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1.
2.
The chiral compounds (R)‐ and (S)‐1‐benzoyl‐2,3,5,6‐tetrahydro‐3‐methyl‐2‐(1‐methylethyl)pyrimidin‐4(1H)‐one ((R)‐ and (S)‐ 1 ), derived from (R)‐ and (S)‐asparagine, respectively, were used as convenient starting materials for the preparation of the enantiomerically pure α‐alkylated (alkyl=Me, Et, Bn) α,β‐diamino acids (R)‐ and (S)‐ 11 – 13 . The chiral lithium enolates of (R)‐ and (S)‐ 1 were first alkylated, and the resulting diasteroisomeric products 5 – 7 were aminated with ‘di(tert‐butyl) azodicarboxylate’ (DBAD), giving rise to the diastereoisomerically pure (≥98%) compounds 8 – 10 . The target compounds (R)‐ and (S)‐ 11 – 13 could then be obtained in good yields and high purities by a hydrolysis/hydrogenolysis/hydrolysis sequence. 相似文献
3.
Elenise Bannwart de Moraes Patricia Fazzio Martins César Benedito Batistella Mario Eusebio Torres Alvarez Rubens Maciel Filho Maria Regina Wolf Maciel 《Applied biochemistry and biotechnology》2006,132(1-3):1066-1076
Molecular distillation was studied for the separation of tocopherols from soya sludge, both experimentally and by simulation,
under different operating conditions, with good agreement. Evaporator temperatures varied from 100°C to 160°C and feed flow
rates ranged from 0.1 to 0.8 kg/h. The process pressure was maintained at 10−6 bar, the feed temperature at 50°C, the condenser temperature at 60°C, and the stirring at 350 rpm. For each process condition,
samples of both streams (distillate and residue) were collected and stored at −18°C before tocopherols analyses. Owing to
the differences between molecular weights and vapor pressures of free fatty acids and tocopherols, tocopherols preferentially
remained in the residue at evaporator temperatures of 100°C and 120°C, whereas for higher temperatures (140°C and 160°C) and
lower feed flow rate, tocopherols tended to migrate to the distillate stream. 相似文献
4.
5.
Unified and generalized Fresnel numbers 总被引:1,自引:0,他引:1
The concept of Fresnel number is discussed and expressions are derived for misaligned optical systems. For the case of perfectly aligned optical elements, the usual number,N, based on a Fresnel zone concept is found to be given byN = (a
2/)(D
1/B
1 +A
2/B
2), whereB
1,D
1 andB
2,A
2 are the transfer matrix elements of the optical systems before and after a circular aperture of radiusa respectively. A modified definition of the Fresnel number is proposed for Gaussian beam propagation. This parameterN
G, is related to the complex beam parameter and may be represented by the angle = tan–1
N
G, found in the familiar Collins chart and its dual representation. A general relation for the transformation of this Fresnel number is found. The expressions for Gaussian beam transformation are thus simplified, since the waist-waist transform is given byN
G1 =N
G2 = 0. Finally, these two kinds of Fresnel numbers are written as tensors when applied to cases involving elliptical apertures, astigmatic beams and nonsymmetrical systems. 相似文献
6.
Chiral ligands (S,S)-1, (S,S)-2, (S,S)-3, (S)-4, (S)-5, (S,S)-6, (S,S)-7, and (S,S)-8 turned out to be effective promoters in the enantioselective addition of diethylzinc to benzaldehyde. Interestingly, diamine (S,S)-3 and amino alcohols (S)-5 and (S,S)-7 induce the preferential formation of carbinol (R)-10 (unlike stereoinduction) whereas amido analogues (S,S)-2, (S)-4, and (S,S)-6 favor (S)-10 (like stereoinduction). Molecular modeling at the semiempirical PM3 level provided a reasonable interpretation based on conformational effects in the corresponding transition structures. Combinations of chiral ligands 1-8 with an achiral, flexible ligand (9) gave rise to an activated catalytic system that resulted in faster and higher yielding reactions. Furthermore, substantial increases in the observed enantiomeric excesses of product 10 confirmed the relevant role of achiral bis(sulfonamide) 9 as activator and "chiral environment amplifier". 相似文献
7.
学习体验是学生对学习内容、过程、方法、意义的自我感受和评估,对学生学习志趣、学习素养提升有积极正向作用。以钠及其化合物复习为例,将各类别物质间转化关系的构建、物质制备原理和条件的优选作为学习体验对象,依据学习体验的内在发展历程设计学习任务及活动,引导学生亲身体验学科认知方式、学科思维方法、学科应用价值,评价体验结果,激励学生自主学习发生。 相似文献
8.
A search for suitable reaction conditions in Mukaiyama-type aldol condensations activated by CeCl(3) and InCl(3) revealed that the reaction proceeds best in i-PrOH/H(2)O (95:5). Contrary to literature precedent, no reaction was observed in pure water, and the encountered destruction of the starting silyl enol ether can be ascribed to initial hydrolysis of the Lewis acid. As anticipated from the dual parameter (pK(h), WERC value) characteristics of CeCl(3) and InCl(3), the former proved more efficient as Lewis acid-promoter, in terms of reaction speed and yield. Nevertheless, InCl(3) was a superior catalyst during evaluation of the diastereoselectivity of the process. In this regard, determination of diastereoselectivity as a function of time showed that the InCl(3)-catalyzed reaction is irreversible, whereas the CeCl(3)-catalyzed reaction is a reversible process. In both cases, formation of the syn product is kinetically preferred, although DeltaDeltaG(++)273K(InCl(3)) = 1.50 kcal/mol versus DeltaDeltaG(++)273K (CeCl(3)) = 0.38 kcal/mol. Molecular modeling (semiempirical PM3, ab initio HF/3-21G*, hybrid B3LYP/3-21G*, and B3LYP/LANL2DZ) of the diastereoselective aldol reaction promoted by InCl(3) supports a "closed", Zimmermann-Traxler transition state. 相似文献
9.
Ericka Santacruz Gabriela Huelgas Sandra K. Angulo Virginia M. Mastranzo Simón Hernández-Ortega Judit A. Aviña Eusebio Juaristi Cecilia Anaya de Parrodi Patrick J. Walsh 《Tetrahedron: Asymmetry》2009,20(24):2788-2794
New chiral thioureas 1–8 containing 1,2-ethylendiamine or trans-1,2-diaminocyclohexane as the carbon skeleton, and containing an (S)-α-phenylethyl group have been prepared (79–98% yield). Thioureas 1–8 were used as ligands for the zinc-based catalyzed asymmetric hydrosilylation of acetophenone with polymethylhydrosiloxane (PMHS). The best result was achieved with monothiourea 1 (up to 75% ee), in toluene and a catalyst load of 5 mol %. 相似文献
10.
建立了超高效液相色谱-电喷雾离子源-串联三重四极杆质谱(UPLC-ESI MS/MS)分析饮用水中高氯酸盐的方法.以300Extend-C18为分析柱,10%甲醇水溶液为流动相,ESI MS/MS串联质谱为检测器,以多重反应监测(MRM)模式监测高氯酸盐m/z 99.5→82.9离子对.方法的线性范围为0.2 ~10 μg/L,相关系数为r2=0.999 9,方法检出限为0.15 μg/L,平均加标回收率为82%,相对标准偏差为4.4%.应用UPLC-ESI MS/MS法测定北京市部分城区饮用水中的高氯酸盐,其中5个水样中检出ClO-4,质量浓度为0.040 ~0.262 μg/L,但在安全阈值范围内,不会对居民健康构成威胁. 相似文献