鸦胆子化学成分的研究 Ⅰ.鸦胆子酮酸等五个苦木素的分离和鉴定

鸦胆子系我国常用中药,从中分得五个苦木素类化合物.其中四种依次鉴定为已知的鸦胆子苦醇(1),鸦胆子苦素D(2),去氢鸦胆子苦素B(3),鸦胆子苦素E(4).另一种为新化合物,经光谱及化学方法推定其结构为5,命名为鸦胆子酮酸.1对S₁₈₀瘤株有边缘活性.2和4有抗疟作用.     

鸦胆子化学成分的研究 Ⅲ.新苦木素——鸦胆子苦烯的分离和结构

从中药鸦胆子中分得一具有新型A环结构的苦木素——鸦胆子苦烯,C_(20)H_(26)O_8.已由IR,~1HNMR,~(13)C NMR及MS推定其结构.它对KB细胞显示抑制活性.     

鸦胆子甙的化学结构研究

鸦胆子甙的分子式已初步定为C_(20)H_(32)O_9,系葡萄糖甙,示性式为C_(10)H_(11)(F)(OH)(CH_3)_3(内酯—O—CO—)(OC_6H_(11)O_5)。     

苦玄参化学成分的研究 ⅤⅢ.苦玄参苷Ⅱ的结构

从苦玄参(Picria fel-tarrae Lour)提取的有抗癌活性的B部分,在分离苦玄参苷IA和IB时,还分离到另一少量新苦味苷——苦玄参苷(Picfeltarraenin)Ⅱ(1).本文报道1的结构测定. 1经8％硫酸水解产生苦玄参苷元Ⅱ(2),所产生的糖经定性鉴定为D-葡萄糖和L-鼠李糖.根据1的FDMS所获得的准分子离子峰[M+Na+1]~+及元素分析,确定其分子式为C_(42)H_(66)O_(15),即1含一个葡萄糖和一个鼠李糖残基.1的~(13)C NMR谱中出现两个异头碳(anomeric carbon)信号,也符合上述推定.     

Syntheses,Crystal Structures,Magnetic and Luminescent Properties of Ni(Ⅱ), Cd(Ⅱ) and Pb(Ⅱ) Coordination Compounds Constructed from 5-Fluoronicotinic Acid

Five coordination compounds, namely [Ni_2(5-Fnic)_2(H_2 O)_4](1), [Ni(5-Fnic)(μ-5-Fnic)(H_2 biim)]n(2), {[Cd((μ-5-Fnic)2(H2 O)2]×4,4'-bipy}n(3), [Pb_2(μ-5-Fnic)_2(μ3-5-Fnic)_2(H_2 O)_2]n(4), and [Pb(5-Fnic)_2(4,4'-bipy)(H_2 O)](5), have been constructed hydrothermally using 5-FnicH(5-FnicH = 5-fluoronicotinic acid), H_2 biim(H_2 biim = 2,2'-biimidazole), 4,4'-bipy(4,4'-bipy = 4,4'-bipyridine), NiCl_2×6 H_2 O, CdCl_2×H_2 O and PbCl_2. The products were isolated as stable crystalline solids and were characterized by IR spectra, elemental analyses, thermogravimetric analyses(TGA), and single-crystal X-ray diffraction analyses. Structures of 1～5 range from discrete 0 D monomers(1 and 5) to 1 D coordination polymers(2 and 4) and 2 D metal-organic network(3). A broad structural diversity of 1～5 is guided by the type of the metal(Ⅱ) node and the introduction of auxiliary ligands. The magnetic(for 2) and luminescent(for 3～5) properties were also investigated and discussed.     

Syntheses,Structures and Catalytic Properties of Two Mn(Ⅱ) and Cd(Ⅱ) Coordination Polymers through in Situ Ligand Reaction

