2, 2, 4, 13, 13, 15, —六甲基—1, 5, 12, 16—四氮杂环二十二烷—N′, N″′—二乙酸及其镧系配合物的合成和表征

本文合成了题头所示大环配体,并制备了它的十四种镧系元素(La～Lu,Pm除外)固体配合物.用元素分析,DTA-TG,红外光谱以及电导测定等手段研究了这些化合物的组成和性质.基于这些分析结果可建议配合物化学式为Ln(H₂L)(NO₃)₃·nH₂O.     

A Novel Diterpenoid,11—O—β—D—glucopyranosylneo—triptophenolide, from Tripterygium wilfordii Hook.f

A new diterpenoid was isolated from the ethanolic extract of the dried root bark of Tripterygium wilfordii Hook.f. It is the first example of abietane diterpenoid glycoside isolated from Tripterygium wilfordii Hook.f.Its structure was identified to be 11-0-β-D-glucopyranosyl-neotriptophenolide based on spectral methods.     

四元尖晶石相Li——M——Mn——O(M=Ni,Cr,Mo,V)嵌入电极的研究

制备了用不同价态的几种金属阳离子(Ni2^+,Cr3^+,V5^+,Mo6^+)修饰的尖晶石LiMn~2O~4嵌入化合物作为锂二次电池的阴极材料,对Li/LiM~yMn~2~-~yO~4电池进行了电化学和X射线衍射研究.结果表明,其它离子的掺杂使标准尖晶石LiMn~2O~4电极对锂的反复脱嵌和嵌入有了更强的承受力,但在不同程度上降低了其初始容量.循环性能的提高归于掺杂的金属阳离子使尖晶石结构趋于更稳定.同时还讨论了修饰离子对尖晶石相在充放电时5V电压平台出现的影响。     

四元尖晶石相Li——M——Mn——O(M=Ni,Cr,Mo,V)嵌入电极的研究

制备了用不同价态的几种金属阳离子(Ni2^+,Cr3^+,V5^+,Mo6^+)修饰的尖晶石LiMn~2O~4嵌入化合物作为锂二次电池的阴极材料,对Li/LiM~yMn~2~-~yO~4电池进行了电化学和X射线衍射研究.结果表明,其它离子的掺杂使标准尖晶石LiMn~2O~4电极对锂的反复脱嵌和嵌入有了更强的承受力,但在不同程度上降低了其初始容量.循环性能的提高归于掺杂的金属阳离子使尖晶石结构趋于更稳定.同时还讨论了修饰离子对尖晶石相在充放电时5V电压平台出现的影响。     

Synthesis of Cholest—5—en—24—oxo—3β,19—Diacetate

Cholest-5-en-24-oxo-3β,19-diacetate was synthesized strarting form stigmasterol 3 via seven step reactions in 21.0% overall yield. It can be served as a key intermediate for the synthesis of many biologically active 19-hydroxylated sterols.     

Synthesis of Cyanobenzaldehydes （m—,o—,p—）by Molecular oxygen Oxidation Methods

Cyanobenzaldehydes (m-,o-,p-) were synthesized by oxidation of corresponding tolunitriles with molecular oxygen,catalyzed by cobalt acetate and sodium bromide.     

Evaluation of Transient Absorption Spectra of N,N,N’,N’—Tetra—（p—methylphenyl）

Photoinduced electron transfer processes between fullerenes(C60/C70)and N,N,N’,N’-tetra-(p-methylphenyl-4,4’-diamino-1,1’-diphenyl ether(TPDAE)have been studied by nanosecond laser flash photolysis.Quantum yields and rate constants of electron trasfer from TPDAE to excited triplet state of fullerenes(C60/C70)in benzonitrile have been evaluated by observing the trasient absorption bands in the near-IR region where the excited triplet state.radical anion of fullerenes(C60/C70)and radical cations of TPDAE appear.     

