Synthesis of Alkyllysophospholipid Analogues with Readily Functionalized 1-O-Alkyl Side Chain

Synthesis of alkyllysophospholipid analogues 5a and 5b are described. These lipids have imide functional group attached on the terminal of 1-O-alkyl side chain suitable for further manipulations. Our approach features the use of mesylate 8 in which the mesyl group serves both as protecting group and electrophile.     

Phyllohydroquinone (Vitamin K1 H2) and Phylloquinone (Vitamin K1): Purification and Spectral Analysis

Abstract

Simple procedures for the preparation of pure phyllohydroquinone and phylloquinone are described. Phylloquinone is reduced by sodium dithionite and the reduced vitamin is purified by reverse phase high performance liquid chromatography. The essential spectral properties of the pure vitamins in ethanol and methanol are cited. The data provide a convenient spectral method for the accurate determination of the absolute concentrations of the oxidized and reduced vitamins and the rates of oxidation of the reduced vitamin. Pure, dry phyllohydroquinone may be safely stored at -70[ddot]C under nitrogen for a period of months. The stability of Phyllohydroquinone in methanol at 25.0 ± 0.1[ddot]C is also reported.     

含柔性侧基聚亚胺酮的合成与性能研究

以1,4-双-(4′-溴苯酰基)苯和含柔性侧基的芳香环二胺基化合物6-[2-(2-十一烷基-1-咪唑基)乙烷]-1,3,5-三嗪-2,4-二胺为单体,通过钯催化的胺基化反应缩聚合成了新型含柔性侧基的聚亚胺酮(PIK-T),其结构经1H NMR和IR表征.对PIK-T的DSC,TG和GPC分析结果表明,由于主链的芳香环及...     

(1R,6R)-(+)-鱼腥藻毒素的合成

鱼腥藻毒素(Anatoxin-a)是自兰藻类水华鱼腥藻(Anabaena flos-aquae)中分离的一种氮杂双环胺类生物碱,其化学结构及绝对构型经X光晶体衍射法测定分析为:(1R,6R)(+)-2-乙酰基-9-氮双环[4.2.1]壬-2-烯,简称为AnTX-a。     

Total syntheses of beta-carboline alkaloids, (R)-(-)-pyridindolol K1, (R)-(-)-pyridindolol K2, and (R)-(-)-pyridindolol.

The total syntheses of beta-carboline alkaloids, (R)-(-)-pyridindolols (1, 5, and 6) are described. The two key steps involved are (1) a thermal electrocyclic reaction of the 3-alkenylindole-2-aldoxime 10 and (2) a thermal cyclization of 3-alkynylindole-2-aldoxime 11 to construct the beta-carboline N-oxides 8, which upon heating with acetic anhydride and sequential treatment with trifluoromethanesulfonic anhydride gave the triflates 18. The Stille coupling reaction of 18 with vinylstannane, followed by cleavage of MOM ether, afforded the 1-ethenyl-3-hydroxymethyl-beta-carboline (7a). Subsequent acetylation of 7a yielded the acetate 7b, which was subjected to the Sharpless asymmetric 1,2-dihydroxylation by AD-mix-beta to produce (R)-(-)-pyridindolol K2 (6). Selective acetylation of 6 was effected by Ac(2)O and collidine to form (R)-(-)-pyridindolol K1 (5). By contrast, hydrolysis of 6 provided (R)-(-)-pyridindolol (1).     

Synthesis and Crystal Structure of 5（R）-（1R,2S,5R）-Menthoxy-4（R）- N-cyclohexylaminobutyrolactone

1INTRODUCTION Substitutedγ-butyrolactones are a group of impor-tant compounds containing unique carbon skeleton of butyrolactone which is widely present in many natural products and have received considerable interest because of their biological and medicinal properties[1～4].Therefore,much attention has been paid to the new asymmetric methods for synthesi-zing these interesting compounds[5～11].The prece-ding results led us to explore the possibility of using cyclohexylamine to convert5(…     

Synthesis, structure and antitumor activity of a water-soluble platinum complex, (1R,3R,4R,5R)-(-)-quinato(1R,2R-cyclohexanediamine)platinum (II).

