Homogeneous Catalysis for the Production of Fine Chemicals. Palladium- and Nickel-Catalysed Aromatic Carbon–Carbon Bond Formation

In this article we describe our recent efforts in the area of palladium- and nickel-catalysed aromatic substitution reactions. Main focus is on low cost and low waste production methods. The use of aromatic carboxylic anhydrides in the Heck reaction leads to a waste-free protocol. In addition these reactions are easy to work up as no ligands or bases are used. For Heck reactions where substrates or products do not tolerate high temperatures we found that use of a bulky phosphoramidite (13b) as ligand for palladium leads to a very fast reaction at low temperatures. Recycle of palladium in ligand-free Heck and Suzuki reactions is easily accomplished by treating the palladium black that precipitates at the end of the reaction on a carrier material with a small excess of I₂ prior to its re-use in the next run. Use of aryl chlorides in the palladium- and nickel-catalysed formation of biaryls can be accomplished by using the nickel-catalysed coupling with arylzinc chlorides. Better still, it was possible to make use of the arylgrignard and use a catalytic amount of ZnCl₂. Whereas the strength of these aromatic substitution reactions lies in their broad tolerance of functional groups, one exception was the Sonogashira reaction on 3-bromoaniline. The problem was solved by making use of in situ catalytic protection of the NH₂ group with benzaldehyde.     

适用于摩托车零件的多层镍电镀工艺

概括目前我国摩托车零件电镀所用镀层组合，对照有关金属覆盖层的国家标准，认为摩托车零件应用多层镍组合，并提供了工艺配方。     

纳米尺寸硫化镍化学增感剂

本文发现了硫化镍纳米粒子对卤化银乳剂的化学增感作用，采用水不溶性的硫化镍纳米粒子作为化学增感剂，与水溶性的硫代硫酸钠增感剂相比，可以在乳剂灰雾增加不大的条件下明显提高乳剂的感光度和反差。     

水扬酸镍的合成表征及结构分析

用流变相反应法合成了Ni(OH)Sal·H2 O和Ni2 (OH) 2 Sal2 ·H2 O。通过元素分析、TG、IR、XRD和磁矩对其结构进行了分析。结果表明两个配合物都属于单斜晶系 ,其晶胞参数为 ,Ni(OH)Sal·H2 O∶a =13.1179,b =11.36 41,c =9.5 6 0 5 ,β =92 .96 2 ,V =14 2 3.31(97) 3,Z =7,Dcalcd .=1.885 g/cm3,Dexpt=1.85 8g/cm3;Ni2 (OH) 2 Sal2 ·H2 O :a =13.12 17,b =11.35 80 ,c =9.5 5 2 2 ,β =92 .978 ,V =14 2 1.72 (95 ) 3,Z =4 ,Dcalc=2 .0 73g/cm3,Dexp=2 .0 0 0 g/cm3。     

Role of Acetic Acid Added to the Reaction Media for the Enantio-differentiating Hydrogenation of Methyl Acetoacetate Over a Tartaric Acid-modified Nickel Catalyst

The role of acetic acid added to the reaction media for the enantio-differentiating hydrogenation of methyl acetoacetate over a (R,R)-tartaric acid-in-situ-modified nickel catalyst was studied from the viewpoint of the hydrogenation rate during repeated runs. The hydrogenation of methyl acetoacetate on the “enantio-differentiating sites” of a tartaric acid-modified nickel catalyst was specifically accelerated by the acetic acid added to the reaction media to increase the enantio-differentiating ability of the catalyst. In order to increase the enantio-differentiating ability, the addition of acetic acid to the reaction media was required in each run during the repeated use of the catalyst.     

超细镍基负载型催化剂成型工艺条件研究

以正硅酸乙酯、钛酸丁酯、硝酸镍为主要原料,采用溶胶-凝胶法(Sol-gel)实验室放大制备10 kg工业中试用催化剂粉料，加胶粘剂A进行挤条成型。催化剂前躯体的物化性能用BET、XRD、TG-DTA、TEM及强度测试仪进行表征，用固定床连续流动微反装置，考察催化剂苯加氢生成环己烷的催化性能。研究结果表明，催化剂的强度随胶粘剂的含量增大而增大，当胶粘剂含量达到13％时，NiO/SiO₂-TiO₂体系产生了新的晶相。胶粘剂的含量对催化剂的催化性能影响很小，该催化剂应用于苯加氢制环己烷实验中，苯转化率均为100％，环己烷的选择性均达到99.0％以上。     

喹喔啉类衍生物与甲基噻吩共聚物的合成及性质

在二价镍配合物催化下,2,5-二溴-3-甲基噻吩格氏试剂与5,8-二溴-萘基喹喔啉和5,8-二溴-菲基喹喔啉共聚,得到相应的喹喔啉类共轭共聚物,收率分别为65%和68%。通过FT IR、1H-NM R对聚合物及中间体的结构进行了表征。聚合物的循环伏安图中,分别在0.66 V(Epa)/0.37 V(Epc)(Copo ly-m er I),0.78 V(Epa)/-0.06V(Epc)和1.26(Epa)/0.46(Epc)(Copo lym erⅡ)处观察到氧化还原峰,表明该类聚合物有电化学活性。在紫外-可见光谱中,分别在263 nm,323 nm处(Copo lym erⅠ)和299 nm,402 nm处(Copo lym erⅡ)出现吸收峰。所得聚合物分别在504 nm和513 nm处出现荧光最大发射峰。     

钛基体化学镀镍及其耐蚀性能

采用化学镀在钛基体上制备Ni-P合金镀层.研究了活化时间、镀液pH值、热处理温度及时间对镀层的影响.用动电位极化曲线法比较镀层的耐均匀腐蚀性能,并用X-射线衍射仪和扫描电子显微镜分别研究镀层结构和表面形貌.结果表明,以HF为主剂的活化液,时间60 s,pH值4.8～5.2的活化工艺以及250 ℃、保温2 h的热处理为最佳工艺.镀层具有较高的耐蚀性能,属于非晶和微晶组成的混晶结构.借助于正交试验,确定了最佳工艺.     

Liquid-phase stereoselective thymol hydrogenation over supported nickel catalysts

The stereoselective hydrogenation of thymol was studied in liquid phase over several nickel catalysts, modified by coimpregnation of inorganic compounds containing chlorine. The total activity of all catalysts studied was decreased and was on the same order of magnitude, indicating that chlorine even after reduction remains on the surface and is responsible for the poisoning effects. Such blocking of accessible sites results in similar reaction rates for the catalysts studied. Selectivity and stereoselectivity to menthols and menthones changed significantly. The modifiers could influence the rate of keto-enol transformations, which is thought to be the key selectivity and stereoselectivity governing step.     

硫酸镍催化合成紫罗兰酮

用硫酸镍催化假性紫罗兰酮的环化反应，得到了较高产率的紫罗兰酮。探索了催化剂用量、反应温度、反应时间、溶剂用量和溶剂的种类等因素对该环化反应的影响。最佳合成条件如下：5．6mL（79．6％）假性紫罗兰酮，催化剂用量为假性紫罗兰酮的3％（摩尔百分率），甲苯（溶剂）用量为8mL，环化反应温度为40～50℃，反应时间为2．5h，在此合成条件下所得紫罗兰酮的产率为67．4％。选择极性较大的物质（如三氯甲烷）作溶剂有利于该环化反应的进行。