N-二异丙基磷酰基-N-[2-(3',4'-亚甲二氧苯基)]乙基甘氨酸的单昌结构的研究

三类杉酯碱是一种具有显著抗肿瘤活性的化合物, 在以磷脱基, 磺酰基乙酰基作N-苯乙基甘氨酸上氨基的保护基进行分子内酰化的Friede-Crafts反应, 合成三尖杉酯碱母核-(N-7,8-亚甲二氧苯并-3-氮杂环庚酮-1)时所得结果相差甚远, 特别是用磷酰基保护甘氨酸衍生物可以避免脱羰, 顺利地进行内酰化反应, 对合成三尖杉酯碱的母核有重要的意义。为了阐明磷酰基对氨基酸中氮原子上的弧对电子的稳定作用, 我们测定了N-二异丙基磷酰基-N-[2-(3',4'-亚甲二氧苯基)]乙基甘氨酸的单晶结构。     

N-二异丙基磷酰基-N-[2-(3′,4′-亚甲二氧苯基)]乙基甘氨酸的单晶结构的研究

三尖杉酯碱是一种具有显著抗肿瘤活性的化合物。在以磷酰基、磺酰基、乙酰基作N-苯乙基甘氨酸上氨基的保护基进行分子内酰化的Friede-Crafts反应,合成三尖杉酯碱母核-(N-7,8-亚甲二氧苯并-3-氮杂环庚酮-1)时所得结果相差甚远。特别是用磷酰基保护甘氮酸衍生物可以避免脱羰,顺利地进行内酰化反应,对合成三尖杉酯碱的母核有重要的意义。为了阐明磷酰基对氨基酸中氮原子上的孤对电子的稳定作用,我们测定了N-二异丙基磷酰基-N-[2-(3’,4’-亚甲二氧苯基)]乙基甘氨酸的单晶结构。     

N-苯乙基甘氨酸和β苯乙胺衍生物的X射线光电子能谱(XPS)研究

本文研究了十六种N-苯乙基甘氨酸和β苯乙胺衍生物的X射线光电子能谱(XPS).着重探讨了这些分子中不同N原子环境对其N_(?)结合能的影响,同时,用Pauling离子特性规则计算了这些分子中N原子上的电荷密度,实验N_(?)和Pauling计算原子电荷很好符合,从而对用磷酰基保护N-苯乙基甘氨酸上的氨基,作分子内的傅氏反应,合成三尖杉酯碱的母核——苯并氮杂环庚酮避免脱羰,保护基易脱去等反应机理提供实验与半经验的理论根据。     

二烷基磷酰基作为氨基保护基的研究

合成了N-烷基-N-磷酰基甘氨酸衍生物。在Lewis酸催化下成功地进行Freidel-Crafts反应,得到分子内环化产物苯并-3-氮杂环庚酮-[1]衍生物,并在温和条件下脱保护基。     

有机磷化合物的研究 XV.合成α-氨基取代苄基膦酸的新方法

在三氟化硼催化下,二乙基磷酰胺、取代苯甲醛和亚磷酸三苯酯反应生成α-二乙基磷酰氨基取代苄基膦酸二苯酯(1),再经溴化氢的乙酸溶液处理,能选择性除去氨基上的保护基,得到相应的α-氨基取代苄基膦酸二苯酯溴化氢盐(2).2可视可合成膦酸肽的中间体,继续酸性水解可得α-氨基取代苄基膦酸(3).这个新的合成方法具有操作简便和产物纯度及得率均较高的特点。     

有机磷化合物的研究 ⅩⅤ.合成α-氨基取代苄基膦酸的新方法

在三氟化硼催化下,二乙基磷酰胺、取代苯甲醛和亚磷酸三苯酯反应生成α-二乙基磷酰氨基取代苄基膦酸二苯酯(1),再经溴化氢的乙酸溶液处理,能选择性除去氨基上的保护基,得到相应的α-氨基取代苄基膦酸二苯酯溴化氢盐(2).2可视为合成膦酸肽的中间体.继续酸性水解可得α-氨基取代苄基膦酸(3).这个新的合成方法具有操作简便和产物纯度及得率均较高的特点.     

在Lewis酸催化下N-苯乙基甘氨酸衍生物的分子内环化反应研究及苯并-3-氮杂环庚酮-1衍生物的合成

本文报导了不同N-苯乙基甘氨酸衍生物在Lewis酸催化下的分子内环化反应的若干规律,以及苯并-3-氮杂环庚酮-1衍生物的合成.     

