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861.
A convenient and efficient method for preparing 3,3,3-trifluoropropanoic acid (1) is reported. The starting material is 1-chloro-3,3,3-trifluoropropene (2) that can be easily transformed into 3,3,3-trifluoropropanal dimethyl acetal (4) on treatment with methanol and KOH followed by acid-catalyzed addition of methanol. Direct transformation of 4 into 1 was efficiently achieved with 30% aqueous hydrogen peroxide (4.0 equiv.) in the presence of FeCl3 (0.025 equiv.) and hydrochloric acid (0.5 equiv.). 相似文献
862.
Yukinori Komiya Ryuji Kajikiya 《NoDEA : Nonlinear Differential Equations and Applications》2016,23(4):49
In this paper, we study the (p, q)-Laplace equation in a bounded domain under the Dirichlet boundary condition. We give a sufficient condition of the nonlinear term for the existence of a sequence of solutions converging to zero or diverging to infinity. Moreover, we give a priori estimates of the C 1-norms of solutions under a suitable condition on the nonlinear term. 相似文献
863.
1,1,3,3-Tetrakis(trifluoromethanesulfonyl)propane was found as an excellent Br?nsted acid catalyst for the Mukaiyama-Michael reaction of alpha,beta-enones with 2-silyloxyfurans; using beta,beta-disubstituted enones as a Michael acceptor, an excellent yield construction of quaternary carbon centers could be achieved; in addition, very low catalyst loading of Br?nsted acid was used in a range from 0.05 to 1.0 mol%. 相似文献
864.
Arai T Horiguchi M Yanagida M Gunji T Sugihara H Sayama K 《Chemical communications (Cambridge, England)》2008,(43):5565-5567
Acetaldehyde was completely oxidized to CO(2) over a Pd/WO(3) photocatalyst under fluorescent-light irradiation in a flow-type reactor, and Pd/WO(3) was also used to completely oxidize toluene to CO(2) in a batch reactor under visible-light irradiation. 相似文献
865.
5-Fluorouracil (5-FU) is used widely as an anticancer drug to treat solid cancers, such as colon, breast, rectal, and pancreatic cancers, although its clinical application is limited because 5-FU has gastrointestinal and hematological toxicity. Many groups are searching for prodrugs with functions that are tumor selective in their delivery and can be activated to improve the clinical utility of 5-FU as an important cancer chemotherapeutic agent. UV and ionizing radiation can cause chemical reactions in a localized area of the body, and these have been applied in the development of site-specific drug activation and sensitization. In this review, we describe recent progress in the development of novel 5-FU prodrugs that are activated site specifically by UV light and ionizing radiation in the tumor microenvironment. We also discuss the chemical mechanisms underlying this activation. 相似文献
866.
Chen LC Nishidate K Saito Y Mori K Asakawa D Takeda S Kubota T Hori H Hiraoka K 《The journal of physical chemistry. B》2008,112(35):11164-11170
Probe electrospray ionization (PESI) has recently been developed, in which the electrospray was generated from a solid needle instead of by using a capillary. In this paper, the characteristics of probe electrospray ionization were studied based on the measurement of spray current, optical microscopy, and PESI mass spectrometry. In the experiment, the solid needle was moved up and down a vertical axis, and a small amount of sample was repeatedly loaded to the needle when the tip of the needle touched the surface of the liquid sample at the lowest position. After the application of high voltage, a liquid droplet was formed on the tip of the solid needle probe, with its size was determined by the size of the needle tip. The liquid flow rate to the tip, as indicated by the spray current, depends on the voltage applied to the needle as well as the loaded liquid amount. Stable electrospray can be maintained until the total consumption of liquid sample. The kilohertz current pulsation takes place in the case of overloading the sample to the needle. The influences of the applied voltage and the liquid flow rate on the PESI mass spectra were also examined. 相似文献
867.
Sakurai S Nishino H Futaba DN Yasuda S Yamada T Maigne A Matsuo Y Nakamura E Yumura M Hata K 《Journal of the American Chemical Society》2012,134(4):2148-2153
Here we show that essentially any Fe compounds spanning Fe salts, nanoparticles, and buckyferrocene could serve as catalysts for single-walled carbon nanotube (SWNT) forest growth when supported on AlO(x) and annealed in hydrogen. This observation was explained by subsurface diffusion of Fe atoms into the AlO(x) support induced by hydrogen annealing where most of the deposited Fe left the surface and the remaining Fe atoms reconfigured into small nanoparticles suitable for SWNT growth. Interestingly, the average diameters of the SWNTs grown from all iron compounds studied were nearly identical (2.8-3.1 nm). We interpret that the offsetting effects of Ostwald ripening and subsurface diffusion resulted in the ability to grow SWNT forests with similar average diameters regardless of the initial Fe catalyst. 相似文献
868.
Miyoshi Y Akatsuka T Okuoka S Tsukajima A Makino M Saito M Yonehara K 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(25):7941-7949
Further study of our aerobic intermolecular cyclization of acrylic acid with 1-octene to afford α-methylene-γ-butyrolactones, catalyzed by the Pd(OCOCF(3))(2)/Cu(OAc)(2)?H(2)O system, has clarified that the accumulation of water generated from oxygen during the reaction causes deactivation of the Cu cocatalyst. This prevents regeneration of the active Pd catalyst and, thus, has a harmful influence on the progress of the cyclization. As a result, both the substrate conversion and product yield are efficiently improved by continuous removal of water from the reaction mixture. Detailed analysis of the kinetic and spectroscopic measurements performed under the condition of continuous water removal demonstrates that the cyclization proceeds in four steps: 1)?equilibrium coordination of 1-octene to the Pd acrylate species, 2)?Markovnikov-type acryloxy palladation of 1-octene (1,2-addition), 3)?intramolecular carbopalladation, and 4)?β-hydride elimination. Byproduct 2-acryloxy-1-octene is formed by β-hydride elimination after step 2). These cyclization steps fit the Michaelis-Menten equation well and β-hydride elimination is considered to be a rate-limiting step in the formation of the products. Spectroscopic data agree sufficiently with the existence of the intermediates bearing acrylate (Pd-O bond), η(3)-C(8)H(15) (Pd-C bond), or C(11)H(19)O(2) (Pd-C bond) moieties on the Pd center as the resting-state compounds. Furthermore, not only Cu(II), but also Cu(I), species are observed during the reaction time of 2-8?h when the reaction proceeds efficiently. This result suggests that the Cu(II) species is partially reduced to the Cu(I) species when the active Pd catalytic species are regenerated. 相似文献
869.
An equatorial attack of TMS-diazomethane was determined to be the first step of the BF(3)-promoted ring expansion reaction of six-membered ketones using TMS-diazomethane. The migration reaction occurred in a conformation in which the carbonyl oxygen and the TMS group were antiperiplanar to predominantly afford trans-seven-membered ketones. 相似文献
870.
S Harada T Sakai K Takasu K Yamada Y Yamamoto K Tomioka 《The Journal of organic chemistry》2012,77(17):7212-7222
Enantio- and diastereoselective one-pot synthesis of three- to seven-membered cis-azaheterocycles was achieved using a triggered asymmetric conjugate addition reaction of lithium amide with an enoate, followed by alkylation of the resulting lithium enolate with α,ω-dihaloalkane and N-alkylation. Isomerization of cis-azaheterocycles with a base yielded the trans-product, constituting a one-pot synthesis of cis-azacycles and a two-step synthesis of trans-azacycles. The four-step asymmetric synthesis of nemonapride highlights the general utility of the method. 相似文献