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841.
Lemoucheux L Rouden J Ibazizene M Sobrio F Lasne MC 《The Journal of organic chemistry》2003,68(19):7289-7297
Efficient and rapid preparations of carbamoyl chlorides and unsymmetrical ureas from tertiary amines and phosgene or its safe equivalent triphosgene [bis(trichloromethyl)carbonate, BTC] are described. First, the reaction of stoichiometric amounts of phosgene with secondary amines was revisited, and it was shown that the formation of carbamoyl chlorides in high yields required careful adjustments of experimental conditions and the use of pyridine as an HCl scavenger. A phosgene-mediated dealkylation of triethylamine was observed when this base was used instead of pyridine. Taking advantage of this observation, a strategy of synthesis of carbamoyl chlorides from tertiary amines and phosgene has been developed. N-Alkyl-N-benzyl(substituted)tetrahydroisoquinolines, -piperazines, -piperidines, or -anilines were treated with stoichiometric amounts of phosgene (or BTC) in CH(2)Cl(2). Tertiary amines bearing electron-enriched benzyl group(s) afforded carbamoyl chlorides in excellent yields and without any contamination by symmetrical ureas. Subsequent additions of primary or secondary amines to these carbamoyl chlorides produced unsymmetrical ureas in single-pot and high-yielding operations. This methodology was applied in (11)C-chemistry. From [(11)C]phosgene, a common precursor used in the preparation of radiotracers for positron emission tomography, a rapid and efficient synthesis of (11)C-carbamoyl chlorides and (11)C-unsymmetrical ureas derived from tetrahydroisoquinoline and piperazine is described. The first example of (11)C-amide formation from the reaction of a (11)C-carbamoyl chloride and an organometallic (cyanocuprate or a Grignard reagent in the presence of a nickel catalyst) is also presented. 相似文献
842.
Laurent N Lafont D Dumoulin F Boullanger P Mackenzie G Kouwer PH Goodby JW 《Journal of the American Chemical Society》2003,125(50):15499-15506
Several 4-(4'-N,N-didodecylaminophenylazo)phenyl 1,2-trans glycosides 5a-e with various carbohydrate heads (beta-D-gluco, beta-D-galacto, beta-lacto, beta-D-xylo, and alpha-D-manno) have been synthesized. The key step was the formation of phenyldiazonium tetrafluoroborates 2a-e from the per-O-acetylated 4-aminophenyl glycosides 1a-e. These salts were condensed with N,N-didodecylaniline under phase transfer conditions and the per-O-acetylated 4-(4'-N,N-didodecylaminophenylazo)phenyl 1,2-trans glycosides 4a-e were fully de-O-acetylated by the Zemplén method. The self-organizing liquid crystal properties of the compounds were investigated by a variety of techniques, including polarized light microscopy, differential scanning calorimetry, and X-ray diffraction. All but one of the materials exhibited smectic A, lamellar phases. Remarkably, the glucose derivative exhibited a rectangular disordered columnar phase. This result has implications with respect to the induced curvature created by the recognition processes of the glucose headgroup relative to the other sugar moieties and to the prevalence of various glycolipids in cell membranes 相似文献
843.
We show that, under conditions about the microcharacteristic variety of a coherent
-module, the Cauchy problem is well-posed in the spaces of formal power series with Gevrey growth. We deduce that the filtration of the Irregularity Sheaf of a holonomic
-module, which we defined in a previous work, is preserved under inverse image if some rather general geometric conditions are fullfilled. 相似文献
844.
845.
Extending the analogous result of Cannon and Wagreich for the fundamental groups of surfaces, we show that, for the -regular graphs
associated to regular tessellations of the hyperbolic plane by m-gons, the denominators of the growth series (which are rational and were computed by Floyd and Plotnick) are reciprocal Salem polynomials. As a consequence, the growth rates of these graphs are Salem numbers. We also prove that these denominators are essentially irreducible (they have a factor of X + 1 when m 2 mod 4; and when = 3 and m 4 mod 12, for instance, they have a factor of X
2 – X + 1). We then derive some regularity properties for the coefficients f
n
of the growth series: they satisfy K
n
– R < f
n
< K
n
+ R for some constants K, R < 0, < 1. 相似文献
846.
847.
Ganapathy S Kumar R Delevoye L Amoureux JP 《Chemical communications (Cambridge, England)》2003,(16):2076-2077
[27Al]-1H REAPDOR (Rotational Echo Adiabatic Passage DOuble Resonance) NMR experiments distinguish structurally dissimilar Br?nsted acid sites located in main 8 and 12 membered-ring channels of the zeolite mordenite. 相似文献
848.
Nardello V Caron L Aubry JM Bouttemy S Wirth T Saha-Möller Chantu R Adam W 《Journal of the American Chemical Society》2004,126(34):10692-10700
The chiral allylic alcohols 1a-d and their acetate (1e) and silyl ether (1f) derivatives have been oxidized by the H2O2/MoO4(2)- system, a convenient and efficient chemical source of singlet oxygen. This chemical peroxidation (formation of the allylic hydroperoxides 2) has been conducted in various media, which include aqueous solutions, organic solvents, and microemulsions. The reactivity, chemoselectivity, and diastereoselectivity of this chemical oxidation are compared to those of the sensitized photooxygenation, with the emphasis on preparative applications in microemulsion media. While a similar threo diastereoselectivity is observed for both modes of peroxidation, the chemoselectivity differs significantly, since in the chemical oxidation with the H2O2/MoO4(2)- system the undesirable epoxidation by the intermediary peroxomolybdate competes efficiently with the desirable peroxidation by the in situ generated singlet oxygen. A proper choice of the type of microemulsion and the reaction conditions furnishes a high chemoselectivity (up to 97%) in favor of threo-diastereoselective (up to 92%) peroxidation. 相似文献
849.
Sladkov V Fourest B David F Venault L Lecomte M 《Analytical and bioanalytical chemistry》2003,376(4):455-459
Capillary electrophoresis (CE) with direct UV detection is proposed for speciation of inorganic Se in high-level liquid waste. In this aim, the optimal conditions of measurements (pH, electrolyte buffer concentration) and the influence of nitrate excess on the quantitative determination of Se(IV) and Se(VI) were studied. Different electrolyte buffers were considered: carbonate, phosphate and citrate. It was found, that citrate buffer is the most suitable for the application under consideration. Under the chosen optimal conditions (20 mmol L(-1) citrate buffer, pH 2.5), calibration curves for Se(IV) and Se(VI) are linear in the concentration range 10(-4)-10(-3) mol L(-1). The detection limits are 4x10(-6 )for Se(IV) and 2x10(-5) for Se(VI). The accuracy of the procedure was checked by calculating the recovery by spiking simulation solutions. Relative standard deviation (S(r)) is less than 10%. 相似文献
850.
Duursma A Lefort L Boogers JA de Vries AH de Vries JG Minnaard AJ Feringa BL 《Organic & biomolecular chemistry》2004,2(12):1682-1684
A library of 96 unique monodentate phosphoramidite ligands has been synthesized in solution and used in the asymmetric conjugate addition of potassium vinyltrifluoroborate to enones resulting in up to 88% ee. 相似文献