苯并-3-氮杂环庚酮-1衍生物及N-二烷氧基磷酰基-N-取代苯乙基甘氨酸衍生物的电子电离质谱

应用高分辨质谱,准确质量测定和亚稳态离子的测定结果,对五个苯并-3-氮杂环庚酮-1衍生物及六个N-二烷氧基磷酰基-N-取代苯乙基甘氨酸衍生物的断键机理进行了研究。在EIMS条件下,前者的分子离子峰比后者强;N原子上发生电离的几率最大;除磷酰基上取代基为甲基的两个化合物外,其他九个化合物均含有m/z110(CH_5O_3NP)碎片离子;由于受磷酰基的影响,这些化合物都发生C—N键特征断裂。     

氯化两面针碱合成方法的改进

以6-溴-3,4-二甲氧基苯甲醛和6,7-亚甲二氧基-1-萘胺为起始原料,经还原胺化、分子内Heck偶联、氧化芳构化、甲基化以及离子交换等五步反应,完成了氯化两面针碱的合成,并对关键步骤分子内Heck偶联反应条件进行了探索,结果表明该偶联反应在醋酸钯、三(邻甲苯基)膦和N,N'-二甲基甲酰胺体系中反应效果最佳,收率显著提高.该优化条件为结构类似苯并[c]菲啶类生物碱母核结构的构建提供了借鉴.     

比阿陪南双环母核的合成

从水杨酰胺出发,通过环合、酰化、Reformatsky反应、取代和Dieckmann环化反应,合成了碳青霉烯类抗生素比阿陪南的关键中间体--比阿陪南双环母核{(4R,5R,6S)-6-[(R)-1-叔丁基二甲基硅氧乙基]-3-二苯基磷酰氧基4-甲基-7-氧代-1-氮杂双环-[3.2.0]庚-2-烯-2-羧酸烯丙酯},总收率43.1%,其结构经1H NMR确证.     

Polynuclear bismuth-oxo clusters: insight into the formation process of a metal oxide

The reaction of the bismuth silanolates [Bi(OSiR2R')3] (R = R' = Me, Et, iPr; R = Me, R' = tBu) with water has been studied. Partial hydrolysis gave polynuclear bismuth-oxo clusters whereas amorphous bismuth-oxo(hydroxy) silanolates were obtained when an excess of water was used in the hydrolysis reaction. The metathesis reaction of BiCl3 with NaOSiMe3 provided mixtures of heterobimetallic silanolates. The molecular structures of [Bi18Na4O20(OSiMe3)18] (2), [Bi33NaO38(OSiMe3)24].3 C7H8 (3.3 C7H8), [Bi50Na2O64(OH)2(OSiMe3)22].2 C7H8.2H2O (4.2 C7H8.2 H2O), [Bi4O2(OSiEt3)8] (5), [Bi9O7(OSiMe3)13].0.5 C7H8 (6. 0.5C7H8), [Bi18O18(OSiMe3)18)].2C7H8 (7. 2C7H8) and [Bi20O18(OSiMe3)24].3C7H8 (8.3C7H8) are presented and compared with the solid-state structures of [Bi22O26(OSiMe2tBu)14] (9) and beta-Bi2O3. Compound 2 crystallises in the triclinic space group P1 with the lattice constants a = 17.0337(9), b = 19.5750(14), c = 26.6799(16) A, alpha = 72.691(4), beta = 73.113(4) and gamma = 70.985(4) degrees ; compound 3.3C7H8 crystallises in the monoclinic space group P2(1)/n with the lattice constants a = 20.488(4), b = 22.539(5), c = 26.154(5) A and beta = 100.79(3) degrees ; compound 4.2C7H82 H2O crystallises in the monoclinic space group P2(1)/n with the lattice constants a = 20.0518(12), b = 24.1010(15), c = 27.4976(14) A and beta = 103.973(3) degrees ; compound 5 crystallises in the monoclinic space group P2(1)/c with the lattice constants a = 25.256(5), b = 15.372(3), c = 21.306(4) A and beta = 113.96(3) degrees ; compound 6.0.5C7H8 crystallises in the triclinic space group P1 with the lattice constants a = 15.1916(9), b = 15.2439(13), c = 22.487(5) A, alpha = 79.686(3), beta = 74.540(5) and gamma = 66.020(4) degrees ; compound 7.2C7H8 crystallises in the triclinic space group P1 with the lattice constants a = 14.8295(12), b = 16.1523(13), c = 18.4166(17) A, alpha = 75.960(4), beta = 79.112(4) and gamma = 63.789(4) degrees ; and compound 8.3C7H8 crystallises in the triclinic space group P1 with the lattice constants a = 17.2915(14), b = 18.383(2), c = 18.4014(18) A, alpha = 95.120(5), beta = 115.995(5) and gamma = 106.813(5) degrees . The molecular structures of the bismuth-rich compounds are related to the CaF2-type structure. Formally, the hexanuclear [Bi6O8]2+ fragment might be described as the central building unit, which is composed of bismuth atoms placed at the vertices of an octahedron and oxygen atoms capping the trigonal faces. Depending on the reaction conditions and the identity of R, the thermal decomposition of the hydrolysis products [Bi(n)O(l)(OH)(m-)(OSiR3)(3n-(2l-m))] gives alpha-Bi2O3, beta-Bi2O3, Bi12SiO20 or Bi4Si3O12.     

