硝酸镧联吡啶冠醚混配合物La（NO3）3（bipy）（H2O）2（B—15—C—5）的合成及晶体结构

本文报道了La(NO3)3(bipy)(2H2O)(B-15-C-5),(Mr=785.46)的合成和晶体结构。晶体属单斜晶系，空间群为P21／n，晶胞参数：a=11.951(6),b=18.181(7),c=14.754(5)A,B=96.19(3),V=3187,0A3,Z=4,Dc=1.637g/cm3，晶体结构由直接法和Fourier合成解出，使用对角块矩阵和全矩阵最小二乘法对原子参数进行修正，最后偏离因子R＝0．035（5261个1＞3σ（I）射衍，单晶结构分析表明，在该配合物中，直接参与位的是联吡啶上的两上氮原子，三个NO3中的六个氧原子以及两个水分子中的氧原子，La^3 的配位数为10，B－15－C－5是通过氢键与2O分子 相连的。     

Metal Ion Enhanced Phosphorescence of 2,3—Naphtho—10—aza—15—crown—5：A Possible Molecular Photonic Operator

A novel crown ether,2,3-naphtho-10-aza-15-crown-5(NAC) was synthesized.This compound does not show strong fluorescence and phosphorescence due to photoinduced intramolecular electron transfer from the nitrogen lone pair of electrons to the singlet excited state of the naphthalene chromophore.Complexation with heavy-metal ions results in the quenching of the fluorescence and enhancement of the phosphorescence significantly.These observations were interpreted in terms of the binding interactions,between the nitrogen lone pair electrons and the metal cation,which prevent photoinduced intramolecular electron transfer,and the heavy-atom effects which induce quenching of the fluorescence and enhancement of the phosphorescence.These azacrown and heavy-metalbased systems could be useful as potential chemical sensors and molecular photonic devices.     

ZnO—Ga2O3／HZSM—5分子筛催化剂对C3—4烷烃芳构化反应的催化作用

用浸渍法将Ga、Zn以氧化物的形式负载于HZSM－5上,研究了其对C3－4烷烃芳构化的催化活性。结果表明,分别加入2％Ga和2％Zn后,当温度为520℃、空速为0．76h^-1时,具有较高的催化活性和芳烃选择性;反应进行100h后,催化活性无明显降低,显示出对C3－4烷烃芳构化良好的稳定性。用TPD和正丁胺Hammett酸性滴定法,测定了催化剂的表面酸性,发现加入Ga、Zn等组分后,催化剂的总酸量变化不大,而酸强度却有所增加;加入Zn组分后,催化剂的孔径变小,对二甲苯选择性增加。     

SYNTHESIS OF LINEAR POLYSILOXANE WITH PENDANT BENZO—15—C—5 MOIETIES AND ITS TRANPORT PROPERTIES IN BULK LIQUID MEMBRANE SYSTEM

Linear polysiloxanes with pendant benzo-15-crown-5 moieties have been synthesized from 3′-or 4′-allylbenzo-15-C-5 via hydrosilylation of methyldichlorosilane,followed by polycondensation with silanol-terminated polydimethylsiloxane.It was found that the polysiloxanes could be used as carriers in bulk liquid membrane to transport ions.Factors influencing transport rate have been investigated.     

希土硝酸盐冠醚Yb(NO3)3·3H2O/B15C5配合物的研究

用改进的半微量相平衡方法研究了Yb(NO_3)_3·3H_2O-Bl5C5-CH_3COCH_3三元体系在18℃时的溶解度,测定了各液相的折光率。结果指出只有一种化学计量的配合物(Yb(NO_3)_3·B15C5·3H_2O·2CH_3COCH_3)生成。分离、洗涤、浓硫酸干燥器中恒重后,经化学分析,确定配合物的组成为:Yb(NO_3)_3·B15C5·3H_2O·065CH_3COCH_3。用红外光谱、DTG、TG及DSC等对配合物进行了研究。测得配合物的脱溶剂与热分解的热焓值(△H)。按照Kissinger法,求得配合物热分解过程的表现活化能。     

