西红花酸的合成

以E-1,4-二溴-2-丁烯和亚磷酸三乙酯为起始物, 通过Wittig-Horner反应合成化合物2,7-二甲基-2,4,6-辛三烯-1,8-二醛; 然后以E-2-甲基-2-丁烯酸为起始物经过溴代、酯化合成E-2-甲基-2-丁烯酸甲酯-4-膦酸二乙酯. 两化合物通过Wittig-Horner反应生成西红花酸二甲酯. 西红花酸二甲酯水解得西红花酸.     

低压液相色谱法分离、制备西红花甙

采用低压液相色谱法制备西红花有效成分西红花甙。最佳分离、制备条件 :填料为键合正丁烷的苯乙烯 二乙烯苯聚合物 ,其粒度为 57～ 76μm ;制备柱为 50cm× 1 .5cm ;纯化柱为 60cm×0 .80cm ;流动相为甲醇 水溶液 ,梯度洗脱范围是 50 / 50～ 95/ 5(V/V) ;样品量为 2 0mL( 1 0 0g/L) ;工作压力为 2× 1 0 5Pa。在上述条件下 ,制备了 5种西红花甙 ,经过高效液相色谱法测定 ,其纯度均在 97%以上。其中 ,西红花甙 1和西红花甙 5的纯度在 99%以上。此方法具有操作简便 ,制备纯度高且运行成本低等优点 ,在西红花对照品的制备中具有广泛的应用前景     

铜催化共轭乙烯基联烯硅和1,3-二烯硅合成

在温和反应条件下,铜催化间隔烯炔衍生物与有机硅烷硼酸酯化合物发生反应,通过调控有机硅硼试剂的用量,以较高产率分别制备共轭乙烯基联烯硅和1,3-共轭二烯硅产物.该方法为制备多取代立体选择性官能团化联烯和1,3-共轭二烯产物提供了简单、高效的合成工具.     

共轭多烯异核双金属配合物的合成及性质

分子电子器件是近年来的一个热门课题,共轭有机分子是形成分子导线、分子开关等分子电子器件的模型化合物之一,其中一些已经得到应用.过去几年中,以sp碳为骨架的共轭桥联双金属配合物备受关注,长度为20个碳原子的此类双金属配合物已合成,大多数此类配合物金属端基之间有电子相互作用,具有良好的光电性质.由于合成的困难,以sp2碳为骨架的共轭多烯双金属配合物,近年来才有报道[1,2],且都是同核双金属配合物.共轭多烯异核双金属配合物的报道很少,由于分子的不对称,它们具有非线性光学性质.本文选用一取代二茂铁的三苯基磷盐与醛发生Wittig反应,生成的多烯单炔金属配合物与金属氢化物RuHCl(CO)(PPh3)3发生插入反应,合成了一系列长度为6个碳的稳定的共轭多烯异核双金属配合物(Scheme 1).     

光诱导的糖类化合物的合成与修饰

近年来光诱导的氧化还原催化反应在糖类化合物合成与修饰中取得重要进展.概述了该领域的最新成果,重点介绍光催化策略在O-糖苷化反应、C-糖苷化反应、糖类化合物的官能团修饰和硫醇-烯烃偶联反应等四个方面的应用.     

由有机盐简便合成不饱和醛、酮、酰胺以及有关天然产物

本文报道有机盐和各种不同的醛在固-液相转移条件下, 以碳酸钾为碱, 简便合成共轭不饱和醛、共轭不饱和酮以及共轭不饱和酰胺.以此合成方法, 还合成了一些具有生物活性的天然产物. 该合成方法操作简便, 反应条件温和, 产物高度立体选择性, 产率优良, 这为多烯醛, 多烯酮, 多烯酰胺以及有关天然产物的合成提供了实用途径.     

11-脱氧甘草次酸乙酯3-单糖链皂苷的合成及其活性研究

合成了5种11-脱氧甘草次酸3-单糖链皂苷并初步探讨其生物活性.以苯甲酰基保护的糖基三氯乙酰亚胺酯为供体,在三氟甲磺酸三甲基硅脂(TMSOTf)的催化作用下与11-脱氧甘草次酸乙酯C(3)位羟基发生糖苷化反应,以较好的产率制备得苯甲酰基保护的11-脱氧甘草次酸乙酯3-单糖链皂苷7a～7e,用NaOMe/MeOH溶液脱除苯甲酰基得11-脱氧甘草次酸乙酯3-单糖链皂苷8a～8e.合成的5个11-脱氧甘草次酸3-单糖链皂苷均为新化合物,结构经1H NMR、质谱、元素分析确证,活性实验表明化合物8a对高浓度N,N-二甲基甲酰胺(DMF)中枯草芽孢杆菌的生长具有保护作用,化合物8e对高浓度DMF中大肠杆菌、酵母菌的生长具有保护作用.     

