2－脱氧－烟酰胺基－β－D－氨基葡萄糖的合成和表征

A new nicotinic acid derivative,2-deoxy-2-nicotinoylamido-β-D-glucopyranose, was synthesized with β-configuration exclusively. The structure and properties of the product were characterized by ^1H NMR, PT-IR, MS, DSC and polarimeter. The details of ^1H NMR spectrum and the mass spectrum proved that there are a great amount of hydrogen bonds in the product.     

Enzymatic Enantioselective Synthesis of （R）－2－Trimethylsilyl－2－hydroxyl－propionitrile by Defatted Apple Seed Meal

IntroductionOverthepastyears ,thesynthesisofchiralaldehyde cyanohydrinswaswellstudied .1Incontrasttochiralalde hyde cyanohydrins ,therewereonlyfewreportsaboutthepreparationofopticallyactiveketone cyanohydrins ,2 whichareusefulstartingmaterialsandintermediatesforthesyn thesisofmanychiralnaturalproducts .3Wethereforefo cusedonthepreparationofopticallyactivesiliconcontain ing (R ) ketone cyanohydrin ((R ) 2 trimethylsilyl 2 hy droxyl propionitrile)usingacetonecyanohydrinastran scyanationagen…     

4-(4-羟基丁基－2－炔氧基)－3-（苯磺酰基）－1，2，5－噁二唑－2－氧化物与牛血清白蛋白结合作用的光谱法研究

The interaction between 4-(4-hydroxybut-2-ynyloxy)-3-(phenylsulfonyl)-1,2,5-oxadiazole-2-oxide(FB)andbovine serum albumin(BSA)was studied by spectroscopic methods including fluorescence and UV-Vis absorptionspectroscopy.The quenching mechanism of fluorescence of BSA by FB was considered to be a dynamic quenchingprocedure.The number of binding sites n and apparent binding constant K were measured by fluorescence quench-ing method.The results indicate that there is FB molecular binding with BSA,and forming 1∶1 complex.Thethermodynamic parameters such as ΔH,ΔG and ΔS,etc.,were calculated.The results indicate that the binding reac-tion is mainly entropy-driven and hydrophobic forces play major role in the binding reaction.The distance r be-tween donor(BSA)and acceptor(FB)was obtained according to Frster theory of non-radioactive energy transfer.     

Efficient Synthesis of 2－ （8－Quinolinoxy）－4H－imidazolin－4－ones

The title compounds 2-(8-quinoltnoxy)-4H-imidazolin-4-ones (4) were synthesized by means of base catalytic reactions of 8-hydroxyquinoline with each of carbodiimides 2, which were obtained via aza-Wittig reactions of iminophosphoranes 1 with the corresponding aromatic isocyanates.     

Synthesis of 3－（1－Cyclohexenyl）－2－butanone via Environmentally Friendly Catalysts

We substituted several environmentally friendly catalysts which included HY and H-β zeolites, various cation-exchanged β zeolites, and solid-supported ferric chloride for conventional catalysts for the synthesis of 3-(1-cyclohexenyl)-2-butanone from the reaction of ethylidenecyclohexane with acetic anhydride at room temperature. HY zeolite was found to be the most effective for this reaction, and gave the acYlated product in a 72% yield under the conditions of n(ethylidenecyclohexane)/n(acetic anhydride)/m(HY zeolite)= 1 mmol/10 mmol/0. 100 g, reaction temperature 25 ℃ and reaction time 2 h. The used HY zeolite can be recovered, regenerated and gave almost the same yield as the fresh one. The lifetime of the HY zeolite is over 80 h. The effect of different factors on the reaction has also been investigated.     

A High－efficiency Preparation, Properties and Structure of （R, S ）－and （ S, S）－Pyrrolidine－2－carboxylic Acid 3,5－Dioxa－4－boracvclo.hepta [ 2,1－α; 3,4－α′] dinaphthalen－4－yl Esters

A highly-efficient preparative procedure for ( R, S )- and ( S, S)-pyrroHdine-2-carboxyHc acid 3,5-dioxa-4-boracyclohepta[2, 1-α ; 3,4-α′] dlnaphthalen-4-yl esters [ namely ( R, S )-BNBAP and (S, S )-BNBAP] is described and the crystal structure of (R, S )-BNBAP was obtained. The data indicate that ( R, S )-BNBAP is a spirocyclic inner borate salt with almost normal te-trahedral configuration. This structural form may be the basic reason for their high chemical, optical and thermodynamic sta-bility.     

