含膦,氮配体的混合膦酸锆—钯催化剂的研制

用氯化二苯基膦为膦化试剂,首次对多乙烯多胺乙基膦酸－磷酸氢锆Ｚｒ（ＨＰＯ４）１．３５（Ｏ２ＰＣＨ２ＣＨ２（ＮＨＣＨ２ＣＨ２）ｍＮＨ２）０．６５·Ｈ２Ｏ（ＺＰ－ＰＥＰＡＥＰＡ,ｎ＝０,１,２,３,４）载体表面进行二苯基膦化,合成了一类含膦氮配体的新型混合膦酸锆载体及负载钯催化剂。研究了有机膦酸侧链不同链长和Ｐｈ２ＰＣｌ用量对配体载体制备的影响,并用ＩＲ,ＴＧ,ＤＴＧ,ＤＴＡ对这类载体及催化剂进行表征     

胍乙基-双腈乙基胺乙基及胺乙基-膦酸锆-钯催化剂的催化加氢性能

由胺乙基膦酸、胍乙基膦酸和Ｎ,Ｎ双腈乙基胺乙基膦酸制得相应无定形混合磷酸锆载体及其相应的钯催化剂．用ＩＲ、ＴＧ、ＤＴＡ和ＸＰＳ对其进行了表征．研究了影响钯催化剂常压催化加氢活性的各种因素．催化剂对各种取代烯烃和硝基苯有很高的催化加氢活性、选择性和重复使用性．将这类催化剂与钯炭催化剂进行了比较．     

WO3／ZrO2固体强酸催化剂上异丁烷—丁烯烷基化反应的研究：Ⅲ.超 …

制备了以超细ＺrＯ２为载体的ＷＯ３／ＺrＯ２、ＳＯ４＾２－／ＺrＯ２、ＭoＯ３／Ｚr Ｏ２固体强酸催化剂,并用ＸＲＤ、ＤＴＡ－ＴＧ、Ｈ２－ＴＰＲ、ＮＨ３－ＴＰＤ等方法表征了其晶型结构、表面状态和酸性。结果表明,超细ＺrＯ２中的Ｔ－晶相所占比例虽有所下降,但具有更大的比表面积、酸强度和对金属氧化物的负载能力,且酸强度随焙烧温度升高而增强,表明其表面状态亦有较大变化。研究了以超细ＺrＯ２为载体的固体强酸催化     

感耦等离子体质谱法（ICP—MS）测定高纯氧化镝中痕量稀土杂质

本文报道用２－乙基己基膦酸单酯萃淋树脂为固定相，ＨＣｌ为淋洗液的萃取色谱法研究了高纯Ｄｙ２Ｏ３中的痕量稀土杂质和Ｄｙ２Ｏ３基体的分离条件，并用ＩＣＰ－ＭＳ法测定了高纯Ｄｙ２Ｏ３中的１４个稀土杂质，稀土元素的测定限为０．００１－０．００５ＩＣＰ－ＭＳ法测定了高纯Ｄｙ２Ｏ３     

RECl3与丝氨酸配合行为的研究

依据相平衡结果，于水中合成了ＲＥ（Ｓｅｒ）Ｃｌ３．３Ｈ２Ｏ和ＲＥ（Ｓｅｒ）２Ｃｌ３．５Ｈ２Ｏ（ＲＥ＝Ｌａ－Ｎｄ，Ｓｍ－Ｇｄ，Ｄｙ，ｙｂ，Ｙ）等２０种固态配合笺，利用化学分析，摩尔电导，ＩＲ、ＵＶ、ＦＳ、Ｘ射线衍射分析及ＴＧ－ＤＴＧ等手段对配合物进行了表征。     

异丁烷-丁烯烷基化反应催化剂的研究

制备了一系列不同焙烧温度的Ｚｒ（ＳＯ４）２及Ｚｒ（ＳＯ４）２负载量不同的Ｚｒ（ＳＯ４）２／Ａｌ２Ｏ３（ＳｉＯ２）固体强酸催化剂,用ＸＲＤ、ＩＲ、ＢＥＴ、ＴＧ－ＤＴＡ、ＮＨ３－ＴＰＤ、Ｈａｍｍｅｔｔ指示剂等方法研究了该催化体系的晶型、结构、比表面、酸量及酸强度随负载量和焙烧温度的变化规律。将Ｚｒ（ＳＯ４）２负载在Ａｌ２Ｏ３和ＳｉＯ２两种载体上呈现不同的特性。在Ａｌ２Ｏ３上明显地延缓了Ｚｒ（ＳＯ４）２     

