铅与硝酸反应及影响因素

铅与硝酸的反应比较复杂,在无机化学教材和相关资料中对铅与硝酸反应的阐述不一致,这将不利于学生在无机化学学习中对铅的基本性质的掌握。针对无机化学教材中存在的问题,本文通过大量实验探究了铅与硝酸反应的条件以及硝酸浓度、反应温度、反应时间等对铅与硝酸反应的影响,并考查了硝酸铅在不同浓度硝酸中溶解度的变化,利用红外光谱(IR)和X射线粉末衍射(XRD)对铅与浓硝酸的反应产物进行了表征,明确了铅易溶于稀硝酸而在浓硝酸中溶解度小的实质。     

光替代谷氨酸氧化酶及荧光法测定谷氨酸

在弱碱性介质中,紫外光的照射引起谷氨酸的光化学反应,产生Ｈ２Ｏ２和ＮＨ３,与谷氨酸氧化酶存在下的酶促反应等效。利用氯化血红素（ｈｅｍｉｎ）作为过氧化酶的替代物,催化Ｈ２Ｏ２与对羟基苯乙酸（ＨＰＡ）的偶合荧光反应,建立了间接荧光法测定谷氨酸的方法。     

The formation and structure of phenylcamphoric acid and related compounds

The complete structure and stereochemistry of (+)-phenylcamphoric acid has been determined. The acid obtained from the Friedel-Crafts reaction of benzene with isolauronolic acid is identified as (±)-phenylcamphoric acid, α-Campholytic acid is shown to be a likely precursor of phenylcamphoric acid in these reactions. The Friedel-Crafts reaction of 3-cyano-1,2,2-trimethylcyclopentanecarbonyl chloride or 3-cyano-2,2-dimethyl-1-methylenecyclopentane with benzene provides a mixture of phenylcamphornitrile and an isomer. Isofenchocamphoric anhydride similarly provides a mixture of the epimeric 4-phenyl-2,2,4-trimethylcyclopentanecarboxylic acids.     

Preparation and utilization of perillyl acetate

Perillyl acetate is a fragrance compound that was prepared by the reaction of β-pinenoxide with acetic anhydride and using acetic acid as an acid catalyst. Several selected catalysts were tested (homogenous: phosphoric acid, boric acid, acetic acid, and citric acid; heterogeneous: zeolite USY, SSA, and montmorillonite K-10) and the reaction conditions optimized for this reaction. The yield 78.7 % of perillyl acetate was obtained. Mayol (4-isopropylcyclohexylmethanol), a valuable fragrance compound, was further obtained by a two-step synthesis from perillyl acetate. Firstly, perillyl acetate was saponified to perillyl alcohol. The yield of alcohol was 94.4 %. The last step of the entire preparation was the hydrogenation of perillyl alcohol to Mayol. The yield of the desired product of this reaction was 94.6 %.     

