软珊瑚群柱虫中新的二萜化合物-群柱内酯萜的分离和结构测定

A new bicyclo[9.3.0]tetradecane diterpenoid (dolabellane) lactone named clavulactone (I) was isolated from soft coral qunzhuchong (Clavularia sp.). Its partial structure was determine by spectral anal. and hydrogenation reaction. X-ray anal. established the complete mol. structure of I and the relative configuration. Finally, according to the neg. Cotton effect of n畃* and CD band of a,b-unsatd. d-lactone at 252 nm, the absolute configuration was assigned.     

海洋软珊瑚群柱虫化学成分的分离与鉴定

海洋软珊瑚中已发现了许多具有强烈生理活性和化学结构特殊的化合物.本文报道软珊瑚群柱虫(clavularia sp~≠)的化学成分研究.采得之样品,一部分浸泡于95％乙醇中(以下称湿品),一部分晒干(以下称干品).各按实验部分所述的方法提取分离,可得到化合物1和6及一些酯类混合物,兹分述于下:(一)化合物1为无色透明液体,分子式 C_(20)H_(32),[α]_D~(12) 20.4°(c0.225,CHCl_3).UV210nm 以上无吸收,表明无共轭双键.v_(max):3050,1640,885cm~(-1);δ_H:5.19(1H,t,J=7Hz),5.07(1H,t,J=7Hz),4.99(1H,t,J=7Hz)ppm,分别为三个三取代双键的氢.4.72(1H,s),4.66(1H,s)ppm为 C(?)CH_2的两个氢.1.66(3H,s),1.59(3H,s),1.57(6H,s)ppm 为四个连接在双键上的甲基.1以 PtO_2-H_2常压氢化,吸收四摩尔当最的 H_2生成饱和化合物2,分子式 C_(20)H_(40),[α]_D~(12) 0.6°(c1.71,CHOl_3),含有一个碳环.1经臭氧化、铬酸     

柳珊瑚酸的分子结构和绝对构型

本文首次应用X射线单晶衍射法证实了一种新的倍半萜骨架,并测定了柳珊瑚酸的分子结构和绝对构型。柳珊瑚酸的晶体属于正交晶系,空间群:D_2~ -P2_12_12_1,晶胞参数:a=16.135,b=13.189,c=12.901,α=β=γ=90°。单胞中分子数为8,不对称单位含两个分子,用直接法导出全部非氢原子位置,经最小二乘法修正后,最终偏离因子R=0.056。文中还对柳珊瑚酸分子的结构进行了讨论,并对核磁共振溶剂效应有关理论进行了较深入的讨论,初步探讨了分子结构与其毒性之间的关系。     

奇蒿内酯晶体结构及绝对构型的测定

奇蒿内酯是从中草药刘寄奴提取的新化合物.用X射线单晶衍射方法确定了其三维结构,此单晶属单斜晶系,空间群:P21,晶胞参数:a=12.184(7),b=7.480(14),c=10.424(9)A,β=-104.44(6);Z=2.用直接法RANTAN)得分子初结构模型,采用块对角矩阵最小二乘法对此初结构进行修正,最后一致性因子R=0.085.并利用氧原子反常散射确定了分子的绝对构型。     

绝对构型的测定

几乎所有具有生理活性的天然产物在其分子中都是含有不对称碳原子的。一般说来,这些具有生理活性的天然产物,它们的结构一经解决以后,人们就可从事于这些化合物的合成,不过要在这些化合物的绝对构型确定以后,才能真正地合成出和天然产物完全相同的物质。如果合成物与天然物的绝对构型不同,则合成物往往会失去或减低应有的生理活性。一个具有旋光活性的天然产物,如果它的绝对构型尚未解决,就不能说它的结构已经完全确定。本篇所述有旋光活性的     

华佗豆碱甲氢溴酸盐晶体结构和绝对构型

(+)华佗豆碱甲已经从中草药华佗豆(Ipomoea hardwickii Hemsl.)中分离到。它的氢溴酸盐晶体属正交晶系,空间群P 2_12_12_1。晶胞参数:a=10.078(2)(?),b=17.303(3)(?),c=9.022(1)(?),Z=4。用四圆衍射仪收集强度数据,得到独立可观察点共1248个。用重原子法确定结构,经块对角矩阵最小二乘法修正结构参数,最终的偏离因子R为0.051。根据Br的反常散射确定华佗豆碱甲阳离子的绝对构型为S型,命名为S-1,2,3,5,8,9-六氢-6-对苯酚基-7-甲基吲嗪。晶胞内四个分子两两一对,通过氢键NH…Br…HOH…OHAr形成在晶体内沿b方向无限伸展的分子链。     

光活性酮咯酸衍生物的拆分及绝对构型的测定

酮咯酸与L-脯氨酸苄酯在缩合剂作用下形成酰胺，用柱层析分离了一对非对映异构体并进行了表征.用单晶X衍射测定了酮咯酸脯氨酸苄酯酰胺一个异构体的晶体结构，并用内参法确定了其绝对构型.晶体属正交晶系，空间群P212121，晶胞参数a=0.896 45（1）nm，b=1.271 23（2）nm，c=2.076 21（4）nm， V=2.366 04（6）nm3，Z=4，最终偏离因子R1=0.046 4.     

南极柳珊瑚代谢物3-Furanoeudesmene的立体选择性全合成及绝对构型确定

报道了对桉烷倍半萜天然产物3-furanoeudesmene的首次全合成.从商品化手性试剂(+)-马鞭烯酮出发,以关环烯烃复分解反应及三步法呋喃环构建为关键步骤,总共八步反应实现了目标分子的立体选择性合成.通过比对合成的目标分子的旋光值与天然产物的旋光值,确定出天然产物的绝对构型.     