The reaction of dihydroxo(1R,2R-cyclohexanediamine)platinum(II) with (-)-quinic acid gave a water soluble complex, (-)-quinato(1R,2R-cyclohexanediamine)platinum(II). The crystal structure of the complex was determined by X-ray analysis. The data indicate a chelation of the alpha-hydroxycarboxylic acid part of quinic acid to platinum(II). The complex shows moderate antitumor activity against murine leukemia L1210 at high doses (T/C x 100 = 179% at a dose of 200 mg/kg).     

短侧链可溶性聚酰亚胺的制备和表征

利用3种廉价易得的含短侧链(甲基或乙基)芳香族二胺单体分别与3,3′,4,4′-二苯甲醚四酸二酐(ODPA)进行溶液缩聚反应制备了聚酰胺酸,再在三乙胺催化、乙酸酐脱水作用下进行化学亚胺化反应,成功制备出聚酰亚胺(PI)。通过红外光谱(FT-IR)证明PI已经完全亚胺化。溶解性实验表明这3种PI具有优异的溶解性能,如:在极性非质子溶剂1-甲基-2-吡咯烷酮(NMP)、N,N-二甲基甲酰胺(DMF)、N,N-二甲基乙酰胺(DMAc)、二甲基亚砜(DMSO)乃至低沸点溶剂氯仿和四氢呋喃(THF)中都可以溶解。采用DSC、TG、频谱分析仪、交流耐压试验装置、电阻测量仪、万能电子拉力机等多种手段对PI薄膜进行了性能测试。结果表明这3种PI保持了优良的热性能、电性能、力学性能等。     

在共聚物P(GMA-co-MMA)侧链实现卟啉化合物的同步合成与键合

采用溶液聚合的方法, 先合成了甲基丙烯酸缩水甘油酯(GMA)与甲基丙烯酸甲酯(MMA)的线型共聚物P(GMA-co-MMA); 然后通过环氧基团的开环成醚反应, 将对羟基苯甲醛(HBA)键合于共聚物的侧链上, 形成键合有苯甲醛(BA)的聚合物BA-P(GMA-co-MMA); 最后采用Adler方法, 以BA-P(GMA-co-MMA)、苯甲醛及吡咯为反应物, 在均相反应体系中, 成功地实现了苯基卟啉(PP)在共聚物P(GMA-co-MMA)侧链的同步合成与键合, 制得了卟啉功能化的线型大分子PP-P(GMA-co-MMA). 通过FTIR及1H-NMR对功能大分子PP-P(GMA-co-MMA)的化学结构进行了表征, 对其谱学性能进行了研究, 较为深入地分析了其光物理行为. 实验结果表明, 大分子PP-P(GMA-co-MMA)具有与四苯基卟啉(TPP)相同的电子吸收光谱与荧光发射光谱. 随着侧链上PP键合量的增大, 大分子PP-P(GMA-co-MMA)的Soret与Q吸收带的峰强均不断增强, 而Q发射带的强度则呈现先增大后有所减弱的规律, 这是由大分子内的能量转移所致.     

New Route to Vicasol,a Water-Soluble Form of Vitamin K3

A procedure was suggested for preparing vicasol in an approximately 85% yield in a two-phase system consisting of concentrated (5-6 M) aqueous solution of NaHSO₃ and a solution of 2-methyl-1,4-naphthoquinone in an incombustible organic solvent (e.g., chloroform or trichloroethylene).     

谷氨酸赖氨酸无规共聚物和谷氨酸精氨酸无规共聚物的合成及性能

采用氨基酸-N-内羧酸酐(氨基酸-NCA)开环聚合的方法, 并通过改变开环聚合时谷氨酸-N-内羧酸酐(BLG-NCA)与赖氨酸-N-内羧酸酐[Lys(Z)-NCA]的投料比以及BLG-NCA与鸟氨酸-N-内羧酸酐[Orn(Z)-NCA]的投料比, 经过脱保护和胍基化反应得到一系列谷氨酸赖氨酸无规共聚物Poly(E,K)和谷氨酸精氨酸无规共聚物Poly(E,R). 核磁共振氢谱(¹H NMR)和核磁共振定量碳谱(¹³C NMR)分析结果表明, 合成了无规共聚物Poly(E,K)和Poly(E,R), 且二者中不同氨基酸的摩尔比接近开环聚合时相应NCA的投料比. 动态光散射(DLS)测定结果表明, 无规共聚物在pH=7.4的正常生理环境中形成的胶束粒径均一、 尺寸小于200 nm. Zeta电位表征结果表明, 无规共聚物Poly(E,K)和Poly(E,R)的Zeta电位值随着溶液pH值的变化而变化, 具有pH敏感性.     

