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61.
Hydroboration of the syn, anti-[Fe(CO)3]2 double complex 24 of the readily available 5,6,7,8-tetramethylidene-2-bicyclo[2.2.2]octene ( 22 ) gave the corresponding doubly complexed 2-bicyclo[2.2.2]octanol 25. CrO3-oxidation furnished ketone 27 . The syn-Fe(CO)3-groups in 25 and 27 were oxidized selectively with trimethyl-amine oxide and yielded the corresponding anti-Fe(CO3)-monocomplexed tetraenes 26 and 28. The anti-Fe(CO)3-group in 28 could be removed, and 5,6,7,8-tetramethylidene-2-bicyclo[2.2.2]octanone ( 11 ) was obtained. NaBH4-reduction of 11 afforded tetraenol 10. TCE-cycloadditions to 10 and 11 (k1) were at least 10 times as fast as those (k2) to the corresponding monoadducts 35/36 and 34 , respectively. This Diels-Alder reactivity difference vanishes (k1 ≈ k2) with methyl propynoate. The latter dienophile added to the anti-Fe(CO)3-monocomplexed tetraenone 28 with ‘para’-regioselectivity. 相似文献
62.
Simultaneous separation of flavanone glycosides and polymethoxylated flavones in citrus juices using liquid chromatography 总被引:5,自引:0,他引:5
We present a simultaneous liquid chromatographic method for the separation of two flavonoid compound families, flavanone glycosides (FGs) and polymethoxylated flavones (PMFs), which are usually found in citrus fruit species and varieties. This technique permits the quantitation of six FGs (narirutin, naringin, hesperidin, neohesperidin, didymin, poncirin) and six PMFs (sinensetin, hexamethoxyflavone, nobiletin, scutellarein, heptamethoxyflavone and tangeretin). This technique, to be used to characterize a citrus juice by its polyphenolic profile, has been applied to the determination of flavonoid compounds in grapefruit- and orange juice. Differentiation of orange juice varieties and mixtures containing tangor juice using polyphenolic profiles and flavonoid content has been achieved. 相似文献
63.
Sofiane Ben Hamouda Quang Trong Nguyen Pierre Schaetzel 《European Polymer Journal》2006,42(11):2994-3005
Ethylene/ethane sorption characteristics were determined for dry Pebax™ (poly(amide 12-block-tetramethylenoxide) copolymer)/AgBF4 membranes by using an electronic microbalance. The membranes containing 0.7 and 22 wt.% AgBF4 showed a dual-mode sorption isotherm. The ethane isotherms for all the membranes were of the Henry-type, which is the normal sorption for gases in rubbery polymers. The abnormal presence of Langmuir sorption sites only for ethylene in the rubbery copolymer, never reported sofar, is attributed to the silver-based specific complexation sites. The silver salt which dissolved in limited amounts in the rubbery copolymer had a much smaller Langmuir sorption capacity than the salt that crystallized in the copolymer. The sorption kinetics indicate that the crystallized salt did adsorb slowly ethylene according to a zeroth-order kinetics, but not ethane. The gas uptake kinetics resulting from a step of the pressure surrounding the copolymer exhibited one stage for ethane but two stages for ethylene. For the latter, there was first a fast Fickian sorption stage, then a drift of the zeroth-order sorption of ethylene on salt crystals, which contributes for a large part to the total uptake. The zeroth-order sorption suggests that the sorbed ethylene amount in the second-stage is independent of the crystal-surface coverage. The value of the Fickian diffusion coefficient calculated by fitting the kinetics with a solution of the second Fick’s law was 5 × 10−12 m2/s for both ethylene (the first stage) and ethane, and is typical for small organic compounds in a rubbery material. 相似文献
64.
To obtain the intrinsic acidity constant of a carboxylic ion-exchanger, we propose a method of graphical double extrapolation. The results for an ion-exchanger made of polyvinyl alcohol grafted with acrylic acid are close to those published for the corresponding linear polyacid. 相似文献
65.
Francis Garnier Pierre Krausz Jacques-Emile Dubois 《Journal of organometallic chemistry》1979,170(2):195-201
The photoinduced metathesis [W(CO)6CCl4hν] of cis- and trans-RCH=CHMe gives 2-butene in a very high trans but low cis stereoselectivity. Propene behaves like a cis olefin. These results are consistent with the proposal of a dinuclear tungsten intermediate, which requires high steric constraints in the transalkylidenation step. 相似文献
66.
Javad Mostaghimi Pierre Proulx Maher I. Boulos 《Plasma Chemistry and Plasma Processing》1984,4(3):199-217
A theoretical investigation of the effect of different parameters on the flow and the temperature fields in a radiofrequency
inductively coupled plasma is carried out. The parameters studied are: central injection gas flow rate, total gas flow rate,
input power, and the type of plasma gas. The results obtained for argon and nitrogen plasmas at atmospheric pressure indicate
that the flow and the temperature fields in the coil region, as well as the heat flux to the wall of the plasma confinement
tube, are considerably altered by the changes in the torch operating conditions. 相似文献
67.
An additive procedure (SIBFA) is developed for the rapid computation of conformational energy variations in very large molecules. The macromolecule is built out of constitutive molecular fragments and the intramolecular energy is computed as a sum of interaction energies between the fragments. The electrostatic and the polarization components are calculated using multicenter multipole expansions of theab initio SCF electron density of the fragments. The repulsion component is obtained as a sum of bond and lone pair interactions.Tests of the procedure on a series of model compounds containing ether oxygens and pyridine-like nitrogens are reported and compared with the results of correspondingab initio SCF calculations. The resulting methodology is compatible with the simultaneous computation of intermolecular interactions. 相似文献
68.
Electron attachment to polar molecules and their non-covalent complexes can lead to different kinds of anions which differ from their excess electron localization. Spectroscopic methods for studying anion structures are reviewed. In many cases, the neutral and anion structures are identical and can be deduced from the electron attachment properties. Examples are given for complexes containing polar solvents or building blocks of biomolecules (nucleobases, amino acid residues...). 相似文献
69.
Sb4Te3 and Sb8Te9 are members of the homology (Sb2Te3)m.(Sb2)n, with structures consisting of Sb2- and Sb2Te3-type slabs stacked along [001]; electrical conductivity and thermopower are reported for several members of this family. 相似文献
70.
The uncatalyzed 1,4-addition of phenylmagnesium bromide and furylmagnesium iodide to methyl 5-methoxy-1,5-cyclohexadienylcarboxylate (), directly followed by alkylation and hydrolysis leads to the corresponding cyclohexanones of type (R1 and R2 trans) in moderate to high yield. 相似文献