卟啉及BODIPY衍生物设计合成及光物理性质研究基于分子玻璃主体材料的极紫外(EUV)光刻胶研发

<正>第一部分卟啉及BODIPY衍生物设计合成及光物理性质研究大π共轭有机化合物因其优良光电性质近年来引起广泛关注.卟啉和BODIPY是两类具有特殊电子结构和光谱性质的共轭化合物,通过功能化修饰可以实现对其光电性质的调控。本论文工作针对基于卟啉和BODIPY结构的大π共轭化合物的合成和光物理性质开展研究工作。具体研究内容如下:1.设计合成了分别以咔唑、芴和芴酮为桥的β-β桥联环状锌卟啉化合物。共轭桥对卟啉环电子离域     

α-乙酰基二硫缩烯酮Vilsmeier反应在共轭三烯化合物合成中的应用

以α-乙酰基二硫缩烯酮为起始原料,通过与Vilsmeier试剂反应得到亚胺盐正离子中间体,利用亚胺盐正离子中间体与碳亲核体反应,成功制备了多取代共轭三烯类化合物.该方法具有原料易得、反应条件温和及实验步骤简单等优点.该反应不仅建立了一种简单、有效合成多取代共轭三烯化合物新方法,而且扩展了α-乙酰基二硫缩烯酮类化合物在有机合成中的进一步应用.     

电子等排体的噻吩多烯与苯多烯同系递变的比较I

为了进一步研究苯多烯化合物的电子等排体噻吩多烯化合物的结构与性能间的定量关系,确定噻吩基的端基当量,合成了三个末端带拉电子基团的噻吩多烯化合物,测定了它们在乙醇和环己烷中的电子光谱,结果表明,和相应苯多烯化合物的电子光谱相比 ,普通红移25-30nm,即相差一个插烯双键引起的红移.以2-噻吩基的端基当量为3,噻吩多烯化合物的电子光谱波数与同系因子(1/2)^2^/^N形成良好的直线,相关系数r>0.99;并与相应苯多烯化合物的同系直线相距很近.其差距可用苯多烯系列增加一个烯链的增量与改换一个电子等排体2-噻吩基的增量之比作定量描述.结果证明2-噻吩基的端基当量比苯基大.     

Simultaneous quantification of five major biologically active ingredients of saffron by high-performance liquid chromatography.

A simple, sensitive and specific high-performance liquid chromatography-UV (HPLC-UV) method has been developed for the first time to simultaneously quantify the five major biologically active ingredients of saffron, namely crocin 1, crocin 2, crocin 3, crocin 4 and crocetin. Calibration curves were derived by spiking authentic compounds and internal standard, 13-cis-retinoic acid, into herbal samples prior to extraction. Extraction was conducted simply by stirring dried herb (20 mg) with 80% aqueous methanol (5 ml) at ambient temperature in the dark for 2 h. The HPLC assay was performed on a reversed-phase C18 column with linear gradient elution using methanol and 1% aqueous acetic acid. Calibrations were linear (r2 = 0.999) for all five analytes, with overall intra- and inter-day RSDs of less than 11%. The assay was successfully applied to the determination of four crocins and crocetin in three saffron samples and two Zhizi, another crocin-containing herb. Results indicate that the developed HPLC assay can be readily utilized as a quality control method for crocin-containing medicinal herbs.     

Saffron yellow: characterization of carotenoids by high performance liquid chromatography with electrospray mass spectrometric detection

Saffron is one of the oldest natural dyestuffs and is obtained from the dried stigmata of Crocus sativus L. Nowadays, saffron is considered as an invaluable spice of golden‐yellow hue, a precious ingredient in the Eastern and Mediterranean cuisines. It is characterized by a bitter taste that is caused by the chemical properties of its constituents. The yellowness of saffron results from the presence of crocins (glycosyl esters of crocetin), its main color compounds, which are examined in the present study in the crude methanol extracts by high performance liquid chromatography (HPLC) coupled with spectrophotometric and electrospray mass spectrometric detection (HPLC–UV‐Vis–ESI MS). This technique allowed the separation and identification of trans‐ and cis‐isomers of crocins. Their mass spectra registered in the negative ion mode comprised the quasi‐molecular and fragment ions, as well as a range of other ions. Doubly charged ions were found for trans‐isomers only, due to the high symmetry of their molecules. Modification of the eluent allowed the identification of several signals corresponding to adduct ions of crocins with the used additives. Copyright © 2009 John Wiley & Sons, Ltd.     

