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61.
The synthesis of α-halo β-keto-sulfones using potassium halide and hydrogen peroxide as a chemoselective mono halogenation reagent and the synthesis of α,α-symmetrical and asymmetrical dihalo β-keto-sulfones and α-halo, α-alkyl and β-keto-sulfones is described. Base induced cleavage of α-halo β-keto-sulfones, α,α-dihalo β-keto-sulfones, and α-halo, α-alkyl β-keto-sulfones afforded the corresponding halomethyl sulfones, dihalomethyl sulfones and haloalkyl sulfones.  相似文献   
62.
Al-Arfaj NA 《Talanta》2004,62(2):255-263
A flow-injection (FI) methodology using (2,2′-dipyridyl) ruthenium(II) [Ru(dipy)32+] chemiluminescence (CL) was developed for the rapid and sensitive determination of metoclopramide hydrochloride. The method is based on the CL reaction of metoclopramide with Ru(dipy)32+ and KMnO4 in a sulfuric acid medium. Under the optimum conditions, a calibration graph was obtained over the concentration range 0.005-3.5 μg ml−1 with a limit of detection (S/N=2) of 1 ng ml−1. The correlation coefficient was 0.99993 (n=8) with a relative standard deviation of 0.48% for 10 determinations of 1 μg ml−1 of drug. The method was successfully applied to the determination of metoclopramide in pharmaceutical preparations and biological fluids after IP administration of 25 mg kg−1 dose to rats. The elimination half-life was 2.5±0.4 h.  相似文献   
63.
Boiling temperature measurements have been made at ambient pressure for saturated ternary solutions of NaCl + KNO3 + H2O, NaNO3 + KNO3 + H2O, and NaCl + Ca(NO3)2 + H2O over the full composition range, along with those of the single salt systems. Boiling temperatures were also measured for the four component NaCl + NaNO3 + KNO3 + H2O and five component NaCl + NaNO3 + KNO3 + Ca(NO3)2 + H2O mixtures, where the solute mole fraction of Ca(NO3)2, x{Ca(NO3)2}, was varied between 0 and 0.25. The maximum boiling temperature found for the NaCl + KNO3 + H2O system is ≈134.9 C; for the NaNO3 + KNO3 + H2O system is ≈165.1 C at x(NaNO3) ≈ 0.46 and x(KNO3) ≈ 0.54; and for the NaCl + Ca(NO3)2 + H2O system is 164.7 ± 0.6 C at x{NaCl} ≈ 0.25 and x{Ca(NO3)2} ≈ 0.75. The NaCl + NaNO3 + KNO3 + Ca(NO3)2 + H2O system forms molten salts below their maximum boiling temperatures and the temperatures corresponding to the cessation of boiling (dry-out temperatures) of these liquid mixtures were determined. These dry-out temperatures range from ≈300 C when x{Ca(NO3)2} = 0 to ≥ 400 C when x{Ca(NO3)2} = 0.20 and 0.25. Mutual deliquescence/efflorescence relative humidity (MDRH/MERH) measurements were also made for the NaNO3 + KNO3 and NaCl + NaNO3 + KNO3 salt mixture from 120 to 180 C at ambient pressure. The NaNO3 + KNO3 salt mixture has a MDRH of 26.4% at 120 C and 20.0% at 150 C. This salt mixture also absorbs water at 180 C, which is higher than expected from the boiling temperature experiments. The NaCl + NaNO3 + KNO3 salt mixture was found to have a MDRH of 25.9% at 120 C and 10.5% at 180 C. The investigated mixture compositions correspond to some of the major mineral assemblages that are predicted to control brine composition due to the deliquescence of salts formed in dust deposited on waste canisters in the proposed nuclear repository at Yucca Mountain, Nevada.  相似文献   
64.
