硝基化合物的还原羰基化反应

硝基化合物与CO之间进行的还原羰基化反应是有机催化的新研究领域。通过硝基化合物的还原羰基化反应可以合成许多重要的含氮有机化合物如异氰酸酯，氨基甲酸酯、脲、偶氮化合物和n-杂环化合物等。本文就还原羰基化反应，催化剂及催化作用机理的研究进展作一评述，其中也提及我们实验室的研究工作

A STUDY ON THE OXIDATIVE CARBONYLATION OF ANILINE

以Ｐｄ／Ｃ为催化剂，以ＮａＩ为助催剂，以无水乙醇为溶剂，进行了苯胺氧化羰基化反应。研究了苯胺氧化羰基化的最佳工艺条件，解释了碘化钠在本反应中所起的助催作用。在１７０℃，反应两小时后，Ｐｄ／Ｃ显示了高活性（９７.４９％）和高选择性（８５．２６％）。最后，提出了苯胺氧化羰基化反应的机理。The oxidative carbonylation of aniline to carbamate over Pd-based catalyst was studied by using NaI and absolute ethanol as the promoter and solvent, respectively. The optimum process conditions for this reaction were investigated. At 170 C, after 2 h of reaction, the Pd/C catalyst exhibited high activity (97.49%) and high selectivity (85.26%). The promoter role of NaI was discussed, and a mechanism for the title reaction was proposed

改进型XC502低压甲醇合成催化剂的研究 Ⅱ.催化剂的活性位

采用ＸＰＳ－Ａｕｇｅｒ、ＸＲＤ和ＦＴＩＲ等方法，对５组分Ｃｕ－Ｚｎ－Ａｌ－Ｍ１－Ｍ２改进ＸＣ５０２铜基低压甲醇合成催化剂进行了表征。ＸＰＳ－Ａｕｇｅｒ结果表明，ＸＣ５０２催化剂出现主峰为３３６．４ｅＶ（Ｃｕ＋），而Ｃｕ－Ｚｎ－Ａｌ催化剂主峰为３３４．９ｅＶ（Ｃｕ０）；ＸＲＤ结果表明，两种工作态催化剂比氧化态新增峰的２θ分别为３６．５°（Ｃｕ＋）和４３．３°（Ｃｕ０），ＸＣ５０２催化剂这两峰的强度比Ｉ３６．５／Ｉ４３．３是Ｃｕ－Ｚｎ－Ａｌ催化剂的２．１倍，说明工作态ＸＣ５０２催化剂单位Ｃｕ０中的Ｃｕ＋含量比Ｃｕ－Ｚｎ－Ａｌ催化剂多；ＦＴＩＲ谱显示，ＸＣ５０２和Ｃｕ－Ｚｎ－Ａｌ两种工作态催化剂新增波数分别为６２２ｃｍ－１和６２７ｃｍ－１的振动峰，此新增峰可能是Ｃｕ＋－Ｏ或Ｃｕ＋－Ｏ－Ｚｎ２＋的振动峰。改进型铜基甲醇合成催化剂的活性位可能是Ｃｕ０－Ｃｕ＋－Ｏ－Ｚｎ２＋／Ａｌ２Ｏ３－ＭＯｘ