Two coordination polymers, namely [Mn(μ-Hcpia)(bipy)(H_2O)_2]_n(1) and [Cd_3(μ_3-Hcpia)_2(μ-Hbiim)_2(μ-H_2biim)(H_2O)_2]_n(2), have been constructed hydrothermally using H_2cbia(H_2cbia = 5-(4'-cyanobenzoxy)isophthalic acid), bipy(bipy = 4,4'-bipyridine), H_2biim(H_2biim = 2,2'-biimidazole), and manganese or cadmium chlorides at 160℃. Interestingly, the H_3cpia(H_3cpia = 5-(4'-carboxylphenoxy)isophthalic acid) ligand was generated by in situ hydrolysis of cyano group in H_2cbia. The products were isolated as stable crystalline solids and were characterized by IR spectra, elemental analyses, thermogravimetric analyses(TGA), and single-crystal X-ray diffraction analyses. Both compounds crystallize in the triclinic system, space group P1. Compound 1 discloses a 1D linear chain of the 2C1 topological type. Adjacent chains are assembled into a 2D supramolecular sheet through O–H···O/N hydrogen bonds. Compound 2 features a 3D framework with a 3,4,4 T25 topology. The luminescent and catalytic properties of two compounds were investigated. Compound 1 exhibits a superior catalytic activity in the cyanosilylation at room temperature.     

鸦胆子化学成份的研究 II.鸦胆子苦素E-葡萄糖苷

A new quassinoid glucoside, yadanzigan (1a), has been isolated from Brucea javanica (L) Merr. 1a has formula C26H38O14(M+574), m.p. 243-245C, (α)D^2^3 60.0 (c. 1.70, H2O). The structure has been established as brucein E-2-β-D-glucopyranoside by enzymatic hydrolysis of 1a and elemental analyses, ^1H NMR, ^1^3C NMR and mass spectral analyses of 1a and its aglycone 2a.     

Effect of pH/Auxiliary Ligand on the Structures of Coordination Compounds Based on a Novel Ligand 2,6-Bis(pyrazin-2-yl)pyridine-4-carboxylate

Four new coordination compounds, [Zn(bppc)_2(H_2O)_2]·3 H_2O(1), [Zn2(bppc)2(mbdc)(H_2O)4]·7 H_2O(2), [Zn(bppc)2(H_2O)2]n·n(m-Hbdc)·n(H_2O)(3), [Zn2(bppc)(btc)(H_2O)3]n·5 n H_2O(4)(Hbppc = 2,6-bis(pyrazin-2-yl)pyridine-4-carboxylate, H2(m-bdc) = 1,3-benzenedicarboxylic acid, H3 btc = 1,3,5-benzene-tricarboxylic acid), have been hydrothermally synthesized and structurally characterized. Compound 1 shows a mononuclear structure and 2 shows a dinuclear structure. Compound 3 is a one-dimensional chain structure, which is extended into a 3D supramolecular network by intermolecular hydrogen interactions. In 4, a 1D loop-like chain is connected by(btc)3-anions to generate a 2D layer structure. The structure differences of 1~4 show that the p H and aromatic acid as auxiliary ligand have important influence on the final structures.iAdditionally, the luminescent properties of 1~4 have been investigated with fluorescent spectra in the solid state, and 1~4 display a strong fluorescent emission at room temperature and have potential applications as fluorescent-emitting materials.     

Synthesis of La(Ⅲ), Y(Ⅲ) complexes with polyglycol aldehyde-amino acid Schiff base and their high resolution solid state ~(13)C NMR spectra

La(Ⅲ), Y(Ⅲ) complexes with diglycol aldehyde bis-arginine (H_2DAAR) and tetraglycol aldehyde bislysine (H_2TALY) Schiff bases were synthesized. They were characterized and formulated as La(H_2DAAR) (NO_3)_3·6H_2O and Y (H_2TALY)(NO_3)_3·5H_2O separately by elemental analyses. The obtained complexes were investigated in detail by high resolution solid state (HRSS) ~(13)C NMR using cross polarization, magic angle spinning (CPMAS), and total suppression of sidebands (TOSS)techniques. The results are supported by the liquid state 2D-~1H-~(13)C COSY NMR spectra. Some new information about the splitting peaks of ~(13)C for—CH=N—group and alkene carbon bands, etc. in HRSS ~(13)C NMR spectra are given.     