聚苯醚的结构效应:1,4-二苯氧基苯和1,4-双(4-甲氧基苯氧基)苯的晶体结构

用单晶X射线衍射分析方法测得1,4-二苯氧基苯(Ⅰ)和1,4-双(4-甲氧基苯氧基)苯(Ⅱ)的晶体结构。它们的晶胞参数分别为:(Ⅰ)α=5.876(2),b=7.832(2),c=1.5455(6)nm, β=95.33(3)°;空间群为P2_1/c,Z=2。(Ⅱ)α=6.017(1),b=7.577(1),c=3.6404(5)nm;空间群为Pcab,Z=4.(Ⅰ),(Ⅱ)的分子构象、键长和键角数据表明氧桥两边的苯环的共轭极化效应不能贯通,而苯氧基只是分子中的一个独立片断。从而也阐明了此类聚苯醚体系的电子吸收光谱的同系直线斜率小的原因。     

Preparation and Crystal Structure of 15α-Hydroxyl-oleanolic Acid

The compound 15α-hydroxyl-oleanolic acid was biotransformed from oleanolic acid with Colletotrichum lini AS3.4486,and its structure was characterized by 1H NMR,13C NMR,HR-ESI-MS and single-crystal X-ray diffraction.The crystal of the title compound belongs to monoclinic,space group R3 with a=34.255(5),b=34.255(5),c=6.8671(14),β=90°,Z=9,V=6978(2)3,Mr=490.70,Dc=1.051 mg/m3,μ=0.069 mm-1,F(000)=2430,R=0.0375 and wR=0.0808.The title compound is stacked into a three-dimensional network through hydrogen bonds.     

Crystal Structure and Biological Activities of N-（5-（4-Chloro-2-（trifluoromethyl）phenyl）furan-2-carbonyl）-N＇-（4,6,dimethylpyrimidin-2-yl）thiourea

The new title compound N-（5-（4-chloro-2-（trifluoromethyl）phenyl）furan-2-carbon-yl）- N＇-（4,6-dimethylpyrimidin-2-yl）thiourea （C19H14C1F3N4O2S） has been synthesized, and its crystal structure and biological behaviors were studied. The title compound crystallizes in the monoclinic system, space group P21/c with a = 7.932（5）, b = 33.46（2）, c = 7.556（5） A, β = 98.058（9）°, V = 1986（2） A^3 Mr = 454.85, Z = 4, Dc = 1.521 g/cm^3, μ = 0.349 mm^-1 and F（000） = 928. The structure was solved by direct methods and refined to R = 0.0724 and wR= 0.1429 for 3494 observed reflections （I 〉 2σ（I））. Intermolecular hydrogen bonds along the b axis together with the continuous π-π interactions construct the three-dimensional architecture of the title compound. The preliminary biological tests show definite herbicidalactivity for the title compound.     

Crystal Structure and Biological Activities of N-(5-(4-Chloro-2-(trifluoromethyl)phenyl)furan-2- carbonyl)-N'-(4,6-dimethylpyrimidin-2-yl)thiourea

The new title compound N-(5-(4-chloro-2-(trifluoromethyl)phenyl)furan-2-carbon-yl)- N?-(4,6-dimethylpyrimidin-2-yl)thiourea (C19H14ClF3N4O2S) has been synthesized, and its crystal structure and biological behaviors were studied. The title compound crystallizes in the monoclinic system, space group P21/c with a = 7.932(5), b = 33.46(2), c = 7.556(5) , β = 98.058(9)°, V = 1986(2) 3, Mr = 454.85, Z = 4, Dc = 1.521 g/cm3, μ = 0.349 mm–1 and F(000) = 928. The structure was solved by direct methods and refined to R = 0.0724 and wR = 0.1429 for 3494 observed reflections (I > 2σ(I)). Intermolecular hydrogen bonds along the b axis together with the continuous π-π interactions construct the three-dimensional architecture of the title compound. The preliminary biological tests show definite herbicidal activity for the title compound.     

