Xn:Harmful;112-40-3Relevant articles and documents
Solvent-dependent substrate reduction by {Sm[N(SiMe3)2]2(THF)2}. An alternative approach for accelerating the rate of substrate reduction by Sm(II)
Chciuk, Tesia V.,Hilmersson, G?ran,Flowers, Robert A.
, p. 9441 - 9443 (2014)
The impact of solvent on electron transfer from Sm(II) to substrates was measured by determining the rate of reduction of 1-bromo-, 1-chlorododecane, and 3-pentanone in THF and hexanes using the highly soluble reductant {Sm[N(SiMe3)2]2(THF)2}. Rates were found to be 3 orders of magnitude faster in hexanes than THF, and reductions of alkyl halides were inverse first order in THF. These findings show the solvent milieu signifi cantly impacts the rate of substrate reduction, a consideration that may prove useful in synthesis. (Chemical Equation Presented).
Development of radical reactions with zirconocene complexes as electron transfer reagents
Fujita, Kazuya,Yorimitsu, Hideki,Oshima, Koichiro
, p. 1727 - 1736 (2004)
Bis(cyclopentadienyl)zirconium chloride hydride (Schwartz reagent) proved to be an efficient radical chain carrier for radical reduction of organic halides. Treatment of 1-bromoadamantane with Cp2Zr(H)Cl in THF at 25°C in the presence of triethylborane furnished adamantane quantitatively. Radical cyclization of 2-haloalkyl allyl ethers afforded five-membered products under the same reaction conditions. Reduction with Cp2Zr(H)Cl generated in situ from Cp2ZrCl2 and sodium bis(2-methoxyethoxy)aluminium hydride (Red-Al) also proceeded smoothly. Moreover, the reduction could function by using a catalytic amount of Cp 2ZrCl2. A zirconocene-olefin complex also induced reductive radical cyclization of 2-haloalkyl allyl ethers in THF. This complex served as a single electron transfer reagent to promote the radical cyclization. Furthermore, the cyclization reaction in DME afforded 3- tetrahydrofuranylmethylzirconium efficiently.
Alkylidene fluorene liquid crystalline semiconducting polymers for organic field effect transistor devices
Heeney, Martin,Bailey, Clare,Giles, Mark,Shkunov, Maxim,Sparrowe, David,Tierney, Steve,Zhang, Weimin,McCulloch, Iain
, p. 5250 - 5256 (2004)
Organic electronic devices comprising arrays of organic field effect transistors (OFETs) are expected to create a range of novel applications for which the ability to be fabricated in large areas, on flexible substrates, with nonconventional shapes, and at low cost are key enabling factors. To improve the electrical performance of such devices, new solution processable organic semiconductors are required with high charge carrier mobilities and environmental stability. This work describes the molecular design of a p-type charge transport liquid crystalline polymer, in an attempt to control the factors responsible for both mobility and stability. Molecules were designed that were able to exhibit closely packed, π stacked morphologies, which can result in efficient intermolecular charge hopping and hence high mobility. Molecular manipulation of the conjugated π electron system was required to optimize the HOMO energy level, to both resist oxidation and be able to readily accept holes from a source electrode.
Prominent hydrogenation catalysis of a PVP-stabilized Au34 superatom provided by doping a single Rh atom
Hasegawa, Shingo,Takano, Shinjiro,Yamazoe, Seiji,Tsukuda, Tatsuya
, p. 5915 - 5918 (2018)
A single rhodium atom was precisely doped into a gold cluster Au34 stabilized by poly(N-vinyl-2-pyrrolidone) (Au:PVP) as revealed by mass spectrometry. The Rh-atom-doped Au:PVP exhibited remarkable catalytic activity for hydrogenation reactions of olefins, which was much higher than that of recently reported Pd-atom-doped Au:PVP.
DISSOLVING METAL REDUCTION WITH CROWN ETHER----- REDUCTIVE DECYANATION
Ohsawa, Tomihiko,Kobayashi, Takao,Mizuguchi, Yuko
, p. 6103 - 6106 (1985)
Toluene radical anion generated from potassium metal/dicyclohexano-18-crown-6/toluene system has been proved to be highly effective for reductive decyanation reaction of primary, secondary and tertiary cyanides.