特丁醇和水混合溶剂多组分电解质热力学HCl—NaCl—tert—C_4H_9OH—H_2O体系(5～45℃)

本文在恒定特丁醇质量分数x=0.10的条件下,应用电动势法测定了无液接界电池(A)和电池(B)的电动势:Pt,H_2(1.013×10~5Pa)HCl(m),tert.-C_(4)H_9OH(x),H_2O(1-x)AgCl-Ag(A)Pt,H_2(1.013×10~5Pa)|HCI(m_A),NaCl(m_B),tert,-C_4H_9OH(x),H_2O(1-x)|AgCl-Ag(B)根据电池(A)电动势确定了混合溶剂中的Ag-AgCl电极的标准电极电势,讨论了HCl的迁移性质;利用电池(B)的电动势计算了HCl在该体系中的活度系数γ_A,结果表明,在恒定总离子强度下,HCl的活度系数服从Harned规则.计算了HCl的一级、二级和总介质效应.     

二元羧酸二(二茂镱)的合成

本文报道了五个新的二元羧酸二(二茂镱)的合成:(COO)_2Yb_2(C_5H_5)_4(1),CH_2(COO)_2Yb_2(C_5H_5)_4(2),(CH_2COO)_2Yb_2(C_5H_5)_4(3),o-C_6H_4(COO)_2Yb_2(C_5H_5)_4(4),p-C_6H_4(COO)_2Yb_2(C_5H_5)_4(5),并考察了它们对空气的稳定性。     

Syntheses of(C_8H_8)Ln(C_9H_7)·(THF)_2(Ln=Pr,Nd)and crystal structure of(C_8H_8)Pr(C_9H_7)·(THF)_2

This paper reports two lanthanide complexes of formula (C_9H_7)Ln(C_8H_8)·(THF)_2 whereLn is Pr or Nd,C_9H_7 is indenyl,and C_8H_8 is cyclooctatetraene (COT).The complexes were preparedby the reaction of LnCl_3 with K(C_9H_7) and K_2(C_8H_8) in THF.(C_9H_7)Pr(C_8H_8)·(THF)_2 crystallizes inTHF at - 15℃ in the monoclinic space group P2_1:with unit cell dimensions a=8.446(0),b=10.083(2),c=13.407(3),β=105.48(1)°,V=1100.43(35)~3,Dc=1.52g/cm~3 and Z=2.The final R valueis 0.033,R_w value is 0.030,respectively.In (C_9H_7)Pr(C_8H_8)·(THF)_2 a five-membered ring centroid ofC_9H_7,the C_8H_8 ring centroid and the two oxygen atoms from the two THF molecules form a distortedtetrahedral geometry around the metal.     

4-偕胺肟双吡啶季铵碘盐的合成

双吡啶醛肟季铵盐类对某些有机磷酸酯类中毒具有明显的对抗作用,因此合成了一类4-偕胺肟双吡啶季铵碘盐化合物(1a～1n),以期找出更有效的抗毒剂. CONR_2取代在3位:NR_2=NH_2(a),N(CH_3)_2(b),N(C_2H_5)2(c),NHC_3H_(7-n)(d),NHC_3H_(7-i)(e),NHC_4H_9n(f),NHC_4H_(9-i)(g), CONR_2取代在4位:NR_2=NH_2(1),NHC_3H_(7-n)(m),这类新化合物的合成是以4-吡啶甲酸(2)制得4-氰基吡啶(3),再与盐酸羟胺作用制得4-吡啶偕胺肟(4),然后与α,α’-二氯甲醚作用制得N-氯甲氧甲基-4-吡啶偕胺肟氯盐(简称单氯盐,5),最后与相应的N-取代吡啶甲酰胺(6)作用而得.     

SYNTHESIS AND STRUCTURE OF Cu(Ⅱ)COMPLEXES BY OXIDATIVE ADDITION OF DIBENZOYL PEROXIDE ON METALLIC COPPER

Dibenzoyl peroxide undergoes oxidative addition on metallic copperpowder with 2,2′-bipyridine(or imidazole)in a mixed solvent(methanol andtetrahydrofuran),and affords the Cu(Ⅱ)complexes-[Cu(Ce(C_6H_5COO)_2(2,2'-bipy)]H_2O(1)and[Cu(C_6H_5COO)_2(C_3H_4N_2)_2](2).The structure was solved by direct methodsand Fourier synthesis.C_(24)H_(20)N_2O_5Cu (1),Mr=479.78,space group P2(1)/c,a=6.986(7),b=18.833(I),c=17.021(3),α=γ=90°,Z=4,V=2218.1~3,Dc=1.443g/cm\+3,R=0.055Rw=0.062.Complex(2),C_(20)H_(18)N_4O_4Cu(2),Mr=441.74,space group P2(1)/n,a=8.699(4),b=9.840(6),c=12.399(5),α=γ=90°,β=100.8°,Z=4,V=1010.9~3,Dc=1.654g/cm\+3,R=0.055,Rw=0.062.     