二丁胺甲基膦酸锆的苄基季胺化合物及其相转移催化作用

制得了二丁胺甲基膦酸－亚磷酸氢锆Ｚｒ（ＨＰＯ３）２－ｘ．（Ｏ３ＰＣＨ２ＮＢｕ２）．Ｈ２Ｏ（ｘ＝０．８，０．６，０．５，０．４，０．３５），用溴化苄季铵化，得部分季铵化产物，溴化苄基二丁铵甲基膦酸－二丁胺甲基膦酸－亚磷酸氢锆Ｚｒ（ＨＰＯ３）２－ｘ．（Ｏ３ＰＣＨ２ＮＢｕ２）ｘ－ｙ．（Ｏ３ＰＣＨ２Ｎ＾＋Ｂｕ２．ＣＨ２Ｐｈ．Ｂｒ＾－）．Ｈ２Ｏ（ｙ＜ｘ），用作相转移催化剂，对液／液或固／固／液相转移催化的取     

1,9—双（1′—苯基—3′—甲基—5′—氧代吡唑—4′—基）壬二酮—（1,9）与三？…

研究了１，９－双（１′－苯基－３′－甲基－５′－氧代吡唑－４′－基）壬二酮－（１，９）（ＢＰＭＰＮＤ，Ｈ２Ａ）与三辛基氧膦（ＴＯＰＯ，Ｂ）的氯仿溶液，从硝酸介质中对Ｌａ（Ⅲ），Ｄｙ（Ⅲ）的协同萃取，计算了体系的酸性协萃系数ＲＡ和协萃系数Ｒ，用斜率法测得协萃合物的组成ＬａＡ．ＨＡ．Ｂ和ＤｙＡ．ＨＡ．Ｂ计算了协萃取平衡常数，研究了温度对协萃反应的影响，用萃取法制得了固态协萃合物，并对其组成，ＩＲ及ＴＧ     

镝对固体超强酸催化剂ZrO2-Dy2O3/SO42--HZSM-5的酸性和稳定性的影响

合成了固体超强酸催化剂ＺｒＯ２－Ｄｙ２Ｏ３／ＳＯ４＾２－,并将其负载于分子筛ＨＺＳＭ－５上,制成复合型固体超强酸催化剂ＺｒＯ２－Ｄｙ２Ｏ３／ＳＯ４＾２－ＨＺＳＭ－５）以下简称催化剂ＺＤＳＨ）,采用Ｈａｍｍｅｔｔ批示剂法,吸附吡淀的ＴＰＤ法,考察催化剂ＺＤＳＨ的酸强度及其分布;通过热重分析（ＴＧＡ）、差热分析（ＤＴＡ）方法,考察镝对催化剂ＺＤＳＨ稳定性的作用;运用红外光谱（ＩＲ）法,分析催化剂ＺＤＳ     

SO_4~（2－）／TiO_2和SO_4~（2－）／Fe_2O_3固体超强酸研究

用ＸＲＤ、ＴＧ－ＤＴＧ、ＳＥＭ和化学分析等手段研究了浸渍Ｈ_２ＳＯ_４的无定形ＴｉＯ２和Ｆｅ_２Ｏ_３在焙烧过程中的晶化、相变、失水及失硫情况，总结出ＳＯ４２－／ＭｘＯｙ型固体超强酸具有与ＳＯ４２－／ＺｒＯ２体系相同的形成规律；用ＩＲ光谱和常温正戊烷异构化反应对ＳＯ４２－／ＴｉＯ２和ＳＯ４２－／Ｆｅ_２Ｏ_３的超强酸性进行了表征，表明它们与／ＺｒＯ_２体系具有相似的表面酸位结构，无水状态主要为Ｌ酸位，吸水后部分Ｌ酸位可转变为Ｂ酸位，但这两种体系的超强酸性均比ＳＯ４２－／ＺｒＯ_２弱，其Ｈ０大约在－１３～－１４之间．     

Structure and Physicochemical Properties of Substituted Porphyrins

Reactions of substituted porphyrins: 2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetraphenylporphine, 2,3,7,8,12,13,17,18-octamethyl-5,10,15,20-tetraphenylporphine, and dodecaphenylporphine with organic bases (pyridine, piperidine, dimethylformamide, dimethyl sulfoxide) and acetic acid were studied by spectrophotometry. Acid-base interaction between porphyrins and organic bases and formation of ionic species in toluene solution containing an organic base were revealed for the first time. The effect of electronic and structural factors on the acid-base interactions of porphyrin ligands with organic bases is discussed. The stability constants were calculated for complexes of 2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetraphenylporphine with organic bases, and electronic absorption spectra of substituted porphyrins in basic organic solvents were recorded.     