手性尼莫地平绝对构型的确定和关联

概述了手性1, 4-二氢吡啶类（1, 4-DHPs）钙拮抗剂的立体化学结构及其药效与绝对构型的关系,以及尼莫地平（nimodipine）的多晶型现象。采用单晶X射线衍射与固体和溶液圆二色（ECD）光谱直接关联的方法,对自发拆分获得的一对尼莫地平外消旋聚集体进行了绝对构型确定,首次获得了手性1, 4-DHPs类化合物的固体和溶液ECD光谱图。本方法对确认有机小分子的绝对构型,以及关联系列手性1, 4-DHP衍生物的绝对构型具有重要参考价值,同时提供了有别于常规非手性方法鉴别优势手性药物晶型的有效手段。     

Scobidiynediol的合成及绝对构型

本文报道了以光学活性乳酸为手性元对目标化合物的所有可能的四个异构体所进行的合成。根据合成样品与天然产物的核磁及旋光数据比较，标题化合物的相对及绝对构型都得以完全确立，其完整结构定为(2S,3S)-4,6-庚二炔-2,3-二醇。     

CRYSTAL AND MOLECULAR STRUCTURE OF A NEW DITERPENE DERIVATIVE FROM SOFT CORAL

<正> Introduction. The crystal and molecular structure of an acetylated derivative of a new diterpene from soft coral (Clavularia sp.) has been determined by X-ray crystal structure analysis.     

CRYSTAL AND MOLECULAR STRUCTURE OF A NEW QUINOLINE DERIVATIVE PROM THE CHINESE SOFT CORALS

<正> INTRODUCTION. 7-hydroxy-8-methoxy-4(1H) quinolone(Q), C_(10)H_9NO_3, is a new compound isolated from the Chinese soft coral, Sinularia Polydacryla. This compound has a marked effect on increasing the circulation of blood in a white mouse brain system or heart system and on alleviating the hypoxia suffeting. It could mitigate the arrhythmia caused by aconitine. Up to now, only a few structures of quinoline derivatives have been determinated by X-ray diffraction.     

STRUCTURAL STUDY OF GORGOSTEROL FROM SOFT CORAL

<正> The title compound was isolated from the Lobophytum Chevalieri soft coral of the South China Sea and identified by X-ray diffraction to be (22R,23R,24R)-22,23-methylene-23,24-dimetylcholest-5-en- 3β - ol. The crystal is monoclinic space group P21, a=9. 666(3) ,b=7. 503(2),c= 37. 108(4) A ,β=91. 30(2)°,V = 2690. 7 A3,Z = 4,and Dc= 1. 076gcm-3. The structure was solved by direct methods and refined to R=0. 084 for 4147 observed MoKa reflections. There are two independent molecules in each asymmetric unit which have the same orientation. The intermolecular hydrogen bonds between water molecule and hydroxy as well as between hydroxy groups link the molecules into infinite double layers which are parallel with the (001) plane.     

R、S-三[N-(邻-氧α-萘亚甲基)-α-苯乙胺]合钴的合成、晶体结构及分子绝对构型

合成了R,S一三[N-(邻-氧α-萘亚甲基)-α-苯乙胺]合钴。x射线单晶衍射衍射测定了晶体结构及分子的绝对构型。晶体属正交晶系,D_2~4-P2_12_12_1空间群,晶胞参数:α=12.587(3),b=14.166(3),c=25.652(14)(?),v=4574.2(?)~3,z=4。用重原子法及差值Fourier合成解出结构,最后的R值为0.074。利用Co~( )对CuKa反常散射测定了分子的绝对构型。Co~( )为六配位,d~2sp~3杂化近正八面体构型。     

钩吻素子的晶体及分子结构

钩吻素子(Koumine)是钧吻生物碱(Kou-Wen Alkaloids)中的单体之一,其分子式为C_(20)H_(22)N_2O。它的晶体属单斜晶系,空间群为P2_1,晶胞参数为:α=8.422(0),b=13.209(1),c=7.881(1)A,β=108.201(9)°,V=834.995A~3;Z=2;D_c=1.29g/cm~3。 本文报道的钩吻素子是1981年Khuong-Huu F等人报导的钩吻素子的一个立体异构体,它们是钩吻素子的两个非对映体旋光异构体。     

CRYSTAL AND MOLECULAR STRUCTURE OF RABDOSERRIN-B

<正> INTRODUCTION. Four compounds of diterpenoids that have in vitro cytotoxity against cultured Hala cells have been obtained by means of extraction from Rabdosia serra(Maxim) Hara, a chinese medical herb. They are Rabdoserrin A (Rab A), Rabdoserrin B (Rab B), Excisanin A and Kamebakaurin (Kam). Among them, Rab A and Rab B are new compounds. Crystal structures of Rab A and Kam have been solved. The chemical structure of Rab B has been     

CRYSTAL AND MOLECULAR STRUCTURE OF STEMOTININE

<正> C18H25NO5, Mr = 335.40, tetragonal, P41212, a = 15.578(4), c =14.723(3) A, V =3573(2) A3, Z = 8, D = 1.247 g cm-3, MoKα,λ= 0.71069 A, μ = 0.;85 cm-1, T = 293K, final R .= 0.100 and RW (on F2) = 0.080 for 1095 observed data [|FO| > 2σ(|FO|)]. The structure confirms the spectrbscopic assignment of a pentacyclic skeleton containing two α-methyl-γ-lactone rings, one ether and one tertiary amine.