Cs/ZSM-35 分子筛催化甲缩醛和乙酸甲酯发生一步法羟醛缩合反应

丙烯酸及其酯是重要的化工原料, 广泛应用于涂料、粘结剂、纤维等领域, 目前工业上常采用丙烯两段氧化法进行制备. 然而该方法以石油基原料丙烯为源头, 采用 V/Mo/Bi 等金属催化剂, 不符合可持续发展理念, 且存在环境污染及氧气下产物易过度氧化等问题. 因此, 如何高效、安全、大规模工业化制备丙烯酸及其酯是研究者追求的目标. 以乙酸甲酯(MAc) 和甲醛为原料, 通过羟醛缩合一步制备丙烯酸及其酯是一条完全不同于丙烯氧化法的合成路径, 原料均可由煤基甲醇得到, 符合我国"富煤、贫油、少气"的基本能源结构, 且该方法碳原子利用率为 100%, 副产物仅为水, 属于绿色环保合成路径.羟醛缩合是典型的碳链增长反应, 可在酸性催化剂、碱性催化剂、以及酸碱双功能催化剂存在下发生. 碱性催化剂一般为负载型碱金属氧化物, 例如以 SiO2为载体的负载型 Na, K, Cs 氧化物催化剂等, 但都存在活性组分流失的问题, 进而导致催化剂的失活, 难以实现工业化. 酸碱双功能催化剂是目前研究的热点, 由于具有酸催化剂的高选择性和碱催化剂的高活性, 其反应性能要远优于单一酸性催化剂和单一碱性催化剂, 广大研究者对此进行了深入广泛的研究, 目前基本处于实验室阶段. 相对而言, 目前酸性催化剂上通过羟醛缩合反应制备丙烯酸及其酯的研究工作较少, 特别是以固体酸为催化剂进行乙酸甲酯和甲醛气固相反应研究非常少见.我们以甲缩醛为甲醛源, 创新性地采用固体硅铝分子筛为酸性催化剂, 催化甲缩醛 (DMM) 和 MAc 发生羟醛缩合反应来制备丙烯酸. 硅铝分子筛具有较高的活性, 可高效地催化羟醛缩合反应, 且由于分子筛催化剂具有很好的再生性能, 即使催化剂寿命较短, 也可采用流化床或移动床等反应器进行工业化, 因此存在良好的工业化前景. 为了进一步深入研究酸性位和碱性位各自对 DMM 和 MAc 羟醛缩合反应的影响, 本文以 HZSM-35 分子筛为载体, 采用浸渍法制备不同碱金属铯氧化物含量的催化剂, 利用氮气吸附/脱附方法和化学程序升温 (NH3-TPD) 方法对其孔结构和酸性质进行表征, 并进一步考察催化剂的性能. 结果表明, 微孔体积随着碱金属 Cs 负载量的增加而逐渐减小, 当 Cs 负载量增加至 10 wt% 时, 样品微孔体积从初始 0.105 cm3/g 降至 0.063 cm3/g. NH3-TPD 结果显示, 当 Cs 负载量为 1 wt%, 酸性催化剂载体上的强酸和弱酸活性位被大量碱性氧化物占据; 当负载量超过 5 wt% 时, 所有的酸性位均被覆盖. 随后考察负载不同碱金属含量分子筛的羟醛缩合反应性能, 发现碱金属氧化物的引入不利于羟醛缩合反应的进行, 这主要是由于作为甲醛源的 DMM 只有在酸中心上才能进行分解产生甲醛, 促使羟醛缩合反应顺利进行. 当采用 DMM 为甲醛源时, 体系中必须有酸性位存在. 同时得知, 分子筛 HZSM-35 中强酸和弱酸均是羟醛缩合反应的有效酸性位, 但强酸同时催化原料发生类甲醇制烯烃过程, 致使大量烃类副产物生成, 产生较重的积炭物种. 羟醛缩合反应在含有大量弱酸催化剂上 (如γ-Al2O3) 也可顺利进行, 且具有较高的活性和稳定性.     

Contribution to the chemistry of the Belousov-Zhabotinsky reaction. Products of the Ferriin-Bromomalonic acid and the Ferriin-Malonic acid reactions

In the present mechanistic schemes of the ferroin-catalyzed oscillatory Belousov-Zhabotinsky (BZ) reaction the oxidation of the organic substrates (bromomalonic or malonic acid) by ferriin (the oxidized form of the catalyst) plays an important role. As the organic products of these reactions were not yet identified experimentally, they were studied here by an HPLC technique. It was found that the main organic oxidation product of bromomalonic acid is bromo-ethene-tricarboxylic acid (BrEETRA), the same compound that is formed when bromomalonic acid is oxidized by Ce4+ (another catalyst of the BZ reaction). Formation of BrEETRA is explained here by a new mechanism that is more realistic than the one suggested earlier. To find any oxidation product of malonic acid in the ferriin-malonic acid reaction was not successful, however. Neither ethane-tetracarboxylic acid (ETA) nor malonyl malonate (MAMA), the usual products of the Ce4+- malonic acid reaction, nor any other organic acid, not even CO2, was found as a product of the reaction. We propose that malonic acid is not oxidized in the ferriin-malonic acid reaction, and it plays only the role of a complex forming catalyst in a process where Fe3+ oxidizes mostly its phenantroline ligand.     