甲醇和碳酸丙烯酯合成碳酸二甲酯的研究

采用浸渍法以ZrO2为载体，以碱金属氢氧化物和碳酸盐为前驱体制备了不同的固体碱催化剂，在温和反应条件下考察了催化剂的酯交换扳应性能，并通过BET、XRD和CO2－TPD等方法对催化剂进行了表征，结果表明：Na2CO3负载到不同载体上，其催化性能明显不同，Na2CO3/ZrO2催化剂获得了较高的酯交换活性。载体的比表面和孔结构与催化剂的反应活性无一定的依存关系。而催化剂表面的酸碱性是影响酯交换活性的重要因素。     

固体碱碱性位对丙酮和碳酸二甲酯反应的影响

考察了固体碱不同的碱性位对丙酮和碳酸二甲酯反应的影响,并对反应在不同碱性位上的反应机理进行了推测．实验结果表明,由表面羟基引起的弱碱位有利于丙酮自身缩合反应的进行,主产物为二丙酮醇、4-甲基-3-戊烯-2-酮和4-甲基4-戊烯-2-酮;Lewis酸碱离子对有利于碳酸二甲酯的甲基化反应的发生,主产物为2-甲氧基丙烯;而由固体碱表面配位不饱和的O^2-所造成的强碱位有利于碳酸二甲酯的甲氧基羰基化产物的生成,主产物为乙酰乙酸甲酯;同时发现各种产物的收率与对应的各碱性位的碱量之间均具有较好的线性关系．     

Synthesis of dimethyl adipate from cyclopentanone and dimethyl carbonate over solid base catalysts

A facile route for the synthesis of dimethyl adipate (DAP) from cyclopentanone and dimethyl carbonate (DMC) in the presence of solid base catalysts has been developed.It was found that the intermediate carbomethoxycyclopentanone (CMCP) was produced from cyclopentanone with DMC in the first step,and then CMCP was further converted to DAP by reacting with a methoxide group.The role of the basic catalysts can be mainly ascribed to the activation of cyclopentanone via the abstraction of a proton in the α-position by base sites,and solid bases with moderate strength,such as MgO,favor the formation of DAP.     

Sensitivity and selectivity of the reaction of vanadium(V) with 4-(2-Pyridylazo)resorcinol on a solid support containing anion-exchange groups and modified with 8-hydroxyquinoline or 8-hydroxyquinoline-5-sulfonic acid

The effect of the modification of a solid support with 8-hydroxyquinoline (HQ) and 8-hydroxyquinoline-5-sulfonic acid (HQ-SFA) on analytical characteristics of the reaction of vanadium(V) with 4-(2-pyridylazo)resorcinol (PAR) on a solid phase was studied for polyacrylonitrile fiber filled with the AV-17 anion exchanger. Diffuse reflection spectra of the initial and modified supports and of vanadium(V) complexes of PAR on these supports were recorded. It was found that vanadium reacts with PAR on modified supports only in acid solutions. The conditions for the adsorption of vanadium and the dependences of the analytical signal on the acidity of the PAR solution and on the concentration of the modifier on the support were determined. The limits of vanadium detection by the reaction with PAR were calculated (0.5 and 1 ng/mL for AV-17-HQ and AV-17-HQ-SFA, respectively). The selectivity of the reaction of vanadium with PAR on modified supports was estimated with respect to copper, aluminum, iron(III), and zinc. It was found that the modification of the support with HQ and HQ-SFA impairs the analytical characteristics of the reaction of vanadium with PAR on the solid phase and that the use of modified supports for the color reaction of vanadium with PAR is inappropriat     

Elimination of oxidative degradation during the per-O-methylation of carbohydrates