化学模拟生物固氮——Ⅸ 铁钼辅基模型化合物的合成和性能表征

本文曾在全国化学摸拟生物固氮协作组领导小组扩大会议(昆明,1980,8)上宣读。[中文文摘]采用乙二醇基阴离子作为活插头(可通过水解除去的双配位螯形配位体),对前文提出的合成方法作了重要改进,以期所合成的铁钼辅基模型化合物中Mo~(Ⅳ(Ⅲ))第一配位界内两个不稳定的配位体处于相邻的位置,如厦门模型Ⅲ(或厦门模型Ⅱ)所要求。合成和重组活性评价结果,重组活性比使用乙腈等为活插头的提高2个数量级,化学催化活性和选择性接近于天然FeMo-co水平。[英文文摘]A significant improvement has been made to the method previously proposed[3] for synthesizing FeMo-co modeling compounds. With the use of ethylene glycolate anion as labilizable blocking agent (hydrolyzable bidentatc chelating ligand)to protect two neighboring coordination sites in the first coordination sphere of MoIV(III) of the synthesized FeMo-co modeling compound, an increase in reconstituted-nitrogenase activity of 2 orders of magnitude of the sample synthesized (as compared with the use of acetoni-trile or other monodentare ligands as bloeking agents)has been obtained.Catalytic activity and selectivity assays as well as preliminary characterization by EPR method have also been made

Production of Gasoline From Waste Plastics by Catalytic Cracking

介绍了由废旧塑料通过热裂解和催化裂解制备汽油的方法，着重介绍了由废旧塑料制得的重油经催化裂解获取汽油的反应装置、催化剂、反应条件、产物分析和可能的反应途径。Pyrolytic and catalystic cracking methods For production of gasoline From waste plastecs are introduced with emphasis on the reaction apparatus, catalysts, reaction conditions, ana lysis of products and possible reaction pathways in the production of gasoline by catalytic cracking of heavy oil obtained From waste plastics

The Study of Reactive Conditions of Oxidative Carbonylation of Aniline

苯胺氧化羰基化采用Pd/C 为催化剂， 产物为苯氨基甲酸乙酯， 是均相催化反应多相化的典型例子- 通过对温度、反应时间、氧分压等的仔细摸索， 找到了反应的最佳条件， 并分析和弄清了反应副产物及其来源The oxidative carbonylation of aniline with Pd/C as catalyst can produce ethy1 N-phenyl carbamate, which is a typical example of homogeneous catalytic reaction We have found the optimum reactive condition after studying on temperature、reactive time、oxygen partial pressure et al We have analysed the byproducts and have affirmed their sourc

The Study of Catalytic System for the Oxidative Carbonylation of Aniline

考察了催化剂Pd/C的制备、回收使用及助催剂的情况, 并比较了Pd/C反应前后的XPS谱. 通过实验, 还发现PdCl2 和PdO 同Pd/C相比有相同的催化活性. 最后, 建议了氧化羰基化的机理.The preparation of catalyst Pd/C and its reuse information and the promoter have been studied,the XPS spectrums of catalyst before and after reaction are compared with each other.PdCl 2 and PdO are found that have the same catalytic activity as that of Pd/C.At last,we propose the mechanism of aniline oxidative carbonylation

Oxidative Carbonylation of Aniline by Pd/C Catalyst

研究了催化剂制备条件、助催化剂对负载型Pd/C催化剂性能的影响及氧分压、原料苯胺中硝基苯的加入对苯胺氧化羰基化反应的影响；用X光电子能谱（XPS）、程序升温还原（TPr）和现场红外（Ir）表征钯催化剂；根据实验结果提出在Pd/C-nAI催化剂体系、醇介质中，苯胺氧化羰基化可能的反应机理.The eFFects of the preparation conditions of Pd/C catalyst and the promoters on the catalytic property have been investigated.The inFluences of partial oxygen pressure and addition of nitrobenzene on the oxidative carbonylation of aniline to ethyl Nphenyl carbamate also have been tested.The Pd/C catalyst was characterized by XPS, TPR and insitu IR techniques.A possible mechanism of the oxidative carbonylation of aniline catalyzed by Pd/CNaI system in alcohol medium has been proposed

Study of a modiFied low pressure copperbased catalyst XC502 For methanol synthesis