硫杂蒽酮的合成和表征

为了寻求合成硫杂蒽酮的高效新方法,以2,2′-二硫代二苯甲酸和苯酚为原料,硫酸为溶剂和催化剂,考察了沸石分子筛、Al2O3和P2O5、温度、原料的物质的量之比、反应时间对反应收率的影响,确定了最佳反应条件,推测了可能的反应过程;进而以2,2′-二硫代二苯甲酸和相应的苯衍生物为原料,在H2SO4-P2O5体系中于最佳反应条件下制备了13个硫杂蒽酮类化合物,并利用柱色谱分离以及红外光谱与核磁共振谱对产物进行表征.结果表明,在反应体系中引入P2O5有利于促进反应的完成;最佳反应条件为:温度70℃、2,2′-二硫代二苯甲酸/苯衍生物物质的量之比1∶6、反应时间6h.邻苯二酚与二硫代水杨酸的反应产物——化合物11(a)和11(b)为同分异构体.     

N,N-二甲基羟胺与HNO2的反应动力学

分别在高氯酸和硝酸介质中研究了N,N-二甲基羟胺(DMHAN)与HNO₂的反应动力学,通过考察溶液酸度、还原剂浓度、离子强度和温度等因素对反应过程的影响,获得高氯酸介质中反应动力学速率方程为-d[HNO₂]/dt=k[DMHAN][HNO₂],在18.5 ℃,离子强度μ=0.73 mol/L时,反应速率常数k=(12.8±1.0) mol/(L·min),反应活化能Ea=41.5 kJ/mol。 在硝酸介质中DMHAN与HNO₂的反应比较复杂,硝酸浓度较高时,硝酸将参与反应重新生成HNO₂,且硝酸浓度越大,HNO₂的生成速度越快,HNO₂与DMHAN的反应是自催化氧化的。 对DMHAN与HNO₂的反应产物进行了分析,并推导了硝酸体系中DMHAN与HNO₂的反应机理。     

Fmoc保护氨基酸与Wang树脂的缩合反应

研究了保护氨基酸、Wang 树脂取代度、树脂粒度、搅拌方式对Fmoc-氨基酸-Wang树脂连接效率的影响. 结果表明, 保护氨基酸分子量的大小会因产生不同的位阻而影响缩合反应的效率, 分子量越小缩合效率越高; Wang树脂的取代度较高时, 已缩合的氨基酸给后续保护氨基酸的缩合形成阻碍, 使缩合效率降低; 粒径较小和搅拌较好时, 对保护氨基酸的粒内外扩散有利, 可提高反应速度和缩合效率.     

Production of Sugars and Levulinic Acid from Marine Biomass Gelidium amansii

This study focused on optimization of reaction conditions for formation of sugars and levulinic acid from marine algal biomass Gelidium amansii using acid catalyst and by using statistical approach. By this approach, optimal conditions for production of sugars and levulinic acid were found as follows: glucose (reaction temperature of 139.4°C, reaction time of 15.0 min, and catalyst concentration of 3.0%), galactose (108.2°C, 45.0 min, and 3.0%), and levulinic acid (160.0°C, 43.1 min, and 3.0%). While trying to optimize the conditions for the production of glucose and galactose, levulinic acid production was found to be minimum. Similarly, the production of glucose and galactose were found to be minimum while optimizing the conditions for the production of levulinic acid. In addition, optimized production of glucose required a higher reaction temperature and shorter reaction time than that of galactose. Levulinic acid was formed at a high reaction temperature, long reaction time, and high catalyst concentration. The combined results of this study may provide useful information to develop more economical and efficient systems for production of sugars and chemicals from marine biomass.     

