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排序方式: 共有221条查询结果,搜索用时 15 毫秒
1.
Norio Shibata 《Journal of fluorine chemistry》2007,128(5):469-483
The selective construction of carbon-fluorine bonds is of great interest to medicinal chemists because the replacement of a hydrogen or an oxygen atom with a fluorine atom in biologically active molecules can confer the molecules with improved physicochemical properties and biological activities. Since the first discovery of enantioselective fluorination using N-fluorocamphorsultam, our synthetic interest had been focused on the development of chiral N-fluorosulfonamide derivatives capable of enantioselective fluorination. However, these initial efforts revealed several limitations in both chemical yields and enantioselectivities of the fluorinated products. We present here the background of our personal story of the enantioselective fluorination reaction and some successful applications of the methods to the design and synthesis of biologically active products. Two novel approaches using cinchona alkaloid/Selectfluor® combinations and chiral ligands/metal complexes have been pursued, respectively. In addition, the recent advances in this area by other groups are also described briefly. 相似文献
2.
Tsuyoshi Nakajima 《Journal of fluorine chemistry》2007,128(4):277-284
Recent results on the surface modification of petroleum cokes and their electrochemical properties as anodes of secondary lithium batteries are summarized. The surface of petroleum coke and those heat-treated at 1860-2800 °C were fluorinated by elemental fluorine (F2), chlorine trifluoride (ClF3) and nitrogen trifluoride (NF3). No surface fluorine was found except only one sample when ClF3 and NF3 were used as fluorinating agents while surface region of petroleum coke was fluorinated when F2 was used. Transmission electron microscopic (TEM) observation revealed that closed edge of graphitized petroleum coke was destroyed and opened by surface fluorination. Raman spectra showed that surface fluorination increased the surface disorder of petroleum cokes. Main effect of surface fluorination with F2 is the increase in the first coulombic efficiencies of petroleum cokes graphitized at 2300-2800 °C by 12.1-18.2% at 60 mA/g and by 13.3-25.8% at 150 mA/g in 1 mol/dm3 LiClO4-ethylene carbonate (EC)/diethyl carbonate (DEC) (1:1, v/v). On the other hand, main effect of the fluorination with ClF3 and NF3 is the increase in the first discharge capacities of graphitized petroleum cokes by ∼63 mAh/g (∼29.5%) at 150 mA/g in 1 mol/dm3 LiClO4-EC/DEC. 相似文献
3.
An increasing number of biologically active compounds in the pharma and agro-chemical sector contain carbon fluorine bonds. One of the most common methods to introduce fluorine into intermediates is the well-investigated halogen-exchange reaction, in which chloro- and bromoaromatics activated towards nucleophilic substitution, react with a fluoride source to yield the corresponding fluoroarenes. In general, the reaction is supported by phase-transfer catalysts. The use of a new class of very active phase-transfer catalysts gives the possibility of substituting even halogens with weak activation giving a convenient access to interesting compounds that are not available so far and opening up new synthetic routes in Halex chemistry. Our new classes of catalysts, CNC+ (1a), PNC+ (2a) and several different approaches presented by other groups are described and experimental results discussed. 相似文献
4.
Natural graphite samples with average particle sizes of 5, 10 and 15 μm (NG5 μm, NG10 μm and NG15 μm, respectively) were fluorinated by ClF3 (3 × 104 Pa) at 200 and 300 °C for 2 min. X-ray photoelectron spectra of surface-fluorinated samples showed that surface fluorine concentration increased with increase in the particle size of graphite and reaction temperature. Small amounts of chlorine were also detected in all the fluorinated samples. Raman spectra of original and surface-fluorinated samples indicated that the surface disordering was increased for NG10 μm and NG15 μm. Surface areas were decreased by the fluorination for NG5 μm and NG10 μm but unchanged for NG15 μm. The mesopores with diameter of 1.5-2 nm increased while those of 2-3 nm decreased for all the samples. First coulombic efficiencies for NG10 μm and NG15 μm were highly increased by surface fluorination in 1 mol/dm3 LiClO4-EC/DEC/PC (EC: ethylene carbonate, DEC: diethyl carbonate, PC: propylene carbonate) solution. 相似文献
5.
Achim Hiller Jörg T. Patt Jörg Steinbach 《Journal of organometallic chemistry》2006,691(18):3737-3742
To evaluate the suitability of [18F]perchorylfluoride [18F]FClO3 as an electrophilic fluorination agent for the preparation of radiopharmaceuticals, the reactivity non-radioactive FClO3 towards 4-substituted trimethyltin aromatic compounds was studied. Contrary to the expectation, an electrophilic fluorination of the aromatic nucleus did not occur. The reaction of perchlorylfluoride with aromatic trimethylstannyl compounds resulted in the formation of trimethyltin fluoride and the respective destannylated aromatics in variable yields. 相似文献
6.
7.
Jean-Claude Jacquesy 《Journal of fluorine chemistry》2006,127(11):1484-1487
This is a summary of a lecture presented at the 100th Anniversary, Moissan Symposium in Paris on Friday 10th November 2006.In HF/SbF5, Vinca alkaloids react selectively at the D’ring of the molecule. In the presence of CHCl3 (or CCl4), vinorelbine yields 20′,20′-difluoro-3′,4′-dihydrovinorelbine (vinflunine), presently in phase III experimentation for treatment of bladder cancer and non small cell lung cancer. 相似文献
8.
E. Bernhardt 《Journal of fluorine chemistry》2004,125(6):967-973
First examples for the syntheses of trifluoromethyl transition metal complexes by conversion of a cyano into a trifluoromethyl ligand are described. The fluorination of [][Au(CN)4] with ClF in CH2Cl2 leads to the formation of a mixture of gold complexes of the type [AuFxCly(CF3)4−x−y]− (x=0-4, y=0-2). Ligand exchange reactions of [AuFxCly(CF3)4−x−y]− (x=0-4, y=0-2) with (CH3)3SiY (Y=Cl, CN) are performed resulting in anions of the type [AuYx(CF3)4−x]− (x=0-4). All products are characterised by - and NMR spectroscopy. 相似文献
9.
The effect of steric interactions on the regioselectivity of fluorination of para alkyl substituted phenols was investigated and the strong effect of size of the alkyl substituent, the structure of the F-N reagent and the solvent on the site of fluorination was established. The course of reaction obeyed a second order rate equation, while the fluorination process required higher ΔH≠ activation than oxidation or oxidative demethylation. Solvent polarity variations had a small effect on the rate of functionalisation, while an excellent Hammett correlation with ρ+=−2.3 was determined. 相似文献
10.
In this contribution we report on fluorotrimethyl[(Z)-pentafluoropropen-1-yl]phosphorane as a phosphorus based fluorinating reagent. Its solid state structure can be described as a trigonal bipyramid featuring elongated axial bonds due to the formation of a 3-center 4-electron bond. Abstraction of the fluoride ion leads to a shortening of the axial P–C bond. Thus the title compound can be utilized for substitution of bromine with fluorine and for the transfer of fluoride ions onto electrophilic compounds. Reaction with Sn(C2F5)2Br2 afforded salt [P(CH3)3(C3F5)]2[Sn(C2F5)2F4]. When fluorotrimethyl[(Z)-pentafluoropropen-1-yl]phosphorane was treated with P(C2F5)2F the primarily produced anion is sufficiently nucleophilic to attack the propenyl group of the cation in β-position to the phosphorus atom to yield zwitterionic [Me3PCF=C(CF3)–PF3(C2F5)2]. 相似文献