Stereoselective effects in the solid-phase hydrogenation of unsaturatedl-hydroxyproline derivatives

The solid-phase catalytic hydrogenation of (R-4tert-butoxy-Δ¹-pyrroline-2-carboxylic) acid under the action of hydrogen spillover was studied. The reaction proceeds stereoselectively with the predominant formation of thel-amino acid. The configuration of the asymmetric center formed is determined by that of the asymmetric C(4) atom. The major portion of the isotope label is incorporated into the allylic C(3) and C(5) positions, and the β-H atoms are more mobile. Using quantum-chemical calculations, the geometric structure of thel-hydroxyproline molecule was calculated, and the spin-spin coupling constants for this tritium-labeled amino acid were determined. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1820–1823, October, 1997.     

Regio- and Stereocontrolled Nucleophilic Addition Reactions of An Unsymmetrically Disbustituted Butadiene η4-Molybdenum Cationic Complex

The reactions of a new cationic complex, [Cp(CO)₂Mo(η⁴-2-methyl-3-SPh-C₄H₄)]⁺ PF^?₆ (3), with carbon, hydride, and nitrogen nucleophiles were found to give only the C-1 addition products in good yield. The X-ray crystal structures of two of the addition products 4a and 4e confirm the regio- and stereochemistry of the nucleophilic additions.     

PS-b-P4VP两嵌段共聚物的合成及其自组装的研究

双硫酯 (PhC(S)SCH2 Ph)作为链转移剂 ,AIBN作为引发剂 ,用可逆的加成 断裂链转移 (RAFT)活性自由基聚合方法 ,合成了PS大分子链转移剂 .然后在AIBN引发下 ,利用制得的大分子链转移剂 ,以DMF为溶剂 ,80℃下采用RAFT方法 ,合成了PS b P4VP两嵌段共聚物 ,通过核磁共振谱及动力学的研究证明了其活性聚合的特征 .结果表明聚合反应在 2 4h内转化率可达 95 % .并用透射电子显微镜 (TEM )和扫描电子显微镜(SEM)研究了PS b P4VP两嵌段共聚物在选择性溶剂硝基苯 四氢呋喃中的自组装行为 ,研究结果表明改变聚合物的浓度以及选择性溶剂 ,可观察到自组装行为的变化 .     

微波-同时蒸馏萃取分离肉桂挥发性成分分析

经粉碎的肉桂干燥树皮置于去离子水中微波加热处理后,用自制的同时蒸馏-萃取装置,以重蒸乙醚为溶剂将试样中的挥发组分萃取分离。用旋转蒸发器除去乙醚后即得到含有试样中挥发组分的透明的黄色液体,收得率为6.5%,应用GC/MS法对黄色液体的组分进行定性和定量分析。借助于联机的计算机和相关软件并用峰面积-归一化计算测得其中共有27个化合物,其中含量最高的是肉桂醛,达94.36%。另取部分上述挥发油(即黄色液体),用加成分解法将其中肉桂醛转化为一种加成产物以沉淀形式析出,即将黄色液体与NaHSO3共置于微波炉中,在不超过10℃的条件下处理直至加成物完全析出。将此加成物分出,并用0.1 mol.L-1盐酸进行水解处理,使加成物恢复成纯度较高的肉桂醛,用IR及MS对其组成及结构作进一步确认。     

Copper(II) tetrafluoroborate as a novel and highly efficient catalyst for Michael addition of mercaptans to α,β-unsaturated carbonyl compounds

Copper(II) tetrafluoroborate has been found to be a new and highly efficient catalyst for Michael addition of thiols to α,β-unsaturated carbonyl compounds under solvent-free conditions and in H₂O at room temperature. The reactions are very fast and are completed in 2 min to 1 h affording high yields. The rate of thiol addition was dependent on the steric hindrance at the β-carbon of the α,β-unsaturated carbonyl substrate. In the case of chalcones, the reactions are best carried out in MeOH as solvent.     

