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In this thesis, we developed chiral proton N-O type ligands and employed them in the enantioselective addition of diethylzinc to N-diphenylphosphinoyl imines. The relationship between the structure of the ligands and the enantioselectivity was systematically studied. Furthermore, enantioselective butylation of N-diphenylphosphinoyl imines withBu〓Zn and enantioselective diphenylzinc addition to imine were also examined.

本文致力于亚胺的不对称催化有机锌试剂加成反应的研究:以手性质子型N-O配体为促进剂,对N-二苯基次膦酰亚胺进行不对称乙基锌加成反应而展开研究工作,系统地考查了手性配体的结构对反应的影响;另外,对N-二苯基次膦酰亚胺的不对称催化丁基锌加成进行了研究,并首次对亚胺的不对称苯基锌加成反应进行了初步探索。

Chemiluminescent immunoassay is one of the advanced immunoassay ofnon-radioisotopic immunoassay because of its high sensitivity, wide dynamic range,high accuracy, stable labeled protein, full automation and extensive application field.CLIA using acridinium ester derivatives as chemiluminescent label has advantages oflow background, high signal-to-noise ratio, no need of catalyst and simpleluminescence system. Different aspects associating the DMAE·NHS-based CLIA were studied in thisthesis, including synthesis of acridinium ester, chemiluminescentcharacteristics of DMAE·NHS, labelling antibody or streptavidin with DMAE·NHS,two-site sandwich chemiluminescent immunoassay for TSH, two-sitesandwich chemiluminescent immunoassay involved biotin-streptavidinsystem for TSH, and competitive chemiluminescent immunoassay usingbiotin-streptavidin system for TT〓. The desired acridinium ester, DMAE·NHS, was synthesized according to thereference method with some modifications. The products were identified by IR, NMR,MS and elemental analysis. In our method, KOH was used in place of NaOH tosynthesize benzyl ester of 3,5-dimethyl-4-hydroxybenzoic acid,2',6'-dimethyl-4'-(n-succinimidyloxycarbonyl) phenyl-acridinium-9-carboxylate waspurified on a silica gel column with chloroform/ethylacetate(4:1, v/v) as eluent andfurther purified by triturating with hexane/acetone(2:1, v/v).

DMAE·NHS的合成是本论文的关键和难点,我们对文献方法进行改进:文献方法用氢氧化钠与3,5-二甲基-4-羟基苯甲酸反应制得3,5-二甲基-4-羟基苯甲酸钠,再用3,5-二甲基-4-羟基苯甲酸钠与苄氯作用制备3,5-二甲基-4-羟基苯甲酸苄酯,我们用氢氧化钾代替氢氧化钠,使合成取得成功;在合成2',6'-二甲基-4'-苯基-吖啶-9-甲酸酯时,文献方法对粗产品进行两次硅胶柱层析纯化,第一次柱层析用氯仿/乙酸乙酯(4∶1,V∶V)作溶剂和淋洗剂,第二次柱层析用己烷/丙酮(2∶1,V∶V)作溶剂和淋洗剂,按照文献方法得到的不是所需要的化合物,我们只进行第一次柱层析纯化,然后用己烷/丙酮(2∶1,V∶V)进行研磨,过滤,洗涤,除去溶于己烷/丙酮(2∶1,V∶V)的部分,得到所需要的产品。

The present invention relates to sulphonyloxazolamines of general formula, wherein R, R represent independently from each other H, A,-(CH2)n-Ar or alkenyl with 2-6 C atoms, R and R together also represent a mononuclear saturated heterocycle with 1-2 N, O and/or S atoms, Z is H, A, CF3, NO2, Hal, OH, OA, NH2, NHA or NA2, A represents alkyl with 1-6 C atoms, Ar is Z-monosubstituted or Z-disubstituted phenyl, halogen is F, Cl, Br or I, n is 1 or 2 or the physiologically acceptable salts or solvates thereof.

本发明涉及式磺酰基∴唑胺或其生理上可接受的盐或溶剂化物,其中R 1 ,R 2 每一个相互独立为H、A、-(CH 2 )n-Ar或具有2到6个C原子的链烯基,R 1 和R 2 也一起为具有1到2个N、O和/或S原子的单核饱和杂环,Z为H、A、CF 3 、NO 2 、卤素、OH、OA、NH 2 。NHA或NA 2 ,A为具有1到6个C原子的烷基,Ar为被Z取代的或Z二-取代的苯基,卤素为F、Cl、Br或I,n为1或2。

Compared to bis(1-phenylisoquinolyl-N,C2') iridium, the iridium complex containing the triarylamine-based picolinic acid displays increased MLCT transition and low oxidation potential and is expected to be a promising red phosphorescent material.