微管中的酸化反应:沉淀及界面效应

利用玻璃微管模拟孔隙性油藏, 研究了微乳酸(O/W)、土酸(即HCl/HF混合物)在不同内径的玻璃微管中的反应. 结果表明, 土酸对微管内表面的溶蚀速率较快, 且在反应过程中发现有氟硅酸钾/钠沉淀析出; 而微乳酸的反应速度较慢, 反应过程中只发现一些蚀斑. 微管内径越小, 则反应产生的气泡越易发生聚并, 形成气液环状分布. 土酸在管内不同位置处的反应速率不同, 液气界面处的反应明显较快. 在相同压力梯度下, 50及25 μm微管经两种酸液体系酸蚀后蒸馏水在其中的流速均有不同程度的增加(在管中反应 24 h), 即其流动能力明显增大; 蒸馏水在经微乳酸酸化后的微管中流动能力增加得更明显. 这不仅直观地证明了土酸在砂岩储层中酸化引起的二次沉淀反应, 而且土酸在微管中反应的界面效应也制约了酸化效果, 微乳酸在反应过程中不产生沉淀并能消除界面效应, 因而是一种较理想的酸化体系.     

Isocyanide based multicomponent reactions of oxazolidines and related systems

N-Alkyloxazolidines react in a multicomponent reaction with carboxylic acids and isocyanides to give N-acyloxyethylamino acid amides. The previously reported reaction conditions were improved using a design of experiments approach (DoE). Under the optimised conditions, good yields of the N-acyloxyethylamino acid amide products are obtained both via a three- or four-component approach from N-alkylethanolamines, aldehydes/ketones, isocyanides and carboxylic acids. The reaction of oxazolidines without a nitrogen substituent was found to give either the expected Ugi products or the N-acyloxyethylamino acid amides depending on the choice of reaction conditions. Optimised reaction conditions were also developed for the ring-expansion of oxazolidines to morpholin-2-ones via reaction with an isocyanide followed by hydrolysis. The mechanistic pathway of the multicomponent reaction was briefly investigated using an ¹⁸O labelling experiment. The carboxylic acid component can be replaced by a range of other acidic nucleophiles including thiobenzoic acid, thiophenol or 5-phenyltetrazole, which are incorporated via an alternative pathway. These latter reactions can also be applied to 2-aminotetrahydrofurans, 2-aminotetrahydropyrans or 4-hydroxybut-2-one, further extending the structural diversity of the multicomponent reaction products.     

Reaction kinetics and pathway of hydrothermal decomposition of aspartic acid

The kinetics and pathway of hydrothermal decomposition of aspartic acid were studied using a continuous‐flow tubular reactor. The reaction was carried out in the temperature range of 200–260°C and at a pressure of 20 MPa. Deamination was the primary reaction, indicated by the presence of significant amount of ammonia, fumaric acid, or maleic acid in the products. Other reaction products were pyruvic acid, malic acid, and traces of succinic and lactic acid. Traces of alanine were also detected, showing the possibility of decomposing high‐molecular weight amino acids to obtain simple amino acids such as glycine or alanine. Results on the effect of reaction parameters demonstrated that decomposition of aspartic acid is highly temperature dependent under hydrothermal conditions. For a slight temperature difference of 60°C (from 200 to 260°C), the first‐order reaction rate constants of 0.003 significantly increased to 0.231 s^?1. The activation energy was 144 kJ/mol, as calculated by the Arrhenius equation. No significant effect was exhibited by other reaction parameters such as pH and pressure. The results are useful in controlling the hydrolysis of proteinaceous materials toward high yield of aspartic acid under hydrothermal conditions. © 2007 Wiley Periodicals, Inc. 39: 175–180, 2007     

Total synthesis of the alkaloids martinelline and martinellic acid via a hetero Diels-Alder multicomponent coupling reaction

[reaction: see text] A concise synthesis of the guanidine alkaloids, (+/-)-martinelline and (+/-)-martinellic acid, using a protic acid catalyzed 2:1 hetero Diels-Alder coupling reaction between N-Cbz 2-pyrroline and methyl 4-aminobenzoate, is described. Protic acid catalysis, rather than Lewis acid catalysis, was necessary to achieve the desired sense of diastereocontrol in the coupling reaction.     

