运行10万小时加氢反应器试块脆化与断裂性能测试

炼油和石油化工工业中大量使用加氢工艺，由于加氢反应器等关键设备的材料为高温临氢服投，开展材料损伤研究和剩余寿命预测分析具有重要的工程意义和学术价值。本文对扬子石化公司芳烃联合装置加氢反应器DC—101A随机试块进行了解剖与性能测试，包括拉伸、冲击、断裂等试验，获得了2．25Cr—1Mo钢在17．47MPa和427℃下运行10万小时后的材料性能，并与运行了4．3万小时时取出的另一随机试块解剖测试结果进行了初步对比。     

草酸二甲酯加氢Cu/SiO2催化剂前体的研究

分别以碳酸铵和氨水为沉淀剂，硅溶胶为栽体，采用沉淀沉积法制备了Cu／SiO2(ωCu=0．20)催化剂。其中以氨水为沉淀剂通过均匀蒸氨沉淀沉积法制得的催化剂具有较高的草酸二甲酯加氢活性。通过XRD、FT—IR、热重(TG)等分析，证实了催化剂前体是一种具有矿物硅孔雀石结构的物质，它具有较高的热稳定性和低温催化活性。通过热分析和不同焙烧温度对催化剂活性的影响，得出具有硅孔雀石结构的催化剂前体在450℃焙烧后进行还原，具有较高的活性组分分散度和Cu2O含量，因而对草酸二甲酯加氢反应有较高的活性。     

Convenient methods for the synthesis of d4, d2 and d6 isotopomers of 4‐(4‐fluorobenzyl)piperidine

Pure 4‐(4‐fluoro‐[2,3,5,6‐²H₄]benzyl)piperidine was prepared via the Grignard reaction of 4‐fluoro‐[2,3,5,6‐²H₄]bromobenzene and pyridine‐4‐aldehyde followed by consecutive deoxygenation and heteroatomic ring saturation in the presence of palladium on carbon catalyst. An improved method for the catalytic H/D exchange in benzylic positions of 4‐(4‐fluorobenzyl)piperidine and its d₄ derivative has also been described. Copyright © 2005 John Wiley & Sons, Ltd.     

Gas Transport Properties of Hydrogenated and Fluorinated Polynorbornene Dicarboximides

The synthesis and further hydrogenation of fluorinated polynorbornene dicarboximides is reported, using p‐toluenesulfonyl hydrazide and Wilkinson's catalysts, respectively. Despite improving the resistance to thermo‐oxidative degradation, it is observed that the hydrogenation of the backbone double bonds in the polymer also decreases the thermomechanical properties. Afterward, a comparative study of gas transport in membranes based on these hydrogenated polynorbornenes, as well as in their unsaturated analogues, is carried out. The gases studied are hydrogen, oxygen, nitrogen, carbon dioxide, methane, ethane, ethylene, and propylene. After hydrogenation, the gas permselectivity of the membranes is enhanced as a consequence of the decrease of both the gas solubility and the gas diffusion.

     

含第一过渡金属和钯的双金属高分子催化剂及其催化加氢性能的研究

高分子金属催化剂的性能,不仅与金属离子的种类有关,而且与高分子配体的结构有关。作者在以SiO_2负载的聚苯乙烯马来酸酐共聚物的苯胺氨解产物——钯单金属高分子催化剂(P—C_6H_5NH·Pd) 中引入少量的第一过渡金属离子,形成双金属高分子金属催化剂(P-C_6H_5NH·Pd·M)。研究结果表明,由于第一过渡金属离子的引入,使单金属高分子催化剂的催化加氢性能(活性、选择性和稳定性)得到了改善。而且发现,第一过渡金属离子的助催化作用与它的晶体场稳定化能(Crystal Field Stablization Energy,CFSE)有关。     

Isolation and identification of metabolites of osthole in rats

1. Osthole (Ost), one of the major components of Cnidium monnieri (L.) Cusson, is had the structure of an isopentenoxy-coumarin with a range of pharmacological activities. In the present study, the metabolism of Ost in male Sprague-Dawley rats was investigated by identifying Ost metabolites excreted in rat urine.