Preparation and Standard Formation Enthalpy of 2－Amino－4,6－dimethylpyrimidine and Its Related Complexes of Copper

IntroductionThe pyrimidine and its derivatives are knownto possess extraordinary biological properties thatare generally distinguished qualitatively by havingbeen used as pesticide,herbicide,bactericide,andmedicine intermediates[1] .A survey of these appli-cations and a number of the related variations thathave been developed recently,such as the extraor-dinary effective herbicide of sulfonyl sulfourea,re-veals that the biological properties are just becauseof the wide existence of pyrimidine …     

2－戊基环戊－2－烯酮的合成研究

以环戊酮、正戊醛为原料，采用相转移催化技术进行羟醛缩合，经脱水得到２－戊叉环戊酮，再经异构化，合成了２－戊基环戊－２－烯酮。文章对相转移催化合成２－戊叉环戊酮及其异构化的条件进行了研究。     

1，1－二氨基2，2－二硝基乙烯（DADE）的热化学性质、热行为和热分解机理

The constant-volume combustion energy, △cU （DADE, s, 298.15 K）, the thermal behavior, and kinetics and mechanism of the exothermic decomposition reaction of 1,1-diamino-2,2-dinitroethylene （DADE） have been investigated by a precise rotating bomb calorimeter, TG-DTG, DSC, rapid-scan fourier transform infrared （RSFT-IR） spectroscopy and T-jump/FTIR, respectively. The value of △cHm （DADE, s, 298.15 K） was determined as （-8518.09±4.59） j·g^-1. Its standard enthalpy of combustion, △cU （DADE, s, 298.15 K）, and standard enthalpy of formation, △fHm （DADE, s, 298.15 K） were calculated to be （-1254.00±0.68） and （- 103.98±0.73） kJ·mol^-1, respectively The kinetic parameters （the apparent activation energy Ea and pre-exponential factor A） of the first exothermic decomposition reaction in a temperature-programmed mode obtained by Kissinger＇s method and Ozawa＇s method, were Ek=344.35 kJ·mol^-1, AR= 1034.50 S^-1 and Eo=335.32 kJ·mol^-1, respectively. The critical temperatures of thermal explosion of DADE were 206.98 and 207.08 ℃ by different methods. Information was obtained on its thermolysis detected by RSFT-IR and T-jump/FTIR.     

Synthesis, Crystal Structure of Ruthenium 1,2－Naphthoquinone－1－oxime Complex and Its Mediated C－－C Coupling Reactions of Ter－minal Alkynes

Substituted decarbonylation reaction of ruthenium 1,2‐naphthoquinone‐1‐oxime (1‐nqo) complex, cis‐, cis‐[Ru| ζ²‐N(O)C₁₀‐H₆O|₂(CO)₂] (1), with acetonitrile gave cis‐, cis‐[Ru | ζ²‐ N(O)C₁₀H₆O|₂(CO)(NCMe)] (2). Complex 2 was fully characterized by ¹H NMR, FAB MS, IR spectra and single crystal X‐ray analysis. Complex 2 maintains the coordination structure of 1 with the two naphthoquinonic oxygen atoms, as well as the two oximato nitrogen atoms located cis to each other, showing that there is no ligand rearrangement of the 1‐nqo ligands during the substitution reaction. The carbonyl group originally trans to the naphthoquinonic oxygen in one 1‐nqo ligand is left in its original position [O(5)‐Ru‐C(1), 174.0(6)°], while the other one originally trans to the oximato group of the other 1‐nqo ligand is substituted by NCMe [N(1)‐Ru‐N(3), 170.6(6)°]. This shows that the carbonyl trans to oximato group is more labile than the one trans to naphthoquinonic O atom towards substitution. This is probably due to the comparatively stronger ± back bonding from ruthenium metal to the carbonyl group trans to naphthoquinonic O atom, than the one trans to oximato group, resulting in the comparatively weaker Ru–‐CO bond for the latter and consequently easier replacement of this carbonyl. Selected coupling of phenylacetylene mediated by 2 gave a single trans‐dimerization product 3, while 2 mediated coupling reaction of methyl propiolate produced three products: one trans‐dimerization product 4 and two cyclotrimeric products 5 and 6.     

Novel Photo－induced Coupling Reactions of 9－Fluorenylidene－malononitrile or l,l－Diphenyl－2,2－dicyanoethylene with 10－Methyl－9,10－dihydroacridine. A Study on the Photophysics of the Reaction

9‐Fluorenylidenemalononitrile (FDCN) or 1, 1‐diphenyl‐2,2‐dicyanoethylene (DPCN) reacted with 10‐methyl‐9,10‐dihydroacridine (AcrH₂) under irradiation (λ 320 nm) to give couping products. In order to gain further insight into the mechanism of the photo‐induced reaction, the photophysics of the reactions of FDCN or DPCN with AcrH₂ have been investigated by using UV‐vis spectroscopy, fluorescence spectroscopy, excitation spectroscopy and time‐resolved fluorescence spectroscopy, respectively. The results show that FDCN or DPCN interacts with AcrH₂ in the ground states to form a charge transfer complex, which further reacts to give the coupling product upon. irradiation.     