Crystal Structures and Antimicrobial Activity of Two Phosphorus Compounds

1 INTRODUCTION Both phosphorus and sulfur are the non-metal ele- ments rich in biological bodies. Phosphorus is the core element of nucleic acid, which is the principal ingredient of lives; and sulfur is the important ele- ment in the skeleton of nitrogen-fixing enzyme’s activity center[1]. It has been found that LR, 4-bis(4- methoxyphenyl)-1,3,2,4-dithiadiphosphe-tane-2,4- disulfide (Scheme 1), is an effective thiation reagent for ketones, carboxamides, esters, S-substituted thio- est…     

钼簇合物的簇解反应和两个多钼酸盐化合物的晶体结构

含μ-Cl桥的三核钼簇阴离子[Mo~3(μ~3-O)(μ-Cl)~3(μ-OAc)~3Cl~3]^-在Fe^3^+作用下发生簇解反应, 形成钼同多酸盐[FeCl(DMF)~5][Mo~6O~1~9]。在合成[Mo~3(μ~3-S)(μ-S~2)~3(dtp)~3Cl]簇合物的反应中如果有CuI存在, 则形成钼磷杂多酸盐(Et~4N)~4[PMo~1~2O~4~0](DMF)~2。本文报道这两个多钼酸盐化合物的晶体结构, 并讨论有关的簇解反应。     

Synthesis and Crystal Structure of Ethyl 5-Amino-1-[(5''-methyl-1''-t-butyl-4''-pyrazolyl)carbonyl]-3- methylthio-1H-pyrazole-4-carboxylate

The title compound, ethyl 5-amino-1-[(5'-methyl-1'-t-butyl-4'-pyrazolyl)carbonyl] -3-methylthio-1H-pyrazole-4-carboxylate 5, has been synthesized by the treatment of 4 with ethyl 2-cyano-3,3-dimethylthioacrylate, and its crystal structure was determined by X-ray diffraction method. The crystal belongs to monoclinic, space group P21/c with a = 12.194(4), b = 12.909(4), c = 11.607(4) (A), β= 90.183(5)°, V = 1827.2(10) (A)3, Mr = 365.45, Z = 4, Dc = 1.328 g/cm3, μ = 0.203 mm-1, F(000) = 776, R = 0.0586 and wR = 0.1558. Preliminary bioassays indicated that the title compound shows fungicidal and plant growth regulation activities.     

Synthesis and crystal structure of Ae(2)LiInGe(2) (Ae = Ca, Sr): new Zintl phases with a layered silicate-like network

Two new Zintl phases Ae(2)LiInGe(2) (Ae = Ca 1; Sr 2) were obtained from stoichiometric reactions of the pure elements in sealed Nb tubing at 1000-1050 degrees C. The isomorphous polar intermetallic phases crystallize in the orthorhombic space group Pnma, with cell constants of a = 7.2512(7), b = 4.4380(5), and c = 16.902(1) A for compound 1, and a = 7.5033(8), b = 4.6194(5), and c = 17.473(2) A for compound 2. The crystal structure can be derived from the vertex-sharing of InGe(4/2) tetrahedral units that form "corrugated" sheets normal to the crystallographic c-axis. Calcium and lithium atoms act as "spacers" that effectively separate the anionic [InGe(2)](5-) layers. The layered anionic substructure is similar to those exhibited by layered metal oxides, sulfides, and silicates. The connectivity of the tetrahedral building unit, [InGe(4/2)](5-), is analogous and isoelectronic to the silicate [SiO(4/2)] unit.     

Preparation and Crystal Structure of Sarcosine 5-Nitrosalicylic Acid Organic Adduct

1 INTRODUCTION Nonlinear optical second harmonic generation(SHG) material is one important embranchment ofnonlinear optical materials. The main advantages oforganic nonlinear optical materials over the inor-ganic ones are as follows: bigger nonline…