2. Following an oral dose of 40 mg/kg Ost, 10 phase I and 3 phase II metabolites were isolated from the urine of rats, and their structures identified on the basis of a range of spectroscopic data, including 2D-NMR techniques. These metabolites were fully characterized as 5′-hydroxyl-osthole (M-1), osthenol (M-2), 4′-hydroxyl-osthole (M-3), 3, 5′-dihydroxyl-osthole (M-4), 5′-hydroxyl-osthenol (M-5), 4′-hydroxyl-2′, 3′-dihydro-osthenol (M-6), 4′-hydroxyl-osthenol (M-7), 3, 4′-dihydroxyl-osthole (M-8), 2′, 3′-dihydroxyl-osthole (M-9), 5′-hydroxyl-2′, 3′-dihydroosthole (M-10), osthenol-7-O-β-D-glucuronide (M-11), osthole-4′-O-β-D-glucuronide (M-12) and osthole-5′-O-β-D-glycuronate (M-13). This is the first identification of M-1, M-3 to M-13 in vivo.

3. On the basis of the metabolites profile, a possible metabolic pathway for Ost metabolism in rats has been proposed. This is the first systematic study on the phases I and II metabolites of 8-isopentenoxy-coumarin derivative.

     

C2-对称面手性RuPHOX-Ru催化的不对称氢化反应及其在手性药物合成中的应用

相比于中心手性和轴手性的配体,具有面手性(主要是基于二茂铁)的配体受到的关注较少,基于二茂钌骨架的面手性配体更是鲜有报道。二茂铁与二茂钌的2个环戊二烯负离子环之间的距离分别是0.332 nm和0.368 nm,即二茂钌的2个环戊二烯负离子环之间的距离要比相应的二茂铁的长约10%,这使得以二茂钌为骨架的面手性配体在电子效应与立体效应方面与以二茂铁为骨架的有所差异。本课题组开发的基于二茂钌的C2-对称双膦-(口恶)唑啉配体RuPHOX在许多反应,特别是钌催化的不对称氢化反应中,显示出了优异的化学稳定性和催化性能。其与金属络合后具有双金属反应中心,在提高反应活性的同时,形成更大的空间位阻,合成的RuPHOX的钌络合物RuPHOX-Ru可直接用于含C=O或C=C键底物的不对称氢化反应中。本文简要综述了RuPHOX-Ru催化的含C=O、C=C以及同时含C=O和C=C双键等底物的不对称氢化反应,以及其在手性药物合成中的应用。     

Preparation of high specific activity tritium labeled 6α,9,‐difluoro‐11β,21‐dihydroxy‐16α,17‐[(1‐methylethylidene)bis(oxy)]pregna‐1,4‐diene‐3,20‐one,fluocinolone acetonide

Fluocinolone acetonide was tritiated by selective reduction of the 1,2‐double bond of the O‐protected analog under tritium, followed by re‐establishment of the 1,2‐double bond and deprotection. Protection of both hydroxyl functionalities was required. The product was obtained with specific activity 36.8 Ci/mmol. Copyright © 2009 John Wiley & Sons, Ltd.     

罗替戈汀手性中间体S(-)2-(N-正丙基)胺基-5-甲氧基四氢萘的合成

目的 合成罗替戈汀关键手性中间体S(-)2-(N-正丙基)胺基-5-甲氧基四氢萘.方法 以5-甲氧基-2-四氢萘酮为起始物,经过正丙胺胺化、10％钯炭催化氢化还原、手性拆分3个步骤合成得到该中间体.结果手性中间体S(-)2-(N-正丙基)胺基-5-甲氧基四氢萘的总收率为21.5％.结论该路线的原料廉价易得、收率高,...     

萘丁美酮的钯催化偶联合成工艺研究

改进了Ａｓｉａｍ的萘丁美酮（１）合成法，以２－甲氧基萘计算，总收率８２％。其中２的萘环５位溴原子的脱除和４侧链碳－碳双键的氢化还原均采用高选择性的钯炭／甲酸铵催化氢转移反应。以在原位生成的二（三苯膦）二氯化钯催化偶联反应，并免用价昂的Ｎ－甲基吡咯烷酮。