N-2-氯苄基苯甲酰胺的固相合成及其晶体结构分析

N-2-氯苄基苯甲酰胺采用固相法制备.聚苯乙烯磺酰氯(1)在吡啶存在下与2-氯苄胺反应得到N-2-氯苄基磺酰胺树脂(2),进一步在吡啶催化下用苯甲酰氯进行酰化得到N-2-氯苄基-N-苯甲酰基磺酰胺树脂(3).用TiCl₄/Zn/THF试剂处理,从树脂3上解脱得到产物N-2-氯苄基苯甲酰胺(4),产率92%.N-2-氯苄基苯甲酰胺的晶体属于单斜晶系,P2₁空间群,晶胞参数:a=0.7149(3)_nm,b=0.8772(4)_nm,c=0.9704(4)_nm;β=95.172(7)°;晶体结构中存在两种分子间氢键相互作用.     

有机环四硅氧烷液晶的合成及其相变行为

两种环四硅氧烷分别和６种液晶基元化合物（Ｍ１－６）反应，合成了６种仅含１个介晶侧基的环四硅氧烷（１－６）。它们的化学结构已由＾１ＨＮＭＲ、ＩＲ和元素分析证实，借助ＤＳＣ和偏光显微镜观察研究了１２个化合物的相变行为。     

新型固体超强酸催化剂的制备与裂解性能研究

采用浸渍法，将活性超强酸SO4^2-/ZrO2引入Si-MCM-41介孔分子筛，得到一种新型的固体超强酸催化剂SO4^2-/ZrO2 /Si-MCM-41，其PKA值可达-12.7，酸度分布曲线表明强酸中心数量远低于弱酸中心，XRD结果显示，Si-MCM-41骨架部分塌陷，但保留了主要骨架结构，采用Py-IP法，测定SO4^2-/ZrO2 /Si-MCM-41上酸类型以L酸为主，在催化1，3，5-三异丙苯裂解反应中该催化剂的性能优于微孔分子筛。     

A Solid Phase Synthesis of Chalcones by Claisen-Schmidt Condensations

In previous papers1,2, we reported our recent findings that chalcone (l,3-dipheny1-2-propen-1-one) derivatives are novel potential antimalarials that are active against chloroquine-resistant strains of Plasmodium falciparum. According to our structure-activity relationships (SAR) and computer modeling data1,2, we expect the chalcone derivatives with hydroxyl functionality on one of the aromatic rings and with some other appropriate substitutions on the other ring will be even more potent as a…     

An Improved Solid Phase Spectrophotometry Method for the Determination of Aromatic Esters

Abstract

A method based on Solid Phase Spectrophotometry was developed for the determination of methyl benzoate. Hydroxamic acid formed by the reaction between the above and hydroxylamine, reacts with V(V) and oxalate yielding a violet compound, which is sorbed on an anion-exchange resin. The absorbance of the resin phase at 546 and 750 nm is measured directly. The calibration graph is linear for the 4.8–23 μM concentration range. RSD is shown as 3.7%, with a detection limit of 0.09 mg. 1^?1. This method has been applied to the determination of aromatic esters in brandies.     

相转移催化合成N,N′-二(3,5-二甲基吡唑)烷

近年来,多齿含氮配体在金属有机配合物的合成和研究中日益受到重视,不仅用在高氧化态、缺电子中心的高价过渡金属有机配合物上,而且已开始在低氧化态、富电子中心的低价过渡金属有机配合物上应用,其中一个重要原因是自然界里许多的金属酶普遍含有以氮为配位原子的配体。因此,本文试图研究N,N′-二(3,5-二甲基吡唑)烷的合成。70年代初,Trofimenko 用3,5-二甲基     

Rapid Stability Indicating Uv-Assay of Methenamine Mandelate In Tablets Using Solid Phase Extraction

Abstract

A rapid stability-indicating method was developed to quantitatively determine methenamine mandelate in tablets. After dissolution of the sample in water methenamine is separated from its decomposition product formaldehyde by the use of solid-phase extraction. the determination of methenamine may then be carried out by several procedures. A spectrophotometric assay following hydrolysis of methenamine to formaldehyde appeared to be most suitable.