Highly substituted pyrrolidinones and pyridones by 4-CR/2-CR sequence

[reaction: see text] By combining a Ugi four-component reaction of isocyanides, phosphonoacetic acids, primary amines, and glyoxals or alternatively 3-keto aldehydes with a subsequent Wittig ring-closing reaction (using the Horner/Wadsworth/Emmons variant (HWE)), highly substituted 5-oxo-2,5-dihydro-1H-pyrrole-2-carboxylic acid amides and 6-oxo-1,2,3,6-tetrahydro-pyridine-2-carboxylic acid amides can be assembled, respectively. The corresponding tandem of a Passerini reaction on 3-keto aldehydes and subsequent Wittig ring closure does not afford the expected six-membered 6-oxo-3,6-dihydro-2H-pyran-2-carboxylic acid amides but instead leads to the formation of 4-oxo-pent-2-enoic acid amides via an elimination route.     

脂肪酶催化乳酸与乙醇合成乳酸乙酯的反应动力学

对脂肪酶催化乳酸与乙醇合成乳酸乙酯反应的动力学进行了研究,根据乒乓机制和双底物抑制的特性建立了反应速率方程.反应时间常数(tR)和扩散时间常数(tD)的计算结果表明,酯化反应速率未受到明显的限制.反应速率方程可以很好地预测实验结果,由非线性拟合得到的动力学参数中,乳酸(A)和乙醇(B)的抑制常数分别为KiA=10.7mmol/L和KiB=275.0mmol/L.这说明乳酸作为短链极性脂肪酸,对酶的失活作用远大于乙醇.乳酸在微液层中聚集并产生了使酶失活的低pH值环境,同时在酯化反应中存在竞争性抑制作用.     

烟酸的电化学行为与测定

用循环伏安法研究了不同支持电解质溶液中烟酸的电化学行为。烟酸在玻碳电极表面有良好的电化学响应信号。在碱性介质中,烟酸被不可逆氧化,氧化产物具有电活性,可发生准可逆氧化还原反应;在酸性介质中,烟酸发生两步准可逆氧化还原反应。结合红外、紫外光谱分析,提出了烟酸在不同酸度的介质中的电化学反应历程。并根据－０．１３Ｖ处的氧化峰电流与烟酸浓度的关系,提出了电化学测定烟酸的新方法     

肉桂酸的逆合成分析、合成设计及实验制备——一次设计型实验课的探索

以肉桂酸为目标产物,通过逆合成分析、合成设计,采用不同的实验方法合成制备,介绍了水相Heck反应、无溶剂Perkin反应、水相Wittig反应、水相Knoevenagel反应,拓展了学生的合成设计思维。本实验涵盖了目标产物的合成、纯化与表征,让学生认识和完成了一个基本的科研过程,提高了学生的综合能力。     

透明质酸的改性及在生物医用材料领域的应用研究

透明质酸(HA)是人体内最为常见的一种粘多糖,具有优良的生物相容性和可降解性,可广泛应用于药物输送、皮肤填充材料、组织工程、药物载体和3D仿生学等方面,是当前生物医用材料领域的研究热点之一。HA具有独特的结构使其显示出特定的物理化学性质,可通过物理或化学方法修饰,赋予其新功能和新应用。本文从HA的分子结构出发,重点综述了HA的官能团羧基、羟基和乙酰胺基的化学改性和物理改性,主要包括羧基的酰胺化反应和酯化反应,羟基与环氧化物的开环反应、与有机硫化物的反应、酯化反应、与卤化物的反应和氧化反应,以及HA脱乙酰基反应;介绍了HA在生物医用材料领域的应用,并对其前景进行展望。     

Synthesis of mixed acid anhydrides from methane and carbon dioxide in acid solvents

[reaction: see text] The reaction of CH(4) with CO(2) has been performed in anhydrous acids using VO(acac)(2) and K(2)S(2)O(8) as promoters. NMR analysis establishes that the primary product is a mixed anhydride of acetic acid and the acid solvent. In sulfuric acid, the overall reaction is CH(4) + CO(2) + SO(3) --> CH(3)C(O)-O-SO(3)H. Hydrolysis of the mixed anhydride produces acetic acid and the solvent acid. When trifluoroacetic acid is the solvent, acetic acid is primarily formed via the reaction CH(4) + CF(3)COOH --> CH(3)COOH + CHF(3).