Fatty methyl ester hydrogenation to fatty alcohol Part II: Process issues
Rieke,Thakur,Roberts,White
, p. 341 - 345 (1997)
Fatty alcohols are produced by hydrogenating fatty methyl esters in slurry phase in the presence of copper chromite catalyst at temperatures of 250-300 °C and hydrogen pressures of 2000-3000 psi. The fatty methyl ester, catalyst, and hydrogen are fed to the reactor cocurrently. The product slurry is passed through gas-liquid separators and then through a continuous filtration system for removal of the catalyst. A portion of the used catalyst in crude alcohol is recycled to the hydrogenator. The overall efficiency of the process depends upon the intrinsic activity, life, and filterability of the catalyst. The fatty alcohol producer therefore requires a catalyst with high activity, long life, and good separation properties. The main goal of the present laboratory investigation was to develop a superior copper chromite catalyst for the slurry-phase process. Two copper chromite catalysts, prepared by different procedures, were tested for methyl ester hydrogenolysis activity, reusability, and filtration characteristics. The reaction was carried out in a batch autoclave at 280 °C and 2000-3000 psi hydrogen pressure. The reaction rates were calculated by assuming a kinetic mechanism that was first-order in methyl ester concentration. The catalyst with the narrower particle size distribution was 30% more active, filtered faster, and maintained activity for several more uses than the catalyst with the broader particle size distribution. X-ray photoelectron spectroscopy data showed higher surface copper concentrations for the former catalyst.
Spurring radical reactions of organic halides with tin hydride and TTMSS using microreactors
Fukuyama, Takahide,Kobayashi, Masahide,Rahman, Md Taifur,Kamata, Naoya,Ryu, Llhyong
, p. 533 - 536 (2008)
Tributyltin hydride-mediated radical reactions of organic halides were successfully carried out in a continuous flow system using a microreactor. The reactions proceeded within a very short period of time, coupled with quickly decomposing radical initiators such as V-65 and V-70. The continuous flow reaction system was applied to gram scale synthesis of a key intermediate for furofuran lignans.
Conversion of biomass-derived fatty acids and derivatives into hydrocarbons using a metal-free hydrodeoxygenation process
Li, Xing-Yu,Shang, Rui,Fu, Ming-Chen,Fu, Yao
, p. 2790 - 2793 (2015)
A metal-free hydrodeoxygenation process was developed for the production of hydrocarbons from biomass-derived fatty acids and derivatives. Biomass-derived fatty acids and derivatives were converted to alkanes and alkenes under mild reaction conditions. Furthermore, this catalytic system can also be applied to convert real biomass with satisfactory results.
Interactions of alkoxides. XVII. Properties of complex bases from organolithium compounds and various sodium alkoxides affected by the structure and concentration of the alkoxide
Lochmann, L.
, p. 1 - 6 (1989)
In reactions of a substrate with complex bases (CB) prepared from organolithium compounds and heavier alkalimetal alkoxides the reaction rates and relative product yields depend on the structure and concentration of the CB components.For the model reaction of C6 with alkyl bromides, changes in the identity and concentration of the alkoxide reduced reaction half-times by as much as three orders of magnitude and higher yields of the product of Wurtz coupling were obtained.Sodium 3-methyl-pentoxide-3 was found to be considerably more effective than sodium t-butoxide.
Polycyclic aromatic compounds-mediated electrochemical reduction of alkyl mesylates
Senboku, Hisanori,Takahashi, Megumi,Fukuhara, Tsuyoshi,Hara, Shoji
, p. 228 - 229 (2007)
Electrochemical reduction of alkyl mesylates was successfully carried out by using an undivided cell equipped with a Pt cathode and an Mg anode in the presence of biphenyl and t-BuOH. The reaction could proceed efficiently under mild conditions to give the corresponding alkanes in moderate to good yields. This procedure could also be applicable to chemoselective reduction of mesylates having functional groups such as epoxide, olefin, acetal, hydroxy, or cyano groups. Copyright
