用萘酐合成染料中间体苝二酐的研究

介绍了用1,8-萘酐为原料合成染料和颜料中间体3,4,9,10-苝二酐的新方法,缩合过程由溶剂法取代熔融法,不仅可使苝二酐的产率高达85％,产品纯度可达90％。     

药物中间体2-[(2′-氰基联苯-4-基)甲基氨基]-3-硝苯甲酸乙酯的制备

本文介绍了以3-硝基-2-叔丁氧甲酰氨基苯甲酸乙酯为原料，在碱性条件下与4-(2-氰基苯基)-1-溴甲苯发生亲核取代反应制备2-[(2′-氰基联苯-4-基)甲基氨基]-3-硝苯甲酸乙酯的方法，产品经核磁共振验证其结构，产品收率达83％。本合成工艺条件温和，适合工业化生产。     

间溴苯甲醚的合成研究

硝基苯经过溴化、还原、重氮化、甲基化得到间溴苯甲醚,总收率为40%。     

溴素法α-溴代间氯苯丙酮合成研究

在金属卤化物催化剂 HD2 0 0 1存在下 ,溴与间氯苯丙酮在乙酸中反应得到盐酸安非他酮中间体 α-溴代间氯苯丙酮。最佳反应条件是 :n(间氯苯丙酮 )∶n(溴 ) =1∶ 1 ,催化剂用量为 1 %(质量分数 ) ,溴滴加时间为 1 h,反应温度为 1 0°C,此条件下 ,产物纯度为 98.83%,收率为 96.1 %。     

3-(S)-(-)-(1-氨甲酰基-1,1-二苯基甲基)吡咯烷的制备

3-(S)-(-)-1-氨甲酰基-1,1-二苯基甲基)吡咯烷是合成抗尿失禁药物达非那新的重要中间体。它由3-(S)-( )-3-羟基吡咯烷盐酸盐经磺酰化和烷基化反应得到3-(S)-( )-(1-氰基-1,1-二苯基甲基)-1-甲苯磺酰基吡咯烷,再经过去磺酰化和水解4步反应制得,总产率为5.1%。     

1-甲基-4-哌啶酮的合成

以甲胺的甲醇溶液和丙烯酸甲酯为原料,经Michael加成、Dieckmann环合和脱羧反应合成得到了1-甲基-4-哌啶酮,并对各步反应的工艺参数进行了优化,在n(丙烯酸甲酯)/n(甲胺)=2.2,n(甲醇钠)/n〔甲基-二-(β-甲氧羰乙基)胺〕=1.14,Michael加成反应温度25℃,Dieckmann环合反应温度80～83℃,脱羧反应温度100～103℃的条件下,1-甲基-4-哌啶酮的总收率为58%,并按该工艺顺利完成了500L反应釜中试。     

Natural rubber–ethylene‐propylene‐diene rubber covulcanization: Effect of reinforcing fillers

Filled covulcanizates of elastomer blend comprising natural rubber (NR) and ethylene‐propylene‐diene rubber (EPDM) of commercial importance were successfully prepared by using a multifunctional rubber additive; namely, bis(diisopropyl)thiophosphoryl disulfide (DIPDIS). A Two‐stage vulcanization technique further improved the physicochemical properties of the blend vulcanizates by restricting, through the formation of polar rubber bound intermediates, the migration of curative and filler from lower to highly unsaturated rubber. Scanning electron microscopy studies indicate homogeneity and coherency in the morphology of the two‐stage vulcanizates. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1001–1010, 2002; DOI 10.1002/app.10361     

Pd-Cu/La_(0.5)Pb_(0.5)MnO_3上氧化羰基化合成碳酸二苯酯

针对氧化羰基化合成碳酸二苯酯反应过程在低氧浓度下催化剂活性低的特点,研制出一种高效负载型双金属催化剂Pd-Cu/La0.5Pb0.5MnO3,并采用向反应体系中连续通入CO、O2的混合气体对苯酚氧化羰基化合成碳酸二苯酯(DPC)。实验表明,Pd-Cu/La0.5Pb0.5MnO3催化剂适宜的n(Cu)∶n(Pd)=1∶1,在苯酚50 g,催化剂1.0 g,通氧速度15 mL/min,CO进料速度285 mL/min,反应压力1.0 MPa,反应温度80℃条件下,反应5 h时,DPC产率达16.4%。     

6-氟-3,4-二氢-2H-1-苯并吡喃-2-甲酸的合成

6-氟-3,4-二氢-2H-1-苯并吡喃-2-甲酸是制备新型抗高血压药奈必洛尔的关键中间体.今以4-氟苯酚为起始原料,经酯化、Fries重排、环化、氢化等6个步骤得到目标产物,总收率27%.4-氟苯酚Ⅰ与乙酸酐酯化得4-氟苯基乙酸酯Ⅱ,Ⅱ在AlCl3催化下Fries重排得4-氟-2-乙酰基苯酚Ⅲ,比从4-氟苯酚的Friedel-Crafts酰化收率更高,二步总收率58%;Ⅲ与酰化试剂乙二酸二乙酯经酯化、环合及碱性水解得到6-氟-4-氧代-4H-1-苯并吡喃-2-甲酸Ⅵ,用一种试剂完成了酰化、环化并引入羧基;Ⅵ在乙酸介质中,以10%Pd/C催化加氢得外消旋6-氟-3,4-二氢-2H-1-苯并吡喃-2-甲酸Ⅶ.以上所述的方法具有条件温和、试剂常见易得、易于工业化的优点,并首次给出了关键中间体及目标产物的光谱图,表明产物结构正确.     

Surface modification of macroporous Al2O3 tubes with carbon-doped TiO2 intermediate layer and preparation of highly permeable palladium composite membranes for hydrogen separation

ABSTRACT

To prepare H₂-permeable palladium composite membranes, a novel carbon-doped microporous TiO₂ intermediate layer was introduced to modify the surface of macroporous Al₂O₃ substrates. The Pd/TiO₂–C/Al₂O₃ membrane was prepared via electroless plating, and thereafter, carbon residue in the intermediate layer was removed by calcination in air, yielding a Pd/TiO₂/Al₂O₃ membrane. Experimental results indicate that the carbon residue shrinks the pore size of the intermediate layer and facilitates a decrease of membrane defects. Additionally, carbon removal induces a higher effective membrane area at the permeate side, which enhances hydrogen permeability. Furthermore, the apparent activation energy (E_A) and stability of the as-prepared Pd/TiO₂/Al₂O₃ membrane were investigated.