(-)-(1R,2S)-肉豆蔻木脂素的不对称合成

报道了天然产物(-)-肉豆蔻木脂素的全合成. 以香草醛为起始原料, 经Wittig反应、LiAlH₄还原和Sharplass不对称双羟化等反应构建了苏式结构的中间体; 以焦性没食子酸为原料, 经Claisen重排反应制得另一种苯丙素片段; 2个中间体通过Mitsunobu反应, 缩合并使构型翻转, 得到赤式-(-)-肉豆蔻木脂素. 为赤式8-O-4′新木脂素的合成提供了一种新方法.     

多磺化侧链型聚芳醚的合成及性能

本文通过对聚合物的结构设计,采用亲和取代的途径制备了含有甲氧基侧链的聚芳醚聚合物,然后去醚化得到了侧链含有羟基的聚芳醚材料,最后通过接枝的方法将磺酸基团引入聚合物成功的制备出多磺化侧链型聚芳醚质子交换膜材料。此类材料表现出好的热化学稳定性, 80 oC时的质子传导率可达到0.192 S/cm,超过了Nafion 117 薄膜的传导率.同时此类材料表现出低的尺寸稳定性。因此此类材料很有希望在质子交换膜领域得到应用     

手性1,2-二苯基乙二醇衍生物的合成及催化性能研究

合成了3种含吡啶环的手性1,2-二苯基乙二醇衍生物,并通过1HNMR、13CNMR、LCMS和IR的结构表征。将3种衍生物用于催化苯甲醛与二乙基锌的不对称加成反应的结果表明,其中的(1R,2R)-2-(2-吡啶甲氧基)-1,2-二苯基乙醇具有较好的催化活性,获得了78%的收率和56%e.e.。     

Bengazoles C-G from the Sponge Jaspis sp. Synthesis of the Side Chain and Determination of Absolute Configuration

Five new antifungal bengazoles (C-G) were isolated and fully characterized from a marine sponge of the genus Jaspis sp. Bengazoles C-G, together with the known bengazoles A and B, comprise a homologous series of n, iso, and anteiso fatty acid esters (C(13)-C(16)) of the same heterocyclic bis(oxazolyl)methanol parent. The complete relative and absolute configurations of the bengazoles were determined by application of the modified Mosher method and interpretation of exciton coupling in the CD spectra of the tetra-p-bromobenzoate derivatives of bengazole A and that of a model tetrol synthesized in seven steps from L-fucose.     

Synthesis,cytotoxicity, and interaction with DNA of platinum(II) complexes of (1R,2R)-N1-2-amyl-1,2-diaminocyclohexane

(1R,2R)-N¹-2-amyl-1,2-diaminocyclohexane, which has an amyl substituent as compared with 1,2-diaminocyclohexane, was used as the carrier group to construct three platinum(II) complexes. MTT assay revealed that the complexes showed decent cytotoxicity against all of the four tested tumor cell lines with the IC₅₀ values ranging from 1.08 to 253.36 μM. Particularly, the IC₅₀ values of 2 against A549 and HCT-116 reached 3.32 and 1.08 μM, respectively, which were much lower than those of cisplatin and oxaliplatin. Flow cytometry demonstrated that 2 inhibited HepG2 cells proliferation and caused cytotoxicity by inducing apoptosis and arresting cells in the G2 phase. Furthermore, agarose gel electrophoresis showed that 2 had the ability to interact with DNA in a manner different from cisplatin and oxaliplatin, indicating the carrier ligand with an alkyl moiety had an influence on the action mode of the complex.     

Synthesis of indole-containing analogs of (1R)-cis-chrysanthemic acid and N-substituted (1R)-cis-chrysanthemylamines

The indolic analogs of (1R)-cis-chrysanthemic acid and N-substituted (1R)-cis-chrysanthemylamines were obtained by Fischer indole synthesis using the acetonylcyclopropanes derived from (+)-car-3-ene. The cyano- and N-cyanamido groups in the starting carbonyl compounds did not hinder indolization. The reduction of the nitrile group bound to the asymmetrical atom of the cyclopropane ring by LiAlH₄ in ether can be accompanied by epimerization or racemization.