 Potassium salts of N-decanoylglycine and N-decanoyl-L-alanine oligopeptides (monomer, dimer and trimer) were synthesized. For these oligomer salts in aqueous solutions, the microstructures of micelles have been investigated by small-angle neutron-scattering (SANS). In the calculation of SANS intensity data, the thickness of the hydrophilic layer was altered by changing the conformation of the oligomer moiety (helical and β-sheet structures). For micelles of the trimer salts, the helical structure models provide the best fit to the observed SANS intensity data. For micelles of the monomer-and dimer-salts, the β-sheet model provides the best fit to the observed data. For the monomer-and dimer-micelles, the aggregation number (n) is not dependent on the species of amino acid residue, imply-ing that the decanoyl group plays a critical role in micelle formation. However, for the trimer micelles, the n value is dependent on the species of amino acid residue. Received: 11 July 1996 Accepted: 11 September 1996  相似文献   
65.
Preparation, Characterization and Reaction Behaviour of Sodium and Potassium Hydridosilylamides R2(H)Si—N(M)R′ (M = Na, K) — Crystal Structure of [(Me3C)2(H)Si—N(K)SiMe3]2 · THF The alkali metal hydridosilylamides R2(H)Si—N(M)R′ 1a‐Na — 1d—Na and 1a‐K — 1d‐K ( a : R = Me, R′ = CMe3; b : R = Me, R′ = SiMe3; c : R = Me, R′ = Si(H)Me2; d : R = CMe3, R′= SiMe3) have been prepared by reaction of the corresponding hydridosilylamines 1a — 1d with alkali metal M (M = Na, K) in presence of styrene or with alkali metal hydrides MH (M = Na, K). With NaNH2 in toluene Me2(H)Si—NHCMe3 ( 1a ) reacted not under metalation but under nucleophilic substitution of the H(Si) atom to give Me2(NaNH)Si—NHCMe3 ( 5 ). In the reaction of Me2(H)Si—NHSiMe3 ( 1b ) with NaNH2 intoluene a mixture of Me2(NaNH)Si—NHSiMe3 and Me2(H)Si—N(Na)SiMe3 ( 1b‐Na ) was obtained. The hydridosilylamides have been characterized spectroscopically. The spectroscopic data of these amides and of the corresponding lithium derivatives are discussed. The 29Si‐NMR‐chemical shifts and the 29Si—1H coupling constants of homologous alkali metal hydridosilylamides R2(H)Si—N(M)R′ (M = Li, Na, K) are depending on the alkali metal. With increasing of the ionic character of the M—N bond M = K > Na > Li the 29Si‐NMR‐signals are shifted upfield and the 29Si—1H coupling constants except for compounds (Me3C)(H)Si—N(M)SiMe3 are decreased. The reaction behaviour of the amides 1a‐Na — 1c‐Na and 1a‐K — 1c‐K was investigated toward chlorotrimethylsilane in tetrahydrofuran (THF) and in n‐pentane. In THF the amides produced just like the analogous lithium amides the corresponding N‐silylation products Me2(H)Si—N(SiMe3)R′ ( 2a — 2c ) in high yields. The reaction of the sodium amides with chlorotrimethylsilane in nonpolar solvent n‐pentane produced from 1a‐Na the cyclodisilazane [Me2Si—NCMe3]2 ( 8a ), from 1b‐Na and 1‐Na mixtures of cyclodisilazane [Me2Si—NR′]2 ( 8b , 8c ) and N‐silylation product 2b , 2c . In contrast to 1b‐Na and 1c‐Na and to the analogous lithium amides the reaction of 1b‐K and 1c‐K with chlorotrimethylsilane afforded the N‐silylation products Me2(H)Si—N(SiMe3)R′ ( 2b , 2c ) in high yields. The amide [(Me3C)2(H)Si—N(K)SiMe3]2·THF ( 9 ) crystallizes in the space group C2/c with Z = 4. The central part of the molecule is a planar four‐membered K2N2 ring. One potassium atom is coordinated by two nitrogen atoms and the other one by two nitrogen atoms and one oxygen atom. Furthermore K···H(Si) and K···CH3 contacts exist in 9 . The K—N distances in the K2N2 ring differ marginally.  相似文献   
66.
