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81.
A convenient and large-scale preparation of retinoic acid 1 from β-ionone in five steps with 38% overall yield is described.The key steps are the epoxidization of 2 with a new methylated agent and the condensation 4 with tetraethyl methylenediphophonate in one-pot procedure to prepare 6. 相似文献
82.
Tetraalkyltin complexes, SnR4 (R = Me, Et, Pr, Bu) could react with Pt/HY at 193, 243, 273 and 333 K, respectively. The reactions occurred on the surface of the zeolite and the organotin grafted zeolites were characterized in detail. The framework and the microporous structure of the grafted Pt/HY zeolites were retained. However, the modified zeolites showed better size selectivity in the absorption of hydrocarbons. 相似文献
83.
One of the successful transformations within the field of organocatalysis, the organocatalytic asymmetric addition of nitromethane to α,β‐unsaturated aldehydes and ketones, has been studied by quantum chemical modeling. The level of accuracy of the hybrid density functional theory method B3LYP/6‐31G(d) was compared to a high level ab initio benchmark for this reaction. It is concluded that B3LYP/6‐31G(d) performs very well for this reaction type, giving good estimates of critical energies. The reaction between acrolein and nitromethane was studied in detail. The reaction mechanism revealed an intermediate oxazolidin structure, which is currently unknown. Alkyl substitution in various positions on the amine catalyst or α,β‐unsaturated carbonyl compound influences the reactivity in a predictive fashion. The iminium ion, prop‐2‐en‐iminium, is less activated towards nucleophilic attack compared to protonated acrolein. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
84.
The growth mechanism of the peritectic η phase involving the peritectic reaction and peritectic transformation in Cu-70%Sn alloy was investigated under directional
solidification. The results show that a major growth mechanism in thickening of the peritectic η-layer is not the peritectic reaction but the peritectic transformation. The transformation temperature and isothermal time
play crucial roles in determining the volume fraction and the thickness of the peritectic η phase. With the increase of the temperature and isothermal time, the volume fraction of the peritectic η phase increases. The regressed data show that the relationship between the thickness of η phase (Δx) and the transformation temperature (T) meets the following equation In Δx=6.5−1673 1 / T. Additionally, there exists a relationship between the thickness of the η phase (Δx) and the isothermal time (t) at the 9 mm solidification distance below the peritectic reaction interface, Δx=0.72t
1/2, which is consistent with the theoretical model.
Supported by the National Science Foundation of China (Grant No. 50395102) 相似文献
85.
Govindarajan Sankar A. Sultan Nasar 《Journal of polymer science. Part A, Polymer chemistry》2007,45(8):1557-1570
A series of substituted N‐methylaniline‐blocked polyisocyanates based on 4,4′‐methylenebis(phenyl isocyanate) and poly(tetrahydrofuran) were prepared and characterized thoroughly with FTIR, 1H NMR, and 13C NMR spectroscopy methods. Compared with unsubstituted N‐methylaniline, a blocking agent with an electron‐releasing substituent at the para position took a shorter time, whereas those with an electron‐releasing substituent at the ortho position or an electron‐withdrawing substituent at the ortho and para positions took longer times for the blocking reaction. The thermal dissociation reactions of blocked polyisocyanates were carried out with an FTIR spectrophotometer attached to hot‐stage accessories under dynamic and isothermal conditions. The dynamic method was used to determine the deblocking temperature, and the isothermal method was used to calculate the deblocking kinetics and activation parameters. The cure times of blocked polyisocyanates with hydroxyl‐terminated polybutadiene were also determined. The deblocking temperatures, the results of cure‐time studies, and the kinetic parameters revealed that the thermal dissociation of the N‐methylaniline‐blocked polyisocyanates was retarded by electron‐donating substituents and facilitated by electron‐withdrawing substituents. The action of N‐methylanilines as blocking agents for isocyanate was explained by the formation of a four‐center, intramolecularly hydrogen‐bonded ring structure during the thermal dissociation of the blocked polyisocyanates. The formation of such a hydrogen‐bonded ring structure was confirmed and supported by variable‐temperature 1H NMR studies and entropy parameters, respectively. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1557–1570, 2007 相似文献
86.
87.
析氢反应动力学的交流阻抗法研究 总被引:1,自引:0,他引:1
利用交流阻抗法测定析氢电化学动力学参数,得到与极化曲线法一致的结果,为确定复杂析氢过程速率的决定步骤提供了判据。 相似文献
88.
Gabor Schmera Adi Bulsara David Pierson Frank Moss Enrico Di Cera 《Journal of statistical physics》1993,71(5-6):1179-1190
We consider the class of experiments which can be characterized by a Fokker-PIanck dynamics corresponding to the overdamped motion of a state point in a suitable stochastic potential. We assume that the general form of the potential is known (or can be guessed with reasonable accuracy), but that its parameters are to be determined experimentally by measurements made with a noisy instrument. This possible method for determining the potential parameters, which exploits the system's own internal stochastic motion in order to explore rapidly its available parameter space, is substantially more efficient than traditional methods involving time averages of single point measurements, and yet does not appear to have been previously considered. The method could be important when, for example, the experiment must be completed in a limited time owing either to the expense of the experimental materials or to the temporary stationarity of the preparation, situations which are commonly encountered in experimental biochemistry and biology. 相似文献
89.
90.