三元体系Y（ClO_4）_3·3H_2O—B15C5—CH_3OH（25℃）的半

采用半微量相平衡方法研究了三元体系Ｙ（ＣｌＯ４）３·３Ｈ２Ｏ－Ｂ１５Ｃ５—ＣＨ３ＯＨ在２５℃的溶解度，测定了各饱和溶液的折光率．该体系在２５℃生成三种化学计量的配合物，其组成分别为：４Ｙ（ＣｌＯ４）３·３Ｂ１５Ｃ５·１２Ｈ２Ｏ·１２ＣＨ３ＯＨ（Ⅰ）、Ｙ（ＣｌＯ４）３·Ｂ１５Ｃ５·３Ｈ２Ｏ·１．５ＣＨ３ＯＨ（Ⅱ）与Ｙ（ＣｌＯ４）３·２Ｂ１５Ｃ５·３Ｈ２Ｏ·ＣＨ３ＯＨ（Ⅲ），其中配合物（Ⅰ）和（Ⅱ）是溶解不一致化合物．在甲醇溶剂中，分离制备了配合物（Ⅲ），在６９—７２℃下干燥得到配合物Ｙ（ＣｌＯ４）３·２Ｂ１５Ｃ５·３Ｈ２Ｏ．利用ＩＲ光谱、电导测量及Ｘ－射线衍射分析对配合物进行了表征．     

Crystal Structure of 5—（l—Menthyloxy）—3—chloro—4— Pyrrolidinyl—2（5H0—f

The molecular structure of the title compound 5-(l-menthyloxy)-3-chloro-4-pyrrolidinyl-2(5H)-furanone, C18H28ClNO3(Ⅰ), has been determined by X-ray diffraction at 296(1)K. The crystal is monoclinic with space group P21, a=9.457(3), b=10.413(3), c=9.525(2), β=95.19(2)°, V=934(1) 3, Z=2, Mr=341.88, Dx=1.22 g/cm3, μ=2.15 cm-1, F(000)=368. The final R factor is 0.059, and Rw is 0.065 for 1020 observed reflections with I≥3σ(I). The absolute configuration at C(14) of the acetal carbon was proved to be S, taking into account the known configuration of 1R, 2S, 5R-menthyl moiety. There are three rings in the molecule of this compound: the furanone ring, the pyrrolidine ring and the mentholoxy group ring. The franone ring is connected with the pyrrolidine ring and the mentholoxy ring by N atom and μ2-O bridge atom respectively.     

A New Method for Synthesis of Methyl 3—Azido—3—deoxy—2—O—mesyl—5—O—benzoylxylofuranoside

A new method for synthesis of 3-azido-3-deoxyxylofuranoside was described. D-ribose was methylated, then treated with methanesulfonyl chloride to give Ⅱ.Ⅱ was selectively replaced by benzoate at the 5-position to give Ⅲ. All these processes gave good yields. Ⅲ was treated with sodium azide to afford Ⅳ, whose structure was determined by ^1H NMR and ^13C NMR.     

Syntheses of Two Chiral Clusters [η5—C5H4C（NR）CH3]—RuNiM（CO）5（μ3—S）（R=NH—C6H3—2,4—（NO2）2,M=Mo,3;M=W,4）and the Single—crystal Structure of Cluster 3

1 INTRODUCTION The synthesis of chiral clusters containing four different atoms at the vertexes of the tetrahedron has been extensively studied because the chiral cluster can induce an asymmetric catalysis potentially[1]. Until now, many tetrahedron-type chiral clusters have been reported, but only a few of the reactions about the organic group in these clusters were investi- gated[2～4]. In this paper, we described the syntheses of clusters 3 and 4, and the structure of the former. 2 …     

A New Solution—phase Parallel Synthesis of 2—Alkyamino—3—aryl—5—phenylmethylene—3,5—dihydro—4H—imidazol—4—ones

Thirteen new 2-alkylaminoimidazolones(4) wre rapidly synthesized by a new solution-phase parallel synthetic method,which includes aza-Wittig reaction of iminophosphorane(1) with aromatic isocyanate to give carbodi-imide(2) and subsequent reaction of 2 with various aliphatic primary amine in a parallel fashion.The products were confirmed by ^1H NMR,MS,IR and X-ray crystallographic analysis.The unusual selectivity of the cyclization was probably due to the deometry of the guanidine intermediate.     

卟啉化合物研究（Ⅸ）——聚5—邻丙烯酰胺苯基—10，15，20—三苯基卟啉及

将丙烯酰氯和5－邻丙烯酰胺苯基－10，15，20－三苯基卟啉（I）相连合成了5－邻丙烯酰胺苯基－10，15，20－三苯基卟啉（Ⅱ），在引发剂作用下，Ⅱ进一步聚合，生成聚5－邻丙烯酰胺苯基－10，15，20－三苯基卟啉（Ⅲ），同时还合成了单体和聚合物的钴配合物，通过元素分析、核磁共振谱、红外光谱和可见吸收光谱对单体和聚合物的结构进行了鉴定。