 160°C than that of ethyl phenyl sulfoxide used as a reference, while those of 2a and 2b were 107 and 155 times faster, respectively. The results indicate that the lone pair of electrons on the α-heteroatoms has a larger rate acceleration effect than the electronegativity of them. The substituent effects of the phenyl group of 2a and 2b gave positive Hammett ρ-values (ρa= 0.76 and ρb= 0.80 vs. σ). Activation parameters for 2a and 2b are as follows: 2a, ΔH?= 112 kJmol-1, ΔS?= -20 JK-1mol-1; 2b, ΔH?= 107 kJmol-1, ΔS?= -29 JK-1mol-1. Large deuterium kinetic isotope effects for 1-acetoxyethyl-2,2,2-d3 phenyl sulfoxides (2ad and 2bd) were observed (kH/kD= 3.5 ～ 4.1). These results suggest that the pyrolysis of -heteroatom substituted ethyl phenyl sulfoxides proceeds via a five-membered transition state deviated to E1-like in character. On the other hand, from the results of kinetics for the pyrolysis of 3, 4, and 5, no effect by the β-halogen atoms or some deceleration effect by the β-methoxy group was observed. Thus the reaction seems to proceed via an E1-like mechanism. Copyright Taylor & Francis Group.
Convenient criterion for the distinction between electrophilic and electron transfer reactions of electron-rich alkenes
Bauld, Nathan L.,Aplin, J. Todd,Yueh, Wang,Endo, Stephanie,Loving, Angie
, p. 15 - 24 (2007/10/03)
Both experimental and theoretical studies confirm that the formation of aryl vinyl ether and aryl vinyl sulfide cation radicals from the corresponding neutral substrates correlates with the Brown σ+ parameters as opposed to Hammett σ values. Peak oxidation potentials for both classes of substrates correlate preferentially with σ+, as do gas-phase ionization energies calculated by both semi-empirical and ab initio methods. In contrast, the protonation energies of the same substrates, which relate to carbocation formation, correlate preferentially with σ values, as do rates of protonation and other electrophilic additions. These observations permit a sharp distinction between electrophilic and electron transfer reactions of these two common classes of electron-rich substrates. Using this criterion, the cycloadditions of tetracyanoethylene to these substrates are found to proceed via an electrophilic mechanism, rather than by a previously proposed electron transfer mechanism.
A non-outer sphere mechanism for the ionization of aryl vinyl sulfides by triarylaminium salts
Bauld, Nathan L.,Aplin, J. Todd,Yueh, Wang,Loinaz, Ainhoa
, p. 11381 - 11389 (2007/10/03)
Evidence is presented that the formation of aryl vinyl sulfide cation radicals from the corresponding neutral precursors via reaction with tris(4- bromophenyl)aminium hexachloroantimonate in the context of a cation radical Diels-Alder addition to 1,3-cyclopentadiene does not occur via outer sphere electron transfer but by a mechanism involving strong covalent interaction between the aminium salt acting as an electrophile and the aryl vinyl sulfide substrate acting as a nucleophile.
SYNTHESIS OF A SERIES OF 5-METHYL-1H-IMIDAZOLE-4-YLMETHYL SULFIDES
Kmonicek, Vojtech,Vejdelek, Zdenek,Protiva, Miroslav
, p. 1602 - 1612 (2007/10/02)
5-Methyl-1H-imidazole-4-ylmethanethiol (V) hydrochloride