The possible oxidative degradation mechanism occurring during the per-O-methylation of carbohydrates in dimethyl sulfoxide with methyl iodide in the presence of base is described. Evidence is presented that this process occurs only under anhydrous conditions when there is a long reaction time between the carbohydrate dissolved in dimethyl sulfoxide and methyl iodide, followed by reaction with the base. Under these specific conditions, the oxidative degradation of alditols, and cyclic carbohydrates, with and without a free hemiacetal group, is observed. The reaction between carbohydrate and methyl iodide in dimethyl sulfoxide can result in a complete oxidative degradation depending on the type of carbohydrate and the time of reaction. The oxidative degradation can be accelerated by replacing methyl iodide with dimethyl sulfate. Mass spectrometric identification of the degradation products of d-glucitol indicates simultaneous oxidation processes at all the hydroxyl groups, with site dependent rates of their reactivity. This oxidative process is not a characteristic of the methylation of carbohydrates in dimethyl sulfoxide with methyl iodide in the presence of solid sodium hydroxide and can be totally avoided by treating the carbohydrate with powdered sodium hydroxide before introduction of methyl iodide under nonanhydrous conditions, or by adding a trace of water in dimethyl sulfoxide before methyl iodide, or by using N,N-dimethylacetamide as the solvent. The degradation of the per-O-methylated carbohydrates in the liquid-liquid extraction process is also taken into account, and it is found that the degradation process can be avoid by neutralization of the base before extraction, by using benzene or tetrachloromethane as extraction solvent, and by drying the final organic extract.     

碳酸二甲酯在固体碱上吸附和活化的原位红外光谱研究

采用原位红外技术研究了碳酸二甲酯在氧化镁、氟化镁、镁铝复合氧化物和氟改性的镁铝复合氧化物4种固体碱表面上的吸附和活化行为。结果表明:碳酸二甲酯以单、双齿两种形态吸附于固体碱的表面,双齿吸附的比单齿吸附的更易活化。碳酸二甲酯吸附于氧化镁和镁铝复合氧化物上活化生成甲氧基,吸附于氟化镁上活化生成甲氟基;而吸附于氟改性的镁铝复合氧化物上优先活化生成甲氟基,随着吸附表面温度的升高,逐渐有甲氧基生成,说明氟改性的镁铝复合氧化物是一种优良的甲基化反应催化剂。     

Functional monomers and polymers. CXXXI.. Synthesis and interaction studies on polyacrylamide and polymethacrylamide derivatives containing nucleic acid bases

Acrylamide and methacrylamide derivatives of nucleic acid bases were prepared from the corresponding aminoethyl derivatives. Free-radical polymerization of these monomers in water or in organic solvents gave their polymers. From the studies of the polymer complex formation by UV spectroscopy, it was found that extremely stable polymer complexes were formed between complementary polymers containing nucleic acid bases.     

Supramolecular assemblies and molecular recognition of amphiphilic schiff bases with barbituric acid in organized molecular films

A bolaform Schiff base, N,N'-bis(salicylidene)-1,10-decanediamine (BSC10), has been synthesized and its interfacial hydrogen bond formation or molecular recognition with barbituric acid was investigated in comparison with that of a single chain Schiff base, 2-hydroxybenzaldehyde-octadecylamine (HBOA). It has been found that while HBOA formed a monolayer at the air/water interface, the bolaform Schiff base formed a multilayer film with ordered layer structure on water surface. When the Schiff bases were spread on the subphase containing barbituric acid, both of the Schiff bases could form hydrogen bonds with barbituric acid in situ in the spreading films. As a result, an increase of the molecular areas in the isotherms was observed. The in situ H-bonded films could be transferred onto solid substrates, and the transferred multilayer films were characterized by various methods such as UV-vis and FT-IR spectrosopies. Spectral changes were observed for the films deposited from the barbituric acid subphase, which supported the hydrogen bond formation between the Schiff bases and barbituric acid. By measuring the MS-TOF of the deposited films dissolved in CHCl3 solution, it was concluded that a 2:1 complex of HBOA with barbituric acid and a 1:2 complex of BSC10 with barbituric acid were formed. On the other hand, when the multilayer films of both Schiff bases were immersed in an aqueous solution of barbituric acid, a similar molecular recognition through the hydrogen bond occurred. A clear conformational change of the alkyl spacer in the bolaform Schiff base was observed during the complex formation with the barbituric acid.     

Preparation of Enamines Catalyzed by Lewis Acids in the Presence of Solid Supports

A simple and effective preparation of enamines from bulky ketones and secondary amines has been achieved with the aid of Lewis acid on various solid supports. The optimized yields were higher than those obtained without the solid support. Factors affecting the yield and regioselectivity of these reactions were also studied. Evidence showed that the reaction proceeded simultaneously in solution and on the solid support.