有机锡9-芴酮-4-甲酸酯的合成、结构及抗癌活性

合成了 3 个有机锡 9-芴酮-4-甲酸酯:三苯基锡 9-芴酮-4-甲酸酯[(C₆H₅)₃Sn(C₁₄H₇O₃)] (1)、三环己基锡 9-芴酮-4-甲酸酯[(C₆H₁₁)₃Sn(C₁₄H₇O₃)] (2)和三(2-甲基-2-苯基丙基)锡 9-芴酮-4-甲酸酯[(C₆H₅C(CH₃)₂CH₂)₃Sn(C₁₄H₇O₃)] (3)。通过元素分析、红外光谱、核磁共振谱(¹H、¹³C和 ¹¹⁹Sn)、热重分析进行了表征;用单晶X射线衍射方法测定了化合物的晶体结构,并对其进行了量子化学计算和体外抗癌活性研究。结果显示:化合物1为一维链状结构,中心锡原子为五配位的畸变三角双锥构型;化合物2和3均为单核分子,锡原子均为四配位的畸变四面体构型。化合物对人宫颈癌细(HeLa)、人肝癌细胞(HUH-7)、人非小细胞肺癌细胞(A549)、人肺腺癌细胞(H1975)和人乳腺癌细胞(MCF-7)都有较好的抑制活性。     

2-呋喃甲酸锶的晶体结构

在水溶液中合成并培育了2-呋喃甲酸锐Sr₆(C₅H₃O₃)₁₂单晶。经元素分析、红外光谱、差热热重分析、密度测定以及X射线衍射结构分析确定了该化合物的组成、结构和部分性质。结构分析结果表明:该晶体属单斜晶系,空间群P2₁/n,a=2.3090(7)nm,b=1.3376(4)nm,c=2.3093(6)nm,β=107.06(2)°,Z=4,R=0.0603.D_c=1.82×10³kg/m³,D_m=1.81×10³kg/m³.化合物通过羧氧桥联形成三维网状结构,其中Sr-O键的平均键长为0.2641nm,而Sr-O(羧氧)为0.2535nm,Sr-O(呋喃环氧)为0.2861nm.     

三个有机锡2，2′-联苯二甲酸酯的微波溶剂热合成、结构及体外抗癌活性

以2,2′-联苯二甲酸(H2DPA)分别与双(三(2-甲基-2-苯基丙基)锡)氧化物、三环己基氢氧化锡和二丁基氧化锡反应,合成了3个有机锡2,2′-联苯二甲酸酯：[((Ph C(Me)₂CH₂)₃Sn)₂(DPA)](1)、[(Cy)₃Sn(DPA)]_n (2)和[(n-Bu)₂Sn(DPA)]_n (3)。通过IR、NMR、元素分析、热重及X射线单晶衍射对配合物进行表征分析。配合物1、2、3均属单斜晶系,配合物1为双核结构,配合物2、3为一维链状结构,锡原子的配位数依次增大,分别为4、5、6。体外抗癌活性实验表明,配合物1、2、3对人肺癌细胞(NCI-H460)、人乳腺腺癌细胞(MCF-7)、人肝癌细胞(Hep G2)的增殖具有较强的抑制作用。     

三苄基和三丁基锡4-吡啶甲酸酯聚合物的合成、性质及晶体结构

用三苄基氯化锡及三丁基氯化锡与4-吡啶甲酸钠反应,分别合成了三苄基锡4-吡啶甲酸酯(1)和三丁基锡-4-吡啶甲酸酯(2),并进行了红外光谱、核磁共振氢谱及质谱表征.X射线单晶衍射分析结果表明,化合物1属单斜晶系,P2₁/n空间群,晶胞参数:a=0.96564(8)nm,b=1.64085(14)nm,c=1.49403(13)nm,β=97.681(2)₀,V=2.3460(3)nm₃,Z=4,D_c=1.456g/cm³.化合物2属单斜晶系,P2₁/n空间群,晶胞参数:a=0.96673(14)nm,b=2.3845(4)nm,c=0.97071(14)nm,β=112.463(3)o,V=2.0679(5)nm₃,Z=4,D_c=1.324g/cm³.两个化合物均通过4-吡啶甲酸配体的氮原子桥联,形成五配位三角双锥构型的一维无限链聚合物.     