Heterometal–organic frameworks: Three novel copper(Ⅱ)–lanthanide(Ⅲ) 15-metallacrown-5 complexes based on pyrazinohydroxamic acid as new multiple-binding pentagonal platform

Reactions of copper(Ⅱ) sulfate or copper(Ⅱ) perchlorate,samarium(Ⅲ),erbium(Ⅲ) or neodymium(Ⅲ)nitrate(5/1 equiv.) with pyrazinohydroxamic acid(H_2Pyzha) in H_2O/Me0 H led to three new heterobimetallic 15-metallacrown-5 complexes.In a MeOH/H_2O solution,when adding inorganic salts,the ligands exist as protonated metallacrowns.In the solid state,their structures are more complicated as confirmed by X-ray analysis:metallacrown[Sm(H_2O)_3 {Cu(pyzha)}_5(H_2O)_2(MeOH)(HSO_4)_2]·(H_2O)_2(HSO_4)(1);[Nd(H_2O)_2(MeOH) {Cu(pyzha)}_5(ClO_4)_2(H_2O)_5(NO_3)](2);[Eu(H_2O)_2(MeOH) {Cu(pyzha)}_5(ClO_4)_2(H_2O)_5(NO_3)](3).The differentiation of atomic and ionic radii between the encapsulated lanthanide(Ⅲ) could be used to control the bowl-shape distortion of the metallacrowns from the planar geometry.The complex 1 clearly exhibits fluorescence behavior of samarium(Ⅲ),while 2and 3 show that of copper(Ⅱ) and ligand.     

Synthesis and Characterization of Organoboryl Germanium (Ⅱ) Oxides Containing Ge-O-B and Ge-O-B-O-Ge Cores

Organoboryl germanium(Ⅱ) oxides were synthesized from the 1,4-addition reaction of L'Ge(L'=HC[C(CH_2)N(Ar)]C(Me)N(Ar),Ar=2,6-iPr_2C_6H_3) with selected monosubstituted arylboronic acids RB(OH)_2(R=2,6-Me_2C_6H_3,2,4,6-Me_3C_6H_2,1-Naph) at the molar ratios of 1:1 and 2:1.The mononuclear products RB(OH)OGeL(L=CH[C(Me)N(Ar)]_2,Ar=2,6-iPr_2C_6H_3;R=2,6-Me_2C_6H_3(1),2,4,6-Me_3C_6H_2(2),1-Naph(3)) containing the Ge-O-B core were obtained smoothly through the 1:1 reaction.However,the reaction of L'Ge with 2,6-Me_2C_6H_3B(OH)_2 in a 2:1 ratio gave only the mononuclear product(1) instead of the expected binuclear one.What's more,a new borate compound [(2,6-Me_2C_6H_3)_4B_5O_6]~-[H:C]~+(4)(:C=C[N(iPr)C(Me)]_2) was concomitantly formed when the in situ prepared L'Ge was used as the precursor.In contrast,the use of 2,4,6-Me_3C_6H_2B(OH)_2 or1-NaphB(OH)_2 as the organoboryl source in the similar reaction led to the formation and isolation of the binuclear products RB(OGeL)2(R=2,4,6-Me_3C_6H_2(5),1-Naph(6)) containing the Ge-O-B-O-Ge core in a straight way.Compounds 1~6 were determined by single-crystal X-ray diffraction analysis.     