Semi-Preparative Isolation of Crocins from Saffron (Crocus sativus L.)

Two-step, low-pressure liquid chromatography has been used to isolate crocins, the most abundant compounds in the hydroalcoholic extract of saffron. A mixture of styrene–divinylbenzene copolymer and modified starch polymers was used as stationary phase. A 600 mm × 15 mm i.d. column was used in the first step; the best resolution was achieved by gradient elution with an aqueous methanol gradient with the methanol content changing from 50 to 95%. The highest yield of crocins from this step was achieved by use of 20 mL of 300 mg mL^?1 saffron extract. Under these conditions the yellow pigments of the saffron extract were separated into twenty fractions. In the second step use of a 700 mm × 8 mm i.d. column resulted in crocin-1 [crocetin (di- -D-gentobisyl) ester], crocin-2 [crocetin (mono- -D-gentobisyl-mono- -D-glycoside) ester], and crocin-3 [crocetin ( -D-gentobisyl)-ester] with purity as high as 99.04%, 97.40%, and 96.70%, respectively.     

西红花的药理作用和分离制备及分析方法概况

本文通过文献资料评述了西红花的药理作用、西红花有效成份－西红花糖甙的分离、制备、分析的方法。结合作者的实验,对这些方法作了评述和展望。     

In‐chain neutral hydrocarbon loss from crocin apocarotenoid ester glycosides and the crocetin aglycon (Crocus sativus L.) by ESI‐MSn (n = 2, 3)

The stigmas of Crocus sativus L. have been used as spice and colorant agent (i.e. saffron) for more than 4000 years. For an updated structural investigation of the aglycon present in the glycosylated crocetin apocarotenoids (i.e. crocins), seven representative derivatives ranging from one up to five glucosyl‐residues with a maximum number of three monosaccharides per glycosylation site (glucose, gentiobiose, gentiotriose and neapolitanose) were isolated and purified by high‐performance liquid chromatography. The compounds selected for further mass spectrometric investigation include glucosyl‐, bis‐glucosyl‐, gentiobiosyl‐, gentiobiosyl‐glucosyl‐, bis‐gentiobiosyl‐, gentiobiosyl‐gentiotriosyl‐ and gentiobiosyl‐neapolitanosyl‐crocetin. Electrospray ionization in combination with low‐energy collision‐induced dissociation/tandem mass spectrometry of sodiated crocin precursor ions utilizing either a 3D‐ion trap (MSⁿ, n = 2, 3) or a QqTOF instrument, with the latter providing accurate mass determination with an accuracy of ±1–3 ppm or better at a resolution of 10 000 (full width at half maximum), was used. Major fragmentation pathways included loss of either one or two carbohydrate substituents leading to the sodiated aglycon without interglycosidic bond cleavage during in MS²‐experiments. All sodiated precursor ions and major product ions were accompanied by a loss of 92 Da, which was elucidated as C₇H₈‐loss from the aglycon by skeletal rearrangement via an eight‐membered transition state as previously described for intact C₄₀‐carotenoids. Copyright © 2013 John Wiley & Sons, Ltd.     

硝基化合物的不对称迈克尔加成反应

从以下三方面对硝基化合物的不对称迈克尔加成反应进行了较为详细的综述： （1）手性催化剂催化的迈克尔加成，（2）共轭硝基物与手性亲核试剂的迈克加成 ，（3）脂肪族硝基物对手性迈克加成受体的迈克尔加成。     

Asymmetric Syntheses Aided by Biocatalysts

This article summarizes the achievements of the authors‘ group in the area of biocatalyst-catalyzed organic reactions in recent 10 years. A strain of Geotrichum sp. obtained by screeninu is capable of stereoselectlvely reducing a number of carbonyl compounds. In many cases, the stermghemistry is complementary with that obtained by baker‘ s yeast. Therefore, this microorganism provides a useful pathway to the preparation of alcohol eompounds with specific configurations. On the other hand, a nmmber of plant sourees have been screened for oxynitrilases and the hydrocyanation reactions of various arylcarboxalde-hydes have been investigated.A“micro-aqueous reaction system“ was invented,by which a serles of novel optically active cyanohydrins were prepared.On this hasis,a high through-put comtimasous reaction system has been designed.This paper also deseribes examples of the syntheses of bio-active compounds by using the optieally active compounds obtained from the above mentioned catalytic reactions as precursors.     

氮杂Wittig反应的最近进展

综述了最近几年氮杂Wittig反应的研究进展,包括分子间氮杂Wittig反应、分子内氮杂wittig反应及串联的氮杂Wittig反应。讨论了氮杂Wittig反应在一些含氮杂环、稠杂环及天然产物合成中的应用。