N,O,O',—三(对—甲苯磺酰基)双(2—羟乙基)胺的合成

二乙醇胺和对—甲苯磺酰氯在三乙胺的作用下.反应生成N.O,O'-(三对甲苯磺酰基)双(2—羟乙基)胺,产率为93％。从反应混合物中分离得到产物N,O-二(对—甲苯磺酰基)双(2—羟乙基)胺。     

（E,E）—3,7—二甲基—2,6—癸二烯—1,10—二醇的高立体选择？…

1969年 Meinwald等 [1] 从一系列雄性蝴蝶的“hair pencils”中分离得到一组信息素成分 ,包括一类新颖的开链倍半萜骨架化合物 1— 3.尽管这些化合物在结构上与香叶醇相似 ,但利用香叶醇为原料进行合成的报道 [2～ 5] 还不多见 .本文以香叶醇为原料 ,报道了化合物 3的一条简便、高立体选择性的合成路线 .其关键反应步骤是 2 ,3-环氧醇的碘代重排反应和烯丙基烯基醚的克莱森重排反应 .a.Ac2 O,Pyridine,r.t.,2 h,yield 98% ;b.Se O2 ,t-Bu OOH,CH2 Cl2 ,r.t.,3 h,yield 73 % ;c.VO( acac) 2 ,t-Bu OOH,reflux,2 h,yield 90 % ;d.Ph3…     

Synthesis of 2— and 5—（1,1—Dimethy1—,2,5,6—tetrahydropyridinium—3—yl）oxadiazoline Iodides

A series of 2- and 5-(1,1-Dimethy1-,2,5,6-tetrahydropyridinium-3-yl)oxadiazoline Iodides,which might be used as M1 muscarinic receptor agonists,was synthesized from nicotinaldehyde and nicotinhydrazine,respectively.Their structures were characterized by ^1H NMR,IR,MS spectra and elemental analysis.     

Aa—Bb,Cc,Dd缩聚反应的固化理论

本文讨论了A_a-B_b,C_c,D_d缩聚反应.给出了溶胶-凝胶分配公式、凝胶化条件、分布函数和适合固化全过程的高分子矩的循环公式,以及k次矩的解析表示式.     

The Structure of Ammonium,D,L—Tartrate

1 INTRODUCTION The enantiomers separated by a co- crystallization method using an appropriate chiral as separating reagent has attracted many attentions in the past years[1]. Recently we are interested in enantiomeric discrimination by chiral amino acid. When racemic D,L-tartaric acid was tried to be separated by the L-glutamine in a hot aqueous solution, the well shaped crystals were obtained. The determination of melting point (220℃) and density (1.66 g穋m－3) showed it is…     

Three-dimensional 3d-4d Heterometallic Coordination Polymer——Synthesis,Structure,Magnetic and Luminescent Properties

A new three-dimensional 3d-4d heterometallic coordination polymer,[Cd2Mn(H2O)4(BTC)2]·2H2O(BTC=1,3,5-benzenetricarboxylate) was prepared under hydrothermal conditions and characterized by single crystal X-ray diffraction.This compound crystallized in the monoclinic space group C2/c,with cell parameters a=1.9452(4) nm,b=0.7094(2) nm,c=1.8064(4) nm,β=118.02(3)°,V=2.2004(8) nm3 and Z=4.Its structure contains trinuclear mixed metal clusters,which are further connected by BTC to form a three-dimensional framework.The compound exhibits intense photoluminescence at room temperature.Magnetic studies of the compound show a dominant antiferromagnetic exchange between the Mn(Ⅱ) ions.     

Synthesis and Structure of Vanadium—barium Complex of 2, 4, 6—Tripicolinato with 20—Member Macrocyclic Cavities

Recently, the thermal decomposition of heteronuclear complexes has become apromising method for the preparation of di- or tri-metallic oxides because the complex as precursor has the special microstructure, the controlled stoichiometry of the metals and lower decomposition temperature 1. In order to investigate Ba-V-O system, which has the special magnetic behavior 2, we synthesized the title complex as the precursor of this material. On the other hand, microporous constructions existing in…     

ESR STUDIES OF SPIN-TRAPPED RADICALS IN GAMMA-IRRADIATED POLYCRYSTALLINE PYRIMIDINE NUCLEOSIDES——CYTIDINE, DEOXYCYTIDINE, URIDINE AND DEOXYURIDINE