系列Ln(Ⅲ)配位聚合物(Ln=Eu,Sm,Tb,Pr,Gd)的合成及其荧光分析

采用水热法合成了4个具有1D结构的Ln(Ⅲ)配位聚合物,[Eu₂(C₉H₇O₂)₆(C₉H₇O₂H)(C₂H₅OH)]n(1)、[Sm(C₉H₇O₂)₃]n(2)、[Tb(C₉H₇O₂)₃]n(3)和[Gd(C₉H₇O₂)₃]n(4)(C₉H₈O₂=肉桂酸)。 通过X射线单晶衍射确定了它们的结构。 这4个Ln(Ⅲ)配合物中,Ln(Ⅲ)的配位数均为9,桥配体均为肉桂酸根,但其配位方式有差异。 对配合物进行了IR、UV-Vis-NIR和荧光光谱等表征。 分析了各配合物的荧光发射,结果表明,在可见区,配合物1发射较明显的红光,配合物2、3发射绿光,配合物4发射蓝光,但很弱。 讨论了具有刚柔相混杂性质的肉桂酸配体对配位聚合物的构筑及稀土离子发光的影响。     

三种六氯铈(Ⅳ)酸有机盐的研究

合成了2,6-二甲基-γ-吡喃酮、咪唑和吡啶铈(Ⅳ)的氯化物,化学式为(C₇H₈O₂H)₂CeCl₆、(C₃H₄N₂H)₂CeCl₆和(C₄H₉NH)₄CeCl₈.采用差热、热重分析法比较了上述三种化合物的热稳定性,并配合以电导、红外、紫外光谱等手段进行了结构分析.     

三(2-甲基-2-苯基丙基)锡衍生物的合成及生物活性研究

三(2-甲基-2-苯基丙基)锡氧化物(Torque,苯丁锡,[(C₆H₅CMe₂CH₂)₃Sn]₂O)是-个已商品化的有机锡杀螨剂^[1]。为了研究三烃基锡衍生物中阴离子配体对生物活性的影响,本文用苯丁锡与酚或羧酸反应,合成了四个系列的含氧三(2-甲基-2-苯基丙基)锡衍生物。     

新型金属-双二硫杂戊烯(M-BDT)配合物的合成、表征及X射线的指标化

合成了4个新型NiBDT配位化合物,BDT为具有9个S原子的杂戊烯.元素分析、IR谱、UV谱确定这4个新配合物的化学式分别为[(CH₃)₄N]₂[Ni(C₅S₉)₂](1),[(C₂H₅)₄N]₂·[Ni(C₅S₉)₂](2),[(C₄H₉)₄N]₂[Ni(C₅S₉)₂](3),[(C₆H₅)(CH₃)₃N]₂[Ni(C₅S₉)₂](4).采用Ito法对配合物1的X射线粉末图进行了指标化,确定该晶体属单斜晶系,简单晶格,晶胞参数:a=0.680nm,b=0.714nm,c=2.302nm,γ=111.4°,Z=2.     

(S)-1-(2-氯乙酰基)吡咯烷-2-甲酸的制备及晶体结构

以L-脯氨酸和氯乙酰氯为原料合成维格列汀的重要中间体(S)-1-(2-氯乙酰基)吡咯烷-2-甲酸(1)。甲醇体系室温挥发14 d培养得到1的无色透明块状晶体，通过单晶X-射线衍射技术对其进行结构解析。结果表明1晶胞属于正交晶系，P2₁2₁2₁空间群，分子式为C₇H₁₀NO₃Cl，相对分子质量为191.61 g/mol，立体构型和预测构型一致，确证了1的空间结构。      

稀土冠醚类络合物的研究(Ⅲ)——硝酸钪与邻苯二酮-17-冠-5及邻苯二酮-14-冠-4固态络合物的合成与性质

制得硝酸钪与两种冠醚的固态络合物,确定其组成为Sc(NO₃)₃·C₁₆H₂₀O₇·H₂O及Sc(NO₃)₃·C₁₄H₁₆O₆·H₂O。研究了冠醚本身及其钪的相应络合物的合成及有关性质。     

Syntheses,characterizations, crystal structures,and in vitro antitumor activities of chiral triorganotin(IV) complexes containing (S)-(+)-2-(4-isobutyl-phenyl)propionic and (R)-(+)-2-(4-hydroxyphenoxy)propionic acid ligands