The simplicity and accuracy of the method compares favourable with the U.S.P. XXI method. the procedure can be advantageously used in stability and quality control studies of methenamine containing dosage forms.

Precision and accuracy were checked by comparing the results of 10 identical raw material samples and 10 tablet samples that were both assayed by this method and the USP XXI procedure (Tables 4 and 5).

The assay values for methenamine and the relative standard deviations were similar for both procedures in both raw material and tablets.

Above results show that the SPE procedures give accurate, precise and reliable values for the methenamine assay. Since no titrant standardizations or lengthly sample pretreatments have to be carried out the method is fast, which makes it very suitable for industrial quality control purposes. the method is also economical. No precious instruments are necessary; a simple colorimetric device is sufficient.

The extraction columns can be reused several times. Even after 10 regenerations the columns did not show any deterioration.     

含L－氨基酸结构的手性液晶化合物的合成及其相变行为

合成了９种具Ｌ－氨基酸衍生物结构的介晶化合物（Ｉ－Ⅲ，Ⅳａｂ，Ⅴａ，ｂ，Ⅵａ，ｂ）、４种氨基酸衍生物（Ａ１－４）和６种介晶化合物（Ｍ１－６）．新化合物（Ⅰ－Ⅲ，Ⅳａ，ｂ，Ⅴａ，ｂ，Ⅵａ，ｂ，Ａ４，Ｍ３－６）的化学结构通过ＩＲ、１ＨＮＭＲ和元素分析证实；并用偏光显微观察和ＤＳＣ分析研究了其相变行为，结果表明有８种化合物（Ｍ３－６，Ⅵａ，ｂ，Ⅴｂ，Ⅵｂ）呈现液晶相变。测定了它们的比旋光度。通过Ｘ射线衍射研究了化合物Ⅵｈ１２０～１３０℃和Ⅵｂ１７０～１８０℃的近晶结构，Ⅵｂ显，Ⅵｂ呈。测定了化合物Ⅳｂ的电滞回线，证明其具铁电性。     

Microwave Induced Synthesis of 3,4-Dihydro-2H-pyran-2-carboxaldehyde: A Versatile Linker for Solid Phase Combinatorial Library

Procedures for the dimerization of acrolein to form 3,4-dihydro-2H-pyran-2-carboxaldehyde by microwave induced synthesis have been developed. Significant rate-enhancement and yield increase were observed. 3,4-Dihydro-2H-pyran-2-carboxaldehyde was obtained in 91% yield under microwave irradiation for 5 minutes instead of 39% yield by reacting at 190 °C for 40 min or at 160 °C for 4 hr.     

Microwave-Assisted Solid Phase Organic Synthesis.Application to Indole Library Construction

Microwave-assisted organic synthesis (MAOS) has attained increasing popularity due to recent advancement in the instrumentation of microwave technology. Now, MAOS can be performed under controlled temperature and pressure to yield reproducible results. For combinatorial chemistry,the dramatically increased reaction rate under microwave irradiation at high temperature provides an ideal solution to those sluggish reactions, in particular the combinatorial reactions carried out on solid supports. In this presentation, we describe our results on microwave-assisted solid-phase organic synthesis (MASPOS) applied to the construction of indole libraries such as 5. Compounds 4 were synthesized on the Rink amide resins using IRORI MicroKanTM reactors encoded with a radio-frequency (Rf) tag. The resin-bound terminal alkynes 2, prepared via the amide bond, were cross-coupled with the nitroaryl triflate under the conditions adopted from the solution reactions developed by us1,2. The nitro group of 3 was then reduced and sulfonylated to give 4. Ring closure reactions within 4 with Cu(OAc)2 were examined initially in refluxing DCE for 24 h, but no indole product was detected after cleavage from the resin. Therefore, the same reactions were carried out under microwave irradiation at 200 ℃ for 10 min on a Personal Chemistry Emrys Creator, the desired indoles 5 were obtained in 60-95% overall yields calculated from 1 and in ＞90% purities in most cases3. It is necessary to mention that the IRORI microreactors cannot tolerate the high temperature and the resin-bound 4 must be transferred to the reaction vials for the microwave-assisted ring closure reactions. A traceless synthesis of an indole library via MASPOS will be discussed as well.4     