Room-temperature free radicals produced in four gamma-irradiated polycrystalline pyrimidine nucleosides (cytidine, deoxycytidine, uridine and deoxyuridine) were studied by an improved spin trapping and ESR methods with NtB (nitroso-t-butane) serving as the spin trap. The presence of three types of radicals was ascertained in all samples, i.e. —C(5)H—C(6) H_2—and —C(5)H_2—C(6)H— base radicals, and —C(5')H_2— ribose radical evolving from HOC(5')H—C(4')H<. In addition, radicals in which the unpaired electron was located on ribose C(1') and C(4') sites were tentatively distinguished. Stress was laid on the discussion of the mechanism of formation of ribose radicals.     

SUBSTITUTION REACTIONS OF ALKANES——BROMINATION OF PENTANE,HEXANE AND HEPTANE

In the photo-bromination of pentane, hexane and heptane with bromine, N-bromo-diethylamine or N-bromo-succinimide, the authors found that the mono-bromo-pentanes, -hexanes and-heptanes obtained contain the isomers in the same proportions disregarding whatever brom-inating reagent is used. Among the isomers, 2-bromo-compounds occur in dominant quantitieswhile 1-bromo-compounds are nearly nil. The authors attributed these phenomena mainly tothe low mobility of bromine molecules but the rearrangement of the alkyl free radicals fromprimary to the secondary. Compared with chlorination, chlorine molecules are more mobileand combine with alkyl free radicals rather rapidly before rearrangement occurs, which makes1-chloro-isomer more abundant.     

β,γ—不饱和酰胺合成新方法

α-芳基和α-烯基羰基结构是一类天然生物分子的重要特征结构.我们曾用二烷基烯烃基铝同α-卤代酸酯反应立体选择性地合成β,γ-不饱和酸酯.本文通过二烷基烯烃基铝与丁基锂形成的酸根型配合物,与α-卤代酰胺反应制备β,γ-不饱和酰胺.     

A NEW CHILOTHERE SKULL FROM HEZHENG,GANSU, CHINA——WITH SPECIAL REFERENCE TO THE CHINESE "DICERATHERIUM"

In this paper a new chilothere species, Acerorhinus hezhengensis represented by associated skull andlower jaw from Late Miocene deposits of Hezheng, Gansu, is described. The Chinese "Diceratherium"problem is reviewed and analysed. Systematically, the Chinese "Diccratherium" has scarcely any direct rela-tion with the true Diceratherium of North America. Heissig's referral of the Chinese "Diceratherium" toChilotherium as a subgenus is here disputed. A series of distinctive characters warrant the Chinese "Di-ceratherium" a generic rank, for which Acerorhinus created by Kretzoi in 1942 is adopted. Acerorhinusshares common apomorphic features exclusively with Chilotherium. They may represent a separate tribein the subfamily Acerotheriinae: Chilotherini.     

Efficient Synthesis of 2—Ethyl—A—ring Analogues of 19—Nor—1α,25—dihydroxy Vitamin D3

The novel 19-nor-1α,25-dihydroxy vitamin D3 analogues possessing an ethyl at the 2-position(4 and 5).were synthesized by coupling 25-hydroxy Windaus-Grundmann ketone derivative 20 with A-ring synthons(15 and 19)respectively.The enantioselective synthesis of substituted bicyclic[3,1,0]hexanes structure A-ring synthons,started from all-cis-3,5-dihydroxy-4-ethyl-1-(methoxycarbonyl)cyclohexane via lipase-catalyzd asymmetrization,was demonstratcd.     

Nonlinear Optical Properties of Tri—nuclear Transition Metal Clusters M—（μ—S）s—M′（M=Mo,W;M′=Cu,Ag,Au）

The static polarizabilities and the second-order hyperpolarizabilities of a series of tri-nuclear metal cluster models MS4(M′PPh3)2(M′PPh3)(M=Mo,W;M′=Cu,Ag,Au)have been calculated within the first-principle theoretical framework. The model clusters have two fragments of rhombic units and it is the charge ransfer from one of these moieties to the other that is responsible for nonlinear optical property. This kind of electronic delocaization, differentiated from that of planar π-system, is very interesting and is worthy for further investigation.