Four new chiral triorganotin(IV) carboxylates, [(R₃Sn)(O₂C₁₃H₁₇)] _n (R?=?Me 1, Ph 2), [(R₃Sn)(O₂C₁₃H₁₇)] (R?=?n-Bu 3), and [(R₃Sn)(O₄C₉H₉)] _n (R?=?Me 4), have been synthesized by reaction of (S)-(+)-2-(4-isobutyl-phenyl)propionic acid and (R)-(+)-2-(4hydroxyphenoxy)propionic acid with triorganotin(IV) chloride in the presence of sodium ethoxide. The complexes have been characterized by elemental analyses, FT-IR, NMR (¹H, ¹³C, and ¹¹⁹Sn) spectra, and X-ray crystallography diffraction analyses. Structural analyses show that 1 has a 1-D infinite chiral zigzag chain structure. Complexes 2 and 4 have a 1-D spring-like chiral helical chain with a channel, while 3 is a monomer. Antitumor activities of 1–4 have been studied.     

Organotin(IV) azepane dithiocarbamates: Synthesis and characterization of the first organotin(IV) complexes with seven-membered cyclic dithiocarbamates

Abstract

We report the synthesis and spectroscopic characterization of the first organotin(IV) complexes with cyclic seven-membered dithiocarbamate ligands: the azepane-1-carbodithioate and the homopiperazine-1,4-bis-carbodithioate with two different organotin entities, di-n-butyltin and tri-cyclohexyltin: [(C₄H₉)₂Sn{S₂CN(CH₂)₆}₂] (3), [(C₆H₁₁)₃Sn{S₂CN(CH₂)₆}] (4), and [(C₆H₁₁)₃Sn}₂ (μ-S₂CN(C₅H₁₀)NCS₂)] (5). Compounds (3–5) are air-stable both in solid-state and in solution, and were characterized by elemental analyses, IR, FAB⁺–MS, and multinuclear NMR (¹H, ¹³C, and ¹¹⁹Sn) spectroscopy. Their molecular structures were unambiguously established by single-crystal X-ray diffraction studies. The geometrical arrangement around the tin atom can be described as distorted octahedral for (3) and distorted trigonal bipyramid for (4) and (5). The coordination mode for both ligands is considered as asymmetric bidentate, as happens in other organotin(IV) dithiocarbamates. Furthermore, (4) and (5) do not exhibit intermolecular secondary interactions, while (3) presents intermolecular interactions between the tin and a sulfur atom with the reciprocally neighboring molecule, giving rise to a zig-zag polymeric structure.     

2, 4‐Dimethylpenta‐1, 3‐dien‐ und 2, 4‐Dimethylpentadienyl‐Komplexe des Rhodiums und Iridiums

2, 4‐Dimethylpenta‐1, 3‐diene and 2, 4‐Dimethylpentadienyl Complexes of Rhodium and Iridium The complexes [(η⁴‐C₇H₁₂)RhCl]₂ ( 1 ) (C₇H₁₂ = 2, 4‐dimethylpenta‐1, 3‐diene) and [(η⁴‐C₇H₁₂)₂IrCl] ( 2 ) were obtained by interaction of C₇H₁₂ with [(η²‐C₂H₄)₂RhCl]₂ and [(η²‐cyclooctene)₂IrCl]₂, respectively. The reaction of 1 or 2 with CpTl (Cp = η⁵‐C₅H₅) yields the compounds [CpM(η⁴‐C₇H₁₂)] ( 3a : M = Rh; 3b : M = Ir). The hydride abstraction at the pentadiene ligand of 3a , b with Ph₃CBF₄ proceeds differently depending on the solvent. In acetone or THF the “half‐open” metallocenium complexes [CpM(η⁵‐C₇H₁₁)]BF₄ ( 4a : M = Rh; 4b : M = Ir) are obtained exclusively. In dichloromethane mixtures are produced which additionally contain the species [(η⁵‐C₇H₁₁)M(η⁵‐C₅H₄CPh₃)]BF₄ ( 5a : M = Rh; 5b : M = Ir) formed by electrophilic substitution at the Cp ring, as well as the η³‐2, 4‐dimethylpentenyl compound [(η³‐C₇H₁₃)Rh{η⁵‐C₅H₃(CPh₃)₂}]BF₄ ( 6 ). By interaction of 2, 4‐dimethylpentadienyl potassium with 1 or 2 the complexes [(η⁴‐C₇H₁₂)M(η⁵‐C₇H₁₁)] ( 7a : M = Rh; 7b : M = Ir) are generated which show dynamic behaviour in solution; however, attempts to synthesize the “open” metallocenium cations [(η⁵‐C₇H₁₁)₂M]⁺ by hydride abstraction from 7a , b failed. The new compounds were characterized by elemental analysis and spectroscopically, 4b and 5a also by X‐ray structure analysis.     