Theoretical study of the reaction of alkynes with furan catalyzed by AuCl3 and AuCl

A general scheme for the endo‐ and exo‐cyclization of furan reactivity with [L ‐Au^{III, I}Cl_x] with (x = 3, 1 and L ‐acetylene and vinylidene) complexes is investigated using density functional theory (DFT) code. Two conceivable mechanisms via a [4 + 2] Diels–Alder process or carbene complex are analyzed. According to the activation energy values of the gold (III and I) catalyst, the first mechanism, which implies the Diels–Alder reaction of Au^III, is thermodynamically favored and gives more evidence of the intramolecular addition of the furan with the alkynes. The second mechanism, presumably assisted by the spontaneous formation of the exo‐vinylidene complexes and intermediates of gold (III, I) by forming the carbene complex, is kinetically favored. Additionally, we compare our results with other structures with intramolecular additions that exhibit the quasi‐similarity of gold analogue structures. Differences in activation energies are observed, according to the functional used. Finally, we probe the solvent effects, which decrease the energy barrier in the path. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007     

Covering projective planar graphs with three forests

It is known that all planar graphs and all projective planar graphs have an edge partition into three forests. Gonçalves proved that every planar graph has an edge partition into three forests, one having maximum degree at most four [5]. In this paper, we prove that every projective planar graph has an edge partition into three forests, one having maximum degree at most four.     

Regio- and stereoselectivity in the addition reactions of CH-acids to aldehydes under the conditions of phase-transfer catalysis

The regio- and stereoselectivity of the reactions of carbanions, generated from alkanals, carboxylates of the type XYCHCOOEt (X = EtOOC, CN, Ac; Y = H, Br), or derivatives of 3-methyl-4-phosphono-2-butenoic acid using PTC techniques, with aldehydes of various types (alkanals, ,-enals, cross-conjugated enedials, benzaldehydes,etc.) are reviewed. The factors affecting the outcome of these reactions are discussed. The carbanion analogs, triphenylphosphorus ylides, are shown to attack selectively at one of the aldehyde groups of aromatic dialdehydes. The regularities found for the title reactions were used in the syntheses of some biologically active isoprenoids.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1867–1885, October, 1995.     

Polynitro-substitutedN-alkylalkaneimidoyl chlorides

The reaction of -fluorosubstituted polynitroalkylaldimines with HCl results in replacement of the fluorine atom by a chlorine atom. The hitherto unknown -chlorosubstituted polynitroalkylaldimines have been obtained, and their X-ray structural investigation has been performed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 440–443, March, 1994.     

A new procedure for bovine milk digestion in a focused microwave oven: gradual sample addition to pre-heated acid

Milk samples can be efficiently digested using a focused microwave oven, however the conventional procedure of addition of concentrated acids to the liquid sample leads to digestates with elevated acidity and residual carbon concentrations. In this work a focused microwave oven was applied for acid digestion of bovine milk samples using a conventional and an alternative procedure based on gradual sample addition to hot and concentrated acids. A two-level 2³ full factorial design experiment with eight runs was carried out to evaluate the optimum experimental conditions for reducing both the residual carbon and the final acidity of digestates. The three studied parameters were: temperature of the digestion medium for sample addition, addition of sulfuric acid before the sample or during the first step, and number of aliquots of the sample gradually added. The best conditions were attained by adding small aliquots of milk (ten-fold a volume of 0.5 ml added during 5.0 min) to a digestion mixture containing 3.0 ml nitric acid plus 1.0 ml sulfuric acid heated at 105 °C. It was demonstrated that the digestion efficiency of the alternative procedure was better than the conventional procedure, i.e. 98 and 80%, respectively. The alternative procedure was applied for determination of Ba, Ca, Cu, K, Mg, Na, P, and Zn in whole and non-fat bovine milk. The accuracy was proved using two certified reference materials (whole and non-fat milk powder).