人胰酶抑制剂的固相合成

本文用固相多肽合成法以逐步和片段缩合并用的方武首次合成了人胰酶抑制剂,其中采用了TMSOT_t-硫代茴香醚/TFA糸统切断载体-肽的连接键及脱除全部侧链保护基,合成产物经脱氢胰酶亲合层析与HPLC精制,总产率6.3％.合成品对牛胰酶有很强的抑制能力,其活性约为天然产物的97％。     

萘并吡喃类固态光致变色化合物的合成及性能研究

合成了化合物 ２,２－二芳基萘并吡喃（２ａ－２ｐ）,产物结构和组成通过１Ｈ ＮＭＲ, ＭＳ和元素分析证实．测定了化合物光照前后的紫外可见吸收光谱．部分化合物表现出良好的固态光致变色性能,分析了它们的结构与光致变色性能间的关系．     

固相合成法制备组氨酸-苯丙二肽及其自组装研究

本文以组装性能良好的苯丙氨酸二肽(FF)为母体分子,用组氨酸对其进行化学修饰,通过多肽固相合成法合成了组氨酸-苯丙二肽(HisFF)凝胶因子。合成的HisFF分子通过质谱(MS)、核磁共振(NMR)和液相色谱(HPLC)方法测试确定精确的结构和纯度。HisFF聚集体的形貌结构通过透射电子显微镜(TEM)和扫描电子显微镜(SEM)观察。HisFF分子在甲苯、氯仿和乙酸乙酯溶剂中形成凝胶强度不同,TEM实验结果表明纤维强度和聚集形态影响其凝胶的强度。组氨酸-苯丙二肽在多种溶剂中,通过不同组装方法可以组装成各种各样的纳米结构。例如,HisFF在丙酮、甲醇和乙酸乙酯溶剂中可组装成纳米颗粒、纳米管和螺旋状纳米纤维;组氨酸-苯丙二肽先经HFIP溶解再通过溶剂稀释后,可得到不同直径的纳米纤维。但是在四氢呋喃、乙醇和乙腈溶剂中,两种方法组装的形貌几乎无变化。     

利多卡因分子印迹聚合物的制备及其在固相萃取中的应用

以利多卡因(LD)分子印迹聚合物为研究体系,利用分子模拟计算功能单体与模板分子之间的相互作用能,并通过作用实验加以验证,确定衣康酸为最佳单体。以乙二醇二甲基丙烯酸酯为交联剂,N,N-二甲基甲酰胺(DMF)为溶剂,采用本体聚合法合成分子印迹聚合物(MIP);采用高效液相色谱检测。实验发现,聚合物具有较高的印迹指数和选择性;在乙腈加载、5%甲醇-乙腈淋洗、5%HCl-甲醇洗脱条件下,聚合物具有最佳印迹效果。通过渗漏实验考察聚合物键合容量。实验发现,在乙腈溶液中每100mg MIP与空白聚合物(NIP)可分别键合1.62和0.92mg LD分子;采用光度法测定牛血清中利多卡因的含量,其平均回收率达到84.6%。     