Syntheses and structural characterization of organotin(IV) complexes derived from reaction of 2,3-diphenylpropionic acid and various alkyltin salts

Five new organotin(IV) complexes, [(R₃Sn)(O₂C₁₅H₁₃)] _n (R?=?Me: 1; nBu: 2), [RSn(O)(O₂C₁₅H₁₃)]₆ (R?=?Ph: 3), [(R₂Sn)₂(O₂C₁₅H₁₃)₂(μ ₃-O)]₂ (R?=?Me: 4), and [(R₂Sn)(O₂C₁₅H₁₃)₂] (R?=?nBu: 5), have been prepared by the reaction of 2,3-diphenylpropionic acid and the corresponding organotin chloride with sodium ethoxide in methanol. All the complexes were characterized by elemental analysis, FT-IR, NMR (¹H, ¹³C, ¹¹⁹Sn) spectroscopy, TGA, and X-ray crystallography. The structural analyses reveal that 1 and 2 are 1-D infinite polymeric chains with Sn in syn–anti conformation. Complex 3 has a drum structure with six Sn centers. Complex 4 has a supramolecular chain-like ladder through weak intermolecular Sn?···?O interactions. Complex 5 is a monomer, connected into a 1-D polymer through intermolecular C–H?···?O interactions. Complexes 1 and 5 crystallize in the orthorhombic space groups P212121 and P21212, which are chiral space groups.     

Organotin(IV) complexes with 2-hydroxynaphthaldehyde-N(4)-ethylthiosemicarbazone: Synthesis,characterization, and in vitro antibacterial activity

Four new organotin(IV) complexes with 2-hydroxynaphthaldehyde-N(4)-ethylthiosemicarbazone [(H₂DNET), (1)] of the type [MeSnCl(DNET] (2), [BuSnCl(DNET)] (3), [PhSnCl(DNET)] (4), and [Ph₂Sn(DNET] (5) have been synthesized by the direct reaction of H₂DNET (1) with organotin(IV) chloride(s) in the presence of potassium hydroxide in absolute methanol. All the compounds were characterized by elemental analyses, molar conductivity, UV-Vis, IR, ¹H, ¹³C, and ¹¹⁹Sn NMR spectral studies. The molecular structure of ligand (1) has been confirmed by X-ray single crystal diffraction. Spectroscopic data clearly suggested that Sn(IV) center is coordinated with the ONS tridentate ligand (H₂DNET) and exhibits a five-coordinate geometry in solution. Antibacterial studies were carried out in vitro against four bacterial strains. All organotin(IV) compounds (2–5) showed good activity against various bacteria but lower activity than the reference drug (Ciprofloxacin). The results demonstrate that organic groups attached to tin(IV) moiety have significant effect on their biological activities. Among them, diphenyltin(IV) derivative 5 exhibits significantly good activity than the other organotin(IV) derivatives (2–4).     

Synthesis and characterization of di‐n‐butyltin(IV) complexes with 4′/2′‐nitrobiphenyl‐2‐carboxylic acids: X‐ray crystal structures of [{(n‐C4H9)2Sn(OCOC12H8NO2−4′)}2O]2 and (n‐C4H9)2Sn{OCOC12H8NO2−4′}2