丙烯酰胺－丙烯酸甲酯－2－丙烯酰胺基－2－甲基丙磺酸共聚物的合成及表征

以丙烯酰胺（ＡＭ），丙烯酸甲酯（ＭＡ）和２－丙烯酰胺基－２－甲基丙磺酸（ＡＭＰＳ）为原料，通过水溶液共聚，合成了一种新的三元共聚物。研究了影响共聚反应的因素，并对其结构进行了表征。     

SO_4~（2－）／Fe_2O_3－Dy_2O_3催化α－萘乙酸与甲醇酯化反应的色谱法研究

ＳＯ２－４／Ｆｅ２Ｏ３－Ｄｙ２Ｏ３是一种新的稀土改性固体超强酸，研究结果表明它对α－萘乙酸与甲醇酯化反应有很高的催化活性和良好的稳定性。反应混合物在ＮｏｖａｐａｋＣ１８（３．９×１５０ｍｍ，４μ）色谱柱上以甲醇－水（７０∶３０，Ｖ／Ｖ）作流动相８分钟内可实现良好分离。该反应产率高、工艺简便、无腐蚀。     

DL－丙交酯与2－氢－2－氧－1，3，2－二氧磷杂环己烷的开环共聚合研究

在三异丁基铝催化下ＤＬ－丙交酯与２－氢－２－氧－１，３，２－二氧磷杂环己烷开环共聚，制备了一类新型水溶性共聚物Ｐ（ＬＡ－ｃｏ－ＴＭＰ）。用１ＨＮＭＲ、ＩＲ谱对其结构进行了表征，并研究了催化剂用量及不同单体配比对总转化率、共聚物组成及特性粘度的影响。     

4－羟基－2，5－二甲基－3（2H）呋喃酮的合成

总结了食品增香剂４－羟基－２．５－二甲基－３（２Ｈ）呋喃国的合成方法，包括近期的合成研究进展，对一些合成方法的优缺点作了评述。参考文献２８篇。     

Synthesis and Crystal Structure of One－dimensional Chain Complexes [K （18－C－6） ]2[M （mnt）2] （M=Zn, Hg）

The reactions of 18-crown-6 with each of K2[M (mnt)2] (M=Zn, Hg; mnt = 1,2-dicyanoethene-1,2-dithiolate, C2S2 (CN)2^2-) were studied and novel complexes [K(18-C-6)]2[Zn(mnt)2] (1) and [K (18-C-6)]2 [Hg(mnt)2] (2) were characterized by elemental analysis, IR spectrum and X-ray diffraction analysis. Complex 1 displays a one-dimensional chain of [K(18-C-6)]2[Zn(mnt)2] bridged by K-O interactions between adjacent [K(18-C-6)]^ units. Complex 2 is also a one-dimensional chain of [K(18-C-6)]2[Hg(mnt)2] bridged by K…S weak interactions between adjacent [K(18-C-6)]^ and [Hg(mnt)2]^2-.     

LaCl_3－SrCl_2－MgCl_2三元体系相图

本文借助于ＤＴＡ和Ｘ射线结构分析测定了ＬａＣｌ_３－ＳｒＣｌ_２－ＭｇＣｌ_２三元体系相图，发现它属简单低共熔型，体系内有对应于ＬａＣｌ_３、ＳｒＣｌ_２和ＭｇＣｌ_２的３个液相面、３条２次结晶线和１个三元低共熔点Ｅ（１５．０ｗｔ％ＬａＣｌ_３，４９．５ｗｔ％ＳｒＣｌ_２，３５．５ｗｔ％ＭｇＣｌ_２；５４５℃），并且在固相下有一个不稳定的化合物生成，在约５００℃时分解。     

Asymmetric Synthesis of （ － ）－（2R ,3R, 6S ）－Irnigaine

Asymmetric synthesis of irnigaine was achieved starting from an enantiopure β-amino ester 5 using the condensation of amino al-cohol 2 with acetylacetone and the subsequent intramolecular cycllzation as the key steps.     

Synthesis and One－dimensional Structure of Cobalt（Ⅱ） Complex [－ （NaOC2H5） CoL2]n

The treatment of bis (2-hydroxybenzyl)-amine (HL) with NaOH and Co ( Ⅱ )(NO)2 gives isostructural one-dimensional coordination polymers [-(NaOC2H5)CoL2]n(1). The cobalt ions have an octahedral geometry and are coordinated by two erystallographicaUy independent ligands which are further linked by β-Ophenol bridged Co and Na atoms to give a one-dimentional structure.     

2-芳基-2-吗啉醇的合成

醇胺分别与2-溴-4′-甲氧基苯乙酮、2-溴-3′-氯苯丙酮、2-溴-4′-苄氧基苯基丙酮、2-溴-4′-苄氧基苯戊酮、6-甲氧基-2-溴乙酰基萘和6-甲氧基-2-(2-溴丙酰基)萘反应,合成相应的2-芳基-2-吗啉醇(产率80.7%～97.5%)及其盐酸盐.其结构经1H NMR,IR,MS确证.