BaZrO3基质固体电解质的水热合成与表征

利用水热晶化法制备了BaZrO₃纯相和BaZr_1-xM_xO_3-α(M=Al,Ga,In;x≤0.20)体系固体电解质,通过XRD、SEM、IR、²⁷AlMASNMR和化学分析,对产物的物相、粒度和掺杂质进入晶格的数量进行了表征。结果表明,产物为立方钙钛矿结构,粒度为3～5μm,在0≤x≤0.20范围内,产物的金属离子比与投料比基本一致。     

Thermodynamic Phase Transition of Three-Dimensional Solid Additives Guiding Molecular Assembly for Efficient Organic Solar Cells

Fine-tuning the thermodynamic self-assembly of molecules via volatile solid additives has emerged to be an effective way to construct high-performance organic solar cells. Here, three-dimensional structured solid molecules have been designed and applied to facilitate the formation of organized molecular assembly in the active layer. By means of systematic theory analyses and film-morphology characterizations based on four solid candidates, we preselected the optimal one, 4-fluoro-N,N-diphenylaniline (FPA), which possesses good volatility and strong charge polarization. The three-dimensional solids can induce molecular packing in active layers via strong intermolecular interactions and subsequently provide sufficient space for the self-reassembly of active layers during the thermodynamic transition process. Benefitting from the optimized morphology with improved charge transport and reduced energy disorder in the FPA-processed devices, high efficiencies of over 19 % were achieved. The strategy of three-dimensional additives inducing ordered self-assembly structure represents a practical approach for rational morphology control in highly efficient devices, contributing to deeper insights into the structural design of efficient volatile solid additives.     

Solid Phase Synthesis of 3‐Toluenesulfonylglutarimides

A novel route for the synthesis of 3‐toluenesulfonylglutarimides on a solid support is described. The cyclization step involves stepwise [3+3] strategy of Rink Amide resin bound onto an α‐toluenesulfonyl group with various α,β‐unsaturated esters.     

N-对甲基苄基苯甲酰胺的固相合成及其晶体结构分析

标题化合物采用固相法合成: 聚苯乙烯磺酰氯树脂1与对甲基苄胺反应得到N-对甲基苄基磺酰胺树脂2, 用苯甲酰氯酰化得到N-对甲基苄基-N-苯甲酰基磺酰胺树脂3。用TiCl4/Zn/THF处理从树脂3上经自由基解脱的方法得到N-对甲基苄基苯甲酰胺4, 产率为76%。晶体结构在Bruker SMART 1000 CCD X-射线衍射仪上, 用石墨单色器单色化的MoK嵘湎?l = 0.071073 nm)测定。非氢原子坐标用直接法解出, 用最小二乘法对非氢原子进行各向异性温度因子修正。N-对甲基苄基-苯甲酰胺: 化学计量式为: C15H15NO, Mr = 225.28, 晶体属于正交晶系, Pna21空间群。晶胞参数: a = 0.9549(6), b = 1.1169(7), c = 1.1774(7) nm, V = 1.2557(13) nm3, Z = 4, Dc = 1.192 g/cm3, m = 0.075 mm-1, F(000) = 480;最终结构偏离因子R = 0.0478, wR = 0.1013, S = 0.912。化合物4的晶体结构中有分子间氢键相互作用。     

多孔固相放射免疫测定载体的合成和应用研究

合成了一种具有交联结构的多孔性甲状腺素（T4）固相放射免疫测定载体微球，并对载体微球的功能基转化、悬臂的引入和功能基的化反应进行了研究，用合成的载体微球与甲状腺素抗体偶联，通过测定甲状腺素的实验证明，该微球具有较高的结合率。     

Caspase抑制剂的结构及合成

Caspase在细胞凋亡中起着关键作用,因此Caspase抑制剂的研究成为当今生命科学领域的重要课题之一。人工合成的Caspase抑制剂主要分为肽类和非肽类。本文着重介绍了常见肽类和非肽类Caspase抑制剂的结构及合成方法,并介绍了相关高活性抑制剂的活性数据。