The synthesis of 2,5-bis{(diethyl-3′-indolyl)methyl}furan by the acid catalysed condensation of 2,5-bis(diethylhydroxymethyl)furan with indole is presented. Dilithium, disodium and dipotassium derivatives are prepared by the reaction of the bis(indole) with n-BuLi, NaH and K, respectively, in the presence of various Lewis bases. The X-ray structures of 2,5-bis{(diethyl-3′-indolyl)methyl}furan and the dilithiated derivative (as a polymeric tetrahydrofuran adduct) are reported.  相似文献   
67.
The solid state structures of three nitroformate (NF) salts were determined using single crystal X‐ray crystallography. The NF anion was found to be a non‐planar moiety which adopts either the commonly observed C2v conformation or distorted propeller conformation (D3) in the case of the silver salts, or, a C2 conformation in the case of the potassium salt. This latter C2 conformation has been uniquely observed for potassium nitroformate. All structures exhibit cation‐anion interactions that influence the structure of the anion. The 13C and 14N NMR spectra of the NF anion show broad singlets, which indicates the equivalence of the nitro groups in solution within the NMR time‐scale. In addition, the vibrational and mass spectra of potassium nitroformate and silver nitroformate monohydrate were recorded. Furthermore, the gaseous decomposition products of potassium nitroformate at 25 °C were detected using IR spectroscopy and mass spectrometry.  相似文献   
68.
The transport of Na+ out of the cell and K+ into the cell against a concentration gradient is catalyzed by a (Na+ + K+)-activated ATPase. The way in which the cations pass through the cell membrane has not yet been elucidated. Studies on the ATP hydrolysis revealed a Na+-dependent phosphorylation of the enzyme protein; the conformation of the enzyme also appears to change. The energy required for transport of the cations against their concentration gradients is probably provided by K+-dependent hydrolysis of the enzyme-bound phosphate. The enzyme can synthesize ATP from inorganic phosphate and ADP on reversal of the cation concentration gradient. By keeping the enzyme in a particular conformation, the cardiac glycoside ouabain specifically inhibits the Na+ pump.  相似文献   
69.
A highly sensitive spectrophotometric method for the determination of nitrite in water and soil has been developed. The reaction of nitrite with acidified potassium iodide to liberate iodine which oxidizes leuco‐crystal violet (LCV) to form crystal violet having absorption maxima at 590 nm forms the bases of this method. In aqueous medium the system obeys Beer's law in the range of 0.1 to 1.0 μg per 25 mL (0.004–0.04 ppm), while in an extractive system the range is 0.025–0.25 μg in 100 mL (0.00025–0.0025 ppm). The molar absorptivity and Sandell's sensitivity were found to be 1.54 × 106 1 mol?1 cm?1 and 44 pg cm?2, respectively.  相似文献   
70.
Kin-ichi Oyama 《Tetrahedron》2004,60(9):2025-2034
We have succeeded in the first total synthesis of apigenin 7,4′-di-O-β-d-glucopyranoside (1a), a component of blue pigment, protodelphin, from naringenin (2). Glycosylation of 2 according to Koenigs-Knorr reaction provided a monoglucoside 4a in 80% yield, and this was followed by DDQ oxidation to give apigenin 7-O-glucoside (12a). Further glycosylation of 4′-OH of 12a with 2,3,4,6-tetra-O-acetyl-α-d-glucopyranosyl fluoride (5a) was achieved using a Lewis acid-and-base promotion system (BF3·Et2O, 2,6-di-tert-butyl-4-methylpyridine, and 1,1,3,3-tetramethylguanidine) in 70% yield, and subsequent deprotection produced 1a. Synthesis of three other chiral isomers of 1a, with replacement of d-glucose at 7 and/or 4′-OH by l-glucose (1b-d), and four chiral isomers of apigenin 7-O-β-glucosides (6a,b) and 4′-O-β-glucosides (7a,b) also proved possible.  相似文献   
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