采用XPS-AugEr、Xrd和fTIr等方法，对5组分Cu-zn-Al-M1-M2改进XC502铜基低压甲醇合成催化剂进行了表征。XPS-AugEr结果表明，XC502催化剂出现主峰为336.4EV（Cu＋），而Cu-zn-Al催化剂主峰为334.9EV（Cu0）；Xrd结果表明，两种工作态催化剂比氧化态新增峰的2θ分别为36.5°（Cu＋）和43.3°（Cu0），XC502催化剂这两峰的强度比I36.5/I43.3是Cu-zn-Al催化剂的2.1倍，说明工作态XC502催化剂单位Cu0中的Cu＋含量比Cu-zn-Al催化剂多；fTIr谱显示，XC502和Cu-zn-Al两种工作态催化剂新增波数分别为622CM-1和627CM-1的振动峰，此新增峰可能是Cu＋-O或Cu＋-O-zn2＋的振动峰。改进型铜基甲醇合成催化剂的活性位可能是Cu0-Cu＋-O-zn2＋/Al2O3-MOX。pectroscopic　characterization　of　the　active　site　of　a　modiFied　low　pressure　copperbased　catalyst　XC502,　prepared　by　adding　a　small　amount　of　metal　oxides　of　the　VI　B　and　VB　groups　to　a　CuZnAl catalyst　For　methanol　synthesis,　is　carried　out　by　XPSAuger,　XRD　and　FTIR.The　main　peaks　are　detected　by　XPSAuger　to　be　336.4eV(Cu+)　and　334.9eV(Cu0)　on　the　surFaces　of　XC502　and　the　CuZnAl　catalyst,　respectively.The　XRD　result　shows　that　two　new　peaks　appear　at　2θ=36.5°(Cu+)　and　43.3°(Cu0)　For　those　Functioning　catalysts,　but　I36.5/I43.3　of　XC502　is　twice　as　large　as　that　of　the　CuZnAl　catalyst,　showing　that　the　surFace　of　the　Functioning　XC502　catalyst　has　higher　Cu+/Cu0　ratio　and　valence　stability　than　those　of　the　CuZnAl　catalyst.By　applying　FTIR　spectroscopy,　bands　at　622　cm-1　and　627cm-1　are　observed　on　the　Functioning　XC502　and　CuZnAl　catalysts,　respectively,　and　the　band　may　be　assigned　to　Cu+OZn2+　bond　vibration.In　light　of　the　above　results,　it　is　suggested　that　the　active　site　on　the　Functioning　XC502　copperbased　catalyst　For　methanol　synthesis　at　low　pressure　is　probably　　Cu0Cu+OZn2+/Al2O3MOx

Chemical Modeling of Biological Nitrogen FixationⅡ. Selective Reduction of Acetylene as a criterion of Polynuclear Coordination of Substrates on Cluster Active-center

[中文文摘]系统地比较了FeMo-co和固氮酶的各种模拟体系在KBH_4还原乙炔为乙烯的反应中的催化活性和选择性。FeMo-co(活性:转变数为34;选择性:99％C_2H_4)和本实验室合成的模型化合物(活性:转变数为20～30;选择性;91～95％)比其它固氮酶的模拟体系(MoO_4~(2-)-CySH;MoO_4~(2-)—CySH—Fe~(2+);MoOS_4~(2-)—胰岛素;[Fe_4S_4(SCH_2Φ)_4]~(2-);和MoS_4~(2-))具有较高的活性和选择性;这可作为FeMo—co及其合成模拟物的原子簇活性中心多核络合活化底物分子的一种判据.[英文文摘]The catalytic activities and sclectivities of FeMo-co and various nitrogenase-modeling systems in the reduction of acetylene to ethylcne by KBH4 have been compared. The high selectivities and high activities of FeMo-co (activity: turn-over number 34 min-1, selectivity: 99% C2H4) and the modeling compounds synthesized in this laboratory (activity: turnover number 20-30 min-1, selectivity: 91-95%), in comparison with many other nitrogenase modeling systems (MoO24-CySH, MoO42--CySH-Fe2+, MoO42--insulIN, [Fe4S4(SCH2Φ)4]2- and MoS4(2-)),may be regarder as a criterion indicating polynuclear coordination activation of the substrate molecules on cluster active-center of FeMo-co and of the synthetic modeling compounds