与传统的二(1-苯基异喹啉)(吡啶-2-甲酸)合铱配合物相比,设计的环金属铱配合物具有增强的MLCT电子跃迁吸收和低的氧化电位,是一种有发展潜力的红色磷光材料。

Bicyclic compounds containing a phenyl or pyridyl ring fused to a cycloalkyl or heterocyclic ring, to which is attached a 5-membered heterocyclic ring, including pharmaceutically acceptable salts and prodrugs thereof, are agonists of G-protein coupled receptor 40 (GPR40) and are useful as therapeutic compounds, particularly in the treatment of Type 2 diabetes mellitus, and of conditions that are often associated with this disease, including obesity and lipid disorders, such as mixed or diabetic dyslipidemia, hyperlipidemia, hypercholesterolemia, and hypertriglyceridemia.

本发明涉及含有连接在5元杂环上的稠合至环烷基或者杂环的苯基或者吡啶基环的二环化合物,包括其药学上可接受的盐和前药,它们是G蛋白偶联受体40(GPR40)激动剂并且可以用作治疗性化合物,特别是在2型糖尿病和与这些疾病相关的症状中用作治疗性化合物,这些症状包括肥胖病和脂质疾病,比如混合或者糖尿病型血脂异常症、血脂质过多、高胆甾醇血和高甘油三酯血症。

Benzoylated phenyl a - and B - 2 - thio - D - fructofuranosides were synthesized and coupled with protected sucrose acceptor to synthesize a - D - fructofuranoside - linkage stereospecifically by employing NIS/AgOTf as catalysts.

在果糖的合成研究中,合成了四苯甲酰基苯基果糖硫苷,并首次将其用作糖苷化反应的给体,在NIS/AgOTf的促进之下,与乙酰化保护的蔗糖受体反应,从而以高产率立体专一地合成了α构型的呋喃果糖苷。

Simultaneously we prepared benzimidazolines with two methods by the of reduction benzimidazolium salts with NaBH_4 and Grignard addition with benzimidazolium salts. Thus we provided a new biomimic synthetic method for 13 kind of tetrahydroisoquinoline starting from carboxylic aicd and halid, gave a new idea of the synthesis for new drugs.It can make many kind ofβ-carboline alkaloids which have bioactivity to antibacterium, antivirus and antitumor to start from 1,2,3,4-tetrahydro -β-carboline.

本文以1,3-二甲基苯并咪唑碘盐和2-取代的1,3-二甲基苯并咪唑碘盐为原料,采用了NaBH_4还原和Grignard试剂加成两种方法,制备了13种1,3-二甲基苯并咪唑烷和2-取代的1,3-二甲基苯并咪唑烷作为四氢叶酸辅酶一碳单元转移新模型,在酸性条件下,以2-(3,4-二甲氧基苯基)乙胺作为接收一碳转移的亲核试剂,完成了13种重要的四氢异喹啉类化合物的新合成方法研究。

The method to purify compound 4 was resolved. A novel method to prepare the intermediate from phenylacetyl chloride was selected in this paper. The facile synthetic scheme put forward in this work is simple to operate and has the characteristic of high yield and good feasibility.

解决了终产品4的分离纯化难题,采用生成衍生物再进行水解的方法达到了纯化目的;提出了合成中间体3-羟基-4-苯基-吡喃-2,5-二酮(7)的较为新颖的方法,操作简单,各步中间体无需作进一步纯化便可进行下一步反应,从而得到了结构较新颖的终产品4。

A new convenient synthesis of a series of 1-aryl-2-propanones using aromatic amines as precursors, via diazo reaction and improved Meerwein arylation reaction under mild conditions, was achieved. In addition, 1-[3,5-bisphenyl]-2-propanone is a new compound among the synthesized compounds. This approach is an efficient synthetic method for the aryl-propanones with the different substituting groups.

以芳香胺为原料,经重氮化和改进的Meerwein芳基取代反应,合成了一系列的1-芳基-2-丙酮,其中1-(3,5-二三氟甲基苯基)2-丙酮是一个新化合物改进后的方法简化了合成步骤,提高了收率,可方便地用于在苯环上具有不同取代基的芳基丙酮的合成。

A plausible process of this reaction is as following: Aldehyde was in equilibrium with the enol form, aldehyde reacted with aniline catalyzed by 2,2,2-trichloroacetic acid to afford imine, the generated imine immediately reacted with enol to form intermediate via intramolecular cyclization.

我们发现一分子芳基叠氮和一分子三苯基磷反应生成一分子磷亚胺,后者与由两分子取代的苯氧乙酰氯原位生成的烯酮反应生成4-亚烷基-β-烷基-内酰胺,其串联过程涉及烯酮亚胺的形成及其与烯酮的[2+2]的环加成反应。

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