Metal-induced Coordination Networks Using a C_(2v)-based Hexacarboxylate Ligand:Syntheses,Structures and Properties

Metal-organic frameworks(MOFs), consisting of metal, anion and organic ligands, have attracted much attention. The structure of MOFs is affected by various factors. To explore the effects of metal ions, we synthesized six complexes, namely {[Me_2NH_2][Zn_4(H_2L)(L)]·2 H_2O·2 DMF}_n(1), {[Me_2NH_2]_2[Cd_2(L)]·2H_2O}_n(2), {[Me_2NH_2]_2[Ca_3(L)(μ-OH)_2(DMF)_2]·2H_2O}_n(3) and {[Me_2NH_2]_2[M_2(L)(μ-OH)]· H_2O·2DMF}_n(M = Co, 4; Ni, 5; Mn, 6), from a C_(2v)-based hexacarboxylate ligand([1,1';4',1']terphenyl-3,5,2',5',3',5'-hexacarboxylic acid(H_6L)) using metal-induced strategy. These MOFs were thoroughly characterized by single-crystal and X-ray diffraction, elemental analysis, Fourier-transform infrared spectra(FTIR) and photoluminescence.     

含烯烃配体的过渡金属卡宾配合物的研究 Ⅱ.异戊二烯二羰基[乙氧基(芳基)卡宾]铁配合物的异构化产物的合成、波谱和结构研究及四羰基[乙氧基(五氯苯基)卡宾]铁的晶体结构

异戊二烯三羰基铁(1)与芳基锂ArLi(Ar=C_6H_5,p-CH_3C_6H_4,p-CH_3OC_6H_4,p-CF_3C_6H_4)在低温下反应,再用Et_3OBF_4烷基化,可获得组成为C_5H_8(CO)_2FeC(OC_2H_5)Ar的标题化合物的异构化产物(2—5).当用LiC_6Cl_5作亲核试剂,在相同条件下与1反应时,只生成已知的配合物(CO)_4FeC(OC_2H_5)C_6cl_5(6).由单晶X射线衍射数据推断出,2和6的分子结构都属于单斜晶系,Z=4.2的空间群为C_(2h)~5-P_2(1/n),α=8.544(2),b=14.494(5),c=12.309(4)A,β=96.16(2)°;6的空间群为C_(2h)~5-P2_(1/c),a=14.126(3),b=6.805(1),c=19.182(5)A,β=103.58(2)°.2和6的结构用SHELXTL直接法程序解出并经块矩阵最小二乘法修正,R分别为0.066和0.043.     

Hydrothermal Synthesis and Crystal Structure of a Cd~(2+) Supramolecular Coordination Complex{[Cd_2(HCAM)_2(H_2O)_4]·3.5H_2O}_n with a 3D Metal-organic Open Framework

<正>A three-dimensional coordination polymer {[Cd_2(HCAM)_2(H_2O)_4]·3.5H_2O}_n was synthesized by the hydrothermal reaction of H_3CAM(H_3CAM=4-hydroxypyridine-2,6-dicerboxylic acid)and Cd(NO_3)_2·4H_2O.The structure was characterized by elemental analysis,thermal gravimetric analysis,infrared spectroscopy and single-crystal X-ray diffraction.It crystallizes in triclinic,space group P_1~-with a= 9.4389(19),b=11.009(2),c=11.192(2)(?),α=87.87(3),β= 74.63(3),γ=81.22(3)°,V=1108.2(4)(?)~3,Z=2,D_c=2.164g/cm~3,μ=2.011 mm~(-1),F(000)=710,R =0.0419 and wR=0.1170.X-ray analysis reveals that the title compound adopts a one-dimensional staircase structure by carboxyl of H_3CAM and water molecules,and it is further linked by hydrogen bonds to form a 3-D metal-organic open framework.The thermal gravimetric analysis displays that the framework exists stably below 300℃.     

二茂镱苯甲酸衍生物的合成

本文合成了六种新的二茂镱苯甲酸衍生物:Cp_2YbOCOC_6H_4(o-OC_2H_5),Cp_2YbOCOC_6H_4-(o-OCH_2CH_2CH_3),Cp_2YbOCOC_6H_4(o-Cl),Cp_2YbOCOC_6H_4(o-Br),Cp_2YbOCOC_6H_4(o-I)及Cp_2YbOCOC_6H_4(D-NHC_6H_5)。这些化合物经元素分析、红外光谱、质谱及光电子能谱鉴定,确证为羧酸阴离子与二茂镱的桥式配位二聚体结构。分子中苯甲酸阴离子的邻位取代基上的配位原子(O,Cl,Br,I,N)与镱均有微弱的络合。这些化合物在空气中均较它们的母体(Cp_2YbOCOC_6H_5)稳定。