Reactions of di‐n‐butyltin(IV) oxide with 4′/2′‐nitrobiphenyl‐2‐carboxylic acids in 1 : 1 and 1 : 2 stoichiometry yield complexes [{(n‐C₄H₉)₂Sn(OCOC₁₂H₈NO₂?4′/2′)}₂O]₂ ( 1 and 2 ) and (n‐C₄H₉)₂Sn(OCOC₁₂H₈NO₂?4′/2′)₂ ( 3 and 4 ) respectively. These compounds were characterized by elemental analysis, IR and NMR (¹H, ¹³C and ¹¹⁹Sn) spectroscopy. The IR spectra of these compounds indicate the presence of anisobidentate carboxylate groups and non‐linear C? Sn? C bonds. From the chemical shifts δ (¹¹⁹Sn) and the coupling constants ¹J(¹³C, ¹¹⁹Sn), the coordination number of the tin atom and the geometry of its coordination sphere have been suggested. [{(n‐C₄H₉)₂Sn(OCOC₁₂H₈NO₂?4′)}₂O]₂ ( 1 ) exhibits a dimeric structure containing distannoxane units with two types of tin atom with essentially identical geometry. To a first approximation, the tin atoms appear to be pentacoordinated with distorted trigonal bipyramidal geometry. However, each type of tin atom is further subjected to a sixth weaker interaction and may be described as having a capped trigonal bipyramidal structure. The diffraction study of the complex (n‐C₄H₉)₂Sn(OCOC₁₂H₈NO₂?4′)₂ ( 3 ) shows a six–coordinate tin in a distorted octahedral frame containing bidentate asymmetric chelating carboxylate groups, with the n‐Bu groups trans to each other. The n‐Bu? Sn? n‐Bu angle is 152.8° and the Sn? O distances are 2.108(4) and 2.493(5) Å. The oxygen atom of the nitro group of the ligand does not participate in bonding to the tin atom in 1 and 3 . Crystals of 1 are triclinic with space group P1 and of that of 3 have orthorhombic space group Pnna. Copyright © 2003 John Wiley & Sons, Ltd.     

四个基于酰腙配体的双核苄基锡配合物的合成、晶体结构及体外抗癌活性

通过微波"一锅法"合成了4个双核苄基锡配合物:{[C_4H_3S(O)C=N-N=C(Me)COO](PhCH_2)_2Sn(MeOH)}_2(C1)、{[C_4H_3S(O)C=NN=C (Me)COO](p-Cl-C_6H_4CH_2)_2Sn (MeOH)}_2(C2)、{[C_4H_3S (O)C=N-N=C (PhCH_2)COO](PhCH_2)_2Sn (MeOH)}_2(C3)、{[C_4H_3S (O)C=N-N=C(PhCH_2)COO](p-Cl-C_6H_4CH_2)_2Sn(MeOH)}_2(C4),利用元素分析、IR、~1H NMR、~(13)C NMR、~(119)Sn NMR、HRMS以及X射线单晶衍射等表征了配合物结构。4个配合物分子均为双锡核分子,以Sn_2O_2四元环为中心对称,且中心锡原子与配位原子形成七配位畸变五角双锥构型。测试了配合物C1～C4的热稳定性以及配合物对癌细胞H460、HepG2、MCF7的体外抑制活性,结果表明:配合物C2是4个新合成的配合物中抑制癌细胞效果最好的化合物。     

Supramolecular Systems Based on Ca2+, [Mo3O2S2Cl6(H2O)3]2s-, [Mo3S4Cl6.75Br0.25(H2O)2]3s- and Cucurbit[6]uril

Adducts of cucurbit[6]uril with Ca²⁺ and trinuclear cluster chloroaquacomplexes (H₉O₄)₂(H₇O₃)₂[(Ca(H₂O)₅)2(C₃₆H₃₆N₂₄O₁₂)]Cl₈·0.67H₂O (1) and [(Ca(H₂O)₅)₂(C₃₆H₃₆N₂₄O₁₂)]× [Mo₃O₂S₂Cl₆(H₂O)₃]₂·13H₂O (2) are obtained and structurally characterized. The structures of both compounds contain polymeric [Ca(H₂O) _n ]₂² CB[6]∞ cations that form infinite columns; the space between them is filled with Cl^s- (1) and [Mo₃O₂S₂Cl₆(H₂O)₃]^2s- (2). A new (H₇O₃)₂(H₅O₂)× [Mo₃S₄Cl_6.25Br_0.25(H₂O)₂](C₃₆H₃₆N₂₄O₁₂)·CH₂Cl₂·6H₂O complex (3) is also obtained and structurally characterized.